Aromatic substitutions with carbanion nucleophiles. IV. The kinetics and mechanism of the reaction of picryl bromide with diethylmalonate anion

1977 ◽  
Vol 55 (14) ◽  
pp. 2664-2669 ◽  
Author(s):  
Kenneth T. Leffek ◽  
Anna E. Matinopoulos-Scordou
Keyword(s):  
Equilibrium Constant ◽  
Rate Constants ◽  
Activation Parameters ◽  
Solvent System ◽  
Stopped Flow ◽  
Substitution Product ◽  
Picryl Chloride ◽  
Uv Visible ◽  
The Individual ◽  
Mechanism Of The Reaction

The reaction of picryl bromide with sodium diethylmalonate has been studied in benzene–DMSO 7:1 v/v by means of stopped-flow and uv–visible spectrophotometers. A Meisenheimer-like intermediate was detected, decomposing to yield the stable violet anion of the substitution product. The rate constants of the individual steps have been measured and the activation parameters calculated. Comparison with those obtained for picryl chloride support a bimolecular substitution via the 1,1-complex. The reaction with 1,3,5-trinitrobenzene is too fast to be measured in the same solvent system. The equilibrium constant is estimated to be of the order of 104–105.

Aromatic substitutions with carbanion nucleophiles. III. The kinetics of the reaction of picryl chloride with diethylmalonate anion

1977 ◽  
Vol 55 (14) ◽  
pp. 2656-2663 ◽  
Author(s):  
Kenneth T. Leffek ◽  
Anna E. Matinopoulos-Scordou
Keyword(s):  
Rate Constants ◽  
Activation Parameters ◽  
Stopped Flow ◽  
Aromatic Substitution ◽  
Picryl Chloride ◽  
Uv Visible ◽  
Excess Base ◽  
Kinetics Of

The reaction between 1-chloro-2,4,6-trinitrobenzene (picryl chloride) and diethylmalonate anion in benzene–DMSO 7:1 v/v solvent has been investigated by means of stopped-flow and uv–visible spectrophotometers. The results support a simple bimolecular aromatic substitution with a fast formation of a Meisenheimer-like coloured intermediate, followed by a slower decomposition to the picryl ester. The latter is rapidly deprotonated by the excess base. The steps of the reaction were followed separately and the rate constants and activation parameters have been measured.

The kinetics, isotope effects, and mechanism of the reaction of 2,2-di(4-nitrophenyl)-1,1,1-trifluoroethane with alkoxide bases in alcohol solvents

1985 ◽  
Vol 63 (3) ◽  
pp. 576-580 ◽  
Author(s):  
Arnold Jarczewski ◽  
Grzegorz Schroeder ◽  
Wlodzimierz Galezowski ◽  
Kenneth T. Leffek ◽  
Urszula Maciejewska
Keyword(s):  
Rate Constants ◽  
Isotope Effects ◽  
Activation Parameters ◽  
Tert Butanol ◽  
Deuterium Isotope Effects ◽  
Alcohol Solvents ◽  
Multistep Reaction ◽  
Mechanism Of The Reaction

The reaction between 2,2-di(4-nitrophenyl)-1,1,1-trifluoroethane and the alkoxide bases ŌCH3, ŌC2H5, ŌnC4H9, ŌCH(CH3)2, and ŌC(CH3)3 in their corresponding alcohol solvents is a multistep reaction with several intermediates: 2,2-di(4-nitrophenyl)-1,1-difluoro-1-alkoxyethane (A), 2,2-di(4-nitrophenyl)-1-fluoro-1-alkoxyethene (B), 2,2-di(4-nitrophenyl)-1,1-dialkoxyethene (C), 2,2-di(4-nitrophenyl)-1,1-difluoroethene (D), and 4,4′-dinitrobenzophene (E). Rate constants and activation parameters have been measured for the appearance of the two stable products B and C. The kinetic deuterium isotope effects for the appearance of B fell in the range of kH/kD = 1 to 2 at 25 °C for the primary and secondary alkoxides, whereas kH/kD = 5.4 at 30 °C for the appearance of D with tert-butoxide. Exchange experiments showed that H/D exchange took place between the substrate and solvent to the extent of 100% with methoxide, 50% with ethoxide and isopropoxide, and 0% with tert-butoxide. It is concluded the HF elimination from the substrate follows an (ElcB)R mechanism with methoxide/methanol, changing to (ElcB)I or E2 with tert-butoxide/tert-butanol.

Aromatic Substitutions with Carbanion Nucleophiles. II. The Kinetics and Mechanism of the Reaction of 1-Fluoro-2,4-dinitrobenzene with the Diethyl Malonate Anion

1973 ◽  
Vol 51 (10) ◽  
pp. 1659-1664 ◽  
Author(s):  
Kenneth T. Leffek ◽  
Paul H. Tremaine
Keyword(s):  
Dimethyl Sulfoxide ◽  
Sodium Salt ◽  
Rate Constants ◽  
Activation Parameters ◽  
Diethyl Malonate ◽  
Kinetics And Mechanism ◽  
Reaction Solution ◽  
Red Color ◽  
Unstable Intermediate ◽  
Mechanism Of The Reaction

The reaction of fluoro-2,4-dinitrobenzene with the sodium salt of diethyl malonate to form diethyl (2,4-dinitrophenyl)malonate is fast in dimethyl sulfoxide solvent. The stable red color of the reaction solution is due to the anion of the product, although the initially formed unstable intermediate between the substrate and the anion nucleophile is also red and can be observed at times less than 200 ms after mixing.The rate constants for all the steps in the reaction have been measured and the activation parameters for the three processes involved in the nucleophile substitution have been calculated.

Kinetic studies of the reactions of 4-nitrobenzofuroxan with cyanide ion and isopropoxide ion in isopropanol

1980 ◽  
Vol 58 (16) ◽  
pp. 1691-1696 ◽  
Author(s):  
Michael E. Moir ◽  
Albert R. Norris
Keyword(s):  
Rate Constants ◽  
Activation Parameters ◽  
Kinetic Studies ◽  
Specific Rate ◽  
Stopped Flow ◽  
Cyanide Ion ◽  
Temperature Range ◽  
Flow Reaction

Kinetic studies of the reactions in isopropanol of 4-nitrobenzofuroxan with cyanide ion and isopropoxide ion have been carried out over the temperature range 15.0 to 35.0 °C. For both bases, the first species identifiable using stopped-flow reaction techniques is postulated to be a C-7 σ-complex of 4-nitrobenzofuroxan and base. Specific rate constants and activation parameters for the formation of these σ-complexes are compared to corresponding data relating to the formation of cyanide ion and isopropoxide ion—σ-complexes of 1,3,5-trinitrobenzene in isopropanol.

Kinetic and Mechanistic Study on the Reactions of [Pd(dien)H2O]2+ and [Pt(dien)H2O]2+ with L-Cysteine and S-Methyl-L-cysteine

2005 ◽  
Vol 58 (7) ◽  
pp. 544 ◽  
Author(s):  
Biljana V. Petrović ◽  
Živadin D. Bugarčić
Keyword(s):  
Rate Constants ◽  
Activation Parameters ◽  
Second Order ◽  
Mechanistic Study ◽  
Stopped Flow ◽  
Substitution Reactions ◽  
Order Rate ◽  
Increase With Increase ◽  
Naclo4 Solution ◽  
Entropy Of Activation

The reactions of [Pd(dien)H2O]2+ and [Pt(dien)H2O]2+ (dien = diethylenetriamine or 1,5-diamino-3-azapentane) with l-cysteine and S-methyl-l-cysteine were studied in an aqueous 0.10 M NaClO4 solution using stopped-flow and conventional UV-vis spectrophotometry. The second-order rate constants for the reactions of [Pd(dien)H2O]2+ at pH 1.0 are k1298 = (9.11 ± 0.11) × 102 M−1 s−1 for l-cysteine, and k1298 = (33.79 ± 0.63) × 102 M−1 s−1 for S-methyl-l-cysteine. The second-order rate constants for the reactions of [Pt(dien)H2O]2+ at pH 1.0 with l-cysteine is k1298 = (1.28 ± 0.08) × 10−2 M−1 s−1 and for S-methyl-l-cysteine is k1298 = (3.87 ± 0.02) × 10−2 M−1 s−1. Activation parameters were determined for all reactions, and the negative values of entropy of activation support an associative complex formation mechanism. Substitution reactions were also studied at pH 0.5, 1.0, and 1.5. The rate constants increase with increase in pH. These results are discussed in terms of protolitic equilibrium.

Kinetic study of formation of nickel (II)-isoquinoline complex in water and nonaqueous solvents

1976 ◽  
Vol 54 (16) ◽  
pp. 2540-2547 ◽  
Author(s):  
Praphulla Kumar Chattopadhyay ◽  
Byron Kratochvil
Keyword(s):  
Kinetic Study ◽  
Rate Constants ◽  
Activation Parameters ◽  
Nonaqueous Solvents ◽  
Stopped Flow ◽  
Multidentate Ligands ◽  
Monodentate Ligands

Rate constants and activation parameters for the formation of the monocomplex of nickel(II) with isoquinoline in water, methanol, dimethylsulfoxide, and N,N-dimethylformamide were obtained from measurements by stopped-flow spectrophotometry. The data are compared with previously reported work by other authors for substitution at nickel(II) with related monodentate and multidentate ligands. The results in all solvents except dimethylsulfoxide are consistent with an Id mechanism. In dimethylsulfoxide substitution at nickel(II) proceeds in a similar way for all monodentate ligands but whether the mechanism is Id or D cannot be ascertained.

Mutarotation of D(+)-glucose. II. Volumes of activation for the uncatalysed and copper(II)-catalysed rates

1983 ◽  
Vol 36 (2) ◽  
pp. 279 ◽  
Author(s):  
CJ O'Conner ◽  
AL Odell ◽  
AAT Bailey
Keyword(s):  
High Pressure ◽  
Reaction Mechanism ◽  
Equilibrium Constant ◽  
Rate Constants ◽  
Reaction Mechanisms ◽  
Sodium Perchlorate ◽  
Continuous Series ◽  
Aqueous Sodium ◽  
The Individual ◽  
Individual Rate

The effect of high pressure on the rate of mutarotation of α-and β-D(+)-glucose in aqueous sodium perchlorate solutions has been evaluated. The observed rate constant kΨ = kα + kβ increases with pressure while the equilibrium constant Keq = kα /kβ is nearly unchanged from the 1.7 found at 1 bar. From the experimental results, the individual rate constants kα and kβ and the corresponding activation volumes ∆V‡α and ∆V‡β can be evaluated. The values obtained, -10.7 � 0.1 and -10.0 � 0.1 cm3 mol-1, are discussed in relation to the reaction mechanism. In the presence of Cu(ClO4)2 the values of ∆V: form a continuous series, dependent upon the pH and the concentration of copper(II) catalyst, up to + 1.3 cm3 mol-1. The activation volumes for mutarotation by monomeric and dimeric copper(II) catalysts, ∆V‡(Cu2+) and ∆V‡ {CU((OH)2Cu)2+}, are -1.2 � 0.2 and + 3.6 � 0.2 cm3 mol-1 respectively. Reaction mechanisms are discussed to account for these values of ∆V‡.

scholarly journals Kinetics of the Reversible Transformation of 2,3-Dioxogulonic Acid into its Enol as a Function of the pH of the Medium

1978 ◽  
Vol 33 (10) ◽  
pp. 1184-1189
Author(s):  
J. Zuluaga ◽  
P. Martínez
Keyword(s):  
Kinetic Study ◽  
Equilibrium Constant ◽  
Rate Constants ◽  
Disodium Salt ◽  
Stopped Flow ◽  
Free Energies ◽  
Reversible Transformation ◽  
Flow Method ◽  
Kinetic Coefficients ◽  
Kinetics Of

Abstract 2,3-dioxogulonic acid and the disodium salt of its enol were synthesised, isolated and identified both chemically and spectroscopically. A kinetic study was carried out on its equilibrium by means of the “stopped flow” method for rapid processes, and the rate constants for the forward and backward reaction were determined as a function of the pH of the medium. The kinetic coefficients involved, equilibrium constant and Gibbs free energies were also determined.

Kinetics and mechanisms of the reaction of 2,4,6-trinitrocumene and 2,4,6-trinitroethylbenzene with 1,1,3,3-tetramethylguanidine in N,N-dimethylformamide solvent

1987 ◽  
Vol 65 (5) ◽  
pp. 1007-1011 ◽  
Author(s):  
Mihir K. Biswas ◽  
Arnold Jarczewski ◽  
Kenneth T. Leffek
Keyword(s):  
Carbon Atom ◽  
Complex Formation ◽  
Proton Transfer ◽  
Equilibrium Constant ◽  
Rate Constants ◽  
Equilibrium Constants ◽  
Activation Parameters ◽  
Reaction Parameters ◽  
Deuterium Isotope Effect ◽  
Constant Rate

The reaction of tetramethylguanidine (TMG) with trinitrocumene (TNC) and trinitroethylbenzene (TNEB) in dimethylformamide solvent has been studied with respect to products and kinetics. For TNC only σ-complex formation with the benzene ring was observed, for which the equilibrium constant, rate constants, and activation parameters were measured. For TNEB, both σ-complex formation and proton transfer from the σ-carbon atom of the ethyl group were observed. The equilibrium constants, rate constants, and activation parameters were separately determined for each reaction and a primary deuterium isotope effect, kH/kD = 13.6 (at 20 °C), was found for the proton transfer. The reaction parameters are compared to those for proton transfer from TNT to tetramethylguanidine in DMF solvent.

Kinetics and mechanism of oxidation of hydroxylamine by hexachloroiridate(IV) ion in buffer solutions

1993 ◽  
Vol 71 (12) ◽  
pp. 2164-2170 ◽  
Author(s):  
Ms. Rekha ◽  
Aditya Prakash ◽  
Raj N. Mehrotra
Keyword(s):  
Acetic Acid ◽  
Spectral Analysis ◽  
Rate Constants ◽  
Main Product ◽  
Activation Parameters ◽  
Acetate Buffer ◽  
Stopped Flow ◽  
Stoichiometric Ratio ◽  
Buffer Solutions ◽  
Mechanism Of Oxidation

The oxidation of hydroxylammonium ion by [IrCl6]2− ion in acetic acid – acetate buffer solutions, studied by stopped flow, has the stoichiometric ratio Δ[IrCl6]2−/Δ[NH2OH] = 1. The oxidation involves the species [IrCl6]2− and NH3OH+ although spectral analysis of the spent reaction mixture indicates [IrCl5(OH2)]2− to be the main product (almost to the extent of 80%). This anomaly arises because of the aquation of the reduced product [IrCl6]3−. The rate is retarded both by H+ and Cl− ions and the plots of [Formula: see text] against respective concentrations are linear. The proposed mechanism is given by reactions [i]–[v].[Formula: see text]The values of the rate constants at 25 °C are as follows: k1 = 147 dm3 mol−1 s−1 and 102ketKia = 2.8 s−1. The related activation parameters are [Formula: see text], and,[Formula: see text], and [Formula: see text] and [Formula: see text], respectively. The value of Kipd is 2.91 ± 0.03 mol dm−3 and that of Kipa (= 1/Kipd) is 0.344 ± 0.004 dm3 mol−1; both values are almost independent of temperature.

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