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Six Peroxide Groups in One Molecule – Synthesis of Nine‐Membered Bicyclic Silyl Peroxides
Author(s) -
Arzumanyan Ashot V.,
Terent'ev Alexander O.,
Novikov Roman A.,
Lakhtin Valentin G.,
Chernyshev Vladimir V.,
Fitch Andrew N.,
Nikishin Gennady I.
Publication year - 2014
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201402895
Subject(s) - chemistry , silylation , geminal , peroxide , bicyclic molecule , regioselectivity , alkyl , medicinal chemistry , molecule , ring (chemistry) , stereochemistry , organic chemistry , catalysis
Compounds containing two nine‐membered peroxide rings bridged by an ethane, ethene, or ethyne group were synthesized by the reactions of 1,2‐bis[dichloro(alkyl)silyl]ethanes, ( E )‐1,2‐bis[dichloro(methyl)silyl]ethene, or 1,2‐bis[dichloro(methyl)silyl]ethyne with 1,1′‐dihydroperoxydicycloalkyl peroxides. Each ring is formed by the replacement of two geminal chlorine atoms at the silicon atom with the hydroperoxide groups of one peroxide molecule. The cyclization is regioselective. The possible 12‐membered bicyclic peroxide products are not produced. Unexpectedly, the peroxides are extremely explosive. The reactions of 1,2‐bis[dichloro(alkyl)silyl]ethanes with 1,1‐dihydroperoxy‐ tert ‐butylcyclohexane give only bicyclic peroxides containing two six‐membered rings also through the replacement of two geminal chlorine atoms at the silicon atom by the hydroperoxide groups of one dihydroperoxide molecule.