Z9-dodecen-1-yl acetate (1) is the sex pheromone of Argyroploce schistaceana(Snellen), Spodoptera frugiperda and other insects, or one of the components of other sex pheromones. It can be successfully used for pest prediction and is hopeful to be used for pest control. Because the Argyroploce schistaceana(Snellen) is also very harmful in China, we have carried out research on synthesis.




(1) The synthesis can be generally carried out through C+ C. Coupling or C+ C. Coupling is realized, but the former is based on butyne-1, which has a low boiling point and is inconvenient to operate [4], so we choose the latter coupling method. The mono-substituted acetylene (4) generated from acetylene on halogenated alkane (3) is coupled with bromoethane to obtain (5), and the alkyne bond in (5) is partially hydrogenated, reduced and acetylated to obtain product (1).

According to the literature, in the reaction with acetylene, if (3) is reacted with lithium acetylene and ethylenediamine in dimethyl sulfoxide for 18 hours, the product (4) is obtained, and the yield is only 69% [6]. At first, we used the method of butyl lithium ether solution and acetylene to generate lithium acetylene, and then condensed with halogenated alkanes [@]. However, due to the fact that n-butyl lithium ether solution is easy to generate white precipitate of lithium acetylene with acetylene [7], the subsequent condensation reaction is not complete. After changing to n-butyl lithium hexane solution, we overcame the above difficulties, so that the yield of each step is more than 90%, and the total yield of the reaction from (2) to (1) is 62%. In order to identify the purity of the cis geometric isomer in the compound (1), we use lithium aluminum hydride to reduce the three bonds of (5) to prepare the trans (7) for comparison. Because (1) and (7) are not easy to achieve good separation effect in ordinary packed column gas chromatography, (1) and (7) are respectively made into epoxy derivatives and then identified [8] (see table). Gas chromatography showed that the geometric isomer purity of (1) was 98%. The bioassay showed that (1) it had sexual attraction activity to the male sugarcane yellow borer in the field.