Thermal curtius rearrangement of N-acyl-S,S-diphenylsulfilimine.

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概要

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• Several <I>N</I>-acyl-<I>S</I>,<I>S</I>-arylphenylsulfilimines were prepared and subjected to thermal decomposition. They decomposed readily at 130–190 °C to give isocyanates together with diphenyl sulfide, quantitatively. However, <I>N</I>-tosyl-<I>S</I>,<I>S</I>-diphenylsulfilimine did not decompose even upon heating at 200 °C for 24 h. A kinetic study revealed that the rates of pyrolysis of <I>N</I>-aroyl-<I>S</I>,<I>S</I>-arylphenylsulfilimines (<I>p</I>-Y–C<SUB>6</SUB>H<SUB>4</SUB>(Ph)S→NCOC<SUB>6</SUB>H<SUB>4</SUB>–X-<I>p</I>) are nicely correlated with the Hammett σ-values, ρ<SUB>X</SUB>=−1.2 and ρ<SUB>Y</SUB>=+0.92, respectively, being obtained. The activation enthalpies and entropies were <I>ΔH</I><SUP>\neweq</SUP>=38.7 kcal/mol and <I>ΔS</I><SUP>\neweq</SUP>=6.0 e.u. for Ph<SUB>2</SUB>S→NCOPh and <I>ΔH</I><SUP>\neweq</SUP>=32.3 kcal/mol and <I>ΔS</I><SUP>\neweq</SUP>=5.5 e.u. for (<U>Remark: Graphics omitted.</U>), respectively. The rearrangement was accelerated considerably by <I>o</I>-methyl substituent in the aryl group. The effect of solvent on the rate of pyrolysis was small. The results indicate that the pyrolysis of sulfilimine proceeds <I>via</I> a concerted migration of the R group from carbonyl carbon to imino nitrogen similar to the Curtius type rearrangement of acid azide.

• 公益社団法人 日本化学会の論文

著者

• Furukawa Naomichi

  Department Of Chemistry And Tsukuba Advanced Research Alliance Center University Of Tsukuba

• Nishio Takehiko

  Department Of Chemistry University Of Tsukuba

• Oae Shigeru

  Deparment of Applied Chemistry Faculty of Engineering Osaka City University

• Fukumura Mitsuo

  Department of Chemistry, University of Tsukuba

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