77379-02-3

Upstream product

• 123-75-1 pyrrolidine 
• 88-88-0 2,4,6-trinitrochlorobenzene 
• 154393-31-4 (4-bromo-phenyl)-picryl sulfide 
• 92568-45-1 (4-nitro-phenyl)-picryl sulfide 
• 6973-40-6 2,4,6-trinitrophenyl phenyl ether 
• 4732-14-3 2,4,6-trinitro-phenetole 
• 115828-62-1 3-Bromo-benzaldehyde O-(2,4,6-trinitro-phenyl)-oxime 
• 115828-63-2 4-nitro-benzaldehyde-(O-picryl-seqtrans-oxime ) 
• 115828-61-0 4-methoxy-benzaldehyde-(O-picryl-seqtrans-oxime ) 
• 115828-60-9 (E)-O-Picrylbenzaldoxime 
• 51030-13-8 picryl-p-tolyl sulfide 
• 13029-07-7 1-diethylamino-2,4,6-trinitro-benzene 
• 2493-31-4 N,N-dimethyl-2,4,6-trinitro-aniline 
• 14678-56-9 phenyl-picryl sulfide 

Downstream Products

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

Relevant academic research and scientific papers

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

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.

Reactions of (E)-O-Arylbenzaldoximes with Secondary Amines in Acetonitrile. Effect of β-Aryl Substituents upon the Competition between E2 and SNAr Reactions

Reactions of (E)-O-arylbenzaldoximes in which the O-aryl group is 2,4-dinitrophenyl (1a-d) and picryl (2a-d) with secondary amines in acetonitrile have been studied kinetically.The reactions proceeded via competing E2 and SNAr mechanisms.For eliminations from 1a-d promoted by R2NH in MeCN, the transition state was changed toward E1cb-like by a more electron-withdrawing β-aryl substituent and a stronger base.On the other hand, the transition states for eliminations from 2a-d and for the SNAr reactions of all substrates were relatively insensitive to the variation of either β-aryl substituent or base strength.The yield of SNAr product increased with base concentration, electron-withdrawing ability of the O-aryl group, and base strength.When the electron-withdrawing ability of the β-aryl substituent is increased, the yield of SNAr product from 1a-d decreased, although no clear trend was observed for 2a-d.From these results, factors that influence the competition between E2 and SNAr reaction pathways are assessed.

Kinetic and Equilibrium Studies of ?-Adduct Formation and Nucleophilic Substitution in the Reactions of Ethyl Thiopicrate with Aliphatic Amines in Dimethyl Sulfoxide

Kinetic and equilibrium results are reported for the reaction of ethyl thiopicrate with butylamine, pyrrolidine and piperidine in dimethyl sulfoxide.The most rapid reaction involves attack at the unsubstituted 3-position to give anionic ?-adducts.The rate-limiting step in this process changes from nucleophilic attack by amine with butylamine to proton transfer from the zwitterionic intermediate with piperidine; pyrrolidine shows intermediate behaviour.Attack by amine at the 1-position results in displacement of the ethylthio group, although intermediates are notobserved during this process.It is suggested that base catalysis observed in the reaction with pyrrolidine may result from rate-limiting proton transfer from the zwitterionic intermediate. 1H NMR measurements using 0.1 mol dm-3 solutions of substrate show that the displaced ethanethiolate ion may attack ring-carbon atoms of either unreacted substrate or substitution products.

Aromatic nucleophilic substitution reactions of 1-dialkylamino-substituted activated benzenes with various amines in dimethyl sulfoxide

In the reactions of 1-dlalkylamino-2,4,6-trinitro- and 1-dialkylamlno-2, 4-dinitrobenzenes with various amines in dimethyl sulfoxide, 1-dialkylamino group is easily replaced with primary n-alkylamines at room temperature, and in a low yield with pyrrolidine only among secondary amines.