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Method for preparing p-methoxypheny-lethyl acid from natural anethole

A technology of p-methoxybenzene and p-methoxybenzaldehyde, which is applied in the field of preparing p-methoxyphenylacetic acid from natural anethole, can solve the problems of harsh reaction conditions, difficult preparation and recovery, and low reaction yield. The effect of simplified operation, mild reaction conditions and simple reaction conditions

Inactive Publication Date: 2008-11-05
GUANGZHOU INST OF GEOCHEMISTRY - CHINESE ACAD OF SCI
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Problems solved by technology

[0003] The preparation method of p-methoxyphenylacetic acid mainly contains the following several at present: (1) cyanide method: take p-methoxybenzaldehyde as raw material and generate cyanohydrin after reacting with cyanide, then obtain p-methoxybenzaldehyde through hydrolysis and reduction Phenylacetic acid; but this method uses highly toxic raw material cyanide, which seriously pollutes the environment
(2) benzyl cyanide hydrolysis method: benzyl cyanide hydrolysis method is the traditional production method of phenylacetic acid, that is, under normal temperature and pressure, sodium cyanide and benzyl chloride generate benzyl nitrile, and then obtain phenylacetic acid through acidic hydrolysis or alkaline hydrolysis; but The reaction yield of this method is low, and sodium cyanide is a highly toxic substance, which is very harmful to operators and the environment
(3) Grignard reagent method: take p-methoxy-substituted benzyl chloride and metal magnesium as raw materials to react with carbon dioxide to obtain p-methoxyphenylacetic acid; but this method has harsh reaction conditions and is difficult to industrialize
(4) Oxylation method: use methoxyl substituted benzyl chloride as raw material, under the action of carbonylation catalyst, under lower pressure (<1.5Mpa) and mild temperature, carbon monoxide is used in a two-phase system of sodium hydroxide and organic solvent Carry out carbonylation reaction to generate sodium phenylacetate, which is acidified into phenylacetic acid under acidic conditions; but the catalyst in this method is expensive, easily poisoned and inactivated, and difficult to prepare and recycle, and carbon monoxide is more toxic
(5) Phenylacetamide hydrolysis method: use methoxyl substituted styrene as raw material, react with ammonia sulfur to generate corresponding phenylacetamide, and then generate methoxyl substituted phenylacetic acid through hydrolysis; but the by-product of this method is 2 -Phenylethanthiol has a strange smell and pollutes the environment, and the reaction needs to be carried out under pressure, which limits the application of this method
(6) Acetophenone rearrangement method: by p-methoxyacetophenone as raw material, ethanol, sulfur and piperazine hexahydrate were added to the reaction pot and refluxed for 4 hours, then the ethanol was evaporated, and the obtained sulfurized piperazine was mixed with p- Methoxyacetophenone undergoes rearrangement reaction at 135-140°C, then hydrolyzes with sodium hydroxide, and then acidifies with hydrochloric acid to obtain p-methoxyphenylacetic acid; but the by-product hydrogen sulfide of this method is very smelly and pollutes the environment

Method used

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  • Method for preparing p-methoxypheny-lethyl acid from natural anethole

Examples

Experimental program
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Effect test

Embodiment 1

[0031] Add 14.8g (0.1mol) of anethole, 8.88g of acetic acid, and 35.52g of cyclohexane in the reaction flask, stir evenly, control the reaction temperature at 20°C, and feed 2.7L (0.12mol) of O 3 , carry out ozonation reaction, 20min oxidation finishes. Add NaHSO with a concentration of 200g / L in the three-necked flask 3 Aqueous solution 57mL, then slowly add ozonide dropwise, react at 80°C for 60min, cool down to 50°C, adjust to pH ≥ 10 with sodium hydroxide solution, stand and separate layers, the upper layer is crude p-methoxybenzaldehyde, the lower layer is water The phase is extracted with cyclohexane and incorporated into the crude product of p-methoxybenzaldehyde. The crude product of p-methoxybenzaldehyde is dried with anhydrous sodium sulfate and rectified under reduced pressure. When the pressure is 667Pa and the temperature is 110-120°C, The distillate is a colorless or light yellow liquid which is p-methoxybenzaldehyde, weighing 10.88g, and the yield is 80.0%.

Embodiment 2

[0033] Add 14.8g (0.1mol) of anethole, 8.88g of acetic acid, and 35.52g of cyclohexane in the reaction flask, stir evenly, control the reaction temperature at 0°C, and feed 2.24L (0.10mol) of O 3 Carry out ozonation reaction, 40min oxidation finishes. Add NaHSO with a concentration of 200g / L in the three-necked flask 3Aqueous solution 52mL, then slowly add ozonide dropwise, react at 60°C for 90min, cool down to 50°C, adjust to pH ≥ 10 with sodium hydroxide solution, stand and separate layers, the upper layer is crude p-methoxybenzaldehyde, the lower layer is water The phase was extracted with cyclohexane and incorporated into the crude p-methoxybenzaldehyde; the crude p-methoxybenzaldehyde was dried with anhydrous sodium sulfate and rectified under reduced pressure. When the pressure was 667Pa and the temperature was 110-120°C, The distillate is a colorless or light yellow liquid which is p-methoxybenzaldehyde, weighing 9.79g and yielding 71.9%.

Embodiment 3

[0035] Add 14.8g (0.1mol) of anethole and 44.4g of ethanol in the reaction flask, stir well, control the reaction temperature at 0°C, adjust the ozone flow, and then feed 4.48L (0.20mol) of O 3 Carry out ozonation reaction, 40min oxidation finishes. Add concentration of 200g / L Na in the three-necked flask 2 SO 3 Aqueous solution 57mL, then slowly add ozonide dropwise, react at 60°C for 90min, cool down to 50°C, adjust to pH ≥ 10 with sodium hydroxide solution, stand and separate layers, the upper layer is crude p-methoxybenzaldehyde, the lower layer is water The phase is extracted with cyclohexane and incorporated into the crude product of p-methoxybenzaldehyde. The crude product of p-methoxybenzaldehyde is dried with anhydrous sodium sulfate and rectified under reduced pressure. When the pressure is 667Pa and the temperature is 110-120°C, The distillate was a colorless or pale yellow liquid, which was p-methoxybenzaldehyde, weighing 9.52 g, and the yield was 70.0%.

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Abstract

The invention discloses a method for preparing methoxyphenylacetic acid by natural anethole; the natural anethole is taken as a raw material and generated into the anisicaldehyde by oxidation reaction, then anisic mandelic acid (salt) is generated by the insertion reaction of carbine; finally the methoxyphenylacetic acid is obtained by reduction. The method has the advantages of reproducible raw material, simple operation and high yield, etc.; furthermore, the method can prepare the methoxyphenylacetic acid which can replace the source of petrochemical industry.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a method for preparing p-methoxyphenylacetic acid from natural anethole. Background technique [0002] P-methoxyphenylacetic acid is an important intermediate in organic synthesis, widely used in medicine and dyes. For example: use p-methoxyphenylacetic acid as a raw material to synthesize quinolinone derivatives with anti-osteoporosis activity (Acta Pharmaceutica Sinica, 1995, 30(10): 792-795); p-methoxyphenylacetic acid is a synthetic An important raw material for α, β-diaryl substituted acrylic acid. α, β-Diaryl substituted acrylic acid not only has anti-hypoxia and contraceptive activity, but also synthesizes phenanthrene parallel compound with anti-tumor, anti-fungal and anti-bacterial effects. An important intermediate of pyridine alkaloids (Chemical Reagents, 2006, 28 (7): 441); a new generation of antidepressant venlafaxine (venlafaxine) was synthesized from p-methoxyphe...

Claims

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Application Information

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IPC IPC(8): C07C59/64C07C51/16C07C51/377
Inventor 邹永都建立陈大峰
Owner GUANGZHOU INST OF GEOCHEMISTRY - CHINESE ACAD OF SCI
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