Experimental and Theoretical Study of [2 sigma+2 sigma+2 pi]-Cycloaddition of Quadricyclane and Ethylenes Containing Three Silyl-Groups

Experimental and Theoretical Study of [2 sigma+2 sigma+2 pi]-Cycloaddition of Quadricyclane and Ethylenes Containing Three Silyl-Groups Full article

Journal

Silicon
ISSN: 1876-990X , E-ISSN: 1876-9918

Output data

Year: 2015, Volume: 7, Number: 2, Pages: 117-126 Pages count : DOI: 10.1007/s12633-014-9263-6

Tags

Norbornene; Tricyclononene; Quadricyclane; [2+2+2]-cycloaddition reaction; Silylethylenes; Silicon-containing monomers

Authors

Bermeshev Maxim ¹ , Chapala Pavel ¹ , Lakhtin Valentin ² , Genaev Alexander ³ , Filatova Marina ¹ , Peregudov Alexander ⁴ , Utegenov Kamil ⁴ , Ustynyuk Nikolai ⁴ , Finkelshtein Eugene ¹

Affiliations

1	(Данные Web of science) Russian Acad Sci, AV Topchiev Inst Petrochem Synth, Moscow 119991, Russia
2	(Данные Web of science) State Sci Ctr, Russian Federat State Res Inst Chem & Technol Org, Moscow 111123, Russia
3	(Данные Web of science) Russian Acad Sci, NN Vorozhtsov Inst Organ Chem, Siberian Branch, Novosibirsk 630090, Russia
4	(Данные Web of science) Russian Acad Sci, AN Nesmeyanov Inst Organoelement Cpds, Moscow 119991, Russia

The reaction of [2 sigma + 2 sigma + 2 pi]-cycloaddition of quadricyclane with olefins is an attractive way for regio- and sterospecific synthesis of norbornene derivatives (exo-tricyclononenes) with desired substituents. The presence of Cl3Si-containing groups in such compounds permits different monomer modifications for the development of new materials. Herein, for the first time the theoretical and experimental study of the behavior of different ethylenes containing three silyl-groups in the reaction of [2 sigma + 2 sigma + 2 pi]-cycloaddition with quadricyclane was systematically performed. Based on the data obtained for this reaction the activity scale of the ethylene derivatives was established, and the explanations for an ethylene activity were suggested. As a result, a new family of Si-containing tricyclononenes was successfully synthesized. As an example of a possible modification, the methylation of the sterically hindered cycloadducts was investigated and the conditions for full methylation were found. Considering that gas permeability of polymers increases with the increase of a number of the side Me3Si-groups, the compounds are interesting monomers for synthesis of membrane polymers possessing high gas permeability values.

Bermeshev M. , Chapala P. , Lakhtin V. , Genaev A. , Filatova M. , Peregudov A. , Utegenov K. , Ustynyuk N. , Finkelshtein E.
Experimental and Theoretical Study of [2 sigma+2 sigma+2 pi]-Cycloaddition of Quadricyclane and Ethylenes Containing Three Silyl-Groups
Silicon. 2015. V.7. N2. P.117-126. DOI: 10.1007/s12633-014-9263-6 WOS Scopus

Published online:	Dec 13, 2014
Published print:	Apr 1, 2015

Web of science	WOS:000354546500007
Scopus	2-s2.0-84941736609
OpenAlex	W2460937727