Acta Phys. -Chim. Sin. ›› 2007, Vol. 23 ›› Issue (03): 399-403.doi: 10.3866/PKU.WHXB20070322

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Reaction of Methyl Alcohol with Thionyl Chloride in Solution

ZHANG Cheng-Gen;LI Wen-Zuo;HUANG Ming-Bao   

  1. (College of Chemistry and Chemical Engineering, Graduate University of the Chinese Academy of Sciences, Beijing 100049, P. R. China; Science and Engineering College of Chemistry and Biology, Yantai University, Yantai 264005, Shandong Province, P. R. China)
  • Received:2006-08-03 Revised:2006-11-14 Published:2007-03-07
  • Contact: HUANG Ming-Bao E-mail:mbhuang1@gucas.ac.cn

Abstract: Reaction of CH3OH with SOCl2 producing CH3Cl and SO2 in two nonpolar (ε<15) and two polar (ε>15) solvents was studied using the B3LYP method and the SCIPCM model of the SCRF theory for simulating solution effects. The reaction process consists of reaction (1) and reaction (2) with CH3OS(O)Cl being a product of reaction (1) and the reactant of reaction (2). Reaction (2) has front-side substitution (via transition state TS3f) and back-side substitution (ionization of CH3OS(O)Cl followed by substitution via transition state TS3b) mechanisms. The calculations predicted that in gas phase and in the four solvents reactions (1) and (2) were exothermic and reaction (1) had the same reaction path (TS1→IM1→TS2). The calculations indicated that reaction (2) experienced very strong effects of solvent. In gas phase and in nonpolar solvents the front-side substitution was favored over the back-side substitution since TS3f is lower in energy than the (CH3OSO++Cl-) ion pair (IM2); and in polar solvents the back-side substitution was favored over the front-side substitution since IM2 and TS3b are lower in energy than TS3f.

Key words: B3LYP, SCIPCM model, CH3OH+SOCl2 reaction, Solvent effect, Configuration conversion