Mesoporous material as catalyst for the production of fine chemical: Synthesis of dimethyl phthalate assisted by hydrophobic nature MCM-41

Aluminum, iron and zinc containing MCM-41 molecular sieves were prepared by the hydrothermal method. The catalyst was characterized by the XRD, BET (surface area), FT–IR and ²⁹Si, ²⁷Al MAS–NMR techniques. The catalytic activity of these molecular sieves was tested with esterification reaction used with phthalic anhydride (PAH) and methanol (MeOH) in the autoclave at 135 °C, 150 °C and 175 °C. Conversion increases with an increase in temperature and mole ratio. The activity of these catalysts followed the order: Al-MCM-41 (112) > Fe-MCM-41 (115) > Al-MCM-41 (70) > Al-MCM-41 (52) > Fe-MCM-41 (61) > Al, Zn-MCM-41 (104) > Al-MCM-41 (30). The reaction yielded both monomethyl phthalate (MMP) and dimethyl phthalate (DMP). The nature of the catalyst sites has been proposed using with water as an impurity. The selectivity of the dimethyl phthalate increases with increase in temperature and mole ratio. The weight of the catalyst was optimized at 0.07 g. The hydrophilic and hydrophobic nature of the catalyst has been explained by the influence of water and the external surface acidity also facilitates the reaction and this has been confirmed by the supporting reaction.     

Study of the reaction of chalcone analogs of dehydroacetic acid and o-aminothiophenol: synthesis and structure of 1,5-benzothiazepines and 1,4-benzothiazines

Treatment of α,β-unsaturated carbonyl compounds, obtained by the reaction of DHA and aromatic (or heteroaromatic) aldehydes, with o-aminothiophenol results in the formation of 1,5-benzothiazepines and/or 1,4-benzothiazines depending upon the reaction conditions and structure of the aldehydes. The products were characterized by the combined use of multinuclear 1D and 2D NMR and GIAO/DFT calculations of ¹H, ¹³C and ¹⁵N chemical shifts. The tautomerism of these compounds in solution was determined, they have an exocyclic CC double bond.     

The effect of vibrational bond stretching on rotational inelastic electron-molecule scattering

Differential cross sections for state-to-state rotationally inelastic electron-Na₂ scattering, with the molecule being in the vibrational levelv′'=31, are measured at a collision energy of 150 eV. Angular momentum transfer of up to Δj=26 is observed, which is even more than previously obtained for the vibrational ground statev′'=0. Good agreement is found with theoretical results from a spectator scattering model. This work, in general, elucidates the role of vibrational excitation in collision dynamics under vibrationally sudden conditions.     

A Method for the Acetylation of Alcohols Catalyzed by Heteropolyoxometallates

Summary. Esterifications of acetic acid with some linear, secondary, tertiary, and benzylic alcohols mediated by catalytic amounts of Keggin, Wells–Dawson, and Preyssler type heteropolyacids were carried out under reflux at mild reaction conditions with good to excellent yields. Among the examined catalysts, H₃PW₁₂O₄₀ and H₁₄NaP₅W₃₀O₁₁₀ revealed better results than other heteropolyacids. This work was performed with the aim of simplifying the esterification process by omitting any solvents and mineral acid catalysts. Easy work-up, low cost, and acidic waste reduction, which are all important features from the environmental and economical points of view, are distinct aspects of this protocol. Heteropolyacid catalysts could be separated after a simple work-up and reused for several times.     

Structural features of some small carbonyls in the 1,3nπ states: An mcscf study

Structural features of a series of tetraatomic carbonyls in the ^1,3nπ* states are studied by using a recently proposed MCSCF algorithm at the INDO/2 level. The computed geometrical parameters and the inversion barrier heights agree quite well with the available experimental or ab initio theoretical data. The calculated transition energies turn out to be somewhat lower than the experimental counterparts. The specific MCSCF algorithm used is found to have excellent convergence properties.     

Amperometric determination of organic isothiocyanates

An amperometric titration method is described for the determination of 1-5 mg of organic isothiocyanates, based on their quantitative reaction with n-butylamine in dimethylfonnamide to form N,N-disubstituted thioureas which are then titrated amperometrically in aqueous ammonia-ammonium nitrate buffer with silver nitrate (dropping mercury electrode at -0.56V). The end-point corresponds to a silver:thiourea ratio of 2:1, with precipitation of silver sulphide. The method is simple, accurate, widely applicable, and gives reproducible results.     

Electronic, cyclic voltammetry, IR and EPR spectral studies of copper(II) complexes with 12-membered N4, N2O2 and N2S2 donor macrocyclic ligands

A new series of copper(II) complexes have been synthesized with macrocyclic ligands having three different donating atoms in the macrocyclic ring. It has been shown that the stereochemistry of complexes is dependent on the coordinated anions. These complexes are characterized by various physicochemical techniques, viz. elemental analysis, molar conductance, magnetic susceptibility measurements, IR, electronic, 1H NMR and EPR spectral studies. Cyclic voltammetric behavior of the complexes has also been discussed. The observed anisotropic g-values indicate that the chloro and acetato complexes are six-coordinate tetragonal. Whereas the sulfato and nitrato complexes are found to have five-coordinate square-pyramidal and four-coordinate square-planar geometry, respectively.     

Oxidation of cyclohexane with molecular oxygen using a Schiff base cobalt complex bonded to carbamate-modified silica gel

The Schiff base [1,2-bis(salicylidene amino)phenylene]cobalt(II) complex, chemically bonded to a carbamate-modified silica gel catalyst, has been prepared by a four step procedure. The oxidation of cyclohexane was studied in the presence of this catalyst under relatively mild conditions (150–200 °C, 15–20 atm) using molecular oxygen. The catalyst was found to be very selective for the production of cyclohexanol, with cyclohexanone formed in only a small amount (45:1). This is in contrast to the commercially available processes in which cyclohexanol and cyclohexanone are both formed in appreciable amounts. The t.g.a. analysis shows the catalyst to be stable up to 211 °C and atomic absorption spectroscopy indicated negligible metal loss during 50 h use of the catalyst up to 180 °C.     

Water as an Efficient Solvent for Oxygenation Transformations with 34% Hydrogen Peroxide Catalyzed by some Heteropolyoxometalates

Summary. A highly efficient, selective, fast, and cheap protocol is developed for oxidation of aromatic amines and alcohols utilizing 34% hydrogen peroxide in water catalyzed by some W- and Mo-based heteropolyoxometalates. Findings showed that dodecatungstophosphoric acid, H₃PW₁₂O₄₀, was the most efficient catalyst in the examined oxidation reactions. This methodology may prove to be a valuable alternative for eco-friendly green oxidation. Inherent simplicity, easy work up, and using regenerable catalysts were other key aspects of this oxidation protocol.     

Headspace solvent microextraction of trihalomethane compounds into a single drop

Headspace solvent microextraction (HSME) into a single drop is developed for the determination of six trihalomethanes, CH2Cl2, CHCl3, C4H9Cl, CCl4, C2HCl3, and C2Cl4, in aqueous solution. A drop of benzyl alcohol containing bromoform, as an internal standard, is used for extraction. The analytes are extracted by suspending a 3-microL drop directly from the needle of a microsyringe. The needle passes through the septum of a vessel, and the needle tip appears above the surface of the solution. After the prescribed extraction time, the drop is drawn back into the syringe. The syringe is then removed, and its content is injected directly into a gas chromatography column for analysis. The main parameters affecting the HSME process, such as stirring speed, microdrop volume, sample solution temperature, microsyringe needle temperature, sample volume, solution pH, extracting solvent, and ionic strength of the solution, are studied. Also, the linear range and precision of the method are examined.