Oxathiolanes

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Oxathiolanes form a class of substances in the field of heterocycles . They are 5-membered ring systems with exactly one sulfur and one oxygen heteroatom each. There are therefore two basic structures of the oxathiolane: the 1,2-oxathiolane and the 1,3-oxathiolane . Also ionic structures exist. Most of the research has been done on 1,3-oxathiolane.

Left: 1,2-oxathiolane, right: 1,3-oxathiolane

The saturated variants are referred to under the name "Oxathiolane" according to the Hantzsch-Widman-Patterson nomenclature . Under Oxathiolen other hand, is understood to mean unsaturated derivatives having otherwise the same constitution. Classes of compounds, which in the broader sense also belong to the oxathiols, are the sultines and sultones .

presentation

There is an abundance of different synthesis routes for the representation. 1,2-Oxathiolane-2-oxides can be synthesized, for example, via chlorination of 1,3-thioalcohols with the intermediate in brackets or via treatment with NCS or NBS from similar starting materials . This must be done under hydrochloric acid conditions. Even simple oxidation of 1,3-thioalcohol with sodium periodate leads to the desired product.

Three reactions to the presentation

The representation of a ring expansion of cyclopropanes by means of sulfur oxides is interesting . Examples are the reactions of arylcyclopropanes with sulfur dioxide and TFA, which gives two regioisomers :

Cyclopropane derivative to Oxathiolan.svg

As well as those of 1,1 '- (cyclopropylidenemethylene) dibenzene with sulfur trioxide , which delivers the product directly without a catalyst :

Olefinic cyclopropane derivative to Oxathiolan.svg

Oxidative ring expansion of 4-ring heterocycles is also possible. Conversely, the ring reduction of the corresponding 6-ring heterocycles with Et 2 O * BF 3 has also been described:

Sulfuric acid ester to oxathiolane.svg

A standard method for the production of 1,3-oxathiolanes is the condensation of mercaptoethanol with ketones . In order to obtain significant yields, it is necessary here to remove the condensation from the equilibrium. This can be a p-toluene sulfonic acid / benzene - azeotrope be accomplished; However, the use of an excess of boron trifluoride etherate gives even better yields for most ketones .

meaning

Dual S -oxidierte 1,2-oxathiolane-5-one analogous fragment in sulfur dioxide and the corresponding α-β-unsaturated carbonyl.

Starting from 1,2-oxathiolane-2-oxides, specific substitutions with Br 2 or PCl 3 are possible:

Possible reactions of 1,2-oxathiol-2-oxide

literature

  • J. Alvarez-Builla, JJ Vaquero, J. Barluenga: Modern Heterocyclic Chemistry. Volume 2, Wiley-VCH Verlag & Co.KGaA, 2011, ISBN 978-3-527-33201-4 , pp. 966-980.
  • DL Rakhmanklov, VV Zorin, FN Latypova, SS Zlotski, RA Karakhanov: In: Russian Chemical Reviews. Volume 52, 1983, p. 350.
  • P. Wimmer: Methods of organic chemistry. Houben-Weyl, 1991.

Individual evidence

  1. ↑ JF King, R. Rathore: An easy preparation of simple sultines and hydroxyalkanesulfinate salts . In: Tetrahedron Letters . tape 30 , no. 21 . Pergamon Press plc, London 1989, pp. 2763-2766 .
  2. ↑ RMJ Liskamp, ​​HJ Zeegers, HCJ Ottenheim: Synthesis and Ring-Opening Reactions of Functionalized Sultines. A New Approach to Sparsomycin . In: J. Org. Chem. Band 46 . Nijmegen July 31, 1981, p. 5408-5413 .
  3. ↑ S. Yolka, R. Fellous, L. Lizzani-Cuvelier, M. Loiseau: Oxidation of 3-Suifanyl-aicohois with Sodium metaperiodate: New Synthesis of Sultines . In: Tetrahedron Letters . tape 39 . Pergamon, 1998, p. 991 f .
  4. ↑ EV Grigoriev, AV Yatsenko, NV Novozhilov, LG Saginova, VS Petrosyan: Determination of Structure and Configuration of diastereomeric 3,5-diaryl-1,2-oxathiolanes-2-oxides, Sulfur Addition Products to 1,2-diarylcyclopropanes . In: Vestnik Moskovskogo Universiteta Seriya 2, Khimia . tape 34 , no. 1 . Moscow 1993, p. 87-93 .
  5. ↑ BH Bakker, H. Cerfontain, HPM Tomassen: Reactions of Adamantylidenealkanes and Cyclopropylidenealkanes with Sulfur Trioxide . In: J. Org. Chem. Band 54 . Amsterdam June 27, 1988, p. 1680-1684 .
  6. ↑ H. Kohn, P. Charumilind, SH Simonsen: 3,3,4,4-Tetraphenyl-1,2-oxathiolan-5-one 2-Oxide. Synthesis, Structure, and Selected Chemistry . In: JACS . tape 101 , no. 18 . Houstin, Austin August 1979, p. 5431-5432 .
  7. ↑ G. Edwin Wilson, Jr., MG Huang, WW Schloman, Jr .: Facile Synthesis of 1,3-Oxathiolanes from Ketones and 2-Mercaptoethanol . Ed .: The Journal of Organic Chemistry. tape 33 , no. 5 . Polytechnic Institute of Brooklyn, New York October 9, 1967, p. 2133, f ., Doi : 10.1021 / jo01269a103 .
  8. ↑ K. Nishitomi, T. Nagai, N. Tokura: The Thermal Decompositions and Mass Spectral Studies of the Cyclic Anhydrides of Some β-Sulfocarboxylic Acids . In: Bulletin of the Chemical Society of Japan . tape 41 , no. 6 , 1968, p. 1388-1394 .