70951-77-8Relevant academic research and scientific papers
S NH Arylamination of 3-Nitropyridine: A Competitive Formation of 2-Arylamino-5-nitropyridines and 2-Arylamino-5-nitrosopyridines
Borovlev, Ivan V.,Demidov, Oleg P.,Amangasieva, Gulminat A.,Avakyan, Elena K.,Borovleva, Anastasia A.,Pobedinskaya, Diana Yu.
, p. 3520 - 3530 (2018/06/26)
Arylamination of 3-nitropyridine via the nucleophilic substitution of hydrogen leads to a mixture of 2-arylamino-5-nitropyridines and novel 2-arylamino-5-nitrosopyridines, with the latter as the major product. The proposed mechanism includes the formation of σ H -adducts and their further aromatization proceeding either through an oxidative pathway or intramolecular Red/Ox pathway of the S NH reaction. Moreover, we have shown that nitroso compounds can be selectively oxidized with m -chloroperbenzoic acid to give the corresponding nitro derivatives or their N -oxides, depending on the reaction temperature and the amount of oxidant.
Solvent hydrogen bonding and structural effects on the reaction of 2-halo-5-nitropyridines with parasubstituted anilines in dimethylsulfoxide/ acetonitrile mixtures
Kalaimani,Rathinam,Bhuvaneshwari
experimental part, p. 409 - 417 (2012/02/05)
Substitution reactions of some parasubstituted anilines with 2-chloro-5-nitropyridine and 2-bromo-5-nitropyridine were carried out conductometrically in dimethylsulfoxide/acetonitrile mixtures. The correlation of second order rate constants with Hammett's substituent constants yields a fairly linear straight line with a negative slope. The correlation of rate data with Kamlet-Taft's solvatochromic parameters is excellent (100R2= 97%) in both the substrates. The solvation model proposed is well supported by the solvatochromism exhibited by aniline in the solvent mixture under investigation. The molar extinction coefficient (εmax) of aniline varies appreciably up to ～25% with the change in composition of the mixture. The multivariate correlation analysis of εmax (with α, β, π) suggests that the solvation around NH2 moiety of aniline through hydrogen bond donor (HBD) property is found to be dominant in the solvation process and consequently in altering the rate. The observation is that the dominance of HBD property in solvation is further confirmed by the cyclic voltammetric oxidation of aniline in the solvent mixture.
Kinetics and reactivity of substituted anilines with 2-chloro-5-nitropyridine in dimethyl sulfoxide and dimethyl formamide
El-Bardan, Ali A.,El-Subruiti, Gehan M.,El-Hegazy, Fatma El-Zahraa M.,Hamed, Ezzat A.
, p. 645 - 650 (2007/10/03)
The kinetics of the reaction of substituted anilines with 2-chloro-5-nitropyridine were studied in dimethyl sulfoxide (DMSO) and dimethyl formamide (DMF) at different amine concentrations and temperatures in the range 45-60°C. In both solvents the reaction was not a base-catalyzed one. A plot of ΔH# versus ΔS# for the reaction in DMSO and DMF gave good straight lines with isokinetic temperatures 128°C and 105°C, respectively. Good linear relationships were obtained from the plots of log k1 against σ° values at all temperatures with negative ρ values (- 1.63 to - 1.28 in DMSO) and (- 1.26 to -0.90 in DMF).
