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Schild, F. (1954) Preparation of certain thioanilides: mechanism of decomposition of alkyl chloroformates and chlorosulphinates in the presence of tertairy bases. Doctoral thesis, Northern Polytechnic.
Part I. Preparation of Certain Thioanilides:
Modes of preparation of a number of thioanilides have been examined with a view to improving technique and to the study of the formation of certain dyes which were to have been examined spectroscopically. Such difficulties were encountered in the preparation of the intermediate, that it became clear, that an extension of the work to the preparation of the dyes themselves would become an unduly protracted operation. Certain observations are, however, recorded.
Part II. Mechanism of Decomposition of Alkyl Chloroformates and Chlorosulphinates in the presence of Tertiary Bases:
Growing interest in the chemistry of alkyl sulphites and chlorosulphinates, particularly from the point of view of their likely industrial applications, led to the decision to clarify a certain confusion in published descriptions, not only of thionyl chloride - but also of carbonyl chloride - alcohol systems. The main confusion involves the function of pyridine. The earlier observations of Carré and Libermann have led to the propagation of descriptions which are not in accord with more detailed study. It is now shown that chlorosulphinates and chloroformates of ordinary alcohols react quickly with both pyridine and quinoline; but whereas the chlorosulphinates quickly give a mixture of alkylchloride, sulphur dioxide, tertiary base, and quaternary salt, chloroformates form complexes. The decomposition of pyridine complex fairly quickly gives rise to the alkyl chloride, carbon dioxide and base; but the quinoline complex does this much more slowly. The influence of base hydrochloride is different from that of free base. Base hydrochloride facilitates the decomposition of chloro- sulphinates, much more effectively than it does the chloroformates. Some justification for the present investigation accrues from a very recent paper which appeared in the J. Amer. Chem. Soc., 1954, 76, 1207.
The interaction of hydrogen chloride with alkyl sulphites and with alkyl carbonates is discussed.
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