Synthesis And Repellent Activity Of Hydronopylformic Acid And Its Derivatives

?-pinene is a main component of turpentine which possesses high production and cheap characteristics in China.Through the chemical modification of ?-pinene,a lot of derivatives which can be developed into high quality insect repellents can be obtained.Such research will not only increase the variety and quality of ?-pinene deeply-processed products,but also enhance the economic value of turpentine.In this thesis,Hydronopyl chloride or hydronopyl bromide was obtained from?-pinene through Prins,catalytic hydrogenation,and substitution reaction.Then twenty-one compounds including hydronopylformic acid and its acyl chloride,ester and amide derivatives were synthesized from hydronopyl chloride or hydronopyl bromide by Grignard,hydrolyze reaction of diluted acid with carbon dioxide,chloridization,esterification,and amidation reaction.Particularly,seventeen derivatives were new compounds.The structures of the products were characterized and analyzed by IR,1HNMR,13C NMR and MS methods.The mosquito repellent activities of nineteen compounds including hydronopic acid and its derivatives of amide,as well as hydronopylformic acid and its derivatives were estimated using Aedes albopictus as test specie.The results showed that N,N-dimethyl hydronopylformamide,N-methy hydronopic acidamide and N,N-dimethyl hydronopic acidamide displayed some repellent activities.The protection time lasts 2.5?3.5 h at the mass concentration of 20%.By using filter paper diffusion method,repellency of 45 bridge-ring terpenoids compounds on the adult male Blattella germanica was determined.Among those bridge-ring terpenoids compounds,six compounds,such as hydronopyl chloride,hydronopyl n-amyl ether,hydronopyl benzoate,hydronopic acidamide,N-methy hydronopic acidamide and N-methyl hydronopylformamide,displayed the most powerful activities with the dosage of 340 ?g/cm2.Their repellencies were 71.48%,69.86%,86.48%,61.38%,73.24%,66.10%,respectively.All these six repellents showed to be more effective than DEET which was 53.61%.Especially,the repellency level of hydronopyl benzoate was classed as the best repellency level(V)which is much higher than the repellency level of DEET(?).