Thermolysis of Alkyl Sulfoxides and Derivatives:  A Comparison of Experiment and Theory

• Published in: Journal of organic chemistry Vol. 66; no. 26; pp. 8722 - 8736
• Main Authors: Cubbage, Jerry W, Guo, Yushen, McCulla, Ryan D, Jenks, William S
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 28-12-2001
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo0160625

Gas-phase activation data were obtained for model sulfoxide elimination reactions. The activation enthalpy for methyl 3-phenylpropyl sulfoxide is 32.9 ± 0.9 kcal/mol. Elimination by methyl vinyl sulfoxide to form acetylene has an enthalpic barrier of 41.6 ± 0.8 kcal/mol and that of 3-phenylpropyl methanesulfinate to form hydrocinnamaldehyde is 34.6 ± 0.6 kcal/mol. Calculations at the MP2/6-311+G(3df,2p)//MP2/6-31G(d,p) level for simplified models of these reactions provide barriers of 32.3, 40.3, and 32.7 kcal/mol, respectively. A series of other compounds are examined computationally, and it is shown that the substituent effects on the sulfoxide elimination reaction are much more straightforward to interpret if ΔH data are available in addition to the usually determined ΔH ⧧. The activation enthalpy of the reverse addition reaction is also subject to structural variation and can usually be rationalized on the basis of nucleophilicity of the sulfur or polarity matching between the sulfenic acid and olefin derivative.