6663-95-2Relevant academic research and scientific papers
The Solvolysis of 3-Cyclooctatetraenylpropyl and 4-Cyclooctatetraenylbutyl p-Nitrobenzenesulfonates in 2,2,2-Trifluoroethanol and 1,1,1,3,3,3-Hexafluoropropan-2-ol
Ferber, Peter H.,Gream, George E.,Wagner, Rudolf D.
, p. 1569 - 1588 (2007/10/02)
The advantage of the use, compared to acetic acid, of 2,2,2-trifluoroethanol and 1,1,1,3,3,3-hexafluoropropan-2-ol for promoting ?-participation in the solvolytic reactions of 3-cyclooctatetraenylpropyl and 4-cyclooctatetraenylbutyl p-nitrobenzenesulfonates is demonstrated. 3-Cyclooctatetraenylpropyl p-nitrobenzenesulfonate solvolyses in buffered trifluoroethanol and hexafluoropropan-2-ol with ?-participation occurring to the extent of 73 and 99.5percent, respectively.The sole cyclized products is 2,9a-dihydro-1H-cyclopentacyclooctene. 4-Cyclooctatetraenylbutyl p-nitrobenzenesulfonate solvolyses in buffered trifluoroethanol and hexafluoropropan-2-ol with ?-participation occurring to the extent of 94 and 100percent, respectively.In buffered trifluoroethanol, the major cyclized products are two isomers of 10a-(2',2',2'-trifluoroethoxy)-1,2,3,4,4a,10a-hexahydrobenzocyclooctene (61.7percent) and 1,2,3,10a-tetrahydrobenzocyclooctene (28.9percent).The tetraene is almost the exclusive product (98.8percent) in buffered hexafluoropropan-2-ol.The probable involvement of substituted homotropylium ions and the role of ion-pairs in the solvolyses are discussed.
