RI 6698 Mass Spectra Of Organic Sulfur Compounds

Correlations between mass spectra and molecular structures of 186 organic sulfur compounds are discussed. The olefinic ions, the alkyl ions, the CnE2n+1 ions, the m/e 61 ions, and the m/e 35 ions in the spectra of thiols are related to molecular structure. In the spectra of sulfides, the olefinic ions, the m/e 61 ions, the m/e 35 ions, the CnH2n+1S+ ions, and the CnH2n+1SH+ ions are correlated with molecular structure. For disu1fides, the correlations relate HSSF+& and RSSH+ ions to molecular structure. Base peaks of alkylthiophenes are correlated to their molecular structures. Some unimolecular reactions of sulfur compounds in the mass spectrometer are considered. A cyclic intermediate is suggested for the reaction which produces m/e 47, CH3S+, and m/e 48, CH4S+, ions in the spectra of sulfides. An expanded ring is suggested as a possible intermediate in the reactions of thiophenes. Heats of formation of sulfur-containing ions and their appearance potentials are presented in tabular form. Ionization potentials for sulfur-containing radicals and molecules are also given. Discussion of the spectra, tabulated in the appendixes, provides an insight into the relationship of the molecular structure of a compound to the mass-to-charge ratios and the intensities of the ions in its mass spectrum. Correlations of the mass spectra with molecular structures are empirically developed by observing regularities in the spectra of the reference compounds. Correlations extend the usefulness of mass spectra because they can be employed to determine the molecular structure of an unknown compound.