CN102391104A - Process for synthesizing and separating (R)-(+)-2-para hydroxyphenoxypropionic acid - Google Patents

Process for synthesizing and separating (R)-(+)-2-para hydroxyphenoxypropionic acid Download PDF

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CN102391104A
CN102391104A CN2011102754796A CN201110275479A CN102391104A CN 102391104 A CN102391104 A CN 102391104A CN 2011102754796 A CN2011102754796 A CN 2011102754796A CN 201110275479 A CN201110275479 A CN 201110275479A CN 102391104 A CN102391104 A CN 102391104A
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oxygen base
acid
propionic acid
para hydroxybenzene
resorcinol
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周耀明
朱贲孝
金宽洪
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NANTONG JIAHE CHEMICAL CO Ltd
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NANTONG JIAHE CHEMICAL CO Ltd
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Abstract

The invention relates to a process for synthesizing (R)-(+)-2-para hydroxyphenoxypropionic acid. The synthesis process is shown as an equation (described in the specification), wherein R1 is methyl, phenyl or 4-tolyl; R2 is methyl or ethyl, and the synthesis process comprises the following steps of: adding a solvent into hydroquinone in a formula (3) in the presence of alkali and under the protection of nitrogen, keeping in the dark place and stirring for 2-5 hours, then cooling to the temperature of 10-12 DEG C, slowly dropwise adding (S)-2-substituted acyloxy propionate in a formula (2), completing dropwise adding within 3-5 hours, and stirring for 12-15 hours at the temperature of 25-30 DEG C, so as to obtain a reaction mixture containing the target product (R)-(+)-2-para hydroxyphenoxypropionic acid shown as a formula (1). The process provided by the invention has the advantages of high product yield, simple process and lower cost.

Description

Synthetic and the separating technology of a kind of (R)-(+)-2-para hydroxybenzene oxygen base propionic acid
Technical field
The present invention relates to the synthesis technique of a kind of (R)-(+)-2-para hydroxybenzene oxygen base propionic acid, belong to chemical field.
The invention still further relates to the separating technology of a kind of (R)-(+)-2-para hydroxybenzene oxygen base propionic acid, belong to chemical field.
Background technology
(R)-(+)-2-para hydroxybenzene oxygen base propionic acid is a kind of pesticide intermediate, CasNo.x:94050-90-5
English name: (R)-(+)-2-(4-Hydroxyphenoxy) propionicacid
Structural formula:
Figure 2011102754796100002DEST_PATH_IMAGE001
Virtue phenoxy propionic acid ester weedicide is optically active new herbicides, have efficient, low toxicity, herbicidal spectrum is wide, selectivity is high, administration time period is long, to advantages such as succession crop safety, have the dozens of kind up to now and emerge.(R)-(+)-2-para hydroxybenzene oxygen base propionic acid is the important intermediate of many fragrant phenoxy propionic acid ester weedicides such as synthetic alkynes grass ester, fenoxapropPethyl, quizalofopPethyl, haloxyfopPmethyl.
(R)-(+)-and other production technique of 2-para hydroxybenzene oxygen base propionic acid is to begin from (D)-lactic acid, generates (S)-2-chloropropionic acid through chloro, the latter reacts with Resorcinol and obtains (R)-(+)-2-para hydroxybenzene oxygen base propionic acid.The shortcoming of this technology is that (D)-lactic acid is somewhat expensive.
Zhejiang Polytechnical University's journal (2009 the 4th phases; The 362-365 page or leaf) compound method about (R)-2-para hydroxybenzene oxygen base propionic acid of report; Though reaction process is simple, do not finish the back separating mixture about reaction, cause superfluous product more.Therefore, need provide a kind of new technical scheme to solve the problems referred to above.
Summary of the invention
The purpose of this invention is to provide a kind of simple to operate, synthesis technique of being easy to industrialized (R)-(+)-2-para hydroxybenzene oxygen base propionic acid.
Another object of the present invention provides the separating technology that a kind of extraction is easy to (R)-(+)-2-para hydroxybenzene oxygen base propionic acid.
The technical scheme that the present invention adopts is:
The synthesis technique of a kind of (R)-(+)-2-para hydroxybenzene oxygen base propionic acid, said synthesis technique is shown in following equation:
Figure 605587DEST_PATH_IMAGE002
Wherein, R 1Represent methylidene, phenyl or 4-tolyl;
R 2Represent methylidene or ethyl;
Resorcinol in the said formula [3] under nitrogen protection, adds solvent again in the presence of alkali; Lucifuge stirred 2-5 hour, was cooled to 10-12 ℃ then, and (the S)-2-that slowly drips in the formula [2] replaces the sulfonyloxy propionic ester; In 3-5 hour, drip off; In the time of 25-30 ℃, stirred 12-15 hour, get reaction mixture; Said reaction mixture comprises (R)-(+)-2-para hydroxybenzene oxygen base propionic acid in the title product formula [1], excessive Resorcinol and by product tosic acid; Said Resorcinol with (S)-ratio that 2-replaces the mole number of sulfonyloxy propionic ester reaction is 4:1-3; The ratio of the mole number of said alkali and Resorcinol reaction is 4-3:1-2, said Resorcinol with (S)-ratio that 2-replaces the mole number of sulfonyloxy propionic ester reaction is preferably 4:3; Said alkali is preferably 3:2 with the ratio of the mole number of Resorcinol reaction.
Said solvent is the mixed solvent of a kind of and water in methyl alcohol, ethanol, methylene dichloride, toluene, water or methyl alcohol, ethanol, methylene dichloride, the toluene, and said solvent is preferably methyl alcohol or ethanol.
Said alkali is salt of wormwood, yellow soda ash, Pottasium Hydroxide or sodium hydroxide, and said alkali is preferably sodium hydroxide.
The separating technology of a kind of (R)-(+)-2-para hydroxybenzene oxygen base propionic acid, after reaction finished, the solvent in the reaction mixture in the claim 1 was reclaimed in underpressure distillation; Distillation finishes, and replenishes 50-200ml water while hot, and solid is all dissolved; Cool to room temperature is regulated PH=6.0～6.5 with the reaction mixture in the claim 1 with acid, reclaims Resorcinol with organic solvent extraction then; Water layer after the extraction is continued to regulate PH=1～1.2 with acid, use organic solvent extraction again, discard water layer; Merge the ketone layer, ketone is reclaimed in underpressure distillation, obtains (R)-2-para hydroxybenzene oxygen base propionic acid bullion; This bullion water is carried out recrystallization, obtain (R)-2-para hydroxybenzene oxygen base propionic acid, yield 65-70%.
Acid in the water layer after acid in the conditioned reaction mixture extracts with adjusting is hydrochloric acid or sulfuric acid; The organic solvent that title product is reclaimed in the organic solvent of extraction recovery Resorcinol and extraction is MIBK, methylene dichloride or trichloromethane, and the acid in the water layer after the acid in the conditioned reaction mixture extracts with adjusting all is preferably hydrochloric acid; The organic solvent of Resorcinol is reclaimed in extraction and the organic solvent of extraction recovery title product all is preferably MIBK.
(S)-2-in the formula [2] replaces the sulfonyloxy propionic ester and can be obtained with replacing the SULPHURYL CHLORIDE reaction by (L)-lactic acid by currently known methods, (L)-lactic acid is more cheap, and total manufacturing cost is relatively low.
Advantage of the present invention: the product of the first step reaction need not separate and directly get into the reaction of second step; The separation that the second step reaction finishes the back mixture is a gordian technique: since in the mixture except purpose product (R)-the 2-para hydroxybenzene oxygen base propionic acid, also contain superfluous Resorcinol and by product tosic acid, these three kinds of materials all are dissolved in basic soln; Through changing pH value; Utilize solvent to carry out extracting operation respectively, these three kinds of separating substances are come, product yield of the present invention is high; Technology is simple, and cost is lower.
Embodiment
Below embodiment in order to explanation the present invention, but do not limit the present invention.
Embodiment 1
The synthesis technique of a kind of (R)-(+) of the present invention-2-para hydroxybenzene oxygen base propionic acid, synthesis technique is shown in following equation:
Figure 336783DEST_PATH_IMAGE002
Wherein, R 1Represent methylidene;
R 2Represent ethyl;
In being furnished with the 500ml there-necked flask of vacuum distillation apparatus, add 0.24mol Resorcinol, 0.72mol sodium hydroxide; Under the nitrogen protection, add the 360ml absolute ethyl alcohol again, lucifuge stirred 2 hours; Be cooled to 10 ℃ then; Slowly drip 0.12mol (S)-2-tolysulfonyl oxygen base ethyl propionate, drip off in 4 hours, drip to finish and stirred 15 hours at 30 ℃; Get reaction mixture, reaction mixture comprises (R)-(+)-2-para hydroxybenzene oxygen base propionic acid in the title product formula [1], excessive Resorcinol and by product tosic acid.
The separating technology of a kind of (R)-(+)-2-para hydroxybenzene oxygen base propionic acid, after reaction finished, ethanol was reclaimed in underpressure distillation, and distillation finishes; Replenish 50ml water while hot, solid is all dissolved, cool to room temperature is regulated PH=6.0 with the reaction mixture in the claim 1 with hydrochloric acid; Reclaim Resorcinol with MIBK 120ml extraction then, the water layer after the extraction is continued to regulate PH=1 with hydrochloric acid, with the extraction of 120ml MIBK, discard water layer again; Merge the ketone layer, ketone is reclaimed in underpressure distillation, obtains (R)-2-para hydroxybenzene oxygen base propionic acid bullion; This bullion water is carried out recrystallization, obtain (R)-2-para hydroxybenzene oxygen base propionic acid, yield 65%.
Embodiment 2
The synthesis technique of a kind of (R)-(+) of the present invention-2-para hydroxybenzene oxygen base propionic acid, synthesis technique is shown in following equation:
Figure 392464DEST_PATH_IMAGE002
Wherein, R 1Represent methylidene;
R 2Represent ethyl;
In being furnished with the 500ml there-necked flask of vacuum distillation apparatus, add 0.24mol Resorcinol, 0.96mol sodium hydroxide, under the nitrogen protection, add the 360ml absolute ethyl alcohol again, lucifuge stirred 3 hours.Be cooled to 11 ℃ then; Slowly drip 0.06mol (S)-2-tolysulfonyl oxygen base ethyl propionate; Drip off in 3 hours; Drip to finish at 25 ℃ and stirred 12 hours, get reaction mixture, reaction mixture comprises (R)-(+)-2-para hydroxybenzene oxygen base propionic acid in the title product formula [1], excessive Resorcinol and by product tosic acid.
The separating technology of a kind of (R)-(+)-2-para hydroxybenzene oxygen base propionic acid, after reaction finished, ethanol was reclaimed in underpressure distillation, and distillation finishes; Replenish 80ml water while hot, solid is all dissolved, cool to room temperature is regulated PH=6.1 with the reaction mixture in the claim 1 with hydrochloric acid; Reclaim Resorcinol with MIBK 120ml extraction then, the water layer after the extraction is continued to regulate PH=1 with hydrochloric acid, with the extraction of 120ml MIBK, discard water layer again; Merge the ketone layer, ketone is reclaimed in underpressure distillation, obtains (R)-2-para hydroxybenzene oxygen base propionic acid bullion; This bullion water is carried out recrystallization, obtain (R)-2-para hydroxybenzene oxygen base propionic acid, yield 66%.
Embodiment 3
The synthesis technique of a kind of (R)-(+) of the present invention-2-para hydroxybenzene oxygen base propionic acid, synthesis technique is shown in following equation:
Figure 209110DEST_PATH_IMAGE002
Wherein, R 1Represent methylidene;
R 2Represent methylidene;
In being furnished with the 500ml there-necked flask of vacuum distillation apparatus, add 0.24mol Resorcinol, 0.48mol Pottasium Hydroxide; Under the nitrogen protection, add the 360ml anhydrous methanol again, lucifuge stirred 4 hours; Be cooled to 11 ℃ then; Slowly drip 0.06mol (S)-2-tolysulfonyl oxygen base methyl propionate, drip off in 4 hours, drip to finish and stirred 13 hours at 27 ℃; Get reaction mixture, reaction mixture comprises (R)-(+)-2-para hydroxybenzene oxygen base propionic acid in the title product formula [1], excessive Resorcinol and by product tosic acid.
The separating technology of a kind of (R)-(+)-2-para hydroxybenzene oxygen base propionic acid, after reaction finished, methyl alcohol was reclaimed in underpressure distillation, and distillation finishes; Replenish 50ml water while hot, solid is all dissolved, cool to room temperature is regulated PH=6.2 with the reaction mixture in the claim 1 with hydrochloric acid; Reclaim Resorcinol with MIBK 120ml extraction then, the water layer after the extraction is continued to regulate PH=1.1 with hydrochloric acid, with the extraction of 120ml MIBK, discard water layer again; Merge the ketone layer, ketone is reclaimed in underpressure distillation, obtains (R)-2-para hydroxybenzene oxygen base propionic acid bullion; This bullion water is carried out recrystallization, obtain (R)-2-para hydroxybenzene oxygen base propionic acid, yield 67%.
Embodiment 4
The synthesis technique of a kind of (R)-(+) of the present invention-2-para hydroxybenzene oxygen base propionic acid, synthesis technique is shown in following equation:
Figure 509904DEST_PATH_IMAGE002
Wherein, R 1Represent methylidene;
R 2Represent methylidene;
In being furnished with the 500ml there-necked flask of vacuum distillation apparatus, add 0.24mol Resorcinol, 0.36mol Pottasium Hydroxide; Under the nitrogen protection, add the 360ml anhydrous methanol again, lucifuge stirred 4 hours; Be cooled to 12 ℃ then; Slowly drip 0.32mol (S)-2-tolysulfonyl oxygen base methyl propionate, drip off in 5 hours, drip to finish and stirred 15 hours at 28 ℃; Get reaction mixture, reaction mixture comprises (R)-(+)-2-para hydroxybenzene oxygen base propionic acid in the title product formula [1], excessive Resorcinol and by product tosic acid.
The separating technology of a kind of (R)-(+)-2-para hydroxybenzene oxygen base propionic acid, after reaction finished, methyl alcohol was reclaimed in underpressure distillation, and distillation finishes; Replenish 50ml water while hot, solid is all dissolved, cool to room temperature is regulated PH=6.4 with the reaction mixture in the claim 1 with hydrochloric acid; Reclaim Resorcinol with MIBK 120ml extraction then, the water layer after the extraction is continued to regulate PH=1.2 with hydrochloric acid, with the extraction of 120ml MIBK, discard water layer again; Merge the ketone layer, ketone is reclaimed in underpressure distillation, obtains (R)-2-para hydroxybenzene oxygen base propionic acid bullion; This bullion water is carried out recrystallization, obtain (R)-2-para hydroxybenzene oxygen base propionic acid, yield 69%.
Embodiment 5
The synthesis technique of a kind of (R)-(+) of the present invention-2-para hydroxybenzene oxygen base propionic acid, synthesis technique is shown in following equation:
Figure 95606DEST_PATH_IMAGE002
Wherein, R 1Represent methylidene;
R 2Represent ethyl;
In being furnished with the 500ml there-necked flask of vacuum distillation apparatus, add 0.24mol Resorcinol, 0.36mol salt of wormwood; Under the nitrogen protection, add the 360ml absolute ethyl alcohol again, lucifuge stirred 5 hours; Be cooled to 10 ℃ then; Slowly drip 0.18mol (S)-2-tolysulfonyl oxygen base ethyl propionate, drip off in 4 hours, drip to finish and stirred 15 hours at 30 ℃; Get reaction mixture, reaction mixture comprises (R)-(+)-2-para hydroxybenzene oxygen base propionic acid in the title product formula [1], excessive Resorcinol and by product tosic acid.
The separating technology of a kind of (R)-(+)-2-para hydroxybenzene oxygen base propionic acid, after reaction finished, ethanol was reclaimed in underpressure distillation, and distillation finishes; Replenish 50ml water while hot, solid is all dissolved, cool to room temperature is regulated PH=6.5 with the reaction mixture in the claim 1 with hydrochloric acid; Reclaim Resorcinol with trichloromethane 120ml extraction then, the water layer after the extraction is continued to regulate PH=1.2 with hydrochloric acid, use the 120ml chloroform extraction again, discard water layer; Merge the trichloromethane layer, trichloromethane is reclaimed in underpressure distillation, obtains (R)-2-para hydroxybenzene oxygen base propionic acid bullion; This bullion water is carried out recrystallization, obtain (R)-2-para hydroxybenzene oxygen base propionic acid, yield 70%.
Embodiment 6
The synthesis technique of a kind of (R)-(+) of the present invention-2-para hydroxybenzene oxygen base propionic acid, synthesis technique is shown in following equation:
Wherein, R 1Represent methylidene;
R 2Represent ethyl;
In being furnished with the 500ml there-necked flask of vacuum distillation apparatus, add 0.24mol Resorcinol, 0.36mol yellow soda ash, under the nitrogen protection, add the 360ml absolute ethyl alcohol again, lucifuge stirred 2 hours.Be cooled to 10 ℃ then; Slowly drip 0.18mol (S)-2-tolysulfonyl oxygen base ethyl propionate; Drip off in 4 hours; Drip to finish at 30 ℃ and stirred 15 hours, get reaction mixture, reaction mixture comprises (R)-(+)-2-para hydroxybenzene oxygen base propionic acid in the title product formula [1], excessive Resorcinol and by product tosic acid.
The separating technology of a kind of (R)-(+)-2-para hydroxybenzene oxygen base propionic acid, after reaction finished, ethanol was reclaimed in underpressure distillation, and distillation finishes; Replenish 50ml water while hot, solid is all dissolved, cool to room temperature is regulated PH=6.3 with the reaction mixture in the claim 1 with sulfuric acid; Reclaim Resorcinol with methylene dichloride 120ml extraction then, the water layer after the extraction is continued to regulate PH=1.2 with sulfuric acid, use the 120ml dichloromethane extraction again, discard water layer; The combined dichloromethane layer, methylene dichloride is reclaimed in underpressure distillation, obtains (R)-2-para hydroxybenzene oxygen base propionic acid bullion; This bullion water is carried out recrystallization, obtain (R)-2-para hydroxybenzene oxygen base propionic acid, yield 69.7%.
(R)-(+)-solvent used in the synthesis technique of 2-para hydroxybenzene oxygen base propionic acid can also be the mixed solvent of a kind of and water in methylene dichloride, toluene, water or methyl alcohol, ethanol, methylene dichloride, the toluene.
More than among six embodiment, (R)-(+)-R in the formula [2] of the synthesis technique of 2-para hydroxybenzene oxygen base propionic acid 1With R 2Combination also exist below several kinds of situation:
R 1Represent phenyl, R 2Represent methylidene;
R 1Represent phenyl, R 2Represent ethyl;
R 1Represent the 4-tolyl, R 2Represent methylidene;
R 1Represent the 4-tolyl, R 2Represent ethyl.
Other process steps are with above-mentioned embodiment.
Learn through the foregoing description: reaction formula [3] is too high with the ratio of the mole number of reaction formula [2], can increase the recovery cost of Resorcinol; The ratio of mole number is low excessively, can increase the ratio of by product.
(S)-2-in the reaction formula of the present invention [2] replaces the sulfonyloxy propionic ester and can be obtained with replacing the SULPHURYL CHLORIDE reaction by (L)-lactic acid by currently known methods, (L)-lactic acid is more cheap, and total manufacturing cost is relatively low.The product of the first step building-up reactions need not separate and directly get into second the step separating reaction; The separation that the second step separating reaction finishes the back mixture is a gordian technique: since in the mixture except purpose product (R)-the 2-para hydroxybenzene oxygen base propionic acid, also contain superfluous Resorcinol and by product tosic acid, these three kinds of materials all are dissolved in basic soln; Through changing pH value; Utilize solvent to carry out extracting operation respectively, these three kinds of separating substances are come, product yield of the present invention is high; Technology is simple, and cost is lower.

Claims (9)

1. the synthesis technique of (R)-(+)-2-para hydroxybenzene oxygen base propionic acid, it is characterized in that: said synthesis technique is shown in following equation:
Figure 84377DEST_PATH_IMAGE001
Wherein, R 1Represent methylidene, phenyl or 4-tolyl;
R 2Represent methylidene or ethyl;
Resorcinol in the said formula [3] under nitrogen protection, adds solvent again in the presence of alkali; Lucifuge stirred 2-5 hour, was cooled to 10-12 ℃ then, and (the S)-2-that slowly drips in the formula [2] replaces the sulfonyloxy propionic ester; In 3-5 hour, drip off; In the time of 25-30 ℃, stirred 12-15 hour, get reaction mixture; Said reaction mixture comprises (R)-(+)-2-para hydroxybenzene oxygen base propionic acid in the title product formula [1], excessive Resorcinol and by product tosic acid; Said Resorcinol with (S)-ratio that 2-replaces the mole number of sulfonyloxy propionic ester reaction is 4:1-3; Said alkali is 4-3:1-2 with the ratio of the mole number of Resorcinol reaction.
2. the synthesis technique of a kind of (R)-(+) according to claim 1-2-para hydroxybenzene oxygen base propionic acid, it is characterized in that: said solvent is the mixed solvent of a kind of and water in methyl alcohol, ethanol, methylene dichloride, toluene, water or methyl alcohol, ethanol, methylene dichloride, the toluene.
3. the synthesis technique of a kind of (R)-(+) according to claim 2-2-para hydroxybenzene oxygen base propionic acid, it is characterized in that: said solvent is methyl alcohol or ethanol.
4. the synthesis technique of a kind of (R)-(+) according to claim 1-2-para hydroxybenzene oxygen base propionic acid, it is characterized in that: said alkali is salt of wormwood, yellow soda ash, Pottasium Hydroxide or sodium hydroxide.
5. the synthesis technique of a kind of (R)-(+) according to claim 4-2-para hydroxybenzene oxygen base propionic acid, it is characterized in that: said alkali is sodium hydroxide.
6. the synthesis technique of a kind of (R)-(+) according to claim 1-2-para hydroxybenzene oxygen base propionic acid is characterized in that: said Resorcinol with (S)-ratio that 2-replaces the mole number of sulfonyloxy propionic ester reaction is 4:3; Said alkali is 3:2 with the ratio of the mole number of Resorcinol reaction.
7. the separating technology of (R)-(+)-2-para hydroxybenzene oxygen base propionic acid is characterized in that: after reaction finished, the solvent in the reaction mixture in the claim 1 was reclaimed in underpressure distillation; Distillation finishes, and replenishes 50-200ml water while hot, and solid is all dissolved; Cool to room temperature is regulated PH=6.0～6.5 with the reaction mixture in the claim 1 with acid, reclaims Resorcinol with organic solvent extraction then; Water layer after the extraction is continued to regulate PH=1～1.2 with acid, use organic solvent extraction again, discard water layer; Merge the ketone layer, ketone is reclaimed in underpressure distillation, obtains (R)-2-para hydroxybenzene oxygen base propionic acid bullion; This bullion water is carried out recrystallization, obtain (R)-2-para hydroxybenzene oxygen base propionic acid, yield 65-70%.
8. according to the separating technology of a kind of (R)-(+)-2-para hydroxybenzene oxygen base propionic acid of claim 7, it is characterized in that: the acid in the conditioned reaction mixture is hydrochloric acid or sulfuric acid with acid in the water layer of regulating after the extraction; The organic solvent of Resorcinol is reclaimed in extraction and the organic solvent of extraction recovery title product is MIBK, methylene dichloride or trichloromethane.
9. according to Claim 8 the separating technology of a kind of (R)-(+)-2-para hydroxybenzene oxygen base propionic acid is characterized in that: the acid in the conditioned reaction mixture is hydrochloric acid with acid in the water layer of regulating after the extraction; The organic solvent of Resorcinol is reclaimed in extraction and the organic solvent of extraction recovery title product is MIBK.
CN2011102754796A 2011-09-16 2011-09-16 Process for synthesizing and separating (R)-(+)-2-para hydroxyphenoxypropionic acid Pending CN102391104A (en)

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CN104725219A (en) * 2015-02-11 2015-06-24 华中农业大学 Preparation method of S-2-(4-methoxyphenoxy) sodium propionate
CN105837427A (en) * 2016-04-26 2016-08-10 张家港市三联化工科技有限公司 Method for synthesizing (R)-(+)-2-(4-hydroxy phenoxy) propionic acid
CN108314619A (en) * 2017-12-12 2018-07-24 南京红太阳生物化学有限责任公司 A kind of synthetic method of R- (+) -2- (4- hydroxyphenoxies) propionic acid
CN112321428A (en) * 2020-10-26 2021-02-05 安徽丰乐农化有限责任公司 Synthesis method of R- (+) -2- (4-hydroxyphenoxy) ethyl propionate

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104725219A (en) * 2015-02-11 2015-06-24 华中农业大学 Preparation method of S-2-(4-methoxyphenoxy) sodium propionate
CN104725219B (en) * 2015-02-11 2017-08-08 华中农业大学 The preparation method of S 2 (4 methoxyphenoxy) sodium propionate
CN105837427A (en) * 2016-04-26 2016-08-10 张家港市三联化工科技有限公司 Method for synthesizing (R)-(+)-2-(4-hydroxy phenoxy) propionic acid
CN108314619A (en) * 2017-12-12 2018-07-24 南京红太阳生物化学有限责任公司 A kind of synthetic method of R- (+) -2- (4- hydroxyphenoxies) propionic acid
CN112321428A (en) * 2020-10-26 2021-02-05 安徽丰乐农化有限责任公司 Synthesis method of R- (+) -2- (4-hydroxyphenoxy) ethyl propionate

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Application publication date: 20120328