Formation of Thioethers in Ethylenediamine

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Bibliographic Information

Other Title
  • エチレンジアミン中でのチオエーテル化反応
  • アミンによって活性化された硫黄化合物の反応　ＩＩＩ　　エチレンジアミン中でのチオエーテル化反応

Description

Formation of thioethers from the reaction of thiols with alkyl chlorides has been studied in ethylenediamine at 15-45° C. The BrOnsted's catalytic constant (a) for the thiol was O. O2-4. The reactivity of alkyl chlorides was remarkably influenced by their structure; the rate constants decreased in the order: n-C9H7Cl>n-C4H9Cl>n-C8H17Cl>i-C4H9Cl>i-C3H7Cl>s-C4H9Cl. The reactions of thiols of high pKa e. g., 1-octhanethiol and 1-buthanethiol, were accelerated only in primary diamines such as ethylenediamine whereas benzenethiol reacted with butyl chloride in butylamine at 30° C. It was suggested that the thiols of low pKa such as benzene- thiol are dissociated into the thiolate anion in amine and the thiols of high pKa are not: although the S-H bond of the thiols appeared to be elongated by ethylenediamine. The interesting behaviors of the thiols of high pKa in ethylenediamine were explained by the formation of such a proton-transfer type complex as follows:<BR>Therefore, it may be concluded that the reactions between the thiols of low pKa and alkyl chlorides are bimolecular nucleophilic substitutions of ion-dipolar type and those of the thiols of high pKa are substitutions of dipolar-dipolar type.

Journal

  • NIPPON KAGAKU KAISHI

    NIPPON KAGAKU KAISHI 1975 (10), 1776-1779, 1975-10-10

    The Chemical Society of Japan

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