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Petroleum Chemistry

, Volume 59, Issue 1, pp 66–70 | Cite as

Theoretical Study of the Mechanism of Catalytic Alkylation of Adamantane with 2,2,4-Trimethylpentane Cracking Products

  • E. I. BagriiEmail author
  • Yu. A. Borisov
  • Yu. A. Kolbanovskii
  • A. L. Maksimov
Article
  • 3 Downloads

Abstract

Quantum-chemical calculations on the mechanism of catalytic alkylation of adamantane with isooctane cracking products using the density functional theory DFT B3LYP/6-31G* have been carried out. It has been shown that the initial stage of transformations is the interaction of AlCl3 · HCl (as a model of an acid catalyst) with isooctane. At the first cracking stage, proton transfer from the catalyst to isooctane occurs (activation energy is calculated to be 24.64 kcal/mol) to give intermediate 1, which consists of three interacting subsystems: the cation (СН3)3С+; the anion \({\text{AlCl}}_{4}^{ - }\); and СН3–СН(СН3)2, i.e., isobutane. The second stage is proton transfer from the carbocation (СН3)3С+ to form the olefin CH2=C(CH3)2. The activation energy of this stage was calculated to be 7.85 kcal/mol. This is the final stage of isooctane cracking, yielding an olefin and an alkane smaller than the parent one. The mechanism of formation of the adamantyl cation has been considered, in which the cation adds the olefin without activation energy and the resulting complex can form either 1-isobutylenyladamantane (unsaturated byproduct of adamantane alkylation) via deprotonation by the catalyst anion or the final product 1-isobutyladmantane via interaction with another adamantane molecule. The latter can also be formed by the joint action of isobutane and the catalyst anion on the adamantyl cation, with the activation energy being 26.79 kcal/mol.

Keywords:

acid catalysis catalytic cracking of isooctane alkylation of adamantane PES of reactions DFT calculations 

Notes

REFERENCES

  1. 1.
    K. P. Lavrovskii, Selected Works (Nauka, Moscow, 1976) [in Russian].Google Scholar
  2. 2.
    E. I. Bagrii, Adamantanes: Preparation, Properties, and Applications (Nauka, Moscow, 1989) [in Russian].Google Scholar
  3. 3.
    E. I. Bagrii, T. Yu. Frid, and P. I. Sanin, Izv. Akad. Nauk SSSR, Ser. Khim., No. 2, 498 (1970).Google Scholar
  4. 4.
    Gaussian 09W, Version 7.0 (Gaussian, Wallingford, 1995).Google Scholar
  5. 5.
    R. G. Parr and Y. Yang, Density-Functional Theory of Atoms and Molecules (Oxford Univ. Press, Oxford, 1989.Google Scholar
  6. 6.
    A. D. Becke, Phys. Rev. A 38, 3098 (1988).CrossRefGoogle Scholar
  7. 7.
    C. Lee, W. Yang, and R. G. Parr, Phys. Rev. B 37, 785 (1988).CrossRefGoogle Scholar
  8. 8.
    C. Gonzalez and H. B. Schlegel, J. Phys. Chem. 94, 5523 (1990).CrossRefGoogle Scholar
  9. 9.
    H. B. Schlegel and M. A. Robb, Chem. Phys. Lett. 93, 43 (1982).CrossRefGoogle Scholar
  10. 10.
    H. B. Schlegel, Modern Electronic Structure Theory, Ed. by D. R. Yarkony (World Scientific, Singapore, 1995), p. 459.Google Scholar

Copyright information

© Pleiades Publishing, Ltd. 2019

Authors and Affiliations

  • E. I. Bagrii
    • 1
    Email author
  • Yu. A. Borisov
    • 2
  • Yu. A. Kolbanovskii
    • 1
  • A. L. Maksimov
    • 1
  1. 1.Topchiev Institute of Petrochemical Synthesis, Russian Academy of SciencesMoscowRussia
  2. 2.Nesmeyanov Institute of Organoelement Compounds, Russian Academy of SciencesMoscowRussia

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