Chemistry of N-thiosulfinylanilines. II. Thermolysis and photolysis of N-thiosulfinylanilines.

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概要

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• Thermolysis of 2,4-di-<I>t</I>-butyl-6-methyl-<I>N</I>-thiosulfinylaniline (<B>1</B>) in refluxing benzene afforded 2,4-di-<I>t</I>-butyl-8-thia-9-azabicyclo[4.3.0]nona-2,4,6,9-tetraene (<B>6</B>) and 2,4-di-<I>t</I>-butyl-6-methylaniline (<B>7</B>), while its photolysis resulted in the formation of <I>N</I>,<I>N</I>′-bis(2,4-di-<I>t</I>-butyl-6-methylphenyl)sulfur diimide (<B>17</B>) and <B>7</B>. The mechanism of the thermolysis involving 1,5-hydrogen migration and <I>o</I>-quinonoid intermediate has been proposed. The electronic spectrum of the initial intermediate in the photolysis was obtained in EPA matrix and tentatively assigned to a dithionitro compound (<B>42</B>) or a dithiaziridine (<B>41</B>). Thermolysis of 2,4,6-tri-<I>t</I>-butyl-7,8-dithia-9-azabicyclo[4.3.0]nona-2,4,9-triene (<B>4b</B>) equilibrated with 2,4,6-tri-<I>t</I>-butyl-<I>N</I>-thiosulfinylaniline (<B>4a</B>) gave 4,6-di-<I>t</I>-butyl-3<I>H</I>-1,2,3-benzodithiazole 2-oxide (<B>26</B>) and 2,4,6-tri-<I>t</I>-butylaniline (<B>27</B>). The reaction in the presence of a catalytic amount of <I>p</I>-toluenesulfonic acid improved the yield of both <B>26</B> and <B>27</B>, suggesting the ionic decomposition pathway. However, an ESR signal was observed during the thermal decomposition of <B>4</B> in the absence of oxygen, implying a concurrent homolytic pathway if not a major one. The mechanism of these reactions are briefly discussed. The photolysis of <B>4</B> led to <B>27</B> and <I>N</I>,<I>N</I>′-bis(2,4-di-<I>t</I>-butyl-6-methylphenyl)sulfur diimide (<B>43</B>).

• 公益社団法人 日本化学会の論文

著者

• Inamoto Naoki

  Department Of Chemistry Graduate School Of Science The University Of Tokyo

• Okazaki Renji

  Department Of Chemical And Biological Sciences Faculty Of Science Japan Women's University

• Inamoto Naoki

  Department of Chemistry, Faculty of Science, The University of Tokyo

• Inagaki Yoshio

  Department of Chemistry, Faculty of Science, The University of Tokyo

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