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Abstract
2-Methyl-thiophenoles 1 react after bis-lithiation with dialkyl chlorophosphates 2 under formation of dialkyl (2-mercaptophenyl)methanephosphonates 3. The migration of the phosphoryl group from the sulfur of the S-aryl-O-dialkyl phosphate intermediates to the ortho methyl group is preferred to the nucleous position.