Author:
Ferber PH,Gream GE,Wagner RD
Abstract
The advantage of the use,
compared to acetic acid, of 2,2,2- trifluoroethanol and
1,1,1,3,3,3-hexa-fluoropropan-2-ol for promoting π-participation in the
solvolytic reactions of 3-cyclooctatetraenyl- propyl and
4-cyclooctatetraenylbutyl p-nitrobenzenesulfonates is demonstrated. ��� 3-Cyclooctatetraenylpropyl
p-nitrobenzenesulfonate solvolyses in buffered trifluoroethanol and
hexafluoropropan-2-ol with π- participation occurring to the extent of 73
and 99.5 %, respectively. The sole cyclized product is 2,9a-dihydro-1H-cyclopentacyclooctene. 4-Cyclooctatetraenylbutyl
p-nitrobenzenesulfonate solvolyses in buffered trifluoroethanol and
hexafluoropropan-2-ol with π- participation occurring to the extent of 94
and 100%, respectively. In buffered trifluoroethanol, the major cyclized
products are the two isomers of 10a-(2',2',2'-tri-fluoroethoxy)-1,2,3,4,4a,10a-
hexahydrobenzocyclooctene (61.7%) and 1,2,3,10a-tetrahydrobenzo-
cyclooctene (28.9%). The tetraene is almost the
exclusive product (98.8%) in buffered hexafluoro-propan-2-ol. ��� The probable involvement of substituted
homotropylium ions and the role of ion-pairs in the solvolyses are discussed.
Cited by
10 articles.
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