The Synthesis Of The Herbicide Of Tembotrione And The Insecticide Of Spirotetramat

Tembotrione(CAS registry number:335104-84-2)is a triketone herbicide,which was commercialized by Bayer Corporation.Tembotrione is broadly applied to corn field and annual grass weeds and broadleaf weed.It's a HPPD inhibitor.Spirotetramat(CAS registry number:382608-10-8),a new insecticide,was also developed by Bayer Corporation.It is used to control broad-spectrum pests.Spirotetramat belong to spirocyclic tetronic acid derivative,it is an acetyl-coa carboxylase inhibitor,which is used to destroy the fat synthesis in the insect.This thesis has studied the synthetic routes of tembotrione and spirotetramat.With the method of literature reports as the basis,research on synthesis methods are analyzed,and improvement.An inexpensive,feasible and environment-friendly syntheticprocess was finally developed for each of tembotrione and spirotetramat.The target product and some of intermediates were identified with high performance liquid chromatography and~1HMNR.2-chloro-6-methylmercaptotoluene was obtained by the reaction of sodium nitrite,3-chloro-2-methylaniline and sodium methanethiol,followed by acylation with acetyl chloride.2-chloro-3-methyl-4-methanesulfonylbenzoic acid was obtained by oxidation with hydrogen peroxide and then halogenation reaction with sodium hypochlorite.2-chloro-3-bromomethyl-4-methylsulfonylbenzoic acid methyl ester was obtained by esterification with methanol and bromination reaction with NBS.Finally,2-chloro-3-bromomethyl-4-methylsulfonylbenzoic acid methyl ester was reacted with trifluoroethanol to give 2-chloro-3-(2,2,2-trifluoroethoxy)methyl-4-methanesulfonyl benzoic acid;In the presence of acetone cyanohydrin,2-chloro-3-(2,2,2-trifluoroethoxy)methyl-4-methanesulfonyl benzoic acid was reacted with cyclohexanedione to afford the target product of tembotrione.The total yield is 22.9%.Cis-8-Methoxy-1,3-diazaspiro[4,5]decane-2,4-dione was hydrolyzed to give the cis-4-methoxycyclohexane-1-aminocarboxylic acid and esterified to give the cis-4-methoxycyclohexyl-1-methyl carbamate,which then reacted with 2,5-dimethyl benzeneacetylchloridetogivethecis-1-[2-(2,5-dimethylphenyl)acetamido]-4-methoxycyclohexyl methyl formate.Then,closed the ring under the effect of alkali,and the nucleophilic substitution reaction with ethyl chloroformate could produce the target product of spirotetramat.The total yield is 44.7%.Through the feasibility study on the synthesis of tembotrione and spirotetramat,this thesis has found an optimal process route,analyzed the factors that influence the yield of product,and obtained a set of relatively ideal parameters for the process route.In the present method,the entire process routeis relatively moderate,has a very good development prospect for the product in our country after industrialize production and farmland application to lay a solid foundation.