Recent Pheromone Research in the Netherlands on Muskrats and

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5 Recent Pheromone Research in the Netherlands on Muskrats and Some Insects F. J. RITTER, I. E. M. BRÜGGEMANN, J. GUT, and C. J. PERSOONS

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Netherlands Organization for Applied Scientific Research TNO, Delft, Netherlands The paper describes research on three p e s t s , intro­ duced from America i n t o Europe: the muskrat, Ondatra z i b e t h i c u s , the American cockroach, P e r i p l a n e t a americana, and the beet armyworm, Spodoptera e x i g u a . Screening of a variety of muskrat l u r e s in the field and in pens showed that e x t r a c t s of the p r e p u t i a l glands of male muskrats were most attractive. GC/MS a n a l y s i s proved that the composition of the musk i n these glands changes w i t h season. The e x t r a c t s con­ tain at l e a s t 13 m a c r o c y c l i c ketones, the major ones of which are the (Z)-5 isomers of cycloheptadecenone and cyclopentadecenone, and the corresponding s a t u ­ rated ketones. They are probably biogenetically r e l a t e d to the f a t t y acids found to be present i n the same glands. The identification of p e r i p l a n o n e - A , one of the two sex pheromones of the American cockroach, is r e p o r t ­ ed. I t i s a s e s q u i t e r p e n o i d , C H O, which r e a d i l y isomerizes to a more s t a b l e but biologically inac­ tive compound. The s t r u c t u r e s of both compounds are deduced from spectroscopic d a t a . P e r i p l a n o n e - A i s 7-methylene-4-isopropyl-12-oxa-tricyclo [4.4.2.0 ] -9-dodecene-2-one: 15

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0097-6156/82/0190-0107$07.00/0 © 1982 American Chemical Society

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

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From females of the beet armyworm, Spodoptera e x i g u a , the ( Z , E ) - and ( Z , Z ) - t e t r a d e c a d i e n y l a c e t a t e s , the ( Z ) - 9 - and ( Z ) - 1 1 - t e t r a d e c e n y l acetates and t e t r a decanyl acetate were i s o l a t e d and identified. Syn­ thetic mixtures of some of these components a t t r a c t male moths in field t e s t s .

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Mammalian Pheromones: An A r e a N e g l e c t e d b y A p p l i e d B i o l o g i s t s and P e s t i c i d e Chemists Legends and o l d h i s t o r i c a l r e c o r d s p r o v e t h a t e v e n i n a n c i e n t t i m e s man h a s shown i n t e r e s t i n o d o u r o u s s e c r e t i o n s o f a n i m a l s , s u c h as t h e musk d e e r and t h e c i v e t , t o u s e i n p r e c i o u s p e r f u m e s . T h i s i s t h e m a i n r e a s o n why c h e m i s t s h a v e a n a l y s e d , s y n t h e s i z e d and m i m i c k e d t h e components o f t h e s e s e c r e t i o n s l o n g b e f o r e a n y i n s e c t pheromone was i s o l a t e d and i d e n t i f i e d . One may t h e r e f o r e wonder why s o l i t t l e a t t e n t i o n h a s b e e n p a i d b y s c i e n t i s t s t o t h e b e h a v i o u r a l r o l e , t h e c h e m i s t r y and t h e a p p l i c a t i o n o f s u c h mammalian c h e m i c a l s i g n a l s . T h i s p a r t l y c a n be a t t r i b u t e d t o g r e a t e x p e r i m e n t a l d i f f i c u l ­ t i e s i n s t u d y i n g mammalian pheromones (J_) . Compared w i t h b e h a v ­ i o u r a l and p h y s i o l o g i c a l b i o a s s a y s u s e d i n i n s e c t pheromone r e s e a r c h , r e l i a b l e , r e p r o d u c i b l e and s i g n i f i c a n t b i o a s s a y s f o r mammalian pheromones a r e h a r d t o d e v i c e . Such a s s a y s a r e e s s e n ­ t i a l f o r c h e m i s t s t o g u i d e t h e i r i s o l a t i o n and i d e n t i f i c a t i o n and f o r b i o l o g i s t s t o d e t e r m i n e t h e b i o l o g i c a l s i g n i f i c a n c e o f a com­ pound f o r t h e b e h a v i o u r o f t h e a n i m a l . The r e a c t i o n o f mammals t o o l f a c t o r y s t i m u l i i s c e r t a i n l y much more i n f l u e n c e d b y e x p e r i e n c e , e n v i r o n m e n t a l f a c t o r s a n d other sensory i n p u t s than i s the r e a c t i o n o f i n s e c t s t o phero­ mones. M o r e o v e r , t h e same o d o u r may s e r v e d i f f e r e n t b e h a v i o u r a l f u n c t i o n s and t h e s e may b e d e p e n d e n t on s u c h v a r i a b l e s as s e a s o n , age, e t c . . E v e n t h e w o r d "pheromone" f o r c h e m i c a l s i g n a l s i n mammals h a s b e e n q u e s t i o n e d (2). A l t h o u g h t h e o b j e c t i o n s were r e b u t t e d (3) t h e t e r m i s t o d a y s t i l l a m a t t e r o f c o n t r o v e r s y o r at l e a s t d i s c u s s i o n ( 4 ) . A n o t h e r r e a s o n f o r t h e r e l a t i v e l a c k o f i n t e r e s t i n mammalian pheromones l i e s i n t h e f a c t t h a t - a p a r t f r o m t h e u s e i n p e r ­ fumes - o n l y one a c t u a l a p p l i c a t i o n o f mammalian pheromones i s known so f a r . T h i s i s n o t i n c o n n e c t i o n w i t h a p e s t b u t w i t h a v e r y u s e f u l a n i m a l , t h e d o m e s t i c p i g ( 5 ) . The s a l i v a and sweat g l a n d s o f t h e s e x u a l l y a r o u s e d b o a r c o n t a i n two s t e r o i d s w i t h a musky s m e l l , Δ ~androstenol a n d A - a n d r o s t e n o n e . These a r e a c t u a l pheromones e m i t t e d b y t h e male a n d e l i c i t i n g a c h a r a c t e r i s ­ t i c b e h a v i o u r i n t h e f e m a l e . Sows i n h e a t r e a c t t o t h e s c e n t o f t h e s e compounds b y a s s u m i n g a c h a r a c t e r i s t i c c o p u l a t i n g s t a n c e . The pheromone i s c o m m e r c i a l l y a v a i l a b l e as a n a i d i n a r t i f i c i a l i n s e m i n a t i o n , t o show when a y o u n g sow i s i n o e s t r u s . The m a j o r p a r t o f mammalian pheromone r e s e a r c h , much o f w h i c h i s m e n t i o n e d i n r e c e n t b o o k s a n d symposium p r o c e e d i n g s (5-10) i s n o t d i r e c t e d t o any a p p l i c a t i o n . T r a p p e r s , h o w e v e r , h a v e u s e d mammalian s e c r e t i o n s i n t h e i r l u r e s l o n g b e f o r e t h e 16

1 6

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

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t e r m pheromone was c o i n e d , and t h e p o s s i b i l i t y o f a p p l i c a t i o n o f mammalian c h e m i c a l s i g n a l s has b e e n s u g g e s t e d by s c i e n t i s t s l i k e C h r i s t i a n s e n and D i v i n g f o r c o n t r o l o f s m a l l r o d e n t s (11) and by M a r s h and Howard f o r c o n t r o l o f r o d e n t s i n g e n e r a l ( 1 2 ) . Although they p o s i t i v e l y e v a l u a t e the p o t e n t i a l i t i e s of these a g e n t s i n r o d e n t c o n t r o l , t h e few p u b l i c a t i o n s i n t h i s a r e a r e l a t e r a t h e r to l a b o r a t o r y experiments than to a c t u a l a p p l i c a t i o n i n pest c o n t r o l . T h i s i s p a r t i c u l a r l y s u r p r i s i n g i n t h e c a s e o f common r a t s s i n c e we know t h a t t h e m a l e p r e p u t i a l g l a n d c o n t a i n s a m i x t u r e o f a l i p h a t i c a c e t a t e s w h i c h a p p e a r s t o a c t as an a t t r a c t i v e s e x pheromone t o t h e f e m a l e ( 1 3 ) . T h i s g l a n d a l s o a p p e a r s t o h a v e an important f u n c t i o n i n c o n s p e c i f i c chemical communication i n mice. I t s w e i g h t i s i n v e r s e l y r e l a t e d t o p o p u l a t i o n d e n s i t y (14) and i s l a r g e r i n dominant than i n s u b o r d i n a t e males ( 1 5 ) . E x t r a c t s of t h e s e g l a n d s a t t r a c t f e m a l e m i c e (16) and p r e p u t i a l e c t o m y a f f e c t s male f i g h t i n g b e h a v i o u r ( 1 7 ) . Many o t h e r s k i n g l a n d s o f mammals a l s o p r o d u c e o d o u r o u s s e c r e t i o n s to which b e h a v i o u r a l f u n c t i o n s are a t t r i b u t e d : marking of t e r r i t o r i e s , r e c o g n i t i o n o f s p e c i e s , o f s e x o r i n d i v i d u a l s , e t c . . They may a l s o s e r v e i n f a m i l i a r i z a t i o n w i t h s t r a n g e s u r r o u n d i n g s e.g. " g a i n i n g c o n f i d e n c e " as e x e m p l i f i e d by t h e b e h a v i o r o f r a b b i t s (_1_) . A r e c e n t r e v i e w on t h i s s u b j e c t i s g i v e n by M u l l e r - S c h w a r z e (18) . The M u s k r a t :

A P o p u l a r F u r A n i m a l , A N i g h t m a r e i n The

Netherlands

I n most c o u n t r i e s i n t h e N o r t h e r n h e m i s p h e r e t h e m u s k r a t , O n d a t r a z i b e t h i c u s , i s m a i n l y a p p r e c i a t e d f o r i t s b e a u t i f u l muskr a t o r " b i s a m " f u r . I t was f o r t h i s r e a s o n t h a t i t was i n t r o d u c e d f r o m A m e r i c a i n t o C z e c h o s l o v a k i a and o t h e r E u r o p e a n c o u n t r i e s e a r l y i n t h e 2 0 t h c e n t u r y . I n t h e N e t h e r l a n d s , h o w e v e r , i t i s now a m a j o r p e s t , damaging t h e b a n k s o f t h e many c a n a l s and d i k e s , so v i t a l f o r a c o u n t r y l y i n g l a r g e l y b e l o w s e a l e v e l . T h i s t h r e a t i s e v i d e n t f r o m t h e s c h e m a t i c d r a w i n g o f F i g u r e 1. I n t h e b e g i n n i n g o f W o r l d War I I t h e r a t s i n v a d e d t h e N e t h e r lands, which f o r b r e v i t y , I w i l l c a l l H o l l a n d , although t h i s i s a p a r t of the Netherlands i n which t h i s rodent i s s t i l l r a r e . U n l i k e t h e German army, h o w e v e r , t h e m u s k r a t f i r s t c r o s s e d t h e B e l g i a n , and l a t e r t h e German b o r d e r . B e t w e e n 1950 and t h e p r e s e n t day t h e m u s k r a t has c o n s t a n t l y e x p a n d e d i t s t e r r i t o r y and i t now occupies the l a r g e r p a r t of the country, i n s p i t e of constant t r a p p i n g by g o v e r n m e n t - e m p l o y e d p r o f e s s i o n a l t r a p p e r s . T h e r e f o r e t h e D u t c h government d e c i d e d t o l o o k f o r a l t e r n a t i v e methods t o s t o p and c o n t r o l t h e i n t r u d e r , and o u r r e s e a r c h group was a s k e d t o l o o k i n t o t h e p o s s i b i l i t i e s o f u s i n g p h e r o mones o r any o t h e r s e m i o c h e m i c a l s . T h e r e i s a v a s t l i t e r a t u r e a b o u t t h e m u s k r a t . A r e v i e w by H o f f m a n n (19) m e n t i o n s 6858 r e f e r e n c e s , 1669 o f w h i c h came f r o m t h e USSR. Not a l l o f t h e s e s o u r c e s a r e r e a d i l y a v a i l a b l e , b u t f r o m t r a n s l a t e d t i t l e s and f r o m t h e E n g l i s h and German l i t e r a t u r e i t

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

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seems t h a t l i t t l e has b e e n p u b l i s h e d a b o u t c h e m i c a l c o m m u n i c a t i o n i n muskrats. I l l - d e f i n e d c o n c o c t i o n s have f o r c e n t u r i e s been used t o l u r e m u s k r a t s i n t h e USA, b u t we h a v e l o o k e d i n v a i n f o r p u b l i s h e d d a t a w h i c h p r o v e t h e e f f e c t i v e n e s s o f t h e s e l u r e s . O n l y one v e r y b r i e f s t a t e m e n t by W i l l i a m s (20) a b o u t t h e e f f e c t i v e n e s s o f a d d i t i o n o f " m u s k r a t s c e n t " t o c a r r o t - b a i t e d t r a p s was f o u n d i n t h e J o u r n a l o f W i l d l i f e Management o f 1951. A t a b l e showed t h a t t h e " a v e r a g e t r a p p i n g s u c c e s s " i n c r e a s e d f r o m 23.6 t o 4 2 . 8 % , b u t t h e two s e r i e s o f e x p e r i m e n t s ( c o n t r o l s and s c e n t e d c a r r o t s ) w e r e n o t made s i m u l t a n e o u s l y , so t h e s e r e s u l t s h a r d l y p r o v e t h e a t t r a c t a n c y o f t h e scent. One of o u r f i r s t t a r g e t s was t h e r e f o r e t o f i n d o u t w h e t h e r o r n o t a t t r a c t i o n by m u s k r a t musk o r any o t h e r t r a d i t i o n a l l u r e can be d e m o n s t r a t e d . T h i s was i n i t i a l l y i n v e s t i g a t e d by a p p l y i n g t r a p p i n g methods n o r m a l l y u s e d by t r a p p e r s i n H o l l a n d ; t h i s was done i n c o l l a b o r a t i o n w i t h e x p e r i e n c e d t r a p p e r s and u s i n g a v a r i e t y of l u r e s . Methods f o r F i e l d - T r a p p i n g M u s k r a t s I n H o l l a n d t h e m u s k r a t u s u a l l y l i v e s i n b u r r o w s i n dams, d i k e s and b a n k s o f t h e c a n a l s and l a k e s , as d e p i c t e d i n F i g u r e 1. The " m u s k r a t h o u s e s " o r " w i n t e r h u t s " , w e l l - k n o w n i n t h e USA, are r e l a t i v e l y r a r e i n H o l l a n d . They a r e u s u a l l y f o u n d i n w e t l a n d s and marshes w h e r e no d i k e s a r e a v a i l a b l e . They a r e c o n s p i c u o u s and r e l a t i v e l y e a s y t o f i n d . T h i s i s n o t t h e c a s e w i t h t h e b u r rows i n t h e b a n k s and d i k e s . The e n t r a n c e s a r e b e l o w w a t e r l e v e l and c a n o n l y be o b s e r v e d when t h e l e v e l d r o p s . E x p e r i e n c e d t r a p pers have, however, a v a r i e t y of c l u e s t o d e t e c t the p r e s e n c e o f an e n t r a n c e , e.g. by swimming t r a i l s , o r h e a p s of s a n d removed from the burrows. I n H o l l a n d , t h e use o f p o i s o n e d b a i t s w h i c h c o u l d k i l l o t h e r w i l d l i f e , and g r o u n d t r a p s w h i c h w o u l d n o t k i l l t h e a n i m a l immed i a t e l y , a r e p r o h i b i t e d . The d e v i c e s most o f t e n u s e d a r e : - b a i t e d t r a p s , a f l o a t on r a f t s , i n w h i c h a p p l e s a r e o f t e n u s e d as b a i t , - "Conibear t r a p s " , p l a c e d at the entrance below the water s u r f a c e , - metal hoop-nets, e i t h e r p l a c e d at the entrance of a burrow or at the i n t e r c o n n e c t i o n o f waterways o r under a b r i d g e o r , according to a r e c e n t l y developed technique, i n "fake entrances", made o f p l a s t i c t u b e s o r p i p e s ( F i g u r e 2 ) , - a v a r i e t y of f l o a t i n g " v a l v e - t r a p s " or o t h e r c o n t r a p t i o n s , usually baited with apples. A number o f f i e l d t e s t s u s i n g s u c h methods w e r e made i n o r d e r to s c r e e n a v a r i e t y o f l u r e s , e i t h e r o b t a i n e d t h r o u g h t h e h e l p o f P r o f . M u l l e r - S c h w a r z e o f New Y o r k S t a t e U n i v e r s i t y i n S y r a c u s e , w i t h whom we c o l l a b o r a t e , o r made by o u r s e l v e s f r o m c o l l e c t e d glands or commercially a v a i l a b l e f r a g r a n c e s .

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

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-ι ι* JUUU 24 23 22

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Figure 2. Top: Scheme of 4 rafts with baited traps and 24 funnel traps placed in "artificial burrows" at the Berkel on the German border. Bottom: Funnel trap in plastic pipe placed below the water surface. Λ scented cork is stuck fust above the trap. Results of 2 series of experiments with such traps are shown in Figures 3 and 4.

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

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R e s u l t s of F i e l d T e s t s w i t h Muskrat Lures F i e l d t e s t s w e r e made a t a v a r i e t y o f l o c a t i o n s n e a r t h e German o r B e l g i a n b o r d e r and i n an a r e a b e t w e e n r i v e r s , s o u t h o f the Rhine. I n t h i s p a p e r we c a n n o t sum up a l l t h e r e s u l t s , many o f w h i c h were i n c o n c l u s i v e . We a t t r i b u t e t h e l a t t e r t o an i n s u f f i c i e n t number o f m u s k r a t s i n t h e t e s t a r e a ( a p a r t f r o m t r a p p i n g , no r e l i a b l e method was a v a i l a b l e t o e s t i m a t e t h e s i z e o f t h e p o p u l a t i o n ) o r t o t h e l a c k o f a t t r a c t i v e n e s s o f t h e l u r e s i n mid-summer, o u t s i d e t h e m a t i n g o r m i g r a t i o n s e a s o n . We h a v e t o s t r e s s , t h e r e f o r e , t h a t t h e f o l l o w i n g r e s u l t s must be c o n s i d e r e d as p r e l i m i n a r y ones and a r e a s e l e c t i o n of o n l y t h o s e r e s u l t s w h i c h seem t o be statistically significant. The most c o n v i n c i n g e v i d e n c e of t h e e f f e c t i v e n e s s o f some l u r e s was o b t a i n e d a t t h e B e r k e l , a l i t t l e b o r d e r r i v e r b e t w e e n Germany and H o l l a n d . H e r e we m a i n l y u s e d t h e method w i t h a r t i f i c i a l e n t r a n c e s , i n which funnel-shaped t r a p s were p l a c e d ( F i g u r e 2 ) . I n t h e s l o p e o f t h e bank 24 h o l e s w e r e dug i n w h i c h p i p e s w i t h t r a p s w e r e p l a c e d . T h r e e d i f f e r e n t l u r e s were t e s t e d i n s i x f o l d a g a i n s t an e q u a l number of c o n t r o l s . I n a d d i t i o n , 4 f l o a t i n g t r a p s , b a i t e d w i t h a p p l e s , and t h e same l u r e s w e r e t e s t e d . F i v e d r o p s o f l u r e w e r e a p p l i e d t o c o r k s p l a c e d on s t i c k s above t h e f u n n e l t r a p s and s i m i l a r c o r k s were u s e d on t h e r a f t s . A t l e a s t once a week t h e t r a p s w e r e c h e c k e d and f r e s h d r o p s o f l u r e s a p p l i e d . The r e s u l t s w i t h t h e f u n n e l s a r e shown i n F i g u r e 3. The s a m p l e s t e s t e d w e r e : A. S c e n t g l a n d e x t r a c t s o f m a l e m u s k r a t s , c a u g h t i n M a r c h i n t h e same v i c i n i t y b u t somewhat more t o t h e N o r t h ( t h e p r o v i n c e o f D r e n t h e ) . The two b a t c h e s t e s t e d (26 and 29 i n F i g u r e 3) were o b t a i n e d by c e n t r i f u g a t i o n o f h o m o g e n i z e d g l a n d s i n e t h a n o l . The s u p e r n a t a n t u s e d r e p r e s e n t e d 5 ml e x t r a c t p e r g l a n d , and t h e 5 d r o p s c o r r e s p o n d e d r o u g h l y w i t h 0.1 ml o r 1/50 o f t h e e x t r a c t f r o m one g l a n d . B. C o m m e r c i a l l y a v a i l a b l e A m e r i c a n " M u s k r a t Musk" ( P e r k i n s H i l l Ltd., C a z e n o v i a , N.Y.) ( s a m p l e 28 i n F i g u r e 3 ) . C. A m i x t u r e o f o i l o f sweet f l a g i n g l y c e r i n e (1 : 2 ) , made a c c o r d i n g t o one o f t h e t r a d i t i o n a l t r a p p e r s r e c i p e s , k i n d l y p r o v i d e d by P r o f . M.M. A l e x a n d e r , S y r a c u s e , N.Y. ( s a m p l e 13 i n F i g u r e 3). As t h e F i g u r e shows, o n l y 4 m u s k r a t s w e r e c a u g h t d u r i n g t h e w h o l e t e s t p e r i o d - w h i c h r a n f r o m September 15, 1980 t o June 5, 1981 i n t h e c o n t r o l s compared w i t h 19 i n t h e t r a p s w i t h t h e home-made g l a n d e x t r a c t s . I n t h e f i r s t two months t h e s e numbers w e r e e v e n 1 and 10. W i t h sweet f l a g and A m e r i c a n musk t h e t o t a l c a t c h e s o v e r t h e w h o l e p e r i o d w e r e 6 and 9, r e s p e c t i v e l y . U n f o r t u n a t e l y , t h e w a t e r l e v e l d r o p p e d c o n s i d e r a b l y d u r i n g t h r e e p e r i o d s , as i n d i c a t e d i n t h e F i g u r e , b u t t h i s does n o t a f f e c t t h e c o n c l u s i o n t h a t t h e g l a n d e x t r a c t was b e s t . I n t o t a l 4 f e m a l e s and 34 m a l e s w e r e caught.

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

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The b a i t e d t r a p s on t h e r a f t s seemed l e s s s u i t e d f o r s c r e e n i n g a t t r a c t a n t s , as t h e a p p l e s a t t r a c t h u n g r y m u s k r a t s and o n l y s l i g h t , i f any, improvement was o b t a i n e d by a d d i n g t h e l u r e s , w i t h t h e e x c e p t i o n of t h e A m e r i c a n musk w h i c h seemed t o enhance t h e a t t r a c t i v i t y o f t h e b a i t s d u r i n g t h e months M a r c h and A p r i l . An a d d i t i o n a l p r o b l e m w i t h t h e b a i t e d t r a p s i s t h a t t h e y a l s o c a t c h o t h e r a n i m a l s . I n t h e t e s t p e r i o d 37 m a l e and 2 f e m a l e muskr a t s w e r e c a u g h t t h i s way, b u t a l s o 9 common b r o w n r a t s . A t t h e Hegebeek, a n e a r b y l o c a t i o n , a t t h e s l o p e s o f a s m a l l p o o l n e a r a l o c k , t h e l u r e s A, Β and C c o u l d o n l y be t e s t e d s i n g l y , i n t e r ­ s p a c e d b y two n o n - s c e n t e d t r a p s ( b l a n k s ) ( F i g u r e 4 ) . H e r e a g a i n , t h e e x t r a c t s of t h e D u t c h m u s k r a t s came o u t b e s t , a l t h o u g h t h e o t h e r t r a p s and even one o f t h e b l a n k s w e r e n o t i n e f f e c t i v e . A c c o r d i n g to the t r a p p e r s , the predominance of males i s not u n u s u a l a t t h e s e l o c a t i o n s n e a r t h e German b o r d e r . I t i s a t t r i ­ buted t o the o b s e r v a t i o n t h a t d u r i n g m i g r a t i o n the males t r a v e l first. F i e l d t e s t s w i t h b a i t e d t r a p s and t h e same t h r e e l u r e s i n t h e m i d d l e of the c o u n t r y between the branches o f the R h i n e , d i d not a l l o w c o n c l u s i o n s a b o u t t h e a t t r a c t a n c y of t h e l u r e s t o be r e a c h e d , b u t t h e y showed t h a t h e r e a b o u t e q u a l numbers o f m a l e s and f e m a l e s w e r e c a u g h t . A t t h i s l o c a t i o n a s t a b i l i z e d c o l o n y o f m u s k r a t s had s e t t l e d . These p r e l i m i n a r y r e s u l t s seem t o c o n f i r m t h a t e x t r a c t s o f m u s k r a t p r e p u t i a l g l a n d s and p o s s i b l y a l s o o f sweet f l a g c a n i n d e e d enhance t h e c a t c h e s o f m u s k r a t s , e s p e c i a l l y i n s c e n t e d f u n n e l t r a p s i n a r t i f i c i a l p i p e s a t r i v e r b a n k s , where m i g r a t i n g m u s k r a t s p a s s . The a n i m a l s c a u g h t a r e t h e n m a i n l y m a l e s w h i c h p r e f e r e n t i a l l y e n t e r a r t i f i c i a l p i p e s s c e n t e d w i t h e x t r a c t s of musk g l a n d s w h i c h - i t s h o u l d be r e m a r k e d h e r e - a r e p r o d u c e d by other males. Screening Lures w i t h Muskrats

i n Captivity

A number o f m u s k r a t s c a u g h t i n l i v e - t r a p s n e a r t h e B e l g i a n b o r d e r w e r e u s e d f o r s c r e e n i n g l u r e s i n two s e r i e s o f t e s t s . The f i r s t one was made i n a c o n c r e t e b a s i n , 7 m l o n g , 1.5 m w i d e and 1.6 m deep ( F i g u r e 5 ) , i n w h i c h 4 t o 8 m u s k r a t s w e r e k e p t . N e s t b o x e s w e r e made i n t h e c o r n e r s and two c o u n t i n g c a g e s were p l a c e d on a r a f t n e a r t h e m i d d l e of t h e b a s i n . A n i m a l s v i s i t ­ i n g t h e cages w e r e c o u n t e d m e c h a n i c a l l y by a d e v i c e a t t a c h e d t o a f l a p which c o u l d swing i n both d i r e c t i o n s . A v a r i e t y o f l u r e s was s c r e e n e d h e r e i n d u a l c h o i c e t e s t s . A p e r f o r a t e d aluminum c a p s u l e , c o n t a i n i n g f i v e d r o p s o f t h e t e s t s a m p l e on f i l t e r p a p e r , was a t t a c h e d t o t h e b a c k w a l l o f one c a g e ; t h e o t h e r cage c a r r i e d a b l a n k c a p s u l e . The a v e r a g e t e s t p e r i o d was one week, i n t h e m i d d l e o f w h i c h t h e p l a c e s o f t h e cages w e r e i n t e r c h a n g e d and t h e s a m p l e s w e r e renewed. A f t e r e a c h t e s t t h e cages w e r e t h o r o u g h l y r i n s e d w i t h c l e a n w a t e r . The c o u n t s were r e c o r d e d d a i l y and t h e t e s t s were made a t l e a s t i n duplicate.

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

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Figure 3. Results of the screening experiment at the Berkel on the German border. Key: A, ( ), Dutch muskrat musk 26 and 29; B, (- · - -), American muskrat musk 28; C,( ), sweetflag13; and blank (- · -).

25 Sep

5 Nov

5Dec

5 Jan

5 Feb

5 Mar

~~i

5 Apr

5 May

5Jun

1

1980

1981

Figure 4. Results of the screening experiment at the Hegebeek on the German border. Key: A, ( · ), Dutch muskrat musk 26 and 29; B, (- · - -), American muskrat musk 28; blank 1, ( ); C, (- · -), sweet flag 13; and blank 2, ( ).

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I

t 1.5 m

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t r a p s with counter

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nest-boxes \sliding

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l V////// Figure 5.

j_j_J

_L

"^waterlevel

ν

wall

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j

1

Schematic representation of the basin for keeping muskrats at Rijswijk. Top shows view from above, and bottom shows view from the side.

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

Downloaded by PURDUE UNIV on August 28, 2014 | http://pubs.acs.org Publication Date: June 18, 1982 | doi: 10.1021/bk-1982-0190.ch005

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W i t h i n the framework of t h i s paper i t i s not p o s s i b l e to d i s c u s s a l l t h e s c r e e n i n g r e s u l t s . F o r t h o s e who a r e i n t e r e s t e d , a d e t a i l e d r e p o r t (21) ( i n D u t c h ) i s a v a i l a b l e . I t may s u f f i c e h e r e t o r e l a t e t h a t t h e home made g l a n d e x t r a c t A ( b a t c h 29, w h i c h a l s o p e r f o r m e d b e s t i n t h e f i e l d t e s t s o f F i g u r e s 4 and 5) was t h e b e s t a t t r a c t a n t , f o l l o w e d by a m i x t u r e o f t h e o i l s o f sweet f l a g and c a t n i p ( r e c i p e o b t a i n e d t h r o u g h t h e c o u r t e s y o f P r o f . A l e x a n d e r ) and t h e A m e r i c a n m u s k r a t musk, w h i c h was a l s o u s e d i n t h e f i e l d t e s t s . As an e x a m p l e , t h e r e s u l t s o f one o f t h e s e t e s t s i s shown i n F i g u r e 6. The s e c o n d s e r i e s o f t e s t s i s a t p r e s e n t b e i n g c a r r i e d o u t i n an " o l f a c t o m e t e r " , w h i c h c o n s i s t s o f a r o u n d " m u s k r a t p e n " w i t h a d i a m e t e r o f 10 m, c o n t a i n i n g a swimming p o o l ( F i g u r e 7 ) . E i g h t cages w h i c h a r e c o n n e c t e d t o e l e c t r i c c o u n t i n g d e v i c e s and a r e c o r d e r , a r e e q u a l l y s p a c e d r o u n d t h e p e r i p h e r y o f t h e pen (Figure 8). A t p r e s e n t t h e b e h a v i o u r o f t h e m u s k r a t c o l o n y i n t h e pen and t h e i n d i v i d u a l r e a c t i o n s o f t h e m u s k r a t s t o d i f f e r e n t l u r e s i s b e i n g s t u d i e d by s t u d e n t s o f P r o f . Wiepkema i n Wageningen. They w a t c h t h e a n i m a l s f r o m an o b s e r v a t i o n h i d e d u r i n g t h e d a r k and l i g h t p e r i o d s o f g r e a t e s t a c t i v i t y and k e e p r e c o r d o f t h e number and d u r a t i o n of t h e v i s i t s t o s c e n t e d cages and c o n t r o l s . T h i s pen and i t s e q u i p m e n t h a v e o n l y r e c e n t l y b e e n i n s t a l l e d and a r e b e i n g t e s t e d o u t a t p r e s e n t . We hope t h a t t h e y w i l l c o n t r i b u t e t o a b e t t e r u n d e r s t a n d i n g o f t h e g e n e r a l b e h a v i o u r and t h e c h e m i c a l c o m m u n i c a t i o n o f m u s k r a t s and a t t h e same t i m e w i l l a l l o w us t o s c r e e n d i f f e r e n t l u r e s i n a s y s t e m a t i c manner, t o d e t e r m i n e t h e i r o p t i m a l c o n c e n t r a t i o n s , and t o s t u d y t h e e f f e c t o f t h e v a r i o u s components f o u n d i n t h e e x t r a c t s o f t h e s c e n t gland. P a r a l l e l s t u d i e s on t h e b e h a v i o u r a l f u n c t i o n o f t h e musk odour o f m u s k r a t s a r e b e i n g done i n t h e USA by P r o f . M u l l e r Schwarze i n Syracuse, N.Y. P o s s i b l e F u n c t i o n o f Musk G l a n d S e c r e t i o n and S e a s o n a l i t s Chemical Composition

Changes o f

F u n c t i o n . The p r e p u t i a l g l a n d o f t h e m u s k r a t e n l a r g e s g r e a t l y i n t h e b r e e d i n g s e a s o n . I t i s r e a s o n a b l e t o assume t h a t t h i s s t r o n g - s m e l l i n g s e c r e t i o n has a t l e a s t one and p o s s i b l y s e v e r a l f u n c t i o n s i n t h e c h e m i c a l c o m m u n i c a t i o n b e t w e e n members of t h i s s p e c i e s . In muskrats these glands are present i n both sexes, but they a r e much l a r g e r i n m a l e s , i n w h i c h s i z e o f t h e g l a n d s and s t r e n g t h o f t h e o d o u r s e c r e t i o n p a r a l l e l t h e c y c l i c changes i n testes size. The v a r i e t y o f p o s s i b l e f u n c t i o n s o f p r e p u t i o n a l g l a n d s e c r e t i o n s o f mammals h a v e b e e n m e n t i o n e d b e f o r e . I t i s s t i l l n o t c l e a r w h i c h o f t h e s e f u n c t i o n s a p p l y t o m u s k r a t s . They may i n c l u d e s e x a t t r a c t i o n , r e p u l s i o n o f members o f t h e same s e x , marki n g o f n e s t s o r h i d i n g p l a c e s , g e n e r a l a t t r a c t i o n o f young and a d u l t members o f t h e same s p e c i e s by a f a m i l i a r o d o u r , m a r k i n g of

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

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Figure 6. Results of one of the tests in the basin in Rijswijk (see Figure 5) obtained during screening of a variety of muskrat lures. Attractant No. 29 ("muskoil") was obtained (December 5-11, 1980) by extraction of preputial glands with ethanol.

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Figure 7. Schematic representation of the "olfactometer" consisting of a round muskrat pen of iron gauze (diameter 10 m; height 2.20 m). An iron swimming pool was placed in the middle. Key: 1-8, counting cages with encoder box (see Figure 8); and D, door.

box with encoder system

Figure 8.

Cage with encoder box in which time, number and duration of visits of muskrats are signaled and transmitted to a recorder.

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

Downloaded by PURDUE UNIV on August 28, 2014 | http://pubs.acs.org Publication Date: June 18, 1982 | doi: 10.1021/bk-1982-0190.ch005

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117

t e r r i t o r y as w e l l as s t i m u l a t i o n ( " p r i m i n g " ) o f e n d o c r i n e p r o c e s ses, e t c . . Among t h e few c l u e s f o u n d i n t h e l i t e r a t u r e w h i c h m i g h t i n d i c a t e a f u n c t i o n , a r e t h o s e o f Akkerman (22) who o b s e r v e d t h a t a m a l e m u s k r a t was " s c e n t - m a r k i n g " a f e m a l e d u r i n g c o u r t s h i p and m a t i n g w h i c h o c c u r s w h i l e t h e y a r e swimming. He a l s o f o u n d t h a t f a e c a l p i l e s a r e h i g h l y i m p o r t a n t i n m u s k r a t c o m m u n i c a t i o n , as Muller-Schwarze r e c e n t l y d e s c r i b e d f o r beavers (23). I n s p r i n g the f a e c a l p i l e s of muskrats a r e found where they l e a v e the w a t e r . These p i l e s a r e produced where p o p u l a t i o n d e n s i t i e s a r e h i g h , which again p a r a l l e l s the s i t u a t i o n i n beavers (23). The m u s k r a t s e c r e t e s i t s musk d u r i n g s c e n t m a r k i n g t h r o u g h t h e p e n i s . The s o l e s o f t h e h i n d f e e t p i c k up t h e f l u i d and t h r o w i t behind the animal (22). C h e m i c a l c o m p o s i t i o n and s e a s o n a l changes o f musk g l a n d s e c r e t i o n The p r e p u t i a l (musk) g l a n d o f t h e m u s k r a t c o n t a i n s a numb e r o f m a c r o c y c l i c k e t o n e s , s u c h as i s o m e r s o f c i v e t o n e ( c i s - 9 c y c l o h e p t a d e c e n o n e ) , t h e m a i n odourous component o f t h e s e c r e t i o n of t h e c i v e t . I n t h e m u s k r a t t h e m a i n m a c r o c y c l i c component i s t h e c i s - 5 - i s o m e r o f c i v e t o n e ( F i g u r e 9 ) . The g l a n d s o f b o t h a n i m a l s a l s o c o n t a i n a number o f o t h e r m a c r o c y c l i c compounds and a v a r i e t y o f f a t t y a c i d s (24,25,26) w h i c h c o u l d be p r e c u r s o r s o f m a c r o c y c l i c k e t o n e s and a l c o h o l s as p r o p o s e d by S t e v e n s i n 1945 (25). The v a s t l i t e r a t u r e o n t h e m u s k r a t m e n t i o n e d b e f o r e , as summ a r i z e d by E r r i n g t o n (27) and H o f f m a n n (19) m a i n l y c o n c e r n s e c o l o g y , taxonomy, anatomy, p a r a s i t o l o g y and economy. O n l y a few c h e m i c a l s t u d i e s h a v e b e e n c a r r i e d o u t and t h e i n t e r e s t i n t h e b i o l o g i c a l f u n c t i o n s o f t h e components f o u n d i n t h e g l a n d s e c r e t i o n seemed t o be n e g l i g i b l e . I n 1973, Van Dorp e t a l . f o u n d a number o f i n t e r e s t i n g m a c r o c y c l i c compounds, i n c l u d i n g some w i t h b o t h d o u b l e and t r i p l e u n s a t u r a t e d bonds (26) , b u t made no a t t e m p t t o d e t e r m i n e t h e i r b i o l o g i c a l s i g n i f i c a n c e . They compared t h e m a c r o c y c l i c k e t o n e s and the f a t t y a c i d s f o u n d i n c i v e t and m u s k r a t g l a n d and c o n c l u d e d t h a t t h e r e i s e v i d e n t l y no c o r r e l a t i o n b e t w e e n t h e m a c r o c y c l i c k e t o n e c o m p o s i t i o n and t h e f a t t y a c i d c o m p o s i t i o n . F o r e x a m p l e , c y c l o h e p t a d e c a n o n e was t h e most p r o m i n e n t peak i n t h e m u s k r a t g l a n d (41% of t h e m a c r o c y c l i c k e t o n e s ) , whereas the s t e a r i c a c i d f r o m w h i c h i t c o u l d h a v e b e e n f o r m e d , was among t h e m i n o r compon e n t s (3%) o f t h e f a t t y a c i d s . We a n a l y s e d e t h a n o l i c e x t r a c t s o f p r e p u t i a l g l a n d s o f m u s k r a t s c o l l e c t e d d u r i n g a f u l l a n n u a l c y c l e by one t r a p p e r , i n ZeeuwschV l a a n d e r e n , n e a r t h e B e l g i a n b o r d e r . The m a j o r i t y o f t h e g l a n d s w e r e t a k e n f r o m a d u l t m a l e s , b u t some g l a n d s o f a d u l t f e m a l e s and y o u n g f e m a l e s and m a l e s w e r e a l s o c o l l e c t e d and a n a l y s e d s e p a r a t e l y (GC and MS; SE-30 c a p i l l a r y c o l u m n ) . T a b l e s I and I I compare t h e compounds w h i c h we h a v e f o u n d so f a r w i t h t h o s e f o u n d b y Van Dorp e t a l . A l t h o u g h we h a v e n o t y e t

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

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b e e n a b l e t o d e f i n i t e l y e s t a b l i s h t h e p o s i t i o n o f most o f t h e d o u b l e o r t r i p l e b o n d s , t h e d a t a show t h a t p r o b a b l y n i n e k e t o n e s w e r e f o u n d by b o t h g r o u p s , w h e r e a s two components i d e n t i f i e d by Van D o r p e t a l . h a v e n o t y e t b e e n f o u n d by us and f o u r o f o u r compounds w e r e n o t f o u n d by t h e o t h e r g r o u p . A g a i n w i t h some r e s e r v e r e g a r d i n g t h e p o s i t i o n o f t h e d o u b l e bonds, T a b l e I I shows t h a t we f o u n d a l l t h e a c i d s m e n t i o n e d by Van Dorp e t a l . , b u t , i n a d d i t i o n , n i n e more a c i d s l a c k i n g f r o m t h e i r list. There i s , however, a g r e a t s i m i l a r i t y w i t h r e g a r d t o the q u e s t i o n w h i c h w e r e t h e m a j o r and w h i c h t h e m i n o r components i n t h e two g r o u p s o f compounds. We c a n n o t , h o w e v e r , s u p p o r t t h e o p i n i o n t h a t t h e r e i s no c o r r e l a t i o n b e t w e e n t h e k e t o n e s and f a t t y a c i d s . A n a l y s e s made o v e r a one y e a r p e r i o d seem t o i n d i c a t e t h a t t h e p e r c e n t a g e o f m a c r o c y c l i c k e t o n e s i s o f t e n h i g h when t h a t o f t h e a c i d s i s low and v i c e v e r s a . T h i s w o u l d s u p p o r t S t e v e n s ' h y p o t h e s i s , w h i c h was c h a l l e n g e d by Van Dorp e t a l . ( 2 6 ) , t h a t t h e k e t o n e s a r e f o r m e d by c y c l i z a t i o n and d e c a r b o x y l a t i o n o f f a t t y a c i d s ( 2 5 ) . As an e x a m p l e , F i g u r e 10 shows t h e s e a s o n a l c h a n g e s i n t h e r e l a t i v e p e r c e n t a g e o f a l l t h e 17-membered r i n g k e t o n e s t o g e t h e r and t h o s e o f t h e C i 8 a c i d s and e s t e r s . T h e s e d a t a n o t o n l y s u p p o r t t h e b i o g e n e t i c r e l a t i o n s h i p b e t w e e n a c i d s and m a c r o c y c l i c k e t o n e s b u t a l s o s u g g e s t t h a t t h e compounds w i t h t h e musk o d o u r a r e m a i n l y p r o d u c e d d u r i n g f a l l and w i n t e r . The p e r c e n t a g e o f t h e musk compounds d r o p s s h a r p l y d u r i n g t h e f i r s t t h r e e months o f t h e y e a r and i n c r e a s e s a g a i n i n s p r i n g . The a n a l y s e s o f t h e f e m a l e g l a n d s showed t h a t t h e s e a l s o c o n t a i n some m a c r o c y c l i c compounds b u t t h a t t h e i r r e l a t i v e p e r c e n t a g e s a r e much l o w e r t h a n t h o s e f o u n d i n t h e m a l e s and t h a t , c o r r e s p o n d i n g l y , the percentage of f a t t y a c i d s i s l a r g e r . We w i s h t o t h a n k U n i l e v e r , V l a a r d i n g e n f o r s u p p l y i n g s a m p l e s o f m a c r o c y c l i c k e t o n e s and Dr. P . E . J . V e r w i e l and I n g . A. L a k w i j k f o r c a r r y i n g o u t GC/MS e x p e r i m e n t s . The w o r k was s u p p o r t e d by a g r a n t f r o m t h e D u t c h D e p a r t m e n t s o f W i l d l i f e Management and P u b l i c Works. We a l s o t h a n k Dr. W.J. Doude v a n T r o o s t w i j k and h i s c o l l a b o r a t o r s o f t h e C o m m i t t e e f o r M u s k r a t C o n t r o l f o r t h e i r v a l u a b l e h e l p and advices. S t r u c t u r e E l u c i d a t i o n of

Periplanone-A

The names p e r i p l a n o n e - A and p e r i p l a n o n e - B w e r e f i r s t c o i n e d by R i t t e r and P e r s o o n s i n 1974 a t t h e I n t e r n a t i o n a l C o n g r e s s o f P e s t i c i d e C h e m i s t r y i n H e l s i n k i , i n a g e n e r a l p a p e r on pheromone r e s e a r c h i n the N e t h e r l a n d s . I n t h i s paper the i s o l a t i o n o f a number of pheromones w e r e d e s c r i b e d , i n c l u d i n g t h e two p e r i p l a n o n e s , b o t h s e x pheromones, p r e s e n t i n t h e e x c r e t a o f t h e f e m a l e A m e r i c a n c o c k r o a c h , P e r i p l a n e t a a m e r i c a n a . The e l e m e n t a r y f o r m u l a e o f t h e s e two s e s q u i t e r p e n o i d s , C15H20O2 and C15H20O35 w e r e g i v e n and t h e c a r b o n s k e l e t o n o f p e r i p l a n o n e - B , a g e r m a c r a n e d e r i v a t i v e , was r e v e a l e d . U n f o r t u n a t e l y , we w e r e i n f o r m e d , one y e a r a f t e r t h e

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

5.

Pheromone

RiTTER E T A L .

H

(CH )

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2

Figure 9.

Research

on Muskrats

H

H

H

I I

I I

C=C

C =C (CH )

7

2

7

(CH ) 2

and Insects

(CH^h

3

Structures of the main macrocyclic ketones of the civet (left) and the muskrat (right).

I x

1

1

1 I l _ l '



'

• '

Nov Dec Jan FebrMarApr May Jun J u l AugSept 7 1979

1980

Figure 10. Variation with season of the proportion of macrocyclic C ketones and of their possible precursors (bottom), the C acids and their esters (top). Sum of all compounds detected by the GC analysis is 100%. 17

18

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

119

120

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Table I MACROCYCLIC KETONES I N THE PREPUTIAL GLAND OF THE MUSKRAT Compound

V. Dorp e t a l . R i t t e r e t a l .

-

Cyclotridecanone

+++ · +++ +

Cyclopentadecanone Cyclopentadecenone, (Z)-5C y c l o p e n t a d e c y n o n e , 5-*

+

Cyclohexadecanone Cyclohexadecenone*

-

C y c l o h e p t adecanone Cycloheptadecenone, (Z)-5Cycloheptadecenone, (Z)-7-* Cycloheptadecadienone, (Z,Z)-5,11-* C y c l o h e p t a d e c y n o n e , 5-* Cycloheptadecen-5-ynone, (Z)-7-* Cyclononadecanone Cyclononadecenone, Cyclononadecenone*

+ +++ +++ + + +

+++ +++ ++ ++ + ++

+++ +++ ++

+

+ + +

-

(Z)-9-*

++

* P o s i t i o n o f double bond(s) n o t y e t e s t a b l i s h e d i n o u r work. +++ ++ +

^ 10% r e l a t i v e o f t h e m a c r o c y c l i c > 1% " " ^ 1 7 " M M M 11

11

ketones 11

M

not found, o r not i d e n t i f i e d

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

5.

RiTTER E T A L .

Pheromone

Research

on Muskrats

and Insects

Table I I FATTY ACIDS I N THE PREPUTIAL GLAND OF THE MUSKRAT

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Fatty Number o f C-atoms

acid Number o f double bonds*

V. Dorp e t a l . R i t t e r e t a l .

0 1

14 14

0 1

++

16 16 16

0 1 1

+++ ++

-

+++ ++ ++

17

0

-

+

18 18 18 18

0 1 1 2

++ +++ ++

++ +++ + ++

19

1

-

+

20 20 20

0 1 2

+

+ + +

-

-

-

* P o s i t i o n of double bond(s) not y e t e s t a b l i s h e d +++ +

+ +

12 12

++ +

i n o u r work.

^ 10% r e l a t i v e o f t h e f a t t y a c i d s > 17 " It II II II < 1% " " " not f o u n d , o r n o t i d e n t i f i e d 11

11

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

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c o n g r e s s , t h a t none o f t h e symposium p a p e r s c o u l d be p u b l i s h e d and t h a t we had t o s e e k p u b l i c a t i o n e l s e w h e r e . T h i s we d i d i n t h e N e t h e r l a n d s J o u r n a l o f Z o o l o g y i n 1975 ( 2 8 ) . M e a n w h i l e we h a d p u b l i s h e d the e x p e r i m e n t a l d e t a i l s i n our communication to the R o y a l D u t c h Academy o f S c i e n c e s ( 2 9 ) . A s i m i l a r p a p e r had b e e n r e j e c t e d f o r p u b l i c a t i o n i n 1973, f i r s t by S c i e n c e , and t h e n by Experientia. We s u s p e c t t h a t t h e r e l u c t a n c y o f a u t h o r i t a t i v e j o u r n a l s o u t s i d e H o l l a n d t o p u b l i s h our d a t a r e s u l t e d from f e a r of r e p e a t i n g the u n f o r t u n a t e events a f t e r the premature p u b l i c a t i o n of a w r o n g s t r u c t u r e f o r t h i s s e x pheromone by e m i n e n t A m e r i c a n s c i e n t i s t s i n 1963 ( 3 0 ) , who h a d t o w i t h d r a w t h e i r s t r u c t u r e two years l a t e r (31). A few y e a r s ago t h e c o m p l e t e s t r u c t u r e o f p e r i p l a n o n e - B , a p a r t f r o m i t s s t e r e o c h e m i s t r y , was e l u c i d a t e d and p u b l i s h e d by our r e s e a r c h team (32,33,34) w i t h P e r s o o n s as t h e p r i n c i p a l i n v e s t i g a t o r , who i n c l u d e d t h i s w o r k i n h i s d o c t o r a l t h e s i s ( 3 5 ) , and s h a r e d t h e R o y a l D u t c h S h e l l P r i z e f o r 1978 w i t h R i t t e r f o r t h i s w o r k and t h e s t r u c t u r e e l u c i d a t i o n o f f a r a n a l , t h e t r a i l pheromone o f t h e P h a r a o h s a n t , Monomorium p h a r a o n i s ( 3 6 , 3 7 ) . The d e t e r m i n a t i o n o f t h e a b s o l u t e c o n f i g u r a t i o n o f p e r i p l a none-B by A m e r i c a n s c i e n t i s t s i n c o o p e r a t i o n w i t h P e r s o o n s (38) and t h e c o n f i r m a t i o n o f t h e s t r u c t u r e by t h e e l e g a n t s y n t h e s i s o f S t i l l a t t h e C o l u m b i a U n i v e r s i t y (39) f o l l o w e d i n 1979. The p l a n a r and s t e r e o s t r u c t u r e o f p e r i p l a n o n e - B a r e shown i n F i g u r e 11. We c a n now r e p o r t t h e s t r u c t u r e e l u c i d a t i o n o f t h e o t h e r i s o l a t e d compound: p e r i p l a n o n e - A . I t i s , as we m e n t i o n e d i n e a r l i e r p a p e r s (28,29) an u n s t a b l e s e s q u i t e r p e n o i d w i t h t h e g e n e r a l f o r m u l a Ci5H2o02» I t s s t r u c t u r e , l i k e t h a t o f p e r i p l a n o n e - B , i s r a t h e r c o m p l i c a t e d compared w i t h t h o s e o f o t h e r known s e x pheromones. I t c o u l d be d e d u c e d f r o m c o m p a r i s o n o f i t s NMR, UV, I R and mass s p e c t r a w i t h t h o s e o f an i n a c t i v e rearrangement product ( F i g u r e 12), the carbon s k e l e t o n of which resembles t h a t of p e r i p l a n o n e - B , apart from b e i n g b i c y c l i c i n s t e a d o f h a v i n g a 10-membered . r i n g . T h i s r e a r r a n g e m e n t p r o d u c t , w i t h t h e same e l e m e n t a r y f o r m u l a as p e r i p l a n o n e - A i s r e a d i l y f o r m e d f r o m i t when k e p t i n NMR c a p i l l a r i e s i n c a r b o n d i s u l f i d e o r h e x a n e . On t h e b a s i s o f NMR c o u p l i n g c o n s t a n t s and i t s o t h e r s p e c t r o s c o p i c a l data i t would have the c o n f i g u r a t i o n shown i n F i g u r e 13. I t c a n be s e p a r a t e d f r o m p e r i p l a n o n e - A by GC, u s i n g DEGS o r OV 101 as t h e s t a t i o n a r y p h a s e . S c r u t i n o u s a n a l y s i s o f t h e NMR s p e c t r a o f m i x t u r e s c o n t a i n i n g d e c r e a s i n g amounts o f p e r i p l a n o n e - A w i t h t h e NMR spectrum o f t h e r e a r r a n g e m e n t p r o d u c t y i e l d e d t h e NMR s i g n a l s a t t r i b u t a b l e to p e r i p l a n o n e - A . Assuming t h a t s i g n a l s w i t h s i m i l a r c h e m i c a l s h i f t s and p a t t e r n s i n t h e s p e c t r a o f p e r i p l a n o n e - A and i t s r e a r r a n g e m e n t p r o d u c t a r o s e f r o m i d e n t i c a l p a r t i a l s t r u c t u r e s and subsequent c o m b i n a t i o n of these p a r t i a l s t r u c t u r e s , t o g e t h e r w i t h a c o n s i d e r a t i o n o f c h e m i c a l s h i f t s and c o u p l i n g c o n s t a n t s , l e a d 1

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

Pheromone

Research

on Muskrats

and Insects

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RiTTER E T A L .

Figure 13.

Expected configuration for the rearrangement product of periplanone-A.

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

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TECHNOLOGY

t o t h e s t r u c t u r e f o r p e r i p l a n o n e - A , shown i n F i g u r e 14. A c c o r d i n g t o IUPAC n o m e n c l a t u r e i t i s 7-methylene-4-isopropyl-12-oxat r i c y c l o [4.4.2.0 ]-9-dodecene-2-one. The s t r u c t u r e o f p e r i p l a n o n e - A as w e l l as t h a t o f i t s r e a r rangement p r o d u c t s t i l l r e q u i r e s c o n f i r m a t i o n by s y n t h e s i s , b u t a l l t h e i r s p e c t r a l d a t a a r e i n c o m p l e t e agreement w i t h t h e p r o posed s t r u c t u r e s . A paper i n which a l l these d e t a i l s are g i v e n i s i n press (40). P e r i p l a n o n e - A and p e r i p l a n o n e - B h a v e b e e n f o u n d t o o c c u r i n a r a t i o o f 1:10 i n f a e c a l m a t e r i a l o f P e r i p l a n e t a a m e r i c a n a , b u t o n l y p e r i p l a n o n e - B has b e e n f o u n d i n i n t e s t i n a l t r a c t s . T h i s c o u l d s u g g e s t t h a t p e r i p l a n o n e - B i s a g e n u i n e s e x pheromone, w h e r e a s p e r i p l a n o n e - A c o u l d be a b i o l o g i c a l l y a c t i v e t r a n s f o r m a t i o n p r o d u c t , w h i c h i n t u r n c a n i s o m e r i z e i n t o a more s t a b l e b u t i n a c t i v e compound. We h a v e g i v e n h y p o t h e t i c a l schemes f o r s u c h a t r a n s f o r m a t i o n elsewhere (32,40). T h i s would i n v o l v e a r e d u c t i o n of the 1(2)-epoxigroup of p e r i p l a n o n e - B , f o l l o w e d by a t r a n s a n n u l a r r e a c t i o n o f t h e o t h e r e p o x i g r o u p ( t h e e x o - e p o x i d e a t C i r j ) w i t h t h e t r a n s - d o u b l e bond o f a h y p o t h e t i c a l i n t e r m e d i a t e at C , which would y i e l d p e r i p l a none-A. V i a another h y p o t h e t i c a l i n t e r m e d i a t e , the 5 - c i s isomer, p e r i p l a n o n e - A c o u l d t h e n be t r a n s f o r m e d i n t o a s t a b l e , b u t i n a c t i v e compound ( F i g u r e 1 5 ) . R e c e n t l y e l e c t r o p h y s i o l o g i c a l e x p e r i m e n t s by S a s z h a v e y i e l d e d r e s u l t s which would i n d i c a t e t h a t not o n l y p e r i p l a n o n e - B , b u t a l s o p e r i p l a n o n e - A c o u l d be a g e n u i n e pheromone. W i t h s i n g l e c e l l r e c o r d i n g t e c h n i q u e s he d e m o n s t r a t e d t h e p r e s e n c e o f many o l f a c t o r y h a i r s on t h e a n t e n n a e o f P e r i p l a n e t a a m e r i c a n a t h a t w e r e v e r y s e n s i t i v e t o p e r i p l a n o n e - A , whereas o t h e r s were s e n s i t i v e f o r periplanone-B (41). A l t h o u g h p e r i p l a n o n e - A i s a v e r y p o t e n t s e x pheromone, i t s p r a c t i c a l a p p l i c a t i o n m i g h t meet more d i f f i c u l t i e s t h a n t h a t o f p e r i p l a n o n e - B and w o u l d r e q u i r e a s o l u t i o n o f t h e p r o b l e m s r e l a t e d to i t s i n s t a b i l i t y . We w i s h t o a c k n o w l e d g e t h e c o n t r i b u t i o n o f W.J. N o o i j e n t o t h e i s o l a t i o n and o f P . E . J . V e r w i e l t o t h e NMR a n a l y s e s o f p e r i planone-A.

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1 , 5

5

The

Sex Pheromone o f t h e B e e t Armyworm, S p o d o p t e r a

exigua

The b e e t armyworm, S p o d o p t e r a e x i g u a , i s a r a t h e r r e c e n t p e s t i n H o l l a n d , where i t i s now c a l l e d t h e F l o r i d a moth. A f t e r i t was a c c i d e n t a l l y i n t r o d u c e d i n t o t h e N e t h e r l a n d s i n 1976, i t i m m e d i a t e l y became a g r a v e p e s t i n g r e e n h o u s e s , m a i n l y f o r chrysanthemums and g e r b e r a e , b u t t o a l e s s e r e x t e n t a l s o f o r e g g - p l a n t s . As a p p l i c a t i o n o f i n s e c t i c i d e s s u c h as s y n t h e t i c p y r e t h r o i d s , i n i t i a l l y e f f e c t i v e , s o o n p r o v e d t o have become i n a d e q u a t e , o t h e r methods w e r e n e e d e d , and pheromones w e r e i n v e s t i g a t e d as p o s s i b l e alternatives.

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

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

Figure 15.

Hypothetical scheme for the transformation of periplanone-B into periplanone-A of periplanone-A into the stable, biologically inactive product.

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and

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126

INSECT P H E R O M O N E

TECHNOLOGY

B r a d y and G a n y a r d i d e n t i f i e d (Z,E)-9,12-tetradecadienyl a c e t a t e i n t h i s moth ( 4 2 ) , b u t t r a p p i n g e x p e r i m e n t s w i t h t h i s com­ pound, a l o n e o r i n c o m b i n a t i o n w i t h ( Z ) - 9 - t e t r a d e c e n y l a c e t a t e were u n s u c c e s s f u l (43,44). A j o i n t e f f o r t t o r e i n v e s t i g a t e t h i s p r o b l e m was t h e r e f o r e s t a r t e d by r e s e a r c h teams i n D e l f t and Wageningen. F r a c t i o n s obtained from abdominal t i p s , e x c i s e d glands or t r a p p e d a i r v o l a t i l e s o b t a i n e d f r o m v i r g i n f e m a l e s w e r e t e s t e d by electroantennography and a b e h a v i o u r a l b i o a s s a y (Van d e r K r a a n , p u b l i c a t i o n i n p r e p a r a t i o n ) . The l a t t e r u s e d w i n d t u n n e l s w i t h f u n n e l s u p w i n d and a common chamber downwind. T e s t s a m p l e s w e r e p l a c e d i n t h e f u n n e l s , and t h e b e h a v i o u r o f m a l e m o t h s , r e l e a s e d i n t h e m i d d l e o f t h e t u n n e l s , as w e l l as t h e numbers t r a p p e d i n the f u n n e l s , were examined. Of 150 m o d e l compounds s c r e e n e d by t h e EAG t e c h n i q u e , o n l y t h e ( Z , E ) - 9 , 1 2 - 1 4 : A c i s o l a t e d by B r a d y and G a n y a r d gave a c l e a r p o s i t i v e response. The b e h a v i o u r a l a s s a y o f f r a c t i o n s e l u t e d f r o m s i l i c a g e l w i t h , r e s p e c t i v e l y , h e x a n e , 10% e t h e r i n h e x a n e , 50% e t h e r i n h e x a n e and e t h e r , i n d i c a t e d t h a t t h e a c t i v i t y was c o n f i n e d t o t h e f r a c t i o n c o n t a i n i n g Cii+ a c e t a t e s ( t h e 10% e t h e r f r a c t i o n ) . Combi­ n a t i o n w i t h other f r a c t i o n s d i d not i n c r e a s e the a c t i v i t y . A n a l y s e s by mass s p e c t r o m e t r y , o z o n o l y s i s and r e t e n t i o n i n d i c e s r e v e a l e d t h e p r e s e n c e o f t h e ( Z , E ) - 9 , 1 2 and t h e ( Z ) - 9 com­ pounds m e n t i o n e d e a r l i e r , b u t , i n a d d i t i o n , a l s o o f t h e ( Z , Z ) 9,12 d i - u n s a t u r a t e d , t h e (Z)-11 m o n o u n s a t u r a t e d and t h e s a t u r a t e d Cii+ a c e t a t e s . The d e t a i l s o f t h e a n a l y s e s and t h e d i f f e r e n t r a t i o s f o u n d i n a b d o m i n a l t i p s , e x c i s e d g l a n d s and a i r v o l a t i l e s a r e given i n a recent communication (45). The b e h a v i o u r a l a s s a y i n d i c a t e d t h a t t h e ( Z , E ) - 9 , 1 2 and t h e ( Z ) - 9 components a p p e a r e d t o be n e c e s s a r y f o r u p w i n d s e a r c h b e h a v i o u r , w h i l e t h e ( Z , Z ) - 9 , 1 2 compound i s i m p o r t a n t f o r s h o r t r a n g e c o u r t s h i p b e h a v i o u r , l i k e h a i r p e n c i l d i s p l a y and c o p u l a t i o n attempts. F i e l d e x p e r i m e n t s w e r e c a r r i e d o u t by T.C. B a k e r n e a r R i v e r ­ s i d e i n C a l i f o r n i a , who u s e d P h e r o c o n - 2 s t i c k y t r a p s and p o l y ­ e t h y l e n e c a p s as d i s p e n s e r s . The p r e l i m i n a r y r e s u l t s show t h a t t r a p s w i t h m i x t u r e s o f t h e f o u r u n s a t u r a t e d a c e t a t e s c o l l e c t e d as an a v e r a g e s l i g h t l y more m a l e s t h a n t r a p s w i t h l i v e f e m a l e s d i d . R e m a r k a b l y , m i x t u r e s o f t h e two compounds f o u n d t o be i n e f f e c t i v e by M i t c h e l l and D o o l i t t l e (44) c a u g h t o n l y s l i g h t l y f e w e r m a l e s t h a n t h e s e two l i v e v i r g i n females d i d . W h i l e our most r e c e n t c o m m u n i c a t i o n was i n p r e s s (45) , a p u b l i c a t i o n on t h e same s u b j e c t by T u m l i n s o n , M i t c h e l l and S o n n e t a p p e a r e d ( 4 6 ) . They i s o l a t e d 11 compounds f r o m f e m a l e S p o d o p t e r a e x i g u a , but t h e i r f i e l d t e s t s demonstrated t h a t a m i x t u r e of o n l y two o f them, (Ζ,E)-9,12-tetradecadienyl a c e t a t e and t h e f r e e a l c o h o l , ( Z ) - 9 - t e t r a d e c e n o l , i n a r a t i o o f 5:4, w e r e needed f o r a t t r a c t a n c y . Such a m i x t u r e was e q u a l i n a c t i v i t y t o l i v e f e m a l e s ,

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

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5.

RiTTER E T A L .

Pheromone

Research

on

Muskrats

and

Insects

127

t o t h e t o t a l h e x a n e wash o f f e m a l e s and t o a m i x t u r e o f a l l 11 compounds i n a t t r a c t i n g w i l d m a l e s i n t h e f i e l d . To o b t a i n a t t r a c t i o n c o m p a r a b l e t o t h a t o f l i v i n g f e m a l e s , the a u t h o r s u s e d about 4 5 mg o f t h e i r m i x t u r e i n p o l y e t h y l e n e v i a l s , w h i c h i n o u r o p i n i o n , i s an e x c e s s i v e l y h i g h d o s e . We a l w a y s u s e d d o s e s b e l o w t h e 1 mg l e v e l . T a b l e I I I compares t h e r e s u l t s o b t a i n e d by M i t c h e l l and D o o l i t t l e i n 1 9 7 6 ( 4 4 ) , by T u m l i n s o n e t a l . i n 1 9 8 1 ( 4 5 ) and by P e r s o o n s e t a l . ( 4 6 7 7 I t l i s t s t h e 1 1 compounds f o u n d by T u m l i n s o n e t a l . . Of t h e f i v e a c e t a t e s w h i c h we i n v e s t i g a t e d , f o u r w e r e a l s o f o u n d by t h e o t h e r g r o u p . The r e s u l t s o f t h e f i e l d t e s t s d i f f e r w i d e l y . Whereas M i t c h e l l and D o o l i t t l e f o u n d no a t t r a c t a n c y i n t h e two-component m i x t u r e , B a k e r s ' f i e l d t e s t s f o u n d a s i m i l a r m i x t u r e t o be a l m o s t as a t t r a c t i v e as l i v e females. V e r y r e c e n t l y , B a k e r compared t h e two-component m i x t u r e o f Tumlinson e t a l . w i t h our four-component m i x t u r e i n f i e l d t e s t s n e a r R i v e r s i d e . A l t h o u g h , due t o low p o p u l a t i o n d e n s i t i e s , t h e c a t c h e s were r a t h e r poor, t h e r e s u l t s are c l e a r l y i n f a v o u r o f the f o u r - c o m p o n e n t m i x t u r e ( T a b l e I V ) . We c o n s i d e r a l l t h e s e f i e l d t e s t s s t i l l t o be p r e l i m i n a r y . They w i l l h a v e t o be r e p e a t e d on a l a r g e r s c a l e and i n d i f f e r e n t l o c a t i o n s and c o u n t r i e s b e f o r e a c o m p l e t e p i c t u r e c a n be g a i n e d . The work on S p o d o p t e r a e x i g u a i n H o l l a n d was done i n c o l l a b o r a t i o n w i t h W.J. N o o i j e n o f t h e D e l f t group and C. v a n d e r K r a a n and S. V o e r m a n o f t h e I n s t i t u t e f o r P e s t i c i d e R e s e a r c h i n Wageningen. We a l s o g r a t e f u l l y a c k n o w l e d g e t h e f i e l d t e s t s by T.C. Baker- i n R i v e r s i d e and t h e s u g g e s t i o n s and c r i t i c a l comments by A.K. M i n k s of t h e I n s t i t u t e f o r P l a n t P r o t e c t i o n i n Wageningen.

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

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TECHNOLOGY

Table I I I RESPONSE OF WILD SPODOPTERA EXIGUA MALES TO SYNTHETIC PHEROMONE IN POLYETHYLENE CAPS M i t c h e l l and D o o l i t t l e 1976

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mg 14:Ac (Z)-7-14:Ac (E)-9-14:Ac (Z)-9-14:Ac (Z)-11-14:Ac (Z,E)-9,12-14:Ac (Z,Z)-9,12-14:Ac 14:OH (E)-9-14:OH (Z)-9-14:OH (Z,E)-9,12-14:OH (Z,Z)-9,12-14:OH χ no. c r / t r a p / n i g h t

mg

+

3

5

+

7

5

0.0

3 ?

Tumlinson e t a l . 1981

Persoons e t a l . 1981

μΐ

μg

μΐ

4?

+ + + + 12.5

19.7

(+) + 450 300 + 45 + 450 600 +22.5

26.7 12.0

8.5 7.8 8.0

+ compound d e t e c t e d

Table IV RESPONSE OF A LOW POPULATION OF WILD SPODOPTERA EXIGUA MALES TO SYNTHETIC PHEROMONE I N POLYETHYLENE CAPS. COMPARATIVE FIELD TEST OF "TUMLINSON AND "PERSOONS" MIXTURES, TESTED BY BAKER 11

Persoons

Tumlinson

(Z)-9-14:Ac (Z)-11-14:Ac (Z,E)-9,12-14:Ac (Z,Z)-9,12-14:Ac (Z)-9-14:0H

500

5000

400

4000

χ no. d'/trap/night

0.4

0.0

2?

+

+ 25 25 + + + + 20. 20 + 10 +

0.0 5.3

pg

μ8

μ8

600 60 400 20

200 20 200 10

1.8

2.0

1000 100 750 37.5 1 .5

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

5.

RITTER E T A L .

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Literature

Pheromone

Research

on Muskrats and Insects

129

cited

1. Mykytowycz, R., in: Ritter, F.J., Ed.; "Chemical Ecology: Odour Communication in A n i m a l s " ; Elsevier: Amsterdam, 1979; pp. 105-115. 2. Beauchamp, G . K . ; Doty, R.L.; Moulton, D . G . ; Mugford, R . A . J. Chem. E c o l . 1979, 5, 301-305. 3. K a t z , R.A.; Shorey, H . H . J. Chem. E c o l . 1979, 5, 299-301. 4. Rutowski, R . L . J. Chem. E c o l . 1981, 7, 481-484. 5. C l a u s , R. "Pheromone b e i Säugetieren unter besonderer Berücks i c h t i g u n g des Ebergeruchstoffes und s e i n e r Beziehung zu anderen Hodensteroiden", Paul Parey: Hamburg, 1979. 6. M ü l l e r - S c h w a r z e , D.; M o z e l l , M . M . , E d s . ; "Chemical S i g n a l s in V e r t e b r a t e s " ; Plenum: New York, 1977. 7. M ü l l e r - S c h w a r z e , D.; Silverstein, R . M . , E d s . ; "Chemical S i g ­ n a l s . Vertebrates and Aquatic I n v e r t e b r a t e s " ; Plenum: New Y o r k , 1980. 8. Ritter, F.J., Ed.; "Chemical Ecology: Odour Communication i n A n i m a l s " ; E l s e v i e r : Amsterdam, 1979. 9. Shorey, H . H . "Animal Communication by Pheromones"; Academic P r e s s : New Y o r k , 1978. 10. B i r c h , M . C . , Ed.; "Pheromones"; E l s e v i e r : New Y o r k , 1974. 11. C h r i s t i a n s e n , Ε . ; Døving, K., in: Hanson, L.; Nilson, B., E d s . ; " B i o c o n t r o l of Rodents"; Swed. N a t l . Res. C o u n c i l : Stockholm, 1975; 221-227. 12. Marsh, R.E.; Howard, W.E. Pest C o n t r o l 1979, 7, 22-23. 13. Stacewycz-Sapuntzakis, M . ; Gawienowski, A . M . J. Chem. E c o l . 1977, 3, 411-417. 14. Christian, J.J. Am. J. P h y s i o l . 1955, 182, 292-300. 15. D a v i s , D.E.; Christian, J.J. Nav. Med. Res. I n s t . Res. Rep. 1957, 15, p 311. 16. Bronson, F.H.; Caroom, D. J. Reprod. Fertil. 1971, 25, 279-282. 17. McKinney, T . D . ; Christian, J.J. P r o c . Soc. exp. Biol. Med. 1970, 134, 291-293. 18. M ü l l e r - S c h w a r z e , D., in: E i s e n b e r g , J.F.; K l e i m a n , D.G., E d s . ; "The Behavior of Mammals"; Amer. Soc. Mammalogists P u b l . ( i n press). 19. Hoffmann, M. Z. angew. Z o o l . 1976, 63, 187-239. 20. W i l l i a m s , R . M . J. Wildlife Management 1951, 15, 117-118. 21. Brüggemann, I.E.M.; Ritter, F.J.; Gut, J. "Onderzoek naar s i g n a a l s t o f f e n voor de muskusrat"; 1981; TNO report CL 81/24. 22. Akkermann, R. Z. angew. Z o o l . 1975, 62, 281-338. 23. M ü l l e r - S c h w a r z e , D.; Heckman, S. J. Chem. E c o l . 1980, 6, 81-95. 24. Stevens, P.G.; E r i c k s o n , J.L.E. J . Am. Chem. Soc. 1942, 64, 144-147. 25. Stevens, P . G . J. Am. Chem. Soc. 1945, 67, 907-909. 26. Van Dorp, D.A.; K l o k , R . ; Nugteren, D . H . Rec. Trav. Chim. Pays-Bas 1973, 915-928.

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38. 39. 40. 41. 42. 43. 44. 45.

46.

INSECT P H E R O M O N E

TECHNOLOGY

E r r i n g t o n , P.L. "Muskrat P o p u l a t i o n s " ; Iowa State U n i v . P r e s s : Ames, 1963. Ritter, F.J.; Persoons, C.J. Neth. J. Z o o l . 1975, 261-275. Persoons, C.J.; Ritter, F.J.; Lichtendonk, W . J . P r o c . Kon. Ned. Akad. Wetensch. S e r i e s C 1974, 77, 201-204. Jacobson, M.; Beroza, M.; Yamamoto, R . T . Science 1963, 139, 48-49. Jacobson, M.; Beroza, M. Science 1965, 147, p 749. Persoons, C.J.; Ritter, F.J., in: Ritter, F.J., Ed.; "Chemical Ecology: Odour Communication i n A n i m a l s " ; Elsevier: Amsterdam, 1979, pp. 225-236. Persoons, C.J.; V e r w i e l , P.E.J.; Talman, E.; Ritter, F.J. J. Chem. E c o l . 1979, 5, 221-236. Talman, E.; V e r w i e l , P.E.J.; Ritter, F.J.; Persoons, C.J. Israel J. Chem. 1978, 17, 227-235. Persoons, C.J. " S t r u c t u r e e l u c i d a t i o n of some i n s e c t phero­ mones; a c o n t r i b u t i o n to the development of s e l e c t i v e pest c o n t r o l agents"; T h e s i s , Wageningen, 1977. Ritter, F.J.; Brüggemann, I.E.M.; V e r w i e l , P.E.J.; Talman, E.; S t e i n , F.J.; Persoons, C.J., in: K l o z a , Μ., Ed. in c h i e f ; " R e g u l a t i o n of Insect Development and Behaviour"; Wroclaw Techn. U n i v . P r e s s : Wroclaw 1981; pp. 871-882. Ritter, F.J.; Brüggemann-Rotgans, I.E.M.; V e r w i e l , P.E.J.; Persoons, C.J.; Talman, E . Tetrahedron L e t t e r s 1977 (30), 2617-2618. Adams, M . A . ; N a k a n i s h i , K.; Still, W . C . ; A r n o l d , E.V.; C l a r d y , J.; Persoons, C.J. J. Am. Chem. Soc. 1979, 101, 2495-2498. Still, W.C. J. Am. Chem. Soc. 1979, 101, 2493-2495. Persoons, C.J.; V e r w i e l , P.E.J.; Ritter, F.J.; Nooijen, W.J. J. Chem. E c o l . ( i n p r e s s ) . Sasz, H., in: Van der S t a r r e , H., Ed.; " O l f a c t i o n and Taste VIII"; I n t . R e t r i e v a l Ltd.: London, 1980; p 194. Brady, U . W . ; Ganyard, M . C . Ann. E n t . Soc. Am. 1972, 65, 898-899. Campion, D . G . Meded. F a c . Landbouw Gent 1975, 40, 283-292. Mitchell, E . R . ; Doolittle, R . E . J. Econ. Entomol. 1976, 69, 324-326. Persoons, C.J.; Van der Kraan, C.; N o o i j e n , W.J.; Ritter, F.J.; Voerman, S . ; Baker, T . C . Entomol. exp. et a p p l . 1981, 30, 98-99. Tumlinson, J.H.; Mitchell, E . R . ; Sonnet, P . E . J. E n v i r o n . S c i H e a l t h 1981, A16, 189-200.

RECEIVED February 24,

1982.

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