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

Amanzhan Saginayev; Marina Kursina; Altynai Kalauova

doi:doi:10.11648/j.sjc.20180604.13

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

Amanzhan Saginayev, Marina Kursina, Altynai Kalauova

Published in Science Journal of Chemistry (Volume 6, Issue 4)

Received: 3 September 2018 Accepted: 26 September 2018 Published: 22 October 2018

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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.

Published in	Science Journal of Chemistry (Volume 6, Issue 4)
DOI	10.11648/j.sjc.20180604.13
Page(s)	50-55
Creative Commons	This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.
Copyright	Copyright © The Author(s), 2024. Published by Science Publishing Group

Keywords

Propyladamantane, Dimethylethyladamantane, Tetramethyladamantane, Butyladamantane, DFT Calculations

References

[1]	Bagrii E. I. Adamantanes: Synthesis, Properties and Application. Moscow: Nauka, 1989, 264 p. [in Russian].
[2]	Hargittai I., Hedberg K. Molecular Structures and Vibrations. Amsterdam: Elsevier, 1972, 340 p.
[3]	Kruppa G. H., Beauchamp J. L. J. Am. Chem. Soc. Vol. 108, 1985, p. 2126.
[4]	Tian S. X., Kishimoto N., Ohno K. J. Phys. Chem. A. Vol. 106, 2002, p. 6541.
[5]	Kira M., Akiyama M., Ichinose M., Sakurai H. J. Am. Chem. Soc. Vol. 111, No. 21, 1989, p. 8256.
[6]	Rienstra-Kiracofe J. C., Tschumper G. S., Schaefer H. F. Chem. Rev. Vol. 102, No. 1, 2002, p. 231.
[7]	Borisov Yu. А., Saginayev А. Т. Petrochemistry. Vol. 54, No. 4, 2014, pp. 270-274.
[8]	Borisov Yu. А., Saginayev А. Т., Bagrii E. I. Petrochemistry. Vol. 56, No. 2, 2016, pp. 166- 170.
[9]	Saginayev А. Т. Novosti nauki Kazakhstana. No. 1, 2004, pp. 23-28. [in Russian].
[10]	Bagrii E. I., Sanin P. I. US Patent 3637876. 1972.
[11]	Bagrii E. I., Saginayev А. Т. Petrochemistry. Vol. 22, No. 6, 1982, pp. 729-734.
[12]	Saginayev А. Т., Bagrii E. I. Sb. Tr. Mezhdunarodnoi conferencii po analyticheskoi chimii. Almaty, 1998, pp. 78-84. [in Russian].
[13]	Saginayev А. Т., Bagrii E. I. Poisk, 1999, pp. 19-23. [in Russian].
[14]	Frisch M. J., Trucks G. W., Schlegel H. B., Scuseria G. E., Robb M. A., Cheeseman J. R., Zakrzewski V. G., Montgomery Jr. J. A., Stratmann R. E., Burant J. C., Dapprich S., Millam J. M., Daniels A. D., Kudin K. N., Strain M. C., Farkas O., Tomasi J., Barone V., Cossi M., Cammi R., Mennucci B., Pomelli C., Adamo C., Clifford S., Ochterski J., Petersson G. A., Ayala P. Y., Cui Q., Morokuma K., Malick D. K., Rabuck A. D., Raghavachari K., Foresman J. B., Cioslowski J., Ortiz J. V., Stefanov B. B., Liu G., Liashenko A., Piskorz P., Fox D. Gaussian 98, Revision A. 5, Inc. Pittsburgh. PA. 1998.
[15]	Becke A. D. J. Chem. Phys. Vol. 98, 1993, p. 1372.
[16]	Lee C., Yang W., Parr R. G. Phys. Rev. B. Vol. 37, No. 2, 1988, p. 785.
[17]	Borisov Yu. A., Bagrii E. I. Reports of the Academy of Sciences, physical chemistry. Vol. 463, No. 1, 2015, pp. 54-57. [in Russian].
[18]	Udhayakala P., Jayanthi A., Rajendiran T. V., Gunasekaran S. International J. of ChemTech Research CODEN. Vol. 3, No. 4, 2011, pp. 1851-1862.
[19]	Zaitsau D., Paulechka E., Firaha D. S., Blokhin A. V., Kabo G. J., Bazyleva A., Kabo A. G., Varfolomeev A. M., Sevruk V. M. J. Chem. Thermodynamics. 91, 2015, pp. 459-473.
[20]	Karabacak M., Kose E., Atac A., Cipiloglu M. A., Kurt M. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 97, 2012, pp. 892-908.
[21]	Sechadri S., Rasheed M. P., Sangeetha R. IOSR Journal of Applied Physics. Vol. 7, No. 6, 2015, pp. 56-70.
[22]	Dereli O., Erdogdu Y., Gulluoglu M. T., Sundaraganesan N., Turkkan E., Sayin U., Ozmen A. Optics and Spectroscopy. Vol. 116, No. 2, 2014, pp. 205-213.
[23]	Benia H. M., Myrach P., Nilius N., Freund H.-J. Surface Science. 604, 2010, pp. 435-441.
[24]	McQuarrie D. A. Statistic Thermodynamics. Harper and Row. N. Y. 1973, 194 p.
[25]	Bagrii E. I., Sanin P. I. Patent 239302 USSR. [in Russian].

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APA Style

Amanzhan Saginayev, Marina Kursina, Altynai Kalauova. (2018). Syntheses, Geometrical and Electronic Structure of Alkyladamantanes and Their Thermodynamic Characteristic According to the Density Functional Theory. Science Journal of Chemistry, 6(4), 50-55. https://doi.org/10.11648/j.sjc.20180604.13

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ACS Style

Amanzhan Saginayev; Marina Kursina; Altynai Kalauova. Syntheses, Geometrical and Electronic Structure of Alkyladamantanes and Their Thermodynamic Characteristic According to the Density Functional Theory. Sci. J. Chem. 2018, 6(4), 50-55. doi: 10.11648/j.sjc.20180604.13

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AMA Style

Amanzhan Saginayev, Marina Kursina, Altynai Kalauova. Syntheses, Geometrical and Electronic Structure of Alkyladamantanes and Their Thermodynamic Characteristic According to the Density Functional Theory. Sci J Chem. 2018;6(4):50-55. doi: 10.11648/j.sjc.20180604.13

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@article{10.11648/j.sjc.20180604.13,
  author = {Amanzhan Saginayev and Marina Kursina and Altynai Kalauova},
  title = {Syntheses, Geometrical and Electronic Structure of Alkyladamantanes and Their Thermodynamic Characteristic According to the Density Functional Theory},
  journal = {Science Journal of Chemistry},
  volume = {6},
  number = {4},
  pages = {50-55},
  doi = {10.11648/j.sjc.20180604.13},
  url = {https://doi.org/10.11648/j.sjc.20180604.13},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.sjc.20180604.13},
  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.},
 year = {2018}
}

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TY  - JOUR
T1  - Syntheses, Geometrical and Electronic Structure of Alkyladamantanes and Their Thermodynamic Characteristic According to the Density Functional Theory
AU  - Amanzhan Saginayev
AU  - Marina Kursina
AU  - Altynai Kalauova
Y1  - 2018/10/22
PY  - 2018
N1  - https://doi.org/10.11648/j.sjc.20180604.13
DO  - 10.11648/j.sjc.20180604.13
T2  - Science Journal of Chemistry
JF  - Science Journal of Chemistry
JO  - Science Journal of Chemistry
SP  - 50
EP  - 55
PB  - Science Publishing Group
SN  - 2330-099X
UR  - https://doi.org/10.11648/j.sjc.20180604.13
AB  - 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.
VL  - 6
IS  - 4
ER  -

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Author Information

Amanzhan Saginayev

Laboratory of Petrochemistry, Atyrau of Oil and Gas University, Atyrau, Kazakhstan
Marina Kursina

Department of Chemistry and Chemical Technology, Atyrau of Oil and Gas University, Atyrau, Kazakhstan
Altynai Kalauova

Department of Chemistry and Chemical Technology, Atyrau of Oil and Gas University, Atyrau, Kazakhstan

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APA Style

Amanzhan Saginayev, Marina Kursina, Altynai Kalauova. (2018). Syntheses, Geometrical and Electronic Structure of Alkyladamantanes and Their Thermodynamic Characteristic According to the Density Functional Theory. Science Journal of Chemistry, 6(4), 50-55. https://doi.org/10.11648/j.sjc.20180604.13

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ACS Style

Amanzhan Saginayev; Marina Kursina; Altynai Kalauova. Syntheses, Geometrical and Electronic Structure of Alkyladamantanes and Their Thermodynamic Characteristic According to the Density Functional Theory. Sci. J. Chem. 2018, 6(4), 50-55. doi: 10.11648/j.sjc.20180604.13

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AMA Style

Amanzhan Saginayev, Marina Kursina, Altynai Kalauova. Syntheses, Geometrical and Electronic Structure of Alkyladamantanes and Their Thermodynamic Characteristic According to the Density Functional Theory. Sci J Chem. 2018;6(4):50-55. doi: 10.11648/j.sjc.20180604.13

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@article{10.11648/j.sjc.20180604.13,
  author = {Amanzhan Saginayev and Marina Kursina and Altynai Kalauova},
  title = {Syntheses, Geometrical and Electronic Structure of Alkyladamantanes and Their Thermodynamic Characteristic According to the Density Functional Theory},
  journal = {Science Journal of Chemistry},
  volume = {6},
  number = {4},
  pages = {50-55},
  doi = {10.11648/j.sjc.20180604.13},
  url = {https://doi.org/10.11648/j.sjc.20180604.13},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.sjc.20180604.13},
  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.},
 year = {2018}
}

Copy | Download

TY  - JOUR
T1  - Syntheses, Geometrical and Electronic Structure of Alkyladamantanes and Their Thermodynamic Characteristic According to the Density Functional Theory
AU  - Amanzhan Saginayev
AU  - Marina Kursina
AU  - Altynai Kalauova
Y1  - 2018/10/22
PY  - 2018
N1  - https://doi.org/10.11648/j.sjc.20180604.13
DO  - 10.11648/j.sjc.20180604.13
T2  - Science Journal of Chemistry
JF  - Science Journal of Chemistry
JO  - Science Journal of Chemistry
SP  - 50
EP  - 55
PB  - Science Publishing Group
SN  - 2330-099X
UR  - https://doi.org/10.11648/j.sjc.20180604.13
AB  - 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.
VL  - 6
IS  - 4
ER  -

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