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高等学校化学研究 ›› 2001, Vol. 17 ›› Issue (1): 95-101.

• Articles • 上一篇    下一篇

Effects of Pressure, Solvent, and Substituenton the Thermal Isomerization of 2-Oxo-spiro［diazirine-3,3'-indoline］

Yoshimi Sueishi, Genta Okazaki   

  1. Department of Chemistry, Faculty of Science, Okayama University, Tsushima Naka 3-1-1, Okayama 700-8530, Japan
  • 收稿日期:1999-12-27 出版日期:2001-01-24 发布日期:2011-08-04

Effects of Pressure, Solvent, and Substituenton the Thermal Isomerization of 2-Oxo-spiro［diazirine-3,3'-indoline］

Yoshimi Sueishi, Genta Okazaki   

  1. Department of Chemistry, Faculty of Science, Okayama University, Tsushima Naka 3-1-1, Okayama 700-8530, Japan
  • Received:1999-12-27 Online:2001-01-24 Published:2011-08-04

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摘要： The kinetic effects of pressure, solvent, and substituent on the thermal isomerization from 2-oxospiro［diazirine-3,3'-indoline］ to 3-diazo-2-oxo-indoline have been examined. The rate constants of the thermal isomerization increased with increasing external pressure and were related to the σ+P substituent constant of Hammett correlation. The results suggest that the thermal isomerization proceeds via a dipolar transition state involving heterolytic bond fission. However, the kinetic solvent effects on the thermal isomerization were not observed. The special solvent effects were discussed on the basis of the linear free energy relationship.

关键词: Kinetic study, Pressure effect, Substituent effect, Thermal isomerization, Diazirine

Abstract: The kinetic effects of pressure, solvent, and substituent on the thermal isomerization from 2-oxospiro［diazirine-3,3'-indoline］ to 3-diazo-2-oxo-indoline have been examined. The rate constants of the thermal isomerization increased with increasing external pressure and were related to the σ+P substituent constant of Hammett correlation. The results suggest that the thermal isomerization proceeds via a dipolar transition state involving heterolytic bond fission. However, the kinetic solvent effects on the thermal isomerization were not observed. The special solvent effects were discussed on the basis of the linear free energy relationship.

Key words: Kinetic study, Pressure effect, Substituent effect, Thermal isomerization, Diazirine