Synthesis And Herbicidal Activity Of Carane-3,4-diol And Its Derivatives

Carane-3,4-diol is a deeply processed product of 3-carene and has biological activities such as mosquito repellent、insecticide and moisturizing properties,it has broad application and development potential as a plant pesticide.For carane-3,4-diol traditional synthetic method of operation process of complex,chloroform solvent toxicity is high,and the few herbicidal activity of literature at home and abroad,this paper explores the carane-new technology of synthesis of carane-3,4-diol,synthesized carane-3,4-diol esters and ethers derivatives,and carries on the herbicidal activity and study,it provides basic research for the development of carene derivative herbicides.The main research contents and results are as follows:（1）Using H₂WO₄,H₂MoO₄,H₃PO₄ and dioctadecyl bis quaternary ammonium salt as raw materials,five kinds of bis quaternary ammonium phosphotungstate molybbate catalysts were prepared by changing the molar ratio of W and Mo to catalyse the one-step conversion of 3-carene to carane-3,4-diol.GC method was used to investigate the effects of catalyst and solvent type,catalyst dosage,reaction temperature,hydrogen peroxide dosage and reaction time on the conversion rate of3-carene and selectivity of carane-3,4-diol,and the optimal process conditions were as follows:3-carene 12mmol,solvent free,reaction temperature 50℃,catalyst dosage 0.082g,hydrogen peroxide 1.5m L,reaction time 9h.Under these conditions,the conversion rate of 3-carene and selectivity of carane-3,4-diol reached 97.0%and85.5%,respectively.（2）GC method was used to study the esterification reaction of carene-3,4-diol with acyl chloride and the etherification reaction with benzyl chloride.The ratio and time of materials were investigated to synthesize 9 ester derivatives（2a-i）and 4 ether derivatives（3a-d）.The molecular structure of the product was determined by IR,HRMS,~1H NMR and ¹³C NMR.（3）The inhibitory effect of carane-3,4-diol and its ester and ether derivatives on elongation of radicle and germ of ryegrass and rape was measured by pan culture method,and the inhibitory rate was calculated.The statistical software SPSS was used to analyze the inhibitory rate,and the regression equation of virulence and semi-inhibitory concentration(IC₅₀)were obtained.The results showed that carane-3,4-diol could inhibit the elongation of radicle and embryo of ryegrass and rape,and showed herbicidal activity related to concentration.The introduction of ester and ether functional groups could change the hydrophilicity and regulate or enhance the herbicidal activity.The ester derivatives 2a-c,2e and ether derivatives 3a could inhibit the elongation of ryegrass and rape better than carane-3,4-diol.The herbicidal activity of derivative 2c was higher than that of glyphosate（0.48 and 0.45 mmol/L）,respectively.（4）The effects of compound 2c with high herbicidal activity on the growth of stems and leaves of ryegrass and rape seedlings were studied by stem and leaf spray treatment,and the herbicidal action mode of carane-3,4-diol derivatives was preliminarily discussed.The results showed that compound 2c had different effects on stem and leaf growth of rape and ryegrass seedlings.After application,stem and leaf of rape seedlings withered simultaneously,while only leaf of Ryegrass seedlings withered.