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Syntheses of heterocyclic compounds containing B-N coordinate bonds as models for thermally stable polymers

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Syntheses of heterocyclic compounds containing B-N coordinate bonds as models for thermally stable polymers
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McCormick, Charles Lewis, 1946-
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viii, 140 leaves. : illus. ; 28 cm.

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Distillation ( jstor )
Ethers ( jstor )
Flasks ( jstor )
Infrared spectrum ( jstor )
Liquids ( jstor )
Mass spectra ( jstor )
Nitrogen ( jstor )
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Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
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Thesis -- University of Florida.
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Bibliography: leaves 134-139.
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Typescript.
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Vita.

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5':;:T :F:.: OF H.TE: .'CYCLIC COrMPOUNDS CONTAIMNiI B--N COCRINA[E

B9C.....- AS MODELS

FOPR TI: I-.L:.Y STABLE POLYMERS











CHARLES LEWI MCCOR!ICK III









A DISSERTATION PRESENTED TO Th-E G -))ADUATF 7U0J;CEL 0, TE JNIVE-T: *F

FLOPIDA IN PASTA FULLILL T OF REQI 'L.i'' "'LT

OCR THE DEGRE OrF DOCTORR G FHIL.SuPH


t' r~; -'''




















This dissertation is dedicated in memory of

Mr. Claude Stuart

who dedicated his life to teaching chemistry

in the Greenville, Mississippi, Public School

System.

















ACKNOWLEDGEMENTS


I wish to express my gratitude and appreciation to Dr. G. B. Butler

for his patience, guidance, and understanding during the course of this

research. My appreciation is also extended to Dr. T. E. Hogen Esch, Dr.

Paul Tarrant, Dr. Martin Vala, and Dr. Henry C. Brown for serving on my

supervisory committee.

Grateful thanks are extended to my colleagues in the laboratory for

their frienship and good humor, which made work quite enjoyable.

The financial assistance received from the National Science Founda-

tion is gratefully acknowledged (grant number GH32766 and GH17926i)

I also wish to thank my parents for their support and encoragement

during my graduate studies.

A special expression of gratitude goes to my wife, Pat, for her love,

encouragement, and assistance in completion of this project.














TABLE OF CONTENTS


Page


Acknowledgements..... ... .

List of Tables .

List of Figures. .

Abstract. vi

Chapter

I. IIITF.CDUCTI .

A. Polymers Exhibiting Principles of Thermal Stability
B. Boron-Nitrogen polymers .
C. Boron-Oxygen Polymers .
D. Boron-Carbon Polymers. .. ..
E. Amine-Boranes as Hydroborating Agents .
F, Boron-Nitrogen Coordinate Bonds in Cyclic and
Bicyclic Compounds .... .
G. Statement of Problem .

II. SYNTHESES OF UNSATURATED TERTIARY ANILINES .

A. Syntneses of Para-substituted-N.N-Diallylanilines
B. Synthesis of N,N,N',N'-Tetraallyl-p-
phenylenediamine .
C. Synthesis of N,N-Di-3-butenylaniline .


III. 'FFiPAF.'iION OF BORON INTERMEDIATES .


Synthesis of Grignard Reagents
Preparation of Substituted Pbenylboronic Acids
Syntheses of Borate Esters of Substituted
PhenylDooronic Acids .
Cyclotriboroxenes .
Preparation of Triethyl- .- fr.-!;, Lboranes
Preparation of Pyridine-Phenylborane .













IV. SYNTHESES AND REACTIONS.OOF BORON HETEROCYCLES 31

A. Reaction of Triethylamine-Phenylborane with
N,N-Diallylaniline .. 31
B. Mechanism of Formation of Azaborolidines and
Azaborabicyclo(3.3.O.)octanes .. .35
C. Deuterium Labeling Studies 41
D. Preparation of 3-Deuteropropene by an
Alternate Method .. .. 50
E. Preparation and Reactions of p-Substituted 1,5-
Diphenyl-l-aza-5-borabicyclo(3.3.0. )cctanes 50
F. Preparation of Bic-L,L4-[L5-( 4-m-ethylphenyl.)-1-
aza-5-borabicyclo(3.3.0.)octyl]benzene and
Bis-1.,4-[5-( 4-chlorophenyl )-l-aza-5 -borabicycio-
(3.3.0.)octyl]benzene .
G. Reaction of N,N,N',N'-Tetraallyl-p-phc.ylene-
diamine with p-Phenylenediborane .. 62
H. llBoron Nuclear Magnetic Resonunc Studies .
I. Temperature Studies by Differential Scanning
Calorimetry 64
J. Synthesis of 1,6-Diphenyl-"-a.zt-6-borabic,'..-
(4 4.0.)decans .
K. Conclusions .. .

V. EXPERIMENTAL .

A. Equip,:tert and Trx:-atment: of a,t: 7-
B. Syntheses and Characterizaton 7'



2i li.ography .


Biograph ica Ske. tch


. *0i
















LIST OF TABLES


Table Page

1 Skeletal Bond Energies 4

2 Substituted 1,5-Diphenyl-l-aza-5-borabicyclo(3.3.0)octanes
and i,2-Diphenyl-1 ,2-azaborolidines 54

3 Physical Data of Substituted 1,5-Diphenyl-l-aza-5-bora-
bicyclo(3.3.0)octanes 55,56

4 Spectral Data of Substituted 1,5-Diphenyl-l-aza-5-bora-
bicyclo(3.3.0)octanes 57,58
















LIST OF FIGURES

Figure Page

1 Nmr Spectrum of 1,5-Diphenyl-1-aza--5-borabicyclo(3.3.0)-
octane 34

2 Infrared Spectrum of 3-Deuteropropene 45

3 Nmr Spectrum of 3-Deuteropropene 46

4 Infrared Spectrum of 3,7-Dideutero-l,5-diphenyl-1-aza-
5-borabicyclo(3.3.0)octane 48

5 Nmr Spectr'un of 3,7-Dideutero-l,5-diphenyl-i-aza-5-bora-
bicyclo(3.3.0)octane 49

6 Nmr Spectra of 1,5-Bis-(4-cblocropheiiyl)-i-aza-5-bo'a-
bicyclo(3.3.0)octane and 1,2-.ic-(4-chlorophenyl)-1,2-
azaboroli.dine 60


















Abstract of Dissertation Presented to the
Graduate Council of the University of Florida in Partial Fulfillment
of the Requirements for the Degree of Doctor of Philosophy

SYNTHESES OF HETEROCYCLIC COMIPCUOIOD CONTAINING B-N COORDINATE
BONDS AS MODELS
FOR THERMALLY STABLE POLYMERS

By

CHARLES LEWIS MCCORMICK III

June, 1973

Chairman: Dr. G. B. Butler
Major Department: Chemistry

The major goals of this research were to exaAine the mechanisnI of

tha reaction of triethylaimine-phernyloranrT. with NN-d- alylani.L:' i a"-

to extend this reaction to the preparation of compounds which could be

utilized for the synthesis of high molecular weight, thermally stable

pclymers.

1,5-Diphenyl-l-aza-5-borabicyclo (3.3.0) octane, 1 ,2-d.phernyl-, 2-

azaborolidine, and propene were isolated as the major products of the

reaction of triethylamine-pheny Iborane with N,N-diallylaniline. Thes-

compounds were characterized by nuclear magnetic resonance, infrared,

mass spectroscopy, and elemental analyses.

Two mechanisms were proposed for the forration of propene arnd

l,2-diphe.nyl--1,2-azaboro Lidine.

Triethylami ne-dideuterophanriyboran-;? ,a prepsard anri s'bsequelntly

reacted with N,N--diallylanilin'e to give 3,7-dideutero-i,5-diphenyi-l--aza

5-borabicyclo( 3.0) octane, 3-deutero- 2--diphieny1- 2- xa;borolidiTie,









and 3-deuteropropene. These products were consistent with one of the

proposed mechanisms, a concerted, facile elimination of propene. This

elimination mechanism was supported by model studies of the transition

states.

Triethylamine-phenylborane was reacted with N,N-di-3-butenylaniline

to give 1,2-diphenyl-l-(3-butenyl),2-hydro-azaboracyclohexane and 1,6-

diphenyl-l-aza-6-borabicyclo(4.4.0)decane. No butene gas was eliminated,

giving further support for the proposed mechanism.

Several substituted derivatives of 1,5.-diphenyl-l-aza-5-borabicyclo-

(3.3.0)octane were prepared. The B-N coordinate bonds in these compounds

were studied by nuclear magnetic resonance, 1B nuclear magnetic resonance,

infrared spectroscopy, and differential scanning calorimetly. The B

chemical shifts in these ccrapounds varied from 2.2 to 6.0 p.p.m. relative

to trimWethylborate. The B-N coordinate bonds e:xhibited absorb'inc-, near
-1
1275 cm. Temperatures for the dissociation of the boron-nitrogen coor-

dinate bond, determined by differential scanning calorimetry appeared to

be near 5200 K. The heats of dissociation of the B-N bond for bis-l,4-

[5- 4-methylphenyl)-l-aza-5-borabicyclo(3.3.0)octyl]benzeue, and bis-1,4-

[5- (4-o-'~.o ophenyl)-l-aza-5-borabicy.lo(3.3.0)octyl]benzene were calciu-

lated to 28.5 krai/m-ole and 30.3 kcal/zioli,, respectively.

Sev-eral substituted derivatives of i,5-diphenyi-i-aza-5-borabicyclo-

(.3.3.0)octane were prepared which are excellent monomer precursoTs for

condensation polymerization.


v .1i.
















Chapter I

INTRODUCTION

A. Polymers Exhibiting Principles of Thermal Stability

The demands of the space program, and more recently the garment

industry, have led to extensive research in the area of thermally stable

polymers and flame retardant polymers.

Ladder polymers, 1, or double-stranded polymers have been made

which show good thermal stability. The increased thermal stability of

these polymers was attributed to the added stability cf the ring systems.

Cleavage must occur twice within a given ring of the polymer for chain
1,2,3,4,5
degradation. i,2 ,4,5












.1

Recently, ladder polyamerrs cabls in air above '09' C and based

on ,inyJ-acetylenes, have been p -paro.

Hete.roatom pclyners show a higher resistance to oxidative degra-

d.cion at elevated telera:ture's. keletl bonds, s'nch as Al-0, Si-O,

Si-N, P-N, B-0, and 3-N, might: b cxpected to show resistance to ther-

mal oxidation, and polymers wicih r.hei:e units should be --ore inert ra

high temperature. Bon c.A is:i:, ..c:rgies arc given in Table









Polyphenyleneoxadiazoles, polyphecQylenetriazoles, polyphenylaee-

thiazoles, and polybenzimidazoles have been shown to be capable of

forming thermally stable films aid fibers.8,9,10,11 Another series of

thermally stable heterocyclic polymers, 2, was prepared by the conden-

sation of 3,3'-diaminobenzidine with tetrabutyl esters of diboronic
12
acids.





NH--/\ -\N \

I NH ./ "NH



2
13,14
butler and Stackman demonstrated the high resistanc" of

cyclic polydia.lylriphenyl silanes, 3, to thermal degr-a-atici. Po..-

atrs ;containiag bodith eteroatonm stability aid "ladder' ralili.y 'i-

been prepared by the hydrolysis of phenyltrichlorosilane in ai o.rg c ic

solvni1

Ph Ph


"' -- L .-' *- I- --
S1


0J





3

i recent yvet:s, a number of hete;o:or3 a riug and chain syyste.;s';,

sucI; as; carbazeno, 4, orazenes, 5, phosphazenes, .6, bcr~oeaes, .,

si.lo-':na"e-, n3, ad silazanes, 9, have sho.:n remarkable therial st .biity.









I \/

V./B P

"C"/ N
S4 5 I 6

S\/,S Si
0 0 0 0 NN N
I I I I

7 8 9


This stability has been interpreted in terms of resonance stabili-

zation inherent in these systems. An intensive investigation into the

possibilities of incorporating these compounds into polymers for flame
16 .17
retardance is currently of top priority in the fibers industry.

.-:trcatom polyiners containing C-N, C-0, B-N, F-C, P-N, Si--N, and Si-0

bonds have been reiewLed.

Tberaoplasti.: ccati-gs and fibers have been prepared from cyclic

polys loxanes, Methylphenylcyclotetrasiloxanes have been polym..ri:ed to

give polymers with thermal stability dependent upon phenyl substitution.

He~eroato:m pclymers containing boron have been known for Tiany years.

Boric oxide consi..-s of a three-dimensicnal network of distorted 30,

retrahedra. HexagRorna boron nitcide, _10, has a hexagonal layer struc-

ture and is som-atl n ca.ll.d ,h.ite graphite. These materials have ex-

cellent th er:i. ability 2'"h0'0C) and other useful. properties whii

bave coamnerci.ai utility. Th iey have stimulated research efforts toward
N N



.- .. ', -,

i i
















TABLE 1. SKELETAL BOND ENERGIES (kcal/m.ole)


128

106.5

106


89

86

85.,

82 .6


Bond

Si-C

C-N

Si-S
P=N

P-N
P-C

C-S

Al-C

S-N


Bond

C=N

Al-- 0

B-0
B--N

Si-O
Si-N


P-O

C--C
C--C:


S-0


D

",50

80




68

68
-'70


9,104


91i


83


E

IV78

72.8

'v70

68-76




65

61
"'6 c

,55





5



high molecular weight polymers based on boron. Certain phases of boron

chemistry also find their counterparts in the technologically important

area of silicon chemistry. Since the bond energies of boron-oxygen

(~130 kcal) and boron-nitrogen ('100 kcal) are high, there should be

high temperature applications.

Most polymeric boron compounds have not been characterized ade-

quately. Little information is available on reactivity, molecular
20,21
weights, and solubility in many cases.2



B. Boron-Nitrogen Polymers
22
Since the discovery of borazene and its stability at 500C,22

mai-y publications have appeared attempting to incorporate this com-

pound into thermally stable polymers. Reviews covering all phases

of borazene chemistry may be found in the literature. An impor-

tant aspect of borazene chemistry is the strong driving force for

formation of cyclotriborazenes from dehydrogenation of substituted

amine-borane adducts (Scheme I).

SCHEME I
-2
PNH2 + H2BR' ---- R2 N-->BH2R' --- rN-.-' '
(1) Monoborazans (2) Monoborazeac




3 \


H 2 H
R' R' -3H (4)
I I /

H A --.-3H. ()/

Cyclotriborazane R- B-R'


Cy clotri -raze
Cy clotril 2r"zene.:









The monoborazine would be electronically unstable and should form

polymers. However, the stabilizing influence of suitable bond angles

and n-bonding in the cyclic trimer favors this homologue.

Three main avenues have been investigated for the formation of
19
boron-nitrogen polymers. The first involves the opening of various

borazene rings, and the second, reactions of the unstable mcnoborazines.

The final method has been an attempt to link borazene rings in an

ordered fashion, avoiding cross-linking.

As a general rule, cyclotriborazenes do not undergo ring opening

to liear polymers, However, the polymerization of N- and/or B-methyl--,

ary]-, or triazinylcyclotriborazenes in a closed system at 3500 to

600'C, oc in the presence of catalysts, led to hard, glassy, irsolub~le

resins.' No molecular weight was given. An open-chain, low

,o.leccular weight polyiser of the structure, (PhB-NC4H9)n, where n=20 to 40

was prepared by rhhe reaction of pheny1borondichloride with isobucyi.amias."

Ctross-.lin2ked polymer was formed by the pyrolysis of B-trichloro-N--tri-'

arlcyclotrlborazeues, (C6-BAr) 3, from room temperature up to 500"C."

r'y,:.oboraene rings, havpb been linked to give polymers, ,1 of high

mol.cuiar weight. Benzene solivle polymer i7as formed fhan ;yycloborazene
27
vings ware linked by :oe process:2



Me Me !

n i + 2n KC5.
.-.N -. N.-Hs- hen B..h :.
;.I Bu
n
1.1



Cvc3tr'iboraznc- : rics ,hav,, a.l.so bee :inked v react etg dio!p ithi








N-triphenylcyclotrihoraane: 28




Ph h
HBP B H -
2 I i + HO(CH2)200H -2B. 20
PhN BNPh PhN 2BNPh
H 6(CH2 )2


12


Other examples have been reported in which B,N'-dichlorocycletri-

borazenes and diamines reacted to give polymers stable up to 250-

300CC.29 Copolymers have been prepared by the free-radical poly-

merization of B-trivinyi--N-triphenylcyclotriborazene wich styrene

and methyl methacrylate.30 The reaction of aniline with an equi-

molar concentration of trimethox'-yclotriborexene was reported to
31
give a poly :er with the following structure:


OMe


S0
.B ----- N

13 h -n

High boiling diamines have been known to polymerize upon

heati'-ng with various alkylborates. For example, ethylenediamiine

reacts with tri'ethyLbcrate to givw" a polymer with the following
32
structure: -
i i
N-- --B -
S/ ,

!jn









The reaction of p-aminophenol and tripropoxyborane resulted

in the formation of a resin. The structure assigned to the poly-
33
mer was:



B NH 0- -- --NH -- --- B
j n

15



C. Boron-Oxygen Polymere

Oligomeric compounds containing boron-oxygen links have been

made by heating al ky.-- or arylboronic acids. Most of the resulting

compounds are easily hydrolyzed, although they exhibic remarkable

thermal stability. As in the borazene series, the trimers, cyclo-

triboroxenes, sec. To be the most favored thermndyaa;micaly.y Cycle.

triboroxenes have bce'n reported to have 10-20% aroima-.ic chadrcrx:e.








.23 17


35
boronic acids under !vauu',- le first ainhydrlde of phenyiboroni.

acid was prepared in 1836 Te structure of triphenycyclotri-
G 37




38
phenylboronic acid yielded th cyclic triTer:

ChOOCOPh',

D '~Ci









Cyclotriboroxenes disproportionate to boric oxide and trialkyl or
39
triaryl boranes at elevated temperatures. This fact seems to

rule out the possibility of ring-opening polymerizations of these

cyclic trimers.

Benzenediboronic acids have been prepared as starting materials

for polymerization. These acids were formed by the extension of the

synthesis of phenylboronic acid, 19.,41



-gBr (1) (CH30)3B -B(OH).
(2) H30
19

42 40
Diboronic acids were prepared by Nielsen4 and Musgrave43 by

reaction of a bis-Grignard reagent with trimethylborate in tetra-

hydrofuran. Subsequent hydrolysis yielded the diboronic acid, 20.



2(0H)B- --B(OH)2


20

Polyesters from diboronic acids have been reported, but no mo3!ecular

weights were given.4 Mixtures of boric acids with glycols gave high

molecular weight polymers. No structure det.erminations were made,

alti;'..",h cross-l-inking is inevitable in these systres. Polymeric
,'6
glycol borates and esters of borcnic acids have hben studied. A

careful steady of the condensation reactions of orthoboric aci-3l with
47 48
diols has also been made. RecenLly, Svarcs a.t al. reported th-

preparation of a copolymer, 21, of pentaerythritol and boric a.cid.


!0

I c








D. Boron-Carbon Polymars

Polymers containing only boron and carbon are rare. Tri-n-

hexylboron decomposed on heating to produce two polymeric materials.4

A dark solid was assigned the structure [-B(C6H13)BH-]nand a vis-

cous liquid [-B(C6H13)-(C6H12)-B(CHI13)-In Pyrolysis of Me2BCH2CHIa Me2
50
yielded trimethylboron and polymers with the following structures:0



B-CH-CH-B -- -CH2--CHi B / -
1, \_2 -
I n
22 23

A patent has been awarded for the synthesis of a polymer, 24, pre-

pared by reacting a boron halide or ester with the di-Grignard of
51
p-dibrotobenzrne.

-2-B

OH
IIn

24

Several other polymeric boron-carbon compounds have been re-
ported.21,52,53,54
ported.




55
The first organoboranes were synthesized in 1862 by FranklanAd

by tle reaction of diaikyl zinc compounds with Lriethylborate. He

He observed the ability of these boranes to coordinate with ammonia.

Since that time countless papers on other boron-nitrogen coordi-

nation compounds have appeared.

Koster first utilized triethylaiine-borane in 1957 in the hyiro-









boration of cyclododeca-l,5,9-triene. Hawthorne57 observed that

pyridine borane would react with olefins in diglyne at 100C to pro-

duce trialkylboranes. Nielsen58 observed that phenylborane readily
59
disprcportionated to triphenylborane and diborane. Hawthorne59 pre-

pared pyridine and triethylamine adducts of phenylborane and aryl-

substituted phenylboranes which were white crystalline materials stable

in air and had melting points from 50 to 80*C. Pyridine- and tri-

ethylamine-alkylboranes0 and -arylboranes59,61 were prepared by the

presence of the amine bases.

Hawthorne reported the reduction of substituted cyclotriboroxenes

by lithium aluminum hydride and the presence of pyridine, trimerhyl-

amine, or triethylamine to give the corresponding amine-bcranes.

Ashby64 reacted several trialkynamine-boranes with olefins to

form trialkylboranes in 78--95% yields.

The mechanism for hydrobor.ltion by amine-boariic is believed ;:o

involve the rate determining dissociation of the smine-borane. A

sufficiently high temperature is required for the dissociation of the
65
B-N bond.65 B-H addition can then proceed via the boron p-orbital

interaction with che T-elect-rcns of the olefin (Schem.e II).66

SCHEME II

:.' -R RN + RMH,




--. -
S--C--.-
tBH/2 + ..=.. ... = -- --- -- C--- C -
H ---- -H.....uuR

P,








Cyclic boranes were prepared by Koster6768 by the reactions of

trialkylamine-boranes with diolefins. Hawthorne9,70 reacted trimethyl-

amaine-t-butylborane with a number of olefins and diolefins. Reaction

with divinyl ether and divinyl silane gave corresponding heterocyclic

compounds.

The coordination compounds formed by substituted alkyl- and aryl-

borons with amines have been studied relating steric factors to B-N

bond stability. Heats of dissociation of the complexes of trimethylboron

with various amines are all about -7.26 0.21 kcal/mole.7

Aaine-boranes may undergo dehydrogenation to give monoborazenes

or aemnoboranes (Scheme I). When B-trimethylborazane, 25, was heated
72
to 2800C under 20 atm.. pressure, B-dimethylborazena, 26, was forqpd.

1his compound was further dealkylated to yield B-trimethylcyclotri.-

borazene, (HN-BMe)3, Both of the above steps required cbe eliim ati-.on

of :.ethaiv.



H3N-BMe ------- N-BMe CH
3 3 Me. 2 4 t
25 26


Further examples of elimination were the formation of B-a-llyl-
73
vonoborazenes by the following reactions:



-:B(C 3 ------.- EtN-B(C + C h

27

H3N+B(C3)3 -------- f ,2N-B(C3H5)2 + C3


Pyrol.-:. of amine--phenylborane adducts leads to aminoboranes. The









heating of diethylamine-phenylborane at 80--110C under vacuum resulted
7 Lk
in 88% yield of diethylaminoborane, 29.'




Et2NH-BH2Ph -- H2 + Et2N-BHPh

29



Several papers were presented dealing with amine-boranes and

aninoboranes at an international symposium on boron-nitrogen chemistry.7

Heteroaromatic boron-nitrogen compounds have also been reviewed in
7,75
some detail.



F. Cyclic and Bicyclic Compounds with Boron-Nitrogen Coordinate Bonds

The bicyclic ester, 30, formed by the azeotropic dehydration of an

equimolar mixture of l,l,l-trimethy.letLhane and boric acid was re-

ported in a patecrn in 1959.76 This compound upon heating yielded a

glassy polymer.
/ 0
C-- ------- Polymer

--0


Similar bicyclic compounds bad been prepared by 3rown in 1951

by the reaction of trit.anolam~ne vi.th boric acid'. 'he prodlu;:t was

a white crystalli:ne solid, m.p. 236.5-237.5C. Two possible struc-

tures were proposed:

---. -I



\ C\ \ \,i
)--B--0 C) -V--yB~-~G









In the cage structure, 31, boron maintains trigonal coplanar hybridi-

zation. In the second structure, 32, a transannular boron-nitrogen

interaction gives boron sp hybridization. Triethanolamine borate

was concluded to have structure 32 on the basis of unreactivity with
77
methyl iodide as compared to quinuclidine, 33, and triethanolamine.






H 33



Further evidence for the B-N transannular bond was found in the 11B

nuclear magnetic resonance chemical shift, relative to boron tri-

fluoride etherate, of triethanolamine borate, which is found at

higher fields (6-10.7) in aqueo'us solution than most aikyl- and aryl-

borates (6-14 to 6-19). The shift was interpreted to be due ;-o

increased sl.iel'i.g around the boron atom as a result of B-N 'r : 'ir,g

mad, therefore, increased tetrahedral character and number of bonding

electrons around the boron atom.

Later studies showed that an equilibrium could exist bet w ern

structures 31 and 32. In water and butanol the equiliibrium mixture

contained 20% of the tetrahedral species, 32, and in aprctic solvents

95% of the tetrah2dral for. Iquil.ibrium s tudics of the estr-

ification of 1:oric acid -ith triethanol.amine indicate a shift in

eq.ii.ibriu- tr ard structure 3. w0 th an -icrhesze in tefperatu-re.

Zi.merman reported the resultS off -ydril;vysis exi-erilments on bcrox-

azoldinCs." H -elated T.he -T bond stc.nc tn to rat s of hydroyivis

for several c- .'n.-i ic.itudii. aze following, 34-37:












B -- C)0
0.


R


NI
0--.B 0/


Ph --<-N---CHK-CH-- --?--Ph
/ \ 2 2
0 j0


Sf83,84,85,86 83,36,87,8,889,0
A vir.ety of boronates, b.or.inat?, >*
91,99
triisopropylamine borates 99 have been postulated to ha;-r tra;ns-

annular boron-nitrogen bonds. Syntheses directed towa-;d boron-

containing amino acids for cancer chemotherapy have led to prepa-

ration of a series of substituted trietlanolamine borates. -' i -

isopropy1-91,92 and tri-n-propylamine borates have also been s uiJ.ed.

Substituted aryl boronic acids and 2-aminoethanol were heat-6 in

toluene to give the corresponding diethanolamiine arylborate,:, 4;0.",



Ar -- B<-NH
/ \

40


Recently polymers with improved antistatic properLies and flame

resistance were prepared by addition c f B-N ircllsioan .irpcunds. Fcr


R,



R- --0
R









example, the following compound (3% by weight) was mixed with poly--
95
et0hylene:95


/ MZie -CH-2 OPh
PhOCH 2- 0 CH2Ph
\06 39


Adams and Poholsky96 prepared the first reported 1,2-aza-boro-

cycloalkane, 41, by reacting N,N'-dimethyl-allylamine with triethyl-

amine-borane in toluene. The following structure was assigned:

CH I
CH --- B N H
3




97
In 1963 White reported the synthesis of 1-methyl-2-phenyl-

1,2-azoboro.id:lne, 42_, and 2--2phenyl-!,9--azboracyc che-an.', -3-, fr.:

the reactions of triethy lamine-pher'ylboraae with N-!'.ethylailyl-n.-i

and 3-butenylaiine, respectively.



( N1

Ph___ 'B H--N 3___., f P...--- F h
P- i B











Ph h
t;12 i3

In i95o3 Statton and Butler o reported t he foni.-ation of .& ef.'j.rs

substituted aza-3-borabiryclo(3.3,0)octane
of diallyletiryJ amire with crimethylam ne-phenyhborane yielded com--

pounds with the following structures:
Ph


N"--./ k ....-- N '.








The B-N coordinate bond in the bicyclic compound, 45, was believed
-l
responsible for a strong infrared absorbance at 1266 cm. The
-l
azaborolidine, 44, showed strong peaks at 1512 cm.- which were at-

tributed to the =N bond. 11B resonance signal in the nmr spec-

trum of 44 was recorded at -23 p.p.m. and of 45 at 8.9 p.p.m. rela-

tive to trimethylborate.

In 1965 Butler and Statton99 reported the preparation of four

substituted l-aza-5-borabicyclo(3.3.0)octanes and four previously

unreported 1,2-azaborolidines. These compounds were prepared by the

reaction of triethylamine-phenylborane with tertiary diallylamines.

A mechanism for the reaction was proposed based on qualitative data

which involved the cleavage of an allylic carbon-nitrogen bond. Two

of the 1,2-azaborolidines were also prepared by the reaction of tri-

ethylaziine-phanyiborane with secondary allyla.ines. The l-aza-5-

borabicyclo(3.3.0)octanes exhibited strong infrard absorption bands

at 1250-1270 cm.-, which were assigned to the B-N coordinate bond.

A new compound, 1-phenyl-1-bora-5-azoniaspiro(4.5)decane, 46, was

prepared as well as a telomer, 4Y.



Ph 3 6
---B
,....


A new bicyclic .icoipound containing a B-P coordinate bond was
100
prepared having the following structure:



<0>P 0>)
i _.j)"' -- ,/









G. Statement of Problem

The major goals of this research were to examine the mechanism

of the reaction of triethylamine-phenylborane with N,N'-diallylaniline

and to extend this reaction to the preparation of compounds which could

be utilized in the synthesis of high molecular weight, thermally stable
101
polymers.

The first step was to prepare 1,5-diphenyl-l-aza-5-borabicyclo-

(3.3.0)octane, 49, and 1,2-diphenyl-l,2-azaborolidine, 50, (R,R'=H) to

serve as models.




k -R-~^' RB=N --(=--= N---R'


50
49

The next step wuuJd be to e.a.in; i-. ,chaaistica:!ly -h-:.- o r ncot

formation of 49 and 50 occurs in a competitive -manner, 01hvioirsly,

this reaction requires loss of three carbon units for formation of

50. Since no gaseous products or other products consistent with
S102
this three-carbon chain had been previously detected, one goal

w.is ro isolate and identify :;his product.

After i.ni:ial investigation begau, it became obvious that deu-

terium labeling st.udics would be necessary. Therefore, an idea wa.r

conceived which would differentiate between two possible mechanisms.

Ano::ber goal .a.3 pr-inarat-.on of several selected derivatives of

f9, both for -synthetic purposes and property studies. Substituents

should have ielectrcnic and stacic .ffec-:s on the re.laive yields of

49 and 50. The boron.- it.o.en coordinat-. bond could be detected









by infrared, 1B nuclear magnetic resonance, and proton magnetic

resonance. The B-N bond dissociations for the various compounds

could be followed by differential scanning calorimetry. These

studies should have important meaning when extended to polymeric

systems.

Another important objective was the study of the stability

of these compounds to various conditions necessary for introducing

functionality for monomer formation.

The ultimate objective of the boron research in these labora-

tories is the incorporation of the bicyclic structure into several

thermally stable polymeric systems, 51.




SI
(CH,) r(CH )





(CH 2x H2
'. 2,,
5_1

These polymers should have some i:tult tst'irn properties. Thermal

dissociation of the dati-re bonds along the polymer backbone could

oczur without cleavage of the polyTer chains, alliing the polym'er

chain to "breathe" or function liK bellows. This cleaavage should

result in an iLncrease in the dei-r.;- of freedom along the longUI udin-'

axis of the polymer chain, and should impart additional elasticity

to the polymer.
















Chapter II

SYNTHESES OF UI Sj'ATED TERTIARY ANILINES

A. Syntheses of Para-substituted-NN-Diallylanilines

p-Substituted-N,N-diallylanilines, 52, were prepared by the
103
method of Butler and Bunch.0 3-Bromopropene was added dropwise

to a slurry of sodium carbonate and the para-substituted-aniline

in water. The reactions were allowed to proceed at 100 C for 24

to 48 hours. The resulting organic layer was separated, dried, and

vacuum dis killed,




--H,( -:- 2 3-bromoprcpene -- X- )


52


The lol. owing compounds were prepared by the above method:

N.N--diallyla.nline, 37.6%; p-bromo-N,N-diallylariline, 74.5%;

p-.lc ro--N :::-I -.. -I l.lanil ine, 72.5% ; p-me thyl-N ,N-diallylaniline,

70 .1a; and p-methoxy-N.,.-diallylaniline, 88%

The ccrr spending se-ondar' :,onoallyian.ilnes were also ob-

t:Aine-d: fror, early .ractitns in the di.sillation.



B. Sy z h.iofN N' -T etralyl -p- henLvenediamine

p-Pnen)ilnediaminfe was i; ic.ed ,'t:ith 4 moles of allylbromide

in a slurry of sodium carbonate in water. The resulting viscous,

syrupy siatarial. wes diluted with water and the organic layer ex-

/ r\









tracted in ether. This solution was filtered, dried over sodium

sulfate, and then distilled under vacuum yielding a pale yellow

liquid (46.5%, b.p. 138-140* C @ 0.55 mm.).



C. Synthesis of N,N-Di-3-butenylaniline

N,N-Di-3-butenylaniline was prepared using a similar proce-

dure as in preparation of the other diallylanilines. 4-Bromo-

butene was added dropwise to a slurry of aniline in sodium car-

bonate in water. The organic layer was extracted, filtered, and

vacuum distilled yielding a colorless liquid (37%, b.p. 74-75 C

@ 0.10 mm.),

















Chapter !II

PREPARATION OF BORON INTERMEDIATES

A. Syntheses of Grignard Reagents '

The boron intermediates were prepared by modifications of

procedures reported in the literature (Scheme III).

The mono-Grignard reagents of bromobenzene, p-dibromobenzene,

p-chlorobromobenzene, p-methylbromobenzene, p-methoxybromobenzene,

and p-ethoxybromobenzene were prepared by reacting the substituted

bromcbenzenes with an equimolair quantity of Ta!nesi.m in diethyl

ether, dried over zcdium. The substituted bromobenzene was added

dropwise at a rate which maintained a jow reflux.. In each reaction,

a small crystal of iodine or i d:op of ethylenabromicde was necessary

to initiate the reaction. T1.:e induction periods varied froTm 10 to

40 minute .

An attempt was made to prepare the Grignard reiaent of p-bromo-

phenylbenzyl ethei. T1'r. ether wvs prepared by reeccing p-bromophenol

with benzylch..rid.e in acetone, .'te reutin-lg p7brtiphenylbenzyl

ether was recrysta,'lized twice from hot netlhno!. It wzas then diS-

s,-Ived in diethyl ethai, distilled from lithium a.lum'-num hydride.

Initial addition of the p-braphenylbenyl, et'-he to the -.>c.;n:liun

did not result ir iny -caction.r Cystals of iodii.r : :-d ethylene

bromide were employed to initiate the reaction. However, the addition

of further p-bromophenylbenzyv ether appea're to stop tche reaction.

Entrai~nenit and heat were eiloyed,I yet tt: re-.c:iOer' c;Old not be
































: tOH
---A-


\ / H


S-0 3(OH-)3

/- 2)


t /I) LiAH4

:4 2):;NE3


ic--
/ ;


r,0
C'l


Scheme III









forced. Only a small amount of the magnesium reacted. Perhaps

another solvent, such as tetrahydrofuran, might yield better results.

The bis-Grignard reagent was prepared from p-dibromobenzene,

Tetrahydrofuran was employed as a solvent. It became necessary to

control the heat evolved in the reaction with an ice bath. The high

viscosity of the resulting Grignard reagent presented problems in

filtering and addition through the small opening in the dropping

funnel.



B. Preparation of Substituted Phenylboronic Acids

The phenylboronic, or phenylboric, acids, 53, were prepared by

the reaction of substituted phenylmagnesium bromides with trimethyl
104
borated, followed by hydrolysis.04


(CH 0)3B H 30
X-,- MgBr --- -- X- -B(OII) + 2CH^OO


53


The trimethyl borate was added to dry diethyl ether and cooled under

nitrogen to -70 C in a dry ice-isopropanol bath., The appropriate

substituted phenylmagnesiumbromide was then added s3cwl' to the stir-

ring mixture. Too fast an addition resulted in formation of sub-

stituted biphenyls from coupling reactions, The resulting white solid-

slush was hydrolyzed slowly oy dropwise addition to the reaction mix-

ture, cooled in an ice bath. Addition without the ice bath resulted

in formation of a large yield of the substittutje t-rihenylCyclo-

triboroxine, 54. The cyclotriboroxenes were probably fo-nred by the

acid catalyzed dehydration of the phenylboro-ic ;cids. 53.










+ VhX

3 X ( B(H H30 /Bo
S(OH)

XPh N 0- PhX
53 54

The crude phenylboronic acids were recrystallized from hot

water. The following boronic acids were prepared by the above

method: phenylboronic acid (m.p. 214-216 C, 88.8%), p-chloro-

phenylboronic acid (m.p. 280-281" C, 83.5%), p-bromophenylboronic

acid (m.p. 271-2720 C, 93.5%), p-methylphenylboronic acid (m.p. 255-

2570 C, 31.0%), p-methoxyphenylboronic acid (m.p. 200-202* C, 69.0%),

and p-ethoxyphenylboronic acid (m.p. 120-122 C, 68.5%).

p-Phenylenediboronic acid 0was prepared by addition of a

tetrahydrofuran solution of the bis-Grignard reagent of p-dobromo-

benzene i-o a solution of trimethyl borate in tetrahydrofuran i.lder

nitrogen and cooled to -700 C. Addition presented problems due Lo

the thick, milky texture of the Grignard reagent, The resulting

solution was hydrolyzed with 15% sulfuric acid to give p-phpnyl-

diboronic acid (m.p. >3150 C, 74.5%).



C. Syntheses of Borate Esters of Substituted Phenylboronic Acdid

The substituted phenylboronic acids were converted to the-

corresponding dierhyl esters, 5_5, by reaction with ethanol, followed
106,107
by azeotropic distillation.10


x 5-- B(5(OH)2 + EtOH + H, 0

53 55









After all water had been distilled, the remaining solvent was re-

moved from the crude esters. The esters were then distilled under

vacuum. The following esters were prepared: diethyl phenylboronate

(b.p. 68-69 C @ 0.35 mm., 90%), diethyl p-bromophenylboronate (b.p.

76-77 C @ 0.25 mm., 41%), diethyl p-chlorophenylboronate (b.p. 92-

930 C @ 0.75 mm., 65.3%), diethyl p-methylphenylboronate (b.p. 58-

590 C @ 0.15 mm., 93.2%), diethyl p-ethoxyphenylboronate (b.p. 130-

1350 C @ 1.5 mm., 40%), diethyl p-methoxyphenylboronate (b.p. 108-

1100 C @ 2.0 mm., 60%), and tetraethyl p-phenyldiboronate (b.p. 102-

104 C @ 0.35 mm., 41%). Several of these esters have not been re-

ported previously in the literature.



D. Cyclotriboroxenes

After distillation of the substituted diethyl phenylborcaate, a

whitee residue remained in the distillation flask. These residues ve:e

recrystallized and examined by nmr, ir, and analyses. The nmr speztra

showed intense aromatic resonance signals in the 6 7.0 to 6 7.3 region.

The infrared spectra showed intense absorption in the 1350-1450 cMu.

regicT. assigned to the B-0 asymmetrical stretching modes. The melting

points were extremely high. The compounds were identical to those

formed by the dehydration of the substituted phenylboronic acids under

heat and vacuum. On this basis and elemental analysis, the structures

were assigned to be the corresponding substituted triphenylcyclocri-

boroxenes, 56. The following reaction would explain product formation.
PhX

0' 0 56
3 X-( -B(OEt) --- > + 3 EtOH
'- PhX o FhX









Several cyclotriboroxenes were recovered as by-products from

the distillation of their parent esters: triphenylcycloboroxene,

tri(p-bromophenyl)cyclotriboroxene, tri(p-chlorophenyl)cyclotri-

boroxene, tri(p-methylphenyl)cyclotriboroxene, tri(p-ethoxyphenyl)-

cyclotriboroxene, and tri(p-methoxyphenyl)cyclotriboroxene.

The distillation of tetraethyl p-phenyldiboronate yielded a

tan-colored solid which did not melt and was insoluble in all

common solvents tried. In acetone nte compound swelled and even-

tually became gel-like in structure. In analogy with the formation

of cyclotriboroxenes, 56, the compound was assumed to be a poly-

meric, 3-dimensional network, 57.

r0h
/B-

r i I.
B--- Ph OP Ph
IL -' /0
i I


57
Ph

/ \\

E. Preparation of Triethllamine-Phenylbor-anes

Several new triethylamine-phenylboranes, 58, were prepared by

modification of the method of Hawthorne. The p-substituted diethyl

phenylboronates were reduced in. the presence of triethyilamine at low

temperature under nitrogen. The reactions were carried out with slow

addition of the diethy phenyiboronate to a mixture of lithium a],in-

inum hydride in diethyl ether and triethylamine. A"ter complete di-

tion, the mixture was allowed to warm to room temperature, Filrration

followed to remove the excess lithiiru alu-ninum hydride ::d other in-









soluble salts. The triethylamine-phenyiboranes were isolated by

cooling the filtrate to -70 C and quick vacuum filtration under

nitrogen.

Li-IIH 4B
X Q B(OEt)2 -, X-- -BH-2NEt3 + salts
NEt3

58

Several of the triethylamine-phenylboranes exhibited peculiar

properties on attempted filtration. For example, the triethylamine-

(p-bromo)phenyl-borane formed a solid (crystals) at -72* C in a dry

ice-isopropanol bath. On removing the ether solvent, these crystals

seemed to melt away. At room temperature only a white residue re-

mained. This reaction could possibly be a disproportionation to

p-bromotriphenylboron, iriethylamine, and diborane. Evidence

against disproportionaticn was that the residue was insoluble in

every solvent tried, and the infrared gas spectrum showed no diborane

evolved. The second possibility would be the elimination of ethane

across the boron-nitrogen coordinate bond to give the monoborazene.

This process, though, usually requires heac and vacuum conditions.

Also, no ethane gas was evolved,

The following compounds were prepared, which are relatively

stable at room temperature: triethylamine-phenylborane (m.p. 65-6b6 C,

73%), triethylamine-(p-chloro)phenylborane (m,p. 62-63 C, 75%),

triethylamine-(p-methiyl)phenylborane (m.p. S0-830 C, 869,.), triethyl-

ainine-(p-ethoxy)phenylborane (m.p. 63-64' C, 84%), and triethylamine-

(p-toethoxy)phenylborane (m.p. 63-64' C, 82%).










The triethylamine-(p-ethoxy)phenylborane and triethylamine-

(p-methoxy)phenylborane did, however, decompose after one week,

even under nitrogen. These compounds and triethylamine-(p-bromo)-

phenylborane could be kept in toluene or benzene solvents without

decomposition.



F. Preparation of Pyridine-Phenylboranes

An attempt was made to prepare the di(triethylamine)-p-

phenylenediborane, 59, by the same general method as described

above. Tetraethyl-p-phenyldiboronate was added dropwise to a cold

mixture of lithium aluminum hydride in diethyl ether and triethyl-

amine. After complete addition, the resulting mixture was allowed

to warm to room temperature and filtered. The filtrate was cooled

to -72 C in a dry ice-isopropenol bath. No crystals were foimed.

The solution was concentrated to one-half its volume and cooled once

more. Fine, white crystals formed. These crystals were found to be

unstable in nitrogen and were, therefore, kept in the solvent. The

nmr spectrum showed only one mole of triethylamine completed to the

p-phenylenediborane. The ir spectrum showed the B-H stretching ab-
-1
sorbance at 2200 to 2420 cm.


NtN HT- i --
3 2


59


It was thought that, perhaps, a different base, such as pyridine

with less face-strain, would complex more strongly with the p-phenylene-

diborane. The same general procedure was followed using pyridine as the

base. A yellow oil was obtained from the initial react:tjn.. This ol :as









crystallized from cold diethyl ether. A small amount of yellow crystals

(m.p. 60-68 C) was obtained. The crystals were unstable in air. The nmr

spectrum showed a broad multiple at 5 8.8, which was consistent with the

expected pyridinium resonance, and an aromatic resonance at 67.3. How-

ever, only one pyridine molecule was completed to the p-phenylenediborane.

A possible reason for the complexation of only a single base mole-

cule to the diborane could be a resonance or electronic effect. A signi-


B.-B B..-/ -B


60 61


ficant contribution from 60 would allow only single coordination with the

nucleophilic bases. This problem could possibly be eliminated by pre-

paring bis-boranes, 62, with insulation from electronic effects.









EtI- BI0 -32 Bp----^^
















Chapter IV

SYNTHESES AND REACTIONS OF BORON HETEROCYCLES

A. Reaction of Triethylamine-Phenylborane with N,N-Diallylaniline

Triethylamine-phenylborane was reacted with an equimolar quantity

of N,N-diallylaniline in refluxing toluene. After 12 hours, the

solvent was removed on a rotary evaporator. The residual, phospho-

rescent-green liquid was distilled under vacuum to give three fractions.

The first fraction proved to be unreacted N,N-diallylaniline. The

second fraction was identified as 1,2-diphenyl-l,2-azaborolidine; the

third was 1,5-diphenyl-l-aza-5-borabicyclo(3.3.0)octane. A gumy

residue in the distilling flask defied all attempts at purification

dile to its insolubility. These products were consistent with those
98,93
reported by Butler and Statton.9

Examination of the two major, isolated products of the above

reaction indicated that a unit of 3 carbon atoms was needed to complete

tne balanced chemical equation (Scheme IV). Statton100 had suggested

that the loss of an allyl group would give the 1,2-dipher'yl-1,2-azaboro-

lidine, 61-. However, he was unable to trap or detect any alkcne during

the course of the reactions studied.

Since ona goal included improving the yield of the bicyclic

compound, 63, over that of the monocyclic compound, 64, while studying

the mechanism of the reaction, ic became important to isolate the miss-

ing 3-carbon unit. The reaction outlined in Scheme IV was repeated.

This time, however, the apparatus was modified to include a gas outlet









Scheme TV


Toluene
reflux


-/ -


Propene


: NEt3


1-,2- Diphe:yl- ,2 ozaboro!idine

1,5 Dipheny -- zaa--boroaicyclo (3,3,0) octane









to an infrared gas cell. The triethylamine-phenylborane and N,N-

diallylaniline were dissolved in toluene in a flask equipped with

a magnetic stirrer and heater. The solution was slowly heated. Gas

samples, as well as solution samples, were taken at regular intervals

over a temperature range from 260 C to 1100 C. The boron-hydrogen
-l
bond absorbance at 2340 cm.- was monitored, and it was found that

the initial hydroboration occurred at approximately 500 C. Little

change occurred in the intensity up to 970 C. At this point, the B-H

absorbance decreased with time. The infrared gas samples gave the

best information. Only triethylamine and toluene vapors were observed

below 92 C. However, at 95 C the spectra began to show traces of
-3
propene gas. The broad, spiked peak at 910 cm. I was the most easily

followed absorbance. At 980 C large amounts of propene were being

pumped into the ir gas cell. The spectra were identical with the one

for propene given in the Sadtler Midget Edition, No. 6403.

After 12 hours, the green reaction solution was cooled, filtered,

and roto.;aced to remove the toluene. The viscous, green liquid was

transferred under nitrogen to a small, round-bottomed flask for vacuum

distillation. Again, the 1,2-diphenyl-1,2-azaborolidine, 64 (b.p. 8&-

860 C @ 0.30 imm.), was isolated. The nmr spectrum showed resoInance

signals at 67.2 (i, 10); 53.8 (t, 2); and 61.3 (n, 4), :corespc:ring

to the aromatic, carbon-5, and carbons-6 and-7, respectively (Figure 1),
-i
The infrared spectrum exhibited an absorbance at 1389 cm~-, which was

assigned to the boron-nitrogen double bond.

1,5-lipheny-l-l-aza-5-borabicyclo(3.3.0)oc-ane, 63, distilled as a

light ye.liow oil (b.p. 125-130' C @ 0.30 mm.). This compound was

rccrystallized from hot ethanol, yielding white crystals (m.y, 80~-81i' C)










I0

f 11












ppm (8
Figure 1. Nmr spectrum of 1,5diphenii 1aza5orabicyclo(3.3.0)octane
r i' i















4.0 3.o 2.0 1.0 0
ppm (8) t.)
Figure 1. Nmr spectrum of 1,5-diphenyl-l-aza-5-borabicyclo(3.3.0)octane









The nmr spectrum is shown in Figure 1. The aromatic protons give

resonance signals centered at 66.85 (m, 10). The a protons give

a multiple (area 4) at 63.35. The b protons exhibit a distorted

quintet (area 4) at 62.1. The c protons are assigned to the multiple

(area 4) centered at 61.1. All chemical shifts are relative to tetra-

methylsilane in deuterochloroform. The B1 nmr spectrum showed a

chemical shift at 3.6 p.p.m. relative to trimethylborate. This chem-

ical shift value is strong evidence for the boron-nitrogen coordinate

bond since increased shielding around the boron atom would result in

an upfield shift. The chemical shift value for diethylamine-borane

is 3.1 p.p.m. and for the 3.3.0. bicycloborate esters of triethanolamine

3.4 p.p.m,1
-1
The infrared spectrum showed a strong absorbance at 1285 cm. ,

which was assigned to the boron-nitrogen coordinate bond. The mass

spectrum showed a parent peak at 263 tl. The elemental analysis for

1,5-diphenyl-l-aza-5-borabicyclo(3.3.0)octane agreed with that cal-

culated for the model compound.

Anal. Calcd. for C8 H22 N: C, 82.13; H, 8.42; 3, 4.11; and N,
-- 10 z22

5.32. Found: C, 82.15; H, 8.51; B, 4.21; and N, 5.41.



B. Mechanism of Formation of Azaborolidines and Azabo1rabicYclo-
(3.3.0)octanes

The proposed mechanism for the reaction cf triethylaaine-

phenylborane with N,N-diallylaniline is outlined in Schemes V and VI.

The triethylamine-phenylborane, 65, dissociates to give the free

phenylborane, 66, and triethylamine, One of the allyl groups of the

N,N diallylaniline, 76, undergoes a single hydroboration to give the







Scheme V


I -5
H-aE~


'/

^xCH


+ :N(Et)3


I,---.. ~ N -5
~ ~/(


67


-C4

'-^/<--.--


4,-


~-- -


~-~














Scheme VI


.7n


\69


() ri"(2)
"'i' .


/' ."`
I, s ---F;-


+ prope ne


I

\ul
~









uncoordinated intermediate, 69. This involves a four-membered

transition state, 68. In solution there is probably an equilibrium

between the uncoordinated, 69, and the coordinated, 70, intermediates.

Above 90 C in toluene, competitive pathways (Scheme VI) would lead

to formation of the final products 71 and 72 (X=H). The 1,5-diphenyl-

l-aza-5-borabicyclo(3.3.0)octane, 72, could be formed by a second

hydroboration with boron adding to the terminal end of the remaining

double bond. This might occur by either pathway 1 or pathway 2.

Brown66 proposed a four-centered transition state for the general

process of hydroboration. Following this proposal, the transition

state for the coordinated fonr, 73, would have much more strain than

that of the uncoordinated form, 74. Therefore, it seems likely that

the second hydroboration proceeds along pathway 2,

Tle foi.r-tion of the 3,2-jiphenyl-1,2-azaborolidine, 71, is

accompanied by the elimination of propene gas. Amnine-boranes have
73
been reported to dealkylate at very high temperatures under vacuum,

as discussed in the introduction. Obviously, this system is a special

one which allows for very facile propene elimination at relatively

low temperatures, atmospheric pressure, ancr mild conditions.

The coordinated intermediate, 70, is perfectly si'ited for a

concerted elimination of propene as shown below:



-X--X X-: piopene
H7 71
70 71









A six-membered transition state would allow for a relatively

strain-free addition of hydrogen to the terminal end of the double

bond of the allyl group and the ensuing electron shifts.

A second mechanism may be proposed which would lead to the

same products (Scheme VII). The triethylamine in the reaction

mixture could act as a base in abstracting a proton in the 1,5-

diphenyl-l-aza-5-borabicyclo(3.3.0)octane, 72, at either of the

two beta-carbons to the quaternary ammonium group. This is the
109
well-known Hofmann elimination.0 The resulting allylborane, 75,

then could conceivably undergo a thermal cleavage to give the aza-

borolidine, 71, and propene. Alkylboranes have been reported to

undergo this type of thermal cleavage.64

The most important aspect of the concerted mechanism (Scheme

VI) involves the cquilibri~u between structures 69 and 70. This

equilibrium must likely exist for the competetive formation of

the mcnocyclic, 71, and bicyclic, 72, products. A stronger

coordination, or shift toward intermediate 70 of the equilibrium

should favor the monocyclic product. A shift toward the un-

coordinated form should yield more of the bicyclic product. The

most obvious studies, therefore, would be directed toward deter-

mining tihe electronic effects of substituents demonstrated beicw -

/ \\ ),-,



76 77

Electron-withdrawing subscituents in the para-position should

increase the electron deficiency on boron aTd would shift the equi-










Scheme VII


75









librium toward the coordinated form of the intermediate, 76.

Electron-donating substituents would be expected to have the

opposite effect. Electron-donating substituents on the aniline

ring would increase the basicity of the amine, resulting in

stronger coordination. Again, the opposite effect would be

expected for withdrawing substituents.

The Hofmann elimination mechanism would also be expected

to show similar effects of substitution. In this case, the

elimination would be possible only if the quaternized form,

72, were present.



C. Deuterium Labeling Studies

After several syntheses of substituted l,5-diphenyl-l-aza-

'-borabicyclo (3,3.0)octanes (discussed later in t!h-is 7-r ),

it was evident that substituent effects would not give a clear-

cut distinction between the concerted rrechanism and the Hofmann

elimination. Therefore, deuterium labeling studies were proposed.

If triethylamine-dideutero-phenylborane could be prepared, it

should then be possible to distinguish quite clearly the two pro-

posed mechanisms.

The proposed concerted mechanism is shown in Scheme VIII.

The triethylamine-dideuterophenylborane, 78,would dissociate to

give the free dideuterophenylborane, 79, which would undergo an

initial deuteroboration to give intermediate 80 and the coordinated

form of the intermediate, 81, by an equilibration of the two forms.

The deuterium ends up in the 3-position on the ring. A second

deuteroboration through pathway A would lead to the dideuterated











Scheme VIII





x-< )H-B--,.B3 --- <- ( xy .... -.,NEis
f_; g-- D:))-/ D


7- --9

79


-+ ,-x .--

67


,.1


DC cr~CH --CH 2


80
IA
i,


C ~---~






Scheme IX


1'hN t3


D



A
~g,,~


82
'0


ii
Cti-5'C CFAti









bicyclic product, 84. A concerted elimination, with deuterium

adding to the terminal end of the double bond in intermediate 81

and the ensuing electron shifts, wguld yield the mono-deuterated

azaborolidine, 82, and 3-deuteropropene, 83.

The expected Hofmann elimination mechanism is shown in Scheme

IX. The triethylamine in solution would attack the dideuterated

1,5-diphenyl-l-aza-5-borabicyclo(3.3.0)octane, 84, at a hydrogen

atom or deuterium atom on the beta-carbon to the quaternary nitro-

gen. Abstraction of a proton should be slightly favored over

deuterium abstraction, due to an isotope effect. Intermediate 85

could then undergo thermal cleavage to give the mono-deuterated

azaborolidine, 82, and 2-deuteropropene. If a deuterium were

abstracted rather than a proton, propene gas would be generated.

Triethylamine-dideuterophanylborane was prepared by reducing

dicthyl phenylboronate with litbiuni aluminu~n deuteride i-: ether

with triethylamine at low temperature. The triethylamine-dideutero-

borane crystals (m.p. 64-655 C) were characterized by mass spectral,

nmr, ir, and elemental analyses. The infrared spectrum showed a
.-1
broad boron-deuterium absorbance at 1680 to 1765 cm. .

N,N-Diallylaniline was added to an equimolar quantity of the

triethylamine-dide uterophenylborane in p-xylene. The reaction

vessel was provided with a gas outlet, which was attached to an

infrared gas cell and, in turn, to a dry ice--isoprcpanol gas trap.

Several gas samples were taken at: various temperatures. Above

950 C deuteropropene gas was evolved. The infrared spectrum is
-1
given in Figure 2. The absorbance at 2175 em. was consistent:

with that expected for the alylic carbon-deuterfrm stretching







WAVE'LENGTH IN MICRONS


2.7






60
1

i-


i


L




501-

40
iO-
30 j-
LI, t


53.00


25n00


WAVENUMBER CM"

Figure 2. Infrared spectrum of 3-deuteropropene.


.j- j.u~s;r;?:.


2000


i












lei















r .'c Hl II






~ I /
I i





Ij i ii

I ..4


--lr. J~~~~~ Ic.c.: ,!.. .~~... rr-Llr-* ---~-U-r j1^I -~
E 55.; .3G -.


Figure 3. Nmr spectrum of 3-deuteropropene.


"I
,~~










frequency. The mass spectrum gave a parent peak at 43, consistent

with the molecular weight.

The nmr spectrum (Figure 3) of the gas was obtained by adding

deuterochloroform to the trapped liquid propene. Resonances were

assigned as follow: the allylic protons at 51.7 (finely split

signal, area 2); protons a and b at 65.0 (finely split triplet, 2);

and proton c at 65.8 multiplee, 1). The above spectral evidence

surely indicates that the trapped gas was 3-deuteropropene rather

than 2-deuteropropene. 2-Deuteropropene would have shown no signal

in the 65.8 region and, of course, would not have shown the 2:2:1

integration pattern.

At this point, a model gas, 1-butene, was obtained to be sure

that the chemical shift assignments for 3-deuteropropene were correct.

The only expected difference in the two nnmr spectra would be the

added splitting due to the methyl group being substituted for

deuterium. The allylic proton signal moved slightly to 62.0 and was

a slightly distorted, finely divided quintet. The signals at 65.0

and 65.8 were almost identical to those of 3-deuteropropene.

The structure of the 3-deutero-1,2-diphenyl-l,2-azaborolidine,

82, was confirmed by mass, nmr, and ir spectra

The structure of the 3,7-dideutero-l,5-dipbeinyl-l-aza-5-hora-

bicyclo(3.3.0)octane, 84, was also confirmed by spectral data and

analysis of the high-boiling fraction (b.p. 64-680 C @ 0.15 mm.).

This material was recrystallized to give white, flaky crystals

(m.p. 78-79 C). The infrared spectrum exhibited absorbances

characteristic of the dipheny3-aza-borabiryclc(..3.0)octanes. In
-1
addition, the carbcu-deuteriumn absorbance appeared a'it 2150 cm.












WAVELENGTH IN MICRONS


3000
WAVENUMBER CM'Y


Figure 4. Infrared spectrum of 3,7-dideutero-l,5-diphenyl-l-aza-
5-borabicyclo(3.3.0 )octane.


2000



















i I









.... ..-.L _. .. .*- I I I 1 I I I I *
4.0 3.0 2.0 1.0 o


Figure 5. Nmr spectrum of 3,7-dideutero-1,5-diphenyl-l-aza-5-borabicyclo(3.3.0)octane.










(Figure 4). The nmr spectrum of 72 is given in Figure 5. Resonances

occur at 61.1 (m, 2); 62.15 (broad m, 1); 63.45 (m, 2); and the aromatic

resonance at 67.0 (m, 5). The mass spectrum gave a parent peak at
j-
265 -1, corresponding to the correct molecular weight. The analysis

agreed with structural assignment.

Anal. Calcd. for C8H20D 2BN: C, 81.52; H, 7.60; D, 1.52; B, 4.08;

and N, 5.28. Found: C, 81.74; B, 4.20; and N, 5.18.



D. Preparation of 3-Deuteropropene by Alternate Method

To cast aside any lingering doubts as to the identity of the

isolated gas, 3-deuteropropene was prepared by an alternate method.

The infrared and nmr spectra were compared.

Allylmagnesium bromide was added to deuterium oxide in a small

flask equipped with a gas outlet. Gas samples were trapped it' an

infrared gas cell. Samples for the nmr were obtained by liquefying

the gas in a trap, cooled by dry ice-isopropanol, and mixing with

deuterochloroform.

The infrared and nmr spectra were identical to those of the

3-deuteropropene, 83, obtained from the reaction in Schere VIII.



E. Preparation and Reactions of -Substituted 1, .5-Diphenv1-1-aza -
5-borabicyclo(3.3.0)ocranes

The next goal was the synthesis of a series of substituted 1,5-

diphenyl-l-aza-5-borabicyclo(3.3.0) octanes which would have functional

groups in the para-positions of the phenyl rings capable of conversion

to monomers.










The most obvious approach might appear to be that of electro-

philic aromatic substitution. However, boron is, in theory, a

better leaving group than hydrogen in these substitutions. Tri-

phenylboroxene was reacted with aluminum chloride and, also,

phosphorus pentachloride to yield benzene as the only identifiable

product.110 The boron atom on triphenylboroxene, or triphenyl-

cyclotriboroxene, however, might be a better leaving group than

the coordinated structure of the 1,5-diphenyl-l-aza-5-borabicyclo-

(3.3.0)octane, 63. Li 11 reacted 63 with acetyl chloride and

aluminum chloride to give acetophenone and other unidentified





+ X
C)
.63 ACI4 4










A second approach would involve nucleophilic aromatic substi-

tut.Icn. .,o major problems present themselves in this method. Both

are due to the stre:.gt'n of the bases employed in these substitutions.

If an equilibrium exists between the coordinated, 63, and un-

coordinated, 63A, forms of the bicyclic system, different chemical re-

activity would be expected for the two forms. Strong bases would be

expected to attack the electronically-deficient boron atom in struc-

ture 63A.











BN- Q '



63 63A


Structure 63 would be susceptible to Hofmann elimination by

strong bases as shown below:
H B




0 -


63

Some experimental data support the possibility of cleavage

of the bicyclic unit by the above mechanism. The 1,5-diphenyl-

l--aza-5-borabicyclo(3.3.0)octane system was destroyed by .'

reaction with butyllithium. The starting material was not

recovered, but tne products were not identified. Trinapthyl-
112
borane was reacted with methanol to give trimethoxybcrane.112

The only feasible approach in preparing 1,5-diphenyl--azn-

5-borabicyclo(3.3.0)octane with phany! substituents was to start

with the substituted bromobenzenes and to build the desired pro-

ducts. The synthesis of trietbylaitine-phenylboranes (Scheme III)

involves Grignards, acids, lithium aluminum hydride, alcohols,

heat, and Lewis bases. The preparation of substituted NN-diailyl-

anilines involves the heating of a sodium carbonate-water solution

to reflux. The desired substituents must also be readily converted

to monomer without destroying the bicyclic structure.










Preliminary studies of the 1,5-diphenyl-l-aza-5-borabicyclo(3.3.0)-

octane showed the stability to boiling water, dilute mineral acids, tri-

ethylamine, and dilute sodium hydroxide. The compound was not stable

to peroxides in sodium hydroxide or strongly acidic conditions. Oxi-

dizing conditions with bromine in acetic acid destroyed the bicyclic

structure.

Carbon-boron bond cleavage has been reported to occur with n-butyl-
113
lithium, bromine, peroxides, and acetylchloride in pyridine.1

Several previously unreported, substituted 1,5-diphenyl-l-aza-5-

borabicyclo(3.3.0)octanes were prepared along with their monocyclic

by-products. These are listed in Table 2. Each synthesis involved

essentially the same procedures as were outlined for the model com-

pounds. Some modifications were, however, necessary in nearly every

case due to the new functional groups. The average time required for

synthesis and isolation of each pair of bicyclic and monocyclic cos--

pounds was approximately 4 to 5 weeks. Physical properties, nmr, ir,

mass spectra, and elemental analyses are given in Tables 3 and 4 for

the bicyclic compounds. The details of each synthesis are given in

the experimental section and will not be repeated in this chapter.

Instead, the preparation of 1,5-bis-(4-chloropbenyl)-l-aza-5-borabi-

cyclo(3.3.0)occane. 93, and 1,2-bis-(4-chlorophenyl)-1,2-azaoor-lidine,

94, will be presented to give the reader an idea of the approach to

synthesis, separation, work-up, and analysis of these compounds.

Triethylamine-(p-chloro)phenylborane was dissolved in a large

volume of toluene in a round-bottopied flask under nitrogen. The

contents were heated to 550 C, and then the p-chloro-N,N-diallyl-

aniline was added dropwise to the stirring mixture. As the reactio-.










TABLE 2
SUBSTITUTED 1,5-DIPHENYL-1-AZA-5-BORABICYCLO-
(3.3.0)OCTANES AND 1,2-DIHENYL-1,2-AZABOROLIDINES


j )- Y
-\_. ^ _T


.1,-Diphenyl-l-aza-5-borabicyclo(3.3.0.)octane

Cpd. No. X

63 H H

87 H Er

89 H Cl

91 Ci HC

U. 3 Cl Cl

95 Br H

97 Dr Br

SCHI


'OC i, OCH3

1 "C3 ,CHC CCHI3
2 0


1,2-Diphenyl-1,2-azaborolidine

Cpd. No. X Y

64 H H

88 H Br

90 H Cl

92 Cl H

94 Cl Cl

96 Br H

98 Br Br

100 CH3 CIH

104 OC23 OCH3
102 OCH3 OCH

104 OCH2CH3 OCH3
23 3










TABLE 3. PHYSICAL DATA OF SUBSTITUTED
1,5-DIPHENYL-1-AZA-5-BORABICYCLO(3.3.0.)OCTANES


Cpd. No.


Name


63 1,5-Diphenyi-l-aza-5-
borabicyclo(3.3.0.)octane

84 3,7-Dideutero-1,5-diphenyl-1-
aza-5-borabicyclo( 3.3.0. )octane


87 l-(4-Bromophenyl),5-phenyl-l-
aza-5-borabicyclo(3.3.0.)octane



S9 i-(4-Chlorophenyl),5-phenyj-1-
aza-5-borabicyclc(3.3., )octane



91 l-Phenyl,5-(4-c l--. p.eiyl)-l-
aza-5 -borabicyclo (3.3.0.)octane


93 1,5-Bis-(4-chlorophenyl)-1-
aza-5-borabicyclo(3.3.0.)octane


Formula

C18H22BN


CI8H20D2BN



C H 21ENBr





18 21




C H2i ::C1



CI8H0 BNC12
1820 2


M.P.(0C)


80-81


78-79


Analysis (Calculated, Found)

C,82.13; H,8.42; N,5.32; B,4.11
C,82.15; H,8,51; N,5.41; B,4.21


C: C,81.52;
B,4.08
F: C,81.74;


116-118 C: C,63.19;
Br,23.36
F: C,63.11;
Br,23.24


95-96


93-95


C: C,72.63;
01,11.91
F: C,72.66;
C1.12.04

C: 0,72.63;
C1,11.91
F: C,72.59;

C: C,65.08;
C1,21.36
F: C,64.97;


H,7.60; D,1.52; N,5.28;

N,5.18; B,4.20

H,6.19; N,4.09; B,3.16;

H,6.29; N,3.96; B,2.90;


H,7.11; N,4.70; B,3.64;

H,7.06; N,4.59; B,3.73;


H,7.11;

i-1,7.12;


N,4.70; B,3.64;

N,4.71; cl.12.08


H,6.07; N,4.22; B,3.26;

H,5.99; N,4.15; 01,21.13










TABLE 3 (continued)


M.P.(C)


Analysis (Calculated, Found)


97 1,5-Bis-(4-bromophenyl)-l-
aza-5-borabicyclo(3.3.0.)octane


99 1,5-Bis-(4-Tmthylphenyl)-l-
aza-5-borabicyclo(3.3.0.)octane


C18H2BNBr2


93-94


C20H26BN 107-108 C:
F:


C: C,51.35;
Br,37.96
F: C,51.89;


H,4.78; N,3.33; B,2.57;

H,4.74; Br,37.96


C,82.46; H,9.00; N,4.81; B,3.72
C,82.21; H,9.05; N,4.96; B,3.71


l,5-Bis-(4-methoxyphenyl )-1-
aza-5-borabicyclo(3.3.0. )octane


1-(4-Methoxyphenyl),5-
(-ethoxyphenyl)-l-aza-
5-borabicyclo (3.3. )octane

Bis- ,4-[5-(4-nmethylphenyl)-
l-aza-5-borabicyclo(3.3.0.)-
octyl]benzene

Bis-1,4-[5 -(4-chlorophenyi)-
l-aza-5-borabicyclo(3.3.0.)-
octyl]benzene


C20 H2 T)j'2



C2 H 2BNO2
C21H28B2N



C32"42B2N2


112-114 C: C,74.32;
0,9.90
F: C,74.19;


166-137 C:
F:


202-204 C:
F:


CoH 36B 2N2Cl2 198-200
3.0 36 i'


H,8.11; N,4.33; B,3.35;

H,8.01; N,4.16; B,3.36


C,74.79; H,8.37
C,75.23; H,8.29


C,80.69; H,8.89; N,5.88; B,4.54
C,80.39; H,8.71; N,5.70; B,4.72


C: C,69.67;
C1,13.71
F: C,64.47;
C1,14.02


H,7.02; N,5.42; B,4.18;

H,6.86; N,5.45; B,4.27;


Cpd. No.


Name


Formula


101



103



104











TABLE 4. SPECTRAL DATA OF SUBSTITUTED
1,5-DIPHENYL-1-AZA-5-BORABICYCLO(3.3.0.)OCTANES


1Be (p.p.m.)
Chemical Shift


3.6


i.9





2.8


NMR
(5) *


Chemical Shift


Compound
Number


63


Areas

9.8
4.0
4.0
4.1

10.4
4.0
2.0


6.85
3.3
2.1
1.1

7.0
3.45
2.15
1.1

6.9
3.3
2.05
1.1

7.0
3.3
2.05
1.1

7.0
3.3
2.05
1.05

7.2
3.4
2.15
1.15


IR (cm.-1)
B-N Absorbance


1275




1273


1270




1270


1280


1275


Mass Spectrum
Parent Peak


263 *1




265 1


342 1




297 1


297 +1




332 1


* Chemical shift relative to trimiethyl borate
** Chemical shift relative to tetramethylsilane


in deuterochloroform


4.0
4.2
4.0

9.0
4.0
4.2
4.0

9.1
4.0
4.0
4.1

8.2
4.0
4.0
4.0











TABLE 4 (continued)


lB* (p.p.m.)
Chemical Shift


NMR
16 .0


Chemical Shift


7.05
3.35
2.10
1.15


4.7


6.8
3.4
2.1
1.1


6.0


103


3.35
2.1
1.1

6.9
3.7
3.3
2.0
1.3


Areas


8.1
4.0
4.0
S.1


8.0
3.8
10.1
4.1


6.1
2.1
2.0
2.1

8.3
9.1

4.1
4.2


IR (cm.-1)
B-N Absorbance


1275


1275


1281


1278


Mass Spectrum
Parent Peak


421 1


291 1


323 1


337 1


Double Peak
1273 and 1286



Double Peak
1260 and 1273


Compound
Number


4.


1.05


6.9
3.2
2.1
1.1


12.2
8.0
14.1
8.2

12.3
8.0
8.0
8.1


6.90
3.23
2.05
1.05


476 1




517 1









proceeded and the temperature raised, a brilliant green color appeared.

Infrared gas samples indicated the formation of propene gas. The reac-

tion was allowed to proceed at 920 C for 24 hours. The contents were

cooled, filtered, and then the solvent was removed on a rotary evapo-

rator. The residual liquid was transferred to a small flask for dis-

tillation on a spinning band column. Several fractions were collected.

The first fraction proved to be unreacted p-chloro-N,N-diallylaniline.

The second fraction was a clear, viscous liquid (b.p. 130-135 C @ 0.20

mm.). This compound turned brown on exposure to air. The third frac-

tion was the same compound. The infrared spectrum was consistent with

the azaborolidine structure, 94, with the B=N absorbance assigned at
-i
1400 cm. -. The mass spectrum gave a parent peak at 289 1, consistent

with the molecular weight. The nmr spectrum (Figure 6) shows resonances

at 57,05 (m, 8); 63.75 (t, 2); 61.7 (m, 4) for the aromatic, a, and b.c

protons respectiialy.

Anal. Calcd. for C ,H 1BNC1 : C, 62.09; H, 4.87; N, 4.83; B, 3.73;
la 14 2
and Cl, 24.46. Found: C, 61.78; H, 5,01; and Cl, 24.45.

The fourth fraction (b.p. 170-175' C) was very viscous and solidi-

fied in the side arm. This material was recrystallized from ethanol to

give a crystalline solid (m.p. 93-950 C). The ir spectrum gave a strong

absorbance at 1275 cm.-1 which was assigned to the B-4 coordinate bond.

The mass spectrum gave a peak at 332 *1, corresponding to the correct

molecular weight. The nmr spectrum (Figure 6) showed resonances at 67.2

(m, 8); 63.4 (m, 4); 62.15 (q, 4); and 61.15 (in, 4) for the aromatic, a,

b, and c protons respectively.

Anal. Calcd. for C H 20BNCi,: C, 65.08; H, 6.07; N, 4.22; B, 3.26;

and Cl, 21.36. Found: C, 64.97; H, 5.99; N, 4.15; and Cl, 21.13.














CA C-


S-93


9Li.


-~~~ ~~ t' .r-,-. -~---- r~u --


Figure 6. Nmr spectra of 1,5-bis-(4-chlorophenyl)-l-aza-5-borabicyclo-
(3.3.0)octane and 1,2-bis-(4-chlorophenyl)- ,2-azaborolidine.


-i-r ~l-r.---+- --i ui--C----. -~- -)- -J--..rL--c--~---Lu~~- -1' C- ~ 1


LiiL/lt /*-Wy^' -.!'


?*.;*>(&


s~l
"M?~~h;-l;~lrY.Y-*~C~/










A comparison of the spectra in Figure 6 reveals some interesting

effects. A look at models gives some insight into these effects. In

the monocyclic structure, 94, the phenyl rings are far apart and the

ring must be nearly planar. As a result, the b protons are moved

upfield and the c protons are deshielded, resulting in an overlap of

the protons on carbons b and c. The a protons are also slightly

deshielded, probably due to the planar positioning of the phenyl groups

relative to the 5-membered ring. In the bicyclic structure, 93, the

a, b, and c protons give three distinct resonance absorptions. The

model of this compound shows the phenyl groups tied back, much like

butterfly wings, relative to the B-N bond axis. The two propylene

bridges are also forced back in the opposite direction to the phenyl

groups. The b_ protons are in the region expected for 5-membered,

bicyclic rings. The a and c protons are s-ielded relative to the

azaborolidine, resulting in upfield shifts of 4 co 5 p.p.m.

The B1 nmr spectrum of 93 exhibited a chemical shift of 2.2

p.p.m., relative to trimethyl borate. This compares with 3.6 p.p.m.

for the unsubstituted 1,5-diphenyl-l-aza-5-borabicyclc(3.3.0) otane.



F. Preparation of Bis- 14-15--(4-methj Lphenvl)-l-aza-5-borabicyclo-
(3.3.0)octyl]benzene and Bis-1,4- [5- (4-hioEronvl )-l-aza-5-bora-
bicyclo(333.0)oct_1 benzene

Bis-1, 4- [5- (4-me thy lphenyl)-l-aza-5-bora-bicyclo ( 3..0) oetyl] -

benzene, 104, and bis-l,4-[5-(4-chlorophenyl)-l-aza--5-bcrabicyclo-

(3.3.0)octyljbenzene, 105, were prepared by reacting N,N,N',N''-

tetraallyll--pphcnylen di a-ine with tried thy la:mine-(4-;:e thy ) phenyl-

borane and triethylamine(4-chicro)phenyiborane. These compounds,

of course, were not distillable and were purified using silica ge.i









chromatography and recrystallization. Physical and spectral data are

given in Tables 3 and 4.






CH Q ----CH3 Cl- -Cl


104 105





The high molecular weights of these compounds and their molecular

structures make them excellent models for the study of polymers with

similar structures. The boron-nitrcgen coordinate bonds in these com-

pounds exhibited double absorbances in the 7.8 to 8.0 micron region

compared to single absorbances in the 1,5-diphenyl-l-aza-5-borabicyclo-

(3.3.0)octaees. These compounds were the best models for differentiAl

scanning calorimetry studies, described later in this chapter.



G. Reaction of N,N,N',N'-Tetraallyl-p-phenylenediaamine with
p-Phenvienediborane

The relatively high yields of 104 and 105 encouraged attempts

to prepare oligomeric or polymieric products. It seemed that the

above synthesis should be extended by reacting a bis-borane com-

pound, 107, with 1,N,N',N'-tetraallyl--pphenylneediamiue, 106, to

yield a polymer, 1.08. Attempts to prepare the pure di(pyridine)-

p-phenylenediborane and di(triethylamine)-p-phenylenediborane are

described in Chapter III. The resulting crude compound, 107, was

reacted with the tetraallyl compound, 106. A viscous, brown com-

pound was obtained. This compound was insoluble in every solvent










CH2=CHCH CHCH=CH rR-
2 2,N & /z 2c R.oN

CH2=CHCH/ 2CHCH=CH2
2 2 2 107
106





108



tried, but swelled to a gel-like material in acetone after several

weeks. The material appeared to be cross-linked, as might be

expected by examination of the above equation.



H. !Boron Nuclear Magnetic Resonance Studies

11 nmr spectra were obtained for the substituted bicyclic

compounds listed in Table 4. The chemical shifts in chlorof rm

were measured in p.p.m. relative to trirethy borate by a Varian

XL-100 instrument. The chemical shift values varied from 1.9 to

5.2 p.p.m. for the compounds studied. These shifts are very close

to those given in the literature for dietbylamine-borane (3.2 p.p.m.),

pyridine-borane (4.7 p.p.m.), and for the (3.3.3)bicycloborate

ester of the triethanolainines (3.2 p.p.m.).8 The chemical shift

of these bicyclob.,rate caters to somewhat higher fields than other

alkyl borates was attributed to increased shielding around the

boron atom duep to the boron-nitrogen coordinate bond, thus increasing

the tetrahedral character and the number of bonding electrons around

the boron atoms.
11
Some of the iB cheraical shifts in Table 4 might be interpreted

in light of the above discussion. The electronic effects of the









phenyl substituents on the bicyclic structure 109 should be reflected

in the boron-nitrogen bond strength and in the tetrahedral character

of this bond. The bicyclic structure, for which both _x and y are


x 0 --y


)j 109
chlorine atoms, gives a chemical shift of 2.2 p.p.m. When x is

chlorine and y is hydrogen, the chemical shift is 5.2 p.p.m. This

may be interpreted as a result of the withdrawing effect of chlorine

increasing the electron deficiency of boron and, therefore, strength-

ening the B-N coordinate bond. If x is hydrogen and y is bromine,

the chemical shift drops to 1.9 p.p.m. This effect is consistent

with a decrease in the basicity of the amine, thus decreasing the

B-N bond strength. Less reduction is noticed when x is hydrogen and

y is chlorine; this compound, 89, gives a chemical shift of 2.8 p.p.m.

In the dibromo-bicyclic compound, 97., electronic effects of the sub-.

stituents might be expected to cancel each other. The chemical shift,

3.1 p.p.m., is close to that of the unsubstituted compound, 63, at 3.6

p.p.m. The symmetrical bicyclic compounds 104 and 105 show chLem.cal

shifts of 4.4 and 4.7 p.p.m., respectively.



I. TeTrperature Studies by Differential Scanning Calorimetry

A Perkin-Elmer DSC-1B Differential Scanning Calorimeter was used

for studies of the B-N coordinate bond dissociation for all substituted

1,5-diphenyl-l-aza-5-borabicyclo(3.3.0)octanes which were prepared.

Samples were weighed and then placed in special sample holders to

reduce volitalization. Temperature scanning increments were set at 20

per minute. Melting points were easily observable and served ao









excellent calibration marks. At higher temperatures, sublimation of

the samples occurred. No decomposition peaks were observed prior to

sublimation, showing the remarkable stability of these relatively

heavy compounds. A broad endotherm appeared in all spectra beginning

at 520-540* K. This temperature seemed to be consistent with that

expected from B-N coordinate bond dissociation. However, the peak

area could not be measured due to volitalization of the sample,

beginning at a slightly higher temperature.

The bis-l,4-[5-. (4-methylphenyl)-I-aza-5-borabicyclo(3.3.0)octyl]-

benzene, 104, and the bis-l,4 -[5-(4-chlorophenyl)-l-aza-5-borabicyclo-

(3.3.0)octyl]benzene, 105, were much better models for the temperature

studies. These compounds sublimed at a much higher temperature and

allowed the observance of endotherai.s which seemed consistent with

those expected for the boron-nitrogen bond dissociation. Broad,

double peaks were observed beginning at 5320 K and ending at 6170 K

for compound 104. Similar peaks were observed for compound 105

beginning at 5410 K and ending at 6270 K. The heat of this transition

for compound 10_4 was calculated to be 60 cal./g. or 28.5 kcal./mole.

Compound 105 gave a value of 58.2 cal./g. or 30.3 kcal./mole. These

values are very close to those predicted by Butler.1



J. Synthesis of 1,6-Dipbeny-l--aza-6-borabicyclo(4.4.0)decane

The final synthetic effort in this research was an extension

of the hydroboration by triethylamine-phenylborane of N,N-di-

3-butenylaniline, 10. This reaction would be expected to yield

1,6-diphenyl-l-aza-6-borabicyclo(4.4.0)decane, 114. 1,2-Diphenyl-
















(O -NTEt3


65


i.j


110


112
i


2
V.. /
,i


\ I-


1.14


1-butene


SCHEME X


I -\
@ Oj


ill


77
<0 4. Cy


113









azaboracyclohexane, 113, should not be formed by a concerted

mechanism as was the case for the azaborolidines in our previous

studies (Scheme X). This compound could, however, conceivably be

formed by the pyrolysis of intermediate 111 at high temperature

under vacuum. The elimination could be tested, as before, by

monitoring gases produced from the reaction in p-xylene. If the

competing pathway 1 were followed at the reaction temperature,

butene gas would be detected. If only pathway 2 were followed,

the bicyclic compound should be formed in relatively higher yield.

This higher yield, obviously, would be more attractive for monomer

preparation than the yields obtained for the 1,5-dipheny-l--aza-

5-borabicyclo(3.3.0)octanes.

N,N-Di-3-butenylaniline, triechylamine-phenyiborane, and p-

xylene were slowly heated under nitrogen. Gas samples were taken

at various temperatures and time intervals. A bright green color

developed during the course of the reaction, but no butene gas was

evolved during heating. The resulting solution was filtered, roto-

vaced, and divided into two portions. The first portion was then

dissolved in benzene and passed through a neutral silica gel column.

The eluted solution was rotovaced. A white, gummy material was

obtained. This was recrystallized from ethanol to give white

crystals (m.p. 143-145 C). The compound was consistent with the

structure assigned to 1,6-diphenyl-l--aza-6-borabicyclo(4.4.0)decane.

The mass spectrum gave a parent peak at 291 tl. The infrared spectrum
--].
gave a broad absorbance at 1280 cm. consistent with that expected

for the B-N coordinate bond. The nmr spectrum exhibited resonance









signals at 60.95 (m, 4); 61.6 (m, 8); 63.5 (m, 4); and 67.3 (m, 10).

Anal. Calcd. for C20H26BN: C, 82.48; H, 9.00; B, 3.71; and

N, 4.81. Found: C, 81.98, H, 8.61; B, 3.64; and N, 4.76.

The second portion of the reaction mixture was distilled under

vacuum on a spinning band column. Several fractions were obtained.

The first fraction proved to be unreacted N,N-di-3-butenylaniline.

The second fraction (b.p. 75-78 C @ 0.50 mm.) exhibited absorbances

in the infrared spectrum and resonances in the nmr spectrum con-

sistent with the structure of 1,2-diphenyl-azacyclohexane, 113.

The third fraction (b.p. 90-95 C @ 0.50 mm.) was a pale yellow

liquid. The spectra were consistent with the assignment of 1,2-

diphenyl-l-(3-butenyl) ,2-hydro-azaboracyclohexane, 112. The nmr

spectrum showed the presence of an allyl group with resonances at

65.8 (m, 0.5); and 65.1 (m, 1). Other resonances for compound 112

occurred at 60.8 (m, 2); 61.65 (m, 6); 63.35 (m, 4); and 67.4 (m, 12).
-I
The ir spectrum showed the presence of a C=C double bond at 1645 cm.
-1
as well as the presence of a B-H bond at 2250 cm. The distillation

flask contained a gummy, brown residue, which was recrystallized from

ethanol to give a white, crystalline material. This compound was

identical to that obtained from the silica gel column chromatography.

The above results gave strong support to the mechanism proposed

for the facile, concerted elimination of propene gas in the competitive

formation of l,5-diphenyl-l-aza-5-borabicyclo(3.3.0)octanes, 72,

and 1,2-diphenyl-1,2-azaborolidine, 71 (Scheme VI).











K. Conclusions

This research has attained many of its projected goals. The

model compound, 1,5-diphenyl-l-aza-5-borabicyclo(3.3.0)octane was

prepared and its properties investigated. All of the products of

the reaction of triethylamine-phenylborane with N,N-diallylaniline

were isolated, purified, and carefully characterized by nmr, ir,

mass spectral, and elemental analyses. Propene gas was isolated

and identified as a by-product.

Mechanistic studies with deuterium labeling gave strong

support to the proposed mechanism of the facile, concerted elimi-

nation of propene. These studies ruled out a Hofmann-type elimi-

nation mechanism.

The stability of the model compou-:nd, 49, to various synthetic

conditions, such as thy;:.e necessary for iu!Icleophilic or' electro-

philic aromatic substitutions, waq deternmied. Its reactivity in

various solvents, acids, and bases was also studied.

Several substituted derivatives of 49 have been prepared which

should be excellent monomer precursors. P3relimTinary studies .sh

evidence for the formatiecn of the bis-Grignard reagt from ~ 5-

bis- ( '--bromophcnyl-l--..n. .-' -5-bor~-abi .yclc, (3.3.0 )oc.t-.::. e corra-

sponding bis.-(4- -methcx:yphenyl) compound has be-n converted to snall.

amount& of the 1,5-bis- (4-hydro;eyphenyl' --l--aa-borabi.cyclo (3.3.0)-

octarn by the reaction of lithiiml iodide in collidine. Thess two

reactions have excellent potential fir the formation of dicarboxylil

and diphenolic derivatives of -9. These compounds 1.ould be interest-

ing co-monomers for several] possible condensation pol7ym-erization











reactions. Several other compounds listed in Table IV have function-

ality which could be utilized in monomer preparation. In all, over

40 new compounds have been synthesized and characterized in this

research.

The boron-nitrogen coordinate bond has been investigated

extensively by nmr, ir, 1B nmur, and by differential scanning

calorimetry. Chemical shifts, boron-nitrogen stretching frequencies,

and heat of transition studies have given us valuable information

which has opened many avenues for future research on these hetero-

cyclic compounds and other related systems.
















Chapter V

EXPERIMENTAL

A. Equipment and Data

All temperatures are reported uncorrected in degrees centigrade.

Nuclear magnetic resonance (nmr) spectra were obtained with a Varian

A-60A Analytical NMR Spectrometer. The chemical shifts were measured

in deuterochloroform, unless otherwise specified, relative to tetra-

methylsilane.

Infrared spectra were obtained with a Beckman IR-8 Infrared

Spectrophotometer.

1IBorcn nuclear magnetic resonance spectra were obtained,

courtesy of Dr. Wallace S. Brey, with a Varian X-L 100 High Resolution

NMR Suectrometer.

Mass spectra were obtained with a Hitachi Perkin-Elmer RilU

Mass Spectrometer.

Thermal analyses were carried out on a Perkin--Elmer Differential

Scanning Calorimeter DSC-1B.

Elemental analyses were performed by Galbraith Laboratories,

Inc., Knoxville, Tennessee.









B. Syntheses and Characterization

Preparation of N,N-Diallylaniline

Aniline (186.0 g., 2.0 mol.), sodium carbonate (420.0 g., 4.0 mol.),

and 300 ml. of water were placed in a 3-liter, 3-necked, round-bottomed

flask equipped with an overhead stirrer, dropping funnel, and water-

cooled condenser. The mixture was heated to low reflux using a

heating mantle and variac. Allyl bromide (484.0 g., 4.0 mol.) was

added dropwise over a period of 4 to 5 hours with constant stirring.

The brown, syrupy liquid which resulted was stirred for 4 more hours

and then filtered into a 2-liter separatory funnel. The two resulting

layers were separated and the aqueous layer washed with 3 100 ml. por-

tions of ether. The ether was removed on a rotary evaporator. The

resulting residue was combined with the crude organic layer. This oily,

brown liquid was then added carefully to the 30% solution of sodium

hydroxide in 300 ml. of water. This solution was then transferred to

a 3-necked, 3-liter, round-bottomed flask equipped with mechanical

stirrer and addition funnel. Benzenesulfonyl chloride (100 mi.) was

added dropwise with stirring. T:.r resulting slush was cooled in a:-

ice bath and neutralized with 10% hydrochloric acid. The organic

layer was separated and dried with sodium sulfate. The crude N,,- di-

allylaniline was filtered and placed in a 1--liter, round-bottomed

flask for distillation. Using a vacuum distillation apparatus, consist-

ing of a Vifereaux column, fraction cutter, and receiving flasks, an

97.6% yield' of a clear liquid (293.0 g., b.p. 104-i06 C ( 3.5 mm.) was

obtained.-








Synthesis of p-methyl-N,N-diallylaniline

p-Toluidine (214.0 g., 2.0 mol.), sodium bicarbonate (420.0 g.),

and 1000 ml. of water were placed in a 3-liter, 3-necked, round-

bottomed flask equipped with thermometer, overhead stirrer, addition

funnel, and condenser. The mixture was heated on a heating mantle

until the temperature of the liquid reached 700 C. Allyl bromide

(581.0 g., 4.8 mol.), was added dropwise with stirring. The resulting

mixture was heated overnight. The brown liquid separated into 2 phases

on sitting. The layers were separated using a 1-liter separatory

funnel. The oily layer was washed with 3 100 ml. portions of water

and then dried over sodium sulfate. The crude p-methyl-N,N-diallyl-

aniline was filtered and then vacuum distilled yielding 262.3 g. (70.1%)

of a pale yellow liquid (b.p. 80-850 C. @ 0.350 mm.).

The infrared spectrum (ir) gave absorbances at 1520 (m), 1240 (s,

split), 800 (m), 1620 (s, split), 920 (s, split) 1340 (m), 1360 (s),

1390 (s), 1410 (m), 1425 (m), 1450 (w), 1180 (s), 990 (s), 2990 (s),

2950 (s), 3000 (s), 3020 (s), and 3110 (m) cm. .

The nmr gave resonance signals at 68.8 (m, 4); from 64.9 to 66.2

(m, 6); 63.8 (m, 4); and 62.2 (s, 3).



Synthesis of p-bromo-N ,N-diall.ylani ine

p-Bromoaniline (100 g., 0.582 mol.), sodium carbonate (126.0 g.,

1.2 mol.), and 230 ml. of water were placed in a 2-liter, 3-necked,

round-bottomed flask equipped with a mechanical stirrer, drcpi.-:n

funnel, and water-cooled condenser. The mixture was heated on a heat-

ing mantle until low reflux was obtained. Allyl bromide (146.0 g.,

1.2 mol.) was added over a 3 to 4 hour period through an addition









funnel. Stirring was continued for 12 hours, after which a syrupy,

brown liquid was obtained, along with an aqueous layer. The layers

were separated in a 1-liter separatory funnel. The aqueous layer

was washed with 2 350 ml. portions of ether. The ether was then re-

moved on a rotary evaporator and the resulting layer combined with

the crude p-bromo-N,N-diallylaniline. This crude liquid was added

dropwise to a 30% solution (100 ml.) of sodium hydroxide in water

in a 2-liter, round-bottomed flask equipped with a mechanical stirrer

and addition funnel. Benzenesulfonyl chloride (34.0 ml.) was added

dropwise. Since the reaction was exothermic, an ice bath was used

to control the temperature. The resulting cooled solution was neu-

tralized with 10% hydrochloric acid solution. The organic layer was

separated and dried with sodium sulfate. The crude product was fil-

tered and placed in a 200 ml. round-bottomed flask for vacuum distil-

lation. The distillation yielded 69.5 g. (a7.5%) of a colorless liquid

(b.p. 93-940 C @ 0.250 nm.).



Preparation of p--bromo-N,N-diallylaniline

D-Bromoaniline (200.0 g., 1.15 mol.), sodium bicarbonate (242.0 g.,

2.9 mol.), and 400 ml. of water were placed in a 2-liter, 3-necked,

round-bottomed flask equipped with stirrer, condenser, addition funnel,

and heating mari-e. The mixture was heated to low reflux. Allyl

broride (278.3 g., 2.3 mol.) was added dropwise over a two-hour period

with constant stirring. The lower, oily layer was dried with sodium

sulfate. The crude product was vacuum distilled yielding 215.3 g. (74.5%)

of a clear liquid (b.p. 113-1140 C @ 0.100 rm.).











Synthesis of p-methoxy-N,N-diallylaniline

p-Methoxyaniline (187.0 g., 1.0 mol.), sodium carbonate (210.0 g.,

2.0 mol.), and 500 ml. of water were placed in a 2-liter, 3-necked,

round-bottomed flask equipped with stirrer, addition funnel, and con-

denser. The mixture was heated to reflux on a Glas-col heating mantle.

Allyl bromide (266.0 g., 2.2 mol.) was added dropwise to the mixture.

The resulting mixture was allowed to stir at reflux overnight and was

then transferred to a 2-liter separatory funnel. The water layer was

discarded; the organic layer was dried with magnesium sulfate. The

liquid was filtered and then vacuum distilled yielding 183.4 g. (88.0%)

of a clear liquid (b.p. 87-880 C @ 0.350 mm.).

The ir spectrum showed only a small residual N-H absorbance at
-l
3420 cm.-. Other absorbances were present at 3100 (m), 2840 to 3020

(s, broad, detailed), 1840 (w, broad), 1645 (m), 1622 (w), 1580 (w),

1515 (s, broad), 1463 (m), 1442 (m), 1422 (m), 1403 (w), 1385 (w),

1360 (w), 1332 (w), 1300 (w), 1278 (w), 1240 (s, broad), 1180 (s),

1130 (m), 1040 (s), 918 (s), 815 (s), 760 (w), 712 (m) cm.-1

The nmr spectrum showed resonance signals at 66.65 (m, 4); 65.85

(m, 2); 65.1 (m, 4); and 67.1 (m, 7).



Synthesis of p-chloro-N,N-diallylaniline

p-Chloroaniline (225.0 g., 2.0 mol.), sodium carbonate (420.0 g.),

and 500 ml. of water were placed in a 2-liter, 3-necked, round-bottomed

flask equipped with stirrer, addition funnel, and condenser. The

mixture was heated to reflux on a heating mantle. Allyl bromide (484.0

g., 4.0 mol.) was added dropwise with stirring. Heating and stirring








were continued overnight. The resulting liquid was poured through a

filter into a separatory funnel in which two layers formed. The lower

layer was discarded and the brown, oily layer was dried with sodium

sulfate. The crude p-chloro-N,N-diallylaniline was distilled under

vacuum yielding 300.4 g. (72.5%) of a colorless liquid (b.p. 85-860

C @ 0.350 mm.). Nmr and ir spectra agreed with the assigned structure.



Preparation of N,N-di-3-butenvlaniline

Aniline (14.0 g., 0.15 mol.), sodium carbonate (32.0 g.), and

50 ml. of water were placed in a 250 ml., 3-necked, round-bottomed

flask equipped with a mechanical stirrer, addition funnel, and cold-

water condenser. The mixture was heated to a low reflux. 4-Bromobutene

(40.5 g., 0.30 mol.) was added dropwise with constant stirring. The

reaction was allowed to proceed for 24 hours. The contents were

cooled and filtered. The amine layer was separated, dried over sodium

sulfate, and distilled under vacuum. A clear, colorless liquid (11.2

g., 37%) was obtained (b.p. 74-750 C @ 0.100 mm.).

The ir spectrum exhibited absorbances at 695 (s), 748 (s), 915

(s), 992 (s), 1040 (w), w) ), 1180 to 1220 (w, detailed), 1283 (m),

1360 (m), 1395 (w), 1420 (w), 1430 to 1460 (w, detailed), 1503 (s),
-1
1600 (s), 1640 (m), and 2950 to 3050 (s, detailed, broad) cm. .

The nmr spectrum gave resonance signals at 52.25 (quartet, 4);

63.3 (m, 4); 65.1 (m, 4); 65.8 (m, 2); and 66.8 (m, 5).



Synthesis of N,N,N',N'-tetraallyl-p-phenylenediamine

p-Phenylenediamine (125.0 g., 1.15 mol.) and sodium carbonate

(530.0 g.) were added to a 3-liter, 3-necked, round-bottomed flask

fitted with a Claisen adapter, thermometer, addition funnel, and









reflux condenser. Water (1500 ml.) was added; the mixture was heated

to reflux to dissolve the solid. The solution was then cooled to 700

C and 3-bromopropene (559.7 g., 4.63 mol.) added dropwise with stirring.

The solution was refluxed overnight before extracting the oily layer

with ether. The ether layer was then dried over sodium sulfate and

filtered. The brown, oily compound was then distilled yielding 124.6 g.

(46.5%) of a pale yellow liquid (b.p. 138-1400 C @ 0.550 mm.).



Synthesis of phenylboronic acid

A mixture of ethyl ether and magnesium (36.0 g., 1.5 g. atoms)

was placed in a 1-liter, 3-necked, round-bottomed flask equipped with

a mechanical stirrer, addition funnel, and cold-water condenser. Bromo-

benzene (157.0 g., 1.0 mol.) in 200 ml. of ether was added dropwise

with stirring. After the reaction was started, the round-bottomed

flask was cooled in ice water to control the temperature. After all

the bromobenzene had been added, the contents of the flask were allowed

to warm to room temperature, Trimethylborate (103.9 g., 1.0 mol.) and

800 ml. of diethyl ether were placed in a 3-liter, 3-necked, round-

bottomed flask equipped with a mechanical stirrer, low-temperature

thermometer, and Claisen adapter with nitrogen inlet tube and addition

funnel. The Grignard reagent was filtered through glass wool into the

addition funnel. The solution in the 3-liter flask was cooled to -700

C in a dry ice-jsopropanol bath. The Grignard reagent was added drop-

wise and the temperature was controlled between -70 and -550 C. The

mixture, after cooling overnight, was hydrolyzed with 10% sulfuric

acid. The ether layer was separated and placed in a 3-liter, 3-necked,

round-bottomed flask fitted with a Claisen distilling head, mechanical









stirrer, addition funnel, and heating mantle. The ether solution was

concentrated while adding 1000 ml. of water dropwise. At this point

the temperature at the distilling head had reached 980 C. The solu-

tion was cooled. Fluffy, white crystals were observed. These were

filtered and washed with 3 10 ml. portions of hexane yielding 108.1 g.

(88.8%) of phenyl boronic acid (m.p. 214-2160 C).



Preparation of diethyl phenylboronate

Phenylboronic acid (50.0 g., 0.41 mol.), benzene (320.0 g.), 138

g. of absolute ethanol, and 2 drops of sulfuric acid were placed in a

1-necked, 1-liter, round-bottomed flask. An azeotropic distillation

apparatus consisting of a packed column, cold-water condenser, ther-

mometer, Claisen head, drying tube, and Dean-Stark trap was assembled.

The flask was heated on a Glas-col heating mantle. A ternary azeotrope

of water, ethanol, and benzene distilled over at 640 C. fi;. layers

formed in the trap. The lower (water) layer was removed as the reaction

progressed. After 2 days, the temperature at the distilling head had

reached 680 C, indicating the reaction was complete. The binary azec-

trope of benzene and ethanol distills at this temperature. The remain-

ing solvent was distilled and the resulting liquid placed in a 100 ml.

round-bottomed flask for vacuum distillation. The distillation yielded

65.5 g. (90.1%) of a clear liquid (b.p. 68-690 C @ 0.350 mm.).



Preparation of triethylamine-phenylborane

Lithium aluminum hydride (12.0 g., 0.32 m'ol.) was added to 400 ml.

of dried diethyl ether in a 3-necked, 1-liter, round-bottomed flask

equipped with condenser and drying tube, addition funnel, low-tempera-








ture thermometer, nitrogen inlet tube, addition funnel connector,

and a mechanical stirrer. The mixture was refluxed for thirty

minutes and then cooled to -720 C in a dry ice-isopropanol bath.

Triethylamine (37.4 g., 0.37 mol.) was added with stirring. Then

a solution of diethyl phenylboronate (65.5 g., 0.37 mol.) in ether

was added dropwise with stirring, keeping the temperature below

-650 C. The solution was stirred at -720 C for another hour and

then allowed to warm to room temperature. The mixture was filtered

through a sintered-glass funnel. The filtrate was concentrated and

then cooled in a dry ice-isopropanol bath resulting in the formation

of 51.9 g. (73.0%) of white, needle-like crystals (m.p. 65-660 C).



Preparation of 1,2-diphenyl-l,2-azaborolidine and 1,5-diphenyl-l-aza-
5-bora-bicyclo(3.3.0)octane

A solution of 1.25 liters of toluene, triethylamine-phenylborane

(18.0 g., 0.094 mol.), and N,N-diallylaniline (16.3 g., 0.094 mol.)

was distilled at atmospheric pressure in a 2-liter, 1-necked, round-

bottomed flask until the temperature reached 1200 C at the distilling

head. The remaining toluene was removed on a rotary evaporator,

resulting in a phosphorescent-green solution. This solution was dis-

tilled on a spinning band distillation column yielding two major pro-

ducts. The lower boiling component, 4.10 g., was a clear liquid (b.p.

84-860 C @ 0.30 mm.). The spectral data agreed with the assignment
99
of 1,2-diphenyl-1,2-azaborolidine. The ir spectrum gave absorba.ces

at 3430 (w), 3250 (w), 3060 (s), 2950 (s), 2880 (s), 1600 (s), 1490 (s),

1400 to 1440 (s, broad), 1300 (s), 1190 (m), 1150 (w), 1080 (w), 1050

(m), 1000 (m), 750 (s), 700 (s) cm.-1









The nmr spectrum gave resonances at 67.2 (m, 10); 63.8 (t, 2);

and a broad multiple at 61.8 (n, 4). The mass spectrum showed a

peak at 220 1.

Anal. Calcd. for C15H16BN: C, 81.47; H, 7.29; N, 6.34; and

B, 4.89. Found: C, 81.42; H, 7.31; N, 6.21; and B, 5.01.

The higher boiling fraction (b.p. 125-1300 @ 0.30 mm.) was

dissolved in acetone and cooled in a dry ice-isopropanol bath after

which white crystals formed. These crystals were filtered and dried

yielding 4.47 g. (m.p. 80-810 C). The spectral data and analysis

agreed with the assignment of 1,5-diphenyl-l-aza-5-borabicyclo(3.3.0)-

octane.9 The ir spectrum showed absorbances at 3040 (m), 2900 (s),

2820 (m), 1.925 (s), 1850 (w), 1580 (s), 1420 to 1480 (s, broad), 1260

(s), 1215 (m), 1175 (s), 1150 (m), 1125 (s), 1075 (m), 1040 (m), 1020

(s), 980 (s), 950 (s), 930 (m), 880 (s), 830 (w), 810 (s), /75 (s),
--1o
745 (w), 725 (s), 670 (s), and 610 (!w) cm. .

The nmr spectrum gave resonance signals at 66.85 (m, 10); 63.3

(m, 4); 62.1 (q, 4); and 61.1 (m, 4).

The mass spectrum gave a parent peak at 262 1.

Anal. Calcd. for CSH22 BN: C, 82.13; H, 8.42; N, 5.32; and

B, L.11. Found: C, 82.15; H, 8.51; N~ 5.41; and F, 4.21.



Synthes-is of p-bLroophenylboronic acid

A mixture of magnesium (27.0 g., 1.1 g. atoms) and 100 ml. of dry

diethyl ether was placed in a 1-liter, 4-necked, round-bottomed flask

equipped with a stirrer, addition funnel, and reflux condenser. p--Di-

bromobenzena (237.0 g., 1.0 moi.) in dLethyl ether was added dropwise

with stirring after the initial reaction was started. An ice bath was









used to control the reaction rate. The reaction mixture was stirred

for an additional 30 minutes at room temperature. Trimethylborate

(103.9 g., 1.0 mol.) and 800 ml. of diethyl ether were placed in a

3-liter, 3-necked, round-bottomed flask equipped with a mechanical

stirrer, low-temperature thermometer, and Claisen adapter for an

addition funnel and nitrogen inlet tube. The Grignard reagent was

filtered through glass wool into the addition funnel. The solution

in the 3-liter flask was cooled to -700 C in a dry ice-isopropanol

bath. The system was flushed with a slow stream of nitrogen. The

Grignard reagent was added dropwise with stirring and the temperature

was kept below -650 C. The mixture was allowed to warm to room tem-

perature with continuous stirring and was hydrolyzed with 10% sulfuric

acid. The ether layer was separated and placed in a 3-necked, 3-liter,

round-bottomed flask equipped with mechanical stirrer, Claisen head,

and addition funnel. Using a heating mantle and variac, the ether was

distilled away while adding 1000 ml. of water dropwise. When the tem-

perature at the distilling head reached 980 C, the solution was trans-

ferred to a l-.liter Erlenmeyer flask and allowed to cool. White, fluffy

crystals were obtained and washed with 3 10 ml. portions of hexane.

The total yield was 187.4 g. (93.5%) of p-bromophenylboronic .aci (a:.p.

27:1-272 C).

The ir spectrum showed absorbances at 3300 (broad, s), 2400 (w),

600 (s), 1500 (m), 1435 (s), 1350 (broad, s), 1280 (w), 1185 (s), 1090

(s), 1070 (w), 1010 (broad, s), 920 (w). 760 (m), 690 (s), and 630 (s)
-1
cm.

The nmr spectrum exhibited resonance signals at 67.5 (mi, 4) and

62,75 (s, 2).









Preparation of diethyl p-bromophenylboronate

p-Bromophenylboronic acid (100.8 g., 0.5 mol.), benzene (320.0 g.),

and absolute ethanol (138.0 g.) were placed in a 2-liter, 1-necked,

round-bottomed flask. An azeotropic distilling apparatus consisting

of a packed column, Claisen head, thermometer, condenser with drying

tube, and a Dean-Stark trap was assembled. The round-tottomed flask

was heated on a Glas-col mantle until a ternary azeotrope of benzene,

ethanol, and water distilled at 640 C. The water layer that resulted

was continuously removed through the Dean-Stark trap. After all of

the water had been collected, the temperature had reached 680 C the

temperature at which the binary azeotrope of benzene and ethanol dis-

till. The remaining benzene and ethanol were distilled away and the

remaining brownish liquid placed in a 100 ml. round-bottomed flask

and vacuum distilled. The distilltion yielded 47.2 g. (41.0%) of a

clear liquid (b.p, 76-770 C @ 0.250 mm.).

The ir spectrum showed absorbances at 2995 (s), 2940 (s), 2920 (s),

1920 (w), 1650 (w), 1585 (s), 1560 (w), l1187 (s), 1470 (w), 1415 (s),

1375 (s), 1270 to 1350 (broad, s), 1255 (s), 1175 (4), 1125 (s), 1375

(s), 1100 (s), 1070 (s), 1040 (s), 1005 (s), 900 (s), 815 (s), 720 (s),
-i
650 (m), and 620 (m) cm. .

The nmr spectrum showed resonances at ~7.L5 (s, 4), 64.05 (quartet,

4), and 61.25 (t, 6).


p-Bromophenylmagnesium bromide

Magnesium (27.0 g., 1.1 g. atoms) and 500 ml. of dry diethyl ether

were placed in a flamed, 1-liter, 3-necked, round-bottomed flask

equipped with mechanical stirrer, addition funnel, and cold-water









condenser. The mixture was refluxed for 30 minutes. p-Dibromobenzene

(235.9 g., 1.0 mol.) was dissolved in dry diethyl ether and placed in

a 500 ml. addition funnel. Then the mixture was activated with a small

crystal of iodine; a few ml. of the solution were added. An ice bath

was necessary to control the reflux rate while the remainder of the di-

bromobenzene was added dropwise to the stirring mixture. The resulting

solution was filtered to remove the unreacted magnesium.



Diethyl p-bromophenylboronate

p-Bromophenylboronic acid (80.0 g., 0.4 mol.), benzene (320.0 g.),

and ethanol (138.0 g.), along with a small amount of sulfuric acid,

were placed in a 2-liter, 1-necked, round-bottomed flask. An azeotropic

distillation apparatus was assembled, consisting of a packed column.

Claisen head, thermometer, condenser with drying tube, and Dean-Stark

trap. A ternary azeotrope of benzene, water, and ethanol distilled at

640 C, forming two layers in the trap. Ths lower (water) layer was

continuously removed as the reaction proceeded. The reaction appeared

complete as the temperature at the distilling head reached 670 C-the

temperature at which the binary azeotrope of benzene and ethanol dis-

tills. Most of the remaining benzene and ethan:,l were distilled away

and the remaining liquid placed in a 200 ml. round-bottomed flask.. The

brown liquid was then distilled under vacuum yielding 77.4 g. (60%) of

a clear liquid (b.p. 94-950 C @ 0.50 mm.).

The infrared spectrum showed absorbances at 2995 (s), 2940 (s),

2920 (s), 1920 (w), 1650 (w), 1585 (s), 1560 (w), 1487 (s), 1470 (w),

1415 (s), 1375 (s), 1270 to 1350 (broad, s), 1255 (s), 1175 (w), 1125 (s),

1100 (s), 1070 (s', 1040 (s), 1o005s 0 s), 00 (s), S.S (s), 720 (s), 550

(m), and 920 (m) cm.-









The nmr spectrum exhibited resonances at 67.45 (s, 4); 64.05

(quartet, 4); and 61.25 (t, 6).



Preparation of triethylamine-(p-bromo)phenylborane

Lithium aluminum hydride (5.5 g., 0.15 mol.) was added to 400 ml.

of diethyl ether in a 4-necked, 1-liter, round-bottomed flask equipped

with a mechanical stirrer, condenser with drying tube, addition funnel

with nitrogen inlet tube, and low temperature thermometer. The mix-

ture was refluxed for 30 minutes on a heating mantle and then cooled

to -720 C in a dry ice-isopropanol bath. Triethylamine (15.8 g., 0.192

mol.) was added with stirring. A solution of diethyl p-bromophenyl-

boronate (49.3 g., 0.192 mol.) was added dropwise with stirring, keep-

ing the temperature below -650 C. The reaction mixture was allowed to

warm to room temperature and then filtered to remove the unreacted

lithium aluminum hydride. The filtrate was cooled in a dry ice-iso-

propanol bath to -700 C. White, needle-like crystals were formed.

These were unstable and appeared to melt during filtration, even under

nitrogen. The remaining material was immediately dissolved in toluene.



Preparation of 1-(4-bromophenyl)-2-phenyl-1,2-azabcrol idine and
-( 4-bromophenyl) -5--phenyl-l-aza-5-borabicyclo. 3.3.0 )octane

Triethylamine-phenylborane (19,3 g., 0.1 mol), p-bromo-N,N--diallyl-

aniline (25.2 g., 0.1 mol.), and 1.25 liters of toluene were placed in

a 2-liter, round-bottomed flask. The toluene was slowly distilled from

the flask through a fractionating column and condenser. On initial

heating the contents of the flask turned a bright yellow-green color.

When the temperature at the distilling head reached 1200 C, the residual









green liquid was transferred to a 50 ml. round-bottomed flask and

distilled on a spinning band column. Four fractions were obtained.

The two lowest boiling fractions (7.8 g.) were clear, pale yellow,

viscous liquids (b.p. 120-1230 C @ 0.15 mm.) Nmr and ir data were

consistent with the assignment of l-(4-bromophenyl)-2-phenyl-l,2-

azaborolidine. The ir spectrum gave absorbances at 3080 (s), 3060 (s),

2950 (s), 2870 (s), 1960 (w), 1890 (w), 1820 (w), 1765 (w), 1700 (w),

1630 (w), 1590 (s), 1570 (m), 1480 (broad, s), 1425 (broad, s), 1385

(s), 1300 (broad, s), 1240 (s), 1185 (m), 1150 (m), 1140 (w), 1100 (m),

1067 (s), 1050 (s), 1030 (m), 1000 (s), 960 (w), 910 (w), 880 (m), 820
-i
(s),770 (w), 740 (s), 695 (s), and 640 (m) cm. The nmr gave

resonance signals at 67.2 (m, 9); 63.75 (t, 2); and 61.7 (broad m, 4).

Anal. Calcd. for C, H BNBr: C, 60.03; H, 5.04; N, 4.67; B,
_- 5 15
3.61; and Br, 26.65. Found: C, 60.14; H, 5.12; N, 4.59; B, 3,64;

and Br, 26.52.

The two remaining fractions (b.p. 130-1320 C @ 0.15 mm.) were

dissolved in small amounts of acetone and cooled in a dry ice-iso-

propanol bath, resulting in the formation of white crystals. These

were filtered and dried yielding 6.7 g. (m:.p. 116-1180 C).

The ir, r.mr, and mass spectra were consistent with the.assignment

of structure as (4-bromophenyl)--5-phenyl-!-aza- 5-bopabicyclo(3.3.0)--

octane. The ir spectrum showed absorbances at 3050 (m), 3010 (m),

3000 (m), 2920 (s), 2825 (s), 1950 (w), 1880 (w), 1820 (w), 1700 (w),

1475 (broad, s), 1425 (m), 1400 (m), 1350 (w), 1310 (w), 1265 (s),

1227 (s), 1190 (w), 11.70 (w), 1.155 (m), 1130 (broad, -), 1080 (m), 1050

(m), 1035 (m), 1020 (m), 1000 (s), 980 (m), 950 (m), 930 (n), 890 (m),









810 (s), 740 (s), 700 (broad, s), 675 (s) cm." The nmr showed

resonance signals at 66.9 (m, 9); 63.3 (m, 4); 62.05 (quintet, 4);

and 61.1 (m, broad, 4). The mass spectrum gave a parent peak of

342 1.

Anal. Calcd. for C18H21BNBr: C, 63.19; H, 6.19; N, 4.09;

B, 3.16; and Br, 23.24. Found: C, 63.11; H, 6.29; N, 3.96; B, 2.90;

and Br, 23.36.



Preparation of l-(4-chlorophenyl)-2-phenyl-1,2-aza-borolidine and
l-(4-chlorophenyl)-5-phenyl-l-aza-5-borabicyclo(3.3.0)octane

Triethylamine-phcnylborane (32.7 g., 0.17 mol.), p-chloro-N,N-

diallylaniline (35.3 g., 0.17 mol.), and 1.5 1. of toluene were

placed in a 2-liter, round-bottomed flask. The contents were heated

on a heating mantle. Toluene (200 ml.) was slowly distilled through

a fractionating column and condenser. The mixture was slowly re-

fluxed; then the remainder of the toluene was distilled until the

temperature at the distilling head reached 1200 C. The remaining

toluene was removed on the rotary evaporator under reduced pressure.

The gir n, phosphorescent liquid was transferred to a 50 ml. flask

and distilled on a spinning band column. Three fractions were

collected. The two lowest boiling fractions (15.6 g.) were viscous,

colorless liquids (b.p. 130-1320 C @ 0.20 mm.) which turned brown

in air. A portion of the viscous liquid was sealed under vacuum for

analysis. The ir, nmr, and mass spectra were consistent with the

structure assignment of l-(4-chlorophenyl)-2-phenyl-l,2-azaborolidine.

The infrared spectrum exhibited absorbances at 3450 (w), 30'C (m),

3060 (m), 2950 (s), 2880 (s), 1960 (w), 1390 (w), 1820 (w), 1765 (w),









1640 (w), 1595 (s), .575 (w), 1490 (broad, s), 1430 (broad, s) 1393

(s), 1315 (s), 1290 (s), 1265 (m), 1245 (m), 1185 (m), 1153 (m), 1140
-1
(w), 1093 (s), 915 (m), 925 (s), 740 (s), 720 (m), and 595 (s) cm.1

The nmr spectrum gave resonance signals at 67.1 (m, 9); 63.75 (t, 2);

62.25 (m, L). The mass spectrum gave a molecular weight of 255 1l.

Anal. Calcd. for C H5 BNC1: C, 70.48; H, 5.92; B, 4.23; and

01,13.88. Found: C, 70.57; H, 6.06; N, 5.27; B, 4.40; and Cl, 13.88.

The highest boiling fraction (b.p. 144-146 C @ 0.20 mm.) was

dissolved in a small amount of acetone and cooled in a dry ice-iso-

propanol bath, resulting in the formation of 4.6 g. of flaky, white

crystals (m.p. 95-960 C.). The ir, nmr, mass spectrum and analysis

were consistent with the structure of 1-(4-chlorophenyi)-5-phenyl-l-

aza-5-borabicyclo(3.3.0)octane. The "r spectrum showed absorbances

at 3080 (m). 3060 (m), 3040 (m), 3020 (m), 2920 (broad, s), 2837 (s),

2600 (w), 1958 (w), 1893 (w), 1823 (w), 1765 (w), 1640 (w), 595 (),

1485 (broad, s), 1450 (m), 1430 (s), 1390 (m), 1345 (n), 1330 (s), 1275

(broad, s), 1255 (w), 1230 (s), 1190 (s), 1175 (s), 1160 (s), 1132 (s),

1120 (m), 1096 (s), 1053 (s), 1038 (m), 1022 (m), 1008 (s). 980 (s),

957 (m), 933 (m), 895 (s), 860 (w), 820 (s), c10 (m), 745 (s), 700 (s),

and 648 (s) cm. The nmr spectrum exhibited resonances at 67.0 (broad

m, 9); 63.3 (m, 4); 62.05 (quintet, 4); 61.1 (broad m, 4). Th mass

spectrum gave a parent peak at 297 -3

Anal. Calcd. for C18H2,BNCI: C, 72.63; H, 7.11; N, 4.70; B, 3.64;

and Cl, 11.91. Found: C. 72.66: H, 7.06; N, 4.59; B, 3.73; and Cl,

12.04.









Synthesis of p-chloro-phenylboronic acid

Magnesium turnings (36.4 g., 1.5 g. atoms) were placed in a 2-liter,

3-necked, round-bottomed flask equipped with mechanical stirrer, con-

denser with drying tube, and a 500 ml. addition funnel. Dried diethyl

ether (50 ml.) was added and the mixture refluxed for 15 minutes. p-Bromo-

chlorobenzene (287.1 g., 1.5 mol.), dissolved in I liter of dried diethyl

ether, was added dropwise after the initial reaction had started. After

complete addition, the mixture was refluxed for an additional 30 minutes.

The resulting Grignard reagent was filtered through glass wool into a 500

ml. addition funnel. Trimethylborate (155.8 g., 1.5 mol.) and 1 liter

of dry diethyl ether were placed in a 3-liter, 3-necked. round-bottomed

flask equipped with mechanical stirrer, low-temperature thermometer, and

Claisen adapter for an addition funnel and nitrogen inlet tube. The

solution was cooled to -700 C in a dry ice-isoprcpanol bath and the

Crignard reagent added dropwise with stirring. Nitrogen flow was main-

tained throughout the system during the course of the addition. The

temperature was kept below -650 C. The solution was allowed to warm to

room temperature overnight with continuous stirring. The resulting

mixture was hydrolyzed with a 15% sulfuric acid solution. The temperature

was controlled by cooling the flask in an ice bath. The two resulting

layers were separated in a 2-liter sparatory funnel and the aqueous

layer discarded. The ether layer was then placed in a 3-liter, 3-necked,

round-bottomed flask equipped with mechanical stir.rer, addition funnel,

Claisen distilling head, condenser, and heating mantle. The ether layer

was slowly distilled while adding water dropwise. when the temTiperature

at the distilling head reached 980 C, the hot solution was transferred

to a 2-liter Erlenmeyer flask and allowed to cool. :.pFroximrately 1500









ml. of water had been added as the ether was replaced. After cooling,

filtering, and washing with 3 20 ml. portions of hexane, white, fluffy

crystals, 195.2 g. (83.5%), were obtained (m.p. 280-281 C).

The ir spectrum showed absorbances at 3200 (broad, s), 1920 (w),

1880 (w), 1800 (w), 1730 (w), 1650 (w), 1590 (s), 1560 (m), 1350 (broad,

s), 1250 (w), 1170 (m), 1080 (s), 1010 (s), 820 (s), 720 (s), 670 (s),
-!
and 640 (m) cm.-

The nmr spectrum exhibited resonance signals at 57.6; and 63.1

(s, 2).



Synthesis of p-chlcrophenylboronate

p-Chl:c.'chen lboronic acid (100.0 g., 0.64 mol.) was placed in a

2-liter, round-bottomed flask. To this, ethanol (230.0 g., 5.0 mol.)

and benzene (546.0 g.) were added. An azeotropic distillation

apparatus was constructed consisting of a fractionating column,

Claisen head, thermometer, Dean-Stark trap, and condenser with dry-

ing tube. A small amount of sulfuric acid was added. The mixture

was heated on a Glas-col mantle. A ternary azeotrope of benzene,

ethanol, and water distilled ar 64 C. Two layers formed in the

trap and the lower lave" was con tinuously removed. Approximately

23 to 24 ml. of water were collected in the trap. After the temp-

erature had stabilized at 58 C, the temperature at which the binary

azeotrope of benzene and ethanol boils, the remaining solvent was

removed on the rotary evaporator. The residual crude eCter was

placed in a 200 -m., rout:d-bottomed flask and distilled under vacuum.

A clear liquid, 60.2 g. ('44.3%), was obtained (b.p. 92-930 C @ 0.75 mmn.).









The ir spectrum showed absorbances at 3100 (w), 3050 (w), 2990

(s), 2945 (s), 2920 (s), 1920 (w), 1660 (w), 1593 (s), 1563 (m),

1487 (s), 1430 (s), 1415 (s), 1375 (s), 1325 (broad, s), 1280 (s),

1258 (s), 1175 (w), 1127 (s), 1100 (s), 1087 (s), 1040 (s), 1018 (s),
-1
904 (s), 820 (s), 725 (s), 650 (s), and 625 (s) cm.-1

The nmr spectrum showed resonances at 67.4 (quartet, 4); 64.0

(quartet, 4); and 61.24 (t, 6).



Synthesis of triethylamine-(p-chlorophenyl)borane

Lithium aluminum hydride (5.32 g., 0.14 mol.) was added to 600

ml. of dry diethyl ether in a l-liter, 4-necked, round-bottomed flask

equipped with mechanical stirrer, condenser with drying tube, addition

funnel with nitrogen inlet tube, and low-temperature thermometer. The

mixture was refluxed for 30 minutes on a heating mantle and then

cooled to -70 C in a dry ice-isopropanol bath. Triethylamine (28.6

g., 0.28 mol.) was added with stirring. The system was flushed with

nitrogen; diethyl p-chlorophenylboronate (58.9 g., 0.28 mol.) was added

dropwise. The temperature was kept below -55 C. The mixture was

then filtered through a sintered-glass funnel. A watch-glass was

placed over the funnel mouth to prevent evaporation of the ether. The

filtrate was concentrated and then cooled in a dry ice-isopropanol-bath,

resulting in the precipitation of a white cry3talline substance. The

material, 47.7 g. (75%), was filtered and dried yielding whites, needle-

like crystals (m.p. 63-64 C).

The ir spectrum exhibited absorbances at 3080 (w), 3000 (s), 2950

(s), 2980 (m), 2360 (broad, s), 1910 (w), 1798 (w), 1660 (w), 1578 (s),

1475 (s), 1450 (m), 1420 (w), 1380 (s), 1345 (m), 1300 (s), 1288 (w),









1193 (s), 1170 (s), 1150 (s), 1085 (s), 1065 (m), 1040 (m), 1013 (s),

900 (m), 860 (m), 820 (s), 775 (m), 750 (s), 720 (w), and 630 (s) cm. .

The nmr spectrum showed resonance signals at 67.3 (m, 4); 62.7

(quartet, 6); and 61.2 (t, 9).



Preparation of l-phenyl-2-(4-chlorophenyl)-1,2-azaborolidine and
l-phenyl-5-(4-chlorophenyl)-l-aza-5-borabicyclo(3.3.0)octane

Triethylamine-(p-chlorophenyl)borane (22.7 g., 0.10 mol.), N,N-

diallylaniline (17.3 g., 1.0 mol.), and 1.25 1. of dry toluene were

placed in a 2-liter, round-bottomed flask. The contents were heated

on a Glas-ccl mantle and distilled through a packed column, Claisen

head and condenser. Initial heating caused a light green coloration

of the solution. After the temperature reached 1200 C at the distill-

ing head, the remainder of the solvent was removed on a rotary evap-

orator. During the distillat.ion, several infrared samples of the

solution, distillate, and gas above the solution were obtained. Propene

gas was trapped. Confirmation of this was obtained by comparison of

the gas sample spectrum with that in the Sadtler Spectra Index. The

crude, green-brown liquid was transferred to a 50 ml. round-bottomed

flask and placed on a spinning band distillation column. Four fractions

were obtained. The lowest boiling fractions were pale yellow liquids

(b.p. 120-1210 C @ 0.10 man.). This material, 15-16 g., was unstable

in air; several samples were sealed in ampoules. The nmr, ir, mass

spectrum, and analysis were consistent with the structure assignment

of l-phenyl-2-(4-chlorophenyl)-l,2-azaborolidine. The ir spectrum ex-

hibited absorbances at 3090 (m), 3060 (m), 2960 (s), 2890 (s), 1945 (w),

1920 (w), 1875 (w), 1800 (w), 1740 (w), 1595 (s), 1.560 (m), 1500 (s),




Full Text
TABLE 4 (continued)
Compound
xl3* (p.p.ra.)
NMR
IR (cm.-1)
Mass Spectrum
Number
Chemical Shift
Chemical Shift (o'**
Areas
B-N Absorbance
Parent Peak
7.05
8.1
97
3.1
3.35
4.0
1275
421 1
2.10
4.0
1.15
4 .1
6.8
8.0
99
4.7
3.4
3.8
1275
291 1
2.1
10.1
1.1
4.1
6.9
8.3
3.7
6.1
101
6.0
3.35
2.1
1281
323 1
2.1
2.0
1.1
2.1
6.9
8.3
3.7
9.1
103

3.3
1278
337 1
2.0
4.1
1.3
4.2
6.9
12.2
104
4.4
3.2
8.0
Double Peak
476 1
2.1
14.1
1273 and 1286
1.1
8.2
6.90
12.3
105
4.7
3.23
8.0
Double Peak
517 1
2.05
8.0
1260 and 1273
1-05
8.1


127
funnel. Hydrated lithium iodide (3.0 g.) was placed in a 25 ml., 3-
necked, round-bottomed flask and heated under nitrogen to 200 C until
only a white residue remained. The salt was allowed to cool to 100 C
before the collidine solution was added. The mixture was heated to
reflux under nitrogen for 15 hours and then cooled to room temperature.
The mixture was acidified with 10% hydrochloric acid and extracted with
ether. The ether was removed on a rotary evaporator. The white material
which remained was dissolved in a small amount of acetone(dr) for an
b
analysis by nmr. A second sample was dissolved in aeuter-ated dimethyl-
sulfoxide. Thin layer chromatography showed at least 3 compounds in
the final reaction mixture. A small scale column chromatography was
carried out in silica gel prepared from benzene. Ten fractions were
collected. Fractions 1-4 showed only two resonances in the nmr (acetone
(dg)) at (S3.15 (broad singlet, 4) and 56.S (m, 7). Fractions 5-7 showed
resonances identical to the starting material, but the methoxy peak at
53.76 was reduced from a double peak at a single peak-indicating cleavage
of only one methoxy group to a hydroxyl group. The final fraction, 25
mg., showed no methoxy groups present; the nmr rwas consistent with that
expected for the desired l,5-bis-(4-hydroxyphenyl)-l-aza-5-borabicyclo-
(3.3.G)octane. The nmr spectrum of the crude material showed resonances
at 60.8 (m, 2); 51.8 (m, 2); 63.1 (m, 2.5); and 67.1 (m, 10). Spectra
of all fractions showed large amounts of a phenyl-substituted impurity.
Therefore, it seems that degradation of the molecule occurred to some
extent and this reaction must be modified for a reasonable synthesis
of the desired bis-hydroxy compound.


94
The highest boiling component (b.p. 170-175 C) was a viscous,
phosphorescent oil which solidified to a tan material (m.p. 49-50 C)
after several days. The ir, nmr, and mass spectra were consistent
with the assigned structure of l,5-bis-(4-chlorophenyl)-i-aza-5-
borabicyclo(3.3.0)cctane. The ir spectrum showed absorbances at
3450 (w), 3260 (w), 3080 (m), 2325 (broad, s), 2600 (w), 2530 (w),
2365 (w), 2320 (w), 1895 (bread, s), 1775 (broad, m), 1640 (s), 1590
(broad, s), 1560 (m). 1475 (broad, s), 13S5 (very broad, s), 1235
(broad, s), 1288 (s), 1175 (s), 1169 (m), 1130 (m), 1080 (s), 1055
(m), 1035 (w), 1008 (s), 990 (m), 960 (m), 890 (s), 800 (s), 770 (m),
730 (m), 71S (m), 670 (s), and 510 (m) cm. \ The nmr spectrum
showed resonance signals at 7.2 (m, 8); 63.4 (m, 4); 62.15 (quintet,
4); and 1.15 (m, 4). The mass spectrum gave a molecular weight of
332 ll.
Anal. Caled, for C, 3NC10: C, 65.08; H, 6.07; N, 4.22;
B, 3.26; and Cl. 21.36. Found: C, 64.97; H, 5.99; N, 4.15; and Cl,
21.13.
Synthesis of_p-methylphenylboronic aoid
A mixture of 50 ml. of dry diethyl ether and magnesium (24,3 g.,
1.0 mol.) was placed in a flamed, 2-liter, 3-necked, round-bottomed
flask equipped with mechanical stirrer, addition funnel, and reflux
condenser with calcium chloride drying tube. p-Bromotoluene (171.0 g.,
1.0 mol.) in 600 ml. of diethyl ether was placed in the addition funnel
An iodine crystal
toluene, added to
the reaction rate
was added to the flask and a few ml. of the
initiate the reaction. An ice bath was used
as the remainder of the p-bremotoluene was
o-Dromo-
aaaea arou


87
1640 (w), 1595 (s), 1575 (w), 1490 (broad, s), 1430 (broad, s) 1393
(s), 1315 (s), 1290 (s), 1265 (m), 1245 (m), 1185 (m), 1.153 (m), 1140
(w), 1093 (s), 915 (m), 925 (s), 740 (s), 720 (m), and 595 (s) cm."1.
The nmr spectrum gave resonance signals at 67.1 (m, 9); 53.75 (t, 2);
52.25 (m, 4). The mass spectrum gave a molecular weight of 255 11.
Anal. Caled, for C,CH,_BNC1: C, 70.48; H, 5.92; B, 4.23; and
Cl,13.38. Found: C, 70.57; H, 6.06; N, 5.27: B, 4.40; and Cl, 13.88.
The highest boiling fraction (b.p. 144-146 C @ 0.20 mm.) was
dissolved in a small amount of acetone and cooled in a dry ice-iso-
propanol bath, resulting in the formation of 4.6 g. of flaky, white
crystals (m.p. 95-96 C.). The ir, nmr, mass spectrum and analysis
were consistent with the structure of l-(4~chlorophenyl)-5-phenyl.-l-
aza-5-borabicyclo3.3.0)octane. The .ir spectrum showed absorbances
at 3080 (m). 3060 (m), 3040 (m), 3020 (m), 2920 (broad, s), 2837 (s),
2600 (w), 1958 (w), 1393 (w), 1823 (w), 1765 (w), 1640 (w), 1595 (s),
.1485 (broad, s), 1450 (m), 1430 (s), 1390 (m), 1345 (m), 133.0 (s), 1275
(broad, s), 1255 (w), 1230 (s), 1190 (s), 1175 (s), .1160 (s), 1132 (s),
1120 (m), 1096 (s), 1053 (s), 1038 (m), 1022 (m), 1008 (s), 980 (s),
957 (m), 933 (m), 395 (s), 860 (w), 820 (s), 810 (m), 745 (s), 700 (s),
and 648 (s) cm. 1. The nmr spectrum exhibited resonances at 67.0 (broad
m, 9); 63.3 (m, 4): 62.05 (quintet, 4); ol.l (broad m, 4}
Th
spectrum gave a parent peak at 297 tl.
Anal. Caled, for C,0H01BNC1:
y zi.
and Cl, 11.91. Found: C, 72.66: H,
C, 72.63; H, 7.11; N, 4.70; B, 3.64;
7.06; N, 4.59: B, 3.73; and Cl,
12.04.


132
(double peak, m), 1220 (w), 1310 (s), 1400 (s), 1410 (in), 1450 and
1450 (d, m), 1515 (s), 1610 (s), 2900 (s), and 3150 (s, broad, de
tailed) cm. The nmr spectrum gave resonance signals at 60.82
(m, 2); 61.5 (m, 4); 63.5 (m, 2); and 67.2 (m, 10.5). The mass
spectrum gave a peak at 235 *1, but also some higher peaks.
Anal. Caled, for C, _H BN: C, 81.73; H, 7.72; B, 4.60; and
N, 5.36. Found: C, 78.42: H, 8.19; B, 4.99; and N, 3.75.
The fourth fraction distilled as a light yellow oil (b.p. 95-
105 C), which solidified in the side arm. This material, 1.2 g.,
was recrystallized from ethanol. A white, crystalline solid (m.p.
140-143 C) was obtained. On the basis of spectral data and the
elemental analysis, the structure was assigned as 1,6-diphenyl-l-
aza-6-borabicyclo(4.4.0)decane. The ir spectrum showed absorbances
at 700 (s), 755 (s), 768 (s), 810 (m), 870 (w), 910 (d, s), 970 (w),
1000 (s), 1030 (s), 1066 (s), 1180 and 1200 (d, s), 1250 to .1430 (b,
s), 1450 (s), 1510 (s), 1610 (s), 2900 to 3300 (b, s) cm."1. The
nmr spectrum gave resonances at 6G.95 (m, 4); 61.6 (m, 8); 63.5 (m,
4); and 67.3 (m, 10). The mass spectrum showed a parent peak at 291
1. The second portion of the original reaction solution was chroma
tographed to give a material with spectra identical to those of the
above compound. The solid was recrystallized from ethanol to yield
1.1 g. of a white, crystalline material (m.p. 143-145 C).
Anal. Caled, for C0nH0BN: C, 82.48; H, 9.00; B, 3.71; and N,
4.81. Found: C, 81.98; H, 8.81; B, 3.64; and N, 4.76.
A solid material, 1.4 g. (m.p. >350 C), was isolated from the
reaction vessel. The nmr showed only an aromatic resonance at 67.3.
A structure of triphenylcyclotriborazene was assigned to the compound.


133
Preparation of 3-deuteropropene from allylmagnesium bromide
Allylmagnesium bromide (20 ml., 0.50 mol./liter in ether) was
placed in a 500 ml., round-bottomed flask. A few drops of deuterium
oxide were added, resulting in gas evolution. The gas was condensed
in a trap cooled in dry ice-isopropanol. The condensed gas was then
mixed with carbon tetrachloride and deuterochloroform for nmr studies.
An infrared gas cell was used to trap some of the gas for ir analysis.
The ir spectrum exhibited absorbances at 855 and 865 (s, double peak),
940 (broad, s), 1006 (m), 1100 (broad, s), 1330 (s), 1455 (s, spiked),
1870 (w), 1995 (s), 2200 (m), 2340 (w), and 2940 to 3300 (broad, s,
detailed) cm. *. The nmr showed resonance signals at 51.65 (finely
split signal, 2); 54.8 (finely split triplet, 2); and 55.65 (m, 1).


c
I II
HSw
! 4
A,
i i
0
.B.
/ N. V
*N N'
/ B -,. s: ,
N"
\/
/SK
0 0
i I
.Si .Si-
7 ^0^ \
s
\/
.p
I 6
N
\/
A
"A
. I
^Si Si
7 7
I 9
This stability has been interpreted in terns of resonance stabili
zation inherent in these systens An intensive investigation into the
possibilities of incorporating these compounds into polymers for flame
1f, 17
retardance is currently of top priority in the fibers industry, *
Eeteroatom polymers containing C-N, C-0, B-N, F-C, P-N, Si-N, and Si-0
bonds have been reviewed.
Thermoplastic coatings and fibers have been prepared from cyclic
polysiloxanes, Methyipheny.l.cyclotetrasiloxanes have been polymerised to
18
give polymers with thermal stability dependent upon phenyl substitution,
Re tero.atom polymers containing boron have been known for many 7/ears.
Boric oxide consists of a three-dimensional network of distorted 30,
tetrahedra. Hexagonal boron nitride, 10, has a hexagonal layer struc
ture and is some
reliant thermal
have commercial
.times called white graphite. These materials have ex-
stability (2000C) and other useful properties which
utility.
They have stimulated research efforts toward
'r¡
N


25
+
3 X B(OH)
0^Bn0
I ¡
53
54
The crude phenylbcronic acids were recrystallized from hot
water. The following boronic acids were prepared by the above
method: phenylboronic acid (m.p. 214-216 C, 38.8%), p-chlcro-
phenylboronic acid (m.p. 280-281'* C, 83.5%), p-bromophenylboronic
acid (m.p. 271-272 C, 93.5%), p-methylphenylboronic acid (m.p. 255-
257 C, 31.0%), p-methoxyphenylboronic acid (m.p. 200-202 C, 69.0%),
and p-ethoxyphenylboronic acid (m.p. 120-122 C, 68.5%).
105
p-xhenylenediboronic acid was prepared by addition of a
tetrahydrofuran solution of the bis-Grignard reagent of p-dcbremo
to enz ene to a solution of trimethyl borate in tetrahydrofuran under
nitrogen and cooled to -70 C. Addition presented problems due to
the thick, milky texture of the Grigrtard reagent. The resulting
solution was hydrolyzed with 15% sulfuric acid to give p-phenyi-
diboronic acid (m.p. >315 C, 74.5%).
C. Syntheses of Borate Esters of Subs tltuted _Phenylboronic Acids
corresponding diethyl esters, 55, by reaction with ethanol, followed
... 106,107
by azeotropic distillation.
53
DO
X
Eton


109
mixture was then hydrolyzed with a 10% sulfuric acid solution. The
acidification resulted in a clear' aqueous layer. The two layers were
separated in a 2-liter separatory funnel. The aqueous layer was
washed 2 times with ether and added to the ether layer. This combined
layer was placed in a 2-liter, 3-necked, round-bottomed flask equipped
with mechanical stirrer, addition funnel, and distilling head with
condenser and thermometer. The ether was distilled away as water was
added to the reaction flask. When the temperature at the distilling
head reached 99 C, the hot solution was poured into two 1-liter
Erlenmeyer flasks and allowed to coo.1. White, needle-like crystals,
56.0 g. (69%), of p-methoxyphenylboronic acid (m.p. 200-202 C) were
obtained. The spectral data were consistent with this assignment.
The ir spectrum showed absorbances at 3400 (broad, s), 2850 to 3150
(detailed, s), 1910 (w), 1605 (s), 1571 (s), 1512 (m), 1310 to 1460
(broad, s), 1235 (s), 1245 (s),-1145 to 1180 (broad, s), 1100 (s),
1025 (s), 999 (s), 315 (s), 780 (s, broad), 730 (m), 538 (m), and 620
cm. ^. The nmr spectrum exhibited resonances at 67.8 (d, 2) and 66.85
(d, 2), characteristic of aromatic para-substitution; 63.3 (s, 3);
ana 62.3 (s,2).
Preparation of p-ethoxyphenylboror.ic acid
Magnesium (9.7 g.) and 50 ml. of dry diethyl ether were placed
in a flamed, 1-liter, 3-necked, round-bottomed flask equipped with
mechanical stirrer, addition funnel, and condenser with drying tube.
The mixture was refluxed for 15 minutes on a Glas-col heating mantle.
The solution was cooled as the system was filled with nitrogen, p-
Bromoethoxybenzene (78.4 g., 0.374 mol.) was dissolved in 300 ml. of
ether and placed in the addition funnel.
This solution was added


91
1193 (s), 1170 (s), 1150 (s), 1035 (s), 1065 (m), 1040 (m), 1013 (s),
900 (m), 860 (m), 820 (s), 775 (m), 750 (s), 720 (w), and 630 (s) cm."1.
The nmr spectrum showed resonance signals at 57.3 (m, 4); 52.7
(quartet, 6); and 51.2 (t, 9).
Preparation of l-phenyl-2-(4-chlorophenyl)-l,2-azaborolidine and
l-phenyl-5-(4-chlorophenyl)-l-aza-5-borabicyclo(3.3.0)octans
Triethylamine-(p-chlorophenyl)borane (22.7 g. 0.10 mol.), N,N-
diallylaniline (17.3 g., 1.0 mol.), and 1.25 1. of dry toluene were
placed in a 2-liter, round-bottomed flask. The contents were heated
on a Glas-ccl mantle and distilled through a packed column, Claisen
head and condenser. Initial heating caused a light green coloration
of the solution. After the temperature reached 120 C at the distill
ing head, the remainder of the solvent was removed on a rotary evap
orator. During the distillation, several infrared samples of the
solution, distillate, and gas above the solution were obtained. Propane
gas was trapped. Confirmation of this was obtained by comparison of
the gas sample spectrum with that in the Sadtler Spectra Index. The
crude, green-brown liquid -was transferred to a 50 ml. round-bottomed
flask and placed on a spinning band distillation column. Four fractions
ware obtained. The lowest boiling fractions were pale yellow liquids
(b.p. 120-121 C @ 0.10 mm.). This material, 15-16 g., was unstable
in air; several samples were sealed in ampoules. The nmr, ir, mass
spectrum, and analysis were consistent with the structure assignment
of i-phenyl-2-(4-chlorophenyl)-l,2-azaborolidine. The ir spectrum ex
hibited absorbances at 3090 (m), 3060 (m), 2960 (s), 2890 (s), 1945 (w),
1920 (w), 1875 (w), 1800 (w), 1740 (w), 1595 (s), 1560 (m), 1500 (s),


104
to warm to room temperature under nitrogen. The mixture was filtered
through a sintered-glass funnel and then washed with tetrahydrofuran.
The solution was then concentrated to 150 ml. and placed in a dry
ice-acetone bath. No crystals formed. The solution was concentrated
to 50 ml. and cooled again. A small number of fine, white, powdery
crystals were obtained upon filtration. These were unstable under
vacuum and nitrogen. The nmr spectrum of this material, prior to com
plete decomposition, showed only partial complexation of the triethyl-
amine to the diborane. The singlet at 67.25 was consistent with that
expected for a di-substituted. aromatic compound. Multiplets consistent
with the ethyl groups of triethylamine were observed at 63.8 and 61.9,
but the peak areas were not correct for di-substitution.
Attempted preparation, isolation, and reactions of di(pyridine)-p~
phenylene diborane
Lithium aluminum hydride (3.8 g., 0.1 mol.) was dissolved in 500 mi
of dry diethyl ether and placed in a 1-liter, 3-necked, round-bottomed
flask equipped with mechanical stirrer, addition funnel, Claisen adapter
low-temperature thermometer, and condenser with drying tube. The con
tents were refluxed for 30 minutes under nitrogen and then cooled to
-70 C in a dry ice-isopropanol bath. Pyridine (12.0 ml., 0.15 mol.)
was added in a single portion. Tetraethyl-p-phenylenediboronate (20.6
g., 0.075 mol.), dissolved in 70 ml. of ether, was added slowly with
vigorous stirring under nitrogen. The solution was then allowed to warm
t
to room temperature. A solution of 10 ml. of pyridine in 24 ml. of
water was added. The sludge was filtered and the filtrate concentrated
under vacuum. The resulting yellow oil was dissolved in diethyl ethez


52
Structure 6_3 would be susceptible to Hofmann elimination by
strong bases as shown below:
r- :B
Some experimental data support the possibility of cleavage
of the hi cyclic unit by the above, mechanism. The 1,5-diphenyl-
T-aza-5-borabicyclo(3.3.0)octane system was destroyed by the
111
reaction with butyllithium.
The starting material w7as not
recovered, but tne products were not identified. Trinapthy1-
112
borane was reacted with methanol to give trimethoxybcrane.
The only feasible approach in preparing 1,5-diphenyl-i-aza--
5~borabicyclo(3.3.0)octane with phenyl substituents was to start
with the substituted brotnobenzenes and to build the desired pro
ducts. The synthesis of triethylauiine-phenylboranes (Scheme III)
involves Crigr.ards, acids, lithium aluminum hydride, alcohols,
heat, and Lewis bases. Tne preparation of substituted N,N-diailyl-
anilines involves the heating of a sodium carbonate-water solution
to reflux. The desired substituents must also be readily converted
to monomer without destroying the bicyclic structure.


7
N-triphenylcyclotriborasane
28
Ph
,N
HB
BH
PhNx ,NPh
D
I
H
+ ho(ch2)20oh-
2^
-f
PhN^g^NPh
(ch2)2q
12
Other examples have been reported in which B,N'-dichlorocyclctri-
borazenes and diamines reacted to give polymers stable up to 250-
29
300C. Copolymers have been prepared by the free-radical poly
merization of B-trivinyi-K-triphenylcyciotriborazene with styrene
30
and methyl methacrylate. The reaction of aniline with an equi
molar concentration of trimethoxycyclotriborexene was reported to
give a polymer with the following structure:
OMe
o-'B-o
B /B-
13
j. n -Jn
High boiling diamines have been known to polymerize upon
heating with various alkylborates. For example, ethylenediamine
reacts with triethy lbcrate to give a polymer with the following
32
r
! N B
structure:'
i /
\
HH j
14
Jn


TABLE 1
SKELETAL BOND ENERGIES (kcal/mole)
Bond
D
E
C-N

147
Al-0
133

o
¡
m

128
B-N

106.5
Si-0

106
Si-N
%104

B-C

89
P-0
91
86
o
i

"-SO
85.0
c-c
S3
32.6
Bond
D
E
Si-C
"'-'50
n/78
C-N
80
72,8
Si-S

V70
P=N

68-76
P-N
68

P-C
68

c-s
V70
65
Al-C

61
S-N

V6C
S-0
--
n-55


15
. .... 4 83,84,85,86 83,36,87,88,89,50
A variety of coronates, b or inates, -asi
92 9?
triisopropylamine borates have been postulated to have trams
annular boron-nitrogen bonds. Syntheses directed toward boron-
containing amino acids for cancer chemotherapy have led to prepa-
93
ration of a series of substituted triethanolamine borates."'' fri-
91 92
isopropyl- and tri-n-propylamine borates have also been studied.
Substituted aryl boronic acids and 2-aminoethanoi were heated in
toluene to give the corresponding diethanolamine ary 3-borates;, 40
,n 33,84,88
Recently polymers with improved antistatic properties and flame
94
resistance were prepared by addition of B-N inclusion compounds.* For


12
67 68
Cyclic boraiies were prepared by Koster by the reactions of
trialkylamine-boranes with diolefins. Hawthorne^reacted trimethyl-
araine-t-butylborane with a number of olefins and diolefins. Reaction
with divinyl ether and divinyl silane gave corresponding heterocyclic
compounds.
The coordination compounds formed by substituted alkyl- and arvl-
borons with amines have been studied relating steric factors to B-N
bond stability. Heats of dissociation of the complexes of trimethylborcn
with various amines are all about -7.26 0.21 kcal/mole.'1
Amine-bo ran es may undergo dehydrogenation to give monob orazeu.es
or aminoboranes (Scheme I). When B-trimethylborazane, 25, was heated
72
to 280C under 20 atm. pressure, B-dimethylborazene, 26, was formed,
lhis compound was further dealkylated to yield B-trimethyIcyclotri-
borazene, (HN-BMe), Both of the above steps required the elimination
of methane
H3N-HBMe3
25
HN~BMe + CH.
7 2 4
26
Further examples of elimination were the formation of B-allyi
73
monoborazenes by the following reactions:
Et,HN-*B(C3K5)3
- Et2N-B(C3H5)2 + C.,H,
27
ILN-B(C-H_), + C,H,
i. 0 0 2 Jo
28
Pyrolysis of amine-phenylborane adducts leads to aminoboranes. The


33
to an infrared gas cell. The triethylamine-phenylborane and N,N~
diallylaniiine were dissolved in toluene in a flask equipped with
a magnetic stirrer and heater. The solution was slowly heated. Gas
samples, as well as solution samples, were taken at regular intervals
over a temperature range from 26 C to 110 C. The boron-hydrogen
bond absorbance at 2340 cm. ^ was monitored, and it was found that
the initial hydroboration occurred at approximately 50 C. Little
change occurred in the intensity up to 97 C. At this point, the B-H
absorbance decreased with time. The infrared gas samples gave the
best information. Only triethylamine and toluene vapors were observed
below 92 C. However, at 95 C the spectra began to show traces of
propene gas. The broad, spiked peak at 910 cm. was the roost easily
followed absorbance. At 98 C large amounts of propene were being
pumped into the ir gas ceil. The spectra were identical with the one
for propene given in the Sadtier Midget Edition, No. 6403.
After 12 hours, the green reaction solution was cooled, filtered,
and rotovaced to remove the toluene. The viscous, green liquid was
transferred under nitrogen to a small, round-bottomed flask for vacuum
distillation. Again, the l,2-diphenyl-l,2-azaborolidine, 6>4 (b.p. 84-
86 C r 0.30 mm.), was isolated. The nmr spectrum showed resonance
signals at 67.2 (m, 10); 53.8 (t, 2); and 61.8 (m, 4), corresponding
to the aromatic, carbon-5, and carbons-6 and-7, respectively (Figure. 1),
The infrared spectrum exhibited an absorbance at 1389 cm. \ which was
assigned to the boron-nitrogen double bond.
l,5-I)iphenyl-l-aza-5-borabicyclo(3.3.0)octane, 63, distilled as a
light yellow oil (b.p. 125-130 C @ 0.30 mm.). This compound was
rccrystallized from hot ethanol, yielding white crystals (m.p. 80-81 C).


,'J
l!
:. ¡-i J';
J1'!
N ?!
i? j! i* .i
31 3 i
/vV^'iv
A /H j< \¡\ I fj
vvty/ i f 1 f (
!] | i
ll!
j| ¡|j |
r -!C H,
¡ ¡ /
QJC~C
i V
1
. w
¡4
i
,rH
6.0
j r%
2.0
1.0
O
pprr¡t f>
Figure 3. Nror spectrum of 3-deuteropropene.
F
CTi


16
example, the following compound (3% by weight) was mixed with poly*
. 95
ethylene:
FhOCH,
m'
iTe V
\Qs^
.CHOPh
39
96
Adams and Poholsky' prepared the first reported
cycloalkane, 41, by reacting N,N?-dimethyl-allylamine
amine-borane in toluene. The following structure was
1,2-aza-boro-
with triethyl-
assigned:
/ \
\ x
n/ 41
97
In 1963 White reported the synthesis of 1-methy1-2-phenyl-
1,2-azoboroltdine, 42, and 2-phenyl-1, ?.-azoboracyclohexaue, 43, frca*.
the reactions of triethylamine-phenylborane with N-methylallylamine
and 3-butenylamine, respectively.
A
\
/
/
Ph B N J2Hr
V >
Ph B-~N H
-i-
43
98
In 1963 Station and Butler reported the formation of the first
substituted asa-3-borabicyclo(3.3.0)octane systems, 45, The reaction
of diallyletnyiamine with trimethylamne-phenyIhorane yielded com
pounds with the following structures:
Ph'
B-
ii y
44


13
heating of diethylamine-phenylborane at 80-110C under vacuum resulted
4 7A
in 88% yield of diethylaminoborane, 29.
Et2NH->BH2Ph
H2 + Et2N~BHPh
29
Several papers were presented dealing with amine-boranes and
anincfcoranes at an international symposium on boron-nitrogen chemistry.
Heteroaromatic boron-nitrogen compounds have also been reviewed in
, .. 7,75
some detail.
F. Cyclic and 51cyclic Compounds with Boron-Nitrogen Coordinate Bonds
The bicyclic ester, 30, formed by the azeotropic dehydration of an
equimolar mixture of 1,1,1-trimethylolathane and boric acid was re-
70
ported in a patent in 1959. This compound upon heating yielded a
glassy polymer.
CK3^
O'/
o/
Polymer
30
Similar bicyclic compounds had been prepared by Brown^ in 1951
by the reaction of triethanolamine with boric acid. The product was
a white crystalline solid, m.p. 236.5-237.5C. Two possible struc
tures were proposed:
3_i
32


122
sorbances at 530 (w), 640 (w), 670 to 732 (s, broad, detailed), 695
(m), 715 (s), 740 (m), 945 (s), 995 (m), 1015 (m), 1030 (s), 1068 (m),
1108 (m), 1150 (s), 1200 (s), 1245 (s, broad), 1285 (m), 1297 (m),
1345 (s, broad), 1380 (m), 1405 (w), 1435 (w, shoulder), 1445 (m),
1470 (m), 1500 (s), 1562 (m), 1595 (s), 1860 (w), 1895 (w), 1922 (w),
1950 (w), 2480 to 3100 (broad, s, detailed), and 3318 (s) cm. ^. The
nmr spectrum showed resonances at 62.35 (s, 3.8); 63.75 (d, 2); 67.2
(m, 5.2); and 56.75 (m, 1). This white material, on sitting, separated
in the vial to a white solid and a light, brown oil. The solid (m.p.
122-124 C) was isolated and characterized by nmr. The spectrum gave
only two reasonable signals in acetone (dg): 63.8 (doublet) and 66.9
(very broad rnultiplet). No assignment could be made. The light, brown
oil was unstable in air. The rarer spectrum gave resonance signals at
60.8 (t, 2); 61.7 (quintet, 2); 53.0 (t, 2); 66.9 (m, 10) and 63.65 (2
peaks, 5). On the basis of this nmr spectrum, the liquid was assigned
the structure of l,2-bis-(4-methoxyphenyl)-l,2-azaborolidine.
The filtrate from the reaction mixture was passed through the
silica gel column again for further purification. The solvent was
then removed on a rotary evaporator and the oily residue placed in
a 25 ml. round-bottomed flask for vacuum distillation on a spinning
band column. The only fraction which distilled (b.p. 9^C @ 0.75 mm.)
proved to be unreacted p-roethoxy-N,N-diallylaniline, 2.3 g. The
residue in the distillation flask was recrystallized from hot ethanol
yielding 10.0 g. of white, flaky crystals (in.p. 112-114 C). All
spectra and analyses were consistent with the structure assignment cf
1,5-bis~(4-methoxyphenyl)-l-aza-5-borabicyclo(3.3.0)octane. The ir
spectrum showed absorbances at 630 (w), 668 (m), 713 (w), 728 (w), 755


72
B. Syntheses and Characterization
Preparation of N,N-Diallylaniline
Aniline (186.0 g. 2.0 mol.), sodium carbonate (420.0 g., 4.0 mol.),
and 300 ml, of water were placed in a 3-liter, 3-necked, round-bottomed
flask equipped with an overhead stirrer, dropping funnel, and water-
cooled condenser. The mixture was heated to low reflux using a
heating mantle and variac. Allyl bromide (484.0 g., 4.0 mol.) was
added dropwise over a period of 4 to 5 hours with constant stirring.
The brown, syrupy liquid which resulted was stirred for 4 more hours
and then filtered into a 2-liter separatory funnel. The two resulting
layers were separated and the aqueous layer washed with 3 100 ml. por
tions of ether. The ether was removed on a rotary evaporator. The
resulting residue was combined with the crude organic layer. This oily,
brown liquid was then added carefully to the 30% solution of sodium
hydroxide in 300 ml. of water. This solution was then transferred to
a 3-necked, 3-liter, round-bottomed flask equipped with mechanical
stirrer and addition funnel. Benzenesulfonyl chloride (100 mi.) was
added dropwise with stirring. The resulting slush was cooled in an
ice bath and neutralized with 10% hydrochloric acid. The organic
layer was separated and dried with sodium sulfate. The crude N,M-di-
ailylaniiine was filtered and placed in a 1-liter, round-bottomed
flask for distillation. Using a vacuum distillation apparatus, consist
ing of a Vigereaux column, fraction cutter, and receiving flasks, an
o
37.6% yield of a clear liquid (293.0 g. b.p. 104-106 C @ 3.5 mm.) was
obtained.


70
reactions. Several other compounds listed in Table IV have function
ality which could be utilized in monomer preparation. In all, over
40 new compounds have been synthesized and characterized in this
research.
The boron-nitrogen coordinate bond has been investigated
extensively by nmr, ir, nrar, and by differential scanning
calorimetry. Chemical shifts, boron-nitrogen, stretching frequencies,
and heat of transition studies have given us valuable information
which has opened many avenues for future research on these hetero
cyclic compounds and other related systems.
0


11
57
boration of cyclododeca-l5,9-triene. Hawthorne observed that
pyridine borane would react with olefins in diglyne at 100C to pro
duce trialkylboranes. Nielsen"*^ observed that phenylborane readily
59
disprcportionated to triphenylborane and diborane. Hawthorne pre-
pared pyridine and triethylamine adducts of phenylborane and aryl-
substituted phenylboranes which were white crystalline materials stable
in air and had melting points from 50 to 80C. Pyridine- and tri
ethy lamine-alky lboranes^ and -ary lboranes^ were prepared by the
presence of the amine bases.
Hawthorne reported the reduction of substituted cyclotriboroxenes
by lithium aluminum hydride and the presence of pyridine, trimethyl-
amine, or triethylarairie to give the corresponding amine-bcranes.
64
Ashby reacted several triaIkyIamine-boranes with olefins to
form trialkylboranes in 78-95% yields.
The mechanism for bydroboratjon by amine-boratics is believed to
involve the rate determining dissociation of the amine-borane. A
sufficiently high temperature is required for the dissociation of the
65
B-N bond. B-H addition can then proceed via the boron p-orbical
65
interaction with che TT-electrcns of the olefin (Scheme II).
II
NBR R
R3N r RBH
p


Scheme IV
¡, 5 -Diphenyl
i-aza*-borobicyclo (3,3,0/octcne
Propene
!NEt3
CO
ro


This dissertation is dedicated in memory of
Mr. Claude Stuart
who dedicated his life to teaching chemistry
in the Greenville, Mississippi, Public School
System


I
4.0
I 0
x
Figure 6. Nmr spectra of l,5-bis~(4-chlorophenyl)-l~aza-5-borabicyclo-
(3.3.0)octane and 1,2-bis-(4-chlorophenyl)-l,2-azaborolidine.
1
0
CD
O


75
Synthesis of p-methoxy-N,N-diallylaniline
p-Methoxyaniline (187.0 g. 1.0 mol.), sodium carbonate (210.0 g.,
2.0 mol.), and 500 ml. of water were placed in a 2-liter, 3-necked,
round-bottomed flask equipped with stirrer, addition funnel, and con
denser. The mixture was heated to reflux on a Glas-col heating mantle.
Allyl bromide (266.0 g., 2.2 mol.) was added dropwise to the mixture.
The resulting mixture was allowed to stir at reflux overnight and was
then transferred to a 2-liter separatory funnel. The water layer was
discarded; the organic layer was dried with magnesium sulfate. The
liquid was filtered and then vacuum distilled yielding 183.4 g. (88.0%)
of a clear liquid (b.p. 87-88 C @ 0.350 mm.).
The ir spectrum showed only a small residual N-H absorbance at
3420 cm. \ Other absorbances were present at 3100 (m), 2840 to 3020
(s, broad, detailed), 1840 (w, broad), 1645 (m), 1622 (w), 1580 (w),
1515 (s, broad), 1463 (m), .1442 (m), 1422 (m), 1403 (w), 1385 (w),
1360 (w), 1332 (w), 1300 (w), 1278 (w), 1240 (s, broad), 1180 (s),
1130 (m), 1040 (s), 918 (s), 815 (s), 760 (w), 712 (m) cm.-1.
The nmr spectrum showed resonance signals at 66.65 (m, 4); 65.85
(m, 2); 65.1 (m, 4); and 67.1 (m, 7).
Synthesis of p-chloro-N,N-diallylaniline
p-Chloroaniline (225.0 g., 2.0 mol.), sodium carbonate (420.0 g.),
and 500 ml. of water were placed in a 2-liter, 3-necked, round-bottomed
flask equipped with stirrer, addition funnel, and condenser. The
mixture was heated to reflux on a heating mantle. Allyl bromide (484.0
g. 4.0 mol.) was added dropwise with stirring. Heating and stirring


21
tracted in ether. This solution was filtered, dried over sodium
sulfate, and then distilled under vacuum yielding a pale yellow
liquid (46.5%, b.p. 138-140 C @ 0.55 ran.).
C. Synthesis of N,N-Di-3-butenylanlline
N,N-Di-3~butenylaniline was prepared using a similar proce
dure as in preparation of the other diallylanilines. 4-Bromo-
butene was added dropwise to a slurry of aniline in sodium car
bonate in water. The organic layer was extracted, filtered, and
vacuum distilled yielding a colorless liquid (37%, b.p. 74-75 C
@ 0.10 mm.)


103
Preparation of tetraethyl-p-phenyldiboronate
p-Phenylenedibcronic acid (26.0 g. 0.158 mol.), 100 ml. of ethanol,
and 2 drops of sulfuric acid were placed in a 500 ml. round-bottomed
flask equipped with condenser, fractionating column, Dean-Stark trap,
and thermometer. The liquid was heated on a heating mantle. The ter
nary azeotrope of benzene, ethanol, and water distilled at 64 C the
temperature at which the binary azeotrope of ethanol and benzene boils.
The remaining ethanol and benzene were removed on a rotary evaporator
and the resulting brown liquid was vacuum distilled. The distillation
yielded 18.0 g. (41%) of a clear, colorless liquid (b.p. 102-104 C @
0.350 mm.).
The ir spectrum showed absorbances at 650 (m), 700 (s), 723 (m),
740 (w), 758 (w), 818 (m), 903 (s), 1010 (s), 1043 (s), 1072 (s), 1103
(s), 1138 (s), 1175 (broad, w), 1255 to 1440 (bread, s), 1487 (s),
1588 (s), 1-602 (w), and 2900 to 3100 (broad, detailed, s) cm. ".
The nmr spectrum showed resonances at 61.25 (t, 12); 54.08 (quar
tet, 8); and 67.6 (s, 4).
Attempted preparation of di(triethylamine)-p-phenylenediborane
Lithium aluminum hydride (3.8 g., 0.10 mol.) was added to 250 ml.
of dry tetrahydrofuran in 500 ml., 3-necked, round-bottomed flask
equipped with a mechanical stirrer, condenser, and adapter with nitro
gen inlet tube and addition funnel. The mixture was refluxed for
45 minutes and then cooled to -70 C in a dry ice-isopropanol bath.
Triethylamine (14.0 g., 0.13 mol.) was added in a single portion. The
system was flushed with nitrogen. Tetraethyl-p-phenyldiboronate was
added drepwise with stirring to the cold mixture; the temperature was
kept below -65 C. After complete addition, the mixture was allowed


86
810 (s), 740 (s), 700 (broad, s), 675 (s) cm. \ The nmr showed
resonance signals at 56.9 (m, 9); 53.3 (m, 4); 52.05 (quintet, 4);
and 5l.l (m, broad, 4). The mass spectrum gave a parent peak of
342 1.
Anal. Caled, for C10H01BNBr: C, 63.19; H, 6.19; N, 4.09;
B, 3.16; and Br, 23.24. Found: C, 63.11; H, 6.29; N, 3.96; B, 2.90;
and Br, 23.36.
Preparation of l-(4-chlorophenyl)-2-phenyl-l ,2-aza-borolidine and
l-(4-chlorophenyl)-5-phenyl-l-aza-5-borabicyclo(3.3.0)octane
Triethylamine-phcnylborane (32.7 g., 0.17 mol.), p-chloro-N,N-
diallylaniline (35.3 g. C.17 mol.), and 1.5 1. of toluene were
placed in a 2-liter, round-bottomed flask. The contents were heated
on a heating mantle. Toluene (200 ml.) was slowly distilled through
a fractionating column and condenser. The.mixture was slowly re
fluxed; then the remainder of the toluene was distilled until the
temperature at the distilling head reached 120 C. The remaining
toluene was removed on the rotary evaporator under reduced pressure.
The green, phosphorescent liquid was transferred to a 50 ml. flask
and distilled on a spinning band column. Three fractions were
collected. The two lowest boiling fractions (15.6 g.) 'were viscous,
colorless liquids (b.p. 130-132 C @ 0.20 mm.) which turned brown
in air. A portion of the viscous liquid was sealed under vacuum for
analysis. The ir, nmr, and mass spectra were consistent with the
structure assignment of l-(4-chlorophenyl)-2-phenyl-l,2-azaboroiidine.
The infrared spectrum exhibited absorbances at 3450 (w), 3080 Cm),
3060 (in), 2950 (s), 2880 (s), I960 (w), 1390 (w), 1820 (w), 1765 (w),


Chapter III
PREPARATION OF BORON INTERMEDIATES
A. Syntheses of Grignard Reagents *.
The boron intermediates were prepared by modifications of
procedures reported in the literature (Scheme III).
The mono-Grignard reagents of bromobenzene, p-dibromobenzene,
p-chlerobromobenzene, p-methyIbromobenzene, p-methcxybromobenzene,
and p-ethoxybromobenzene were prepared by reacting the substituted
bromobenzenes with an equimolar quantity of magnesium in diethyl
ether, dried over sodium. The substituted bromobenzene was added
dropwise at a rate which maintained a low reflux. In each reaction,
a small crystal of iodine or a drop of ethylenebromide was necessary
to initiate the reaction. The induction periods varied from 10 to
40 minutes.
An attempt was made to prepare the Grignard reagent of p-bromo-
phenylbenzyl ether. The ether was prepared by reacting p~bromophenol
with benzylchlorida in acetone, The resulting p-broxaophenylbenzyi
ether was recrystallized twice from hot methanol. It was then dis
solved in diethyl ether, distilled from lithium aluminum hydride.
Initial addition of the p-brcm ophenyibenzy1 ether to the magnesium
did not result in any reaction. Crystals of iodine and ethylene
bromide were employed to initiate the reaction. However, the addition
of further p-bromophenyIbenzy1 ether appeared to stop the reaction.
Entrainment and heat were employed, yet the. reaction could not be
'} )


Abstract of Dissertation Presented to the
Graduate Council of the University of Florida in Partial Fulfillment
of the Requirements for the Degree of Doctor of Philosophy
SYNTHESES OF HETEROCYCLIC COMPOUNDS CONTAINING B-N COORDINATE
BONDS AS MODELS
FOR THERMALLY STABLE POLYMERS
By
CHARLES LEWIS MCCORMICK III
June, 1973
Chairman: Dr. G. B. Butler
Mai or Department: Chemis try
The major goals of this research were to examine the mechanism of
the reaction of trlethylamine-phenylborane with N#N-di&llylaniIine au.i
to extend this reaction to the preparation of compounds which could be
utilized for the synthesis of high molecular weight, thermally stable
polymers.
l,5-Diphenyl~l-aza-5-borabicyclo(3.3.0)octane, I,2-diphenyl-1,2-
azaborolidine, and propene were isolated as the major products of the
reaction of triethylamine-phenylborane with N,N-diallylaniline. These
compounds were characterized by nuclear magnetic resonance, infrared,'
mass spectroscopy, and elemental analyses.
Two mechanisms were proposed for the formation of propene and
1,2-diphe ay !- 1,2- azab ore Li dine.
Triethylamine-dideuterophanylborane was prepared and subsequently
reacted with NsN-diallylanilina to give 3,7~dideutero-l,5-diplienyl~l'-aza-
5-bo rabi cy clo ( 3.3.0) octane, 3-den tero-1,2riiphenyl~l,?.~azaborolidine,


81
used to control the reaction rate. The reaction mixture was stirred
for an additional 30 minutes at room temperature. Trimethylborate
(103.9 g. 1.0 mol.) and 800 ml. of diethyl ether were placed in a
3-liter, 3-necked, round-bottomed flask equipped with a mechanical
stirrer, low-temperature thermometer, and Claisen adapter for an
addition funnel and nitrogen inlet tube. The Grignard reagent was
filtered through glass wool into the addition funnel. The solution
in the 3-liter flask was cooled to -70 C in a dry ice-isopropanol
bath. The system was flushed with a slow stream of nitrogen. The
Grignard reagent was added dropwise with stirring and the temperature
was kept below -65 C. The mixture was allowed to warm to room tem
perature with continuous stirring and was hydrolyzed with 10% sulfuric
acid. The ether layer was separated and placed in a 3--necked, 3-liter,
round-bottomed flask equipped with mechanical stirrer, Claisen head,
and addition funnel. Using a heating mantle and variac, the ether was
distilled away while adding 1000 ml. of water dropwise. When the tem
perature at the distilling head reached 9 8 C, the. solution was trans
ferred to a 1-liter Erlenmeyer flask and allowed to cool. White, fluffy
crystals were obtained and washed with 3 10 ml. portions of hexane.
The total yield was 187.4 g. (33.5%) of p-bromophenylboronic.acid (m.p.
271-272 C).
The ir spectrum showed absorbances at 3300 (broad, s), 2400 (w),
1600 (s), 1500 (m), 1435 (s), 1350 (broad, s), 1230 (w), 1185 (s), 1030
(s), 1070 (w), 1010 (broad, s), 920 (w), 760 (m), 690 (s), and 630 (s)
-1
cm.
The nmr spectrum exhibited resonance signals at 67.5 (m, 4) and
62.75 (s, 2).


UNIVERSITY OF FLORIDA
3 1262 08554 4327


128
Reaction of l,5-bis-(4-methcxyphenyl)-l-asa-5-borabicyclo(3.3.Q)octane
with 10% hydrochloric acid
1.5-Bis-(4-methoxyphenyl)-l-aza-5-borabicyclo(3.3.0)octane (1.0 g.)
was mixed in a sample vial with 10% hydrochloric acid. The organic
material was extracted with ether. The nmr spectrum showed no change.
Starting material (1.0 g.) was recovered.
Model reaction of N-bromosucclnimlds with toluene
Toluene (3.0 g. 0.033 mol.), N-bromosuccinimide (5.4 g., 0.033 mol),
and 20 ml. of chloroform were placed in a 25 ml., round-bottomed, 3-
necked flask equipped with a mechanical stirrer, condenser, and nitrogen
inlet tube. The contents were stirred under nitrogen for 5 hours at
35 C. As the reaction proceeded, the N-bromosuccinimide, which had
settled on the bottom, was converted to succinimide, which floated to
the top of the chloroform as white crystals. The succinimide (m.p. 126-
127 C) was filtered yielding 3.0 g. (89%). Benzylbromide, 5.1 g.
(95%) was recovered from the chloroform solution. The nmr and ir spectza
were identical to those in the Sadtler series.
Reaction of 1,5-bis-(4-methyiphenyl)--l-aza-5--borabicyclo(3.3.O')octane
with N-bromosuccinimide
1.5-Bis-(4-methylphenyl)-l-aza-5-borabicyclo(3.3.0)octane (0.62S g.,
0.002 mol.) and N-bromosuccinimide (0.775 g. 0.004 mol.) were placed 5.n
a 25 ml., 3-necked, round-bottomed flask under nitrogen, along with 18
ml. of chloroform. The mixture was heated to 40 C. The solution
turned orange as the reaction proceeded. The reaction mixture was
stirred for 6 hours and then 20 ml. of water were added. The chloro
form layer- was separated, washed 2 times with water, and dried ever


TABLE 3 (continued)
Cpd. No.
Name
Formula
M.P.(C)
Analysis 1
(Calculated, Found)
97
1,5-Bis-(4-bromophenyl)~l-
C18H2CBNBr2
93-94
C:
C ,51.35;
H ,4.78 ;
N,3.33 ;
B,2.57 ;
aza-5-borabicyclo(3.3.0.)octane
Br,37.96
F:
C,51.89 ;
H ,4.74;
Br,37.96
99
l,5-Bis-(4~msthylphenyl)-l-
C20H26BN
107-108
C:
C,82.46 ;
H ,9.00 ;
N,4.81;
B,3.72
aza-5-borabicyelo(3.3.0. )octane
F:
C,82.21;
H ,9.05 ;
N,4.96 ;
B,3.71
101
1,5-Bis-(4-methoxyphenyl)-l-
C20H26BN02
112-1.14
C:
C ,74.32;
H,8.11;
N,4.33 ;
3,3.35;
aza-5-borabicyclo(3.3.0.Joctane
F:
0,9.90
C ,74.19;
H,8.01;
N,4.16 ;
B,3.36
103
l-(4-Methoxyphenyl),5-
C21H28BK02
166-157
C:
C,74.79 ;
H,8.37
(-ethoxyphenyl)-l-aza-
5-borabicyclo(3.3.0.)oetane
F:
C,75.23;
H,8.29
104
Bis-1,4-[5-(4-methylphenyl)~
C32H42B2N2
202-204
C:
C ,80.69;
H,8.89 ;
N,5.88;
B,4.54
l-aza-5-borabicyclo(3.3.0. )-
octyl]benzene
F:
C,80.39 ;
H,8.71;
N,5.70 ;
B,4.72
105
Bis-l,4-[5-(4-chlorophenyl)-
l-aza-5-borabicycio(3.3.0. )-
C30H36B2N2C12
198-200
C:
C,69.67 ;
Cl,13.71
H,7.02 ;
N,5.42;
B,4.18;
octyllbenzene
F:
C ,64.47;
Cl,14.02
H,6.86 ;
N,5.45;
B.4.27;


I
Figure 1. Nmr
ppm (3)
spectrum of 1,5 -diphenyl-l-aza-5-borabicyclo( 3.3.0 )octane
0
CO
p


47
frequency. The mass spectrum gave a parent peak at 43, consistent
with the molecular weight.
The nmr spectrum (Figure 3) of the gas was obtained by adding
deuterochloroform to the trapped liquid propene. Resonances were
assigned as follow: the allylie protons at 51.7 (finely split
signal, area 2); protons _a and Id at 65.0 (finely split triplet, 2);
and proton c at 65.8 (multiplet, 1). The above spectral evidence
surely indicates that the trapped gas was 3-deuteropropene rather
than 2-deuteropropene. 2-Deuteropropene would have shown no signal
in the 65.8 region and, of course, would not have shown the 2:2:1
integration pattern.
At this point, a model gas, 1-butene, was obtained to be sure
that the chemical shift assignments for 3-deuterepropene were correct.
The only expected difference, in the two nmr spectra would be the
added splitting due to the methyl group being substituted for
deuterium. The allylie proton signal moved slightly to 62.0 and was
a slightly distorted, finely divided quintet. The signals at 65.0
and 65.8 were almost identical to those of 3-deuteropropene.
The structure of the 3-deutero-l,2-diphenyl-l,2~azaboro.lidine,
82, was confirmed by mass, nmr, and ir spectra
The structure of the 3,7-dideutero-l,5-diphenyl-l-aza-5-bora-
bicyclo(3.3.0)octane, J34, was also confirmed by spectral data and
analysis of the high-boiling fraction (b.p. 64-68 C @ 0.15 mm.).
This material was recrystallized to give white, flaky crystals
(ra.p. 78-79 C). The infrared spectrum exhibited absorbances
daracteristic of the diphenyi-aza-borabicyclo(3.3.0)octanes. In
addition, the carbon-deuterium absorbance appeared at 2150 cm.


TV.
SYNTHESES AND REACT IONS,>0? BORON HETEROCYCLES .
A
. 0
A. Reaction of Triethylamine-P'nenylborane with
N,N-Diallylaniline 31
B. Mechanism of Formation of Azaborolidines and
Azaborabicyclo(3.3.0.)octanes 35
C. Deuterium Labeling Studies 41
D. Preparation of 3-Deuteropropene by an
Alternate Method 50
E. Preparation and Reactions of p-Substituted 1,5-
Diphenyl-l-aza-5-borabicyclo(3.3.0.)octanes . 50
F. Preparation of Bis-1,4-[5-(4-methyiphenyl)-l-
aza-5-borabicyc.lo(3.3.0. )octyl]benzene and
Bis-l,4-[5-(4-chlorophenyl)-l-aza-5-borabicycIo-
(3.3.0.)octyl]benzene ......... 51
G. Reaction of N,N,N',N-Tetraallyl-p-phenylene-
diamine with p-Phenylenediborane 62
H. lifioron Nuclear Magnetic Resonance Studies . 63
I. Temperature Studies by Differential Scanning
Calorimetry ...... 54
J. Synthesis or l,6-Diphenyl-l-az?t-5-borabicyc.Lo-
(4.4.0.)dec-one 65
K. Conclusions S3
EXPERIMENTAL ......... ... 71
A. Equipment and Treatment: of Data . ... 71
B. Syntheses and Characterization .... 72
Bibliography
Biographical Sk e t: eh
134
1 '40
¡V


135
18. K. A. Andrianov, S.E. Yakushkina, Kremniiorg. Soedin, tr.
Soevesch, 3_, 64 (1966).
19. A. L. McCloskey, Inorganic Polymers, Academic Press, New York
(1962), p. 159.
20. A. B. Burg, J. Chem. Ed., 37, 482 (1960).
21. V. A. Zamyatina, N. I. Bekasova, Russ. Chem. Revs., 30, 22 (1961).
22. A. Stock and E. Pohland, Ber. Deut. Chem. Ges., 59B, 2215 (1926).
23. J. C. Sheldon, E.C. Smith, Quart. Revs. (London), 14, 200 (1960).
24. U.S. Borax and Chemical Corp. British Patent 877,324, 1961.
25. W. Gerrard and E. F. Mooney, Soc. Chem. Ind. 13, 328 (1961).
26. W. Gerrard, E. F. Mooney, and D. E. Pratt, J. Appl. Chem.. ,13,
127 (1963).
27. V. Guttmann, A. Meiler, and R. Schlegel, Monatseh. Chem., 95,
314 (1964).
28. V. V. Korshak, V. A. Zamyatina, and R. M. Oganesyan, Izv. Akad.
Nauk. 10_, 1850 (1962).
29. K. Nagasawa, l'norg. Chem., 5, 442 (1966).
30. J. Pelln, W. G. Beichert, and W. M. Thomas, J. Poly. Sci., 55,
153 (1961).
31. E. L. Quill, P. R. Ogle, L. G. Kallander, and W. T. Lippincott,
Abstr. 129th Natl. Am. Chem. Soc. Meeting, Dallas, 1956, p. 4QN.
32. E. S. Gould, S. V. Urs, C. G. Overburger, F. Martinez, and R.
Brill, Boron Polymers Final Report, April 30, 1952.
33. M. H. Wuyts, A. Duquesne, Bull. Soc. Chim. Beiges, 48, 77 (1939).
34. H. Steinberg, Organoboron Chemistry, Wiley Interscience, New York
(1964), p. 444~
35. C. R. Kinney and B. F. Pontz, J. Am. Chem. Soc. 58, 196 (1936).
36. Ber. Btsch. Chem. Ges., 27, 244 (1894).
37. E. V?. Abel, S. H. Dandegaonker, W. Gerrard, and M. F. Lappert,
J. Chem. Soc., 4697 (1956).
38. S. H. Dandegaonker, W. Gerrard, and F. Lappert, J. Chem. Soc.,
2076 (1959).


24
forced. Only a small amount of the magnesium reacted. Perhaps
another solvent, such as tetrahydrofuran, might yield better results.
The bis-Grignard reagent was prepared from p-dibromobenzene,
Tetrahydrofuran was employed as a solvent. It became necessary to
control the heat evolved in the reaction with an ice bath. The high
viscosity of the resulting Grignard reagent presented problems in
filtering and addition through the small opening in the dropping
funnel.
B. Preparation of Substituted Phenylboronic Acids
The phenylboronic, or phenyiboric, acids, 53, were prepared by
the reaction of substituted phenylraagnesium bromides with trimethyl
berated, followed by hydrolysis.
53
The trimethyl borate was added to dry diethyl ether and cooled under
nitrogen to -70 C in a dry ice-isopropanol bath. The appropriate
substituted phenylmagnesiumbroraide was then added slowly to the stir
ring mixture. Too fast an addition resulted in formation of sub
stituted biphenyls from coupling reactions. The resulting white solid-
slush was hydrolyzed slowly by dropwise addition to the reaction mix-
in formation of a large yield of the substituued triphenyIcydo-
triboroxine, 54. The cyclotriboroxenes were probably formed by the
acid catalyzed dehydration of the phenylbo
-i ,-x
53-


82
Preparation of diethyl p-bromophenylboronate
p-Bromophenylboronic acid (100.8 g. 0.5 mol.), benzene (320.0 g.),
and absolute ethanol (138.0 g.) were placed in a 2-liter, 1-necked,
round-bottomed flask. An azeotropic distilling apparatus consisting
of a packed column, Claisen head, thermometer, condenser with drying
tube, and a Dean-Stark trap was assembled. The round-bottomed flask
was heated on a Glas-col mantle until a ternary azeotrope of benzene,
ethanol, and water distilled at 64 C. The water layer that resulted
was continuously removed through the Dean-Stark trap. After all of
the water had been collected, the temperature had reached 68 C the
temperature at which the binary azeotrope of benzene and ethanol dis
till. The remaining benzene and ethanol were distilled away and the
remaining brownish liquid placed in a 100 ml. round-bottomed flask
and vacuum distilled. The distillation yielded 47.2 g. (41.0%) of a
clear liquid (b.p, 76-77 C @ 0.250 mm.).
The ir spectrum showed absorbances at 2935 (s), 2940 (s), 2920 (s),
1920 (w), 1650 (w), 1585 (s), 1560 (w), 1487 (s), 1470 (w), 1415 (s),
1375 (s), 1270 to 1350 (broad, s), 1255 (s), 1175 (w), 1125 (s), 1375
(s), 1100 (s), 1070 (s), 1040 (s), 1005 (s), 900 (s), 815 (s), 720 (s),
650 (m), and 620 (m) cm. \
The nmr spectrum showed resonances at 57.45 (s, 4), 64.05 (quartet,
4), and 51.25 (t, 6).
p-Bromophenylmagnesium bromide
Magnesium (27.0 g., 1.1 g. atoms) and 500 ml. of dry diethyl ether
were placed in a flamed, 1-liter, 3-necked, round-bottomed flask
equipped with mechanical stirrer, addition funnel, and cold-water


high molecular weight polymers based on boron. Certain phases of boron
chemistry also find their counterparts in the technologically important
area of silicon chemistry. Since the bond energies of boron-oxygen
(~130 kcal) and boron-nitrogen ('"100 kcal) are high, there should be
high temperature applications.
Most polymeric boron compounds have not been characterized ade
quately. Little information is available on reactivity, molecular
20 21
weights, and solubility in many cases.*
B. Boron-Nitrogen Polymers
22
Since the. discovery of borazene and its stability at 500C,
many publications have appeared attempting to incorporate this cora-
pound into thermally stable polymers. Reviews covering all phases
23
of borazene chemistry may be found in the literature.An impor
tant: aspect of borazene chemistry is the strong driving force for
formation of cyclotriborazenes from dehydrogenation of substituted
amine-borane adducts (Scheme I).'
SCHEME I
BNHj, + H?3R'
rh2n>bh2r'
(1) Monoborazans
-T*
RHN--EHR
(2) Monoboraze.no
H f
1 R
A R'
R H
Cy ciotriborazane
(6)
-3H
R <4>/
,\ -
SN-BR'
Monoborazine
/
RJ-B ^3-R;
! '
R-N, >-R
ve"
R;
Cyclo tribo razene


100
Grignard reagent was added slowly to the reaction pot. After com
plete addition, the milky liquid was allowed to warm to room temper
ature. The round-bottomed flask was placed in an ice bath and the
reaction mixture was hydrolyzed with 15% sulfuric acid. After the
addition of over 2 liters of acid, the layers became clear. The
resulting layers were separated; the ether layer was dried over
sodium sulfate and then filtered. The ether was removed on a rotary
evaporator. The crude acid was recrystallized from hot water yield
ing 123.0 g. (74.5%) of white crystals (m.p. above 315 C).
Synthesis of bis-1,4-[5-(4-methylphenyl)-l-aza-5-borabicyclo(3.3.0)-
octyl]benzene ~
Triethylamine-(p-methylphenyl)borane (12.0 g., 0.058 mol.) and
500 ml. of toluene were added to a 1-liter, 3-necked, round-bottomed
flask equipped with magnetic stirrer, addition funnel, reflux con
denser, and Claisen adapter with thermometer and nitrogen inlet. The
solution was heated to 55 C under nitrogen. N,N,N,N'-Tetraa.llyl-p-
phenylenediamine (15.5 g., 0.053 mol.), dissolved in 200 ml. of toluene,
was added dropwise. After addition of a few ml., the reaction solution
turned light blue. This color darkened with further addition and then
lightened (finally turning yellow). Propene gas evolution was monitored
over several temperature ranges. Small amounts of the gas were produced
at 65 C. At higher temperatures (80-85 C) large amounts were observed
in the ir spectra. The solution was cooled to 70 C and allowed to stir
overnight. The toluene was then removed on a rotary evaporator. Thin
layer chromatography on silica gel in benzene indicated at least 3 pro
ducts in the reaction vessel. One product appeared to react with the
silica gel. A silica gel column, 45 cm. long and 2 cm. in diameter,


93
placed in a 2-liter, round-bottomed flask. The contents were heated
on a heating mantle and the benzene was slowly distilled through a
packed column, Claisen head with thermometer, and condenser. The
distillate was collected in a 2-liter, round-bottomed flask. Gas
samples were taken during the course of the reaction by connecting
an ir gas cell to the take-off of the adapter on the cold-water con
denser. The characteristic green color of these reactions appeared
shortly after heating had begun. Propene gas was trapped as a by
product of this reaction. After the temperature at the distilling
head had reached 85 C, the remaining benzene was removed on a rot
ary evaporator. The crude, green, viscous liquid was then trans
ferred to a 50 ml., round-bottomed flask and distilled under re
duced pressure. Four fractions were obtained. The two lowest
boiling fractions (b.p, 150-155 C) formed 10.4 g. of pale yellow
crystals (m.p. 60-61 C) on cooling. The spectral data indicated
the structure 1,2-bis-(4-chlorophenyl)-l,2-azaborolidine. The ir
spectrum exhibited absorbances at 3450 (w), 3275 (w), 3080 (m), 3060
(m), 2950 (s), 2880 (s), 2800 (m), 2600 (w), 1920 (w), 1985 (w), 1795
(w), 1765 (w), 1740 (w), 1720 (w), 1700 (w), 1640 (w), 1630 (w), 1590
(s), 1558 (m), 1490 (bread, s), 1430 (s), 1400 (s), 1390 (s), 1305
(broad, s), 1225 (m), 1185 (m), 1155 (m), 13.40 (m), 1090 (s), 1055.
(s), 1015 (s), 960 (w), 970 (w), 880 (m), 810 (broad, s), 730 (s),
700 (m), and 615 (m) cm. The nmr spectrum showed resonances at
57.05 (m, 8); 53.75 (t, 2); and 61.7 (m, 4). The mass spectrum gave
a parent peak at 289 tl.
Anal. Caled, for
H BHC1
15 14 2
C, 52.09; H, 4.87; N, 4.83;
and 5, 3.73. Found: C, 61.78;
H, 5.01; and Cl, 24.45.


73
stirrer, addition funnel, and heating mantle. The ether solution was
concentrated while adding 1000 ml. of water dropwise. At this point
the temperature at the distilling head had reached 98 C. The solu
tion was cooled. Fluffy, white crystals were observed. These were
filtered and washed with 3 10 ml. portions of hexane yielding 108.1 g.
(88.8%) of phenyl boronic acid (m.p. 214-216 C).
Preparation of diethyl phenylboronate
Phenylboronic acid (50.0 g. 0.41 mol.), benzene (320.0 g.), 138
g. of absolute ethanol, and 2 drops of sulfuric acid were placed in a
1-necked, 1-liter, round-bottomed flask. An azeotropic distillation
apparatus consisting of a packed column, cold-water condenser, ther
mometer, Claisen head, drying tube, and Dean-Stark trap was assembled.
The flask was heated on a Glas-col heating mantle. A ternary azeotz'ope
of water, ethanol, and benzene distilled over at 64 C. Two layers
formed in the trap. The lower (water) layer was removed as the reaction
progressed. After 2 days, the temperature at the distilling head had
reached 68 C, indicating the reaction was complete. The binary azeo
trope of benzene and ethanol distills at this temperature. The remain
ing solvent was distilled and the resulting liquid placed in a 100 ml.
round-bottomed flask for vacuum distillation. The distillation yielded
65.5 g, (90.1%) of a clear liquid (b.p. 68-59 C @ 0.350 mm.).
Preparation of triethylamine-phenylborane
Lithium aluminum hydride (12.0 g., 0.32 mol.) was added to 400 ml.
of dried diethyl ether in a 3-necked, 1-liter, round-bottomed flask
equipped with condenser and drying tube, addition funnel, low-tempera-


Chapter I
INTRODUCTION
A. Polymers Exhibiting Principles of Thermal Stability
The demands of the space program, and more recently the garment
industry, have led to extensive research in the area of thermally stable
polymers and flame retardant polymers.
Ladder polymers, _1, or double-stranded polymers have been made
which show good thermal stability. The increased thermal stability of
these polymers was attributed to the added stability of the ring systems.
Cleavage must occur twice within a given, ring of the polymer for chain
i ? 3 4 5
degradation.
T
/ \
Y
I
n
Recently, ladder polymers, stable, in air above 4004 C and based
-i 1 5 b
on vinyl-acetylenes, nave been prayaren.
Heteroatom polymers show a higher resistance to oxidative degra
dacin at elevated temperatures. Skeletal bonds, such as Al-O, Si-0,
Si-N, P-N, B-0, and 3-N, might be expected to show resistance to ther
mal oxidation, and polymers with these units should be more inert at
high temperature, Bond dissociation energies arc given in Table I.
l


123
(w, shoulder), 810 (s), 890 (s), 905 (w, shoulder), 920 (w), 933 (w),
962 (m), 983 (m), 1027 (s), 1055 Cm), 1068 (w, shoulder), 1108 (w),
1120 and 1132 (d, m), 1155 (m), 1179 (s), 1128 (m), 1245 (s), 1282 (s),
1308 (s), 1343 (w), 1370 (w), 1399 (w), 1425 (w), 1455 (s), 1508 (s),
1569 (s), 1840 (w), 1860 (w), 1887 (w), and 2818 to 3100 (s, broad,
detailed) cm. \ The nmr spectrum showed resonance signals at 5l.l
(m, 4); 62.1 (quintet, 4); 63.35 (m, 4); 63.7 (2 peaks, s, 6); and 66.9
(m, 8). The mass spectrum shewed a parent peak at 323 1.
Anal. Caled, for Co.H_cBN0_: C, 74.32; H, 8.11; N, 4.33; B, 3.35
and 0, 9.90. Found: C, 74.19; H, 8.01; N, 4.16; and B, 3.36.
Preparation of triethylamine-(phenyl)dideuteroborane
Lithium aluminum deuteride (3.36 g. 0.08 mol.) vas added to 200
mi. of anhydrous diethyl ether, distilled from lithium aluminum hydride
in a 3-necked, 500 ml., round-bottomed flask equipped with mechanical
stirrer, addition funnel, condenser with drying tube, low-temperature
thermometer, and nitrogen inlet tube. The lithium aluminum deuteride-
ether mixture was refluxed for 20 minutes and then cooled at -72 C in
a dry ice-isopropanol bath. Triethylamine (15.2 g., 0.15 mol.) was
added in a single portion. Diethylphenylboronate (19.0 g, 0.1C7 mol.)
vas added dropwise with stirring; the temperature was kept below -65
C during the entire addition. The mixture was allowed to stir until
it had warmed to room temperature. The mixture was then filtered
through a sintered-glass funnel to remove the excess lithium aluminum
deuteride. The filtrate was cooled in a dry ice-isopropanol bath.
White, needle-like crystals, 17.5 g. (84%), of triethylamine-(pheityl)-
dideuteroberane (m.p. 64-65 C) were filtered and dried.


35
The ninr spectrum is shown in Figure 1. The aromatic protons give
resonance signals centered at 66.85 (m, 10). The a. protons give
a multiplet (area A) at 63.35. The _b protons exhibit a distorted
quintet (area 4) at 62.1. The c_ protons are assigned to the multiplet
(area 4) centered at 61.1. All chemical shifts are relative to tetra-
methylsilane in deuterochloroform. The mar spectrum showed a
chemical shift at 3.6 p.p.m. relative to trimethylborate. This chem
ical shift value is strong evidence for the boron-nitrogen coordinate
bond since increased shielding around the boron atom would result in
an upfield shift. The chemical shift value for diethylamine-borane.
is .3.1 p.p.m. and for the 3.3.0. bicycloborate esters of triethanolamine
108
3.a p.p.ny
The infrared spectrum showed a strong absorbance at 1285 cm. *,
which was assigned to the boron-nitrogen coordinate bond. The mass
spectrum showed a parent peak at 263 il. The elemental analysis for
1,5-diphenyl-l-aza-5-bcrabicyclo(3.3.0)octane agreed with that cal
culated for the model compound.
Anal. Caled, for C.gH^EN: C, 82.13; H, 8.42; 3, 4.11; and F,
5.32. Found: C, 82.15; H, 8.51; B, 4.21; and N, 5.41.
B_. Mechanism of Formation of Azaborolidines and Azaborabicyclo-
(3.3.0)octanes
The proposed mechanism for the reaction cf trietnylaraine-
phenylborane with N,N-diallylaniline is outlined in Schemes V and VI.
The trie thylamine-phenylb orane, 65, dissociates to give the free
phenylborane, 66, and triethylamine, One of the ally1 groups of the
N,N _diallylaniline, J6_, undergoes a single hydroboration to give the


14
In the cage structure 31, boron maintains trigonal coplanar hybridi
zation. In the second structure, _3_2, a transannular boron-nitrogen
3
interaction gives boron sp hybridization. Triethanolamine borate
was concluded to have structure 32_ on the basis of unreactivity with
77
methyl iodide as compared to quinuclidine, _33, and triethanolamine.
Further evidence, for the B-N transannular bond was found in the
nuclear magnetic resonance chemical shift, relative to boron tri
fluoride etherate, of triethanolamine borate, which is found at
higher fields (6-10.7) in aqueous solution than xaost alkyl- and aryl-
78
borates (6-14 to 6-19). The shift was interpreted to be due to
increased shielding around the boron atom as a result of B-N bonding
and, therefore, increased tetrahedral character and number of bonding
electrons around the boron atom.
Later studies showed that an equilibrium could exist between
structures _31 and _32. In water and butanol the equilibrium mixture
contained 20% of the tetrahedral species, 32, and in aprotic solvents
79 go
95% of the tetrahedral form. Equilibrium studies of the ester*;
ification of boric acid with triethanolamine indicate a shift in
81
equilibrium toward structure 31 with an increase in temperature.
Zimmerman reported the results of hydrolysis experiments on bevox-
82
azoldines. He related the BM bond sfccengtr* to ratas of hydrolysis
for several compounds including the. following, 34-37:


85
green liquid was transferred to a 50 ml. round-bottomed flask and
distilled on a spinning band column. Four fractions were obtained.
The two lowest boiling fractions (7.8 g.) were clear, pale yellow,
viscous liquids (b.p. 120-123 C @ 0.15 mm.) Nmr and ir data were
consistent with the assignment of l-(4-bromophenyl)-2-phenyl-l,2-
azaborolidine. The ir spectrum gave absorbances at 3080 (s), 3060 (s),
2950 (s), 2870 (s), 1960 (w), 1890 (w), 1820 (w), 1765 (w), 1700 (w),
1630 (w), 1590 (s), 1570 (m), 1480 (broad, s), 1425 (broad, s), 1385
(s), 1300 (broad, s), 1240 (s), 1185 (m), 1150 (m), 1140 (w), 1100 (m),
1067 (s), 1050 (s), 1030 (m), 1000 (s), 960 (w), 910 (w), 880.(m), 820
(s), 770 (w), 740 (s), 695 (s), and 640 (in) cm. The nmr gave
resonance signals at 67.2 (m, 9): 63.75
Anal. Caled, for C,rH BNBr: C,
_i_v> J.D
3.61; and Br, 26.65. Found: C, 60.14;
(t, 2); and 61.7 (broad m, 4).
60.03; H, 5.04; N, 4.67; B,
H, 5.12; N, 4.58; B, 3,64;
and Br, 26.52.
The two remaining fractions (b.p. 130-132 C @ 0.15 mm.) were
dissolved in small amounts of acetone and cooled in a dry ice-iso
propanol bath, resulting in the formation of white crystals. These
viere filtered and dried yielding 6,7 g. (m.p. 116-118 C).
The ir, nmr, and mass spectra were consistent with the.assignment
of structure as l-(4-bromophenyl)-5-phenyl-l-azs-5-borabicyclo(3.3.0)-
octane. The ir spectrum showed absorbances at 3050 (m), 3010 (m),
3000 (m), 2920 (s), 2825 (s), 1950 (w), 1880 (w), 1820 (w), 1700 (w),
1475 (broad, s), 1425 (m), 1400 (m), 1350 (w), 1310 (w), 1255 (s),
1227 (s), 1190 (w), 1170 (w), 1155 (m), 1130 (broad, s), 1080 (m), .1050
(m), 1035 (m), 1020 (m), .1000 (s), 980 (m), 950 (m), 930 (m), 890 (m),


TABLE OF CONTENTS
Page
Acknowledgements ii
List of Tables v
List of Figures vi
Abstract vii
Chapter
I.INTRODUCTION 1
A. Polymers Exhibiting Principles of Thermal Stability 1
B. Boron-Nitrogen polymers 5
C. Boron-Oxygen Polymers 8
D. Boron-Carbon Polymers 1C
E. Amine-Boranes as Hydrohorating Agents ... 10
F. Boron-Nitrogen Coordinate Bonds in Cyclic and
Bicyclic Compounds 13
G. Statement of Problem 13
II.SYNTHESES OF UNSATURATED TERTIARY ANILINES ... 20
A. Syntbeses of Para-substituted-N.N-Diallylanil.ines 20
B. Synthesis of N,N,N',N'-Tetraallyl-p-
phenylenediamine 20
C. Synthesis of N,N-Di~3-butenylaniline .... 21
III.PREPARATION OF BORON INTERMEDIATES ...... 22
A. Synthesis of Grignard Reagents 22
B. Preparation of Substituted Phenylboronic Acids 24
C. Syntheses of Berate Esters of Substituted
Phenylboronic Acids ... 25
D. Cyclotriboroxer.es 26
E. Preparation of Triethylamine-Phenylboranes . 27
F. Preparation of Pyridine-Phenylborane .... 29
in


Scheme V
66
CO
CD


K, Conclusions
This research has attained many of its projected goals. Hie
model compound, l,5-diphenyl-l-aza-5-borabicyclo(3.3.0)octane was
prepared and its properties investigated. All of the products of
the reaction of triethylamine-phenylborane with N,N-diailylaniline
were isolated, purified, and carefully characterized by nmr, ir,
mass spectral, and elemental analyses. Propene gas was isolated
and identified as a by-product.
Mechanistic studies with deuterium labeling gave, strong
support to the proposed mechanism of the facile, concerted elimi
nation of propene. These studies ruled out a Hofmann-type elimi
nation mechanism.
Hie stability of the modal compound, 49, to various synthetic
conditions, such as those necessary for nucleophilic or electro
philic aromatic substitutions, was determined, its reactivity in
various solvents, acids, and bases was also studied.
Several substituted derivatives of 49 have been prepared which
should be excellent monomer precursors. Preliminary studies show
evidence for the formation of the bis-Grignard reagent from 1,5-
fcis-(4-bromopheny 1)-1--aza-5-borabicyclo(3.3.0octane. The corre
sponding bis-(4-snethoxypbenyl) compound has been converted to small
amounts of the l,5-bis-(4~hydroxyphenyl)--l-aza-borabicyclo(3.3.0)-
octane by the reaction of lithium iodide in collidine. These two
reactions have excellent potential for the formation of dicarboxyl!
and diphenolic derivatives of 49. These compounds would be interes
ing co-monomers for several possible condensation polymerization


39
A six-membered transition state would allow for a relatively
strain-free addition of hydrogen to the terminal end of the double
bond of the allyl group and the ensuing electron shifts.
A second mechanism may be proposed which would lead to the
same products (Scheme VII). The triethylamine in the reaction
mixture could act as a base in abstracting a proton in the 1,5-
diphenyl- l-aza-5-borabic3Tclo(3.3.0)octane, 2iL> at either cf the
two beta-carbons to the quaternary ammonium group. This is the
109
well-known Hofmann elimination. The resulting allylborane, 75,
then could conceivably undergo a thermal cleavage to give, the aza-
borolidine, 71, and propene. Alkyiboranes have been reported to
6 h
undergo this type of thermal cleavage.
The most important aspect of the concerted mechanism (Scheme
VI) involves the equilibrium between structures 69 and 70. This
equilibrium must likely exist for the competetice formation of
the monocyclic, J71, and bicyclie, 72, products. A stronger
coordination; or shift toward intermediate _70 of the equilibrium
should favor the monocyclic product. A shift toward the un
coordinated form should yield more of the bicyclic product. The
most obvious studies, therefore, would be directed toward deter-
77
76
increase the. electron deficiency on boron and would shift the equi-


74
funnel. Stirring was continued for 12 hours, after which a syrupy,
brown liquid was obtained, along with an aqueous layer. The layers
were separated in a 1-liter separatory funnel. The aqueous layer
was washed with 2 350 ml. portions of ether. The ether was then re
moved on a rotary evaporator and the resulting layer combined with
the crude p-bromo-N,N-diallylaniline. This crude liquid was added
dropwise to a 30% solution (100 ml.) of sodium hydroxide in water
in a 2-liter, round-bottomed flask equipped with a mechanical stirrer
and addition funnel. Benzenesulfonyl chloride (34.0 ml.) was added
dropwise. Since the reaction 'was exothermic, an ice bath was used
to control the temperature. The resulting cooled solution was neu
tralized with 10% hydrochloric acid solution. The organic layer was
separated and dried with sodium sulfate. The crude prcduct was fil
tered and placed in a 200 ml. round-bottomed flask for vacuum distil
lation. The distillation yielded 69.5 g. (u7.5%) of a colorless .Liquid
(b.p. 93-94 C @ 0.250 mm.).
Preparation of p-bromo-N,N-diallylaniline
p-Bromoaniline (200.0 g. 1.15 mol.), sodium bicarbonate (242.0 g.,
2.9 mol.), and 400 ml. of water were placed in a 2-liter, 3-necked,
round-bottomed flask equipped with stirrer, condenser, addition funnel,
and heating mantle. The mixture was heated to low reflux. Allyl
bromide (278.3 g. 2.3 mol.) was added dropwise over a two-hour- period
with constant stirring. The lower, oily layer was dried with sodium
sulfate. The crude prcduct was vacuum distilled yielding 215.3 g. (74.5%)
of a clear liquid (b.p. 113-114 C @ 0.100 mm.).


106
tetrahydrofuran in a 500 ml., 3-necked, round-bottomed flask equipped
with mechanical stirrer, cold-water condenser with drying tube, and
addition funnel with nitrogen inlet tube. The mixture was heated to
reflux on a gently warmed heating mantle. After 30 minutes, the heat
was removed and the flask cooled to -70 C in a dry ice-isopropanol
bath. Pyridine (19.0 g. 0.24 mol.) was added and the system was
purged with nitrogen. The solution in the 300 ml. addition funnel
was then added at a rate to keep the temperature belowr -65 C. After
complete addition, the reaction m5.xture was allowed to warm to room
temperature. The mixture was filtered through a sintered-glass
funnel. The filtrate was concentrated on a rotary evaporator. A
small amount of diethyl ether was added resulting in immediate pre
cipitation of yellow crystals (m.p. 124-134 C). The crystals were
unstable in a5.r but an nmr in chloroform was obtained. The nmr
spectrum showed resonances at 58.3 (m, 2.7); 57.4 (m, 8); 54.63 (s,
1); and 52.15 (s, 3). The peak at 2.15 could not be explained on the
basis of the desired structure. Also, the integration did not agree
with complexation of two pyridine molecules to one of p-phenylenediborane.
Preparation of bis-1,4-[5-(4-chlorophenyl)-l-aza-5-borabicyclo(3.3.0)-
octyl]benzene
p-Chlorotriethylamine-phenylborane (20.0 g., 0.088 mol.) was added
to 800 ml. of toluene in a 3-necked, round-bottomed flask equipped with
a cold-water condenser, addition funnel, and thermometer. The solution
was stirred with a magnetic stirrer and heated to 50 C. N,N,N',N'-
tetraallyl-p-phenylenediamine was added to 1000 ml. of toluene and added
dropwise to the stirring solution. After addition of a few ml., the


IS
G. Statement of Problem
The major goals of this research were to examine the mechanism
of the reaction of triethylamine-phenylborane with N,N'-diallylaniline
and to extend this reaction to the preparation of compounds which could
be utilized in the synthesis of high molecular weight, thermally stable
i 101
polymers.
The first step was to prepare 1,5-diphenyl-l-aza-5-borabicyclo-
(3.3.0)octane, 49^ and 1,2-diphenyl-l,2-azaborolidine, 50_, (R,R:-=H) to
serve as models.
formation of 49. anc- 50. occurs in a competitive manner, Obviously,
this reaction requires loss of three carbon units for formation of
50. Since no gaseous products or other products consistent with
] 02
this three-carbon chain had been previously detected, one goal
was to isolate and identify this product.
After initial investigation began, it became obvious that deu
terium labeling studies would be necessary. Therefore, an idea was"
conceived which would differentiate between two possible mechanisms.
Another goal was preparation of several selected derivatives of
49_, both for synthetic purposes and property studies. Substituents
should have electronic and static affects on the relative yields of
49 and 50. The boron-nitrogen coordinate bond could be detected


136
39. H. Steinberg, Organoboron Chemistry, Wiley Interscience, New
York (1964), p. 102.
40. W. P. Cowie, A. H. Jackson, and 0. C. Musgrave, Chem. and Ind.,
1248 (1959).
41. R. M. Washburn, F. A. Billig, M. Bloom, C. F. Albright, and E.
Levens, Organoboron Compounds, Adv. in Chem. Series, 32,
208 (1961).
42. D. R. Nielsen, W. E. McEwen, and C. A. Vander Werf, Chem. and
Ind., 1069 (1957).
43. 0. C. Musgrave, Chem. and Ind. 1552 (1957).
44. J. Goubeau and R. Epple, Chem. Ber., 90, 171 (1957).
45. H. Bennett, U.S. Patent 1,953,741, April 3, 1934.
46. L. E. Stout and D. F. Chamberlain, W.A.D.C. Tech. Rept., 1952.
47. A. W. Laubengayer, R. G. Hayter, W. J. Watt, Abstr. 132nd
Meeting of the Am. Chem. Soc. New York, 1957, p. 10N.
48. E. Svarcs, V. Grundsteins, A. levins, Latv. RSR Zinat. Akad.
Vestis, Kim. Ser., 240 (1370). CA: 73, 35801w (197~0).
49. P. Winternitz and A. Carotti, J. Am. Chem. Soc., 82, 2430 (1960),
50. G. Urry, I. Kerrigan, T, D. Parsons, and H. I. Schlesinger,
J. Am. Chem. Soc., 76, 5299 (1954).
51. C. A. Pearce, British.Patent 358,817, Jan. 18, 1961.
52. S. H. Dandegaonker, W. Gerrard, and M. F. Lappert, J. Chem. Soc.
2076 (1959).
53. U. Kruerke. Z. Naturforsch. lib, 364 (1956).
54. B. M. Mikhailov and F. B. Tutorskaya, Izvest. Akad. Nauk. SSSR
. Ctdel. Khim. Nauk., 1127 (1959). -
55. E. Frankland, J. Chem. Soc.,15, 363 (1862).
56. R. Koster, Angew. Chem., 69, 687 (1957).
57. M. F. Hawthorne, J. Org. Chem,, 23, 1788 (1958).
58. D. R. Nielsen, K. E. McEwen, and C. A,. Yanderwerf, Chem. and Ind.,
37, 1069 (1957). ~


Chapter IV
SYNTHESES AND REACTIONS OF BORON HETEROCYCLES
A. Reaction of Trie thy lamine-Pher.v lb or ane with N,N-Diallylanillpe
Triethylamine-phenylborane was reacted with an equimolar quantity
of N,N-diallylaniline in refluxing toluene. After 12 hours, the
solvent was removed on a rotary evaporator. The residual, phospho
rescent-green liquid was distilled under vacuum to give three fractions.
The first fraction proved to he unreacted N.N-diallylaniline, The
second fraction was identified as l,2-diphenyl-l,2-azaborolidine; the
third was 1,5-diphenyl-l-aza-5-borabicyclo(3.3.0)octane. A gummy
residue in the distilling flank defied al.1 attempts at purification
due to its insolubility. These products were consistent with those
98 99
reported by Butler and Station.'
Examination of the two major, isolated products of the above
reaction indicated that a unit of 3 carbon atoms was needed to complete
100
the balanced chemical equation (Scheme IV). Station had suggested
that the loss of an allyl group would give the l,2-diphenyl-l,2-azaboro-
lidine, 64. However, he was unable to trap or detect any alkene during
the course of the reactions studied.
Since, one goal included improving the yield of the bicyciic
compound, 6_3, over that of the monocyclic compound, 64, while studying
the mechanism of the reaction, it became important to isolate the miss
ing 3-carbon unit. The. reaction outlined in Scheme IV was repeated.
This time, however, the apparatus was modified to include a gas outlet


ppm (8)
Figure 5. Nmr spectrum of 3,7-dideutero-l,5-diphenyl-l-aza-5-borabicyclo(3.3.0)octane.
-F
to


96
azeotropic distillation apparatus consisting of a packed column, cold-
water condenser, thermometer, Claisen head, drying tube, and Dean-Stark
trap was assembled. The flask was heated on a Glas-col heating mantle.
A ternary azeotrope of water, ethanol, and benzene distilled at 64 C.
Two layers formed in the trap. The lower (water) was removed con
tinuously as the reaction progressed. After 5 days, the temperature
at the distilling head had reached 58 C, indicating that the reaction
was complete. The remaining solvent was removed on a rotary evaporator
and the residual liquid placed in a 100 ml. round-bottomed flask. The
compound was distilled yielding 47.5 g. (93.2%) of a colorless liquid
(b.p. 58 C @ 0.15 mm.).
The ir spectrum showed absorbances at 645 (s), 670 (m), 740 (s),
825 (s), 915 (m), 1040 (m), 1055 (s), 1120 (m), 1140 (s), 1200 (m),
1230 (v:), 1275 (s), 1300 (s, broad), 1330 (s, broad), 1385 (s), 1425
(s), 1440 (m, shoulder), 1500 (m), 1530 (w), 1628 (s), 2610 (w), 2640
(w), 2570 (m, doublet), 3020 (s), 3060 (m), 3090 (w), and 3125 (w) cm.-1.
The nmr spectrum gave resonances at 57.3 (quartet, 4); 5M.05
(quartec, 4); 62.35 (s, 3); and 61.2 (t, 6).
Synthesis of triethylamine-(p-methylphenyl)borane
Lithium aluminum hydride (6.85 g. 0.246 mol.) wTas added to 350
ml. of dry diethyl ether in a 1-l.iter, 3-necked, round-bottomed flask
equipped with condenser and drying tube, addition funnel, low-temper
ature thermometer, nitrogen inlet tube, and mechanical stirrer. The
mixture was refluxed for 30 minutes and then cooled to -72 C in a
dry ice-isopropanol bath. Triethylamine (24.9 g. 0.246 mol.) was
added in one portion to the reaction vessel. The system was kept


129
sodium sulfate. The chloroform was removed by the rotary evaporator.
The nmr showed resonances at 60.7 (m,4); 51.8 (m,4); 62.3 (s,4); 53.1
(m,4); and 67.2 (m,7). The lack of a signal at 64.9 seemed to eli
minate any bromination on the methyl groups. The aromatic region
showed two types of absorbance and the correct area for mono-bromi-
nation of one phenyl ring. The mass spectrum showed peaks at 370
and 291 indicating a mixture of starting material and mono-brominated
material. The analysis was too low in carbon for monobromination.
Anal. Caled, for C^H^BNBr: C, 64.83; H, 6.81; B, 2.92; N, 3.78;
and Br, 21.6. Found: C, 58.03; H, 6.84; N, 4.36; and Br, 12.13.
Preparation of p-nitrophenylbenzyl ether
Potassium carbonate (138 g.), benzylchlorids (126.58 g., 1.0 mol.),
and p-bromophenol (173 g., 1.0 mol.), along with 400 ml. of acetone,
were placed in a 3-necked, round-bottomed flask equipped with stirrer
and cold-water condenser. The contents were refluxed on a Glas-col
heating mantle for 12 hours. The heat was removed and the mixture
diluted with 300 ml. of diethyl ether. The ethei"1 layer was separated
and washed 3 times with water and once with 100 ml. of 10% sodium
hydroxide. It was then dried over sodium sulfate, filtered, and then
the solvent removed. A white slush was obtained which crystallized
on standing. A white crystalline material (213.4 g., 82%) was ob
tained (m.p. 58-60C). The nmr spectrum showed resonance signals at
64.6 (s,2); and 67.4 (m,9). The infrared absorbances at 630 (s), 749
(m), 810 (s), 840 (m), 862 (w), 910 (w), 995 (w), 1020 (m), 1055 (m),
.1102 (m), 1160 (m), 1200 (m), 1247 (s), 1320 (m), 1422 (s), 1440 (m),
1480 (m), 1500 (m), 1528 (m), and 2960 to 3200 (broad, s, detailed) cm,


61
A comparison of the spectra in Figure 6 reveals some interesting
effects. A look at models gives some insight into these effects. In
the monocyclic structure, Sj4, the phenyl rings are far apart and the
ring must be nearly planar. As a result, the protons are moved
upfield and the c_ protons are deshielded, resulting in an overlap of
the protons on carbons lb and £. The a_ protons are also slightly
deshielded, probably due to the planar positioning of the phenyl groups
relative to the 5-membered ring. In the bicyclic structure, 9_3, the
_a, 1j, and £ protons give three distinct resonance absorptions. The
model of this compound shows the phenyl groups tied back, much like
butterfly wings, relative to the 3-N bond axis. The two propylene
bridges are also forced back in the opposite direction to the phenyl
groups. The b_ protons are in the region expected for 5-membered,
bicyclic rings. The _a and £ protons are shielded relative to the
azaborolidine, resulting in upfield shifts of A to 5 p.p.m.
The nmr spectrum of 9_3 exhibited a chemical shift of 2.2
p.p.m., relative to trimethyl borate. This compares with 3.6 p.p.m.
for the unsubstituted l,5-diphenyl-l-aza-5-borabicyclc(3.3.0)octane.
F. Preparation of Bis-1,4-[5-(4-methyLphenyl)-l-aza-5-borabicyclo-
(3.3.0)octyl]benzene and Bis-1,4- [5-(4-chiorophanyl)-l-aza-5-bor_a^_
bicyclo(3.3.0)octyl]benzer.e
Bis-1,4-[5-(4-methylphenyl)-l-aza-5-borabicyclo(3.3.0)octyl]-
benzene, 104, and. bis-1,4-[5-(4-chlorophenyl)-l-aza--5-borabicyclo-
(3.3.0)octyljbenzene, 105, were prepared by reacting U,N,NT,N-
te traally1-p-phenylenediamine with trie thylamine-(4-methy1)phenyi-
borane and triethylamine(4-chloro)phenylborane. These compounds,
of course, were not distillable and were purified using silica gel


112
Isolation of tri(p-ethoxyphenyl)cyclotriboroxene
A white residue remained in the flask after vacuum distillation
of p-ethoxyphenylboronate. A small amount of this compound (m.p.
160-162 C) was recrystallized from acetone and analyzed. The
same compound was prepared by heating 1.0 g. of p-ethoxyphenylboronic
acid to 200 C under vacuum. Spectral analyses were consistent with
the assignment of tri(p-ethoxyphenyl)cyclotriboroxene. The ir spec
trum showed absorbances at 2890 to 3090 (broad, detailed, s), 1605
(s), 1570 (m), 1515 (m), 1475 (m), 1460 (shoulder, m), 1415 (s), 1300
to 1400 (broad, s), 1290 (in), .1260 (m), 1245 (s), 1173 (s), 1113 (s),
1080 (m), 1042 (s), 1010 (m), 920 (s), 840 (s, broad), 805 (m), 745
(s), and 688 (s) cm. The nmr showed resonances at 67.5 (m, 4);
64.1 (quartet, 6); and 61.4 (t, 9). The mass spectrum gave a parent
peak at 444 tl.
Anal. Caled, for CllHo.73o0,: C, 69.94; H, 6.13; B, 7.31: and
4 t o o
0, 21.62. Found: C, 64.76; H, 6.06; and B, 7.19.
Synthesis of triethylamine-(p-ethoxyphenyl)borane
Lithium aluminum hydride (3.03 g. 0.08 mol.) was added to 200 ml.
of dry diethyl ether in a 3-neck.ed, 500 ml., round-bottomed flask
equipped with mechanical stirrer, condenser with drying tube, addition
funnel with nitrogen inlet, and low-temperature thermometer. The mix
ture was refluxed for 30 minutes on a Glas-col heating mantle and then
cooled to -72 C in a dry ice-isopropanol bath. Triethylamine (9.5 g.,
0.094 mol.) was added in one portion with stirring. The system was
purged with nitrogen. A solution of p-ethoxy-diethylphenylboronate
( 21.0 g., 0.04 mol.) in dry diethyl ether was added dropwise, keeping
the temperature below -65 0. The solution vas allovied to warm to room


H. K. Zimmerman and H. Weidmann, Ann. 628, 37 (1959).
13 8
81.
82.
83.
84.
85.
86.
87.
88.
89.
90.
91.
92.
H. K. Zimmerman, Advances in Chem., 42, 23 (1964).
R. L. Letsinger and I. Skoog, J. Am. Chem. Soc., 77,
2491 (1955). '
0. C. Musgrave and T. 0. Park, Chem. and Ind., 1552 (1955).
W. L. Ruigh, C. E. Erikson, F. Gunderloy, and M. Sedlak,
W.A.D.C. Tech. Rept., 55-26, Part II, May 1955.
H. Weidmann and H. K. Zimmerman, Ann. 619, 28 (1958).
R. L. Letsinger and N. Remes, J. Am. Chem. Soc., 77, 2489 (1955).
R. L. Letsinger and I. Skoog, J. Am. Chem. Soc. 77, 5175 (1955).
R. L. Letsinger and I. Skoog, J. Am. Chem. Soc., 76_,4047 (1954).
C. S. Ronndestvedt, R. M. Scribner, and C. E. Wulfman, J. Org.
Chem., 20, 9 (1955).
H. Steinberg and D. L. Hunter, Ind. Eng. Chem., 49, 174 (1951).
G. W. Wheland, Advanced Organic Chemistry, John Wilev and Sons,
New York (1967), p. 76.
93. A. A. Schleppnik and C. D. Gutsche, J. Org. Chem., 25,
1378 (1960). "
94. S. J. Groszos and N. E. Day, U. S. Pat. 2,942,021.
95. J. H. Ludwig and K. Witsken, Ger. Offen. 1,908,344, Sept. 1969.
CA: 72^, 4052c (1970).
96. R. M. Adams and F. D. Poholsky, Inorg. Chem. 2, 640 (1963),
97. D. G. White, J. Am. Chem. Soc., 85, 3634 (1963).
98. G. L. Statton and G. B. Butler, J. Am. Chem. Soc., 86,518 (1964).
99. G. B. Butler, G. L. Statton, and W. S. Brey, J. Org. Chem., 30,
4194 (1965).
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B.
Butler and G. L.
Statton
, J. Am.
Chem. Soc., 86, 5045 (1965)
101.
G.
B.
Butler, National
Science
Foundat
ion Proposal, "Polymers
Possessing a Thermally Initiated Flexibilizing Mechanism Resulting
from Dissociation of Dative Bonds," March 4, 1970.



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PAGE 151

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PAGE 152

81,9(56,7< 2) )/25,'$


27
Several cyclotriboroxenes were recovered as by-products from
the distillation of their parent esters: triphenylcycloboroxene,
tri(p-bromophenyl)cyclotriboroxene, tri (p-chlorophenyl) cyclotri-
boroxene, tri(p-methylphenyl)cyclotriboroxene, tri(p-ethoxyphenyl)-
cyclotriboroxene, and tri(p-methoxyphenyl)cyclotriboroxene.
The distillation of tetraethyl p-phenyldiboronate yielded a
tan-colored solid which did not melt and was insoluble in all
common solvents tried. In acetone the compound swelled and even
tually became gel-like in structure. In analogy with the formation
of cyclotriboroxenes, 5jj, the compound was assumed to be a poly
meric, 3-dimensional network, 57.
r-h
\
B Ph
Ph
I I .
Ph
^B sQ
j [
57
Ph

/ \
E. Preparation of Triethylamine-Phenylboranes
Several new triethylamine-phanylboranes, 58, were prepared by
10 7
modification of the method of Hawthorne. The p-substituted diethyl
phenylboronates were reduced in the presence of triethylamine at low
temperature under nitrogen. The reactions were carried out with slow
addition of the diethy phenyiboronate to a mixture of lithium alum
inum hydride in diethyl ether and triethylamine. After complete addi
tion, the mixture was allowed to warm to room temperature. Filtration
followed to remove the excess lithium aluminum hydride and other in-


99
spectrum showed a parent peak at 290 1, in agreement with the expected
molecular weight.
Anal. Caled, for C0.H.cBN C, 82.46; H, 9.00; N, 4.81; B, 3.72.
ZU Zb
Found: C, 82.21; H, 9.05; N, 4.96; and B, 3.71.
Upon sitting for six days, a small amount of crystalline material
precipitated from the fourth fraction. This compound was found to be
l,2-bis-(4-methylphenyl)-l,2-azaborolidine by analysis and mass spectrum.
A parent peak was observed at 249 tl.
Anal. Caled, for C^H^BN: C, 81.93; K, 8.10; N, 5.6; and B,
4.35. Found: C, 81.51; H, 8.80; N, 5.3; and B, 3.94.
Synthesis of p-phenylenediboronic acid
Magnesium (55.0 g. 2.25 g. atoms) was placed in a flamed, 2-
liter, 3-necked, round-bottomed flask equipped with a mechanical
stirrer, addition funnel, and cold-water condenser. Tetrahydro-
furan (200 ml.) was added; the mixture was --e fluxed for 30 minutes.
p-Dibromobenzene (235.9 g. 1.0 mol.) was dissolved in 500 ml. of
tetrahydrofuran and added dropwise to the stirring mixture. A small
crystal of iodine was necessary to initiate the reaction. A.n ice
bath was used to control the reaction rate. After all of the p-
dibromcbensene had been added, the reaction mixture was heated over
night. Some problems were encountered with the thickness of the
Grignard reagent and dilution was necessary. Trimethylborate (207.8
g., 2.1 mol.) was added to 1 liter of dry diethyl ether in a 5-liter,
3-necked, round-bottomed flask equipped with condenser, low-tempera
ture thermometer, addition funnel, and nitrogen inlet tube. The con
tents were cooled to -68 C in a dry ice-isopropanol bath. The


83
condenser. The mixture was refluxed for 30 minutes. p-Dibromobenzene
(235.9 g. 1.0 mol.) was dissolved in dry diethyl ether and placed in
a 500 ml. addition funnel. Then the mixture was activated with a small
crystal of iodine; a few ml. of the solution were added. An ice bath
was necessary to control the reflux rate while the remainder of the di-
bromobenzene was added drcpwise to the stirring mixture. The resulting
solution was filtered to remove the unreacted magnesium.
Diethyl p-bromophenylboronate
p-Bromophenylbcronic acid (80.0 g., 0.4 mol.), benzene (320.0 g.),
and ethanol (138.0 g.), along with a small amount of sulfuric acid,
were placed in a 2-liter, 1-necked, round-bottomed flask. An azeotropic
distillation apparatus was assembled, consisting of a packed column,
Claicen head, thermometer, condenser with drying tube, and Dean-Stark
trap. A ternary azeotrope of benzene, water, and ethanol distilled at
64 C, forming two layers in the trap. The lower (water) layer was
continuously removed as the reaction proceeded. The reaction appeared
complete as the temperature at the distilling head reached 67 C-the
temperature at which the binary azeotrope of benzene and ethanol dis
tills. Most of the remaining benzene and ethanol were distilled away
and the remaining liquid placed in a 200 ml. round-bottomed flask The
brcwn liquid was then distilled under vacuum yielding 77.4 g. (60%) of
a clear liquid (b.p. 94-95 C @ 0.50 mm.).
The infrared spectrum showed absorbances at 2995 (s), 2940 (s).
2920
(s), 1920
(w),
1650
(w),
1585 (s),
1560
(w), 1487 (s), 1470
(w),
1415
(s), 1375
( c; )
1270
to iv
350 (broad
, s),
1255 (s), .1175 (w),
.1125 (s),
1100
(s), 1070
(S ,
1040
(s),
1005 (s),
900
s), 815 (s), 720 (s)
, 550
(m),
and 520 (n
i) cm.
-1


BIOGRAPHICAL SKETCH
Charles Lewis McCormick III, was born July 25, 1946, in Bogalusa,
Louisiana. At age 12, he received the Eagle Scout Award and later the
God and Country Award. He graduated with honors from Greenville High
School in Greenville, Mississippi, in May 1964.
He received his Bachelor of Science degree in chemistry, cum laude,
from Millsaps College in Jackson, Mississippi, in June 1968. A.s an
undergraduate he was social chairman of Kappa Sigma Fraternity, vice-
president of Theta Nu Sigma and Chi Chi Chi science honorarias, and a
member of the M-Club. He was a member of the varsity tennis team, ¡bile
at Millsaps he held the Dr. Elbert Alstron Cheek Scholarship. He re
ceived the Junior Scholastic Award and participated in the Tulane Fellows
and Scholars Program and the National Science Foundation Undergraduate
Participation Program.
In September 1968, he enrolled in the Graduate School of the Univer
sity of Florida to pursue the degree of Doctor of Philosophy.
He is a member of the American Chemical Society, and captain of the
University of Florida Soccer Club.
On July 19,1969, he married the former Patricia Ann Marshall of
Gautier, Mississippi.
14 0


92
-1
1485 (m), 1460 (m), 1420 (broad, s), 1390 (m), 1315 (broad, s), 1295
(s), 1263 (w), 1255 (w), 1230 (w), 1205 (w), 1160 (w), 1090 (s), 1060
(s), 1018 (s), 975 (w), 965 (w), 920 (w), 905 (w), 885 (w), 850 (w),
820 (s), 795 (s), 765 (s), 725 (s), 695 (s), 660 (m), and 610 (m) cm.'x.
The nmr spectrum exhibited resonance signals at 7.1 (m, 9); 63.75 (t,
2); and 61.75 (m, 4). The mass spectrum gave a parent peak at 255 1.
Anal. Caled, for C,CH,cBNCl: C, 70.48; H, 5.92; N, 5.48; B,
4.24; and Cl, 13.88. Found: C, 70.20; H, 5.84; and Cl, 13.99.
The highest boiling component, 10.5 g. was a dull red liquid
(b.p. 135-136 C @ 0.10 mm.). This viscous liquid did not crystallize.
The nmr, ir, mass spectrum, and analysis were consistent with the
structure of l-phenyl-5-(4-chlorophenyl) -1,2-aza-5-borabicyclo(3.3.0)-
octane. The ir spectrum showed absorbances at 3440 (w), 3260 (w), 3078
(m), 3040 (w), 2950 (broad, s), 2840 (in), 2000 (w), 1885 (w), 1605 (s),
1580 (m), 1560 (w), 1500 (broad, s), 1230 (s), 1190 (w), 1180 (w), 1160
(w), 1140 (w), 1090 (s), 1060 (w), 1035 (m), 1015 (m), 990 Cm), 965 (m),
950 (w),. 910 (w), 895 (w), 870 (w), 830 (s), 810 (m), 790 (m), 750 (s),
720 (w), 700 (s), 670 (w), and 640 (w) cm. ". the nmr spectrum showed
resonance signals at 57.0 (m, 9); 63.3 (m, 4); 62.05 (quintet, 4); and
61.05 (m, 4). The mass spectrum showed a molecular weight of 297 I,
Anal. Caled, for C10H01BNC1: C, 72.62; H, 7.12; N, 4.71; B, 3.64;
and Cl, 11.92. Found: C, 72.59; H, 7.12; N, 4.71; and Cl, 12.08.
Preparation of l,2-bis-(4-chlorophenyl)-l,2-azaborolidine and
1,5-bis-(4-chlorophenyl)-l-aza-5-borabicyclo(3.3.0)octane
Triethylamine-(p-chlorophenyl)borane (22.7 g., 0.10 mol.), p-chloro-
N,N-diallylaniline (20.8 g., 0.1 mol.), and 1.25 liters of benzene were


120
low-temperature thermometer and condenser. The solution was refluxed
for 30 minutes on a Glas-col heating mantle and then cooled to -79 C
in a dry ice-isopropanol barn. Triethylamine (15.3 g., 0.15 mol.)
was added in a single portion. The system was then purged with nitro
gen. The diethyl p-methoxyphenyiboronate (27.4 g., 0.132 mol.) was
added dropwise with stirring, keeping the temperature below -65 C.
After complete addition, the reaction mixture was allowed to warm to
room temperature. The gray lithium salts were filtered using a sin
tered -glass funnel. The filtrate was then cooled in a dry ice-acetone
bath. White, needle-like crystals, 24.3 g. (82%), of triethylamine-
(p-methoxyphenyl)borane (m.p. 63-64 C) were isolated.
The ir spectrum exhibited absorbances at 633 (m), 700 (w), 748
(d, strong), 780 (w), 805 (s, shoulder), 820 (s), 850 (w, shoulder),
860 (m, broad), 900 (w), 910 (w), 923 (w), 945 (w), 1015 (m, shoulder),
1030 (s), 1058 (w), 1085 (m), 1105 (m), 1118 (w), 1148 (s), 1175 (s),
1192 (s),1240 (s), 1275 (s), 1303 (w), 1342 (w), 1353 (w), 1378 (s),
1440 (m), 1460 (m), 1480 (m), .1498 (s), 1545 (w, shoulder), 1560 (in),
1590 (s), 1902 (w), 2200 (w, d),.2288 (w, shoulder), 2322 (s), 2422 (m),
2488 (w), 2848 (m), 2900 to 3100 (broad, s, detailed), and 3450 to
3400 (broad, m, detailed) cm. ~.
The nmr spectrum showed resonances at 6l.l (t, 9); 52,68 (quartet,
6); 63.7 (s, 3); and 67.05 (quartet, 4).
Preparation and characterization of 1 ^-bis-^-methoxyphenylj-l-aza-
S-borabicyclot 3.3.0)octane
Triethylamine-(p-methoxyphenyl)borane (22.3 g., 0,10 mol.) was
dissolved in 500 ml. of toluene in a 1-necked, 1-liter, round-bottomed
flask equipped with an air-cooled condenser. p-Methoxy-N,N-d.iallyl-


o
The monoborazine would be electronically unstable and should form
polymers. However, the stabilizing .influence of suitable bond angles
and iT-bonding in the cyclic trimer favors this homologue.
Three main avenues have been investigated for the formation of
19
Hie first involves the opening of various
boron-nitrogen polymers
borazene rings, and the second, reactions of the unstable mcnoborazines.
The final method has been an attempt to link borazene rings in an
ordered fashion, avoiding cross-linking.
As a general rule, cyclotriborazenes do not undergo ring opening
to linear polymers. However, the polymerization of N- and/or B-methy1--,
aryl-, or triazinylcyclotriborazenes in a closed system at 350 to
6003C, or in the presence cf catalysts, led to hard, glassy, insoluble.
resins. No molecular weight was given. An open-chain, low
molecular weight polymer of the structure, (PhB-NC^Hg)^, where n=20 to 40
was prepared by the reaction of phenylborondichloride with isobucy.lamine.
Cross -.linked polymer was formed by the pyrolysis of B-tricbloro-N-tri-
26
atylcyclotriborazenes, (CIB-BAr) .., from room temperature up to 500"C.
Cyt .oborazene rings have been linked to give polymers, 11, of high
molecular weight. Benzene soluble polymer was formed whan cyeloborazene
. , 21
rings were iinkea by the process:
Me
+ 2n KC1
HoN- ^NMe
Bu
n
11


'
¡001
501
|
so!
I
i
70
0
I
50!
40
V' 0

20!
j
o;
i
40
4
5
V/AVE LENGTH IX MICRONS
3
t r i rrp ri j 1 1 r ¡ 1 r
3-Dou6¡rcproper.e
L
' -----
. !
j i .... i i i
. 1 ,
1..
00
3500
0000
WAVENUMBER CM
2500
2000
Figure 2.
Infrared spectrum of 3-deuteropropene.


62
chromatography and recrystallization. Physical and spectral data are
given in Tables 3 and 4.
The high molecular weights of these compounds and their molecular
structures make them excellent models for the study of polymers with
similar structures. The boron-nitrogen coordinate bonds in these com
pounds exhibited double absorbances in the 7.8 to 3.0 micron region
compared to single absorbances in the l,5-diphenyl-l-aza-5-borabicyclo~
(3.3.0)octanes. These compounds were the best models for differential
scanning calorimetry studies, described later in this chapter.
G. Reaction of N,N,N',K'-Tetraallyi-p-phenylenediaralne with
p-Phenvlenediborane
The relatively high yields of 104 and 105 encouraged attempts
to prepare oligomeric or polymeric products. It seemed that the
above synthesis should be extended by reacting a bis-borane com
pound, 107, with K,N,N'jN'-tetraallyl-p-phenylenediamiue, 106, to
yield a polymer, 103. Attempts to prepare the pure di(pyridine)
p-phenylenedibcrane and di(triethylamine)-p-phenylenediborane are
described in Chapter III. The resulting crude compound, 107, was
reacted with the tetraallyl compound, 106. A viscous, brown com
pound was obtained. This compound was insoluble in every solvent


LIST OF TABLES
Table Page
1 Skeletal Bond Energies 4
2 Substituted l,5-Diphenyl-l-aza-5-borabicyclo(3.3.0)octanes
and l,2-Diphenyl-l,2-azaborolidines 54
3 Physical Data of Substituted 1,5-Diphenyl-l-aza-5bora-
bicyclo(3.3.0)octa.nes 55,56
4 Spectral Data of Substituted 1,5-Diphenyl~l-aza--5-bora-
bicyclo(3.3.0)cctanes 57,58
v


89
ml. of water had been added as the ether was replaced. After cooling,
filtering, and washing with 3 20 ml. portions of hexane, white, fluffy
crystals, 195.2 g. (83.5%), were obtained (m.p. 280-281 C).
The ir spectrum showed absorbances at 3200 (broad, s). 1920 (w),
1880 (w), 1800 (w), 1730 (w), 1650 (w), 1590 (s), 1560 (m), 1350 (broad,
s), 1250 (w), 1170 (m), 1080 (s), 1010 (s), 820 (s), 720 (s), 670 (s),
and 640 (m) cm. \
The nmr spectrum exhibited resonance signals at 57.6; and 53.1
(s, 2).
Synthesis of p-chlcrophenylborcnate
p-Chlorophenylboronic acid (100.0 g., 0.64 mol.) was placed in a
2-liter, round-bottomed flask. To this, ethanol (230.0 g., 5.0 mol.)
and benzene (546.0 g.) were added. An azeotropic distillation
apparatus was constructed consisting of a fractionating column,
Claisen head, thermometer, Dean-Stark trap, and condenser with dry
ing tube. A small amount of sulfuric acid was added. The mixture
vas heated on a Glas-coi mantle. A ternary azeotrope of benzene,
ethanol, and water distilled at 64 C. Two layers formed in the
trap and the lower layer was continuously removed. Approximately
23 to 24 ml. of water were collected in the trap. After the temp
erature had stabilized at 58 C, the temperature at which the binary
azeotrope of benzene and ethanol boils, the remaining solvent was
removed on the rotary evaporator. The residual crude ester was
placed in a 209 mi., round-bottomed flask and distilled under vacuum.
A clear liquid, 60.2 g. (44.3%). was obtained (b.p. 92-93 C @ C.75 mm.).


113
temperature overnight with stirring. The solution was then filtered to
remove insoluble salts and unreacted lithium aluminum hydride. The
filtrate was concentrated to 1/2 its original volume and then cooled in
a dry ice-isopropanol bath resulting in the formation of 18.8 g. (84%)
of white crystals (m.p. 63-64 C). These appeared to melt at the edges
in air and were quickly dissolved in toluene.
Synthesis of triethylamine-(p-bromophanyl)borane
Lithium aluminum hydride (3.79 g. 0.10 mol.) was added to 350 ml.
of dry diethyl ether in a 3-necked 1-liter, round-bottomed flask
equipped with mechanical stirrer, condenser with drying tube, addition
funnel with nitrogen inlet, and low-temperature thermometer. The
mixture was refluxed for 30 minutes on a heating mantle and then cooled
to -70 C in a dry ice-isopropanol bath. Triethylamine (10.1 g., 0.10
mol) was added in one portion with stirring. Under nitrogen, diethyl
p-bromophenylboronate (25.7 g., 0.10 mol.) in 50 ml. of ether was added
dropwise. The temperature was maintained belev; -65 C during the addition
and then the bath was removed. After the solution had warmed to room
temperature, the excess lithium aluminum hydride was removed by filtration
through a sintered-glass funnel. The filtrate was concentrated to 1/2
its original volume and cooled in a dry ice-isopropanol bath. White,
needle-like crystals formed in the solution. These were filtered under
nitrogen yielding 21.3 g. (78.5%) of the white crystals. This compound
was not stable to air and, therefore, was dissolved in toluene for
storage.
The nmr spectrum showed resonances at 57.35 (m, 4); 53.50 (quartet,
6); and 51.15 (t, S.5).


30
crystallized from cold diethyl ether. A small amount of yellow crystals
(m.p. 60-68 C) was obtained. The crystals were unstable in air. The nmr
spectrum showed a broad multiplet at 5 8.8, which was consistent with the
expected pyridinium resonance, and an aromatic resonance ato 7.3. How
ever, only one pyridine molecule was complexed to the p-phenylenediborane,
A possible reason for the complexation of only a single base mole
cule to the diborane could be a resonance or electronic effect. A signi-
61
60
ficant contribution from 6_0 would allow only single coordination with the
nucleophilic bases. This problem could possibly be eliminated by pre
paring bis-boranes, 6_2, with insulation from electronic effects.
EtN-BH
62


29
The triethylamine-(p-ethoxy)phenylborane and triethylamine-
(p-methoxy)phenylborane did, however, decompose after one week,
even under nitrogen. These compounds and triethylamine-(p-brcmo)-
phenylborane could be kept in toluene or benzene solvents without
decomposition.
F. Preparation of Pyridine-Phenylboranes
An attempt was made to prepare the di(triethylamine)-p-
phenylenediborane, _5£, by the same general method as described
above. Tetraethyl-p-phenyldiboronate was added dropwise to a cold
mixture of lithium aluminum hydride in diethyl ether and triethyl
amine. After complete addition, the resulting mixture was allowed
to warm to room temperature and filtered. The filtrate was cooled
to -12 C in a dry ice-isopropanol bath. No crystals were formed.
The solution was concentrated to one-half its volume and cooled once
more. Fine, white crystals formed. These crystals were found to be
unstable in nitrogen and were, therefore, kept in the solvent. The
mar spectrum showed only one mole of triethylamine cosnplexed to the
p-phenylenediborane. The ir spectrum showed the 3-H stretching ab-
-1
sorbanee at 2200 to 2420 cm.
It was thought that, perhaps, a different base, suele as pyridine
with less face-strain, would complex more strongly with the p-phenylene
diborane. The same general procedure was followed using pyridine as the
base. A yellow oil was obtained from the initial reaction. This oil was


38
uncoordinated intermediate, 69b This involves a four-membered
transition state, 68. In solution there is probably an equilibrium
between tne uncoordinated, 69_, and the coordinated, 7^0, intermediates.
Above 90 C in toluene, competitive pathways (Scheme VI) would lead
to formation of the final products _7JL and 72_ (X=H) The 1,5-diphenyl-
l-aza-5-borabicyclo(3.3.0)octane, 72_, could be formed by a second
hydroboration with boron adding to the terminal end of the remaining
double bond. This might occur by either pathway _1 or pathway 2_.
Brown'- proposed a four-centered transition state for the general
process of hydroboration. Following this proposal, the transition
state for the coordinated form, _735 would have much more strain than
that of the uncoordinated form, 74. Therefore, it seems likely that
the second hydroboration proceeds along pathway 2_.
The formation of the'l,2-diphenyl-l,2-azaborolidine, 71, is
accompanied by the elimination of propene gas. Amine-boranes have
73
been reported to dealkylate at very high temperatures under vacuum*
as discussed in the introduction. Obviously, this system is a special
one which allows for very facile propene elimination at relatively
low temperatures, atmospheric pressure, and mild conditions.
The coordinated intermediate, 70, is perfectly suited for a
concerted elimination of propane as shown below;
70
7.1


108
The mass spectrum showed a parent peak at 517 *1.
Anal. Caled, for C_.H_.N_B.C1.: C, 69.67; H, 7.02; N, 5.42;
oU do jl Z Z
B, 4.18; and Cl, 13.71. Found: C, 69.47; H, 6.86; N, 5.45; B, 4.27;
and Cl, 14.02.
Preparation of p-methoxyphenylmagnesium bromide
Magnesium (19.4 g. 0.80 mol.) and 200 ml. of dry diethyl ether
were placed in a 1-liter, 3-necked flask equipped with mechanical
stirrer, addition funnel, cold-water condenser, and drying tube.
The mixture was allowed to reflux for 30 minutes. A small amount
of ethylene bromide was added to activate the solution. p-Bromo-
anisole (100.0 g., 0.534 mol.) was dissolved in 100 ml. of dry
diethyl ether and then added dropwise to the stirring mixture. An
ice bath was used to control the reaction rate. The remai.ni.ng p-
bromoanisole was added at a rate to maintain a low reflux. The
mixture was stirred for three hours after complete addition and
then filtered to remove the excess magnesium.
Preparation of p-methoxyphenylboronlc acid
Trimethylborate (55.5 g., 0.53 mol) was placed in a 3-liter, 3-
necked, round-bottomed flask equipped with mechanical stirrer, lowr-
temperature thermometer, and Claisen adapter with nitrogen inlet
and addition funnel. Diethyl ether (500 ml.) was added. The solu
tion was cooled to -70 C in a dry ice-isopropanol bath. The p-
methoxyphenylmagnesium bromide (0.53 mol.) was added dropwise with
stirring, keeping the temperature below -65 C. The mixture was
allowed to warm to room temperature with stirring. The reaction


101
was prepared with benzene as the solvent. The tacky reaction product
was dissolved in benzene and introduced in 25 ml. portions on the
column. Fortunately, the desired product was eluted in the first few
fractions collected. These were tested by thin layer chromatography.
Appropriate fractions were combined and the solvent was removed on a
rotary evaporator. The crude b.is-l,4-[5-(4-methyiphenyl)-l-aza-5-
borabicyclo(3.3.0)octyl]benzene was then recrystallized from hot
ethanol, resulting in the formation of 6.9 g. (25%) white crystals
(m.p. 202-204 C).
The ir spectrum showed absorbances at 680 (s), 730 (w), 778 (w),
795 (w),
810 (
s), 840 (s)
, 910 (s), 970
(m),
1000 (
m),
1025
(m),
1045
(w), 1068
(m),
1220
(w),
1247 (s), 1273
(w),
1287 (
s).
1312
(w),
1322
(w), 1355
(w),
1383
(w),
1405 (w), 1440
(in),
1475 (
s) ,
1490
(w),
1520
(s), 1618
(w),
1650
(w),
2882 (m), 2900
(m),
2950 (
s) ,
3005
(m),
3040
(w), 3068
(m),
3130
(wO,
and 3160 (w) cm
-1
[ >
The nmr exhibited resonances at 66.9 (broad m, 12); 63.2 (broad
t, 8); 62.1 (broad m, 14); and 61.1 (broad m, 8).
The mass spectrum showed a parent peak at 476 *1.
Anal. Caled, for C, 80.69; H, 8.89; B, 4.54; and
N, 5.88. Found: C, 80.39; H, 8.71; B, 4.7?; and N, 5.70.
Isolation of tri(p-chlorophenyl)cyclotriboroxene
A white, crystalline material was recovered from the distilling
flask after preparation of diethyl(p-chlorophenyl)boronate. The
compound melted at 293-294 C. The ir spectrum exhibited absorbances
at 675 (s), 730 (s). 773 (m), 820 (m), 1010 (s), 1083 (s), 1100 (m),
1173 (m). 1200 to 1500 (broad, s), 1563 (m), 1592 (s), 2900 to 3.100
(bread, weak, detailed), and 3450 (broad, m) cm.
The nmr showed


118
material passed through the column in the .initial fractions. These
were combined; the solvent was removed cn the rotary evaporator. The
residue was recrystallized from ethanol yielding 2.3 g. of white
needle-like crystals (m.p. 166-167 C). Spectra and analysis confirmed
the assignment of the structure of l-(p-methoxyphenyl) ,5-(p-ethoxyphenyl)-
l-aza-5-borabicyclo(3.3.0)octane. The mass spectrum showed a parent
peak at 336 1. The ir spectrum exhibited absorbances at 2780 and 3100
(broad, s), 2710 (w), 2610 (w), 2540 (w), 2150 (w), 1970 (w), 1880 (m),
1601 (s), 1560 (s), 1430 to 1500 (s, broad), 1480 (s), 1230 to 1310 (s,
broad), 1275 (s), 1030 (s), 1015 (w), 967 (m), 920 (s), 885 (s), 800 to
840 (s, broad), 750 (s), and 720 (m) cm. \ The nmr spectrum shewed
resonances at <56.9 (m, 8); <53.3 (m, 4); 63.7 (m, 5); 62,0 (m, 4); and
61.3 (m, 6).
Anal. Caled, for ConH BN0o: C, 74.79; and H, 8.37. Found:
C, 75.23; and H, 8.29.
Preparation of diethyl p-methoxyphenylboronate
p-Methoxyphenylborcnic acid (56.0 g., 0.358 mol.), ethanol (148.0 g.)
benzene (350 ml.), and a drop of sulfuric acid were placed in a 1-liter,
1-necked, round-bottomed flask equipped with Dean-Stark trap for azeo
tropic distillation. The mixture was heated on a Glas-col heating man
tle and the water was removed continuously from the trap. After 1 week
the esterification had reached completion. The remaining ethanol and
benzene were removed on the rotary evaporator. The resulting greenish-
brown liquid was transferred to a 50 ml., round-bottomed flask. Distil
lation yielded 45.8 g. (50%) of a colorless liquid (b.p. 108-110 C @
2.0 nan.).


80
The nmr spectrum gave resonances at 67.2 (in, 10); 63.8 (t, 2);
and a broad multiplet at 51.8 (in, 4). The mass spectrum showed a
peak at 220 *1.
Anal. Caled, for C,CH1CBN: C, 81.47; H, 7.29; N, 6.34; and
18 lb
B, 4.89. Found: C, 81.42; H, 7.31; N, 6.21; and 3, 5.01.
The higher boiling fraction (b.p. 125-130 @ 0.30 mm.) was
dissolved in acetone and cooled in a dry ice-isopropanol bath after
which white crystals formed. These crystals were filtered and dried
yielding 4.47 g. (m.p. 80-81 C). The spectral data and analysis
agreed with the assignment of l,5-diphenyl-l-aza-5-borabicyclo(3.3.0)-
octane. The ir spectrum showed absorbances at 3040 (m), 2900 (s),
2820 (m), 1925 (s), 1850 (w), 1580 (s), 1420 to 1480 (s, broad), 1260
(s), 1215 (m), 1175 (s), 1150 (in), 1125 (s), 1075 (m), 1040 (m), 1020
(s), 980 (s), 950 (s), 930 (m), 880 (s), 830 (w), 810 (s), 775 (s),
745 (w), 725 (s), 670 (s), and 610 (w) cm."1.
The nmr spectrum gave resonance signals at 56.85 (m, 10); 63.3
(m, 4); 62.1 (q, 4); and 61.1 (m, 4).
The mass spectrum gave a parent peak at 262 -1.
Anal. Caled, for C-^H^BN: C, 32.13; H, 8.42; N, 5.32; and
B, 4.11. Found: C, 82.15; K, 8.51; N, 5.41; and B, 4.21.
Synthesis of p-bromophenylboronic acid
A mixture of magnesium (27.0 g., 1.1 g. atoms) and 100 ml. of dry
diethyl ether was placed in a 1-liter, 4-necked, round-bottomed flask
equipped with a stirrer, addition funnel, and reflux condenser. p-Di-
bromobenzene (237.0 g. 1.0 mol.) in diethyl ether vas added dropwise
with stirring after the initial reaction was started. An ice bath was


TABLE 3 PHYSICAL DATA OF SUBSTITUTED
1,5-DIPHENYL~l-AZA-5-BORABICYCLO(3.3.0.)OCTANES
Cpd. No.
Name
Formula
M.P.(C)
Analysis (Calculated, Found)
63
l,5-Diphenyi-l-aza-5-
C18H22BN
80-31
C:
C,82.13 ;
H,8.42;
N,5.32 ;
B,4.11
borabicyclo(3.3.0.)octane
F:
C,82.15;
H,8,51;
N,5.41;
B,4.21
84
3,7-Dideutero-1,5-diphenyl-l-
C18H20D2BN
78-79
C:
0,81.52;
H,7.60;
D,1.5.2;
N,5.28;
aza-5-borabicyclo3.3.0.)octane
F:
B,4.08
C,81.74;
N,5.18;
B,4.20
87
1-(4-Bromcphenyl),5-phenyl-l-
aza-5-borabicyclo(3.3.0.)octane
C18H21ENBr
116-118
C:
C,63.19;
Br ,23.36
H, 6.19 ;
N ,4.09;
B,3.16 ;
F:
C,63.11;
Br,23.24
H,6.29;
N,3.96 ;
B,2.90 ;
S9
1- (4-Chlorophenyl), 5-phenyl-l-
C18H21BNC1
95-96
C:
C ,72.63 ;
H,7.11j
N ,4.70;
B,3.64;
aza-5-borabicyclo3.3,0.)octane
F:
Cl, 11.91
C ,72.66;
Cl.12.04
K,7.06 ;
N,4.59 ;
B,3.73;
91
1-Phenyl,5-(4-chlorophenyl)-1-
C18H2.1BNC1

C:
C ,72.63;
H,7.11;
N ,4.70 ;
B ,3.64 ;
aza-5-borabicyclo(3.3,0.)octane
F:
Cl ,11.91
C,72.59 ;
H,7.12;
N,4.71;
cl.12.08
93
1,5-B.is-(4-chlorophenyl)-1-
93-95
C:
C ,65.08 ;
H,6.07 ;
N,4.22;
B,3.26 ;
aza-5-borabicyclo(3.3.0.)octane
F:
Cl,21.36
C ,64.97;
H,5.99;
N,4.15 ;
Cl,21.13


68
signals at 60.95 (m, 4); 61.6 (m, 8); 63.5 (m, 4); and 57.3 (m, 10).
Anal. Caled, for C^H^BN: C, 82.48; H, 9.00; B, 3.71; and
N, 4.81. Found: C, 81.98, H, 8.81; B, 3.64; and N, 4.76.
The second portion of the reaction mixture was distilled under
vacuum on a spinning band column. Several fractions were obtained.
The first, fraction proved to be unreacted N,N-di-3-butenylaniline.
The second fraction (b.p. 75-78 C @ 0.50 mm.) exhibited absorbances
in the infrared spectrum and resonances in the nmr spectrum con
sistent with the structure of 1,2-diphenyl-azacyclohexane, 113.
The third fraction (b.p. 90-95 C @ 0.50 mm.) was a pale yellow
liquid. The spectra were consistent with the assignment of 1,2-
diphenyl-l-(3-butenyl),2-hydrc-azaboracyclohexane, 112. The nmr
spectrum showed the presence of an ally! group with resonances at
65.8 (m, 0.5); and 65.1 (m, 1). Other resonances for compound 112
occurred at 60.8 (m, 2); 51,6.5 (m, 6); 63.35 (m, 4); and 67.4 (m, 12).
The ir spectrum showed the presence of a C-C double bond at 1645 cm. \
as well as the presence of a B-H bond at 2250 cm. ^. The distillation
flask contained a gummy, brown residue, which was recrystallized from
ethanol to give a white, crystalline material. This compound was
identical to that obtained from the silica gel column chromatography.
The above results gave strong support to the mechanism proposed
for the facile, concerted elimination of propene gas in the competitive
formation of l,5-diphenyT-l-aza~5-"borabicycio(3.3.0)octanes, 72,
and 1,2-diphenyi-l ,2-azaborolidine, 71 (Scheme VI).


79
ture thermometer, nitrogen inlet tube, addition funnel connector,
and a mechanical stirrer. The mixture was refluxed for thirty
minutes and then cooled to -72 C in a dry ice-isopropanol bath.
Triethylamine (37.4 g. 0.37 mol.) was added with stirring. Then
a solution of diethyl phenylboronate (65.5 g. 0.37 mol.) in ether
vas added dropwise with stirring, keeping the temperature below
-65 C. The solution was stirred at -72 C for another hour and
then allowed to warm to room temperature. The mixture was filtered
through a sintered-glass funnel. The filtrate v/as concentrated and
then cooled in a dry ice-isopropanol bath resulting in the formation
of 51.9 g. (73.0%) of white, needle-like crystals (m.p. 65-66 C).
Preparation of 1,2-diphenyl -1,2-azaborolidine and 1,5-diphenyl-l-az-a-
5-bora-bicyclo(3.3.0)octane
A solution of 1.25 liters of toluene, triethylamine-phenylborane
(18.0 g., 0.094 mol.), and N,N-diallylaniline (16.3 g., 0.094 mol.)
was distilled at atmospheric pressure in a 2-.liter, 1-necked, round-
bottomed flask until the temperature reached 120 C at the distilling
head. The remaining toluene was removed on a rotary evaporator,
resulting in a phosphorescent-green solution. This solution was dis
tilled on a spinning band distillation column yielding two major pro
ducts. The lower boiling component, 4.10 g., was a clear liquid (b.p.
84-86 C @ 0.30 mm.). The spectral data agreed with the assignment
99
of 1,2-diphenyl-1,2-azaborolidine. The ir spectrum gave absorbances
at 3430 (w), 3250 (w), 3060 (s), 2950 (s), 288C (s), 1600 (s), 1490 (s),
1400 to 1440 (s, broad), 1300 (s), 1190 (m), 1150 (w), 1080 (w), 1050
(m), 1000 (m), 750 (s), 700 (s) cm."1.


139
102. G. L. Station, Ph.D. Dissertation, University of Florida,
April, 1964.
103. G. B. Butler and R. L. Bunch, J. Am. Chem. Soc., 71,
3120 (1949).
104. R. M. Washburn et al., Advances in Chem. Ser., 23, 102 (1959).
105. D. R. Nielsen and W. E. McEwen, J. Am. Chem. Soc., 79,
3081 (1957).
106. R. M. Washburn et al., Advances in Chem. Ser., 23, 129 (1959).
107. M. F. Hawthorne, J. Am. Chem. Soc. 80, 4291 (1958).
108. T. P. Onak and R. E. Williams, J. Phys. Chem., 67(8),
1741 (1963).
109. R. L. Lukes and J. Trojanek, Coll. Czech. Chem. Comm., 32,
16, 603 (1951).
110. R. N. Keller and E. M. Vander Wall, Advances in Chem. Ser.,
32, 221 (1961).
111. Miao-hsun Li, Unpublished Results, University of Florida, 1973.
112. C. R. Rondestvedt, R. M. Scribner, and C. E. Wulfman,
J. Org. Chem., 20, 9 (1955).
113. W. Gerrard, The Organic Chemistry of Boron, Academic Press,
London (196lTTp- 202.


with deuterochloroform for analysis by nmr. The nmr spectrum exhibited
resonances at 51.7 (finely split, d, 2); 65.0 (finely split, t, 2)j and
55.8 (finely split, m,l). The mass spectrum showed a peak at 43, al
though the sample was very dilute. The reaction was allowed to continue
for 12 hours. The pale green reaction mixture was filtered and the fil
trate rotovaced to remove the xylene solvent. The remaining viscous,
green liquid was placed in a 50 ml., round-bottomed flask and distilled
under vacuum on a spinning band column. The first fraction, 1.3 g.
(b.p. 50-54 C @ 0.15 mm.), gave spectra consistent with 3-deutero-l,2-
diphenyl-l,2-azaborolidine. The ir spectrum showed absorbances at 637
(m), 695 (s), 740 and 760 (d, s), 870 (m), 900 (w), 960 (w), 988 (w),
1003 (w), 1030 and 1044 (s, d), 1008 (m), 1112 (w), 1158 (m), 1188 (w),
1212 (w), 1233 (w), 1265 to 1350 (s, broad), 1415 (s), 1438 (s), 1480
and 1495 (s, d), 1600 (s), 2175 (s), 2880 and 2980 (broad, detailed), and
3060 (s) cm. \ The nmr spectrum exhibited resonances at 61.65 (d, 2);
62.0 (broad, m, 1); 53.75 (d, 2); and 67.15 (m, 10). This compound
decomposed to a white, insoluble solid (rn.p. 90-100 C).
The third and fourth fracti.ons, 1.8 g. (b.p. 64-6 8C @ 0.15 mm.),
were recrystallized from hot ethanol yielding a white crystalline com
pound (rn.p. 77-79 C). The residue from the distillation flask was also
recrystallised from hot ethanol to give 3.2 g. of white crystals (rn.p.
78-79 C). Spectral data and the elemental analysis confirmed the assign
ment of 3,7-dideutero-l,5-d.iphenyl-l-aza-5-borabicyclo(3.3.0)octane. The
ir spectrum exhibited absorbances at 690 (s), 718 (m), 730 (m), 745 (m),
765 (s), 802 (w), 825 (w), 865 (s), 903 and 912 (d, m), 985 (s), 1000
(w, shoulder), 1029 (s), 1085 (s), 1100 (m), 1133 (m), 1160 (w), 1168
(m), 1185 (s), 1200 (s), 1225 (m), 1245 (s), 1273 (s), 1299 (w), 1328 (m)


ACKNOWLEDGEMENTS
I wish to express my gratitude and appreciation to Dr. G. B. Butler
for his patience, guidance, and understanding during the course of this
research. My appreciation is also extended to Dr. T. E. Hogen Esch, Dr.
Paul Tarrant, Dr. Martin Vala, and Dr. Henry C. Brown for serving on my
supervisory committee.
Grateful thanks are extended to my colleagues in the laboratory for
their frienship and good humor, which made work quite enjoyable.
Tire financial assistance received from the National Science Founda
tion is gratefully acknowledged (grant number GH32766 and GH17926).
I also wish to thank my parents for their support .and encouragement
during iny graduate studies.
A special expression of gratitude goes to my wife, Pat, for her love,
encouragement, and assistance in completion of this project.


and 3-deuteropropene. These products were consistent with one of the
proposed mechanisms, a concerted, facile elimination of propene. This
4 i
elimination mechanism was supported by model studies of the transition
states.
Triethylamine-phenylbcrane was reacted with N,N-di~3-butenylaniline
to give l,2-diphenyl-l-(3-butenyl),2-hydro-azaboracyclohexane and 1,6-
diphsnyl-1-aza--borabicyclo(4.4.0)decane. No butene gas was eliminated,
giving further support for the proposed mechanism.
Several substituted derivatives of 1,5-diphenyl-l--aza-5-borabicyclo-
(3.3.0)octane were prepared. The B--N coordinate bonds in these compounds
were studied by nuclear magnetic resonance., nuclear magnetic resonance,
infrared spectroscopy, and differential scanning calorimetry. The 1 *3
chemical shifts in these cciapounds varied from 2.2 to 6.0 p.p.m. relative
to trims thy .lb or ate. The B-N coordinate bonds exhibited absorb anees near
-1
1275 cm. Temperatures for the dissociation of the boron-nitrogen coor
dinate bond, determined by differential scanning calorimetry appeared to
be near 520 K. The heats of dissociation of the B-N bond for bis-1,4-
[5-C4-methyIpheny1)-l-aza-5-borabicyclo(3.3,0)octyljbenzeue, and bis-1,4-
[5- (4-chlorophenyl)-l-aza~5-borabicyclo(3.3.0)octyl]benzene were calcu
lated to 28.5 kcal/mole and 30.3 kcal/mole, respectively.
Several substituted derivatives of .1,5~diphenyi~i-aza-5-borabicy-cla~
(3.3.0)octane were prepared which are excellent monomer precursors for
condensation polymerization.
viii


131
Reaction of N,N-di-3-butenylaniline with triethylarnine-phenylborane
N,N-di-3-butenylaniline (11.2 g., 0.056 mol.), triethylarnine-
phenylborane (14.1 g. 0.072 mol.) and 500 ml. of p-xylene were
placed in a 1-liter, 3-necked flask equipped with a magnetic stirrer,
nitrogen inlet tube, and cold-water condenser. The temperature was
varied from 80 C to 110 C. A bright green color developed during
heating. Gas samples were taken at regular intervals for infrared
analysis. No butene gas was observed during the course of the reac
tion. The reaction was allowed to proceed for 24 hours. The resulting
solution was filtered, rotovaced, and divided into two portions. The
first portion of the viscous liquid was placed, on the spinning band
column for distillation. Four fractions were collected. The first
fraction, 0.8 g., proved to be unreacted N,N-di-3-butenylaniline (b.p
75 C @ 0.5 mm.). The third fraction, 1.4 g,, was assigned a struc
ture consistent with l,2-diphenyl-l-(3-butenyl),2-hydro-azaboracyclo-
hexane (b.p. 90-35 C @ 0.50 mm.). The ir spectrum exhibited absor
bances at 700 (s), 750 and 765 (double peak, s), 800 to 880 (w, d),
890 to 950 (m, detailed), 1995 (double peak, m), 1028 (m), 1150 (m),
1190 (m), 1325 to 1450 (broad, s), 1145 (m), 1500 (s), 1600 (s), 2300
(broad, m), and 2900 to 3100 (s) cm. 1. The nmr spectrum showed
resonance signals at 60.8 (m, 2); 51.65 (m. 6); 63.35 (m, 4); 55.1
(m, 0.5); and 67.4 (in, 12).
The second fraction, 1.2 g., was thought to be 12-diphenyl-
azaboracyclohexane. However, the spectral data and the elemental
analysis were not consistent with this assignment. The infrared
spectrum exhibited absorbances at 700 (s), 750 (s), 865 (w), 330
(m), 955 (w), 1000 (m), 1048 (in), 1065 (m), 1.120 (w), 1280 and 1300


130
Preparation of p-bromophenylbenzyl ether
Potassium carbonate (138.0 g.), benzoyl chloride (126.6 g., 1.0
mol.), and p-bromophenol (173.0 g., 1.0 mol.), and 400 ml. of acetone
were placed in a 3-necked, 1-liter, round-bottomed flask equipped with
mechanical stirrer and condenser. The contents were refluxed on a Glas
ed heating mantle for 8 hours. The solution was diluted with 300 ml.
of ether and then washed 3 times with 50 ml. portions of water and 2
times with 10% sodium hydroxide. It was then dried over sodium sul
fate, filtered, and rotovaced. The resulting white solid was re
crystallized from hot methanol yielding 221.4 g. (84%) of white crys
tals (m.p. 59-61C). The nmr exhibited resonances at 65.1 (s,2) and
57.1 (m,9).
Attempted preparation of p-benzyloxyphenylmagnesiumbromlde
Magnesium (21.9 g. 0.9 g. atoms) was placed with 200 ml. of dry
diethyl ether in a flamed, 3-necked, 1-liter, round-bottomed flask
equipped with mechanical stirrer, addition funnel with nitrogen inlet
and cold-water condenser with drying tube. The ether was refluxed
for 10 minutes cn a Glas-col heating mantle. p-3enzyloxypbenylbromide
(211.3 g., 0.8 mol.) in 400 ml. of dry diethyl ether and 20 ml. of
ethylene bromide was added. The reaction seemed very sluggish, even
with entrainment. Most of the magnesium metal did not react. A
second attempt with recrystallized p-benzyloxyphenylbromide and ether
distilled from lithium aluminum hydride yielded similar results.


2
Polyphenyleneoxadiazoles, polyphenylenetriazoles, polyphenylene-
thiazoles, and polybenzimidazoles have been shown to be capable of
forming thermally stable films and fibers.^ Another series of
thermally stable heterocyclic polymers, 2, was prepared by the conden
sation of 3,3'-diaminobenzidine with tetrabutyl esters of diboronic
a 12
acids.
R B
i3
3utler and Stackman demonstrated the high resistance of
cyclic polydiallyldiphenyl silanes, 3, to thermal degradation.
Pol"'
mars containing both heteroatom stability and "ladder stability U-xv
been prepared by the hydrolysis of phenyltrichlorosilane in an organ
15
solvent
4. r
Si
/
0
i \
! si
a
\
/
\
in recent years, a number of heteroatom ring and chain systems,
such as carbazeues, 4, borazenes, 5, phosphazsnes, 6, bcroxeaes, 7,
siloxaner- 3, and silazaues, 9. have shown remarkable thermal stability


Scheme VI
O?


50
(Figure 4). The nmr spectrum of _72 is given in Figure 5. Resonances
occur at 61.1 (m, 2); 62.15 (broad m, 1); 63.45 (m, 2); and the aromatic
resonance at 67.0 (m, 5). The mass spectrum gave a parent peak at
JL
265 -1, corresponding to the correct molecular weight. The analysis
agreed with structural assignment.
Anal. Caled, for ClgH20D2BN: C, 81.52; H, 7.60; D, 1.52; B, 4.08
and N, 5.28. Found: C, 81.74; B, 4.20; and N, 5.18.
D. Preparation of 3-Deuteropropene by Alternate Method
To cast aside any lingering doubts as to the identity of the
isolated gas, 3-deuteropropene was prepared by an alternate method.
The infrared and nmr spectra were compared.
Allylmagnesium bromide was added to deuterium oxide in a small
flask equipped with a gas outlet. Gas samples xvere trapped in an
infrared gas cell. Samples for the nmr were obtained by liquefying
the gas in a trap, cooled by dry ice-isopropanol, and mixing with
deuterochloroform.
Tlie infrared and nmr spectra were identical to those of the
3-deuteropropene, obtained from the reaction in Scheme VIII.
E. Preparation and Reactions of p-Substituted 1,5-I>ipheny 1-1-aza- '
5-borabicyclo(3.3.0)octanes
The next goal was the synthesis of a series of substituted 1,5-
diphenyl- l-aza-5-borabicyclo(3.3.0)cctanes which would have functional
groups in the para-positions of the phenyl rings capable of conversion
to monomers.


137
59.
M.
F.
Hawthorne,
J.
Am.
Chem.
Soc. ,
80,
4291
(1958).
60.
M.
F.
Hawthorne,
J.
Am.
Chem.
Soc. ,
83,
831
(1961).
61.
M.
T?
L
Hawthorne,
J.
Am.
Chem.
Soc. ,
83,
4293
(1958).
62.
M.
F.
Hawthorne,
J.
Am.
Chem.
Soc. ,
81,
5836
(1959).
63.
M.
F.
Hawthorne,
J.
Org.
. Chem
., 22,
1001 (1957).
64. E. C. Ashby, J. Am. Chern. Soc., 81, 4791 (1959).
55. Vi. Girrard, Organic Chemistry of Boron, Academic Press,
London (1961), p. 155.
66. H. C. Brown, Hydroboration, W. A. Benjamin, Inc., New York
(1962), p. 13:
67. R. Koster, Angew, Chern.,72, 626 (1960).
68. R. Koster, Angew. Chern., 71, 520 (1959).
69. M. F. Hawthorne, J. Am. C'nem. Soc., 8_2_, 748 (1960).
70. M. F. Hawthorne, J. Am. Chern. Soc. 83, 2541 (1961).
71. H. C. Brown, J. Chern. Soc., 1243 (1956).
72. E. Wiberg, K. Hertwig, and A. Bolz, Z. Anorg. Allgem. Chern. ,
256, 177 (1943).
73. B. M. Mikhailov and F. B. Tutorskaya, Izv. Akad. Nauk. SSSR
Otd. Khim. Nauk., 1158 (1961).
74. B. M. Mikhailov, V. A. Dorokhov, Pi~oc. Acad. Sci. USSR,
13_8_, 51 (1961).
75. R. F. Gould, "Boron-Nitrogen Chemistry, Advances in Chemistry"
Ser. 42, ACS (1964).
76. R. J. McManimie, U, S. Pat. 2,909,550, 1959 .
77. H. C. Brown, E. A. Fletcher, J. Am. Chern. Soc. 73, 2808 (1951).
78. T. P. Onak, R. E. Williams, H. Landesinan, and I. Shapiro,
J. Phys. Chem., £3, 1533 (1959).
79. C. A. Luchesi, Univ. Microfilms Publ. No. 13, 109; Dissertation
Abstr., 15_, 2007 (1959); Ph.D. Thesis, Northwestern Univ., D. D.
DeFord, 955.
C. A. Lucchesi and D. D. DeFord, J. Inorg. and Nucl. Chern., 14,
290 (1960).
80.


Ill
absorbances at 3350 (broad, s), 2900 to 3050 (s, detailed), 1605 (s),
1570 (in), 1520 (w), 1473 (m), 1320 to 1440 (broad, s), 1285 (s), 1250
(s), 1185 (in), 1155 (s), 1118 (in), 1098 (m), 990 to 1045 (broad, s),
918 (m), 845 (m), 805 (s), 733 (m), 645 (m), and 620 (m), cm. 1. The
nmr spectrum gave resonance signals at 56.85 (d, 4); 54.05 (quartet,
2); 52.85 (s, 2); and 51.35 (t, 3). The mass spectrum showed a parent
peak at 166 1.
Anal. Caled, for CoH-,0.B: C, 57.89; H, 6.68; 0, 28.92; and B,
6,52. Found: C, 57.63; H, 5.41; and B, 6.26.
Preparation of p-ethoxy-dlethylphenyiboronate
p-Ethoxyphenylboronic acid (148.0 g. 0.24 mol.), ethanol (148.0 g.),
and 300 ml. of benzene were placed in a 1-liter, round-bottomed flask
equipped for azeotropic distillation with a Bean-Stark trap, condenser,
and fractionating column. The mixture was heated on a Glas-col heating
mantle. The solution was heated to reflux and water was removed as
it formed in the side arm. The reaction was allowed to proceed for 4
days until no more water separated in the trap. The remaining solvent
was removed on a rotary evaporator. The crude ester was distilled
yielding 21.2 g. (40%) of a clear liquid (b.p. 130-135 C @ 0.15 mm.).
The ir spectrum exhibited absorbances at 3105 (w), 3050 (w), 2997
(s), 2930 (doublet, s), 2890 (shoulder, m), 1604 (s), 1580 (m), 1510 (m),
1432 (m), 1423 (s), 1375 (s), 1320 (s, broad), 1280 (m, broad), 3245 (s),
1180 (s), 1128 (s), 1043 (s), 922 (m), 902 (m), 838 (m), 810 (m), 755
(w), and 735 (m) cm.
The nmr spectrum gave resonance signals at 57.2 (quartet, 4); 54,0
(m, 6); and 51.25 (m, 9).


115
signals at 57.05 (in, 8); 63.2 (m, 4); 62.1 (m, 4); and 61.15 (m, 4).
The mass spectrum gave a parent peak at 421 tl.
Anal. Caled, for c18h20BNBiV C, 51.35; H, 4.78; B, 2.57; N,
3.33; and Br, 37.96. Found: C, 51.89; H, 4.74; and Br, 37.96.
The reaction of 1,5-diphenyl-l-aza-5-borabicyclo(3.3.0)octane with
n-butyllithium
1.5-Diphenyl-l-aza-5-borabicyclo(3.3.0)octane (0.5 g., 0.0019
mol.) was dissolved in 30 ml. of diethyl ether in a 50 ml., round-
bottomed flask. The flask was placed in the dry-box and then stopper
ed with a rubber serum cap. The flask was cooled to -70 C in a dry
ice-isopropanol bath. n-Butyllithium (1.0 g., 0.004 mol.) was added
through a syringe, while the contents were stirred with a magnetic
stirring bar. Approximately 1/2 of the resulting yellow solution
was hydrolyzed with dilute hydrochloric acid. The organic material
was extracted with ether, dried over sodium sulfate, and rotovaced.
The nmr spectrum indicated that starting material was recovered.
However, only 0.08 g. was recovered. The remaining 1/2 of the yellow
liquid was poured over crushed dry ice and then hydrolyzed with dilute
i
hydrochloric acid. The nmr and ir showed a complex mixture of products.
This result seem to indicate this method is impractical for formation
of the dicarboxylic acid derivative from the bicyclic compound.
Attempted preparation of the bis-Grignard reagent of l,5-bis-(4-bromo-
pnenyl )-l-aza-5 -borabicyclo (3.3.0.) octane
1.5-Bis-(4-bromophenyl)-l-aza-5-borabicyclo(3.3.0)octane (0.33 g.,
0.0066 mol.) was dissolved in a small portion of dry diethyl ether
and placed in an addition funnel.- Magnesium (0.02 g., 0.049 g. atoms)


unreacted p-methyl-N,N-diallylaniline. The third fraction (b.p.
160-180 C @ 0.250 mm.) and fourth fraction (b.p. 190-195 C @
0.250 mm.) gave identical ir spectra. Thin layer chromatography
on silica gel with benzene as the solvent showed the presence of
2 compounds. The combined fractions and the residual material in
the distilling flask were chromatographed on a 45 cm. long by 2
cm. diameter silica gel column. Several fractions were collected.
Each of these fractions was tested by thin layer chromatography.
The above procedure proved to be an excellent method for purifying
the 1,5-bis-(4-methylphenyl)-l-aza-5-borabicycio(3.3.0)octane.
The other material in the distillate apparently reacted with the
silica gel column and passed only sluggishly through the column,
if at all. A brown discoloration was observed near the top of the
column. The first 8 fractions off the column wTere combined and
the solvent removed. The residual material was recrystallized
from hot ethanol yielding 6.5 g. of white, flaky crystals (m.p.
107-108 C). The ninr, ir, and mass spectra confirmed the assign
ment of the bicyclic structure. The ir spectrum showed absorbances
at 670 (s). 710 (w), 725 (w), 750 (w), 790 (s), 805 (s), 82C (m),
843 (w), 892 (s), 922 (m), 935 (w), 963 (m), 995 (m), 1018 (m),
1014 (in), 1058 (m), 1100 (w), 1130 (s), 1150 (in), 1162 (m), 1180
(s), 1238 (m), 1257 (m), 1275 (s), 1310 (m),- 1368 (w), 1395 (w),
1430 (m), 1450 (s), 1470 (m), 1480 (w), 1510 (s), 1608 (in), 1900
(w), 2850 (m), 2922 (s), 2950 (s), 2975 (m), 2998 (m), 3020 (m),
1
3040 (m), and 3080 (w) cm. x. The nmr gave resonances at 65.8 (m,
8); 3.4 (m, 4); a broad multiplet with superimposed methyl absorp
tion at 62.1 (m, 10); and a broad signal at 1.1 (m, 4). The mass


121
aniline (20.3 g., 0.10 mol.) was added to the solution. The mixture
was stirred magnetically and heated on a Glas-col heating mantle.
Gas samples were taken at intervals over various temperature ranges.
These were then characterized by infrared spectroscopy. Samples at
57, 60, and 68 C showed only triethylamine and toluene. Comparisons
were made to the Standard Sadtler Spectra. At 71 C, propene gas was
evolved. The ir spectrum showed absorbances at 912 (broad, spiked, s),
930 (s), 1043 (w), 1070 (m), 1380 (m, shoulder), 1445 and 1470 (d, s),
1635 and 1663 (d, s), 1315 and 1840 (d, m), and at 2860 and 3000 (d,
detailed, s) cm. \ This spectrum matched that of propene (#6403) in
the Standard Sadtler Spectra. Samples at 77 C showed moderate amounts
of propene. At 88 and 90 C, increasingly large amounts of propene
were detected. Since the threshold temperature for propene evolution
appeared to be 71 C, the reaction was allowed to proceed at 68 C for
4 hours. The resulting yellow solution was cooled and filtered. The
filtrate was saved for further work-up. A white, waxy material, 1.2
g., was obtained from the filtration. A medium filter was required
to remove all of the suspended material. On heating, this compound
lost solvent, softened at 100 C, and melted at 230-232 C. The
spectra for this compound were identical with those reported for tri-
(p-methoxyphenyl)cyclotriboroxene.
The filtrate from the reaction mixture was passed through a 30 cm.
by 5 cm. column of neutral silica gel. The top of the column darkened
as the filtrate was introduced. The eluted solution was collected in
a 500 ml., Erlenmeyer flask. After 1 hour at room temperature, a white
material began to precipitate. This material, 1.2 g. (m.p. 95-97 C),
was filtered and characterized nmr and ir. The ir spectrum gave ab-


102
only an aromatic quartet at 57.6. The mass spectrum gave a parent
peak at 415 tl.
Anal. Caled, for C gH BgO^Clg: C, 52.06; H, 2.92; B, 7.82;
and Cl, 25.64. Found: Analysis #1: C, 49.95; H, 3.17; B, 7.43;
and Cl, 24.63. Analysis #2: C, 49.93; H, 2.76; B, 7.85; and Cl,
26.21.
An identical compound was synthesized by heating p-chlorophenyl-
boronic acid at 200 C in a vacuum of 0.025 mm. for 8 hours and re
crystallizing from chloroform.
Tri(p-methylphenyl)cyclotriboroxene
A white, powdery material was recovered from the flask following
the distillation of diethyl p-tolylboronaxe. An identical product
was synthesized by heating 1.5 g. of p-methylphenylboronic acid to
200 C under vacuum, Infrared, nmr, and mass spectra confirmed the
assignment of tri(p-rnethylphenyl)cyclotriboroxene. The ir spectrum
showTed absorbances at 680 (s), 710 (s), 732 (s), 818 (m), 1023 Cm),
1083 (m), 1112 (m), 1183 (s), 1210 (w), 1300 to 1400 (broad, s). 1405
(s), 1518 (m), 1563 (w), 1613 (s), 2880 to 3100 (broad, s, detailed),
and 3300 (broad, to) cm. \ The nmr showed an aromatic quartet cen
tered at 57.7 (q, 12) and a singlet at 52.4 (s, 9). The compound
melted at 264-265 C. The mass spectrum gave a parent peak at 353 _1.
Anal. Caled, for C, 71.3; H, 5.98; and B, 9.20.
Found: C, 69.3; H, 6.12; and B, 9.5-'-'.


88
Synthesis of p-chloro-phenyiboronic acid
Magnesium turnings (36.4 g. 1.5 g. atoms) were placed in a 2-liter,
3-necked, round-bottomed flask equipped with mechanical stirrer, con
denser with drying tube, and a 500 ml. addition funnel. Dried diethyl
ether (50 ml.) was added and the mixture refluxed for 15 minutes. p-Bromo-
chlorobenzene (287.1 g., 1.5 mol.), dissolved in 1 liter of dried diethyl
ether, was added dropwise after the initial reaction had started. After
complete addition, the mixture was refluxed for an additional 30 minutes.
The resulting Grignard reagent was filtered through glass wool into a 500
ml. addition funnel. Trimethylborate (155.8 g., 1.5 mol.) and 1 liter
of dry diethyl ether were placed in a 3-liter, 3-necked, round-bottomed
flask equipped with mechanical stirrer, low-temperature thermometer, and
Claisen adapter for an addition funnel and nitrogen inlet tube. The
solution was cooled to -70 C in a dry ice-isoprcpanol bath ana the
Grignard reagent added dropwise with stirring. Nitrogen flow was main
tained throughout the system during the course of the addition. The
temperature was kept below -65 C. The solution was allowed to warm to
room temperature overnight with continuous stirring. The resulting
mixture was hydrolyzed with a 15% sulfuric acid solution. The temperature
was controlled by cooling the flask in an ice bath. The two resulting
layers were separated in a 2-liter separatory funnel and the aqueous
layer discarded. The ether layer was then placed in a 3-liter, 3-necked,
round-bottomed flask equipped with mechanical stirrer, addition funnel,
Claisen distilling head, condenser, and heating mantle. The ether layer
was slowly distilled while adding water dropwise. When the temperature
at the distilling head reached 98 C, the hot solution was transferred
to a 2-liter Erlenmeyer flask and allowed to cool. Approximately 1500


17
The B-N coordinate bond in the bicyclic compound, _45, was believed
responsible for a strong infrared absorbance at 1266 cm. \ The
azaborclidine, ^4, showed strong peaks at 1512 cm. ^ which were at
tributed to the ii= bond. resonance signal in the nmr spec
trum of 44 was recorded at -23 p.p.m. and of 45 at 8.9 p.p.m. rela
tive to trimethylborate.
99
In 1965 Butler and Station reported the preparation of four
substituted l-aza-5-borabicyclo(3.3.0)octanes and four previously
unreported 1,2-azaborolidines. These compounds were prepared by the
reaction of trie thy lamine-phenylborane with tertiary d.i ally lamines.
A mechanism for the reaction was proposed based on qualitative data
which involved the cleavage of an allylic carbon-nitrogen bond. Two
of the 1,2-azaborolidines were also prepared by the reaction cf tri-
ethylamine-phonyibcrane with secondary allylamines. The l-aza-5-
bcrabicyclo(3.3.0)octanes exhibited strong infrared absorption bands
at 1250-1270 cm. a which were assigned to the B-N coordinate bond.
Anew compound, l-phanyl-l-bora-S-azoniaspiro(4.5)decane, 46, was
prepared as well as a telomer, 47.
t
A new bicyclic compound containing a B-P coordinate bond was
100
prepared having the following structure:


95
wise. The resulting brown solution was filtered through glass wool
to remove the unreacted magnesium and then placed in an addition
funnel fitted on a 3-liter, 3-necked, round-bottomed flask, equipped
with a mechanical stirrer, low-temperature thermometer, Claisen
adapter and nitrogen inlet tube. Trimethylborate (103.9 g., 1.0
mol.) was placed in the flask along with 800 ml. of dry diethyl
ether and cooled under nitrogen to -68 C in a dry ice-isopropanol
bath. The Grignard reagent was added dropwise with stirring. The
temperature was kept below -65 C during the addition. The result
ing mixture was allowed to warm up to room temperature overnight.
The white mixture was then hydrolyzed with 150 ml. of 30% hydro
chloric acid. At this point, the aqueous phase wTas clear. The
ether layer was separated, washed 3 times with 30 ml. portions of
water, and then placed-in a 3-liter, 3-necked, round-bottomed flask
fitted with a Claisen distilling head, condenser, mechanical stirrer,
addition funnel, and heating mantle. The ether solution was concen
trated by distillation and simultaneous dropwise addition of water.
After addition of 1 liter of water, the temperature at the distill
ing head had reached 98 C. The solution was transferred to 2 1000
ml. Erlenmeyer flasks and allowed to cool. Fluffy, white crystals,
42.7 g. (31%), ware isolated and washed with 3 10 ml. portions of-
hexane; this material gave a melting point of 255-257 C.
Synthesis of diethyl p-tolylboronate
p-Methylphenylboronic acid (36.C g., 0.264 mol.), benzene (200 g.),
and ethanol (46.0 g. 1.0 mol.), and a catalytic amount of sulfuric
acid were placed in a 1-necked, 1-liter, round-bottomed flask. An


reaction solution turned a pale blue. Upon further addition, the
color deepened to a magnificent, deep blue. The color gradually
changed to green and then yellow as the addition continued. Gas
samples were taken and studied by infrared as the temperature was
regulated. From 50 to 80 C, no propene gas was detected. At 85-
95 C, large amounts were evident. The reaction was allowed to
proceed at 80 C for 2 hours and then the contents were cooled.
The solvent was removed on a rotary evaporator. A white, insoluble
compound was filtered from the solution. This compound proved to
be tri(p-chlorophenyl)cyclotriboroxene. The remaining viscous liquid
was dissolved in benzene. Thin layer chromatography showed at least
four reaction products. A column 45 cm. by 2.2 cm. was prepared
from silica gel in'benzene. Approximately 1/4 of the solution was
placed on the column; 10 ml. samples were collected. The desired
product was eluted from the column in the first few fractions. These
were tested by thin layer chromatography, combined, and concentrated.
The residue was dissolved in a small amount of acetone and recrystallized
by cooling in a dry ice-isopropanol bath. Filtration yielded 2.8 g. of
white, needle-like crystals (m.p. 198-200 C).
The complicated infrared spectrum showed absorbances at 665 (s),
700 (w), 718 (w), 765 (m), SCO (s), 833 (m), 900 (s), 955 (m), 973 (m),
1012 (s), 1025 (w), 1055 (m), 1085 (s), 1135 (s), 1165 (s), 1185 (w),
1230 (s), 1260 (s), 1272 (s), 1300 (m), 1342 (w), 1381 (m), 1427 (m),
1463 (s), 1480 (s), 1510 (s), 1575 (w), 2840 (m), 2900 (m), 2937 (s),
2980 (m), 3015 (m), 3030 (s), and 3150 (w) cm. "L.
The nmr spectrum exhibited resonances at 61.05 (m, 8); 62.05 (m, 8);
53.23 (t, 8); 66.60, 66.95, and 67.22 (three singlets, total area = 12).


116
and 15 ml. of dry diethyl ether were placed in a 50 ml., round-bot
tomed, 3-necked flask equipped with a dry ice condenser, nitrogen
inlet tube, and.addition funnel. The mixture was heated and stirred
for 10 minutes. A few ml. of the bicyclic compound were added, along
with a small crystal of iodine. This procedure failed to initiate
the reaction, so an entrainment procedure was used. Ethylene dibro
mide (2.0 g.) was dissolved in 20 ml. of diethyl ether and then added
dropwise to the refluxing solution at a very slow rate. After 2
hours, a syrupy layer formed in the flask. The reaction was allowed
to continue for 8 hours with stirring. The excess magnesium was
removed by filtration. Carbon dioxide gas was bubbled into the flask.
Finally, crushed dry ice was added. A brown solid precipitated. This
material was carefully acidified with 10% hydrochloric acid. The two
resulting layers were separated. Sodium chloride was added to break
the suspension. The ether layer was dried over sodium sulfate. The
ether was then removed on a rotary evaporator. The residue was analyzed
by nmr and ir. The nmr spectrum gave resonance signals at 67.0 (m, 3);
53.4 (in, 4); 62.1 (m, 4); and two strong multiplets at 60.9 and 61.4
which have not been assigned. The ir spectrum exhibited absorbances at
3430 (broad, s), 3090 (w), 2860 to 2980 (s, broad), 1720 (s), 1600 (m),
1500 (w), 1450 (s), 1380 (w), 1280 (s, broad), 1230 (m), 1190 (w), 1140
(m), 1085 (w), 1038 (s), 990 (m), 900 (m), 790 (w), 740 (m), and 630
(s) cm.
Synthesis and Isolation of l-(p-methoxyphenvl),5-(p-ethoxyphenyl)-1-aza-
5-borabicyclo(3.3.0)octane
Triethylamine-(p-ethoxyphenyl)borane (16.6 g., 0.074 mol.) was
dissolved in 200 mi. of p-xylene and added to a 1-liter, 3-nec.ked,


7G
were continued overnight. The resulting liquid was poured through a
filter into a separatory funnel in which two layers formed. The lower
layer was discarded and the brown, oily layer was dried with sodium
sulfate. The crude p-chloro-N,N-diallylaniline was distilled under
vacuum yielding 300.4 g. (72.5%) of a colorless liquid (b.p. 85-86
C @ 0.350 mm.). Nmr and ir spectra agreed with the assigned structure.
Preparation of N,N-di-3-butenylaniline
Aniline (14.0 g., 0.15 mol.), sodium carbonate (32.0 g.), and
50 ml. of water were placed in a 250 ml., 3-necked, round-bottomed
flask equipped with a mechanical stirrer, addition funnel, and cold-
water condenser. The mixture was heated to a low reflux. 4-Bromobutene
(40.5 g., 0.30 mol.) was added dropwise with constant stirring. The
reaction was allowed to proceed for 24 hours. The contents were
cooled and filtered. The amine layer was separated, dried over sodium
sulfate, and distilled under vacuum. A clear, colorless liquid (11.2
g. 37%) was obtained (b.p. 74-75 C @ 0.100 mm.).
The ir spectrum exhibited absorbances at 695 (s), 748 (s), 915
(s), 992 (s), 1040 (w), 1100 (w), 1180 to 1220 (w, detailed), 1283 (m),
1360 (m), 1395 (w), 1420 (w), 1430 to 1460 (w, detailed), 1503 (s),
1600 (s), 1640 (m), and 2950 to 3050 (s, detailed, broad) cm.
The nmr spectrum gave resonance signals at 62.25 (quartet, 4);
63.3 (m, 4); 65.1 (m, 4); 65.8 (m, 2); and 66.8 (m, 5).
Synthesis of N,N,N*,N,-tetraallyl-p-phenylenediamine
p-Phenyienediamine (125.0 g., 1.15 mol.) and sodium carbonate
(530.0 g.) v?ere added to a 3-liter, 3-necked, round-bottomed flask
fitted with a Claisen adapter, thermometer, addition funnel, and


64
phenyl substituents on the bicyclic structure 109 should be reflected
in the boron-nitrogen bond strength and in the tetrahedral character
of this bond. The bicyclic structure, for which both x and are
chlorine atoms, gives a chemical shift of 2.2 p.p.m. When x is
chlorine and is hydrogen, the chemical shift is 5.2 p.p.m. This
may be interpreted as a result of the withdrawing effect of chlorine
increasing the electron deficiency of boron and, therefore, strength
ening the B-N coordinate bond. If x is hydrogen and y_ is bromine,
the chemical shift drops to 1.5 p.p.m. This effect is consistent
with a decrease in the basicity of the amine, thus decreasing the
B-N bond strength. Less reduction is noticed when x is hydrogen and
y is chlorine; this compound, 89, gives a chemical shift of 2,8 p.p.m.
In the dibromo-bicyclic compound, 97, electronic effects of the sub
stituents might be expected to cancel each other. The chemical shift,
3.1 p.p.m., is close to that of the unsubstituted compound, 63, at 3.6
p.p.m. The symmetrical bicyclic compounds 104 and 105 shot/ chemical
shifts of 4.4 and 4.7 p.p.m., respectively.
I. Temperature Studies b:y Differential Scanning Calorimetry
A Perkin-Elmer DSC-1B Differential Scanning Calorimeter was used
for studies of the B-N coordinate bona dissociation for all substituted
l,5-diphenyl-l-aza-5-borabicyclo(3.3,0)octanes which were prepared.
Samples were weighed and then placed in special sample holders to
reduce volitalization. Temperature scanning increments were set at 20
Melting points were easily observable and served a-
ner minute.


BIBLIOGRAPHY
1. R. J. Angelo, Polymer Preprints, 4, 32 (1963).
2. S. locker, J. Am. Chem. Soc., 85, 640 (1963).
3. N. G. Gaylord, I. Kessler, M. Stolka, and J. Vodehnal, J. Am.
Chem. Soc., 85, 64 (1963).
4. N. G. Gaylord et al. Polymer Preprints, 4_, 69 (1963).
5. I. Kossler, M. Stolka, and K. Mach, International Symposium on
Macromolecular Chemistry, Paris, July, 1963.
6. Y. G. Kryazhev, T. I. Yushmanova, and L. I. Borodin, Vysokomol.
Soedin., Ser. B, 12(7), 487 (1970).
7. H. R. Allcock, Heteroatom Ring Systems and Polymers, Academic
Press, New York (1967), p. 273.
8. Proceedings, Conf. on High Temp. Polymer and Fluid Research, I_,
1, 8, 89, and 312, Dayton, Ohio, 1962.
9. Polymer Preprints, 4(2). 1-5, 6-14 (1963).
10. C. L. Segal, High Temperature Polymers, Marcel Dekker, Inc.,
New York, N. Y. (19677.
11. Polymers in Space Research Symposium, Jet Propulsion Laboratory,
California Institute of Technology, July, 1968.
12. J. E. Mulvaney, J. J. Bloomfield, and C.S. Marvel, J. Poly. Sci.
62_, 59 (1962).
13. G. B. Butler and R. W. Stackman, J. Org. Chem., 25, 1643 (1950).
14. Proceedings, Conf. on High Temp. Polymer and Fluid Research, 1_,
53-72, Dayton, Ohio, 1962.
15. J. F. Brown, I. L. H. Vogt, I. A. Katchman, J. W. Eustance, K. M
Riser, and K. W. Krantz, J. Am. Chem. Soc., 82, 6, 194 (1960).
16. A. D. Delman, J. Hacromol. Sci. C3(2). 1 (1969).
17. J. L. Speier, U.S. Patent 3,445,425, May 20, 1969.
134


44
bicyclic product, 84. A concerted elimination, with deuterium
adding to the terminal end of the double bond in intermediate ^1
and the ensuing electron shifts, would yield the mono-deuterated
azaborolidine, £!2, and 3-deut:eropropene, 83.
The expected Hofmann elimination mechanism is shown in Scheme
IX. The triethylamine in solution would attack the dideutsrated
l,5-diphenyl-l-aza-5-borabicyclo(3.3.0)octane, 84, at a hydrogen
atom or deuterium atom on the beta-carbon to the quaternary nitro
gen. Abstraction of a proton should be slightly favored over
deuterium abstraction, due to an isotope effect. Intermediate 85
could then undergo thermal cleavage to give the mono-deuterated
azaborolidine, 82_, and 2-deuteropropene. If a deuterium were
abstracted rather than a proton, propane gas would be generated.
Triethylamine-dideuterophenylborane was prepared by reducing
diethyl phenylboronate with lithium aluminum deuteride in ether
with triethylamine at low temperature. The triethylamine-dideutero-
borane crystals (m.p. 64-65 C) were characterized by mass spectral,
nrar, ir and elemental analyses. The infrared spectrum showed a
1
broad boron-deuterium absorbance at 1680 to 1765 cm. J.
N,N-Da.llylan 1 line was added to an equimolar quantity of the
triethylamine-dideuterophenylborane in p-xylene. The reaction
vessel was provided with a gas outlet, which was attached to an
infrared gas cell and, in turn, to a dry ice-isopropanol gas trap.
Several gas samples were taken at various temperatures. Above
95 C deuteropropene gas was evolved, The infrared spectrum is
given in Figure 2. The absorbance at 2175 cm. ~ was consistent:
with that expected for the allylie carbon-deuterium stretching


Scheme VIII
DCH2-CH-CH2
83
X
p
K)


67
azaboracyclohexane, 113, should not be formed by a concerted
mechanism as was the case for the azaborolidines in our previous
studies (Scheme X). This compound could, however, conceivably be
formed by the pyrolysis of intermediate 111 at high temperature
under vacuum. The elimination could be tested, as before, by
monitoring gases produced from the reaction in p-xylene. If the
competing pathway 1 were followed at the reaction temperature,
butene gas would be detected. If only pathway wTere followed,
the bicyclic compound should be formed in relatively higher yield.
This higher yield, obviously, would be more attractive for monomer
preparation than the yields obtained for the 1,5-diphenyl-1-aza-
5-borabicyclo(3.3.0)octanes.
N,N-Di-3-butenylaniline, triethylamine-phenyiborane, and p-
xylene were slowly heated under nitrogen. Gas samples were taken
at various temperatures and time intervals. A bright green color
developed during the course of the reaction, but no butene gas was
evolved during heating. The resulting solution was filtered, roto-
vaced, and divided into two portions. The first portion was then
dissolved in benzene and passed through a neutral silica gel column.
The eluted solution was rotovaced. A white, gummy material was
obtained. This was recrystallized from ethanol to give whits
crystals (m.p. 143-145 C). The compound was consistent with the
structure assigned to l,6-diphenyl-l-aza-6-borabicyclo(4.4.0)decane.
The mass spectrum gave a parent peak at 291 1. The infrared spectrum
gave a broad absorbance at 1280 cm. consistent with that expected
for the B-N coordinate bond. The nmr spectrum exhibited resonance


TABLE 4. SPECTRAL DATA OF SUBSTITUTED
1,5-DIPHENYL-l-AZA-5-30RABICYCL0(3.3.0.)OCTANES
Compound
lln(t ,
tss< (p.p.m.J
NMR
IR (cm. 1)
Mass Spectrum
Number
Chemical Shift
Chemical Shift (5)**
Areas
B-N Absorbance
Parent Peak
6.85
9.8
1
63
3.6
3.3
4.0
1275
263 1
2.1
4.0
1.1
4.1
7.0
10.4
84

3.45
4.0
1273
265 1
2.15
2.0
1.1
4.0
6.9
9.2
87
1.9
3.3
4.0
1270
342 1
2.05
4.2
1.1
4.0
7.0
9.0
89
2.8
3.3
4.0
1270
297 1
2.05
4.2
1.1
4.0
7.0
9.1
91
5.2
3.3
4.0
1280
297 1
2.05
4.0
1.05
4.1
7.2
8.2
93
2.2 ,
3.4
4.0
1275
332 1
2.15
4 .0
1.15
4.0
* Chemical shift relative to trirnethyl borate
** Chemical shift relative to tetramethyisilane in deterochloroform


65
excellent calibration marks. At higher temperatures, sublimation of
the samples occurred. No decomposition peaks were observed prior to
sublimation, showing the remarkable stability of these relatively
heavy compounds. A broad endotherm appeared in all spectra beginning
at 520-540 K. This temperature seemed to be consistent with that
expected from B-N coordinate bond dissociation. However, the peak
area could not be measured due to volitalization of the sample,
beginning at a slightly higher temperature.
The bis-1,4-[5~(4-methylphenyl)-l-aza-5-borabicyclo(3.3.0)octyl]-
benzene, 104, and the bis-1,4-[5-(4-chlorophenyl)-l-aza-5-borabicyclo-
(3.3.0)oct7/lJbenzene} 105, were much better models for the temperature
studies. These compounds sublimed at a much higher temperature and
allowed the observance of endotherms which seemed consistent with
those expected for the boron-nitrogen bond dissociation. Broad,
double peaks were observed beginning at 532 K and ending at 617 K
for compound 104. Sinn lar peaks were observed for compound 105
beginning at 541 K and ending at 627 K. The heat of this transition
for compound 104 was calculated to be 60 cal./g. or 28.5 kcal./mole.
Compound JL05 gave a value of 58.2 cal./g. or 30.3 kcal./mole. These
values are very close to those predicted by Butler.
J Synthesis of 1.6-Diphenyl-l-aga-6-borabicyclo(4.4.0)decane
The final synthetic effort in this research was an extension
of the hydroboration by triethylamine-phenylborane of N,N-di-
3-butenylaniline, 110. This reaction would be expected to yield
l,6-diphenyl-l-aza-6-borabicyclo(4.4.0)decane, 114. 1,2-Diphenyl-


3.9
by infrared, B nuclear magnetic resonance, and proton magnetic
resonance. The B-N bond dissociations for the various compounds
could be followed by differential scanning calorimeti'y. These
studies should have important meaning when extended to polymeric
systems.
Another important objective was the study of the. stability
of these compounds to various conditions necessary for introducing
functionality for monomer formation.
The ultimate objective of the boron research in these labora
tories is the incorporation of the bicyclic structure into several
thermally stable polymeric systems, 51.
These polymers should have some interesting properties. Thermal
dissociation of the dative bends along the polymer backbone could
occur without cleavage of the polymer chains, allowing the polymer
chain to "breathe" or function like bellows. This cleavage should
result in an increase in the degree of freedom along the longitudinal
axis of the polymer chain, and should imp art additional elasticity
to the polymer.


53
Preliminary studies of the l,5-diphenyl-l-aza-5-borabicyclo(3.3.0)-
octane showed the stability to boiling water, dilute mineral acids, tri-
ethylamine, and dilute sodium hydroxide. The compound was not stable
to peroxides in sodium hydroxide or strongly acidic conditions. Oxi
dizing conditions with bromine in acetic acid destroyed the bicyclic
structure.
Carbon-boron bond cleavage has been reported to occur with n-butyl-
113
lithium, bromine, peroxides, and acetylchloride in pyridine.
Several previously unreported, substituted 1,5-diphenyl-l-aza-5-
borabicyclo(3.3.0)octanes were prepared along with their monocyclic
by-products. These are listed in Table 2. Each synthesis involved
essentially the same procedures as were outlined for the model com
pounds. Some modifications were, however, necessary in nearly every
case due to the new functional groups. The average time required for
synthesis and isolation of each pair of bicyclic and monocyclic com
pounds was approximately 4 to 5 weeks. Physical properties, nmr, ir,
mass spectra, and elemental analyses are given in Tables 3 and 4 for
the bicyclic compounds. The details of each synthesis are given in
the experimental section and will not be repeated in this chapter.
Instead, the preparation of l,5-bis-(4-ehlorophenyl)-I-aza-5-borabi-
cyclo(3.3.0)octane, 93, and l,2-bis-(4-chlorophenyl)-l,2-azaborolidine,
94, will be presented to give the reader an idea of the approach to
synthesis, separation, work-up, and analysis of these compounds.
Trzetnylamine-(p-chloro)phenylborane was dissolved in a large
volume of toluene in a round-bottomed flask under nitrogen. The
contents were heated to 55 C, and then the p-chloro-N,N-d:Laliyl-
aniline was added dropwise to the stirring mixture. As the reaction


90
The ir spectrum showed absorbances at 3100 (w), 3050 (w), 2930
(s), 2345 (s), 2920 (s), 1920 (w), 1660 (w), 1593 (s), 1563 (m),
1487 (s), 1430 (s), 1415 (s), 1375 (s), 1325 (broad, s), 1280 (s),
1258 (s), 1175 (w), 1127 (s), 1100 (s), 1087 (s), 1040 (s), 1018 (s),
904 (s), 820 (s), 725 (s), 650 (s), and 625 (s) cm.-1.
The nmr spectrum showed resonances at 67.4 (quartet, 4); 64.0
(quartet, 4); and 51.24 (t, 6).
Synthesis of triethylamine-(p-chlorophenyl)borane
Lithium aluminum hydride (5.32 g. 0.14 mol.) was added to 600
ml. of dry diethyl ether in a 1-liter, 4-necked, round-bottomed flask
equipped with mechanical stirrer, condenser with drying tube, addition
funnel with nitrogen inlet tube, and low-temperature thermometer. The
mixture was refluxed for 30 minutes on a heating mantle and then
cooled to -70 C in a dry ice-isop'ropanol bath. Triethylamine (28.6
g., 0.28 mol.) was added with stirring. The system was flushed with
nitrogen; diethyl p-chlorophenylboronate (58.9 g., 0.28 mol.) was added
dropwise. The temperature was kept belev/ -55 C. The mixture was
then filtered through a sintered-glass funnel. A watch-glass was
placed over the funnel mouth to prevent evaporation of the ether. The
filtrate was concentrated and then cooled in a dry ice-isopropanol- bath,
resulting in the precipitation of a white crystalline substance. The
material, 47.7 g. (75%), was filtered and dried yielding white, needle
like crystals (m.p. 63-54 C).
The ir spectrum exhibited absorbances at 3080 (w), 3000 (s), 2950
(s), 2980 (m), 2360 (broad, s), 1910 (w), 1798 (w), 1660 (w). 1578 (s),
1475 (s), 14S0 (m), 1420 (w), 1380 (s), 1345 (rn), 1300 (s), 1288 (w),


63
tried, but swelled to a gel-like material in acetone after several
weeks. The material appeared to be cross-linked, as might be
expected by examination of the above equation.
11
H. ~Boron Nuclear Magnetic Resonance Studies
nmr spectra were obtained for the substituted bicyclic
compounds listed in Table 4. The chemical shifts in chloroform
were measured in p.p.m. relative to trimethylborate by a Varian
XL-100 instrument. The chemical shift values varied from 1.9 to
5.2 p.p.m. for the compounds studied. These shifts are very close
to those given in the literature for diathyiamine-borane (3.2 p.p.m.),
pyridine-borane (4.7 p.p.m.), and for the (3.3.3)bicycioborate
108
ester of the triethanolamines (3.2 p.p.m.). v The chemical shift,
of these bicycloborate esters to somewhat higher fields than other
alkyl borates was attributed to increased shielding around the
boron atom due to the boron-nitrogen coordinate bend, thus increasing
the tetrahedral character and the number of bonding electrons around
the boron atoms.
Some of the chemical shifts in Table 4 might be interpreted
in light of the above discussion. The electronic effects of the


26
After all water had been distilled, the remaining solvent was re
moved from the crude esters. The esters were then distilled under
vacuum. The following esters were prepared: diethyl phenylboronate
(b.p. 63-69 C @ 0.35 mm., 90%), diethyl p-bromophenylboronate (b.p.
76-77 C @ 0.25 mm., 41%), diethyl p-chlorophenylboronate (b.p. 92-
93 C @ 0.75 mm., 65.3%), diethyl p-methylphenylboronate (b.p. 58-
59 C @ 0.15 mm., 93.2%), diethyl p-ethoxyphenylboronate (b.p. 130-
135 C @ 1.5 mm., 40%), diethyl p-methoxyphenylboronate (b.p. 108-
110 C @ 2.0 mm., 60%), and tetraethyl p-phenyldiboronate (b.p. 102-
104 C {§ 0.35 mm., 41%). Several of these esters have not been re
ported previously in the. literature.
D. Cyclotriboroxenes
After distillation of the. substituted diethyl phenylboronate, a
white residue remained in the distillation flask. These residues were
recrystallized and examined by nmr, ir, and analyses. The nmr spectra
showed intense aromatic resonance signals in the 57.0 to 57.3 region.
The infrared spectra showed intense absorptions in the 1350-1450 cm.
region assigned to the B-0 asymmetrical stretching modes. The melting
points were extremely high. The compounds were identical to those.
formed by the dehydration of the substituted phenylboronic acids under
heat and vacuum. On this basis and elemental analysis, the structures
were assigned to be the corresponding substituted triphenylcyclocri-
boroxenes, 5_6. The following reaction would explain product formation
PhX
PhX'
,3
0
I
Ik
56
PhX
+ 3 EtOH


Scheme IX


TABLE 2
SUBSTITUTED 1,5-DIPHENYL-l-AZA-5-BORABICYCLO-
(3.3.0)OCTANES AND 1,2-DIPHENYL-1,2-AZABOROLIDINES
lphenyi-l--aza-5'
-bor>a.bieyc.lo( 3.3
.0.)octane
1,2-Diphenyl-l
, 2-azaborolidine
Cpd. No.
X
rr

Cpd. No.
X
Y
63
H
H
64
H
H
87
H
Er
88
H
Br
89
H
Cl
90
H
Cl
9.1.
Cl
H
92
Cl
H
93
Cl
Cl
94
Cl
Cl
95
Br
H
96
Br
H
97
Br
Br
98
Br
Br
99
ch3
CH*
100
ch3
CH3
101
0CHo
0CH3
102
CO
o
o
OCH
103
CCH CK
2
OCH_
o
104
OCHgCHg
0CH
cn
-T-


10
D. Boron-Carbon Polymers
Polvmers containing only boron and carbon are rare. Tri-n-
49
hexylborcn decomposed on heating to produce two polymeric materials.
A dark solid was assigned the structure [-BCCgH^jBH-^and a vis
cous liquid [-B(C^H^^)-(CgH12)-B(CgH12)-]n* Pyrolysis of Me0BCH2CH7BMe2
yielded trimethylboron and polymers with the following structures:
50
BCH CH;
2.
22
n
CH,
-CH,
B/\
W
23
A patent has been awarded for the synthesis of a polymer, 24^ pre
pared by reacting a boron halide or ester with the di-Grignard of
p d ib r cm ob en/.ene. ^
i B
i !
OH

n
ported
24_
Several other polymeric boron-carbon compounds have been re-
21,52,53,54
E. Amin-a-Boranes as Hydruborating Agents
c;
Hie first, organoboranes were synthesized in 1862 by FranklanrT
by the reaction of dialkyl zinc compounds with trietliyiborate. He
He observed the ability of these boranes to coordinate with ammonia
Since that time countless papers on other boron-nitrogen cocrdi-
5
nation compounds have appeared.
o
Koster first utilized trie thy lamine-borane in 195? in the. hydro-


SYNTHESES OF HETEROCYCLIC COMPOUNDS CONTAINING B-N
BONDS AS MODELS
FOP. THERMALLY STABLE POLYMERS
COORDINA'!]
By
CHARLES LEWIS MCCORMICK III
A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF THE JN1VEP.SITY OF
FLORIDA IN PARTIAL FULLFILLHENT OF THE REQUIREMENTS
ICR THE DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA


110
dropwise to the ether-magnesium mixture which had been activated by a
crystal of iodine. The p-bromoethcxybenzene was added at a rate suit
able for maintaining a low reflux. The reaction was stirred for an
additional hour after complete addition. The solution was then cooled
and filtered to remove the excess magnesium.
Trimethyiborate (38.0 g. 0.374 mol.) and 400 ml. of dry diethyl
ether were placed in a 2-liter, 3-necked, round-bottomed flask equipped
with a mechanical stirrer, low-temperature thermometer, and Claisen
adapter for an addition funnel and nitrogen inlet tube. The solution
was cooled to -70 C in a dry ice-isopropanol bath. The Gri.gnard
reagent was placed in the addition funnel and added dropwise with
stirring over a 3-hour period, keeping the temperature below -65 C.
After complete addition, the reaction was allowed to continue with
stirring as the contents warmed to foom temperature. The reaction
mixture was then hydrolyzed with 10% sulfuric acid. The aqueous
layer at this point was very acidic. The two layers were separated
in a 2-liter separatory funnel. The aqueous layer was washed twice
with 200 ml. portions of ether. These, ether layers were combined
with the original ether-extract. The etherial solution was then placed
in a 2-liter, 3-necked, round-bottomed flask equipped with a mechanical
stirrer, addition funnel, and distilling head with water-cooled con
denser. The ether layer was concentrated while adding 1 liter of water
dropwise to the solution. When the temperature at the distilling head
reached 99 C, the solution was transferred to 2 1000 ml. Erienmeyer
flasks and allowed to cool. White, needle-like crystals, 42.3 g. (68.5%),
of p-methoxyphenylboronic acid (m.p. 120-122 C) were isolated. The
spectral data agreed with this assignment. The ir spectrum exhibited


soluble salts. The triethylamine-phenyiboranes were isolated by
cooling the filtrate to -70 C and quick vacuum filtration under
nitrogen.
+ salts
58
Several of the triethylamine-phenylboranes exhibited peculiar
properties on attempted filtration. For example, the triethylamine-
(p-bromo)phenyl-boraae formed a solid (crystals) at -72 C in a dry
ice-isopropanol bath. On removing the ether solvent, these crystals
seemed to melt away. At room temperature only a white residue re
mained. This reaction could possibly be a disproportionation to
p-broffiotriphenylboron, criethylamine, and diborane. Evidence
against disproportionation was that the residue was insoluble in
every solvent tried, and the infrared gas spectrum showed no diborane
evolved. The second possibility would be the elimination of ethane
across the boron-nitrogen coordinate bond to give the monoborazene.
This process, though, usually requires heat and vacuum conditions.
Also, no ethane gas was evolved,
The following compounds were prepared, which are relatively
stable at room temperature: triethylamine-phenylborane (m.p. 65-66. C,
73%), triethylamine-(p-chloro)phenylborane (m.p. 62-63 C, 75%),
triethylamine-(p-methyl)phenylborane (m.p. 80-83 C, 69%), triethyl-
amine- (p-ethoxy)phenylbcrane (m.p. 63-64 C, 84%), and triethylamine-
(p-methoxy)phenylborane (m.p. 63-64 C, 82%).


114
Synthesis and isolation of l,5-bts-(4-bromopheny.l)-l-aza~5-borablcyclo-
(3.3.0)octane ~
A solution of triethylamine-(p-bromophenyl)borane (10.8 g., 0.04
mol.) in 500 ml. of toluene was placed in a 3-necked, 1-liter, round-
bottomed flask equipped with air-cooled condenser, addition funnel,
thermometer, and magnetic stirrer-heater unit. The entire apparatus
was assembled in the dry-box. The contents of the flask were heated
to 55 C. p-Bromo-N,N-diallylaniline (10.0 g., 0.04 mol.) in 80 ml.
of toluene was added dropwise. The mixture was then heated to 85 C.
After 50 minutes of stirring, the solution had turned an iridescent-
green. Gas evolution was followed by infrared spectroscopy. Above
88 C, propene gas was generated. The reaction mixture was heated
for 5 more hours. The solvent was then removed on a rotary evaporator.
The remaining liquid was chromatographed through a silica gel column
in benzene. The progress cf the column chromatography was followed
using thin layer chromatography. The first 5 25 ml. portions eluted
from the column were combined. The benzene was then removed by a
rotary evaporator. The residual, viscous oil was recrystallized from
ethanol yielding 3.8 g. cf a white, flaky material (m.p. 93-34 C).
The nmr, ir, mass spectrum and analysis were consistent with the struc
ture of l,5-bis-(4-bromophenyl)-l-aza-5-borabicycio(3.3.0)octane. The
ir spectrum showed absorbances at 3080 (in), 3040 (w), 3020 (w), 2983 to
2843 (s, detailed), 1574 (s), 1480 (s), 1460 (m), 1430 (w), 1403 (v),
1379 (s), 1343 (w). 1302 (w), 1275 (s), 1228 (s), 1105 to 1190 (broad,
s, detailed), .1075 (s), 1058 (m), 1040 (w), 1005 to 995 (s, doublet),
963 (m), 940 (broad, m), 895 (s), 823 (m), 803 (s), 768 (m), and 630
to 720 (broad, detailed, s) cm. ^. The nmr spectrum gave resonance


59
proceeded and the temperature raised, a brilliant green color appeared.
Infrared gas samples indicated the formation of propene gas. The reac
tion was allowed to proceed at 92 C for 24 hours. The contents were
cooled, filtered, and then the solvent was removed on a rotary evapo
rator. The residual liquid was transferred to a small flask for dis
tillation on a spinning band column. Several fractions were collected.
The first fraction proved to be unreacted p-chloro-N,N-diallylaniline.
The second fraction was a clear, viscous liquid (b.p. 130-135 C @ 0.20
mm.). This compound turned brown on exposure to air. The third frac
tion was the same compound. The infrared spectrum was consistent with
the azaborolidine structure, 9_4, with the B=N absorbance assigned at
1400 cm. \ The mass spectrum gave a parent peak at 289 +1, consistent
with the molecular weight. The nmr spectrum (Figure 6) shows resonances
at 57.05 (a, 8); 53.75 (t, 2); 51.7 (m, 4) for the aromatic, a, and b,c
protons respectively.
Anal. Caled, for C-^H^BNC^: C, 62.09; H, 4.87; N, 4.83; B, 3.73
and Cl, 24.46. Found: C, 61.78; R, 5.01; and Cl, 24.45.
The fourth fraction (b.p. 170-175 C) was very viscous and solidi
fied in the side arm. This material was recrystallized from ethanol to
give a crystalline solid (m.p. 93-95 C). The ir spectrum gave a strong
absorbance at 1275 cm. ~ which was assigned to the B-H coordinate bond.
The mass spectrum gave a peak at 332 *1, corresponding to the correct
molecular weight. The nmr spectrum (Figure 6) showed resonances at 67.2
(hi, 8); 53.4 (m, 4); 62.15 (q, 4); and 61.15 (in, 4) for the aromatic, a,
, and c_ protons respectively.
Anal. Caled, for C^H^BNCl,,: C, 65.08; H, 6.07; N, 4.22; B, 3.26
and Cl, 21.36. Found: C, 64.97: H, 5.99; N, 4.15; and Cl, 21.13,


LIST OF FIGURES
Figure Page
1 Nmr Spectrum of l,5-Diphenyl-I-aza~5~borabicyclo(3.3.0)-
octane 34
2 Infrared Spectrum of 3-Deuteroprcpene 45
3 Nmr Spectrum of 3-Deuteropropene 46
4 Infrared Spectrum of 3,7-Di de ut ero-1,5~dipheny 1-1- az a-
5-borabicyclo(3.3.0)octane 48
5 Nmr Spectrum of 3,7-Dideutero-l ,5-Giphenyl-l-aza-5-bora-
bicyclo (3. 3.0) octane 49
6 Nmr Spectra of 1,5-Bis-(4-chloropheuy1)-l-asa-5-bora-
bicyclo(3.3.0
a?, abo roll dine
60


Sohsme III


105
and recrystallized by coding in a dry ice-isopropanol bath. A small
number of yellow crystals (m.p. 60-68 C) were isolated but 'were not
stable in air. An nmr spectrum of these crystals, dissolved in diethyl
ether, showed a broad multiplet at 68.8 which was consistent with the
expected pyridinium resonance. Aromatic resonance signals centered at
67.3 and a singlet at 64.65 were also consistent with the expected
product. Integrated areas, however, showed less than two pyridine
molecules complexed to the phenyldiborane.
The product from the above reaction was added to 600 ml. of
toluene in a 1-liter, 3-necked, round-botromed flask equipped with
a magnetic stirrer, condenser, addition funnel with nitrogen inlet,
and thermometer. The mixture was heated to 50 C on a Glas-col heat
ing mantle. N,N,N*,N*-Tetraallyl-p-phenylenediamine (15.0 g., 0.056
mol.) was added dropwise with stirring to the heated mixture while
nitrogen swept the system. The temperature was slowly raised until
some solvent began to distill away. Several gas samples were taken
and analyzed by ir. Only pyridine vapor and toluene vapor were
detected. After the temperature had stabilized at 110 C, the sol
ution was cooled. The remaining solvent was removed on a rotary
evaporator leaving behind a viscous, sticky, brown material. The
structure of this material could not be determined.
Attempted preparation and isolation of dl(pyridine)-p-phenylenodiborane
p-Phenylenediboronic acid (50.0 g.) was heated at 100 C at 1.0
mm. for 3 hours. The resulting material (20.0 g.) was then dissolved
in tetrahydrofuran and placed in a 300 ml. addition funnel. Lithium
aluminum hydride (4.0 g., 0.106 mol.) was added to 250 mi. of dry


Chapter V
EXPERIMENTAL
A. Equipment and Data
All temperatures are reported uncorrected in degrees centigrade.
Nuclear magnetic resonance (nmr) spectra were obtained with a Var-ian
A-60A Analytical NMR Spectrometer. The chemical shifts were measured
in deuterochloroform, unless otherwise specified, relative to tetra-
methylsilane.
Infrared spectra were obtained with a Beckman IR-8 Infrared
Spectrophotometer.
^'u Boron nuclear magnetic resonance spectra were- obtained,
courtesy of Dr. Wallace S. Brey, with a Varian X-L 100 High Resolution
NMR Spectrometer.
Mass spectra were obtained with a Hitachi Perkin-Elmer RMU
Mass Spectrometer.
Thermal analyses were carried out on a Perkin-Elmer Differential
Scanning Calorimeter DSC-1B.
Elemental analyses were performed by Galbraith Laboratories, -
Inc., Knoxville, Tennessee.


117
rouna-bottomed flask equipped with magnetic stirrer, condenser, and
addition funnel with adapter and gas cutlet. All operations were
carried out in a dry-box. The contents of the flask were stirred
and heated to 50 C. p-Methoxy-N,N-diallylaniline (15.0 g., 0.074
mol.) was added dropwise. The reaction mixture was then heated to
100 C. The reaction gases were monitored by infrared spectroscopy.
The lowest temperature at which propene gas evolution was observed
appeared to be 93-95 C. The temperature range monitored was from
80 C to 115 C. The reaction mixture was stirred for 12 hours and
then allowed to cool under nitrogen. A pale green solution resulted.
The xylene solvent was removed oh a rotary evaporator. The residual
material, a phosphorescent-green liquid, was distilled on a spinning
band column under vacuum. Two fractions were obtained with boiling
points of 65-70 C and 75 00 C @ 0.250 mm. A bright yellow solid
remained in the distillation flask. The lowest boiling fraction
proved to be unreacted p-methoxy-N,N~diallylaniline. The second
fraction was analyzed by nmr and ir. The spectra were consistent
with the structure assignment of l-(p-methoxyphenyl),2-(p-ethoxy-
phenyl)-l,2-azaborolidine. The ir spectrum showed absorbances at
3420 (m), 2840 to 3100 (s, broad, detailed), 1843 (s, broad), 1640
(w), 1620 (w), 1605 (w), 1580 (w), 1514 (s), 1470 (w), 1443 (w),
1420 (w), 1240 (s), 1180 (s), 1125 (rn), 1040 (s), 995 (m), 950 (w,
shoulder), 915 (s), 315 (s), and 708 (m) cm. \ The nmr spectrum
gave resonances at 66.8 (m, 8); 63.7 (m, 7); 61.9 (m, 2); and 61.5
(m, 5). The residual material in the distilling flask was dissolved
in benzene and chromatographed on a silica gel column. The remain
ing azaborolidine apparently reacted with the column. The bicyclic


WAVELENGTH IN MICRONS
WAVENUMBER CM'1
Figure 4. Infrared spectrum of 37-dideutero-l,5-diphenyl-l-aza-
5-borabicyclo(3.3.0)octane. ^
00


9
Cyclotriboroxenas disproportionate to boric oxide and trialkyl or
39
triaryl boranes at elevated temperatures. This tact seems to
rule out the possibility of ring-opening polymerizations of these
cyclic trimers.
Benzenediboronic acids have been prepared as starting materials
for polymerization. These acids were formed by the extension of the
synthesis of phenylboronic acid, _19.
(JV-MgBr (1) (CH30)3B
(2) H,0+
3(0H)
19
42
43
Diboronic acids were prepared by Nielsen and Musgrave by
reaction of a bis-Grignard reagent with trimet'hylborate in tetra-
hydrofuran. Subsequent hydrolysis yielded che diboronic 3cid, 20,
/\
(0H)B< (j > B (OH)
2C
Polyesters from diboronic acids have been reported, but no molecular
4
weights were given. Mixtures of boric acids with glycols gave high
45
molecular weight polymers. No structure determinations were made,
although cross-linking is inevitable in these systems. Polymeric
glycol borates and esters of borcnic acids have been studied
46
careful study of the condensation reactions of orthoboric acids with
47 48
diols has also been made. Recently, Svarcs at al. reported the
preparation of a copolymer, 21, of peutaerythritoi and boric acid.
0\ o-
/ Y'
x C /\ 0
21
n


66
SCHEME X
1-butene


Scheme VII
-p
o


124
The ir spectrum showed absorbances at 620 (m), 710 (s), 752 (s),
817 (w), 850 and 867 (d,s), 900 (w), 925 (s), 1018 (s), 1065 (m), 1095
(m), 1118 (w), 1152 and 1163 (d, s), 1189 (s), 1258 (w), 1300 (w), 1282
(w), 1340 (w, shoulder ), 1360 (m), 1378 (s), 1430 (m), 1465 and 1477 (d,
s), 1565 (w), 1622 (w), 1685 (s), 1765 (s), 830 (w), 1850 (w), 1890 (w),
1905 (w), I960 (w), 1975 (w), 2350 (w), 2850 to 3100 (s, broad, detailed),
and 3400 to 3600 (w, broad) cm. \
The nmr spectrum exhibited resonances at 51.2 (t, 9); 52.75 (quartet,
6); and 57.25 (m,5).
Anal. Caled, for C10HonD0BN: C, 74.63; H, 10.44; N, 7.25; B, 5.60;
i zu z
and D, 2.08. Found: C, 73.05; H, 11.12; N, 6.31; and B, 5.83.
Preparation and isolation of 3,7-dideutero-l,5-diphenyl-l-aza-5-
borablcyclo(3.3.0)octane, 3-deutero-l,5-diphenyl-1,2-azaborolidine,
and 3-deuteropropene
p-Xylene, 300 ml., tas placed in a 3-necked, 1-liter, round-
bottomed flask equipped with a mechanical stirrer, thermometer, and
gas outlet. The outlet was connected by tygon tubing to an infrared
gas cell and then to a gas trap cooled by a dry ice-isopropanol
mixture. Several gas samples were taken at 90, 98, 104, 96, and
97 C. The ir spectrum showed absorbances at 912 (s, spiked, broad),
985 (w), 1002 (w), 1012 (w), 1080 (w), 1140 (s), 1250 to 1310 (m, broad,
detailed), 1410 to 1490 (m, broad, detailed), 1638 and 1655 (d, s), 1820
and 1840 (d, w), 2175 (spiked, s), 2880 (s), 3940 to 3920 (s, broad,
-1 -1
detailed) and 3090 and 3110 (d, s) cm. The peak at 2175 cm. was
consistent with the carbon-deuterium stretching frequency expected for
3-deuteropropene. The threshold temperature for formation of 3-deutero
propene appeared to be 95-96 0. The liquified, trapped gas was mixed


73
Synthesis of p-methyl-N,N-diallylaniline
p-Toluidine (214.0 g. 2.0 mol.), sodium bicarbonate (420.0 g.),
and 1000 ml. of water were placed in a 3-liter, 3-necked, round-
bottomed flask equipped with thermometer, overhead stirrer, addition
funnel, and condenser. The mixture was heated on a heating mantle
until the temperature of the liquid reached 70 C. Allyl bromide
(531.0 g., 4.8 mol.), was added dropwise with stirring. The resulting
mixture was heated overnight. The brown liquid separated into 2 phases
on sitting. The layers were separated using a 1-liter separatory
funnel. The oily layer was washed with 3 100 ml. portions of water
and then dried over sodium sulfate. The crude p-methyl-N,N-diallyl-
aniline was filtered and then vacuum distilled yielding 262.3 g. (70.1%)
of a pale yellow liquid (b.p. 80-85 C. @ 0.350 mm.).
The infrared spectrum (ir) gave absorbances at 1520 (n), 1240 (s,
split), 800 (m), 1620 (s, split), 920 (s, split) 1340 (m), 1360 (s),
1390 (s), 1410 (m), 1425 (m), 1450 (w), 1180 (s), 990 (s), 2390 (s),
2950 (s), 3000 (s), 3020 (s), and 31.10 (m) cm."1.
The nmr gave resonance signals at 56.8 (m, 4); from 64.9 to 56.2
(m, 6); 63.8 (m, 4); and 62.2 (s, 3).
Synthesis of p-bromo-N,N-diallylc.tnljine
p-Bromoaniline (100 g., 0.582 mol.), sodium carbonate (126.0 g.,
1.2 mol.), and 230 ml. of water were placed in a 2-liter, 3-necked,
round-bottomed flask equipped with a mechanical stirrer, dropping
funnel, and water-cooled condenser. The mixture was heated on a heat
ing mantle until low reflux was obtained. Allyl bromide (146.0 g.,
1.2 mol.) was added over a 3 to 4 hour period through an addition


I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.
George B. Butler, Chairman
Professor of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.
Henry C. Biown
Professor of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.
Thieo E. Hogen EsK
Assistant Professor of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.
Paul Tarrant
Professor of Chemistry


51
The most obvious approach might appear to be that of electro
philic aromatic substitution. However, boron is, in theory, a
better leaving group than hydrogen in these substitutions. Tri-
phenylboroxene was reacted with aluminum chloride and, also,
phosphorus pentachloride to yield benzene as the only identifiable
product."^ The boron atom on triphenylboroxene, or triphenyl-
cyclotriboroxene, however, might be a better leaving group than
the coordinated structure of the l,5-diphenyl-l-aza-5-borabicyclo-
111
(3.3.0)octane, 6_3. Li reacted 63 with acetyl chloride and
aluminum chloride tc give acetophenone and other unidentified
producto. I
A second approach would involve nucleophilic aromatic substi-
are due to the strength of the bases employed in these substitutions.
If an equilibrium exists between the coordinated, 6_3, and un
coordinated, 63A, forms of the bicyclic system, different chemical re
activity would be expected for the two forms. Strong bases would be
expected to attack the eleccronically-deficient boron atom in struc
ture 63A


126
1342 (w), 1350 (w), 1429 (s), 1450 (s), 1468 (s), 1493 (s), 1595 (s),
1735 (w), 1800 (w), 1870 (w), 1938 (w), 2170 (s), 2840 (s), 2925 (s),
and 2980 to 3080 (s, detailed, broad) cm. 1. The nmr spectrum gave
resonances at 61.1 (m, 2); 62.15 (broad m, 1); and 57.0 (m, 5). A
fourth resonance was observed at 63.45 (m, 2). The mass spectrum
gave a parent peak at 265 1.
Anal. Caled, for c18H2oD2BN: C, 81.52; H, 7.60; D, 1.52;
B, 4.08; and N, 5.28. Found: C, 81.74; B, 4.20; and N, 5.18.
Cleavage of 2-methoxynaphthalene with lithium iodide in collidine
Lithium iodide (3.0 g.) was placed in a 3-necked, 25 ml., round-
bottomed flask equipped with a nitrogen inlet tube. The salt was
heated by an oil bath. The material was heated at 230 C for 3 hours
under nitrogen. The flask was then cooled to 110 C; 2-methoxy-
naplvthalene (1.0 g.) in 8 ml. of collidine was added to the salt.
The temperature vas raised to 170 C and the collidine was allowed to
reflux under nitrogen for 8 hours. The reaction mixture v/as allowed
to cool to room temperature and then was acidified with 10% hydrochloric
acid. The organic material was extracted with ether. The extract was
rotovaced giving 1.2 g. (66%) of a white solid, 2-hydroxynaphthalene
(m.p. 110-111 C). The nmr spectrum showed the absence of the methoxy
absorption at 53.9, The only observable signal was at 67,5.
Attempted preparation of 1,5-bis-(4-hydroxyphenyl)-l-aza-5-borabicyclo-
(3.3.0)octane from 1,5-bis-(~4-methoxyphenyl)-l-aza-5-borabicyclo(3.3 ,0)-
octane by cleavage with lithium iodide in collidine
i,5-Bis-(4-methoxyphenyl)-l-aza-5-borabicyclo(3.3.0)octane (1,0 g.,
0.003 mol.) was dissolved in 8 ml. of collidine and placed in an addition


I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.
Martin Vala, Jr.
Associate Professor of Chemistry
This dissertation was submitted to the Department of Chemistry in
the College of Arts and Sciences and to the Graduate Council, and was
accepted as partial fulfillment of the requirements for the degree of
Doctor of Philosophy.
June, 1973


s
The reaction of p-aminophenol and triprcpoxyborane resulted
in the formation of a resin. The structure assigned to the poly-
33
mer was:
NH -
0 B
NH
0-
n
15
C. Boron-Oxygen Polymers
Oligomeric compounds containing boron-oxygen links have been
made by heating alkyl- or arylboronic acids. Most of the resulting
compounds are easily hydrolyzed, although they exhibit remarkable
thermal stability. As in the borazene series, the trimers, cycle-
triborcxenes, seem to he the most favored thermodynamically. Cycle-
3;
triboroxanes have been reported to have 10-20% aromatic character.'
f
I
A
0
T 6
/A'
+ 0' No +
l (j
+
17
Cyciotribcrovcene can be prepared by the thermal dehydration of
boronic acids under vacuum.^ The first anhydride of phenyiboronic.
acid was prepared in 1682, The structure of triphenylcyclotri-
37
bcroxene, (PhB-0). was confirmed later. Treatment of p-methoxy-
38
phenylborcnic acid yielded the cyclic trimer:"
PhOCH.,
tr"B"c
B.
CH0Fh
dv e
muta.


97
under nitrogen. Diethyl p-tolylbcronate (^-6.5 g., 0.246 mol.) was
then added dropwise at a rate which kept the temperature below -65
C. The solution was stirred overnight and allowed to warm to room
temperature. The mixture was filtered through a sintered-glass
funnel and the resulting filtrate concentrated to 1/2 its original
volume. The filtrate was then placed in a dry ice-isopropanol bath
resulting in formation of white, needle-like crystals. The crystals
were filtered quickly through a sintered-glass filter and placed
immediately under vacuum in a desiccator to dry. The crystals appeared
to decompose on slow filtration, even in an inert atmosphere. However,
if the ether was quickly removed, the dry crystals were stable in air.
The white crystals, 35.3 g. (69%), melted at 80-83 C.
Preparation of 1,5-bis-(4-methy.lphenyi )-l-aza-5-borabicyclo(3.3.0)-
cctane
Triethylamine-(p-methylphenyi)horane (17.7 g., 0.085 mol.) and
1000 ml. of benzene were added to a 2-liter, round-bottomed flask
equipped with a Claisen adapter, drying tube, addition funnel, and
reflux condenser. A gas take-off from the condenser was connected
to an infrared gas cell by a tygon tube to monitor the release of
propene gas during the reaction. The mixture was heated to reflux
and then p-methyi-N,N-diallylaniline (16.0 g. 0.085 mol.) in 250 ml.
of benzene was added dropwise. Gas samples, compared to the Sadtler
spectra, confirmed evolution of propene gas. The remaining benzene
was removed on the rotary evaporator and the residual liquid was
distilled under reduced pressure. Four fractions were, recovered.
I
The first two fractions (b.p. £5-90 C @ 0.250 mm.) proved to be


84
The nmr spectrum exhibited resonances at 67.45 (s, 4)j 64.05
(quartet, 4); and 61.25 (t, 6).
Preparation of triethylamine-(p-bromo)phenylborane
Lithium aluminum hydride (5.5 g., 0.15 mol.) was added to 400 ml.
of diethyl ether in a 4-necked, 1-liter, round-bottomed flask equipped
with a mechanical stirrer, condenser with drying tube, addition funnel
with nitrogen inlet tube, and low temperature thermometer. The mix
ture was refluxed for 30 minutes on a heating mantle and then cooled
to -72 C in a dry ice-isopropanol bath. Triethylamine (15.8 g. 0.192
mol.) was added with stirring. A solution of diethyl p-bromophenyl-
boronate (49.3 g., 0.192 mol.) was added dropwise with stirring, keep
ing the temperature below -65 C. The reaction mixture was allowed to
'warm to room temperature and then filtered to remove the unreacted
lithium aluminum hydride. The filtrate was cooled in a dry ice-isc-
propanol bath to -70'C. White, needle-like crystals were formed.
These were unstable and appeared to melt during filtration, even under
nitrogen. The remaining material was immediately dissolved in toluene.
Preparation of l-(4-bromophenyl)-2-phenyl-l,2-azaborolidlne and
l-(4-bromophenyl)-5"phenyl-l-aza-5-borabicyclo(3.3.0)octane
Triethylamine-phenylborane (19:3 g. 0.1 mol), p-bromo-N,N-d.iallyl-
aniline (25.2 g. 0.1 mol.), and 1.25 liters of toluene were placed in
a 2-liter, round-bottomed flask. The toluene was slowly distilled from
the flask through a fractionating column and condenser. On initial
heating the contents of the flask turned a bright yellow-green color.
When the temperature at the distilling head reached 120 C, the residual


41
librium toward the coordinated form of the intermediate, 76.
Electron-donating substituents would be expected to have the
opposite effect. Electron-donating substituents on the aniline
ring would increase the basicity of the amine, resulting in
stronger coordination. Again, the opposite effect would be
expected for withdrawing substituents.
The Hofmann elimination mechanism would also be expected
to show similar effects of substitution. In this case, the
elimination would be possible only if the quaternized form,
72, were present.
C. Deuterium Labeling Studies
After several syntheses of substituted 1,5-diphenyl-l-aza-
5-borabicyclo (3.3.0)octanes (discusse.d later in this chapter),
it was evident that substituent effects would not give a clear-
cut distinction between the concerted mechanism and the Hofmann
elimination. Therefore, deuterium labeling studies were proposed.
If triethylamine-dideutero-phenylborane could be prepared, it
should then be possible to distinguish quite clearly the two pro
posed mechanisms.
The proposed concerted mechanism is shown in Scheme VIII.
The triethylamine-dideuterophenylbcrane, 78,would dissociate to
give the free dideuterophenylborane, 79_, which would undergo an
initial deuteroboration to give intermediate 80 and the coordinated
form of the intermediate, 81, by an equilibration of the two forms.
The deuterium ends up in the 3-position on the ring. A second
deuteroboration through pathway A would lead to the dideuterated


119
The infrared spectrum shewed absorbances at 633 (ir.), 650 (m), 735
(m), 792 (w), 827 (s), 873 (m), 902 On), 1005 (m), 1035 (s), 1108 (m),
1128 (m), 1180 (s), 1240 to 1350 (broad, s), 1360 (s), 1413 (s), 1415
(m), 1440 (w), 1458 (w), 1483 (m), 1512 (s), 1570 (m), 1600 (s), 2060
(w), 2847 (m), and 2900 to 3090 (broad, s, detailed) cm. \
The nmr spectrum gave resonance signals at 61.25 (t, 6); 63.75
(s, 3); 64.05 (quartet, 4); and 67.2 (m, 4).
Isolation of tri(p-methoxyphenyl)c.yclotriboroxene
Following the vacuum distillation of diethyl (p-methoxyp'nenyl)-
boronate, a white, crystalline material, 2.0 g., m.p. 204-206 C,
was recovered from the flask. An identical product was obtained
from the heating of 1.5 g. of p-methoxyphenylboronic acid under vacuum
to 150 C. Infrared, nmr, mass spectrum and analysis confirmed the
structure assignment of tri(p-methoxvphenyl)cyclotriboroxene. The mass
spectrum gave a parent peak at 401 *1. The ir spectrum exhibited ab
sorbances at 630 (m), 685 (s), 745 (s), 801 (s), 823 (s), 1020 (s),
1060 (w), 1080 (m), 1105 (s), 1170 (s), 1250 (s, broad), 1290 to 3060
(broad, m, detailed), and 3480 (broad, w) cm. The nmr showed res
onance signals at 63.25 (s, 3); and an aromatic quartet at 66.8 (q, 4),
Anal. Caled, for Co1Ho1B0_: C, 62.77; H, 5.27; B, 8.08; and
1 o b
0, 23.88. Found: C, 63.42; H, 5.48; and B, 7.33.
Preparation of triethylamine-(p-methoxyphenyl)borane
Lithium aluminum hydride (3.79 g. 0.1 mol.) was dissolved in 200
ml. of dry diethyl ether in a 1-liter, 3-necked, round-bottomed flask
equipped with mechanical stirrer, addition funnel with nitrogen inlet,


77
reflux condenser. Water (1500 ml.) was added; the mixture was heated
to reflux to dissolve the solid. The solution was then cooled to 70
C and 3-bromopropene (559.7 g., 4.63 mol.) added dropwise with stirring
The solution was refluxed overnight before extracting the oily layer
with ether. The ether layer was then dried over sodium sulfate and
filtered. The brown, oily compound was then distilled yielding 124.6 g
(46.5%) of a pale yellow liquid (b.p. 138-140 C @ 0.550 mm.).
Synthesis of phenylboronic acid
A mixture of ethyl ether and magnesium (36.0 g., 1.5 g. atoms)
was placed in a 1-liter, 3-necked, round-bottomed flask equipped with
a mechanical stirrer, addition funnel, and cold-water condenser. Bromo
benzene (157.0 g., 1.0 mol.) in 200 ml. of ether was added dropwise
wixh stirring. After the reaction was started, the round-bottomed
flask was cooled in ice water to control the temperature. After all
the bromobenzene had been added, the contents of the flask were allowed
to warm to room temperature. Trimethylborate (103.9 g. 1.0 mol.) and
800 ml. of diethyl ether were placed in a 3-liter, 3-necked, round-
bottomed flask equipped with a mechanical stirrer, low-temperature
thermometer, and Claisen adapter with nitrogen inlet tube and addition
funnel. The Grignard reagent was filtered through glass wool into the
addition funnel. The solution in the 3-liter flask was cooled to -70
C in a dry ice-isopropanol bath. The Grignard reagent was added drop-
wise and the temperature was controlled between -70 and -55 C. The
mixture, after cooling overnight, was hydrolyzed with 10% sulfuric
acid. The ether layer was separated and placed in a 3-liter, 3-necked,
round-bottomed flask fitted with a Claisen distilling head, mechanical


Chapter II
SYNTHESES OF UNSATURATED TERTIARY ANILINES
A. Syntheses of Para-substituted-N,N-Diallylanilines
p-Substituted-N,N-diallylanilines, 52_, were prepared by the
10 3
method of Butler and Bunch. J 3-Rrotaopropene was added dropwise
to a slurry of sodium carbonate and the para-substituted-aniline
in water. The reactions were allowed to proceed at 100 C for 24
to 48 hours. The resulting organic layer was separated, dried, and
vacuum distilled.
X- vr./
bromoprcpene
X( O )N
| //
The i'oiJowing compounds were prepared by the above method:
N,N"diallylaniline, 87.6%; p-broiuo-N,N-dially laniline, 74.5%;
p-chloro-N,N-diallylanilLne, 72.5%; p--methyl-N,N-diallylaniline,
70.1%; and p-methoxy-NjN-diallylaniline, 88%r
The corresponding secondary monoallylaxsilines were also ob
tained from early fractions in the distillation.
3. Synthesis of N,N,N',N-Tetraally1-p-phenylenediamine
p-Pnenylenediamine was reacted with 4 moles of aliylbromide
in a slurry of sodium carbonate in water. The resulting viscous,
syrupy material was diluted with water and the organic layer ex-