7262-20-6Relevant academic research and scientific papers
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.
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.
