C:Corrosive;
111-14-8Relevant articles and documents
Fast and Selective Oxidation of Primary Alcohols to Aldehydes or to Carboxylic Acids and of Secondary Alcohols to Ketones Mediated by Oxoammonium Salts under Two-Phase Conditions
Anelli, Pier Lucio,Biffi, Carlo,Montanari, Fernando,Quici, Silvio
, p. 2559 - 2562 (1987)
Primary alcohols are quantitatively oxidized to aldehydes in a few minutes at 0 deg C in CH2Cl2-0.35 M aqueous NaOCl in the presence of catalytic amounts of 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (3b).Cocatalysis by Br- and buffering of pH at 8.6 with NaHCO3 are also required.Secondary alcohols are converted to ketones.Further oxidation of aldehydes to carboxylic acids is slow, but the reaction is completed in a few minutes under the same conditions by addition of catalytic amounts of phase-transfer catalyst.All reactions are highly selective.Onlya slight excess of NaOCl is required.The method can be applied to saturated alkyl and aryl alkyl substrates.
Vanadium-catalyzed carboxylation of linear and cyclic C5 and C6 alkanes
Reis, Patricia M.,Silva, Jose A.L.,Palavra, Antonio F.,Frausto Da Silva, Joao J.R.,Pombeiro, Armando J.L.
, p. 333 - 340 (2005)
Cyclopentane, cyclohexane, pentane, and hexane are carbonylated in single-pot processes and under mild conditions to carboxylic acids (highest yields of 54-33% and turnover numbers [TONs] of 76-50) by vanadium (IV) and (V) complexes in TFA. These complexes present N,O- or O,O-ligands, namely basic forms of aminoalcohols and of (hydroxyimino)dicarboxylic acids, trifluoroacetate, or triflate. The effects of various parameters (e.g., catalyst type, oxidizing agent, CO pressure, temperature, reaction time, type of solvent) were investigated. The use of either too low or too high CO pressures is discouraged, because the former promote the formation of trifluoroacetate esters and the latter, above a certain level, do not result in higher yields or TONs of the carboxylic acids. Carbon- and oxygen-centered radical mechanisms are suggested by experiments with radical traps and by acid product distribution.
Catalytic oxidation of α-alkenes with hydrogen peroxide to carboxylic acids in the presence of peroxopolyoxotungstate complexes
Pai,Selivanova,Oleneva,Berdnikova,Beskopyl'nyi
, p. 45 - 49 (2017)
Fine organic synthesis investigation has been performed, focusing on the possibility of efficient oxidation of α-alkenes by hydrogen peroxide under conditions of phase transfer catalysis using bifunctional metal complex catalysts based on peroxotungsten compounds of general formula Q3{PO4[WO(O2)2]4}, where Q is organic cation containing quaternary nitrogen atom. Catalysts screening has been done at oxidation of octene-1, decene-1 and dodecene-1 by 30% aqueous hydrogen peroxide to obtain carboxylic acids: heptanoic, nonanoic and undecanoic acids being of importance since used as precursors in the synthesis of various organic and biologically active compounds. This approach to the synthesis of carboxylic acids may be of interest for the processes of “green chemistry” occurring under mild conditions (Т??100?°С, Р – atm) in one stage without organic solvents, and providing high target product yields (86–97%).
An efficient and ultrastable single-Rh-site catalyst on a porous organic polymer for heterogeneous hydrocarboxylation of olefins
Yuan, Qiao,Song, Xiangen,Feng, Siquan,Jiang, Miao,Yan, Li,Li, Jingwei,Ding, Yunjie
, p. 472 - 475 (2021)
A heterogeneous hydrocarboxylation process of olefins to obtain carboxylic acids with one more carbon was first realized using a single-Rh-site catalyst formed on porous organic polymer (Rh1/POPs). The in situ formation of hydrophilic porous ionic polymer from hydrophobic POPs with the help of CH3I led to high activity and superb stability.
Oxoperoxo molybdenum(VI) and tungsten(VI) and oxodiperoxo molybdate(VI) and tungstate(VI) complexes with 8-quinolinol: Synthesis, structure and catalytic activity
Maiti, Swarup K.,Banerjee, Surajit,Mukherjee, Alok K.,Abdul Malik,Bhattacharyya, Ramgopal
, p. 554 - 563 (2005)
A solution obtained by dissolving MoO3 in a moderate excess of H2O2 reacts with 8-quinolinol (QOH) to give [MoO(O 2)(QO)2] (1), but, when the same reaction is conducted with a large excess of H2O2, an anionic complex is formed, which reacts with PPh4Cl to give the corresponding salt [MoO(O 2)2(QO)][PPh4] (2 · PPh4). Freshly prepared WO3 behaves the same way and, depending on the amount of H2O2 used, as above, produces either [WO(O 2)(QO)2] (3) or [WO(O2)2(QO)] [PPh4] (4 · PPh4), respectively. Crystallographic analyses reveal the coordination geometries around the metal center in these complexes to be distorted pentagonal bipyramids. These compounds show interesting catalytic properties in the oxidation of alcohols using H 2O2 as the terminal oxidant. In the case of aromatics, including benzylic and cinnamylic alcohols, the oxidation occurs selectively, affording aldehydes or ketones with reasonably high turnover numbers. Taking benzyl alcohol as a representative case, a probable mechanism of the alcohol-to-aldehyde conversion mediated by the prepared catalysts is suggested. The oxidation of aliphatic primary alcohols, under the same conditions, does not show the above selectivity: the reaction yields the corresponding aldehydes as well as carboxylic acids. The work was also extended to study the catalytic activity towards the oxidation of phenol and various sulfides and amines using the same oxidants. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2005.
Organoboranes. 35. Reaction of Alkylthioboronic Esters with Trichloromethyllithium: Preparation of One-Carbon-Extended Carboxylic Acids and Thioacetals from Alkenes via Hydroboration
Brown, Herbert C.,Imai, Toshiro
, p. 892 - 898 (1984)
Various 2-alkyl-1,3,2-dithiaborolanes, RB(S2C2H4) (1), were converted to the corresponding carboxylic acids, RCO2H (2), by using LiCCl3 in THF, followed by oxidation with alkaline hydrogen peroxide.For R=hexyl, a reaction intermediate is converted by solvent into another compound, C6H13C(S2C2H4)B2 (9a), characterized spectroscopically.The yields of 2 decreased with increasing bulkiness of the alkyl groups R.Although the configuration of R= trans-2-methylcyclopent-1-yl (1k) was retained in the product (>98percent trans), a significant degree of epimerization tookplace for R= exo-norbornyl (1j) during the oxidation (exo : endo = 86 : 14).More uniquely, the intermediates 9 were easily hydrolyzed by heating the reaction mixture with aqueous NaOH to give the corresponding 2-alkyl-1,3-dithiolanes 3.Stereochemical integrity was retained in the products derived from 1j and 1k.Since 1 was prepared by the hydroboration of alkenes, this sequence provides a new method for introducing oxycarbonyl or thioacetal functionality into alkenes in a regioselective manner, and, in the case of 3, also with stereocontrol.
Cationic ruthenium(II) complexes supported on mesoporous silica as catalyst precursors in the selective oxidative cleavage of 1-octene
Kotzé, Hendrik,Mapolie, Selwyn
, (2017)
The selective oxidative cleavage of 1-octene to heptanal and heptanoic acid is reported. A range of model and silica-immobilized ruthenium(II) systems were evaluated. The MCM-41 and SBA-15 immobilized systems were found to show superior activity when compared to their homogeneous counterparts and were found to exert control over the selective formation of aldehydes or carboxylic acids. This could be achieved by varying the reaction times with very high yields being achieved at relatively short reaction times and low metal concentrations. The immobilized catalysts were characterized using nitrogen sorption, powder X-ray diffraction, transmission and scanning electron microscopies, solid-state NMR spectroscopy and thermogravimetric analysis.
Catalytic activity of cyclophosphazenic polypodands in phase-transfer reactions. Comparison with open-chain analogues
Landini, Dario,Maia, Angelamaria,Corda, Luciana,Maccioni, Antonio,Podda, Gianni
, p. 7477 - 7488 (1991)
The catalytic activity of cyclophosphazenic polypodands 1a-c was evaluated in typical reactions performed under solid-liquid (SL) and liquid-liquid (LL) phase-transfer catalysis (PTC) conditions. Such activity is largely determined by the complexation extent of 1a-c which is in turn related to the number of binding sites of the ligand (1a+Y- (Na+>K+2>Rb+ and SCN- I-> Br-). Also the presence of water was found to play an important role. Comparison with open-chainanalogues PEG 2 and TRIDENT 3 showed that polypodands 1a-c due to their excellent stability simplicity of preparation and high complexing ability can be considered promising phase transfer catalysts especially under SL-PTC conditions. Cyclophosphazenic polypodands are efficient catalysts in anion promoted reactions (e.g. nucleophilic substitution, alkylation, reduction, oxidation reactions) under SL and LL-PTC conditions. Catalytic activity is mainly related to their complexation capability.
Catalyst parameters determining activity and selectivity of supported gold nanoparticles for the aerobic oxidation of alcohols: The molecular reaction mechanism
Abad, Alberto,Corma, Avelino,Garcia, Hermenegildo
, p. 212 - 222 (2008)
As previously reported for for solventless reactions, gold nanoparticles supported on ceria are also excellent general heterogeneous catalysts for the aerobic oxidations of alcohols in organic solvents. Among organic solvents it was found that toluene is a convenient one. A systematic study on the influence of the particle size and gold content on the support has established that the activity correlates linearly with the total number of external gold atoms, and with the surface coverage of the support. Amongst catalysts with different supports, but similar gold particle size and content, gold on ceria exhibits the highest activity. By means of a kinetic study (influence of σ+ parameter, kinetic isotopic effect, temperature, alcohol concentration and oxygen pressure) a mechanistic proposal consisting of the formation of metalalcoholate, β-hydride shift from carbon to metal and M-H oxidation has been proposed that explains all experimental results.
ONE-POT SYNTHESIS OF (Z)-4-ALKENOIC ACIDS
Fujisawa, Tamotsu,Sato, Toshio,Kawara, Tatsuo,Naruse, Kouichi
, p. 1123 - 1124 (1980)
The reaction of β-propiolactone with di-(Z)-1-alkenylcuprates, prepared from Grignard reagents, copper(I) iodide and acetylene, gave (Z)-4-alkenoic acids in high yields in one-pot operation.
