Silica Chloride (SiO2-Cl), a New Heterogeneous Reagent,for the Selective and Efficient Conversion of Benzylic Alcohols to Their Corresponding Chlorides and Iodides

Abstract

Structurally different benzylic alcohols were efficiently converted to their corresponding chlorides by silica chloride (SiO₂-Cl) in CHCl₃ at room temperature. Silica chloride is also able to convert benzylic alcohols to their iodides in the presence of NaI in a mixture of CH₃CN/CHCl₃ in excellent yields.     

A Rapid and Convenient Synthesis of Homoallylic Alcohols by the Barbier‐Grignard Reaction

Abstract

The use of the Barbier‐Grignard reaction, where premixed allyl bromide and the carbonyl compound are added to magnesium in ether, is reported for the synthesis of homoallylic alcohols. This reaction provides good to excellent yields of most homoallylic alcohols with minimal formation of Wurtz coupling products.     

SELECTIVE OXIDATION OF BENZYLIC ALCOHOLS USING CAN SUPPORTED ONTO SILICA GEL UNDER MICROWAVE IRRADIATION

Cerium ammonium nitrate (CAN) adsorbed on HNO ₃ /silica gel is a mild reagent for selective oxidation of benzylic alcohols to the corresponding aldehydes under microwave irradiation in solventless system.     

Complexation and transport of amino acid esters and their salts with synthesised chiral novel aza crown ether derivatives

The syntheses of four aza-15-crown-5 ethers bearing phenyl and phenoxymethyl moieties attached to a stereogenic centre on the crown ring were achieved. Macrocycles have exhibited strong binding ability (K_a = 5364–12,969 M^? 1) and modest enantiomeric discrimination towards the enantiomers of amino acid methyl ester salts by UV titration method in CHCl₃ at 25°C. Computer modelling results supported experimental data providing a detailed understanding of the molecular recognition mode between hosts and guests and the likely binding sites involved. Macrocycles were used for chiral discrimination of amino acids in their zwitterionic forms or as potassium and sodium salts in transport experiments across a bulk chloroform membrane with satisfactory selectivity.     

Novel Effectively Carbonaceous and Sulfurated Hydrogen Corrosion Inhibitors on the Basis of Organosulfurphosphorus Compounds

Abstract

Novel ammonium salts of O,O-dialkyl dithiophosphoric acids were obtained by one-pot synthesis from white phosphorus, elemental sulfur, industrial alcohols or phenols, and amines. Long-chain S-alkyl O,O-dialkyldithiophosphonates were prepared by the reaction of red phosphorus with elemental sulfur, alcohols, and the cheap industrial fractions of С₁₆–С₁₈ and С₂₀–С₂₆ of higher α-olefins in the presence of Lewis acid catalyst. The dithiophosphates obtained possess the high anticorrosion activities toward mild steel.     

On the formation of carbonate adducts of fatty alcohols, sterols, and sugars in biological conditions

The formation and properties of carbonate adducts of some organic hydroxy compounds in aqueous medium were investigated. Fatty alcohols and sugars were chosen as representative classes of biological interest, and the medium was carbonated aqueous solution with pH ranging from 3.0 to 8.3. Capillary electrophoresis with two capacitively coupled contactless conductivity detectors (C⁴Ds) was used for quantitation and to obtain the mobility of the monoalkyl carbonates (MACs), which were used to determine the equilibrium and kinetic constants of the reaction as well as the diffusion coefficients. For increasing chain length of the alcohols, the equilibrium constant tends to the unit, which suggests that fatty alcohols can form the corresponding MACs. The formation of MACs for cyclohexanol and cyclopentanol also suggest the existence of similar species for sterols. Carbonate adducts of fructose, glucose, and sucrose were also detected, which suggests that these counterparts of the well‐known phosphates can also occur in the cytosol. Our calculations suggest that one in 1000 to one in 10 000 molecules of these hydroxy compounds would be available as the corresponding MAC in such a medium. Experiments carried out at pH values less than 3.0 showed that there is a catalytic effect of hydronium on the interconversion of bicarbonate and a MAC. Taking into account the great number of hydroxy compounds similar to the ones investigated and that bicarbonate is ubiquitous in living cells, one can anticipate the existence of a whole new class of carbonate adducts of these metabolites.     

An Al(OTf)3-catalyzed environmentally benign process for the propargylation of indoles

Al(OTf)₃ catalyzed the alkylation of indoles using secondary/tertiary propargylic alcohols to produce 3-propargylated indoles in excellent yields with high selectivity. The reactions were performed in air with commercial grade solvents, and water was the only side product of the process. The catalyst was recovered after completion of the reaction and re-used with minimum loss of activity over three cycles.     

Mechanistic Insights into the Rhenium‐Catalyzed Alcohol‐To‐Olefin Dehydration Reaction

Rhenium‐based complexes are powerful catalysts for the dehydration of various alcohols to the corresponding olefins. Here, we report on both experimental and theoretical (DFT) studies into the mechanism of the rhenium‐catalyzed dehydration of alcohols to olefins in general, and the methyltrioxorhenium‐catalyzed dehydration of 1‐phenylethanol to styrene in particular. The experimental and theoretical studies are in good agreement, both showing the involvement of several proton transfers, and of a carbenium ion intermediate in the catalytic cycle.