75113-69-8Relevant academic research and scientific papers
A probable hydrogen-bonded meisenheimer complex: An unusually high S NAr reactivity of nitroaniline derivatives with hydroxide ion in aqueous media
Imoto, Mitsutaka,Matsui, Yasunori,Takeda, Motonori,Tamaki, Akihiro,Taniguchi, Hisaji,Mizuno, Kazuhiko,Ikeda, Hiroshi
, p. 6356 - 6361 (2011)
Observations show that nitroanilines exhibit an unusually high S NAr reactivity with OH- in aqueous media in reactions that produce nitrophenols. SNAr reaction of 4-nitroaniline (2a) in aqueous NaOH for 16 h yields 4-nitrophenol (4a) quantitatively, whereas a similar reaction of 4-nitrochlorobenzene (1a) gave 4a in 2% yield together with recovered 1a in 97%, suggesting that the leaving ability of the NH2 group far surpasses that of Cl under these conditions. An essential feature of SNAr reactions of nitroanilines is probably that the NH2 leaving group participates in a hydrogen-bonding interaction with H 2O. Density functional theory (DFT) calculations for a set of 4-nitroaniline, OH-, and H2O suggest a possible formation of a Meisenheimer complex stabilized by hydrogen-bonding interactions and a six-membered ring structure. The results obtained here contrast with conventional SNAr reactivity profiles in which nitroanilines are nearly unreactive with nucleophiles in organic solvents.
Azo dyes containing 1,3,4-thiadiazole fragment: Synthesis and properties
Amosov, Evgeny,Bagryanskaya, Irina,Karpova, Elena,Selivanova, Galina,Shundrina, Inna,Skolyapova, Alexandrina,Wang, Jiaying
supporting information, p. 1929 - 1942 (2022/01/31)
New 1,3,4-thiadiazole derivatives containing a diazenyl group, as well as both a diazenyl and an imino group, were synthesized and their optical and thermal properties were investigated. Initially, new azo compounds containing an azo group directly in the thiadiazole block were obtained by the coupling of diazonium bisulfates based on the previously known 5-derivatives of 2-amino-1,3,4-thiadiazoles with N,N-dialkyl anilines (N(n-Bu)2, NEt2, and NEt(EtOH)). Schiff bases were obtained by the interaction of p-toluidine, p-phenylenediamine and p-aminophenol with azo compounds containing an aldehyde group in the 1,3,4-thiadiazole ring. The new dyes were characterized by spectral (IR, UV, 1H NMR, 13C NMR and mass spectra) and X-ray analyses. This journal is
Photoredox catalyzed dealkylative aromatic halogen substitution with tertiary amines
Dilman, Alexander D.,Frumkin, Alexander E.,Levin, Vitalij V.,Lipilin, Dmitry L.,Tyurin, Alexey Yu.
, (2021/06/18)
A reaction of aromatic halides bearing electron-withdrawing groups with tertiary amines in the presence of an iridium catalyst under blue light irradiation is described. Products of the aromatic substitution of the halide by the dialkylamino fragment are
The Anomalous Reactions of Some Fluoronitrobenzenes with Some N,N-Dialkylamines
Gale, Douglas J.,Rosevear, Judi,Wilshire, John F. K.
, p. 997 - 1008 (2007/10/02)
The reactions of 1-fluoro-2,4,- and -2,6-dinitrobenzene with certain N,N-dilkylamines in dimethyl sulfoxide solution in the presence of potassium carbonate give the corresponding dinitrophenyl N,N-dialkylcarbamates as well as corresponding N,N-dialkyldinitroanilines.The extent of carbamate formation is governed by steric factors.The corresponding reactions of 1-fluoro-4-nitrobenzene with diisopropylamine and di-s-butylamine give poor yields of the corresponding 4-nitrophenyl N,N-dialkylcarbamates but none of the corresponding N,N-dialkyl-4-nitroanilines; in these reactions, the major product is 4,4'-dinitrodiphenyl ether.The 1H and 13C n.m.r. spectra of the 2,4- and 2,6-dinitrophenyl N,N-dialkylcarbamates reveal that their aliphatic protons and carbon atoms are magnetically non-equivalent.
REACTIONS OF SUBSTITUTED HALOGENOBENZENES WITH TRIBUTYLAMINE
Ivanova, T.M.,Shein, S.M.
, p. 891 - 897 (2007/10/02)
The reactions of 2,4-dinitrohalobenzenes and 2-nitro-4-trifluoromethylsulfonylchlorobenzene with tributylamine in DMFA lead to the formation of two products, i.e., substituted N,N-dibutylanilines and phenols.The reactions occur with an induction period, which disappears with increase in temperature, and with fractional orders in the reagents.The effective activation was determined by means of the transformation coefficients.The ordes of mobility of the halogens in the reaction of 2,4-dinitrohalogenobenzenes with tributylamine is Br >= Cl > F.The effect of substituents on the mobility of the chlorine corresponds to their accepting characteristics: SO2CF3 > NO2.
