Search results for "Solvent"

Über gemischte Gruppe 14—Gruppe 14-Bindungen

1991

Abstract p-Tol6PbSn has been synthesized by reaction of p-Tol3PbLi with p-Tol3SnI in THF/ether (1:2) at −78°C. The crystal structures of p-Tol4Pb (I 4 ) and of p-Tol6Sn2, p-Tol6PbSn and p-Tol6Pb2 have been determined. The three dinuclear compounds crystallize not strickly isomorphous. They exhibit the same space group (R 3 and rather similar unit cell dimensions. Yet according to the solvent of crystallization, two types with differing atomic position parameters can be distinguished (“homoeotypism with differences of parameters” in the definition of Laves). In both types, the individual molecules have a chiral C3-symmetric conformation and the non-chiral unit cell encloses both enantiomers.…

A density functional theory study for the Diels–Alder reaction between N-acyl-1-aza-1,3-butadienes and vinylamines. Lewis acid catalyst and solvent e…

2002

Abstract The molecular mechanism for the Diels–Alder reaction of N-acyl-1-aza-1,3-butadiene with dimethylvinylamine has been studied using density functional theory methods. This cycloaddition is the nucleophilic attack of the vinylamine to the conjugate position of the unsaturated acyl imine with concomitant ring-closure. The presence of a Lewis acid catalyst coordinated to the acyl oxygen atom decreases markedly the activation energy associated to the nucleophilic attack. This results from an increasing of the electrophilicity of the 1-aza-1,3-butadiene that shift the mechanism from a highly asynchronous concerted process to a polar stepwise one.

Crystal structures and thermal behavior of bis[dibenzyldimethylammonium]CuBr4, bis[dibenzyldimethylammonium]CuCl4 and bis[dimethyldi(2-phenylethyl)am…

2006

Abstract Bis[dibenzyldimethylammonium]CuBr4, bis[dibenzyldimethylammonium]CuCl4 and bis[dimethyldi(2-phenylethyl)ammonium]CuBr4 were crystallized from acetonitrile and/or dilute HX solutions. Five different kinds of single crystals were obtained. In the case of bis[dibenzyldimethylammonium]CuX4 (X=Br or Cl), the acetonitrile molecules cocrystallized into the crystal structure when acetonitrile solution was used. As a result, the isomorphic structures of Bis[dibenzyldimethylammonium]CuX4·0.5 CH3CN (X=Br or Cl) in monoclinic space group P21/n were obtained. When a dilute HX solution was used, the bis[dibenzyldimethylammonium]CuX4 (X=Br or Cl) crystallized without solvent molecules. The formed…

Fluorinated heterocyclic compounds. A photochemical synthesis of 3-amino-5-perfluoroaryl-1,2,4-oxadiazoles

2001

Abstract A photochemical methodology for the synthesis of 3-amino- (or 3- N -substituted amino) 5-pentafluorophenyl-1,2,4-oxadiazoles is reported. Irradiation of 3-pentafluorobenzoylamino-4-methyl-1,2,5-oxadiazole (Furazan) at 254 nm in methanol and in the presence of ammonia, primary or secondary aliphatic amines produces 3-amino-, 3-( N -alkylamino)-, 3-( N , N -dialkylamino)-5-pentafluorophenyl-1,2,4-oxadiazoles. The photoreaction follows the fragmentation pattern of the furazan ring with the extrusion of acetonitrile and the formation of a counterpart fragment which the nitrogen nucleophile will capture. Depending on the nature of the reagent, displacement of a fluoride anion at the C(5…

PAINTS | Organic Solvent-Based

2005

Raman and theoretical study of the solvent effects on the sizable intramolecular charge transfer in the push-pull 5-(dimethylamino)-5'-nitro-2,2'-bit…

2006

In this paper, we analyze the degree of intramolecular charge transfer in a push-pull π-conjugated system, 5-(dimethylamino)-5'-nitro-2,2'-bithiophene, from changes in frequencies and relative intensities of its strongestRaman scatterings in a bunch of solvents with different polarities. Density functional theory (DFT) was used as a support of the experimental study. Solvent effects on the molecular and electronic structures and on the vibrational properties were estimated by performing B3LYP/6-31G** calculations within the framework of the polarized continuum model (PCM) developed by Tomasi. Calculations reveal that the molecule is highly polarized in the ground state and behaves as a very…

Conductance in isodielectric mixtures. I.n-butyronitrile with dioxane, benzene, and carbon tetrachloride

1974

The conductance of tetrabutylammonium tetraphenylboride, picrate, nitrate, and bromide has been measured at 25°C inn-butyronitrile and in mixtures of this solvent with dioxane, benzene, and carbon tetrachloride covering the range of dielectric constants from 10–24.26. For the picrate, nitrate, and bromide, the association constants at a given dielectric constant are independent of the chemical composition of the solvent. The changes of Walden products with solvent composition, however, are different, depending on which other solvent is mixed with the butyronitrile.

Conductance in isodielectric mixtures. III.i-butyronitrile with chlorobenzene,o-dichlorobenzene,p-dichlorobenzene, 1,2-dichloroethane, andn-pentanol

1975

The conductance of tetrabutylammonium tetraphenylboride, picrate, perchlorate, and nitrate has been measured at 25°C in mixtures ofi-butyronitrile with chlorobenzene,o-dichlorobenzene,p-dicholorobenzene, 1,2-dichloroethane, andn-pentanol covering the range of dielectric constants 10≤D≤20. In these mixtures of polar solvents, both association constants and ionic mobilities depend on ion-solvent interaction energies and on free volume in a manner that is specific for each system. This failure of the primitive model (rigid charged spheres in a continuum) is shown to be the consequence of short-range spatial and energetic interactions between ions and adjacent solvent molecules.

The role of distannoxanes in the synthesis of dimethyl carbonate from carbon dioxide

2003

Abstract The synthesis, characterization, and reactivity of 1,3-dimethoxytetrabutyldistannoxane were investigated in connection to the mechanism of the selective synthesis of dimethyl carbonate from CO2 and methanol. A new distannoxane, 1-methoxy-3-methylcarbonatotetrabutyldistannoxane, resulting from a 1:1 adduct with CO2 was isolated and characterised by volumetry, multinuclear NMR and IR spectroscopies. When this compound was submitted to 20 MPa of CO2 at 423 K in toluene no dimethyl carbonate was formed, conversely to dibutyldimethoxystannane. However, when methanol was the solvent, dimethyl carbonate was selectively produced. A promoting effect of Si(OCH3)4 was evidenced through methox…

Structural and spectroscopic study of the Br2...3-Br-pyridine complex by DFT calculations.

2007

Abstract The structure and the Raman vibrational spectrum of the complex Br 2 ⋯3-Br-pyridine are determined by DFT calculations using different parametrizations. The calculations are performed taking into account the effects of the dichloromethane as solvent by the CPCM method. A value of 39 kJ mol −1 for the formation enthalpy and of 1 kJ mol −1 for the formation free energy at room temperature in presence of the solvent is found. The predicted Raman spectrum is compared with the experimental one and the essential features of the spectrum are well reproduced by the B3LYP parametrization. The intensity changes of the bands when going from the free moieties to the complex are also generally …