Pheromones, insect sex

Jallon J-M, Wicker-Thomas C (2003) In Blomquist GJ.Vogt RG (eds) Insect sex pheromone biochemistry and molecular biology. Academic Press... 

The predators discussed up to this point search for prey by using their ability to perceive certain chemical clues. Some unusual predators have evolved the ability to attract their prey with scents that mimic the odor of a valuable resource (see reviews of chemical mimicry in refs. 9 and 39). Several groups of spiders lure male insect prey with scents that mimic the sex pheromone scents of females of the prey species (see reviews in refs. 9,13,40, and 41). To the best of our knowledge, these spiders are the only predators that mimic sex pheromones. However, the spiders share some similarities with the diverse orchids which mimic insect sex pheromones to lure pollinators (9, 42, 43) and with the predatory fireflies, which practice elaborate mimicry of visual sexual signals to lure their prey heterospecific male fireflies (44). 

McDonough, L. M., Brown, D. F., and Aller, W. C. (1989). Insect sex pheromones. Effect of temperature on evaporation rates of acetates from rubber septa.. Journal of Chemical... 

Apoptosis-inducing brain factors in maturation of an insect sex pheromone gland during differentiation. Differentiation 63 53-58. 

Sharpless epoxidation of (E)-(l,2-dialkyl)vinylsilanols 13, prepared from hydrolysis of ( )-( 1,2-dialkyl )vinyldimethylbutoxysilanes 12, gave silylepoxides 14, which were treated with Et4NF in MeCN to afford epoxides 15 in 62-70% overall yield and 44-70% ee (Scheme 6AA.6).7 The overall transformation can be considered as asymmetric epoxidation of simple internal alkenes. This approach was applied to the synthesis of a naturally occurring insect sex pheromone (+)-disparlure.7... 

A number of insect sex pheromones are long-chain internal olefins or their epoxides and can be prepared via metathesis reactions, for example the reaction of dec-l-ene with pentadec-l-ene to give tricos-9-ene, the cis isomer of which is a sex pheromone of the housefly (Musca domestica)173.174. see ajso Kiipper and Streck175,176. 

Analytical Properties Separation of polyaromatic hydrocarbons and insect sex pheromones Reference 5... 

Shorey H. H. (1974) Environmental and physiological control of insect sex pheromone behavior. In Pheromones, ed. M.C. Birch, pp 62-80. New York, American Elsevier. 

Villet R. H. (1978) Mechanism of insect sex-pheromone sensory transduction role of adenyl cyclase. Comp. Biochem. Physiol. 61C, 389-394. 

Jacobson M. (1972) Insect Sex Pheromones. Academic Press, New York. 

Klun J. A., Chapman O. L., Mattes K. C., Wojtkowski P. W., Beroza M. and Sonnet P. E. (1973) Insect sex pheromones minor amounts of opposite geometrical isomer critical to sex attraction. Science 162, 661-663. 

Acetate functional groups are quite prevalent in insect sex pheromones and have been introduced into a wide variety of alkyl bromides by reaction with sodium acetate in DMF372 or acetic acid371. As is generally the case, the use of PTC allows reaction under milder conditions and significantly improves yields and reduces reaction times. In one example the reaction of alkyl halides with formate anion has given excellent yields of a variety of alkyl formates212. 

The presence of pyrrolizidine alkaloids in arctiid moths that had been reared on Senecio and Crotalaria species has been established by Rothschild et al.4S These alkaloids are stored in the moths, and serve as a deterrent to vertebrate predators and as precursors for insect sex pheromones. A pyrrolizidine alkaloid metabolite from the Cinnabar moth (Tyria jacobaea L.), named callimorphine, has been shown to have the structure (49) on the basis of mass-spectral and degradative evidence.46 The structure (49) was confirmed by synthesis of callimorphine and a diastereo-isomer by treatment of 9-chlororetronecine with the sodium salt of ( )-2-acetoxy-2-methylbutanoic acid. 

Insects commonly use pheromones as chemical signals for species identification orto signal alarm or to advertise for prospective mates. Esters, particularly acetate esters, are some of the most common insect sex pheromones. 

We finish this pair of chapters about pericyclic reactions with a synthesis whose simplicity is outclassed only by its elegance. Periplanone B is a remarkable bis-epoxide that functions as the sex pheromone of the American cockroach. Insect sex pheromones often have economic importance because they can form the key to remarkable effective traps for insect pests. 

In the approximately thirty years since the first identification of an insect sex pheromone (1), interest in the chemistry of these compounds has increased dramatically. This is due both to academic interest and to the use of these compounds for insect monitoring and control. More recently, the biochemistry of these compounds has been studied (2-3). In this paper, we discuss the biosynthesis of a class of these compounds and consider some of the key enzymes involved in the biosynthetic pathway. 

Considerable progress has been made over the past decade in the application of insect sex pheromones to pest control programs. As the commercial applications of pheromones have expanded, the demand for larger quantities of certain of these compounds has increased, but many of the published syntheses cannot readily be carried out on a kilogram scale. 

We have extensively investigated alternative synthetic methods for the preparation of pheromones in high stereochemical purity. In this paper we discuss some of the practical aspects of the larger scale synthesis (lOOg to kilogram quantities) of insect sex pheromones with emphasis on the types of compounds that are of potential use in agriculture. 

Asymmetric syntheses directed toward construction of enantiomers of the western and southern corn root-worm pheromones are described. A brief review of the subject of asymmetric synthesis as it is related to the synthesis of insect sex pheromones is presented. The laboratory s previous research with chiral pheromones is summarized (Japanese beetle, white peach scale, and lesser tea tortrix) before detailing synthetic work on the pheromones of the aforementioned rootworm species. Throughout the course of the synthetic effort, cholesteric stationary phases for GLC have found use. Their superior ability to separate crucial diastereomeric intermediates for synthesis is detailed. 

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