CN111187155B - 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 PDFInfo
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- CN111187155B CN111187155B CN202010216837.5A CN202010216837A CN111187155B CN 111187155 B CN111187155 B CN 111187155B CN 202010216837 A CN202010216837 A CN 202010216837A CN 111187155 B CN111187155 B CN 111187155B
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- 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
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- 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
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- 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
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- 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
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
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
The 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 aryloxy phenoxy propionate herbicides such as quizalofop-p-ethyl, fluazifop-p-butyl, haloxyfop-p-butyl and the like which are downstream products for producing the intermediates. The aryloxy phenoxy propionate herbicide is a herbicide for efficiently preventing and removing gramineous weeds, has the characteristics of high efficiency, low toxicity and safety to succeeding crops, and is a herbicide which is developed rapidly and continuously to develop new varieties. This type of herbicide was first developed by hoehst in germany, and is currently produced internationally mainly by manufacturers of Dow chemical in the united states and japanese chemical industries in japan. With the wide application of aryloxy phenoxy propionate herbicides in China, in recent years, many local manufacturers in China also concern the research, development and production of the herbicides. The aryloxy phenoxy propionate herbicides have the following common features: firstly, the stem and leaf treatment is mainly used, and the strong absorption activity and selectivity of the stem and leaf are shown; ② used for preventing and killing annual and perennial broadleaf weeds; the propionic acid part has chiral carbon, isomer, R body and S body, wherein the R body type active body is expressed as 'fine-', 'high efficiency-', and the like; low toxicity to mammals; easy degradation and little pollution to environment.
The traditional synthetic method mainly comprises the following steps: (1) the raw materials of the route 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, with a yield of 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 as an initiator with alpha-halopropionate, oxidizing and hydrolyzing to obtain raceme 2- (4-hydroxyphenoxy) propionic acid, and then splitting to obtain the target compound R- (+) -2- (4-hydroxyphenoxy) propionic acid with a yield of 48.2%, the method has the disadvantages of complex operation, long steps and more loss, and the used raw materials and splitting reagents are expensive, the production cost is high, and the method is not suitable for industrial production; (4) hydroquinone is used as an initiator to react with alpha-halopropionate to obtain racemic ester, and the yield is 60-70%. The reaction route is simple, but the conditions are not well controlled because hydroquinone is very easy to oxidize under alkaline conditions, and unreacted hydroquinone and disubstituted substances generated in the reaction are difficult to remove in the post-treatment; (5) taking L-lactic acid with optical activity as an initial raw material, carrying out three steps of reactions of esterification, sulfonylation and etherification, and carrying out configuration inversion in the etherification reaction to finally obtain the R- (+) -2- (4-hydroxyphenoxy) propionic acid.
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 dropwise2WO4The aqueous solution is continuously stirred and heated until the solution is dripped1/5 (volume is original volume), filtering to remove precipitate, standing the filtrate for 24 hr, precipitating crystal, and recrystallizing twice 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 (5)
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 materialsThe nitrogen is used as carrier gas, hydroquinone and 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 way 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 ℃; the supported heteropoly acid is supported on active 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.
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 gas-phase catalytic synthesis of R- (+) -2- (4-hydroxyphenoxy) propionic acid according to claim 1, 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.
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Citations (3)
| 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 |
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Patent Citations (3)
| 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 |
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