Iminodithiocarbonates. III. Reactions with Some Electrophiles and the Structural Effect on Nucleophilic Reactivities and Basicities
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概要
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With a view toward demonstrating the structural effect on the reactivity of iminodithiocarbonates, the reactions of some electrophilic reagents with the following four iminodithiocarbonates have been studied; 2-methylimino-(IVa) and 2-phenylimino-1,3-dithiolane (IVb) and <I>S</I>,<I>S</I>′-dimethyl-<I>N</I>-methyl-(Va) and <I>S</I>,<I>S</I>′-dimethyl-<I>N</I>-phenyliminodithiocarbonate (Vb). Cyclic IVa and its <I>N</I>-ethyl homologue reacted with an equimolar amount of phenyl isocyanate at room temperature giving 1:2 cycloadducts. However, the other imino compounds (IVb, Va, and Vb) did not react at all even at elevated temperature. All these imino compounds reacted with acid chlorides to afford the corresponding <I>N</I>-acyliminium salts which could, in some cases, be isolated; however the rate of formation of the salts varied significantly with the structure of the imino compound. Some reactions with alkyl halides and phenyl isothiocyanate were also attempted. From the present results and those previously obtained on their reactions with epoxides and with ketenes, it has been concluded that the nucleophilic reactivity of the imino compounds increases in the order Vb<Va<IVb<IVa. Furthermore, it was found that the basicity of the imino compounds increased in the order Vb<IVb<Va<IVa. The observed ring effect and <I>N</I>-substituent effect on the reactivity and basicity of the imino compounds are discussed in connection with similar effects on the stability of closely related tri(hetero)carbonium ions, <I>i.e.</I>, bis(alkyl thio)-dialkylaminocarbonium ion (I).
- 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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Ueno Yoshio
Research Institute For Biosciences And Department Of Toxicology And Microbial Chemistry Faculty Of Pharmaceutical Sciences Science University Of Tokyo
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Nakai Takeshi
Research Laboratory of Resouces Utilization, Tokyo Institute of Technology
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