Studies of reactions of amines with sulfur trioxide. V. Transsulfonation of amine salts of some N-substituted amidosulfuric acids.

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概要

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• 4-Methylanilinium butylamidosulfate, butylammonium (4-methylphenyl)amidosulfate, and 4-methylanilinium (4-methylphenyl)amidosulfate were heated separately under reduced pressure at different temperatures ranging from 80 to 180 °C. Butylammonium butylamidosulfate was heated with 4-methylaniline under atmospheric and reduced pressure. The product compositions were determined as functions of reaction time and temperature, and the components were separated and identified. At lower temperatures (4-methylphenyl)amidosulfate and 4-methylaniline-<I>N</I>,2-disulfonate were the major products, while at higher temperatures 4-methylaniine-2-sulfonate and 2,6-disulfonate were the major products. The ease of N–S bond cleavage of the amidosulfate salts (RNHSO<SUB>3</SUB>–R′NH<SUB>3</SUB><SUP>+</SUP>) (<B>1</B>) depends largely on the basicity of both the parent amine (R′NH<SUB>2</SUB>) (<B>2</B>) and the salt-forming base (R′NH<SUB>2</SUB>) (<B>3</B>). The results suggest that the initial step of the transsulfonation involves the dissociation of <B>1</B> into <B>3</B> and the free acid followed by an equilibration between RNHSO<SUB>3</SUB>H and RNH<SUB>2</SUB><SUP>+</SUP>SO<SUB>3</SUB><SUP>−</SUP> (<B>4</B>). It is considered that <B>4</B> may be the sulfonating species and the free amines, <B>2</B> and <B>3</B>, should be the receptors of a sulfonate group. In contrast to the widely accepted scheme (transsulfonation and subsequent intramolecular rearrangement), our results show that both the transsulfonation and the rearrangement process occur concurrently and the same type of mechanism (a bimolecular displacement, <I>viz.</I>, B<SUP>+</SUP> : SO<SUB>3</SUB><SUP>−</SUP>+B′: \rightleftarrowsB<SUP>+</SUP>: +B<SUP>+</SUP>: SO<SUB>3</SUB><SUP>−</SUP>) may be operative.

• 公益社団法人 日本化学会の論文

著者

• Yamaguchi Hachiro

  Department Of Applied Chemistry Faculty Of Engineering Hiroshima University

• Kanetani Fujio

  Department of Applied Chemistry, Hiroshima University

• Kanetani Fujio

  Department of Applied Chemistry, Faculty of Engineering, Hiroshima University

関連論文

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• Bis(p-methoxyphenyl) selenoxide as a mild and selective oxidizing agent.
• Studies of reactions of amines with sulfur trioxide. V. Transsulfonation of amine salts of some N-substituted amidosulfuric acids.
• Preparation of arylimidobis(sulfates).
• Flash pyrolysis of selenides. Syntheses of bibenzyls, olefins, and related compounds.

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