Oxidation of alcohols to carbonyl compounds with chromium(V) reagents

Two pentavalent chromium complexes have been used effectively for the oxidation of alcohols to carbonyl compounds.     

Oxidation of alcohols to carbonyl compounds with diisopropyl azodicarboxylate catalyzed by nitroxyl radicals

A nitroxyl-radical-catalyzed oxidation of alcohols using diisopropyl azodicarboxylate (DIAD) as the terminal oxidant is reported. A variety of primary and secondary alcohols including aliphatic, benzylic, and allylic alcohols are efficiently oxidized to their corresponding aldehydes and ketones without overoxidation to carboxylic acid. 1,2-Diols are oxidized to hydroxyl ketones or diketones depending on the amount of DIAD used.     

The co-solubility of 2-ethylhexanoic acid and some liquid alcohols in supercritical carbon dioxide

The co-solubility in supercritical carbon dioxide of 1-butanol, 1-pentanol, 2-ethyl-1-hexanol, or 1-decanol in the presence of 2-ethylhexanoic acid in the pressure range of 100–180 bar and at 313 or 323 K was measured. The solubility of these alcohols in the presence of 2-ethylhexanoic acid is lower than in the systems alcohol + CO₂ and remains nearly constant in the pressure range of 120–180 bar, with the exception of 1-decanol. The lower selectivities in the ternary systems are explained by strong intermolecular hydrogen bonding between alcohol molecules and 2-ethylhexanoic acid molecules. The FT-IR spectra of mixtures of alcohols and 2-ethylhexanoic acid at a 1:1 mole ratio in the liquid CCl₄ confirmed this conclusion.     

Oxidation of allylic alcohols to alpha,beta-unsaturated carbonyl compounds with aqueous hydrogen peroxide under organic solvent-free conditions

Allylic alcohols are chemoselectively oxidized to alpha,beta-unsaturated carbonyl compounds in high yield with aqueous H(2)O(2) in the presence of Pt black catalyst under organic solvent-free conditions. The catalyst is easily recyclable and effective for at least 7 cycles.     

Homogeneously catalysed isomerisation of allylic alcohols to carbonyl compounds

Isomerisation of allylic alcohols forms an elegant shortcut to carbonyl compounds in a completely atom-economical process that offers several useful applications in natural-product synthesis and in bulk chemical processes. This review focuses on the heart of isomerisation catalysis: the catalyst. Combinations of transition metals (from Group 4 to 10), ligands and reaction conditions are compared with respect to yield, turnovers, rate and selectivity. A selected number of clever solutions to synthetic problems are highlighted, such as the synthesis of enols and enolates, chiral carbonyl compounds and silyl substituted ketones. Furthermore, a general overview of the mechanisms proposed for the isomerisation of allylic alcohols is given while some catalyst systems are singled out to discuss mechanistic research.     

Reactions of chlorine dioxide with organic compounds. 2. Oxidation of thiols

The method for the synthesis of 4-aryl-2,6,6-trimethyl-5-oxo-5,6-dihydro-4H-thieno[3,2-b]pyrroles from accessible 4-aminothiophene derivatives was developed.     

Coating carbon nanotubes with polymer in supercritical carbon dioxide

A facile and efficient method has been developed for coating MWNTs with solvent resistant polymer in scCO2, which permits the selective deposition of high molecular weight fluorinated graft poly(methyl vinyl ether-alt-maleic anhydride) polymer onto MWNTs in scCO2 under 100-170 bar at 40 degrees C and forms quasi one-dimensional nanostructures with conducting cores and insulating surfaces.     

Treatment of paper with basic agents in alcohols and supercritical carbon dioxide to neutralize acid and prolong storage time

The efficiency of treatment of paper prepared from 100% sulfite cellulose with basic agents (solutions of magnesium alkoxides or methoxycarbonate in alcohols or in supercritical carbon dioxide) to neutralize acid was studied, as influenced by the following factors: concentration of a basic agent in the neutralizing solutions, repetition of impregnation of paper with a neutralizing solution and hydrolysis of the neutralizing agent after each impregnation cycle, temperature and pressure of supercritical carbon dioxide, mixing of a neutralizing agent with supercritical CO₂, and conditions (dynamic or static) the paper treatment with a neutralizing solution.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 12, 2004, pp. 2042–2046.Original Russian Text Copyright © 2004 by Dobrodskaya, Egoyants, Ikonnikov, Romashenkova, Sirotin, Dobrusina, Podgornaya.     

在超临界CO2流体中的化学反应

超临界CO2流体中的化学反应是继超临界流体应用于萃取分离过程之后进一步将其应用于化学反应的新尝试。本文重点综述了超临界CO2流体中的化学反应研究进展, 并对其发展前景作了展望。     

Solubility of chelating agents and metal-containing compounds in supercritical fluid carbon dioxide

The solubility of 49 metal-containing compounds and 15 "free" ligands in supercritical fluid carbon dioxide is reviewed. Solubilities were found to range over eight orders of magnitude, with the highest value of solubility being 56 g l(-1). Metals complexed with fluorine substituted ligands were found to be the most soluble, and metals complexed with phenyl-substituted ligands the least soluble. A general trend for increasing solubility with increasing oxidation state is observed and this is correlated with the increased number of coordinating ligands protecting the metal center from interaction with the supercritical fluid and also due to the increased number of solvation interactions with the increased number of ligand groups.     

Reactions on a surface. 1. Condensation of 3-methyl-3-buten-1-ol with carbonyl compounds on SiO2 and Al2O3

3-Methyl-3-buten-1-ol reacts with various aldehydes and ketones on silica gel and Al₂O₃ surfaces in the absence of solvents and conventional catalysts for this reaction to form derivatives of di- and tetrahydropyrans.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1326–1328, October, 1989.     

Reactions of carbon dioxide with metal carbonyl anions

The reactivity of a series of metal carbonyl anions with CO₂ has been found to parallel their relative nucleophilicities. The highly nucleophilic species, C₅H₅Fe(CO)^?₂, reacts readily to give the dimer, (C₅H₅Fe(CO)₂)₂, and carbonate while Co(CO)^?₄ is unreactive. The reaction of ¹³CO₂ with C₅H₅Fe(CO)^?₂ results in the formation of the ¹³CO enriched dimer.     

Sulfenamide catalyzed oxidation of alcohols to the corresponding carbonyl compounds with anhydrous chloramine-T

N-tert-Butylbenzenesulfenamide (1) catalyzed oxidation of various alcohols with stoichiometric amount of anhydrous chloramines-T (2) proceeded smoothly at room temperature to afford the corresponding carbonyl compounds in good yields.     

Reactions of 2-methylene-3-oxoquinuclidine with carbonyl compounds

The reaction of 2-methylene3-oxoquinuclidine with ketones, -diketones, keto esters, and cyano esters was studied. Products of mono- and diaddition of the unsaturated ketone are formed in the presence of catalytic or equimolar amounts of sodium ethoxide, as well as without a catalyst (in the case of -keto esters and -diketones).Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1387–1391, October, 1981.     

Dissolution of uranium dioxide in supercritical fluid carbon dioxide

Uranium dioxide can be dissolved in supercritical CO2 with a CO2-philic TBP-HNO3 complexant to form a highly soluble UO2(NO3)(2).2TBP complex; this new method of dissolving UO2 that requires no water or organic solvent may have important applications for reprocessing of spent nuclear fuels and for treatment of nuclear wastes.