Syntheses, Geometrical and Electronic Structure of Alkyladamantanes and Their Thermodynamic Characteristic According to the Density Functional Theory

Abstract

Propyladamantanes synthesized by of alkylation adamantane with isopropyl alcohol temperature range from 5 to 40°C in the presence of 96% sulfuric acid. Tetramethyl- and Dimethylethyladamantanes synthesized by of isomerization of Perhydroanthracene in the presence of aluminium oxide catalyst on the setting of the flow type. Isomers Butyladamantanes was obtained by the reaction of alkylation of the adamantane with n-butane and isobutane. Adamantane and its derivatives have been the subject of many experimental and theoretical studies. The molecular structure of adamantane was studied by gasphase electron diffraction, Penning ionization electron spectroscopy, photoelectron spectroscopy, electron spin resonance, and quantum calculations of ionization potentials (IP) and electron affinity (SE). The structure 1-n-propyladamantane (1), 1-isopropyladamantane (2), 2-n-propyladamantane (3), 1,2-di-n-propyladamantane (4), 1,3-dimethyl-5-ethyladamantane (5), 1,3,5,6-tetramethyladamantane (6), 1,3,5,7-tetramethyladamantane (7), perhydroanthracene (8), 1-n-butyladamantane (9), 1-isobutyladamantane (10), 1-sec-butyladamantane (11) has been studied using the Becke–Lee–Yang–Parr (B3LYP) hybrid energy functional of electron density with the 6-31G* basis set. The geometric and electronic characteristics of the compounds and their total energy, normal vibration frequencies have been calculated. It has been shown that the calculated Gibb free energies of formation for the perhydroanthracene isomerization products are in qualitative agreement with the experimental product composition of the isomerate and alkylation of adamantane with isopropyl alcohol are in qualitative agreement with the experimental composition of the products. Obtained good agreement of calculated and experimental data on the composition of equilibrium mixtures.