Thermodynamic dissociation constants of salicylic and monochloroacetic acids in mixed solvent systems from conductance measurements at 25°C

The molar conductances of dilute solutions of salicylic and monochloroacetic acids in binary mixtures of methanol, ethanol, 1-propanol, N,N-dimethylformamide, acetone, acetonitrile, tetrahydrofuran and dioxane with water have been measured at 25°C. The Lee-Wheaton conductance equation was fitted to the data in order to derive thermodynamic dissociation constants and limiting molar conductances. The results were compared with those in the literature pertaining to analogous media, mostly derived potentiometrically. The findings are interpreted in terms of a solvent effect on the ionization of these acids in mixed solvent systems.This paper is dedicated to the late Professor Raymond M. Fuoss on his 3^rd anniversary.     

Theoretical investigation of 1,4-dioxane complexes with water in the <Emphasis Type="Italic">chair</Emphasis> conformation by semiempiric MNDO/PM3 method

The structure and relative stability of 1,4-dioxane-water, (Diox)_n·(H₂O )_m (n = 1, 2, m = 1–6), molecular complexes have been calculated by semiempirical MNDO/PM3 method. A considerable variety of (Diox)_n·(H₂O )_m isomeric structures was stated. The mean energy of O_Diox…H_W-O_W hydrogen bond in (Diox)_n·(H₂O)_m complexes formed by 1,4-dioxane molecules in the chair conformation amounts to ?2.293 ± 0.210 kcal/mol with the average bond length 2.797 0.015 Å.     

Structural Study of C-undecylcalix[4]resorcinarene Solvate with Dioxane

The crystal structure of the molecular complex of C-undecylcalix[4]resorcinarene with dioxane has been determined by X-ray analysis. The asymmetric unit contains one host and four guest molecules. The calix[4]resorcinarene moiety adopts a bowl conformation with C_4v symmetry. Four undecyl chains are axially oriented. Calix molecules are packed in a bowl-to-bowl fashion with alternating hydrophilic and hydrophobic layers. One of the hydrophilic dioxane molecules is located at the rim of the calix moiety and is hydrogen bonded to the other one. There is no interaction to attract, or direct the dioxane molecule into the interior of the cavity. There is an exo complex formed. The dioxane molecules – located in the hydrophobic part – are highly disordered.     

Free energies of transfer of complexes of the type MCl2py4 between pyridine and other solvent media

Solubility isotherms are reported for the NiCl₂·4py, MnCl₂·4py, and MnCl₂·2py solid pyridinates in a number of pyridine+diluent mixtures at 25°C. Activity coefficients of the solvent components have been derived from the total vapor pressures measured by a static method. The standard free energies of transfer for the NiCl₂py₄ and MnCl₂py₄ complexes are the same, within the experimental error, in the pyridine+aprotic diluent mixtures, while marked differences are observed in the pyridine+chloroform mixtures. Marked deviations are observed for chloroform and 1,2-dichloroethane from a correlation between the standard free energy of transfer of the complexes, on one hand, and the Hildebrand's solubility parameter of the solvent, on the other, the latter correlation being roughly valid for aprotic solvents. The deviations are tentatively ascribed to hydrogen bond formation of the type H... between the protic solvents and the coordinated pyridine molecules, enhanced by the d electron delocalization.     

Vibrational Spectroscopic Investigations of M(Imidazole)2Ni(CN)4·2 Dioxane Clathrates

Four new clathrates of the formula M(Im)2Ni(CN)4·2·Dioxane (where M = Co, Ni, Cu, Cd; Im = Imidazole) have been prepared in powder form and their FT-IR and laser-Raman spectra are reported for the first time. These clathrates are analogues to the previously reported classical Hofmann type clathrates except for the copper clathrate. The Cu clathrate has different spectral features in comparison with its analogues due to the Jahn-Teller effect.     

Freezing temperatures of aqueous solutions of methyl formate and ethyl acetate with a variety of nonelectrolytes. Gibbs energy of interaction of the ester group with other functional groups

Freezing temperatures of dilute aqueous solutions of ethyl acetate and mixtures with myo-inositol, D-mannitol, formamide, 1,3,5-trioxane, 1,4-dioxane, acetamide, hexamethylenetetramine, and methyl formate have been measured. In addition, freezing temperatures of dilute aqueous solutions of methyl formate and mixtures with the above solutes have been measured. From these data, the pairwise molecular Gibbs energies of interaction between the molecules were calculated. Using the additivity principle, the pairwise functional group Gibbs energies of interaction were calculated for ester group interactions with a variety of other functional groups.     

无外加催化剂条件下芳香醛与活性亚甲基化合物的缩合反应和迈克尔加成反应

在DMF溶剂中,不外加催化剂使芳香醛(1)与2,2-二甲基-1,3-二氧六环-4,6-二酮(2)发生缩合反应生成2,2-二甲基-5-芳亚甲基-1,3-二氧六环-4,6-二酮(3a～f)。在同样条件下,芳香醛与5,5-二甲基-1,3-环己二酮(4)则发生缩合和迈克尔加成反应生成2,2’-芳亚甲基双(3-羟基-5,5-二甲基-2-环己烯-1-酮)(5a～h)。用单晶X-射线分析法确定了产物5b的晶体结构。     

N‐Methylpiperidine—A Useful Base Catalyst in the Morita–Baylis–Hillman Reaction

N‐methylpiperidine, a commercially available mild base, has effectively been utilized as a catalyst in the Morita–Baylis–Hillman reaction. Moderate to excellent yields (34–95%) and significant rate enhancement have been observed.     

Capillary zone electrophoretic studies of ion association between inorganic anions and tetraalkylammonium ions in aqueous-dioxane media

Ion association between inorganic anions and symmetrical tetraalkylammonium ions, R4N+ (R = Me, Et, Pr, n-Bu, n-Am, and 2-methyl butyl {isoamyl = iAm}) was investigated using ordinary silica capillary by capillary zone electrophoresis. An improved version of the Williams-Vigh method was used for the first time to measure the mobilities of the inorganic anions. Plots of log Kass against log dielectric constant in various media, revealed a smaller change in Kass compared to dielectric constant. These plots suggest that the Bjerrum's equation is inadequate in accounting for the associations of ions in a CZE setup.