2,6-dimethyl-l,5-heptadien-3-ol acetate

In 1980, we reported the structure of the Comstock mealybug, Pseudococcus comstocki (Kuwana), pheromone as 2,6-dimethyl-l,5-heptadien-3-ol acetate (24, 25) and in 1981, we identified the pheromone of the citrus mealybug, Planococcus citri (Risso), as (lR-cis)-(+)-2,2-dimethyl-3-(l-methylethenyl)cyclobutanemethanol acetate (26). Both of these pheromones have been synthesized and are currently being used as baits in monitor traps in California and Texas. These compounds are more volatile than the pheromones for most other insects and therefore formulations for controlled release need to be modified from those described earlier. 

The [2,3]-rearrangement of amine iV-oxides was utilized in an efficient S5mthesis of 2,6-dimethyl-l,5-heptadien-3-ol acetate 61, a pheromone of the insect Pseudococcus comstocki tScheme lS.12id Dimethylpyridine 55 was converted in two steps into silylated piperidine 56, which was oxidized with m-CPBA to generate cyclic amine A-oxide 57. Sila-Cope elimination furnished O-silylhydroxylamine 58, which was methylated and desilylated in the presence of Mel and CsF to yield acyclic amine A-oxide 59. Heating this ammonium zwitterion facilitated the [2,3]-Meisenheimer rearrangement to O-allylhydroxylamine 60, which was transformed to the desired pheromone 61 in three steps. 

Scheme 15.12 Synthesis of the pheromone 2,6-dimethyl-l,5-heptadiene-3-ol acetate.

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