Synthesis And Biological Activity Of Hydronopol And Its Derivatives

Producing high value products through chemical modification of main component of natural resources is an important direction of natural product research. Turpentine is an important natural renewable resource.α-pinene and β-pinene are the main component of turpentine. Thereinto.,β-pinene and paraformaldehyde are able to produce nopol by Prins reaction.In this thesis.23derivatives were synthesized from nopol, by addition reaction, substitution, condensation reaction, esterification reaction, oxidation reaction, reduction reaction, and so on. The23derivatives include hydronopol,3hydronopyl alkylogens,6hydronopyl alkyl ethers.7hydronopyl carboxylic ethers, hydronopic acid, hydronopic acyl chloride and4hydronopic acidamide.17derivatives which were hydronopyl alkyl ethers, hydronopyl carboxylic ethers and hydronopic acidamide were synthesized for the first time.Hydronopol was prepared from the hydrogenation of nopol in the presence of Raney Ni. And there would be give more cis-hydronopol in this way. Less than5%of the produc-tions of the method was trans isomer.Hydronopyl chloride and hydronopyl bromide were synthesized from hydronopol with thionyl chloride, sodium bromide and sulfuricacid respectively. Hydronopyl iodide was synthesized from hydronopyl chloride and sodium iodide.Hydronopyl alkyl ethers were obtained from the Williamson classic reaction. Hydronoply chloride reacted with sodium alcoholate of6alcohols respectively would give homologous alkyl ethers.Hydronopyl carboxylic ethers were synthesized by the way of classic esterification reaction at the presence of acid. Hydronopol readily reacts with7carboxylic acid to produce new compounds of hydronopyl carboxylic ether series.Hydronopol could be oxidated by CrO3in AcOH to give hydronopic acid. Then hydronopic acyl chloride, which was synthesized from hydronopic acid and thionyl chlo-ride, reacted with4amines respectively would produce homologous hydronopic acida-mide.The products were purified by the way of reduced pressure distillation, column chro-mategraphy or recrystallization. Gas phase chromatography was used to analysize their purity, and refractometer for refractive index. Identification and structural analysis were done using IR,1H NMR,13C NMR and MS methods.The repellent activity of hydronopol, hydronopyl alkyl ethers and hydronopyl carboxylic ethers was studied. The results indicated that:hydronopol (2), hydronopyl formate (5a) and acetate (5b) showed some repellent activity against Aedes albopictus. The protect time was for2.5-3h when the mass concentration above was20%.Compounds2.4d,4e.4f.5c.5d were found to have repellent activity against Monomorium pharaonis at the concentration of10%. The repellent ratio was more than65%, and the repellent ratio of4d and5c reached100%.