Contrasting Photosolvolytic Reactivities of 9-Fluorenol vs 5-Suberenol Derivatives. Enhanced Rate of Formation of Cyclically Conjugated Four ? Carbocations in the Excited State
The photosolvolysis of 9-fluorenol (1) and several of its derivatives, as well as related systems, has been studied in aqueous methanol and acetonitrile solutions.The primary aim of this study was to examine the effect of the internal cyclic array (ICA) of these compounds in promoting photosolvolysis with respect to the number of ? electrons available in the ICA.It was observed that 9-fluorenol derivatives photosolvolyze much more efficiently than any of the related systems studied in this work.In contrast, ground-state 9-fluorenol derivatives are the least reactive systems with respect to solvolysis.Quantum yields for methyl ether formation for photosolvolysis in 50percent MeOH-H2O are reported for 1-3.Rate constants for solvent-assisted photodehydroxylation (ks) are calculated on the basis of the proposed mechanism of heterolytic C-OH bond rupture in the primary photochemical step and are in the range (1.3-1.6)x1E10 s-1 for 1-3.
Wan, Peter,Krogh, Erik
p. 4887 - 4895
(2007/10/02)
Photo-induced Reduction of Fluoren-9-ol and its Acetate by Aliphatic Amines
Irradiation of fluoren-9-ol and its acetate in the presence of an aliphatic amine gave fluorene as the major product.The yield of fluorene depended upon the character of amine and increased in the order of primary methanol and acetonitrile) it was revealed that the major process was electron transfer followed by proton transfer.A radical reaction also participated as a minor process.A possible reaction mechanism similar to the photo-induced Birch reduction was proposed.
Ohashi, Mamoru,Furukawa, Yuji,Tsujimoto, Kazuo
p. 2613 - 2616
(2007/10/02)
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