Cyclization reactions of long-lived 10,10-dimethyl-9-phenylethynyl-9,10-dihydrophenanthren-9-yl cation

According to the NMR data, long-lived 10,10-dimethyl-9-phenylethynyl-9,10-dihydrophenanthren-9-ylium in acid medium undergoes cyclization whose direction is determined by the acidity of the medium. The cyclization in HSO 3 F-SbF 5 superacid involves the aromatic ring in the phenanthrene core as nucl...

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Bibliographic Details
Published inRussian journal of organic chemistry Vol. 49; no. 9; pp. 1313 - 1321
Main Authors Sal’nikov, G. E., Genaev, A. M., Bushmelev, V. A., Shubin, V. G.
Format Journal Article
LanguageEnglish
Published Boston Springer US 01.09.2013
Springer Nature
Subjects
Chemistry
Chemistry and Materials Science
Chemistry, Organic
Organic Chemistry
Physical Sciences
Science & Technology
Cyclization Reaction
Trifluoroacetate
Trifluoromethanesulfonic Acid
Methyl Proton Signal
Vinyl Cation
REARRANGEMENTS
CARBOCATIONS
MOLECULES
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Summary:According to the NMR data, long-lived 10,10-dimethyl-9-phenylethynyl-9,10-dihydrophenanthren-9-ylium in acid medium undergoes cyclization whose direction is determined by the acidity of the medium. The cyclization in HSO 3 F-SbF 5 superacid involves the aromatic ring in the phenanthrene core as nucleophilic component and yields 5a,6-dimethyl-4-phenyl-4,5,5a,6-tetrahydroacephenantrylene-4,6-bis(ylium). In trifluoroacetic acid the nucleophilic component is the side-chain phenyl group, and the cyclization product is neutral 8b,14b-dimethyl-8b,14b-dihydrobenzo[ g ]chrysen-10-yl trifluoroacetate. Both cyclization directions are observed in moderate-strength trifluoromethanesulfonic acid.
ISSN:1070-4280
1608-3393
DOI:10.1134/S1070428013090121