E/Z Oxime Isomerism in PhC(NOH)CN |
| |
| Authors: | Prof D Scott Bohle Zhijie Chua Dr Inna Perepichka Kristopher Rosadiuk |
| |
| Institution: | Department of Chemistry, McGill University, 801 Sherbrooke St. W. Montreal, H3A 2K6, Quebec (Canada), Fax: (+1)?514‐398‐3797 |
| |
| Abstract: | The reaction of nitric oxide with benzyl cyanide in the presence of potassium methoxide at low temperature gave the dipotassium salt of a bis‐diazeniumdiolate 2 in excellent yield. Two new stereospecific syntheses of E or Z 2‐(hydroxyimino)‐2‐phenylacetonitrile from 2 have been found. The thermodynamics of the E/Z isomerization has been investigated spectroscopically in solution, in the solid state by differential scanning calorimetry (DSC), and theoretically in the gas phase. Evidence of catalysis by NO of E/Z oxime isomerization has been observed. |
| |
| Keywords: | density functional calculations isomerization oximes spin catalysis stereochemistry |
|
|
