The Synthesis And Application Of2-amino-5-chloro-N,3-dimethyl Benzoyl Amine And Carboxylic Acid Derivatives

Chlorantraniliprole, developed by DuPont, is the first insecticide having thestructure of anthranilic diamides. Compared with traditional pesticides, it ownedthe novel mechanism that it could activate the ryanodine receptor (RyR) toimbalance the calcium cation so that the pest died. As an efficient,broad-spectrum, low toxic, high selective pesticide, it had been concernedwidely since it was appeared on the market in2008. In2011the global sales ofchlorantraniliprole reached580millions dollars, with the growth rate of nearly50%per year.2-amino-5-chloro-N,3-dimethyl benzamide and2-amino-5-chloro-3-methylbenzoicacid were the intermediate to synthesize chlorantraniliprole. After summarizing thesynthesis methods on the articles, a rational route was chosen and its process wasoptimizing. A new route whose starting material was7-methyl isatin was designed.1. The reaction was starting with o-toluidine, chloral hydrate and hydroxylaminesulfate to synthesize2-hydroxyimino-N-o-tolylacetamide and then gain7-methyl isatinin concentrated sulfuric acid by a ring closure reaction, and the yield was56.1%. Theprocess conditions were optimized, but also new methods to synthesize twointermediates were explored.2. Starting with7-methyl isatin,2-amino-5-chloro-N,3-dimethyl benzamide wasprepared, through oxidation with peracetic acid, ammonolysis of methylamine andchlorination. Based on that, the new route was designed and tested through chlorination,oxidation and ammonolysis of methylamine. The yields were61.3%and62.0%respectively. In addition, starting with7-methyl isatin,2-amino-5-chloro-3-methyl-benzoic acid was prepared, through oxidation with hydrogen peroxide and chlorination,and the yield was50.6%.