scholarly journals Proton Transfer Reactions of Carbon Acids. III. Effect of Solvent Change on the Equilibrium and Kinetic Parameters of the Reaction of Di-(4-nitrophenyl)methane with Alkoxide Bases

1973 ◽  
Vol 51 (17) ◽  
pp. 2805-2809 ◽  
Author(s):  
Jae-Hang Kim ◽  
Kenneth T. Leffek
Keyword(s):  
Proton Transfer ◽  
Kinetic Parameters ◽  
Rate Constants ◽  
Equilibrium Constants ◽  
Mixed Solvents ◽  
Activation Parameters ◽  
Transfer Reactions ◽  
Effect Of Solvent ◽  
Proton Transfer Reactions ◽  
Carbon Acids

The equilibrium constants, the second-order rate constants, and the activation parameters have been determined for the proton transfer from di-(4-nitrophenyl)methane to ethoxide ion in a series of mixed solvents containing various amounts of acetonitrile in ethanol. The quantities have been interpreted in terms of the general postulates of the Miller–Parker theory of solvation effects.

Kinetics of Proton Transfer Reactions of Carbon Acids. II. Reaction of Di-(4-nitrophenyl)methane with Alkoxide Bases

1972 ◽  
Vol 50 (1) ◽  
pp. 24-30 ◽  
Author(s):  
A. Jarczewski ◽  
K. T. Leffek
Keyword(s):  
Proton Transfer ◽  
Transition State ◽  
Rate Constants ◽  
Activation Parameters ◽  
Transfer Reactions ◽  
Activation Process ◽  
Proton Transfers ◽  
Proton Transfer Reactions ◽  
Carbon Acids ◽  
Kinetics Of

The second-order rate constants have been measured over a range of temperatures for the proton-transter reactions from di-(4-nitrophenyl)methane to ethoxide, isopropoxide, and t-butoxide ions in solvents consisting of the corresponding alcohols containing 10% toluene by volume. The activation parameters ΔH≠ and ΔS≠ have been calculated and an interpretation of them is given in terms of solvation effects during the activation process. A comparison between the activation parameters for proton transfers and E2 olefin-forming β-elimination reactions is made and discussed with respect to transition state character of the latter reactions.

Proton transfer reactions between ortho-methyl substituted derivatives of 4-nitrophenylphenylcyanomethane and nitrogen bases in acetonitrile solvent

1988 ◽  
Vol 66 (6) ◽  
pp. 1454-1458 ◽  
Author(s):  
Kenneth T. Leffek ◽  
Przemyslaw Pruszynski
Keyword(s):  
Proton Transfer ◽  
Isotope Effect ◽  
Rate Constants ◽  
Isotope Effects ◽  
Equilibrium Constants ◽  
Activation Parameters ◽  
Transfer Reactions ◽  
Methyl Groups ◽  
Methyl Group ◽  
Proton Transfer Reactions

Equilibrium constants, rate constants, primary deuterium isotope effects, and activation parameters have been measured for the proton transfer reactions in acetonitrile solvent of 4-nitrophenylphenylcyanomethane and 2-methyl-4-nitrophenylphenyl-cyanomethane with tetramethylguanidine base and for the reactions of 2-methyl-4-nitrophenylphenylcyanomethane and 2,6-di-methyl-4-nitrophenylphenylcyanomethane with 1,5-diazabicyclo[5.4.0]undec-7-ene base. Introduction of the ortho-methyl groups in the substrate molecule caused significant reductions in the equilibrium and rate constants. The expected rise in the kinetic primary deuterium isotope effect was not observed when the first ortho-methyl group was introduced, but a 20% increase did accompany the introduction of the second ortho-methyl group. Enthalpy of activation measurements indicated that there was no increase in the proton tunnelling contribution to the isotope effect when the amount of steric hindrance is increased with ortho-methyl groups.

Proton transfer reactions between 4-nitrophenylphenylcyanomethanes and cyclic nitrogen bases in acetonitrile solvent

1990 ◽  
Vol 68 (10) ◽  
pp. 1657-1661 ◽  
Author(s):  
Miroslaw Dworniczak ◽  
Kenneth T. Leffek
Keyword(s):  
Proton Transfer ◽  
Isotope Effects ◽  
Equilibrium Constants ◽  
Activation Parameters ◽  
Transfer Reactions ◽  
Nitrogen Bases ◽  
Conjugate Acid ◽  
Proton Transfer Reactions ◽  
Carbon Acids ◽  
Cyclic Nitrogen

3,3,6,9,9-Pentamethyl-2,10-diazabicyclo[4.4.0]dec-1-ene has been synthesized and its proton transfer reactions, together with those of the bases 2,2,6,6-tetramethylpiperidine and 1,2,2,6,6-pentamethylpiperidine, have been studied with the carbon acids 4-nitrophenylphenylcyanomethane and 2-methyl-4-nitrophenylphenylcyanomethane. Equilibrium constants, rate constants, primary deuterium isotope effects, and activation parameters are reported for the reactions in acetonitrile solvent. Values of the pKa in acetonitrile have been measured for the conjugate acid of each base and the Brønsted β value of 0.56 in acetonitrile has been determined for the proton transfer from 4-nitrophenylphenylcyanomethane. Keywords: proton transfer reactions, kinetic isotope effects, cyclic nitrogen bases.

Study of the dissociation of the products of some proton transfer reactions in acetonitrile solvent

1992 ◽  
Vol 70 (3) ◽  
pp. 935-942 ◽  
Author(s):  
Wlodzimierz Galezowski ◽  
Arnold Jarczewski
Keyword(s):  
Proton Transfer ◽  
Rate Constants ◽  
Isotope Effects ◽  
Equilibrium Constants ◽  
Ion Pair ◽  
Transfer Reactions ◽  
Side Reactions ◽  
First Order ◽  
Kinetic Isotope ◽  
Proton Transfer Reactions

The conductometric study of the products of the proton transfer reactions of C-acids (nitriles, nitroalkanes, and 2,4,6-trinitrotoluene) with the strong amine bases (1,1,3,3-tetramethylguanidine (TMG), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,8-bis(dimethylamino)naphthalene (DMAN), and piperidine) in acetonitrile shows their large degree of dissociation into free ions. The dissociation constant values have been estimated at 25 °C to be larger than 1 × 10−4 M. This weakens the formalism commonly accepted in spectrophotometric kinetic studies of these systems of reactions, based on the assumption that the product is an ion pair. Spectrophotometric equilibrium and kinetic measurements provided evidence that reverse reaction is a second-order process (pseudo-first order because cation concentration is controlled by side reactions). The influence of the common cation (TMGH+) on the equilibria of the proton abstraction from 2-methyl-1-(4-nitrophenyl)-1-nitropropane and 4-nitrophenylcyanomethane with TMG base in acetonitrile at 25 °C was examined and was found to be compatible with the assumption of large dissociation of the reaction product for free ions. "Equilibrium constants" estimated by the Benesi and Hildebrand method (which assumes an ion-pair product) decreased with increasing concentration of added TMGH+ cation, but these "equilibrium constants" multiplied by [TMGH+] are constant. The observed pseudo-first-order rate constants of the proton transfer reaction, measured at large excess of the base over C-acid, grow with the cation concentration due to the increase of the backward reaction rate. The concentration of added common cation shows a negligible influence on the observed rate constants of deuteron transfer reaction. Thus, as a result of side reactions, in which extra amounts of cation are formed, some second-order rate constants [Formula: see text] and also kinetic isotope effects (KIEs) [Formula: see text] that have been measured in acetonitrile can be substantially overestimated. Keywords: ion-pair dissociation, proton transfer reactions, kinetic isotope effects.

Kinetics of Proton Transfer Reactions of Carbon Acids. IV. Primary Deuterium Isotope Effect in the Reaction of Di-(4-nitrophenyl)methane-d2 with t-Butoxide

1974 ◽  
Vol 52 (4) ◽  
pp. 592-596 ◽  
Author(s):  
Jae-Hang Kim ◽  
Kenneth T. Leffek
Keyword(s):  
Proton Transfer ◽  
Isotope Effect ◽  
Activation Parameters ◽  
Proton Transfer Reaction ◽  
Transfer Reactions ◽  
Deuterium Isotope Effect ◽  
Enthalpy Of Activation ◽  
Proton Transfer Reactions ◽  
Carbon Acids ◽  
Kinetics Of

The primary deuterium isotope effect has been measured for the proton transfer reaction from di-(4-nitrophenyl)methane to t-butoxide ion in a solvent consisting of 10% v/v toluene in t-butanol at a series of temperatures between 20 and 45 °C. The isotopic rate ratio, kH/kD, is 7.3 at 25 °C. The activation parameters showed an enthalpy of activation difference (ΔHD≠ − ΔHH≠) of only ca. [Formula: see text] kcal mol−1 and an entropy isotope effect (ΔSD≠ − ΔSH≠) of −2.4 cal mol−1 deg−1. The latter indicates, according to the theory of Bell, that tunnelling of the proton through the energy barrier is unimportant in this reaction. This result is compared to other reactions in the literature, in which tunnelling has been postulated to occur.

scholarly journals Equilibrium and kinetic study of the proton transfer reactions between nitroalkanes and strong organic bases — phosphazenes in tetrahydrofuran solvent

2010 ◽  
Vol 8 (3) ◽  
pp. 582-586
Author(s):  
Iwona Binkowska ◽  
Włodzimierz Gałęzowski ◽  
Arnold Jarczewski
Keyword(s):  
Proton Transfer ◽  
Kinetic Study ◽  
Activation Parameters ◽  
Transfer Reactions ◽  
Organic Bases ◽  
Proton Transfer Reactions ◽  
Carbon Acids

AbstractProton transfer reactions rates between carbon acids 1-nitro-1-(4-nitrophenyl)ethane (NPNE), 2-methyl-1-nitro-1-(4-nitrophenyl)propane (MNPNP)) and phosphazenes (BEMP, BTPP, P1-t-Oct) in tetrahydrofuran have been measured, and the activation parameters were determined. The results are compared with those previously obtained for P1-t-Bu phosphazene, guanidines and amidines.

A Potentiometric Study on Proton-Transfer Equilibria and Cationic Conjugation in Pyridine N-Oxide Systems in Acetone and Methanol

1996 ◽  
Vol 49 (9) ◽  
pp. 931 ◽  
Author(s):  
L Chmurzynski ◽  
E Kaczmarczyk ◽  
M Nesterowicz ◽  
G Wawrzyniak ◽  
Z Warnke
Keyword(s):  
Proton Transfer ◽  
Equilibrium Constants ◽  
Proton Donor ◽  
Heterocyclic Amines ◽  
Transfer Reactions ◽  
Oxide Systems ◽  
Experimental Systems ◽  
Proton Transfer Reactions ◽  
Potentiometric Titration Method

The potentiometric titration method has been used to study the equilibria of cationic in sytems formed by substituted pyridine N-oxides in the polar, non-aqueous solvents acetone and methanol. For comparison, the systems with trimethylamine N-oxide as a representative of aliphatic amine N-oxides and pyridine representing parent heterocyclic amines were also studied. The cationic heteroconjugation constants, i.e. the equilibrium constants for conjugation reactions between free and protonated N-bases leading to the formation of unsymmetric BHB'+ cations, were determined in experimental systems with and without proton transfer. It was found that there were significant differences in the values of the cationic heteroconjugation constants determined in these two acid-base systems. The proton-transfer reactions limit and even preclude the determination of the cationic heteroconjugation constants. On this basis it was concluded that the heteroconjugation constants should be determined in systems without proton transfer. In such systems, in the amphiprotic solvent methanol, cationic heteroconjugation was ascertained in all substituted pyridine N-oxide systems, the values of heteroconjugation constants being relatively low (logarithms of their values of the order of 2-2.5), and only negligible in systems involving trimethylamine N-oxide. A more pronounced tendency towards cationic heteroconjugation of the [OHO]+ type was observed in the aprotic protophobic acetone, where heteroconjugation constants were determined for all amine N-oxide systems studied including those containing protonated trimethylamine N-oxide as a proton donor. However, the values of the cationic heteroconjugation constants were found to be, in methanol likewise, relatively low (log KBHB'+ of the order of 2-3). On the contrary, a greater extent of cationic heteroconjugation equilibria was observed in methanol than in acetone in the case of systems containing pyridine, i.e. [NHO]+ type bridges formed by amine N-oxides and heterocyclic amines. In methanol the heteroconjugation constants turned out to be determinable for all such systems studied (logarithms of the equilibrium constants being of the same order as for N-oxide systems), whereas in acetone the hetero constants were indeterminable for all systems.

Gas-phase proton-transfer reactions of the hydronium ion at 298 K

1979 ◽  
Vol 57 (12) ◽  
pp. 1518-1523 ◽  
Author(s):  
Gervase I. Mackay ◽  
Scott D. Tanner ◽  
Alan C. Hopkinson ◽  
Diethard K. Bohme
Keyword(s):  
Proton Transfer ◽  
Gas Phase ◽  
Rate Constants ◽  
Transfer Reactions ◽  
Flowing Afterglow ◽  
Hydronium Ion ◽  
Proton Transfer Reactions

Rate constants measured with the flowing afterglow technique at 298 ± 2 K are reported for the proton-transfer reactions of H3O+ with CH2O, CH3CHO, (CH3)2CO, HCOOH, CH3COOH, HCOOCH3, CH3OH, C2H5OH, (CH3)2O, and CH2CO. Dissociative proton-transfer was observed only with CH3COOH. The rate constants are compared with the predictions of various theories for ion–molecule collisions. The protonation is discussed in terms of the energetics and mechanisms of various modes of dissociation.

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