- Efficient oxidation of cycloalkanes with simultaneously increased conversion and selectivity using O2 catalyzed by metalloporphyrins and boosted by Zn(AcO)2: A practical strategy to inhibit the formation of aliphatic diacids
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The direct sources of aliphatic acids in cycloalkanes oxidation were investigated, and a strategy to suppress the formation of aliphatic acids was adopted through enhancing the catalytic transformation of oxidation intermediates cycloalkyl hydroperoxides to cycloalkanols by Zn(II) and delaying the emergence of cycloalkanones. Benefitted from the delayed formation of cycloalkanones and suppressed non-selective thermal decomposition of cycloalkyl hydroperoxides, the conversion of cycloalkanes and selectivity towards cycloalkanols and cycloalkanones were increased simultaneously with satisfying tolerance to both of metalloporphyrins and substrates. For cyclohexane, the selectivity towards KA-oil was increased from 80.1% to 96.9% meanwhile the conversion was increased from 3.83 % to 6.53 %, a very competitive conversion level with higher selectivity compared with current industrial process. This protocol is not only a valuable strategy to overcome the problems of low conversion and low selectivity lying in front of current cyclohexane oxidation in industry, but also an important reference to other alkanes oxidation.
- Shen, Hai-Min,Wang, Xiong,Ning, Lei,Guo, A-Bing,Deng, Jin-Hui,She, Yuan-Bin
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- Method for catalytic oxidation of cycloalkane by confinement porphyrin Co (II)
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The invention relates to a method for catalytic oxidation of cycloalkane by confinement porphyrin Co (II). The method comprises the following steps: dispersing confinement cobalt porphyrin (II) in cycloalkane, sealing the reaction system, heating to 100-130 DEG C while stirring, introducing oxygen to 0.2-3.0 MPa, keeping the set temperature and oxygen pressure, stirring to react for 3.0-24.0 h, and carrying out post-treatment on a reaction solution to obtain products naphthenic alcohol and naphthenic ketone. The method achieves high selectivity of naphthenic alcohol and naphthenic ketone, andeffectively inhibits the generation of aliphatic diacid. The aliphatic diacid is low in selectivity, so that the continuity of the cycloalkane oxidation process and the separation of the products arefacilitated; the method has the potential of solving the problem that naphthenic alcohol and naphthenic ketone are easily and deeply oxidized to generate aliphatic diacid in the industrial cycloalkanecatalytic oxidation process; and the method is a novel efficient and feasible method for selective catalytic oxidation of cycloalkane.
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Paragraph 0067; 0068
(2020/05/01)
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- Confinement porphyrin Co (II), and preparation method and application thereof
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Confinement porphyrin Co (II). A preparation method includes: under acidic condition, performing condensation on aromatic aldehyde and pyrrole in equal molar ratio to obtain a phenylporphyrin compound, and carrying out metallization in a chloroform-methanol solution to obtain porphyrin Cu (II), performing bromination and demetalization by perchloric acid to obtain confinement porphyrin, performingstirring reflux on the confinement porphyrin in a methanol solution for 12.0-24.0 h to obtain confinement porphyrin Co (II). An application includes: dissolving the confinement porphyrin Co (II) in naphthenic hydrocarbon and sealing the reaction system, stirring and heating the reaction system to 100-130 DEG C and feeding oxygen to 0.2-3.0 MPa; maintaining the set temperature and oxygen pressureand performing a stirring reaction for 3.0-24.0 h; performing after treatment on the reaction liquid to prepare the product. In the invention, generation of fatty diacid is effectively inhibited, andcontinuity of a naphthenic hydrocarbon oxidization process and product separation is facilitated. The invention has the potential of solving the problem that naphthene alcohols and naphthene ketones are liable to undergo deep oxidization and form the fatty diacid in an industrial naphthenic hydrocarbon catalytic oxidation process.
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Paragraph 0099-0100
(2020/04/17)
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- Method for synergistically catalyzing and oxidizing cycloparaffin through confined metalloporphyrin cobalt (II)/Cu (II) salt
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The invention discloses a method for synergistically catalyzing and oxidizing cycloparaffin through confined metalloporphyrin cobalt (II)/Cu (II) salt. The preparation method comprises the following steps: dispersing confined metalloporphyrin cobalt (II) (0.001%-5%, g/mol) and Cu (II) salt (0.01%-10%, mol/mol) into cycloparaffin; and sealing the reaction system, heating the temperature to 90-150 DEG C while stirring, introducing an oxidant, keeping the set temperature and pressure, carrying out stirring and reacting for 2.0-24.0 hours, and carrying out after-treatment on the reaction solutionto obtain the products cycloalkyl alcohol and cycloalkyl ketone. The method disclosed by the invention has the advantages of high cycloalkyl alcohol and cycloalkyl ketone selectivity, low reaction temperature, few byproducts, small environmental influence and the like. In addition, the content of cycloalkyl hydroperoxide is low, and the safety coefficient is high. The invention provides an efficient, feasible and safe method for synthesizing cycloalkyl alcohol and cycloalkyl ketone through selective catalytic oxidation of cycloparaffin.
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Paragraph 0041-0042
(2020/12/10)
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- Method for preparing naphthenic alcohol and naphthenone by using molecular oxygen to selectively oxidize naphthenic hydrocarbon under synergistic catalysis of cobalt (II) salt/copper (II) salt
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The invention provides a method for preparing naphthenic alcohol and naphthenone by using molecular oxygen to selectively oxidize naphthenic hydrocarbon under synergistic catalysis of a cobalt (II) salt/copper (II) salt. The method comprises the following steps: in an agate ball-milling tank, ball-milling a main catalyst cobalt (II) salt and a cocatalyst copper (II) salt at room temperature according to a molar ratio to obtain a cobalt (II) salt/copper (II) salt composite catalyst; in a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene liner, dispersing the cobalt (II) salt/copper (II) salt composite catalyst into the naphthenic hydrocarbon, sealing the reaction kettle, conducting stirring and heating, and introducing an oxidizing agent oxygen; maintaining a settemperature and oxygen pressure to perform stirring reaction; and after the reaction, adding triphenylphosphine into a reaction mixture, and conducting stirring to reduce a generated peroxide at roomtemperature, so as to obtain the naphthenic alcohol and the naphthenone. The catalyst is cheap and easily available and the synthesis cost is low; the selectivity is high and generation of aliphatic diacid is effectively inhibited; and the aliphatic diacid selectivity is low, and continuity of the naphthenic hydrocarbon oxidization process and separation of products are facilitated.
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Paragraph 0104-0105
(2020/01/03)
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- Method for synergistically catalyzing and oxidizing cycloalkane by porphyrin cobalt (II)/zinc (II) salt
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The invention discloses a method for synergistically catalyzing and oxidizing cycloalkane by porphyrin cobalt (II)/zinc (II) salt. The method comprises the following steps: dispersing porphyrin cobalt(II) and a zinc (II) salt in cycloalkane, sealing the reaction system, carrying out heating to 100-130 DEG C while stirring, introducing oxygen to 0.2-3 MPa, keeping a set temperature and oxygen pressure, carrying out stirring for reacting for 3-24 hours, and then carrying out after-treatment on the reaction solution to obtain product naphthenic alcohol and naphthenic ketone. According to the method disclosed by the invention, the naphthenic alcohol and the naphthenic ketone are high in selectivity, and generation of aliphatic diacid is effectively inhibited; a cocatalyst is cheap and is easily available, and synthesis cost of the naphthenic alcohol and naphthenic ketone is low; the aliphatic diacid is low in selectivity, so that continuity of a cycloalkane oxidation process and separation of products are facilitated; and the method has a potential of solving the problem that naphthenic alcohol and naphthenic ketone are easily and deeply oxidized to generate aliphatic diacid in industrial cycloalkane catalytic oxidation processes. The method is a novel efficient feasible method for selective catalytic oxidation of cycloalkane.
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Paragraph 0083; 0084
(2019/12/25)
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- Copper-Catalyzed Oxidation of Alkanes with H2O2under a Fenton-like Regime
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Copper complexes bearing readily available ligand systems catalyzed the oxidation of alkanes with H2O2as the oxidant with high efficiency in remarkable yields (50–60 %). The reactions proceeded with unprecedented selectivity to give alkyl hydroperoxides as the major products. Detailed scrutiny of the reaction mechanism suggests the involvement of C-centered and O-centered radicals generated in a Fenton-like fashion.
- Garcia-Bosch, Isaac,Siegler, Maxime A.
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supporting information
p. 12873 - 12876
(2016/10/04)
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- METHOD FOR PRODUCING OXIDATION PRODUCT OF CYCLOALKANE
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Disclosed is a method for industrially efficiently producing a corresponding useful oxidation product such as a cycloalkyl hydroperoxide, a cycloalkanol, and/or a cycloalkanone, especially a particularly useful cycloalkanone, from a cycloalkane with a high selectivity in a good yield at low cost. This method is advantageous in respect of energy and process. Specifically, an oxidation product of a cycloalkane is obtained by oxidizing the cycloalkane in a liquid-liquid two phase system using an aqueous solvent in the presence of a nitrogen atom- containing cyclic compound which contains, as its ring constituent, a structure represented by following Formula (I): wherein X represents an oxygen atom or an -OR group, and wherein R represents a hydrogen atom or a hydroxyl-protecting group, and which has a solubility in water at 25°C of 0.5 g/100 g-H2O or more.
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Page/Page column 12; 14
(2009/09/26)
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- ORGANOBORANES FOR SYNTHESIS. 6. A CONVENIENT, GENERAL SYNTHESIS OF ALKYLHYDROPEROXIDES via AUTOXIDATION OF ORGANOBORANES
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The low temperature autoxidation of organoboranes in tetrahydrofuran leads to the formation of diperoxyboranes, which provide the corresponding alkylhydroperoxides in excellent yields, upon treatment with hydrogen peroxide.However, only two of the three alkyl groups on boron are used for the formation of hydroperoxides.This difficulty was solved by employing alkyldichloroborane etherates instead of trialkylboranes.The alkyldichloroborane etherates react cleanly with one molar equivalent of oxygen in ether solvent.The product is readily hydrolyzed to form the corresponding hydroperoxides in excellent yields.The autoxidation of organoboranes is inhibited by iodine or such free-radical scavengers.A study of the inhibition by iodine of the oxidation of representative trialkylboranes indicates that the rate of initiation decreases with an increase in the steric crowding about the boron atom.The rate of inhibition of the autoxidation of trialkylboranes by iodine reveals that the reaction involves a relatively slow rate of radical initiation, followed by a very fast rate of chain propagation.
- Brown, Herbert C.,Midland, M. Mark
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p. 4059 - 4070
(2007/10/02)
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