Scavenging of dpph* radicals by vitamin E is accelerated by its partial ionization: the role of sequential proton loss electron transfer

[reaction: see text] Rate constants for reaction of alpha-tocopherol, 2,2,5,7,8-pentamethyl-6-hydroxychroman, and 2,6-di-tert-butyl-4-methylphenol with 2,2-diphenyl-1-picrylhydrazyl radical were measured in solvents of different polarity and H-bond basicity. In ionization supporting solvents besides hydrogen atom transfer (HAT), the kinetics of the process is partially governed by sequential proton loss electron transfer (SPLET). Addition of acetic acid reduces the rate by eliminating SPLET to leave only HAT, while addition of water increases the rate by enhancing phenol deprotonation.     

Podand Solvents for Organic Reactions

Three tris(oxaalkyl)phenylsilanes and two tris(oxaalkyl)phosphates were used as podand solvents in kinetic studies of proton transfer reactions between C-acids: dimethyl (4-nitrophenyl)malonate or phenyl-4-nitrophenylcyanomethane and the strong base: 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD). The acceptor numbers were measured for all new podand solvents. The kinetic parameters for studied reactions were obtained, discussed and compared with those of acetonitrile and OP(OEt) 3 as non-podand solvents. This study demonstrated that the second order rate constants strongly decreased and the energy barrier increased for the proton transfer reaction in podand solvents. Spectroscopic observations showed that ionic products were strongly stabilised and therefore their lifetime was relatively long. The podand solvents formed the ionic channels in which ionic products are strongly solvated.     

Proton transfer in nanoconfined polar solvents. 1. Free energies and solute position

The reaction free energy curves for a model phenol-amine proton-transfer system in a confined CH3Cl solvent have been calculated by Monte Carlo simulations. The free energy curves, as a function of a collective solvent coordinate, have been obtained for several fixed reaction complex radial positions (based on the center-of-mass). A smooth, hydrophobic spherical cavity was used to confine the solvent, and radii of 10 and 15 A have been considered. Quantum effects associated with the transferring proton have been included by adding the proton zero-point energy to the classical free energy. The results indicate the reaction complex position can be an important component of the reaction coordinate for proton-transfer reactions in nanoconfined solvents.     

TS-1催化丙烯环氧化过程中环氧丙烷的开环反应研究

环氧丙烷的开环反应是TS-1催化丙烯环氧化制备环氧丙烷过程的副反应,本文对醇溶剂中开环反应进行了研究,分析了该反应的酸性催化机理,酸性主要来自TS-1与H2O2的相互作用产生的质子酸,醇溶剂能显著增强体系酸性从而加快环氧丙烷的开环反应速度。三种醇按酸性增强程度的顺序为甲醇>异丙醇>仲丁醇。根据反应的Eley-Rideal 机理（吸附态的PO与游离态的醇发生开环反应,表面反应为控制步骤）再考虑各组分在TS-1上的吸附特点提出反应的机理模型。用实验数据进行了回归,得到了令人满意的动力学方程式,实验数据与模型计算值平均偏差小于10％。     

Mechanism of the thermal dehydrochlorination of poly(vinyl chloride) models in the liquid phase

The thermal dehydrochlorination of model compounds of PVC has been investigated in the liquid phase in an inert atmosphere. Electrophilic catalysis and the effect of various solvents on this reaction have been studied. It has been found that the electron-accepting power of the reaction medium is the decisive rate-determining factor, while the dielectric constant comes second. A mechanism of thermal dehydrochlorination has been suggested, in which a reaction between the substrate and the proton giving rise to the carbonium ion is the rate-determining step for the whole process.     

On the Decarboxylation of Metal Trichloroacetates

The decarboxylation of trichloroacetate ion in basic solvents produces the intermediate trichlorocarbanion which may split into chloride and dichlorocarbene or combine with a proton to chloroform. Conditions under which protonation predominates were examined for possible use of the reaction for synthesizing metal compounds in non-aqueous solvents.     

The Baeyer-Villiger oxidation of ketones with Oxone in the presence of ionic liquids as solvents

Cyclic and linear ketones were readily oxidised with Oxone^® at 40 °C in ionic liquids as solvents and short times (2.5-20 h), affording their corresponding lactones and esters in high yields (65-95%). Both, aprotic and protic ionic liquids were used. The best conversion of ketones and the highest yields of products were obtained with 1-buty-3-methylimidazolium tetrafluoroborate and 1-methylimidazolium acetate as solvents. These ionic liquids were also efficiently recycled in the Baeyer-Villiger reaction without significant loss of activity. Several factors, such as the partial solubility of KHSO₅ in the ionic liquid, its viscosity and the presence of a proton in protic ionic liquids, have an influence on the course of the reaction.     

Catalytic hydrogen production at cobalt centres

The catalytic properties of a wide range of cobalt complexes with respect to proton reduction are discussed. Electrocatalytic as well as photocatalytic systems are addressed and to allow comparison between the different systems reported considerable attention is paid to the reaction conditions used. For the photocatalytic proton reduction a range of ruthenium, iridium and rhenium complexes are discussed as potential photosensitizers. The photocatalytic systems are discussed in detail and issues such as the nature of the sacrificial agent and the solvents used. Both intermolecular and intramolecular photocatalysis are considered. The results obtained are considered with respect to the need to the development of sustainable energy sources.     

Dual fluorescence of ellipticine: excited state proton transfer from solvent versus solvent mediated intramolecular proton transfer

Photophysical properties of a natural plant alkaloid, ellipticine (5,11-dimethyl-6H-pyrido[4,3-b]carbazole), which comprises both proton donating and accepting sites, have been studied in different solvents using steady state and time-resolved fluorescence techniques primarily to understand the origin of dual fluorescence that this molecule exhibits in some specific alcoholic solvents. Ground and excited state calculations based on density functional theory have also been carried out to help interpretation of the experimental data. It is shown that the long-wavelength emission of the molecule is dependent on the hydrogen bond donating ability of the solvent, and in methanol, this emission band arises solely from an excited state reaction. However, in ethylene glycol, both ground and excited state reactions contribute to the long wavelength emission. The time-resolved fluorescence data of the system in methanol and ethylene glycol indicates the presence of two different hydrogen bonded species of ellipticine of which only one participates in the excited state reaction. The rate constant of the excited state reaction in these solvents is estimated to be around 4.2-8.0 × 10(8) s(-1). It appears that the present results are better understood in terms of solvent-mediated excited state intramolecular proton transfer reaction from the pyrrole nitrogen to the pyridine nitrogen leading to the formation of the tautomeric form of the molecule rather than excited state proton transfer from the solvents leading to the formation of the protonated form of ellipticine.     

Theoretical study on molecular structures, intramolecular proton transfer reaction, and solvent effects of 1-phenyl-3-methyl-4-(6-hydro-4-amino-5-sulfo-2,3-pyrazine)-pyrazole-5-one

The molecular structures and intramolecular proton transfer reaction of 1-phenyl-3-methyl-4-(6-hydro-4-amino-5-sulfo-2,3-pyrazine)-pyrazole-5-one have been investigated with both ab initio method and the density functional theory. The solvent effects are simulated using the self-consistent reaction field (SCRF) method within the framework of the polarizable continuum model (PCM). The results show that the computed geometrical parameters at the B3LYP levels are in better agreement with experimental values than those at the RHF levels, and the choice of functional in DFT plays an important role in describing the title compound. It is found that strong hydrogen bonds (O–H···N and O···H–N) exist in the title compound, and in the proton transfer process, the O–H bond is broken while the N–H bond is formed. In addition, the order of stability of the isomers remains the same in different solvents, while the barrier height of the proton transfer reaction and dipole moments for the title compound grow with the increase of the solvent polarity. Eventually, the NBO analysis shows that the strength of the hydrogen bond reduces with the increase of the solvent polarity.     

水杨酸及其酯类化合物在不同溶剂中吸收光谱和荧光光谱的研究

本工作测定了水杨酸和水杨酸甲酯在不同溶剂中的吸收光谱和荧光光谱,并按在不同温度下测得的结果计算出它们在不同溶剂中平衡过程的函变△H.数据表明,在质子溶剂中,上述化合物有较小的△H值,即形成的分子内氢键只有较低的稳定性.根据这些结果可对该类化合物在不同溶剂中形成内氢键的能力作出恰当的评价.     

Solid-state tautomerism in 2-carboxyindan-1,3-dione

The structure of 2-carboxyindan-1,3-dione was investigated using a combination of quantum-chemical calculations and solid-state NMR and IR spectroscopy. Due to poor solubility of the compound in different solvents, no single crystals could be obtained. Two dimeric structures formed from the tautomers of 2-carboxyindan-1,3-dione are likely to coexist in the solid state. The dimers interconvert via intramolecular proton transfer in one of the tautomeric forms constituting the dimers. The energy barrier of the intramolecular proton transfer reaction is calculated as 5.82 kcal mol(-1) at the MP2/6-31++G level of theory.     

Kinetic study of the reaction of triphenylphosphine with acrylic acid in alcohol media

Kinetic study of the reaction of triphenylphosphine with acrylic acid in alcohol media was carried out by spectrophotometric method. Use of alcohols as solvents is shown to introduce a specific feature in the kinetic picture of the reaction due to the appearance of parallel channels of proton transfer: from alcohol and from another molecule of acrylic acid in the solution.     

Synthesis of 1,4-dihydropyridines under solvent free conditions and investigation of their photo physical properties

Synthesis of five 4-aryl substituted 1,4-dihydropyridines was developed following condensation of multi component reaction strategy using yttrium triflate as a catalyst. The absorption and fluorescence properties of structurally related 4-aryl 1,4-dihydropyridines in different solvents of varied polarities was investigated. The absorption maxima of these compounds follow no order of solvent polarity and nature of substitution. The spectral characteristics are solvent and compound specific. Fluorophores with electron withdrawing group have larger fluorescence quantum yields and greater solvatochromism than the compounds with electron donating groups. Protic solvents yielded higher fluorescence quantum efficiency. The chemical shift of the proton attached to C-4 and the carbonyl stretching frequency of bis acetyl groups at 3 and 5-positions exhibited a linear relationship with Hammett's para substituent constants while no such relationship exists between the latter and electronic absorption maxima, fluorescence emission maxima, fluorescence quantum efficiency and Stokes shift.     

Molecular spectroscopy of symmetric fragmentary exchange in N-oxypyridinium salts

A number of N-acetyloxypyridinium salts has been studied, using molecular spectroscopy methods. These compounds exist in solutions of bipolar solvents as ions and ion pairs of various structure. The association to ion pairs effects the frequences and intensities of characteristic vibrations, the chemical shifts of proton peaks, and the reaction rate of symmetric exchange of acetyl groups. Based on the spectrochemical correlations, data on the structure of the salts, the acetyl exchange reaction mechanism, and the influence of the solvent nature, the reagent structures, the additions of the base electrolyte and crown-ether on its kinetic characteristics have been obtained.     

醇与极性有机溶剂间氢键的多核NMR研究

醇是一类重要的有机溶剂,对其结构和性质的研究已有很长历史。由于OH的存在,醇分子间存在着较强的氢键缔合作用,使其结构变得复杂,因而较难对它得到一个很清楚的认识。用NMR方法研究氢键也有几十年历史。早在五十年代,Arnold,Becker等就用~1HNMR研究了EtOH在CCl_4中的行为,测量了化学位移随浓度的变化。Becker认为当醇浓度很稀时,体系中只存在单体-二聚体平衡,井结合IR数据求得了平衡常数及缔合物位移。有     

NMR imaging studies of coal

The permeation, transportation and swelling behavior of solvents into coal are investigated by NMR imaging using pyridine-ds and acetone-d6. Images of coal swollen with deuterated solvents illuminate proton distributions of mobile phases within the coal macromolecular networks. More information about the chemical and physical structure of coal can be obtained using NMR imaging techniques.     

An efficient synthesis of tertiary amines from nitriles in aprotic solvents

Tertiary amines are utilized extensively as non-nucleophilic proton scavengers for a number of organic transformations. Herein we report the efficient syntheses of tertiary alkyl amines from their corresponding alkyl nitriles in the presence of a heterogeneous palladium catalyst and a source of dihydrogen in aprotic solvents. The reaction is atom economic, the conditions are mild, and the isolated yields are virtually quantitative. The degree of amine alkylation shows some solvent dependency; in polar protic solvents such as ethanol or methanol, the reaction affords a mixture of products with the secondary alkyl amine as the major product.     

2-(3-巯基-2-吡啶基)苯并咪唑分子内质子转移及溶剂化效应

在B3LYP/6-31G(d,p)和TD B3LYP/6-31++G(d,p)//CIS/6-31G(d,p)水平上,研究了2-(3-巯基-2-吡啶基)苯并咪唑(MPyBI)在气相和七种溶剂(环己烷、苯、三氯甲烷、乙醇、乙腈、二甲亚砜和水)中基态和激发态的分子内质子转移(GSIPT和ESIPT)过程.在基态势能面的研究中发现,该化合物存在分子内双质子转移,其中分步的双质子转移在动力学上具有优势.同时对激发态质子转移势能面及激发态转移过程中的光物理现象进行了研究,结果表明该化合物存在快速的无能垒的激发态分子内质子转移,随着溶剂极性的增强,可以降低基态过渡态的能垒,改变硫醇式与硫酮式互变异构体的比例,从而灵敏地控制荧光的强度.