Studies On The Synthetic Process Of Novel Insecticide Chlorantraniliprole

Based on the consulting of the literatures about insecticides, the current world and the domestic pesticide condition and the new ryanodine receptor insecticide condition were summarized, the discovery and the recent development of anthranilic diamides were described, chlorantraniliprole, the first Anthranilic diamides-type Ryanodine receptor insecticide is commercially available, its toxicity, function mechanism and application activity were given a comprehensive review The reported preparation about chlorantraniliprole and its intermediates were also introduced in detailWith the market requesting and literature researched, the thesis focuses on the preparation of chlorantraniliprole,it make its possible to industrialize by technical design. Adopting 2-nitro-3-methylbenzoic acid and 2,3-dichloropyridine for the main beginning raw material, chlorantraniliprole was prepared with 2-amino-5-chloro-N,3-dimethyl benzamide and 3-bromo-l-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxy lic. The total yield reached to 35.4%In this paper the process development of chlorantraniliprole was studied and a detailed study on each reaction and the post treatment method were made and the optimal conditions of each reaction were gotten. During preparing of 8-methyl-2H-3,1-benzoxazine- 2,4(1H)-dione, the most important intermediates, a wrong way of addition was rectified in detail, which reduced the by-products consumedly, the synthesis of 2-amino-3-methylbenzoic acid and the synthesis of 8-methyl-2H-3,1-benzoxazine-2,4(1H)-dione were put into one step, life-time of Pd/C catalyst can be prolonged by the mean of controlling capacity of H2 and alkali wash, which also reduced the cost and the work intensity. During preparing of 2-amino-5-chloro-N,3-dimethylbenzamide, the expensive reagent NCS was avoided by the improvement of chlorinated reagent and the craft operates were made easy, and the yield exceeds literature to a 10%. During preparing of 3-chloro-2(1H)-pyridinone hydrazone, the proper reaction condition was decided and hydrazine hydrate was recovered from continuous evaporation process, and the yield of the product reached 98.3% and the purity of the product was 98.5% which have been not reported in the available literature. Especially in the synthesis of main intermediate ethyl 2-(3-chloro-2-pyridinyl)-5-oxo-3-pyrzaolidinecarboxylate, a proper way of addition was selected in detail and two main by-products in the synthetic process were obtained, their structures were confirmed and their synthetic mechanism and reaction conditions were studied, and the yield exceeds literature to a 10%, the product purity reaches 99.1 % above, which resolved the crux problem on synthesis of chlorantraniliprole and obtained a more great innovation. During preparing of 3-bromo-l-(3-chloro-2-pyridinyl)-4,5-dihydro-1H-pyrazole-5-carboxylate, which was synthesized by ethyl 2-(3-chloro-2-pyridinyl)-5-oxo-3-pyrazolidinecarboxylate through esterification, bromination, the expensive and toxic reagent phosphorus oxybromide was avoided, which also reduced the cost and the work intensity. During the preparing of chlorantraniliprole, acetylating reagent and catalyst were replaced and a proper way of addition was selected in detail, and the yield reaches 95.5%, the product purity reaches 95.7% above. By the creative method above, the yield in this way increased about 12%, and its cost reduced to about 600 thousands yuan.The ultimate product and its important intermediates were proveded to be consilient with the molecule constructure of by nuclear magnetic resonance spectra and mass spectroscopic.