Selective formation of aromatic amines by selenium-catalyzed reduction of aromatic nitro compounds with CO/H2O under atmospheric pressure

An efficient method for the catalytic reduction of aromatic nitro compounds to the corresponding aromatic amines is reported. In the presence of selenium as a catalyst, the aromatic nitro compounds are quantitively reduced by CO/H2O to form the corresponding amines under atmospheric pressure. The reduction occurs in high selectivity regardless of other reducible functionalities present on the aromatic ring. There exists a phase transfer process of the catalyst selenium in the reaction. (C) 2004 Elsevier B.V. All rights reserved.

Efficient reductive selenation of aromatic aldehydes to symmetrical diselenides with Se/CO/H2O under atmospheric pressure

An efficient method for the synthesis of symmetrical diselenides is described. Reductive selenation of aromatic and heterocyclic aromatic aldehydes (ArCHO) with Se/CO/H2O in DMF afforded diselenides (ArCH2SeSeCH2Ar) in yields up to 94% under atmospheric pressure without use of a base.

Pd/C-catalyzed hydrodehalogenation of aromatic halides in aqueous solutions at room temperature under normal pressure

The hydrodehalogenation of aromatic halides, catalyzed by Pd/C in aqueous solutions, yields arenes in short reaction times at room temperature under normal pressure. The nature of the solvents has an important influence on the reaction rates and the activity of the catalyst. The catalyst shows the highest activity in water. In the hydrodechlorination of 4-chlorohypnone, it was in water that C-Cl bond was easier to be hydrogenated, and in isopropanol that C=O was easier to be hydrogenated. (C) 2004 Elsevier B.V. All rights reserved.

Ultrafast dynamics of dye molecules in solution as a function of temperature

Femtosecond time-resolved studies using fluorescence depletion spectroscopy were performed on Rhodamine 700 in acetone solution and on Oxazine 750 in acetone and formamide solutions at different temperatures. The experimental curves that include both fast and slow processes have been fitted using a biexponential function. Time constants of the fast process, which corresponds to the intramolecular vibrational redistribution (IVR) of solute molecules, range from 300 to 420 fs and increase linearly as the temperature of the environment decreases. The difference of the average vibrational energy of solute molecules in the ground state at different temperatures is a possible reason that induces this IVR time-constant temperature dependence. However, the time constants of the slow process, which corresponds to the energy transfer from vibrational hot solute molecules to the surroundings occurred on a time scale of 1-50 ps, changed dramatically at lower temperature, nonlinearly increasing with the decrease of temperature. Because of the C-H...O hydrogen-bond between acetone molecules, it is more reasonable that acetone molecules start to be associated, which can influence the energy transfer between dye molecules and acetone molecules efficiently, even at temperatures far over the freezing point.

Orientation and alignment of reagent molecules by two-photon excitation

The expressions used for describing the angular distribution of oriented and aligned reagent molecules are derived. The algebraic forms of orientation and alignment parameters of molecules in the excited states are obtained for two-photon excitation. The reagent molecules after absorbing two-photon may produce the higher order orientation and alignment than doing one-photon. (C) 2002 Elsevier Science B.V. All rights reserved.

Ultrafast vibrational and thermal relaxation of dye molecules in solutions

Intra- and intermolecular relaxations of dye molecules are studied after the excitation to the high-lying excited states by a femtosecond laser pulse, using femtosecond time-resolved stimulated emission pumping fluorescence depletion spectroscopy (FS TR SEP FD). The biexponential decays indicate a rapid intramolecular vibrational redistribution (IVR) depopulation followed by a slower process, which was contributed by the energy transfer to the solvents and the solvation of the excited solutes. The time constants of IVR in both oxazine 750 and rhodamine 700 are at the 290-360 fs range, which are insensitive to the characters of solvents. The solvation of the excited solutes and the cooling of the hot solute molecules by collisional energy transfer to the surrounding takes place in the several picoseconds that strongly depend on the properties of solvents. The difference of Lewis basicity and states density of solvents is a possible reason to explain this solvent dependence. The more basic the solvent is, which means the more interaction between the solute and the neighboring solvent shell, the more rapid the intermolecular vibrational excess energy transfer from the solute to the surroundings and the solvation of the solutes are. The higher the states density of the solvent is, the more favorable the energy transfer between the solute and solvent molecules is.

Autler-townes splitting in the multiphoton resonance ionization spectrum of molecules produced by ultrashort laser pulses

We report for the first time the proper conditions to observe Autler-Townes splitting (ac-Stark splitting) from vibrationally coherent states belonging to the different electronic terms of a diatomic molecule. Wave packet dynamics simulations demonstrate that such a process is feasible by multiphoton resonance ionization of the molecule Na-2 with a single ultrashort intense laser pulse. With the ultrahigh time resolution of a femtosecond laser pulse, one can directly measure the absolute value of the transition dipole moment between any kinds of molecular states by this kind of Autler-Townes splitting, which is a function of the internuclear distance R.

Controlling the orientation and alignment of reagent molecules by a polarized laser

The expressions used for controlling the alignment and orientation of reagent molecules are derived. The problem to the control of the orientation and alignment of reagent molecules by the polarization direction and propagation direction of laser is discussed.

Analysis of aromatic amines by high-performance liquid chromatography with pre-column derivatization by 2-(9-carbazole)-ethyl-chloroformate

2-(9-Carbazole)-ethyl-chloroformate (CEOC), a novel pre-column fluorescence derivatization reagent, has been developed for the analysis of aromatic amines. Taking five monocyclic aromatic amines (o-toluidine, aniline, 3,4-dimethylaniline, N-ethyl-p-toluidine, and p-phenylenediamine) as testing compounds, derivatization conditions such as pH of borate buffer, reaction time and fluorescent tagging reagent concentration have been investigated. By a one-step procedure, CEOC reacts readily with the aromatic amines to form stable derivatives with excitation and emission wavelengths, respectively, at 293 and 360 nm. This derivatization reaction could be finished within 20 min even at room temperature. The peak shapes of the derivatized aromatic amines can be improved greatly without any addition of competition amines into the mobile phase. Furthermore, this method can offer excellent quantitative precision with high tolerance of the matrix of samples. (C) 2003 Elsevier B.V. All rights reserved.