Effective Catalytic Method of Diamantane Isomer Synthesis
DOI:
https://doi.org/10.18321/ectj545Abstract
General principles of effect of the nature of metal-catalyst, carrier, solvent, method of preparation and temperature of catalyst reduction and other parameters (PH2, T, etc) on the process of hydrogenolysis of “binor-S” into pentacyclotetradecane have been studied and stated. On the basis of the results obtained a new effective and economical method of diamantane isomer synthesis has been elaborated. The presence of supported platinum catalyst (10-15% Pt/C) allows to proceed the reaction under mild conditions (0.1-10MPa, 60-80°C and in non-aggressive medium (water) with a quantitative yield of the product.It was stated with the help of a complex of physico-chemical methods of investigation (RPES, IR-spectroscopy, NMR, 13C, PMR, etc) that the methods of preparation and the temperature range of reduction of supported platinum catalysts contributing to the formation of highly dispersed metal particles (2.5-5.0 mm)
and their uniform distribution on the carrier surface increase the activity and selectivity of platinum in the reaction of hydrogenolysis of “binor-S” into pentacyclotetradecane. It was shown that the more is the dispersity of metal and the value of the carrier surface, the higher is the activity and selectivity of supported platinum catalysts due to the peculiarity of electronic structure of small particles as well as the influence of the carrieron stabilization of the metal surface structure, i.e. the process of hydrogenolysis of “binor-S” belongs to the type of structure-sensitive reactions.
References
(2). Kurisaki K. Kagaki to kogyo-chem. And chem Industry, 1978, V. 31, No. 4, pp. 270-273.
(3). Gavrilov B.G., Kosnikovskaya O.S., Nikolaeva T.N. J. Applied Chemistry, 1984, V. 57, No. 2, pp. 419-431
(4). Flid V.R., Manulik O.S., Dmitriev D.V., Kouznetsov V.B., Evstigneeva E.M., Belov A.P. and Grigorev A.A. Euvrasian Chemico-Technological Journal, 2001, V. 3, No. 2, pp. 73-90.
(5). Kulazhanov K.S., Omarkulov T.O., Suleimenova M.Sh., Zhamanaev E.K. Effects of dispersivity of platinum catalysts on the reaction rates and selectivity of heptacyclotetradecane hydrogenolysis. J. Poisk, 2001. Series Natural Sciences, No. 3, p. 7-10.
(6). Gund T.M., Williams V.Z., Jr., Osawa E., Schleyer P.R. J. Org. Chem., 1974, V. 39, No. 20, pp. 2979-2987.
(7). Gund T.M., Williams V.Z., Jr., Osawa E., Schleyer P.R.. A convenient, high-yield preparation of diamantane (congressane). Tetrahedron Lett., 1970, No. 44, pp. 3877-3880.
(8). Gund T.M., Schleyer P.v.R., Gund P.X. Computer analysis of structural formulae of polycyclic hydrocarbons. Mechanism of diamantane formation from different pentacyclotetradecanes. J. Amer. Chem. Soc., 1975, V. 97, No. 4, pp.-745.
(9). Schrauzer G.N., Bastian B.N., Fosselius G.A. ГЂ Complex Multicenter Reactions Promoted by Binuclear Catalyst Systems. “Binor-S”, a New Heptacyclotetradecane via stereospecific Dimerization of Bicycloheptadiene. J. Amer. Chem. Soc., 1966, V. 88, No. 21, pp. 4890-4894
(10). Scharf D., Weisgerber G., Hover H. Kationische umlagerung von norbornadiendimeren in den kaefigkohlenwasserstoff heptacyclo (9.3.0 1,11.0,6. 03,10. 04,8. 07,14. 09,13) tetradecan. Tetrahedron Lett., 1967, No. 43, pp. 4227-4229.
(11). Schrauzer G.N., Bastian B.N., Fosselius G.A. ГЂ Complex Multicenter Reactions Promoted by Binuclear Catalyst Systems. “Binor-S”, a New Heptacyclotetradecane via stereospecific Dimerization of Bicycloheptadiene. J. Amer. Chem. Soc., 1966, V. 88, No. 21, pp.4890-4894.
(12). Omarkulov T.O., Sokolsky D.V. Hydrogenation under hydrogen pressure. Alma-Ata, Nauka, 1986, p. 191.
(13). Frampton V.L., Edwards J.D.,Jr., Henze H.R. The preparation of a platinum oxide catalyst of reproducible activity. J. Amer. Chem. Soc., 1951, V. 75, No. 9, pp. 4432-4434.
(14). Zelinsky N.D., Turova-Poliak M.V. Noble metals as hydro- and dehydrogenation catalysts. Proceedings of USSR AS IOChem., 1955, V. 3, pp. 271-276.
(15). Polkovnikov B.D., Balandin A.A., Taber A.M. On the catalytic properties of borides of platinum group metals. Reports of USSR AS, 1962, V. 145, pp. 809-811.
(16). Omarkulov T.O., Zhamanaev E.K., Pak A.M. Hydrogenolysis of heptacyclotetradecane (“binor-S”) on the spongy blacks of platinum group metals under hydrogen pressure. Izv. RK NAS. Series Chem., 1991, No. 6, p. 34-38.
(17). Schrauzer G.N., Ho R.K.Y., Schlezinger G. New catalysts of stereospecific norbornadiene dimerization to “Binor-S”, (1,2,4:5,6,8-dimetheno-sindacene). Tetrahedron Lett., 1970, No. 8, pp. 543-545.
(18). Omarkulov T.O., Zhamanaev E.K., Nurgozhaev K.Kh. Hydrogenolysis of “binor-S” on supported platinum catalysts under hydrogen pressure. J. Phys. Chem., 1993, V. 67, No. 5, pp. 944-947.
Downloads
Published
How to Cite
Issue
Section
License
You are free to: Share — copy and redistribute the material in any medium or format. Adapt — remix, transform, and build upon the material for any purpose, even commercially.
Eurasian Chemico-Technological Journal applies a Creative Commons Attribution 4.0 International License to articles and other works we publish.
Subject to the acceptance of the Article for publication in the Eurasian Chemico-Technological Journal, the Author(s) agrees to grant Eurasian Chemico-Technological Journal permission to publish the unpublished and original Article and all associated supplemental material under the Creative Commons Attribution 4.0 International license (CC BY 4.0).
Further distribution of this work must maintain attribution to the author(s) and the published article’s title, journal citation, and DOI.