Method for catalytically synthesizing aryl oxazole compound by using nickel complex

A technology of nickel complexes and aryl oxazoles, which is applied in nickel organic compounds, organic compound/hydride/coordination complex catalysts, chemical instruments and methods, etc., and can solve problems such as high reaction temperature and large catalyst equivalent , to achieve the effects of high product yield, stable physical and chemical properties, and high substrate universality

Active Publication Date: 2022-04-05
SHANGHAI INST OF TECH
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Problems solved by technology

[0003] Kalyani et al. reported a nickel-catalyzed arylation reaction of benzoxazole, but the reaction required the use of air-sensitive Ni(COD) 2 It is a catalyst (J.Org.Chem.2019,84,13092), and the equivalent of the catalyst is relatively large, and the reaction temperature is relatively high. These factors limit the industrial application of the system

Method used

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  • Method for catalytically synthesizing aryl oxazole compound by using nickel complex
  • Method for catalytically synthesizing aryl oxazole compound by using nickel complex
  • Method for catalytically synthesizing aryl oxazole compound by using nickel complex

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preparation example Construction

[0031] The preparation method of the nickel complex containing the ortho carboryl benzothiazole structure comprises the following steps:

[0032] 1) Add the n-BuLi solution to the ortho-carborane solution at -80°C to -75°C, stir and react at room temperature for 30-60min;

[0033] 2) Add bromobenzothiazole and react at room temperature for 6-8h;

[0034] 3) Add NiCl 2 , and react at room temperature for 3-5h, after post-treatment to obtain nickel complexes.

[0035] In step 1), the n-BuLi solution is n-BuLi n-hexane solution, and the ortho carborane solution is ortho carborane tetrahydrofuran solution.

[0036] In step 3), the post-treatment process is: standing and filtering after the reaction, decompressing to dry the solvent to obtain the crude product, and then subjecting the crude product to column chromatography separation; during the column chromatography separation process, the eluent is petroleum ether and A mixed solvent of tetrahydrofuran, and the volume ratio of...

Embodiment 1

[0039] Synthesis of nickel complexes containing ortho carboryl benzothiazole structure:

[0040] At -78°C, n-BuLi n-hexane solution (1.6 mmol) was slowly added dropwise to the ortho-position carborane o-C 2 B 10 h 12 (0.64mmol) in tetrahydrofuran solution, stirred at this temperature for 30 minutes, slowly rose to room temperature and continued to react for 1 hour, then added bromobenzothiazole (0.64mmol), and continued to react at room temperature for 6 hours. Then NiCl 2 (0.64 mmol) was added to the reaction system and reacted for another 3 hours. After the reaction, stand and filter, and dry the solvent under reduced pressure. The obtained crude product is separated by column chromatography (by volume, petroleum ether / tetrahydrofuran=6:1), and the brown target product is obtained, which is the ortho carbon-containing The nickel complex (yield 78%) of boryl benzothiazole structure, the reaction formula is:

[0041]

[0042] Among them, "·" represents the boron-hydrog...

Embodiment 2

[0045] Nickel complexes catalyze the synthesis of aryl oxazole compounds, the specific process is as follows:

[0046]Using the nickel complex prepared in Example 1 as a catalyst, the nickel complex (0.001mmol), benzoxazole (1.0mmol), chlorobenzene (1.1mmol) and potassium carbonate (1.2mmol) were dissolved in 2 mL of toluene, and reacted at room temperature After 100 minutes, after the end, the concentrated reaction solution was directly separated by silica gel column chromatography, dried until the mass remained constant, and the corresponding product C was obtained. 13 h 9 NO (90% yield), the reaction formula is:

[0047]

[0048] 1 H NMR (400MHz, CDCl 3 )δ: 8.12(d, J=8.0Hz, 2H), 7.44(s, 1H), 7.36(d, J=8.0Hz, 1H), 7.10-7.01(m, 5H). HRMS theoretical value C 13 h 9 NO(M) + : 195.0684, actual measured value: 195.0688.

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Abstract

The invention relates to a method for catalytically synthesizing an aryl oxazole compound by using a nickel complex, which comprises the following steps: by taking the nickel complex containing an ortho-carborane benzothiazole structure as a catalyst and taking benzoxazole and aryl halide compounds as raw materials, carrying out oxidative coupling reaction at room temperature in the presence of alkali, thereby obtaining the aryl oxazole compound. The aryl oxazole compound is obtained. Compared with the prior art, the method has the advantages that the nickel complex containing the ortho-carborane benzothiazole structure is utilized to efficiently catalyze the multi-component reaction at room temperature to synthesize the aryl oxazole compound through the one-pot method, synthesis of the aryl oxazole compound at room temperature is achieved, the using equivalent of the catalyst is low, the reaction condition is mild, the substrate universality is high, raw materials are low in price and easy to obtain, and the method is suitable for industrial production. The product yield is high.

Description

technical field [0001] The invention belongs to the technical field of preparation of aryl oxazole compounds, and relates to a method for catalytically synthesizing aryl oxazole compounds using nickel complexes. Background technique [0002] Arylazole structural motifs widely exist in substances and drug molecules with physiological activity, such as the anti-inflammatory and analgesic drug flunoprofen has this structure. Among the many methods for the synthesis of such compounds, the use of transition metals to catalyze the C-H bond arylation of azole compounds is a simple, efficient and atom-economical method. Most reports in this field are reaction systems in which noble metal palladium and rhodium compounds are used as catalysts (Chem. Rev. 2007, 107, 174), but the catalysts for these reaction systems are expensive and require the use of complex ligands. Subsequent research has gradually focused on the design and synthesis of cheap metal catalysts, such as the nickel-ca...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D263/57C07D413/04C07F15/04B01J31/22
CPCY02P20/584
Inventor 姚子健王珂卞明高永红刘振江
Owner SHANGHAI INST OF TECH
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