Synthetic method for p-hydroxybenzaldehyde

Abstract

The invention discloses a synthetic method for p-hydroxybenzaldehyde. The synthetic method comprises the following steps: with phenol and formic acid as raw materials, subjecting the raw materials toan esterification reaction under the action of a catalyst A so as to produce phenyl formate; and subjecting phenyl formate to a Fries rearrangement reaction under the action of a catalyst B so as to produce p-hydroxybenzaldehyde. According to the invention, the conversion rate of the raw materials is high, product yield is high, and the method is novel method for preparing p-hydroxybenzaldehyde from phenol and formic acid; and phenol and formic acid undergo the esterification reaction under the action of the catalyst A so as to produce phenyl formate, phenyl formate undergoes the Fries rearrangement reaction under the action of the catalyst B so as to produce p-hydroxybenzaldehyde, and then recrystallization and purification are carried out, so product purity can reach 99% or more, and overall product yield is as high as 95%. The method uses widely available raw materials and cheap and easily available catalysts, and is simple in reaction process, free of severe requirements on production equipment, low in equipment investment and convenient for industrial application.

Description

technical field

[0001] The invention belongs to the technical field of fine chemicals, and in particular relates to a synthesis method of p-hydroxybenzaldehyde. Background technique

[0002] p-Hydroxybenzaldehyde is an important spice, polymer material, medicine, and pesticide intermediate. Using p-hydroxybenzaldehyde as a raw material, various fragrances such as vanillin, ethyl vanillin, jasminal, syringaldehyde, anisaldehyde and raspberry ketone can be synthesized. In the field of pesticides, p-Hydroxybenzaldehyde is mainly used to synthesize the herbicides Bromoxynil and Hydrochlorenil. In the field of medicine, p-hydroxybenzaldehyde is mainly found in amoxicillin (amoxicillin), antibacterial synergist trimethoprim (TMP), 3,4,5-trimethoxybenzaldehyde, p-hydroxyglycine, amoxicillin Synthesis of cephalosporin, artificial Gastrodia elata, Rhododendron, Esmolol and other drugs. In addition, p-hydroxybenzaldehyde is also used in the synthesis of fungicides, photographic emu...

Examples

Embodiment 1

[0025] Such as figure 1 As shown, the method of the present embodiment includes the following steps:

[0026] Step 1. Weigh 18.8g (0.2mol) of phenol, 11.04g (0.24mol) of formic acid, 3.8g (0.02mol) of p-toluenesulfonic acid and 200mL of toluene, and add them to a reaction flask equipped with a heating mantle and a condensing reflux device. Under the action of magnetic stirring, heat the reaction liquid in the reaction bottle to 105°C through the heating mantle to carry out the esterification reaction for 4 hours, stop heating after the esterification reaction, and distill the reaction liquid when the temperature of the reaction liquid drops to 40°C , collecting fractions at 171°C to 173°C to obtain 24.0g of colorless phenyl formate with a yield of 98.4% and a purity of 99.2% (GC purity);

[0027] Step 2. Weigh 12.2g (0.1mol) of phenyl formate, 27.2g (0.2mol) of zinc chloride and 100mL of toluene, and add them to a reaction flask equipped with a heating mantle and a reflux con...

Embodiment 2

[0031] Such as figure 1 As shown, the method of the present embodiment includes the following steps:

[0032] Step 1. Weigh 18.8g (0.2mol) of phenol, 11.04g (0.24mol) of formic acid, 2.0g (0.02mol, 98%) of concentrated sulfuric acid and 200mL of toluene, and add them to the reaction flask equipped with a heating mantle and a condensing reflux device , under magnetic stirring, heated to 105°C; kept for 4h, stopped heating, and cooled the system; when the system temperature dropped to 40°C, distilled the system, collected fractions at 171-173°C, and obtained 23.0 g of colorless phenyl formate, Yield 94.3%, purity 99.1% (GC purity);

[0033] Step 2. Weigh 12.2g (0.1mol) of phenyl formate, 26.7g (0.2mol) of zinc ions or aluminum trichloride and 100mL of toluene, and add them to the reaction flask equipped with a heating mantle and a condensing reflux device, and stir under magnetic force. , heated to 110°C; after keeping for 4 hours, stop heating and cool down the system; when t...

Embodiment 3

[0037] Such as figure 1 As shown, the method of the present embodiment includes the following steps:

[0038] Step 1. Weigh 18.8g (0.2mol) of phenol, 11.04g (0.24mol) of formic acid, 3.8g (0.02mol) of p-toluenesulfonic acid and 200mL of o-dichlorobenzene, and add them to the reaction chamber equipped with heating mantle and condensing reflux In the bottle, under magnetic stirring, heat up to 180°C; after keeping for 4 hours, stop heating to cool down the system; when the system temperature drops to 40°C, distill the system, collect fractions at 171-173°C, and obtain 24.0 g of colorless phenyl formate Liquid, yield 98.4%.

[0039] Step 2. Weigh 12.2g (0.1mol) of phenyl formate, 27.2g (0.2mol) of zinc chloride and 100mL of p-xylene, and add them to the reaction flask equipped with a heating mantle and a condensing reflux device. Under magnetic stirring, heat to 135°C; after keeping for 4 hours, stop heating and cool down the system; when the temperature of the system drops to ...

technical field

[0001] The invention belongs to the technical field of fine chemicals, and in particular relates to a synthesis method of p-hydroxybenzaldehyde. Background technique

[0002] p-Hydroxybenzaldehyde is an important spice, polymer material, medicine, and pesticide intermediate. Using p-hydroxybenzaldehyde as a raw material, various fragrances such as vanillin, ethyl vanillin, jasminal, syringaldehyde, anisaldehyde and raspberry ketone can be synthesized. In the field of pesticides, p-Hydroxybenzaldehyde is mainly used to synthesize the herbicides Bromoxynil and Hydrochlorenil. In the field of medicine, p-hydroxybenzaldehyde is mainly found in amoxicillin (amoxicillin), antibacterial synergist trimethoprim (TMP), 3,4,5-trimethoxybenzaldehyde, p-hydroxyglycine, amoxicillin Synthesis of cephalosporin, artificial Gastrodia elata, Rhododendron, Esmolol and other drugs. In addition, p-hydroxybenzaldehyde is also used in the synthesis of fungicides, photographic emu...

Examples

Embodiment 1

[0025] Such as figure 1 As shown, the method of the present embodiment includes the following steps:

[0026] Step 1. Weigh 18.8g (0.2mol) of phenol, 11.04g (0.24mol) of formic acid, 3.8g (0.02mol) of p-toluenesulfonic acid and 200mL of toluene, and add them to a reaction flask equipped with a heating mantle and a condensing reflux device. Under the action of magnetic stirring, heat the reaction liquid in the reaction bottle to 105°C through the heating mantle to carry out the esterification reaction for 4 hours, stop heating after the esterification reaction, and distill the reaction liquid when the temperature of the reaction liquid drops to 40°C , collecting fractions at 171°C to 173°C to obtain 24.0g of colorless phenyl formate with a yield of 98.4% and a purity of 99.2% (GC purity);

[0027] Step 2. Weigh 12.2g (0.1mol) of phenyl formate, 27.2g (0.2mol) of zinc chloride and 100mL of toluene, and add them to a reaction flask equipped with a heating mantle and a reflux con...

Embodiment 2

[0031] Such as figure 1 As shown, the method of the present embodiment includes the following steps:

[0032] Step 1. Weigh 18.8g (0.2mol) of phenol, 11.04g (0.24mol) of formic acid, 2.0g (0.02mol, 98%) of concentrated sulfuric acid and 200mL of toluene, and add them to the reaction flask equipped with a heating mantle and a condensing reflux device , under magnetic stirring, heated to 105°C; kept for 4h, stopped heating, and cooled the system; when the system temperature dropped to 40°C, distilled the system, collected fractions at 171-173°C, and obtained 23.0 g of colorless phenyl formate, Yield 94.3%, purity 99.1% (GC purity);

[0033] Step 2. Weigh 12.2g (0.1mol) of phenyl formate, 26.7g (0.2mol) of zinc ions or aluminum trichloride and 100mL of toluene, and add them to the reaction flask equipped with a heating mantle and a condensing reflux device, and stir under magnetic force. , heated to 110°C; after keeping for 4 hours, stop heating and cool down the system; when t...

Embodiment 3

[0037] Such as figure 1 As shown, the method of the present embodiment includes the following steps:

[0038] Step 1. Weigh 18.8g (0.2mol) of phenol, 11.04g (0.24mol) of formic acid, 3.8g (0.02mol) of p-toluenesulfonic acid and 200mL of o-dichlorobenzene, and add them to the reaction chamber equipped with heating mantle and condensing reflux In the bottle, under magnetic stirring, heat up to 180°C; after keeping for 4 hours, stop heating to cool down the system; when the system temperature drops to 40°C, distill the system, collect fractions at 171-173°C, and obtain 24.0 g of colorless phenyl formate Liquid, yield 98.4%.

[0039] Step 2. Weigh 12.2g (0.1mol) of phenyl formate, 27.2g (0.2mol) of zinc chloride and 100mL of p-xylene, and add them to the reaction flask equipped with a heating mantle and a condensing reflux device. Under magnetic stirring, heat to 135°C; after keeping for 4 hours, stop heating and cool down the system; when the temperature of the system drops to ...

Images