Separation of polar and steric effects in the oxidation of ortho-substituted benzaldehydes by N-bromobenzamide

The kinetics of the oxidation of twelve ortho-substituted benzaldehydes by N-bromobenzamide (NBB) to the corresponding benzoic acids have been studied. The reaction is first order with respect to NBB, the aldehyde and hydrogen ions. The addition of benzamide has no effect on the reaction rate. (PhCONH₂Br)⁺ has been postulated as the reactive oxidising species. The correlation of rates with the single substituent-parameter equations is poor. The correlation with Charton’s equation of inductive, resonance and steric parameters is satisfactory. However, excellent correlations were obtained, when Charton’s steric parameter was used along with Taft’s σ₁; andσ _R ⁺ substituent constants. The polar reaction constants have negative values. The reaction is subject to steric hindrance by the ortho-substituents.     

The reactivity of organothallium compounds. Kinetics and mechanism of iodination of diarylthallium salts by molecular iodine in dioxane

The kinetics and mechanism of the reactions of diarylthallium, trifluoroacetates with molecular iodine in dioxane solutions have been studied. The reaction has the overall second order with the first order with respect to each reagent. The effect of substituents in the aromatic ring on the rate constant of iodination is described by the equation logk ₂ρσ⁺(ρ=-1.60, r=0.97). The reaction is catalyzed by the iodide ion. The activation enthalpies and entropies of iodination of diarylthallium trifluoroacetates in dioxane and di(p-anisyl)thallium trifluoroacetate in various solvents have been calculated. The effect of solvents on the rate constant of iodination of di(p-anisyl)thallium trifluoroacetate has been studied. The reaction mechanism is considered as an electrophilicS _EC process. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 451–455, March, 1999.     

Micellization of Alkyltriphenylphosphonium Bromides in Ethylene Glycol and Diethylene Glycol + Water Mixtures: Thermodynamic and Kinetic Investigation

The thermodynamics of micellization and other micellar properties of alkyl- (C₁₀-, C₁₂-, C₁₄- and C₁₆-) triphenylphosphonium bromides in water + ethylene glycol (EG) (0 to 30% v/v) mixtures over a temperature range of 298 to 318 K and cetyltriphenylphosphonium bromide in water + diethylene glycol (DEG) mixtures (0 to 30% v/v) at 298 K have been studied conductometrically. In all cases, an increase in the percentage of co-solvent results in an increase in the cmc values. On the basis of these results, the thermodynamic parameters, the Gibbs energy (ΔG _m^o), enthalpy (ΔH _m^o) and entropy (ΔS _m^o) of micellization have been evaluated. In addition to the conductivity measurements, kinetic experiments have also been done to determine the dependence of observed rate constant for the nucleophilic substitution reaction of p-nitrophenyl acetate and benzohydroxamate ions in the presence of the surfactant cetyltriphenylphosphonium bromide with a varying concentration of EG and DEG ranging from 0 to 50% v/v at pH=7.9 and 300 K. All of the reactions followed pseudo-first-order kinetics. An increase in the surfactant concentration results in an increase in the reaction rate and for a given surfactant concentration, the rate constant decreases as the concentration of co-solvent in the mixture increases. The kinetic micellar effects have been explained by using the pseudophase model. The thermodynamic and structural changes originating from the presence of solvents control the micellar kinetic effects.     

Kinetics and mechanism of oxidation of some para-, meta-, and ortho-substituted ethyl S-phenylmercaptoacetates by chloramine-B(CAB)

The kinetics of oxidation of ethyl S-phenylmercapto acetate and several para-, meta-, and ortho-substituted ethyl S-phenylmercaptoacetates by chloramine-B have been studied in 50% (V/V) aqueous ethanol medium containing phosphate buffer. This oxidation is of first order with respect to substrate and zero order with respect to oxidant. A catalytic effect of mercury is observed and the order with respect to mercury is fractional (0.74). The increase in pH decreases the rate of oxidation and the order with respect to H⁺ is 0.05. In general electron-releasing substituents accelerate the rate while electron-attracting groups retard the rate. A good correlation is found to exist between log k ₁ and Hammett constants. Susceptibility of the reaction to the steric effect of ortho-substituents has been analyzed in the light of application of Taft's steric energy parameters. © John Wiley & Sons, Inc.     

Spectrophotometric determination of basicities of substituted acetylbiphenyls and biphenyl carboxylic acids

The basicities of several 2′-, 3′-, and 4′-substituted 4-acetylbiphenyls and biphenyl-4-carboxylic acids have been determined spectrophotometrically in sulphuric acid media at 30°C. The pK_BH ⁺ of 3′- and 4′-substituted compounds are correlated by the Hammett equation. The 4′-methoxy group deviates considerably in the Hammett plot. This is attributed to its conjugative interaction with the carbonyl or carboxyl group aided by protonation. Good correlation exists between pK_BH ⁺ and σ⁺. The basicities of 2′-substituted 4-acetylbiphenyls and biphenyl-4-carboxylic acids reaffirm the existence of π-electron steric effect of 2′substituents.     

Effect of the substituents on radical copolymerization of dialkyl fumarates with some vinyl monomers

Radical copolymerization of dialkyl fumarates (DRF) with various vinyl monomers was carried out in benzene at 60°C. The monomer reactivity ratios, r₁ and r₂, were determined from the comonomer-copolymer composition curves. The relative reactivity of DRFs with various ester substituents toward a polystyryl radical was revealed to depend on both steric and polar effects of the ester groups. It has also been clarified that α-substituents of the polymer radical have a significant role in addition of DRF, from the comparison of the monomer reactivity ratios determined in copolymerizations with monosubstituted and 1,1-disubstituted ethylenes. The absolute cross-propagation rate constants were also evaluated and discussed. © 1992 John Wiley & Sons, Inc.     

Kinetics of the Reaction of 2-Chloro-quinoxaline with Hydroxide Ion in ACN–H2O and DMSO–H2O Binary Solvent Mixtures

The kinetics of alkaline hydrolysis of 2-chloroquinoxaline (QCl) with hydroxide ion was investigated spectrophotometrically at different percentages of aqueous–organic solvent mixtures with acetonitrile (10–60% v/v) and with dimethylesulphoxide (10–80%) over the temperature range from 25 to 45 °C. The reaction was performed under pseudo first order conditions with respect to 2-chloroquinoxaline (QCl). An increase in the percentage of organic solvent (v/v) has different effects on the reaction rate constants, presumably due to hydrogen bond donor and acceptor differences of the media and other solvatochromic parameters. The data were discussed in terms of the Kamelt-Taft parameter and E _T(30). A nonlinear relation between the logarithm of the rate constant and reciprocal of the dielectric constant suggests the presence of selective solvation by the polar water molecules. Activation parameters ΔH ^#, ΔS ^# and ΔG ^# were determined and discussed.     

Solvolysis of 2‐chloro‐2(3,4‐disubstituted) phenylpropanes: Validity of Hammett–Brown σ+ constants in assessing additive effects of substituents

The objective of this study is to test the suitability of the extended Hammett–Brown equation, log (k_XX/k_HH) = ρ⁺Σσ⁺, in depicting satisfactorily additive effects of electronegative atom‐bearing substituents, which are known to possess diverse and multicomponent influences on the side chain reactions of polysubstituted benzenes. The equation has been used to correlate, for the first time, the additive effect of substituents in the specific rates of solvolysis of 2‐chloro‐2‐phenylpropanes ( 3b–3f ) having 3‐F,4‐Me, 3‐Br,4‐Me, 3‐I,4‐Me, 3‐Me,4‐Me, or 3‐MeO,4‐Me substituents. The rates were determined titrimetrically at 288, 298, and 308 K using 90% aqueous acetone as solvent. Measured additive effects of these substituents on the solvolysis rate and activation parameters of the parent cumyl chloride (2‐chloro‐2‐phenylpropane) are found to be well correlated using the equation given above. Plots of log (k_XX/k_HH) of 3b–3f together with mainly di‐, but also tri‐ and mono‐substituted cumyl chlorides from previous studies against Σσ⁺ give a linear correlation coefficient of 0.990 as a measure of the validity of the equation to depict such systems. The halogen substituents' extent of conformity with additivity reflected in their relative (k_obsd/k_calcd) rate ratios is found to correlate with the steric size of substituents. Plots of rate ratios against Taft's steric factor of each halogen give a linear correlation coefficient of 0.994 for the 3‐halo substituents. The 3,4‐dimethyl substituents' relative rate ratio of 1.03 shows excellent additivity, whereas the 3‐methoxy‐4‐methyl ratio of 1.43 shows the methoxy group to be far less deactivating than predicted. Similar trends were found for the free energy of activation (ΔG? – ΔG₀?) differences, which correlated linearly with a coefficient of 0.983 with Taft's steric factor of halogen atoms. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 514–523, 2012     

Nitrosation of Phenolic Compounds: Effects of Alkyl Substituents and Solvent

Summary.  Nitrosation reactions of phenol, o-cresol, 2,6-dimethylphenol, o-tert-butylphenol, 2-hydroxyacetophenone, and 2-allylphenol in water and water/acetonitrile were studied. Kinetic monitoring of the reactions was accomplished by spectrophotometric analysis of the nitrosated products at 345 nm. The dominant reaction was C-nitrosation via a mechanism consisting of an attack on the nitrosatable substrate by NO⁺/NO₂H₂ ⁺ followed by a slow proton transfer. The values of the rate constants of phenolic C-nitrosation were increased by electron donating substituents, and a good Hammett correlation was observed with ρ = −6.1. The results also revealed the strong effect of pH and the permitivity of the reaction medium on the rate constant, whose maximum values were observed for pH ≈ 3, decreasing strongly for higher pH values. The study in water/acetonitrile with up to 25% acetonitrile showed that it is possible to inhibit the reaction strongly by increasing the percentage of the organic component. The conclusions drawn show that (i) it is possible to predict the rate of nitrosation of phenolics as a function of the meta-substituents on the phenol ring and (ii) the nitrosation of phenolics can be strongly inhibited by increasing the pH of the reaction medium as well as by lowering its dielectric constant. Received July 13, 2001. Accepted (revised) September 18, 2001     

Effects of the temperature and substituents in chiral TiIV(salen) catalysts on the enantioselectivity of the addition of Me3SiCN to PhCHO

The enantiomeric purity (ee) of the addition product of Me₃SiCN to PhCHO at ∼20 °C catalyzed by chiral Ti^IV complexes, which were preparedin situ from Ti(OPrⁱ)₄ and the Schiff bases (condensation products of substituted salicylaldehydes with (1R, 2R)-1,2-diaminocyclohexane), was, on the average, 20–30% lower than that achieved at −80 °C. The substituents at position 5 of 3-tert-butylsalicylaldehyde exert only the steric effect. It was shown that the stereochemical result of the reaction is controlled by the stage which involves the formation of the C−C bond rather than the transfer of the Me₃Si group. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1139–1141, June, 1999.     

On the Role of the Solvent and Substituent on the Protonation Equilibria of Di-Substituted Anilines in Dioxane–Water Mixed Solvents

Protonation constants of a number of di-substituted anilines were determined potentiometrically in 0, 20, 30, 40, 50, and 60% (v/v) dioxane–water mixtures at (25.00 ± 0.02) ^∘C with an ionic strength of 0.10 mol-dm⁻³ sodium perchlorate. The data are discussed in terms of the electronic character of the substituents. Two different methods were used to study the effects of the solvents on the protonation constants; one involved a single polarity parameter, the Dimroth–Reichardt parameter E_T(30); the other involved the Kamlet–Taft multi-parametric method. The protonation constants of di-substituted anilines correlate with the molecular parameters for the dipolarity/polarizability of the solvent, π^∗, and its hydrogen-bond acceptor ability, β.     

Nitrosation of Phenolic Compounds: Effects of Alkyl Substituents and Solvent

 Nitrosation reactions of phenol, o-cresol, 2,6-dimethylphenol, o-tert-butylphenol, 2-hydroxyacetophenone, and 2-allylphenol in water and water/acetonitrile were studied. Kinetic monitoring of the reactions was accomplished by spectrophotometric analysis of the nitrosated products at 345 nm. The dominant reaction was C-nitrosation via a mechanism consisting of an attack on the nitrosatable substrate by NO⁺/NO₂H₂ ⁺ followed by a slow proton transfer. The values of the rate constants of phenolic C-nitrosation were increased by electron donating substituents, and a good Hammett correlation was observed with ρ = −6.1. The results also revealed the strong effect of pH and the permitivity of the reaction medium on the rate constant, whose maximum values were observed for pH ≈ 3, decreasing strongly for higher pH values. The study in water/acetonitrile with up to 25% acetonitrile showed that it is possible to inhibit the reaction strongly by increasing the percentage of the organic component. The conclusions drawn show that (i) it is possible to predict the rate of nitrosation of phenolics as a function of the meta-substituents on the phenol ring and (ii) the nitrosation of phenolics can be strongly inhibited by increasing the pH of the reaction medium as well as by lowering its dielectric constant.     

Substituent effects on the activation parameters of S<Subscript>N</Subscript>ar reactions

The reaction constants δΔH ^≠ and δΔS ^≠ derived from the dependences of the ΔH ^≠ and ΔS ^≠ activation parameters on substituent constants σ in S_NAr reactions of substituted benzenes with anionic and neutral nucleophiles in various solvents were found to be linearly related upon variation of substituents in the substrate and nucleophile. The δΔH ^≠—δΔS^≠ dependences make it possible to estimate the contribution of the internal enthalpy δΔH^≠ _t into the enthalpy reaction constant δΔH ^≠. The δΔH ^≠ _int values are linearly related to the Hammett p values. Deviations from the linear dependence δΔH≠ _int—n were interpreted in terms of change of the reaction mechanism. Substituent effect on the development of charge in the transition state is determined by the δΔH ^≠ _int value.     

Reaction of ethyl bromoacetate with substituted naphthoate ions

Rate constants for the reaction of ethyl bromoacetate with three series of substituted naphthoate ions have been measured in an acetone-water mixture (90% v/v). Using σ _p values rate constants at 30^o correlate well with the Hammett equation yielding ρ=−0.54, −0.19 and −0.25 for (4,1−), (6,1−) and (6,2−) series, respectively. Comparison of these ρ values with those of the reaction of phenacyl bromide reveals the failure of the reactivity-selectivity principle RSP in these reactions. Failure of RSP has been explained in terms of isoselective temperature.     

Etude en Résonance Magnétique Nucléaire du Carbone-13 de N-Aryl Pyrazolines-2 Diversement Substituées. Effets de Substituant et Etude Conformationnelle

The ¹³C chemical shifts of 1-phenyl-2-pyrazoline and 25 N-nitrophenyl-2-pyrazolines, with different substituents on the heterocyclic ring, have been assigned. These values are discussed as a function of the steric and electronic nature of the various substituents. The steric effects produced conformational modifications, both in the nitrophenyl and 2-pyrazoline moieties, which explain some of the chemical shifts.     

Mixed-ligand Copper(II) Complexes: Investigation of their Spectroscopic, Catalysis, Antimicrobial and Potentiometric Properties

Schiff base ligands HL¹–HL⁶ have been prepared from the reaction of 2,6-diformyl-4-t-butylphenol and 2,6-di-formyl-4-methylphenol with various aromatic amines in ethanolic solution. The Schiff base ligands 2,2′-dipyridine (dp) mixed-ligand Cu^II complexes have been obtained. Mixed-ligand Cu^II complexes containing the dp ligand have ionic nature and they conduct the electricity in solution media. The complexes have been obtained in two different forms: one of them is [Cu₂(Lⁿ)Cl₃] (n: 1, 2, 3, 4, 5 and 6) and other complexes have the general formula [Cu₂(Lⁿ)(dp)₂]3Cl. Ligands and their complexes have been characterized by elemental analyses, FT-IR, electronic spectra, molar conductance, ¹H(¹³C)-n.m.r. and mass spectral data. Their stoichiometric protonation constants have been determined potentiometrically in dioxan using a combined pH electrode at 25 °C, under a nitrogen atmosphere. For the calculation of the protonation constants, PKAS computer programme has been used. The effects of the substituents on the protonation constants and the additivities of these effects are discussed. The antimicrobial activity studies of the ligands and their complexes have been studied against the Bacillus megaterium, Micrococcus luteus, Corynebavterium xenosis, Enterococcuc faecalis, bacteria and Saccoramyces cerevisia, yeast. The catalytic properties of the complexes have been studied on the ascorbic acid, catechol and 2,6-di-t-butylphenol substrates. Thermal behaviour of the complexes has been studied by thermal techniques.     

Catecholase biomimetic catalytic activity of copper(II) complexes with 2-methyl-3-amino-(3H)-quinazolin-4-one

The oxidation of catechol by molecular oxygen in the presence of a catalytic amount of copper(II) complex with 2-methyl-3-amino-(3H)quinazoline-4-one (MAQ) and various anions (Cl⁻, Br⁻, ClO ₄ ⁻ , SCN⁻, NO ₃ ⁻ and SO ₄ ^– ) was studied. The catecholase biomimetic catalytic activity of the copper(II) complexes has been determined spectrophotometrically by monitoring the oxidative transformation of catechol to the corresponding light absorbing o-quinone (Q). The rate of the catalytic oxidation reaction was investigated and correlated with the catalyst structure, time, concentration of catalyst and substrate and finally solvent effects. Addition of pyridine or Et₃N showed a dramatic effect on the rate of oxidation reaction. Kinetic investigations demonstrate that the rate of oxidation reaction has a first order dependence with respect to the catalyst and catechol concentration and obeying Michaelis–Menten Kinetics. It was shown that the catalytic activity depends on the coordination environment of the catalyst created by the nature of counter anions bound to copper(II) ion in the complex molecule and follows the order: Cl⁻ > NO ₃ ⁻ > Br⁻ > SO ₄ ^– > SCN⁻ > ClO ₄ ⁻ . To further elucidate the catalytic activity of the complexes, their electrochemical properties were investigated and the catecholase mimetic activity has been correlated with the redox potential of the Cu²⁺/Cu⁺ couple in the complexes.     

Cautions regarding the physical interpretation of statistically based separation of the ortho substituent effect into inductive,mesomeric, and steric components—II : Acid catalysed esterification of benzoic acids by methanol and cyclohexanol

In order to attain a better insight into the composition of Taft E_s^o, constants the rate data of hydrion catalysed esterification of both m,p-substituted and o-substiluted benzoic acids by cyclohexanol and methanol were submitted to a statistical analysis using inductive mesomeric and steric substituent constants and various dummy variables differently structured. Furthermore a principal component analysis with subsequent identification of the first principal component via multiple regression analysis was applied. It has been demonstrated that in the reactions of m,p substituted compounds some substituents capable of exerting strong mesomeric effects show peculiar characteristics deviating from the general trend. Since the same result was obtained in the correlations of ortho substituted benzoic acids this effect was taken into account using an appropriate dummy variable which in all cases improved the multiple coefficient of determination. It is concluded that the esterification rates of the ortho substituted compounds depend essentially upon inductive and steric effects (taken away OMe OEt and NO₂) as proposed by Taft. While generally the E_s^o values may be regarded as some measure of a steric effect, this is not true for the methoxy and ethoxy groups.     

Correlation analysis of reactivity in the addition of substituted benzylamines to benzylidenemalononitrile

The kinetics of addition of a number of ortho‐, meta‐, and para‐substituted benzylamines to benzylidenemalononitrile (BMN) in acetonitrile have been studied. The reaction is first‐order with respect to BMN. The order with respect to the amine is more than one. It has been shown that the reaction followed two mechanistic pathways, uncatalyzed and catalyzed by the amine. The enthalpy of activation for the catalyzed path is negative indicating the presence of a preequilibrium (k₁, k₋₁) leading to the formation of a zwitterion. The values of rate constant, k₁, for the nucleophilic attack have been determined for twenty‐eight benzylamines. The rate constant, k₁ was subjected to correlation analyses using various single‐ and multi‐parametric equations. The best correlation is obtained in terms of Charton's LDR and LDRS equations. The polar regression coefficients are negative indicating the formation of a cationic species in the transition state. The reaction is subject to steric hindrance by ortho‐substituents. © 1999 John Wiley & Sons, Inc., Int J Chem Kinet 31: 245–252, 1999     

First steps of the reactions of alkanes and arenes with adamantyl cations in sulfuric acid in comparison with other reagents

Solutions of 1-adamantanol in sulfuric acid at T < 100 °C interact with alkanes (RH, [H₂SO₄] > 85%) and arenes (ArH, [H₂SO₄] > 59%). The data on the kinetics, kinetic isotope effect (KIE), effects of the structure of RH and ArH and acidity of the medium, and the observation of 1,4-cis-dimethylcyclohexane isomerization indicate that adamanyl cations (Ad⁺) serve as reactive species. In the reactions with alkanes, the Ad⁺ cation abstracts the hydride ion from RH in the rate-determining step. Compensation dependences appear between the activaion parameters for the KIE and “effect 5/6” (ratio of the rate constants for the C–H bond cleavage in cyclopentane and cyclohexane) in the reactions of cycloalkanes with Ad⁺ and other electrophilic reagents, such as “anthracene” (An₂)H⁺ and hydroxymethyl (CH₂OH)⁺ cations and Hg^II ions, including the points of the lower selectivity limit (k _H/k _D) = 1.4, (“5/6”) = 1. In the reactions with the Ad⁺ cation, the bond selectivity 3⁰: 2⁰ of alkanes is higher, while 2⁰: 2⁰ is lower compared to other reagents. In the first case, the selectivity is probably determined predominantly by the energies of the cleaved C–H bonds, whereas in the second case it is determined by steric hindrances. Judging by the kinetic and selectivity data in the series benzene—toluene—o-xylene—m-xylene and the absence of the reaction with p-xylene, mesitylene, and pseudocumene, it can be concluded that the main contribution to the Ad⁺ + ArH interaction is made by adamantylation to the para- and meta-positions of the benzene ring, whereas the ortho-positions are inaccessible to the attack because of steric hindrances. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1581–1596, August, 2008.