Kinetics of the alkaline hydrolysis of isatin and N-methylisatin in water and water-N,N-dimethylacetamide mixtures

The kinetics of amide bond cleavage of isatin and N-methylisatin in the presence of N,N-dimethylacetamide (DMA) was followed spectrophotometrically in the range of solvent composition (0–48.53 wt.%) and temperatures (40–70 °C) using piperidine as a nucleophile. The reaction was studied under pseudo-first-order kinetics. The rate of the reaction decreases largely with increasing organic solvent content. The thermodynamic activation parameters were calculated and discussed in terms of solvation of the activated complex. No linearity was observed between log rate constant and the reciprocal dielectric constant for the solvent used suggesting that there is a selective solvation by higher polar solvent (water). Finally, a mechanism for the ring opening for isatin and N-methylisatin was proposed.     

杂环反铂(Ⅱ)抗癌药物水解反应机理的DFT研究

用DFT-B3LYP方法和IEF-PCM溶剂化模型研究了反铂抗癌药物trans-[PtCl2(piperidine)(Am)](Am=2-picoline(1),3-picoline(2),4-picoline(3)),trans-[PtCl2(piperidine)(piperazine)](4),trans-[PtCl2(pipera-zine)2](5)and trans-[PtCl2(iminoether)2](6)的水解过程.水解反应是药物与DNA靶分子作用的关键活化步骤.全优化和表征了一水解和二水解反应经由一般的SN2路径过程所有物种的势能面稳定点.结果发现反应过程遵循已经建立的平面正方形配合物的配体取代反应理论,即取代反应通常通过一个三角双锥过渡态结构的铂配体交换反应发生.得到的过渡态结构与以前的相关工作一致,所有反应都是吸热反应;所有体系的二水解能垒都高于一水解.与顺铂相比,这些配合物都有更快的水解反应速率;并与以前类似的反铂配合物的研究做了比较.研究结果提供了这些配合物水解反应过程的详细能量变化,对理解药物与DNA靶分子的作用机理和新型反铂抗癌药物的设计有帮助.     

Electrochemistry and [60]fullerene displacement reactions of (dihapto-[60]fullerene) pentacarbonyl metal(0) (M = Cr, Mo, W)

Cyclic voltammetry (CV) measurements on (eta(2)-C(60))M(CO)(5) complexes (M = Cr, Mo, W) in dichloromethane show three [60]fullerene-centered and reversible reduction/oxidation waves. The E(1/2) values of these waves are shifted to positive values relative to the corresponding values of the uncoordinated [60]fullerene in the same solvent. A Jahn-Teller type distortion of the spherical surface of [60]fullerene promoted by [60]fullerene-metal pi-backbonding may explain the observed positive shifts. Lewis bases (L = piperidine and triphenyl phosphine) displace [60]fullerene from (eta(2)-C(60))M(CO)(5) complexes. Analysis of the activation parameters for the metal-[60]fullerene dissociation, the metal-[60]fullerene bond enthalpies (from DFT computations), and metal-solvent (benzene) bond enthalpies (from DFT computations) suggests appreciable solvent contribution to the transition state leading to formation of the intermediate species solvent-M(CO)(5). Appreciable transition state stabilization due to solvation of the intermediate species is inferred for M = Mo and W. For M = Cr, stabilization of the intermediate species due to solvation is not accompanied by the corresponding transition state stabilization.     

Kemp elimination: a probe reaction to study ionic liquids properties

The amino induced elimination of benzisoxazole into the relevant o-cyanophenolate ion (Kemp elimination) has been studied in [bmim][BF 4] solution at 298 K. To have information about the interactions between reactants and ionic liquid, the reaction has been carried out at different temperatures (293-313 K). Several primary, secondary, and tertiary amines have been used to study the effect of amine structure on the reaction rate. The collected data show that the amine structure seems to have a crucial role in determining the reaction rate. Furthermore, as different cation or anion structures of an ionic liquid can significantly affect its properties, the title reaction has been performed in four different ionic liquids ([bmim][PF6], [bmim][NTf 2], [bm 2im][NTf 2], and [bmpyrr][NTf 2]), using pyrrolidine and piperidine as model amines. An H-donor negative solvent (MeOH and [bmim][NTf 2]) effect on reaction rate was detected. Finally, a narrow range of activation parameters was calculated both for the reaction induced by different amines and for pyrrolidine and piperidine, in the presence of different ILs. This fact suggests the occurrence of an "early" transition state.     

Aquation kinetics of chloro- and bromo-pentamminecobalt(III) ions in water-acetone mixtures

Summary The aquation kinetics of [Co(NH₃)₅Cl]²⁺ and [Co(NH₃)₅Br]²⁺ ions in acetone-water have been investigated over a wide range of solvent compositions and temperatures. The variation of thermodynamic properties of the activated complex with the mole fraction of acetone reveals the existence of specific solvation. The correlation of the rate constant with dielectric constant of the medium is examined and discussed. A reaction mechanism which describes the solvent effect on reaction rate is proposed.     

Kinetics of proton transfer from cationic carbon acids in water and aqueous DMSO. Effect of activating groups and solvent on intrinsic rate constants

[reaction: see text] Acidity constants and rates of reversible deprotonation of acetonyltriphenylphosphonium ion (1H+), phenacyltriphenylphosphonium ion (2H+), N-methyl-4-phenacylpyridinium ion (3H+), and N-methyl-4-(phenylsulfonylmethyl)pyridinium ion (4H+) by amines in water, 50% DMSO-50% water (v/v), and 90% DMSO-10% water (v/v) have been determined. From the respective Br?nsted plots, log k(o) values for the intrinsic rate constants of the various proton transfers were obtained. Solvent transfer activity coefficients of the carbon acids and their respective conjugate bases were also determined which helped in understanding how the pKa values and intrinsic rate constants depend on the solvent. Some of the main conclusions are as follows: (1) The pK(a) values of 1H+, 2H+, and 3H+ are significantly higher than that of 4H+ because of a stronger resonance stabilization of the corresponding conjugate bases 1, 2 and 3, respectively. (2) The electronic effects of the PPh3+ and the N-methyl-4-pyridylium group are similar but the mix between inductive and resonance effect is different. (3) All four acids become more acidic upon addition of DMSO to the solvent. In all cases, the main factor is the stronger solvation of H3O+ in DMSO; for 1H+, 2H+, and 3H+ but not 4H+ this factor is significantly attenuated by stronger solvation of the carbon acid in DMSO. (4) The intrinsic rate constants for proton transfer are relatively high for all four carbon acids and show little solvent dependence; this contrasts with nitroalkanes which have much lower intrinsic rate constants and show a strong solvent dependence. These results can be understood by a detailed analysis of the interplay between inductive, resonance, and solvation effects.     

A theoretical investigation into the inversion barrier of dipole-stabilized alpha-aminoorganolithiums

[reaction: see text] Results from density functional theory calculations (B3LYP/6-31+G) suggest that inversion of the monomer of 2-lithio-N-formylpyrrolidine (2) in coordinating ethereal solvent occurs with an activation barrier of 15.7 kcal/mol, while the inversion of the monomer in a noncoordinating hydrocarbon solvent is considerably slower. However, aggregation into a trimer in hydrocarbon solvent restores the low inversion barrier. This study suggests that solvation and aggregation may influence the mechanism and rate of racemization of dipole-stabilized alpha-aminoorganolithiums.     

Solvation model in the allylation of 2-mercaptobenzothiazole

The kinetics of the reaction of allyl bromide with 2-mercaptobenzothiazole has been studied in different protic and aprotic solvents conductometrically. The rate data were correlated with solvation parameters using linear multiple regression analysis. From the regression coefficients, which describe the susceptibility towards rate of different solvent parameters, information regarding solvent interactions is obtained and solvation models are proposed. The reaction has also been studied at different temperatures and thermodynamic parameters ∆H^≠, ∆S^≠, ∆G^≠ are computed.     

Effect of the composition of a solution on the enthalpies of solvation of piperidine in methanol-acetonitrile and dimethylsulfoxide-acetonitrile mixed solvents

Heat effects of dissolution of piperidine (ppd) are measured by calorimetry at 298.15 K over the range of composition of acetonitrile-methanol (AN-MeOH) mixed solvents. Based on the Δ_sol H ^○(ppd)_AN-MeOH values obtained using the literature data on Δ_sol H ^○ (ppd) in acetonitrile-dimethylsulfoxide (AN-DMSO) mixed solvents and the vaporization enthalpy of ppd, the enthalpies of solvation of amine in AN-MeOH and AN-DMSO binary mixtures are calculated. A rise in the exothermicity of solvation of piperidine is observed upon the transition from AN to DMSO and MeOH, due mainly to the enhanced solvation of the amino group of ppd as a result of changes in the acid-base properties of the mixed solvent.     

Effects of Solvents and the Structure of Amines on the Rates of Reactions of α,β-Unsaturated Nitriles and Amides with Secondary Amines

The kinetics of reactions between ,-unsaturated compounds (UCs) (acrylonitrile (AN), acryl-amide (AA), and methacrylamide (MAA)) and secondary amines (As) (piperidine, morpholine, diethanolamine, diethylamine, and dipropylamine) in water, as well as in DMF, DMSO, formamide, and 1,4-dioxane for acrylonitrile, was studied. It was found that w= k[HC]₀[A]₀for all of the test pairs. Viscosity, permittivity, and solvation characteristics, such as solvent polarity, nucleophilicity, and electrophilicity, were taken into account in considering the solvent effect on the overall reaction rate. The electrophilicity (acidity) of a medium was found to exert the greatest effect on the reaction rate. It is believed that an increase in the electrophilicity is favorable for the rapid protonation of the UC–amine intermediate complex. The effects of amine basicity, ionization potential, and dipole moment and the steric parameters of substituents in amine molecules on the rates of reactions between the unsaturated compounds and secondary amines were considered.     

Theoretical Study on the Cyclization Mechanism of Dipeptides

Cyclization is an important chemical reaction for the dipeptides containing N‐alkyl groups. The cyclization mechanism has been examined by theoretical calculations. Our calculation results indicate that the most favorable mechanism is the piperidine‐catalyzed stepwise mechanism, in which piperidine acts as a proton shuttle. The attack of the N‐terminal amino nitrogen at the C‐terminal carbonyl carbon along with the proton transfer is the rate‐limiting step. The effect of the alkyl substituent on the amide N on the cyclization reaction was then examined. Finally, the influence of the solvation effect, electronic effect and steric effect on the cyclization was investigated. It is found that all of these effects contribute to the cyclization.     

Theoretical study on solvation effects in chemical reactions: A vibrational coupling model

A vibrational coupling model to treat the solvation effects in chemical reaction rate calculations is proposed and applied to the intramolecular hydrogen transfer reaction CH₃O· → ·CH₂OH in the condensed phase. The effect of solvation is taken into account in two ways: (1) the solvent effect on the activation energy of the reaction is simulated by including 39 surrounding water molecules, represented by fractional charges at the assumed atomic positions, in the potential energy surface calculation; and (2) the vibrational couplings between the 10 nearest solvent molecules and the molecules constituting the reaction system are explicitly included in a vibrational frequency calculation. RRKM theory with Miller's tunneling correction included is employed to calculate the rate constants. The effect of solvation causes a significant change in the chemical reaction rate, mainly through a lowering of the activation energy. The vibrational coupling causes a slight increase of the rate constant in the tunneling region by perturbing the vibrational frequencies of the reactant and transition states, which appear in the rate-constant expression, but has little effect at higher temperatures.     

Influence of Solvent on the Reaction of Diphenyl Carbonyl Oxide with Benzaldehyde

Influence of the solvent on the relative rate constant for the reaction of benzophenone oxide with benzaldehyde has been studied. The solvent influence can be quantitatively described by the semi-empirical Koppel-Palm equation. It is shown that non-specific solvation due to electrostatic interactions lowers, while polarizability enhances the reactivity of diphenyl carbonyl oxide. The specific solvation affects the reaction mainly through the parameter of electrophilicity by decreasing the carbonyl oxide reactivity.     

Effect of nucleophilic solvent on the kinetic parameters of the reactions of unimolecular heterolysis. Mechanism of the covalent bond heterolysis

Reactions of unimolecular heterolysis occur through consecutive formation of four ion pairs: contact, spatially separated, separated by one solvent molecule, and solvent-separated. In the limiting stage, the contact ion pair interacts with the solvent cavity. Nucleophilic solvation hinders the separation of ions in the transition state. At the heterolysis of secondary substrates this is compensated by the nucleophilic solvation of the incipient carbocations from the rear and the reaction rate does not depend on the solvent nucleophilicity. In the case of heterolysis of tertiary substrates, only partial compensation occurs, and nucleophilic solvent reduces the reaction rate through reducing the activation entropy.     

Solvent polarity and organic reactivity in mixed solvents: evidence using a reactive molecular probe to assess the role of preferential solvation in aqueous alcohols

Product selectivities [S = ([ester product]/[acid product]) x ([water]/[alcohol solvent])] are reported for solvolyses of p-methoxybenzoyl chloride (2) in aqueous methanol, ethanol, 2,2,2-trifluoroethanol, n-propyl alcohol, isopropyl alcohol, and tert-butyl alcohol at 25, 35, and 45 degrees C. S values are small and depend significantly on the alcohol cosolvent, varying from 1.3 in methanol to 0.1 in tert-butyl alcohol, but S depends only slightly on the solvent composition, and on the temperature. As S adjusts the product ratios for changes in bulk solvent compositions, it is suggested that preferential solvation by either alcohol or water at the reaction site is not a major factor influencing rates or products. Logarithms of rates of solvolyses of 2 correlate well with Kosower Z values (based on solvatochromism). In contrast, another solvatochromic polarity index, E(T)(30), shows "dispersion" in correlations with the solvent ionizing power parameter, Y(OTs), probably due to aromatic ring and other solvation effects.     

Influence of the composition of acetonitrile-dimethyl sulfoxide solvent on the thermodynamics of silver(I) complexation with piperidine

The influence of the composition of the acetonitrile-dimethyl sulfoxide solvent on the main thermodynamic characteristics (ΔG°, ΔH°, ΔS°) of the complexation between silver(I) and piperidine was studied by the calorimetric and potentiometric methods. Analysis of the obtained experimental material was carried out using the solvation approach based on the thermodynamic solvation characteristics of the reactants.     

Solvent effect on the kinetics of carbamoylation of alcohols

Solvent effect on the rate of the reaction of phenyl isocyanate with alcohols may be described by multiparameter linear equations. Correlation analysis of the effects of various factors showed that specific solvation inhibits the reaction and that increased solvent polarity favors the process.     

Thermometric titration of some amines in water—acetone mixtures

The enthalpies of protonation of some N-bases in H₂O—acetone, 0, 0.25, 0.5, 0.75 and 0.95 mole fraction at 298 K have been determined by calorimetry. Solutions of amines in each solvent system were titrated enthalpimetrically with HClO₄ solution. The bases studied were piperidine, n-butylamine, 2-amino-2-methyl-1,3-propanediol, (AMP), tris(hydroxymethyl) aminomethane, tris, 2,2-bis-(hydroxymethyl-2,2′,2″-nitrilotriethanol, (bis-tris) and pyridine.The results are discussed in terms of the preferential solvation of ions by two types of solvent molecules. The enthalpy of protonation of all the bases passes through a minimum at a solvent composition of 0.75 mole fraction of acetone.