TiroxAs P.ONAK,F
33ih
J.MES
GERHART, AXII ROBERTE. l i F ~ ~ ~ ~ , ~ ~ L'ol. i ~ s3 ~
TABLE I D 4 T A FOR T H E C O X V E R S I O S O F 1)IHYDROCARBORASES T O CARDORAXES
Ilihydrocarburane
O t h e r material present
M i n i m u m pyrolytic T e m p , 'C Hr.
Volatile products----Carhnrane-2,.i s y i n ~ C a r h u r a n e ~ 2 , 4
Ia
A-orie
290
20
I I a , 25',1
I I I a , 5'/;,
Ih
Sone
300
20
IIb, 30
IIlb, 2
Ia Ib
Tritneth?-lariiine Trimethylamine
260 280
20
6
IIn, 15 I I b , 15
IIIa, 2 5 I I I b , 20
Ia
I sohutane
280
35
IIa, 30
IIIa, 5
from the dihydrocarboranes (perhaps the alkyl groups interfered with the ejection of a BH3 group). Alkyl were R ~ isolated; H ~ however, no derivatives of s ~ ~ - C ~ alkyl derivatives of u n . ~ y m - C ~ B were ~ H ~ ~observed. Surprisingly, C-alkyl derivatives of C2B5H7were produced in unanticipated aburidance.
Experimental Preparation of Dihydrocarboranes. ( a ) C,C'-Dimethyldihydrocarborane-2,4 iIa).-To 10 nil. of 2,G-lutidine (Mathesoti Coleman and Bell)1owere added 17 nioles of pentaborane ( O h I I 'l'hi, investigatiijn \ \ a i ~ u l , l i i r t e d in part hy t h e O f i c e rrf S a v a l Re,each ( 2 ) Particil,ant in S a t i u n a l Science Foundation U n d e r g r a d u a t e Research Pri,#ram 1G 218U,'3), S u m m e r , 1!)82 (:O I< E Williams. C I ) G w d a n d I Shapiro, Ahstracts, 140th S a t i o n a l &[eeting of t h e American Chemical Society, Chicago, 111 , S e p t e m h e r , 1961, LAX, .I A m ( h r r n S O L , 84, 3837 ( l Y 6 1 1 ~ 4 C j I 1 G00d a n d I< 1; \Villiams, 1: S P a t e n t :3,090,28'3(1962) i . i ~'1' P O n a k . K E Williams. a n d H G Weiss, J A m Chem .Yoc , 84,
,,
18:30 [ 1962) (ti) T h e discovery ol t h e parent dihydrocarbnrane, CzBdHs, by H G Weiss i t a isolation 1,)- C 1) Good3 has heen r e p o r t e d . I . Shapirn. Pacific Coast c,ml Anal C h e m a n d Appl Spectroscopy, P a s a d e n a , C a l i f , I ) e c , 1'362 r71 \Vc iuhacrihe t o t h e \uKgrstiun3 t h a t CzRsHs is hetter t h a n BiCiHs i n that it rcflects t h e c a r h n tmmn urder in t h e n a m e , it would appear t h a t carlji,rane 2 , : $ noulrl l i e Ilrtter t h a n carhurane ,'3 cir trihnratlimeth) n e since rarhoranea with 4 or t \ , etc , c a r h o n i a n d hyrlrr~carboraneswith more or less t h a n tire, carI)oiis w i l l probably Lie discuvered (8, I< H d i m a n n a n d \k' S I.ilisc,~mtj,I i i i i r ~ f ' h r i n , 2 , 2:31 il!lO:O ! I ) 'l'he suKcesti
