Front Cover
 Title Page
 Table of Contents
 List of Tables
 List of Figures
 Experimental procedures
 Infrared spectra
 Biographical sketch
 Committee report
 Back Cover

Group Title: study of the synthesis of some derivatives of borazene by Grignard-type reacions
Title: A study of the synthesis of some derivatives of borazene by Grignard-type reacions
Full Citation
Permanent Link: http://ufdc.ufl.edu/UF00098013/00001
 Material Information
Title: A study of the synthesis of some derivatives of borazene by Grignard-type reacions
Alternate Title: Synthesis of some derivatives of borazene by Grignard-type reactions
Physical Description: v, 82 l. : illus. ; 28 cm.
Language: English
Creator: Harris, James Joseph, 1930-
Publisher: s.n.
Place of Publication: Gainesville
Publication Date: 1958
Copyright Date: 1958
Subject: Borazene   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
Thesis: Thesis - University of Florida.
Bibliography: Bibliography: l. 78-79.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Vita.
 Record Information
Bibliographic ID: UF00098013
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000424001
oclc - 11062890
notis - ACH2406


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Table of Contents
    Front Cover
        Front Cover 1
        Front Cover 2
    Title Page
        Page i
        Page ii
    Table of Contents
        Page iii
    List of Tables
        Page iv
    List of Figures
        Page v
        Page 1
        Page 2
        Page 3
    Experimental procedures
        Page 4
        Page 5
        Page 6
        Page 7
        Page 8
        Page 9
        Page 10
        Page 11
        Page 12
        Page 13
        Page 14
        Page 15
        Page 16
        Page 17
        Page 18
        Page 19
        Page 20
        Page 21
        Page 22
        Page 23
        Page 24
        Page 25
        Page 26
        Page 27
        Page 28
        Page 29
        Page 30
        Page 31
        Page 32
        Page 33
        Page 34
        Page 35
        Page 36
        Page 37
        Page 38
        Page 39
    Infrared spectra
        Page 40
        Page 41
        Page 42
        Page 43
        Page 44
        Page 45
        Page 46
        Page 47
        Page 48
        Page 48a
        Page 48b
        Page 49
        Page 50
        Page 50a
        Page 50b
        Page 51
        Page 52
        Page 52a
        Page 53
        Page 54
        Page 55
        Page 56
        Page 57
        Page 58
        Page 59
        Page 60
        Page 61
        Page 62
        Page 63
        Page 64
        Page 65
        Page 66
        Page 67
        Page 68
        Page 69
        Page 70
        Page 71
        Page 72
        Page 73
        Page 74
        Page 75
        Page 76
        Page 77
        Page 78
        Page 79
    Biographical sketch
        Page 80
        Page 81
    Committee report
        Page 82
        Page 83
    Back Cover
        Page 84
        Page 85
Full Text




L I \


alilS~ ~r~~l






Augur., 19iS


The author wishes to express his sincere appre-

ciation to his advisor, Dr. Harry 11. Sisler, whose advice

and encouragement made it possible to complete this work.

In addition, he would like to thank Dr. George E. Rysah-

kewitsch for his constant interest and many valuable sug-

gestions and ideas throughout the course of this research.

He would also like to thank the members of his supervisory

committee, other members of the staff, and his fellow

graduate students for aid furnished 9t various times in

the course of this research.

He also wishes to express his heartfelt gratitude

to Koppers Inc., whose generous financial assistance made

this work possible.

mrA mmm mm lialHm

4S Pass

i .. i m b..m p i

... ..... .....
C pomp 9 ow

-.l........ ..i.i ^';^e m ..... .....
.. .. . .

migasi i ipi -
.... a


Table Page

1. Infrared Absorption Bands for B-sub-
stituted Borazenes 42

2. Infrared Absorption Bands for N-tri-
methyl-B-substituted Borazenes 44

S mm cmW."4

.. .. a.. l Pi )pim ig-
.. ....wt. da. .... -


Borazene, a six-membered ring of alternate boron and

nitrogen atoms, each bonded externally to a hydrogen, was

discovered in 1926 by Stock and Pohland (28). They correct-

ly assigned the ring structure to it on the basis of its

chemical properties. This has been verified by electron

diffraction studies which show that the compound is planar

with bond angles of 1200 (1, 4).

Because of the difficulty of its synthesis only slow

progress has been made, until recently, in the study of its

chemical behavior and in the preparation of different types

of compounds containing the borazene ring. Originally the

synthesis involved the pyrolysis of the addition product of

ammonia and diborane (28), so that the synthesis of large

quantities of borazene was not practical. Synthesis of N-

alKyl substituted borazenes could be effected by starting

with amines rather than ammonia (26). B-alkyl-borazenes

have been synthesized by using boron trialkyls (25), alkyl

boron dichloride (21), or by treating borazene with boron

trinethyl (26). The synthesis of borazene has been facil-

itated by the use of lithium borohydrlde in place of dlbo-

rane (23). Sodium borohydride has also been found to be

practical for the synthesis (8). Jones and Kinney (11)

found that N-aryl-B-haloborazenes could be synthesized from

the reaction of boron trihalides and aromatic amines in an

iOWemO slMvent. This OrateaelS aIs bseesr attja toa iL-
att allr ntalteM Of :iNsiu. e shlari*s (1 64) al LWL

t b.t.eI.a with beron trdhLMdflg. *a SliuiM-
IMOl ter h tfatuM urMs thie ewO Mtan at .-tfsidMN..
cl|:ll Uith llF ith buwihuearAL (*), or sdlium baIgm
sui"e ().
*hul"eiSi Wele a t* *At aA am lastIraf puat &snipdo
IIfI lfMlg aid St as ielnnae par lner, tsall ii -Sw
igWiiiW f N IltDWl pi ends bet*ag Dimd, in mditibn
I VMI ligemal sAlm baida. In rioerdewse 4 w tbid, em
bead apinulse i isdiiOte* in the rFIg (320), asoi bm"at*
old"s tbew-pttia in tIn ultpral-iaie raigien of the apIedfi]aM
*tSsiimpttag to mobile elsetreaT (9, 18, 20). sene&e Vf
th-ta, same a*uthorn haitr assigned 8j dinbu ismed ra"eae
scetutupre to bweseq (16). The inRtenal coar.Litaiten imladi
hrve i*S result ofi ple8aig a pofrtial Mragati&vw swrPi an I
Le- *a."i s ut rHal pee ||rs. hw bge on the rita li.C
at bis, the- hAeegg emO the herean It eMe-i t eSS GiU

1 It i4 te I btwneaese Sd hyfle"tIi e fhie ri,

L erpin bremi&Sswisleli sai*4l-, 1ss., *d ii.t...i e*t.i.
l af thOs i :I|e :PSMiduabeks dIsa9pesw tb.egive swbth
blodt bamI1iams PFeo sXIJample*, UN. SlMiteBn t hyld-inges 1boe-
uCl Imi bulhibA ultiaNtdly rvaults in the fmlaiia6 -of
##IA3 J*r4-. B35 36 ---B I3t383 + 3

Some cases of substitution reactions have been ob-

served. Borazene will react with boron trimethyl to give

B-trimethylborazene (26), and with boron triehlorlde and

boron tribromide to give B-mono-, di-, or trichloroborasene

and B-mono-, di-, or tribromoborazene, respectively (23).

It can be seen that the types of borazenes which

have been prepared are few. In preparing derivatives of

borazene it has been common to custom-bild the borazene

by use of the appropriate starting materials, rather than

by working with the borazene group itself. The object of

this research was to attempt to expand the field of borasene

chemistry by finding general synthetic methods applicable to

the preparation of borazene derivatives in good yields, and

of different functional types. In the field of organic

chemistry the use of organo-metallic compounds has been of

tremendous value in the preparation of organic compounds of

different classes. In particular the Grignard reagent, pre-

pared from an organic halide and magnesium, has been inval-

uable. Since B-haloborazenes are easily prepared in quantity

from readily obtainable starting materials, it was decided

to attempt to prepare borazene analogs of Grignard reagents

and to use these in the general preparations of other substi-

tuted borazenes.

a e. .M... ..r aw.... ... ..
.... S .... .... a.. -...
as wee. t us u. a. ... P .
+tt. tt ttt E .. t lu... ... ................. : l t .. ........ ... ..... ........ ..a. .

.a n a a. ... .: .. ..... ..... .... :.
b a MKi.. .... .+ ...... i f ........... S i .......... . 4w fl.......... n
b gii p + it+- age lihimbitp@ + ++..,.,... ..+ h .ig. .... g

.. "E> .. il..... 1E .. .. .. .:

a...is .m.... .. .. i..s em aaU au .
.. ::::::: :. . .

Se o me l: -r -U ----- t j e an

ON.: Iu..e .a Ml -a w .".: I o:

....t .i.... ...... .. .m
S .:.....:. .::..:: : .... ::. :..: ........i
..... ... .. ..

outside through the hood. The other side neck was fitted

with a dry-ice condenser connected to a trap containing a

weighed quantity of boron trichloride. The center neck was

fitted with a stirrer if large quantities of reactants were

used. A quantity of boron trichloride, not exceeding 600

grams, was condensed into a previously weighed trap, and the

weight of boron trichloride taken. From this weight, the

equivalent quantity of methylanine hydrochloride, based

upon the above equations, was calculated and 95 per cent

of this quantity was added to the flask along uith 800-900

ml. of chlorobonzene. The mixture was heated to reflux with

a Glaa-col heating mantle and then the boron trichloride was

added slowly at such a rate that the boron trichloride fell

dropwise from the exit dry-ice condenser. Allowing the trap

containing boron trichloride to stand at room temperature

usually gave a satisfactory rate of boron trichloride addi-

tion. Otherwise the trap was warmed or cooled as necessary.

Addition of the boron trichloride took from four to eight

hours, depending upon the quantities used. If any boron

trichloride escaped into the dry-ice trap, it was re-added.

Excosa boron trichloride was kept in the reaction system

for six hours after its addition was completed, by keeping

the exit dry-ice condenser filled. After this time the ex-

cess boron trichloride was allowed to escape into the dry-

ice trap. As shown by the equations, hydrogen chloride is

HpIqitd s(i @qM)s W S'SAMton, mad tve nfn at felas.$ Wo
ie N W ia -*t&e oef *tfluti ef biyo lf, iMRIettie
MWat Va I MamnI ol11 bHalerw. itfle*A wVA iRtfamAd
rt tu niahaa teemparte at o hlerolWmass. mtil thr ,Tvo-
Jstlm: *ia apwl eea hl*l.w1 s**ed salmt mat nely. This
"amAtanl rmI thirtfa-mi bet fewtr-ei.Lt hew.e After fabl
&IO M Ad *i s mpd, td amxtu t wa tramWIFfrtSd. be elhehtn
Sn a" t pa oelvnnt emdi. It mas found meat ea *fi i-
Ilif to I, m Wt sheet te wr~ g a.th of the WIleTSat by die-
tiilenIto at atimOefrte prwsanu aim th is mmrino al
oisti3J *0fEl with n oil bath with the flask at abetl
1 Am. g. Pial Om*Iv. orf thie 4lr s was e tfflmI. by
lat^ing hMo flisk in an oilt bth bt 80P C. for ems t"tm
heaMis *et 1 m :. Tnsi Wau renW abelt this MaduSS- Cn o-
lmaiv lose oes prodmit du e to ablization. After the
ala-t of tie olve*at we empleted, the ftaesk 4m its
edifati wa~re traemefwoNa to a vameim sublimtieam sppme-
W iMrd the prtuswt Mus Sublimea. At about 1 AML, E aft
In t biopvtfwi s a.f 110-120& C. was r quirel to give a
j* pabiH! ratso of aublimation. Thei predit sensiated et
UiSi aif*aS: meeting at 152-lI4* C. Ti yituhda, apin
W. t "e luntity of .leth. tam hydiielrSik*L te wiei wrie
M Ailtli The praidet w aitttS, wh, Oe. Cb sl nl a
aI brx, f r ievrwl matia.

Analysis showed: eB 9N 9C1

Found 14.36 18.51 46.5

Calculated for B Cl N (CH ) 14.36 18.59 47.1

When reaction times of six to ten hours were used

two products were found. The first product was soluble in

the solvent at room temperature and was identified as N-tri-

methyl-B-trichloroborazene from analysis, sublimation, and

melting points. The second product was insoluble In the

solvent at room temperature and crystallized as long white

needles. It did not sublime at 1 mm. ig until a bath tem-

perature of 1800 had been reached.

Analysis showed: (B ,N 9ci

Found 9.26 11.22 64.21

Calculated for (CH 3HDCI2)n 9.68 12.53 63.44

Calculated for CH3 NK2:ECl3 7.30 9.45 71.75

From the analysis it seems probable that this product

was either CH NHECI2 or its polymer. On the basis of its

low volatility it could be the trainer or a relatively low

molecular weight polymer. Without molecular weight data no

distinction between these possibilities could be made.

Addition of fresh solvent to this solid and continued re-

fluxing resulted in additional hydrogen chloride evolution

and formation of more tN-trimethyl-B-trichloroborazene.

Besides chlorobenzene, xylene was used as a solvent

4 .lglilp 4 a. a f. t&. Qhbu mom.se I 4 w"iapneemlL
in. ae this qiemi "md gives b*etil jyt'eilp ad a
ai.iae ft ytem at slte ~snp~ltrm tS thue iam~
ftM. A 9 Ubito prOl ea1: W mite* rdMtly st Wa wi e
a RitWiNm i uwiE. i; iO;el.ail hlormebein a, ii tmb
*#li*a V tlhet fur.S po W mildsiatlao, *ired a wl lir pu t
SEe e e~re i~et it lot in the i entity of dift, tBin t ul MS
:0l1 poimiod.
Meittnhia tiAbl ii" grae m hebro trisetlawril ws uvAfL
i **BnBsS*d fatimw a 14dture bottle. A Maill am-tait am oik-
wsletle mIFe'liswL usually remind In the tfap pfte adil-
is of beuire: triiMWlridse vw" amtupled.
The mflibeli|aei luydimhlti:e used was *abbtuti I me
NIaMIln, Fisher t Y-Maltmaen, MNI sf a cm and Boll. It Sit
hpIed wvr safltina tllatfi in a ohoeAtet before uief

Tit. sppfleue w"s Similar to thit *sdrtib4t b4 MHlL
fl In thif ts 1 AtftlrItng is seSatial. aid ga, aeI"

iEthllr autliiM M -aa a iupfEsant foe the alrumm ouiiC ..ii
(), M MittMed with *aly ma glght lw at lini. Via
i0iS MiW1 prediftn as satlime6 aeos fer tlb pEg.amn
inl el Ial.lMigptre-tatMheaesa *e6 feiwes, lbft
tioh aa11aw ,pean itiet-. see-- 4ase. ta" HmI Sauth-
tuie Ae X le.% *a d u w** age irat (.49 e00a4) ef hown
tadiSiui lliilltail i 0m (2.6 oInW) a. yt efiiki i i,

and 703 ml. of chlorobenzene. Complete addition of boron

trichloride required slightly more time than during the pre-

vious preparation. However, the reaction was usually fin-

ished, as judged from the cessation of hydrogen chloride

evolution, within an hour after the addition of boron tri-

chloride was completed.

After the reaction was completed the contents of the

flask were transferred to another flask, and about half of

the solvent was removed by distillation at atmospheric pres-

sure. The remainder of the solvent was removed under re-

duced pressure (.5 mm. Hg) with the flask at room tempera-

ture. It was necessary to keep the flask cool, in contrast

to the previous preparation, because of the greater vola-

tility of B-trichloroborazene as compared with N-trlnetbyl-

B-trlchloroborazene. After the solvent had been removed

the B-trichloroborazene was sublimed as white crystals. The

yield varied from 55 to 60 per cent.

Analysis showed: 3B AN-H ClI

Found 17.63 24.42 58.15

Calculated for B Cl 1N3H 17.65 24.51 57.86

If more than a month had elapsed since purification, it was

necessary to resublime the material before use.

No attempt was made to improve the yield reported

above. The lower yield of B-trichloroborazene, as compared

to N-trimethyl-B-trichloroborazene, could be attributed to


* iAiit MIIe f dtI VO Cm, T ONA .....il.l Ut
ki i)t *f willMe (B) at the tomPe i pt ne a ifd Simuig
i16I6 Mi00um4f ta ihr tiL he eM ngg at the rms tiles,
a 11iWi ili l wsmacked mt wbtih M-tmtehlireemfeame i daM
g lie:pin isspfly IWO it Li iBiag pws*itbd by Mt
if.. 1ln...Brev the 7llflB ewild int be Latapsl WI

tI$ilMlasa t^he PS6tion tbSi a1m tr do" In the pskpuiliam
* bbraaeaigrl-aketrealwwbenraatn*.
A *elid presia4 puiehably a barsn nitarld, is 1-
Wrlp Stand In the r*etioe flask. TWhAM slid wialitme we
*SPMAted from the l 6d salyf a Laaiint*tisn, sw E fM ,f
Ml Suld war tra*mfril to t ahe Urb aiamtiaw fleeak, brat
Lhis siianda no areit hlrM.. Othelfr uthibee (A)O) iaM. go"air
trlus the p1situr. to* aaivt the *laid.

ItlS bHe es trit-ihlimhtl it 1b4 fselatile th"M li- Sawa
ii0ilr tWil:4es smwihat different Pfoiw.. tilam iil-.
H:iai fory h oin:g llthe fpW CiSa pwp ta 1iiBMI4d.
fl emlMr meik of a twuesekud Clg*t -W hstibd WaliOMS
thlt ubilm.eH$ mumneeted to A urnewl ell bu-bble te Ml0
#fhM tIInIeI'Is heli4 *fl9at1tin leitr Seditiew of sh&-
.i..i.itill ul.i iii amine hy-dAohleridr to tihe reAtin
alli 5 .z1 g|ast Msiea 9t? inm turlmile O wa ay.tgtN
a.SiSIB i*nS: S .--inft -d Pail0W b ttM Culck M a. Sit
S-S" g fil Ldws fo llb 1--.9 qt -tflas. a i-etlfT

hydrogen halide was slowly evolved. Insoluble material

was formed during the first hour of reaction and remained

throughout the reaction period. After the reaction mix-

tare was cooled, the supernatant liquid was decanted from

thesolid. The solvent was removed under reduced pressure

and the NU-trimethyl-B-chloro-B-bromoborazene sublimed at

an oil bath temperature of 120 to 1350 C. and 1 mm. Hg.

The yield, which is based upon the average molecular weight

of 301, calculated from the analysis given below, was 42

per cent. No additional product was recovered by adding

fresh solvent to the flask residue and further refluxing.

Analysis showed: %B %N-CH3 %C1 Br

Found 10.85 29.16 16.04 43.94

Calculated for
B3C13 3(CH3)3 14.36 38.54 47.10 0.00

Calculated for
3Br3" 3(CH 3)3 9.03 24.23 0.00 66.72

The product prepared from this reaction is apparent-

ly a mixture of II-trimethyl-B-trichloroborazene, N-tri-

methyl-B-dichloro-B-bromoborazene, N-trimethyl-B-chloro-

B-dibromoborazene, and N-trlmethyl-B-tribromoborasene.

This preparation will be discussed more fully in another

section of this dissertation.

Preparation of B-tribromoborazene

The apparatus and procedure wore similar to those


1:1 fl Uemnbla*i/BuemauiubromSUt ji A
ea g ipB tin ut ma CIon vs tblvm haowin *S
N--i-Ig- ta hean tii uuieabqid result C ti:ignuig diia
fl lr i0a Rfopa balmfr ats siailat lamt -a Iea. gnreatl,|| Wie
.f ..n . n a t.plc.l retia 1.. r... ..t a 3* a
lilal wMin 4, 4^ fro (11.7 .n 3) or 1i. t..in.
iki ..i 8.O0 .1 0! &h ler*.ileJ..4 n*. .a. ..a ........W
y ftl was about o100 ....a ( ...3 .im li pf ..f.id .w.. -h.
t lliM sMaMMf. yield 60 pem: *m ts but u ams hiLh us 80
PIr MPt whtna rarllsr qaintiltiefs f rStartini4 rnutletfl SML

tlti;g p-rolnt, teunS lr*I2?y* o.
itilllia psiM, libelatspm Cjky l86-fiW0 e.
tM|" 1 e saw.r Si ...
___l 10.lo.58 12.97 1096
IflflmCfed tee *i3f31 10.23 13.25 7%.%7

* :i~ings* tiMi -ilLiOn uei nath, the B5eaibi 60 nsaI mpiigiei
ail spea.M4j Wei.ge *urn.

slhbliu ioe aS Im akioimhel&=i )or : wl ~h *l r aft .ildB

il1imir =eii 15 game (|:M .ii me of .."^sonaliMpl-n=
fpwt L blini pUii of thsi wma *i th a ShinSeteul*a
t A'1bW$@ UM I~004 -me momth the n~w~mS.4sflaS'

flask fitted with a reflux condenser vented to the atmos-

phere through a drierite column. No spontaneous reaction

occurred with gentle warming. The mixture was refluxed

for several hours with no apparent effect. After refluxing

was stopped, the solvent was distilled at reduced pressure

and the unreacted N-trimethyl-E-trlchloroborazene recovered

by sublimation at reduced pressure. In addition to the N-

trimethyl-a-trichloroborazene a small amount of gummy ma-

terial was found.

Tetrahydrofuran is a more powerful solvent for Grig-

nard reactions than ethyl ether. Consequently, tetrahydro-

furan, dried with sodium and calcium hydride, was tried as

a solvent. The sane quantities of reactants as described

above were used. The iodine color completely disappeared

in aboat ton minutes, but no spontaneous reaction started.

The mixture was refluxed for several hours. During this

time the magnesium darkened and etched considerably and the

solution turned a reddish color. The solution was decanted

from unreactod magnesium and the solvent distilled under

reduced pressure. No N-trimethyl-B-trichloroborazene could

be recovered from the mixture at the normal sublimation

temperature. A light brown solid remained.

Analyals of the solid showed:

43 1 6.og SC1

10.3 13.7 6.03 23.3

..l ....i...li... .41 ftgllr mit reamaess Oe eapm wea ad
ik)J.ii S~hI .Cw~I rSia ias Hi .s ai~

.. ...t.......... (lC ) 3c...i g

... ....t........ a w.i..a. oig 4n . a n

in attni t. o* to ownt oat^apMskA, 3atfPlg
a i d ...i1 i gh iiLt4ii. l, a m Sd..aiw rgo&. w .ilT .
f ,wh ..5 tIW AS.Sl ft Wllti e m a

AmN IOt a tEssl m aa i untiem amimagSi a. o
NMEm~is, cia, As sh eLat1- SW **bama loe

.IH.. I ..lr .. ......... r.t.. ... ..
-eiSiniU tts AP OMils of 46hyl WenM, *#w* walts"iLt 6 41W.
ilt ., It ismIfmiA i n Oat l. mflte utgheaOlin A W O *.
(IqapS Ril .ill aci: at mnler f am wit ives** ia k..
....i... ... ...il...I. -iM-: Li004i0 layOs wre fwiigtpI I a "
spainghiign remmie agemWl a ke :pth-ie v e W 9p lower -

.gal~iW sailill:, tesfeliglft age *U gam imwat delip1 e e.
,Ml#|Ath l4faf .,aMlrd kiPrawt s Woethe wtfh aV -leb% AUD,

neither layer reacted with methyl iodide. ielther layer

showed any tendency to c ouple with II-trimethyl-B-trichloro-

borazone. When magnesium was added slowly to a solution of

B-tribronioboraz.ene in ethyl other a precipitate was formed.

As more magnesium was added, the precipitate went into solu-

tion, or suspension, giving a two-layer mixture similar to

that observed above at the completion of the reaction.

No reaction was observed between E-tribromoborazene

and magnesium in refluxing benzene, even with iodine added

as a catalyst.

Removal of the solvent from the above layers at room

temperature and 1 mm. Hg gave uhite solids.

Analysis showed: %.B 4N BEr 4Mg Remainder

Top-layer residue 9.85 13.89 28.9 7.33 39.53

Bottom-layer residue 3.41 4.52 50.47 8.31 33.29

If the remainder is arbitrarily assigned to ethyl

ether, which may be present as a complex, an etherate, or may

be trapped in the solid, we get atom ratios of

B3 ti3'gBr(Et20)1.5 for the solid from the top layer, and

DnB 313gBr6(Et20)4.5 for the solid from the bottom layer.

Upon pyrolysis at 100 to 2500 C. and 1 mm. Hg, the

solids from both layers gave small amounts of a colorless

liquid. The liquids from both layers had identical infrared
spectra and gave the same analysis for boron and nitrogen,

so it was concluded that both layers gave the same pyrolysis

rail~nm hM0:14Pq4ld deiaEbSi at 65 to 660
Alilpa IeHaU1HI: ga
NWpllbt 3Mili.la prletuet 16,14
*a :l Li* pynjilie pfre t 16, 87

1i.a th eami 1iql.da td:
.Hi.. 16.29 10.24 f7.

3. (.4 ).


20lo 0ia
*5 (IS
8,80 1tal.

15*26 19.76 33.38 8.53
16.5i 21,37 36Mh 9.82
17.96 23.26 398AS 1.w 4
vwe SfuAd tla diffOaimnrm)

1a 7

this 4i4*, *aintinlnU that tte aitngii umsUely
ll lt flaMMt 5 plw eMLt i Slin to Aintfest eat 015

ThE tip dLgrn' fm I" hu mastaii4a belwtn B-tflfA-ii
lliilgli-. .n ip.K t.4 eyl ltbhr r *"etd l nthlilealiL
4Wlpab4l+ll *i. Au bsTrilen to glTve tian-Lagr *rt l-.,
.. A.i... i* wew Uiseekted frame the bottes liser, 1.0ihk
we0 ab alr t1 L F babteo a Ageuinsu ppuemld. nTe i p

Is t- a iqid tfth & l. b g t rt ie 40

V l&.li01, .- a, r) 914". r A
.i.t I 8.. f.n. I .smed 1247i. 1.447
Am orin a 8e.je. trestles 4al 12J1.7 14. y

ns4atea ,tftri

995 ('0234 EWAtt
AsM te b

The last part of the high boiling fraction was less

volatile than would be expected for a product monomeric in

borazene rings, so it is possible that the liquid contained

coupled borazene rings.

A reaction between magnesium and B-tribromoborazene

was carried out in the presence of N-trimethyl-B-trichloro-

borazene. A solution of 30.1 grams (.133 moles) of N-trl-

methyl-E-trichloboborazene in 150 ml. of ethyl ether, and

2.3 grams (.09 moles) of magnesium was placed in a 300 ml.

two-necked flask. Then a solution of 10 grams (.032 moles)

of B-tribromoborazene in ethyl ether was added slowly. The

reaction was slow and lasted for about an hour, after which

the mixture was refluxed gently. A white precipitate formed

slowly during the course of the reaction. Only one layer

was present in this reaction, indicating that only relative-

ly small amounts of magnesium bromide were formed. The

white precipitate was filtered through a fitted disc Buch-

nor funnel, washed with ethyl ether, and then kept at about

1 mm. Hg at room temperature overnight to remove excess

ethyl ether. The precipitate was soluble in hot water. The

precipitate was weighed and analyzed for boron, nitrogen,

halogens, and magnesium.

Analysis showed: %EB N 9Cl tBr 4Mg Remainder

.23 .35 10.80 47.32 10.73 30.57

Therefore the precipitate consisted primarily of magnesium

lunt *ta d tii iiB.. ..rriia p0SL*. 2% gnu- (1.11
....ill.l g.r I*Mut p.lr .e.g*.i.a....i*, 75 al, tP ilaIg
*Al ilt, I ritml af ieftr, a* mmltie iteirrlag bar, adi
9 gnii (.37 *mtl*) of lmaeieiu. TBe tewlr it"r s:k fitt
il. aih aR. fT fftle*nt waLet enaiwsr tepdSl by a irmylef
*9lmrrl vIlitd ti tle tir thasiak a d tl*ilte tubll, A
4meppiag finamel *eai-filat 40 aii- (a 3'smliel) tof ill
ilelt* Wi pUleed iM tIh *ild Smak. ia aMI. t! *etirl lb-w
Mi b oi.t, aMi if tte ra Etion did nat start e pih.e
ilfl tiO fmifi w.i e gwfmd to it ri tbq l wtiets
iMniV tt wael eii:it itl staiL., siLgrl baml ire wi aist.
I nili ip tmit g filogi fuwnl.t, wIt ttfIng, at a a SL
Ml i i. iM *f lux iat li. ifetl lar. A
iIM;6 ipift st Sagesitti hal ldS ren alfiiet B u6et-
Il.. ..f.i eatianlla' to fees tlm~lgabout the e0upae of ms
& il| le iii Pties o. etihl ba.it4q Ma.Itesd lAe t Ni e
. ...... .
6"li !M *a hi tiditi f aOtr tb wlitis was splet
OI48 lielS l sM imiauel. fe 1 se t fIsef ii t. i tw
.i.. .sa. ..t. .mM. slates. wet .ie.af t etS i a:
TiifiiO dhalgi&b t tinl.. tha: seplitpli p w iMI

several tines with ethyl other, the washings being combined

uith the filtrate. The combined filtrate and washings were

transferred to a flask and the solvent removed at reduced

pressure. The flask was then placed in a fractionation ap-

paratus and the product, which was a colorless liquid, was

distilled at reduced pressure. The yield of purified N-tri-

methyl-B-trlethylborazeno was about 65 por cent.

Analysis showed: ,B N %Cl

Found 15.86 19.45 0.6

Calculated for B3(C25 )3 3(CH3)3 15.70 20.33 0.00

The boiling point was 820 C. (.65 mm. Hg) and 980 C.

(1.8 in. Hg). The melting point was 1 to 20 C. The re-

fractive index at 22.50 C. was 1.4791.

Reaction of N-trimethyl-B-trlchloroborazene with n-butyl

magnesium bromide

The same procedure as outlined above for the pre-

paration of N-trimethyl-B-triethylborasene was used for this

reaction. In the reaction 22.3 grams (.0987 moles) of N-

trimethyl-B-trichloroborazene, 7.2 grams (.30 molea) of mag-

nesium, and 40.6 grams (.296 moles) of n-butyl bromide were

used. After fractionation at reduced pressure 21.2 grams

of a colorless liquid were obtained. This was a yield of

74 per cent.

--e 10.92 11073 0.00

pabll b3Cm( 13 )3 11.16 14,45 0.n

i lU.ifaha piat was 140e G. (i.1 m. M.), *O the

JiL m plr w* -g fe -Ar ta -176. Tlb farVe*ti* iAds at
ab A I. ww 1.4o9.

Less then thr* oalei *Of arigaatrl 3smget osfr MR
aNlAe f A-triathyl-B-twishlerehNrenbn wee Uged fOr t*ug
P etLmn. A se ltti f aowbatyl itagmeitim broitid la i4ftyi
vAr*a wes pepanEd by the reaction of magnesluM with 40
pa (.29 ales) &E aft-tyl b~lfgtl. A solutiea of I-trt--
|trFhl"B-triehlaraebpfl$p. in between was plaC.ed in a tH-
hai: flsacek equipped with a vater esenda*er topped wit *a
4le01 ieI4Rmer vested to the aetiasurhepe with 0 driofitq
e.iamau. A l-pping fmmnael seaoalining the n-batyl aiftlntum
b.Mi|t V plited in the olde nmik. With the stifrlig of
wLn ltst the a-batyl msepi. u braiI vs.adedi
S t:. Tbq flnsk b"ame" be, booves: the re-
.MMi.l M ilt ai iiBAIN Th.& g 40t addition *as mst **: th9*
tao mA* niMikmn uMseatHeiet utiwanff Iy dispotand in aO

Si a airwd aheat a half IBWr. After aditate oE
maihi :pggt1a bemiwadde wi twipsleted, tih Ita4rpe was

refluxed for about four hours to insure complete reaction.

The flask's contents were filtered through a Buchner frit-

ted disc funnel, and washed with ethyl ether as before.

The solvent was removed at reduced pressure and the liquid

residue placed in a vacuum fractionation apparatus. The

liquid was fractionated to give 45 per cent II-trimethyl-B-

tri-(n-butyl)-bora-ene, 35 per cent N-trimethyl-B-di-

(n-butyl)-2-chloroborazene, and 20 per cent H-trlmethyl-

B-(n-butyl)-B-dlchloroborazene. The overall yield of bora-

zene derivatives was approximately 75 per cent.

The boiling point of N-trimethyl-E-dl-(n-butyl)-

B-chloroborszene was 1220 C. (1.13 mm. Hg), and its refrac-

tive index at 22.50 C. was 1.4807.

Analysis showed: IB N .1C

Found 12.19 15.22 12.73

Calculated for
23(C4H0)2C1N)3(C13)3 12.05 15.61 13.17

The boiling point of N-trlmethyl-B-(n-butyl)-B-dl-

chloroborazene was 1010 C. (1.1 mm. Hg), Its freezing point

was -4 to -60 C., and its refractive index at 22.50 C. was


Analysis showed: .SB 4N ZCl

Found 13.04 16.53 27.61

Calculated for
B3C4i9C12N3((CH3)3 13.11 16.91 28.05

A -g g rrr *rw p*i to peparn Ulrtm.1thyl-B-dielw1l-
..*^aaBtushi~mabaiB anI tWittrfa3yl IBe tihyl-B-id lhlreelhrawmeg
ia tSi' im nimter at deeejritd iabte. After sublibltion ef
uflat Sd N-trlmnthyl-B-trithlornebofMAwb the rFlatatig 11-
quid wt fatiCilonated in an efficient oluan. In me Glad

,l :|t ]lupribl to isolate s fra#tioa that oerrsspaaded e.
* 401|tSt omnpon&tion. On prselisgd refluxing or regeoejd
Ssl|MipatimB, N-tlJrithrll-Btsrhlersebee.si vi we obtaald.
1iat l llA.rau.s of th di-stillato Wos eesm*eLtmt with
IaLoW etof partially Altylated AfLivatives. For naple, p
fle aliih distilled At 83.U C. (1.42 mm. g) was a.nlA ed
'R saireL aBd -bloriew.
Sfly.i. sheved: M *1
Pow 14.93 28.34
9AlsuLated for B3321 0B 1(e3 )3 14.79 32.30
oGluleted fer B3(C2L )zOI 3Cx3) 3 15.2.3 16.63

S lit^L, a A pple distilling at 8e5 C. (1.45 m Mg) 9a#O
2f peir et ch]EOla. Thie aJnlyeas Indieatb th t the
wa*we re a mixtn of the desired prodaets.

a..E........ m. k n.a..beasss with ... .. a

tiM p'iralme of Vatritafkyl-B-trish-uenbB er-*0 *V.-
JhtiSHt1 BM.G it gaheteM to be stit f the IfEtio ofi Alkyl
:anpelshpm WMeae e. Tha fPmitsmie at of e n*dgaa ueot 1ft

allyl bromide and magnesium was not successful in the pre-

sence of N-trlmethyl-B-trichloroborazene. It was necessary

first to form the Grignard reagent from magnesium and allyl

bromide in ethyl ether and to add it slowly to a solution

of N-trimethyl-B-trichloroborazene in ethyl ether. Allyl

magnesium bromide was prepared from the reaction of 60 grams

(.50 males) of allyl bromide and 1L.6 grams (.58 moles) of
magnesium in ethyl other. A solution of 30 erams (.133

moles) of -trethy-trimth-trichloroborazene in ethyl ether

was placed in a two-necked flask fitted with a reflux con-

denser topped with a dry-ice condenser vented to the atros-

phere through a drierite column. The allyl magnesium bro-

mide was added slowly from a dropping funnel fitted into the

second neck. The mixture was then handled as in previous

cases. The N-trlmethyl-B-triallylborazene was distilled at

reduced pressure as a colorless liquid in about 50 per cent

yield. Its boiling point was 110 to 1120 C. (1.3 iran. Hg),

its frescing point was -37 to -390 C., and its refractive

index at 22.50 C. was 1.5047.

Analysis showed: i 4N 'Cl

Pound 13.32 16.66 0.00

Calculated for E3(C3Hlc)3N3(CH3)3 13.37 17.31 0.00

Reaction of N-trlmethyl-B-di-(n-butyl)-B-chloooroborane with

1,4-dichlorobutane and magnesium

Into a 100 ml. flask were placed 5.6 grams (.021

miss) ef ELwtamflF* l-Bmi4 taLBal) Bfs'ifterebsWa*eame, 1.4

yMsu (.01l mftd) i t 1D,4OlahidreBbutJtmi *" *042 gamU
(.0mS asks) of meplulium, ad 90 a1. 60 e.thI 46eth. The
rftaIiie did net start apontedlwE ly, nor ws It i~itq* by

a sriyal of ladipa. A few dress of n-butyl bsiad6q *as
*uSta, maT a rkehtien started iMedimtely but soan o6jlWUd
Mtwib I heating seer a period of several he~rs aaamd fl
lO atib'ia of a white prtipitate. The mlixtus was then f-1-
tfsd sad the paeeipitat* washed with ttIhtL 7 peter. The k6I

*wet was removed fr m the embixnd filtlrate and tsMingE Ati
ridaped preaPbt A mall a3 1 mt t of liquid distilled t a
bath templeaturme of 170 to 200 0. This eoreepjndedl te
sithul* unrea ti starting material eo NE.trimthyl-R-twl-
({n-4ttyl)-boreaemm. At a brah t0tper~ turns of 2k40 C., l
quid again stared to distill. Po att;mpt was mad to die&
till this fraction, bat tbe flask wa. rmeved from the blit
e0 ae elled. T lm eontlnt of the flask were dissolv*4 in a

fn mal. oe i hyl ether and filtered. BSrrisLh Imorpkmas mh
ttal unftited an the filter, the filtrate b eng light It--
la-. the ithyl *tler was rplmerd at redaead pressure, leaSAl
a whibe ery tall in solid melting frea 65 to 86 C. ThiS 11-
qild distilled at a bath tsoperature of T87 to 3r00 C. at
.2 me. Mg. Gaesoepie meeIaruiw*s med with a pltimwse re-
siEtal W thihallmtfl&, me ml ing eyelrlemamae dried with 41t-

siins hydFri.& .e thk elteant, geao * lenlar weight ef 4899.

The calculated value for l,l-di-(I-trimethyl-R-dl-n-butyl-

berazene) butama is 523.74.

Analysis showed: :3 0

Pound 12.28 15.51
Calculated for B6K6C26H56 12.39 16.05

M stion of U -trlmethl-B-trlehloreberazBae with l.-dl-

ehlorobutane ned manelium in ethyl ether

For each mole of N-trimethyl-r-triehloreboramne,

1.5 moles of magnesium and l,L-dlchlorobitane were used.
This should presumably lead to erosallnking of the bor-

amene rings with tetramethylene groups. To 16 gram (.071

males) of N-tritmethyl-B-triohloroboramene In a 250 ml.

flask were added 125 ml. of ethyl ether and 5.1 gram (.21

moles) of eagneslum. Then 13 graas (.102 moles) of 1,4-

diehlorobutane were added slowly from a dropping funnel.

A slow reaction started. By external hating the mixture

was refluxed for eight hours. Upon standing overnight,

some of the precpltabe turned to a resinous solid. This

solid was not decomposed by standing in water and was only

slightly affected by standing for one hour in 50 per cent

sulfuric acid at room temperature. Very little of the solid

material was solable In ethyl ether, and only a very mall

amount of this was volatile even at 2500 C. and .75 mS. ug.

Some of the hard resinous material was extracted by bemaene

in a Soxhlet extractor. Analysis for boron and chlorine

a a a n iM--~I s If tSSE U
"i "" m .i '... .. .... .a .t .... i.:

m a.... b.. ...

j U a te WS Sati a wMufill#ii I fo t
wa Weo teia, aWheOe is a

".mm.. i .i ":- Ie P t
uMANNI mIa 'NEMstow * inMMO * W te--i W

.. .... ... .....:

w lsow.- iH IN.it iaugAgm0mv w:.,
I wa", U 'IW.. .....f.. IblI a .. . ...

Golii tl *iIeBemOE nellt: staid.teast e vemW- 1W sea
U.ilIsh (iig tin) se" f s IBM*a

-tiOa Sm. sgii (ram ln*,) r ngt sMt lObag

owi -Di. ntnt aito fggpt ot llt tl i' I m an aS

S Vtjmi-, i- ii @*t r MS twi Sdl liM M
J~t .jj.g~ ^.,^ ^^ .. ^.gy fc. *.- ^ i~iiPS' i|^.""|.**" g,^^ ^^ .t.NN"*! JJ||.AW:
i^ME'ql'^^f^^r^^^^~ll^I~q^^^l *jfll ^ T^^f" '*^I^^^B :)M 1 B-^ ^^P~ H ....... .....'^ *

flask fitted with a water condenser topped with a dry-ice

condenser vented to the atmosphere through a drierlte col-

umn. A slightly exothermic reaction occurred. Two layers

separated during the course of the reaction, Indicating that

the etherate of magnesium bromide had been formed (27). The

top layer was colorless and clear, and the bottom layer was

gray and cloudy, The two layers were separated In a sepa-

ratory funnel and the solvent removed from each layer under

reduced pressure. AbouLt .07 mole of ethyl bromide was re-

covered from the solvent. It was identified by formation of

the Grignard reagent, addition of dry-loe, and then acidifi-

cation to liberate the free acid which was titrated with

standard sodium hydroxide. The residue from the top layer

gave a small amount of liquid condensing at 1 mi. Hg at room

temperature. Analysis showed that the liquid contained 9.73

per cent boron and 10.49 per cent nitrogen. The sample was

redlstilled at atmospheric pressure. Some ethyl ether was

recovered at 35 C. The bulk of the liquid boiled at 110 to

1160 C. at atmospheric pressure. Upon analysis this sample

showed 10.02 per cent boron and 10.84 per cent nitrogen.

The infrared spectrum was very similar to the infrared spec-

trum of the compound produced from the reaction of B-triehlo-

roborazene with ethyl magnesium bromide. The bottom layer

upon pyrolysis gave a small amount of liquid whose infrared

spectrum corresponded to the infrared spectra of the pyroly-

sls products previously mentioned in the reaction of mag-

mtieS iSC A0-trinbrembesiel sae* in ethyl ether.

MRN go Btm mo i n-uW1.jl Msan ls. b

Les thk*w thib mele of Grigaerd rpagjnt per met 4
eof *.mib~*m.sehouoBnmg mnew amd In an attempt ta pempaue
useqmsmtuigallyeub.ktitutpd B- (ahatyl) -B-bwerDmwageps. A
4leWtiEo et a-bu-tyl iagmeAum bairaie war prepared free tke
Swlation of 15.5 prm (.113 mel.e) of n-nbtyl bFILuul with
2~7 eald (.111 MWlr ) ot magmneaum In Othyl ether. 1%4'
nabutyl nwimfiltLua bjaiUe.. waks a*ued slowly fromia droppig

fusal to a eealation of 18 greep (.057 atele) of BD-ribua-
elureM ew in Sebyl be ls a A 20h mi. tw*seelked fluear
Sfite with a vefIla age-.eUm vyeaitd fo th) aitaphwe
teKa a* d:riritse eelsm. A lightly e*xthrmnle reseatte
66lHdb With the formatfl'6 t two layer.. The 1. 69. wee
aspswted and the solvest rvnWd from F i top layer at: rw.
uad pruseare. Theaw rumaiaeid a liquid which di illed at
91 to 930 0. (.33 mi. Ig) Th3 yil old we 3.: gseem. Asaew
Lg lSlt the preettet *ar BSAtri-(n-*nbatyl)terasen, this was
A y#ld of 37 per esat bAed upon the quantity t of igard
r4Umti used, mad l0 per o*rt b*a44 uptn the quantity of
thErbatbluaem used.

Analysis showed: .B IS

Found 13.5 17.50

Calculated for B3(C4H9)3N3H3 13.04 16.89

The analyses for both both boron and nitrogen are

high. The temperature used for the distillation was suf-

ficiently high to cause cleavage of ethyl ether, if any

were present. Cleavage of ethyl ether could place ethyl or

ethoxy groups on the boron in the borazene ring. This would

lower the molecular weight of the compound formed and raise

the boron and nitrogen content.

Reaction of D-trichloroborazene with Sodium Ethylate

At one time B-trlethoxyborazene was considered to be

a possible compound formed from the pyrolysis of the product

formed from the reaction of magnesium with B-tribromobor-

asene in ethyl ether. To prepare B-triethoxyborazene the

reaction of sodium ethylatew th a solution of E-trichloro-

borazene was used (2).

Sodium ethylate was prepared by slowly adding abso-

lute ethanol to metallic sodium. In order to obtain complete

reaction it was necessary to add sufficient ethanol to dis-

solve completely these odium ethylate formed. After the re-

action was complete, the excess ethanol was removed at re-

duced pressure. To remove the excess ethanol, the flask was

heated in an oil bath for two hours at 800 C. at reduced

pkfbl#Mi, ltm.p lheeMd that thie :l1t1 obsiaMs had
.U01 4 dmllamtam / gl*e M6 bim M a i ee *twm to a Gal-
uAMi tuiea* St .01 69 fquitelltbe / gram.
16 a tN-oemek*d 2o0 al. flask were added 12 Mr.. of

dIry Wheafi e aw 21i.3 j'** (*114 males) of B-triehlorebr-
44imi. The p9th mg k wmp f itt-e with a soltld additles
MlO tenetIning 23.4 arms (.314 mles) ef medium ethylate.
k* 6d4iut ethylatb was addid slowly, by xnatioon o thd
Adi itin tube, owtr a period of two hacr*e with the sraktutew
*rLw d by a magntie stirrer. The mixture wea Vfbaned
fir tn hours afatr addition of *adium *trlate was m-M
plte The nmestiles MiWar egas filtwod mna thu pefitpi-
ift L4ohed with ethyl Other. The solvent was removed fmra
Ut a6t1i6d flltant* Md whings at r*Oid~ ad pressure.
-.. remat'inng liquid was dirtilled through a small oelum,
1he product solidified in the rteivoere. The distillation

t4eliWratui ws 7T* G. (.1 ma. Hg).
Amtylu i showed: %B 1 0C EV t A:
inAd .15.17 19.69 33.85 8.-3 224:A
eHAtlatM* for
( U9g;i 3")013 15.26 19.76 33.88 8.53 21.67
(tAt y agm loMaent waU fend by diffbremid)

Atfilfl SynthIres. for I-meaneumi seMi asai r

fti farther el aidate thee sUe of the reasti: s be-
twoea BafHabWaebae s and magamwlasi, thl Wipar: teia O

B-monobromoborazenes was attempted. One possible course of

this reaction is a Wurtz-type coupling of borazene rings.

Since E-tribronoborazene is trifunctional, this could lead

to a complex polymer. If a monofunctional B-monobromebor-

azeno were used in the reaction the end product would be a

dimer, which could easily be evaluated. Since reactions of

the Grignard reagent with B-trlbromoborazene gave low yields

and no partially-substituted borazenes, it was not felt that

this reaction would be a feasible one for the preparation.

One approach used an attempted brominatlon of B-

chloroborazene or B-alkylboraeene linkages with boron tri-

bromide. It was hoped that reactions represented by the

following equations would occur:

3B3R2CClN H + BBr ---- 3B RBrN H + BC1

3B3 33 H 3 + BBr3 -- 3B3R2BrN H + 3RBr

The reaction of B-trichloroborazene with less than

three moles of ethyl magnesium bromide for each mole of

B-trichloroborazene was used to prepare a mixture of B-chlo-

ro-B-ethylborazenes and B-trlethylborazene. No attempt was

made to separate this mixture. The mixture of borazenes was

then heated with boron tribromide dissolved in benzene at

slightly less than the reflux temperature of the mixture,

for eight hours. There was extensive decomposition and no

products were isolated. Apparently the borazenes present

are unstable under these conditions.

*ow ethtem was beal upon ,: tetaBnayij m-
'WON, k -u ma i R of Ultoi tflin b to-
Sl**iU e. the. A atMan gr S4&prtmlb ls-m ad *S tr1-
thit awwe. prupenWd wrn the reseotioan of ethil Mgima
Omdffg* with BL.tromlermMl*la ., wee lhiared in a all a11 ll
Ot iS GO for an 9ek-hearvo prlAed in the hope of p~eIMIatg
t: lt propwrtionation a ai.xtinr l a' the uM*tya briisal sea
penil. Tihe d#sinrd creation was!

B3W R 5 3 33 + 3 93 33
B3(C2J5)DvEn3U + WeQ3
a3( 25)2ev3 33 3 21?a Ru313

uW.iea at the end af this peeled only B-trib*hylbeseflmd
Met ,iJIfcted, tadd no Bl-titbrm'iwhBoran or D-bf-tem-B-ithl-
baNebn* could be rmeieva d.
LThe ext preesdure tried rwas the partial l l etim0 ef
B-ipibramaboraeal with lithblua bihereq ilde (24) !nRlh"iLe to

t2t + 535 D B2II6 + 2LiBr + D3M.E)

A elutiaon eof 3t goSmW (.120 meslos) aof B-trthbrwfror-
rusar wtil qtl ri wea prepared in a 250 ml. twe-malll
fl-Lk. Lkte eilter net w l fitted with a reflux emil.emdik ,
M i 00Hi e rdiltLoe tue* eolMtnm-i g 4.5 ameIs (.20a6 Ma46)
di Itlima bdiiiyt'ide. was plised in the aide bmek ftt4W tOh
*yeti.uset* fluipmd thoroughly with dry nftr esn. Then 1ith-
1*m: meaPukyrdrlde we. d4 :leily to the siymr A &e"y

vigorous reaction took place. Addition of the lithium bor-

ohydrlde required ten hours. After the reaction was complete

the ether was distilled at atmospheric pressure. The bor-

azsne derivatives were then removed at reduced pressure.

The distillate contained no halogen, so partially substi-

tuted B-bromoborazenes were not produced.

A reduction using lithium aluminum hydride (24) was

tried according to the equation:

23Br3N3H3 + LiAlH --->LBr + AlBr + 2B BrH2N31 H

Into a 250 ml. two-necked flask were placed 26 grams

(.032 moles) of B-tribromoborazene and 1.30 grams (.0344

moles) of lithium aluminum hydride. The center neck of the

flask iuas fitted with a reflex condenser vented to the at-

mosphere through a drierite column. The side neck was fit-

ted with a dropping funnel containing 125 ml. of ethyl eth-

er. After the system was flushed with nitrogen, ethyl eth-

er was added. A vigorous reaction took place. The reaction

was continued for fifteen hours. Then the ethyl ether was

removed by distillation at atmospheric pressure. After re-

moval of solvent was complete the flask was evacuated, but

no borazenes were recovered, even by heating the flask to

1000 C. in an oil bath.

amlfttaF o -tg Ibae-!lneas4 with 4teb*hydnefleea-

AS tlt ttt toa* set B-tribomPwboteain6 with Wi gs*-
stwH L WB presewIIe of tOb)hydpefuran, dprid with eeleie
hrlf t f-iled beanRuse ef n exoltermic reatlon between
tlewhydrefjara aMnd Beitribrmoomberame. This otetion obet
pla*e with pure tetrahydrefuran, with tabthydrefuta die'
sealvf in baems*.e, aa with tetrahydrefuran diLselved in

*t*il ether. A *aeation of 13.94 grows (.3U mflmi) of
BtAibraimboreser e ua* p parepd in dry ethyl ether. Thae
t lhawbd ,ofura was added slowly from a dreppiag fuarnl.
A*lw the) reaction eo med eeplet4 a 5 mi. exets wsL a i-
d4. The melveat afl eible* tetrahydrefuran ew.e r6me fi bY
-.pimag the flhak at .1 m.. Kg at srem temperature until it
ts rphiAbld a constant weight. This required about tweety
hias. It was r and that 9.36 gram (.130 moles) of taeb-

hpFlWmIJan had bee. taken up. This gives & P1ti o of 1 me16
of B-tibPsnoromr se e to 2.9% mslA of toetahydrefuran.
S&la t remall Sount of material was lost during r ~rval of

e lt't, it is probable that the true ratio is one to theOf
Th :amet of thne abev resetion was a whit e *lid whiek
weas babJaT in oem4 tetrehyd ikretlren.
lke prouet of the abeve piseties iould be d**Msp4se
upa heating to 850 C. at 1 ia. Ng te give a liquid with a
beolit point raoe- from 65 to 1609 C. (.4 am. Eg). It
4eMr probable that this liquid product ese lste of B-ihf

stituted borazenea formed from ether cleavage resulting

from the pyrolysis of the addition product between B-tri-

bromoborazene and tetrahydrofuran.

General Techniques

The samples were analyzed by hydrolysis to boric

acid, ammonia or the amine, and halogen ion, if present.

The acid-base titrations were made using a Beckmann Model

G pH meter.

Hydrolysis of the B-haloborazenes was effectively

accomplished by addition of water and refluxing for a

short period. A water trap was placed at the condenser

outlet to prevent the loss of hydrogen halide, amine, or

ammonia. Hydrolysis of the B-haloborazenea gives a very

slightly acidic solution.

Hydrolysis of the B-alkylborazenes or the B-allyl-

borazenes was effected by boiling in 20 per cent sulfuric

acid for a half hour, then adding 30 per cent hydrogen

peroxide and refluxing for another two hours to oxidize to

boric acid the alkyl boronic acid (29) produced. A water

trap was placed at the condenser outlet as before. Basse

hydrolysis was not used because of the danger of contam-

inating the solution with boron from the glassware.

Mixtures containing magnesium were hydrolyzed as

described above for B-alkylborazenes.

JCi gu: rvn itera.piind by fitt titrating 64
gal 4fu wMb standardd udt-lai hydrxide to the first tv-e
lMM ina U1 itaptias lea uro, usually occurring at a pEH f
Sili t6 l1. St m, mlll *lfe intl in large *"e .*eid asitfArtfln
to 1 tirst break. TU 4Iff6iaes in Telmes betsoi thU
itn qmipeinBs represited the brtle oild content of tqw=
agUpi th eManmitel complex of 'be' e maid obeig baase s.
Tm prseei4du w*a satisfaetowy is the pseo *es Of athy1l-
vtios, or snwnia. The sharpn1ie of the endpeint in re*

dubeid *lightly in the presaoe of methylamtin a Ad is re-
iduEd eonliderably in the presence of ammania.
imunila or nethylamlin was detrmined by ditille-
tiUl feem baele solution inte beries msd. The be-rs
Mid eil; ioa-me eof mamm* a or miethylaine may thum be tiA*be
t- directly with staBeadaf hydrochloric cild. Ste ex*-
tpe beerte acid buffers thk Mslution Wrd r8nteh*S tihe *ip-
u4 of the endpoint, a ndnim quantity of boric acid ew

Imiase wea demeisied by the Velhard method. To
h aoidified sample. was added a slight Msese af sbadl'd
ilitrla nitbae*, as judged by oA6gulation of the presipi-
thte et thU p iLnLt. Then 1 ml. of fsflioe .anlium aul-

fi aflu- wran aw added ae as indieator, and if chloride
wfl f hDL dete.vteaedi 4. to 5 ml. et nitrvebeu emoe woe xWed.
Ih M1ilS!t eam thea t1iteAte to the ferrle thiseysma4t

endpoint with standard potassium thiocyanate solution. The

difference between the titers is equivalent to the halogen

content of the sample. Mixtures of bromide and chloride

ions were determined by potentiometric titration using a

glass electrode as the reference electrode and a silver

electrode for the indicator electrode, and the Beckmann

Model G pH meter as the potentiometer.

Magnesium was determined gravimetrically by preci-

pitation with 8-hydroxyquinoline and weighing of the dihy-

drate dried at 105 C.

In general, all transfers, filtrations, and other

operations which would have involved the exposure of the

borazene compounds to atmospheric moisture were carried

out in a dry box. In a few cases, such as the determina-

tion of the refractive indices, transfers were made by

flushing the immediate area with nitrogen which was dried

by passing cylinder nitrogen through sulfuric acid and then

magnesium perchlorate. Determination of the infrared spee-

tra was made on solutions that had been prepared and placed

in a hypodermic syringe in the dry box. The hypodermic

syringe was quickly transferred to the infrared cell in the

instrument room where the relative humidity was low. In

the case of B-tribromoborazens and B-trichloroborazene the

infrared cell was filled in the dry box. It was necessary

to clean the syringes immediately after use to prevent them

gho N@gtef*tive ladtis were deteraied with an Abbe

6aia tisee o-leride, u4sd ns a* sL*tat for t'b ea.-

pg iru obt1inlag Wi il iE f -ed spet4fa, was d1i-d with e*l-
uISum hydride. Iummedistoly befoi u*e, the carfan totsplo-

ride was filtoesd twI the ealeinu hydride in lth dr beox.

All the ethyl other used in thAs resPerek was Iill-

inmkredt anksfdran greDe d wRJ au&d at supplied. The

ekiyl u1her sans were opened in the dry bex. Aftor bhatng
plupp the etbgL other was storp" in the dry box.
tammabal ek:L nrl me from Dew hemaJel Company,
nPq|lKt gus fSle NMerk, MW Fisher Gertifi4ed gradi wVe

al w6fLd *qaelly iuetawifutllp with no further trea-6F at tor
tMh .B6i3ttlet tf the hitferelDsMsa.
Labrebc ga fiJde 'bugeiup was stored over cltsim by-f

dride ad filterS iijmiu*eely before b*eig used.

aThe bethF.ltaBelseai wae reflu.-ed with eCl.eiM 1by-

iwltp, then is-iT1bul-4-d a stored over ealeimea hyldrie aOl
f1t M M-n ntMe d.
Standard tigmerid gi1ae magaeelum turning. weoe aced

foE u bP rigs gnrd rewamtiamM.
S*ll haiki lidae Wu1e ue* of ae Aepplied by Celamtbil

Tfagga GlTMhaaqlSkS&t Serlts.lls
The allyl bemMri. WuM distilled free haleia sulftte


before use.

Matheson technical grade boron trichlorlde was used

for the preparation of the B-trichloroborazene and I-tri-


Technical boron tribromide, as supplied by American

Fotash and Chemical Corporation, was used for the prepara-

tion of B-tribromoborazene and II-trimethyl-B-chloro-B-bro-



'UbJ ise a- *psitt wprs .lEiwgta iHn ol iif la l .
t iwMinst in esmten tsWeaplrIw4ie.* SeM. l .pe4tm i rP

Will li Am I9 b ha6s einm r w lmIt pellets Thlar Ap iitri Wve
tijAilyl aBmb a4lioteeh p bo mpuHe the abs saOipti beaes
AsiA u9 ly oory braid and diffUsei. The bands alee ipr
p&asS& to Us shifted sesHAatI tr Obeir letatln wMIa Sb.o

$wMiftld in e arbal tetrachlorilf selutein. ThI inftairk$l-
ses:tr were reeardwd On s Perkln-Elmor M30w1 21 di.ibl
Wban gpe*tuspltMsaWM1teS. BTh spe8tra MINan ik tUe f~iapeM
wise neft 4*d with the sOl V t in a .20n mlB. *411 il i nsm
te a .06 aMR. *.1 mld for the sa1Wpl, mA*ept fr the kpne.
%w of Brieh1oerobeS*kn* and B -ttflibimbc ass far -f01Ah

asptoloI Maxitm.

w il was isei es th L apEd. Th, sipes t thlei iaetns t
Sh f igtaum at tke had this "hpm~A i lSiMh.i-
with thi hAnd of the iueppuRd. Thk, irst figgm* shnma R
ergmapm at tiM Six to gight ilereoa iregiia f t -tril.Sl-
B-triebeiekebnssi N-trtmethyl-B-disfhlre-B- ( n-bvtyl)I-
b- .trftrls-tlsmlDMhi i-*re -d-ii-(n-buty1i-,( n-beulu -
'AaipKlia 1ICktlrljll-,!-@ai'ilekaiP-d l- ( n--(l'~l ) -lir,
gerntwrlaB~atsrx (n-batyl) -bn*btene, Nwti*ithyll-S-tfi-

laorlhiab1a sad iA-tzt'taSM-tiaalfyibereeAeM. Fig-
u ,, aqadp tm istei a B -taAehlmlsn.hbsas ad 8-trim

bromoborazene. Figure 3 shows the spectra of N-trimethyl-

B-dichloro-B-(n-butyl)-borazene and t-trimethyl-B-chloro-

B-di-(r-butyl)-borazene while Figure 4 contains the spectra

of N-trimethyl-t6-trichloroborazene and l,h-di-(N-trimethyl-

B-chloro-B-di-(n-butyl)-borazene)-butane. Figure 5 has the

spectra of 1I-trimethyl-B-tri-(n-butyl)-borazene and N-tri-

methyl-B-triethylborazene. Figure 6 contains the spectra of

N-trimethyl-B-triallylborazene and B-triethoxyborazene.

In Table 1 there is listed the absorption maxima

found for borazenes containing hydrogen on the nitrogen,

while Table 2 contains the spectra of the N-trimethylbor-

azenes. The abbreviations used are: vs, very strong; s,

strong; ms, medium strong; m, medium; mw, medium weak; and

w, weak. The tables list the absorption bands in microns.

The 2.9 micron band found in all the compounds in

Table 1 represents a nitrogen-hydrogen stretching frequency.

The frequencies at 3.36 and 3.35 microns are carbon-hydro-

gen stretching bands. The 6.97 and 6.92 micron peaks found

for B-tribronoborazene and B-trichloroborazene, respective-

ly, may be assigned to ring vibration. The absorption max-

Ima at 8.73 microns found for B-triethoxyborazene and for

B-diethoxy-B-ethylborazone is the carbon-oxygen band.



m 0g9pe3 s ?33C13 m3a3 3(%)3 B,?J3C tE (09 9)a

8.98 a 2.89 a 2.87 n 2.87 m
3.4 O 3.35 a
3.47 w .7 i
*4.7 v* 6.92 vS 6.67 V 6.67 re
6.80 ve 6. 78
7.alt i 7.27 a 7.19 v* 7.19 vs
7.33 a 7.34 m
7.51 a 7.50 a 7.51 w
7.75 -
8.07 S
8.42 s 8.42 ve
8.T3 m 8T.3ge
8.t i 8.94 k 9.03 m 9.03 9
9.4.2 a
9.74 *e 9.69 vs 9.55 vs 9.55 m
10.5 w &
I. = vs. 14.23 vs ~4.10 Va 14.o1-.20 ip
14.30 Vt 14.31-.0e *i
14.95 va 14.4-.5o "


the veru strong bead foaud at 14.20 mines for 5-
MabmibawUegemi asd at 34..-3 alePero for B-teleIbl.etobre
&Mab may be tsaipedi to nltreen-hydb*~m In pl-eSr bfltISa
Slowing the addigni uEr ts of otbhe woritrs (19). Th* etker
piapsamnm listed aben also undoubtedly Shw tkia rMn, but
beelt. af the elooessa of otbhr inpCtioe an asgmiPmE t
asp fit be S*e. Similarly, it is difficult to arsiga the
7 ithSa vtibatieat in thase eewuplida beauMs of tuhe s.ren
6asii to hfb,1me bands iras riag in the *s M regLes. FPe

the compound N-trimethylborazene, modes occurring at 6.68

and 7.22 microns have been assigned to CH2 and CH3 defor-

mations, respectively (19). On the basis of this, one

could assign the ring vibration to 6.80 and 6.78 microns

for B-triethoxyborazene and B-ethyl-B-diethoxyborozene,

respectively. However, this is a somewhat higher frequency

than is usually assigned to the ring vibration. The ab-

sorption band found at 8.42 microns in B-triethoxyborazene

and B-diethoxy-B-ethylborasene is assigned as the boron to

oxygen stretching frequency.

The data In Table 2 are for N-trimethyl-P-alkyl,

allyl, or chloroborazene. They were furnished through the

courtesy of George Ryschkewitsch. The table heading refers

to the boron substituent.

The absorption bands found in the 3.4 micron region

are the carbon-hydrogen stretching modes. The 6.11 micron

band found in the spectra of N-trimethyl-B-triallylborazene

is associated with the cnrbon-carbon double bond. The very

strong bend found at about 7.1 microns is assigned to the

ring vibration. It is seen from Figure 1 that this band

splits when the borazone is unsymmetrical. This is similar

to the results found when other ring compounds are unsym-

metrically substituted. This peak in N-trimethyl-B-tri-

ethylborasene has a small peak at 7.283 microns which gives

it the appearance of splitting. However, this sample con-


...:::.....:..... ..... .... . .... ..............

S:3.1:.3 3.45 "
(3.C54B *

6.110 S
.11% usv

j T 7.139 I 7.1h2 vs
i... 7.14....

7?170 7.7Cn a

74iqa -s 8..295z 8.97 a

8.493 do. .,Am

Srr 'A S

IL.lq we w
11. 1$fl

---- -------- ;i W- ----
bi.t.s f .le .. ...i. .E.iL .. t h S.h tbw t *...m..m. .
... m .g .. ..S ..ti..
mo.". dipslolam: A

TABLE 2 Continued

B3(CRH9) B 3C(C H9)2 B3C12CH9 B 3C3

3.418 s
3.499 s

6.800 vo
6.832 v
6.920 v
7.084 v
7.227 v
7.370 w
7.465 w

3.280 w
8.394 w
8.485 w
9.089 m
9.261 m
9.590 -
9.599 m
q.985 -
10.000 w
10.280 m
10.575 w
11.390 -
11.405 w

3.414 s
3.503 a

6.808 vs

6.910 vs
7.102 vs
7.231 vs

7.467 w

7.750 mw
7.998 w
8.380 w
8.487 w
9.252 s
9.637 ms

10.074 ms
10.272 ms
10.565 w
11.320 w

13.950 w
14.720 -
14.750 m

3.398 s
3.50 a
5.905 w
6.022 w
6.079 w
6.115 w
6.828 vi
6.878 v:
7.176 v!

3.425 z
3.505 m

6.850 vs

7.135 vs
7.262 w
7.372 w
7.474 w

8.283 w
8.394 w
8.50 w
9.100 s
9.229 w
9.538 m

10.548 w
11.29 w


7.792 a
7.960 ma

9.224 a

10.272 s

MffuaflI gltiMt Cd it:urilha 9k th Qittl i tng ^
Sllg, l glli- s toi tio the silW fgM it tto epliitttn:A giIHja.

flggA M MM it 19.17 miasmie ii Sfl mfslt;i sins ttji

filfig thijLi mit 'l tai idBi ci ha it$ blla-y
..l. 4r1 nt i. I ttS.i
S&'Hh miroug fqr I-trmmtben -B-diIithelae-- (n-buml3 )bie-lm

SThis pek is nmaW brlte ta Sth3le B-buiutptew

lr l....... witl ti aiE msii ierlan eatwiiin f..r.lii.
6It> wleutsieatat fMli r# is this eweimad seutinuag Siggi

lll thi i i.....ia g. ta1 fzq.yl of ita.ion i t; -

W ;t Pltt. Os thla sqin lats w the ditpsg 9.9
gftlebu land is B-t-ishleenbmpemW baid :w Am

.l. i ..t... .e.. .ea is i te n. rea Mafh, SA .
t gj ,li|fI the .,iislli I flafa ..1i 1, p&, L r
iii IMdI--tbt i would n.gaudtlet idic
-- *j^^ ggiljjjp-nn^ i~r~fr!: W'f B~tr i'i*-" "a~y'JA Ga:- |Mqp : i5

signing the absorption imaxina at 9.74 nicrons found in

B-tribromoborazone to the boron-bromine bond, and It Is

somewhat difficult to rationalize the appearance of this

bond at such a short wave-length.

An absorption band found at approximately 9.25 mi-

crons shows a regular change in intensity from strong to

weak as one proceeds through the series from :-trimethyl-

B-trlchloroborazene to UI-trimethyl-E-tri-(n-butyl)-bor-

azene. A spectral peak Is found close to 9.1 microns in

all the compounds containing two or more boron-carbon

bonds. On this basis this vibration mode is assigned to

bA. boron-carbon bond. A spectral band is found at about

14.75 microns for n-trinethyl-B-trichloroborazene and

N-trimethyl-B-dichloro-B-(n-butyl)-borazene, but in no

other case. This band is then associated with the boron-

chlorine bond.

8 6


F.g. I Comparison of the Six to
I-llfmet hyl-B- subs tituutd Borazenes



6 8

Eight Micron Region of

8 6 8 6





















%V V



0 ----i I I
24 6 8




Fig. 2 Spectra of B-trichloroborazene and

10 12

10 12 14



2 L. 6 8 10







2 4 6 10
Fig. 3 Spectra of N-trimethyl-B-dichloro-B- (n-butyl)-
borsazana arJ N-trimethyl-B-chloro-B-di- (n-butyl)-borazene

12 14

12 14












r, -









and d


4 6 8 10 12 14

12 14

2 4 6 8 10
Fig. 4 Spectra of N-trimethyl-B-trichloroborazene and
1,l-di-(N-trimethyl-B-di-(n-butyl)-borazene) butane




2 4 6 8 10



i -



F1,. 5 Spectre of !i-trimethyl-B-tri-(n-butyl)-borazene


I 1 I I I I
4 6 8 10
F1 . Spectr or fi-trimethyl-B-tri-(n-butyl)-borazene
abr.1 1-t r meth7L-t--tzi ny I ,ora :ere


83ET3N3E 3


12 14

B3BU3N3 E3

12 14













4 6 8 10 12

Fig. 6 Spectra
B-trl trtihort.oraeine

6 8 10 12 14
of N-trimethyl-B-triallyl-borazene and


*aM e*gSmfal p p6a4 of this rebmasmh, A m add in
Ub UitflOstiWn, wl thet prperltion of ua.pleg of rapper
igblItfle geaium in the bevh'fi"mp e yS Msui.e .n.y
aeiMHeaeses-i0d beeon prqnoaed, it w44 a*opilanr to us64
bpinAlJ isn which th* benrt stoam wome wi o-tl4ied wilt
a~iagi Ulifng magiaiam, a Faretiea of the trllaoweBg yIt
i AgI Aght:

3 3 )
Beialear Grirted ffl(sti0 reit with e.in41... ..-.
taimq samtive h"ydreeC (12), end the ireml n mB a*ta"i
,-fein the Panr mE ring proemu bly is santiv, it pn d@e-
.i.ed to uSra boerapem in which the brietmpa as the S tel

oni aid bIma replaced hW mahyl group.. s* u& cli 4ul Sfui
iMM rt fewmstiem wOe 6 eat1lAsked for I.at.iS,.l-Satretloe
*Ul0 Amfli the tfit dlmpetAd triad, ftkn 6tl11 thier w*A
the irlvseat for the ration. It is knwen *theit bif...e.B

fia..p rigPSard renrimts readily, wherea*h 10Ph er gaptatH g
Q -Htmi nemegaife with Sgrair difficulty. Praisand en MI
amlaE sit&thk benaime and the bas*am erans,, the s*Rt -ems:
ptP tried vWe Riguiatl-B3-b !amehiee.:ebeeMae. ThIs
ogniin athe fe|tIed to SihW rfietiUB witeh Tns..h*w. In
A* tiAr nmaumer it AS fanad tat S-trfghblerbenBje

tasag flfl :: tharwag pq age S f thtl pird :en.t


The next compound tried, B-tribromoborazene, showed

a very vigorous reaction with magnesium in ethyl ether.

With present data this reaction is somewhat difficult to

interpret unequivocally, though several possibilities, none

of which are free from objections, can be discussed.

No simple compounds could be isolated from the re-

action mixture after removal of the solvent, or by attem-

pted extraction with benzene. As stated in the experimen-

tal section, two layers with strikingly different proper-

ties were formed during the reaction. Magnesium bromide is

known to form a two-layer system with ethyl ether above

22.80 C. (27). The bottom layer consists of a small quan-

tity of ethyl ether dissolved in magnesium bromide dieth-

erate. The top layer is ethyl ether containing a small

quantity of magnesium bromide. It was consistently found

that only about one-and-one-half moles of magnesium were

consumed for each mole of B-tribromoborazene, whereas if

there were complete reaction to give a B-tribromomagnesium

borazene, there should be three moles of magnesium consumed

per mole of borazene.

Elementary analysis showed that the approximate ratio

of elements in the 'acuum-dried residue from the top layer

was B3D 31MgBr(Et20) 1. For the residue from the bottom

layer, a ratio of 331 Mg,3Sr6(Et 0) was found.
S3 3 b' 6 2 4.5

edC I tll s eeifl sIf to emelist, .uG*a Us
S.. .a... .."..al .i.. .nH 4 fi 9)ni a.eili

...:.A in at Ii li i da a d .... iij ...

:i .J.. k.. Ja t.il ti. ..L. .iii .. .e t illb i I

-, fr Butnleis a was i fblliSE eiiahiaipbin.il
dooloIt TWA. ismtsl afliniflNb" u*Sb I:l 1ili1iti s 1 B

i... iisli .. e ...-ia ity hsel ae a

fSil b ta ScIB ". ra ellin t *itfl h lu ald* Uoin1 w i -ls""^*:i : iBP'W

OitattmPilsnlnll.I ehiel *"Jinga 8 a l NripBB igrPiineP tiflW gBi aid th

....i. .:::..
..... I ....n.irn ; anL. r
:... .r. r-

feestl *n h4 ubowlfin mtait s bs-t aM a s-i
Siii I bsAA thSd l amfi in .t ...li.t i.C6

iig.l sifiWi a iiitr r iiS n: t.. ..tlba.in-.
...... ....
::::;... .::jjjiiawi^ ^ ..jc *|rj||~jM^^~L J.^ Jcl ft~ K i tt dfll' A N ti~if rfcH iWKd.: lf --*h' P'.
............i~ w'^ ~ ie itt *4.. I'^ ^~ ii ^j i .. ..a *-1 ^ .... ...&A
:: '*"*^SISHB^^^'-^^^:!^!^ 'w BHp8 iREC~i~ f sf III jglBffwp::1* Brl~fMa^

m A..w a ffl a $ & -1 :4 ..

azene with magnesium is the reaction of a Crignard-type re-

agent with active hydrogen on the borazene nitrogen. Com-

pounds containing active hydrogen, such as pyrrole, react

with Grignard reagents with the active hydrogen adding to

the organic group to give a hydrocarbon, and the magnesium

halide radical linking with the compound originally con-

taining the reactive hydrogen to give a Orignard reagent of

the compound (12). For example, methyl magnesium iodide

reacts with pyrrole according to the equation:

(CHCH))2 1!1 CH3MgI (CI!CII)2NlglI t CH4

The hydrogen on the nitrogen in borazenes presuma-

bly is active, as explained in the Introduction. There-

fore we could have the first step in the reaction being

the reaction of magnesium with a boron to bromine bond to

form a boron to magnesium to bromine bond.

iB-Br + Mg ----> B-egBr

This compound would then react with the active hydrogen on

the nitrogen to form a nitrogen to magnesium to bromine

bond, and a boron to hydrogen bond.

C D-MgBr B-I
N-H jN-MgBr

This reaction sequence has been discounted almost complete-

ly for a number of reasons. The infrared spectra showed no

evidence of any boron to hydrogen stretching frequencies,

fl gIII g g .. a.inte n ..in m ..ee.a

filhat -MiggliOa amutbt ie uamug aa'gu. as-m.af

.... ..... W1ir. m i ig"t line rim m % l ie iiPes d i im ir t:
'SBBmIf v aS.ILP q pa jw.. t.... e. bwt

S. b.%*mo hls sen maetet tae sted w.mpgla.i^
S:| bettottfiil tal t eisia sno to heat Li@M^ lflscfl
C iMii'"ifffll sYtl g t di it ly La rir k s i skh tM-a a E, iSalt faHE
-i0n Ul#i4i0Pi16a at. -t msfl iaftI nipamltba. altl amts

*aiallii lllE agageolffi iineli^ sliaigates Osugllr |imIf m *s
inikil lli i iSUd1iAoin d the t a lSleu ia siftt a sensi

......l..... .l.l Ni l Ohtitm .u ......it. r ibII I ...3M,
........... .....

ii l bmd bra: roe.nwig |astI U !eaI (.1 0):
l a+ c6Iytar -4--- til* ))-

fl iittiOMIDi! iL this ei ii ttl % eiawis A iifagel b* t f seia
0* ,iegounly etatiUied. Tin brfgiw S waril twigest
eto. ilitM e* e h with m iols. eri-rg* nae uOshsitula to gsv aK
eeii*iimiait lio mit ib essinse.


B3Br H + -MgBr MgBr+

This reaction satisfactorily explains the consumption of

one-and-one-half moles of magnesium for each mole of B-tri-

bromoborazene. However, since the above reaction does net

involve the formation of magnesium bromide, it can not be

the final step of the reaction. It is very possible, how-

ever, that it is on intermediate in the hypothesis discus-

sed below.

The next mechanism considered is a Wurtz-type coup-

ling of the borazene rings to give polyieric species.

Since the boron to halogen bond has been shown to react

with Orignard reagents to give condensation products and

magnesium halide, it is conceivable that a Grignard reagent

is first formed, and then immediately couples with boron to

bromine bonds present in the reaction mixture. This would

give rise to a polymeric species of borazeme rings linked

together with boron to boron bonds between the rings.

Since B-tribromoborazene is trifunctional, complete reac-

tion would form a two-dimensional network of borazene

rings. A tetracovalent boron complex discussed above could

be the intermediate in the reaction. The reaction may be

written aa:

a msmeasftl eins noml stiau s-
gLath, N u. irikfk Lp dlH. a --igl o *d eaLM e ngir -, 1 ,
aliiH1". S uE ilm of.r dg cPmift4h -ft"i MS of meial*us

Aitk *1M *OpuSg-le agagined ots b' p.staAhiw4 ma augr q
a* base"* mi a1w Itowe ltr Wy. b a, to t--
wA, wl.cth Sh-e third bewa a ttail mM lokl arslg cowfji b1;r
6:ifgal-m Whta unit. Alute'lmNrSel, n *laW eqAtnl&W
iattfi ofir itamiap braid Mad beasmak #hamie 110M.
vAtlk sgai ium itattmabl to lth* bernmw an oi bqemagMtqM rti
wmW fim Thiauggd ws paDlib3litims ar. rVMiS "imiuilwa by
tbaimeatmagi:I I lMwbo, r4fwatively.

d I
*...... ci:
lht mlm

f Iid

ether, it sl possible t th te boraene ring in the tsp

layer contain no att-ched bromine. it sla ler from the
laek of reactivity ge the top layer towards asgnstiu that

any bromire attached to the ring mist be attached iadimet-

ly through a mnagn.lum. atom. This consideration rules ut

an equillbrium aixture or the type:


Ur filr

For clarity in the 'ollowlng discussion we will aa-

same that Bi-trlbnee-megsael a-borasenr is pn rueed mmd

resets with an approximately equal numbe ar moleeules at

b-trlbronoboraasne to give compound, corresponding to the

analyses of the two layers. The hypothetical nesatlo mry

be written:

513r33 i 3 + 6B3;35r331 ---3

3"3"S^ 3 3r6 79 N31q fter

(This equatloa is not exactly bal ed, but It mist be re-

mmbered that the atom ratios are approximate.) Sek male

of borazene in the top-layer chain leads to the faomatlon

of ene ml.e of mragnsium bromide whieh Is found in the bot-
tam-layer etherate. 3ubtrastlng seven moles of n egmeaum

breaids from the botteo layer leaves us with

.I...i... .... ..S m a ia a l i t.e .b.e

t.i. aH gall matn yem oml S. aii. l i t
l..u Mi a ...imil ii i. .s tHUl.. 7 t.h ...,
E.m. "4 :e" s ia s Lm L ep 80 1 um. .M i.

..... TO at. n t...C.S af b-"s

:i: ...i*I3A 1...bimat ^ il e M: pll taM(imea ii n.. .6.
*Wiafl bosoe fip ladl 11NW *e q57 is Si

w m Miaitil s eto is-n to ha.l p U02
51* jatia t0 ma hip6 100"0 "me,
ji. tBi0S tiIOiliiidi 4kil ii t aefi k-*hii.iiM 9 ii 1liMii,

"ia thSte *iis iiSrtimte a ge0fl e of tde snti f-
W ian WMilUi Os WO h liKft ptfltlatel tft&* tii: weeplLUl
SMUSMW is fuyigak Swi t tiAn the Grilt ""f ii
liiS pIe 11w. the. is lled W uwtti la- all qm am
it es wseif t .ainto. .nr .n..p... 4 bn-
S bngl. f H lims ks : em im, ut eyne*, osple 04.
M- ii I* Sml blmiSu *eii y OUie susu- be ftn
antIA *t i sehi awn. mMo nw| e ltM. wuIlla.,

.enl .., t* fllmi iigS pt fluit i.. tHem qg

* 0 gig ati werfe la tI1 ..b el. at Sqeftae

above. This could be true within experimental error. Al-

ternatively, the assumption could be made that some of the

boron to bromine bonds are buried in the polymer and become

unavailable for reaction.

The reaction of magnesium with B-tribromnoborazene in

the presence of N-trlmethyl-B-ttrichloroborazene seems to

furnish indirect evidence for the formation of a boron to

magnesium to bromine bond. The formation of a precipitate

containing chlorine was observed. Since N-trimethyl-B-

trichloroborazene does not react with magnesium under these

conditions, the N-trimethyl-B-trichloroboraaene must have

reacted with one of the products of the reaction between

magnesium and B-tribromoborazene. Since N-trimethyl-B-tri-

chloroborazene couples with Grignard reagents, it could

react with a Grignard reagent formed from magnesium and

B-tribromoborazene to give magnesium bromide chloride, and

borazene molecules linked between boron atoms according to

the equation:

3 C 3 (CH3)3 + B D3BrN31 + Mg

MgClBr + NH 3BBr2-B Cl2 3(CH)3

An alternate hypothesis would be an exchange of chlo-

rine for bromine between magnesium bromide and N-trlmethyl-

B-trichloroborazsne. The former possibility seems to be the

more likely one. The ratio of bromine to chlorine in the

......... .. . ... : i
*iest '6 ,. - at m 14 .. t... .t
.nu.. E...
....... ..... 001 0"S ON 11e0 Ma 4 a 'e
41 agtitefldhall pij~o l0 *&S tSp 14g9 Ik U00

*llWllk @li lbt1agey Is tsih e a suMSoo oifg. as-
hflllHMk f nUn&i iifi16 oa bai S ftt an 4; al
* l~iHJ lingiiMpia fri ii 1 i m at i s no *ug SiS

lUAU! Ga Mt b tedee itw ImUw eA at a Sig m iM

ie 4f faliD site illb. intlbm ledis e .S ":a i'
emigalhSwi I il.i a. of usane>s bv.14s 2?) ).

m maio aflgi wtlity iA tikAe l1 Siu o Wgbgig

i i#.Ate aeant.. tlud ta. l a. the ta .w siA.

f l M IlMillwh h mi to Uitrf bii Ill !i i UeiSmm fg :-

flof eh flmg e semi ne of thi, tyfm or


Tbh solid produEt from both the top and bottom lay-

ers gave primarily U-ethyl-2-dlethexyberaueaB upon pyroy-

*is at reduced pressure at teperatures frea 100 to 250 C.

The formation of thid product indicates that there has bee

Oleavage of e*tyl ether under tlhe xperlamntal ceedditioe.

It is rkown that Grienard reagents will cleavT ethers to

form nagrneslm halide alkoxide, and be plea an alkyl radi-

eal on the oregaf e groap (12). This moans that .1rigard

reagents en the borsr.ne, In cleaving an ether, should form

B-alkyl gro.is according to the equation:

)B-Mg-Sr + (C2 )20--- )NB-C2 + Mgr(OC29)

Ether cleavage has been reported by boron trihalides

to form alkyl halid*e and horae trial xide (5). If we

asume that the boron to bromine bond in a boratene ea

cleanv ethyl ether, e-ethoxy Cro.pa will be formed as shwmm

by the equation:

)5-Er (C+B5)20---- )BD-.C2e C2AHBr

If the course of the reaction between naweslu end

D-trlbromaberazeno is the formation of bore to boron

lia ed polymers of berawere, as pust.latsd above, the boren

to boron bond mist cleave ethyl ether with a imultmae*as

cleavage of tht boron to boron bond in order to form the

pyrolysis product. The equation for thel postalated Proe

..... :- 4.ii w .a) g^ *.. ........i i

ogm3 .9 g wJS as fSites toalltiinp. a" Flao:

4imls w a I :r pan i din6 maiimsio a ad.m as

1 N saliggi uiigii igP, wheels i urael
lpmat sea Wh9aflhpnb dalttkngma. k r,: II dAge

tjitiatrl s:hd MM auiep the .tQspumition of i ifit aita. iA
$iU itmturv In sidittia, ti h u l fip praeBeit is im
e ::tl-iay- aml YI$*lde (1) to 15 to at -t), ielrtli
mSHit ai e f"rMlei tf the bul- in the alute- ar uap.

*.iltimt ttrbw tvkfl .thyl .tlit May- be isst tr Ito
:| pN| uia of thw ariaid r11 at (12b It vhI bee
1 Milt n11 w- ila tew: 40i gw'ts waih fea e sitr aflb
4t0 dt"I"1 Is 4*ikyl ohier fPm 6 6l in tla g

S Sm 9ali* be tna Seeridiwinam WWm fl fdia iNS

lifI: lE :ilgli. T uuig al.: ilille I li i im i be dif seaesi f w ei lle
1uf1 WbO lb tiam Mutist.

The use of tetrahydrofuran as a solvent for 1-tri-

methyl-2-trichloroorrazene, in the presence of magnesium

and iodine, led to a slow reaction between magnesium and

N-trimethyl-E-trichloroborazene. Analysis of the reaction

product was consistent with a borazene containing boron to

magnesium to chlorine bonds. This reaction needs to be

studied more fully.

In an attempt to prepare the Grignard reagent of

N-trimethyl-b-trichloroborazene by an exchange reaction

with previously prepared ethyl magnesium bromide, it was

discovered that N-trlmethyl-B-trichloroborazene undergoes

a rapid, exothermic coupling with Grignard reagents to form

B-alkyl substituted borazenea. This has been established

as a practical synthesis for the preparation of E-alkyl and

B-allylborazenes in good yield. The reaction appears to be

stepwise according to the equations:

N3(CH3)3j3C13 + RMgX--,. N3(CH3)3B3C1R + Mgcu

Nj(CH3)33C1 2R i RiegX--- N3(CH3)3 B 3C2 + MgCL

N (CH3) 3B 31R + RRgX--- N (CH3)3B3 R + MgClX

For the case where R is C H9 the intermediates could be

isolated. For the case where R is C215 or -CH2-CH=CH2 ,

only mixtures of the intermediates could be isolated. The

fact that both mono- and di-(n-butyl) derivatives can be

obtal:.d in reasonable yields from the same reaction mix-

llp n Spg(. hi K|*t tot elWl uutt itatln S. b A
t5iii atiniii0iW it- S* fhm$*e et* frr ftS -is rWS flw
.a.. Hi. i p wi.. g t.el.e.t pr.d.. t u. ies
iaie ii tf r 0 WI SE @* iuflwbaiat'e rsbtsea n wIith tb
SAll Saimti *ie lt yfilis eRMtiad for thta n-buet C-
ly L ite. | th.wr lueagAu. that t.bs .Slatl .s.fit r
ifi: at it tiirtviutal .tp nsk mait.y d.,ps.lsl by .U.
lttgh|intil riWr tiesa eof the haloain om the hmessiil
MWOti OW pose--ble htiAMes. ia ettiusltism *.He89 weuld bM
Lamas. lKo@Mter, mftl satesiftv weOrk it sOiewSaW befe%tu
1ala lad SI e4.tliished dtatattly.
Addit:Lom of Ash t-taaithyl-Botrichleabomnae to
thu bite:rd suya4ut InsF Si pser pliai fC product. In
g$fltil it w MUfltry teo add4 the Grtgmal rwggut to AM
*M*A Ce tkhe: lbeotlmab ts StA a*tiafatery Praulta.
Th i rLdamt of Sp? Slmaprd ra:g6ot with B-tfih^is-
riadft ao& gives poorer ylbled than in the eiAn. of N-iWryl
it iHT. ti.a. Sil3 early the rs e.tian of Gi.iSperd rvagEt
wia. AI.t-ribnemoba-ora.fse gire perN yields of B-4Wrihlkyllber-
gll- IIf J*Jee than thE*g mioo f Gegmodgd rifmit is
ufII f meH id of B9 teieum easflee, iJt pIstially Subs
attb6tu SA:eat a-uoefa ba.s le a "t ftnMnE Thin

sp. q4vel ways :in Ubla *Ai T*s yild- #n be dwneaosd. The
fiWgsW a agg sat get-14d miats with tbe Sati-es hpr fi.s on

the nitrogen to form Crignard salts on the nitrogen. Also,

the Grignard reagent might exchange functional groups with

the L-tribromoborazene to form a Grignard reagent on the

borazene. This could then polymerize as it presumably did

when magnesium was reacted with B-tribromoborazene.

The path of the reaction between Grignard reagents

and 5-haloborazenes may be postulated as proceeding through

a tetracovalent boron complex (13) that has been mentioned

in a preceding part of the discussion according to the


\B-Cl + HMgX--- ( \B"1 l-gY+ ilfgXCl + )B-R

There has been evidence in this research for dis-

proportionation of B-unsymmetrical borazenes. In attempts

to prepare unsymmetrical N-trimethyl-B-chloro-E-ethylbor-

azene only mixtures of the possible unsymmetrical products

were distilled. During attempted fractionation N-trinethyl-

B-trichloroborazene was formed. When the pyrolysis product

from the reaction of magnesium with B-trlbromoborazene was

allowed to stand for three months at room temperature, it

was found that a liquid with a boiling point range of 56

to 760 C. (.35 nm. Hg) was formed. Originally the liquid

had a boiling point of 660 C. (.4 im. Hg). Apparently the

original liquid, B-ethyl-B-diethoryboramene, had dispropor-

tionated to the other possible products.

The inability to isolate pure derivatives containing

GM .a'iSU llA tS NoMr6 SeWIttiltIon an U* beoarns rinu
h1 ainbid t llli'l tu a: 1dlitr r ia utlUai O Sqatilibtiumu that iS
jtanM AiMi* gthe smrfettan. On the ithter hand, the
SMi WIl- tIen. w**e gmufista-bl2y rWtstaet to rnPat-
haSllt t ea Mmit t* epmateam at tWem uegutmHfrtnl
*aUUilltilir ithe mir-oxftrs.: A bIkfliEd dim" f tPimlletleI MAls
(bg 14) smq be pied iraige iA( ISMlng to the ftllfwtiM bqesn*

1 + B-*4-4 .3 -.0 BSB + B.G01

We I1Mb.I f'lpe If trplO tten futet it is rlagmaalilm t6 ih
pi tihMi on *thyl Veup will tWin oft tl i tI9ge V iiiA *e

fi$il, tWliuir nbatyt aWiP, esastlrisg the dql rim*i a.t
gigilitp ef ebe inan tbriatIyl dima& wih i-i*-s in"
aku r oi aM lip. gmp (17). Since 8-klrh.@B.is9thefirii
iammimn did nOit asW i9ia5i p eyttomate upon dfa0tl.1iilAtilla, it
S awiliU Ai.pn*or tbhl the -'sh*'my greap i liad ipulb to uper
A1 W0Si.i.vl tradition sra than tha ig Wte shiws gp.
..e..ag ..i.. .s.pumufl w%' p.sei l .f........ -
ts pasWet thes lens Af*diiiie 6l:.h Is pflimili:

4llliht lKwidUI ecthe, binmir& eipibt wbritals palent m
*ias: saoNi, rs atm r s iewris bassi: begl.i. t setren
Im oine ae a s stiims whviLh ae mst us*d in hbaod:Lg.
4Wm up4i4e,4 it haen bee famid that beraueutg and diothyl
be* Stit Mil:ditht fglmudail, mattiag *Op tioe 1 diffi-

cult (24). Because nitrogen is bonded to boron in the

ring, there can be internal dative bonds formed to give a

resonance structure similar to the one proposed for ben-

zene by Kealule. The extent of internal double bonding has

not been determined, but will, of course, depend upon the

substituents present on the ring. Donor atoms present on

the boron will reduce the donor-acceptor bonding present

in the ring.

In the present research, it has been shown that

tetrahydrofuran and B-tribromoborazene react exothermical-

ly in benzene, ethyl ether, or without solvent to produce

a white or light-colored precipitate from which B-tribro-

moborazene may not be recovered. Heating this product at

reduced pressure results in the formation of a liquid with

a wide boiling point range. The stoichiometry of the solid

addition compound has been established as one mole of B-tri-

bromoborazene to three moles of tetrahydrofuran, so appar-

ently the tetrahydrofuran has added to the three boron po-

sitions on the ring. It is probable that at higher temper-

atures tetrahydrofuran may be cleaved, resulting in B-alk-

oxy or B-alkyl substitution on the borazene ring, and it is

these substitution products which form the liquid found

upon heating. Tetrahydrofuran should have less steric hin-

drance than ethyl ether for the formation of addition com-

pounds, which could explain why no stable addition compounds

lill-lli 41VI Willlr Modi

I am SUio 6athoe Pad -Urti ilwbime n orIH n.lmMi
am a1waa uitflltflae lly isw 7111a ta N tfl-
..M...Otele buro.ma. *nBintaiii smeIAntlWW1 smainta

o SB leBd h es remltp eit be dis~Wted froei several

paig hq-f view. The pree&t Q*uld be umsitable nd. heU*

sr iie n-d Lha e deaalm e during tho resetion period.
fIl.U *gpamnat n*ws alm the rationalik tht lao yields of
BtWiaehloe6 ber i tna and -tribrneaboMrake. HKqwtr, thfte

is as iyhn to exeet a wanted differeuse In qtabilit

b*ltaela i-tuetaial-B-triesleswber smeln d N-trim thyl-
otr bramIibea sIse. The. preiNet fermid seeds as stable

t-ima ASt*e0 as was JetNiesthltha*af hlowbebnmf. It

sWSw, thdrtfle, itS if Ithe i* fidld is due to a lrik 6f
jrefM.tion bf the t-trme t .hyl-B*tribromlberasonq. This car

be da ribald to s e veal different foetor which are dis-
e*rfL ilR the fellowTing paragraphe
Iapin McfieeL of the poeslble intmwfditte. in the

rumtic. shmw tiat a certain meant af train wild be
pMihant in thB intlarmediateas. This eould ifcMld* the ma-

tivatiln OemgP. for the rgction, thurebh duruMasing the

Wes tion rfl" Sbrixec *trir oian s-net raie aut the ftmos.
thIea at the* itiehdiate Snmtaeintig only bhmmd ii e sr it

is -aBw. thft MU-tali-ethylbosrt9am will add thtc mestee ir
buramEna (22). The thir-d Mpli il &dded terry b lwl, p Wab-

ly because of steric strain. This addition product would

be more strained than any intermediate in the formation of

1H-trimethyl-B-tribroroborazene. Therefore steric strain

may decrease the rate of reaction, but it should not pre-

vent the reaction from occurring.

The ratio of chlorine to bromine found in the pro-

duct was approximately one to one, whereas the ratio in

the reactants was one to three. This indicates that the

rate of formation of the B-chloro product is at least three

times the rate of formation of the B-bromo product. Sines

hydrogen chloride and boron trichlorlde are more volatile

than hydrogen bromide or boron tribromide, the chloro com-

pounds would be preferentially lost by the system. This

would have the effect of increasing the ratio of rates

above the minimum value of three to one. If the frequency

factor in the Arrhenius equation is assumed to be the same

for both reactions, we obtain, by taking the ratio of the

rate equations:


Assuming T to be 1300 C., we findAE sl equal to 876 calo-

ries per mole. This is a minimum value for the differences

of overall activation energies for the two reactions.

The presence of B-chloro groups necessitates an ex-

change of bromine for chlorine at one or several places in

the reaction. Boron tribromlde could exchange with the


.i .eiiiSaiil iith biui btloridia l..la.b. Hleb
- biEiiN been trtUilll wiih ettvlS a. bphd-
shldia w us.binouw *ag .P osea ait otaer paints in tMO

w0AffiStiE oil ufl0 Eilfl r ftilM vflidti-ty off atefln siu-

i00ilis th aakteot, Me AS emrw shIe.- tasr tMh raiktS-
tie. betif.': hydrniir *OhlOihq wed be.c tArbmide: .isai.
IMbe a;sitai.N aessiJa pg then sqatiote
1 + BB 3--+ 01ft' + 2391

lbir vluMe for A for the sAboe e empunmil #w*s
BfPr :il heal..i/e., a -93.5 *kl./Imte, Hil :

aliti lei./sI.l, and Sjt !-12si.54 k1tal./ai.) (6).
UsiU thwMt values, we find that t F for the -FCita witFS
Ul omaimmiaiba gasuwIm and in thft&r ltrnudad s8ieesl 1i
*12lt hMal. fea tUe '9lSiam 4 wyt fi ab*te. Prw this
the *Iquilibriua *ediUhpat ls silaflliu bti be e 6.5 R .li 9.
AJemSaik tblat tUl' if no iajair h! s in thi:e 1 miei aeigeW
a itflncea to a tien6)46 e of kw* c., n o-c th#i a .-U
sMqIl:in M itm, this Blom* rpspetEas dauint Slalm::
il wwe wtes to wan n ew. e iie kii i flele
9mi rilast amml I Mef.e &b14 be a "am iml iRA
*pMii totS mf:AihitilMiip, Aqpitu.IIsIh ed be tikhilsanl jflsr


It can be seen from the foregoing discussion that

chlorine rubstitution on the borazene ring is the result of

the overall chemistry of the system rather than exclusively

steric effects. The fact that th3 reaction times for the

formation of -trlchloroborazene and E-tribrornoborazene are

the same, despite the presence of boron tribromide in much

lsrger concentration, supports Lhe concluolon that steric

effects alone can not be used to explain the low yield of

N-trimethyl-B-tribromoborazeno. It seems probable that a

major extension of the reaction time, or temperature,

should raise the yield in the reaction.


it bem s dewnaflrr t~in: Gt rimrd ri initm

S!i U is bta m d i thas is -tr.m..thy.l ibttbe-..
M *O :- rtebs. Vhs wset hkns bo. cn.tfl .med by te-

4D4 9 t eb* lsbwcst Wpeltthe tin intepti6n at thwo
h (7). It hqW b i stan that this nMetifit tIe
MItki mib te t the fernitlion of endsmstiaLo p1ltn or?

It has better ublisiHe tht& Basleborssceloi will
seiat with-It: umipr thb prpeior esrdittieft. MbS a111k
is aesespj toe elarify the aeiyge ai this nfaostin. TIs
binimeaia *st fsrth for the roseittS between nfhr,tLum

1en 5-tribnrouberei wmws laiUd b1 paMS Sn 9 tir&ele bPsse1
St: A pwFLratlos of 1 r l reuMties- tth 4.>.Alm.t.. A at*m thieh sculd be t7aslf
ief#lAS a shEall b fiErnmsd. The rfetivity 6f wr pmust
M.O tie narltan should beo 6tablitbed. Th* pro$sflt i&k

her intlhpt mw motivity toward *esteap, drr-ie*, apt
GDISM.i-ad wnnasat1i Those rntetioms negS further otudy.
UWS relisetah has wthem tbat B-trlkaloberas*oor will
-e*t3r aEliplvtie and eyelle ethWers Ti6. elavage las *ile*W

visaoly biei riiputled f6r bores trii halid*i (5). FarMie
atbSe of thi.g ftieia ae" 3 %t et: u.itfal.
Th NNeWap -tei y : 1: : i e.ma towward other l-A


als should be found. A small scale experiment in these

laboratories Indicates that sodium reacts with N-trimethyl-



1. Eemt, 1. I8, Hai ay.. jv.., j, 43 (Wir).
2. B~uMUpl ', SJ, fi.B. DEltartation, U~ani~LT lty .f
snidas, ahlat iSIS.
j. B EI, t A.,, had Lad]btagy.er, A. W., ia_ s. SAl

4. Coarnw., D. L., end IHerd, J. L., J. A.. CmEs. 2P.,
j, 1741 (iSE).
5. Gerrard, W., and Lappert, M. F., J. Chem. SNa.,, l~g,
6. GlJ.Aaitem, S. ". bftee p isd fOr Cthaifta," Jb. Von
NMIjninnd Co., NOw York, 1947.
7. GrosseF 4. J., und Stafiej, S. F., Abstneti qf
Papewn, 1314% Mftet.in, marisara C dbisal Seel-
sty, Miami, PFloria, April 1957, 5)-o,
8. H imltit, L. F., and Ima.r th, D. ., CbS m, a Eng.
l ,l Sept. 16, 67 (1957).
9. JAcoba, L. E,, flett, J. R., and S4waeffer, G. W.,

10. JOhn*aa, J. R., SrWder, H. A., and Van Campon, M. G.,
J.-ma Shame Aea1x, 60, 1W1 (1938).
11. Joams, ft. 0., and Kinney, C. R., J. Am. Cheaw. fe,,,
Ag, 1378 (1939).
12. KiRmLE h, M. S.., *d ReNif th, 0., "f1 M.'l d Mslias-
Of rJnmBmtslie Subst-anle," PitieI-+Rell, T h.,
aw" Ysfk, 1954.
13. Lapprt, M. P., .au R.a. 56, 1035 (1956).
14. NeCa.r P. A., h mia, Q. PF, ad A b, E. C.,
SmilA S-e*.. fs, 5*1. (1957).
15. Pesesa R,. BDiw lv.. emh N. B.., And Ritter, D. M.,
Aft. Am....a..^ r91 (O ).

16. Pease, R. S., J. Am. Cher. Soc., 74, 4219 (1952).

17. Pitzer, K. S., and Gutowsky, H. 3., J. Am. Chem. Soc.,
69, 2204 (1946).
18. Flatt, J. R., Klevens, H. B., and Schaeffer, G. W.,
J. Chei. Physics, 1 598 (1947).

19. Price, W. C., Fraser, I. D. B., Robinson, T. S., and
Longuat-Higins, H. C., Disc. Farao. 3oc., 9,
131 (1950).

20. Rector, C. W., Schaoffer, G. W., and Platt, J. R.,
J. Chem. Physics, 17, 460 (1949).

21. Ruigh, W. L., and Gunderly, F. C., Chem. and Eng.
News, April 23, 1994 (1956).

22. Ryschkaeitsch, G. E., private communication.

23. Schaeffer, G. W., Schaeffer, R., and Schlesinger,
H. I., J. Am. Chei. Soc., 73, 1612 (1951).

24. Schaeffer, R., Steindler, M., Hohnstedt, L., Smith,
H. S., Eddy, L. B., and Schlesingcr, U. I.,
J. Am. Cham. Soc., 76, 3303 (1954).

25. Uchlesinger, H. I., Horvitz, L., and Burg, A. B.,
J. Am. Chem. Soc., L, 409 (1936).

26. Schlesinger, H. I., Ritter, D. M., and Burg, A. B.,
J. 4m. Chem. Soc., 60, 1296 (1938).

27. Seidell, A., "Solubilities of Inorganic and "!ecal
Organic Compounds," D. Van Nostrand Co., New
York, 1940,

2(. Stock, A., and Pohland, E., Ber., 59, 2215 (1926).

29. Synder, H. R., Kuck, J. A., and Johnson, J. R.,
J. Am. Chem. Soc., 60, 105 (1938).

w111111111 11111111


Ifw.i lr nSrit- wAS born in GOM4iaw, IlliMAa, -e
lam[Wra T 277 9190. rH pewitrs his- pErimay dusttion la
Int I tUiole an. d his oeuaadary ddsestion in Mtgal ,

Z* Sopt*mbef 19 8 he nte ed MHise Universtiy, Ox-
4ne, Oite, iwheNr t rPstat*ed A BiehMir atf Arts degAA 4
-0 4l6al in 3Juf 1992. Is meun 1993 he rni ived a rea-
t*r f 3ei.6esM degn*a TIrm iinMi Univ#jP0tty. WhIqH at
MS0M tiUiwversity thr hld a CoUttell Psllewehip in CauetA-

ALfte hi4 SfLmlation ftw Inrla Unt lepity, he mtw
AInfld.1 by Ulnion oxa tida OSli6 eda aMpany *a WIatmb
ira a.t, until em~le)a the A-iri Forces in NevemIr 193).
ita in thr AeSip PeFors i whea. It ttslaed at the OCbmioal
0iS f1iNselgufleal LabeatkafLs at the Awy Chlmiesl. Gaitr,

Afftr his eftleation from the Armed Flels, he H-O
ted Ohio S.tate UniLtr Ielt, Columbus, Ohio, in fsaemu
Wb64.l. U@i? at Ohio Stab University hir wai mapLayoi a& a
:arePehk e iifoat. In 3Sepmlinr 1906 he treoaferred to
h4 Ue8fi~ tii f tr PFlrtW, wiu he has bieen deployed as a

Nd Ls a sb-rt of Phi II Stgw. Stawn i Sig.",


Pi flu Epsilon, Gamma Sigma Epsilon, Phi Beta Kappa, Alpha

Cli zigma, and the American Chemical Society.

OUMwmjiegB A~ihisi

figglsriMggelrbtih veS peyoamWlit une teu daM||t~en
uI N 6o alNiima of t Ihe adSi4kmabg I A uu seap* ary whe mitteo
am- b" VeeA appflvOd by *Ll mAMvsti ot that ianuttl*.
It *ep .4~ilAt.lMe te D the De An of the Ceollegs of Art paid

Sataoilg a to ths apwwANq counsel, a: Wnd e *p.ppenvd as
-Nw-it frMitbiemit Ut the 3aqinusp4ti fer th$ degwee df
ei-e COf -hlseaephy.

Mflp) 9, 1 11M

a, tn etts Scheel

G'* /"
( N .

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