Periplaneta americana pheromone

Based on the successful series of transformations summarized in Scheme 1, Schreiber and Santini developed an efficient and elegant synthesis of periplanone B (1),8 the potent sex pheromone of the American cockroach, Periplaneta americana. This work constitutes the second total synthesis of periplanone B, and it was reported approximately five years after the landmark periplanone B synthesis by W.C. Still9 (see Chapter 13). As in the first synthesis by Still, Schreiber s approach to periplanone B takes full advantage of the facility with which functionalized 5-cyclodecen-l-one systems can be constructed via anionic oxy-Cope rearrangements of readily available divinylcyclohexanols.5 7 In addition, both syntheses of periplanone B masterfully use the conformational preferences of cyclo-decanoid frameworks to control the stereo- and regiochemical course of reactions carried out on the periphery of such ring systems.10... 

Abed, D., Cheviet, P, Farine, J. P, Bonnard, O., Fe Quere, J. F. and Brossut, R. (1993c). Calling behaviour of female Periplaneta americana behavioural analysis and identification of the pheromone source. Journal of Insect Physiology 39 709-720. Adams, M. A., Nakanishi, K Still, W. C Arnold, E. V., Clardy, J. and Persoons, C. J. 

Bodenstein, W. G. (1970). Distribution of female sex pheromone in the gut of Periplaneta americana (Orthoptera Blattidae). Annals of the Entomological Society of America 63 336-337. 

Hawkins, W. A. (1978). Effects of sex pheromone on locomotion in the male American cockroach, Periplaneta americana. Journal of Chemical Ecology 4 149-160. 

Hosl, M. (1990). Pheromone-sensitive neurons in the deutocerebrum of Periplaneta americana receptive fields on the antenna. Journal of Comparative Physiology A 167 321-327. 

Isolation procedure of the sex pheromone of the American cockroach, Periplaneta americana L. Applied Entomology and Zoology 11 373-375. 

Okada, K., Mori, M., Shimazaki, K. and Chuman, T. (1990b). Behavioral responses of male Periplaneta americana L. to female sex pheromone components, periplanone-A and periplanone-B. Journal of Chemical Ecology 16 2605-2614. 

W. J. (1976). Sex pheromones of the American cockroach, Periplaneta americana a tentative structure of periplanone-B. Tetrahedron Letters 24 2055-2058. 

Rust, M. K. (1976). Quantitative analysis of male responses released by female sex pheromone in Periplaneta americana. Animal Behaviour 24 681-685. 

Production, release and effectiveness of two female sex pheromone components of Periplaneta americana. Journal of Comparative Physiology A 152 309-317. 

Seelinger, G. and Gagel, S. (1985). On the function of sex pheromone components in Periplaneta americana improved odour source localization with periplanone-A. 

Seelinger, G. and Schuderer, B. (1985). Release of male courtship display in Periplaneta americana evidence for female contact sex pheromone. Animal Behaviour 33 599-607. 

Silverman, J. M. (1977). Patterns of response to sex pheromone by young and mature adult male cockroaches, Periplaneta americana. Journal of Insect Physiology 23 1015-1019. 

Periplaneta americana to periplanone B, a synthetic component of the female sex pheromone. Journal of Chemical Ecology 7 969-979. 

Waldow, U. and Sass, H. (1984). The attractivity of the female sex pheromone of Periplaneta americana and its components for conspeciflc males and males of Periplaneta australasiae in the field. Journal of Chemical Ecology 10 997-1006. 

Zhukovskaya, M. I. (1995). Circadian rhythm of sex pheromone perception in the male American cockroach, Periplaneta americana L. Journal of Insect Physiology 41 941-946. 

The //-alkanes usually range in chain length from 21 to 31 or 33 carbons. Hydrocarbons with fewer than 20 carbons commonly occur as pheromones, defensive compounds and intermediates to pheromones and defensive compounds, but their volatility makes them unsuited to function as cuticular components, n-Alkanes have been found on almost every insect species analyzed, and can range from less than one percent of the total hydrocarbons, as in tsetse flies (Nelson and Carlson, 1986 Nelson et al., 1988) to almost all of the hydrocarbon fraction, as in the adult tenebrionid beetle, Eurychora sp. (Lockey, 1985). Depending upon the species, they can consist of essentially only one major component, such as n-pentacosane in the American cockroach, Periplaneta americana (Jackson, 1972) to a series of //-alkanes, such as the series from C23 to C33 in the housefly, Musca domes-tica (Nelson et al., 1981), with trace amounts to C37 (Mpuru et al., 2001). In all cases, the odd-numbered alkanes predominate, due to their formation from mostly two carbon units followed by a decarboxylation (Blomquist, Chapter 3, this book). Small amounts of even-numbered carbon chain //-alkanes often occur, and presumably arise from chain initiation with a propionyl-CoA rather than an acetyl-CoA. Occasionally, gas chromatographic analyses reveal similar amounts of even-numbered chain //-alkanes and odd-numbered chain components. This is a red flag that the samples must be checked for contamination. 

The names periplanone-A and periplanone-B were first coined by Ritter and Persoons in 1974 at the International Congress of Pesticide Chemistry in Helsinki, in a general paper on pheromone research in the Netherlands. In this paper the isolation of a number of pheromones were described, including the two peripla-nones, both sex pheromones, present in the excreta of the female American cockroach, Periplaneta americana. The elementary formulae of these two sesquiterpenoids, C15H20O2 and C15H20O3, were given and the carbon skeleton of periplanone-B, a germacrane derivative, was revealed. Unfortunately, we were informed, one year after the... 

Periplanone-A and periplanone-B have been found to occur in a ratio of 1 10 in faecal material of Periplaneta americana, but only periplanone-B has been found in intestinal tracts. This could suggest that periplanone-B is a genuine sex pheromone, whereas periplanone-A could be a biologically active transformation product, which in turn can isomerize into a more stable but inactive compound. We have given hypothetical schemes for such a transformation elsewhere (32,40). 

Recently electrophysiological experiments by Sasz have yielded results which would indicate that not only periplanone-B, but also periplanone-A could be a genuine pheromone. With single cell recording techniques he demonstrated the presence of many olfactory hairs on the antennae of Periplaneta americana that were very sensitive to periplanone-A, whereas others were sensitive for periplanone-B (41). 

From 1976 to 1978, tremendous efforts were spent on the isolation of a major component (in a pure form) of the sex pheromone of the female cockroach, Periplaneta americana. The potency of the compound isolated, periplanone B, was truly amazing (threshold limits of 10 pg). It was considered to be a promising agent to control this pest. However, only trace amounts were isolated from natural sources (a total of 0.2 mg isolated from 75 000 specimens). Even the use of modern methods of instrumental analysis did not lead to the elucidation of its complete structure. With the help of these methods it was possible only to ascertain the basic structural features, as shown in formula 59a (Scheme 1.16). The problem of its stereochemistry remained unanswered. This most difficult part of the problem was finally solved only after a total synthesis of three of four possible geometrical isomers of periplanone Comparison of the spectral parameters of synthetic samples with those of the natural periplanone B determined the stereochemistry as shown in structure 59b. A minor component of the same pheromone, periplanone A, was available in even... 

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