
TY  - JOUR
A1  - Ferber, PH 
A1  - Gream, GE 
A1  - Wagner, RD 
T1  - 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
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1980
VL  - 33
IS  - 7
SP  - 1569
EP  - 1588
KW  - 
UR  - https://doi.org/10.1071/CH9801569 
N2  - 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 &#960;-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 &#960;- 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 &#960;- 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. 
ER  -

