Anthonomus grandis pheromone

Attempts to investigate boll weevil (Anthonomus grandis) pheromone biosynthesis have identified isomerization, dehydration, and oxidation of the pheromone alcohols, and anticipated allylic oxidation of myrcene and limonene, but no evidence for the cyclization of acyclic precursors. The aggregation pheromones of bark beetles have been reviewed. Ips calligraphus responds to ipsdienol only in the presence of the c/5-verbenol (32) large additional concentrations of the enantiomer (l/ ,4i ,5/ )-(32) reduce beetle response. 5-(-)-Ipsenol, the pheromone of Ips grandicollis, increases the response of /. avulsus to its own pheromone ipsdienol. ... 

Scheme 54 summarizes Font s synthesis of (+)-grandisol (36), the male pheromone of the cotton boll weevil (Anthonomus grandis) [80]. The key-step is the double [2+2] photocycloaddition of ethylene to bis(a,(3-butenohde) A to give B, which yielded C after glycol cleavage. The recently identified pheromone of the oleander scale (Aspidiotus nerii) possesses a structure similar to that of grandisol (Scheme 54), and its synthesis was reported by Ducrot [81 ] and also by Guerrero [82,83]. 

Mitlin N. and Hedin P. A. (1974) Biosynthesis of grandlure, the pheromone of the boll weevil, Anthonomus grandis, from acetate, mevalonate, and glucose. J. Insect Physiol. 20, 1825-1831. 

Wiygul G., MacGown M. W., Sikorowski P. P. and Wright J. E. (1982) Localization of pheromone in male boll weevils (Anthonomus grandis). Entomol. Exp. Appl. 31, 330-331. 

Dickens J. C. and Mori K. (1989) Receptor chirality and behavioral specificity of the boll weevil, Anthonomus grandis Boh. (Coleoptera Curculionidae), for its pheromone, (+)-grandisol. J. Chem. Ecol. 15, 517-528. 

Hedin P. A., Lindig O. H. and Wiygul G. (1982) Enhancement of boll weevil Anthonomus grandis Boh. (Coleoptera Curculionidae) pheromone biosynthesis with JH III. Experientia 38, 375-376. 

Wiygul G., Dickens J. C. and Smith J. W. (1990) Effect of juvenile hormone HI and beta-bisabolol on pheromone production in fat bodies from male boll weevils, Anthonomus grandis Boheman (Coleoptera Curculionidae). Comp. Biochem. Biophysiol [B] 95, 489 191. 

Sigmatropic rearrangements catalyzed by silver salts have been used in total synthesis. The synthesis of three monoterpene compounds that comprise the pheromone of male boll weevil Anthonomus grandis has been achieved using the silver-carbonate catalyzed rearrangement of an acetoxycyclohexyl acetylene as the key step (Scheme 3.35).56... 

Curculionidae. The boll weevil, Anthonomus grandis, that great despoiler of cotton in the southern U. S., synthesizes a quaternary blend of sex pheromones that have been collectively labeled grandlure. Four compounds that interact synergistically have been identified as (+)-2-(cis-isopropenyl-1-methylcyclobutyl) ethanol (XI), (Z)-2-(3,3-dimethyl cyclohexylidene)ethanol (XII), (Z.)-2-(3,3-dimethylecyclohexylidene)acetaldehyde (XIII), and (Ej-2-(3,3-dimethylcycloh.exylidene)acetaldehyde (XIV) (54). 

Grandisol (8), one of the synergistic mixture of the four compounds (collectively called grandlure ) of sex pheromones of male boll weevil (Anthonomus grandis) has been synthesized by the following two-step procedure (Eq. 7)47). Racemic grandisol... 

The mass spectra of many monoterpenoids have been published. Analysis by gas chromatography of the mixture which constitutes the sex pheromone of the boll weevil Anthonomus grandis Boheman) has been described. It consists of a cyclobutane monoterpenoid (Vol. 1, p. 18), and three 3,3-dimethyl-A -cyclohexane-ethanols and -acetaldehydes. 

C,oH,sO, Mr 154.25, oil, bp, 50-60°C (133 Pa), 22.1° (hexane). Sexual pheromone of the male boll weevil (Anthonomus grandis). G. is also a component of the pheromone system of bark beetles of the genus Pityophthorus. In addition it forms, together with the aldehyde (grandisol, C oH jO, Mr 152.24), the aggregation pheromone of weevils of the genus Pis-sodes. 

The aggregation pheromone grandlure of the male Boll weevil (Anthonomus grandis) (Fig. 8.85) consists of four components. In field trials, the attractive effect of grandlure on both sexes was recognised. [209]... 

WiYGUL and coworkers (775, 176) noted that in the boll weevil Anthonomus grandis the emission of sex pheromone is affected by diet, chemosterilants, bacterial contaminants as well by age, while Wiygul and SiKOROWSKi (f77) demonstrated that enterotoxinB produced by Staphylococcus aureus decreases male sex pheromone production in fat bodies isolated from male boll weevils. 

Wiygul, G., and P.P. Sikorowski The Effect of Glucose and ATP on Sex Pheromone Production in Fat Bodies from Male Boll Weevils Anthonomus grandis Bohe-man (Coleoptera Curculionidae). Comp. Biochem. Physiol. 81 B 1073-1075 (1985). 

The males of the cotton boll weevil Anthonomus grandis, Coleoptera, Plate 6), a serious pest of cotton, produce a sex pheromone to attract females. The pheromone, known as grandlure, consists of a mixture of at least four monoterpenes (Figure 6.7). The males make these compounds from geraniol and nerol (the cw-isomer of geraniol), present in the cotton buds on which they feed. 

The ten farnesylacetone derivatives isolated from Cys-tophora moniliformis are individual insofar as there are several types of carbon skeleton, particularly that of pyro-nane (1,1,2,3-tetramethylcyclohexane). However, the most original compound is probably the one that has the rare cyclobutanic system of grandisol, a sex pheromone of the male boll weevil Anthonomus grandis (Tumlinson et al, 1969). 

As natural products go, insect pheromones have relatively simple structures. This is due in part to the requirement for high volatility and rapid diffusion in air. Identification of these compounds is no easy matter, however, since the amounts produced by an individual are frequently at the nanogram level (or less). Only a decade ago, Tumlinson et al. (38) required 4.5 million boll weevils (Anthonomus grandis) to get enough material for identification. With the improvement in analytical instrumentation and microtechniques, rapid progress in the identification of pheromones has been made in the past few years. Since procedures for identification of pheromones have been reviewed at length (15,27, 34, 39) and lists of identified pheromones have been adequately tabulated elsewhere (15, 21, 40—43), much of the emphasis here will be placed on examples to illustrate the useful techniques. 

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