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CN-119680546-B - Metal catalyst and preparation method and application thereof

CN119680546BCN 119680546 BCN119680546 BCN 119680546BCN-119680546-B

Abstract

The invention discloses a metal catalyst and a preparation method and application thereof. The preparation method comprises the steps of carrying out a first reaction on a mixed reaction system at least comprising metal salt, a cocatalyst and an organic solvent, and then adding an alkaline substance to carry out a second reaction to obtain the metal catalyst. The catalyst precursor adopted in the invention is non-noble metal salt, the reaction condition is mild, the operation is simple, the prepared metal catalyst has wide substrate application range and good functional group tolerance, and the requirement on equipment is low.

Inventors

  • XIE YINJUN
  • ZHANG SHIYUN

Assignees

  • 中国科学院宁波材料技术与工程研究所

Dates

Publication Date
20260512
Application Date
20241216

Claims (6)

  1. 1. The application of the metal catalyst in catalyzing the hydrogenation reduction of aryl compounds and/or heteroaryl compounds to prepare naphthenic compounds and/or saturated heterocyclic compounds is characterized in that the preparation method of the metal catalyst comprises the steps of carrying out a first reaction on a mixed reaction system at least comprising metal salt, a cocatalyst and an organic solvent, and then adding an alkaline substance to carry out a second reaction to prepare the metal catalyst; Wherein the metal salt comprises any one or more of anhydrous cobalt chloride, cobalt chloride hexahydrate, anhydrous cobalt bromide, cobalt bromide hexahydrate, cobalt fluoride, cobalt iodide dihydrate, anhydrous cobalt carbonate, anhydrous cobalt acetate, cobalt acetate tetrahydrate, cobalt nitrate hexahydrate, cobalt acetylacetonate, cobalt sulfate monohydrate, cobalt sulfate heptahydrate, nickel acetylacetonate, bis (1, 5-cyclooctadiene) nickel, nickel acetate, nickel chloride, nickel bromide, dibromo (ethylene glycol dimethyl ether) nickel, and nickel triflate; the cocatalyst comprises any one or more of borane, sodium borohydride, lithium borohydride, potassium borohydride, sodium triethylborohydride, lithium aluminum tetrahydroide, trimethylaluminum, diisobutylaluminum hydride and borane ammonia; the organic solvent comprises any one or more of tetrahydrofuran, methyl tertiary butyl ether, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, methanol, ethanol, isopropanol, tertiary butanol, cyclohexane, n-hexane, heptane and methylcyclohexane; The alkaline substance comprises any one or a combination of a plurality of potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, potassium methoxide, sodium methoxide, lithium methoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide and sodium hydride; The reaction temperature of the first reaction is 0-100 ℃ and the time is 0.1-24 hours, and the reaction temperature of the second reaction is 0-100 ℃ and the time is 0.1-24 hours; The molar ratio of the metal salt to the cocatalyst to the alkaline substance is 1-0.3:0.1-5:0.1-10.
  2. 2. A process for the catalytic hydrogenation reduction of aryl and/or heteroaryl compounds to naphthenic compounds and/or saturated heterocyclic compounds, comprising: Use of a metal catalyst as claimed in claim 1; And, in hydrogen atmosphere, under the action of the metal catalyst, carrying out selective hydrogenation reaction on the aryl compound and/or the heteroaryl compound to prepare a naphthenic compound and/or a saturated heterocyclic compound; Wherein the aryl and/or heteroaryl compound has a structure as shown in formula (I): ; Formula (I); Wherein X is C, N or O, R is selected from monosubstituted or polysubstituted alkyl, ester group, carboxylic acid, amino, amide, hydroxyl, alcohol, alkenyl, alkynyl, alkyl, benzene ring or nitrogen heterocycle with the number of C atoms of 1-20.
  3. 3. The method according to claim 2, which is characterized by comprising the specific steps of carrying out selective hydrogenation reaction on an aryl compound and/or a heteroaryl compound for 3-80 hours under the action of a metal catalyst under the conditions that the hydrogen pressure is 0.1-20 MPa and the temperature is 25-200 ℃ to prepare a naphthenic compound and/or a saturated heterocyclic compound.
  4. 4. The method of claim 2, wherein the molar ratio of the metal salt to the aryl compound and/or heteroaryl compound is 0.01-20:100.
  5. 5. The method of claim 2, wherein the molar ratio of the cocatalyst to the aryl and/or heteroaryl compound is 0.01-40:100.
  6. 6. The method of claim 2, wherein the molar ratio of the basic substance to the aryl compound and/or heteroaryl compound is 0.01-100:100.

Description

Metal catalyst and preparation method and application thereof Technical Field The invention belongs to the field of catalysis and organic synthesis, relates to a metal catalyst and a preparation method and application thereof, and particularly relates to a metal catalyst and a preparation method thereof, and application of the metal catalyst in catalyzing hydrogenation reduction of aryl compounds and/or heteroaryl compounds to prepare naphthenic compounds and/or saturated heterocyclic compounds. Background Organic compounds containing cycloalkyl or heterocyclic structures are important raw materials for the synthesis of pharmaceuticals, pesticides and materials, such as cyclohexanol, cyclohexane, 1, 4-cyclohexanedimethanol, piperazine, etc. Catalyst hydrogenation of benzene or heteroaromatic rings is the most direct and efficient means of synthesizing cycloalkyl-or heterocycle-containing compounds. However, catalytic hydrogenation using benzene rings and heteroaromatic rings has many challenges, including mainly (1) the benzene rings and heteroaromatic rings have aromaticity, the catalytic dearomatization needs to overcome a very high energy barrier, (2) the heterocyclic atom bond of C-O or C-N in the compound is easy to break in the catalytic hydrogenation process, resulting in structural disruption, and (3) the stereoselectivity problem of hydrogenation reaction of polysubstituted (hetero) aromatic hydrocarbons. In 1901, sabatier and SENDERENS reported the first benzene hydrogenation reaction. Various catalytic systems have been developed thereafter, focusing mainly on noble metal-based catalysts such as Ru, rh, pd, pt. For example, 2024, yu Zhixiang, group OrganicLetters, discloses a catalytic system composed of Rh/Pd and Rh/Pt, which are commercially available, to produce cyclohexane derivatives by hydrogenation of aromatic compounds at normal temperature and pressure. However, these catalytic processes often require the use of noble metals as catalysts, which are too costly. Therefore, there is a trend in the development of inexpensive and efficient catalysts. Compared with noble metals, benzene ring hydrogenation catalyzed by non-noble metals is still very difficult. 2023, ANANDNARANI and Kishore Natte et al reported that nitrogen-doped carbon-supported Co 3O4 nanoparticles achieved catalytic hydrogenation of benzene rings and derivatives thereof, but required a large catalyst usage and the catalytic preparation was complicated. Therefore, a catalytic system with simple operation is developed, and the (hetero) arene can be prepared into (hetero) naphthene compounds with high selectivity and high activity under mild reaction conditions, and the (hetero) naphthene compounds have great significance in the aspects of science and future industrialization. Disclosure of Invention The invention mainly aims to provide a metal catalyst, a preparation method and application thereof, so as to overcome the defects of the prior art. In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps: the embodiment of the invention provides a preparation method of a metal catalyst, which comprises the steps of carrying out a first reaction on a mixed reaction system at least comprising metal salt, a cocatalyst and an organic solvent, and then adding an alkaline substance to carry out a second reaction to prepare the metal catalyst. The embodiment of the invention also provides the metal catalyst prepared by the preparation method. The embodiment of the invention also provides application of the metal catalyst in catalytic hydrogenation reaction. The embodiment of the invention also provides a method for preparing naphthenic compounds and/or saturated heterocyclic compounds by catalyzing the hydrogenation reduction of aryl compounds and/or heteroaryl compounds, which comprises the following steps: preparing a metal catalyst by adopting the preparation method; And carrying out selective hydrogenation reaction on the aryl compound and/or the heteroaryl compound in the presence of the metal catalyst in a hydrogen atmosphere to obtain the naphthenic compound and/or the saturated heterocyclic compound. Compared with the prior art, the invention has the beneficial effects that: (1) The method prepares the cheap metal catalyst in situ, does not need complex ligand or specific carrier, has simple catalyst synthesis steps, low preparation cost, convenient operation and easy amplification; (2) The hydrogenation reaction condition in the invention is mild, and the high-selectivity hydrogenation of aryl compounds and/or heteroaryl compounds can be realized under the condition of room temperature; (3) The method provided by the invention has wide application range, can realize the preparation of various cycloalkyl-containing or saturated heterocyclic compounds with excellent industrial prospects, has lower equipment requirements, and has industrialized potential. Drawing