Catalytic Alkylation of Adamantane with Propylene: Quantum-Chemical Calculations and Experimental Data
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lytic Alkylation of Adamantane with Propylene: QuantumChemical Calculations and Experimental Data N. I. Baranova, *, R. E. Safira, E. I. Bagriib, K. V. Bozhenkoa, c, and A. G. Cherednichenkoa a
Peoples’ Friendship University of Russia, Moscow, 117198 Russia Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia c Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, 142432 Russia *e-mail: [email protected] bTopchiev
Received November 19, 2019; revised April 2, 2020; accepted May 12, 2020
Abstract—The mechanism of interaction of adamantane with propylene has been studied by quantum-chemical calculations within the density functional theory (DFT). It has been shown that the main products of adamantane alkylation with propylene in the presence of acid catalysts are hydrocarbons with unbranched (normal-chain) substituents, 1-n-propyl- and 1-n-propenyladamantanes. The main stages of adamantane alkylation and the geometric and electronic structures of the intermediates have been determined. The thermodynamic characteristics of the studied adamantanes have been found, and the mechanisms of individual steps of their transformations have been proposed. The obtained data make it possible to control the process of preparation of substituted adamantanes with a defined structure that are of interest for the development of efficient energy-rich materials, high-density fuels, and thermally stable polymers. Keywords: acid catalysis, propylene, alkylation of adamantane, DFT calculations DOI: 10.1134/S0965544120090042
The discovery of the tricyclic hydrocarbon (HC) adamantane (C10H16) in Hodonín crude oil by Landa and Machácek in 1933 paved the way for the chemistry of petroleum hydrocarbons with the diamond-like structure [1]. The unusual physicochemical properties of HCs of this type, such as high density, thermal stability, lipophilicity, and chemical activity, promoted comprehensive investigation of adamantane derivatives and preparation of thermally stable hydrocarbon fuels, lubricating oils, polymer materials, biologically active compounds, and pharmaceuticals including known antiviral (amantadine, rimantadine) and immunotropic (kemantane, memantine) drugs based on them. It should be noted that in the second half of the 20th century, the major attention of researchers was paid to derivatives of adamantane itself [2]. Currently, polymantanes, bulky adamantane polymers (diamondoids or adamantanoids), are of special interest. These are nanosized molecules containing several adamantyl framework segments, which are also present in petroleums and gas condensates. Due to their unique properties, these compounds and their derivatives are considered promising in many fields including the energy sector, medicine, lithography, electronics, biotechnology, etc. [3–6]. A polymer based on adamantane and pyrene has recently been obtained, which can be used for determining the concentration of explosives,
such as di- and trinitrotoluenes [7]. Coatings based o
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