Sharif Digital Repository

Condensation of pyrrole with various aldehydes in the presence of BF3•etherate as an acid catalyst in water provides good yield of some dipyrromethanes. Prolongation of the reaction time with aldehydes substituted by electron-donating (mesityl) or electron-withdrawing (2,6-dichlorophenyl) groups on the ortho positions of the phenyl did not lead to decomposition or scrambling. Manganese trans disubstituted porphyrin complexes which derive from various dipyrromethanes and manganese tetraaryl porphyrin complexes including various substituents with different steric and electronic properties show good catalytic activity in epoxidation of alkenes by NaIO4 in the presence of imidazole (ImH). The... 

A new method has been developed for the direct conversion of epoxides to α-hydroxyphosphonates by the reaction of a trialkylphosphite with the epoxide in 5 M lithium perchlorate in diethyl ether (LPDE). The reaction is highly regioselective and efficient with excellent yields under mild and neutral conditions. © 2003 Published by Elsevier Ltd  

The reactions of different dithiocarbamate anions with epoxides were investigated in water. With this method, β-hydroxy dithiocarbamate derivatives were synthesized in high yields. The reaction was also carried out in DMF in the presence of lithium perchlorate with a simple work-up procedure, and the results are compared  

Epoxides are important materials in the production of fine chemicals. Selective oxidation of alkenes to epoxides remains a challenge in synthetic chemistry. There has been considerable progress in tungsten-catalyzed epoxidation of alkenes in recent years. This review highlights the use of monomeric and dimeric oxido-peroxido tungsten(VI) complexes as catalysts or oxidants in homogeneous or heterogeneous catalytic systems for epoxidation of olefins  

This review mainly discusses the application of oxido-peroxido Molybdenum(VI) complexes as catalysts or mediators in homogeneous or heterogeneous catalytic systems for oxidations of olefins, sulfides, alcohols, alkanes, and amines toward the synthesis of a variety of organic compounds, such as epoxides, sulfoxides, aldehydes and ketones, carboxylic acids, alcohols and nitroso compounds  

New dioxomolybdenum(VI) complex was prepared by reacting 1-(2,4-dihydroxybenzylidene)-N-methyl-N-phenylthiosemicarbazone (H2L) as ligand and [MoO2(acac)2] in acetonitrile solution. The doubly deprotonated ligand is coordinated to molybdenum through sulfur atom, hydrazinic nitrogen atom and phenolic oxygen atom. The resulting complex with the formula [MoO2L(CH3CN)] which contains an acetonitrile molecule in sixth site of coordination, was characterized by elemental analyses, 1H NMR, IR and electronic spectroscopic studies and single crystal X-ray diffraction analysis. This complex was tested as a catalyst for the homogeneous epoxidation of olefins using tert-butyl hydrogen peroxide (TBHP) as... 

A novel binuclear Mn(II) complex based on a para-nitro substituted amidic ligand (N-(4-nitrophenyl)picolinamide) has been synthesized and characterized by X-ray crystallography. This complex shows a high degree of conversion and epoxide selectivity in Mukaiyama aerobic epoxidation reactions of cyclic olefins in mild conditions  

A new cis-dioxo molybdenum(VI) complex was obtained by reaction of 2,4-dihydroxybenzylidene(5-N,N-methylphenylamino-1,3,4-thiadiazol-2-yl)hydrazone as ligand and [MoO2(acac)2] in methanol and was characterized by elemental analyses, 1H NMR, IR, and electronic spectroscopic studies. The complex was also analyzed by single-crystal X-ray diffraction. The structure determination revealed a distorted octahedral coordination geometry around molybdenum in which the tridentate NNO donor (L2-) is bonded to [MoO2]2+ through phenolic oxygen, hydrazinic nitrogen, and thiadiazole nitrogen. The sixth coordination site is occupied by a weakly bonded methanol. The complex was tested as a catalyst for... 

Two enantiomerically pure chiral dioxidomolybdenum(VI) complexes (1 and 2) of the type [MoO2L] (L = dianionic, tetradentate ONNO-ligand) were synthesized and investigated in enantioselective oxidation reactions. The solid-state structures of complex 1 and 2, determined via single-crystal X-ray diffraction analysis revealed two fundamentally different coordination geometries: a C1-symmetric cis-β isomer (Λ-1), and a C2-symmetric cis-α isomer (Δ-2). In both cases, only one of the two possible helical enantiomers (Λ- or Δ-helix) was formed. The complexes were examined as precatalysts in the epoxidation of the challenging prochiral substrate trans-stilbene, using either tert-butyl hydroperoxide... 

An environmentally benign and efficient process for the preparation of β-hydroxysulfides was developed by a practical and simple reaction of thiols with epoxides in water catalyzed by K2CO3 in high yields and short reaction times  

A new efficient catalytic system was investigated for the epoxidation of various olefins by cis-dioxo-bis[2-(2′-hydroxyphenyl)-oxazolinato]molybdenum(VI), cis-[MoO2(phox)2], and TBHP as oxidizing agent. Using this system as catalyst for the oxidation of aliphatic substrates at 80 °C gives the epoxide as the sole product with yields up to 100% and turnover frequency up to 5000 h-1. The efficiency of the catalyst is strongly influenced by the nature of solvent, reaction time and temperature, and a significant increase in the epoxide yields is observed in higher temperatures and longer reaction times. © 2009 Elsevier B.V  

A heterogeneous nanocatalyst containing polyoxomolybdate immobilized on the internal surface of amino-functionalized SBA-15 pores was prepared and fully characterized by several analytical techniques. The textural property of supported material was found to retain important mesoporous features, compatible with its potential use as heterogeneous catalysts. The catalyst SBA-15-NH3+•{Mo36}–shows excellent catalytic activity for the epoxidation of alkenes as compared to POM, which is attributed to the large specific surface area and highly ordered pore structure of SBA-15, allowing for easy access of reactants to the active sites and removal of products. The prepared catalyst has high... 

SbCl3 supported on montmorillonite K-10 is an efficient catalyst for the ring opening of epoxides with aromatic amines under solvent-free conditions and microwave irradiation to give the corresponding b-amino alcohols in high yields with high regioselectivity  

A simple, rapid, atom economy and highly efficient procedure has been developed for thiolysis of epoxides by aromatic and aliphatic thiols under solvent-free conditions. A high regioselectivity in favor of nucleophilic attack at the benzylic carbon atom of aromatic epoxides, such as styrene oxide, is observed. However, aliphatic unsymmetrical alkenyl oxides undergo selective nucleophilic attack at the sterically less hindered carbon atom. A variety of β-hydroxy sulfides were obtained in short reaction time and excellent yields with nearly complete regioselectivity  

An oxido-peroxido tungsten(VI) complex [WO(O2)L(CH 30H)] using salicylidene benzoyl hydrazine as a tridentate ONO donor Schiff base (H2L) has been synthesized and characterized by elemental analysis, IR, 1H NMR, molar conductance data, and single-crystal X-ray analysis. The complex was used as a catalyst for epoxidation of olefins and oxidation of sulfides. The results show that epoxides and sulfoxides were produced in high yield, turnover number, and selectivity  

Molybdenum complexes bearing a salicylidene 2-picoloyl hydrazone ligand have been synthesized and characterized. The salicylidene 2-picoloyl hydrazone ligand (H2sal-phz) was prepared by reaction of picoloyl hydrazine with salicylaldehyde. Reaction of H2sal-phz with MoO2(acac) 2 generates the dioxo molybdenum complex MoO2(sal-phz) (CH3OH). Treatment of MoO3 in the presence of H 2O2 with H2sal-phz produces the oxo-peroxo molybdenum(VI) complex MoO(O2)(sal-phz)(CH3OH). The new compounds were characterized by 1H NMR and IR spectroscopies, and elemental analysis. The complexes were also characterized by single crystal X-ray diffraction crystallography. The complexes were evaluated for epoxidation... 

A new manganese(III) complex [(N-O)2Mn(OAc)] was synthesized using 2-(2'-hydroxyphenyl)-5,6-dihydro-1,3-oxazine (N-O) as a bidentate O, N donor. The complex has been characterized by elemental analysis, IR, UV-vis spectroscopy, and X-ray structure analysis. Oxidation of sulfides and epoxidation of olefins, respectively, to their corresponding sulfoxides and epoxides were conducted by this catalyst using urea hydrogen peroxide as oxidant at room temperature under air. The catalyst is efficient in oxidation reactions giving high yields and selectivities  

Without using any catalysts, a variety of epoxides undergo ring-opening by aromatic amines to afford the corresponding 1,2-amino alcohols in high to excellent yields with good regioselectivity in the presence of water as solvent and under solvent-free conditions  

The Mn-hydrazone Schiff base has been prepared, characterized, and encapsulated into NaY to prepare a new heterogeneous catalyst. Elemental analysis, UV-Vis, infrared spectroscopic analysis, diffuse reflectance spectroscopy, thermal analysis, small angle X-ray diffraction, and N2 sorption indicate the presence of Mn-hydrazone Schiff base within the nanocavity pores of zeolite-Y. The catalysts showed excellent catalytic efficiency in epoxidation with various olefinic compounds including cyclooctene, using tert-BuOOH as oxidant. Cyclooctene showed high conversion (97%) as well as epoxide selectivity (89%) with tert-BuOOH. Moreover, the encapsulated complex showed good recoverability without...