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Gas-Phase Thermolysis, 14. On the Isomerization of Dimethyl Carbonate and Its Mono-, Di-, and Trithio Analogs (1991)

Egsgaard, Helge ; Carlsen, Lars ; Sülzle, Detlev ; [weitere]

Weinheim : Wiley-Blackwell

Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1265-1270

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ISSN: 0009-2940

Schlagwort(e): Gas-phase pyrolysis ; Tandem mass spectrometry ; Carbonates ; Alkyl migration ; Chemistry ; Inorganic Chemistry

Quelle: Wiley InterScience Backfile Collection 1832-2000

Thema: Chemie und Pharmazie

Notizen: Gas-phase pyrolysis of dimethyl carbonate and its mono-, di-, and trithio analogs has been performed in the temperature range from 1253 to 1404 K applying the gas phase Curie-point pyrolysis technique. Real-time analyses have been carried out by means of mass-spectrometric techniques. The possible isomerizations of the ester functions have been studied by collisional activation mass spectrometry in combination with appropriate D, 18O, and 34S labeling. It is demonstrated that methyl group migrations can be induced pyrolytically in cases where oxygen-to-oxygen or oxygen-to-sulfur isomerizations are involved; in contrast, sulfur-to-oxygen as well as sulfur-to-sulfur isomerizations apparently do not take place.

Zusätzliches Material: 7 Ill.

Materialart: Digitale Medien

URL: http://dx.doi.org/10.1002/cber.19911240546

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Digitale Medien

On the OCS2 Singlet potential energy surfaceOxathiiranes Part VIII; for Part VII see ref. 1. (1982)

Carlsen, Lars

New York, NY [u.a.] : Wiley-Blackwell

Journal of Computational Chemistry 3 (1982), S. 23-27

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ISSN: 0192-8651

Schlagwort(e): Computational Chemistry and Molecular Modeling ; Biochemistry

Quelle: Wiley InterScience Backfile Collection 1832-2000

Thema: Chemie und Pharmazie , Informatik

Notizen: The reaction between atomic oxygen and carbon disulfide is predicted to lead to at least two primary products, which are the dithiiranone (1) and the oxathiirane-thione (2) and/or the carbon disulfide S-oxide (4). The possible intramolecular equilibria 1 ⇄ 2, 1 ⇄ 3, 2 ⇄ 4, and 2 ⇄ 5 as well as the fragmentations of the possible intermediates 1-5 have been studied theoretically within the semiempirical CNDO/B framework as conceivable ground-state reactions. On the basis of MO correlations and potential energy changes along the reaction paths, supplementary with previously reported experimental data, the single molecular transformations and the eventual product formations are discussed.

Zusätzliches Material: 4 Ill.

Materialart: Digitale Medien

URL: http://dx.doi.org/10.1002/jcc.540030105

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