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Gas‐Phase Thermolysis, 14. On the Isomerization of Dimethyl Carbonate and Its Mono‐, Di‐, and Trithio Analogs
Author(s) -
Egsgaard Helge,
Carlsen Lars,
Sülzle Detlev,
Schwarz Helmut
Publication year - 1991
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19911240546
Subject(s) - chemistry , pyrolysis , isomerization , sulfur , oxygen , thermal decomposition , mass spectrometry , decomposition , dimethyl carbonate , gas phase , carbonate , phase (matter) , photochemistry , inorganic chemistry , organic chemistry , catalysis , chromatography
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, 18 O, and 34 S 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.