Insect Pheromone Technology - American Chemical Society

4 Grandisol and Lineatin Enantiomers FRANCIS X . WEBSTER and ROBERT M . SILVERSTEIN

Downloaded by PURDUE UNIV on August 28, 2014 | http://pubs.acs.org Publication Date: June 18, 1982 | doi: 10.1021/bk-1982-0190.ch004

State University of New York, College of Environmental Science and Forestry, Syracuse, NY 13210

The s y n t h e s i s of g r a n d i s o l ( I ) and lineatin(II) is d i s c u s s e d . G r a n d i s o l is a pheromone component in the c o t t o n boll w e e v i l and in Pissodes w e e v i l s . L i n e a t i n is the pheromone of Trypodendron l i n e a t u m . The key i n t e r m e d i a t e , 3 - m e t h y l - 5 - o x o - 3 - c y c l o h e x e n e 1 - c a r b o x y l i c a c i d ( V ) , was r e s o l v e d as the ( - ) - q u i n i n e salt. A new approach to determining the optical p u r i t y of c a r b o x y l i c a c i d s is d i s c u s s e d . G r a n d i s o l ( I ) i s a component o f t h e a g g r e g a t i o n pheromone o f t h e c o t t o n b o l l w e e v i l , Anthonomus g r a n d i s ( 1 ) , a n d i s p r e s e n t i n t h e hindgut o f s e v e r a l s p e c i e s o f male P i s s o d e s w e e v i l s ( 2 ) . L i n e a t i n ( I I ) i s t h e a g g r e g a t i o n pheromone o f t h e f e m a l e a m b r o s i a b e e t l e , T r y p o d e n d r o n l i n e a t u m (3>,4). S i n c e b o t h compounds s h a r e t h e same c a r b o n s k e l e t o n , s y n t h e s i s schemes i n v o l v i n g s i m i l a r i n t e r m e d i a t e s may b e c o n s i d e r e d , a n d t h i s p a p e r d e s c r i b e s s e v e r a l a p p r o a c h e s t o s y n t h e s i z i n g t h e e n a n t i o m e r s o f I and I I . The importance o f c o n s i d e r i n g enantiomeric composition o f c h i r a l s e m i o c h e m i c a l s o f i n s e c t s h a s b e e n d i s c u s s e d (5,j>) a n d s y n t h e t i c approaches have been r e v i e w e d ( 6 , 7 ) . Our c o n c e r n w i t h t h e g r a n d i s o l e n a n t i o m e r s a r i s e s f r o m o u r work w i t h t h e a g g r e g a t i o n pheromones o f s e v e r a l s p e c i e s o f Pissodes weevils ( 2 ) . Although g r a n d i s o l (I) i s present ( t o g e t h e r w i t h t h e c o r r e s p o n d i n g aldehyde, g r a n d i s a l ) i n t h e male h i n d g u t and n o t i n t h e f e m a l e , t h e s y n t h e s i z e d ( r a c e m i c ) compounds d i d n o t r e p r o d u c e t h e a t t r a c t i v i t y o f t h e m a l e s . We presume t h a t i t i s n e c e s s a r y t o r e p r o d u c e t h e e n a n t i o m e r i c c o m p o s i t i o n p r e s e n t i n t h e m a l e s . However, t h e s m a l l s p e c i f i c r o t a t i o n and t h e m i n u t e q u a n t i t i e s a v a i l a b l e o f g r a n d i s o l precluded d e t e r m i n a t i o n o f the o p t i c a l p u r i t y by o p t i c a l r o t a t i o n , and a t t e m p t s t o u s e a c h i r a l s h i f t r e a g e n t o r a c h i r a l d e r i v a t e f a i l e d presumably because t h e f u n c t i o n a l groups i s removed f r o m t h e c h i r a l c e n t e r s . The Hobbs and Magnus p r o c e d u r e (Scheme 1 ) (8) y i e l d e d o n l y ( + ) - g r a n d i s o l . A l t h o u g h M o r i ' s p r o c e d u r e (Scheme 2) (9) y i e l d e d 0097-6156/82/0190-0087$06.00/0 © 1981 American Chemical Society

In Insect Pheromone Technology: Chemistry and Applications; Leonhardt, B., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

TECHNOLOGY


INSECT P H E R O M O N E



4.

WEBSTER A N D siLVERSTEiN

Grandisol

and

Lineatin

Enantiomers

89

b o t h e n a n t i o m e r s , n e i t h e r e n a n t i o m e r was b e t t e r t h a n 80% o p t i c a l l y p u r e , and t h e o v e r a l l y i e l d was p o o r . The s e c o n d s y n t h e s i s by M o r i and Tamada (Scheme 3) (10) r e s u l t e d i n an o p t i c a l p u r i t y o f 94%, b u t o n l y t h e ( - ) - e n a n t i o m e r was o b t a i n e d . M o r i and Tamada (10) r e p o r t e d t h a t b o t h e n a n t i o m e r s ( m i x e d w i t h t h e o t h e r pheromone components) showed e q u a l b i o l o g i c a l a c t i v i t y f o r t h e b o l l w e e v i l . I n most c a s e s , t h e a n t i p o d e (an a r t i f a c t ) o f t h e n a t u r a l l y o c c u r r i n g e n a n t i o m e r shows c o n s i d e r a b l y l e s s a c t i v i t y ( 4 ) . However, i n most o t h e r c h i r a l pheromone c o m p o n e n t s , the f u n c t i o n a l group i s d i r e c t l y a t t a c h e d to the c h i r a l c e n t e r . P o s s i b l y t h e g r e a t e r d i s t a n c e b e t w e e n t h e f u n c t i o n a l g r o u p and the c h i r a l centers of g r a n d i s o l e x p l a i n the l a c k of d i s c r i m i n a t i o n , a l t h o u g h t h e much g r e a t e r d i s t a n c e i n t r o g o d e r m a l (11) d i d n o t i n t e r f e r e w i t h d i s c r i m i n a t i o n by s e v e r a l s p e c i e s o f T r o g o d e r ma b e e t l e s . The e n a n t i o m e r i c c o m p o s i t i o n o f l i n e a t i n i n T r y p o d e n d r o n l i n e a t u m was n o t d e t e r m i n e d , b u t t h e s y n t h e s i z e d (racemic) m a t e r i a l was h i g h l y a c t i v e i n f i e l d t e s t s ( 1 3 , 1 4 ) . Mori et a l . (Scheme 4) (15) and S l e s s o r e t a l . (Scheme 5) (16) s y n t h e s i z e d t h e l i n e a t i n e n a n t i o m e r s and r e p o r t e d s i m i l a r o p t i c a l p u r i t i e s , but because d i f f e r e n t s o l v e n t s were used, the o p t i c a l r o t a t i o n s c a n n o t be compared. S i n c e t h e (+) e n a n t i o m e r was a c t i v e i n f i e l d t e s t s ( 1 6 ) , we may assume t h a t i t i s t h e n a t u r a l l y o c c u r r i n g e n a n t i o m e r ; however t h e p r e s e n c e o f t h e a n t i p o d e c a n n o t be r u l e d out. Exploratory

Studies

I n i t i a l l y , our work resembled M o r i ' s f i r s t s y n t h e s i s o f g r a n d i s o l (Scheme 2) ( 9 ) . Whereas M o r i p a r t i a l l y r e s o l v e d a k e t o a c i d c o n t a i n i n g a b i c y c l o [ 3 . 2 . 0 ] h e p t a n e s k e l e t o n , we a t t e m p t e d to r e s o l v e a k e t o a c i d c o n t a i n i n g a b i c y c l o [ 4 . 2 . 0 ] o c t a n e s k e l e t o n (compound I I I ) . The s y n t h e s i s o f t h e a c i d was s t r a i g h t f o r w a r d (Scheme 6 ) : The c y a n o h y d r i n o f c y c l o h e x a n o n e was h y d r o l i z e d and e s t e r i f i e d , t h e α-hydroxy e s t e r was s m o o t h l y dehydrated w i t h t o s y l c h l o r i d e i n r e f l u x i n g p y r i d i n e . Allylic o x i d a t i o n by c h r o m i c a n h y d r i d e i n a c e t i c a c i d y i e l d e d t h e d e s i r e d enone e s t e r i n 55% y i e l d . A l t h o u g h t h i s y i e l d c o u l d n o t be i m p r o v e d by v a r y i n g t h e c o n d i t i o n s , t h e s t a r t i n g m a t e r i a l c o u l d be r e c o v e r e d f o r r e c y c l i n g . P h o t o c y c l i z a t i o n o f t h e p r o d u c t w i t h e t h y l e n e p r o c e e d e d i n 98% y i e l d . The b i c y c l o k e t o - e s t e r was t h e n hydrolyzed to the d e s i r e d keto a c i d , I I I . The k e t o a c i d c o u l d n o t be r e s o l v e d as e a s i l y as i t was synthesized. Formation of s a l t s w i t h v a r i o u s o p t i c a l l y pure bases i n v a r i a b l y y i e l d e d o i l s . K e t a l i z a t i o n of the keto e t h y l e s t e r w i t h e t h y l e n e g l y c o l f o l l o w e d by r e d u c t i o n w i t h l i t h i u m a l u m i n u m h y d r i d e and t r e a t m e n t w i t h M o s h e r ' s r e a g e n t , ( + ) - a methoxy-a-trxfluoromethylphenylacetyl c h l o r i d e (17,18,19), gave a d i a s t e r e o m e r i c m i x t u r e (Scheme 7 ) , w h i c h u n f o r t u n a t e l y was n o t r e s o l v a b l e by HPLC.



INSECT

PHEROMONE

TECHNOLOGY

(O-Grandlsol Ll§° · •

15.7*(n-hexane)

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2

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Scheme 3.


Grandisol

W E B S T E R A N D siLVERSTEiN

and Lineatin

CH C

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3 ^ A

Enantiomers

3

Steps


HO'

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NAPH-Ç-JOf H

M-Lineatin

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2

HD

+

3

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6

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Scheme 4.

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Scheme 5.


92

INSECT

PHEROMONE

TECHNOLOGY


Ο

Scheme 7.


3


4.

WEBSTER AND

SILVERSTEIN

Grandisol

and

Lineatin

Enantiomers

93

S i n c e our a l t e r n a t i v e s a t t h i s p o i n t were of a l e s s g e n e r a l n a t u r e , we m o d i f i e d o u r o r i g i n a l g o a l o f s y n t h e s i z i n g t h e e n a n t i o m e r s o f b o t h g r a n d i s o l and l i n e a t i n f r o m a common p r e c u r sor. S i n c e we w e r e i n v o l v e d w i t h t h e w h i t e p i n e w e e v i l , t h e s y n t h e s i s o f g r a n d i s o l was g i v e n p r i o r i t y . T h e r e f o r e , we c l e a v e d t h e M o s h e r e s t e r s (MTPA e s t e r s ) , t o s y l a t e d t h e n e o p e n t y l t y p e a l c o h o l (Scheme 8 ) , and r e d u c t i v e l y c l e a v e d t h e t o s y l a t e w i t h l i t h i u m a l u m i n u m h y d r i d e i n THF. The k e t a l m o i e t y was removed i n a two-phase s y s t e m y i e l d i n g t h e d e s i r e d c i s - b i c y c l i c k e t o n e . Zûrflîfe e t a l . (20) o b t a i n e d t h e same compound as an i n t e r m e d i a t e i n t h e i r s t e r e o s p e c i f i c s y n t h e s i s of racemic g r a n d i s o l . This k e t o n e was r e d u c e d a t -78° C w i t h l i t h i u m t r i - t e r t butoxyaluminohydride i n THF y i e l d i n g a s i n g l e ( p r o b a b l y c i s ) s e c o n d a r y a l c o h o l . However, t h e d i a s t e r e o m e r i c MTPA e s t e r s c o u l d n o t be r e s o l v e d by HPLC on a p r e p a r a t i v e s c a l e e v e n t h o u g h t h e s e c o n d a r y OH g r o u p was d i r e c t l y a t t a c h e d t o t h e c h i r a l c e n t e r . N e x t , we i n v e s t i g a t e d t h e s y n t h e s i s o f compound IV w h i c h m i g h t be u s e d as a common i n t e r m e d i a t e i n t h e s y n t h e s i s o f b o t h pheromones. A l t h o u g h IV was n e v e r u s e d f o r t h e s e p u r p o s e s , o u r i n v e s t i g a t i o n l e d t o some i n t e r e s t i n g r e s u l t s . Ethyl levulinate (Scheme 9) was b r o m i n a t e d and d e h y d r o b r o m i n a t e d i n a o n e - p o t s e q u e n c e ( 2 1 ) . The r e s u l t i n g enone was c o n v e r t e d i n t o t h e d i e n e by t r e a t m e n t w i t h t r i m e t h y l s i l y l i o d i d e , f o r m e d i n s i t u f r o m t r i m e t h y l s i l y l c h l o r i d e (22), i n the presence of t r i e t h y l a m i n e . The d i e n e was i s o l a t e d by d i s t i l l a t i o n i n a non-aqueous w o r k - u p . The f o r m a t i o n o f a d i e n e f r o m an a,β-unsaturated k e t o n e seems a g e n e r a l r e a c t i o n . The d i e n e was h e a t e d w i t h m a l e i c a n h y d r i d e i n t o l u e n e y i e l d i n g a s i n g l e a d d u c t . T h i s compound was b r o m i n a t e d , t h e t r i m e t h y l s i l y l b r o m i d e f o r m e d was removed u n d e r vacuum, and d e h y d r o b r o m i n a t i o n was c a r r i e d o u t i n p y r i d i n e . The a n h y d r i d e was h e a t e d w i t h w a t e r y i e l d i n g t h e d i a c i d ; t h i s compound s p o n t a n e o u s l y l o s t c a r b o n d i o x i d e f o r m i n g t h e d e s i r e d compound, I V . N o t e t h a t t h i s s e q u e n c e y i e l d s o n l y one i s o m e r . S i n c e t h e e x c e s s t r i m e t h y l s i l y l b r o m i d e was d i f f i c u l t t o remove, an a l t e r n a t i v e s e q u e n c e was i n v e s t i g a t e d (Scheme 1 0 ) . A f t e r bromination of the s i l y l enol ether, the r e a c t i o n mixture was p o u r e d i n t o w a t e r t o h y d r o l y z e b o t h t h e t r i m e t h y l s i l y l b r o m i d e and t h e a n h y d r i d e . On h e a t i n g t h i s b r o m o a c i d a s b e f o r e , an u n e x p e c t e d compound was f o r m e d . T h i s c a n be r a t i o n a l i z e d as follows: The r e a c t i o n p r o c e e d s f r o m t h e e n o l f o r m , and t h e mechanism i s f o r m a l l y 1,5 e l i m i n a t i o n o f h y d r o g e n b r o m i d e w i t h c o n c o m i t a n t l o s s o f c a r b o n d i o x i d e . The s e c o n d d e c a r b o x y l a t i o n i s a n a l o g o u s t o t h e one s e e n e a r l i e r , and w o u l d be e x p e c t e d o f the a,(3-unsaturated ketone. S y n t h e s i s and R e s o l u t i o n o f t h e Common Key

Intermediate

K e t o a c i d V, a known compound, was u s e d f o r t h e s y n t h e s i s o f b o t h g r a n d i s o l and l i n e a t i n . The f i r s t s t e p o f t h e two s t e p s y n t h e s i s i s an ene r e a c t i o n (23,24) o f i s o b u t y l e n e w i t h m a l e i c


94

PHEROMONE

TECHNOLOGY


INSECT

Scheme 8.


Grandisol

and Lineatin

Enantiomers


W E B S T E R A N D SILVERSTEIN

Scheme 9.


PHEROMONE

TECHNOLOGY


INSECT

Scheme 10.


4.

WEBSTER AND

SILVERSTEIN

Grandisol

and

Lineatin

Enantiomers

97

a n h y d r i d e (Scheme 1 1 ) . We w e r e u n a b l e t o r e p e a t t h e r e a c t i o n as r e p o r t e d (24) u n l e s s a s m a l l amount o f h y d r o q u i n o n e was a d d e d . The p r o d u c t , m e t h a l l y l s u c c i n i c a n h y d r i d e , u n d e r g o e s a c l e a n r e a r r a n g e m e n t i n h o t p o l y p h o s p h o r i c a c i d t o y i e l d enone a c i d V (25). R a c e m i c V c o u l d n o t be r e s o l v e d w i t h p r i m a r y o p t i c a l l y a c t i v e bases presumably because they r e a c t e d i n a M i c h a e l f a s h i o n . F o r m a t i o n o f t h e q u i n i n e s a l t and f i v e r e c r y s t a l l i z a t i o n s f r o m a b e n z e n e / h e x a n e m i x t u r e y i e l d e d an a c i d ( a f t e r h y d r o l y s i s ) whose s p e c i f i c r o t a t i o n was [ a ] j p - 4 7 . However, s i n c e t h e maximum s p e c i f i c r o t a t i o n i s unknown, an a b s o l u t e method o f d e t e r m i n i n g o p t i c a l p u r i t y i s n e e d e d . The u s u a l method i s t r e a t m e n t w i t h an o p t i c a l l y pure d e r i v a t i z i n g reagent to form c o v a l e n t d i a s t e r e o m e r s , whose r a t i o c a n be d e t e r m i n e d by NMR o r c h r o m a t o g r a p h y . ( - ) - Q u i n i n e i s an o p t i c a l l y p u r e d e r i v a t i z i n g r e a g e n t t h a t f o r m s a d i a s t e r e o m e r i c m i x t u r e o f s a l t s whose 13c NMR s p e c t r u m w o u l d be e x p e c t e d t o show i n d i v i d u a l p e a k s f o r t h e d i a s t e r e o m e r s p r e s e n t . A 1 3 NMR o f t h e s a l t f o r m e d f r o m 1 e q u i v a l e n t o f q u i n i n e and 1 e q u i v a l e n t o f r a c e m i c a c i d (V) r e v e a l e d two p e a k s f o r t h e c a r b o n atom 3 t o t h e c a r b o n y l g r o u p . The NMR (25.2 MHz) o f t h e s a l t o f t h e p a r t i a l l y r e s o l v e d a c i d ( F i g u r e 1) i n d i c a t e s t h a t t h e r a t i o o f d i a s t e r e o m e r s i s a p p r o x i m a t e l y t h r e e t o one ( o p t i c a l p u r i t y ~ 7 5 % ) . As i s s e e n i n t h e e x p a n s i o n , o v e r l a p o f peaks p r e c l u d e s p r e c i s e d e t e r m i n a t i o n of e n a n t i o m e r i c c o m p o s i t i o n , b u t a more p o w e r f u l i n s t r u m e n t s h o u l d c o m p l e t e l y r e s o l v e t h e two p e a k s . We a r e c u r r e n t l y i n v e s t i g a t i n g t h e g e n e r a l i t y o f t h i s procedure.


0

C

Synthesis of Grandisol The f i r s t s t e p i n t h e c o n v e r s i o n o f enone a c i d V t o g r a n d i s o l i s f o r m a t i o n o f t h e c y c l o b u t a n e r i n g by i r r a d i a t i o n o f t h e a c i d i n t h e p r e s e n c e o f a c o n t i n u o u s f l o w o f e t h y l e n e (Scheme 12). S i n c e t h e two c h i r a l c e n t e r s o f g r a n d i s o l a r e f o r m e d i n t h i s r e a c t i o n , t h e p r o d u c t ( s ) o f t h e r e a c t i o n must be a n a l y z e d c a r e fully. A p r i o r i , f o u r i s o m e r i c p r o d u c t s c a n be drawn: V I , V I I , V I I I , and I X . S i n c e two o f t h e s e p r o d u c t s h a v e a t r a n s r i n g j u n c t i o n α t o a k e t o n e , t h e y a r e u n s t a b l e and c a n be e p i m e r i z e d to t h e more s t a b l e c i s j u n c t i o n . Hence, a p a i r o f i s o m e r s ( V I and V I I o r V I I I and I X ) i s a c c e p t a b l e b e c a u s e s u c h a p a i r c o u l d be c o n v e r t e d i n t o a s i n g l e i s o m e r . A n a l y s i s o f t h e p r o d u c t r e v e a l e d t h a t two i s o m e r s w e r e present. F i g u r e 2 reproduces the NMR o f t h e c o r r e s p o n d i n g methyl e s t e r s (dimethyl s u l f a t e / p o t a s s i u m carbonate/acetone). S i n c e t h e k e t o n e c a r b o n y l ( a ) and a d j a c e n t b r i d g e c a r b o n (b) a r e e a c h r e p r e s e n t e d by two p e a k s , w h i l e t h e e s t e r c a r b o n y l ( c ) and t h e methoxy c a r b o n (d) a r e e a c h r e p r e s e n t e d by a s i n g l e p e a k , t h e m i x t u r e must c o n s i s t o f one o f t h e a c c e p t a b l e p a i r s m e n t i o n e d above.


INSECT

PHEROMONE

TECHNOLOGY


98



Grandisol

and Lineatin

Enantiomers


4.


99

TECHNOLOGY





Grandisol

and Lineatin

Enantiomers


4.


101

102


TECHNOLOGY

The r e s t o f t h e s y n t h e s i s (Scheme 13) i s c o m p l e t e l y s t e r e o s p e c i f i c and most o f t h e s t e p s a r e known ( 2 0 ) . The b i c y c l i c a c i d was o x i d a t i v e l y d e c a r b o x y l a t e d w i t h l e a d t e t r a a c e t a t e and c o p p e r a c e t a t e ( 2 1 ) . The r e s u l t i n g enone was a l k y l a t e d w i t h methyllithium giving a single crystalline a l l y l i c tertiary alcohol. T h i s compound was c l e a v e d w i t h osmium t e t r o x i d e and sodium p e r i o d a t e . Inverse a d d i t i o n of the W i t t i g reagent effected methylenation i n 85% y i e l d . F i n a l l y , t h e a c i d was reduced w i t h l i t h i u m aluminum h y d r i d e to g r a n d i s o l .


Synthesis of L i n e a t i n Scheme 14 o u t l i n e s t h e s y n t h e s i s t h a t we h a v e d e v e l o p e d f o r lineatin. P h o t o c y c l i z a t i o n w i t h aliène gave p r e d o m i n a n t l y one i s o m e r ( 2 6 , 2 7 ) , w h i c h , a f t e r p u r i f i c a t i o n , was o b t a i n e d a s a s i n g l e c r y s t a l l i n e compound. T h i s r e a c t i o n i s v e r y s a t i s f a c t o r y f o r c h i r a l i n d u c t i o n . The n e x t s t e p i n t h e s y n t h e s i s i s t h e o x i d a t i v e d e c a r b o x y l a t i o n seen e a r l i e r i n the g r a n d i s o l s y n t h e s i s . O x i d a t i v e c l e a v a g e w i t h osmium t e t r o x i d e and s o d i u m p e r i o d a t e y i e l d e d t h e t r i f u n c t i o n a l compound, w h i c h was c o n v e r t e d i n t o t h e c o r r e s p o n d i n g a c e t a l k e t a l e s t e r . T h i s e s t e r was a l k y l a t e d w i t h m e t h y l l i t h i u m and t h e k e t a l g r o u p was h y d r o l y z e d . Although the f o l l o w i n g r e d u c t i o n shown i n t h e scheme has n o t y e t b e e n w o r k e d o u t , t h e p l a n i s d e s i g n e d t o s a v e one s t e p . I f the ketone can be r e d u c e d k i n e t i c a l l y w h i l e t h e h e m i a c e t a l r e m a i n s i n t a c t , t h e n t h e s y n t h e s i s i s v i r t u a l l y c o m p l e t e . However, i f t h e r e d u c t i o n i s u n s u c c e s s f u l , we s h a l l o x y d i z e t h e h e m i a c e t a l and r e d u c e b o t h g r o u p s w i t h DIBAH. I n e i t h e r c a s e , 4 , 6 , 6 - l i n e a t i n w i l l be f o r m e d by c l o s i n g t h e t h i r d r i n g w i t h a c i d c a t a l y s i s .



à? HOOC

Grandisol

Cu(0AO CH

Enantiomers

6?

PbiOAc)^ 2

3

0


and Lineatin

H

3

C ^ ) H

MeLi >

CH

CH

3

3

0

H C v ^ O H 3

OsO^ ΝαΙΟ^ CH

0

3

CH

CH Ph P= CH 3

CH

0

CH

2

2

0

3

CH

3

2

LiAlH

0

3

CH

a

3

Grandisol Scheme 13.



TECHNOLOGY


104


4.


Literature 1.

2. 3.

4.


5.

6.

7. 8. 9. 10. 11.

12.

13. 14. 15. 16.

17. 18. 19. 20. 21.

Grandisol

and Lineatin

Enantiomers

105

Cited

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Olah, G.A.,; Narang, S . C . ; Gupta, B.G.B.; M a l h o r t s , R. J. Org. Chem. 1979, 44, 1247-2451. A l d e r , K.; Pascher, F.; Schmitz, A . B e r . 1943, 76B, 47-49. Phillips, D . D . ; Johnson, A.W. J. Am. Chem. Soc. 1955, 77, 5977-5981. Noyce, D.S.; Dolby, L.J. J . Org. Chem. 1961, 26, 1732-1737. G u t h r i e , R . W . ; V a l e n t a , Z.; Wusner, K . Tetrahedron Lett. 1966, 4645-4654. K e l l y , R.B.; Zamecnik, J.; B e c k e t t , Β.A. Can. J. Chem. 1972, 50, 3455-3464. 1982.


RECEIVED February 24,


Insect Pheromone Technology - American Chemical Society

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