Lycorea ceres

Danaidone (25), which was first isolated from Lycorea ceres ceres (55) and Danaus gilippus berenice 59) by J. Meinwald et al., has been shown to act as an aphrodisiac pheromone necessary for successful courtship in D. gilippus berenice (57) and in D. chrysippus (56), since danaidone-lacking males have reduced courtship success 57,60). It seems likely that a similar role will be found for the closely related aldehydes, hydroxydanaidal (26) and danaidal (27). 

Lepidoptera Nymphalidae (butterflies) Danainae Lycorea ceres ceres M H 25 55,148a... 

Figure 12.1 A Lycorea ceres from Trinidad. B Male of same, with hairpencils everted. (Photos by T. Eisner, from Meinwald et al., 1966, AAAS).

Meinwald J. and Meinwald Y. C. (1966) Structure and synthesis of the major components in the hairpencil secretion of a male butterfly, Lycorea ceres ceres (Cramer). J. Am. Chem. Soc. 88, 1305-1310. 

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,... 

Intramolecular electrophilic substitution of a pyrrole by a nitrile under acidic conditions generates a dihydropyrrolizine after hydrolysis of the iminium ion intermediate. This type of cyclization has received considerable attention. Braunholtz et al. demonstrated that improved yields (70%) in the cyclization step were effected with a melt of the chlorides of aluminum, potassium, and sodium, but the conditions were extremely critical. Meinwald and Meinwald used this method for their preparation of the dihydropyrrolizinone (50). This confirmed the structure of the major component of the hairpencil secretion of the male tropical butterfly Lycorea ceres ceres. None of the isomeric 2-methyl compound was formed during this synthesis [Eq. (17)]. It is suggested that the 3-methyl group of pyrrole activates the adjacent 2-position sufficiently to promote regiospecific intramolecular electrophilic substitution. 

Ac Component fo the hair pencil secretion of male butterflies Lycorea ceres ceres. Dimorphous. Mp 24.2 . Bp205 220-225 , Bpis 200 . 

Component of the hairpencil secretion of male butterflies Lycorea ceres ceres and male Drosophila melanogaster. Bpo.2 128-140°. ... 

The intramolecular Houben-Hoesch acylation of pyrroles has been used for the synthesis of a number of compounds with interesting properties. An intramolecular acylation was reported by the Meinwald group to synthesize the hairpencil secretion of the butterfly Lycorea ceres... 

The oak-leaf-roller moth uses cis-11-tetradecenyl acetate, CHgCHgCH CH(CH2)ioO—COCH3, as a sex pheromone. Hexadecanyl acetate, CH3(CH2) 15O-COCH3, is used for the same purpose by the butterfly Lycorea ceres ceres (E 4). Ethyl trans-2-cis-4-decadienoate, CH3(CH2)4CH= CHCH=CHCO—OC2H5,... 

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