Cooperative hydrogen bonding in solution: Influence of molecule structure

Influence of cooperative interactions on IR stretching vibration frequencies of complexes CCl₃H⋯ROH⋯B (B-base), CCl₃H⋯ROH⋯O(C₂H₅)₂ and CCl₃H⋯ROH⋯ROH in proton donor solvent CCl₃H were studied.Solvent effects on OH stretching vibration frequencies of CF₃CH₂OH⋯B, ROH⋯O(C₂H₅)₂ and ROH⋯ROH complexes in aprotic solvents were calculated using earlier proposed method. Cooperativity factors in CCl₃H⋯CF₃CH₂OH⋯B complexes were determined. Obtained values were significant smaller than for CCl₃H⋯CH₃OH⋯B complexes. Also cooperativity factors for CCl₃H⋯ROH⋯O(C₂H₅)₂ and CCl₃H⋯ROH⋯ROH complexes were determined. It was demonstrated that obtained values slightly depend on length and embranchment of alkyl group in alcohol molecules. The main role in cooperative interactions plays electronic effect.     

Photocatalytic Conversion of a FeCl<Subscript>3</Subscript>–CCl<Subscript>4</Subscript>–ROH System

The photocatalytic transformations of carbon tetrachloride and aliphatic primary alcohols in the presence of iron trichloride and a molar ratio of components FeCl₃: CCl₄: ROH = 1: 300: 2550 were studied. CCl₄ is transformed into chloroform and hexachloroethane after exposure to a mercury lamp (250 W) to the FeCl₃–CCl₄–ROH system at 20°C, whereas the primary ROH alcohols are selectively oxidized into acetals (1,1-dialkoxyalkanes). The maximum conversion of CCl₄ reaches 80%. The kinetics and mechanism of the photocatalytic conversion of the FeCl₃–CCl₄–ROH system are considered.     

The Effect of Acids on the Kinetics of Cyclopentanone Oxidation by Decanesulfonic Peracid in an Acetonitrile Solution

The kinetics of cyclopentanone oxidation by sec-decanesulfonic peracid is studied. The reaction rate in an acetonitrile (MeCN) solution was lower than in CCl₄. Acid additives are shown to accelerate the reaction in a MeCN medium as distinct from the reaction in a CCl₄ solution. In the framework of the known mechanism of the Bayer–Williger reaction, an equation describing the observed relationships is proposed and parameters that characterize the process kinetics are determined.     

The OH(v = 9) + O3 reaction pathway

The oxygen-hydrogen system, including the reactive species H, O, H₂, O₂, O₃, OH, and HO₂, is very complex, and contains numerous reactions whose kinetics and branches have been insufficiently explored. In the present study we use computer modeling to simulate observations made in a 300-K ozone-hydrogen mixture, in which a critical H₂ pressure leads to rapid ozone decomposition, and generation of high concentrations of atomic oxygen. Initiation of the reaction chain involves heterogeneous O and/or H atom production, and the chain branching step is the reaction OH(v) + O₃ → OH + O + O₂, which is shown to be the predominant pathway for these reactants. The critical H₂ pressure (ca. 3 torr) sets important constraints upon the system kinetics.     

Kinetics and mechanism of transesterification of phenyl salicylate

The first-order rate constants, k₁, obtained for methanolysis and ethanolysis of phenyl salicylate (PSH) in aqueous mixed solvents, fit to a relationship: k₁ = A₁ · [ROH]_T/(1 + A₂[ROH]_T) where A₁ and A₂ are the unknown parameters and [ROH]_T is the total concentration of alkanol. It is proposed that the alkanolysis of PSH involves the preequilibrium formation of monomeric ROH from polymeric (ROH)_n, followed by an intramolecular general base-catalysed nucleophilic attack by monomeric ROH on the carbonyl carbon of the ester. In the mixed solvents containing alkanol and MeCN, the k₁ – [ROH]_T profiles obtained in the presence of K⁺ ions are different from those obtained in the presence of Na⁺ ions which could be attributed to the cation-induced changes in the alkanol structure. Negative KCl salt effect has been observed on methanolysis of PSH, while it is essentially unaffected by the presence of tetraalkylammonium iodide salts (R₄NI). The rates of ethanolysis of PSH have been found to increase with increase in [R₄NI] and this increase becomes more pronounced with increasing hydrophobic surface area of R₄NI. The rate constants for methanolysis of PSH in aqueous mixed solvents containing 80% MeOH (v/v) are independent of [ōH] within the [ōH] range of 0.01 to 0.15 M. The rate of methanolysis could not be detected within ca. 47 h in mixed solvents containing 96% HeOH (3.8% MeCN and 0.2% H₂O), 80% MeOH (19.8% MeCN and 0.2% H₂O), and 0.022 M HCl. It is concluded that for efficient transesterification, PSH should exist in ionized form. The reaction of PSH with MeOH is ca. 400 times faster than that with t-BuOH which could be ascribed to the most likely steric effect. The values of ΔH* and ΔS* obtained for methanolysis and ethanolysis are essentially independent of [ROH] within the ROH content of 20% to 96% for MeOH and 50% to 96% for EtOH. The effect of organic co-solvent on rate of hydrolysis of PSH could be explained in terms of organic co-solvent-induced water polarization.     

Reactions of chloroethenes with atomic chlorine in air at atmospheric pressure

Relative rate method at the temperature of 298 K and pressure of 1013 hPa and GC-MS detection were used for the study of kinetics of the reactions of Cl atoms with H₂C=CCl₂, cis-ClHC=CHCl, trans-ClHC=CHCl, ClHC=CCl₂, and Cl₂C=CCl₂. The reaction products were identified by FTIR spectroscopy. A mechanism for the atmospheric degradation of chloro-ethenes has been suggested.     

Rate coefficient for the reaction of CCl3 radicals with ozone

The rate coefficient for the reaction of CCl₃ radicals with ozone has been measured at 303 ± 2 K. The CCl₃ radicals were generated by the pulsed laser photolysis of carbon tetrachloride at 193 nm. The time profile of CCl₃ concentration was monitored with a photoionization mass spectrometer. Addition of the O₃–O₂ mixture to this system caused a decay of the CCl₃ concentration because of the reactions of CCl₃ + O₃ → products (5) and CCl₃ + O₂ → products (4). The decay of signals from the CCl₃ radical was measured in the presence and absence of ozone. In the absence of ozone, the O₃–O₂ mixture was passed through a heated quartz tube to convert the ozone to molecular oxygen. Since the rate coefficient for the reaction of CCl₃ + O₂ could be determined separately, the absolute rate coefficient for reaction ( 5 ) was obtained from the competition among these reactions. The rate coefficient determined for reaction ( 5 ) was (8.6 ± 0.5) × 10^?13 cm³ molecule^?1 s^?1 and was also found to be independent of the total pressure (253–880 Pa of N₂). This result shows that the reaction of CCl₃ with O₃ cannot compete with its reaction with O₂ in the ozone layer. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 310–316, 2003     

Channel‐forming solvates of 6‐chloro‐2,5‐dihydroxypyridine and its solvent‐free tautomer 6‐chloro‐5‐hydroxy‐2‐pyridone

On crystallization from CHCl₃, CCl₄, CH₂ClCH₂Cl and CHCl₂CHCl₂, 6‐chloro‐5‐hydroxy‐2‐pyridone, C₅H₄ClNO₂, (I), undergoes a tautomeric rearrangement to 6‐chloro‐2,5‐dihydroxypyridine, (II). The resulting crystals, viz. 6‐chloro‐2,5‐dihydroxypyridine chloroform 0.125‐solvate, C₅H₄ClNO₂·0.125CHCl₃, (IIa), 6‐chloro‐2,5‐dihydroxypyridine carbon tetrachloride 0.125‐solvate, C₅H₄ClNO₂.·0.125CCl₄, (IIb), 6‐chloro‐2,5‐dihydroxypyridine 1,2‐dichloroethane solvate, C₅H₄ClNO₂·C₂H₄Cl₂, (IIc), and 6‐chloro‐2,5‐dihydroxypyridine 1,1,2,2‐tetrachloroethane solvate, C₅H₄ClNO₂·C₂H₂Cl₄, (IId), have I4₁/a symmetry, and incorporate extensively disordered solvent in channels that run the length of the c axis. Upon gentle heating to 378 K in vacuo, these crystals sublime to form solvent‐free crystals with P2₁/n symmetry that are exclusively the pyridone tautomer, (I). In these sublimed pyridone crystals, inversion‐related molecules form R²₂(8) dimers via pairs of N—H...O hydrogen bonds. The dimers are linked by O—H...O hydrogen bonds into R⁴₆(28) motifs, which join to form pleated sheets that stack along the a axis. In the channel‐containing pyridine solvate crystals, viz. (IIa)–(IId), two independent host molecules form an R²₂(8) dimer via a pair of O—H...N hydrogen bonds. One molecule is further linked by O—H...O hydrogen bonds to two 4₁ screw‐related equivalents to form a helical motif parallel to the c axis. The other independent molecule is O—H...O hydrogen bonded to two related equivalents to form tetrameric R⁴₄(28) rings. The dimers are π–π stacked with inversion‐related dimers, which in turn stack the R⁴₄(28) rings along c to form continuous solvent‐accessible channels. CHCl₃, CCl₄, CH₂ClCH₂Cl and CHCl₂CHCl₂ solvent molecules are able to occupy these channels but are disordered by virtue of the site symmetry within the channels.     

Desulfurization reaction of cis-1,2-diphenyl-3-aryl-1,4,2-diazaphospholidin-5-thione-2-oxides utilizing an Ag+−H2O or ROH system

A desulfurization reaction of the title compounds, as cyclic substrates, utilizing an Ag⁺−H₂O or ROH system, is described in this article. The diastereoisomerism of ring-opening products and the possible reaction mechanism are also discussed. Themolecular structure of α-(3-phenylureido)-α-(2,4-dichlorophenyl)methylphenylphosphinic acid (4a) was determined by X-ray diffraction. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9: 585–590, 1998     

Synthesis of 2‐Phenylquinoline and its Derivatives by Multicomponent Reaction of Aniline,Benzylamine, Alcohols,and CCl4 Catalyzed by FeCl3·6H2O

2‐Phenylquinolines, 2‐phenyl‐3‐methyl‐quinolines, and 2‐phenyl‐3‐ethylquinolines were synthesized in high yields (78–90%) by the reaction of aniline, benzylamine, aliphatic alcohols (ethanol, n‐propanol, n‐butanol), and CCl₄ catalyzed by FeCl₃·6H₂O in tetrachloromethane.     

The reaction of MgCl2·4H2O with CCl2F2

A new reaction of MgCl₂·4H₂O with CCl₂F₂ is investigated by DTA and TG from room temperature to 350 °C. It is observed that MgF₂ was obtained between 252 and 350 °C, Below the temperature, MgCl₂·4H₂O dehydrates and hydrolyzes to MgCl₂ and Mg(OH)Cl, which are the real reactants of the reaction with CCl₂F₂. The formation of MgF₂ is ascribed to the reaction of MgCl₂ and Mg(OH)Cl with HF, which forms by decomposition of CCl₂F₂ with the taking part in of H₂O released from dehydration of hydrated magnesium chloride on the surface of MgCl₂ and Mg(OH)Cl, which catalyzes the decomposition of CCl₂F₂ in this case. Consequently, the reactions are tested in the fluid-bed condition. It is found that MgF₂ formed at temperatures down to 200 °C in a fluid-bed reactor. This reaction may be used as a method of disposing of the environmentally sensitive CCl₂F₂ (rather than release into the atmosphere). It is also a method for the preparation of MgF₂.     

Organic cluster ions from continuous-flow fast atom bombardment

Cluster ions from fast atom bombardment of liquid alcohols and nitriles were examined using a continuous-flow technique. Protonated molecular M_nH⁺ species are the dominant cluster ions observed in molecules of formula M. The abundances of the M_nH⁺ cluster ions decrease monotonically with increasing n, and within a homologous series the M_nH⁺ abundance diminishes more rapidly for higher molecular mass compounds. Reaction products (ROH)_n(H₂O)H⁺ and (ROH)_n(ROR)H⁺ are observed also in the case of alcohols, and the ion abundances decrease with increasing n. Radiation damage yields fragment ions and ionic alkyl reaction products which are captured in solvent clusters. Semi-empirical molecular orbital methods were used to examine the energetics of cluster ion formation and decomposition pathways. Metastable decomposition processes exhibit only evaporative loss of monomers, with the probability of loss increasing sharply with n. The evaporative ensemble model of Klots was used to predict the cluster size-dependent trends of metastable dissociation processes observed for alcohol and nitrile cluster ions.     

Ritter reactions. VI. Crystal structure of a new multicyclic hydroxy amide clathrate

The compound 9-benzamido-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononen-7-ol,3, has been prepared, and found to crystallise as inclusion complexes ( ₂ ·G where the guest G is ethyl acetate or carbon tetrachloride. The host molecule contains a benzo group as part of a rigid polycyclic framework, on which there are hydroxy and benzamido substituents. The crystal structure of the complex with CCl₄ contains the host molecules hydrogen-bonded in layers, with the CCl₄ molecules trapped between the layers. Two types of host-host hydrogen bonds, OH to amide carbonyl O, and amide NH to hydroxyl O, maintain the host layers. The benzo groups protrude normal to these host layers, and six such groups provide the closest surroundings of the CCl₄, which is constrained to two disordered orientations at the one location. This is a layer clathrate structure. Supplementary Data relating to this article are deposited with the British Library as supplementary publication No. SUP 82110 (13 pages).     

Mechanistic Study of Ozone-Water Reaction and Their Reaction Products with Gas Phase Elemental Mercury:A Computational Study

The interaction of oxygen of water and central oxygen of ozone produces stable H₂O‐O₃ complex with no barrier. With decomposition of this complex through H‐abstraction by O₃ and O‐abstraction by H₂O, four possible product channels have been found. The reaction of mercury and the products of water‐ozone reaction have been studied. All geometrical and AIM parameters of intermediate, transition states, and the products of reactions are calculated and thermodynamic parameters are obtained. The negative value of free energy show that channels Hg+H₂OO, Hg+H₂O₂ and Hg+H₂O₄ in hydrogen tetroxide form (HTO) may be the main reaction channels.     

Solvent extraction behaviour of iodine and bromine in aqueous-organic systems,analogy with radioactive decay

The extraction of iodine and bromine under various conditions from their saturated aqueous solutions by CCl₄, C₆H₆ and o-xylene has been studied. The data obtained from the experiments carried out at various temperatures, for H₂O(I₂)−CCl₄ and H₂O(I₂)−C₆H₆ systems, exhibit an Arrhenius behaviour. The overall activation energy calculated for the extraction in the H₂O(I₂)−CCl₄ system, 650±50 cal·mol⁻¹ is lower than that of H₂O(I₂)−C₆H₆, 3600±300 cal·mol⁻¹. The use of the solubility parameter for the interpretation of the data in the extraction of iodine is investigated. The data obtained in multiple extractions are treated by using the analogy between extraction and radioactive decay. The half number of extraction for each system is determined. The complex curves obtained in the H₂O(I₂)−CCl₄ and H₂O(I₂) −Br₂)−CCl₄ systems are resolved into two components.     

State‐state transitions for CCl2(X1A1, A1B1, a3B1) radical and collisional quenching of CCl2(A1B1 and a3B1) by O2, N2, NO,N2O,NH3, and various aminated molecules

CCl₂ free radicals were produced by a pulsed dc discharge of CCl₄ in Ar. Ground electronic state CCl₂(X) radicals were electronically excited to the A¹B₁ (0,4,0) vibronic state with an Nd:YAG laser pumped dye laser at 541.52 nm. Experimental quenching data of excited CCl₂(A¹B₁ and a³B₁) by O₂, N₂, NO, N₂O, NH₃, NH(CH₃)₂, NH(C₂H₅)₂, and N(C₂H₅)₃ molecules were obtained by observing the time‐resolved total fluorescence signal of the excited CCl₂ radical in a cell, which showed a superposition of two exponential decay components under the presence of quencher. The quenching rate constants k_A of CCl₂(A) state and k_a of CCl₂(a) state were derived by analyzing the experimental data according to a proposed three‐level model to deal with the CCl₂(X¹A₁, A¹B₁, a³B₁) system. The formation cross sections of complexes of electronically excited CCl₂ radicals with O₂, N₂, NO, N₂O, NH₃, and aminated molecules were calculated by means of a collision‐complex model. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 351–356, 2002     

Thermal and Other Properties of New 4,4'-bipyridine-trichloroacetato Complexes of Mn(II), Ni(II) and Zn(II)

New mixed-ligand complexes of general formulae Mn(4-bpy)(CCl₃COO)₂⋅H₂O, Ni(4-bpy)₂(CCl³COO)₂⋅2H²O and Zn(4-bpy)₂(CCl₃COO)₂⋅2H²O (where 4-bpy=4,4’-bipyridine) were obtained and characterized. The IR spectra, conductivity measurements and other physical properties of these compounds were discussed. The central atoms M(II) form coordinate bonds with title ligands. The thermal behaviour of the synthesized complexes was studied in air. During heating the complexes decompose via different intermediate products to Mn₃O₄, NiO and ZnO; partial volatilization of ZnCl₂was observed. A coupled TG-MS system was used to the analysis of the principal volatile thermal decomposition products of Mn(II) and Ni(II) complexes. The principal volatile mass fragments correspond to: H₂O⁺, OH⁺, CO⁺ ₂, HCl⁺, Cl⁺ ₂, CCl⁺ and other. This revised version was published online in August 2006 with corrections to the Cover Date.     

Radiation-induced dechlorination of carbon tetrachloride in cyclohexane and n-hexane mixtures. III. The kinetics of liquid-phase reactions of trichloromethyl radicals

The kinetics of gamma-radiation-induced free-radical chain reactions in solutions of carbon tetrachloride in mixtures of varying composition of cyclohexane and n-hexane was investigated in the temperature range of 296°–413°K. Trichloromethyl radicals were produced by the reaction of radiolytically generated alkyl radicals with the solute. The kinetics of the following reactions were studied: The following rate expression was obtained: The error limits are the standard deviation from the least mean-square Arrhenius plots. The present results, combined with previously measured activation parameters for hydrogen-atom abstraction from c-C₆H₁₂ and n-C₆H₁₄ by CCl₃ radicals relative to CCl₃ combination, afford experimental evidence that the decay of trichloromethyl species in alkane solutions is a diffusion-limited process. The thesis that activation energies of reactions (4) and (5) in the liquid phase are equal to their respective values in the gas phase is confirmed.     

Standard Molar Enthalpies of Formation of Ce(TCA)_3·3H_2O(s) and Ce(TCA)(C_9H_6NO)_2(s)

IntroductionBothrareearthions1and 8 hydroxyquinolineareofantibacterialfunction ,2 andtheircomplexeshavemorepowerfuldisinfection .Theirbinarycomplexeswerereport edasearlyasin 196 3.Atthesametime ,theresearchontheirternarycomplexeshavebecomeveryactiveinrecentyears,andtheyarewidelyappliedinmanyfields .3 6Dong6 reportedthesynthesisandcharacterizationofthecomplexesofrareearthtrichloroaceticacidsaltswith 8 hy droxyquinoline.Itsapplicationinleathermouldyproofshowedthatthecomplexeshavepowerfuldisinfe…     

The kinetics of radiation-induced hydrogen abstraction by CCl3 radicals in the liquid phase: Cyclohexene

The kinetics of hydrogen abstraction from cyclohexene by CCl₃ radicals were studied in CCl₄ solution as a function of cyclohexene concentration and temperature in the range of 26–140°C. The CCl₃ radicals were produced both by radiolysis of CCl₄ and by photolysis of CCl₃Br. The rate constant for the reaction was found to be given by the equation where θ = 2.303 RT kcal/mol. This activation energy leads to C? H bond strength for the allylic hydrogen of 85 ± 1 kcal/mol, which means a resonance stabilization energy of 11 ± 1.5 kcal/mol for the C-C₆H₁₁ radical.