17523-59-0

Upstream product

• 110-89-4 piperidine 
• 55526-39-1 pyrrolidinium 
• 51030-13-8 picryl-p-tolyl sulfide 
• 154393-31-4 (4-bromo-phenyl)-picryl sulfide 
• 92568-45-1 (4-nitro-phenyl)-picryl sulfide 
• 144432-14-4 tris(5-methyl-2,4-dinitrophenyl)methane 
• 144432-15-5 tris(3,5-dimethyl-2,4-dinitrophenyl)methane 
• 1254253-36-5 [Rh{κ²-P,O-Ph₂P(CH₂)₃OEt}₂][PF₆] 
• 14678-56-9 phenyl-picryl sulfide 
• 41577-89-3 ethyl-picryl sulfide 

Downstream Products

• 110-89-4 piperidine 
• 51-28-5 2,4-Dinitrophenol 
• 144432-14-4 tris(5-methyl-2,4-dinitrophenyl)methane 
• 144432-15-5 tris(3,5-dimethyl-2,4-dinitrophenyl)methane 
• 41577-89-3 ethyl-picryl sulfide 
• 14678-56-9 phenyl-picryl sulfide 
• 51030-13-8 picryl-p-tolyl sulfide 
• 154393-31-4 (4-bromo-phenyl)-picryl sulfide 
• 92568-45-1 (4-nitro-phenyl)-picryl sulfide 
• 75-52-5 nitromethane 
• 1794-90-7 2-nitropropane-1,3-diol 
• 625-48-9 2-nitro-1-ethanol 
• 4856-94-4 pyrrolidineboraneYpiperidineborane 

Relevant academic research and scientific papers

Mechanistic Studies on the Catalytic Oxidative Amination of Alkenes by Rhodium(I) Complexes with Hemilabile Phosphines

Cationic rhodium(I) complexes with P,O-functionalised arylphosphine ligands are efficient catalysts for the regioselective anti-Markovnikov oxidative amination of styrene with piperidine. The mechanism of the catalytic reaction has been investigated by spectroscopic means under stoichiometric and catalytic conditions. In the presence of piperidine, the catalyst precursor [Rh{κ2-P,O-Ph2P(CH2)3OEt}2]+ (5) gave the piperidine complex [Rh{κ1-P-Ph2P(CH2)3OEt}2(HNC5H10)2]+ (8) that was transformed into the neutral amido-piperidine species [Rh{κ1-P-Ph2P(CH2)3OEt}2(NC5H10)(HNC5H10)] (9) under thermal conditions. NMR studies performed in the presence of styrene under catalytic conditions showed that 9 is a key species in the catalytic oxidative amination of styrene. Related cyclooctadiene-containing catalyst precursors [Rh(cod){κ1-P-Ph2P(CH2)3OEt}n]+ (n=1, 2) also gave 9 under the same conditions. The proposed catalytic cycle has been established by a series of DFT calculations including the transition states of the key steps that have been identified and characterised. These studies have shown that, after elimination of the enamine, regeneration of catalytic active species takes place by direct transfer of the proton of a piperidine ligand to the alkyl group resulting from the insertion of styrene into the Rh-H bond and formation of ethylbenzene. Against the expectations, the formation of a dihydride intermediate by NH oxidative addition is a highly energy-demanding process. Catalyst 5 has also been applied for the oxidative amination of substituted vinylarenes with several secondary cyclic and acyclic amines.

Kinetics and mechanism of the aminolysis of phenyl and 4-nitrophenyl ethyl thionocarbonates

The reactions of the title substrates (PTOC and NPTOC, respectively) with secondary alicyclic amines are subjected to a kinetic study in aqueous solution at 25.0°C, ionic strength 0.2 M (KCl). Under amine excess, pseudo-first-order rate coefficients (kobsd) are found throughout. The order in amine is one for the reactions of piperidine but is of intermediate order between 1 and 2 for the reactions of the other amines. The kinetic results can be accommodated by a reaction scheme with two hypothetical tetrahedral intermediates: a zwitterionic (T±) and an anionic (T-) one, whereby amine catalysis (deprotonation of T± to give T-) is kinetically important. Both the pKa of T± and the rate coefficient for proton transfer (k3 ca. 1010 s-1 M-1) are estimated. The values of the other rate microcoefficients of the scheme are found by a nonlinear least-squares fitting, and these values are compared with those exhibited in the aminolysis of phenyl thionoacetate (PTOA), and S-phenyl and S-(4-nitrophenyl) O-ethyl dithiocarbonates (PDTC and NPDTC, respectively). The Broensted type plots for amine basicity have slopes βN ca. 0.2 for rate-determining amine attack (k1) and βN ca. 0.8 for amine expulsion from T± (k-1), in accord with the βN values found in similar aminolyses. The general base catalysis by amine found in the aminolysis of NPTOC, in contrast with the lack of such catalysis in the aminolysis of 4-nitrophenyl methyl carbonate, is explained by a smaller rate coefficient for expulsion of 4-nitrophenoxide (k2) from T±(which competes with amine deprotonation of T±) relative to the same expulsion from the analogous oxy intermediate.

Steric and kinetic isotope effects in the deprotonation of cation radicals of NADH synthetic analogues

The deprotonation rate constants and kinetic isotope effects of the cation radicals have been determined by combined use of direct electrochemical techniques at micro- and ultramicroelectrodes, redox catalysis, and laser flash photolysis, over a extended

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.

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.

Highly Sterically hindered Carbon Acids: The Intrinsic Reactivity of 5,5',5''-Trimethyl- and 3,3',3'',5,5',5''-Hexamethyl-2,2',2'',4,4',4''-Hexanitrotriphenylmethanes

Rate constants (kpB,kpBH) for the reversible deprotonation of 5,5',5''-trimethyl- and 3,3',3'',5,5',5''-hexamethyl-2,2',2'',4,4',4''-hexanitrotriphenylmethanes (2 and 3) by primary aliphatic amines, piperidine and morpholine as well as by phenoxide anions and hydroxide anion have been measured in H2O-Me2SO (20:80) at 25 deg C.Comparison of the results obtained with those for 2,2',2'',4,4',4''-hexanitrotriphenylmethane (1a) shows that the introduction of methyl groups in positions adjacent to the nitro groups decreases markedly the thermodynamic acidity of theexocyclic CH group: ΔpK2a1a = 1.68; ΔpK3a1a = 6.48.It is suggested that these decreases are very likely the reflection of a twisting of the nitro groups out of their attached aromatic planes and therefore of a reduced resonance stabilization of the conjugated carbanions C-2 and C-3.Other important steric effects are operating in the ionization of 2 and 3.These arise from the accumulation of ortho-nitro groups in the triphenylmethane system which makes the approach of the base reagents from the exocyclic carbon of 2 and 3 very difficult.The finding of extremely low intrinsic reactivities for 2 and 3 and the observation of a much greater catalytic efficiency of primary amines than of secondary amines in assisting the proton transfers are the two most striking manifestations of these F-strain effects.

Ion Confinement in the Collision Cell of a Multiquadrupole Mass Spectrometer: Access to Chemical Equilibrium and Determination of Kinetic and Thermodynamic Parameters of an Ion-Molecule Reaction

Ions can be confined in an rf-only collision cell of a tandem quadrupole mass spectrometer so that ion-molecule reactions can be studied for variable interaction times (0.05-250 ms).The chemical system studied (ammonium ion, pyrrolidine, piperidine) involved the following reactions: proton exchange, formation of proton-bound dimers, and amine exchange between dimers.Chemical equilibrium could be reached for the exchange reactions.The equilibrium constants of these reactions, as well as the rate constants of the different reactions involved, were thus easily determined from the variation of relative abundance of reactant and product ions versus confinement time.