62965-22-4Relevant academic research and scientific papers
Thermolysis of alkyl sulfoxides and derivatives: A comparison of experiment and theory
Cubbage,Guo,McCulla,Jenks
, p. 8722 - 8736 (2007/10/03)
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.
Sulfenic acids in the gas phase: A photoelectron study
Lacombe,Loudet,Banchereau,Simon,Pfister-Guillouzo
, p. 1131 - 1138 (2007/10/03)
Thermolysis of methyl methanethiosulfinate and methyl tert-butyl sulfoxide has been studied by photoelectron (PE) spectroscopy. The electronic structure of methanesulfenic acid (1) generated from both compounds has been determined, and the thermal stability of 1 was checked. 1 appears rather stable in the gas phase, giving rise to thioformaldehyde and water at high temperature. Thermolysis of vinyl tert-butyl sulfoxide gives rise to ethanethial S-oxide (6). At the thermolysis onset, sulfine 6 is observed in a mixture with a compound identified as ethenesulfenic acid (4). These results imply either an easy isomerization of 4 to 6, in agreement with previous theoretical evaluations, or an alternative thermolysis pathway of the starting sulfoxide, directly leading to sulfine 6. The obtained PE spectra complement previous microwave and/or mass spectrometry data and provide a further insight in the electronic structure and thermal stability of sulfenic acids 1 and 4. The experimental ionization potentials are compared throughout this study with ab-initio calculated vertical ionization potentials either within Koopmans' approximation or by difference between the ionic and ground state energies.
A NEW SYNTHESIS OF THIOFLAVONES
Taylor, A. W.,Dean, D. K.
, p. 1845 - 1848 (2007/10/02)
A new synthesis of thioflavones from β-keto sulphoxide (12) is described.
