33414-81-2

Upstream product

• 623-33-6 glycine ethyl ester hydrochloride 
• 97-00-7 1-chloro-2,4-dinitro-benzene 
• 64-17-5 ethanol 
• 1084-76-0 DNP-Gly 
• 156840-00-5 2,4-dinitrophenyl 4-nitrobenzenesulfonate 
• 459-73-4 GlyOEt*HCl 
• 154853-46-0 2,4-dinitrophenyl 4-methoxybenzenesulfonate 
• 70-34-8 2,4-Dinitrofluorobenzene 
• 623-73-4 diazoacetic acid ethyl ester 
• 4143-61-7 diethyl diazodicarboxylate 
• 97-02-9 2,4-Dinitroanilin 
• 156839-99-5 2,4-dinitrophenyl 3-nitrobenzenesulfonate 
• 973-63-7 2,4-dinitrophenyl 4-chlorobenzenesulfonate 
• 742-25-6 2,4-dinitrophenyl 4-methylbenzenesulfonate 

Downstream Products

• 251474-50-7 7-amino-3,4-dihydro-1H-quinoxalin-2-one 

Relevant academic research and scientific papers

Specific nucleophile-electrophile interactions in nucleophilic aromatic substitutions

We herein report results obtained from an integrated experimental and theoretical study on aromatic nucleophilic substitution (SNAr) reactions of a series of amines towards 1-fluoro-2,4-dinitrobenzene in water. Specific nucleophile-electrophile interactions in the title reactions have been kinetically evaluated. The whole series undergoes SNAr reactions where the formation of the Meisenheimer complex is rate determining. Theoretical studies concerning specific interactions are discussed in detail. It is found that H-bonding effects along the intrinsic reaction coordinate profile promote the activation of both the electrophile and the nucleophile. Using these results, it is possible to establish a hierarchy of reactivity that is in agreement with the experimental data. Second order energy perturbation energy analysis highlights the strong interaction between the ortho-nitro group and the acidic hydrogen atom of the amine. The present study strongly suggests that any theoretical analysis must be performed at the activated transition state structure, because the static model developed around the reactant states hides most of the relevant specific interactions that characterize the aromatic substitution process.

HETEROCYCLIDENE-N-(ARYL)ACETAMIDE DERIVATIVE

The blow-described formula (I): [Ch. 1] a compound represented by formula (I) : (wherein k, m, n, and p each represent 0 to 2; j and q represents 0 or 1; R1 represents a halogen atom, a hydrocarbon group, a heterocyclic group, an alkoxy group,

Rhodium-catalyzed, three-component reaction of diazo compounds with amines and azodicarboxylates

A novel, three-component C-N bond forming reaction is described. Reaction of diazo compounds with both azodicarboxylates and arylamines in the presence of dirhodium acetate catalyst gives good yields of the corresponding aminal with high selectivity and, in most cases, N-H insertion side products were suppressed. This is the first example of a C-N bond formation from the addition of ammonium ylides to azodicarboxylates.

Effect of substituent on regioselectivity and reaction mechanism in aminolysis of 2,4-dinitrophenyl X-substituted benzenesulfonates

(Chemical Equation Presented) We report on a kinetic study for the nucleophilic substitution reactions of 2,4-dinitrophenyl X-substituted benzensulfonates (X = 4-MeO, 1a, and X = 4-NO2, 1c) with a series of primary amines in 80 mol % H2O/20 mol % DMSO at 25.0 °C. The reactions proceed through S-O and C-O bond fission pathways competitively. The fraction of the S-O bond fission increases as the attaching amine becomes more basic and the substituent X changes from 4-MeO to 4-NO2, indicating that the regioselectivity is governed by the electronic nature of the substituent X as well as the basicity of amines. The S-O bond fission has been suggested to proceed through an addition intermediate with a change in the rate-determining step (RDS) at pK°a = 8.9 ± 0.1. The electronic nature of the substituent X influences kNS-O and k1 values, but not the k2/k-1 ratios and the pK°a value significantly. Stabilization of the ground state (GS) through resonance interaction between the electron-donating substituent and the electrophilic center has been suggested to be responsible for the decreased reactivity of 1a compared to 1c. The second-order rate constants for the C-O bond fission exhibit no correlation with the electronic nature of the substituent X. The distance effect and the nature of the reaction mechanism have been suggested to be responsible for the absence of the correlation.

Regioselectivity and the nature of the reaction mechanism in nucleophilic substitution reactions of 2,4-dinitrophenyl X-substituted benzenesulfonates with primary amines

Second-order rate constants have been measured for the reaction of 2,4-dinitrophenyl X-substituted benzenesulfonates with a series of primary amines. The nucleophilic substitution reaction proceeds through competitive S-O and C-O bond fission pathways. The S-O bond fission occurs dominantly for reactions with highly basic amines or with substrates having a strong electron-withdrawing group in the sulfonyl moiety. On the other hand, the C-O bond fission occurs considerably for the reactions with low basic amines or with substrates having a strong electron-donating group in the sulfonyl moiety, emphasizing that the regioselectivity is governed by both the amine basicity and the electronic effect of the sulfonyl substituent X. The apparent second-order rate constants for the S-O bond fission have resulted in a nonlinear Bronsted-type plot for the reaction of 2,4-dinitrophenyl benzenesulfonate with 10 different primary amines, suggesting that a change in the rate-determining step occurs upon changing the amine basicity. The microscopic rate constants (k1 and k2/k-1 ratio) associated with the S-O bond fission pathway support the proposed mechanism. The second-order rate constants for the S-O bond fission result in good linear Yukawa-Tsuno plots for the aminolyses of 2,4-dinitrophenyl X-substituted benzenesulfonates. However, the second-order rate constants for the C-O bond fission show no correlation with the electronic nature of the sulfonyl substituent X, indicating that the C-O bond fission proceeds through an SNAR mechanism in which the leaving group departure occurs rapidly after the rate-determining step.

Pyrrolylquinoxalinediones: A new class of AMPA receptor antagonists

Pyrrolylquinoxalinediones were synthesized and their affinities for the AMPA receptor were determined. Most compounds showed moderate to good affinities. The acetic acid derivative 8b exhibited a K(i) value of 70 nM and was equipotent to NBQX 1. Structure activity relationships are discussed. Selected compounds were tested for their potency to inhibit AMPA induced lethal convulsions in mice. In this in vivo model the compounds showed improved potency compared with NBQX.

o-Nitroaniline Derivatives. Part 9. Benzimidazole N-Oxides Unsubstituted at N-1 and C-2

Since previous routes to the title compounds (1) have proved unsatisfactory as general methods, a simple new synthesis has been devised.N-Cyanomethyl-o-nitroanilines (5) are cyclised in basic media, giving 2-cyanobenzimidazole N-oxides (12) in good yield.Hydrolysis of these products with hydrochloric acid gives, directly, the title compounds as their hydrochloride salts (13), which may be isolated and purified, and which give the free N-oxides (1) by treatment with aqueous ammonia followed by evaporation. o-Nitrophenylglycine esters (4) may satisfactorily replace the nitriles (5) in certain cases.A modification of this kind in the related nitropyridylglycine series leads to 3H-imidazolpyridine 1-oxide (20).