Acid degradation of alpha and beta styryl azide

Boyer, J. H.

Krueger, W. E.

Modler, R.

English

NASA Technical Reports Server

* 
.. 
' 
Acid Cata lyzed  Reac t ions  o f  a- and 8-Styryl Azides'' 
*a 
Ho . >c=c (R)N, 
-N2 
-. 
, , -  ,\ 
' I' J. H .  Boyer, W .  E.  Krueger and R .  Modler q; i< ? 
0 
7r 
0 > ) C = C ( R ) N H  +> > C C ( R ) = N H  (b 1 
.lr I 
Department of  C h e m i s t r y ,  U n i v e r s i t y  of I l l i n o i s  
Chicago C i r c l e  Campus, Chicago, I l l i n o i s  60680 'e , I -. 
J/ 1 .  * .  . . < $  ' .', ,,' . 2, 7 ,  .* _ .  
N 68-  3 1 3 4 9  
* -  
Rearrangement d u r i n g  a c i d  deg rada t ion  o f  c e r t a i n  a l k y l  a z i d e s  
3 ' *- is. conce r t ed  w i t h  t h e  e v o l u t i o n  o f  n i t r o g e n . *  Both rearrangement  
~A 
I 4 
b y  path ( a )  and a z i r i n e  r ing -c losu re  b y  pa th  ( c )  may be concer ted  . 
w i t h  n i t r o g e n  e v o l u t i o n  from a v i n y l  a z i d e  and an unrear ranged  hy- 
b r i d  c a t i o n  may be a v a i l a b l e  by pa th  ( b ) .  I f  formed, i t  shou ld  
a f f o r d  c e r t a i n  p roduc t s  der ived  from an unrearranged carbonium i o n  
and o t h e r s  from a n i t r e n i u m  ion4  as w e l l  as r ea r r ange  t o  a new 
a z i d e ,  has been i n v e s t i g a t e d .  
n e a r l y  q u a n t i t a t i v e l y  ( 9 4 % )  t ransformed i n t o  a n i x t u r e  of a c e t a n i l i d e ,  
- 3 ,  and a n i l i n e ,  presumably formed by  h y d r o l y s i s  of - 3 d u r i n g  workup. 
T h i s  appears t o  be a r e a c t i o n  accord ing  t o  pa th  ( a )  and/or p a t h  ( b )  
if i n  t h e  l a t t e r  even t  a "hot"  n i t r e n i u m  i o n  i s  produced and r e -  
I n  e t h a n o l i c  s u l f u r i c  a c i d ,  - 1 i s  
! 
. 
2 
a r r a n g e s  b e f o r e  it l o s e s  energy and becomes a resonance h y b r i d  ca.ti.on. 
https://ntrs.nasa.gov/search.jsp?R=19680021877 2020-03-12T10:13:48+00:00Z
A n  unrear ranged  h y b r i d  c a t i o n ,  _- 4 ,  was n o t  detected i n s o f a r  as pro-  
d u c t s  o fa rea r rangemen t  from carbon t o  carbon were n o t  formed5 and 
o t h e r  carbonium i o n  r e a c t i o n s ,  e . ‘g.,  s o l v a t i o n ,  were no t  d e t e c t e d .  
Hydro lys i s  of t he  2Lphenylazirinium c a t i o n  t o  phenacylamine ,6 wi th -  
out t h e  format ion  o f  a c e t a n i l i d e ,  e l i m i n a t e s  path ( c )  i n  t h e  a c i d  
d e g r a d a t i o n  o f  - 1. 
. 
These r e s u l t s  r e q u i r e d  a r e e v a l u a t i o n  o f  o u r  e a r l i e r  work on an 
A a c i d  c a t a l y z e d  r e a c t i o n  between acetophenone and an a l k y l  azide.’  
resonance  c a t i o n ,  f o r  which a v i n y l  n i t r e n i u m  md a carbonium i o n  
were c o n t r i b u t o r s  and i n  e q u i l i b r i u m  w i t h  a az i r in ium c a t i o n ,  was a 
proposed i n t e r m e d i a t e  f o r  the format ion  o f  benzaldehyde, formalde- 
hyde and a p r i m a r y  amine. We have been unable  t o  repeat  t h e  e a r l i e r  
work and i t  i s  t o  be considered i n a c c u r a t e .  
I n  e t h a n o l i c  s u l f u r i c  ac id ,  B - s t y r y l  azide,  - 5 ,  i s  t ransformed 
i n t o  p h e n y l a c e t o n i l e ,  6 ,  7% y i e l d ,  a t r a c e  amoxit  of 2,5-diphenyl- 
p y r a z i n e ,  1, and i n t r a c t a b l e  t a r .  The n i - t r i l e ,  - 6 ,  appears t o  be a 
2 .  
product  from e i t h e r  a rearrangement conce r t ed  w i t h  n i t r o g e n  e v o l u t i o n  
. by p a t h  ( a )  or from a "hot"  n i t r e n i u m  i o n ,  p a t h  ( b ) ,  whereas t h e  
p y r a z i n e ,  1, appa ren t ly  r e s u l t s  from t h e  se l f - condensa t ion  of e i t h e r  
phenacylamine o r  a-amino-a-phenylacetaldehyde. These i n  t u r n  may be 
h y d r o l y s i s  p roduc t s  o f  i s o m e r i c  p h e n y l a z i r i n e s ,  p a t h  ( c ) .  Phenacyl 
amine a l s o  may 
path ( b ) ,  with 
5 
_ .  
be formed on combination of  t h e  carbonium i o n ,  E, 
water. 
/ 
H 
H 
6 - 
0 0 HOH 
CGH,CH=CHNH e> C,H,CHCH=hTH 4 
, H O  
The sample o f  B - s t y r y l  azide was known t o  conta.in about 20 pe r -  
c e n t  of a -ch lo ros ty rene  which i s  t ransformed by e t h a n o l i c  s u . l f u r i c  
ac id  i n t o  acetophenone, a l s o  i s o l a t e d .  
3 .  
0 Experimental  
, a -S tg rg l  a z i d o  was prepared  accord ing  t o  Snolinsky.6 I n  c o i t r a s t  
6 t o  t h e  e a r l i e r  r e p o r t  of two s i n g l e  sharp  peaks i n  the imr spectrum 
( so lven t  n o t  s p e c i f i e d )  a t  4.32 and 5.32 ppm, J = 0.0 cps,  f o r  t h e  
nonequivalent  t e r m i n a l  methylene p ro tons ,  we havo found a p a i r  o f  
doub le t s  a t  4-87 and.S.34 ppm, J = 2.3 cps,  carbon t e t r a c h l o r i d e  s o l -  
ven t .  6 I '  Phenyl hydrogens showed as a m u l t i p l e t  a t  7.3 ppm. 
l-Phenyl-2-azido-l-ethanol, - A s o l u t i o n  of 100 g (0.5 mole) of 
phenacylbromide i n  375 mL of' e thanol  and 60 rnl  of g l a c i a l  acet4.c 
a c i d  w a s  t r e a t e d  with  64; g (1.0 mole) of  sodium a z i d e O 9  Without  
f u r t h e r  p u r i f i c a t i o n  t h e  product  of  t h i s  r e a c t i o n  was t r e a t e d  wi th  
25 g (0.66 mole) of -sodium borohydride." 
(63%) sample o f  l-phenyl-2-azidoethano1, bp 111-11~/0.~ mm. 
l y t i c a l  sample w a s  p repared  by r e d i s t i l l a t i o n ,  bp ll2-ll4/O.S m-71, 
G6 1.5519. 
(s)  and 2100 cm-l ( v s ) .  The nm- spectrum i n  caybon t e t r a c h l o r i d e  had 
s ignz ls  a t  7.17 ppm (phenyl ) ,  a q u a r t e t  a t  4.57 pprn ( c a r b i n o l  p r o t o n ) ,  
a t  -3.93 pprn (hydroxyl p ro ton ,  becomes 8 doublet i n  DIvlSO-D,) ,' and 
D i s t i l l a t i - o n  gave a 52.4- g 
An ana- 
Tho i n f r a r e d  spectrum (f'rorn a film) had bands at 3400 crvl 
c e n t e r a d  a t  3.15 pprn (nonoquivalent  methylens p r o t o n s )  . 
LIPI Anal. C a l c ~ d .  f o r  CeH,N,O: Cy 58.88; H, 5.56; N, 25.75. Found: 
- laChloro-l -ph~ngl-2-azidostha_ne.  - - A s o l u t i o n  of 17.4 g (0.15 
mole) of t h i o n y l  c h l o r i d e  i n  100 r n l  o f  anhgdrous ether was added t o  
a s o l u t i o n  of 16.5 g (0.1 molo) of l - p h ~ n y l - 2 - ~ i d o e t h a n o l  i n  100  ml 
of d r y  e t h e r  and 20 ml of  p y r i d i n e  a t  G o .  Stj.yi-ing was contLnu.ccl a t  
Oo fop 8 hp ar,d t h e  s o l u t i o n  vas a l lowed  t o  s t m d  ai; room t e x p c k n t u x ~ c  
4. 
I -  * overn igh t .  The o r g a n i c  l a y e r  was washed w i t h  d i l u t e  h y d r o c h l o r i c  
' a c i d ,  water, and thoroughly w i t h  sodium b ica rbona te  s o l u t i o n  t o  
remove a l l  a c i d i c  material. It was then  d r i e d  over  magnesium s u l -  
fa te  and evapora t ed  under vacuum. D i s t i l l a t i o n  of t h e  r e s i d u e  gave 
a 1 0 . 1  g (55%) f r a c t i o n  of l-chloro-l-phenyl-2-azidoethane, bp 78- 
7g0/0.4 mm, n55 1.5530 a f t e r  r e d i s t i l l a t i o n .  
from a f i l m  showed a i  az ide  band a t  2100 cm-'. 
a carbon t e t r a c h l o r i d e  s o l u t i o n  e x h i b i t e d  the  phenyl p r o t o n s  (5) as 
a m u l t i p l e t  c e n t e r e d  a t  7.18 ppm, t h e  methyne p ro ton  (1) as a t r i p l e t  
The i n f r a r e d  spectrum 
The nmr spectrum from 
- 4  
, at 4.78 ppm, and the  nonequivalent  methylene pro tons  ( 2 )  as an o c t e t  
I 
cen te red  a t  3.42 ppm, J = 6 . 8  cps.  
6-Azidostyrene. - A s l u r r y  o f  8.0 g (70 mmole) o f  po tass ium t- 
butoxide  i n  200 m l  of anhydrous e t h e r  was cooled t o  -25' and a so lu-  
t i o n  of 9.0 g (50 mmole) of 1-chloro-1-phenyl-2-azidoethane was added 
dropwise.  Af te r  2 h r  a t  -25' t h e  s o l u t i o n  was allowed t o  w a r m  t o  0' 
and s t o r e d  i n  a re f r igera tor  ove rn igh t .  The e t h e r  s o l u t i o n  was 
washed w i t h  water, d r i e d  o v e r  magnesium s u l f a t e ,  and concen t r a t ed  
under vacuum t o  g i v e  an o i l  t o g e t h e r  w i t h  a s o l i d .  The s o l i d  was 
separated by f i l t r a t i o n  and r e c r y s t a l l i z e d  from benzene t o  g i v e  0 . 2  g 
(3%)  of a yel low s o l i d ,  mp 186-187.5', t e n t a t i v e l y  i d e n t i f i e d  as 
. 
, and 
C6Hs H { p J N  
l - ( B - s t y r y l ) - 4  ( o r  5)-phenyl-1,2,3-triazole, 
I 
CH=CHC sHs 
recognized  as a formal  adduct between - 5 and C6H,CECH. 
Anal. Calc 'd .  f o r  C16H13N3: C ,  77.71; H, 5.30; N ,  16.99.  
Found: C ,  77 .40;  H ,  5.53; N ,  16.92.  
The remain ing  o i l  was d i s t i l l e d  wi th  t h e  p o t  t empera ture  below 
70°, and 1.2 g ( 1 7 % )  of a-chloros tyrene  was c o l l e c t e d ,  bp 28-320/0.6 
5 .  
- mm,’nZ5 1.5606.11 The d i s t i l l a t e  gave a p o s i t i v e  B o i l s t e i n  t e s t  f o r  D 
halogen and t h e  nmr spectrum (carbon t e t r a c h l o r i d e )  showed t h e  phenyl  
p r o t o n s  ( 5 )  as a pa.ir  of m u l t i p l e t s  cen terod  a t  7.52 ppm and 7 . i5  ppm 
and t h e  nonoquivalent  t e r m i n a l  rnsthyl.ene p ro tons  ( 2 )  as a p a i r  o f  
doub le t s  a t  5.39 ppm and 5.59 ppm, J = 1.6 cps ,  
solved i n  n-heptane and chromatographed over  aluniina t o  g i v e  3 .2  g 
(44%) of 8-az idos tyrene .  
The r e s i d u e  was d i s -  . 
The i n f r a r e d  spectrum f rom a f i l m  o r  i n  
chloroform had a strong a z i d e  band a t  2100 cm’l w i th  s m a l l e r  absorp-  
tions a t  2160, 2220, and 2280 cm-l and a g r e a t l y  enhanced C=C absorp-  
t i o n  a t  1645 cm’l, The nmr spectrum (carbon t e t r a c h l o r i d e )  e x h i b i t e d  
t h e  phenyl  p r o t o n s  ( 5 )  as a m u l t i p l e t  cen te red  a.t 7.14 ppm and t h e  
v i n y l  p r o t o n s  ( 2 ) ,  probably t r a n s ,  as a p a i r  of d o u b l e t s  a t  6.32 ppm 
and 6.11 pp:n, J = 14.0 cps .  The a z i d e  could n o t  bo d i s t i l l e d  and 
decomposed below 70 0 12 
a-Azidostyreno w i t h  s u l f u r i c  ac jd .  - Pure a -az idos tyrone ,  2,9 g 
(0.02 mole) ,  was addsd dropwise t o  a s o l u t i o n  or 6 ml o f  s u l f u r i c  
a c i d  i n  16 m l  o f  a b s o l u t e  e thanol .  
thermic  r e a c t i o n  under  c o n t r o l .  IJhen t h e  mixture  began t o  c o o l  a 
h e a t i n g  mantle  was a t t a c h e d  and t h e  r e a c t i o n  was heated under  r e f l u x  
for 1 hr. A f t e r  s t a n d i n g  overnight  t h e  s o l u t i o n  was poured i n t o  75 ml 
of i c e  water .  E x t r a c t i o n  wi th  e t h e r  f o l l o x e d  by d ry ing  over  potass ium 
ca rbona te  and evapora t ion  under vacuum gave 0.8 g (29.6%) o f  a d a r k  ., 
s o l i d ,  mp 110-112° a f t e r  r e c r y s t a l l i z a t i o n  f r o m  benzene. T h i s  s o l i d  
was shown by mixture  m o l t i n g  p o i n t  mid i n r r a r e d  spectrum t o  be 
Care was taksn  t o  keep t h e  exo- 
I 
a c e t a n i l i d e .  
The water  l a y e r  tias made b a s i c  w i t h  excess  sod ium ca rbona te  and 
e x t r a c t e d  t r l t h  e t h e r .  The conbinad organic  l a y s ~ s  were d r i e d  ove r  
a 
6 ,  
t 
m 
potassium carbonate  and evaporated t o  g i v e  1 . 2  g (64 .6%)  o f  a n i l i n e  
as shown by vpc r e t e n t i o n  t ime and i n f r a r e d  spectrum i d e n t i c a l  w i th  
similar d a t e  f o r  an a u t h e n t i c  sample. 
C '  
React ion o f  B-azidostyrene w i t h  s u l f u r i c  a c i d .  - A 1 . 4  g ( 0 . 0 1  
mole) sample of B-azidostyrene was added s lowly t o  a s o l u t i o n  o f  6 m l  
o f  s u l f u r i c  a c i d  i n  1 6  m l  of e thano l .  After  a d d i t i o n  was complete 
t he  mixture  was h e a t e d  a t  60° f o r  1 hr and allowed t o  s t a n d  ove rn igh t  
a t ' r oom tempera ture .  The mix tu re  was poured i n t o  100  m l  i c e  water 
and e x t r a c t e d  w i t h  e t h e r .  The combined o r g a n i c  layers  were d r i e d  over  
potass ium carbonate  'and evaporated t o  g i v e  0 . 6  g o f  a dark o i l .  T h i s  
o i l  was shown by gas chromatographic ana lyses  and nmr spectrum t o  be 
composed o f  a -ch loros tyrene  ( ca .  16%), acetophenone (43%) ,  and phenyl- 
a c e t o n i t r i l e  (17%), corresponding t o  maximum y i e l d s  of  ca .  7$, 1 9 %  and 
7% r e s p e c t i v e l y .  Each component was i d e n t i f i e d  by i t s  i d e n t i c a l  com- 
p a r i s o n  w i t h  vpc r e t e n t i o n  time and nmr s p e c t r a  f o r  a u t h e n t i c  samples.  
The water l aye r  was made b a s i c  w i t h  a l a r g e  excess  of sodium 
ca rbona te  a n d - e x t r a c t e d  w i t h  e t h e r  t o  g i v e  0.5 g o f  a dark o i l  a f t e r  
combining, d r y i n g  o v e r  potassium ca rbona te ,  and e v a p o r a t i n g  t h e  or-  
g a n i c  layers .  
1700 cm- ' .  Treatment o f  t h i s  o i l  w i th  anhydrous hydrogen c h l o r i d e  
gave a few milligrams of a yellow s o l i d  which was shown t o  be 2,s- 
d ipheny lpyraz ine ,  mp 1 9 2 . 4 ,  by  mixture  me l t ing  p o i n t  and i n f r a r e d  
The i n f r a r e d  spectrum had bands a t  3660, 3350, and 
spe  c t rum.  
Reac t ion  of a -ch loros tyrene  wi th  s u l f u r i c  a c i d .  A s o l u t i o n  of  
1 . 7  e; (0 .012  mole) of  a -ch loros tyrene  i n  6 m l  o f  s u l f u r i c  a c i d  and 
1 6  m l  of a b s o l u t e  e t h a n o l  wzs hea ted  under r e f l u x  f o r  4 h r  and 
A .  
7. 
allowed t o  s tand  overn ight  a t  rooin to rqoi -a ture  be fo re  be ing  poured 
i n t o  200 ml of i c e  wa te r .  The mixture  vas ex t r ac t ed  with e t h e r  and 
t h e  combined e x t r a c t s  wero d r i o d  over p o t a s s i u m  carbonate  and evap- 
. -- 
I ora t ed  t o  g i v e  2.1 g (73%) of acstophcnono as B dark  o i l .  Th i s  
assignment was v e r i f i e d  by i n f r a r e d  spectrum and vpc r e t e n t i o n  time. 
,- 
I -‘ Re ferenc  e s 
-- 
- 1. F i n a n c i a l  a s s i s t a n c e  from NASA grant N o .  NGR 14-012-004. 
2. P .  A. S. Smith,  ‘!Rearrangements Involv ing  Migrat ion t o  an 
E l e c t r o n - d e f i c i e n t  Nitrogen o r  Oxygen, i n  I lo lecular  Ream- 
- rangemcnts,  P. de Kayo, ed., pp. 468-471. 
._ 
John Wiley-Inter-  
s c i e n c e ,  New York (2963). 
_. 
3.  A. N. Nesmeyanov and M. I. Rybinskaya, I zves t .  Akad. Rauk SSSR, 
Otdel ,  K h i m .  Nauk, 816 (1962). Eng l i sh  trans. p .  761 r e p o r t s  
+ 4- 
I 
4. From t h o  assignment  o f  a h ighe r  energy t o  ENH 
r e l a t i v e  t o  RCHz (from RCH2Nz 
Mc men, J. Am. Chern. SOC., 77, 4007 (19551, t h e  hybr id  c z t i o n ,  
(from RNmT2 
+ I- 
by R .  F, T i e t z  and I!. E. 
4, would be expected t o  r e a c t  as  a carbonium i o n  e x c i t e d  s t a t e .  
I *  
5. T h i s  evidence a l s o  e l i m i n a t e s  a. migra t ion  from carbon t o  c a r -  
. bon concer ted  w i t h  nitrogon e l i ro ine t ion :  
a. 
. I  
6‘ . 
. 7. 
8. 
9. 
10, 
a 
0 -  
I 4  
12, 
G. Smolinsky, J. Org. Chein,, 27, .3!%7 (1962) 
J. .H. Royar  and 1,. R .  Morgan, J. h e r .  Chm, Soc., SO, 2020 
(1958); 83,  3369 (1959). 
Microanalyses  by Microtech Labora to r i e s ,  Chicago 
J, H. Boyer and D. Str;a.w, J,  Am, ‘Chem. S O C ~ ,  a, 4506 (1962). 
(1958) 
K. V. Auwers, Ber., E, 2799 (1912) r epor t s  1 $ ~ ~ ~ 1 . 5 6 2 3  and 
1.s590, bp 83.5-84O C (23 mm). D 
J. H, Boyer, W. E. Krusger and G. J. Mikol, J, Am, Chem. S O C . ,  


Acid catalyzed reactions of alpha and beta styryl azides

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