|Table of Contents|
Table of Contents
List of Tables
Chapter 1. Introduction
Chapter 2. Preparation of unsaturated secondary and tertiary amines
Chapter 3. Preparation of an unsaturated phosphine
Chapter 4. Preparation of boron intermediates
Chapter 5. Preparation on boron heterocycles
Chapter 6. Summary
THE SYNTHESIS OF BORON HETEROCYCLES
AS MODELS FOR
THERMALLY STABLE POLYMERS
GARY LEWIS STATION
A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
4 nTC '1T 'U 3 3 G' "-I TS3
The author wishes to express his deep appreciation
to Dr. G. B. Butler for his valuable assistance and counsel
during the execution of this research project.
The author wishes also to express his gratitude to
Dr. W. S. Brey, Jr., for obtaining and interpreting the
n.m.r. spectra and to G. L. K. Hunter, U. S. Fruit and
Vegetable Products Laboratory, Winter Haven, Florida, for
the mass spectral data.
The financial support of this research by a National
Lead Fellowship is also gratefully acknowledged.
Finally the author wishes to express his appreciation
to his wife whose help and understanding made this work
TABLE: OL' CONTLNT'3
ACKNCO LEDGii irS . . . . . . . . .
LIST OF TABLES. . . . . . . . . .
I. INTRODUCTION. . . . ... . ...
Criteria for Thermal Stability . *
Statement of the Problem o .*
Historical Notes on Amine-boranes as
Hydroborating Agents. . * .
Source and Purification of Materials .
Equipment and Treatment of Data. .
II. PRL'PARATIOI1 OF UNSATUa'ATLD SECONDARY A!'D
TZRTI.LRY AiIII-S. . . . . . .
General Discussion * * * *
Experimental * * * * *
III. 2"2ARATION OF AN UN3ArU;&jLD PHO.2HIE .
Experimental *. * * * ..
IV. PL2.dRATION 07 BOON IITTRl .JIATJ. ...
General Discussion * * * * .
T'xperimental * * . . *
V. PREPARATION OF BORON HcTEROCYCLES . .
General Discussion and Results * .
Experimental * *. . . .
a a 25
. . 48
VI. SU UIII.Y . . . . . . . . . 62
BIBLIOGRAPHY. . . . # . . . . . .64
BIOGRA2HICAL SKETCH . . . . . . . . 68
LIST OF TABLES
1. Decomposition Temperatures of a Variety of
Compounds and Related Polymers * * * * 5
2. Dissociation and Bond Energies . . . . 5
3. Decomposition Temperatures and Bond Energies
of (C6Hc)xM Compounds of Group VA. . . 6
4. Decomposition Temperatures of Hydrocarbons . 9
5. Products and Yields of the Reaction of
Triethylamine-phonylborane and Tertiary
Diallylamines. . * * * * 3*
6. Infrared Absorption of the B-TT Bond in
Substituted 1,2-Azaborolidines . . . . 36
7. 'T.M.R. Spectral Data of Substituted
1,2-Azaborolidines .. . . . . . . 38
8. N.M.R. Spectral Data of Substituted
l-Aza-5-borabicyclo [3.3.0] octanes. . .. 39
9. IT.M.R. Spectral Data of l,2-Diphenyl-l-bora-5-
phosphabicyclo [3.3.0] octane. . . . . 4-5
Criteria for Thermal Stability
The search for thermally stable polymers has been
given considerable impetus in recent years due to the
advances in aircraft and missile design placing more rigid
requirements on the material components. It was apparent
that the stability of polymers having the usual single
paraffinic backbones would not suffice at high temperatures,
800-1000 degrees Fahrenheit (420-550C), so a massive
research program was initiated by government and industry
to develop polymeric systems with good thermal stability
in the high temperature range.
Most thermal studies up to this time had principally
been on thermal reactions for syntheses or for determination
of dissociation energies of bonds. Unfortunately the
variance in testing conditions and the lack of any practical
definition of decomposition temperature make comparisons
According to the Boltzman law of energy distribution
among molecules, at any temperature a portion of the molecules
will possess energy greater than the bond energy of the
weakest bond. Stability is thus not absolute but a matter
Although an unambiguous definition of decomposition
temperatures may be given by thermodynamics or rigorous
kinetics, most polymers and a large number of compounds
degrade by such complex processes that the practical value
of these terms is limited. The functional applications of
a polymer also define temperature limitations and this
point may be reached before any bond-breaking process takes
place. Thus the extensive studies that have been made were
based on non-rigorous kinetics and the decomposition point
was assigned on an empirical basis. Also these investi-
gations have been directed toward the thermal stability of
molecules which are not polymers but compounds which could
be made repeating units of a polymer. Although exact
correlation between the thermal stabilities of the compound
and the polymer is not always good, as may be seen in Table
1, conclusions as to the general characteristics which lead
to good thermal stability can be made.
Johns192 studied the decompositions of a large number
of compounds by observing isothermal pressure changes with
an isoteniscope and arrived at the following conclusions:
TIMPEIATUIRS OF A V.SAi.2TY OF COMiPOUNDS AND
Compound Decomposition2 Polymer Decompo-
Temperature in sition5
0C. from Iso- Tempera-
Tensiscope ture in
Biphenyl 545 3/^ 1 559
L \ 0- n
N N NN in
1. All bonds in the molecule should have high
2. No easy paths of decomposition should be present.
3. The structure should be stabilized by resonance.
4. Since elimination of hydrogen is one of the more
common reactions of degradation, only molecules
that have firmly bonded hydrogens should be used
or hydrogen should be replaced by tightly bound
atoms. Replacement of a carbon-hydrogen unit in
benzene rings with a boron, sulfur, phosphorus
or nitrogen also helps.
5. Multiple bonding can increase stability.
As a molecule is heated, the vibrational energy
distributed among the bonds of the molecule increases. When
the vibrational energy is equal to the dissociation energy
of a bond, rupture occurs, thus the weakest bond in a
complex molecule sets the maximum limit of stability. Use
of the Arrhenius rate equation and known facts on alkane
decomposition allows a rough calculation of 100-105 kcal./mole
as the minimum dissociation energy needed to have thermal
stability in a polymer at 5380C. Table 2 shows various bond
and dissociation energies commonly found in polymers. A
comparison of the stability of a number of compounds of the
type (C6H5)x-M has shown that a direct correlation exists
between the bond lengths and the decomposition temperatures.5
A comparison of bond energies and decomposition temperatures
also shows a relationship as may be seen in Table 3.
DI3S0CI.,TION AND BONJ 7iT'TRGI7S4
Bond Energy Kcal./mole
C = IT
T'3L 2 3
D.CO:1P0FITIO: T 6 .H CR'.MTUDS _.:i 30::.)
OF (-(C6H)S- COomPOUNDS OF GROUP
Decomposition5 Bond Energy4
Compound Temperature Bond Kcal./mole
p-ph*3nylenediamine 457 ?- 72.8
Triphenylphoqphine 370 P-C 63.0
Triphnyvl arsine 307 As-C 48.0
Triph3nylstibine 266 Sb-C 47.0
Triphenylbismuthine 231 Bi-C 31.0
Blake,5 studying the thermal decomposition of
approximately one hundred organic compounds in twelve
chemical classes, found that blocking the low energy decompo-
sition paths was quite important. On the basis of bond
energies alone, one would predict that .,T'-diphenyl-p-
phenylenediamine would be more stable than N,1'-diphenyl-
IT,:T'-dimethyl-p-phenylenediamine, IN-H, 96 kcal./mole, versus
N-CH3, 68 kcal./mole. However the decomposition tempera-
tures were 2640C. and 526C., respectively. The decompo-
sition of the N,N'-diphenyl-p-phenylenediamine proceeds by
elimination of hydrogen to give J,N'-diphonyl-p-quinone-
diimine. This low energy path, whose activation energy was
only 28 kcal./mole as calculated by an Arrhenius plot, was
prevented by substitution of the methyl groups and thus the
decomposition temperature increased.
The importance of resonance can easily be seen. On
the basis of similarities of spectra of benzborimidazoles
to benzimidazoles, it had been expected that the aromatic
system of benzborimidazoles represented by the following
resonance form should result in good thermal stability.6
Polybenzborimidazole polymers decompose from 500-600C.
The importance of sliniaition of hydrogen may be
shown by the decomposition temperatures of hexafluoro-
benzene ani pyriline, 6710. and 621-648C. when compared
to that of benzene, 5930C.7
The principle of multiple boadinC can increase
thermal stability by two )rocodures. '.Tiea a 3olli0ion
occurs at an atom which has multiple bonding, the eaargy
of collision may be dissipated by more than one path. Also
in such materials as bicyclic and cyclic comdounis, bond
rupture does not necessarily result in decoromositioa. 3ince
the ruptured atoms are held relatively close by the remainder
of the structure, the bond-breaking energy may be redis-
tributed among the multiple bonds allowinS the ruptured bond
to heal.5 Indeed, studies on the decoiio-ition of hy1ro-
carbons have shown a difference in the decomposition
temperatures of alkanes, cycloalkanes, and bicyclic alk-nes
as exemplified in Table 4.
This principle also increases the thermal stability
of polymers. The cyclopolymerization of trimethylene di-
isocyanate was found to produce a linear cyclic polymer
which was thermally stable at 1500C. higher th-n the corres-
ponding linear polymer, rq-ethyl-l-nyJon.9'10 Other cyclo-
polymerizations of vicinal organic polyisocyanates have
also substantiated their greater ther.mal stability.11
DECOMPO. IION TEMPEIATURES 0? HYDROCARBONS8
Dec.lia (ai-cei isomers)
Dimethyl decalin (mixed
Diallyldiphenylsilane, polymerized by the intra-
intermolecular mechanism, has been shown to form thermally
stable polymers (I) which start decomposing at 410C.12
CH CH CH2N
CH2- -CH / ""CH-- ,,CH CHC ,
CH2 CH2 C C
Si CH -CH I
C6H5 S 6H5 n R n
"Ladder" polymers (II) containing only repeating
cyclic units have been obtained from polymerizing butadiene
and chloroprene.13 These polymers decompose at 420 and
Statement of the Problem
Polymers which would have a repeating unit consisting
of alternating phenylene units and bicyclic units containing
boron and another heteroatom should be expected to show some
degree of thermal stability as suggested by the preceding
criteria. However, the absence of information in the
literature on the preparation of aza-bora-bicyclic-alkanes
or bora-phospha-bicyclic-alkanes with structures as shown
ia the above polymer formulation prompted an investigation
of the synthesis of such model comioun.s. 3ince these
laboratories have produced extensive research on unsatu-
rated airies 14-19 and unsaturated phosphorous compounds,20'21
it was felt that the bicyclic compounds could best be
synthesized by the hydroboration of the unsaturated amines
and phosphines by phenylborane or through the use of an
amine complex of phenylborane. A report of the preparation
of a stable tricyclic compound from trimethylamine-borane
and triallylamine also stimulated interest in this
Several difunctional intermediates which would lead
to polymers also were to be synthesized so that polymers
could be made if the model compounds proved obtainable.
Historical Notes on Amine-boranes as Hydroborating Agent
The first literature reference to a borane reacting
with an amine was submitted by Frankland23 in 1862. Since
then, the interest in boron compounds and boranes co-
ordinated with nitrogen in amines has resulted in a countless
number of papers on thcir syntheses. It has only been
recently that their use as synthetic tools for the organic
and inorganic chemist has been realized.
Koster24 reported the synthesis of perhydro-9-b-
boraphalene from the hydroboration of cyclododeca-l,5,9-
triene with triethylaramine-borane in 1957.
Hawthorne2 found that pyridine-borane would react
with terminal olefins using diglyme as solvent at
temperatures of 100C. It was suggested that the amine-
borane decomposed to the borane at the elevated temperatures
and borane then reacted with the olefin.
The reactions of various trialkylamine-boranes with
olefins to form trialkylboranes in 78-95 per cent yields
were reported by Ashley.26 The reactions were run without
solvents. Ashley also concluded that the trialkylamine-
boranes decomposed at elevated temperatures.
r?,rTBH --R-,rT + BH5
Kster27'28 found that the reactions of trialkylamine-
boranes with diolefins provided a convenient route to cyclic
boranes. Hawthorne 29'0 then proceeded a step further by
reacting trimethylamino-t-butylborane with a number of
olefins and diolefins. Two of the olefins, divinyl ether
and divinyl silane, provided the first example of preparation
of heterocyclic compounds containing boron and another
element by this method.
Adams and Poholsky31 recently prepared the first
1,2-aza-boro-cycloalkane by refluxing a toluene solution of
.t'-dim :-.thy!-allylamin. with trimethylamine-borane. A
report on the :)reijrations of 1-mlt l-2- h-ti-l-l,2-aza-
borolidine and 2-pheryl-l,2-azaboracyclohexane from the
reactions of 'T-mathylallylaamine an] 3-butenyl-mine with
trimethylamine-ph-rnylborane in diglyme soon followed. 2
The mechaoii of the reaction of amine-boranes with
olefins has been concluded to require that the amine-borane
reagent dissociates ': an equilibrium reaction as stated
above. The monomne-ric borane then reacts with the olefin.
Brown53'53 has s.,;qes-'9 d that this reaction occurs by a
four-center cis addition.
H-B = + >C=C\ \ C.-.--------C
H--B H B
Source and Purification of Materials
n-?ropyl bromide, sec-butyldiallylamine and lithium
aluminum hydride were obtained from Penninsular Chem
research, Incorporated. The n-propyl bromide and sec-
butyldiallylamine were distilled before use.
p-Dibromobenzene was obtained from Distillation
Products Industries, Division of Eastman Yodak Company and
was used as received.
Diallylamine and allylamine were obtained from the
Shell Chemical Corporation and were distilled before use.
p-?h~ ayle:aediamiae was obtained from Fischor
Scientific Comparny a'ad was used without further purification.
Trimethylborate was obtained from Gallery Chemical
"oapanly anai was used as rZceived.
'T,'J-Diallylaniline, IT-allylaniline, U,:J'-diallyl-
piperazine and 'I-allylpiperiline were prepared by former
students of Dr. George B. Butler and were distilled before
4-Bromo-l-buteLle was prejiared by W. C. 3ond and was
97 per cent pure as determined by gas-liquid chromatographic
Equipment and Treatment of Data
Temperatures record. in this paper are uncorrected
ani are in degrees centigrade.
Infrared data jer-e obtained with a Perkin-Elmer
Infracord Doubl3-beam Infrar3d Recording spectrophotometer.
iTuclear magnetic resonance data were obtained with a
Varian DP-60 High Resolution nuclear Magnetic Resonance
Mass spectral data were obtained on a Bendix Time of
Flight MIass Spectrometer.
Several molecular weights were obtained on a Mechrolab
502 Vapor Pressure Osmometer.
Elemental analyses were performed by Galbraith
Laboratories, Knoxville, Tennessee or Schwarzkopf Micro-
analytical Laboratory, 'Woodside, New York.
PREPARATION OF UN3SATlUATAD SECORfARY AiT TERTIARY AMINES
Not all of the unsaturated seconJdry and tertiu-ry
amines were available commercially, thus it was necessary
to prepare several of them as intermediates. The amines
were prepared either by the method of Butler and Bunch1
or the classical method of Hofmann.35
The former involves the addition of the alkenyl
halide to a slurry of sodium carbonate ani the primary or
secondary amine in water. The reactions were carried out
in a three-necked, rjund-bottom flask fitted with a
mechanical stirrer, a cold-water reflux condenser and an
addition funnel. The reaction mixtures were heated to
approximately 100 by means of a Glass-Col heating mantle
and were maintained at this temperature during the entire
reaction period of 24 to 72 hours. The contents of the
flasks were filtered when cool. The amine layers were
separated and dried over a suitable drying agent. All
amines except I,,. ,!' ,N'-tetraallyl-p-phenylenediamine were
purified by fractional distillation through a 1.5 x 23 cm.
column packed with stainless steel protruled packing and
insulated by an outer glass jacket. N,N,N',NIT'-Tetraallyl-
p-phenylenediamine was purified through preparation of the
hydrochloride salt. The salt was then reacted with base
and the amine distilled in a Hickman molecular still at
pressures of 10-3 to 10-4 am.
The other method for preparation of amines involved
reaction of base with the ammonium salt formed from the
alkyl halide and the appropriate primary or secondary amine.
The reactions were carried out in a one-neck, round-bottom
flask equipped with a cold-water condenser. The amines
were then purified by fractional distillation as in the
Several of the tertiary amines prepared have not
previously been reported in the literature and pirate
derivatives of these amines were prepared by the standard
procedure.36 A sample of the amine was added to a small
quantity of 95 per cent ethanol and this was added to an
equal quantity of a saturated solution of picric acid in
95 per cent ethanol. The solution was heated to boiling,
allowed to cool slowly and the yellow crystals of pirate
were filtered and recrystallized from ethanol.
Synthesis of diallylethylamine.--Diallylamine
(97.2 g., 1.0 mole) and 109.0 g. (1.0 mole) of ethyl bromide
were placed in a 500 ml. flask. The solution was allowed
to stand overnight whereupon a white crystalline solid
formed. After adding 84.0 g. (1.5 mole) of potassium
hydroxide pellets to the solid, the mixture was shaken
occasionally during which time heat was evolved. After ten
hours, the mixture was filtered and the amine was fractionally
distilled at atmospheric pressure yielding 75.5 g. (58'j) of
a clear colorless liquid, b.p. 128-13P, n20 1.43571, lit.37
b.p. 129-1350o, n 1.4560.
Synthesis of diallyl-n-propylamine.--To a 500 ml.
flask were added 126.0 g. (1.3 mole) of diallylamine and
123.0 g. (1.0 mole) of n-propyl bromide. The reagents were
allowed to set overnight during which time a crystalline
solid formed. After 60.0 g. (1.5 mole) of potassium
hydroxide pellets was added, the mixture was shaken
occasionally and allowed to set for a period of two days.
The mixture was filtered and the amine was fractionally
distilled at atmospheric pressure yielding 92 g.(65-0) of a
clear colorless liquid, b.p. 150-151, n21 1.4354; picrate,
Anal. Calcd. for C9H17N: C, 77.64; H, 12.51; N,
10.06. Found: C, 77.41; H, 12.11; N, 10.24.
Synthesis of allyl-n-propylamine.--The Hofmann pro-
cedure was used to synthesize this amine. The reagents,
61.5 g. (.50 mole) of n-propyl bromide and 28.5 g. (.50
mole) of allylamine, were placed in a 200 ml. flask. After
stirring the solution by shaking, an exothermic reaction
occurred and the appearance of small amounts of a white
solid were noted. The mixture was allowed to set overnight,
then 59 g. (.7 mole) of solid potassium hydroxide pellets
was added. The mixture reacted immediately forming a flaky
white solid and a yellow liquid. The mixture was filtered
and the liquid fractionally distilled yielding 23.5 g.
(47%) of a clear colorless liquid, b.p. 109-110, lit.58
Synthesis of allyl-5-butenyl-n-propylamine.--This
synthesis was carried out using the procedure of Butler and
Bunch.14 To vigorously stirring slurry of 10.6 g. (.10
mole) of sodium carbonate, 30 ml. of water and 11 g. (.11
mole) of allyl-n-propylamine, 17.4 g. (.13 mole) of 4-bromo-
1-butene was added dropwise. The mixture, kept at approxi-
mately 100, was stirred for 24 hours, cooled, then filtered.
The amine layer was separated, dried over sodium hydroxide
and fractionally distilled yielding 10.6 g. (66%) of a
clear colorless liqui', b.p. 79-80 (33 mm.), ni 1.4409;
picrate, m.p. 77-78.5.
Anal. Calcd. for C01oH19N: C, 78.36; H, 12.50; T,
9.14. Found: C, 78.78; H, 12.63; iT, 9.335.
Synthesis of di(5-butenyl)-n-propylamine.--The pro-
cedure for preparation of this compound was essentially that
of Butler and Bunch.14 The 4-bromo-l-butene (60.5 g., .45
mole) was added dropwise to a slurry of 32 g. (.30 mole) of
sodium carbonate, 60 ml. of water and 13 g. (.22 mole) of
n-propylamine. The heated mixture was allowed to stir for
24 hours. The mixture on cooling was filtered. The amine
layer was separated, dried over sodium hydroxide pellets
and distilled yielding 19.8 g. (51j) of a clear colorless
liquid, b.p. 93-94 (50 mm.), n22 1.4442; picrate, m.p.
Anal. Calcd. for IAH21N: C, 78.96; H, 12.65; IT,
8.37. Found: C, 73.89; IL, 12.78; iT, 8.52.
Synthesis of AJ,N-di(3-butenyl)aniline.--The procedure
used for preparation was essentially that of Butler and
Bunch. 14The 4-bromo-l-butene (60.5 g., .45 mole) was added
dropwise to a stirring slurry of 32 g. (.30 mole) of sodium
carbonate, 50 ml. of water and 20.5 g. (.22 mole) of aniline.
The mixture was stirred and heated for 72 hours, allowed to
cool, then filtered. The amine layer was separated, dried
over sodium hydroxide pellets and distilled yielding 18.5 g.
(41,?) of a clear colorless liquid, b.p. 91-95 (.6 mm.),
Anal. Calcd. for C1,H19r;: C, 85.54; H, 9.51; N,
6.96. Found: C, 85.58; H, 9.66; N, 6.95.
Synthesis of lN,iI,TT' ,N'-tetraallyl-p-phenylene-
diamine.--The procedure for preparation of this compound
was that of Butler and Bunchl4 with some modifications. A
water solution of 106 g. (1.0 mole) of sodium carbonate,
19.4 g. (.18 mole) of p-phenylenediamine and 96.8 g.
(.80 mole) of allyl bromide was added to a 500 ml. flask.
The mixture was allowed to react for 72 hours, whereupon a
tarry black liquid layer formed. This layer was extracted
with benzene, separated and dried. Gaseous hydrochloric
acid was passed into the benzene solution resulting in the
precipitation of 16 g. of solid which was washed with
acetone. The white solid decomposed at 204-205. This
ammonium salt was then slowly added to a water solution of
sodium carbonate. This solution was extracted with ether.
The ether solution was dried over sodium hydroxide and placed
on a flash evaporator where the ether was removed. The re-
maining liquid was then distilled in a commercial Hickman
still yielding 11.6 g. (223) of a pale yellow liquid, n25
1.5637. A small portion of the pale yellow amine was
redistilled through a micro 10 cm. Vigreux column giving
the boiling point as 133-1534 (.08 mm.). There was no
change in the refractive index or color of the distillate.
Picrate, m.p. 140-142 (dec.).
Anal. Calcd. for C18H2N2: C, 80.54; H, 9.01; N,
10.44. Found: C, 80.353; H, 8.95; N, 10.59.
Ci/adTj1, i III
PREPAJ'ATIO4 OF AIO UF J2UI AD 2HO.)PIII;-i
Synthesis of diallylphenylphosphine.--The procedure
used to pr.pare the phosphine was a modification of the
method of Jones.39 Since the final product is easily
oxidized in air, all transfers and reactions were carried
out under a nitro-gen atmaosphsre. The Grigaard reasent was
prepared by addition of 93.7 g. (.80 mole) of allyl bromide
to a mixture of 500 ml. of ether and 19.2 g. (80 g. atom)
of magnesium in a one-liter, four-neck, round-bottom flask
fitted with a cold-water condenser, an addition funnel, a
low temperature thermometer, ani a mechanical stirr.r. A
nitrogen inlet tube was attached to the condlenser. After
the initial start of the reaction, the flask and contents
were cooled in an ice bath. The addition of the halide was
adjusted so the temperature would remain below 10. After
complete addition of the allyl bromide, the stirring mixture
was allowed to warm to room temperature. The contents of
the flask were cooled to -70 with a dry ice-acetone bath
and an etheral solution containing 59.5 g. (.33 mole) of
dichlorophenylphosphine was added dropwise. The mixture
was allowed to warm to room temperature overnight. It was
hydrolyzed with a 20 per cent water solution of ammonium
chloride resulting in two layers. The ether layer was
separated, dried and fractionally distilled through a
30 cm. vacuum jacketed Vigreux column yielding 29.5 g.
(48.77j) of a clear colorless liquid, b.p. 84-85 (1.1 mm.),
lit.59 b.p. 1270 (14 mm.).
PREPARATION OF BORON INTERMEDIATES
The boron intermediates were prepared by procedures
reported in the literature with some modification. Phenyl-
boronic acid was prepared from trimethyl borate and phenyl-
magnesium bromide using the procedure described by Washburn
and co-workers.40 The phenylboronic acid was converted to
the diethyl ester by azeotropic distillation.41'42 The
diethyl phenylboronate was then reduced by lithium aluminum
hydride in the presence of triethylamine to give triethyl-
Phenylenediboronic acid was prepared by the method
of TTielsen and Mcewen43 from the Grignard reagent of
p-dibromobenzene and trimethyl borate. The previously
unreported tetraethyl ester was then prepared by the same
procedure as diethyl phenylboronate. The attempt to reduce
the tetraethyl-p-phenylenediboronate with lithium aluminum
hydride failed. The reaction was run in diethyl ether and
at the temperature used, the ester and the lithium aluminum
hydride co-precipitated. Possibly the use of a different
solvent would correct the 2ro')lem. All apparatus used in
these reactions were purged with nitrogen for several hours
Synthesis of phenylboronic acid.--PhenylmaGnesium
bromide was prepared by the dropwise addition of 157.0 g.
(1.0 mole) of bromobenzene in ether to a mixture of ethyl
ether and 56.0 g. (1.5 g. atom) of m3gnasium in a one-liter,
four-neck, round-bottom flask equipped with a thermometer,
mechanical stirrer, addition funnel and a cold-water con-
denser. After the reaction was initiated, the contents of
the flask were cooled to 10 with an icebath. UIon complete
addition of the halide, the mixture iias allowed to warm to
room temper-ture. Trimethyl borate (103.9 g., 1.0 mole)
and 800 ml. of ether were placed in a two-liter, three-neck,
round-bottom flask equipped with a mechanical stirrer, a low
temperature thermometer and by means of a Claisen adapter,
a nitrogen inlet tube and an addition funnrl. The solution
was cooled with a dry ice-acetone bath and the Gririard
reagent was added at a rate which kept the reaction mixture
at -65 to -70. During the addition, the reaction mixture
was vigorously stirred. After complete addition, the
mixture was allowed to warm to room temperature overni I-t
and then hydrolyzed with 10 per cent sulfuric acid. The
ether lfCrer was se .rited an'1 placec. in a two-liter, three-
neck, round-bottom flask fitted with an .a-dition funnel,
mechanical sti:-rer and a Claisen distilling hecad. :.s the
ether solution was co-conatrated, 1.0 liter of water was
raIedi slowly until th. tcnp0:rature at the 1istilling head
reached 930. Th- solution was then cooled whereupon a solid
precipitated. The mii:ture was filtered and the solid was
i.shed ;.ith hexane aan,. dried, yielding 10.) g. (90. ) of white
solid, m.p. 212-215, lit.4-0 m.p. 215-216.
Synthesis of diethyl phenylboronate.--Phenylboronic
acid (50.0 g., .41 mole), 320 g. (4.0 mole) of benzene and
158 g. (53.0 mole) of absolute ethyl alcohol were placed in
a two-liter, one-neck, round-bottom flask. The flask was
connected to a azeotropic distillation setup consisting of
a packed distillation column, a Dean-Starke trap, a cold-
water condenser and a drying tube. A thermometer was hung
inside the condenser so that the mercury bulb was slightly
above the overflow in the Dean-Starke trap. The contents
of the flask were heated by a Glass-Col mantle and a ternary
azeotrope of benzene, alcohol and water distilled over at
64 forming two layers in the trap. The lower layer was
continuously removed. After seven days of continuous distil-
lation, the temperature rose to 68 where the binary alcohol
and benzene azeotrope distilled. The trap and condenser
were then replaced by a distilling; head and the remaining
alcohol ani benzene removed. The remaining liquid was
distilled under reduced pressure -iving 69 g. (92;') of a
clear colorless liquid, b.p. 52-55 (.5 m.), lit.4 b.p.
50 (.4 mm.).
Synthesis of trieth:ylamine-phenylborane.--Lithium
aluminum hydride (6.9 g., .18 mole) was added to 600 ml. of
dried diethyl ether in a one-liter, four-neck, round-bottom
flask fitted with a condenser with a nitrogen inlet tube, a
mechanical stirrer, an addition funnel and a low temperature
thermometer. The mixture was refluxed for thirty minutes,
then cooled to -72 with a dry ice-acetone bath. After
52.9 g. (.525 mole) of triethylamine was added to the
stirring mixture, an equal molar quantity of diethyl phenyl-
boronate was added dropwise. After complete addition, the
mixture was stirred for another hour at -72 then allowed
to warm to room temperature. The mixture was then filtered
and the filtrate cooled in a dry ice-acetone bath resulting
in precipitation of a solid. The solid was filtered off
and recrystallized from ether in a similar manner yielding
40 g. (6501) of a white crystalline solid, m.p. 63-65,
lit.42 m.p. 64-65.
Synthesis of p-phenylenediboronic acid.--A solution
of tetrahydrofuran and 47.0 g. (.20 mole) of p-dibromobenzene
was aided dropwiie to a stirring mixture of 1 g. (.45 g.
atom) of magnesium an! 100 ml. of tetrahydrofuran in a
500 ml., three-neck, round-bottom flask equipped with an
addition funnel, stirrer and a cold-water conde ser. After
complete addition, the mixture was refluxed for six hours.
A solution of 300 ml. of diethyl ether and 51.5 g. (.5 role)
of trimethyl borate in a one-liter, four-neck, round-bottom
flask, equipped with a mechanical stirrer, a low temperature
thermometer, an addition funnel and a nitrogen inlet tube,
was cooled to -72. The Grignard reagent was added rapidly,
keeping the temperature at -70. After complete addition,
the mixture of a white solid and ether solution was stirred
at -70 for thirty minutes and then allowed to warm to room
temperature. The mixture was hydrolyzed with dilute hydro-
chloric acid until two layers remained. The organic layer
was separate and dried with anhydrous magnesium sulfate.
The et'eors were removed on a flash ev-porator leaving a
solid which was washed thoroughly with ether, filtered,
washed with water and filtered again. The dry white solid
(26.2 g.) did not melt at up to 250.43
Synthesis of tetraethyl-p-phenyldiboronate.--The
26.2 g. of solid containing p-phenylenediboronic acid,
160 ml. of dry benzene and 200 ml. of absolute ethyl
alcohol were mixed in a 500 ml., round-bottom flask. The
flask was connected to the azootropic distillation setup
described above and treated in a similar manner. The final
fractional distillation yielded 18.1 g. of a clear colorless
liquid, b.p. 128 (1.6 mL.), which hydrolyzed on exposure
to moist air. The overall yield was 31 per cent based on
Anal. Calcd. for CIH2p2L4: C,0 60.49; H, 8.70; B,
7.78. Found: C, 60.26; H, 8.45; B, 7.65.
Attempt to prepare di(triethylamine)-p-phenylene-
diborane.--Lithium aluminum hydride (3.8 g., .10 mole) was
refluxed with 150 ml. of diethyl ether for thirty minutes
in a 300 ml., three-neck, round-bottom flask fitted with a
cold-water condenser, a mechanical stirrer and an addition
funnel. The mixture was cooled to -72* with a dry ice-
acetone bath and 14.0 g. (.15 mole) of triethylamine was
added. The tetraethyl-p-phenylenediboronate (18.1 g.,
.065 mole) was added dropwise and small lumps of grey
material formed. The mixture was stirred for thirty
minutes after complete addition and then allowed to warm to
room temperature. The contents of the flask were filtered
and the filtrate concentrated by removal of ether. The
solution was cooled to -72 but no precipitate resulted and
no evidence of the desired product could be found.
Fu'LPA2ATION OF 30RON HTiLROCYCLES
General Discussion and Results
The syntheses were first atte!2ted by reduction of
diethyl ph.nylboronate with lithium aluminum hydride in
the presence of the unsaturated anine at low temperatures.
The reaction uiturc was then distilled and isolation of
pc-jucts was atte -ptedi by crystallization at low tempera-
tures or distillation. N,.--diallylaniline was used in
these attempts since the bicyclic product from this
compound should be thl b~st nodcl of the proposed polymer.
These reactions did not lead to the stable compounds which
had been c::eocted and tnL easily oxidized p-oJucts could
not be identified. In o'ler to determine if this procedure
was resulting in the hydroboration of the double bond, a
less complex amiae, lT-allylpiperidine, was used since the
number and complexity of the products would be lessened.
The amins was treated in similar fashion and a small amount
of the -ro.uct (135) was isolated.
2 C6H5B(OC2H5)2 + LiAlH4 2 06H5BH2 + LiAl(OC2H5)
C6H5BH2 + CH2-CH-CH2-NCHo 510 CI5-B--N
The product, l-phenyl-l-bora-5-azoniaspiro [4.5] decane was
stable in the atmosphere. The presence of the nitrogen to
boron link could be seen by the shift of the boron-hydrogen
stretching frequency to 4.5 microns which is indicative of
co-ordination compounds of boranes.45
Similar reactions were then run on diallylethylamine
and diallyl-n-propylamine. The only products which could
be isolated were small amounts of clear colorless liquids
which readily oxidized in air. These liquids were later
proved to be substituted 1,2-azaborolidines. Since this
procedure did not appear to give the desired product, the
syntheses were attempted by the use of triethylamine-
phenylborane and the unsaturated amines. These reactions
were performed by heating dilute toluene solutions of the
reagents and slowly distilling the solutions. Two iso-
latable products resulted from these reactions, clear
colorless liquids and white solids. Apparent polymeric
viscous liquids were also formed but were not investigated.
The clear colorless liquids oxidized easily in air, turning
brown after a short period of time. The white solids were
stable in air and were proved to be bicyclic compounds having
C6HsBH2I(C2Hs)3 + (CH2CII-C-H2)2NR--> N(H) +
The liquids were assigned structure II and were the main
isolatable products. Table 5 shows the product and yield
obtained from the appropriate amine.
The structure assignments were made on the basis of
n.m.r. spectra, infrared spectra and analyses. Mass
spectral data and molecular weights were also obtained for
Mass spectral data were obtained for two of the
liquids. The spectra of l-n-propyl-2-phenyl-l,2-aza-
borolidine showed a parent ion peak at 18? mass units which
agrees with the calculated molecular weight of 187.08. The
most intense peak was found at 158 mass units and small
absorptions were recorded at 116 and 89 mass units. The
loss of an ethyl group gives the peak at 158 mass units.
This is consistent with the most probable mode of rupture
of amine compounds.46 The two weak peaks are the result of
PRODUCTS AND YI.-.LDS OF THE REACTION OF TRI ,.THLTI-H.fLBO.i D iRTIIRY
Products and Yields
borabicyclo [3.5.0] octane 7.0,
aza-5-borabicyclo [5- 53.0]-
borabicycio [5.5.0] octane 22.0%
loss of the CH71T-CH2- and C-H N-C H ,- groups. The spectrum
`0 7 3 7 3 6
of l-sec-butyl-2-phenyl-l,2-azaboroliTine showed a parent
ion peak at 201 in agreement with the calculated molecular
weight of 201.11. The most intense peak in the spectrum
was at 172 mass units corresponding to loss of the ethyl
group beta to the nitrogen atom. Three other peaks of
weaker intensity were found at 186, 130 and 89 mass units.
These may be rationalized by considering the loss of -CH3,
04H9N- and C4 :91T-C3H6- groups. The relative intensities
of the peaks also are indicative of the structure assignment.
The spectra shov ed that all peaks resulting from fragmen-
tation in which two bonds were broken were less intense
than the parent ion peak.
The infrared spectra of the liquids were in agree-
ment with the assigned structures. It has been reported
that boron-nitrogen bonds in aminoboranes absorb in the
region of 6.6 to 7.3 microns.32',7',8 Table 6 shows the
boron-nitrogen absorptions of the 1,2-azaborolidines
prepared by this research. The absorptions vere easily
confirmed b,- partial hydrolysis of the substituted 1,2-
azaborolidines which breaks the boron-nitrogren bond and
results in a decra-ise in intensity of the boron-nitrogen
absorption. The infrared spectra also showed the absence
of boron-hydrogen and olefinic bonds.
IFla2CfD B3jRPTION OF TH 2 B-N BOND IN SUBSTITUTED
B-N Absorption Band
in Cm" and Microns
Nuclear magnetic resonance spectra were obtained on
several of the 1,2-azaborolilines. The boron resonance was
obtained for l-ethyl-2-phenyl-l,2-azaborolidine and was
found at -23 ppm. relative to trimethylborate. The proton
magnetic resonance spectral data for three of the 1,2-aza-
borolidines are given in Table 7. The spectra were obtained
on the neat liquids using acetaldehyde as thp external
Two 1,2-azaborolidines were also prepared by the re-
action of secondary allylamines and triethylamine-phenyl-
borane. Thus the reaction of triethylamine-phenylborane with
N-allylaniline resulted in isolation of l,2-diphenyl-l,2-
azaborolidine. Use of allyl-n-propylamine resulted in 1-n-
C6H53H2 (C2H5)3 + CH2=CH-CH2-NHR N(C2 H(5)3 3 +
H2 + O6H5B3 -+R
propyl-2-phenyl-l,2-azaborolidine. The infrared spectra of
the compounds prepared in this manner were identical with
those from the tertiary diallylamines.
The proton magnetic resonance spectral peaks for
several of the l-aza-5-borabicyclo [3.3.0] octanes are given
in Table 8. The spectra were obtained on the solids dis-
solved in carbon tetrachloride using acetaldehyde as the
external standard. The hydrogen absorptions of the first
N.M.R. SPECTiAL DATA OF ..UBSTITUTED 1,2-A ABOROLILINIS
Compound 'Peak Areas
C6H5-B- N+ -CH2-CH3
(l) | (5) (6)
H 3 (8)
CH-B --- N -CH-CH2-CH3
(1) (5)(6) (7
C6H5-B- N -C6H5
(2) j (4)
6 (hidden) -
N.M.R. SPBCTRAL DATA OF SUBSTITUTED 1-AZA-5-
J.LnlYOGLO [5.3.0] O0C,2-S
Compound Peak Areas
I I (YH3 (8)
C6H5--- N -CH-CH2-CH3
(1 I (5)(6) (7)
C6 H 5-B-- N +-CH 2-CH3
(1) I (5) (6)
C H5-B--- N -C H
compound overlapped and could not all be definitely assigned
but the total area does agree with the number of hydrogens.
The spectrum for the ethyl substituted compound appears to
agree on basis of the chemical shifts; however, the total
area does not give complete agreement. The boron resonance
absorption of l-n-propyl-5-phenyl-l-aza-5-borabicyclo
3.53.0] octane was found at +8.9 ppm. relative to trimethyl-
borate. This chemical shift indicates the presence of the
boron-nitrogen bond. 9
The infrared spectra of the substituted l-aza-5-
borabicyclo [5.3.0] octanes showed the absence of boron-
hydrogen and olefinic bonds in the compounds. There were
strong absorptions in the 7.8 to 8.0 micron region which
were tentatively assigned as due to the boron-nitrogen bond.
The boron-nitrogen absorptions of 2'2-iminodiethyl vinyl-
benzeneboronates and of pyridine complexes of boranes have
been assigned near this region.50'51
The formation of the 1,2-azaborolidines from the
reaction of the tertiary diallylamines with triethylamine-
phenylborane is rather unique at the temperatures at which
the reactions were carried out. Amine-boranes which contain
a hydrogen bonded to the nitrogen are known to undergo
elimination of that hydrogen with a group bonded to boron,
on pyrolysis, to form borazines.52 The elimination of
3 BI3 + 3 NH2R -B3NB3N3R3X3 + 5 HX
3 BH3 + 3 N2R B3 I3 R 3113 + 3 H2
3 BH3 + 3 I113 2500 B3I3H6 + 3 H2
hydrogen from amine-boranes has been accomplished at lower
temperatures in solvents.52'53 'When only one hydrogen is
attached to the nitrogen, the reaction stops at conversion
to the aminoborane unless drastic pyrolytic conditions are
employed.5 Amine-boranes which have no hydrogen bonded to
the nitrogen have been found to exhibit good stability.55
If one of the groups on the boron is an alkyl group, then
the compound can disproportionate at high temperatures.56
The most likely mechanism for the formation of the
1,2-azaborolidines isolated in this research must involve
the formation of a cyclic amine-borane which eliminates
the allyl group from the nitrogen. Although no alkene was
ever trapped from the reactions, infrared spectra of samples
taken during the course of the reaction give some substanti-
ation to this mechanism. The samples were taken while a
H5-B NR -C-CH=CH3 HB-NR
solution of the phonylborane complex and diallyl-n-propyl-
amine was being heated to reflux. The boron-hydrogen
absorption at 4.3 microns was followed, and it was found
that the initial hydroboration occurred between 47 and 60.
The sample at 90 showed little change in intensity from
the sample at 730. However at 112, before the solution
started refluxing, the intensity showed a marked decrease
and after refluxing for one and one-half hours, no boron-
hydrogen absorption was found. This suggests that the
mechanism for loss of boron-hydrogen occurs in two suc-
cessive steps which is in agreement with the proposed
The instability of the cyclic amine-borane toward
elimination would be the result of the ease of replacement
of the allyl group. The ability of an ethylenic bond of
an allylic system to delocalize positive or negative charge
over its pi electron system greatly facilitates the re-
actions of a functional group attached. Quaternary ammonium
salts containing allyl groups are known to undergo Hofmann
degradation at much lower temperatures and result in better
yields than corresponding alkyl ammonium compounds.57 Allyl
halides undergo SN2 displacement reactions with ethoxide 37
to 95 times faster than their saturated counterparts.58 Not
only would the allyl group facilitate the elimination but
the reduction of steric hindrance should also aid. In five-
membered rinjs, the chief source of strain is interaction of
non-bonded atoms; removal of the allyl group would reduce
The bicyclic compounds may be formed by initial
intramolecular dihydroborations of the tertiary diallyl-
amines before the nitrogen-boron bonds are formed or the
bicyclics may result from an equilibrium dissociation of
the cyclic amine-boranes followed by hydroboration of the
remaining double bond. The position of equilibrium of the
reaction would be largely toward the cyclic amine-borane.
The stability of the boron-nitrogen bond of the cyclic
amine-borane apparently limits the amount of bicyclic
compound which can be formed.
C6H5- -1 C6H5-B-H :N-R C6H5__-B N -R
octane was treated under conditions of the synthetic
reactions and was found to be completely stable and not a
precursor of any other product.
The reaction of triethylamine-phenylborane with
diallylphenylohobphine under similar conditions gave
l,5-diphenyl-l-bora-5-phosphabioyclo [35.3.0J octane in 28
per cent yield. No monocyclic product was forT-ed by the
reaction and this suggests that the boron-phosphorus bond
was not as stable as the boron-nitrogen bond. Ths dis-
sociation energies for complexes of trimethylamine and tri-
methylphosphine with trimethylborane, have been founl to be
17.6 kcal./mole and 16.5 kcal./mole, res)ectively.59'60
The infrared spectrum of the bicyclic compound
showed the absence of boron-hydrogen and olefinic bonds.
The nuclear magnetic resonance spectral data are given in
Table 9. The soectrum was obtained from a carbon tetra-
chloride solution of the compound using acetaldehyde as the
The molecular weight and analysis also agreed with
the structure assignment.
Similar reactions were atte i;tei uzin.-S T,,T-di(3-
butenyl)aniline, di(5-butenyl)-n-propylamine and allyl-3-
butenyl-n-propylamine. The only product which was isolated
in these reactions was triphenylborane as the pyridine
complex. The reaction of allyl-5-buteiVl-n-propylamine was
rerun and distillation was attempted in a Hickman still at
low pressures. The di'tillate was a thick viscous liquid
which contained no isolatable amount of triphenylborane.
The infrared spectrum showed the presence of boron-hydrogen
absorption at 4-.3 microns and some olefinic bonds.
J.M.2. SzEGC2iAL DATA OF 1,2-JIPH;,NL-1-BORA-5-
PHOSPHABICYCLO [3.3.0] OCTANE
Compound Peak Areas
(3) 1 3.13 10.0 (1)
(2) 4) 1 3.23
( :) (C) 1 3.31
(1) ( 1(I) 4 8.P9 12.5 (2,
(2) (4) 5 9.0. 3,4.)
(3) 2 9.61
Unfor-tunIt!'y use of the Iic1:-"vi still does a)t r.sult in
,:-ool se)paratio-i and no ur"e products could be isolat-i.
Thus the pot ter-ieratures required for distillation of the
products by conventional distillin- apparatus are aar.n-itly
high enou-h to cause mutual replacement.
The -jynthesis of l-:?hen,vl-l-bora-5-az.oniaspiro [4.5]
decade was -ri-eate7 u i'i- the reaction of triettylamine-
ph~nylborane and :T-allylpiperidin.. The infrared Egoctrun
of this product was identical with the infrared spectrum of
the -,ro'-uct isolated by the other procedure. The yield was
increased to 45 ?er ceit.
An attempt to prepare a polymer continin.j a yvclic
unit was made with the reaction of triethylamine-ph3nyl-
borane an. ',&'-diallylpiperazine. Although the stable
product was isolated in ';ool yield, the average degree of
polymerization was only three. The infrared spectrum of
C6H 5 N-C3H6
the product showed an abseace of -tij boron-hy1ro.en bonds
but a small amount of vinyl absorp-tion was present.
The thermal stability of the model compounds prepared
in the paper could not be rigorously tested as the dif-
ferential thermal analyzer was not yet completely assembled.
Use of a melting point assembly with the samples in closed
capillary tubes did show that the l,5-diphenyl-l-aza-5-
borabicyclo E35.5.0] octane darkened at 270 although the
l-sec-butyl-5-phenyl-l-aza-5-borabicyclo E3.35.0] octane
showed no change at 320. The l,2-diphenyl-l-bora-5-
phosphabicyclo E3.3.0J octane also showed no change at 5200.
The procedure used for the reactions between phenyl-
borane and the unsaturated amines involved placing lithium
aluminum hydride with either tetrahydrofuran or diethyl
ether in a nitrogen-purged, four-neck, round-bottom flask
fitted with a mechanical stirrer, a low temperature
thermometer, an addition funnel and a cold-water condenser
fitted with a nitrogen inlet tube. The mixture was refluxed
for thirty minutes then cooled to -72 with a dry ice-acetone
bath. The amine was added in one batch. The diethyl phenyl-
boronate was then added dropwise to the stirring mixture.
After complete addition, the mixture was allowed to warm to
room temperature. The mixture was filtered in a dry box,
then distilled. Further purification depended on the compound
synthesized and will be given in the experimental section.
The procedure which was followed to react the tri-
ethylamine-phenylborane and the unsaturated amines and
phosphine involved placing the reagents and approximately
2.0 liters of toluene in a one-neck, round-bottom flask
with a thermometer well. The flask was then connected to
a 60 cm. packed column with a normal fractional distilling
head. The solution was slowly heated to reflux and the
triethylamine and toluene were slowly distilled. After
the pot temperature reached 120, the remaining small
amount of toluene was removed under reduced pressure. The
residual liquid was then distilled over a short Vigreux
column into several crude fractions. For syntheses giving
the 1,2-azaborolidines, the lower boiling fractions were
redistilled through a 25 plate spinning band column. The
higher boiling fractions were inaividually dissolved in a
small quantity of solvent and cooled to -72 where the
solid compounds precipitate. They were then recrystallized.
Purification details of the compounds synthesized in this
manner are given in the experimental.
All reactions and transfers, except crystallizations,
were carried oub in a nitrogen atmosphere.
Synthesis of l-phenyl-l-bora-5-azoniaspiro [4.5]-
decane from phenylborane and N-allylpiperdine.--Diethyl
ether (500 ml.) and 2.5 g. (.06 mole) of lithium aluminum
hydride were refluxed then cooled to -72. The N-allyl-
piperidine 12.5 g. (.10 mole) was added to the stirring
mixture followed by the dropwise addition of 17.7 g. (.10
mole) of diethyl phenylboronate. After warming to room
temperature, the mixture was filtered. The ether was re-
moved and the residual liquial distilled unler reduced
pressure giving four crude fractions which ranged from 61
(34. mm.) to 150 (.1 mm.). The fraction distilling at 135-
1450 (.1 mm.) slowly crystallized on setting. Thp solid
was dissolved in li.ht petroleum ether and then cooled to
-72 where a white solid precipitated. On filtering, the
solid melted, so the petroleum ether was decanted and the
remaining removed under reduced pressure. Repetition of
the procedure left 3.0 :;* (13A) of a white solid, m.p.
Anal. Calcd. for C14H22B'I: 0, 78.16; H, 10.31; N,
6.51; B, 5.04. Found: C., 77.98; H, 10.15; N, 6.40; B, 5.17.
Synthesis of l-phenyl-l-bora-5-azoniaspiro [4-. 53-
decane from triethylamine-phenylborane and N-allylpiperiiine.--
A solution of 1.7 liters of toluene, 19.1 g. (.10 mole) of
triethylamine-phenylborane and 12.0 g. (.096 mole) of N-
allylpiperidine was distilled at atmospheric pressure until
the pot temperature reached 120. After the remaining
toluene was removed, the residual liquid was distilled into
three crude fractions. The fractions were dissolved in
pentane and cooled to -72. A white solid precipitated
from the fractions distilling at 114-120 and 120-124
(.03-.05 mm.). The pentane was decanted, the solids combined
and the remaining liquid removed under reduced pressure.
repetition of the crystallization gave 9.8 *. (45 5) of a
white solid, n.p. 54-350. The infrared spectrum of this
compound w;as identical to that preored above.
Synthesis of l-ethyl-2-ph-nyl-1,2-asaborolidine and
l-ethyl-5-phenyl-l-aza-5-borabicyclo [5.*.0] octane from
triethylamaine-phanylborane and diallyletbylamine.--A solu-
tion of 2.0 liters of toluene, 28.8 g. (.15 mole) of tri-
ethylamine-phonylborane and 18.8 g. (.15 mole) of diallyl-
ethylamine was distilled at atmospheric pressure until the
pot temperature reached 120. After the remaining toluene
was removed, the residual liquid was distilled into five
crude fractions. The two lowest boiling fractions, 60-92
and 92-1070 (.8 mm.), were redistilled through the spinning
band column iving 5.9 g. (22.8V) of the clear colorless
liquid, l-ethyl-2-ph?ayl-l,2-azaborolildine, b.p. 72.5-
74.0 (1.5 am.).
Anal. Calcd. for C11H163B: C, 73.33; H, 9.52; N,
8.09; 3, 6.25. Found: C, 76.27; H, 9.25; 'T, 8.06; B,
The remaining three fractions were dissolved in a
small amount of acetone and cooled in a dry ice-acetone
bath where a white solid precipitated. The solids were
filtered, combined and recrystallized from acetone yielding
2.3 g. (7,3) of the white solid, l-ethyl-5-phenyl-l-aza-5-
borabicyclo [3.3.0] octane, m.p. 57.5-58.50.
Anal. Calcd. for C14H22BNI: C, 78.16; H, 10.31; N,
6.51; B, 5.05. Found: C, 77.87; H, 10.38; Li, 6.76; B,
Synthesis of l-ethyl-2-phenyl-l,2-azaboroliLine from
phenylborane and diallylethylamine.--A solution of 500 ml.
of dry tetrahydrofuran and 4.0 g. (.11 mole) of lithium
aluminum hydride was refluxed then cooled to -72. Diallyl-
ethylamine (25.0 g., .20 mole) was added to the stirring
mixture followed by the dropwise addition of 35.4 g. (.20
mole) of diethyl phenylboronate. After complete addition,
the mixture was alloited to warm to room temperature. The
mixture was filtered, then the filtrate was distilled at
atmospheric pressure removing the tetrahydrofuran. The
remaining liquid was distilled through a spinning band
column yielding 3.0 g. (8.7'j) of a clear colorless li-iuid,
b.p. 68-70 (1.0 mm.). The infrared spectrum of this
compound was identical with the l-ethyl-5-phenyl-l,2-aza-
borolilJine prepared by the other method.
Synthesis of l-n-propyl-2-phenyl-l,2-azaborolidine
and l-n-propyl-5-phenyl-l-aza-5-borabicyclo 35.5.30 octane
from triethylphenylborane and diallyl-n-propylamine.--A
solution of 2.0 liters of toluene, 25.0 g. (.12 mole) of
triethylamine-phenylborane and 16.6 g. (.12 mole) of
diallyl-n-propylamine was distilled at atmospheric pressure
until the pot temperature reached 1200. After the remaining
toluene was removed, the residual liquid was distilled into
six crude fractions. The lowest boiling fractions, range:
78-83 (1.2 mm.), were redistilled through a spinning band
column yielding 7.0 g. (53l.') of the clear colorless liquid,
l-n-propyl-5-phenyl-l,2-azaborolidine, b.p. 87.5-90
Anal. Calcd. for C12HI8BOT: C, 77.04; H, 9.69; N,
7.48; B, 5.78; mol. wt., 187. Found: C, 77.73; H, 9.55;
N, 7.40; B, 5.62; raol. wt., 187 (mass spectra).
The three high boiling fractions, ranging from 105
to 165 (1.5 mm.), were dissolved in small amounts of
acetone, cooled in a dry ice-acetone bath where a white
solid precipitated from each. The solids were filtered,
combined and recrystallized from acetone yielding 2.2 g.
(8 .) of the white solid 1-n-propyl-5-phenyl-l-aza-5-
borabicyclo [3.3.0] octane, m.p. 61-62.
Anal. Calcd. for C15H24314: 0, 78.61; H, 10.56; N,
6.11; B, 4.78; mol. wt., 229. Found: C, 78.49; H, 10.66;
N, 6.27; B, 4.48; mol. wt., 259 (cryoscopic in cyclohexane).
3_ynthesis of l-n-propyl-2-phenyl-l,2-azaborolidine
from phenylborane and diallyl-n-propylamine.--A solution of
500 ml. of dry tetrahydIrofuran and 5.0 g. (.075 mole) of
lithium aluminum hyjride was reflu:ced then cooled to -72.
The iiallyl-n-propylamine (18.8 g., .155 mole) was aided to
the stirring mixture followed by the dropwise addition of
25.8 g. (.155 mole) of diathyl phanylboronate. After com-
plete addition, the mixture was allowed to warm to room
temperature. The mixture was filtered, and the filtrate
was distilled at atmospheric pressure to remove the tetra-
hylrofuran. Tho residu:. liquid vjas then distilled through
a spinning band column yialing 53.7 g. (14,) of a clear
colorless liquid, b.p. 71 (.5 mmu.). The infrared spectrum
of this compound was identical to the l-n-propyl-5-phenyl-
1,2-azaborolidine prepared by the other procedures.
Synthesis of l-n-propyl-2-phenyl-l,2-azaborolidine
from triethylamine-phenylborane and allyl-n-propylamine.--A
solution of 2.0 liters of toluene, 10.4 g. (.105 mole) of
allyl-n-propylamine and 20.0 g. (.105 mole) of triethyl-
amine-phanylborane was distilled at atmospheric pressure.
hIylrogon evolution was evident soon after heating of the
solution began. After the pot temperature reached 120,
the remaining toluene was removed under reduced pressure.
The residual liLjuid was distilled through a spinning band
column yielding 9.2 g. (47) of a clear colorless liquid,
b.p. 78-79* (.5 mm.). The infrared spectrum of this compound
was identical to the l-n-propyl-2-phcnyl-l,2-azaborolidine
prepared from diallyl-n-propylamine.
Jynthecsis of l-sec-but.71-2-phenjl-,12-azaborolidine
an.l 1-sec-butyl-5-ph.-nyl-l-aza-5-borabicyclo [3.3.0] octane
from triethylamine-phenylborane ?nd sec-butyldiallylamine.--
A solution of 2.0 liters of toluene, 25.6 g. (.167 mole) of
sec-butyldiallylamine and 32.0 g. (.167 mole) of triethyl-
amine-phenylborane was distilled at atmospheric pressure urtil
the pot temperature reached 120. After the remaining toluene
was removed, the residual liquid was distilled into three
cru'le fractions. The lowest boiling fraction, 60-110 (.6
ram.), was redistilled over a spinning band column giving
7.1 g. (1 j) of the clear colorless liquid., l-sec-butyl-2-
phonyl-l,2-azaborolidine, b.p. 81-82 (.8 m.).
Anal. Calcd. for C1320B: C, 77.64; H, 10.02; N,
6.96; B, 5.58; mol. wt., 201. Found: C, 77.61; H, 10.22;
14, 7.00; B, 5.76; mol. wt., 201 (mass spectra).
The fraction distilling at 120-1350 (.55 mm.) was
dissolved in a small amount of acetone and cooled in a dry
ice-acetone bath whereupon a solid precipitated. The solid
was filtered and recrystallized from acetone yielding 5.8 g.
(9.5 ) of the white solid, l-sec-butyl-5-phenyl-l-aza-5-
borabicyclo [5.5.0] octane, m.p. 59-60.5.
Anal. Calcd. for C16126BN: C, 79.03; H, 10.78; I ,
5.76; B, 4.45; mol. wt., 2543. Found: C, 78.85; H, 10.80;
N, 5.74; B, 4.48; mol. wt., 244 (cryoscopic in cyclohexane).
Synthesis of l,2-diphenyl-l,2-azaborolidine and 1,5-
diphenyl-l-aza-5-bor'abicyclo [5.-3.0] octane from triethyl-
lanini-jh.aylborine and 7T,U1-diallylaniline.--A solution of
2.0 liters of toluene, 32.0 G. (.185 mole) of N,.I-dialll-
anilin3 and 35.2 2. (.185 mole) of triethIylaine--henyl-
borane were iistilled at atmospheric pressure until the pot
te',)erat'ure roch el 120. After the remaining toluene was
re moved the residual liquid which hadl a phosphorescent
yellow-jreen color, was distilled into four crude fractions.
The two lowest boiling fr-ictions, 70-130 (.5 mn..), were
redistilled through a spinnin- band column yiellin.; 12.2 g.
(30%) of the colorless liui1, l,2-.iphunyl-l,2-azaborolidine,
b.p. 126-127 (1.1 jmm.).
Anal. Calca. for C015H1631: C, 81.-7; H, 7.29; 1,
6.3-; B, 4.23). Found: C, 81.38; H, 7.42; 'T, 6.14; B, 5.55.
The hi-:hest boiling fractions, 150-160 (.4 nrim.), were
dissolved in a small amount of acetone an? cooled in a dry
ice-acetone bath. The solid which precipitated was filtered,
then recrystallized twice, from acetone, then pentane to
give 11.0 g. (22') of the white crystalline, 1,5-diphenyl-
l-aza-5-borabicyclo [5.3.0] octane, m.p. 80-81.
Anal. Calcd. for C18H22.3T: C, 82.15; H, 8.42; ;,
5.52; B, 4.11; mol. wt., 265. Found: C, 82.13; H, 8.68;
N, 5.48; B, 4.24; mol. wt., 264 (vapor pressure osmometer).
Synthesis of l,2-dipheny-l,2-azaborolidine from
triethylamine-phenylborane and N-allylaniline.--A solution
of 2.0 liters of toluene, 12.7 g. (.095 mole) of N-allyl-
aniline and 20.0 g. (.095 mole) of triethylamine-phenylborane
was distilled at atmospheric pressure until the pot tempera-
ture had reached 120. After the remaining toluene was
removed, the residual liquid was distilled and a crude
fraction 112-118 (.4 mm.) was separated. This fraction was
redistilled through a spinning band column yielding 12.5 g.
(58') of a colorless liquid, b.p. 122-123 (.65 mm.). The
infrared spectrum of this liquid was identical to the 1,2-
diphenyl-l,2-azaborolidine prepared from the N,N-diallyl-
Synthesis of 1,5-diphenyl-l-bora-5-phosphabicyclo-
C3.3.03 octane.--A solution of 2.0 liters of toluene, 28.6 g.
(.15 mole) of diallylphenylphosphine and 28.8 g. (.15 mole)
of triethylamine-phenylborane was distilled at atmospheric
pressure until the pot temperature reached 1200. After the
remaining toluene was removed, the residual liquid was
distilled into five crude fractions with a temperature range
of 160-2600 (.5 to 5.0 mm.). Each fraction was dissolved in
a small amount of acetone and cooled in a dry ice-acetone
bath. A small amount of solid precipitated from each
fraction. The mixtures were filtered, the solids combined
and recrystallized twice, from acetone and from diethyl
ether yiellina 11.6 .. (2i;) of a white ;3oli, m.). 75.5-
Anal. Calcd. for C18H22BP: 0, 77.16; H, 7.92; P,
11.05; 3, 3.36; mol. wt., 280. ?ou.ad: C, 77.08; Ji, 7.71;
2, 10.90; B, 4.02; mol. wt., 287 (vapor pressure osmometer).
8ynthe si 3 o* the telomar from brieathyluiine-phenyl-
jo-Lie aLad ?T,T'-liallyl~iperazine.-A solution of 400 ml.
of toluene, 28.8 j. (.15 mole) of triethyl.-jine-.,h'A nyl-
borine and 24.9 g. (.15 mole) of N,I'-diillylpiperazine
was slowly distilled at atmospheric pressure. After the
pot tea2erature reached 120, the remiininri; toluene was
reacved under reduced pressure with formation of a ,:hitr
solid. The solid was dissolved in benzene and precipitated
by pouring, the benze:aie solution into a large volume of
peatane. The mixture was filtered and dried yielding 23.8 g.
(75%) of a stable white solid which completely melted at
temperatures of 200-220.
Anal. Calcd. for CI6H25lI2: C, 75.01; H, 9.83; I,
10.94; B, 4.22. 2ound: C, 75.11; H, 9.77; ', 10.70; B,
4.27; mol. wt., 660 (va-tor pressure osmoneter).
2?Reaction of triethylamine-phenylborane and N,:1-
di(3-butenl)aniliae.--A solution of 3.0 liters of toluene,
15.9 g. (.083 mola) of tziethylamine-phenylborane and 16.8 g.
(.085 mole) of 'N,II-di(5-butenyl)aniline was distilled at
atmospheric pressure until the pot temperature reached 120.
After the resainiiz toluene w3-. re:-eve1, the residual liquid
was distilled into six crude fraction, e:a-ch con-isting of
a r:3llow--reen liquid with a snr:ill amount of white solil.
Atteaots to ?recioitate the solid failed. A small amount
of solid was isolated by -ouii-?i D-ntJi3, cool to -72
into the mix-ture aq'l filtering irnediately. The solid
decomposed slowly in air. The yellow liiuil-, -'hn in
pnta-ae, decomoosed almost immediately on contact with air.
After settin- in the air ov'3rii-ht, the original solid had
turned brown, lecrystillization of the brown solii from
hexane oroved the material re liining wAs :)he'rlboronic
acid, m.p. 210-214.
Reaction of -i(3-butenyl)-n-1ropyrlamine and tri-
etbhyl i:aine-ph-?nylborane.--A solution of 2.0 liters of
toluene, 15.2 g. (.08 mole) of triethylaiine-ph.3nylborane
a-ad 14.2 g. (.085 mole) of di(7-butenyl)-n-propylamine was
distilled at atmospheric pressure until the -ot tomr)3rture
reached 120. After the remuainin,-: toluene was reDovel under
reduced pressure, the liquid w.s distilled into seven crude
fractions. Six of the fractions, distillin.; from 120-195
(2.0 mm.), contained a light yellow liquid and a white
solid. Both decomnoged in air, turning dark brown. Attempts
at se. -i-iting the solid from the liquid by precipitation
from solution failed. A small amount of the solid was
isolated 'y pouring cold pentane into the mixture f-nd
filtering immediately. The solid was then dissolved in
ether and a small quantity of pyridine added. A solid
precipitated immediately. The remaining fractions were
dissolved in ether and pyridine added. Solids formed
immediately. The solids were combined and recrystallized
frrm acetone yielding 1.5 g. of pyridine-triphenylborane,
m.p. 212-214 (dec.), lit.61 214 (dec.). Under nitrogen
the compound melted at 245-2470.
Reaction of triethylamine-phenylborane and allyl-3-
butenyl-n-propylamine.--A solution of 2.0 liters of toluene,
11.5 g. (.06 mole) of triethylamine-phenylborane and 9.0 g.
(.06 mole) of allyl-3-butenyl-n-propylamine was distilled
at atmospheric pressure until the pot temperature reached
120. After the remAining toluene was removed the residual
liquid was lictillad into three fractions. The first, 115-
100 (1.4 mm.) contained only a few drops of liquid. The
two higher boiling fractions, 160-180 (4.0 mm.) and 175-
1950 (2.0 mm.) contained a white solid and a yellow liquid.
Dissolvin; these in ether and aiding pyri'inn resulted in
a solid which on recrystallization from acetone yielded
5.5 g. (51A) of pyridine-triphenylborane, m.p. 245-2470
The initial portion of the reaction was repeated.
The residual liquid was distilled in a Hickmman still at
pressures of 10-3 to 10- mm. and the infrared spectrum of
the distillate showed the presence of boron-hydrogen
absorption at 4.3 microns and a small amount of vinyl
absorption. No single product was isolated by the distil-
Treatment of l-sec-butyl-5-phenyl-l-aza-5-borabicyclo-
[53.3.0 octane under reaction conditions.--A solution of
100 ml. of toluene and 2.3 g. of l-sec-butyl-5-phenyl-l-
aza-5-borabicyclo [3.3.0] octane was refluxed for thirty-
six hours. The toluene was distilled at atmospheric
pressure until the pot temperature reached 1200. The re-
maining toluene was removed under reduced pressure and the
residual liquid was distilled giving only one fraction at
120 (.1 mm.). The pot temperatures ranged from 160-230
during the distillation. A small amount of acetone was
added to the liquid distillate and the solution was cooled
in a dry ice-acetone bath yielding 2.1 g. of white solid,
Reaction of triethylamine-phenylborane and diallyl-
n-propylamine as followed by infrared absorption.--A
solution of 2.0 liters of toluene, 28.8 g. (.15 mole) of
triethylamine-phenylborane and 20.8 g. (.15 mole) of
diallyl-n-propylamine was placed in a three-neck flask
fitted with a serum cap and a thermometer. The flask was
connected to the distillation apparatus and slowly heated.
Samples of 30 ml, were withdrawn at various temperatures
and immediately cooled. The samples were then concentrated
to 1 ml. under reduced pressure and the infrared spectra
of the sample taken using a cell whose width was .0258 mm.
All spectra were obtained using this cell in order to
assure uniformity. The intensity of the boron-hydrogen
absorption at 4.3 microns was measured from the base line
to the peak.
Temperature of solution Intensity
112 (after refluxing for
of B-H absorption
Four substituted l-aza-5-borabicyclo C5.3.0] octane,
a new class of compounds, and four previously unreported
1,2-azaborolidines were prepared and characterized. The
compounds were obtained from a novel reaction between tri-
ethylamine-phenylborane and tertiary diallylamines. A
mechanism for the reaction was proposed, based on qualita-
tive data. Two of the 1,2-azaborolidines were also
prepared from the reaction between triethylamine-phenyl-
borane and secondary allylamines.
A new compound, l-phenyl-l-bora-5-azoniaspiro [4.53-
decane was prepared by the reaction of triethylamine-
phenylborane and N-allylpiperdine.
A telomer with an unusual structure was prepared
from N,N'-diallylpiperazine and triethylamine-phenylborane.
The compound, 1,5-diphenyl-l-bora-5-phosphabi-
cyclo 3[5.5.0] octane was prepared and characterized. This
compound, representing the first heterobicycloalkane of
this type, was synthesized from the reaction of triethyl-
amine-phenylborane and diallylphenylphosphine.
Tetraethyl-p-phenylenediboronate was prepared and
Several new tertiary unsaturated amines, used as
intermediates, were prepared and characterized.
Although rigorous testing of the thermal stability
of the bicyclic compounds was not possible, several
compounds did show a potential for use in polymers having
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Gary Lewis Statton was born on November 4, 1937, in
New Brighton, Pennsylvania. He attended public schools in
Beaver Falls, Pennsylvania and was graduated from Beaver
Falls Senior High School in 1955. He attended Geneva
College and was awarded the degree of Bachelor of Science
in 1959, graduating with honors.
In September, 1959, he entered the graduate school
of the University of Florida and has been in attendance
since that date. During this time, he has held the position
of graduate assistant and graduate fellow.
The author is a member of the American Chemical
The author is married to the former Shirley Evelyn
Walker and is the father of three children.
This dissertation was prepared under the direction of
the chairman of the candidate's supervisory committee and
has been ai, rove by all members of that committee. It was
submitted to the Dean of the College of Arts and Sciences
and to the Graduate Council, and was approved as partial
fulfillment of the requirements for the degree of Doctor of
April 18, 1964
Dean, College of Arts and Sciences
Dean, Graduate School