160426-48-2Relevant academic research and scientific papers
Is Selective Monosubstitution of Dihalides via SRN1 Reaction Feasible? An Electrochemical Approach for Dichloroarenes
Amatore, Christian,Combellas, Catherine,Lebbar, Nour-Eddine,Thiebault, Andre,Verpeaux, Jean-Noel
, p. 18 - 26 (2007/10/02)
1,4-Dichlorobenzene and dichloropyridines undergo SRN1 reaction with various nucleophiles upon electrochemical initiation.Substitution can compete with reduction only when indirect electrolyses at low current are performed.Selective formation of monosubstitution products is observed when the nucleophiles used behave as electron-donating groups when attached to the aromatic moiety, a situation which is just the opposite of what had been observed when the same reactions were initiated photochemically.This surprising difference in behavior can be rationalized in terms of different capabilities of both activation methods to generate the key monosubstitution anion radical, ArNuX(.-).Kinetic and thermodynamic data concerning the reactivity of dichloroarenes in such processes are presented and discussed.
Electrosynthesis of Unsymmetrical Polyaryls by a SRN1-Type Reaction
Boy, P.,Combellas, C.,Suba, C.,Thiebault, A.
, p. 4482 - 4489 (2007/10/02)
Unsymmetrical polyaryls are electrosynthesized in liquid ammonia by a single-step SRN1 reaction in the presence of a redox mediator starting from aromatic halides and 2,6-di-tert-butyl phenoxide.With monoaryl halides activated by electron-withdrawing substituents (N of pyridyl or quinolyl, trifluoromethyl, cyano, sulfone, ester, ketone, alkyl sulfide, N(1+) of anilinium), biaryls are obtained in good yields (between 50 and 95percent).The yields of ter- and quateraryls are lower (40percent maximum).The reaction is extended to other ortho-disubstituted phenols.Elimination reactions of the tert-butyl groups from the products are achieved by a Friedel-Crafts reaction using either trifluoromethanesulfonic acid or aluminum trichloride as catalysts.
