Experimental and Theoretical Study of [2σ + 2σ + 2π]–Cycloaddition of Quadricyclane and Ethylenes Containing Three Silyl-Groups

Abstract

The reaction of [2σ + 2σ + 2π]-cycloaddition of quadricyclane with olefins is an attractive way for regioand sterospecific synthesis of norbornene derivatives (exotricyclononenes) with desired substituents. The presence of Cl 3 Si-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 [2σ + 2σ + 2π]-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 M. Bermeshev ( ) · P. Chapala · M. Filatova · E. Finkelshtein A.V. Topchiev Institute of Petrochemical Synthesis of Russian Academy of Sciences, 29 Leninsky Prospect, 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 Me 3 Si-groups, the compounds are interesting monomers for synthesis of membrane polymers possessing high gas permeability values.

Synthesis and Gas-Transport Properties of Metathesis Polytricyclononenes Bearing Three Me3 Si Groups per Monomer Unit

“…The initial monomer for the ring‐opening metathesis polymerization (ROMP)—3,3,4‐tris(trimethylsilyl)tricyclononene‐7 ( TCNSi3 ) was synthesized according to Scheme …”

The selective hydrosilylation of norbornadiene-2,5 by monohydrosiloxanes

“…18 This selectively gives the exo-isomer, but only "activated" vinylsilanes (which contain chlorine atoms at silicon) were active in this reaction. [19][20][21][22] This limits the scope of the reaction. Furthermore, it is also necessary to use an additional step to transform the Si-Cl-bonds into the desired silicon-containing group.…”

Synthesis and Gas‐Transport Properties of Novel Copolymers Based on Tricyclononenes Containing One and Three Me3Si‐Groups

“…Toluene was distilled over sodium under argon and it was kept in inert atmosphere (dried argon) with sodium/potassium alloy. 3,3,4‐Tris(trimethylsilyl)tricyclononene‐7 (TCNSi3) and 3‐trimethylsilyltricyclononene‐7 (TCNSi1) were obtained as described elsewhere …”