Tri(hetero) substituted Carbonium Ions. VI. An Anomalous Reaction of 2-Methylthio-1,3-dithiolanylium Ion with <I>N</I>,<I>N</I>-Dimethyldithiocarbamate Anion
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概要
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The reaction of 2-methylthio-1,3-dithiolanylium ion (III) with <I>N</I>,<I>N</I>-dimethyldithiocarbamate anion (<SUP>−</SUP>SN) has been studied with a view toward demonstrating the ambident character of the cation III. It was found that (i) the reaction afforded <I>S</I>-β-(<I>N</I>,<I>N</I>-dimethyldithiocarbamyl)ethyl-S′-methyltrithiocarbonate (IV; normal) together with ethylene bis(<I>N</I>,<I>N</I>-dimethyldithiocarbamate) (V; abnormal); (ii) methylthioxanthate anion (<SUP>−</SUP>SS) was formed in the reaction; (iii) the formation of the abnormal product (V) was more favorable and this could not be ascribed to the attack of <SUP>−</SUP>SN on the normal product (IV). The ambident reactivity of cation III has been compared with that of closely related cations, tris(methylthio)carbonium ion and 2-methylamino-1,3-dithiolanylium ion (Ia). It was also found that the reaction of Ia with ethylthioxanthate anion (<SUP>−</SUP>SS′) afforded the <I>S</I>′-ethyl analog of IV (normal) together with a small amount of abnormal V. The mechanism for the formation of the abnormal product (V) both from III and <SUP>−</SUP>SN and from Ia and <SUP>−</SUP>SS′ has been suggested.
- 公益社団法人 日本化学会の論文
著者
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Okawara Makoto
Research Laboratory Of Resources Utilization Tokyo Institute Of Technology
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Nakai Takeshi
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
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