Skip to main content
SpringerLink
Log in

A new efficient and selective synthesis of ketones from alkanes or cycloalkanes, CO, and silanes in the presences of aprotic superacids

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

Abstract

A new approach to the direct synthesis of ketones from alkanes or cycloalkanes (RH), CO, and silanes is proposed. Ketones were obtained in 50–97% yields from propane, butane, cyclopentane, cyclohexane, and methylcyclopentane on treatment with CO and silanes (Me4Si, Et4Si, orm- andp-XC6H4SiMe3, where X=Cl, Me, OMe) in the presence of CX4·2AlBr3 (X=Br, Cl) superacids at 0°C. The reactions withm- andp-XC6H4SiMe3 (X=Cl, Me) occur regioselectively to givem-ketones fromm-silanes andp-ketones fromp-silanes. However, the only product,p-MeOC6H4COR, is formed both fromm- andp-MeOC6H4SiMe3. The reaction ofcyclo-C5H9CO+ with BzSiMe3 results in an organosilicon ketone, Me3SiCH2C6H4COC5H9, while in the presence of an excess of an acylating system (after alcoholysis), Me2Si(OR′)CH2C6H4COR is formed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. G. A. Olah, G. K. S. Prakash, and J. Sommer,Superacids, Wiley-Interscience, New York, 1985; (b) G. a. Olah and G. K. S. Prakash, inThe Chemistry of Alkanes and Cycloalkanes, Part 13, Eds. S. Patai and Z. Rappoport, Wiley-Interscience, Chichester, 1992, 624; (c) G. A. Olah,Angew. Chem., Int. Ed. Engl., 1995,13/14, 1393.

    Google Scholar 

  2. Activation of Saturated Hydrocarbones by Transition Metal Compounds, Ed. A. E. Shilov, Reidel, Dordrect, 1985; (b)Activation and Functionalization of Alkanes, ed. C. L. Hill, Wiley-Interscience, New York, 1989; (c) B. A. Arndtsen, R. G. Bergman, T. A. Mobley, and T. H. Peterson,Acc. Chem. Res., 1995, 28, 154.

    Google Scholar 

  3. H. Mimoun, inComprehensive Coordination Chemistry, Eds. G. Wilkinson, R. D. Gillard, and J. A. McCleverty, Pergamon Press, New York, 1987, 6.

    Google Scholar 

  4. I. S. Akhrem, A. V. Orlinkov, and M. E. Vol'pin,Usp. Khim., 1996,65, 920 [Russ. Chem. Rev., 1996,65, 849 (Engl. Transl.)].

    CAS  Google Scholar 

  5. I. Akhrem, A. Orlinkov, and M. Vol'pin,J. Chem. Soc., Chem. Commun., 1993, 671.

  6. I. S. Akhrem, A. V. Orlinkov, L. V. Afanas'eva, E. I. Mysov, and M. E. Vol'pin,Izv. Akad. Nauk, Ser. Khim., 1996, 1208 [Russ. Chem. Bull., 1996,45, 1148 (Engl. Transl.)].

    Google Scholar 

  7. I. S. Akhrem, A. V. Orlinkov, L. V. Afanas'eva, and M. E. Vol'pin,Izv. Akad. Nauk, Ser. Khim., 1996, 1214 [Russ. Chem. Bull., 1996,45, 1154 (Engl. Transl.)].

    Google Scholar 

  8. I. Akhrem, S. Bernadyuk, and M. Vol'pin,Mendeleev Commun., 1993, 188.

  9. S. Z. Bernadyuk, I. S. Akhrem, and M. E. Vol'pin,Mendeleev Commun., 1994, 183.

  10. I. Akhrem, I. Churilova, S. Bernadyuk, and M. Vol'pin,Tetrahedron Lett., 1996,37, 5775.

    Article  CAS  Google Scholar 

  11. A. Orlinkov, I. Akhrem, S. Vitt, and M. Vol'pin,Tetrahedron Lett., 1996, 3363; A. Orlinkov, I. Akhrem, L. Afanas'eva, E. Mysov, and M. Vol'pin,Mendeleev Commun., 1997, 61.

  12. M. Koch and W. Haaf,Org. Synthesis, 1964,40, 1; M. Koch and W. Haaf,Angew. Chem., 1960,72, 628.

    Google Scholar 

  13. I. Akhrem,Catal. Lett., 1998, in press.

  14. A. Yu. Yakubovich and G. V. Motsarev,Dokl. Akad. Nauk SSSR, 1953,88, 87 [Dokl. Chem., 1953 (Engl. Transl.)].

    CAS  Google Scholar 

  15. K. Dey, C. Eaborn, and D. R. M. Walton,Organomet. Chem. Synthesis, 1970/71,1, 151.

    Google Scholar 

  16. G. A. Olah, Tse-Lok Ho, G. K. S. Prakash, and B. G. B. Gupta,Synthesis, 1977,10, 677.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

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

    I. S. Akhrem, I. M. Churilova, A. V. Orlinkov, L. V. Afanas'eva, S. V. Vitt & P. V. Petrovskii

Authors
  1. I. S. Akhrem
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. I. M. Churilova
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. A. V. Orlinkov
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. L. V. Afanas'eva
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. S. V. Vitt
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. P. V. Petrovskii
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 947–952, May, 1998.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Akhrem, I.S., Churilova, I.M., Orlinkov, A.V. et al. A new efficient and selective synthesis of ketones from alkanes or cycloalkanes, CO, and silanes in the presences of aprotic superacids. Russ Chem Bull 47, 918–923 (1998). https://doi.org/10.1007/BF02498161

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF02498161

Key words

Search

Navigation