Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Conversion of 1,3-Thiazolidines to Dihydro-1,4-thiazine by Chlorinolysis

  • Lee, Wha-Suk (Organic Chemistry Research Laboraory, Korea Institute of Sciene and Technology) ;
  • Mah, He-Duck (Department of Chemistry, Kyonggi University) ;
  • Nam, Kee-Dal (Organic Chemistry Research Laboraory, Korea Institute of Sciene and Technology) ;
  • Kang, Soon-Bang (Organic Chemistry Research Laboraory, Korea Institute of Sciene and Technology)
  • Published : 1992.02.20
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Abstract

The ring expansion of 1,3-thiazolidines 4 derived from ${\beta}$-ketoacid derivatives to the corresponding dihydro-1,4-thiazines 1 by using the action of chlorine on 4 has been achieved. In the chlorinolysis unisolable sulfenyl chlorides 5 may be formed from chlorosulfonium ions 11 by ${\beta}$-elimination involving carbonyl activated methylene hydrogens. Addition of sulfenyl chloride to the internal double bond appears to form probable thiiranium ions 14, which in turn gave 1 with loss of acidic proton. Imminium ions 15 could be hydrolyzed easily to give enol 8. As a side reaction, dihydrothiazine that was formed was further chlorinated to produce dichlorides 16 which were rearranged readily to the chloromethyl compounds 10.

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References

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  1. Conversion of 1,3-thiazolidine and its sulfoxide to dihydro-1,4-thiazine vol.30, pp.4, 1992, https://doi.org/10.1002/jhet.5570300447
  2. 1,4-티아진 설폭사이드의 위치선택성 Pummerer 반응(I) vol.46, pp.6, 2002, https://doi.org/10.5012/jkcs.2002.46.5.489
  3. 1,4-Thiazine Carboxanilide의 합성: Pummerer 반응에서의 인접기 참여효과 vol.46, pp.4, 1992, https://doi.org/10.5012/jkcs.2002.46.4.330
  4. Phenyliodine(III) Diacetate/I2‐Mediated Domino Approach for Pyrrolo[1,4]Thiazines and 1,4‐Thiazines by a One‐Pot Morin Rearrangement of N,S‐Acetals vol.25, pp.24, 1992, https://doi.org/10.1002/chem.201901111