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Synthetic Communications: AnInternational Journal for RapidCommunication of SyntheticOrganic ChemistryPublication details, including instructions forauthors and subscription information:http://www.tandfonline.com/loi/lsyc20

Heterodiene Synthesis.I. Reaction of 5-Arylidenerhodanine Derivativeswith 1-MorpholinocyclohexeneEnamineM. Abdel-rahman a b , H. Abdel-ghany a & A.-B. A. G.Ghattas aa Chemistry Department, Faculty of Science , AssiutUniversity , Sohag, Egyptb Chemistry Department, Faculty of Science , Sohag,EgyptPublished online: 23 Oct 2006.

To cite this article: M. Abdel-rahman , H. Abdel-ghany & A.-B. A. G. Ghattas (1989)Heterodiene Synthesis. I. Reaction of 5-Arylidenerhodanine Derivatives with 1-Morpholinocyclohexene Enamine, Synthetic Communications: An International Journalfor Rapid Communication of Synthetic Organic Chemistry, 19:3-4, 345-354, DOI:10.1080/00397918908050672

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SYNTHETIC COMMUNICATIONS, 1 9 ( 3 & 4 ) , 345-354 (1989)

HETERODIENE SYNTHESIS, I

REACTION OF 5-ARYLIDENERHODANINE DERIVATIVES

WITH

1-MORPHOLINOCYCLOHEXENE ENAMINE

M. Abdel-Rahman rH. Abdel-Ghany AND A.-B. A. G. Ghattas

Chem is t r y D e p a r t m e n t , F a c u l t y o f S c i e n c e ,

A s s i u W n i v e r s i t y , S o h a g , E g y p t .

ABSTRACT:- C y c l o a d d i t i o n of 5 - a r y l i d e n e r h o d a n i n e d e r i v a t i v e s lamd a s a, B u n s a t u r a t e d c a r b o n y l s y s tem a t t a c h e d t o a h e t e r o c y c l i c n u c l e u s w i t h e n a m i n e E a s a n e l e c t r o n r i c h d i e n o p h i l i t l e a d t o 3 , 4 - d i h y d r o - 2 H - p y r a n s 2, . T h e r e s u l t s d i f f e r e d d e p e n d i n g o n t h e n a t u r e G? t h e s u b s t i t u e n t o f t h e a r y l i d e n e g r o u p . T h e i n t r o d u c t i o n of a n e l e c t r o n - w i t h d r a w i n g g r o u p i n t h e p - p o s i t i o n of a r y l i d e n e m o i e t y s h o u l d increase t h e f a c i l i t y of t h e r e a c t i o n .

T h e p e r c y c l i c r e a c t ion ( 4 n + IT) c y c l o a d d i t i o n

is u s e d m o s t o f t e n i n o r g a n i c s y n t h e s i s . O w i n g t o

t h e m u l t i t u d e o f d i e n e s a n d d i e n o p h i l e s , i t is

p o s s i b l e t o o b t a i n v a r i o u s f u n c t i o n a l i z e d a d d u c t s

* Chem is t r y Departmen t, F a c u l t y o f S c i e n c e , Sohag-EGYPT. ----______----------

34 5

Copyright 0 1989 by Marcel Dekker, Inc

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346 ABDEL-RAHMAN, ABDEL-GHANY, AND GHATTAS

a s s t a r t i n g c o m p o u n d s f o r m a n y i m p o r t a n t n a t u r a l

p r o d u c t s ’ . D i h y d r o p y r a n f o r m a t i o n b y t h e t h e r m a l

c y c l o a d d i t ion r eac t i o n of CI I B - u n s a t u r a t e d k e t o n e s ,

b e h a v i n g a s h e t e r o d i e n e s a r e w e l l k n o w n 2 . T a c c o n i

e t a13. f o u n d t h a t N - a c e t y l - 3 - b e n z a l o x i n d o l e

r eac t s w i t h e n a m i n e s u n d e r g o i n g 1 ’ 4 c y c l o a d d i t i o n .

T h i s r e a c t i o n h a s b e e n s u c c e s s f u l l y e x t e n d e d t o a

l a r g e s e r i e s o f o t h e r h e t e r o c y c l i c d e r i v a t i v e s 3 ’ *

w h i c h a l s o g a v e d i h y d r o p y r a n a d d u c t s . A l s o t h e 5-

a r y l i d e n e - l r 3 - d i o x a n e - 4 , 6 - d i o n e s r e a c t w i t h e n a -

m i n e s r b u t o n l y c o n d e n s e d d i h y d r o p y r a n s a r e

f o rmed5 . R e c e n t i n v e s t i g a t i o n s h a v e d e m o n s t r a t e d

t h a t e l e c t r o n - w i t h d r a w i n g s u b s t i t u e n t s a t t h e a-

p o s i t i o n i n t h e a , $ - u n s a t u r a t e d s y s tern i n c r e a s e t h e

r a t e of t h i s r e a c t i o n s t r o n g l y . 6

Here w e w i s h t o r e p o r t t h e r e s u l t s o b t a i n e d

f rorn t h e r e a c t i o n o f 5 - a r y l i d e n e r h o d a n i n e d e r i v a -

t i v e s l a - d a s a I B - u n s a t u r a t e d c a r b o n y l s y s t e m s

a t t a c h e d t o a h e t e r o c y c l i c n u c l e u s w i t h e n a m i n e E

a s a n e l e c t r o n r i c h d i e n o p h i l e ( S c h e m e 1). We a r e

a l s o i n t e r e s t e d i n t h e e l u c i d a t i o n of t h e r o l e

p l a y e d b y a r y l i d e n e s u b s t i t u e n ts i n t h e s t a b i l i z a -

t i o n of t h e d i p o l a r form ( S c h e m e 2 ) , t h e c o n t r i b u -

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HETERODIENE SYNTHESIS. I 34 7

t i o n of w h i c h c o u l d s t r o n g l y i n f l u e n c e t h e c y c l o -

add i t ion r e a c t i o n .

I n ref l u x i n g a c e t o n i t r i l e t h e r eac t i o n o c c u r r -

e d i n g o o d y i e l d w i t h t h e f o r m a t i o n o f a 1 : l

a d d u c t . C h r o m a t o g r a p h i c s e p a r a t i o n , f r a c t i o n a l

c r y s t a l l i z a t i o n o r b o t h t e c h n i q u e s t o g e t h e r g a v e

t h e a d d u c t s . A c h a r g e - t r a n s f e r c o m p l e x u n d o u b -

t e d l y is f o r m e d d u r i n g t h i s r e a c t i o n a s e v i d e n c e d

b y a t r , a n s i e n t i n t e n s e r e d c o l o u r o f t h e r e a c t i o n

m i x t u re.

F r o m t h e d a t a r e p o r t e d i n ( T a b l e 1) i t c a n b e

s e e n t h a t t h e I R s p e c t r a o f a l l t h e a d d u c t s s h o w :-

a- N o l ac tam C=O b o n d .

b- N o e x o c y c l i c C=C b o n d .

T h e r e f o r e , b o t h t h e d o u b l e b o n d a n d t h e l a c t a m

c a r b o n y l g r o u p m u s t h a v e p a r t i c i p a t e d i n t h e reac-

t i o n , a n d h e n c e a l r 4 - c y c l o a d d i t i o n is s t r o n g l y

s u g g e s t e d a s r e a c t i o n mode. F u r t h e r m o r e , t h e

a d d u c t s s h o w a s t r o n g b a n d i n t h e r e g i o n 1 6 2 0 - 1 6 7 0

ern-', s h o u l d b e a s s i g n e d t o t h e d i h y d r o p y r a n d o u b l e

b o n d ’ . T h e i n v e s t i g a t i o n o f t h e s t r u c t u r e s was

m o n i t o r e d by ’H N M R , w h i c h is i n g e n e r a l c o m p l e x ,

n e v e r t h e l e s s a f e w s i g n a l s can be a s s i g n e d e a s i l y

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348 ABDEL-RAHMAN, ABDEL-GHANY, AND GHATTAS

+

S

- 'a-d P Za-d

R = m-tolyl

a: A r = p-NO Ph 2

b: = p-C1Ph

C: = p-OCH3Ph

d: = Piperonyl

(Scheme 1)

diene dipolar

(Scheme 2 )

I I S

.sy\ R

S

a

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HETERODIENE SYNTHESIS. I 34 9

Table 1: IR Spectroscopic Data canp. ~c=cexocyclic V G C dihydropyran V C X 3 lactam k! 1605 - 1712

(KBr crn-')

- - 1625 - &

2

a(;

- lb 1600 - 1705 - - 1640 - - lc 1590 - 1710 - - 1630 -

1700 -

Table 2: 'H NMR Spectra Comp. CH2-0-CH2

G(CDC13) ppm. a m t i c p r o t ~ n s Note CH3

3.7 (b**,4H) 2.40 (s, 314) 7.0-8.2 Hb - - overlaped a* - - 2r 3.65 ( b , 4H) 2.25 (s, 3 H ) 6.5-7.7 by protons o 2d 3.9 (b, 4H) 2.30 ( s , 3H) 6.8-7.8 e nami ne =

~ - - ~

* * % = (broad). 2b, it is not stable enough for measuring 'H NMR.

Table ( 3 :

Comp. Reaction time (hIa) Yield ( 8 ) b) M.P (OC)')

2a 20 70 140 - - 2b 120 48 128-130

ZE 140

- 2d 65 -

40

57

14 3

130-132 ~-

1--- ~- ~

-~

a) Reactions were followed by H NMR spectra (Showed no vinyl proton signa1)or IR spectra (the carbonyl bands were miss- ing) .

b) Yields are for pure isolated products, elemental analyse were difficult to carry out for the adducts: however, correct analytical data have been obtained in some cases.

c) The adducts decompose at the melting points.

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3 50 ABDEL-RAHMAN, ABDEL-GHANY, AND GHATTAS

s u c h a s CH2-O-CH2 a t 6 = 3.7-3.9 p p m a n d CH2-N-CH2

a t 6 = 2.9-3.4 p p m , m o r o v e r t h e v i n y l i c p r o t o n

d i s a p p e a r e d . W e h a v e t h e r e f o r e c o m b i n e d s e v e r a l

p i e c e s of s p e c t r o s c o p i c e v i d e n c e t o d e m o n s t r a t e

t h a t t h e a d d u c t s a r e t h e d i h y d r o p y r a n s 2,-d.

An e l e c t r o n - a t t r a c t i n g s u b s t i t u e n t o n t h e

a r y l i d e n e decreases t h e I T - e l e c t r o n d e n s i t y o n t h e

b e n z y l i d e n e c a r b o n a t o m , h e n c e a n u c l e o p h i l i c

a t t a c k s h o u l d b e f a v o u r e d . T h i s a s s u m p t i o n was

i n v e s t iga t ed . b y D e S imon i8. T h e n u c l e o p h i l ic a t t a c k

of t h e e n a m i n e on t h e a , 8 - u n s a t u r a t e d c a r b o n y l

s y s t e m g i v e s r i s e t o a d i s c r e t e i n t e r m e d i a t e 2 ,

p r o b a b l y o f zw i t t e r i o n i c c h a r a c t e r , t h e s u b s e q u e n t

c l o s u r e o f w h i c h o c c u r s i n t h e f o r m a t i o n of t h e

d i h y p r o p y r a n r i n g ( S c h e m e 3 ) .

O p i t z ’ d e s c r i b e d t h e f o r m a t i o n o f d i h y d r o -

p y r a n s i n a D i e l s - A l d e r r e a c t i o n . On t h i s b a s i s ,

t h e p r e s e n c e of s t a b l e d i h y d r o p y r a n s i n t h e r e a c -

t i o n o f m e t h y l v i n y l k e t o n e a n d e n a m i n e s , a n d t h e

e x i s t e n c e o f t h e z w i t t e r i o n i c i n t e r m e d i a t e of t h i s

r e a c t i o n was d e m o n s t r a t e d . 10

T h e r a t e of f o r m a t i o n o f d i h y d r o p y r a n s f r o m 5-

a r y l i d e n e r h o d a n i n e s 1 is w e l l e x p l a i n e d i n terms of

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HETERODIENE SYNTHESIS. I 351

a n e t c h a r g e d i s t r i b u t i o n ( t h r o u g h a z w i t t e r i o n i c

p a t h w a y ) . T h e r e l a t i v e i m p o r t a n c e o f t h e r i n g

c l o s u r e o f 2 on o x y g e n s h o u l d i n c r e a s e w i t h i n c r e a -

s i n g s t a b i l i t y of t h e z w i t t e r i o n Z . M o r e o v e r , w h e n

t h e n i t r o g e n l o n e p a i r is p r e f e r e n t i a l l y d e l o c a l i z -

e d o n t h e t h i o c a r b o n y l g r o u p , i t d o e s n o t p e r t u r b

t h e s u c c e e d i n g r i n g c l o s u r e o f i t r e s u l t i n g i n a

1 I 4 - c y c l o a d d i t i o n .

A f u r t h e r r a t i o n a l i z a t i o n a r i s e s f r o m t h e

11 l o w e r s e p a r a t i o n o f t h e f r o n t i e r o r b i t a l s

p r o m o t e d b o t h b y t h e e l e c t r o n - a t t r a c t i n g t h i o -

c a r b o n y l g r o u p i n B - p o s i t i o n o f t h e u n s a t u r a t e d

C=C-C=O s y s tem , a n d b y t h e e l e c t r o n - d o n a t i n g a 1 k y l

g r o u p o f t h e e n a m i n e . F u r t h e r m o r e , t h e i n c r e a s e d

a s y m m e t r y c o e f f i c i e n t , i n a d d i t i o n t o t h e l a r g e

f r o n t i e r c o n t r o l l ' , s t r o n g l y f a v o u r s a z w i t t e r i o n i c

p a t h w a y , a l r e a d y proposed b y F l e m i n g 10 .

I t is i n t e r e s t i n g t o n o t e t h a t t h e i n t r o d u c -

t i o n o f a n i t r o g r o u p i n t h e p - p o s i t i o n of t h e

b e n z y l i d e n e n u c l e u s i n t h e h e t e r o d i e n e s y s tern 1,

i n c r e a s e s t h e f a c i l i t y a n d t h e r a t e w i t h w h i c h t h e

sys tem p a r t i c ipa tes i n a n i n v e r s e e l e c t r o n d e m a n d

( 4 n + 2 n ) c y c l o a d d i t i o n r e a c t i o n w i t h e l e c t r o n r i c h

d i e n o p h i l e s ( e n a m i n e E).

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352

EXPERIMENTAL:-

ABDEL-RAHMAN, ABDEL-GHANY, AND GHATTAS

A l l m e l t i n g p o i n t s a r e u n c o r r e c t e d . I R s p e c t r a

( c m - l ) were r e c o r d e d on a P e r k i n E l m e r 1 3 7 S p e c t r o -

p h o t o m e t e r i n K B r . 'H NMR s p e c t r a were r e c o r d e d a t

60 MHz on a Var i an A-60 S p e c t r o m e t e r . T h e c h e m i c a l

s h i f t s a r e e x p r e s s e d i n 6 v a l u e s ( p p m I r TMS was

u s e d a s i n t e r n a l r e f e r e n c e s t a n d a r e d . E l e m e n t a l

a n a l y s e s were done by M i c r o a n a l y t i c a l L a b o r a t o r y ,

C a i r o Un i v e r s i t y r G i z a r Egypt.

GENERAL PROCEDURE:-

A m i x t u r e of 1 . 0 e q u i v . o f 5 - a r y l i d e n e -

r h o d a n i n e s 1 3 l 1 1.2 e q u i v . o f e n a m i n e E, a n d d r y

a c e t o n i t r i l e a s s o l v e n t was r e f l u x e d u n d e r d r y

c o n d i t i o n s f o r a p p r o p r i a t e t i m e ( T a b l e 3 ) . T h e

y e l l o w c o l o u r r w h i c h is t y p i c a l € o r 5 - a r y l i d e n e -

r h o d a n i n e s d i s a p p e a r e d w h e r e a s a n i n t e n s e r e d

s o l u t i o n was o b t a i n e d . An i n f r a r e d s p e c t r u m of t h e

m i x t u r e showed no a b s o r p t i o n band i n t h e u n s a t u r a t -

e d l a c t a m r e g i o n . E v a p o r a t i o n of t h e s o l v e n t

u n d e r r e d u c e d p r e s s u r e g a v e a v i s c o u s r e s i d u e r

t h a t a f t e r g r i n d i n g w i t h p e t . e t h e r s o l i d i f i e d a s

c o l o u r e d s o l id. The p r o d u c t w a s r e c r y s t a l l i zed from

C H C 1 3 / p e t . e t h e r .

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HETERODIENE SYNTHESIS. I 353

Y i e l d s a n d c o n d i t i o n s of a l l t h e i s o l a t e d

a d d u c t s a r e s u m m a r i z e d i n ( T a b l e 3).

REFERENCES AND NOTES:-

l . W e i n r e b , S. M . a n d S t a i b , R. R . , T e t r a h e d r o n ,

1 9 8 2 1 38, 3087 - 2 . D e s i r n o n i , G. a n d T a c c o n i , G . C h e m . R e v . , 1 9 7 5 ,

75 I 651 a n d references t h e r e i n . - 3.a- D e s i m o n i , G . , T a c c o n i , G . a n d M a r i n o n e , F., G a z z .

C h i r n . I t a l . , 1968 , 9 8 , 1301 . - b- T a c c o n i , G., M a r i n o n e , F., G a m b a , A . a n d

D e s i m o n i , G. , T e t r a h e d r o n , 1 9 7 1 , 2 7 , 561 a n d -

1 9 7 2 , 2 8 , 1 5 1 7 . I

4- D e s i r n o n i , G. a n d T a c c o n i , G . , G a z z . C h i m . I t a l . ,

1968, 981 1329 - - 5- P e n a d e s , S . , K i s c h r H., T o r t s c h a n o f f , K . , M a r g a r e t h

P . a n d P o l a n s k y , 0. E . , M o n a t s h . C h i m . , 1 9 7 3 ,

1 0 4 , 4 4 7 -- 6. I s m a i l , Z . M . a n d H o f f m a n n , H . M. R . , A n g e w .

C h e m . I n t . E d . E n g l . , 1 9 8 2 , 2 1 1 8 5 9 . I

7 . p r a s a d r K . K . a n d G i r i l i a v a l l a b h a n , V . M . r Chern.

I n d . ( L o n d o n ) , 1 9 7 0 , 4 2 6 . 8. C e l l e r i n o , G., D e s i m o n i , G . , R i g h e t t i , P . P. a n d

T a c c o n i , G , , Gazz. C h i m . I t a l . , 1 9 7 3 , 103/ 1 2 4 7 . -

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3 54 ABDEL-RAHMAN, ABDEL-GHANY, AND GHATTAS

9. O p i t z , G. a n d H o l t m a n n , H. , J u s t u s L i e b i g s Ann.

C h e m . , 1 9 6 5 , 6 8 4 , 7 9 . -- 10.a- F l e m i n g , I. a n d K a r g e r , M . H . , J. C h e m . S O ~ .

C i 1 9 6 7 1 2 2 6 . b- R i s a l i t i , A. , V a l e n t i n , E. a n d F o r c h i a s s i n ,

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i n e d by t h e l o w e s t HOMO-LUMO e n e r g y s e p e r a t i o n

a t t a i n a b l e by t h e r e a c t i n g d i e n e / d i e n o p h i l e

c o m p o n e n t s H O M O d i e n e - L U M O d i e n o p h i l e o r

LUMOd iene-HOMOd i e n o p h i l e O f t h e ( 4 + 2 ) c y c l o a d d i -

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r i n g t h e m a g n i t u d e of t h i s e n e r g y s e p a r a t i o n

a c c e l e r a t e t h e r a t e o f t h e D i e l s - A l d e r r e a c -

t i o n . T h e i n v e r s e e l e c t r o n d e m a n d ( L U M O d i e n e

c o n t r o l l e d ) D i e l s - A l d e r r e a c t i o n e m p l o y s a n

e l e c t r o n - d e f i c i e n t d i e n e

e l e c t r o n r i c h d i e n o p h i l e ( i n c r e a s e d d i e n o p h i l e )

1 2 . H o l i k , M . , J a n a k , J. a n d F e e r i e s , M . , C o l l e c t .

( d e c r e a s e d LUMOd iene ) /

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a n d S a n d s t r o m , J., Acta C h i m . S c a n d . , 1 9 6 7 , -- 2 1 ,

4 4 2 . (Received in USA J u l y 7, 1988)

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