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Two Pathways for the Reaction of Ethyl 4-Chloromethyl-6-methyl- 2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate with Thiophenolates: Ring Expansion versus Nucleophilic Substitution
Published: 30 October 2010 by MDPI in The 14th International Electronic Conference on Synthetic Organic Chemistry session General Organic Synthesis
Abstract: Ethyl 4-methyl-2-oxo-7-phenylthio-2,3,6,7-tetrahydro-1H-1,3-diazepine-5-carboxylate and/or ethyl 6-methyl-2-oxo-4-(phenylthiomethyl)-1,2,3,4-tetrahydropyrimidine-5-carboxylate were obtained in the reaction of ethyl 4-chloromethyl-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimi-dine-5-carboxylate with PhSNa or PhSK with or without PhSH, depending on the reagent ratio, reaction time or temperature, as a result of ring expansion and/or nucleophilic substitution. The reaction pathway was affected strongly by the basicity-nucleophilicity of the reaction media. The results obtained were confirmed by reactions of 4-mesyloxymethyl-6-methyl-5-tosyl-1,2,3,4-tetrahydropyrimidin-2-one with PhSNa/PhSH and ethyl 4-chloro-methyl-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate with NaCN/HCN or NaCH(COOEt)2/CH2(COOEt)2.
Keywords: 1,2,3,4-Tetrahydropyrimidin-2-ones; 2,3,4,5-Tetrahydro-1H-1,3-diazepin-2-ones; Ring expansion; Nucleophilic substitution