Dithietane

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Class of chemical compounds

title: "Dithietane" type: doc version: 1 created: 2026-02-28 author: "Wikipedia contributors" status: active scope: public tags: ["dithietanes"] description: "Class of chemical compounds" topic_path: "general/dithietanes" source: "https://en.wikipedia.org/wiki/Dithietane" license: "CC BY-SA 4.0" wikipedia_page_id: 0 wikipedia_revision_id: 0

::summary Class of chemical compounds ::

::figure[src="https://upload.wikimedia.org/wikipedia/commons/8/81/Dithetane.png" caption="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. 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 dithiocarbonyl compound. [[File:Dithiatopazine.svg|thumb|center|200px|Structure of dithiatopazine]]

1,2-Dithietanes are to be distinguished from 1,2-dithietes, containing two adjacent sulfur atoms and two sp2-hybridized carbon centers.

::figure[src="https://upload.wikimedia.org/wikipedia/commons/e/eb/Trans-3,4-diethyl-1,2-dithietane_1,1-dioxide.svg" caption="Structure of ''trans''-3,4-diethyl-1,2-dithietane 1,1-dioxide, the dimer of the onion lachrymatory agent"] ::

A stable 1,2-dithietane derivative is trans-3,4-diethyl-1,2-dithietane 1,1-dioxide, formed by the spontaneous dimerization of the lachrymatory agent syn-propanethial-S-oxide, found in onion.

1,3-Dithietanes

In 1,3-dithietanes, the sulfur atoms are non-adjacent. 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, as shown in the scheme below. 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.

::figure[src="https://upload.wikimedia.org/wikipedia/commons/8/82/Synthesis_of_1,3-dithietane.svg" caption="Synthesis of 1,3-dithietane"] ::

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 and 1,3-dithietane 1,1,3,3-tetraoxide, the so-called sulfene dimer.

::figure[src="https://upload.wikimedia.org/wikipedia/commons/7/7a/1,3-Dithietanes.svg" caption="Left: [[thiophosgene]] dimer, 2,2,4,4-tetrachloro-1,3-dithietane; center: a zwiebelane, found in onion volatiles; right: sulfene dimer"] ::

References

References

  1. Drabowicz, J. (2008). "Four-membered Rings with Two Sulfur Atoms". Comprehensive Heterocyclic Chemistry III.
  2. Zoller, U. (1996). "Four-membered Rings with Two Sulfur Atoms". Comprehensive Heterocyclic Chemistry II.
  3. Nicolaou, KC. (1987). "Dithiatopazine. The first stable 1,2-dithietane". J. Am. Chem. Soc..
  4. Block, E. (1980). "The chemistry of sulfines. 6. Dimer of the onion lachrymatory factor: the first stable 1,2-dithietane derivative". J. Am. Chem. Soc..
  5. Luh, TY. (2007). "Product Subclass 2: 1,3-Dithietanes". Sci. Synth..
  6. Block, E. (1976). "1,3-Dithietane". J. Am. Chem. Soc..
  7. Block, E. (1982). "Synthesis and Thermal Decomposition of 1,3-Dithietane and its ''S''-Oxides". J. Am. Chem. Soc..
  8. Van Der Puy, M.. (1990). "Hexafluoroacetone".
  9. Block, E. (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..
  10. Opitz, G. (1969). "Disulfene". Angew. Chem. Int. Ed..

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dithietanes