Nucleophilic Participation in the Solvolyses of (Arylthio)methyl Chlorides and Derivatives: Application of Simple and Extended Forms of the Grunwald-Winstein Equations.
DennisN Kevill, YoungHoon Park, Byoung-Chun Park, MalcolmJ D'Souza
文献索引:Curr. Org. Chem. 16(12) , 1502-1511, (2012)
全文:HTML全文
摘要
The specific rates of solvolysis of chloromethyl phenyl sulfide [(phenylthio)methyl chloride] and its p-chloro-derivative have been determined at 0.0 _C in a wide range of hydroxylic solvents, including several containing a fluroalcohol. Treatment in terms of a two-term Grunwald-Winstein equation, incorporating terms based on solvent ionizing power (Y(Cl)) and solvent nucleophilicity (N(T)) suggest a mechanism similar to that for the solvolyses of tert-butyl chloride, involving in the rate-determining step a nucleophilic solvation of the incipient carbocation in an ionization process. A previous suggestion, that a third-term governed by the aromatic ring parameter (I) is required, is shown both for the new and for the previously studied related substrates to be an artifact, resulting from an appreciable degree of multicollinearity between I values and a linear combination of N(T) and Y(Cl) values.
相关化合物
相关文献:
Synthesis of α-Haloalkyl Esters from α-Arylthioalkyl Esters. Benneche T, et al.
[Acta Chem. Scand. 43 , 74-77, (1988)]
A new approach to the synthesis of 2-aminoimidazo [1, 2-a]pyridine derivatives through microwave-assisted N-alkylation of 2-halopyridines. Vega JA, et al.
[Tetrahedron 55(8) , 2317-2326, (1999)]