Bimetallic center metalloporphyrin as well as preparation method and application thereof

A metalloporphyrin and bimetallic technology, applied in the fields of organic catalysis and fine organic synthesis, can solve the problems of reducing the selectivity of cycloalkyl alcohols and cycloalkyl ketones, increasing the uncontrollability of the reaction system, and being unfavorable for continuous production, etc. Achieve high selectivity, is conducive to product separation, and is conducive to the effect of continuous

Active Publication Date: 2020-12-18
ZHEJIANG UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Due to the high reaction temperature, the generated cycloalkanol and cycloalkanone are easy to be deeply oxidized to generate aliphatic diacids, which block the pipeline of the catalytic oxidation process of cycloalkane, which is not conducive to continuous production
The main source of the above problems is: the oxidation intermediate product, cycloalkyl hydroperoxide is converted to the target oxidation product cycloalkanol and cycloalkanone through the free radical thermal decomposition path, which increases the uncontrollability of the reaction system and reduces the cycloalkyl hydroperoxide. Selectivity of Alcohols and Cycloalkyl Ketones

Method used

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  • Bimetallic center metalloporphyrin as well as preparation method and application thereof
  • Bimetallic center metalloporphyrin as well as preparation method and application thereof

Examples

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Effect test

Embodiment 66

[0032] Example 66 is a scale-up experiment of the application of the phase bimetallic center metalloporphyrin catalyst in the catalytic oxidation reaction of naphthenes.

[0033] The metalloporphyrins used in the present invention are synthesized with reference to Journal of the American Chemical Society 2017, 139: 18590-18597; Journal of the American Chemical Society 2018, 140: 6383-6390. All reagents used were commercially available of analytical grade.

Embodiment 1

[0035] In a 25mL reaction tube, 0.3189g (0.4mmol) 5,10,15-tris(p-chlorophenyl)-20-(p-hydroxyphenyl)porphyrin zinc (Ⅱ), 0.3156g (0.4mmol) 5,10,15-tris(p-chlorophenyl)-20-(p-hydroxyphenyl)porphyrin cobalt (Ⅱ), 0.0975g (0.4mmol) 1,6-dibromohexane, 0.0083g (0.04 mmol) KI, 0.1106g (0.8mmol) K 2 CO 3 , dissolved in 6mL DMF (except water), N 2 Under protection, react at 100°C for 72h. After the reaction was over, the solution was desolvated under reduced pressure. The resulting solid was dissolved in 300 mL of dichloromethane, washed with 4 × 300 mL of distilled water, anhydrous Na 2 SO 4 After drying, it was desolvated under reduced pressure. Silica gel column chromatography (200-300 mesh, packed with cyclohexane), V 环己烷 :V 二氯甲烷 =9:1, identify the eluent received by thin-layer chromatography (visible light color development), stop receiving when the color of the product becomes light, and collect a single point of the component, decompression precipitation, vacuum After dry...

Embodiment 2

[0037] In a 25mL reaction tube, 1.5941g (2mmol) 5,10,15-tris(p-chlorophenyl)-20-(p-hydroxyphenyl)porphyrin zinc (Ⅱ), 0.3156g (0.4mmol) 5 ,10,15-tris(p-chlorophenyl)-20-(p-hydroxyphenyl)porphyrin cobalt (Ⅱ), 0.0975g (0.4mmol) 1,6-dibromohexane, 0.0083g (0.04mmol )KI, 0.1106g (0.8mmol)K 2 CO 3 , dissolved in 6mL DMF (except water), N 2 Under protection, react at 100°C for 72h. After the reaction was over, the solution was desolvated under reduced pressure. The resulting solid was dissolved in 300 mL of dichloromethane, washed with 4 × 300 mL of distilled water, anhydrous Na 2 SO 4 After drying, it was desolvated under reduced pressure. Silica gel column chromatography (200-300 mesh, packed with cyclohexane), V 环己烷 :V 二氯甲烷 =9:1, identify the eluent received by thin-layer chromatography (visible light color development), stop receiving when the color of the product becomes light, and collect a single point of the component, decompression precipitation, vacuum After drying...

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Abstract

The invention relates to a bimetallic center metalloporphyrin as well as a preparation method thereof, the preparation method of the bimetallic center metalloporphyrin catalyst comprises the followingsteps: putting porphyrin M1 (II), porphyrin M2 (II), potassium carbonate, potassium iodide and dibromoalkane (such as 1,5-dibromopentane, 1,6-dibromohexane and the like) into N,N-dimethylformamide, and carrying out a stirring reaction at 50-200 DEG C for 12.0-120 hours in a nitrogen atmosphere; and carrying out suction filtration, washing, purification, reduced pressure desolvation and vacuum drying on the reaction system to obtain the bimetallic center metalloporphyrin catalyst. The invention also provides an application of the bimetallic center metalloporphyrin catalyst in catalytic oxidation of cycloalkane. The cycloalkyl alcohol and cycloalkyl ketone 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 double-metal center metalloporphyrin, its 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;CN 109180556;Journal of Medicinal Chemistry 2019,62:1837-1858;Russian Journal of GeneralChemistry 2018,88:2646-2652,即世界专利2019046316;世界专利2019030294; World Patent 2019069911; Chinese Patent 108864082; Chinese Patent 109180556; Journal of Medicinal Chemistry 2019, 62: 1837-1858; Russian Journal of Basi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07C45/33C07C29/50C07C49/403C07C49/413C07C35/08C07C35/20C07C35/205C07C49/395C07C35/06
CPCB01J31/183C07C45/33C07C29/50B01J2231/70B01J2531/025B01J2531/16B01J2531/26B01J2531/845B01J2531/72B01J2531/842B01J2531/847C07C2601/08C07C2601/14C07C2601/20C07C2601/18C07C49/403C07C49/413C07C49/395C07C35/08C07C35/20C07C35/205C07C35/06Y02P20/584
Inventor 沈海民张羽孙静
Owner ZHEJIANG UNIV OF TECH
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