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Oxidative radical rearrangement of cycloalkanone cyanohydrins with 1,4-, 1,5-, and 1,6-migration of the cyano group

  • Organic Chemistry
  • Published:
Bulletin of the Academy of Sciences of the USSR, Division of chemical science Aims and scope

Conclusions

  1. 1.

    The action of the S2O 2−8 -Ag+ system on the cyanohydrins of cyclopentanone and 2-methylcyclopentanone leads to isomerization with opening of the cyclopentane ring and 1,5-migration of the cyano group and the formation of 5-cyano-substituted pentanoic and hexanoic acids.

  2. 2.

    2-Methylcyclohexanone cyanohydrin under analogous conditions isomerizes with 1,6-migration of the cyano group to give 6-cyanoheptanoic acid, while cycloheptanone cyanohydrin undergoes 1,4-migration of the cyano group without ring opening to give 4-cyanocycloheptanone.

  3. 3.

    Cyelopentanone and cycloheptanone cyanohydrins are oxidized ∼1.7 times more rapidly by the S2O 2−8 -Ag+ system at 60°C than cyclohexanone cyanohydrin. The cyanohydrins of 2-methyl-substituted cycloalkanones are oxidized about twice as rapidly as their unsubstituted analogs.

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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, É. 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. É. I. Troyanskii
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  5. G. I. Nikishin
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Additional information

For previous communication, see [1].

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2755–2761, December, 1981.

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Ogibin, Y.N., Velibekova, D.S., Katsin, M.I. et al. Oxidative radical rearrangement of cycloalkanone cyanohydrins with 1,4-, 1,5-, and 1,6-migration of the cyano group. Russ Chem Bull 30, 2293–2298 (1981). https://doi.org/10.1007/BF00963691

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  • DOI: https://doi.org/10.1007/BF00963691

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