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Interaction of 1,3λ4δ2,2,4-benzodithiadiazines with neutral and charged S-electrophiles: SCl2, C6F5SCl, and NS2+

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Chemistry of Heterocyclic Compounds Aims and scope

Reactions of 1,3λ4δ2,2,4-benzothiadiazines with SCl2, C6F5SCl, and [NS2][SbF6] leading to 1,2,3-benzodithiazolium salts (Herz salts) were investigated. The relative rate of reaction with SCl2 significantly depends on the nature of the substituent and its position in the carbocycle. Halogen substituents Cl, Br, and I slow down the reaction, especially if located closely to the heterocycle (positions 5 and 8). In the case of C6F5SCl and R = H, chlorination of the carbocycle and opening of the heterocycle also takes place with the formation of 7-chloro-1,3λ4δ2,2,4-benzothiadiazine and C6F5–S–N=S=N–Ar (Ar = 2-Cl-6-F5C6SC6H3), respectively. In the reaction with NS2+, along with contraction of the heterocycle, also its expansion occurs with the formation of 1,2,4λ4δ2,3,5-benzotrithiadiazepine.

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Notes

  1. In the present work, (C6F5)2S was synthesized by a new method using reaction of C6F5MgBr with (SN)4. Although this method does not have significant advantages over those described before,13 it is of interest to note that formation of organic sulfides in reaction of (SN)4 with Grignard reagents was not observed previously.14

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Authors thank the Collective Use Chemistry Service Center of the Siberian Branch of the Russian Academy of Sciences for the instrumental measurements and A. V. Zibarev for discussion of the results and useful suggestions.

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Authors and Affiliations

  1. N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 9 Akademika Lavrentieva Ave., Novosibirsk, 630090, Russia

    Alexander Yu. Makarov & Irina Yu. Bagryanskaya

  2. NMR Research Unit, Faculty of Science, University of Oulu, P. O. Box 3000, Oulu, 90014, Finnland

    Vladimir V. Zhivonitko

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  1. Alexander Yu. Makarov
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  2. Irina Yu. Bagryanskaya
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  3. Vladimir V. Zhivonitko
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Correspondence to Alexander Yu. Makarov.

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Translated from Khimiya Geterotsiklicheskikh Soedinenii, 2020, 56(7), 968–972

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Makarov, A.Y., Bagryanskaya, I.Y. & Zhivonitko, V.V. Interaction of 1,3λ4δ2,2,4-benzodithiadiazines with neutral and charged S-electrophiles: SCl2, C6F5SCl, and NS2+. Chem Heterocycl Comp 56, 968–972 (2020). https://doi.org/10.1007/s10593-020-02760-y

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