Sulfide及びSulfone化合物の合成研究 (第2報)

Diphenylsulfide化合体の生成について その2

抄録

1) The reaction mechanism by which 2mol. p-nitrochlorobenzene is applied with 1mol. Na₂S under the presence of a small amount of Na₂S₂ to form p, p′-dinitrodiphenyl sulfide was observed and it was found that the reaction proceeded as far as the formation of p-nitrothiophenol upon completion of which, the reaction occurrs between this newly formed compound and p-nitrochlorobenzene. It follows, therefore, that when 1mol. p-nitrochlorobenzene is used the reaction stops with the formation of p-nitrothiophenol so that the application of o, p-dinitrochlorobenzene easily gives o, p, p′-trinitrodiphenyl sulfide, m.p. 158-160°.
2) Application of Na₂S₃ on p-nitrochlorobenzene, as in the case of Na₂S₂, gives a mixture of p, p′-dinitrodiphenyl disulfide and sulfide although the formation of the latter is much lower than in the case of Na₂S₂.
3) Application of Na₂S to o-nitrochlorobenzene under the presence of Na₂S₂ hardly formed o, o′-dinitrodiphenyl sulfide which showed that the reaction takes a different course from that in the case of (1).
4) Application of Na₂S₂ on o-nitrochlorobenzene gives solely o, o′-dinitrodiphenyl disulfide and no monosulfide is formed. However, it was found that the application of Na₂S₂ on o, p-dinitro chlorobenzene gave a small amount of monosulfide as well as o, o′, p, p′-tetranitrodiphenyl disulfide.