Tri(hetero)substituted Carbonium Ions. VIII. The Hydride Reduction of Cyclic and Open-chain Dithiocarbamidium Salts

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概要

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• Studies were carried out on the hydride reduction of the following five stable <I>N</I>,<I>S</I>,<I>S</I>-tri(hetero)substituted carbonium ions: <I>N</I>,<I>N</I>,<I>S</I>,<I>S</I>′-tetramethyldithiocarbamidium ion (<B>1a</B>), 2-dimethylamino-1,3-dithiolanylium ion (<B>1b</B>), 2-dimethylamino-1,3-dithianylium ion (<B>1c</B>), 2-methylthio-3-methyl-4,5-dihydrothiazolium ion (<B>1d</B>), and 2,3,5,6-tetrahydrothiazolo[2,3-<I>b</I>]thiazolium ion (<B>1e</B>). Sodium dihydrobis(methoxyethoxy)aluminate (RDB) was found to be a suitable reducing agent. The RDB reduction of the carbonium ions at −5 °C gave the corresponding formamide thioacetals (<B>2</B>) in moderate yields. This provides a practical method for the synthesis of formamide thioacetals. The RDB reduction of <B>1d</B> at higher temperature, however, yielded abnormal products, thiazolin-2-thione (<B>3</B>) and thiazolidine (<B>4</B>) instead of the formamide thioacetal (<B>2d</B>). The mechanism for the formation of <B>3</B> and <B>4</B> has been discussed in terms of the ambident character of the cation (<B>1d</B>). Pyrolytic reactions of the thioacetals (<B>2</B>) and unsuccessful attempts to abstract the methine proton of <B>2b</B> by various bases are also described.

• 公益社団法人 日本化学会の論文

著者

• Okawara Makoto

  Research Laboratory Of Resources Utilization Tokyo Institute Of Technology

• Hiratani Kazuhisa

  Research Laboratory of Resources Utilization, Tokyo Institute of Technology

• Nakai Takeshi

  Research Laboratory of Resouces Utilization, Tokyo Institute of Technology

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