CN112694403A - Method for preparing (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate - Google Patents
Method for preparing (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate Download PDFInfo
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Abstract
The invention provides a method for preparing (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate, belonging to the technical field of preparation of pesticide intermediates. The invention provides a method for preparing (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate, which comprises the following steps: mixing halogenated methyl propionate, hydroquinone, an alkaline reagent and a polar aprotic solvent, and carrying out condensation reaction to obtain (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate; the halogenated methyl propionate is (S) - (-) -2-methyl chloropropionate, (S) - (-) -2-methyl bromopropionate or (S) - (-) -2-methyl iodopropionate. The method takes hydroquinone and halogenated methyl propionate as raw materials, synthesizes (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate (MAQ) in a polar aprotic solvent system by a one-step method, and has the advantages of simple process, environmental protection, good product quality and high yield.
Description
Technical Field
The invention relates to the technical field of pesticide intermediate preparation, and particularly relates to a method for preparing (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate.
Background
The aryloxy propionic acid herbicide is a new herbicide with optical activity, and has the advantages of high efficiency, low toxicity, wide weeding spectrum, high selectivity, easy biodegradation, long application period and safety to cropsAll the characteristics are achieved. Wherein R- (+) -2- (4-hydroxyphenoxy) propionic acid methyl ester (CAS number 96562-58-2, molecular formula C10H12O4The melting point is 64-67 ℃, called MAQ for short) is an important intermediate for synthesizing herbicides such as diclofop-methyl, clodinafop-propargyl, fenflurazon and the like, and the high-efficiency herbicide can selectively prevent and kill off gramineous weeds in one year or many years, has low dosage and is harmless to human and livestock, so the synthesis of the MAQ has important significance. At present, MAQ synthesis methods mainly comprise:
(1) patent application CN102775306 describes a method for synthesizing MAQ by taking R- (+) -2- (4-hydroxyphenoxy) propionic acid as a raw material and reacting the raw material with methanol, and the product is obtained by distilling to remove water, cooling and centrifuging. In the method, water is generated in the reaction process, and the esterification reaction is a reversible reaction in the presence of water, so that water generated in the system needs to be removed by distilling toluene for multiple times, and the method needs to synthesize the raw material R- (+) -2- (4-hydroxyphenoxy) propionic acid first, so that the process operation is complicated.
(2) Patent application CN105753656 describes a method for synthesizing MAQ by reacting hydroquinone as a raw material with (S) - (-) -2-methyl chloropropionate using an aqueous sodium hydroxide solution as a base. In the method, the reaction system contains more water, and the product MAQ is easily hydrolyzed in an alkaline aqueous solution to obtain the R- (+) -2- (4-hydroxyphenoxy) propionic acid, so the product purity and the yield are lower.
(3) Patent application CN108129303 describes a process for the synthesis of MAQ starting from R- (+) -2- (4-hydroxyphenoxy) propionic acid and dimethyl sulphate. But dimethyl sulfate participates in the reaction to generate monomethyl sulfate and sulfuric acid, so that the toxicity is high, the generated wastewater is difficult to treat, and an acid system seriously corrodes equipment.
(4) Asymmetric synthesis of methyl R- (+) -2- (4-hydroxyphenoxy) propionate (agricultural chemical, Qinyanghua et al, vol. 43, 12 th 2004) discloses the use of L-methyl lactate to react with p-toluenesulfonyl chloride to produce L-p-toluenesulfonyl methyl lactate, which is then reacted with phenol to produce methyl R- (+) -2-phenoxylactate, which is then reacted with potassium persulfate under alkaline conditions to produce R- (+) -2- (4-hydroxyphenoxy) lactic acid, which is then reacted with methanol under the catalysis of a strongly acidic exchange resin to produce the desired MAQ product. The route has longer process, complicated operation of the working procedures and low optical content of the product, can only reach about 95 percent, and can not meet the requirement of the market on the quality of the MAQ product.
Disclosure of Invention
The invention aims to provide a method for preparing (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate, which has the advantages of simple process, environmental friendliness, good product quality and high yield.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate, which comprises the following steps:
mixing halogenated methyl propionate, hydroquinone, an alkaline reagent and a polar aprotic solvent, and carrying out condensation reaction to obtain (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate;
the halogenated methyl propionate is (S) - (-) -2-methyl chloropropionate, (S) - (-) -2-methyl bromopropionate or (S) - (-) -2-methyl iodopropionate.
Preferably, the molar ratio of the halogenated methyl propionate to the hydroquinone is (0.8-1.2): 1.
Preferably, the alkaline agent includes at least one of potassium carbonate, sodium carbonate, cesium carbonate, potassium hydroxide, and sodium hydroxide.
Preferably, the molar ratio of the alkaline reagent to hydroquinone is (0.5-2.5): 1.
preferably, the polar aprotic solvent comprises at least one of N, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide, and N-methylpyrrolidone.
Preferably, the dosage ratio of the polar aprotic solvent to the hydroquinone is (200-250) mL: 1 mol.
Preferably, the mixing mode of the halogenated methyl propionate, the hydroquinone, the alkaline agent and the polar aprotic solvent is as follows: hydroquinone, an alkaline agent and a polar aprotic solvent are mixed, and halogenated methyl propionate is added dropwise to the resulting mixture.
Preferably, the condensation reaction is carried out at the temperature of 70-100 ℃ for 2-3 h.
Preferably, the condensation reaction further comprises:
cooling a product system obtained after the condensation reaction, and then carrying out solid-liquid separation to obtain a liquid material;
and carrying out first reduced pressure distillation on the liquid material at the temperature of less than 140 ℃ to remove the polar aprotic solvent, then heating to carry out second reduced pressure distillation, and receiving 150-160 ℃ fractions, namely (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate.
Preferably, the first and second reduced pressure distillation are independently performed at a pressure <500 Pa.
The invention provides a method for preparing (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate, which comprises the following steps: mixing halogenated methyl propionate, hydroquinone, an alkaline reagent and a polar aprotic solvent, and carrying out condensation reaction to obtain (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate; the halogenated methyl propionate is (S) - (-) -2-methyl chloropropionate, (S) - (-) -2-methyl bromopropionate or (S) - (-) -2-methyl iodopropionate. The method takes hydroquinone and halogenated methyl propionate as raw materials, synthesizes (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate (MAQ) in a polar aprotic solvent system by a one-step method, and has the advantages of simple process, environmental protection, good product quality and high yield.
Detailed Description
The invention provides a method for preparing (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate, which comprises the following steps:
mixing halogenated methyl propionate, hydroquinone, an alkaline reagent and a polar aprotic solvent, and carrying out condensation reaction to obtain (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate;
the halogenated methyl propionate is (S) - (-) -2-methyl chloropropionate, (S) - (-) -2-methyl bromopropionate or (S) - (-) -2-methyl iodopropionate.
In the invention, the molar ratio of the halogenated methyl propionate to the hydroquinone is preferably (0.8-1.2): 1, more preferably 1: 1.
in the present invention, the alkaline agent preferably includes at least one of potassium carbonate, sodium carbonate, cesium carbonate, potassium hydroxide and sodium hydroxide, more preferably potassium carbonate, sodium carbonate, cesium carbonate, potassium hydroxide or sodium hydroxide, and further preferably potassium carbonate or cesium carbonate. In the invention, the molar ratio of the alkaline reagent to hydroquinone is preferably (0.5-2.5): 1, more preferably (0.6 to 1.5): 1. in the invention, the alkaline reagent can generate salt with hydroquinone, which is beneficial to the reaction with halogenated methyl propionate.
In the present invention, the polar aprotic solvent preferably includes at least one of N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-Dimethylacetamide (DMAC), and N-methylpyrrolidone (NMP), more preferably N, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide, or N-methylpyrrolidone, and further preferably N, N-dimethylformamide or dimethyl sulfoxide. In the invention, the dosage ratio of the polar aprotic solvent to the hydroquinone is preferably (200-250) mL: 1mol, specifically 200 mL: 1mol, 220 mL: 1mol or 250 mL: 1 mol. In the invention, the polar aprotic solvent has better solubility to the raw material, can prevent the hydrolysis side reaction of the raw material halogenated methyl propionate, and is beneficial to improving the yield of the target product.
In the present invention, the mixing manner of the halogenated methyl propionate, hydroquinone, alkaline agent and polar aprotic solvent is preferably: hydroquinone, an alkaline agent and a polar aprotic solvent are mixed, and halogenated methyl propionate is added dropwise to the resulting mixture. In the invention, hydroquinone, an alkaline reagent and a polar aprotic solvent are mixed, the obtained mixture is heated to 70 ℃, halogenated methyl propionate is dripped, the system is kept to be heated continuously, the dripping speed of the halogenated methyl propionate is based on the control of the temperature of the system within the range of 70-100 ℃, and the uncontrollable temperature caused by the excessively fast addition of the halogenated methyl propionate is prevented.
In the invention, the temperature of the condensation reaction is preferably 70-100 ℃, and particularly, in the actual production process, the temperature of the reaction system can be controlled to be 70-80 ℃, 80-90 ℃ or 90-100 ℃; the time of the condensation reaction is preferably 2-3 h; the time of the condensation reaction is counted by the time of finishing the dropping of the methyl halopropionate, in the embodiment of the invention, the content of hydroquinone in a reaction system is detected by adopting liquid chromatography, and when the area normalized content of the hydroquinone is less than 0.2%, the reaction end point is considered to be reached. In the present invention, the reaction formula of the condensation reaction is as follows:
in the present invention, it is preferable that the condensation reaction further comprises:
cooling a product system obtained after the condensation reaction, and then carrying out solid-liquid separation to obtain a liquid material;
and carrying out first reduced pressure distillation on the liquid material at the temperature of less than 140 ℃ to remove the polar aprotic solvent, then heating to carry out second reduced pressure distillation, and receiving 150-160 ℃ fractions, namely (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate.
According to the invention, a product system obtained after condensation reaction is cooled and then subjected to solid-liquid separation to obtain a liquid material. According to the invention, the temperature of a product system obtained after the condensation reaction is preferably reduced to 20-25 ℃, and the temperature reduction mode is preferably natural temperature reduction. The solid-liquid separation method is not particularly limited, and a solid-liquid separation method known to those skilled in the art, such as filtration, may be used. The invention removes the alkaline reagent in the product system through solid-liquid separation.
After the liquid material is obtained, the liquid material is subjected to first reduced pressure distillation at the temperature of less than 140 ℃ to remove the polar aprotic solvent, then the temperature is raised to perform second reduced pressure distillation, and 150-160 ℃ fractions are received, namely (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate. In the present invention, the first reduced pressure distillation is preferably performed under a pressure <500Pa, and the temperature of the first reduced pressure distillation is preferably 80 to 130 ℃. In the invention, the first reduced pressure distillation temperature is preferably selected according to the type of the polar aprotic solvent, and particularly when the polar aprotic solvent is DMF, the first reduced pressure distillation temperature is preferably 80-100 ℃; when the polar aprotic solvent is DMSO, the temperature of the first reduced pressure distillation is preferably 100-120 ℃; when the polar aprotic solvent is DMAC, the temperature of the first reduced pressure distillation is preferably 90-110 ℃; when the polar aprotic solvent is NMP, the temperature of the first reduced pressure distillation is preferably 110 to 130 ℃. The polar aprotic solvent in the liquid material is removed by first reduced pressure distillation.
In the invention, the second reduced pressure distillation is preferably carried out under the condition that the pressure is less than 500Pa, the temperature of the second reduced pressure distillation is preferably 150-160 ℃, and the fraction at 150-160 ℃ is received in the second reduced pressure distillation process, namely the methyl (R) - (+) -2- (4-hydroxyphenoxy) propionate.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 110.1g of hydroquinone, 200mL of DMF (dimethyl formamide) and 180g of potassium carbonate into a four-mouth bottle, heating until the temperature of the obtained mixture is 80 ℃, dropwise adding 122.5g of (S) - (-) -2-methyl chloropropionate, and keeping the system continuously heated, wherein the dropwise adding rate of the (S) - (-) -2-methyl chloropropionate is based on the temperature of the system controlled within the range of 80-90 ℃; after the dropwise addition, the reaction is carried out for 3 hours, and the area normalization content of the raw material hydroquinone in the reaction system is detected by liquid chromatography to be less than 0.2 percent, namely the reaction end point is reached; after the reaction is finished, naturally cooling the obtained product system to 25 ℃, filtering to remove potassium carbonate in the system to obtain a filtrate, carrying out reduced pressure distillation on the filtrate under the conditions that the pressure P is less than 500Pa and the temperature is 80-100 ℃ to remove DMF in the filtrate, then raising the temperature, receiving 150-160 ℃ fractions to obtain a target product R- (+) -2- (4-hydroxyphenoxy) methyl propionate, collecting 186.4g of the target product R- (+) -2- (4-hydroxyphenoxy) methyl propionate, wherein the yield is 95%, the liquid area normalization content is 99.6%, and the optical content e.e is more than 99%.
Nuclear magnetic and mass spectral characterization of the methyl (R) - (+) -2- (4-hydroxyphenoxy) propionate prepared in example 1 gave the following data:
1H NMR(400MHz，CDCl3)，δ＝1.62(3H，CH3)，3.68(3H，CH3)，4.70(1H，CH)，6.62(2H，ArH)，6.60(2H，ArH)，5.01(s，1H，OH)；
MS(ESI)，m/z：197.2[M+H]+。
example 2
Adding 110.1g of hydroquinone, 220mL of DMF (dimethyl formamide) and 190g of potassium carbonate into a four-mouth bottle, heating until the temperature of the obtained mixture is 70 ℃, dropwise adding 122.5g of (S) - (-) -2-methyl chloropropionate, and keeping the system continuously heated, wherein the dropwise adding rate of the (S) - (-) -2-methyl chloropropionate is based on the temperature of the system controlled within the range of 70-80 ℃; after the dropwise addition, the reaction is carried out for 3 hours, and the area normalization content of the raw material hydroquinone in the reaction system is detected by liquid chromatography to be less than 0.2 percent, namely the reaction end point is reached; after the reaction is finished, naturally cooling the obtained product system to 25 ℃, filtering to remove potassium carbonate in the system to obtain a filtrate, carrying out reduced pressure distillation on the filtrate under the conditions that the pressure P is less than 500Pa and the temperature is 80-100 ℃ to remove DMF in the filtrate, then raising the temperature, receiving 150-160 ℃ fraction to obtain a target product R- (+) -2- (4-hydroxyphenoxy) methyl propionate, collecting 183.4g together, wherein the yield is 93.5%, the liquid area normalization content is 99.4%, and the optical content e.e is more than 99%.
Example 3
Adding 110.1g of hydroquinone, 250mL of DMF (dimethyl formamide) and 170g of potassium carbonate into a four-mouth bottle, heating until the temperature of the obtained mixture is 90 ℃, dropwise adding 122.5g of (S) - (-) -2-methyl chloropropionate, and keeping the system continuously heated, wherein the dropwise adding rate of the (S) - (-) -2-methyl chloropropionate is based on the temperature of the system controlled within the range of 90-100 ℃; after the dropwise addition, the reaction is carried out for 3 hours, and the area normalization content of the raw material hydroquinone in the reaction system is detected by liquid chromatography to be less than 0.2 percent, namely the reaction end point is reached; after the reaction is finished, naturally cooling the obtained product system to 25 ℃, filtering to remove potassium carbonate in the system to obtain a filtrate, carrying out reduced pressure distillation on the filtrate under the conditions that the pressure P is less than 500Pa and the temperature is 80-100 ℃ to remove DMF in the filtrate, then raising the temperature, receiving 150-160 ℃ fractions to obtain a target product R- (+) -2- (4-hydroxyphenoxy) methyl propionate, collecting 184.4g together, wherein the yield is 94.0%, the liquid area normalization content is 99.6%, and the optical content e.e is more than 99%.
Example 4
Adding 110.1g of hydroquinone, 200mL of DMSO and 180g of potassium carbonate into a four-mouth bottle, heating until the temperature of the obtained mixture is 80 ℃, dropwise adding 170g of (S) - (-) -2-bromopropionic acid methyl ester, and keeping the system to be heated continuously, wherein the dropwise adding rate of the (S) - (-) -2-bromopropionic acid methyl ester is based on the temperature of the system controlled within the range of 80-90 ℃; after the dropwise addition, the reaction is carried out for 3 hours, and the area normalization content of the raw material hydroquinone in the reaction system is detected by liquid chromatography to be less than 0.2 percent, namely the reaction end point is reached; after the reaction is finished, naturally cooling the obtained product system to 25 ℃, filtering to remove potassium carbonate in the system to obtain a filtrate, carrying out reduced pressure distillation on the filtrate under the conditions that the pressure P is less than 500Pa and the temperature is 100-120 ℃ to remove DMSO in the filtrate, then raising the temperature, receiving 150-160 ℃ fractions to obtain a target product R- (+) -2- (4-hydroxyphenoxy) methyl propionate, collecting 186.6g in total, wherein the yield is 95%, the liquid area normalization content is 99.6%, and the optical content e.e is more than 99%.
Example 5
Adding 110.1g of hydroquinone, 250mL of DMF (dimethyl formamide) and 200g of cesium carbonate into a four-mouth bottle, heating until the temperature of the obtained mixture is 80 ℃, dropwise adding 170g of (S) - (-) -2-bromomethyl propionate, and keeping the system continuously heated, wherein the dropwise adding rate of the (S) - (-) -2-methyl propionate is based on the temperature of the system controlled within the range of 80-90 ℃; after the dropwise addition, the reaction is carried out for 3 hours, and the area normalization content of the raw material hydroquinone in the reaction system is detected by liquid chromatography to be less than 0.2 percent, namely the reaction end point is reached; after the reaction is finished, naturally cooling the obtained product system to 25 ℃, filtering to remove potassium carbonate in the system to obtain a filtrate, carrying out reduced pressure distillation on the filtrate under the conditions that the pressure P is less than 500Pa and the temperature is 80-100 ℃ to remove DMF in the filtrate, then raising the temperature, receiving 150-160 ℃ fractions to obtain a target product R- (+) -2- (4-hydroxyphenoxy) methyl propionate, collecting 186.3g in total, wherein the yield is 95%, the liquid area normalization content is 99.7%, and the optical content e.e is more than 99%.
Comparative example 1
Adding 182.2g of R- (+) -2- (4-hydroxyphenoxy) propionic acid, 100mL of methanol, 100mL of toluene and 3g of concentrated sulfuric acid with the concentration of 98 wt% into a four-mouth bottle, heating to 70 ℃ for reaction for 3h, distilling to recover the methanol and remove water generated by the reaction, supplementing 50mL of methanol, continuing the reaction at 70 ℃, and repeating the operation for multiple times until the area normalization content of the raw material R- (+) -2- (4-hydroxyphenoxy) propionic acid in a liquid chromatography detection reaction system is less than 0.3%, namely reaching the end point of the reaction; after the reaction is finished, the obtained product system is washed by water to be neutral, then reduced pressure distillation is carried out to remove the solvent in the system, the obtained residue is cooled and crystallized, and the obtained residue is filtered to obtain the target product R- (+) -2- (4-hydroxyphenoxy) propionic acid, wherein the yield is 176.4g, the yield is 90%, and the area normalization content is 99.2%.
From the results, the method of the comparative example 1 needs concentrated sulfuric acid for catalytic reaction, so that the equipment is seriously corroded, and meanwhile, the temperature needs to be raised and lowered repeatedly, the operation process is complex, and the yield of the final product is low; and the raw material R- (+) -2- (4-hydroxyphenoxy) propionic acid is more expensive than hydroquinone and halogenated methyl propionate, and the production cost is high.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A process for the preparation of methyl (R) - (+) -2- (4-hydroxyphenoxy) propionate comprising the steps of:
mixing halogenated methyl propionate, hydroquinone, an alkaline reagent and a polar aprotic solvent, and carrying out condensation reaction to obtain (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate;
the halogenated methyl propionate is (S) - (-) -2-methyl chloropropionate, (S) - (-) -2-methyl bromopropionate or (S) - (-) -2-methyl iodopropionate.
2. The process according to claim 1, wherein the molar ratio of the methyl halopropionate to hydroquinone is (0.8 to 1.2): 1.
3. the method of claim 1, wherein the alkaline agent comprises at least one of potassium carbonate, sodium carbonate, cesium carbonate, potassium hydroxide, and sodium hydroxide.
4. The process according to claim 1 or 3, characterized in that the molar ratio of the alkaline agent to hydroquinone is (0.5 to 2.5): 1.
5. the method of claim 1, wherein the polar aprotic solvent comprises at least one of N, N-dimethylformamide, dimethylsulfoxide, N-dimethylacetamide, and N-methylpyrrolidinone.
6. The method according to claim 1 or 5, wherein the amount ratio of the polar aprotic solvent to hydroquinone is (200-250) mL: 1 mol.
7. The process according to claim 1, wherein the methyl halopropionate, hydroquinone, the alkaline agent and the polar aprotic solvent are mixed in such a manner that: hydroquinone, an alkaline agent and a polar aprotic solvent are mixed, and halogenated methyl propionate is added dropwise to the resulting mixture.
8. The method according to claim 1, wherein the condensation reaction is carried out at a temperature of 70 to 100 ℃ for 2 to 3 hours.
9. The method of claim 1 or 8, further comprising, after the condensation reaction:
cooling a product system obtained after the condensation reaction, and then carrying out solid-liquid separation to obtain a liquid material;
and carrying out first reduced pressure distillation on the liquid material at the temperature of less than 140 ℃ to remove the polar aprotic solvent, then heating to carry out second reduced pressure distillation, and receiving 150-160 ℃ fractions, namely (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate.
10. The process according to claim 9, characterized in that the first and second reduced pressure distillation are independently carried out at a pressure <500 Pa.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057575A (en) * | 2022-01-17 | 2022-02-18 | 苏州开元民生科技股份有限公司 | Synthesis method of R- (+) -2- (4-hydroxyphenoxy) methyl propionate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4625053A (en) * | 1984-12-28 | 1986-11-25 | Nissan Chemical Industries Ltd. | Process for preparing optically active 2-(4-hydroxy-phenoxy) propionic acid compounds |
| JPS6216446A (en) * | 1984-10-26 | 1987-01-24 | Nissan Chem Ind Ltd | Production of optically active 2-(4-hydroxyphenoxy) propionic acid |
| CN105753656A (en) * | 2016-04-26 | 2016-07-13 | 张家港市三联化工科技有限公司 | Synthesizing method for (R)-(+)-2-(4-hydroxy phenoxy) methyl propionate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6216446A (en) * | 1984-10-26 | 1987-01-24 | Nissan Chem Ind Ltd | Production of optically active 2-(4-hydroxyphenoxy) propionic acid |
| US4625053A (en) * | 1984-12-28 | 1986-11-25 | Nissan Chemical Industries Ltd. | Process for preparing optically active 2-(4-hydroxy-phenoxy) propionic acid compounds |
| CN105753656A (en) * | 2016-04-26 | 2016-07-13 | 张家港市三联化工科技有限公司 | Synthesizing method for (R)-(+)-2-(4-hydroxy phenoxy) methyl propionate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114057575A (en) * | 2022-01-17 | 2022-02-18 | 苏州开元民生科技股份有限公司 | Synthesis method of R- (+) -2- (4-hydroxyphenoxy) methyl propionate |
| CN114057575B (en) * | 2022-01-17 | 2023-01-03 | 苏州开元民生科技股份有限公司 | Synthetic method of R- (+) -2- (4-hydroxyphenoxy) methyl propionate |
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