Queen butterfly pheromone

Queen butterfly pheromone, 79 Queen s substance, 217 Quinine, 80, 501 Quinol acetates, 314-315 QuinoUne, 383, 498, 619, 621 Quinoline—Acetic acid, 501 Quinolineearboxylic acids, 450 p-Quinols, 428-429 Quinomycin, 193 Quinones, 120, 121, 555, 556 Quinonimines, 513... 

Snider and colleagues have developed the sequential ene reaction/thia-[2,3]-Wittig reaction which provide appropriately functionalized product 152 at allylic position on simple alkene 150 in two steps involving intermediate 151 (equation 87) . Thia-[2,3]-Wittig rearrangement was often utilized as a key step of natural product synthesis. Masaki and colleagues have demonstrated that the potassium enolate thia-[2,3]-rearrangement of aUyl sulfide 153 to 154 is useful for the synthesis of terpenoid diol component 155 of the pheromonal secretion of the queen butterfly (equation 88) . 

What kindled our interest in this area of research was the seminal paper by Brower et al. (1965) on the courtship of the queen butterfly, Danaus gilippus, and the motion picture that these investigators made of this behavior. Their data showed clearly that the two brush-like structures, or hairpencils, that the males ordinarily kept tucked away in their abdomen are in fact everted and splayed during courtship, and brushed against the female prior to copulation. Glandular in nature, the hairpencils seemed to function as an aphrodisiac device that effected its action chemically. But the nature of the presumed pheromone and its precise communicative significance remained unknown. 

Myers J. and Brower L. P. (1969) A behavioral analysis of the courtship pheromone receptors of the queen butterfly, Danaus gilippus berenice. J. Insect Physiol. 15, 2117-2130. 

Schneider D. (1983) Kommunikation durch chemische Signale bei Insekten Alte und neue Beispiele von Lepidopteren. Verhandl. Dtsch. Zool. Gesellsch. 1983, 5-16. Schneider D. and Seibt U. (1969) Sex pheromone of the queen butterfly electroantennogram... 

Structural investigations on the sex pheromones of male butterflies have yielded several unique insect exocrine products. The major components in the hair pencils of the danaid Lycorea ceres ceres are cetyl acetate, (Z)-vaccenyl acetate, and 2,3-dihydro-7-methyl pyrrolizin-l-one (XXIV) (103) The dihydropyrrol izi none, as well as ( , )-3,7-dimethyldeca-2,6-dien-l,10-diol, have been identified from the hair pencils of the queen butterfly, Danaus gilippus (104), and the former compound possesses pheromonal activity when evaluated electrophysiologically (105) and behaviorally (106). The hair pencils of the monarch butterfly, Danaus plexippus, have yielded ( ,E)-10-hydroxy-3,7-dimethyl-2,6-deca dienoic acid (107) and (E,15)-3,7-dimethyl-2,6-decadien-l,10-dioic acid (108). On the other hand, the Old World monarch, Danaus chrysippus, contains (E)-3,7-dimethyloct-2-en-l,8-diol as well as the pyrrolizinone (XXIV) (109). Recently,... 

A similar rearrangement was used in a stereoselective synthesis of (if, )-3,7-dimethyT2,6-deca-diene-l,10-diol (pheromone of the queen butterfly) in six steps from gcraniol (Table 3, entry 16)310. Use of 2-methoxy-l,3-butadienes and related compounds (e.g., unsaturated acetals311) allows an iterative Claisen rearrangement by reduction of the resulting enone28,309. 

This method was used in a highly stereoselective synthesis of a pheromone diol (6) of the queen butterfly. The key step involved rearrangement of the acetate (4), obtained in several steps from geraniol, to the acid (5). Lithium aluminum hydride reduction of (5) gave the diol (6). 

Pheromonal Secretion of Monardi and Queen Butterfly.—New synthetic routes have been outlined to the degraded terpenoid compounds (198a) and (198b) isolated from the pheromonal secretion of the Monarch butterfly Danausplexippus) and of the related diol (198c) from the male Queen butterfly Danaus gilippus bermice)P ... 

A synthesis of a Queen substance [35] and of the pheromone of Monarch butterfly [36] are additional examples of applications of this particularly useful process. 

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