CN112694403B - 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 novel herbicide with optical activity, and has the characteristics of high efficiency, low toxicity, wide weeding spectrum, high selectivity, easy biodegradation, long application period, safety to crops and the like. Wherein R- (+) -2- (4-hydroxyphenoxy) propionic acid methyl ester (CAS number 96562-58-2, molecular formula is C 10 H 12 O 4 The 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 of 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 using 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 using hydroquinone as a raw material and sodium hydroxide aqueous solution as an alkali to react with (S) - (-) -2-methyl chloropropionate. 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 that the product purity and yield are low.
(3) Patent application CN108129303 describes a method for synthesizing MAQ from R- (+) -2- (4-hydroxyphenoxy) propionic acid and dimethyl sulfate as raw materials. 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 (pesticide Qin Yonghua et al, vol. 43, 12 of 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 catalytic action of a strongly acidic exchange resin to produce the desired MAQ. 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 comprises at least one of potassium carbonate, sodium carbonate, cesium carbonate, potassium hydroxide and sodium hydroxide.
Preferably, the molar ratio of the alkaline agent to hydroquinone is (0.5-2.5): 1.
preferably, the polar aprotic solvent comprises at least one of N, N-dimethylformamide, dimethylsulfoxide, N-dimethylacetamide, and N-methylpyrrolidone.
Preferably, the dosage ratio of the polar aprotic solvent to the hydroquinone is (200-250) mL:1mol.
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 (2) 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 ℃ fraction, 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 present invention, the molar ratio of the methyl halopropionate to hydroquinone is preferably (0.8 to 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 present invention, the molar ratio of the alkali agent to hydroquinone is preferably (0.5 to 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 present invention, the amount ratio of the polar aprotic solvent to hydroquinone is preferably (200 to 250) mL:1mol, specifically 200mL:1mol, 220mL:1mol or 250mL:1mol. 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 added dropwise, the system is kept to be heated continuously, the adding speed of the halogenated methyl propionate is based on the temperature of the system controlled within the range of 70-100 ℃, and the situation that the temperature is uncontrollable due to the fact that the halogenated methyl propionate is added too fast 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 to 3 hours; 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 (2) 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 ℃ fraction, 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. In 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 ℃ fraction is 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 temperature of the first reduced pressure distillation is preferably selected according to the type of the polar aprotic solvent, and particularly when the polar aprotic solvent is DMF, the temperature of the first reduced pressure distillation 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 present invention, the second reduced pressure distillation is preferably carried out under the condition of pressure <500Pa, the temperature of the second reduced pressure distillation is preferably 150-160 ℃, and the fraction of 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 should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. 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 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 to be heated continuously, 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 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 186.4g of the target product R- (+) -2- (4-hydroxyphenoxy) methyl propionate, wherein the yield is 95%, the normalized content of the liquid area =99.6% and the optical content e.e >99%.
Nuclear magnetic and mass spectral characterization of the methyl (R) - (+) -2- (4-hydroxyphenoxy) propionate prepared in example 1 gave the following data:
1 H NMR(400MHz，CDCl 3 )，δ＝1.62(3H，CH 3 )，3.68(3H，CH 3 )，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 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, keeping the system continuously heated, and controlling the dropwise adding rate of the (S) - (-) -2-methyl chloropropionate on the basis of controlling the temperature of the system 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 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 area normalization content of the liquid phase is =99.4%, and the optical content e.e is greater than 99%.
Example 3
Adding 110.1g of hydroquinone, 250mL of DMF 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 to be heated continuously, 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 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 184.4g together, wherein the yield is 94.0%, the normalized content of the liquid area 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 is finished, the reaction is carried out for 3 hours in a heat preservation way, 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, and then 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 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 ℃ fraction to obtain a target product R- (+) -2- (4-hydroxyphenoxy) methyl propionate, collecting 186.6g in total, wherein the yield is 95%, the normalized content of the liquid area =99.6%, and the optical content e.e >99%.
Example 5
Adding 110.1g of hydroquinone, 250mL of DMF and 200g of cesium carbonate into a four-mouth bottle, heating to the temperature of the obtained mixture to be 80 ℃, dropwise adding 170g of (S) - (-) -2-bromopropionic acid methyl ester, keeping the system to be heated continuously, and controlling the dropwise adding rate of the (S) - (-) -2-chloropropionic acid methyl ester to be based on the temperature of the system to be 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 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 186.3g of the target product R- (+) -2- (4-hydroxyphenoxy) methyl propionate, wherein the yield is 95%, the normalized content of the liquid area =99.7% and the optical content e.e >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 98wt% 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, washing the obtained product system with water to be neutral, then carrying out reduced pressure distillation to remove the solvent in the system, cooling and crystallizing the obtained residue, and filtering 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 amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (7)
1. A process for the preparation of methyl (R) - (+) -2- (4-hydroxyphenoxy) propionate comprising the steps of:
mixing hydroquinone, an alkaline reagent and a polar aprotic solvent, dropwise adding halogenated methyl propionate into the obtained mixture, carrying out condensation reaction, cooling the product system obtained after the condensation reaction, and carrying out solid-liquid separation to obtain a liquid material; carrying out first reduced pressure distillation on the liquid material to remove the polar aprotic solvent, then heating to carry out second reduced pressure distillation, receiving a fraction at the temperature of 150-160 ℃, and obtaining (R) - (+) -2- (4-hydroxyphenoxy) methyl propionate;
the halogenated methyl propionate is (S) - (-) -2-methyl chloropropionate, methyl (S) - (-) -2-bromopropionate or methyl (S) - (-) -2-iodopropionate;
the dropping rate of the halogenated methyl propionate is based on the condition that the temperature of the system is controlled within the range of 80-90 ℃;
the temperature of the condensation reaction is 80-90 ℃;
the polar aprotic solvent is N, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide or N-methylpyrrolidone; when the polar aprotic solvent is N, N-dimethylformamide, the temperature of the first reduced pressure distillation is 80-100 ℃; when the polar aprotic solvent is dimethyl sulfoxide, the temperature of the first reduced pressure distillation is 100-120 ℃; when the polar aprotic solvent is N, N-dimethylacetamide, the temperature of the first reduced pressure distillation is 90-110 ℃; when the polar aprotic solvent is N-methylpyrrolidone, the temperature of the first reduced pressure distillation is 110-130 ℃;
the first and second reduced pressure distillations are independently conducted at a pressure <500 Pa.
2. The process according to claim 1, characterized in that the molar ratio between the methyl halopropionate and the 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. A process according to claim 1 or 3, characterized in that the molar ratio of the alkaline agent to hydroquinone is (0.5-2.5): 1.
5. the process according to claim 1, characterized in that the ratio of the amount of polar aprotic solvent to hydroquinone used is (200-250) mL:1mol.
6. 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.
7. The process according to claim 1, wherein the condensation reaction time is 2 to 3 hours.
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