An improved preparation of some insect sex attractants: Synthesis and separation of geometrical isomers by formation of urea complexes

Abstract

Wittig condensations of aldehydes or ketones with phosphonium salts are frequently used methods for the syntheses of straight-chain or branched alkenes. Suitable choice of reaction conditions may provide the desired geometrical isomer as reaction product. However, we have found that mixtures of geometrical isomers can be conveniently separated on a large scale by the relatively inexpensive method of urea inclusion complex formation. The recovery of both isomers from the separation procedure is almost quantitative. Urea inclusion complexes are formed preferentially withE isomers. Formation of the inclusion complex is affected by the skeletal structure and by the nature of the terminal functional group. By applying this method of separation at a convenient stage, several insect pheromones were prepared without the necessity of a stereoselective step. The technique was used for syntheses of (Z)-11-hexadecenal and (Z)-9-tetradecenal (components of theHeliothis virescens pheromone) and for the synthesis of candidate attractants possessing a trisubstituted double bond.