2919-12-2Relevant articles and documents
Anilinolysis of nitro-substituted diphenyl ethers in acetonitrile: the effect of some ortho-substituents on the mechanism of SNAr reactions
Isanbor., Chukwuemeka,Emokpae, Thomas A.
, p. 37 - 49 (2010)
Rate data are reported for the reactions of a series of X-phenyl 2,4,6-trinitrophenyl ethers 1a-e [X = H, 4-NO2,2-NO2, 2,4-(NO2)2, or 2,6-(NO2)2] with substituted anilines 2a-e [Y = H, 2-CH
Modification of the Order of Reaction and Reaction Rate of Nucleophilic Aromatic Substitution in Micellar Solutions
Lelievre, Joel,Haddad-Fahed, Omaima,Gaboriaud, Rene
, p. 2301 - 2310 (1986)
The rate of formation of 2,4,6-trinitrodiphenylamine following the attack of aniline on 1-methoxy-2,4,6-trinitrobenzene has been studied in micellar media.The partial order with reference to the nucleophilic reagent (aniline) is unity in solutions of cationic detergents (positive micelles) and 3/2 in water or solutions of anionic detergents.For such reactions there are two main steps in the reaction scheme: first, the formation of an adduct between reagents, favoured by the effect of local higher concentration in the two kinds of micellar solutions and secondly, ejection of a proton from the adduct formed.The latter reaction is catalysed largely by positive micelles and in this case the kinetics are not limited by the deprotonation step.On the other hand, negative micelles inhibit the ejection of a proton and this opposes, in part, the effect of higher local concentrations.
Anilinolysis of picryl benzoate derivatives in methanol: Reactivity, regioselectivity, kinetics, and mechanism
Ibrahim, Mahmoud F.,El-Atawy, Mohamed A.,El-Sadany, Samir K.,Hamed, Ezzat A.
supporting information, p. 551 - 559 (2013/08/23)
The reaction of picryl benzoate derivatives 1a-g with aniline in methanol proceeds through CO-O and Ar-O bond cleavage pathways. Furthermore, the reactivity of these esters toward anilinolysis is correlated to the energy gap between highest occupied molecular orbital aniline and lowest unoccupied molecular orbital of each ester. The regioselectivity of acyl-oxygen versus aryl-oxygen cleavage is also discussed. The overall rate constants k tot split into kCO-O (the rate constant of acyl-oxygen cleavage) and kAr-O (rate constant of aryl-oxygen cleavage). The CO-O bond cleavage advances through a stepwise mechanism in which the formation of the tetrahedral intermediate is the rate-determining step. The Ar-O bond cleavage continues through a SNAr mechanism in which the departure of the leaving group from the Meisenheimer complex occurs rapidly after its formation in the rate-determining step.
The influence of some steric and electron effects on the mechanism of aromatic nucleophilic substitution (SNAr) reactions in nonpolar solvent
Emokpae, Thomas A.,Atasie, Nkechi V.
, p. 744 - 750 (2008/04/18)
Kinetic studies are reported for the reactions with aniline in benzene of a series of X-phenyl 2,4,6-trinitrophenyl ethers [X = H; 2-, 3-, 4-CH 3; 2,4-, or 2,6-(CH3)2] 1a-f, and the results compared with those of the corre
