ジアリルジサルファイド系化合物の製造法の研究 (第7報)

ヨウ素触媒の存在下で赤燐を用いるフェニルメタンスルホニルクロライドの還元反応 その2

抄録

It had earlier been concluded that the formation of dibenzyl sulfide from phenylmethanesulfonyl chloride by red phosphorus and iodine involved the formation of phenylmethanethiol by reduction. It was assumed that, if phenylmethanesulfonyl chloride is reduced to the thiol, addition of 4-nitrobenzyl chloride in the reaction system of phenylmethanesulfonyl chloride would afford a mixed-type sulfide, benzyl 4-nitrobenzyl sulfide, together with dibenzyl sulfide. The experiment, however, afforded only the symmetrical bis (4-nitrobenzyl) sulfide alone. The reason for this was clarified as follows: phenylmethanesulfonyl chloride is reduced to form phenylmethanethiol, as expected. On the other hand, 4-nitrobenzyl chloride added into this reaction system is changed to 4-nitrobenzyl iodide by hydriodic acid and the condensation of the thiol and the iodide results in the formation of a mixedtype benzyl 4-nitrobenzyl sulfide as an intermediate. This mixed-type sulfide undergoes substitution reaction with 4-nitrobenzyl iodide present in excess and the symmetrical bis (4-nitrobenzyl) sulfide is formed. This substitution is a new reaction in sulfide-type compounds.