The sex pheromone of grapholitha molesta 8(Z/E)-dodecen-1-ol acetate (6) was synthesized by using oleic acids as the raw material. 1,8(Z)-Heptadecadiene (2) was obtained from the decarbonylation reaction of oleic acid (1) in the presence of palladium complexes catalyst. Selective hydroboration and oxidation of 2 by Ca(BH 4) 2/H 2O 2 system gave 8(Z)-heptadecen-1-ol (3), which then was acetylized by treatment with Ac 2O/pyridine to afford 8(Z)-heptadecen-ol acetate(4). The compound 4 was ozonized to form the key intermediate 8-acetoxyoctanal (5), then compound 5 was coupled with the Wittig regents to obtain the title compound 8(Z/E)dodecen-1-ol acetate (6), Z/E molar ratio is 25∶75. The overall yield was 45%. The structures of all the compounds were confirmed by IR, MS and NMR spectra.
Chlorothalonil 1 was treated with anhydrous KF in DMF at 110 ℃ to give the corresponding crystalline fluorine-containing 1,3-benzenedicarbonitrile 2. KF was used in an equivalent to the number of chlorine atoms to be substituted. Compound 2 was subsequently reacted with ammonia to yield compound 3. In addition, halobenzamide 4 were refluxed with oxalyl chloride in anhydrous 1,2-dichloroethane(DCE) to yield benzoylisocyanates 5. Finally, seven novel BPUs chitin inhibitors 6a—6g were synthesized via the selective reaction of compound 3 with benzoylisocyanate derivatives 5, the total yield is over 30%—50%.
