32902-85-5

Upstream product

• 88-88-0 2,4,6-trinitrochlorobenzene 
• 109-73-9 N-butylamine 
• 23309-22-0 (imidazole-1-yl)-2,4,6-trinitrobenzene 
• 99-35-4 1,3,5-trinitrobenzene 
• 2493-31-4 N,N-dimethyl-2,4,6-trinitro-aniline 
• 13029-07-7 1-diethylamino-2,4,6-trinitro-benzene 
• 6973-40-6 2,4,6-trinitrophenyl phenyl ether 
• 67263-27-8 2,4,6-trinitro-1-piperidinobenzene 
• 606-35-9 1-methoxy-2,4,6-trinitrobenzene 
• 131170-45-1 1-(N-Methyl)butylamino-2,4,6-trinitrobenzene 
• 77379-02-3 2,4,6-trinitro-1-pyrrolidinobenzene 
• 92568-45-1 (4-nitro-phenyl)-picryl sulfide 
• 154393-31-4 (4-bromo-phenyl)-picryl sulfide 
• 51030-13-8 picryl-p-tolyl sulfide 

Downstream Products

• 86824-87-5 Butyl-(2,4,6-trinitro-phenyl)-nitramin 
• 88-89-1 2,4,6-Trinitrophenol 

Relevant academic research and scientific papers

IMIDAZOLE AS LEAVING GROUP IN AROMATIC NUCLEOPHILIC SUBSTITUTION REACTIONS

The reaction of N-(2,4,6-trinitrophenyl) imidazole with n-butylamine is pH dependent.A mechanism involving acid catalyzed leaving group departure is suggested.

Electrochemically promoted nucleophilic aromatic substitution in room temperature ionic liquids - An environmentally benign way to functionalize nitroaromatic compounds

The current manuscript shows the electrochemical studies performed to rationalize the mechanism and develop new green synthetic routes for the synthesis of substituted nitroaromatics based on the advantages of the electrochemical approach to the nucleophilic aromatic substitution reaction (such as (a) low cost and ready availability of reagents, (b) atom economy, (c) high yields, approaching 100%) and the use of Room Temperature Ionic Liquids (RTILs) as green alternative solvents to organic aprotic solvents. Four of the most popular RTILs (1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]BF 4), 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF 6), 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)-imide ([BMIM]TFSI) and 1-butyl-3-methylimidazolium acetate ([BMIM]AcO) have been chosen since they have different properties in terms of solvation effects that can increase the regioselectivity of the reaction. The nucleophiles used to study the feasibility and viability of the reaction were the classical hydride, methoxide, ketones, cyanides and amines, whereas the nitroarenes selected were 4-nitrotoluene, 1,3-dinitrobenzene, 2,4-dinitroaniline, 1,3,5-trinitrobenzene, 1,3-dinitronaphthalene, 1-chloro-2,4,6-trinitrobenzene and 2,4,6- trinitroanisole. The electrocatalysis and regioselectivity effects of using RTILs are also investigated. The article concludes by analyzing the economic cost of performing this electrosynthesis in RTILs and organic solvent electrolyte systems, which contain 0.1 M of supporting electrolyte.

Kinetics of snar reactions of 1-phenoxy-nitrobenzenes with aliphatic amines in toluene: Ring substituent and solvent effects on reaction pathways

Rate constants are reported for the reactions of a series of 4-substituted-1-phenoxy-2,6-dinitrobenzenes 1 and 6-substituted-1-phenoxy-2,4- dinitrobenzenes 2 activated by CF3, COOCH3, CN, NO 2 groups or by ring-nitrogen wi

Effects of ortho- and para-ring activation on the kinetics of S NAr reactions of 1-chloro-2-nitro- and 1-phenoxy-2-nitrobenzenes with aliphatic amines in acetonitrile

Rate constants are reported for reaction of 4-substituted 1-chloro-2,6-dinitrobenzenes 1, 6-substituted 1-chloro-2,4-dinitrobenzenes 2, and some of the corresponding 1-phenoxy derivatives, 3 and 4, with n-butylamine, pyrrolidine and pi-peridine in acetoni

Nucleophilic aromatic substitution for heteroatoms: An oxidative electrochemical approach

The nucleophilic aromatic substitution for heteroatom through electrochemical oxidation of the intermediate σ-complexes (Meisenheimer complexes) in simple nitroaromatic compounds is reported for the first time (NASX process). The studies have been carried out with hydride, cyanide, fluoride, methoxy, and ethanethiolate anions and n-butylamine as a nucleophile, at the cyclic voltammetry (CV) and preparative electrolysis level. The cyclic voltammetry experiments allow for detection and characterization of the σ-complexes and they have led us to a proposal for the mechanism of the oxidation step. Furthermore, the power of the CV technique in the analysis of the reaction mixture throughout the whole chemical and electrochemical process is described.

Electrochemical synthesis of nitroanilines

Alkylamines and amides are readily prepared by nucleophilic aromatic substitution of hydrogen in nitroarenes by electrochemical oxidation. Useful yields (15-85%) are achieved in a simple direct and regioselective amination process. The synthetic method has been examined in the absence and presence of external bases, used to promote the first step of the nucleophilic aromatic substitution reaction, i.e. the nucleophilic attack. In both cases, good results were obtained. The unreacted starting material can easily be recovered at the end of the electrochemical oxidation process. This new method represents an environmentally favourable route to amino- and amido-substituted nitroaromatic compounds.

Rapid scan spectrophotometric and kinetic studies in the reactions of 4-substituted-2,6-dinitro-N-n-butylanilines with n-butylamine in dimethyl sulfoxide

The reactions of 2,4,6-trinitro-N-n-butylaniline 6a, 4-cyano-2,6-dinitro-N-n-butylaniline 6b and 4-methoxycarbonyl-2,6-dinitro-N-n-butylaniline 6c with n-butylamine in dimethyl sulfoxide have been investigated by rapid scan spectrophotometry and a stopped-flow method. 6a and 6b react competitively with n-butylamine to give the conjugate bases due to fast proton transfer and anionic σ-adducts by the addition of amine at the 3-position, while 6c reacts to give the conjugate base. The distinct spectra of only the conjugate bases have been observed. The effect of substituents on rate and equilibrium constants obtained for these competitive reactions is discussed.

Kinetic and equilibrium studies of σ-adduct formation and nucleophilic substitution in the reactions of trinitro-activated benzenes with aliphatic amines in acetonitrile

Rate and equilibrium constants are reported for reactions in acetonitrile of butylamine, pyrrolidine and piperidine with 1,3,5-trinitrobenzene, 1, and with ethyl 2,4,6-trinitrophenyl ether, 4a, and phenyl 2,4,6-trinitrophenyl ether, 4b. Rapid nucleophilic attack at unsubstituted ring-positions may yield anionic σ-adducts via zwitterionic intermediates, while slower attack at the 1-position of 4a and 4b may lead to substitution to give 2,4,6-trinitroaniline derivatives. Base catalysis in the substitution reaction reflects rate-limiting proton transfer which may be from the zwitterionic intermediates to amine in the case of 4b, or from a substituted ammonium ion to the ethoxy leaving group in the case of 4a. Comparisons with values in DMSO indicate that values of overall equilibrium constants for adduct formation are ca. 104 lower in acetonitrile, while rate constants for proton transfer are ca. 104 higher. These differences may reflect strong hydrogen-bonding between DMSO and -NH+ protons in ammonium ions and in zwitterions. In acetonitrile homoconjugation of substituted ammonium ions with free amine is an important factor.

Kinetic Studies of the Reactions of Some Phenyl Aryl Sulfides with Aliphatic Amines in Dimethyl Sulfoxide: the Mechanism of Base Catalysis

The reaction of n-butylamine, pyrrolidine and piperidine with 4'-R-phenyl 2,4,6-trinitrophenyl sulfides (R = H, Me, Br, NO2), 4a-d, result in the rapid formation of ?-adducts by attack at the unsubstituted 3-position; rate and equilibrium data are reported and substituent effects examined. Attack by amine at the 1-position of of 4a-d, phenyl 2,4-dinitronaphthyl sulfide 9, and phenyl 2,6-dinitro-4-trifluoromethyl sulfide 11, results in displacement of the phenylthio group.The substitutions by butylamine show a first order dependence on the amine concentration indicating that nucleophilic attack is rate determining.However the substitutions by pyrrolidine are subject to general base catalysis and it is argued that here the rate limiting step is deprotonation of the initially formed zwitterionic intermediate.

?-Adduct Formation and Proton Transfer in the Reactions of N-Substituted Picramides with Amines in Dimethyl Sulphoxide.

The reactions of 1-n butylamino, 1-pyrrolidino-, and 1-piperidino-2,4,6-trinitrobenzenes with their respective parent amines have been examined in dimethyl sulphoxide.N.m.r. spectroscopy indicates that the major interactions involve ?-adduct formation by attack at the 3-position, together with transfer of the side-chain proton in the case of the primary amine derivative.Kinetic and equilibrium data relating to these reactions have been determined, and it has been shown that in formation of the 3-adducts the rate determining step changes from nucleophilic attack by the amine in the case of n-butylamine to proton transfer from the zwitterionic intermediate in the case of piperidine; in the reaction with pyrrolidine proton transfer is partially rate-limiting.The results are discussed in relation to amine-amine exchange reactions which involve nucleophilic attack at the 1-position.