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Simulation of liquid-phase thermal reactions of radiation-induced vinylcyclopropane radical cations using the techniques of frozen freon matrices and liquid-phase spin trappingстатья
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Дата последнего поиска статьи во внешних источниках: 18 июля 2013 г.
- Авторы: Shchapin I.Y., Feldman V.I., Belevskii V.N.
- Журнал: High Energy Chemistry
- Том: 30
- Номер: 6
- Год издания: 1996
- Издательство: Pleiades Publishing, Ltd
- Местоположение издательства: Road Town, United Kingdom
- Первая страница: 388
- Последняя страница: 393
- Аннотация: Thermal transformations of vinylcyclopropane (VCP) radical cations generated by X-irradiation in a CF2ClCFCl2 Freon matrix were studied by ESR technique. It was shown that the primary radical cations converted to the distonic form dist(90,0)-C5H+ . (VII) upon warming of the irradiated samples up to 110 K. This distonic form undergoes transformation to the 2-vinylallyl radical (XI) at 120 K; the 1-vinylallyl radical (X) is formed at 135 K. The conversion of (VII) to (XI) occurs due to hydrogen transfer from VCP to the radical cation (XI) via formation of an intermediate vinylcyclopropyl radical (IX) followed by ring opening. X-ray irradiation of 2,4,6-tri-tert-butylnitrosobenzene (BNB) solutions in vinylcyclopropane at 293 K results in the formation of BNB adducts with n-alkyl (I), allyl (II), 1-vinylcyclopropyl (V), and 2-vinylcyclopropyl (III) and (IV) radicals. The yield of BNB adducts (III) and (IV) was found to be 70% of the total yield of the adducts. A certain part of radicals (IX) results from ion-molecule reactions of the primary radical cations. Ring opening in two kinds of vinylcyclopropyl radicals results in the formation of 1-vinylallyl and 2-vinylallyl radicals.
- Добавил в систему: Фельдман Владимир Исаевич