Boll weevil Anthonomus grandis

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]. 

The number one cotton pest in the United States, the boll weevil (Anthonomus grandis Boh.), occurs in Mexico, Costa Rica, Nicaragua, Colombia, and Venezuela and is probably also the number one pest in these countries. 

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. ... 

For example, gossypol, a terpenoid substance, is an allomone that limits herbivory by several lepidopteran species on cotton (Gossypium spp., MalvaceaeK whereas it is a kairomone for the boll weevil, Anthonomus grandis and acts as a feeding stimulant for this insect (3,21,22) ... 

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. 

Taub-Montemayor T. E. and Rankin M. A. (1997) Regulation of vitellogenin synthesis and uptake in the boll weevil, Anthonomus grandis. Physiol. Entomol. 22, 261-268. 

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. 

Graiidisol Cotton boll weevils Anthonomus grandis) Ms Intramolecular diastereoselectiv c alkylation of a-benxencsulfonyi-y-lactones [198J... 

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