67263-27-8

Upstream product

• 110-89-4 piperidine 
• 88-88-0 2,4,6-trinitrochlorobenzene 
• 10580-80-0 bis(2,4,6-trinitrophenyl) sulfone 
• 606-35-9 1-methoxy-2,4,6-trinitrobenzene 
• 51030-13-8 picryl-p-tolyl sulfide 
• 6973-40-6 2,4,6-trinitrophenyl phenyl ether 
• 4732-14-3 2,4,6-trinitro-phenetole 
• 92568-45-1 (4-nitro-phenyl)-picryl sulfide 
• 154393-31-4 (4-bromo-phenyl)-picryl sulfide 
• 14678-56-9 phenyl-picryl sulfide 
• 111055-14-2 4-Dimethylamino-1-(2,4,6-trinitro-phenyl)-pyridinium; chloride 

Downstream Products

• 7449-27-6 N-ethyl-2,4,6-trinitroaniline 
• 32902-85-5 N-butyl-2,4,6-trinitroaniline 
• 1022-07-7 N-methylpicramide 
• 16876-54-3 N?isopropyl?2,4,6?trinitroaniline 

Relevant academic research and scientific papers

Solvent effect on a model SNAr reaction in ionic liquid/water mixtures at different compositions

The reaction of phenyl 2,4,6-trinitrophenyl ether and piperidine was kinetically evaluated in BMIMBF4/water mixtures as the reaction media. This study shows the dramatic effect of the mixture composition on the reacting pair and its reaction rate, highlighting two strongly demarcated zones. The first one, rich in water, is characterized by strong variations in the rate coefficient values, suggesting the presence of preferential solvent effects in the aqueous phase. The second zone shows high rate coefficient values independent of the composition of the solvent mixture, suggesting predominant "anion" solvent effects. These results were validated using fluorescence spectroscopy and the Kamlet-Taft parameter.

Hydrogen bond contribution to preferential solvation in SNAr reactions

Preferential solvation in aromatic nucleophilic substitution reactions is discussed using a kinetic study complemented with quantum chemical calculations. The model system is the reaction of a series of secondary alicyclic amines toward phenyl 2,4,6-trinitrophenyl ether in aqueous ethanol mixtures of different compositions. From solvent effect studies, it is found that only piperidine is sensitive to solvation effects, a result that may be traced to the polarity of the solvent composition in the ethanol/water mixture, which points to a specific electrophilic solvation in the aqueous phase.

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

Rationalization of the conflicting effects of hydrogen bond donor solvent on nucleophilic aromatic substitution reactions in non-polar aprotic solvent: Reactions of phenyl 2,4,6-trinitrophenyl ether with primary and secondary amines in benzene-methanol mixtures

The kinetics of the reactions of phenyl 2,4,6-trinitrophenyl ether with piperidine and cyclohexylamine respectively were studied at different amine concentrations in benzene. The reaction of cyclohexylamine was not base-catalysed while that of piperidine was catalysed by one molecule of the nucleophilic amine. Addition of small amounts of hydrogen-bond donor solvent, methanol to the benzene medium of the reactions produced different effects - rate diminution followed by rate increase in one and continuous rate diminution in the other. These effects are compared with that of aniline (previously studied) in which a continuous rate increase was observed. The results are rationalized in terms of the effect of amine-solvent interaction on the nucleophilicity of the amines in addition to some other factors operating through cyclic transition states leading to products. It is evident from the rationalization that the idea of 'dimer nucleophile' in nucleophilic aromatic substitution reactions is erroneous.

Amines as leaving groups in nucleophilic aromatic substitution reactions. Part 4. σ-adduct formation in the hydrolysis of 1-amino-2,4,6-trinitrobenzenes

The kinetic study of the reaction of 2,4,6-trinitro-1-pyrrolidinobenzene 3,2,4,6-trinitro-1-piperidinobenzene 1 and 1-morpholino-2,4,6-trinitrobenzene 2 was made in 1,4-dioxane-water mixtures at 25°C. In all cases, several processes were observed, the slowest of them leading to the formation of picrate ion. The fastest processes involved the formation of σ complexes by addition of one or two HO- to unsubstituted ring positions and the ionisation of the 1:1 complex. Besides, for compounds 1 and 3, cis-trans isomerisation of 1:2 complexes was kinetically detected. Substitution occurred by displacement of the amino group on the substrate and the 1:1 complex. The reaction pathway for the formation of phenol which involves the formation of these complexes has lower energy than that which results from addition to the 1 position of the substrate.

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.

1,3-?-Adducts in the Reactions of 1-Dialkylamino-substituted 2,4,6-Trinitrobenzenes with Amines in Dimethyl Sulphoxide

The reactions of pyrrolidin-1-yl (1a), 1-piperidino (1b) and 1-dimethylamino-2,4,6-trinitrobenzene (1c) with n-butylamine, pyrrolidine and piperidine were conducted in dimethyl sulphoxide.Kinetic and equilibrium data were obtained for the formation of 1,3-?-adducts (4) (Scheme).The proton transfer between the zwitterionic intermediates (3) and the 1,3-?-adducts (4) is rapid for n-butylamine, whereas it is partially rate-limiting for pyrrolidine and rate-limiting for piperidine.For a given reactant, Kc and k3 decrease in the order pyrrolidine>piperidine>n-butylamine, and kAm//k-3 and kAmH+ decrease in the order pyrrolidine>piperidine.For a given amine, Kc, k3, kAm/k-3 and kAmH+ increase in the order 1a1b1c.These results are discussed from the standpoint of the structures of the reactants and the nucleophilic amines.

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.