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The sulfinatodehalogenation reaction of α,α-difluorobenzyl halides, ArCF2X ( Ar = C6F5, C6H5; X = Br, I ), with sodium dithionite took place readily in aqueous acetonitrile under mild conditions, giving the corresponding sodium sulfinate. The 1:1 adducts were obtained when alkenes were added to the reaction system in some cases.