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Comparative Study
. 2015 Aug 12;20(8):14576-94.
doi: 10.3390/molecules200814576.

A Qualitative Comparison of the Reactivities of 3,4,4,5-Tetrachloro-4H-1,2,6-thiadiazine and 4,5-Dichloro-1,2,3-dithiazolium Chloride

Andreas S Kalogirou  1 , Panayiotis A Koutentis  2
Affiliations
Comparative Study

A Qualitative Comparison of the Reactivities of 3,4,4,5-Tetrachloro-4H-1,2,6-thiadiazine and 4,5-Dichloro-1,2,3-dithiazolium Chloride

Andreas S Kalogirou et al. Molecules. .

Abstract

The high yielding transformations of 3,4,4,5-tetrachloro-4H-1,2,6-thiadiazine into 3,5-dichloro-4H-1,2,6-thiadiazin-4-one (up to 85%) and 2-(3,5-dichloro-4H-1,2,6-thiadiazin-4-ylidene)malononitrile (up to 83%) have been investigated and compared to the analogous transformations of the closely-related 4,5-dichloro-1,2,3-dithiazolium chloride (Appel's salt) into 4-chloro-5H-1,2,3-dithiazol-5-one and 2-(4-chloro-5H-1,2,3-dithiazol-5-ylidene)malononitrile. Furthermore, cyclocondensation of 3,4,4,5-tetrachloro-4H-1,2,6-thiadiazine with 2-aminophenol and 1,2-benzenediamines gave fused 4H-1,2,6-thiadiazines in 68%-85% yields.

Keywords: 1,2,3-dithiazoles; 1,2,6-thiadiazines; Appel’s salt; heterocycle.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Comparison of 3,4,4,5-tetrachloro-4H-1,2,6-thiadiazine (1) with 4,5-dichloro-1,2,3-dithiazolium chloride (2).
Scheme 2
Scheme 2
Synthesis of synthesis of N-aryl-3,5-dichloro-4H-1,2,6-thiadiazin-4-imines (4) and (Z)-N-aryl-4-chloro-5H-1,2,3-dithiazol-5-imines (5).
Scheme 3
Scheme 3
Synthesis of 3,4,4,5-tetrachloro-4H-1,2,6-thiadiazine (1).
Scheme 4
Scheme 4
Known reactions of 3,4,4,5-tetrachloro-4H-1,2,6-thiadiazine (1).
Scheme 5
Scheme 5
Preparation of the ylidenemalononitrile 10 from tetracyanoethene (TCNE) and SCl2.
Scheme 6
Scheme 6
Synthesis of 2-(4-chloro-5H-1,2,3-dithiazol-5-ylidene)malononitrile (11) from Appel’s salt 2. Structures of isothiazoles 12 and 13 derived from 11.
Scheme 7
Scheme 7
Reaction of tetrachlorothiadiazine 1 with dimethylsulfonium dicyanomethylide 14 and the proposed mechanism for the formation of the pyrimidine 15.
Scheme 8
Scheme 8
Reactions of Appel’s salt 2 with 2-amino-4-chlorophenol or benzene-1,2-diamine.
Scheme 9
Scheme 9
Reactions of thiadiazinone 3 with benzene-1,2-diamine and sodium 2-aminophenoxide.
Scheme 10
Scheme 10
Reactions of the tetrachlorothiadiazine 1 with 2-aminophenol, benzene-1,2-diamine and N′-phenylbenzene-1,2-diamine.
Scheme 11
Scheme 11
Conversion of 4-chloro-10H-[1,2,6]thiadiazino[3,4-b]quinoxaline (19) to 3-aminoquinoxaline-2-carbonitrile (23).
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References

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    1. Peake C.J., Harnish W.N., Davidson B.L. Mono-5-substituted-3-chloro-4H-1,2,6-thiadiazin-4-one Antifungal Agents. 4201780. U.S. Patent. 1980 May 6;
    1. Portnoy R.C. Thiadiazinone Plant Disease Control Agents. 4497807. U.S. Patent. 1985 Feb 5;

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