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Heteroorganic betaines

4. Photolysis and thermolysis of betaines containing the+P−C−Si−S− structural fragment

  • Organic Chemistry
  • Published:
Russian Chemical Bulletin Aims and scope

Abstract

Photolysis and thermal decomposition of betaines R3P−CR1R2−SiR3R4−S− (1) follows two main pathways: (a) a Corey—Chaykovsky type reaction with elimination of Ph3P and generation of silathiirane

(2) and (b) a retro-Wittig type reaction accompanied by elimination of R3P=CR1R2 and generation of silanethione R3R4Si=S (3). Highly reactive compounds2 and3 undergo subsequent transformations to give derivatives of tetrahydro-1,4-dithia-2,5-disilin, 1,3-dithia-2,4-disilolane, and phosphonium salts ofsymm-tetraorganodisilthiane dithiolates [Ph3P+CHR1R2]2[(R3R4SiS−)2S]. The structures of the compounds obtained were established by X-ray diffraction analysis and multinuclear NMR spectroscopy.

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Authors and Affiliations

  1. State Research Center of the Russian Federation “State Research Institute of Chemistry and Technology of Organoelement Compounds”, 38 sh. Enthuziastov, 111123, Moscow, Russian Federation

    I. V. Borisova, N. N. Zemlyanskii, A. K. Shestakova & e. A. Chernyshev

  2. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation

    V. N. Khrustalev

  3. Department of Chemistry, M. V. Lomonosov Moscow State University, Leninskie Gory, 119899, Moscow, Russian Federation

    Yu. A. Ustynyuk

Authors
  1. I. V. Borisova
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  2. N. N. Zemlyanskii
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  3. A. K. Shestakova
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  4. V. N. Khrustalev
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  5. Yu. A. Ustynyuk
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  6. e. A. Chernyshev
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Additional information

For part 3, see Ref. 1.

The betaines Et3P+CHMeSiMe2S− and Et3P+CHMeSiPh2S− with alkyl groups at the phosphorus atom are distinguished by high thermal stability; their spectral characteristics do not change during storage of solutions of these compounds in pyridine-d5 or metastable solutions in benzene-d6 for 1–2 years at −20°C in sealed evacuated tubes or on heating (150°C) for 15 h.

Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1594–1603, September, 2000.

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Borisova, I.V., Zemlyanskii, N.N., Shestakova, A.K. et al. Heteroorganic betaines. Russ Chem Bull 49, 1583–1592 (2000). https://doi.org/10.1007/BF02495164

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  • DOI: https://doi.org/10.1007/BF02495164

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