End-capped 3d cobalt (ii) porphyrin pof material and its preparation method and application
A 3D, porphyrin technology, applied in the field of capped 3D cobalt porphyrin POF material and its preparation, can solve the problems of inability to effectively limit the disordered diffusion of free radicals, promotion, and the inability to realize the selectivity of oxidation products, so as to avoid The use of toxic and harmful organic reagents, low energy consumption, and low cost effects
Active Publication Date: 2022-06-03
ZHEJIANG UNIV OF TECH
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Problems solved by technology
However, metalloporphyrins in a homogeneous state and surface-immobilized metalloporphyrins cannot effectively confine O 2 The disordered diffusion of free radicals during the oxidation of C-H bonds in hydrocarbons cannot achieve a significant increase in the selectivity of partial oxidation products
Method used
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Embodiment 1~ Embodiment 5
[0022] Examples 1 to 5, preparation of end-capped 3D cobalt(II) porphyrin POF materials;
Embodiment 6~ Embodiment 49
[0023] Examples 6 to 49, the case of catalytic oxidation of ethylbenzene and its derivatives;
Embodiment 47~ Embodiment 48
[0024] Embodiment 47~Embodiment 48, comparative case;
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The invention discloses a capped 3D cobalt (II) porphyrin POF material and its preparation method and application. (II), [4‑(4',4',5',5'‑tetramethyl‑1',3',2'‑dioxaborolanephenyl)]methane, potassium carbonate, Pd (PPh 3 ) 4 , the reaction solvent are added to the reactor together, the air in the reaction system is replaced by nitrogen, and the temperature is stirred to react; then the end-capping reagent is added, and the reaction is continued for 1.0~48.0 h; after the reaction is completed, filter, and the obtained solid is vacuum-dried after washing to obtain Capped 3D cobalt(II) porphyrin POF materials. The capped 3D cobalt(II) porphyrin POF material of the present invention catalyzes the method for preparing acetophenone and its derivatives through the selective oxidation of ethylbenzene and its derivatives, has the advantages of convenient operation, mild reaction conditions, etc., and is subjected to capping treatment It can significantly reduce the content of halogenated groups that are not conducive to the reaction in the POF material, thereby effectively improving the catalytic activity of the material, and the selectivity of catalytically generating aromatic ketones is high.
Description
technical field [0001] The invention belongs to the fields of organic chemical industry and fine organic synthesis, and in particular relates to an end-capped 3D cobalt (II) porphyrin POF material and a preparation method and application thereof. Background technique [0002] Acetophenone and its derivatives are an important class of fine chemical intermediates, which are widely used in the synthesis of fine chemical products such as medicines, pesticides, dyes, analytical detection reagents, and high-end intermediates (WO 201611034971; Bioorganic&Medicinal Chemistry Letters 2019,29: 525-528; Bioorganic Chemistry 2019, 82:360-377; ACS Applied Materials & Interfaces 2018, 10:44324-44335). At present, the synthesis of acetophenone and its derivatives mainly uses ethylbenzene, 1-phenethyl alcohol and styrene and their derivatives as raw materials, and is realized by oxidation reaction (US20190002487; CN 108947846; Molecular Catalysis 2019,469:27- 39; Organic Process Research &...
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IPC IPC(8): C08G83/00B01J31/22C07C201/12C07C205/45
CPCC08G83/008B01J31/183C07C201/12B01J2531/845B01J2231/70C07C205/45Y02P20/584
Inventor 沈海民丛淑贞
Owner ZHEJIANG UNIV OF TECH
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