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.
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Breusch,Keskin
, p. 311 (1948)
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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.
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.
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Sam,Simmons
, p. 4024 (1972)
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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.
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Clark,R.D.,Heathcock,C.H.
, p. 2027 - 2030 (1974)
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Thermal stability, decomposition enthalpy, and Raman spectroscopy of 1-alkene secondary ozonides
Cataldo, Franco
, p. 994 - 998 (2015)
The synthesis of a series of 1-alkene secondary ozonides was monitored with Raman spectroscopy which is very effective in the detection of the O-O stretching band of the 1,2,4-trioxolane ring. The 1-alkene secondary ozonides thermal decomposition was studied with DSC (differential scanning calorimetry). For all ozonides studied the decomposition onset was found at about 106 °C and the decomposition peak at about 130 °C. The decomposition enthalpy ΔHdec of the secondary ozonides examined was found in the range of -313 to -347 kJ/mol. Despite the considerable amount of heat evolved, the decomposition was not explosive. The decomposition products of 1-octadecene ozonide were studied by TGA-FTIR (thermogravimetric analysis coupled with FT-infrared spectroscopy) and by GC-MS. The main products detected were formic acid and heptadecanal.
STRUCTURE OF DIPTOCARPILIDINE
Aripova, S. F.,Abdilalimov, O.,Bagdasarova, E. S.,Aizikov, M. I.,Yunusov, S. Yu.,Kurmukov, A. G.
, p. 79 - 81 (1984)
Diptocarpilidine (bp 193-194 deg C (4 mm)) has been isolated from the epigeal part and seeds of Diptychocarpus strictus (Fisch) Trautv., and its structure has been established as 1-cyano-6-methylsulfinylhexane.
Crown Cation Complex Effects. 10. Potassium tert-Butoxide Mediated Penultimate Oxidative Hydrolysis of Nitriles
DiBiase, Stephen A.,Wolak, Raymond P.,Dishong, Dennis M.,Gokel, George W.
, p. 3630 - 3634 (1980)
The failure of phase-transfer catalysis to improve either the yield or rapidity of basic nitrile hydrolysis is due, in part, to the poor solubility of quaternary ammonium hydroxides in nonpolar solutions.An alternative hydrolysis method which involves potassium tert-butoxide mediated oxidative cleavage of the nitrile with loss of the cyano carbon is presented.The isolated yields reported here range from 21-93percent and are found to be highest for long-chain aliphatic nitriles such as cyanohexadecane.
Optimization of the oxidative cleavage with MnO4-IO4. II. Diene- and triene- fatty acids
Grimmer,Jacob
, p. 1004 - 1008 (1969)
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Bawn,Sharp
, p. 1854,1858,1861,1866,1867 (1957)
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Zakharkin et al.
, (1971)
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Effect of Dimethylsulfoxide on Hydrolysis of Lipase
Tsuzuki, Wakako,Ue, Akemi,Kitamura, Yoshiaki
, p. 2078 - 2082 (2001)
To establish an industrially feasible reaction process, the effect of dimethylsulfoxide (DMSO) added to an aqueous solution on the hydrolysis of lipase was investigated using fluorescent substrates. Several lipases from microorganisms were improved in their hydrolysis activities against 4-methylumbelliferyl oleate by DMSO. Variation was found in the effect of DMSO depending on the species of lipase. After the high stability of the lipase from Pseudomonas fluorescens in DMSO solution was confirmed, hydrolysis by this lipase of four acyl-4-methylumbelliferones was studied kinetically at different DMSO concentrations. DMSO added to an aqueous solution increased the Vmax of this lipase for a substrate with strong hydrophobicity, and decreased that value for a substrate with an opposite property. On the other hand, DMSO had a very small effect on Km for each substrate. A fluorometric study suggested that DMSO induced a change of the chemical environment that surrounded tryptophan residues of the lipase. Such conformational change would be one of the causes of the DMSO-induced alteration of its reactive property. These results suggest that the addition of DMSO may be a novel method of 'solvent engineering' of this enzyme.
Catalytic activity of baker's yeast in ester hydrolysis
Bialecka-Florjanczyk, Ewa,Krzyczkowska, Jolanta,Stolarzewicz, Izabela
, p. 288 - 291 (2010)
The hydrolysis of phenyl esters of alkane carboxylic acids in the presence of lyophilized Saccharomyces cerevisiae has been studied. In the case of phenyl acetate the hydrolysis obeyed MichaelisMenten kinetics, behavior typical of esterase-catalyzed reactions. For phenyl laurate our experiments provided evidence for the growth-associated production of lipase by baker's yeast.
SELECTIVE SYNTHESIS OF ENANTHIC ACID BY THE CARBONYLATION OF 1-HEXENE IN THE PRESENCE OF PALLADIUM ANION-EXCHANGE CATALYSTS WITH SnCl2 ADDITIVE
Lapidus, A. L.,Pirozhkov, S. D.,Buiya, M. A.,Karapetyan, L. P.,Saldadze, K. M.,Karakhanov, R. A.
, p. 1333 (1985)
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OXIDATION OF ALDEHYDES BY THIAZOLIUM IONS AND FLAVIN IN A CATIONIC MICELLE
Yano, Yumihiko,Hoshino, Yutaka,Tagaki, Waichiro
, p. 749 - 752 (1980)
The reactions of aldehydes with thiazolium ions and flavin were investigated in the presence of CTABr micelle.The reactions were found to be facilitated by a cationic micelle.
CARBONYLATION OF 1-HEXENE IN THE PRESENCE OF PALLADIUM-ANION-EXCHANGE RESIN CATALYSTS
Lapidus, A. L.,Pirozhkov, S. D.,Buiya, M. A.,Lunin, A. F.,Karapetyan, L. P.,Saldadze, K. M.
, p. 2612 - 2614 (1985)
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Aliphatic aldehyde reductase activity related to the formation of volatile alcohols in vietnamese coriander leaves
Quynh, Cung Thi To,Iijima, Yoko,Morimitsu, Yasujiro,Kubota, Kikue
, p. 641 - 647 (2009)
Vietnamese coriander (Persicaria odorata Lour.) belongs to a group known as cilantro mimics with the 'cilantro' flavor, in which C10 and C12 aldehydes and alcohols have been found as the potent odor compounds. Their composition isolated by different extraction methods varied. The enzyme activity was assayed, and the reductase acting on some aliphatic aldehydes with NADH/NADPH as a coenzyme was found in a crude enzymatic system of fresh leaves. The maximum activity was observed at pH 8.0 in Na-phosphate and at pH 8.5 to 9.0 in a glycine-NaOH buffer, using heptanal as a substrate. The activated reductase that caused the alcohol generation to increase after a time was inhibited by p-hydroxymercuribenzoate. Our results, which are the first to be reported on Vietnamese coriander leaves, reveal the presence of aliphatic aldehyde dehydrogenase, which is responsible for acid formation, and elucidate the strong activity of the aliphatic aldehyde reductase.
Selective Autoxidation of Electron-Rich Substrates under Elevated Oxygen Pressures
Correa, Paul E.,Hardy, Gordon,Riley, Dennis P.
, p. 1695 - 1702 (1988)
We report here the observation of a novel autoxidation pathway which occurs with electron-rich substrates.Tertiary amines, dialkyl thioethers, olefins, and alkynes under high oxygen pressures (>20 bars of O2), in polar solvents, and at elevated temperatures (>90 deg C) yield in good to excellent selectivity amine oxides, sulfoxides, and site-specific olefin and alkyne cleavage products, respectively.The results of mechanistic studies, including high oxygen pressure electrochemical studies, are discussed.A mechanism for this novel oxygenation reaction pathway that is consistent with the observed results is proposed.It involves an initial unfavorable electron transfer from the electron-rich substrate to oxygen to yield superoxide and the radical cation, which reacts with triplet oxygen to yield the oxygenated radical cation intermediate, a suspected potent oxidant.Electron transfer to the oxygenated radical cation from additional substrate (chain reaction) or superoxide yields a zwitterionic intermediate.This intermediate either reacts with additional substrate (O-atom transfer) to yield product (sulfoxide and N-oxide, in the case of thioethers and tertiary amines) or is converted with unimolecular reactivity to dioxetane-like (in the case of alkenes) or dioxetene-like (in the case alkynes) derived products.
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Taylor,Robey
, p. 7331 (1971)
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Heterogeneously catalysed cleavage of carbon-carbon double bonds with hydrogen peroxide using calcined heteropolyacids on oxide supports
Brooks, Christopher D.,Huang, Ling-Chu,McCarron, Moya,Johnstone, Robert A. W.
, p. 37 - 38 (1999)
Reaction of an alkene with aqueous hydrogen peroxide and a catalytic quantity of a heteropolyacid adsorbed onto magnesium, aluminium or zinc oxide leads to complete, rapid cleavage of the alkene to give carbonyl compounds.
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Kornblum,Oliveto
, p. 5173 (1955)
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Poly(ethylene glycol) Ethers as Recoverable Phase-Transfer Agents in Permanganate Oxidations
Harris, J. Milton,Case, Martha G.
, p. 5390 - 5392 (1983)
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Green, homogeneous oxidation of alcohols by dimeric copper(II) complexes
Maurya, Abhishek,Haldar, Chanchal
, p. 885 - 904 (2020/12/18)
Three pyrazole derivatives, 3,5-dimethyl-1H-pyrazole (DMPz) (I), 3-methyl-5-phenyl-1H-pyrazole (MPPz) (II), and 3,5-diphenyl-1H-pyrazole (DPPz) (III), were prepared via reacting semicarbazide hydrochloride with the acetylacetone, 1-phenylbutane-1,3-dione, and 1,3-diphenylpropane-1,3-dione, respectively. Complexes 1–3 were isolated by reacting CuCl2·2H2O with I–III, respectively, and characterized by CHNS elemental analyses, FT-IR, UV-Vis, 1H and 13C NMR, EPR spectra, and TGA/DTA. Molecular structures of the pyrazole derivatives I–III and copper(II) complexes 2 and 3 were studied through single-crystal XRD analysis to confirm their molecular structures. Overlapping of hyperfine splitting in the EPR spectra of the dimeric copper(II) complexes 1–3 indicates that both copper centers do not possess the same electronic environment in solution. The copper(II) complexes are dimeric in solid state as well as in solution and catalyze the oxidation of various primary and secondary alcohols selectively. Catalysts 1–3 show more than 92% product selectivity toward ketones during the oxidation of secondary alcohols. Surprisingly primary alcohols, which are relatively difficult to oxidize, produce carboxylic acid as a major product (48%–90% selectivity) irrespective of catalytic systems. The selectivity for carboxylic acid rises with decreasing the carbon chain length of the alcohols. An eco-friendly and affordable catalytic system for oxidation of alcohols is developed by the utilization of H2O2, a green oxidant, and water, a clean and greener solvent, which is a notable aspect of the study.
FLOW CHEMISTRY SYNTHESIS OF ISOCYANATES
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Paragraph 0008; 0175; 0206, (2021/06/22)
The disclosure provides, inter alia, safe and environmentally-friendly methods, such as flow chemistry, to synthesize isocyanates, such as methylene diphenyl diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and tetramethylxylene diisocyanate.
