American cockroach pheromone

In 1986 Hauptmann in Germany attempted the reisolation of the American cockroach pheromone, and found a potent pheromonally active compound with spectral properties different from those reported for periplanone-A of Persoons. Hauptmann clarified the structure of his compound as 79, and named it periplanone-A. 

In October 1987, there was a pheromone conference in Angers, France, where I was able to listen to the discussion between Drs. Hauptmann and Persoons. I noticed what Hauptmann said to Persoons, You executed the final purification of your periplanone-A by gas chromatography, but I did it by HPLC. It occurred to me immediately to regard Persoons periplanone-A as the product of thermal rearrangement of Hauptmann s periplanone-A (79). During the conference I recognized that many people were eager to know the true structure of Persoons periplanone-A. I therefore decided to solve the problem. 

We secured about 250 mg of the crystalline and naturally occurring enantiomer (—)-79, and examined its pyrolysis. GC-MS analysis of (—)-79 at the column temperature of 180 °C gave a product with a mass spectrum identical to that reported for Persoons periplanone-A. Having been encouraged by the preliminary GC-MS experiment, about 80 mg of (—)-79 was subjected to thermal decomposition at 220 °C on a 3% OV-17 column, which had been employed by Persoons for his purification experiment. After TLC purification of the thermolysis product, we obtained an oil in 71% yield based on (—)-79, whose IR and H-NMR spectra were identical with those reported for Persoons periplanone-A. It was therefore the pyrolysis product of (—)-79, although its structure was still unknown. 

The biologically inactive ketone D is now called isoperiplanone-A.37 Use of preparative GC by Persoons in the final purification of periplanone-A (—)-79 caused its thermal decomposition to D, and confused his 

In this case, the misassigned stereochemistry of the pheromone of G. cornutus caused a considerable problem for us, and the correct structure could be assigned finally by synthesis. 

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Bykhovskaia, M. B. and Zhorov, B. S. (1996). Atomic model of the recognition site of the American cockroach pheromone receptor. Journal of Chemical Ecology 22 869-883. 

Germacrene D (67) provides an active mimic of the American cockroach pheromone, periplanone B (68) (Bowers, 1985). 

In 1952, it was reported that a constituent of excretions from female American cockroaches of the species Periplaneta ameri-cana is an extraordinarily potent sex pheromone.1 Early attempts to isolate and characterize the active compounds were hampered because individual cockroaches store only minute amounts of the pheromone ( 1 pg), and a full 25 years elapsed before Persoons et al. reported the isolation of two extremely active compounds, periplanones A and B.2 The latter substance is present in larger relative measure and its germacranoid structure (1, without stereochemistry) was tentatively assigned on the basis of spectroscopic data. Thus, in 1976, the constitution of periplanone B was known but there remained a stereochemical problem of a rather serious nature. Roughly three years intervened between the report of the gross structure of periplanone B and the first total synthesis of this substance by W. C. Still at Columbia.3... 

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... 

FIGURE 2 Pheromone structures of the American cockroach (periplanone B), the brownbanded cockroach (supellapyrone), bark beetles (ipsdienol enantiomers), and the cabbage looper moth (six acetates). 

Ritter, F. J., Briiggemann, I. E. M., Gut, J., and Persoons, C. J. (1982). Recent pheromone research in the Netherlands on muskrats and some insects pests introduced from America into Europe the muskrat, Odatra zibethicus, the American cockroach, Peri-planeta americana, and the beet army worm, Spodoptera exigua. American Chemical Society Symposium Series 190,107-130. 

Sex pheromone of the American cockroach absolute configuration of periplanone-B. Journal of the American Chemical Society 101 2495-2498. 

Appel, A. G. and Rust, M. K. (1983). Temperature-mediated sex pheromone production and response of the American cockroach. Journal of Insect Physiology 29 301-305. Barth, R. H., Jr (1964). The mating behavior of Byrsotria fumigata (Guerin) (Blaberidae, Blaberinae). Behaviour 23 1-30. 

Bell, W. J. and Kramer, E. (1980). Sex pheromone-stimulated orientation of the American cockroach on a servosphere apparatus. Journal of Chemical Ecology 6 287-295. 

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

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

Manabe, S. and Nishino, C. (1983). Sex pheromonal activity of (+)-bornyl acetate and related compounds to the American cockroach. Journal of Chemical Ecology 9 433 148. 

Manabe, S., Nishino, C. and Matsushita, K. (1985). Studies on relationship between activity and electron density on carbonyl oxygen in sex pheromone mimics of the American cockroach, part XI. Journal of Chemical Ecology 11 1275-1287. 

Nishino, C. and Kimura, R. (1981). Isolation of sex pheromone mimic of the American cockroach by monitoring with male/female ratio in electroantennogram. Journal of Insect Physiology 27 305-311. 

Nishino, C. and Kuwahara, K. (1983). Threshold dose values for sex pheromones of the American cockroach in electroantennogram and behavioral responses. Comparative Biochemistry and Physiology A14 909-914. 

Nishino, C., Takayanagi, H. and Manabe, S. (1982). Comparison of sex pheromonal activity on the American cockroach between acetates and propionates of verbenyl type alcohols. Agricultural and Biological Chemistry 46 2781-2785. 

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

Persoons, C. J., Verwiel, P. E. J., Ritter, F. J. and Nooyen, W. J. (1982). Studies on sex pheromone of American cockroach, with emphasis on structure elucidation of periplanone-A. Journal of Chemical Ecology 8 439-451. 

Still, W. C. (1979). ( )-Periplanone-B. Total synthesis and structure of the sex excitant pheromone of the American cockroach. Journal of the American Chemical Society 101 2493-2495. 

Washio, H., Nishino, C. and Bowers, W. S. (1976). Antennal receptor response to sex pheromone mimics in the American cockroach. Nature 262 487 189. 

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. 

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