5130-47-2Relevant academic research and scientific papers
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
Shen, Hai-Min,Wang, Xiong,Ning, Lei,Guo, A-Bing,Deng, Jin-Hui,She, Yuan-Bin
, (2020/11/20)
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.
Three metal centers (Co _AOMARKENCODEAMPX0AOA) Cu _AOMARKENCODEAMPX0AOA Method using Zn) 2D MOFs/ultraviolet light to catalyze oxidation of cycloalkane
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Paragraph 0028; 0079-0080, (2021/11/06)
The invention relates to a three-metal center (Co _AOMARKENCODEAMPX0AOA). Cu _AOMARKENCODEAMPX0AOA The method comprises Zn) 2D MOFs/ultraviolet light catalytic oxidation of cycloalkane to synthesize cycloalkyl alcohol and cycloalkanone, and belongs to the field of industrial catalysis and fine organic synthesis. To the application method, metalloporphyrin three-metal center (Co _AOMARKENCODEAMPX0AOA) is used. Cu _AOMARKENCODEAMPX0AOA Zn) 2D MOFs dispersed in cycloalkane, wherein metalloporphyrin three-metal center (Co _AOMARKENCODEAMPX0AOA) Cu _AOMARKENCODEAMPX0AOA Zn) 2D MOFs mass is 0.01% - 20%, g / mol of the substance of the cycloalkane, and the reaction system is sealed. An oxidant is introduced, the ultraviolet lamp is a light source, and the reaction liquid of the stirring reaction 2.0-24 . 0h. is subjected to post-treatment to obtain the product cycloalkyl alcohol and cycloalkyl ketone. The method provided by the invention has the advantages of low reaction temperature, mild reaction conditions, high reaction efficiency, high selectivity of cycloalkyl alcohol and cycloalkyl ketone, less byproducts and small environmental impact. The invention provides a high efficiency. Available, safe cycloalkanes selectively catalyze the oxidative synthesis of cycloalkyl alcohols and cycloalkyl ketones.
Catalytic oxidation of cycloalkanes by porphyrin cobalt(II) through efficient utilization of oxidation intermediates
Shen, Hai M.,Wang, Xiong,Guo, A. Bing,Zhang, Long,She, Yuan B.
, p. 1166 - 1173 (2020/09/17)
The catalytic oxidation of cycloalkanes using molecular oxygen employing porphyrin cobalt(II) as catalyst was enhanced through use of cycloalkyl hydroperoxides, which are the primary intermediates in oxidation of cycloalkanes, as additional oxidants to further oxidize cycloalkanes in the presence of porphyrin copper(II), especially for cyclohexane, for which the selectivity was enhanced from 88.6 to 97.2% to the KA oil; at the same time, the conversion of cyclohexane was enhanced from 3.88 to 4.41%. The enhanced efficiency and selectivity were mainly attributed to the avoided autoxidation of cycloalkanes and efficient utilization of oxidation intermediate cycloalkyl hydroperoxides as additional oxidants instead of conventional thermal decomposition. In addition to cyclohexane, the protocol presented in this research is also very applicable in the oxidation of other cycloalkanes such as cyclooctane, cycloheptane and cyclopentane, and can serve as a applicable and efficient strategy to boost the conversion and selectivity simultaneously in oxidation of alkanes. This work also is a very important reference for the extensive application of metalloporphyrins in catalysis chemistry.
Method for catalytic oxidation of cycloalkane by confinement porphyrin Co (II)
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Paragraph 0071; 0072, (2020/05/01)
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.
Confinement porphyrin Co (II), and preparation method and application thereof
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Paragraph 0103-0104, (2020/04/17)
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.
Method for synergistically catalyzing and oxidizing cycloparaffin through confined metalloporphyrin cobalt (II)/Cu (II) salt
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Paragraph 0045-0046, (2020/12/10)
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.
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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Paragraph 0108-0109, (2020/01/03)
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.
Method for synergistically catalyzing and oxidizing cycloalkane by porphyrin cobalt (II)/zinc (II) salt
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Paragraph 0087; 0088, (2019/12/25)
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.
Copper-Catalyzed Oxidation of Alkanes with H2O2under a Fenton-like Regime
Garcia-Bosch, Isaac,Siegler, Maxime A.
supporting information, p. 12873 - 12876 (2016/10/04)
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.
Multifunctional catalyst based on sandwich-type polyoxotungstate and MIL-101 for liquid phase oxidations
Balula, Salete S.,Granadeiro, Carlos M.,Barbosa, André D.S.,Santos, Isabel C.M.S.,Cunha-Silva, Luís
, p. 142 - 148 (2013/07/27)
A sandwich-type polyoxometalate {(TBA)7H3[Co 4(H2O)2(PW9O34) 2]} was immobilized for the first time into the three-dimensional porous metal-organic framework, MIL-101. The composite material Co 4(PW9)2@MIL-101 was prepared and the incorporation of the Co4(PW9)2 was confirmed using a myriad of solid state methods (FT-IR, FT-Raman, powder XRD, SEM-EDX and ICP analysis). Co4(PW9)2@MIL-101 reveals to be an active, selective and recyclable catalyst for the oxidation of different substrates: geraniol, R-(+)-limonene, styrene and cyclooctane, using H 2O2 as eco-sustainable oxidant. The stability and robustness of the heterogeneous catalyst was confirmed by different techniques. The MIL-101 framework demonstrates to be a suitable and efficient support to accommodate catalytically active sandwich-type polyoxotungstates.
