Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Rearrangement of Cyclopropylcarbinyl Chloride Over Protonic Zeolites: Formation of Carbocations and Behavior as Solid Solvents

  • 109 Accesses

  • 1 Citations


The rearrangement of cyclopropylcarbinyl chloride was studied over protonic zeolites and K-10 Montmorillonite. The energy of activation is lower on zeolites, with K-10 showing almost the same value for the rearrangement in 80% aqueous ethanol solution. HUSY showed the lowest energy of activation, whereas HZSM-5 and HYD [dealuminated with (NH4)2SiF6] presented similar energy of activation. This difference may be due to the presence of extra-framework aluminum species. On the other hand, the entropy of activation is significantly less negative on ZSM-5 and may be associated with the narrower pore structure, providing ionization of the substrate without losing many degrees of freedom. Kinetic isotope effects indicated that ionization is assisted by hydrogen bonding of the zeolite OH groups with the leaving halide, similar to the push–pull mechanism proposed for solution chemistry. Hence, zeolites behave as solid solvents, providing a polar microscopic environment for ionic reactions to take place, and solvating the transition state and the ions formed.

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

Scheme 1
Scheme 2
Fig. 1
Fig. 2
Fig. 3
Scheme 3


  1. 1.

    Corma A (1995) Inorganic solid acids and their use in acid-catalyzed hydrocarbon reactions. Chem Rev 95:559–614

  2. 2.

    Farneth WE, Gorte RJ (1995) Methods for characterizing zeolite acidity. Chem Rev 95:615–635

  3. 3.

    Umansky B, Engelhardt J, Hall WK (1991) On the strength of solid acids. J Catal 127:128–140

  4. 4.

    Xu TE, Munson J, Haw JF (1994) Toward a systematic chemistry of organic reactions in zeolites: in situ NMR studies of ketones. J Am Chem Soc 116:1962–1972

  5. 5.

    Gonçalves VLC, Rodrigues RC, Lorençato R, Mota CJA (2007) Assessing the acid strength of solid acid catalysts with the use of linear free energy relationship: H/D exchange with substituted benzene derivatives. J Catal 248:158–164

  6. 6.

    Mota CJA, Martins RM (1991) Hydrogen-deuterium exchange between zeolite Y and 3-methylpentane. J Chem Soc Chem Commun. https://doi.org/10.1039/C39910000171

  7. 7.

    Mota CJA, Nogueira L, Kover WB (1992) Rearrangement of pentacoordinated carbonium ions over zeolite Y. J Am Chem Soc 114:1121–1123

  8. 8.

    Kramer GJ, van Santen RA, Emels CA, Nowak AK (1993) Understanding the acid behavior of zeolites from theory and experiment. Nature 363:529–531

  9. 9.

    Sommer J, Hachoumy M, Garin F, Barthomeuf D (1994) Zeolite Y-catalyzed versus superacid-catalyzed protium-deuterium exchange in alkanes. J Am Chem Soc 116:5491–5492

  10. 10.

    Stepanov AG, Arzumanov SS, Luzgin MV, Ernst H, Freude D, Parmon VN (2005) In situ 1H and 13C MAS NMR study of the mechanism of H/D exchange for deuterated propane adsorbed on H-ZSM-5. J Catal 235:221–228

  11. 11.

    Olah GA, Schlosberg RH (1968) Chemistry in super acids. I. Hydrogen exchange and polycondensation of methane and alkanes in FSO3H-SbF5 (“magic acid”) solution. Protonation of alkanes and the intermediacy of CH5 + and related hydrocarbon ions. The high chemical reactivity of “paraffins” in ionic solution reactions. J Am Chem Soc 90:2726–2727

  12. 12.

    Hogeveen H, Bickel AF (1969) Chemistry and spectroscopy in strongly acidic solutions. Part XXIV: Electrophilic substitution at alkanes. Rec Trav Chim Pays-Bas 88:371–378

  13. 13.

    Olah GA (1973) Carbocations and electrophilic reactions. Angew Chem Int Ed Engl 12:173–212

  14. 14.

    Olah GA, Prakash GKS, Williams RE, Field LD, Wade K (1987) Hypercarbon chemistry. Wiley, New York

  15. 15.

    Olah GA, Prakash GKS, Sommer J, Molnar A (2009) Superacid chemistry. Wiley, New York

  16. 16.

    Aronson MT, Gorte RJ, Farneth WE, White D (1989) Carbon-13 NMR identification of intermediates formed by 2-methyl-2-propanol adsorption in H-ZSM-5. J Am Chem Soc 111:840

  17. 17.

    Haw JF, Richardson BR, Oshiro IS, Lazo ND, Speed JA (1989) Reactions of propene on zeolite HY catalyst studied by in situ variable temperature solid-state nuclear magnetic resonance spectroscopy. J Am Chem Soc 111:2052–2058

  18. 18.

    Haw JF, Nicholas JB, Xu T, Beck LW, Ferguson DB (1996) Physical organic chemistry of solid acids: lessons from in situ NMR and theoretical chemistry. Acc Chem Res 29:259–267

  19. 19.

    Boronat M, Viruela PM, Corma A (2004) Reaction intermediates in acid catalysis by zeolites: prediction of the relative tendency to form alkoxides or carbocations as a function of hydrocarbon nature and active site structure. J Am Chem Soc 126:3300–3309

  20. 20.

    Tuma C, Sauer J (2005) Protonated isobutene in zeolites: tert-butyl cation or alkoxide? Angew Chem Int Ed Engl 44:4769–4771

  21. 21.

    Rosenbach N Jr, dos Santos APA, Franco M, Mota CJA (2010) The tert-butyl cation on zeolite Y: a theoretical and experimental study. Chem Phys Lett 485:124–128

  22. 22.

    Mota CJA, Rosenbach N Jr (2011) Carbocations on Zeolites. Quo vadis? J Braz Chem Soc 22:1197–1205

  23. 23.

    Kling DP, Chagas HC, Machado ESA, dos Santos APA, Rosenbach N Jr, Carneiro JW, Mota CJA (2013) Dynamic behaviour of carbocations on zeolites: mobility and rearrangement of the C4H7 + system. Chem Commun 49:4480–4482

  24. 24.

    Correa RJ, Mota CJA (2002) SN2, E2 reactions of butylchlorides on NaY zeolite: a potential method for studying the formation and reactivity of alkoxy species on the zeolite surface. Phys Chem Chem Phys 4:4268–4274

  25. 25.

    Correa RJ, Mota CJA (2003) Effect of the compensating cation on the adsorption of t-butyl chloride on zeolite Y. Appl Catal A 255:255–264

  26. 26.

    Rosenbach N Jr, Mota CJA (2005) A DFT study of SN2 and E2 reactions of butylhalides on zeolite Y: effect of the leaving group on formation and reactivity of the alkoxy species. J Mol Struct (Theochem) 731:157–161

  27. 27.

    Franco M, Rosenbach N Jr, Ferreira GB, Guerra ACO, Kover WB, Turci CC, Mota CJA (2008) Rearrangement, nucleophilic substitution and halogen switch reactions of alkyl halides over NaY zeolite: formation of the bicyclobutonium cation inside the zeolite cavity. J Am Chem Soc 130:1592–1600

  28. 28.

    Arca HA, Gomes GCC, Mota CJA (2014) Solid solvents: activation parameters for the rearrangement of cyclopropylcarbinyl bromide on mordenite zeolite. New J Chem 38:2760–2762

  29. 29.

    Olah GA, Jeuell CL, Kelly DP, Porter RD (1972) Stable carbocations. CXIV. The structure of cyclopropylcarbinyl and cyclobutyl cations. J Am Chem Soc 94:146-

  30. 30.

    Olah GA, Reddy VP, Prakash GKS (1992) Long-lived cyclopropylcarbinyl cations. Chem Rev 92:69–95

  31. 31.

    Roberts JD, Mazur RH (1951) Small-ring compounds. IV. Interconversion reactions of cyclobutyl, cyclopropylcarbinyl and allylcarbinyl derivatives. J Am Chem Soc 73:2509–2520

  32. 32.

    Mazur RH, White WN, Semenov DA, Lee CC, Silver MS, Roberts JD (1959) Small-ring compounds. XXIII. The nature of the intermediates in carbonium ion-type interconversion reactions of cyclopropylcarbinyl, cyclobutyl and allylcarbinyl derivatives. J Am Chem Soc 81:4390–4398

  33. 33.

    Garralon G, Fornes V, Corma A (1988) Faujasites dealuminated with ammonium hexafluorosilicate: Variables affecting the method of preparation. Zeolites 8:268–272

  34. 34.

    Gilson JP, Edwards GC, Peters AW, Rajagopalan K, Wormsbecher RF, Roberie TG, Shatlock MP (1987) Penta-co-ordinated aluminium in zeolites and aluminosilicates. J Chem Soc Chem Commun. https://doi.org/10.1039/C39870000091

  35. 35.

    van Bokhoven JA, Roest AL, Koningsberger DC, Miller JT, Nachtegaal GH, Kentgens APM (2000) Changes in structural and electronic properties of the zeolite framework induced by extraframework Al and La in H-USY and La(x)NaY: A 29Si and 27Al MAS NMR and 27Al MQ MAS NMR study. J Phys Chem B 104:6743–6754

  36. 36.

    Yan Z, Ma D, Zhuang J, Liu X, Liu X, Han X, Bao X, Chang F, Xu L, Liu Z (2003) On the acid-dealumination of USY zeolite: a solid-state NMR investigation. J Mol Catal A 194:153–167

  37. 37.

    Omegna A, van Bokhoven JA, Prins R (2003) Flexible aluminum coordination in alumino–silicates. Structure of zeolite H–USY and amorphous silica–alumina. J Phys Chem B 107:8854–8860

  38. 38.

    Beyerlein RA, McVicker GB, Yacullo LN, Ziemiak J (1988) The influence of framework and nonframework aluminum on the acidity of high-silica, proton-exchanged FAU-framework zeolites. J Phys Chem 92:1967–1970

  39. 39.

    Carvajal R, Chu PJ, Lunsford JH (1990) The role of polyvalent cations in developing strong acidity: a study of lanthanum-exchanged zeolites. J Catal 125:123–131

  40. 40.

    Mota CJA, Martins RL, Nogueira L, Kover WB (1994) Reactivity of zeolite hydroxyls toward σ-donor bases. H-D exchange with 3-methylpentane. J Chem Soc Faraday Trans 90:2297–2302

  41. 41.

    Wang QL, Giannetto G, Guisnet M (1991) Dealumination of zeolites III. Effect of extra-framework aluminum species on the activity, selectivity, and stability of Y zeolites in n-heptane cracking. J Catal 130:471–482

  42. 42.

    Lónyi F, Lunsford JH (1992) The development of strong acidity in hexafluorosilicate-modified Y-type zeolites. J Catal 136:566–577

  43. 43.

    Mota CJA, Bhering DL, Rosenbach N Jr (2004) Acidity of USY Zeolites: where is the Bronsted/Lewis acid synergism? Angew Chem Int Ed 43:3050–3053

  44. 44.

    Brown HC, Borkowski M (1952) The effect of ring size on the rate of solvolysis of the 1-chloro-1-methylcycloalkanes. J Am Chem Soc 74:1894–1902

  45. 45.

    Bhan A, Gounder R, Macht J, Iglesia E (2008) Entropy considerations in monomolecular cracking of alkaneson acidic zeolites. J Catal 253:221–224

  46. 46.

    Gounder R, Iglesia E (2012) The roles of entropy and enthalpy in stabilizing ion-pairs at transition states in zeolite acid catalysis. Acc Chem Res 45:229–238

  47. 47.

    Laughton PM, Robertson RE (1965) Solvolysis in light and heavy water VI. The role of initial state structure. Can J Chem 43:154–158

  48. 48.

    Craig WG, Hakka L, Laughton PM, Robertson RE (1963) Solvolysis in light and heavy water V. Effect of dioxane on the solvent isotope effect with t-butyl chloride. Can J Chem 41:2118–2120

  49. 49.

    Lowry TH, Richardson KS (1981) Theory and mechanism in organic chemistry. Harper and Row, New York

  50. 50.

    Bhering DL, Ramirez-Solís A, Mota CJA (2003) A density functional theory based approach to extra framework aluminum species in zeolites. J Phys Chem B 107:4342–4347

Download references


Authors thank financial support from CNPq and FAPERJ.

Author information

Correspondence to Claudio J. A. Mota.

Additional information

Dedicated to the fond memories of the late Prof. George A. Olah.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Arca, H.A., Mota, C.J.A. Rearrangement of Cyclopropylcarbinyl Chloride Over Protonic Zeolites: Formation of Carbocations and Behavior as Solid Solvents. Top Catal 61, 616–622 (2018). https://doi.org/10.1007/s11244-018-0911-8

Download citation


  • Zeolites
  • Carbocation
  • Acid catalysis
  • Rearrangement