CN112479877A - Synthesis process of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate - Google Patents
Synthesis process of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate Download PDFInfo
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Abstract
The invention discloses a synthesis process of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate, which comprises the steps of mixing methyl p-hydroxyphenylpropionate and tert-butyl alcohol according to a certain molar ratio, carrying out continuous reaction by a tubular fixed bed reactor filled with a solid catalyst to obtain a crude product of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate, distilling to remove low-boiling water and residual tert-butyl alcohol, and carrying out secondary separation by a rectifying tower to obtain a methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate product. The synthesis process of the invention takes methyl p-hydroxyphenylpropionate and tert-butanol as raw materials, uses granular solid sulfonic acid resin for continuous reaction, and then carries out secondary separation by a rectifying tower to obtain a high-purity methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate product, the yield is higher, the quality is excellent, the unreacted methyl p-hydroxyphenylpropionate is recycled, the industrial production value is good, and the production cost is reduced.
Description
Technical Field
The invention relates to a synthesis process of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate, belonging to the technical field of fine chemical engineering.
Background
The methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate is an important organic fine chemical intermediate, is used as hindered phenol due to the unique structure, has a protective effect on phenolic hydroxyl of the hindered phenol due to a tert-butyl group at the ortho position, can prevent the self-oxidation loss of phenols, and has obviously improved antioxidant performance compared with simple phenols; as a semi-hindered phenol, the hydroxyl group of the semi-hindered phenol is free at the ortho position, the reaction activity is strong, various chemical reactions can be carried out, various compounds such as a stabilizer, a coloring agent, an optical material, a medical intermediate and the like can be synthesized, and the semi-hindered phenol is widely applied to the industries of high polymer materials, printing, auxiliaries, dyes, medicines and the like. The methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate can be directly used as a light stabilizer and a high-efficiency stabilizer of unsaturated polyester, for example, the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate can be used for a silver dye bleaching method to synthesize a new photographic image process. Therefore, the research and development of the 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate have good commercial value.
The prior preparation method of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate takes 3- (3, 5-di-tert-butyl-4-hydroxy) methyl phenylpropionate as a raw material, and removes tert-butyl by using an acidic catalyst to synthesize the 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate. In this process, the catalyst is not reusable; and because of the activity selectivity relationship of the catalyst, the byproduct generation is more, the reaction yield is 75-85%, the raw material waste is caused, and the economic cost is increased.
Therefore, in order to reduce the production cost and avoid the loss of raw materials, the invention provides a preparation method for synthesizing 3- (3-tert-butyl-4-hydroxy) phenylpropionic acid methyl ester by taking p-hydroxy-phenyl methyl propionate and tert-butyl alcohol as raw materials, and the production process has positive significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a synthesis process of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate, which takes methyl p-hydroxyphenylpropionate and tert-butyl alcohol as raw materials, shortens the reaction time, reduces the occurrence of side reactions, reduces the production cost, and improves the yield and quality of the 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate.
In order to achieve the purpose, the invention adopts the following technical scheme: a synthesis process of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate comprises the following steps:
(1) preparation of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate: adding methyl p-hydroxyphenylpropionate and tert-butyl alcohol into a premixing tank at the temperature of 40-45 ℃, uniformly mixing, continuously adding the mixture into a tubular fixed bed reactor filled with a solid catalyst for reaction through an advection pump with the flow rate of 1-2 ml/min, and allowing the material to flow out of a discharge hole of the tubular fixed bed reactor after the material stays in the tubular fixed bed reactor for a period of time to obtain a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate;
(2) separating and purifying a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate: removing water and tert-butyl alcohol from the obtained crude methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate product by an atmospheric distillation still, feeding the crude methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate from the top of a first-stage vacuum distillation tower, extracting methyl p-hydroxyphenylpropionate from the top of the first-stage vacuum distillation tower into a methyl p-hydroxyphenylpropionate storage tank, extracting the rest methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate and a small amount of the by-product methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate from the bottom of the first-stage vacuum distillation tower into the bottom of a second-stage vacuum distillation tower, extracting the by-product methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate from the top of the second-stage vacuum distillation tower into a waste recovery tank, obtaining the product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate.
Wherein the molar ratio of the methyl p-hydroxyphenylpropionate to the tert-butanol in the step (1) is 1: 0.7-0.8.
Further, the molar ratio of methyl p-hydroxyphenylpropionate to tert-butanol in the step (1) is 1: 0.75.
Wherein, the packing height of the tubular fixed bed reactor in the step (1) is 100-120 cm.
Wherein, the solid catalyst in the step (1) is granular solid sulfonic acid resin.
Wherein the reaction temperature of the tubular fixed bed reactor in the step (1) is 100-110 ℃.
Wherein the average residence time of the materials in the tubular fixed bed reactor in the step (1) is 1-2 h.
Wherein the distillation temperature in the atmospheric distillation kettle in the step (2) is 110-120 ℃.
Wherein, the tower top temperature of the first-stage vacuum rectification tower in the step (2) is 130-140 ℃, the tower internal pressure is-0.8-0.5 kPa, and the number of tower plates is 20.
Wherein, the tower top temperature of the secondary vacuum rectification tower in the step (2) is 170-180 ℃, the tower internal pressure is-0.8-0.5 kPa, and the number of tower plates is 10.
The invention has the beneficial effects that: according to the synthesis process, granular solid sulfonic acid resin is used, methyl p-hydroxyphenylpropionate and tert-butyl alcohol are used as raw materials, the product is obtained through synthesis, water with low boiling point and residual tert-butyl alcohol are removed through distillation, secondary separation is carried out through a rectifying tower, the high-purity methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate product is obtained, the yield is high, the quality is excellent, and the unreacted methyl p-hydroxyphenylpropionate is recycled; the molar ratio of the methyl p-hydroxyphenylpropionate to the tert-butyl alcohol in the synthesis process is 1: 07-0.8, so that the conversion rate and the utilization rate of the methyl p-hydroxyphenylpropionate are high on one hand, and the yield and the purity of a methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate product are high on the other hand; the synthesis process uses a tubular fixed bed reactor, the reaction is a continuous reaction, and the synthesis process has good industrial production value and reduces the production cost.
Drawings
FIG. 1 is a chemical reaction scheme of the present invention;
FIG. 2 is a process flow diagram of the present invention.
Detailed Description
In order to more clearly and completely illustrate the present invention, the following examples are given by way of illustration of the present invention, and are not intended to limit the present invention.
The number of plates of the first-stage vacuum distillation column used in examples 1 to 12 was 20; the number of the tower plates of the second-stage vacuum rectifying tower is 10.
Example 1
(1) Preparation of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate: adding 200g of methyl p-hydroxyphenylpropionate and 58g of tert-butanol (the molar ratio is 1:0.7) into a premixing tank at the temperature of 40-45 ℃, uniformly mixing, continuously adding the mixture into a tubular fixed bed reactor filled with granular solid sulfonic acid resin at the temperature of 100 ℃, the inner diameter of 2cm and the filler height of 100cm through an advection pump with the flow rate of 2ml/min for reaction, wherein the average residence time of materials in the tubular fixed bed reactor is 1.04h, and discharging the materials from a discharge port of the tubular fixed bed reactor to obtain a crude product of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate; samples were taken from the outlet of the reactor, and the conversion of methyl p-hydroxyphenylpropionate was 63.31%, the conversion of t-butanol was 91.02%, the content of methyl 3- (35-di-t-butyl-4-hydroxy) phenylpropionate as a by-product was 0.53%, and the content of methyl 3- (3-t-butyl-4-hydroxy) phenylpropionate was 68.85% by quantitative analysis by gas chromatography;
(2) separating and purifying a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate: removing water and tert-butyl alcohol from the obtained crude product of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate by an atmospheric distillation still with the temperature of 110 ℃, feeding the crude product from the top of a first-stage vacuum rectifying tower, extracting methyl p-hydroxyphenylpropionate from the top of the first-stage vacuum rectifying tower into a methyl p-hydroxyphenylpropionate storage tank, extracting 77g of methyl p-hydroxyphenylpropionate, allowing the top of the first-stage vacuum rectifying tower to have the temperature of 130 ℃, allowing the pressure in the tower to be-0.8 kPa, allowing the rest of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate and a small amount of methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate to enter the bottom of a second-stage vacuum rectifying tower from the bottom of the first-stage vacuum rectifying tower, allowing the methyl 3- (3, 5-di-tert-butyl-4-hydroxy), 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate is extracted from the top of a secondary vacuum rectifying tower and enters a finished product recovery tank, the temperature of the top of the secondary vacuum rectifying tower is 170 ℃, and the pressure in the tower is-0.8 kPa, so 159g of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate product with the purity of 99.6 percent is obtained.
Example 2
(1) Preparation of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate: adding 200g of methyl p-hydroxyphenylpropionate and 58g of tert-butanol (the molar ratio is 1:0.7) into a premixing tank at the temperature of 40-45 ℃, uniformly mixing, continuously adding the mixture into a tubular fixed bed reactor filled with granular solid sulfonic acid resin at the temperature of 100 ℃, the inner diameter of 2cm and the filler height of 100cm through an advection pump with the flow rate of 1.5ml/min for reaction, wherein the average residence time of materials in the tubular fixed bed reactor is 1.39h, and discharging the materials from a discharge port of the tubular fixed bed reactor to obtain a crude product of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate; taking a sample at the outlet of the reactor, and quantitatively analyzing by gas chromatography, wherein the conversion rate of methyl p-hydroxyphenylpropionate is 63.97%, the conversion rate of tert-butanol is 92.13%, the content of the byproduct methyl 3- (35-di-tert-butyl-4-hydroxy) phenylpropionate is 0.76%, and the content of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate is 69.11%;
(2) separating and purifying a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate: removing water and tert-butyl alcohol from the obtained crude product of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate by an atmospheric distillation still with the temperature of 115 ℃, feeding the crude product from the top of a first-stage vacuum rectifying tower, extracting methyl p-hydroxyphenylpropionate from the top of the first-stage vacuum rectifying tower to enter a methyl p-hydroxyphenylpropionate storage tank, extracting 76g of methyl p-hydroxyphenylpropionate, controlling the top temperature of the first-stage vacuum rectifying tower to be 135 ℃, controlling the pressure in the tower to be-0.65 kPa, allowing the rest of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate and a small amount of methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate to enter the bottom of a second-stage vacuum rectifying tower from the bottom of the first-stage vacuum rectifying tower, allowing the methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate to exit from the, and 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate is extracted from the top of a secondary vacuum rectifying tower and enters a finished product recovery tank, the temperature of the top of the secondary vacuum rectifying tower is 175 ℃, and the pressure in the tower is-0.65 kPa, so that 160g of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate product with the purity of 99.43% is obtained.
Example 3
(1) Preparation of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate: adding 200g of methyl p-hydroxyphenylpropionate and 58g of tert-butanol (the molar ratio is 1:0.7) into a premixing tank at the temperature of 40-45 ℃, uniformly mixing, continuously adding the mixture into a tubular fixed bed reactor filled with granular solid sulfonic acid resin at the temperature of 100 ℃, the inner diameter of 2cm and the filler height of 100cm through an advection pump with the flow rate of 1ml/min for reaction, wherein the average residence time of materials in the tubular fixed bed reactor is 2.08h, and discharging the materials from a discharge port of the tubular fixed bed reactor to obtain a crude product of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate; samples were taken from the outlet of the reactor, and the conversion of methyl p-hydroxyphenylpropionate was 63.97%, the conversion of tert-butanol was 92.54%, the content of methyl 3- (35-di-tert-butyl-4-hydroxy) phenylpropionate as a by-product was 1.05%, and the content of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate was 68.97% by quantitative analysis by gas chromatography;
(2) separating and purifying a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate: removing water and tert-butyl alcohol from the obtained crude product of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate by a normal pressure distillation kettle with the temperature of 120 ℃, feeding the crude product from the top of a first-stage vacuum rectification tower, extracting methyl p-hydroxyphenylpropionate from the top of the first-stage vacuum rectification tower into a methyl p-hydroxyphenylpropionate storage tank, wherein 75g of the extracted methyl p-hydroxyphenylpropionate is obtained, the temperature of the top of the first-stage vacuum rectification tower is 140 ℃, the pressure in the tower is-0.5 kPa, the rest methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate and a small amount of the methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate as a byproduct enter the bottom of a second-stage vacuum rectification tower from the bottom of the first-stage vacuum rectification tower, and the methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate as, and 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate is extracted from the top of a secondary vacuum rectifying tower and enters a finished product recovery tank, the temperature of the top of the secondary vacuum rectifying tower is 180 ℃, and the pressure in the tower is-0.5 kPa, so that 160g of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate product with the purity of 99.21 percent is obtained.
Example 4
(1) Preparation of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate: adding 200g of methyl p-hydroxyphenylpropionate and 58g of tert-butanol (the molar ratio is 1:0.7) into a premixing tank at the temperature of 40-45 ℃, uniformly mixing, continuously adding the mixture into a tubular fixed bed reactor filled with granular solid sulfonic acid resin at the temperature of 105 ℃, the inner diameter of 2cm and the filler height of 100cm through an advection pump with the flow rate of 1.5ml/min for reaction, wherein the average residence time of materials in the tubular fixed bed reactor is 139h, and discharging the materials from a discharge port of the tubular fixed bed reactor to obtain a crude product of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate; samples were taken from the outlet of the reactor, and the conversion of methyl p-hydroxyphenylpropionate was 64.34%, the conversion of t-butanol was 93.10%, the content of methyl 3- (35-di-t-butyl-4-hydroxy) phenylpropionate as a by-product was 1.12%, and the content of methyl 3- (3-t-butyl-4-hydroxy) phenylpropionate was 69.23% by quantitative analysis by gas chromatography;
(2) separating and purifying a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate: removing water and tert-butyl alcohol from the obtained crude product of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate by an atmospheric distillation still with the temperature of 110 ℃, feeding the crude product from the top of a first-stage vacuum rectifying tower, extracting methyl p-hydroxyphenylpropionate from the top of the first-stage vacuum rectifying tower into a methyl p-hydroxyphenylpropionate storage tank, wherein 75g of the extracted methyl p-hydroxyphenylpropionate is obtained, the temperature of the top of the first-stage vacuum rectifying tower is 130 ℃, the pressure in the tower is-0.8 kPa, the rest methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate and a small amount of the methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate enter the bottom of a second-stage vacuum rectifying tower from the bottom of the first-stage vacuum rectifying tower, and the methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate is extracted from the top of a secondary vacuum rectifying tower and enters a finished product recovery tank, the temperature of the top of the secondary vacuum rectifying tower is 170 ℃, and the pressure in the tower is-0.8 kPa, so 159g of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate product with the purity of 99.16% is obtained.
Example 5
(1) Preparation of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate: adding 200g of methyl p-hydroxyphenylpropionate and 58g of tert-butanol (the molar ratio is 1:0.7) into a premixing tank at the temperature of 40-45 ℃, uniformly mixing, continuously adding the mixture into a tubular fixed bed reactor filled with granular solid sulfonic acid resin at the temperature of 110 ℃, the inner diameter of 2cm and the filler height of 100cm through an advection pump with the flow rate of 1.5ml/min for reaction, wherein the average residence time of materials in the tubular fixed bed reactor is 1.39h, and discharging the materials from a discharge port of the tubular fixed bed reactor to obtain a crude product of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate; taking a sample at the outlet of the reactor, and quantitatively analyzing by gas chromatography, wherein the conversion rate of methyl p-hydroxyphenylpropionate is 64.30%, the conversion rate of tert-butanol is 93.81%, the content of the byproduct methyl 3- (35-di-tert-butyl-4-hydroxy) phenylpropionate is 1.83%, and the content of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate is 68.53%;
(2) separating and purifying a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate: removing water and tert-butyl alcohol from the obtained crude product of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate by a normal pressure distillation kettle with the temperature of 120 ℃, feeding the crude product from the top of a first-stage vacuum rectification tower, extracting methyl p-hydroxyphenylpropionate from the top of the first-stage vacuum rectification tower into a methyl p-hydroxyphenylpropionate storage tank, wherein 75g of the extracted methyl p-hydroxyphenylpropionate is obtained, the temperature of the top of the first-stage vacuum rectification tower is 140 ℃, the pressure in the tower is-0.5 kPa, the rest methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate and a small amount of the methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate as a byproduct enter the bottom of a second-stage vacuum rectification tower from the bottom of the first-stage vacuum rectification tower, and the methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate as, 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate is extracted from the top of a secondary vacuum rectifying tower and enters a finished product recovery tank, the temperature of the top of the secondary vacuum rectifying tower is 180 ℃, and the pressure in the tower is-0.5 kPa, 157g of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate product is obtained, and the purity is 99.60%.
Example 6
(1) Preparation of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate: adding 200g of methyl p-hydroxyphenylpropionate and 62g of tert-butanol (the molar ratio is 1:0.75) into a premixing tank at the temperature of 40-45 ℃, uniformly mixing, continuously adding the mixture into a tubular fixed bed reactor filled with granular solid sulfonic acid resin at the temperature of 105 ℃, the inner diameter of 2cm and the filler height of 100cm through an advection pump with the flow rate of 1.5ml/min for reaction, wherein the average residence time of materials in the tubular fixed bed reactor is 1.39h, and discharging the materials from a discharge port of the tubular fixed bed reactor to obtain a crude product of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate; samples were taken from the outlet of the reactor, and the conversion of methyl p-hydroxyphenylpropionate was 67.70%, the conversion of t-butanol was 91.83%, the content of methyl 3- (35-di-t-butyl-4-hydroxy) phenylpropionate as a by-product was 1.53%, and the content of methyl 3- (3-t-butyl-4-hydroxy) phenylpropionate was 71.87% by quantitative analysis by gas chromatography;
(2) separating and purifying a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate: removing water and tert-butyl alcohol from the obtained crude product of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate by an atmospheric distillation still with the temperature of 115 ℃, feeding the crude product from the top of a first-stage vacuum rectifying tower, extracting methyl p-hydroxyphenylpropionate from the top of the first-stage vacuum rectifying tower into a methyl p-hydroxyphenylpropionate storage tank, extracting 68g of methyl p-hydroxyphenylpropionate, allowing the top of the first-stage vacuum rectifying tower to have the temperature of 135 ℃, allowing the pressure in the tower to be-0.65 kPa, allowing the rest of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate and a small amount of methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate to enter the bottom of a second-stage vacuum rectifying tower from the bottom of the first-stage vacuum rectifying tower, allowing the methyl 3- (3, 5-di-tert-butyl-4-hydroxy), 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate is extracted from the top of a secondary vacuum rectifying tower and enters a finished product recovery tank, the temperature of the top of the secondary vacuum rectifying tower is 175 ℃, and the pressure in the tower is-0.65 kPa, so that 167g of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate product with the purity of 98.89 percent is obtained.
Example 7
(1) Preparation of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate: adding 200g of methyl p-hydroxyphenylpropionate and 66g of tert-butyl alcohol (the molar ratio is 1:0.8) into a premixing tank at the temperature of 40-45 ℃, uniformly mixing, continuously adding the mixture into a tubular fixed bed reactor filled with granular solid sulfonic acid resin at the temperature of 105 ℃, the inner diameter of 2cm and the filler height of 100cm through an advection pump with the flow rate of 1.5ml/min for reaction, wherein the average residence time of materials in the tubular fixed bed reactor is 1.39h, and discharging the materials from a discharge port of the tubular fixed bed reactor to obtain a crude product of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate; samples were taken from the outlet of the reactor, and the conversion of methyl p-hydroxyphenylpropionate was 69.57%, that of tert-butanol was 89.04%, that of methyl 3- (35-di-tert-butyl-4-hydroxy) phenylpropionate as a by-product was 2.16%, and that of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate was 72.93% by quantitative analysis by gas chromatography;
(2) separating and purifying a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate: removing water and tert-butyl alcohol from the obtained crude product of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate in an atmospheric distillation kettle at the temperature of 115 ℃, feeding the crude product from the top of a first-stage vacuum rectifying tower, extracting methyl p-hydroxyphenylpropionate from the top of the first-stage vacuum rectifying tower to enter a methyl p-hydroxyphenylpropionate storage tank, extracting 64g of methyl p-hydroxyphenylpropionate, allowing the top of the first-stage vacuum rectifying tower to have the temperature of 135 ℃, allowing the pressure in the tower to be-0.65 kPa, allowing the rest of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate and a small amount of methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate to enter the bottom of a second-stage vacuum rectifying tower from the bottom of the first-stage vacuum rectifying tower, allowing the methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate to exit, 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate is extracted from the top of a secondary vacuum rectifying tower and enters a finished product recovery tank, the temperature of the top of the secondary vacuum rectifying tower is 175 ℃, and the pressure in the tower is-0.65 kPa, so 169g of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate product with the purity of 99.6 percent is obtained.
Example 8
(1) Preparation of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate: adding 500g of methyl p-hydroxyphenylpropionate and 154g of tert-butyl alcohol (the molar ratio is 1:0.75) into a premixing tank at the temperature of 40-45 ℃, uniformly mixing, continuously adding the mixture into a tubular fixed bed reactor filled with granular solid sulfonic acid resin at the temperature of 100 ℃, the inner diameter of 2cm and the filler height of 110cm through an advection pump with the flow rate of 1.5ml/min for reaction, wherein the average residence time of materials in the tubular fixed bed reactor is 1.39h, and discharging the materials from a discharge port of the tubular fixed bed reactor to obtain a crude product of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate; samples were taken from the outlet of the reactor, and the conversion of methyl p-hydroxyphenylpropionate was 67.86%, that of tert-butanol was 91.94%, that of methyl 3- (35-di-tert-butyl-4-hydroxy) phenylpropionate as a by-product was 1.43%, and that of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate was 72.10% by quantitative analysis by gas chromatography;
(2) separating and purifying a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate: removing water and tert-butyl alcohol from the obtained crude product of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate by an atmospheric distillation still with the temperature of 120 ℃, feeding the crude product from the top of a first-stage vacuum rectifying tower, extracting methyl p-hydroxyphenylpropionate from the top of the first-stage vacuum rectifying tower into a methyl p-hydroxyphenylpropionate storage tank, extracting 169g of methyl p-hydroxyphenylpropionate, allowing the top of the first-stage vacuum rectifying tower to have the temperature of 140 ℃, allowing the pressure in the tower to be-0.5 kPa, allowing the rest of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate and a small amount of methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate to enter the bottom of a second-stage vacuum rectifying tower from the bottom of the first-stage vacuum rectifying tower, allowing the methyl 3- (3, 5-di-tert-butyl-4-hydroxy), and 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate is extracted from the top of a secondary vacuum rectifying tower and enters a finished product recovery tank, the temperature of the top of the secondary vacuum rectifying tower is 180 ℃, and the pressure in the tower is-0.5 kPa, so that 420g of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate product with the purity of 98.97 percent is obtained.
Example 9
(1) Preparation of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate: adding 1000g of methyl p-hydroxyphenylpropionate and 308g of tert-butyl alcohol (the molar ratio is 1:0.75) into a premixing tank at the temperature of 40-45 ℃, uniformly mixing, continuously adding the mixture into a tubular fixed bed reactor filled with granular solid sulfonic acid resin at the temperature of 100 ℃, the inner diameter of 2cm and the filler height of 100cm through an advection pump with the flow rate of 1.5ml/min for reaction, wherein the average residence time of materials in the tubular fixed bed reactor is 1.39h, and discharging the materials from a discharge port of the tubular fixed bed reactor to obtain a crude product of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate; samples were taken from the outlet of the reactor, and the conversion rate of methyl p-hydroxyphenylpropionate was 67.67%, the conversion rate of t-butanol was 91.68%, the content of methyl 3- (35-di-t-butyl-4-hydroxy) phenylpropionate as a by-product was 1.48%, and the content of methyl 3- (3-t-butyl-4-hydroxy) phenylpropionate was 71.89% by quantitative analysis by gas chromatography;
(2) separating and purifying a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate: removing water and tert-butyl alcohol from the obtained crude product of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate by a normal pressure distillation kettle with the temperature of 110 ℃, feeding the crude product from the top of a first-stage vacuum rectification tower, extracting methyl p-hydroxyphenylpropionate from the top of the first-stage vacuum rectification tower into a methyl p-hydroxyphenylpropionate storage tank, wherein 340g of the extracted methyl p-hydroxyphenylpropionate is obtained, the temperature of the top of the first-stage vacuum rectification tower is 130 ℃, the pressure in the tower is-0.8 kPa, the rest methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate and a small amount of the methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate as a byproduct enter the bottom of a second-stage vacuum rectification tower from the bottom of the first-stage vacuum rectification tower, and the methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate as, 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate is extracted from the top of a secondary vacuum rectifying tower and enters a finished product recovery tank, the temperature of the top of the secondary vacuum rectifying tower is 170 ℃, and the pressure in the tower is-0.8 kPa, so 836g of a 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate product with the purity of 98.83 percent is obtained.
Example 10
(1) Preparation of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate: adding 200g of methyl p-hydroxyphenylpropionate and 62g of tert-butanol (the molar ratio is 1:0.7) into a premixing tank at the temperature of 40-45 ℃, uniformly mixing, continuously adding the mixture into a tubular fixed bed reactor filled with granular solid sulfonic acid resin at the temperature of 100 ℃, the inner diameter of 2cm and the filler height of 100cm through an advection pump with the flow rate of 1.5ml/min for reaction, wherein the average residence time of materials in the tubular fixed bed reactor is 1.39h, and discharging the materials from a discharge port of the tubular fixed bed reactor to obtain a crude product of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate; taking a sample at the outlet of the reactor, and quantitatively analyzing by gas chromatography, wherein the conversion rate of methyl p-hydroxyphenylpropionate is 67.71%, the conversion rate of tert-butanol is 91.90%, the content of the byproduct methyl 3- (35-di-tert-butyl-4-hydroxy) phenylpropionate is 1.93%, and the content of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate is 72.67%;
(2) separating and purifying a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate: removing water and tert-butyl alcohol from the obtained crude product of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate in an atmospheric distillation kettle at the temperature of 115 ℃, feeding the crude product from the top of a first-stage vacuum rectifying tower, extracting methyl p-hydroxyphenylpropionate from the top of the first-stage vacuum rectifying tower to enter a methyl p-hydroxyphenylpropionate storage tank, extracting 63g of methyl p-hydroxyphenylpropionate, allowing the top of the first-stage vacuum rectifying tower to have the temperature of 135 ℃, allowing the pressure in the tower to be-0.65 kPa, allowing the rest of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate and a small amount of methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate to enter the bottom of a second-stage vacuum rectifying tower from the bottom of the first-stage vacuum rectifying tower, allowing the methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate to exit, 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate is extracted from the top of a secondary vacuum rectifying tower and enters a finished product recovery tank, the temperature of the top of the secondary vacuum rectifying tower is 175 ℃, and the pressure in the tower is-0.65 kPa, so that 167g of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate product with the purity of 98.84 percent is obtained.
Example 11
(1) Preparation of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate: adding 200g of methyl p-hydroxyphenylpropionate and 53g of tert-butanol (the molar ratio is 1:0.65) into a premixing tank at the temperature of 40-45 ℃, uniformly mixing, continuously adding the mixture into a tubular fixed bed reactor filled with granular solid sulfonic acid resin at the temperature of 100 ℃, the inner diameter of 2cm and the filler height of 100cm through an advection pump with the flow rate of 1.5ml/min for reaction, wherein the average residence time of materials in the tubular fixed bed reactor is 1.39h, and discharging the materials from a discharge port of the tubular fixed bed reactor to obtain a crude product of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate; samples were taken from the outlet of the reactor, and the conversion rate of methyl p-hydroxyphenylpropionate was 59.90%, the conversion rate of t-butanol was 93.62%, the content of methyl 3- (35-di-t-butyl-4-hydroxy) phenylpropionate as a by-product was 0.43%, and the content of methyl 3- (3-t-butyl-4-hydroxy) phenylpropionate was 60.95% by quantitative analysis by gas chromatography;
(2) separating and purifying a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate: removing water and tert-butyl alcohol from the obtained crude product of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate by an atmospheric distillation still with the temperature of 115 ℃, feeding the crude product from the top of a first-stage vacuum rectifying tower, extracting methyl p-hydroxyphenylpropionate from the top of the first-stage vacuum rectifying tower into a methyl p-hydroxyphenylpropionate storage tank, extracting 68g of methyl p-hydroxyphenylpropionate, allowing the top of the first-stage vacuum rectifying tower to have the temperature of 135 ℃, allowing the pressure in the tower to be-0.65 kPa, allowing the rest of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate and a small amount of methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate to enter the bottom of a second-stage vacuum rectifying tower from the bottom of the first-stage vacuum rectifying tower, allowing the methyl 3- (3, 5-di-tert-butyl-4-hydroxy), 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate is extracted from the top of a secondary vacuum rectifying tower and enters a finished product recovery tank, the temperature of the top of the secondary vacuum rectifying tower is 175 ℃, and the pressure in the tower is-0.65 kPa, so that 151.58g of a 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate product with the purity of 99.52 percent is obtained.
Example 12
(1) Preparation of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate: adding 200g of methyl p-hydroxyphenylpropionate and 70g of tert-butanol (the molar ratio is 1:0.85) into a premixing tank at the temperature of 40-45 ℃, uniformly mixing, continuously adding the mixture into a tubular fixed bed reactor filled with granular solid sulfonic acid resin at the temperature of 100 ℃, the inner diameter of 2cm and the filler height of 100cm through an advection pump with the flow rate of 1.5ml/min for reaction, wherein the average residence time of materials in the tubular fixed bed reactor is 1.39h, and discharging the materials from a discharge port of the tubular fixed bed reactor to obtain a crude product of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate; taking a sample at the outlet of the reactor, and quantitatively analyzing by gas chromatography, wherein the conversion rate of methyl p-hydroxyphenylpropionate is 70.58%, the conversion rate of tert-butanol is 86.06%, the content of the byproduct methyl 3- (35-di-tert-butyl-4-hydroxy) phenylpropionate is 3.2%, and the content of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate is 69.92%;
(2) separating and purifying a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate: removing water and tert-butyl alcohol from the obtained crude product of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate by an atmospheric distillation still with the temperature of 115 ℃, feeding the crude product from the top of a first-stage vacuum rectifying tower, extracting methyl p-hydroxyphenylpropionate from the top of the first-stage vacuum rectifying tower into a methyl p-hydroxyphenylpropionate storage tank, extracting 68g of methyl p-hydroxyphenylpropionate, allowing the top of the first-stage vacuum rectifying tower to have the temperature of 135 ℃, allowing the pressure in the tower to be-0.65 kPa, allowing the rest of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate and a small amount of methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate to enter the bottom of a second-stage vacuum rectifying tower from the bottom of the first-stage vacuum rectifying tower, allowing the methyl 3- (3, 5-di-tert-butyl-4-hydroxy), 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate is extracted from the top of a secondary vacuum rectifying tower and enters a finished product recovery tank, the temperature of the top of the secondary vacuum rectifying tower is 175 ℃, and the pressure in the tower is-0.65 kPa, so that 184g of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate product with the purity of 97.14 percent is obtained.
The content of the 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate (product 341) is greater than or equal to 97 percent according to the delivery requirement, and in order to ensure the product quality content, experiments and small tests show that the content of the product 341 is greater than or equal to 98.3 percent according to the test result, so when the reaction feed ratio is determined, if the tert-butyl alcohol feed ratio is lower, the reaction effect is good, but the conversion rate of the methyl p-hydroxyphenylpropionate (raw material 340) is low, the utilization rate of the raw material is low, the yield is low, and the cost is; if the feeding amount of the tertiary butanol is higher, the content of the by-product 3- (3, 5-di-tert-butyl-4-hydroxy) methyl phenylpropionate (35 methyl ester) is increased, and the purity of the 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate product is lower. In conclusion, the molar ratio of the methyl p-hydroxyphenylpropionate to the tert-butanol is 1: 0.7-0.8, the feeding is good, the conversion rate of the methyl p-hydroxyphenylpropionate (raw material 340) is high, the utilization rate of the raw material is high, and the yield and the purity of the methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate product are high.
Finally, it should be noted that the above embodiments are only used for illustrating and not limiting the technical solutions of the present invention, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the present invention without departing from the spirit and scope of the present invention, and all modifications or partial substitutions should be covered by the scope of the claims of the present invention.
Claims (10)
1. A synthesis process of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate is characterized by comprising the following steps:
(1) preparation of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate: adding methyl p-hydroxyphenylpropionate and tert-butyl alcohol into a premixing tank at the temperature of 40-45 ℃, uniformly mixing, continuously adding the mixture into a tubular fixed bed reactor filled with a solid catalyst for reaction through an advection pump with the flow rate of 1-2 ml/min, and allowing the material to flow out of a discharge hole of the tubular fixed bed reactor after the material stays in the tubular fixed bed reactor for a period of time to obtain a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate;
(2) separating and purifying a crude product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate: removing water and tert-butyl alcohol from the obtained crude methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate product by an atmospheric distillation still, feeding the crude methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate from the top of a first-stage vacuum distillation tower, extracting methyl p-hydroxyphenylpropionate from the top of the first-stage vacuum distillation tower into a methyl p-hydroxyphenylpropionate storage tank, extracting the rest methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate and a small amount of the by-product methyl 3- (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate from the bottom of the first-stage vacuum distillation tower into the bottom of a second-stage vacuum distillation tower, extracting the by-product methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate from the top of the second-stage vacuum distillation tower into a waste recovery tank, obtaining the product of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate.
2. The process for synthesizing methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate according to claim 1, wherein the molar ratio of methyl p-hydroxyphenylpropionate to tert-butanol in the step (1) is 1: 0.7-0.8.
3. The process for synthesizing methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate according to claim 2, wherein the molar ratio of methyl p-hydroxyphenylpropionate to tert-butanol in the step (1) is 1: 0.75.
4. The process for synthesizing methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate according to claim 1, wherein the packing height of the tubular fixed bed reactor in the step (1) is 100-120 cm.
5. The process for synthesizing methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate according to claim 1, wherein the solid catalyst in the step (1) is a granular solid sulfonic acid resin.
6. The synthesis process of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate according to claim 1, wherein the reaction temperature of the tubular fixed bed reactor in the step (1) is 100-110 ℃.
7. The synthesis process of methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate according to claim 1, wherein the average residence time of the materials in the tubular fixed bed reactor in the step (1) is 1-2 h.
8. The process for synthesizing methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate according to claim 1, wherein the distillation temperature in the atmospheric distillation kettle in the step (2) is 110 to 120 ℃.
9. The process for synthesizing methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate according to claim 1, wherein the temperature at the top of the first-stage vacuum distillation column in the step (2) is 130 to 140 ℃, the pressure in the column is-0.8 to 0.5kPa, and the number of the trays is 20.
10. The process for synthesizing methyl 3- (3-tert-butyl-4-hydroxy) phenylpropionate according to claim 1, wherein the temperature at the top of the second-stage vacuum distillation column in the step (2) is 170 to 180 ℃, the pressure in the column is-0.8 to 0.5kPa, and the number of the trays is 10.
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