Thianthrene Explained

Thianthrene is a sulfur-containing heterocyclic chemical compound. It is a derivative of the parent heterocycle called dithiin. It is notable for its ease of oxidation.

Structure and synthesis

Like other 1,4-dithiins but unlike its oxygen analog dibenzodioxin, the shape of thianthrene is not planar. It is bent, with a fold angle of 128° between the two benzo groups.^{[1] [2] [3]}

Thianthrene can be prepared by treating benzene with disulfur dichloride in the presence of aluminium chloride.^[4]

History

Thianthrene was first synthesized by John Stenhouse by dry distillation of sodium benzenesulfonate.^[5] Thianthrene is oxidized by sulfuric acid forming a red radical cation.^[6] Thianthrene^•+ has been characterized by Electron paramagnetic resonance. Four different publications describe the crystal structure of salts of thianthrene^•+.^[7]

Notes and References

1. Hosoya . S. . Molecular shapes of thianthrene and related heterocyclic compounds . Acta Crystallographica . 16 . 310–312 . 1963 . 10.1107/S0365110X63000797 . 4. free . 1963AcCry..16..310H .
2. Gallaher . K. L. . Bauer . S. H. . Structure and inversion potential of thianthren . Journal of the Chemical Society, Faraday Transactions 2 . 71 . 1173–1182 . 1975 . 10.1039/F29757101173.
3. Aroney . M. J. . Le Fèvre . R. J. W. . Saxby . J. D. . 92. Molecular polarisability. The apparent conformations of thianthren and of three of its oxides as solutes in benzene . Journal of the Chemical Society (Resumed) . 571–575 . 1965 . 10.1039/JR9650000571.
4. Process for the manufacture of thianthrene . US . 3997560 . patent . 1976-12-14. .
5. Stenhouse. J.. On the Dry Distillation Products from Sulfobenzoic Acid Salts. German. Ueber die Producte der trockenen Destillation der sulfobenzolsauren Salze. Annalen der Chemie und Pharmacie. 149. 247–255. 1869. 10.1002/jlac.18691490216. 2.
6. W. Dilthey: Versammlungsberichte Bonner Chemische Gesellschaft, Angewandte Chemie, Volume 42, Issue 24, pp. 668–670, 15. June 1929; .
7. Book: Shine, Henry J. . https://books.google.com/books?id=1LdKSYIQtPYC&pg=PA202 . EPR and the History of the Thianthrene Cation Radical . Foundations of modern EPR . 978-981-02-3295-5 . July 1998. World Scientific .