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
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.