72332-17-3Relevant articles and documents
The rate of excited-state proton transfer to solvent from trifluoromethylphenols in water
Kaneko, Shigeo,Yoshihara, Toshitada,Tobita, Seiji
scheme or table, p. 312 - 313 (2010/01/16)
The proton-transfer reactions to solvent from electronically excited o-, m-, and p-(trifluoromethyl)phenols (TFOHs) in water have been investigated by picosecond time-resolved fluorescence measurements. The rate constants for the proton dissociation of o-, m-, and p-TFOH are obtained to be 2.2 × 10 9, 8.6 × 108, and 2.5 × 108 s -1, respectively. On the basis of the rate constants, the effects of substituent and deuterium isotope effects on the proton-transfer reactions are revealed. copyright
Electrochemistry of electron-transfer probes. The role of the leaving group in the cleavage of radical anions of α-aryloxyacetophenones
Andersen, Mogens L.,Mathivanan,Wayner, Danial D. M.
, p. 4871 - 4879 (2007/10/03)
The formal reduction potential (E°) of α-phenoxyacetophenone has been determined from the voltammetric peak potential obtained by linear sweep voltammetry in combination with the rate constant for fragmentation of the radical anion which had been determin
Nucleophilic Displacement Reactions at Carbon, Phosphorus and Sulphur Centres: Reaction of Aryl Methanesulphonates with Ethoxide; Change in Mechanism with Change in Leaving Group
Pregel, Marko J.,Buncel, Erwin
, p. 307 - 311 (2007/10/02)
The reactions of ethoxide ion with aryl methanesulphonate esters (1a-c) in anhydrous ethanol at 25 deg C have been investigated in order to determine the effect of leaving group nucleofugality on the balance between substitution and elimination pathways.The reactions of p-nitrophenyl-(1a), m-nitrophenyl-(1b) and p-trifluoromethylphenyl-(1c) methanesulphonates have been examined by means of kinetic studies, sulphene trapping experiments, and deuterium exchange experiments.It is concluded that the para-nitro-substituted ester reacts predominantly by an E1cb-type elimination mechanism via a sulphene intermediate, with nucleophilic substitution as a minor concurrent pathway.Conversely, the meta-nitro-substituted ester reacts predominantly by substitution, with elimination as a minor concurrent pathway.The evidence available indicates that the para-trifluoromethyl-substituted ester reacts solely by substitution.Thus, the mechanism of reaction changes from nucleophilic substitution to elimination-addition as leaving group nucleofugality increases.