The reactions between acyl chlorides RC(O)Cl (a)
[R = Me (1), Pri (2),
But
(3), Ph(4)] and electrogenerated
S3˙-
(⇌ S62-
) ions have been investigated in
N,N-dimethylacetamide by spectroelectrochemistry. With
R = alkyl, thiocarboxylate ions and sulfur resulting from
the fast initial substitutions cause partial formation of both acyl
disulfide ions and diacyl disulfides (b) at a y ratio
[RC(O)Cl]/[S3˙-] of 0.5; the second
step stoichiometrically (y = 1) affords diacyl
disulfides 1b–4b as the presumed products. The formation of these
species only is confirmed on a preparative scale from two sets of
experiments: (i) direction addition of acyl chlorides
(1a–4a) to chemically generated
S⅓- solutions; (ii)
electrolysis of sulfur in the presence of acyl chlorides
2a–4a.
已经通过光谱电
化学方法研究了酰
氯 RC(O)Cl (a) [R = Me (1), Pri (2), But (3), Ph (4)] 与电生S3˙- (⇌ S62-) 离子在N,N-二甲基乙酰胺中的反应。当R为烷基时,迅速的初始取代反应产生的
硫代
羧酸盐离子和
硫导致在[RC(O)Cl]/[S3˙-]的比率为0.5时部分生成酰二
硫酸盐离子和二酰二
硫化物 (b);第二步
化学计量(y = 1)生成二酰二
硫化物1b–4b作为假定产物。通过两组实验的备制结果确认了这些物质的形成:(i) 将酰
氯 (1a–4a) 直接添加到
化学生成的S⅓-溶液中;(ii) 在酰
氯2a–4a存在下电解
硫。