CN111187155A - Method for synthesizing R- (+) -2- (4-hydroxyphenoxy) propionic acid by gas phase catalysis - Google Patents

Method for synthesizing R- (+) -2- (4-hydroxyphenoxy) propionic acid by gas phase catalysis Download PDF

Info

Publication number
CN111187155A
CN111187155A CN202010216837.5A CN202010216837A CN111187155A CN 111187155 A CN111187155 A CN 111187155A CN 202010216837 A CN202010216837 A CN 202010216837A CN 111187155 A CN111187155 A CN 111187155A
Authority
CN
China
Prior art keywords
hydroxyphenoxy
propionic acid
hydroquinone
catalyst
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010216837.5A
Other languages
Chinese (zh)
Other versions
CN111187155B (en
Inventor
杨世刚
唐伟
伏建波
张磊
董卫星
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Sanjili Chemical Co ltd
Original Assignee
Jiangsu Sanjili Chemical Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu Sanjili Chemical Co ltd filed Critical Jiangsu Sanjili Chemical Co ltd
Priority to CN202010216837.5A priority Critical patent/CN111187155B/en
Publication of CN111187155A publication Critical patent/CN111187155A/en
Application granted granted Critical
Publication of CN111187155B publication Critical patent/CN111187155B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a method for synthesizing R- (+) -2- (4-hydroxyphenoxy) propionic acid by gas-phase catalysis, belonging to the field of organic synthesis. Hydroquinone and D-lactic acid are used as raw materials, nitrogen is used as carrier gas, the hydroquinone and the D-lactic acid are completely gasified and then enter a fixed bed reactor, and R- (+) -2- (4-hydroxyphenoxy) propionic acid is continuously synthesized in a gas phase mode under the catalysis of a supported heteropolyacid catalyst. The method has the advantages of mild reaction conditions, simple reaction process, higher effective conversion rate of hydroquinone, high selectivity of R- (+) -2- (4-hydroxyphenoxy) propionic acid, complete suitability for industrial production, excellent catalytic activity of the self-made supported heteropolyacid solid catalyst, strong acidity, good stability, no pollution to the environment and green catalyst.

Description

Method for synthesizing R- (+) -2- (4-hydroxyphenoxy) propionic acid by gas phase catalysis
Technical Field
The invention relates to a preparation method of R- (+) -2- (4-hydroxyphenoxy) propionic acid, in particular to a method for preparing R- (+) -2- (4-hydroxyphenoxy) propionic acid by catalyzing hydroquinone and D-lactic acid with heteropoly acid under a gas phase condition.
Background
R- (+) -2- (4-hydroxyphenoxy) propionic acid is mainly used for synthesizing special intermediates such as R- (+) -2- (4-hydroxyphenoxy) methyl propionate, R- (+) -2- (4-hydroxyphenoxy) ethyl propionate, R- (+) -2- (4-hydroxyphenoxy) butyl propionate and the like, and downstream products thereof such as quizalofop-p-ethyl, fluazifop-p-butyl, haloxyfop-p-ethyl and clodinafop-propargyl are produced.
The traditional synthetic method mainly comprises the steps of (1) reacting hydroquinone with α -bromopropionate to obtain racemic ester, wherein raw materials of the process are expensive, the reaction time is long, and the total yield is low, (2) reacting S- (-) -2-p-toluenesulfonyl ethyl lactate with hydroquinone to obtain R- (+) -2- (4-hydroxyphenoxy) ethyl propionate with reversed configuration, the yield is 70-80%, the reaction yield is high, but the final product needs to be purified by column chromatography and hardly meets the requirement of industrial production, (3) reacting p-hydroxyacetophenone serving as an initiator with α -halopropionate, oxidizing and hydrolyzing to obtain raceme 2- (4-hydroxyphenoxy) propionic acid, and then splitting to obtain a target compound R- (+) -2- (4-hydroxyphenoxy) propionic acid, wherein the yield is 48.2%, the method is complex in operation, long in steps, high in loss, the price of used raw materials and splitting reagents, high in production cost and is not suitable for industrial production, (4) using hydroquinone as an initiator, reacting with the racemic ester with α -halopropionate to obtain the racemic ester, removing the loss, the raw materials, the cost of the raw materials and the etherification reaction is not easily controlled in the conditions of alkaline esterification reaction, the R- (+) -2- (4-hydroxyphenoxy reaction is not easily generated in the final product, and the esterification reaction process, the esterification reaction is not easily controlled in the conditions of the L- (+) -5-alkaline hydrolysis reaction, the initial reaction, the esterification reaction, the L- (+) -2- (4-hydroxyphenoxy reaction, the final product is not easily generated under the conditions, and the conditions are high in.
Disclosure of Invention
The invention aims to provide a novel process for preparing R- (+) -2- (4-hydroxyphenoxy) propionic acid by catalyzing hydroquinone and D-lactic acid by using a supported heteropolyacid as a catalyst aiming at the problems in the conventional process for synthesizing the R- (+) -2- (4-hydroxyphenoxy) propionic acid. The heteropolyacid prepared by the method has strong acidity, high activity, long service life in the reaction and higher effective conversion rate of hydroquinone, and can be applied to large-scale production.
The technical scheme of the invention is as follows:
a method for synthesizing R- (+) -2- (4-hydroxyphenoxy) propionic acid by gas phase catalysis comprises the steps of taking hydroquinone and D-lactic acid as raw materials in a fixed bed reactor, taking nitrogen as carrier gas, completely gasifying the hydroquinone and the D-lactic acid, then feeding the hydroquinone and the D-lactic acid into the reactor, and continuously synthesizing the R- (+) -2- (4-hydroxyphenoxy) propionic acid by gas phase catalysis of supported heteropolyacid. Mixing hydroquinone and D-lactic acid in a ratio of 1: mixing the raw materials according to a molar ratio of 0.1-1.5, then gasifying the raw materials, feeding the mixture into a fixed bed under the condition of carrier gas, and reacting at the temperature of 200-300 ℃.
Optimally, the gasification temperature is 260-: 0.2 to 1; the flow rate of the carrier gas is 90-120 mL/min, and the load of the catalyst is 0.15-0.35 g of hydroquinone/g of catalyst.
Wherein the supported heteropolyacid is supported on activated carbon or SiO2The tungstoperous heteropoly acid compound with Keggin structure comprises heteropoly acid (free acid form) and salts thereof, wherein P: w: the molar ratio of V is 1: (5-20): (2-10), adding methyl cellulose, and performing extrusion forming to obtain the catalyst, wherein the addition amount of the methyl cellulose is 5-10% of that of the catalyst. The preparation process of the supported heteropoly acid comprises the following steps:
(1) reacting NH4VO3And Na2HPO4·12H2O, respectively preparing water solution, adjusting pH =6 with glacial acetic acid, and adding Na2WO4·2H2O is prepared into an aqueous solution, the pH is adjusted to be =4 by 8mol/L sulfuric acid, and Na is added2HPO4The solution was gradually and slowly added to the NH4VO3Stirring thoroughly, adjusting pH =3 with 8mol/L sulfuric acid, heating for 1h in boiling water bath, and adding Na dropwise2WO4Stirring and heating the aqueous solution until the volume of the aqueous solution is 1/5 of the original volume after the aqueous solution is dripped, filtering out the precipitate, standing the filtrate for 24 hours, and recrystallizing twice after crystal precipitation to obtain (NH)4）6HPV4W8O40·14H2A heteropolyacid of O.
(2) Taking SiO2Grinding, drying in oven at 500 deg.C for 4 hr, cooling, soaking in deionized water for 10 hr, and drying at 180 deg.C for 10 hr.
(3) Dissolving the heteropoly acid prepared in the step (1) in water to prepare 10wt% solution, and treating the SiO2Adding, stirring at room temperature for 2 hr, standing for 10 hr, soaking, steaming in water bath to remove excessive water, oven drying at 100 deg.C, adding methylcellulose, extrusion molding, and roasting at 300 deg.C for 5 hr.
And (3) analyzing a reaction product by liquid chromatography, wherein the analysis conditions of the liquid chromatography are as follows:
(1) the chromatographic column is a stainless steel column with the diameter of 250mm 4.6mm (the length of the column is the inner diameter of the column), porous spherical silica gel is filled as a substrate, nonpolar filler with octadecyl functional groups bonded on the surface is filled, and the particle size of the filler is 5 mu m;
(2) the mobile phase is methanol-water solution, the volume ratio is 1:1, and the flow speed is 0.8 ml/min;
(3) the detection wavelength of the detector is 277 nm;
(4) the amount of the sample was 20. mu.L.
The invention has the following beneficial effects:
1. the self-made supported heteropoly acid solid catalyst with excellent catalytic activity. The catalyst has strong acidity, good stability and no pollution to the environment, is a green catalyst, and has strong catalytic activity for preparing R- (+) -2- (4-hydroxyphenoxy) propionic acid.
2. The reaction condition is mild, the reaction process is simple, the one-step synthesis is realized, the effective conversion rate of hydroquinone is high, the selectivity of R- (+) -2- (4-hydroxyphenoxy) propionic acid is high, and the method is completely suitable for industrial production.
3. The corrosion of equipment is small, no waste salt is produced as a byproduct in the process, and the method is environment-friendly.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
Example 1 preparation of supported heteropolyacids, wherein P: w: the molar ratio of V is 1: 8: 5.
(1) 37.5g of NH4VO3And 23.8g of Na2HPO4·12H2O1000 mL and 300mL of aqueous solutions were prepared, and 174.8g of Na was added to the solution adjusted to pH =6 with glacial acetic acid2WO4·2H2Dissolving O in water to prepare 330mL of aqueous solution, adjusting pH =4 with 8mol/L sulfuric acid, and adding Na2HPO4The solution was gradually and slowly added to the NH4VO3Stirring thoroughly, adjusting pH =3 with 8mol/L sulfuric acid, heating for 1h in boiling water bath, and adding Na dropwise2WO4Stirring and heating the aqueous solution until the volume of the aqueous solution is 1/5 of the original volume after the aqueous solution is dripped, filtering out the precipitate, standing the filtrate for 24 hours, and recrystallizing twice after crystal precipitation to obtain (NH)4)6HPV4W8O40·14H2150g of heteropolyacid of O.
(2) 100g of silica gel is ground, dried in an oven at 500 ℃ for 4h, cooled, soaked in deionized water for 10h, and then dried at 180 ℃ for 10 h.
(3) Dissolving 100g of heteropoly acid prepared in the step (1) in water to prepare a 10wt% solution, adding silica gel in the step (2), stirring for 2h at room temperature, standing for 10h, soaking, steaming excess water on a water bath, drying at 100 ℃, adding 10g of methyl cellulose, performing extrusion forming, and roasting for 5h at 300 ℃.
Example 2
50g of the catalyst prepared in the example 1 is loaded into a stainless steel fixed bed reactor with the inner diameter of 20mm, the gasification temperature is controlled at 280 ℃, the reaction temperature is controlled at 240 ℃, 62.5g of hydroquinone and 40.9g of D-lactic acid are uniformly added into a gasification chamber within 5h, the nitrogen flow rate is controlled at 100mL/min, the gasified mixture is taken into the fixed bed reactor by taking nitrogen as carrier gas, and R- (+) -2- (4-hydroxyphenoxy) propionic acid is prepared by reaction under the condition of the catalyst. The product is analyzed by liquid chromatography, the retention time of a hydroquinone raw material peak is 1.965min, the retention time of an R- (+) -2- (4-hydroxyphenoxy) propionic acid product peak is 6.065min, the effective conversion rate of hydroquinone is high, and the selectivity of R- (+) -2- (4-hydroxyphenoxy) propionic acid is calculated to be 80.5%.
Example 3
50g of the catalyst prepared in the example 1 is loaded into a stainless steel fixed bed reactor with the inner diameter of 20mm, the gasification temperature is controlled at 280 ℃, the reaction temperature is controlled at 250 ℃, 62.5g of hydroquinone and 46.0g of D-lactic acid are uniformly added into a gasification chamber within 5h, the flow rate of nitrogen is controlled at 110mL/min, the gasified mixture is taken into the fixed bed reactor by taking nitrogen as carrier gas, and R- (+) -2- (4-hydroxyphenoxy) propionic acid is prepared by reaction under the condition of the catalyst. The product is analyzed by liquid chromatography, the peak-producing time is unchanged, the effective conversion rate of hydroquinone is high, and the selectivity of R- (+) -2- (4-hydroxyphenoxy) propionic acid is calculated to be 80.0%.
Example 4
50g of the catalyst prepared in the example 1 is loaded into a stainless steel fixed bed reactor with the inner diameter of 20mm, the gasification temperature is controlled at 280 ℃, the reaction temperature is controlled at 260 ℃, 62.5g of hydroquinone and 25.6g of D-lactic acid are uniformly added into a gasification chamber within 5h, the nitrogen flow rate is controlled at 100mL/min, the gasified mixture is taken into the fixed bed reactor by taking nitrogen as carrier gas, and R- (+) -2- (4-hydroxyphenoxy) propionic acid is prepared by reaction under the condition of the catalyst. The product is analyzed by liquid chromatography, the peak-producing time is unchanged, the effective conversion rate of hydroquinone is high, and the selectivity of R- (+) -2- (4-hydroxyphenoxy) propionic acid is calculated to be 81.3%.
Example 5
50g of the catalyst prepared in the example 1 is loaded into a stainless steel fixed bed reactor with the inner diameter of 20mm, the gasification temperature is controlled to be 300 ℃, the reaction temperature is controlled to be 300 ℃, 62.5g of hydroquinone and 51.1g of D-lactic acid are uniformly added into a gasification chamber within 5h, the nitrogen flow rate is controlled to be 100mL/min, the gasified mixture is taken into the fixed bed reactor by taking nitrogen as carrier gas, and R- (+) -2- (4-hydroxyphenoxy) propionic acid is prepared by reaction under the condition of the catalyst. The product is analyzed by liquid chromatography, the peak-producing time is unchanged, the effective conversion rate of hydroquinone is high, and the selectivity of R- (+) -2- (4-hydroxyphenoxy) propionic acid is calculated to be 79.3%.
Example 6
50g of the catalyst prepared in the example 1 is loaded into a stainless steel fixed bed reactor with the inner diameter of 20mm, the gasification temperature is controlled to be 260 ℃, the reaction temperature is controlled to be 250 ℃, 62.5g of hydroquinone and 5.1g of D-lactic acid are uniformly added into a gasification chamber within 3.5h, the nitrogen flow rate is controlled to be 90mL/min, the gasified mixture is taken into the fixed bed reactor by taking nitrogen as carrier gas, and R- (+) -2- (4-hydroxyphenoxy) propionic acid is prepared by reaction under the condition of the catalyst. The product is analyzed by liquid chromatography, the peak-producing time is unchanged, the effective conversion rate of hydroquinone is high, and the selectivity of R- (+) -2- (4-hydroxyphenoxy) propionic acid is calculated to be 83.5%.
Example 7
50g of the catalyst prepared in the example 1 is loaded into a stainless steel fixed bed reactor with the inner diameter of 20mm, the gasification temperature is controlled to be 260 ℃, the reaction temperature is controlled to be 220 ℃, 62.5g of hydroquinone and 10.2g of D-lactic acid are uniformly added into a gasification chamber within 5h, the nitrogen flow rate is controlled to be 100mL/min, the gasified mixture is taken into the fixed bed reactor by taking nitrogen as carrier gas, and R- (+) -2- (4-hydroxyphenoxy) propionic acid is prepared by reaction under the condition of the catalyst. The product is analyzed by liquid chromatography, the peak-producing time is unchanged, the effective conversion rate of hydroquinone is high, and the selectivity of R- (+) -2- (4-hydroxyphenoxy) propionic acid is calculated to be 82.8%.
Example 8
50g of the catalyst prepared in the example 1 is loaded into a stainless steel fixed bed reactor with the inner diameter of 20mm, the gasification temperature is controlled to be 260 ℃, the reaction temperature is controlled to be 200 ℃, 62.5g of hydroquinone and 76.7g of D-lactic acid are uniformly added into a gasification chamber within 8.5h, the flow rate of nitrogen is controlled to be 120mL/min, the gasified mixture is taken into the fixed bed reactor by taking nitrogen as carrier gas, and R- (+) -2- (4-hydroxyphenoxy) propionic acid is prepared by reaction under the condition of the catalyst. The product is analyzed by liquid chromatography, the peak-producing time is unchanged, the effective conversion rate of hydroquinone is high, and the selectivity of R- (+) -2- (4-hydroxyphenoxy) propionic acid is calculated to be 75.5%.

Claims (6)

1. A method for synthesizing R- (+) -2- (4-hydroxyphenoxy) propionic acid by gas phase catalysis is characterized in that hydroquinone and D-lactic acid are used as raw materials, nitrogen is used as carrier gas, hydroquinone and D-lactic acid enter a fixed bed reactor after being completely gasified, and R- (+) -2- (4-hydroxyphenoxy) propionic acid is continuously synthesized by gas phase under the catalysis of a supported heteropolyacid catalyst; hydroquinone and D-lactic acid were mixed in a ratio of 1: mixing the raw materials according to a molar ratio of 0.1-1.5, gasifying the mixture, and then feeding the mixture into a reactor along with a carrier gas, wherein the reaction temperature is 200-300 ℃.
2. The method for the gas-phase catalytic synthesis of R- (+) -2- (4-hydroxyphenoxy) propionic acid according to claim 1, wherein the gasification temperature is 260-300 ℃, the reaction temperature is 220-260 ℃, and the molar ratio of hydroquinone to D-lactic acid is 1: 0.2 to 1.
3. The method for the gas-phase catalytic synthesis of R- (+) -2- (4-hydroxyphenoxy) propionic acid according to claim 1, wherein the carrier gas flow rate is 90-120 mL/min.
4. The method for the gas-phase catalytic synthesis of R- (+) -2- (4-hydroxyphenoxy) propionic acid according to claim 1, wherein the catalyst has a loading of 0.15 to 0.35g hydroquinone/g catalyst-h.
5. The process for the catalytic synthesis of R- (+) -2- (4-hydroxyphenoxy) propionic acid in the gas phase according to claim 1, wherein the supported heteropolyacid is supported on activated carbon or SiO2The heteropoly acid compound containing tungstenic acid with Keggin structure, wherein P: w: the molar ratio of V is 1: (5-20): (2-10), adding methyl cellulose into the catalyst, and performing extrusion forming to obtain the catalyst, wherein the addition amount of the methyl cellulose is 5-10% of that of the catalyst.
6. The process for the gas-phase catalytic synthesis of R- (+) -2- (4-hydroxyphenoxy) propionic acid according to claim 1 or 5, characterized in that the supported heteropolyacid is prepared by: (1) reacting NH4VO3And Na2HPO4·12H2O, respectively preparing water solution, adjusting pH =6 with glacial acetic acid, and adding Na2WO4·2H2O is prepared into an aqueous solution, the pH is adjusted to be =4 by 8mol/L sulfuric acid, and Na is added2HPO4The solution was gradually and slowly added to the NH4VO3Stirring thoroughly, adjusting pH =3 with 8mol/L sulfuric acid, heating for 1h in boiling water bath, and adding Na dropwise2WO4Stirring and heating the aqueous solution until the volume of the aqueous solution is 1/5 of the original volume after the aqueous solution is dripped, filtering out the precipitate, standing the filtrate for 24 hours, and recrystallizing twice after crystal precipitation to obtain (NH)4）6HPV4W8O40·14H2A heteropolyacid of O;
(2) taking SiO2Grinding, drying in 500 deg.C oven for 4 hr, cooling, soaking in deionized water for 10 hr, and drying at 180 deg.C for 10 hr;
(3) dissolving the heteropoly acid prepared in the step (1) in water to prepare 10wt% solution, and treating the SiO2Adding, stirring at room temperature for 2 hr, standing for 10 hr, soaking, steaming in water bath to remove excessive water, oven drying at 100 deg.C, adding methylcellulose, extrusion molding, and calcining at 300 deg.C for 5 hr.
CN202010216837.5A 2020-03-25 2020-03-25 Method for synthesizing R- (+) -2- (4-hydroxyphenoxy) propionic acid by gas phase catalysis Active CN111187155B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010216837.5A CN111187155B (en) 2020-03-25 2020-03-25 Method for synthesizing R- (+) -2- (4-hydroxyphenoxy) propionic acid by gas phase catalysis

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010216837.5A CN111187155B (en) 2020-03-25 2020-03-25 Method for synthesizing R- (+) -2- (4-hydroxyphenoxy) propionic acid by gas phase catalysis

Publications (2)

Publication Number Publication Date
CN111187155A true CN111187155A (en) 2020-05-22
CN111187155B CN111187155B (en) 2022-04-05

Family

ID=70704198

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010216837.5A Active CN111187155B (en) 2020-03-25 2020-03-25 Method for synthesizing R- (+) -2- (4-hydroxyphenoxy) propionic acid by gas phase catalysis

Country Status (1)

Country Link
CN (1) CN111187155B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112812002A (en) * 2020-12-30 2021-05-18 锦州三丰科技有限公司 Preparation method of (R) - (+) -2- (4-hydroxyphenoxy) propionic acid

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61158947A (en) * 1984-12-28 1986-07-18 Nissan Chem Ind Ltd Optically active 2-(4-hydroxyphenoxy)propionic acid
CN1852884A (en) * 2003-09-30 2006-10-25 辛根塔有限公司 Production process of optically pure 2- (4-hydroxyphenoxy) - propionic acid compounds
CN108727187A (en) * 2018-07-10 2018-11-02 淮安国瑞化工有限公司 It is a kind of（R）-（+）The preparation method of -2- para hydroxybenzene oxygroup propionic acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61158947A (en) * 1984-12-28 1986-07-18 Nissan Chem Ind Ltd Optically active 2-(4-hydroxyphenoxy)propionic acid
CN1852884A (en) * 2003-09-30 2006-10-25 辛根塔有限公司 Production process of optically pure 2- (4-hydroxyphenoxy) - propionic acid compounds
CN108727187A (en) * 2018-07-10 2018-11-02 淮安国瑞化工有限公司 It is a kind of（R）-（+）The preparation method of -2- para hydroxybenzene oxygroup propionic acid

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112812002A (en) * 2020-12-30 2021-05-18 锦州三丰科技有限公司 Preparation method of (R) - (+) -2- (4-hydroxyphenoxy) propionic acid

Also Published As

Publication number Publication date
CN111187155B (en) 2022-04-05

Similar Documents

Publication Publication Date Title
CA1103272A (en) Process for producing carboxylic esters
EP2495233B1 (en) Method for synthesizing unsaturated carboxylic acid and/or derivative of same
JPS61115049A (en) Catalytic conversion of lactic acid and ammonium lactate to acrylic acid
US10723688B2 (en) Method of making acrylic acid from hydroxypropionic acid
EP2614152A2 (en) Catalytic dehydration of lactic acid and lactic acid esters
CN110183327B (en) Method for preparing ketonic acid ester by catalytic oxidation of hydroxy ester
CN111187155A (en) Method for synthesizing R- (+) -2- (4-hydroxyphenoxy) propionic acid by gas phase catalysis
CN110170327B (en) Mesoporous C/SiO2Supported heteropolyacid catalyst and preparation method and application thereof
KR101187804B1 (en) Process for the preparation of acrylic acid and acrylates from lactates
CN107930687B (en) TS-1 modification method and application thereof in preparation of pyruvate by catalyzing lactate without solvent
CN116328825B (en) Catalyst, preparation method thereof and method for preparing methyl 3-methoxypropionate by using catalyst to catalyze methanol and methyl acetate
CN112517033A (en) Vanadium phosphorus oxide catalyst and preparation method and application thereof
CN100494151C (en) Method for synthesizing crotonic acid by selectively oxidizing croton aldehyde
CN107032993A (en) A kind of gas-phase photocatalysis methanol and ethanol disposably synthesize the preparation and application of the Au catalyst of a variety of esters
CN104119224A (en) Method for catalytic oxidation conversion of levulinic acid and levulinic acid ester
CN107445839B (en) Method for synthesizing glyoxylic ester
CN108129320A (en) A kind of method that carbohydrate prepares ethyl glycolate
CN107445828B (en) Method for synthesizing glyoxylic acid esters
CN114308007B (en) Method for preparing solid acid catalyst for preparing dodecanedioic acid dimethyl ester
CN115772077B (en) Method for preparing chiral D-glyceric acid by catalytic conversion of arabitol
CN116116402B (en) Catalyst, preparation method thereof and method for preparing methyl 3-methoxypropionate by using catalyst to catalyze methanol and methyl acrylate
CN111097540A (en) Catalyst for synthesizing methyl glycolate and preparation method thereof
CN115518685B (en) Carbon-supported p-toluenesulfonic acid catalyst and preparation method and application thereof
CN112979447B (en) Preparation method of fumaric acid
CN111974442B (en) Catalyst for producing acrylic acid and methyl acrylate, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant