957463-15-9Relevant academic research and scientific papers
Dual nucleophilic substitution reactions of O,O-diethyl 2,4-dinitrophenyl phosphate and thionophosphate triesters
Aguayo, Raul,Arias, Felipe,Canete, Alvaro,Zuniga, Carolina,Castro, Enrique A.,Pavez, Paulina,Santos, Jose G.
, p. 202 - 211 (2013/03/14)
The reactions of the title compounds with phenoxides, secondary alicyclic (SA) amines, and pyridines, in 44 wt% ethanol-water, at 25°C and an ionic strength of 0.2 M, were subjected to kinetic and product studies. From analytical techniques (HPLC and NMR), two pathways were detected (nucleophilic attack at the phosphoryl center and at the C-1 aromatic carbon) for the reactions of all the nucleophiles with the phosphate (2) and for the pyridinolysis of the thionophosphate (1). Only aromatic nucleophilic substitution was found for the reactions of 1 with phenoxides and SA amines. For the dual reactions, the nucleophilic rate constants (kN) were separated in two terms: documentclass{article}usepackage{amssymb} pagestyle{empty}begin{document}k-{rm N}^{rm P}end{document} and documentclass{article}usepackage{amssymb}pagestyle{empty}begin{document}k-{ rm N}^{{rm Ar}}end{document}, which are the rate constants for the corresponding electrophilic centers. The absence of a break in the Bronsted-type plots for the attack at P is consistent with concerted mechanisms. The Bronsted slopes, βAr 0.32-0.71, for the attack at the aromatic C-1, are in agreement with stepwise mechanisms where formation of a Meisenheimer complex is the rate-determining step. 2013 Wiley Periodicals, Inc. Int J Chem Kinet 45: 202-211, 2013 Copyright
Mechanistic assessment of SNAr displacement of halides from 1-Halo-2,4-dinitrobenzenes by selected primary and secondary amines: Br?nsted and Mayr analyses
Um, Ik-Hwan,Im, Li-Ra,Kang, Ji-Sun,Bursey, Samantha S.,Dust, Julian M.
supporting information, p. 9738 - 9746 (2013/01/15)
Pseudo-first-order rate constants (kobsd) have been measured spectrophotometrically for nucleophilic substitution reactions of 1-X-2,4-dinitrobenzenes (1a-d, X = F, Cl, Br, I) with various primary and secondary amines in MeCN and H2O
Choice of solvent (MeCN vs H2O) decides rate-limiting step in SNAr aminolysis of 1-fluoro-2,4-dinitrobenzene with secondary amines: Importance of Bronsted-type analysis in acetonitrile
Um, Ik-Hwan,Min, Se-Won,Dust, Julian M.
, p. 8797 - 8803 (2008/09/18)
(Chemical Equation Presented) A kinetic study is reported for nucleophilic substitution reactions of 2,4-dinitro-1-fluorobenzene (DNFB) with a series of secondary amines in MeCN and H2O at 25.0°C. The reaction in MeCN results in an upward curva
