Chemistry of N-thiosulfinylanilines. III. Thiosulfinylamine-5H-1,2,3-dithiazole equilibrium as studied by NMR spectroscopy.

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概要

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• Thermodynamic parameters (Δ<I>H</I>=−4.9 kcal mol<SUP>−1</SUP>, Δ<I>S</I>=−11.3 cal mol<SUP>−1</SUP> deg<SUP>−1</SUP>) were determined for cyclization of 2,4,6-tri-<I>t</I>-butyl-<I>N</I>-thiosulfinylaniline (<B>1b</B>) (the minor component) into 2,4,6-tri-<I>t</I>-butyl-7,8-dithia-9-azabicyclo[4.3.0]nona-2,4,9-triene (<B>1a</B>) (the major component) by means of NMR spectroscopy. Using these values, π-bond of thiosulfinylamino group (–N=S=S) was estimated to be weaker than that of sulfinylamino group (–N=S=O) by, at least, 25 kcal mol<SUP>−1</SUP>. The equilibrium ratio [<B>1a</B>]/[<B>1b</B>] is subject to considerable solvent effect, polar solvents favoring the cyclic form (<B>1a</B>). Similarity of the thiosulfinylamine-dithiazole equilibrium to that of azidoimine-tetrazole has been pointed out.

• 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

• Yamada Koh-ichi

  Faculty Of Pharmaceutical Sciences Josai University

• Okazaki Renji

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

• Kawazura Hiroshi

  Faculty Of Pharmaceutical Sciences Josai University

• Inagaki Yoshio

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

• Inamoto Naoki

  Department of Chemistry and Research Centre for Spectrochemistry, Faculty of Science, The University of Tokyo

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