Structure of long-lived alkynyl-substituted carbocations of the phenanthrene series and their precursors

According to the NMR data, 9-(R-ethynyl)-9-hydroxy-10,10-dimethyl-9,10-dihydrophenanthrenes (R = H, Me, Ph) in superacid medium (HSO 3 F-SO 2 ClF) at low temperature undergo dehydroxylation with formation of the corresponding long-lived 10,10-dimethyl-9-(R-ethynyl)-9,10-dihydrophenanthren-9-yl catio...

Full description

Saved in:
Bibliographic Details
Published in:Russian journal of organic chemistry 2013-06, Vol.49 (6), p.853-859
Main Authors: Bushmelev, V. A., Genaev, A. M., Sal’nikov, G. E., Shubin, V. G.
Format: Article
Language:English
Subjects:
Chemistry
Chemistry and Materials Science
Organic Chemistry
Review
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:According to the NMR data, 9-(R-ethynyl)-9-hydroxy-10,10-dimethyl-9,10-dihydrophenanthrenes (R = H, Me, Ph) in superacid medium (HSO 3 F-SO 2 ClF) at low temperature undergo dehydroxylation with formation of the corresponding long-lived 10,10-dimethyl-9-(R-ethynyl)-9,10-dihydrophenanthren-9-yl cations which do not isomerize to 10-(R-ethynyl)-9,10-dimethyl-9,10-dihydrophenanthren-9-ylium. In contrast, longlived 10,10-dimethyl-9-(3,3,3-trifluoroprop-1-yn-1-yl)-9,10-dihydrophenanthren-9-yl cation derived from 9-(3,3,3-trifluoroprop-1-yn-1-yl)-10,10-dimethyl-9,10-dihydrophenanthren-9-ol undergoes partial isomerization to 10-(3,3,3-trifluoroprop-1-yn-1-yl)-9,10-dimethyl-9,10-dihydrophenanthren-9-yl cation.
ISSN:1070-4280
1608-3393
DOI:10.1134/S1070428013060092