Process for synthesizing sex pheromone of pine caterpillar

Abstract

The invention discloses a process for synthesizing sex pheromone of pine caterpillar, which employs 2-hexyne-1-alcohol as an initial raw material, three-bond positional transference is carried out under the effect of lithium and propane diamine to obtain 5-hexyne-1-alcohol; under acidic condition, 5-hexyne-1-alcohol is reacted with dihydropyran to obtain 1-THP-5-hexyne-1-alcohol protected by THP on hydroxyl, Under co-catalysis of metal palladium and cuprous iodide, 1-THP-5-hexyne-1-alcohol and trans-dichloroethylene are subjected to coupling reaction to generate conjugate enyne(7E)-1-THP-8-chlorine-5-alkyne-7-alkene-1-octanol; under the catalysis of metallic iron, (7E)-1-THP-8-chlorine-5-alkyne-7-alkene-1-octanol and a n-Butyl bromide grignard reagent are further subjected to coupling reaction to obtain (7E)-1-THP-5-alkyne-7-alkene-1-dodecanol, under the catalytic reduction of metal zinc, (5Z, 7E)-1-THP-dodecanol dienol; under the camphor sulfonic acid condition, (5Z, 7E)-1-THP-dodecanol dienol removes the THP protective group to obtain the final target product (5Z, 7E)-dodecanol dienol. The method of the invention has the advantages of easily available synthesis raw materials, low cost, mild reaction condition, easy operation, high yield and good stereoselectivity.

Description

technical field [0001] The invention relates to the technical field of insect sex pheromone preparation, in particular to a method for synthesizing pine caterpillar sex pheromone. Background technique [0002] Pine caterpillars belong to the family Lepidoptera and are the most serious historical pests in the vast pine forests in China. They are widely distributed throughout China. Pine caterpillars can reproduce three generations a year, feed on pine needles with larvae, and can eat up the leaves of the whole tree in a short time, so that the pine tree cannot perform photosynthesis and the tree dies. The pine forest looks like a fire, causing the death of a piece of pine forest, which can be described as a "smokeless fire". The more typical ones are Dendrolimus punctatus, D.tabulaeformis, D.spectabilis, D.houi and D.kikuchii (Tang Zhizhi & Tang Zhifu, 2007, Research on the continuous disaster control and governance model of pine caterpillars in Chaoyang area. Shelter Fores...

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Problems solved by technology

In addition, Wang Dong et al. used the coupling reaction of specific configurations of alkenyl iodide and alkenyl aluminum to construct conjugated dienes and obtained good stereoselectivity. However, due to the use of metals such as aluminum, the reaction conditions were relatively harsh and the yield was low. Not high (Wang Dong et al., 1990 Synthesis of sexual attractant (5Z, 7E)-dodecadienol and its acetate and propionate for Chinese pine caterpillars. Acta Chemie Sinica, 48:489-493)

Later, Tao Yunhai, Gu Kun and others developed a relatively new strategy, using the next step of the joint action of crotonaldehyde and acetylene in lithium bromide and palladium acetate to construct two double bonds of specific configurations, but the method yield Very low, owing to use acetylene gas as reaction raw material and make operation complicated (gu Kun etc., China, in 2004, patent publication number: CN1557796; Tao Yunhai etc., 2005 pine caterpillar sex pheromone (5Z, 7E)-dodeca2 Stereoselective Synthesis of Enols. Chemical Journal of Chinese Universities, 26(6): 1072-1075)

In summary, the reported synthetic methods generally have disadvantages such as expensive raw materials, complicated operation, stereoselectivity and low yield.

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