BP'^^^Sff? ^^- *'- ' ' -^ ' *^ ' ^""^* * '" - ^ ■ !! I — ■ r ■.-„■■-,.,-■..., , ,•_,_,. « ,^^ . .. i 



13 



18. Ayer, W. A., and Browne, L. M. 1974. The transforniation of carvone 



( 



I into racemic grandisol. Can. J. Chem. 52: 1352-1360. 



t 



i 



j , Grandisol (1) is one of the components of the pherumone complex emitted by the 



\ ■ 



{ male boll weevil. We report the transformation of readily available eucarvone 



\ (3), via the photoisomer 4, into grandisol in 20% overall yield. A key step 



t 



I in the synthesis is the Beckmann cleavage of oxime 15, derived in three steps 



[ from 4, to nitrile 16. Hydrolysis of 16 followed by hydride reduction gives 



\ 



I grandisol (1) . 



\ 



i 19. Babler, J. H., and Coghlan, M. J. 1976.' A facile method for the 



I bishomologation of ketones to a,g-unsaturated aldehydes: application 



I to the synthesis of the cyclohexanoid components of the boll weevil 



i sex attractant. Synth. Coimnun. 6: 469-474. 



> 



I The acid-catalyzed isomerization of tertiary vinyl carbinols to the corres- 



i 



\ ponding primary allylic alcohols has been reported numerous times in the 



i 



chemical literature. In addition, the corresponding acetylenic carbinols 



I have been shown to rearrange to a,g-unsaturated aldehydes when treated with 



\ aqueous acid. Since yields are generally low under the conditions required 



f 



I for the latter transformation, a better method involves the isomerization 



f of the corresponding tertiary acetylenic acetate in the presence of silver 



I ion to an allenic acetate, followed by hydrolysis to the desired a,3- 



\ unsaturated aldehyde. 



