ho1996 -isolation, identification, and synthesis of

8/16/2019 Ho1996 -Isolation, Identification, And Synthesis Of

1/15

J o u r n a l o f Ch e m ic a l E c o lo g y . V o l. 2 2 , No . 2 , 1 9 9 6

I S O L A T I O N , I D E N T I F I C A T I O N , A N D S Y N T H E S I S O F

S E X P H E R O M O N E C O M P O N E N T S O F F E M A L E T E A

C L U S T E R C A T E R P I L L A R , n d r aca b i punc tata W A L K E R

L E P I D O P T E R A : B O M B Y C I D A E ) I N T A I W A N

H . Y . H O , I Y . T . T A O , 2 R . S . T S A I , I Y . L . W U , I H . K . T S E N G , 3 a n d

Y . S . C H O W I ' *

t n s ti tu t e ~ ¢ Z o o lo g y , A c a d e m ia S in ± c a

hls ti tu te o f Chemistt3 , Academi~l Sin± ca

Na nka ng 11529, Tuipei. Taiw an

~Taiwan Tea E~periment S t t t i o t l

Puehs in . Hs inehu . Ta iwan

( R e c e i v e d D e c e m b e r 3 . ] 9 9 4 ; a c c e p t e d O c t o b e r 1 2 . 1 9 9 5 )

A b s t r a c t - - O c t a d e c a n a l ( 1 8 : A i d ). ( E ) - I 1 o c t a d e c e n a l ( E l I - 1 8 : A i d ). ( E ) - 1 4 -

o c l ad e c en a l ( E 4 - 1 8 : A i d ) a n d ( E . E ) - I 1 , 1 4 -o c ta d e ca d i en a l ( E l I . E I 4 -

1 8 : A i d ) w e r e i s o l a t e d a n d i d e n t if i ed a s m a j o r c o m p o n e n t s f r o m t h e p h e r o -

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

I ~ i p u n c t a l a .

i n T a i w a n b y

a n a l y z i n g th e m a s s s p e c t ra o f g la n d c o m p o n e n t s a n d t h e i r D M D S a d d u c t s .

G C r e t e n t i o n t i m e s a n d m a s s s p e c t r a o f t h e c o m p o n e n t s w e r e i n a g r e e m e n t

w i t h t h o se o f a u t h e n t i c s y n t h e t ic c o m p o u n d s . T h e a v e r a g e a m o u n t o f 1 8 : A i d ,

E l l - I 8 : A I d . E I 4 - 1 8 : A I d a nd E l I . E I 4 - 1 8 : A I d p e r i'e.m ale g l an d ( I t o 3

da y s o l d ) w a s 121 _+ 76 , 50 ± 20 , 187 + 7 5 , a nd 237 ± 110 ng , r e s pe c t i ve l y ,

in a ra tio o f 2 0 : 8 : 3 1 : 4 1 . S y n th e ti c E I I , E I 4 - 1 8 : A I d c a ug h t m o re m a l es

t h a n e a c h o f t h e o t h e r t h r e e c o m p o n e n t s o r b l a n k c o n t r o l i n f i e l d t r a p p i n g

t e st s . E l I , E I 4 - 1 8 : A I d i s r e p o r te d a s a n i n s e c t s e x p h e r o m o n e f o r t h e fi rs t

t im e . M a l e a n te n n a r es p o n de d t o E l l . E l 4 - 1 8 : A i d s tr o n g ly in a n E A G a n al -

y s i s . F u n b e r m o r e , 4 h r a f te r t h e i n je c t io n o f P B A N ( p h e r o m o n e b i o s y n t h e t i c

a c t i v a t i n g n e u r o p e p t i d e ) i n to d e c a p i t a t e d f e m a l e m o t h s 12 d a y s o l d ) , t h e p e r -

c e n t a g e o f t h e E I I , E I 4 - C I 8 A i d i n t h e g l a n d e x t r a c t i n c r e a s e d f r o n t 0 % t o

7 5 . 5 % , w h i c h w a s a l s o s ig n i f i c a n t l y m o r e t h a n t h a t o f u n l i g a t e d a n d u n i n j e c t e d

c o n t r o l a t 5 5 , 1 % . A l l t h e s e d a t a i n d i c a t e d t h a t E 1 I , E l 4 - 1 8 : A i d i s t h e s e x

p h e r o m o n e o f t h e A n d r a c a b ip u n c ta m i n T a i w a n .

K e y W o r d s - - D e c a p i t a t e d f e m a l e m o t h , o c t a d e c a n a l, ( E ) - I l -o c t a d e c e n a l , ( E ) -

14 - oc t a de c e na l , ( E , E ) - I I , 14 - o c t a de c a d i e na l .

* T o w h o m a l l c o r r e s p o n d e n c e s h o u l d b e a d d r e s s e d .

2 7 1

X ) 9 ~ 0 3 3 1 1 9 6 1 0 2 1 I U 4 ) 2 7 1 5 N 5 0 1 0 c 1 9 0 6 P l e n u m P u b l is h i n g C o r l ~r a l i L~


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272 H o ET AL.

INTRODUCTION

T h e t e a c l u s t e r c a t e r p i l l a r ,

Andraca b ipuncta ta ,

d i s t r i b u t e d m o s t l y i n S u m a t r a ,

J a v a , I n d i a , s o u t h e r n C h i n a a n d T a i w a n , c a u s e s s e v e r e d a m a g e t o t e a p l a n t s ,

o f t e n re s u l t in g in a b a n d o n i n g o f w h o l e t e a p l a n t a t i o n s . C u r r e n t m e t h o d o f c o n -

t r o l l i n g t h i s p e s t w i t h p e s t i c i d e s i s i n e f f e c t i v e B a n e r j e e , 1 9 8 2 ; T se n g , 1 9 9 4 ).

I n p re v i o u s w o r k , w e d e m o n s t r a t e d t h at th e u s e o f t h e f e m a l e s e x p h e r o m o n e

o f t h e s m a l l e r t e a t o r tr ix m o t h , Adoxophyes s p . , f o r m o n i t o r i n g p o p u l a t i o n a n d

m a t i n g d i s r u p t i o n w a s v e r y s u c c e s s f u l in t e a p l a n t a t i o n s in T a i w a n K o u e t a l . ,

1 9 90 ; K o u a n d C h o w , 1 9 9 1; T s a i a n d C h o w , 1 9 9 2) . I t i s c o n t e m p l a t e d t h at t h e

s a m e s t ra t e g y m a y b e a p p l i c a b l e to t h e c o n t r o l o f t h e t e a c l u s t e r c a t e r p i ll a r . T h e

s e x p h e r o m o n e o f t h e t e a c l u s t e r c a t e r p i l la r ,

Andraca b ipunc tam,

h o w e v e r , h a s

n o t b e e n d e s c r i b e d . T o f a c i l it a t e p o s s i b l e fu t u r e u t i l iz a t i o n , w e c h a r a c t e r i z e d

a n d i d e n t i f ie d t h e c h e m i c a l c o n s t i t u e n t s o f t h e s e x p h e r o m o n e g l a n d o f t h e t e a

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

e x t r a c ts a n d t h e ir D M D S a d d u c t s . T h e d o u b l e - b o n d c o n f i g u r a ti o n w a s d e t e r-

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

o n s e v e ra l G C c o l u m n s . T h e e f f ec t iv e n e s s o f e a c h o f th e s y n t h e t ic c o m p o u n d s

w a s t e s t e d b y t h e E A G m e t h o d . S y n t h e t i c c o m p o u n d s o r t h e i r m i x t u r e s w e r e

u s e d to c a t c h m a l e s in fi e l d - t ra p p i n g t e s ts . R e s u l t s s h o w e d t h at E 1 1 , E l 4 - 1 8 : A l d ,

o r m i x t u r e s th a t c o n t a i n e d E l l + E l 4 - 1 8 : A i d e f fe c t iv e l y c a u g h t m o r e m a l e s th a n

t he b l a n k c o n t r o l u n d e r fi el d c o n d i t i o n s . W e c o n c l u d e d t h a t E , E ) - 1 1 , 1 4 - o c t a -

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

A. b ipuncta ta

i n T a i w a n +

P r e v i o u s l y s e x p h e r o m o n e h a s b e e n i d e n t i f i e d f o r o n l y t w o s p e c i e s i n t h e

f a m il y B o m b y c i d a e , Bom bvx too l4 L i n n a e u s ) a n d B. mandar ina M o o r e B u t e -

n a n d t e t a l.+ 1 9 59 ; K u w a h a r a a n d Y e n , 1 9 7 9 ; M a y e r a n d M c L a u g h l i n , 1 9 9 1) .

B o t h s p e c i e s u s e

E ,Z) - lO , 12-hexadecad ien- l-o l

b o m b y k o l ) a s t h e p r i n c i p a l

c o m p o n e n t o f t h e ir s e x p h e r o m o n e . T o o u r k n o w l e d g e , t h is is t he t hi rd m e m b e r

o f B o m b y c i d a e w h o s e p h e r o m o n e h a s b e e n i d e n t i fi e d . It is a l s o th e f ir st id e n -

t i f i c a t i o n o f

E ,

E ) - 1 t , 1 4 - o c t a d e c a d i e n a l a s a n i n s ec t s e x p h e r o m o n e .

METHODS AND MATERIALS

Insects.

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

T a i w a n T e a E x p e r i m e n t S t a ti o n , H s i n c h u , T a i w a n . H a t c h e d l a r v a e w e r e r ea r e d

o n f r es h t e a le a v e s . M a l e a n d f e m a l e p u p a e w e r e h e l d i n se p a r a t e r o o m s a t 2 0 ° C

u n d e r a 1 4 L : 1 0 D r eg im e +

Preparation o f Ph erom one G land Extracts . O v i p o s i t o r s fr o m 1 - t o 3 - d a y -

o l d v i r g i n f e m a l e s w e r e e x c i s e d 2 h r i n t o t h e s c o t o p h a s e a n d i m m e r s e d i n 1 0 p , l

h e x a n e p e r g l a n d f o r 2 r a in . T h e e x t r a c t s w e r e s t o r e d a t 4 ° C u n t il b i o a s s a y a n d

s t ru c t u r e a n a l y s i s K o u a n d C h o w , 1 9 9 1 ).


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SEX PHEROMONE O A bipunct t

73

Derivat izat ion.

D i m e t h y l d i su l f id e D M D S ) d e r i v a ti v e s o f m o n o u n s a t u ra t e d

a n d d i u n s a t u ra t e d c o m p o u n d s w e r e p r e p a r e d a s d e s c r i b e d p r e v i o u s l y B u s e r e t

a l . , 1 9 8 3 ; V i n c e n t i e t a l . , 1 9 8 7 ) .

Chemical Analys i s .

G a s C h r o m a t o g r a p h y G C ) o f t h e e x t ra c t w a s p e r-

f o rm e d o n a V a r i a n 3 7 0 0 G C e q u i p p e d w i th a f la m e i o n i z a t i o n d e t e c t o r . T h r e e

d i ff e re n t c a p i l l a r y c o l u m n s w e r e u s e d : a 3 0 - m x 0 . 2 5 - m m - I D f u s ed s i li c a c a p -

i ll a r y c o l u m n o f D B - W a x p h a s e , a 3 0 - m x 0 . 2 5 - r a m f u s e d s i li c a c a p i l l a r y

c o l u m n o f D B - 2 3 p h a s e , a n d a 3 0 - m x 0 . 2 5 - r a m f u s e d s i l ic a c a p i l l a r y c o l u m n

o f D B - 2 2 5 p h a s e . C h r o m a t o g r a p h i c c o n d i t io n s i n c l u d e d n i t r o g e n c a r r i e r a t 0 . 5

k g / c m z. i so t h e r m a l c o l u m n t e m p e r a t u r e a t 2 0 0 ° C f o r t h e D B - W a x c o l u m n ; a

t e m p e r a t u r e p r o g r a m f ro m 1 0 0 ° C t o 2 5 0 ° C a t 5 ° C / m i n f o r t h e D B - 2 3 c o l u m n ,

a n d a p r o g r a m f r o m 1 0 0 ° C to 2 2 0 ° C a t 4 ° C / r a i n f o r t h e D B - 2 2 5 c o l u m n .

G a s c h r o m a t o g r a p h i c - m a s s s p e c t ro m e t r ic G C - M S ) a n a l y s is w a s c o n d u c t e d

u s i n g a F i n n i g a n M A T I n c o s 5 0 s p e c t r o m e t e r . S a m p l e s w e r e i n t r o d u c e d t h r o u g h

a 3 0 -m x 0 . 2 5 - r a m D B - 2 3 c a p i l l a ry c o l u m n p r o g r a m m e d f ro m 8 0 ° to 2 5 0 ° C

a t 5 ° C / r a i n a n d h e l d a t 2 5 0 ° C t b r 5 r a i n . H e l i u m w a s u s e d a s th e c a r r i e r g a s .

F o r t he a n a l y s i s o f t h e D M D S a d d u c t s o f th e u n s a t u ra t e d c o m p o u n d s a 3 0 -m

x 0 . 2 5 - r a m D B - 5 c a p i l l a r y c o l u m n w a s u se d a n d th e t e m p e r a t u r e w a s p r o -

g r a m m e d f ro m 1 5 0 ° C to 3 2 0 ° C a t l ° C / m i n . E l e c t r o n i m p a c t E l ) m a s s s p e c t ra

w e r e c o l l e c te d a t 7 0 e V w i t h t he s e p a r a t o r a t 2 5 0 ° C a n d t h e s o u r c e a t 1 8 0 ° C .

C hem ical Synthesis:

E ) - I 1 - O c t a d ec e n o t w a s o b t a i n e d fr o m N U - C h e k - P r e p .

I nc . E l y s i a n , M i n n e s o t a . E ) - 2 - H e x e n o l , Z ) - 2 - h e x e n o l , 1 -p e n t yn e , a n d 1 -o c ty n e

w e r e p u r c h a s e d f ro m T o k y o C h e m i c a l I n d u st ry C o . P y r i d in i u m d i c h ro m a t e

P D C ) , 1 0 - b r o m o d e c a n o l , a n d 1 1 - b r o m o u n d e c a n o l w e r e o b t a i n e d f ro m A l d r i c h

C h e m i c a l C o m p a n y , I n c. M i l w a u k e e , W i s c o n s i n ) . 7 - D o d e c y n o l w a s p u r c h a se d

f ro m L a n c a s t e r S y n t h e s i s L t d . L a n c a s h i r e , U n i t e d K i n g d o m ) . O c t a d e c a n o l a n d

d i m e th y l d i su l fi d e w e r e o b t a i n e d f ro m M e r c k C h e m i c a l C o m p a n y .

O c t a d e c a n a l a n d E ) - I 1 - o c ta d e c e n a l w e r e p r e p a r e d f ro m o c t a d e c a n o l a n d

E ) - I 1 - o c t a d e c e n o l , r e s p e c t i v e l y , u s i n g P D C a s a n o x i d i z i n g r e a g e n t a c c o r d i n g

to C o r e y a n d S c h m i d t 1 9 7 9 ) . Z ) - 1 l - O c t a d e c e n a l , Z ) - 1 4 - o c t a d e c e n a l , E ) - 14 -

o c t a d e c e n a l, E , E ) - 1 1 , 1 4 - o c t a d e c a d i e n a l , a nd Z , E ) - 1 1 , 1 4 - o c t a d e c a d i e n a l w e r e

s y n t h e s i z e d a c c o r d i n g t o t h e p r o c e d u r e s o u t l i n e d in F i g u r e 3 b e l o w . E ) - 2 -

B r o m o h e x e n e w a s p r e p a r e d f r o m E ) - 2 - h e x e n o l b y re a c t i n g w i t h H B r v a p o r .

F o r t h e s y n th e s i s o f Z , Z ) - I 1 , 1 4 - o c t a d e c a d i e n a l , th e s a m e s t r a te g y w a s u s e d i n

t h e p r e p a r a t i o n o f

Z, E) -

a n d E , E ) - o c t a d e c a d i e n a l , e x c e p t t h at Z ) - 2 - h e x e n o l

w a s u s e d a s s t a r t i n g m a t e r i a l .

Pheromone Ti ter Determinat ion .

T h e e x t r a c t s w e r e p r e p a r e d a s d e s c r i b e d

a b o v e a n d s u b s e q u e n t l y a n a l y z e d w i t h th e e x t e r n a l s t a n d a r d m e t h o d o f q u a n t i -

t a ti v e a n a l y s i s . P h e r o m o n e b i o s y n t h e s i s a c t i v a t in g n e u r o p e p t i d e P B A N ) , a 3 3 -

a m i n o ac i d p e p t i d e , w a s o b t a in e d fr o m D r. A . R a i n a U S D A I N H L , B l d g 3 0 6 ,

B a r c - E a s t , B e l t s v i l l e , M a r y l a n d 2 0 7 0 5 ) a s a g i f t . F o r P B A N a n a l y s i s , v i r g i n

f e m a l e m o t h s w e r e l ig a t e d b e t w e e n t h e h e a d a n d t h o r a x a n d d e c a p i t a t e d . F o r t y -


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274 H o ET AL.

e i g h t h o u r s a f te r d e c a p i t a t io n , 5 p m o l o f P B A N w a s i n j e c te d i n to th e a b d o m e n ,

a n d 4 h r la t e r t h e s e x p h e r o m o n e g l a n d w a s e x c i s e d a n d e x t r a c t e d w i th h e x a n e .

S a l i n e w a s i n j e c te d i n to t he a b d o m e n o f c o n t r o ls . T h e e x t r a c t w a s s t o r e d a t 4 ° C

f o r l a t e r a n a l y s i s . Q u a n t i ta t i v e a n a l y s i s w a s p e r f o r m e d b y t h e e x t e rn a l s t a n d a r d

m e t h o d a s b e f o r e .

EAG Analysis

C h e m i c a l s o f d if f er e n t d o s a g e w e r e l o a d e d in a 5 - m l g l a s s

s y r i n g e a n d p u ff e d o v e r a n a n t e n n a e . T h e E A G r e s p o n s e f r o m t h e c h e m i c a l s

w a s c o m p a r e d t o th e r e s p o n s e o f t he a n t e n n a e t o a n a i r b l a n k . E a c h c h e m i c a l

w a s t e s te d u s in g E A G w i t h a t le a s t s i x d i f fe r e n t a n t e n n a e . T h e E A G r e s p o n s e

w a s p r e a m p l if ie d 1 0 0 × o r 1 0 0 0 × ) a n d re c o rd e d w i th a V I 0 0 0 v i d e o , 4 0 3 5

d i g it a l s t o ra g e o s c i l l o s c o p e a n d E S 1 00 0 r e c o r d e r G o u l d C o . L t d . ) Y a n g e t a l . ,

1992) .

Field Testing

F i e l d te s t in g o f th e s y n t h e t i c c h e m i c a l f o r m u l a t io n w a s c a r -

r i e d o u t f i r s t f o r r e l e a s e d m a l e s i n a t e a p l a n t a t i o n i n T a i w a n T e a E x p e r i m e n t

S t a t i o n , P u e h s i n , H s i n c h u , T a i w a n , d u r i n g N o v e m b e r 1 9 9 4 , a n d s u b s e q u e n t l y

in a l o c al o p e n t e a p l a n t a ti o n n e a r A c a d e m i a S i n i c a f o r w i l d m a l e s in A p r i l a n d

M a y 1 9 95 . S y n t h e t i c c h e m i c a l s w e r e u s e d s e p a r a t e l y a n d a s a m i x t u r e . A t o t a l

o f 0 .1 m g s y n t h e t ic c o m p o u n d s w a s d i s s o l v e d in h e x a n e a n d l o a d e d in p la s t ic

t u b e s , 5 c m × 1 m m I D . T h e p l a s t i c t u b e w a s s u s p e n d e d o n t h e i n s id e a t t h e

t o p o f a w i n g - s h a p e d s t ic k y t ra p K o u e t a l . , 1 99 2)+ B l a n k t r a p s a n d t r a p s b a i t e d

w i t h t w o f e m a l e e x t r a c ts w e r e u s e d f o r c o m p a r i s o n . T r a p s w e r e p l a c e d 10 m

a p a r t a n d 1 .5 m a b o v e g r o u n d . F o r t h e c a p t u r e o f r e l e a s e d m a l e s , a t o ta l o f 1 20

l a b o r a t o r y - re a r e d 1 - t o 3 - d a y - o l d u n m a t e d m a l e s w e r e r e l e a s e d . E a c h t ra p w a s

c h e c k e d e v e r y a f t e r n o o n f o r e i g h t d a y s . F o r th e w i l d m a l e f ie ld te s t s, t r a p s w e r e

c h e c k e d e v e r y w e e k .

RESULTS AND DISCUSSION

Chem ical Analysis G C a n a l y s i s s h o w e d a to t al o f f o u r m a j o r p e a k s , l a b e l e d

A - D , in t h e c h r o m a t o g r a m o f a g l a n d e x t r ac t F i g u r e 1 ). C o m p o n e n t A , w i th

a m o l e c u l a r w e i g h t o f 2 6 8 , h a d th e s a m e m a s s s p e c t ru m a s o c t a d e c a n a l T a b l e

1 ). C o m p o n e n t s B a n d C , b o t h h a v i n g a m o l e c u l a r w e i g h t o f 2 6 6, h a d v i r t u a ll y

i d e n t i c a l m a s s s p e c t r a , w i t h o n l y a s l i g h t d i f f e r e n c e i n r e l a t i v e in t e n s i t i e s . T h e

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

C o m p o n e n t D h a d a m o l e c u l a r w e i g h t o f 2 6 4 , a n d th e m a s s s p e c tr a l f r a g m e n -

t a t i o n p a t t e r n s u g g e s t e d a n o c t a d e c a d i e n a l .

S y n t h e t ic o c t a d e c a n a l m a t c h e d c o m p o n e n t A f r o m g l a n d e x t r a c t in r e te n t io n

t im e s o n th r e e G C c o l u m n s a n d b y m a s s s p e c t r o m e t r y T a b l e 2 ), a n d w e c o n -

c l u d e d t ha t c o m p o n e n t A is o c t a d e c a n a l F i g u r e 1 ). T h e d o u b l e - b o n d p o s i t i o n

o f t h e m o n o u n s a t u r a t e d a l d e h y d e s , c o m p o n e n t s B a n d C , w e r e i n f e r re d b y t h e

D M D S d e r i v a t iz a t i o n m e t h o d , w h i c h w a s p r e v i o u s l y u s e d f o r t h e d e t e r m i n a t i o n


5/15

SEX PHEROMONE OF A b ipuncta ta 2 7 5

C

T I M E m i n )

~15 2Io

FIG . 1, G a s c h r o m a t o g r a m o f t' em a l e s e x p h e r o m o n e g l a n d c r u d e e x t ra c t . T h e g a s c h r o -

m a t o g r a p h y w a s p e r f o r m e d o n a 3 0 - m x 0 . 2 5 - m m D B - W a x c o l u m n an d th e o v e n te m -

p e r a t u r e w a s i s o t h e r m a l a t 2 0 0 ° C .

T ABL E I . MAS S S P E CT RAL DA T A, AVE RAGE QUANT IT IE S , AND P E RCENT AGE OF F OUR

COMP OUNDS [DE NT IFIE D F ROM S E X P HE ROMONE GL AND OF 1 - TO 3 -D AY -OL D

A b ipuncta ta V I R G I N F E M A LE S ( N = 2 2 )

Co m p o u n d M a s s s p e c tra l d a ta , m/z ( in tens i ty , )

M e a n

q u a n t i ty

(n g / fe ma le } P e rc e n ta g e

(me a n ± S D) (me a n ± S D)

18: A id A)

E I I - 1 8 : A I d ( B )

E I 4 - 1 8 : A I d ( C )

E I 1 , E I 4 - 1 8 : A I d ( D )

250(M*-18 , 4} . 222(5) , 194(4) ,

166(2), 138(10), 124(151, 110(18),

96(63) , 82(90) , 57(100) 121 ± 76

266(M +, 4). 248 (18). 166(8), 135(201,

121(28), 111(32}, 95(5 3). 83(60) ,

69(68) , 55(100) 50 ± 20

266 (M ~ 4), 248(10 ), 166(4), 135(15),

121(20), 111(22), 95(43). 83(45).

69(49) , 55(100) 187 ± 75

264 (M +, 3), 219(2 ), 165(1), 151(3),

123(3), 109(18L 95(33), 81(73),

67(100), 55145)

20 ± 3

8 ± 1

3 1 ± 7

237 ± 110 41 ± 4


6/15

276 Ho ET AL.

TABLE 2 RETENTIONTIMESOF 18:Aid, Ell-18:Ald, E14-18:AId, EII,EI4-

18:Aid, ZI I-1 8:AI d, ZI4 -18:AId, Z I I E I 4 - 1 8 : A I d EII,ZI4-18:Ald,

Z 11 ,Z 14-18 : Aid AND PHEROMONE GLAND EXTRACTOF FEMALE

A. bipunctata oN

THR EE G S CHROM TOGR PHIC COLUMNS

Retention time rain)

Compound Source DB-Wax DB-23 DB-225

1 8 : A i d N a t u r a l I 1 . 7 3 1 9 . 9 8 2 9 . 3 0

S y n t h e t i c I1 ~ 79 2 0 . 0 1 2 9 . 3 4 4

E 11 - 1 8 : A i d N a t u r a l 1 2 . 6 3 2 0 . 3 2 2 9 7 3 4

S y n t h e ti c l 2 . 6 7 2 0 3 4 2 9 . 7 6 0

E 1 4 - 1 8 : A i d N a t u r a l 1 2~ 89 2 0 . 4 6 2 9 . 8 7 5

S y n t h e t ic 1 2 . 9 3 2 0 . 4 8 2 9 9 0 3

E 11 E 1 4 - 1 8 : A i d N a t u r a l 1 4 . 3 9 2 0 . 9 4 3 0 . 4 8 3

S y n t h e t ic 1 4 4 2 2 0 . 9 8 3 0 . 5 3 8

Z 11 - 1 8 : A i d S y n t h e t i c 2 0 . 7 3

Z 1 4 - 1 8 : A i d S y n t h e t i c 2 0 8 9

Z 1 1 E

1 4 - 1 8 : A i d S y n t h e t i c 2 I . 1 6

E 11 Z 1 4 - 1 8 : A i d S y n t h e t i c 2 1 . 3 4

Z I I Z

1 4 - 1 8 : A i d S y n t h e t i c 2 1 . 7 3

of the double-bond position in monounsaturated acetates Buser et al., 1983).

DMDS adducts of the aldehydes were prepared, and the relevant mass spectral

data are shown in Table 3. The mass spectrum of the DMDS derivative of

component B showed a molecular ion at

m / z

360 and two intense ions at

m / z

145 and 215, presumably arising from a cleavage between the vicinal thiomethyl

groups. Two possible aldehydes could yield the observed ions. The parent com-

pound may be l l-octadecenal and the ion at m / z 145 could represent

CH3-- CH2)5--CH=S+CH~, which arises from the distal end of the molecule,

whereas the ion

m / z

215 would represent the funct ional-group-bearing end of

the molecule Figure 2A). Alternatively, the parent compound may be 6-octa-

decenal, with the ion at m / z 215 representing CH3-- CH_,)t0--CH=S+CH3,

arising from the distal end of the molecule, and the ion m / z 145 representing

the functional-group-bearingend of the molecule. In order to distinguish between

11- and 6-octadecenal, the compounds in the gland extract were reduced to

alcohols by LiAIH4 and then derivatized to the DMDS adduct. The mass spec-

trum of the DMDS adduct of the alcohol of component B Table 3) showed that

the major fragments are at m / z 217 and 145, and we concluded that the com-

ponent B is 11-octadecenal. The DMDS adduct of 6-octadecenol would give

major fragments at m / z 147 and 215. Both E ) - ll - and Z)-ll-octadecena l


7/15

SEX

PHErOmOnE OF

A. bipunctata 277

TABLE 3. M AS S SPECTRAL DATA OF D M D S DERIVATIVESOF M ONOUNSATURATEDAND

DIUNS TUR TED LDEHYDES ND LCOHOLS

Compound M ass spectral data of the DM DS derivatives (m/z, %)

E l l - 1 8 : A I d ( B )

E14-18: Aid (C)

E I I - 1 8 : A I c

E I 4 - 1 8 : A I c

E I I . E I 4 - 1 8 : A I d ( D )

El 1,E14-18: Alc

360(M ~ 10), 243(12), 21 5166), 145(95), 97(38), 81 (33). 67(50),

61(85), 55(100)

360(M ~. 10) 257(72), 109(20), 103(60), 95(30), 8t(301, 67(30),

6t(100), 55(68)

362(M ÷, 0.25). 217(14L 145(21), 10 9(7). 95(17), 85(24~, 71(34L

61(29), 57(9l). 55(63)

362(M *. 0 .36), 259(181, 109f8), 103(37), 95(16), 81(20), 67(24),

61(67), 55(61

390(M + 3), 342(9-16), 239(48-100), 215(26-35), 175(20), 127(100),

103(19-38), 55(37-531

392(M' , 2~, 344(5-8), 241(121, 217(16-24)~ 175(10-24), 127(48-

100), 103119). 55(45-65)

The ranges of abundance are due to the presence of chromatographically separated D M DS adduct

isomers w ith slight differences in their m ass spectra.

( F i g u r e 3 A ) w e r e s y n t h e s iz e d a n d r e t e n ti o n t im e s on th e D B - 2 3 c o l u m n w e r e

c o m p a r e d ( T a b le 2 ). ( E ) - I l - O c t a d e c e n a l c o c h r o m a t o g r a p h e d w i th c o m p o n e n t

B o f t h e g l a n d e x t r a c t , s o it w a s c o n c l u d e d t ha t c o m p o n e n t B is E)-I l - o c t a -

d e c e n a l .

S i m i l a r a n a ly s is o f t h e m a s s s p e c t r u m o f t h e D M D S d e r i v a t i v e o f c o m -

p o n e n t C ( T a b l e 3 ) r e v e a l e d t ha t th e p a re n t c o m p o u n d m i g h t b e 1 4 - o c ta d e c e n a l

o r 3 - o c t a d e c e n a l ( F i g u r e 2 B ) . C o m p o n e n t C w a s r e d u c e d t o t h e a l c o h o l b y

L i A I H 4 , a s a b o v e , a n d t h e D M D S a d d u c t o f t he c o r r e s p o n d i n g a l c o h o l w a s

p r e p a re d a n d a n a l y z e d b y G C - M S . T h e m a s s s p e c t r u m ( T a b l e 3) s h o w e d t h at

t he m a j o r fr a g m e n t s w e r e a t m/z 2 5 9 a n d t 0 3 , s u g g e s t i n g th a t t h e c o m p o n e n t

C i s 1 4 - o c ta d e c e n a l , s i n c e t h e D M D S a d d u c t o f 3 - o c t a d e c e n o l w i l l g i v e m a j o r

f r a g m e n t s a t

m/z

1 05 a n d 2 5 7 , B o t h E a n d Z is o m e r s o f 1 4 - 0 c t a d e c e n a l w e r e

s y n t h e s i z e d ( F i g u r e 3B ) a n d c o m p a r e d w i t h c o m p o u n d C o n d i ff e r en t G C c o l -

u m n s ( T a b l e 2 ). T h e r e s u lt s in d i c a te d t h at ( E ) - 1 4 - 0 c t a d e c e n a l c o c h r o m a t o -

g r a p h e d w i th c o m p o n e n t C o f t h e g l a n d e x t ra c t an d c o m p o n e n t C w a s i d e n ti f i e d

a s ( E ) - 1 4 - 0 c t a d e c e n a l .

T h e d i u n s at u r a te d o c t a d e c a d i e n a l w a s d e r i v a t iz e d a c c o r d i n g to t h e p r o c e -

d u r e d e s c r i b e d b y V i n c e n t i e t a l . ( 1 9 8 7 ), G C - M S a n a l y si s o f t h e D M D S a d d u c t

s h o w e d f r a g m e n t s a t m/z 2 1 5 a n d 1 03 ( T a b l e 3 ). F r o m t h is f ra g m e n t a t i o n p a t -

t e rn , c o m p o n e n t D i n t h e g l a n d e x t r a c t c o u l d b e 1 1 , 1 4 - o c t a d e c a d i e n a l o r 3 , 6 -

o c t a d e c a d i e n a l ( F i g u r e 2 C ) . C o m p o n e n t D in t h e g l a n d e x tr a c t w a s r e d u c e d to

a n a l c o h o l b y L i A I H 4 a n d d e r i v a t iz e d to it s D M D S a d d u c t . G C - M S a n a l y si s o f


8/15

2 7 8 H o E T A L

A

SCH~ H

O

E - o r Z - I 1 - o c t a d e c e n a l D M D S a d d u c t

O

E - or Z - 6 - o c ta d e c e n a l D M D S a d d u c t s

103 SCH3

E - o r Z l 4 - o c t a d e c e n a t D M D S a d d u c t

E - o r Z - 3 - o c t a d e c e n a l D M D S a d d u c t

C

- - 2 8 7

1 0 3 - - ~ / - - 2 1 5

175

1 1 1 4 - o c t a d e c a d l e n a l D M D S a d d u c t

S C H 3 S C H 3 Q

3 6 - o c t ad e c a d ~ e n a l D M D S a d d u c t 2 8 7

F ~G 2 . F r a g m e n t a t i o n p a tt e r n s e x p e c t e d f r o m D M D S a d d u c t s o f c a n d i d a t e a l d e h y d e s in

t h e g l a n d e x t r a c t s .


9/15

S X P H R O M O N O F A . bipunct t

(A) Prepa ratmn of(Z)-I 1-octadecenal

Br(CH 2)toOH ~ Ce,HI3C~---C(CH2h~OTHP

Z 1I -CH~(CH 2)sCH= CH(CH2)~CHO

c 1,, Cc,HI~C~C(CH2)mOH

279

(B) Prepa ratmn of(E)- and (Z)-14-octadecenal

Br(CH~hTOH ~ Br(CH2)IoCHO f

• - Br(CH2 oCH=C HC OO CH3

g,h,a _ Br(CH;~)I OTHP J ~ C CH a(CH 2 C~C (CH 2)I ~OH

d ~ E 14 CH3(CH2)2C=C(CH2h ~OH

ZI4-CH s(CH 2)2C:C (CH 2)t 3OH

e i~

E]4-CH3 CH 2)2C=C C H2h3CHO

• Z 14 -CHa(CH~),C.=C(CH:~h3CHO

C) P r e parat ion o f E , E ) - and Z, E) -I

1,14-octadecadlenal

CH3(CH2hC~C (CH2~OH I, aj , , HC ~C(CH 2)mO'IHP

m ~ E 14 _CH3(CH2)2CH=CHCH2C~C(CH2)mOTHP

E 14- CH~(CH )2CH=CH CH2C ~C(CH2h~OH

n, E 1I E 14-CH~(CH2 2CH :CH CH 2C H:C H(C H2 )*~C IO

Z1 I,E I 4- CH~ CH2 2C H= CH CH 2CH =C H CH ? ),~CHO

FiG . 3 . P rep a ra ti o n o f (Z ) - I I -o c t ad ece n a l . (E ) -1 4 -o c t ad ec en a l , (Z ) -1 4 -o c t ad ecen a l ,

(E , E ) - t 1 .14-oc tadec ad iena l , and (Z , E ) - I 1 , t4 -oc tad ecad iena l , Rea gen t s : (a) d ihyd ro-

pymne/p-TSA (p- to luenesu l fon ic ac id ) ; (b ) 1 - o c t y n e / n - B u L i (Schw arz and W aters , 1972);

( c ) MeO H / p -T SA ; (d ) H 2 / Pd / BaSO 4 : ( e ) PD C (p y r i d i n i u m d i ch ro ma t e ) ; ( f ) W i t t i g r eac -

t io n , P h 3 P = C H C O z C H f f C H ~ C I , ; ( g ) H f f P d ; (h ) D I B A L ( d ii s ob u t y la l u m i n u m h y d ri d e)

(Y o o n and G y o u n g , 1 98 5) ; ( j ) p en t y n e / n -B u L i (Sch w a rz an d W at e r s , 1 97 2) ; (k ) L i A 1 H J

dig lym e (d ie thy leneg lyco l d im ethy l e ther) (Ross i and Carp i t a , 1977); ( I) po tass ium

3 -ami n o p ro p y l ami d e (K A PA ) (Bro w n an d Y amas h i t a , 1 9 7 6 ) ; (m) (E ) -2 -b ro mo h ex en e /

n -Bu L i (Sch w arz an d W at e r s, 1 97 2) ; ( n ) N a / N H 3 (Sch w arz an d W at e r s, t 9 7 2 ) . A b b r e -

v ia t ion: T H P, 2 - t e t r ah y d ro p y mn y l .


10/15

280 H o ET AL.

t h e a d d u c t s h o w e d a m o l e c u l a r w e i g h t o f 3 9 2 a n d f r a g m e n t s a t m / z 2 1 7 a n d 1 03

( T a b l e 3 ) . T h e s e r e s u lt s i n d i c a t e d th a t t h e a l c o h o l w a s l l , 1 4 - o c t a d e c a d i e n o l ,

s in c e 3 , 6 - o c t a d e c a d i e n o l w o u l d g i v e m a j o r f ra g m e n t s a t m / z 21 5 a n d 1 05 . T h u s ,

i t w a s c o n c l u d e d t h a t c o m p o n e n t D in t h e g l a n d e x t r a c t w a s l I , 1 4 - o c t a d e c a -

d i en a l . T h e f o u r g e o m e t r i c i s o m e r s o f l l , 1 4 - o c t a d e c a d i e n a l , i . e . ,

( E , E ) - ,

( Z , E ) - ,

( Z , Z ) - ,

a n d

( Z , E ) - l l , 1 4 - o c t a d e c a d i e n a l ,

w e r e s y n t h e s i z e d a n d t h e i r

r e te n t io n t im e s o n G C w e r e c o m p a r e d w i t h th a t o f t he c o m p o n e n t D ( T a b l e 2 ).

C o c h r o m a t o g r a p h y o f ( E , E ) - l l , 1 4 - o c t a d e c a d i e n a l w i th t he n a tu ra l p ro d u c t

s h o w e d a g r e e m e n t o n d i ff e re n t c o l u m n s , T h u s , c o m p o n e n t D i n t he se x p h er -

o m o n e g l a n d e x t r a c t w a s i d e n t i f i e d a s ( E , E ) - I 1 , 1 4 - o c t a d e c a d i e n a l .

Ph erom one Ti ter Determ inat ion and P B A N St imulat ion Tests .

R e c e n t l y ,

R a i n a e t a l . (1 9 8 9 ) r e p o r t e d t h a t p h e r o m o n e b i o s y n t h e s i s a c t i v a t i n g n e u r o p e p t i d e

( P B A N ) r e g u la t e s p h e r o m o n e p r o d u c t i o n in s o m e f e m a l e in s e c ts . W e f o u n d th a t

t he a m o u n t o f t h e f o u r c o m p o n e n t s w a s z e r o i f t h e ad u lt f e m a l e m o t h o f th e t ea

c l u s t e r c a t e r p i l l a r w a s d e c a p i t a t e d a n d s a l i n e w a s i n j e c t e d i n to th e a b d o m e n

( T a b l e 4) . I n c o n tr a s t , i f P B A N w a s i n j e c te d i n s t e ad o f sa l in e i n to th e n e c k -

l ig a t e d a n d d e c a p i t a t e d m o t h , t h e f o u r c o m p o n e n t s w e h a v e i d e n t i fi e d w e r e f o u n d

in th e g l a n d e x t r a c t , a n d t h e p e r c e n t a g e o f E 1 1 , E l 4 - 1 8 : A i d in th e g l a n d e x t r a c t

w a s a s h i g h as 7 5 . 5 % . T h i s i n d i c a te d t h at a ll fo u r c o m p o u n d s w e r e p r o b a b l y

r e la t ed to p h e r o m o n e p r o d u c t i o n . T h e f ac t t ha t t h e p e r c e n t a g e c o n t e n t o f

E 1 1 , E 1 4 - 1 8 : A i d in th e g l an d e x t ra c t o f t he P B A N t re a te d f e m a l e s w a s m o r e

t ha n th a t o f n o r m a l v i r g i n f e m a l e s ( 5 5 . 1 % ) s u g g e s t s t ha t E l 1, E I 4 - 1 8 : A I d is

t h e s e x p h e r o m o n e o f

Andraca b ipuncta ta .

EA G A nalys is .

T h e E A G a n a l y si s o f o c t a d e c a n a l , ( E ) - 1 1 - o c t a d ec e n a l , ( E ) -

1 4 - o c t a d e c e n a l , a n d

(E,

E ) - 1 1 , 1 4 - o c t a d e c a d i e n a l o f d i ff e re n t d o s a g e s h o w e d t h at

t he a n te n n a e o f t h e m a l e s t r o n g l y r e s p o n d e d t o (E, E ) - I I , 1 4 -o c t a d e ca d i e n a l a n d

o n l y sl ig h t l y t o t h e o t h e r th r e e c o m p o n e n t s ( F i g u r e 4 ) . T h e E A G r e s p o n s e o f

e a c h c o m p o n e n t w a s m e a s u r e d o n l y a t d o s e s o f 2 0 0 a n d 3 0 0 n g s in c e th e

r e s p o ns e i n d u ce d b y 2 0 0 o r 3 0 0 n g o f sy n t h e ti c c h e m i c a l s w a s c o m p a r a b l e t o

TABLE 4 EFFECT OF PB AN ON PERCENTAGE OF FOUR COMPONENTS IN FEMALE

PHEROMONE GLAND EXTRACT OF

A bipunct t

WALKER

18 : Aid E l 1-18: Aid E 14-18 : A id

EII,EI4-18:AId

Norm al female (8) ' 18.5 + 4.3a 6,9 ± 1.2a 19.4 ± 2.4a 55.1 ± 4.9b

PB AN injected fem ale (8) I' 9.9 + 2.3b 3.9 ± t . l b 10.5 _+ 1.3b 75.5 __+ 3.3a

Ligated female ( 1 )h 0 0 0 0

~M eans followed by a different rom an letter in the sa m e colum n are significantly different (P =

0.05).

hNum ber of replicates indicated in parentheses.


11/15

S X PH ROMON OF A

bipunctata 281

1-1 Air

[] 200rig

• 300rig

g IF

0

C1 8Atd E I I C1 8 A td E1 4 CIS AId E l l , 1 4 CISAId 1FE

FIG. 4. EAG response of mate

Andraca bipunctata

to 18:Aid, El 1-18: AId, E14-

8 :

Aid, El 1, E14- 18 :Ald, and 1 FE. The vertical ba r indicates the standard error of

the mean.

TABLE 5. NUMBER OF MALE A. bipunctata ATTRACTED TO SYNTHETIC COMPOUNDS,

1 8 : A I d / E t I - t S : A I d / E 1 4 - t S : A l d / E I I ,

EI 4- 18 :A Id 20: 8: 31 :4 1) AND VIRGIN

FEMALE EXTRACT DURING NOVEMBER 6-16, 1994 AT TAIWAN TEA EXPERIMENT

STATION, PUESHIN

18: Ald/E 11-18:AId/

EI4-18:AId/EI

I,E 14-

18:Aid 20:8:31;41)

2 virgin female

Date 0. Img 0.5 mg equivalent Control

1994 Now 6 0 0 0 0

7 3 2 0 0

8 1 2 0 0

9 0 0 0 0

10 0 0 0 0

14 1 4 0 0

15 0 0 0 0

16 0 0 0 0

Total 5 8 0 0

The

lure dispenser was a plastic tube.


12/15

282 Ho ET AL.

that of one female equivalent. The EAG results provided support for E,E) -

l l,14-octadecadienal as the sex pheromone of the insect.

Field Trapping of Released Males.

The results of field trapping of released

males with mixtures of the synthetic compounds in a ratio of 20:8:31:41 and

virgin-female extract are shown in Table 5. A total of 120 males were released

and only 13 were caught. The reason for the poor recapture of males in this

experiment was probably due to the low winter temperature when the trapping

took place.

Field Trapping of Wild Males.

The results of field trapping of wild males

with each of the synthetic compounds and mixtures of the synthetic compounds

are shown in Tables 6 and 7. The results in Table 6 showed that component D

El l, E14-18: AI d) alone, two-component treatments A + D, B + D, C +

D), and mixtures of four synthetic compounds mixed in the same ratio as in

the virgin female extract) caught more males than treatments without component

D. The numbers of moths caught by the different treatments were not signifi-

cantly different as long as component D was present. Table 7 shows the com-

parison of the number of males caught by three-component and four-component

treatments. Although the adult season was almost over in May, and only a few

male moths were caught in this test, the results also showed no difference

between the three-component treatments and four-component treatments. The

fact that the number of males captured by E11, El4 -18 : Aid alone and by mix-

tures of two, three, or four components were not significantly different from

each other support EAG data and PBAN results, and we conclude that E11, EI 4-

18:Ald is the attractive component of the sex pheromone gland of Andraca

bipunctata. Although a single pheromonal component is rare in insect literature,

it is not unprecedented. For example, female gypsy moths use only

7R,8S)-

cis-7,8-epoxy-12-methyloctadecane

to attract males. To see if there is any syner-

getic effect of the other components found in the gland extract, more extensive

field tests will be conducted in the near future.

From our results of PBAN stimulation, EAG analysis, and field trapping

tests, we tentatively conclude that the sex pheromone of

Andraca bipunctata

is

EII,EI4-18:AId. If the additional three components in the gland extract do

not have any function in male attraction, the reason they are present may be

that they are precursors in the biosynthesis of E, E)-11,14-octadecadienal. The

moth may synthesize

Ell.EI4-18:AId

from 18:Ald via Ell-18:AId or via

E14-18:Ald in the pheromone gland. The All desaturase enzyme identified

from some Lepidoptera may produce E11-18:Ald from the saturated 18:Ald

Roelofs and Wolf, 1988), A A14 desaturase is also reported to be involved in

the biosynthesis of pheromone in the Asian corn borer Zhao et al. 1990). Thus

the sex pheromone E11,EI4-18:AId reported here could be produced by cat-

alytic activities of the AI 1 and A14 desaturases in its biosynthetic pathway as

reported in other insects.


13/15

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14/15

2 8 4 H o E T A L.

T A B L E 7 . N U M B E R O F M A L E A n d r a c a b i p u n c t a t a A T T R A C T E D T O SY N T H E TI C S E X

PHEROM ON E 1 8 : A i d ( A ) , E l l - 1 8 : A l d ( B ), E I 4 - 1 8 : A I d ( C ) , E l l , E 1 4 - 1 8 : A I d ( D )

D U R IN G M A Y 1 9 9 5 A T N A N K A N G T E A P L A N TA T IO N N E A R A C A D E M I A S I N IC A a

A + B + D A + C + D B + C + D A + B + C + D C on t r o l

D ate I I I I I I I 1I l l I I I I I l l I I I I I1 I I I 11I

1995 M ay 8 0 2 2 2 0 I 3 1 2 1 2 2 0 0 0

15 1 0 0 1 1 0 1 1 2 0 1 I 0 0 0

25 3 1 5 2 1 0 0 I 4 2 4 5 0 0 0

30 0 1 0 0 1 2 2 0 1 I 3 0 0 0 0

J u n e

5 1

T ot a l

4 4 7 5 3 3 6 3 9 4 1 9

A v e r a g e~ 5 . 0 a 3 . 6 a b 5 . 3 a 7 , 6 a 0 c

T h e

l u r

d i s p e n s e r w a s a p l a s t ic tu b e . T o t a l a m o u n t o f t h e c h e m i c a l s w a s 0 . 1 r a g . 1 , I1 . I l l a re

r e p l i c a t e s .

~ 'T he r a t io o f t h e f o u r c h e m i c a l s w a s 2 0 : 8 : 3 1 : 4 1 .

' A v e r a g e s l o l l o w e d b y t h e s a m e l e t te r a r e n o t s i g n i f i c a n t l y d i f fe r e n t b y D u n c a n ' s m u l t i p l e r a n g e

t e s t ( P = 0 . 05 ) .

A c k n o w l e d g m e n t s - - W e

t h a n k D r . Y . S . H o n o f th e I n s t i tu t e o f C h e m i s t r y . A c a d e m i a S i n i c a .

f o r h e l p f u l s u g g e s t i o n in s y n t h e s i s a n d D r . A . K . R a i n a U S D A . B e h s v i l l e . M a r y l a n d fo r P B A N .

T h e N a t i o n a l S c i e n c e C o u n c i l o f R e p u b l i c o f C h i n a i s g r a t e f u l l y a c k n o w l e d g e d f o r it s f i n a n ci a l

s uppo r t .

R E F E R E N C E S

BANERJEE B . 1982 , A s t r a t e gy f o r t he c on t r o l o f A n d r u c a bipul~ctat t W a l k e r o n t e a , Crop Pro t .

I I 1 ) : l l 5 - 1 1 9 .

B RO W N, C . A . , a n d Y AM A SH IT A, A . 1 9 7 6 . E x c e p t i o n a l l y e a s y i s o m e r i z a t i o n o f a c e t y t e n i c a l c o h o l s

w i t h p o t a s s i u m 3 - a m i n o p r o p y l a m i d e . A n e w , h i g h y i e l d s y n t h e s i s o f t u n c t i o n a l l y d i f fe r e n t ia t e d

~ o - d i f u n c t i o n a l s t r u c t u r e . J , C . S . C h e m . C o m m u m 1 9 7 6 : 9 5 9 - 9 6 0 .

B U SE R , H . - R . , A R N , H . , G U E R IN , P . , a nd R A U SC H E R. S . 1983 . D e t e r m i na t i o n o f doub l e - bo nd

p o s i t i o n in m o n o u n s a t u r a t e d a c e t a t e b y m a s s s p e c t r o m e t r y o f d i m e t h y l d i s u l fi d e ad d u e t s .

Anal.

C h e m . 5 5 : 8 1 8 - 8 2 2 .

BUTENANDT, A . , BECKMAN, R . , STAMM , D . , and HECKt~R, E . 1959. U be r d en Se xu a l lo ck s to f f de s

S e i d e n s p i n n e r Bomb ~r mor i , R e i d a r s t e l l u n g u n d K o n s t i tu t i o n . Z NautrJhrs~47. B H : 2 8 3 - 2 8 4 .

C O R EY . E . J . . a nd S C m .t ID T , G . 1979 . U s e f u l p r oc e du r e s f o r t he ox i da t i o n o f a l c oho l s i nvo l v i n g

p y r i d i n i u m d i c h r o m a t e i n a p r o t ic m e d i a . Tetrahedron Lett. 5 : 3 9 9 - 4 0 2 .

K o t.L R . , a n d C H o w , Y . S . 1 9 9 1 . I n d i v i d u a l v a r i a t i o n in s e x p h e r o m o n e o f s m a l l e r t e a to r t r ix m o t h

A d o x o p h y e s s p . ( L e p i dop t e r a : T o r t r i c i da e ) . J. Chem. Ecol. 1 7: 1 9 1 7 - 1 9 2 3 .

K o u , R . , T A N G , D . S . , C ~ o w , Y . S . , a n d TS E NG , H . K 1 99 0. S e x p h e r o m o n e c o m p o n e n t s o f t h e

s m a l l e r t e a t o r t ri x m o t h . A d o x o p h y e s s p . ( L e p i d o p t e r a : T o n r i c i d a e ) i n T a i w a n . J. Chem. EcoL

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