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Preparation method of 2-phenyl halogenated methyl benzene and derivatives thereof

A technology for methylbenzene and its derivatives, which is applied in the field of preparation of 2-phenylhalogenated methylbenzene and its derivatives, and can solve the problems of complex steps, low final yield, and high cost of 2-arylbenzyl bromide , to achieve the effect of low price

Inactive Publication Date: 2018-01-26
CHINA PETROLEUM & CHEM CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The high cost of 2-arylbenzyl bromide hinders its subsequent commercial application
In 2001, LIN used Grignard reagent and chlorobenzene as raw materials to catalyze 2-methylbiphenyl with anhydrous nickel halide, and selectively brominated methyl to obtain 2-phenylbenzyl bromide. Harsh, and the final yield is not high (PCT / US00 / 33686)
In 2008, people such as Budak Yakup utilized methylmagnesium bromide and cyclohexanone as initial raw materials to prepare 2-phenylbenzyl bromide through four steps, with complicated steps and low yield (Asian Journal of Chemistry 2008,20,1943-1949 )

Method used

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  • Preparation method of 2-phenyl halogenated methyl benzene and derivatives thereof
  • Preparation method of 2-phenyl halogenated methyl benzene and derivatives thereof
  • Preparation method of 2-phenyl halogenated methyl benzene and derivatives thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0018]

[0019] (1) Preparation of 2-phenylformaldehyde

[0020] The reaction system was kept under a nitrogen atmosphere, and N,N-dimethylformamide (60mL), water (30mL), phenylboronic acid: o-bromobenzaldehyde = 1:1 [(3.36g, 27.5mmol) were added to the Schlenk bottle : (3.2mL, 27.5mmol)], sodium carbonate NaCO 3 (3.21 g, 30.3 mmol). Using an ice bath, when the reaction was cooled to 0°C, palladium acetate (0.1-0.5 g) was added. After stirring for about 30 minutes, continue the reaction at room temperature and stir for 10-20 hours. After the reaction, the product turns black, add an appropriate amount of ethyl acetate to dilute, wash with saturated ammonium chloride solution and saturated brine three times, add magnesium sulfate to dry, and place for 30min to 1h. Suction filtration, rotary evaporator concentration, a clear oily product. Finally, the product was separated and purified by column chromatography according to the ratio of petroleum ether (PE) / ethyl acetate (...

Embodiment 2

[0027]

[0028] (1) Preparation of 2-(3,4-dimethoxyphenyl)-4-methoxybenzaldehyde

[0029] The reaction system was kept under a nitrogen atmosphere, and N,N-dimethylformamide (60mL), water (30mL), and 3,4-dimethoxyphenylboronic acid (5g, 27.5mmol) were added to a Schlenk bottle: 2- Bromo-4-methoxybenzaldehyde (5.91g, 27.5mmol), sodium carbonate NaCO 3 (3.21 g, 30.3 mmol). Using an ice bath, when the reaction was cooled to 0°C, palladium acetate (0.1-0.5 g) was added. After stirring for about 30 minutes, continue the reaction at room temperature and stir for 10-20 hours. After the reaction, dilute with an appropriate amount of ethyl acetate, wash with saturated ammonium chloride solution and saturated brine three times, add magnesium sulfate to dry, and stand for 30 minutes to 1 hour. Suction filtration, rotary evaporator concentration, a clear oily product. Finally, the product was separated and purified by column chromatography according to the ratio of hexane / ethyl ace...

Embodiment 3

[0036]

[0037] (1) Preparation of 2-(benzo[d][1,3]-dioxo-5-yl)benzyl alcohol

[0038]The system was kept under a nitrogen atmosphere, and N,N-dimethylformamide (20mL), water (10mL), and 3,4-(methylenedioxy)phenylboronic acid (3g, 18.1mmol) were added to the Schlenk bottle : 2-bromobenzyl alcohol (3.39g, 18.1mmol), sodium carbonate NaCO 3 (2.11 g, 19.9 mmol). Using an ice bath, when the reaction was cooled to 0°C, palladium acetate (0.1-0.5 g) was added. After stirring for about 30 minutes, continue the reaction at room temperature and stir for 10-20 hours. After the reaction, dilute with an appropriate amount of ethyl acetate, wash with saturated ammonium chloride solution and saturated brine three times, add magnesium sulfate to dry, and place for 30 minutes to 1 hour. Suction filtration, rotary evaporator concentration, a clear oily product. Finally, the product was separated and purified by column chromatography according to the ratio of hexane / ethyl acetate (EtOAc)...

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Abstract

The invention discloses a preparation method of 2-phenyl halogenated methyl benzene and derivatives thereof, wherein the preparation method comprises the steps: taking 2-bromobenzaldehyde or substituted 2-bromobenzaldehyde and phenylboronic acid or substituted phenylboronic acid as raw materials, dissolving in a solvent, carrying out a reaction in an anaerobic and alkaline environment and in the presence of a catalyst palladium salt, carrying out a reaction of the obtained reaction product with a reducing agent and reducing into substituted benzyl alcohol, then adding a halogen source, carrying out a reaction, and purifying the obtained product to obtain the 2-phenyl halogenated methyl benzene and the derivatives thereof. The method is simple and the yield of 2-phenyl halogenated methyl benzene and the derivatives thereof is high.

Description

technical field [0001] The invention relates to a preparation method of 2-phenylhalogenated methylbenzene and derivatives thereof. Background technique [0002] Phenanthrenes have attracted much attention due to their extensive physicochemical properties, such as photoconductivity and electroluminescence. In addition to potential applications in materials science, it also exists in a large number of natural or synthetic compounds with different biological activities (Chem. Asian J. 2014, 9, 1525-1529). The market demand for metallocene polypropylene is increasing, and its core catalysts are also receiving more and more attention. Among them, rac-Me 2 Si(2-Me-4-PhInd) 2 ZrCl 2 and rac-Me 2 Si(2-Me-4-NpInd) 2 ZrCl 2 The catalyst can obtain higher isotactic polypropylene (isotacticity reaches 99%) (Organometallics 1994, 13, 954-963). And 2-arylbenzyl bromide and its derivatives are the initial raw materials for preparing phenanthrene (or fluorene) compounds and indenes. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C17/16C07C22/04C07C41/22C07C43/225C07D317/52
Inventor 宋莎钟向宏蔡伟刘振宇梁胜彪李禄建王伟哲
Owner CHINA PETROLEUM & CHEM CORP