34749-63-8Relevant academic research and scientific papers
Electronic and steric effects in the SNAr substitution reactions of substituted anilines with 2,4-dinitrophenyl 2,4,6-trinitrophenyl ether in acetonitrile
Crampton, Michael R.,Emokpae, Thomas A.,Isanbo, Chukwuemeka
, p. 75 - 80 (2007/10/03)
Rate measurements are reported for the reactions of 12 ring-substituted anilines with 2,4-dinitrophenyl 2,4,6-trinitrophenyl ether (1) in acetonitrile. Formation of the products, the correspondingly substituted 2,4,6- trinitrodiphenylamines, occurs without the observation of intermediates in detectable amounts by both base-catalysed and uncatalysed pathways and Hammett ρ value were determined for these processes. The results show that although substituents at the 3- or 4-positions of the anilines have only small steric effects, alkyl substituents at the 2-position may result in considerable reductions in reactivity. These effects are more pronounced for the base-catalysed pathway and in 2,6-dimethylaniline the uncatalysed pathway takes all the reaction flux. In the case of the 2-fluoro substituent the electronic effect, strong inductive electron withdrawal, is dominant over steric effects. Copyright
REACTION OF BIS(2,4,6-TRINITROPHENYL) SULFONE AND ITS DERIVATIVES WITH AMINES
Nurgatin, V. V.,Sharnin, G. P.,Nurgatina, R. B.,Ginzburg, B. M.
, p. 306 - 309 (2007/10/02)
The reaction of bis(2,4,6-trinitrophenyl) sulfone and some of its 3- and 3,3'-substituted derivatives with organic bases leads to the formation of an adduct of 1,3,5-trinitrobenzene or its substituted derivative and the respective amine, sulfur trioxide, and 2,4,6-trinitrodiphenylamine and its derivatives or derivatives of 2,4,6-trinitroaniline.The direction of reaction does not depend on the ratio of the initial compounds or on the temperature.It was established that attack by the nucleophilic reagent takes place at the ring in which the largest positive charge is induced at the carbon atom attached to the sulfur.
Mechanism of the Reactions of Substituted Anilines with Phenyl 2,4,6-Trinitrophenyl Ether in Benzene: Evidence for a Cyclic Transition State involving an Eight-membered Ring
Banjoko, Olayinka,Ezeani, Chike
, p. 1357 - 1360 (2007/10/02)
Rates and activation parameters have been determined for the reactions of phenyl 2,4,6-trinitrophenyl ether with substituted anilines in benzene.For some of the nucleophiles, the rates decrease with increasing temperature in the range 5-35 deg C resulting in negative activation enthalpies (ΔH(excit.) -3.1 to -27.3 kJ mol-1).This is strong evidence for a stepwise mechanism involving (at least) a pre-equilibrium.These base-catalysed nucleophilic substitution reactions are sensitive to the nature of the arylated amine as indicated by the Hammett's constant (ρ -7.7).
