84249-28-5Relevant academic research and scientific papers
Study of kinetics, equilibrium and the influence of steric effects on proton-transfer in the reactions of 2, 2, 4- and 2, 6- substituted anilines with 2-phenoxy-3,5-dinitropyridine in DMSO
Asghar, Basim H.
, p. 253 - 259 (2010)
Kinetic and equilibrium results for the reactions of 2-phenoxy-3,5- dinitropyridine (1), with a series of 2, 2, 4- and 2, 6- substituted anilines (2a-f), in the presence of DABCO in DMSO are reported. The reactions yield the 2- anilino derivatives (5), without the accumulation of intermediates. Kinetics studies are compatible with a two-step mechanism involving initial nucleophilic attack by amine at the ring carbon substituted by phenoxy group followed by either base-catalyzed or uncatalyzed conversion to the product. The base- catalyzed pathway is likely to involve rate-limiting proton-transfer from the zwitterionic intermediate to base. This work indicates a steric effect to proton transfer in reactions involving 2, 6-disubstituted anilines. The results were compared with those for reactions of 1, 3, 5-trinitrobenzene with anilines.
Dearomative (3+2) cycloaddition of 2-substituted 3,5-dinitropyridines and N-methyl azomethine ylide
Bastrakov, Maxim A.,Fedorenko, Alexey K.,Starosotnikov, Alexey M.,Kachala, Vadim V.,Shevelev, Svyatoslav A.
, p. 72 - 77 (2019/02/25)
[Figure not available: see fulltext.] 1,3-Dipolar cycloaddition of various 2-substituted 3,5-dinitropyridines and unstabilized N-methyl azomethine ylide has been studied. It was found that, depending on the nature of the substituent, the reaction results
Dearomatization of 3,5-dinitropyridines - an atom-efficient approach to fused 3-nitropyrrolidines
Bastrakov, Maxim A.,Kucherova, Anna Y.,Fedorenko, Alexey K.,Starosotnikov, Alexey M.,Fedyanin, Ivan V.,Dalinger, Igor L.,Shevelev, Svyatoslav A.
, p. 181 - 190 (2021/03/30)
An efficient and convenient one-step method for the synthesis of decahydrodipyrrolo[3,4-b:3',4'-d]pyridine derivatives was developed on the basis of 1,3-dipolar cycloaddition of unstabilized N-methyl azomethine ylide with 2-substituted 3,5-dinitropyridine
The reaction of 2-phenoxy-3,5-dinitropyridine with substituted anilines in the presence of 1,4-diazabicyclo[2.2.2]octane in dimethyl sulfoxide: Kinetic and equilibrium studies
Asghar, Basim H.
experimental part, p. 198 - 203 (2009/07/04)
The reactions of 2-phenoxy-3,5-dinitropyridine (1) with, a series of substituted anilines (4a-d) in dimethyl sulfoxide (DMSO) in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO) yield the 2-anilino derivatives without the accumulation of intermediate
Kinetic and equilibrium studies of σ-adduct formation and nucleophilic substitution in the reactions of 2-phenoxy-3,5-dinitropyridine and 2-ethoxy-3,5-dinitropyridine with aliphatic amines in dipolar aprotic solvents
Crampton, Michael R.,Emokpae, Thomas A.,Howard, Judith A.K.,Isanbor, Chukwuemeka,Mondal, Raju
, p. 1004 - 1011 (2007/10/03)
The reactions of aliphatic amines with 2-phenoxy-3,5-dinitropyridine, 4, and 2-ethoxy-3,5-dinitropyridine, 5, in DMSO result in the rapid reversible formation of anionic σ-adducts at the 6-position. Kinetic studies show that proton transfer from the initially formed zwitterions to base may be rate-limiting. Slower reactions result, except in the case of 5 and piperidine, in displacement of the 2-substituent via intermediates which have lower thermodynamic stabilities than their 6-isomers. Base catalysis of the substitution process is attributed in the case of 4 to rate-limiting proton transfer from zwitterionic intermediates, but in 5 to acid catalysis of ethoxide departure (SB-GA mechanism). X-Ray crystallography of 5 shows a planar non-strained structure although the structure of 2-piperidino-3,5-dinitropyridine, 10c, shows distortion resulting from steric interactions of the 2- and 3-substituents. Kinetic and equilibrium results are compared with those for related reactions of the more sterically strained 2,4,6-trinitrobenzene derivatives. Results for the reactions of 4 and 5 with pyrrolidine in three dipolar aprotic solvents are compared. Values of equilibrium constants for σ-adduct formation decrease in the order DMSO > DMF ? Acetonitrile, while values of rate constants for proton transfer are in the reverse order.
