Heterogeneous copper porphyrin as well as preparation method and application thereof

A heterogeneous, porphyrin technology, applied in the direction of oxidation reaction preparation, peroxy compound preparation, carbon-based compound preparation, etc., to achieve the effect of inhibiting formation, novel structure and low selectivity

Pending Publication Date: 2020-03-27
ZHEJIANG UNIV OF TECH
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  • 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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  • Heterogeneous copper porphyrin as well as preparation method and application thereof
  • Heterogeneous copper porphyrin as well as preparation method and application thereof
  • Heterogeneous copper porphyrin as well as preparation method and application thereof

Examples

Experimental program
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Effect test

Embodiment 49

[0040] Example 49 is a scale-up experiment of the application of the heterogeneous copper porphyrin catalyst in the catalytic oxidation reaction of naphthenes.

[0041] The preparation method of the hybrid silicon carrier of the present invention can be found in J.Mol.Catal.A-Chem.2010,319,58; Eur.J.Org.Chem.2012,3625; React.Funct.Polym.2013,73,192 , specifically: Dissolve 12.04g of 3-chloropropyltriethoxysilane and 41.67g of ethyl orthosilicate in 150mL of absolute ethanol to obtain solution ①; mix 17.12g of water and 20.0mL of 1M tetrabutyl fluoride The tetrahydrofuran solution of ammonium chloride was dissolved in 100mL of absolute ethanol to prepare solution ②; quickly pour solution ① into solution ②, shake vigorously for 10 seconds, let stand, and age at room temperature for 6.0 days. The obtained solid was washed with absolute ethanol (3×150 mL), and then vacuum-dried at 80° C. for 10 h to obtain 46.58 g of white solid powder (hybrid silicon carrier).

[0042] The metal...

Embodiment 1

[0044] In a 50mL single-port reaction tube, 2.0000g hybrid silicon support, 0.2400g (0.3mmol) 5,10,15-tris(p-chlorophenyl)-20-(p-hydroxyphenyl)porphyrin copper(II ), 0.1200g (0.9mmol) K 2 CO 3 and 0.0300g (0.2mmol) KI were placed in 20mL N,N-dimethylformamide, stirred at room temperature under nitrogen atmosphere for 10min, then the reaction mixture was stirred and heated to 50°C, and stirred for 72.0h. Cool to room temperature, filter with suction, transfer to a 10mL centrifuge tube, centrifuge for 10min, remove the solid in the lower layer, dry DMF and wash (10×8mL) until the upper layer is clear, wash with distilled water (2×8mL) until the upper layer is clear, dry and wash with acetone ( 5×8mL) until the upper layer was clear, and the solid in the lower layer was taken and dried at 80°C for 12.0h. 0.3567 g of pink solid powder (Si@p-Cl-Porp.) was obtained.

Embodiment 2

[0046] In a 50mL single-port reaction tube, 2.0000g hybrid silicon support, 0.2400g (0.3mmol) 5,10,15-tris(p-chlorophenyl)-20-(p-hydroxyphenyl)porphyrin copper(II ), 0.1200g (0.9mmol) K 2 CO 3 and 0.0300g (0.2mmol) KI were placed in 20mL N,N-dimethylformamide, stirred at room temperature under nitrogen atmosphere for 10min, then the reaction mixture was stirred and heated to 120°C, and stirred for 72.0h. Cool to room temperature, filter with suction, transfer to a 10mL centrifuge tube, centrifuge for 10min, remove the solid in the lower layer, dry DMF and wash (10×8mL) until the upper layer is clear, wash with distilled water (2×8mL) until the upper layer is clear, dry and wash with acetone ( 5×8mL) until the upper layer was clear, and the solid in the lower layer was taken and dried at 80°C for 12.0h. 0.5259 g of pink solid powder (Si@p-Cl-Porp.) was obtained.

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Abstract

Provided is heterogeneous copper porphyrin; a preparation method comprises the following steps: putting copper (II) porphyrin, potassium carbonate, potassium iodide and a hybrid silicon carrier into N,N-dimethylformamide, stirring, and carrying out an immobilization reaction for 1.0-120 h in a nitrogen atmosphere at the temperature of 50-200 DEG C; then carrying out suction filtration and centrifugation on the reaction system to obtain a solid substance; and carrying out vacuum drying on the obtained solid substance at the temperature of 60-120 DEG C for 8-36 h to obtain the heterogeneous copper porphyrin catalyst. A method comprises the steps: dispersing heterogeneous copper porphyrin in cycloalkane, sealing the reaction system, heating to 100-130 DEG C while stirring, introducing oxygento 0.2-3.0 MPa, keeping the set temperature and oxygen pressure, stirring to react for 3-24 h, and carrying out after-treatment on the reaction solution to obtain products naphthenic alcohol and naphthenone. The naphthenic alcohol and the naphthenone are high in selectivity, generation of aliphatic diacid is effectively inhibited, and the method is a novel efficient and feasible cycloalkane selective catalytic oxidation method.

Description

[0001] (1) Technical field [0002] The invention relates to a heterogeneous copper porphyrin, a preparation method and its application in the catalytic oxidation of naphthenes, belonging to the field of organic catalysis and fine organic synthesis. [0003] (2) Background technology [0004] 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. 合成(WO 2019046316;WO 2019030294;WO 2019069911;CN 108864082;CN109180556;Journal of Medicinal Chemistry 2019,62:1837-1858;Russian Journal ofGeneralChemistry 2018,88:2646-2652,即世界专利2019046316;世界专利2019030294;世界专利 2019069911; Chinese patent 108864082; Chinese patent 109180556; Journal of Medicinal Chemistry 2019, 62: 1837-1858; Russian Journal of Basic Chemistry 2018, 88...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07C27/16C07C29/48C07C45/53C07C35/08C07C49/403C07C407/00C07C409/14
CPCB01J31/1633B01J31/1815C07C45/53C07C29/48C07C407/00B01J2231/70B01J2531/025B01J2531/16C07C2601/14
Inventor 沈海民孙静佘远斌
Owner ZHEJIANG UNIV OF TECH
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