Propyladamantanes were synthesized by alkylation of adamantane with isopropyl alcohol in the temperature range from 5 to 40 °C in the presence of 96% sulfuric acid. Tetramethyl- and dimethylethyladamantanes were synthesized by isomerization of perhydroanthracene in the presence of aluminium oxide catalyst on the setup of the flow type. Isomers of butyladamantanes were obtained by the reaction of alkylation of the adamantane with isooctane. For each molecule, the optimization of the geometric parameters of atoms was carried out using analytical calculation methods. By calculating the frequencies of normal vibrations using the second derivatives, it was confirmed that the stationary points determined by optimizing the geometry correspond to the minima of the potential energy surface. The structure of 1-n-propyladamantane (I), 1-isopropyl-adamantane (II), 2-n-propyladamantane (III), 1,2-di-n-propyladamantane (IV), 1,3-dimethyl-5-ethyladamantane (V), 1,3,5,6-tetramethyladamantane (VI), 1,3,5,7-tetramethyladamantane (VII), perhydroanthracene (VIII), 1-n-butyladamantane (IX), 1-isobutyladamantane (X), 1-sec-butyladamantane (XI) has been studied using the DFT method with the Becke–Lee–Yang–Parr 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 Gibbs 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. A good agreement of calculated and experimental data on the composition of equilibrium mixtures was obtained. The theoretical geometry of the synthesized alkyladamantanes with Td symmetry very well agrees with the results of electron diffraction. Closest to the results obtained experimentally, the geometry was predicted by B3LYP, in which the lengths of C-C and C-H bonds are close to 1.544 and 1,100Ả, respectively, and the C-Csec-C and C-Cter-C angles are 109°. The results of the calculation using the B3LYP method are in good agreement with the experimental data. There is no definite relationship between the size of the molecules and the convergence of the calculated and experimental data. A practically important conclusion arising from the results of this and previous studies is that the use of the calculation method leads to “chemically accurate” data.
The structure of perhydrofluorene and its isomerization products 1,3,5-trimethyladamantane, 1,3,6-trimethyladamantane, cis-1,3,4-trimethyladamantane, trans-1,3,4-trimethyladamantane, 1-ethyl-3-methyladamantane, cis-1-ethyl-4-methyladamantane, trans-1-ethyl-4-methyladamantane, 1,2,6-trimethyladamantane, and 1,2,8-trimethyladamantane of the general formula C13H22 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, transformation energies, entropies of transformations, and normal vibration frequencies have been calculated. It has been shown that the calculated Gibb free energies of formation for the perhydrofluorene isomerization products are in qualitative agreement with the experimental product composition of the isomerate.
Гибридным методом функционала энергии от электронной плотности БеккеЛиЯнгПарра (B3LYP) в базисе 6-31G* изучено строение пергидроаценафтена (I) и продуктов его превращений: 1,3-диметил-адамантана (II), транс-1,4-диметиладамантана (III), цис-1,4-диметиладамантана (IV), 1,2-диметиладамантана (V), 1-этиладамантана (VI), 2-этиладамантана (VII), имеющих общую формулу С12Н20. Рассчитаны геометрические и электронные характеристики соединений, полные энергии, энергии превращений, энтропии превращений, частоты нормальных колебаний. Определены константы равновесия изомеризации пергидроаценафтена в продукты (IIVII), которые согласуются с экспериментальными данными.
The structure of perhydroacenaphthene (I) and its conversion products 1,3-dimethyladamantane (II), trans -1,4-dimethyladamantane (III), cis -1,4-dimethyladamantane (IV), 1,2-dimethyladamantane (V), 1-ethyladamantane (VI), and 2-ethyladamantane (VII) of the general formula C 12 H 20 has been studied using the Becke-Lee-Yang-Parr (B3LYP) hybrid method for the energy functional of the electron density with the 6–31G* basis set. Geometric and electronic characteristics of the compounds and their total energy, trans-formation energies, transformation entropies, and normal vibration frequencies have been calculated. The equilibrium constants determined for the isomerization of perhydroacenaphthene into products II-VII are consistent with experimental data.
Chemischer InformationsdienstVolume 15, Issue 2 Reviews ChemInform Abstract: UNSATURATED ADAMANTANE DERIVATIVES E. I. BAGRII, E. I. BAGRIISearch for more papers by this authorA. T. SAGINAEV, A. T. SAGINAEVSearch for more papers by this author E. I. BAGRII, E. I. BAGRIISearch for more papers by this authorA. T. SAGINAEV, A. T. SAGINAEVSearch for more papers by this author First published: January 10, 1984 https://doi.org/10.1002/chin.198402360Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume15, Issue2January 10, 1984 RelatedInformation
The literature data on the methods of synthesis and the physical and chemical properties of adamantane derivatives containing C=C double bonds are described systematically and surveyed. Dehydroadamantanes, unsaturated adamantane derivatives with an exocyclic double bond and a double bond remote from the nucleus, as well as their functional derivatives are considered. Much attention is devoted to the reactivity of unsaturated adamantane derivatives. The bibliography includes 165 references.
