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Method for synergistically catalyzing and oxidizing cycloalkane by porphyrin cobalt (II)/zinc (II) salt

A technology of synergistic catalysis, porphyrin cobalt, applied in chemical instruments and methods, oxidation reaction preparation, preparation of organic compounds, etc., to achieve the effects of being conducive to continuity, low selectivity, and inhibiting formation

Inactive Publication Date: 2019-12-13
ZHEJIANG UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although metalloporphyrins as catalysts have the advantages of less catalyst consumption, high catalytic efficiency, easy structure adjustment, good biocompatibility, and environmental protection, but in the process of catalytic molecular oxygen oxidation of cycloalkanes to prepare cycloalkanols and cycloalkanones, there is still no Can reduce and avoid the formation of aliphatic diacids

Method used

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  • Method for synergistically catalyzing and oxidizing cycloalkane by porphyrin cobalt (II)/zinc (II) salt
  • Method for synergistically catalyzing and oxidizing cycloalkane by porphyrin cobalt (II)/zinc (II) salt

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Experimental program
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Effect test

Embodiment 1

[0024] In a 100mL stainless steel autoclave with polytetrafluoroethylene liner, 0.0016g (0.0020mmol) 5,10,15,20- tetrakis (4-chlorophenyl) porphyrin cobalt (II) and 0.0367g (0.20 mmol) anhydrous zinc acetate dispersed in 16.8320 g (200 mmol) cyclohexane, seal the reaction vessel, stir and raise the temperature to 120° C., and feed oxygen to 1.0 MPa. At 120°C, 1.0MPa oxygen pressure, 800rpm stirring reaction for 8.0h. After completion of the reaction, cool to room temperature with ice water, add 1.3115g (5.00mmol) triphenylphosphine (PPh 3 ), stirred at room temperature for 30min to reduce the generated peroxide. Using acetone as solvent, the resulting reaction mixture was adjusted to 100 mL. Pipette 10mL of the resulting solution, and use toluene as an internal standard for gas chromatographic analysis; pipette 10mL of the resulting solution, and use benzoic acid as an internal standard for liquid chromatographic analysis. Cyclohexane conversion 5.39%, cyclohexanol selectiv...

Embodiment 2

[0026]In a 100mL stainless steel autoclave with polytetrafluoroethylene liner, 0.00016g (0.0002mmol) 5,10,15,20- tetrakis (4-chlorophenyl) porphyrin cobalt (II) and 0.0367g (0.20 mmol) anhydrous zinc acetate dispersed in 16.8320 g (200 mmol) cyclohexane, seal the reaction vessel, stir and raise the temperature to 120° C., and feed oxygen to 1.0 MPa. At 120°C, 1.0MPa oxygen pressure, 800rpm stirring reaction for 8.0h. After completion of the reaction, cool to room temperature with ice water, add 1.3115g (5.00mmol) triphenylphosphine (PPh 3 ), stirred at room temperature for 30min to reduce the generated peroxide. Using acetone as solvent, the resulting reaction mixture was adjusted to 100 mL. Pipette 10mL of the resulting solution, and use toluene as an internal standard for gas chromatographic analysis; pipette 10mL of the resulting solution, and use benzoic acid as an internal standard for liquid chromatographic analysis. Cyclohexane conversion 5.22%, cyclohexanol selectiv...

Embodiment 3

[0028] 0.1619g (0.20mmol) 5,10,15,20-tetrakis(4-chlorophenyl) porphyrin cobalt (II) and 0.0367g (0.20 mmol) anhydrous zinc acetate dispersed in 16.8320 g (200 mmol) cyclohexane, seal the reaction vessel, stir and raise the temperature to 120° C., and feed oxygen to 1.0 MPa. At 120°C, 1.0MPa oxygen pressure, 800rpm stirring reaction for 8.0h. After completion of the reaction, cool to room temperature with ice water, add 1.3115g (5.00mmol) triphenylphosphine (PPh 3 ), stirred at room temperature for 30min to reduce the generated peroxide. Using acetone as solvent, the resulting reaction mixture was adjusted to 100 mL. Pipette 10mL of the resulting solution, and use toluene as an internal standard for gas chromatographic analysis; pipette 10mL of the resulting solution, and use benzoic acid as an internal standard for liquid chromatographic analysis. Cyclohexane conversion 5.78%, cyclohexanol selectivity 53%, cyclohexanone selectivity 42%, cyclohexyl hydroperoxide selectivity ...

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Abstract

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.

Description

technical field [0001] The invention relates to a new method for preparing cycloalkanol and cycloalkanone by synergistically catalyzing molecular oxygen selective oxidation of cycloalkane with porphyrin cobalt (II) / zinc (II) salt, which belongs to the field of organic catalysis and fine organic synthesis. Background technique [0002] Catalytic oxidation of naphthenes is an important chemical transformation process. The oxidation products cycloalkanol and cycloalkanone are not only important organic solvents, but also important fine chemical intermediates, which are widely used in the production of fine chemical products such as pesticides, medicines, and dyes. Synthesis (WO 2019046316; WO 2019030294; WO 2019069911; CN 108864082; CN 109180556; Journal of Medicinal Chemistry 2019, 62: 1837-1858; Russian Journal of General Chemistry 2018, 88: 262) In addition, cycloalkanol and cycloalkanone can be further oxidized to prepare aliphatic diacids, which are important precursors fo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/50C07C35/08C07C35/06C07C35/20C07C45/33C07C49/403C07C49/395C07C49/413
CPCC07C29/50C07C45/33C07C2601/08C07C2601/14C07C2601/18C07C35/08C07C35/06C07C35/20C07C49/403C07C49/395C07C49/413
Inventor 沈海民宁磊佘远斌
Owner ZHEJIANG UNIV OF TECH
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