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Ag+-catalyzed oxidation of alkanone cyanohydrins by peroxydisulfate ions: generation and reactions of 1-cyanoalkoxyl radicals

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Bulletin of the Academy of Sciences of the USSR, Division of chemical science Aims and scope

Conclusions

  1. 1.

    Alkanone cyanohydrins of general formula R(CH2)3CR'(OH)CN (R=H or alkyl, R' =alkyl) are efficiently oxidized by the system S2O8 2--Ag+ to 1-cyanoalkoxyl radicals, which then undergo a highly selective rearrangement, with successive migration of the H atom and CN group and oxidation to δ-ketonitriles RCH(CN)CH2CH2COR'.

  2. 2.

    The cyanohydrins of 2-pentanone (Ia), 2-hexanone (Ib), 2-octanone (Ic), and 2-nonanone (Id) are oxidized by the system S2O8 2--Ag+ ∿4-18 times faster than tert-butanol, and in their oxidative ability they fall into the sequence: (Id) > (Ic) > (Ib) > (Ia).

  3. 3.

    A new method was developed for the synthesis of the nitriles of 5-ketoalkanoic acids.

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Authors and Affiliations

  1. N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow

    Yu. N. Ogibin, D. S. Velibekova, M. I. Katsin, E. I. Troyanskii & G. I. Nikishin

Authors
  1. Yu. N. Ogibin
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  2. D. S. Velibekova
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  3. M. I. Katsin
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  4. E. I. Troyanskii
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  5. G. I. Nikishin
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Additional information

See [1] for preliminary communication.

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 149–156, January, 1981.

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Ogibin, Y.N., Velibekova, D.S., Katsin, M.I. et al. Ag+-catalyzed oxidation of alkanone cyanohydrins by peroxydisulfate ions: generation and reactions of 1-cyanoalkoxyl radicals. Russ Chem Bull 30, 127–133 (1981). https://doi.org/10.1007/BF00962268

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  • DOI: https://doi.org/10.1007/BF00962268

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