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Dithiocarboxylic acid

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Dithiocarboxylic acids are organosulfur compounds with the formula RCS2H. They are the dithia analogues of carboxylic acids. A closely related and better studied family of compounds are the monothiocarboxylic acids, with the formula RCOSH.

Dithiocarboxylic acids are about 3x more acidic than the monothiocarboxylic acids. Thus, for dithiobenzoic acid pKa = 1.92. Such compounds are commonly prepared by the reaction of carbon disulfide with a Grignard reagent:

RMgX + CS2 → RCS2MgX
RCS2MgX + HCl → RCS2H + MgXCl

This reaction is comparable to the formation of carboxylic acids using a Grignard reagent and carbon dioxide. Dithiocarboxylate salts readily S-alkylate to give dithiocarboxylate esters:

RCS2Na + R'Cl → RCS2R' + NaCl

Aryldithiocarboxylic acids, e.g., dithiobenzoic acid, chlorinate to give the thioacyl chlorides.

Oxygen transfer to a dithiocarboxylate ester gives a sulfine-like S-oxide that rearranges to an acylsulfenyl thiolate.

References

  1. Grote, Johanna; Friedrich, Felix; Berthold, Katarína; Hericks, Loreen; Neumann, Beate; Stammler, Hans‐Georg; Mitzel, Norbert W. (2018). "Dithiocarboxylic Acids: An Old Theme Revisited and Augmented by New Preparative, Spectroscopic and Structural Facts". Chemistry – A European Journal. 24 (11): 2626–2633. doi:10.1002/chem.201704235. PMID 29266463.
  2. Matthys J. Janssen (1969). "Thiolo, Thiono and Dithio Acids and Esters". In Saul Patai (ed.). Carboxylic Acids and Esters. PATAI'S Chemistry of Functional Groups. pp. 705–764. doi:10.1002/9780470771099.ch15. ISBN 978-0-470-77109-9.
  3. Ramadas, S. R.; Srinivasan, P. S.; Ramachandran, J.; Sastry, V. V. S. K. (1983). "Methods of Synthesis of Dithiocarboxylic Acids and Esters". Synthesis. 1983 (8): 605–622. doi:10.1055/s-1983-30446. S2CID 96087227.
  4. Frederick Kurzer; Alexander Lawson (1962). "Thiobenzoylthioglycolic Acid". Org. Synth. 42: 100. doi:10.15227/orgsyn.042.0100.
  5. Collier, S. J. (2007). "Product class 8: Thiocarboxylic S-acids, selenocarboxylic Se-acids, tellurocarboxylic Te-acids, and derivatives". In Panek, J. S. (ed.). Category 3, Compounds with Four and Three Carbon Heteroatom Bonds: Three Carbon—Heteroatom Bonds: Esters, and Lactones; Peroxy Acids and R(CO)OX Compounds; R(CO)X, X=S, Se, Te. Science of Synthesis. Stuttgart: Georg Thieme Verlag. p. 1651. doi:10.1055/sos-sd-020-01480. ISBN 978-3-13-144691-6.
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