Thianthrene

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Thianthrene
Thianthrene.svg
CSD CIF THIANT08.png
Names
Preferred IUPAC name
Thianthrene [1]
Other names
Thianthren; 9,10-Dithiaanthracene; Di-o-phenylene disulfide
Identifiers
3D model (JSmol)
ChEMBL
ChemSpider
ECHA InfoCard 100.001.998 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 202-197-0
PubChem CID
UNII
  • InChI=1S/C12H8S2/c1-2-6-10-9(5-1)13-11-7-3-4-8-12(11)14-10/h1-8H Yes check.svgY
    Key: GVIJJXMXTUZIOD-UHFFFAOYSA-N Yes check.svgY
  • S1c3c(Sc2c1cccc2)cccc3
Properties [2]
C12H8S2
Molar mass 216.32 g·mol−1
Melting point 151 to 155 °C (304 to 311 °F; 424 to 428 K)
Boiling point 364 to 366 °C (687 to 691 °F; 637 to 639 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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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.

Contents

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. [3] [4] [5]

Synthesis

Thianthrene was first synthesized by John Stenhouse by dry distillation of sodium benzenesulfonate. [6] Thianthrene is oxidized by sulfuric acid forming a red radical cation. [7] Thianthrene can be prepared by treating benzene with disulfur dichloride in the presence of aluminium chloride. [8] [9]

Reactions

Thianthrene•+ has been characterized by Electron paramagnetic resonance. Four different publications describe the crystal structure of salts of thianthrene•+. [10] The cation is nearly planar, depending on the particular salt. In addition to flattening the heterocycle, removal of an electron causes the C-S distances to contract by 3%. [11] It also can function as a Lewis base. [12] Oxidation of thianthrene can also give the sulfoxides and sulfones. [13]

References

  1. ↑ International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. p. 216. doi:10.1039/9781849733069. ISBN   978-0-85404-182-4.
  2. ↑ Thianthrene at Sigma-Aldrich
  3. ↑ Hosoya, S. (1963). "Molecular shapes of thianthrene and related heterocyclic compounds". Acta Crystallographica. 16 (4): 310–312. Bibcode:1963AcCry..16..310H. doi: 10.1107/S0365110X63000797 .
  4. ↑ Gallaher, K. L.; Bauer, S. H. (1975). "Structure and inversion potential of thianthren". Journal of the Chemical Society, Faraday Transactions 2. 71: 1173–1182. doi:10.1039/F29757101173.
  5. ↑ Aroney, M. J.; Le Fèvre, R. J. W.; Saxby, J. D. (1965). "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. doi:10.1039/JR9650000571.
  6. ↑ Stenhouse, J. (1869). "Ueber die Producte der trockenen Destillation der sulfobenzolsauren Salze" [On the Dry Distillation Products from Sulfobenzoic Acid Salts]. Annalen der Chemie und Pharmacie (in German). 149 (2): 247–255. doi:10.1002/jlac.18691490216.
  7. ↑ W. Dilthey: Versammlungsberichte Bonner Chemische Gesellschaft, Angewandte Chemie , Volume 42, Issue 24, pp. 668–670, 15. June 1929; doi : 10.1002/ange.19290422405.
  8. ↑ USpatent 3997560,"Process for the manufacture of thianthrene",issued 1976-12-14.
  9. ↑ Speicher, Samira; Plutschack, Matthew B.; Ritter, Tobias (2021). "Late-stage C-H Functionalization with 2,3,7,8–Tetrafluorothianthrene: Preparation of a Tetrafluorothianthrenium-salt". Organic Syntheses. 98: 531–552. doi:10.15227/orgsyn.098.0531.
  10. ↑ Shine, Henry J. (July 1998). "EPR and the History of the Thianthrene Cation Radical". Foundations of modern EPR. World Scientific. ISBN   978-981-02-3295-5.
  11. ↑ Beck, Johannes; Bredow, Thomas; Tjahjanto, Rachmat Triandi (2009). "Thianthrene Radical Cation Hexafluorophosphate". Zeitschrift für Naturforschung B. 64 (2): 145–152. doi: 10.1515/znb-2009-0201 .
  12. ↑ Roy, Mrittika; Fu, Wen; Baldauf, Lilia M.; Fettinger, James C.; Britt, R. David; Balch, Alan L. (2023). "Reactions of Thianthrene and 10-Phenylphenothiazine with the Lewis Acids─Titanium Tetrachloride, Titanium Tetrabromide, Tin(IV) Tetrachloride, or Antimony(V) Pentachloride: The Competition between Coordination and Oxidation". Inorganic Chemistry. 62 (34): 14055–14063. doi:10.1021/acs.inorgchem.3c02079. PMID   37582091.
  13. ↑ Liu, Ming-Shang (2024). "Metal-Free Aziridination of Alkenes with Free Amines by Thianthrenation". Organic Syntheses. 101: 34–50. doi:10.15227/orgsyn.101.0034.
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