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Self-coupling reaction method of manganses-catalyzed and oxidized chlorobenzene grignard reagent

A technology of aryl Grignard reagent and coupling reaction, which is applied in the field of synthesis of biaryl compounds, can solve the problems of non-negligible price of brominated aromatic hydrocarbons, shorten the reaction time, reduce the cost, etc., and achieve good catalytic effect and high reaction yield Good, cost reduction effect

Inactive Publication Date: 2008-10-15
BEIJING INSTITUTE OF TECHNOLOGYGY
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Problems solved by technology

[0005] In order to solve the shortcoming that brominated aromatic hydrocarbons cannot be ignored and are expensive, the present invention proposes the self-coupling reaction of chloroaryl Grignard reagents using manganese-catalyzed oxidation to overcome the shortcoming in cost, and adopts advanced online infrared technology in the present invention , the entire reaction is monitored, and the process of the entire reaction can be well understood. At the same time, the reaction time is shortened by half according to the monitoring results, which further reduces the cost of similar reactions. See figure 2

Method used

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  • Self-coupling reaction method of manganses-catalyzed and oxidized chlorobenzene grignard reagent
  • Self-coupling reaction method of manganses-catalyzed and oxidized chlorobenzene grignard reagent
  • Self-coupling reaction method of manganses-catalyzed and oxidized chlorobenzene grignard reagent

Examples

Experimental program
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Effect test

Embodiment 1

[0022] Add 30ml of anhydrous tetrahydrofuran (THF) solution of p-chlorotoluene Grignard reagent (which contains 9.7mmol p-chlorotoluene Grignard reagent) into a 50ml three-necked flask, and then add MnCl 2 (126mg, 1mmol), and 1,2-dichloroethane (1.19g, 12mmol) was slowly added dropwise with a syringe, and the addition was completed in 10 minutes. During the addition, nitrogen was protected, and the addition temperature was kept at 25°C. The reaction was stirred for 1 h, the reaction mixture was quenched with 2 ml of methanol, the reaction solution was filtered, and the filter cake was washed with tetrahydrofuran (THF), the filtrates were combined, and the tetrahydrofuran (THF) was evaporated under reduced pressure to obtain 900 mg of 4,4-dimethylbiphenyl crude product , the crude product was purified by silica gel column chromatography (the mobile phase volume ratio was n-hexane:ethyl acetate=50:1), and 850 mg (99% yield) of a white solid was obtained, which was 4,4'-dimethylbi...

Embodiment 2

[0024] The conditions are the same as in Example 1, except that the addition of p-chlorotoluene Grignard reagent is changed to the addition of o-chlorotoluene Grignard reagent, and the reaction result is that the corresponding biaryl compound yield is 87.4%.

Embodiment 3

[0026] The conditions are the same as in Example 1, except that the addition of p-chlorotoluene Grignard reagent is changed to p-methoxychlorobenzene Grignard reagent, and the reaction result is that the yield of the corresponding biaryl compound is 80.4%.

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Abstract

The invention provides a synthetic method which uses manganese chloride as a catalyst and adopts1, 2-ethylene dichloride as a secondary oxidant to catalyze the homo-coupling reaction of a chlorine aryl compound grignard reagent, so as to further obtain a biaryl compound with the corresponding symmetric structure. In the synthesis route, the method uses various chlorine aryl compounds and activated magnesium to generate the grignard reagent, and adds the manganese chloride and the 1,2-ethylene dichloride as the catalyst and the secondary oxidant to catalyze the grignard reagent and obtain the homo-coupling reaction. The synthesis route is simple, the raw materials and the catalyst are cheap, the production rate is high, the operation is convenient, and the purification is easy. The method is applicable to agrochemicals, drugs, natural products, conduction materials and asymmetric synthesis of catalysts.

Description

Technical field [0001] The present invention relates to the synthesis method that uses manganese dichloride as catalyst, 1,2-dichloroethane as re-oxidant to catalyze the self-coupling reaction of chloroaryl Grignard reagent to obtain biaryl compound with corresponding symmetrical structure, It belongs to the field of chemical synthesis. Background technique [0002] The biaryl structure is an important structural module in a large number of agrochemicals, pharmaceuticals, natural products, conductive materials, and catalysts for asymmetric synthesis. In recent years, due to its wide application in chemical synthesis, the research on the direct, effective and environment-friendly synthesis methodology of biaryl structure has received widespread attention and has become a hot spot in synthesis research. [0003] Among them, the oxidative self-coupling reaction using aryl metal reagents is the most effective synthetic method for the synthesis of symmetrical biaryl skeletons, a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B37/00C07C1/32C07C15/14C07C205/11C07C201/12
Inventor 周智明薛为哲
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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