Promoting effects in hydrogenation and hydrodesulfurization reactions on the zirconia and titania supported catalysts

Tetralin hydrogenation (HYD) and thiophene hydrodesulfurization (HDS) were studied for the supported MoS2 and WS2 sulfides, either non-promoted or promoted with Co and Ni. The supports used were ZrO2, alumina-stabilized TiO2 and pure alumina. Preparation of catalysts included presulfidation of non-promoted system with subsequent addition of promoter and resulfidation. It has been found that the nature of promoter plays determining role for the catalytic performance. The most active in both HYD and HDS reactions are Ni-promoted Mo and W catalysts, supported on ZrO2. (C) 2003 Published by Elsevier B.V.

Proton transfer reactions within the pyridazine-methanol cluster ion

The multiphoton ionization of the hydrogen-bonding cluster pyridazine-methanol (C4H4N2-CH3OH) was studied using a time-of-flight mass spectrometer at the wavelengths of 355 and 532 nm. At both wavelengths, a series of protonated C4H4N2-(CH3OH)(n)-H+ cluster ions were obtained. Relevant ab initio calculations were performed with HF and B3LYP methods. Equilibrium geometries of both neutral and ionic C4H4N2-CH3OH clusters, and dissociation channels and dissociation energies of ionic clusters, are presented. The results show that when C4H4N2-CH3OH is vertically ionized, C4H4N2H+ and CH3O are the dominant products via proton transfer reaction. A high energy barrier makes another channel corresponding to the production of C4H4N2H+ and CH2OH disfavored. (C) 2002 Elsevier Science B.V. All rights reserved.

Syntheses, structures and reactions of a series of beta-diketiminatoyttrium compounds

This paper describes the synthesis and selected reactions of a series of crystalline mono(beta-diiminato) yttrium chlorides 3a, 3b, 4a, 4b, 5a, 5b, 5c and 9. The X-ray structure of each has been determined, as well as of [YCl(L-4)(2)] (6), [Y(L-1)(2)OBut] (7) and [Y{CH(SiMe3)(2)}(thf)(mu-Cl)(2)Li(OEt2)(2)(mu-Cl)](2) (8).

Influence of compressed carbon dioxide on hydrogenation reactions in cyclohexane with a Pd/C catalyst

The potential of CO2-expanded liquid media for chemical reactions has been examined in this work, using cyclohexane as a solvent and Pd/C as a heterogeneous catalyst for hydrogenation of styrene, citral, and nitrobenzene with H-2. The rate of hydrogenation reactions is increased, and the product selectivity is altered in the CO2-expanded cyclohexane phase. In the hydrogenation of citral, the selectivity to citronellal decreases with CO2 pressure, which changes from similar to 80% in the neat cyclohexane to similar to 65% at 16 MPa.

Polyethylene glycol-stabilized platinum nanoparticles: The efficient and recyclable catalysts for selective hydrogenation of o-chloronitrobenzene to o-chloroaniline

In the present work, platinum nanoparticles were prepared by in situ reduction with polyethylene glycols (PEGs). The catalytic performance of Pt nanoparticles immobilized in PEGs (Pt-PEGs) is discussed for the hydrogenation of o-chloronitrobenzene (o-CNB). A high selectivity to o-chloroaniline (o-CAN) of about 99.7% was obtained with the Pt-PEGs catalysts at the complete conversion of o-CNB, which is much higher than that (83.4%) obtained over the conventional catalyst of Pt/C. The Pt nanoparticies could be immobilized in PEGs stably and recycled for four times with the same activity and selectivity. It presents a promising performance in the hydrogenation and its wide application in catalytic reactions is expected.

Ring-Opening/Recyclization Reactions of (Dimethylamino)propenoyl-Substituted Cyclopropanes: Facile Synthesis of Halogenated Pyridin-2(1H)-ones

A facile and efficient synthesis Of Substituted pyridin-2(1H)-ones has been developed by the reaction of readily available 1-carbamoyl-]-[3-(dimethylamino)propenoyl]cyclopropanes with phosphoryl chloride or phosphorus tribromide in dichloromethane at room temperature.

Why [6,6]- and 1,2-Benzal-3-N-4-O-Cyclic Phenylimidate C-60 Undergo Electrochemically Induced Retro-Addition Reactions while 1,4-Dibenzyl-2,3-Cyclic Phenylimidate C-60 Does Not? C-H center dot center dot center dot X (X = N, O) Intramolecular Interactions in Organofullerenes

The electrochemical properties of a series of structurally related fullerooxazoles, [6,6] cyclic phenylimidate C-60 (1), 1,2-benzal-3-N-4-O-cyclic phenylimidate C-60 (2), and 1,4-dibenzyl-2,3-cyclic phenylimidate C-60 (3), are described, and the spectroscopic characterizations of their anionic species are reported. The results show that compounds I and 2 undergo retro-cycloaddition reactions that lead to the formation of C-60 and C61HPh, respectively, upon two-electron-transfer reduction. However, compound 3 demonstrates much more electrochemical stability as no retro-cycloaddition reaction occurs under similar conditions. Natural bond orbital (NBO) calculations on charge distribution show there is no significant difference among the dianions of 1, 2, and 3, indicating that the electrochemical stability of 3 is unlikely to be caused by the charge distribution difference of the dianions of three compounds. Examination on the crystal structure of compound 3 reveals close contacts of the C-H group with the heteroatoms (N and O) of cyclic phenylimidate, suggesting the existence of C-H center dot center dot center dot X (X = N, O) intramolecular hydrogen bonding among the addends, which is further confirmed by NBO analysis.

Preparation of TiO2, CeO2, and ZrO2 hierarchical structures in "one-pot" reactions

In this paper, a novel template of carbon foam is used in building hierarchical structures of TiO2, CeO2, and ZrO2. They had multiscale morphologies, from nanowalls, nanoparticles to layer nanostructures. Oil a hundred-micron scale, the product was a sponge-like material constructed by nanowalls. On a hundred-nanometer scale, the electron microscope images showed that the nanowalls were porous and assembled by polycrystalline nanoparticles. Meanwhile, on one nanometer scale, many nanoparticles exhibited layer nanostructures with about 1.1 run of thickness and spacing. In mechanism section, the process analysis and characterizations suggested that the hierarchical structures were the combined result of two templates in a "one-pot" reaction. The mesoporous nanowalls were derived from carbon foams, while the layer nanostructures were the replicas of graphite sheets. The method has potential utilizations in preparation of various adsorbent and catalyst.

Guanidine/Pd(OAc)(2)-catalyzed room temperature Suzuki cross-coupling reaction in aqueous media under aerobic conditions

A highly efficient Pd(OAc)(2)/guanidine aqueous system for the room temperature Suzuki cross-coupling reaction has been developed. The new water-soluble and air-stable catalyst Pd(OAc)(2)(.)(1f)(2) from Pd(OAc)(2) and 1,1,3,3-tetramethyl-2-n-butylguanidine (1f) was synthesized and characterized by X-ray crystallography. In the presence of Pd(OAc)(2)(.)(1f)(2), coupling of arylboronic acids with a wide range of aryl halides, including aryl iodides, aryl bromides, even activated aryl chlorides, was carried out smoothly in aqueous solvent to afford the cross-coupling products in good to excellent yields and high turnover numbers (TONs) (TONs up to 850 000 for the reaction of 1-iodo-4-nitrobenzene and phenylboronic acid). Furthermore, this mild protocol could tolerate a broad range of functional groups.

Efficient synthesis of highly substituted pyrrolin-4-ones via PIFA-mediated cyclization reactions of enaminones

A convenient and efficient synthesis of highly substituted pyrrolin-4-ones is developed via the PIFA-mediated cyclization reactions of readily available enaminones, and a mechanism involving sequential cleavage of N-C bond, formation of new N-C bond, intramolecular addition reaction, and benzilic acid type rearrangement is proposed.

Vilsmeier-Haack reactions of 2-arylamino-3-acetyl-5,6-dihydro-4H-pyrans toward the synthesis of highly substituted pyridin-2(1H)-ones

A facile and efficient one-pot synthesis of highly substituted pyridin-2(IH)-ones was developed via Vilsmeier-Haack reactions of readily available enaminones, 2-arylamino-3-acetyl-5,6-dihydro-4H-pyrans, and a mechanism involving sequential ring-opening, haloformylation, and intramolecular nucleophilic cyclization reactions is proposed.

Thia-michael addition reactions in water using 3-[Bis(alkylthio) methylene]pentane-2,4-diones as odorless and efficient thiol equivalents

3-[Bis(ethylthio)methylene]pentane-2,4-dione (1a) and 3-[bis(benzylthio)methylene]pentane-2,4-dione (1b) have been investigated as non-thiolic and odorless thiol equivalents in thia-Michael addition reactions. In the presence of aqueous p-dodecyl benzenesulfonic acid (DBSA), compound (1) was cleaved and the generated thiols underwent facile conjugate addition to alpha,beta-unsaturated ketones 2 in-situ, affording the corresponding beta-keto sulfides (3) in good yields.