Tridecadienyl acetate

The isolation of the pheromone obtained from the female of the pink bollworm, Pectinophora gossypiella, and the determination of the structure and synthesis of the compound are also associated with the names of Jacobson and co-workers (Jones era/., 1966). The synthetic ( )-10-propyl-5-tridecadienyl acetate (propylure,... 

Modification of the propylure (4) molecule resulted in the synthesis of a mixture of geometrical isomers of 5,9-tridecadienyl acetate (20). This product has an attractant effect on several agricultural insect pests (Warthon and Jacobson, 1967). 

This group of natural compounds is also structurally diverse ranging from the simple dienes like a sex pheromone (4E,7Z)-4,7-tridecadienyl acetate or ( )- , )-coriolic acid through typical polyenes like the all-trans-stereomer of ethyl retinoate to the more complex, optically active calyculins A and B. In the total syntheses of polyenes presented below, the structurally complex phosphonate or bisphosphonate reagents were used in the Horner-Wittig olefination reactions solely or in combination with the Suzuki coupling. 

Dienes, as the simplest polyene systems, are widely encountered in sex pheromones like (4E, 7Z)-4,7-tridecadienyl acetate (100), a component of the sex pheromone of the potato tuberworm moth (Phthorimaea operculella). This compund was synthesized by Kim and Park [54] starting from a protected 5-hexen-l-ol and utilizing the chemistry of thio-substituted phosphonates (Scheme 28). Thus, the Pummerer rearrangement of a-phosphoryl sulfoxide 101 with 5-hexenyl acetate 102 afforded 7-acetoxy-l-methylthiohept-3-enyl phos-phonate 103 as an E/Z=85 15 mixture, being unreactive in the Horner-Wittig reaction, even after OAc deprotection/THP reprotection. However, the reaction of the more reactive a-phosphoryl sulfone 104 with w-hexanal successfully led to the required 1,4-diene 105, as an ElZ = 70 30 mixture, in 86 % yield. The final pheromone 100 was obtained after the desulfonylation of 105 with sodium hydrosulfite and the OTHP OH OAc deprotection/reprotection procedures. 

Jacobson (1969) has separated a mixture of the cis and trans forms of propylure (10-propyl-fru/is-5,9-tridecadienyl acetate) (CXXIXX the sex pheromone of the female pink bollworm moth (Pectinophora gossypiella (Saunders)), into its pure isomers by thin-layer chromatography. The infrared spectrum of the separated frans-propylure had a medium band at 965 cm trans HC=CH) that was absent in the spectrum of the cis isomer. The spectrum of cis-propylure had an inflection at 740 cm. c/s-Propylure inhibited or masked the activity of the trans isomer, as... 

Z,Z )-4,7-tridecadienyl-(5 )-2-yl acetate was identified as the pheromone of the female Douglas-Fir cone gall midge, Contarinia oregonesis Foote (Diptera Cecidomyiidae). The 7 isomer was behaviorally benign. ... 

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