- Routes of Formation of Bifunctional C6 Carboxylic Acids in the Cyclohexane Oxidation Process
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Abstract: The buildup kinetics of the main and side products during uncatalyzed and cobalt naphthenate-catalyzed oxidation of cyclohexane at 150°C have been studied. 6-Hydroxyhexanoic, 6-oxohexanoic, and adipic acids are accumulated in parallel during the oxidation of cyclohexane, cyclohexanone, and 2-hydroxycyclohexanone. The critical consideration of their known formation pathways and the reactivity of possible precursors gives evidence for the predominant formation of 6-hydroxyhexanoic acid at the step of cyclohexanol oxidation and adipic acid from 2-hydroxycyclohexanol.
- Perkel’,Voronina
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p. 587 - 595
(2019/06/24)
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- ALDEHYDE-SELECTIVE WACKER-TYPE OXIDATION OF UNBIASED ALKENES
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This disclosure is directed to methods of preparing organic aldehydes, each method comprising contacting a terminal olefin with an oxidizing mixture comprising: (a) a dichloro-palladium complex; (b) a copper complex; (c) a source of nitrite; under aerobic reaction conditions sufficient to convert at least a portion of the terminal olefin to an aldehyde.
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Page/Page column 0140-0149; 0155-0164; 0166-0168; 0171
(2014/10/29)
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- Perspectives on the kinetics of diol oxidation over supported platinum catalysts in aqueous solution
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The catalytic oxidation of a variety of terminal alcohols was performed over Pt/C with 10 bar dioxygen at 343 K in aqueous solvent at low pH. The influences of Pt particle size, carbon support, alcohol structure, and start-up conditions were explored. Although the turnover frequency was not affected by particle size or the carbon support, the structure of the alcohols affected their initial rate of conversion. Both the rate of oxidation of α,ω-diols and selectivity of the diols to the diacids increased with increasing carbon chain length. The rate of 1,6-hexanediol oxidation was independent of dioxygen pressure and the order of reaction with respect to diol concentration depended on the start-up conditions. A kinetic model involving two types of metal sites was proposed to account for the experimental observations.
- Ide, Matthew S.,Davis, Robert J.
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- Aldehyde-selective wacker-type oxidation of unbiased alkenes enabled by a nitrite co-catalyst
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Breaking the rules: Reversal of the high Markovnikov selectivity of Wacker-type oxidations was accomplished using a nitrite co-catalyst. Unbiased aliphatic alkenes can be oxidized with high yield and aldehyde selectivity, and several functional groups are tolerated. 18O-labeling experiments indicate that the aldehydic O atom is derived from the nitrite salt. Copyright
- Wickens, Zachary K.,Morandi, Bill,Grubbs, Robert H.
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supporting information
p. 11257 - 11260
(2013/11/06)
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- METHOD FOR PRODUCING OXYGEN-CONTAINING COMPOUND
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[Problem] There is provided a method for producing an oxygen-containing compound safely and with improved reaction efficiency, in which an undesired peroxide is unlikely to be produced, and efficient heat exchange of the ozonization can be achieved. [Mean for solving the Problem] The method comprises an ozonization reaction step of continuously supplying, together with an organic compound, ozone having an oxygen content of less than 10% in a dissolved state in high-pressure carbon dioxide to an ozonization reaction section having a thin tubular shape, and reacting the ozone and the organic compound under conditions that suppress generation of oxygen due to thermal decomposition of the ozone, thereby continuously producing an ozonide; and a decomposition reaction step of continuously supplying the ozonide produced in the ozonization reaction step to a decomposition reaction section having a thin tubular shape, thereby continuously producing an oxygen-containing compound, the decomposition reaction step being provided in a manner continuous with the ozonization reaction step.
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Page/Page column 23
(2012/01/11)
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- Mechanistic insights into the conversion of cyclohexene to adipic acid by H2O2 in the presence of a TAPO-5 catalyst
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The stereochemistry of the 1,2-cyclohexanediol intermediate plays an important role with regard to both the rate and selectivity of the production of adipic acid from cyclohexene in the absence of an organic solvent. A titanium-containing aluminophosphate molecular sieve (TAPO-5) is shown to serve as a good heterogeneous catalyst for this reaction.
- Lee, Sang-Ok,Raja, Robert,Harris, Kenneth D. M.,Thomas, John Meurig,Johnson, Brian F. G.,Sankar, Gopinathan
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p. 1520 - 1523
(2007/10/03)
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- Oxidation of 2-Methylcyclohexanone and Cyclohexanone by Dioxygen Catalyzed by Vanadium-Containing Heteropolyanions
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2-Methylcyclohexanone is oxidized by dioxygen in the presence of H(3+n)*aq to give 6-oxoheptanoic acid.Solvent effects are studied.The same precursors with cyclohexanone in aqueous acetic acid give adipic acid as the major product and other dicarboxylic acids by oxidation of 6-oxohexanoic acid.
- Atlamsani, Ahmed,Bregeault, Jean-Marie,Ziyad, Mahfoud
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p. 5663 - 5665
(2007/10/02)
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- HETEROPOLYANIONS AS OXIDATION CATALYSTS IN A 2-PHASE SYSTEM
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Described is a system using heteropoly-11-tungstates as homogeneous catalysts for the oxidation of cyclohexene with hydrogen peroxide.The catalyst is dissolved in an organic solvent while the oxidant resides in the aqueous phase.The oxidation efficiency is high.
- Schwegler, M.,Floor, M.,Bekkum, H. van
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p. 823 - 826
(2007/10/02)
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- FORMATION OF epsilon -CAPROLACTONE DURING OXIDATION OF CYCLOHEXANONE.
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It was suggested in earlier studies of the mechanism of cyclohexanone oxidation that formation of CL results from oxidation of cyclohexanone by the intermediate monoperoxyadipic acid by the Baeyer-Villiger reaction. Certain evidence in support of this route of lactone formation has been obtained only recently. Additional data on the probability of reaction are presented, and the possibility of suppressing the reaction is discussed. It is shown that it is possible in principle to suppress formation of an important byproduct of cyclohexanone oxidation, namely epsilon -caprolactone, by introducing a reagent which decomposes monoperoxyadipic acid selectively into the reaction medium.
- Perkel',Neginskaya,Freidin,Ivko
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p. 1293 - 1296
(2007/10/02)
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- OXIDATION OF CYCLOHEXANONE AND 2-HYDROXYCYCLOHEXANONE IN PRESENCE OF CHROMIUM NAPHTHENATE.
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A comparison of the kinetics of accumulation of the products of oxidation of cyclohexanone and 2-hydroxycyclohexanone in presence of chromium and cobalt naphthenates and in absence of catalysts showed that the composition of the reaction products varies considerably with the nature of the catalytic metal. In distinction from polymethylene hydrocarbons, which form carbonyl compounds, cyclohexanone is concerted in presence of chromium salts predominantly through 2-hydrocyclohexanone. Oxidation of cyclohexanone and 2-hydroxycyclohexanone in presence of chromium naphthenate gives lower yields of 1,2-cyclohexanedione than the noncatalytic reaction or the reaction catalyzed by cobalt napthenate.
- Freidin,Perkel',Borodina
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p. 2483 - 2486
(2007/10/02)
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- Process for preparing alcohols
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An alcohol is produced in a high selectivity with a good yield from the corresponding carboxylic acid by reducing the latter with hydrogen in the presence of a rhenium catalyst in the coexistence of an organic base. An arylacetic acid, which is included in the starting carboxylic acid, can be produced in an excellent yield from the corresponding aryl aldehyde by reacting the latter with carbon monoxide and water in the presence of rhodium or its compound and hydrogen iodide.
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- COMPOSITION OF THE PRODUCTS FROM INITIATED OXIDATION OF CYCLOHEXANONE
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The composition of the products from initial stage of the liquid-phase initiated oxidation of cyclohexanone by oxygen was investigated.It was shown that a series of primary products are formed in the short-chain unbranched oxidation reaction as a result of the transformations of 2-oxocyclohexylperoxyl radicals.The main products are 2-hydroperoxy-1-cyclohexanone, hexanedionic acid, and its monoaldehyde, 6-hexanolide, 1,2-cyclohexanedione, 2-hydroxy-1-cyclohexanone, and 2-hydroxy-6-hexanolide.
- Kucher, R. V.,Opeida, I. A.,Nechitailo, L. G.,Simonov, M. A.
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- OZONOLYSIS OF ALKENES AND REACTIONS OF POLYFUNCTIONAL COMPOUNDS. XVIII. INVESTIGATION OF A NEW OZONOLYTIC SYNTHESIS OF CARBOXYLIC ACIDS
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By identification of the 18O isotope label in the oligomeric peroxide obtained by ozonization of a cyclic olefin in the presence of heavy oxygen and also in the product from catalytic isomerization of this peroxide ( the α,ο-dicarboxylic acids or its dimethyl ester ) it was shown that oxygen enters the ozonolysis product when the reaction is carried out in ether solvents.It is suggested that the increased content of active oxygen in the ozonolysis peroxy product is due to oxidation of the ether solvent to form α-hydroperoxide and addition of the latter to the oligomeric zwitterion, solvated by the polar solvents.It was established that the catalytic and thermal isomerization of the oligomeric peroxides and ozonides of cyclic olefins to the α,ο-dicarboxylic acids and ο-formyl carboxylic acids occurs through the oligomeric α-hydroxy peresters and α-hydroxy esters respectively.
- Odinokov, V. N.,Botsman, L. P.,Ishmuratov, G. Yu.,Tolstikov, G. A.
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p. 453 - 463
(2007/10/02)
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