EXO- AND ENDOHORMONES. XXIV.1A CONVENIENT SYNTHESIS OF (Z)-11-TETRADECEN-l-YL ACETATE,COMPONENT OF LEPIDOPTERA INSECT SEX PHEROMONE

摘要

A new and practical synthesis of (Z)-11-tetradecene-1-yl acetate was developed using commercially raw material. The synthesis was based on a C_(10)+C_2=C_(12) and C_(12)+C_2=C_(14) coupling scheme, starting from 1,10-decane-diol. The route involves, as the key step, the use of the mercury derivative of the terminal alkyne ω-functionalised as intermediate, which is lithiated and then alkylated. The first coupling reaction took place between monosodium acetylene obtained in situ and l-tert-butoxy-10-bromo-decane. The second coupling reaction consisted in directly lithiated of di (t-butoxy-dodec-11-yne) mercury and then alkylated with ethyl bromide obtaining 1-tert-butoxy-tetradec-11-yne. After acetylation and stereoselective reduction in the presence of NiP-2 catalyst of 1-tert-butoxy-tetradec-11-yne gave (Z)-l 1-tetradecene-l-yl acetate with 99% isomeric purity.