Alkane and Cycloalkane Transformations in Superelectrophilic Liquids

  • Chapter
Green Industrial Applications of Ionic Liquids

Part of the book series: NATO Science Series ((NAII,volume 92))

  • 734 Accesses

Abstract

The involvement of alkanes in selective transformations is one of the fundamental problems of organic chemistry. On the one hand, alkanes and cycloalkanes, which are the main components of oil and natural gas, still remain the most promising starting compounds for organic synthesis. On the other hand, present industrial processing of hydrocarbon raw materials requires the development of new technologies based on application of more selective catalysts.

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

Access this chapter

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 169.00
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 219.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free ship** worldwide - see info
Hardcover Book
USD 219.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free ship** worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

Similar content being viewed by others

References

  1. Olah, GA, Prakash, G.K.S., and Sommer, J. (1985) Superacids, Wiley-Interscience, New-York; (b) Olah, G.A., and Prakash G.K.S. (1992) The chemistry of alkanes and cycloalkanes, in: S. Patai and Z. Rappoport (eds.), Wiley & Sons, Chichester, Chap. 13.

    Google Scholar 

  2. Hill, C.L. (Ed.) (1992), Activation and functionaUzation of alkanes, Wiley & Sons, New-York; (b) Crabtree, R.H. (1992) Organometallic chemistry of alkane activation, in: S.Patai and Z.Rappoport (eds.), Wiley & Sons, Chichester, Ch. 14; (c) Arndtsen, B.A., Bergman, R.G., Mobley, T.A., and Peterson, T.H. (1995) Selective intermolecular carbon-hydrogen bond activation by synthetic metal complexes in homogeneous solution, Acc. Chem. Res. 28(3), 154-162; (d) Shilov, A.E. and Shul’pin, G.B. (1997) Activation of C-H bonds by metal complexes, Chem.Rev. 97(8), 2879-2932.

    Google Scholar 

  3. Somorjai, G.A. (1978) Surface science: an old field rejuvenated demands attention and people, Science, 201, 489; (b) Somorjai, G.A. (1992) Correlations and difference between homogeneous and heterogeneous catalysis — as surface science view in perspectives in catalysis, IUPAC Series: Chemistry for the 21 stCentury, J. Thomas and K. Zamaraev (eds.), Blackwell Science Publ., London, pp. 147-167.

    Article  CAS  Google Scholar 

  4. Hill, C.L. (1995) Introduction of functionality into unactivated carbon-hydrogen bonds. Catalytic generation and nonconventional utilization of organic radicals, Acc. Chem. Res. 28, 127–132; (b) Ilhyong, and R., Sonoda, N. (1996) Free-radical carbonylations: then and now, Angew. Chem. Int. Ed. Engl 35, 1050-1066.

    Google Scholar 

  5. Akhrem, I.S., Orlinkov, A.V., Mysov, E.I., and Vol’pin, M.E. (1981) Transformations of cycloalkanes under the action of acylhalides in the presence of AlBr3, Tetrahedron Lett. 22, 3891–3894: (b) Vol’pin, M., Akhrem, I., and Orlinkov A. (1989) Aprotic organic superacids — efficient reagents and catalysts for transformations of alkanes and cycloalkanes under mild conditions, New J. Chem. 13, 771-790.

    Article  CAS  Google Scholar 

  6. Akhrem, I.S., Orlinkov, A.V., and Vol’pin, M.E. (1996) Low-temperature functionaUzation of alkanes and cycloalkanes by “classical” and “nonclassical” (superacidic) Friedel-Crafts complexes, Russ. Chem. Rev. 65 (10), 849-863 (Uspekhi Khimii, 65(10), 920–935).

    CAS  Google Scholar 

  7. Akhrem, I.S., Orlinkov, A.V., Bachmutov, V.I., Afanas’eva, L.V., and Vol’pin, M.E. (1990) Nature of the species responsible for the high activity of RCOX-2A1X3 complexes in reactions with alkanes and cycloalkanes, Russ. Chem. Bull. 39, 2252–2257 (Izv. Akad. Nauk SSSR, Ser. Khim. 39, 2490-2496).

    Article  Google Scholar 

  8. Akhrem, I.S., Orlinkov, and Vol’pin, M.E. (1993) A novel family of aprotic organic superacids for low-temperature alkane and cycloalkane transformations, J. Chem. Soc., Chem. Commun, 671-672; (b) Akhrem, I.S., Afanas’eva, L.V., Orlinkov, A.V., and Vol’pin, M.E. (1994) Halogens (Cl2, Br2, I2) promoted by aluminium halides as effective initiators for alkane cracking, Mendeleev Commun., 131-133: (c) Akhrem, I., Gudima, S., and Vol’pin, M. (1996) Novel sulfur-containing inorganic aprotic superacids as effective initiators of low-temperature cracking and isomerization of alkanes, Chem. Eur. J. 2, 812-814.

    Google Scholar 

  9. Akhrem, I.S., and Orlinkov, A.V. (1998) Novel superelectrophilic complexes for low-temperature alkane and cycloalkane transformations, Russ. Chem. Bull. 47(5), 740–764 (Izv. Akad. Nauk, Ser. Khim. 47(5), 771-795).

    Article  CAS  Google Scholar 

  10. Akhrem, I.S., Orlinkov, A.V., Afanas’eva, L.V., and Vol’pin, M.E. (1998) Cracking n-alkanes under the action of aprotic superacids at room temperature, Dokl. Akad. Nauk SSSR, 298, 107–112.

    Google Scholar 

  11. Orlinkov, A.V., Akhrem, I.S., Afanas’eva, L.V., and Vol’pin, ME. (1986) Isomerization of butane catalyzed by CH3COX-2AtX3, Bull. Acad. Sci. USSR, Div. Chem. Sci., 35, 1286–1289 (Izv. Akad, Nauk SSSR, Ser. Khim., 35, 1416-1419); (b) Orlinkov, A.V., Akhrem, I.S., Afanas’eva, L.V., and Vol’pin, M.E. (1984) Synthesis of isobutane, USSR Author Certificate 1224552.

    Article  Google Scholar 

  12. Orlinkov, A.V., Akhrem, I.S., Afanas’eva, L.V., and Vol’pin, M.E. (1984) USSR Author Certificate 1197370.

    Google Scholar 

  13. Orlinkov, A.V., Akhrem, I.S., Afanas’eva, L.V., Zaharkin, L.I., Ovseenko, S.T., and Vol’pin, M.E. (1990) Isomerization of C12H20 tricyclanes into dimethyl-and ethyladamantanes by the action of acylbromide with aluminium bromide, Russ. Chem. Bull., 39, 290–292 (Izv. Akad, Nauk SSSR, Ser. Khim. 39, 349-352).

    Article  Google Scholar 

  14. Akhrem, I.S., Orlinkov, A.V., Vitt, S.V., and Vol’pin M.E. (1986) Alkylation of adamantane with n-alkanes under mild conditions, Dokl. Akad. Sci. USSR 288(1), 130–134.

    CAS  Google Scholar 

  15. Schwarte, D. (1960) Isomerization of straight-chain hydrocarbons to isoparaffins, US Patent 2, 956,095 [Chem. Abstracts (1961) 55, 5931h].

    Google Scholar 

  16. Mahan, J., and Morell, J. (1974) Isomerisation with arsenic pentafluoride and/or antimony pentafluoride and with trifluoromethanesulfonic acid or hydrogen fluoride and high hydrogen partial pressure, US Patent 3, 839,489 [Chem. Abstracts (1975) 82, 88376d].

    Google Scholar 

  17. Norell, J.R. (1973) Normal paraffin isomerization with liquid-phase arsenic pentafluoride-hydrogen fluoride catalyst, US Patent 3,755,493 [Chem. Abstracts 79, 125794z].

    Google Scholar 

  18. Montgomery, C.W., McAteer, J.H., and Franke N.W. (1937) Catalytic isomerization of n-butane and isobutane, J. Amer. Chem. Soc. 59, 1768–1769.

    Article  CAS  Google Scholar 

  19. Adrianus, J., van Peski, A.J., and Gerardur, H.V. (1940) Isobutane, US Patent 2,249,366 [Chem. Abstracts (1941) 35, 6601g].

    Google Scholar 

  20. Olah, G.A., Laali, K., and Farooq, O. (1984) Chemistry in superacids. 6. Perfluoroalkane sulfonic acid-boron sulfonates: new superacid systems for generation of carbocations and catalysts for electrophilic transformations of hydrocarbons, J. Org. Chem. 49, 4591–4594.

    Article  CAS  Google Scholar 

  21. Brouwer, D.M. and Kiffen, A.A. (1973) Hydride transfer reactions. II. Hydride transfer from alkanes to methyloxocarbonium ion, Rec. Trav. Chim., Pays-Bas 92, 689–697.

    Article  CAS  Google Scholar 

  22. Fort, R.C. (1976) Adamantane, the chemistry of diamond molecules, Dekker, New York; (b) Bagrii, E.I. (1989) Adamantanes: production, properties, application, Nauka, Moscow (and references cited therein).

    Google Scholar 

  23. Akhrem, I.S., Orlinkov, A.V., Afanas’eva, L.V., Mysov, E.I., and Vol’pin, M.E. (1995) Ionic bromination of ethane and other alkanes (cycloalkanes) with bromine catalyzed by polyhalomethane-2AlBr3 aprotic organic superacids under mild conditions, Tetrahedron Lett. 36, 9365–9368; (b) Akhrem, I.S., Orlinkov, A.V., Afanas’eva, L.V., and Vol’pin, M.E. (1996) Functionalization of saturated hydrocarbons by aprotic superacids. 4. Ionic bromination of ethane and other alkanes and cycloalkanes with molecular bromine in the presence of systems based on polyhalomethanes-AlBr3 under mild conditions, Russ.Chem. Bull. 45, 1148-1153 (Izv. Akad, Nauk SSSR, Ser. Khim., 45, 1208-1213).

    Article  CAS  Google Scholar 

  24. Akhrem, I.S., Bernadyuk, S.Z., and Vol’pin, M.E. (1993) Carbonylation of cyclopentane in the presence of aprotic organic superacids, Mendeleev Commun., 188-189.

    Google Scholar 

  25. Orlinkov, A., Akhrem, I., and Vitt S. (1999) The first efficient carbonylation of ethane with CO, Mendeleev Commun. 198–199.

    Google Scholar 

  26. Amiantov, I.Yu., Khotsyanova, T.L., Akhrem, I.S., Orlinkov, A.V., and Vol’pin, M.E. (1984) Study of the structures of the complexes of acylbromide with AlBr3 by 8lBr NQR at — 77K, Zh. Struct. Khim. 25(5), 46–50.

    CAS  Google Scholar 

  27. Akhrem, I.S., Orlinkov, A.V., Bakhmutov, V.I., Petrovskii, P.V., Pekkh, P.I., Lipmaa, E.I., and Vol’pin, M.E. (1985) Study of the nature of the complexes acyl bromide-2(aluminum bromide), acyl chloride-2(aluminum chloride) and acetyl chloride-2(antimony (V) fluoride) using proton, carbon 13, aluminum 27, fluorine 19 and oxygen 17 NMR, Dokl. Akad. Nauk SSSR 284, 627–631.

    CAS  Google Scholar 

  28. Stankevich, I.V., Chistyakov, A.L., Akhrem, I.S., Orlinkov, A.V., and Vol’pin, M.E. (1993) Electronic population structure and stability of organic cations, dications and donor-acceptor complexes. The MNDO calculations of possible intermediates in MeCOCl-nAlCl3 systems, Russ. Chem. Bull. 42, 802–809 (Izv. Akad. Nauk, Ser. Khim., 42, 854-858).

    Google Scholar 

  29. Bertram, J., Coleman, J.P., Fleishmann, M., and Pletcher, D. (1973) The electrochemical behaviour of alkanes in fluorosulfonic acid, J. Chem. Soc., Perkin II, 374–381.

    Google Scholar 

  30. Olah, G.A., Germain, A., Lin, H.C., Forsyth, D.A. (1975) Electrophilic reactions of single bonds. XVIII. Indication of protosolvated de facto substituting agents in the reactions of alkanes with acetyluim and nitronium ions in superacidic media, J. Amer. Chem. Soc. 97, 2928–2929.

    Article  CAS  Google Scholar 

  31. Koch, W., Frenking, G., Schwarz, H., Maquin, F., and Stahl, D. (1985) Theoretical and experimental studies on the ground state potential energy surface of C2H4O dications, Int. J Mass. Spectrom. Ion Processes 63, 59–82.

    Article  CAS  Google Scholar 

  32. Olah, G. A., Burrichter, A., Rasul, G., Prakash, G.K.S., Hachoumy M., and Sommer, J. (1996) Protioacyl dications: hydrogen/deuterium exchange, rearrangements and theoretical studies, J. Amer. Chem. Soc. 118, 10423–10428.

    Article  CAS  Google Scholar 

  33. Olah, G.A. (1993) Superelectophiles, Angew. Chem. Int. Ed. Engl. 32, 767–788.

    Article  Google Scholar 

  34. Olah, G.A., (1995) My search for carbocations and their role in chemistry (Nobel lecture), Angew. Chem. Int. Ed. Engl. 34, 1393–1405.

    Article  CAS  Google Scholar 

  35. (a) Ohwada, T., Yamagata, N., and Shudo, K.(1991) Friedel-Crafts-type reactions involving di-and tri-cationic species. Onium-allyl dications and O, O-diprotonated aci-nitro species bearing a protonated carbonyl group, J. Amer. Chem.Soc. 113, 1364–1377.; (b) Sato, Y., Yato, M., Ohwada, T., Saito, S., and Shudo K. (1995) Involvement of dicationic species as the reactive intermediates Gattermann, Houben-Hoesch and Friedel-Crafts reactions of nonactivated benzenes, J. Amer. Chem. Soc. 117, 3037-3043.

    Article  CAS  Google Scholar 

  36. Chistyakov, A.L., Stankevich, I.V., Akhrem, I.S., Gambaryan, N.P., and Vol’pin, M.E. (1996) Electronic structure, geometry and stability of organic cations, dications and donor-acceptor complexes. 2. Polyhalomethane complexes with aluminium halides, Russ. Chem. Bull. 45, 514–520 (Izv. Akad. Nauk, Ser. Khim. 45, 554-560).

    Article  Google Scholar 

  37. (a) Olah, G.A., Rasul, G., Heiliger, L., and Prakash, G.K.S. (1996) Preparation, and NMR spectroscopic and ab initio/DFT, GIAO-MP2 studies of halomethyl cations, J. Amer. Chem. Soc. 118, 3580–3583; (b) Franking, G., Fau, S., Marchand, C.M., and Grutzmacher, H.(1997) The π-donor ability of the halogens in cations and neutral molecules. A theoretical study of AX3′, AH2X′, YX3 and YH2X (A = C, Si, Ge, Sn, Pd; Y = B, Al, Ga, In, Tl; X = F, Cl, Br, I), J. Amer. Chem. Soc. 119, 6648-6655.

    Article  CAS  Google Scholar 

  38. Olah, G.A., Rasul, G., Yudin, A., Burrichter A., Prakash, G.K.S., Chistyakov, A.L., Stankevich, I.V., Akhrem, I.S., Gambaryan, N.P., and Vol’pin, M.E. (1996) Trihalomethyl cations and their superelectrophilic activation, J. Amer. Chem. Soc. 118, 1446–1451.

    Article  CAS  Google Scholar 

  39. Akhrem, I.S., Chistyakov, A.L., Gambaryan, N.P., Stankevich, I.V., and Vol’pin, M.E. (1997) Polyhalomethanes combined with aluminum halides as generators of superelectrophiles of a novel type, J. Organomet. Chem. 536, 489–495.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Editor information

Editors and Affiliations

Rights and permissions

Reprints and permissions

Copyright information

© 2003 Springer Science+Business Media Dordrecht

About this chapter

Cite this chapter

Akhrem, I.S., Orlinkov, A.V., Vol’Pin, M.E. (2003). Alkane and Cycloalkane Transformations in Superelectrophilic Liquids. In: Rogers, R.D., Seddon, K.R., Volkov, S. (eds) Green Industrial Applications of Ionic Liquids. NATO Science Series, vol 92. Springer, Dordrecht. https://doi.org/10.1007/978-94-010-0127-4_28

Download citation

  • DOI: https://doi.org/10.1007/978-94-010-0127-4_28

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-1-4020-1137-5

  • Online ISBN: 978-94-010-0127-4

  • eBook Packages: Springer Book Archive

Publish with us

Policies and ethics

Navigation