Dithietane

Structure of a 1,3-dithietane (left) and 1,2-dithietane (right), where R is an organic group

A dithietane is a saturated heterocyclic compound that contain two divalent sulfur atoms and two sp3-hybridized carbon atoms.[1][2] Two isomers are possible for this class of organosulfur compounds:

1,2-Dithietanes

1,2-dithietanes, 4-membered rings where the two sulfur atoms are adjacent, are very rare. The first stable 1,2-dithietane to be reported was the dithiatopazine, formed by intramolecular photodimerization of a bis(thionolactone):[3]

Structure of dithiatopazine
Structure of dithiatopazine

Heating dithiatopazine generates eliminates the sulfur atoms as unstable disulfur, and other dithietanes are presumed to decompose similarly.[4]

A stable 1,2-dithietane derivative is trans-3,4-diethyl-1,2-dithietane 1,1-dioxide:

Structure of trans-3,4-diethyl-1,2-dithietane 1,1-dioxide, the dimer of the onion lachrymatory agent
Structure of trans-3,4-diethyl-1,2-dithietane 1,1-dioxide, the dimer of the onion lachrymatory agent

That compound is formed by the spontaneous dimerization of syn-propanethial-S-oxide, the lachrymatory agent found in onions.[5]

Another derivative class of 1,2-dithietanes are the 1,2-dithietes, containing two adjacent sulfur atoms and two trigonal planar carbon centers.

1,3-Dithietanes

In 1,3-dithietanes, the sulfur atoms are non-adjacent.[6] The functional group is used industrially in various biocides. Examples include the antibiotic Cefotetan and the pesticide Fosthietan.[7]

1,3-Dithietane itself, a colorless, easily sublimed, crystalline, unpleasant-smelling solid with melting point 105-106 °C, was first prepared in 1976 by reaction of bis(chloromethyl) sulfoxide with sodium sulfide followed by THF-borane reduction of the first formed 1,3-dithietane 1-oxide:[8][9]

Synthesis of 1,3-dithietane
Synthesis of 1,3-dithietane

Carbon-substituted 1,3-dithietanes are well known, with the first examples being described as early as 1872. Examples include 2,2,4,4-tetrachloro-1,3-dithietane, the photochemically-formed dimer of thiophosgene, and tetrakis(trifluoromethyl)-1,3-dithietane, [(CF3)2CS]2.[10] Symmetric 1,3‑dithietanes are preferably synthesized from thiocarbonyl dimerization.[11] Heating or irradiating dithietanes results in "dedimerization" to give the corresponding thiocarbonyl compounds.[12]

Oxidized forms of 1,3-dithietane are well known, although they are often not prepared from the dithietane. Examples include the so-called zwiebelanes (2,3-dimethyl-5,6-dithiabicyclo[2.1.1]hexane S-oxides) from onion volatiles[13] and 1,3-dithietane 1,1,3,3-tetraoxide, the so-called sulfene dimer:[14]

Left: thiophosgene dimer, 2,2,4,4-tetrachloro-1,3-dithietane; center: a zwiebelane, found in onion volatiles; right: sulfene dimer

They are more acidic than acyclic disulfones, but even so are hard to alkylate.[15]

In the desaurins, each carbon atom is attached to alkylidene substituents (i.e., a double bond).

References

  1. ^ Drabowicz, J; Lewkowski, J; Kudelska, W; Zając, A (2008). "Four-membered Rings with Two Sulfur Atoms". Comprehensive Heterocyclic Chemistry III. 2 (18): 811–852. doi:10.1016/B978-008044992-0.00218-2.
  2. ^ Zoller, Uri (1996). "Four-membered rings with two sulfur atoms". In Padwa, Albert (ed.). Comprehensive Heterocyclic Chemistry. Vol. 1B (Four-membered Rings) (IInd (covering 1982-1995) ed.). Pergamon. pp. 1113–1138. doi:10.1016/B978-008096518-5.00035-6. ISBN 9780080965185.
  3. ^ Nicolaou, KC; Hwang, CK; Duggan, ME; Carroll, PJ (1987). "Dithiatopazine. The first stable 1,2-dithietane". J. Am. Chem. Soc. 109 (12): 3801–3802. Bibcode:1987JAChS.109.3801N. doi:10.1021/ja00246a059.
  4. ^ Zoller 1996, p. 1124.
  5. ^ Block, E; Bazzi, AA; Revelle, LK (1980). "The chemistry of sulfines. 6. Dimer of the onion lachrymatory factor: the first stable 1,2-dithietane derivative". J. Am. Chem. Soc. 102 (7): 2490–2491. Bibcode:1980JAChS.102.2490B. doi:10.1021/ja00527a074.
  6. ^ Luh, TY; Leung, MK (2007). "Product Subclass 2: 1,3-Dithietanes". Sci. Synth. 30: 203–219.
  7. ^ Zoller 1996, p. 1137.
  8. ^ Block, E; Corey, ER; Penn, RE; Renken, TL; Sherwin, PF (1976). "1,3-Dithietane". J. Am. Chem. Soc. 98 (18): 5715–5717. Bibcode:1976JAChS..98.5715B. doi:10.1021/ja00434a061.
  9. ^ Block, E; Corey, ER; Penn, RE; Renken, TL; Sherwin, PF; Bock, H; Hirabayashi, T; Mohmand, S; Solouki, B (1982). "Synthesis and Thermal Decomposition of 1,3-Dithietane and its S-Oxides". J. Am. Chem. Soc. 104 (11): 3119–3130. doi:10.1021/ja00375a030.
  10. ^ Van Der Puy, M.; Anello, L. G. (1990). "Hexafluoroacetone". Organic Syntheses; Collected Volumes, vol. 7, p. 251..
  11. ^ Zoller 1996, p. 1132.
  12. ^ Zoller 1996, p. 1125.
  13. ^ Block, E; Thiruvazhi, M; Toscano, PJ; Bayer, T; Grisoni, S; Zhao, SH (1996). "Allium Chemistry: Structure, Synthesis, Natural Occurrence in Onion (Allium cepa), and Reactions of 2,3-Dimethyl-5,6-dithiabicyclo[2.1.1]hexane S-Oxides". J. Am. Chem. Soc. 118 (12): 2790–2798. Bibcode:1996JAChS.118.2790B. doi:10.1021/ja951134t.
  14. ^ Opitz, G; Mohl, HR (1969). "Disulfene". Angew. Chem. Int. Ed. 8 (1): 73. doi:10.1002/anie.196900731.
  15. ^ Zoller 1996, p. 1129.

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