Synthesis And Antifungal Activity Of Hydronopyl Quaternary Ammonium Salts Derivatives

Turpentine is a natural product with advantages of the cheapest price and natural renewable,its main components are?-pinene and?-pinene.?-pinene have a lively chemical properties,reseachers have obtained series derivatives of excellent performance products,such as amides,ethers,esters and quaternary ammonium salts,by modifying the lively functional group of?-pinene,some of the compounds have a certain biological activity,the series products have been reported on spices,medicine,food,agriculture,foresry and other fields.Quaternary ammonium salts are widely used in cationic surfactants with high surface activity,good adsorption and bactericidal and other biological activities.They have good killing effect on microorganism,such as bacteria,fungi,algae and virus,which has wide application value in many fields and has been widespread attention of pesticide and pharmaceutical industry concern.The research on killing mechanism and performance of quaternary ammonium salts has been the hot research at home and abroad,and has made lots of new progress.In the paper,hydronopyl halides were prepared from nopyl,which was synthesised with?-pinene and paraformaldehyde,then react by catalytic hydrogenation and halogenation reaction.23 derivatives of quaternary ammonium salts containing hydronopyl that are new compounds,were synthesised from hydronopyl halides with the quaternization reaction.The structures of all compounds were characterized by fourier transform infrared spectroscopy?FT-IR?,nuclear magnetic resonance spectroscopy(¹H NMR,¹³C NMR)and mass spectrometry?MS?,and the purity and melting point of compounds were determined.The antifungal activities of the 23 quaternary ammonium salts derivatives to Botryosphaeria dothidea,Phoma citricarpa,Colletotrichum glecosporioides,Pestalotiopsis actinidia,Phomopsis mauritiana were measured by using mycelial growth rate method,80%carbendazim as a positive control.The experimental data were analyzed by SPSS and DPS software in order to obtain the inhibition of medium concentration(EC₅₀)and virulence regression equation of the compounds.The main results are as follows:?1?8 hydronopyl tri-alkyl ammonium halides?4a⁴h?and 8 hydronopyl pyridine ammonium halides?7a⁷h?were synthesised from hydronopyl halides with trimethylamine,triethylamine,tri-n-butylamine,pyridine and its homologues??-methylpyridine,?-methylpyridine,?-dimethylaminopyridine?,respectively.Besides,hydronopyl dialkyl tertiary amine were prepared from hydronopyl halides with dimethylamine,diethylamine,di-n-propylamine,respectively.Then 7 hydronopyl dialkyl benzyl ammonium halides?6a⁶g?were sythesised with hydronopyl dialkyl teriary amine and benzyl halides.?2?The antifungal activity results showed that the 23 quaternary ammonium salt derivatives have a certain inhibitory effect to the five plant pathogens.Among them,N-hydronopyl-N,N-di-n-propyl benzyl ammonium iodide?6g?have the best inhibitory effect on Botryosphaeria dothidea,which EC₅₀ is 44.6250 mg/L;For Colletotrichum glecosporioides and Phoma citricarpa,The inhibitory activity of N-hydronopyl-N,N-dimethyl benzyl ammonium iodide?6c?(EC₅₀ were 190.8725 mg/L and 15.4271 mg/L,respcetively)is better than that of 80%carbendazim(EC₅₀ were 329.7208 mg/L and436.9541 mg/L,respcetively);For Phoma citricarpa and Pestalotiopsis actinidia,The inhibitory activity of N-hydronopyl-?-dimethylamino pyridine ammonium iodide is superior than that of the other compounds.?5?With the increase of compound concentration,the antifungal activity was enhanced;the antifungal activities of quaternary ammonium salts containing benzyl is superior to that of the other two quaternary ammonium salts;the effects of halogem ions on antifungal activities were as follows:iodide ion>bromide ion>chloride ion.