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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 24, Number 6
BKCSDE 24(6)
June 20, 2003 

 
Title
Theoretical Study on the Pyrolysis of Sulphonyl Oximes in the Gas Phase
Author
Ying Xue, Kyung A Lee, Chan Kyung Kim
Keywords
Sulphonyl oximes, Pyrolysis, ONIOM method, Transition state, Substituent effect
Abstract
The reaction mechanism of the pyrolysis of sulphonyl oximes (CH3-C6H4-S(O)2O-N=C(H)-C6H4Y), in the gas phase is studied theoretically at HF/3-21G, ONIOM (B3LYP/6-31G**:HF/3-21G) and ONIOM (MP2/6- 31G**:HF/3-21G) levels. All the calculations show that the thermal decomposition of sulphonyl oximes is a concerted asynchronous process via a six-membered cyclic transition state. The activation energies (Ea) predicted by ONIOM (B3LYP/6-31G**: HF/3-21G) method are in good agreement with the experimental results for a series of tosyl arenecarboxaldoximes. Five para substituents, Y = OCH3, CH3, H, Cl, and NO2, are employed to investigate the substituent effect on the elimination reaction. Linear Hammett correlations are obtained in all calculations in contrast to the experimental finding.
Page
853 - 858
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