CN102241583A - Method for synthesizing 2-chlorobutyric acid - Google Patents
Method for synthesizing 2-chlorobutyric acid Download PDFInfo
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- CN102241583A CN102241583A CN2011101247826A CN201110124782A CN102241583A CN 102241583 A CN102241583 A CN 102241583A CN 2011101247826 A CN2011101247826 A CN 2011101247826A CN 201110124782 A CN201110124782 A CN 201110124782A CN 102241583 A CN102241583 A CN 102241583A
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- acid
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- butanic
- butyric
- butyric acid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 2-chlorobutyric acid, which comprises the following steps that: n-butyric acid and liquid chlorine are reacted in the presence of butyric anhydride serving as a catalyst at 50 to 150 DEG C for 5 to 15 hours, namely chloride ions substitute hydrogen ions at position-2 of the molecules of butyric anhydride to form 2-chlorobutyric anhydride and then the 2-chlorobutyric anhydride reacts with n-butyric acid to form butyric anhydride and 2-chlorobutyric acid; and after reaction, the 2-chlorobutyric acid with a purity of over 99 percent can be obtained by rectification. In the invention, butyric anhydride is used as a catalyst, and by controlling the reaction temperature and chlorine content, the conversion rate can be kept between 85 and 95 percent, the by-products generated can be reduced, and excessive chlorination can be prevented; and after being hydrolyzed, the catalyst can be recycled, and unreacted n-butyric acid can be reclaimed by rectification and can be reused in subsequent production. In the invention, the used amount of chlorine is small, fewer byproducts are produced, the utilization rate of n-butyric acid is high, and the environment-protection effect is improved considerably.
Description
Technical field
The present invention relates to a kind of organic acid synthetic method, relate in particular to a kind of method of Synthetic 2-chloro-butyric acid.
Background technology
It is many to make 2-chloro-butyric acid traditional technology, usually with the muriate of phosphorus and phosphorus as catalyzer, as: with the butanic acid is raw material, and phosphorus pentachloride is a catalyzer, and logical chlorine carries out chlorination reaction.Normal pressure, 150～200 ℃ of temperature controls, reaction times 20～50h.After reaction finishes, coarse fodder rectifying.The mol ratio of butanic acid and phosphorus pentachloride, liquid chlorine is respectively 1: 0.2～0.5: 3～6.
Though this reaction transformation efficiency is (97%～99%) better, by product 3-chloro-butyric acid more (5%～10%), the reaction times is longer, and temperature is higher, and catalyzer can't recycling, becomes solid useless.
Summary of the invention
The method that the purpose of this invention is to provide a kind of Synthetic 2-chloro-butyric acid to reduce 3-chloro-butyric acid and other by products, improves the recovery utilization rate of material.
The method of Synthetic 2-chloro-butyric acid of the present invention, under butyryl oxide catalysis, butanic acid and liquid chlorine made chlorion replace hydrogen ion on 2 of the butyryl oxides in 5～15 hours 50 ℃～150 ℃ reactions, form 2-neoprene acid anhydrides, control butanic acid transformation efficiency 85%～95% with the butanic acid reaction, generates butyryl oxide and 2-chloro-butyric acid again, after reaction finishes, again through obtaining the 2-chloro-butyric acid of purity more than 99% after the rectifying.
Its technical scheme that is adopted of the present invention is specific as follows:
1) in reaction vessel, adds butanic acid and butyryl oxide, stir the mass ratio of butanic acid and butyryl oxide 1: 0.2～2 at normal temperatures;
2) logical continuously chlorine, temperature of reaction is controlled at 50 ℃～150 ℃, normal pressure, 5～15 hours reaction times, the mol ratio 2～5: 1 of logical chlorine dose and butanic acid, control butanic acid transformation efficiency 85%～95%;
3) add and the equimolar water of butyryl oxide, under condition of normal pressure, 30 ℃～100 ℃ are hydrolyzed into butanic acid; Contain 2-chloro-butyric acid, 3-chloro-butyric acid, butanic acid and other by products in the coarse fodder of hydrolysis, control butanic acid transformation efficiency 85%～95%;
4) coarse fodder is carried out rectifying, obtain content 99% above 2-chloro-butyric acid, 2-chloro-butyric acid yield 83%～93%.
Rectifying can also obtain content 99% above butanic acid, the butanic acid rate of recovery 6%～15%.The butanic acid recycling, the 2-chloro-butyric acid is done derived product.
The beneficial effect that technical solution of the present invention realizes:
The present invention adopts butyryl oxide as catalyzer, by control reflection temperature and logical chlorine dose, control transformation efficiency 85%～95%, reduce the generation of by product, can reduce the generation of excessive chlorination situation, recyclable utilization after the catalyzer hydrolysis is reclaimed unreacted butanic acid by rectifying and can be used for subsequent production once more.Chlorine consumption of the present invention is few, and by product is less, butanic acid utilization ratio height, and environmental protection effect significantly improves.
Embodiment
Below describe technical scheme of the present invention in detail.
Embodiment 1
1) in reaction vessel, adds butanic acid and butyryl oxide, stir the mass ratio of butanic acid and butyryl oxide 1: 0.5 at normal temperatures;
2) logical continuously chlorine, temperature of reaction is controlled at 95 ℃, normal pressure, 5 hours reaction times, the mol ratio of logical chlorine dose and butanic acid 2: 1 (in the reaction process, check the transformation efficiency of butanic acid, be controlled at 85%～95%, to prevent excessive chlorination);
3) add and the equimolar water of butyryl oxide, under condition of normal pressure, 50 ℃ are hydrolyzed into butanic acid; Contain 2-chloro-butyric acid, 3-chloro-butyric acid, butanic acid and other by products in the coarse fodder of hydrolysis.Through gas chromatographic detection: 2-chloro-butyric acid 65%, butanic acid 33%, 3-chloro-butyric acid 0.99%, 4-chloro-butyric acid 0.46%, other 0.55%.
4) coarse fodder is carried out rectifying, obtain content 99% above 2-chloro-butyric acid (use gas chromatographic detection, have peak valley to occur in 2-chloro-butyric acid position), 2-chloro-butyric acid yield 98%.
Rectifying can also obtain content 99% above butanic acid (gas chromatographic detection has peak valley to occur in the butanic acid position), butanic acid yield 98%.
Embodiment 2
1) in reaction vessel, adds butanic acid and butyryl oxide, stir the mass ratio of butanic acid and butyryl oxide 1: 1 at normal temperatures;
2) logical continuously chlorine, temperature of reaction is controlled at 90 ℃, normal pressure, 7 hours reaction times, the mol ratio of logical chlorine dose and butanic acid 2.5: 1 (in the reaction process, check the transformation efficiency of butanic acid, be controlled at 85%～95%, to prevent excessive chlorination);
3) add and the equimolar water of butyryl oxide, under condition of normal pressure, 50 ℃ are hydrolyzed into butanic acid; Contain 2-chloro-butyric acid, 3-chloro-butyric acid, butanic acid and other by products in the coarse fodder of hydrolysis;
4) coarse fodder is carried out rectifying, obtain content 99% above 2-chloro-butyric acid, 2-chloro-butyric acid yield 98%.
Rectifying can also obtain content 99% above butanic acid, butanic acid yield 99%.
Claims (2)
1. the method for a Synthetic 2-chloro-butyric acid, under butyryl oxide catalysis, butanic acid and liquid chlorine made chlorion replace hydrogen ion on 2 of the butyryl oxides in 5～15 hours 50 ℃～150 ℃ reactions, form 2-neoprene acid anhydrides, control butanic acid transformation efficiency 85%～95% with the butanic acid reaction, generates butyryl oxide and 2-chloro-butyric acid again, after reaction finishes, again through obtaining the 2-chloro-butyric acid of purity more than 99% after the rectifying.
2. the method for Synthetic 2-chloro-butyric acid according to claim 1 is characterized in that method is as follows:
1) in reaction vessel, adds butanic acid and butyryl oxide, stir the mass ratio of butanic acid and butyryl oxide 1: 0.2～2 at normal temperatures;
2) logical continuously chlorine, temperature of reaction is controlled at 50 ℃～150 ℃, normal pressure, 5～15 hours reaction times, the mol ratio 2～5: 1 of logical chlorine dose and butanic acid, control butanic acid transformation efficiency 85%～95%;
3) add and the equimolar water of butyryl oxide, under condition of normal pressure, 30 ℃～100 ℃ are hydrolyzed into butanic acid; Get the hydrolysis coarse fodder;
4) coarse fodder is carried out rectifying, obtain butanic acid and 2-chloro-butyric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101247826A CN102241583A (en) | 2011-05-13 | 2011-05-13 | Method for synthesizing 2-chlorobutyric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101247826A CN102241583A (en) | 2011-05-13 | 2011-05-13 | Method for synthesizing 2-chlorobutyric acid |
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| CN102241583A true CN102241583A (en) | 2011-11-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2011101247826A Pending CN102241583A (en) | 2011-05-13 | 2011-05-13 | Method for synthesizing 2-chlorobutyric acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105385621A (en) * | 2015-11-20 | 2016-03-09 | 浙江昌明药业有限公司 | Acinetobacter junii zjutfet-1 and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1253140A1 (en) * | 2000-02-04 | 2002-10-30 | Kaneka Corporation | Process for cyclizing optically active 4-amino-2-halogenobutyric acids |
| EP1415985A1 (en) * | 2001-08-08 | 2004-05-06 | Kaneka Corporation | Process for producing optically active azetidine-2-carboxylic acid |
| JP2005035904A (en) * | 2003-07-17 | 2005-02-10 | Toray Fine Chemicals Co Ltd | Method for producing 2-hydroxycarboxylic acid |
| CN101503351A (en) * | 2009-03-20 | 2009-08-12 | 淮海工学院 | Brominated rare-earth carboxylate, as well as preparation and use thereof |
-
2011
- 2011-05-13 CN CN2011101247826A patent/CN102241583A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1253140A1 (en) * | 2000-02-04 | 2002-10-30 | Kaneka Corporation | Process for cyclizing optically active 4-amino-2-halogenobutyric acids |
| EP1415985A1 (en) * | 2001-08-08 | 2004-05-06 | Kaneka Corporation | Process for producing optically active azetidine-2-carboxylic acid |
| JP2005035904A (en) * | 2003-07-17 | 2005-02-10 | Toray Fine Chemicals Co Ltd | Method for producing 2-hydroxycarboxylic acid |
| CN101503351A (en) * | 2009-03-20 | 2009-08-12 | 淮海工学院 | Brominated rare-earth carboxylate, as well as preparation and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| 侯仲轲等: "4-氯丁酸甲酯的绿色合成研究", 《精细化工中间体》, vol. 39, no. 4, 28 August 2009 (2009-08-28), pages 14 - 16 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105385621A (en) * | 2015-11-20 | 2016-03-09 | 浙江昌明药业有限公司 | Acinetobacter junii zjutfet-1 and application thereof |
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Application publication date: 20111116 |