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WO1999000350A1 - Procede de production d'acides libres a partir de carboxylates d'ammonium - Google Patents

Procede de production d'acides libres a partir de carboxylates d'ammonium Download PDF

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Publication number
WO1999000350A1
WO1999000350A1 PCT/JP1998/002844 JP9802844W WO9900350A1 WO 1999000350 A1 WO1999000350 A1 WO 1999000350A1 JP 9802844 W JP9802844 W JP 9802844W WO 9900350 A1 WO9900350 A1 WO 9900350A1
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WIPO (PCT)
Prior art keywords
document
ether
substituent
date
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP1998/002844
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English (en)
Japanese (ja)
Inventor
Kouichi Hayakawa
Masatsugu Hatayama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Soda Co Ltd
Original Assignee
Nippon Soda Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Soda Co Ltd filed Critical Nippon Soda Co Ltd
Priority to AU79337/98A priority Critical patent/AU7933798A/en
Publication of WO1999000350A1 publication Critical patent/WO1999000350A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids

Definitions

  • the present invention is industrially important as a raw material for synthesizing various pharmaceuticals, agricultural chemicals, organic electronic materials, and the like, and some carbon dioxides used as food additives or feed additives are used.
  • the present invention relates to a method for producing an acid.
  • the most common method of producing a free acid from a carboxylic acid ammonium salt is a method of neutralizing with a mineral acid such as sulfuric acid.
  • a mineral acid salt such as ammonium sulfate is produced in an equivalent amount or more.
  • Mineral salts have to be treated, which creates a large amount of waste management problems.
  • a method of obtaining unsaturated fatty acids by adding a small amount of water to an ammonium salt of unsaturated fatty acids and freeing ammonia while completely refluxing in an organic solvent at a temperature of 80 or more to remove ammonia (UK Patent Publication No. 2) Add an organic solvent that azeotropes with water to a 10 to 50% aqueous solution of (meth) acrylic acid ammonium salt, and heat at 60 to 100 to azeotropically distill the water and simultaneously release ammonia To obtain (meth) acrylic acid by distilling off
  • the target carboxylic acid exhibits a high acid dissociation constant, so that it can be easily deammonified in principle.
  • a carboxylic acid ammonium salt is used.
  • the degree of dissociation of ammonia from water is small, it is difficult to remove ammonia, and it takes a long time to remove most of the ammonia. Or requires the addition of large amounts of organic solvents or large amounts of water.
  • An object of the present invention is to provide a method for producing a free acid of a carboxylic acid from an ammonium salt of a carboxylic acid in a high yield, which is a method which does not cause a problem of waste treatment and which is applicable to carboxylic acid having a high acidity. To provide.
  • the present invention relates to the general formula [1]
  • R is a hydrogen atom, an alkyl group which may have a substituent, an alkyl group which may or may not have a substituent, an aryl group or a substituent which may have a substituent
  • R represents a saturated or unsaturated heterocyclic group which may have the following formula:
  • the carboxylic acid ammonium salt represented by the formula is heated in an ether solvent having two or more ether bonds to liberate ammonia and eliminate distillation. This is a method for producing a carboxylic acid.
  • R ′ represents a hydrogen atom, a C 1-6 alkyl group which may have a substituent, or an aryl group which may have a substituent.
  • [1] is excellent as a method for producing a carboxylic acid from a carboxylic acid ammonium salt represented by the following formula:
  • the ammonium salt of a carboxylic acid according to the present invention can be produced by the biological or catalytic hydrolysis of the corresponding nitrile amide. Further, when carboxylic acid is obtained as a metal salt by a hydrolysis reaction of nitrile or amide with an inorganic base or a microbial reaction, for example, Japanese Patent Application Laid-Open No. Show It can be converted to ammonium salt in the same way. That is, the metal of the carboxylic acid - by adding NH 3 and C 0 2 in an aqueous solution of a salt may be converted into carboxylic acid-en ⁇ Niu unsalted, it can be subjected to the present invention.
  • an ammonium carboxylate can be obtained by adding an inorganic base.
  • a large amount of mineral salts is by-produced.
  • Examples of the substituent of R of the carboxylic acid represented by the general formula [1], which is an object of the present invention, include an alkyl group, an alkoxy group, an alkylthio group, an acyl group, a halogen such as chlorine, bromine, a hydroxy group, Examples include an amino group, a nitro group, a thiol group, a phenyl group, and a heterocyclic group.
  • the heterocyclic group for R include a 3 to 7-membered ring containing at least one kind of nitrogen, oxygen or sulfur as a hetero atom.
  • R ′ of the carboxylic acid represented by the general formula [2], which is an object of the present invention examples include a halogen such as an alkoxy group, an alkylthio group, an acyl group, chlorine, and bromine, and an aryl group.
  • a halogen such as an alkoxy group, an alkylthio group, an acyl group, chlorine, and bromine, and an aryl group.
  • acetic acid chloroacetic acid, benzoic acid, paraaminobenzoic acid, phenylacetic acid, chenylacetic acid, glycolic acid, lactic acid, mandelic acid, ⁇ -hydroxybutyric acid, ⁇ -hydroxyisobutyric acid, ⁇ —Hydroxy— 4—Methylthiobutyric acid, ⁇ -Hydroxypropionic acid, / 3 , Nicotinic acid, picolinic acid and the like.
  • the carboxylic acid ammonium salt is converted to an ether bond.
  • Ammonia is liberated by heating in an ether solvent having two or more solvents, distilling out together with the ether solvent and, in the case of using an aqueous solution, the mixed vapor of water,
  • the free carboxylic acid is obtained by distilling off.
  • the ether solvent distilled off can be recovered and used as it is.
  • the distillate can be collected with a condenser, and a very small amount of dissolved ammonia can be degassed, and then the ether solvent and water can be separated and collected. Most of the distillate ammonia can be recovered from the condenser tower as gas.
  • the method of the present invention does not require the presence of water, and the carboxylic acid ammonium salt used can be used in an aqueous solution when it can be obtained in an aqueous solution, and a stable carboxylic acid ammonium salt is used as it is. be able to.
  • the amount of water is small because the water is distilled.
  • reaction device various distillation devices can be used, but those having a stirrer to increase the evaporation area and those forming a liquid film are particularly advantageous.
  • the reaction temperature is usually in the range of 60 to 200 ° C, preferably 80 to 150 ° C.
  • the end point of the reaction is the time at which distilling of the mon monies stops.
  • the reaction system usually reacts under atmospheric pressure, but may be in a pressurized state or a reduced pressure state in order to adjust the reaction temperature depending on the ether solvent used.
  • Examples of the ether solvent having two or more ether bonds used in the reaction include ethylene glycol diethylene glycol, ethylene glycol gelatin ester, and ethyl alcohol.
  • the use of the ether solvent used is mixed with an inert solvent that separates from water, so that the solvent recovery operation is easy. Become. Further, by using a mixed solvent, the amount of expensive ether solvent used can be reduced, and the economic efficiency can be improved.
  • the solvent used by being mixed with the ether solvent include hydrocarbon solvents such as toluene, xylene and mesitylene, and chlorine solvents such as dichloroethane.
  • the amount of ether solvent used depends on the type of solvent, the type of carboxylic acid ammonium salt, etc., but in the case of a batch type, the weight ratio of ether solvent / ammonium carboxylate is usually 1 to 10 times. Is selected.
  • the mixing ratio is selected in the range of 0.2 to 10 times by weight based on the ether solvent.
  • carboxylic acid amide may be formed as a by-product.
  • the by-product rate can be suppressed to 1% or less.
  • polyesters may be formed as a by-product due to dehydration condensation between molecules, but this is also reduced to 5% or less by selecting an organic solvent or increasing the evaporation area. Can be suppressed.
  • carboxylic acid ammonium salt is obtained as an aqueous solution, it may be used for the reaction without being concentrated, but it is better to reduce the water content as much as possible to remove ammonia more efficiently and to reduce the by-products. Generation is also suppressed.
  • Carboxylic acid and carboxylic acid amides were analyzed by high performance liquid chromatography, and ammonia was analyzed by the method of ultraviolet absorbance measurement using NADH to glutamate dehydrogenase (Methods of Enzymatic Analysis). , Bergmeyer HU ed., 3rd ed., Vol.8, pp.454-461) Quantification.
  • Example 1 A straight tube was attached to a 50 ml flask equipped with a stirrer, a thermometer, and a gas inlet tube, and a fractionation head equipped with a thermometer and a reflux condenser was attached to the top of the straight tube. .
  • ⁇ -hydroxy-4-methylthiobutyronitrile was subjected to biological hydrolysis and then concentrated, and ⁇ -hydroxy-4-methylthiobutyric acid ammonium salt, 21.8 millimoles, was added.
  • the azeotropic distillation stopped about 40 minutes after the start of the distillation, and the reaction was completed about 10 minutes after the distillation of almost only toluene.
  • the total amount of the distillate was 64.5 g, and the total amount of the solution after the reaction was 58.8 g.
  • the solution was concentrated under reduced pressure to obtain 5.6 g of a foil. According to the analysis results, the residual ratio of ammonia was 56.6%, the by-product ratio of ⁇ -hydroxy 4-methylthiobutyrate amide was 0.5%, and ⁇ -hydroxy-
  • the by-product of the linear dimer of 4-methylthiobutyric acid was 3.2%.
  • the yield of free acid with respect to the ammonium salt charged with 4-hydroxy-4-methylthiobutyric acid was 37.2%.
  • the bottom flask was heated in an oil bath at 150 ° C, and the amount of retained liquid was kept almost constant at a top distilling temperature of 99 to 100 and a distilling speed of 20 m1 / hr.
  • the ammonia water was distilled off, and a total of about 80 m 1 of ammonia water was obtained in about 4 hours.
  • the total amount of the solution after the reaction was 21.9 m 1. According to the analysis results, the residual ratio of ammonia was 70.8%, and the yield of free acid with respect to the ammonium salt charged with ⁇ -hydroxy-14-methylthiobutyric acid was 24. 8%.
  • Examples 2 to 14 Based on the operation method of Example 1, the reaction was carried out by changing the raw materials, the solvent, and the reaction conditions, and the results shown in Tables 1 and 2 were obtained.
  • the residual ammonia ratio, amide by-product ratio, and free acid yield are the molar yields relative to the raw material ammonium salt.
  • HMB A ⁇ -Hydroxy-4-methylthiobutyric acid
  • Solvent type A Ethylene glycol dimethyl ether
  • the method of the present invention is suitable from an industrial point of view and is fertile for various reasons;
  • ammonia When producing free carboxylic acid from carboxylic acid ammonium, ammonia can be recovered as ammonia gas or a concentrated aqueous solution of ammonia, so that it has high utility value and does not generate ammonium salt waste.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production d'acides carboxyliques, consistant tout d'abord à chauffer un carboxylate d'ammonium de formule générale (1) RCOO-NH4+ (dans laquelle R est l'hydrogène, un alkyle pouvant être substitué, un cycloalkyle pouvant être substitué, un aryle pouvant être substitué, ou un groupe hétérocyclique saturé ou insaturé pouvant être substitué), dans un solvant d'éther présentant deux liaisons éther ou plus, par exemple le diméthyléther d'éthylèneglycol, afin de libérer de l'ammoniaque. Ce procédé consiste enfin à éliminer cet ammoniaque par distillation.
PCT/JP1998/002844 1997-06-26 1998-06-25 Procede de production d'acides libres a partir de carboxylates d'ammonium Ceased WO1999000350A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU79337/98A AU7933798A (en) 1997-06-26 1998-06-25 Process for producing free acids from ammonium carboxylates

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP18585697 1997-06-26
JP9/185856 1997-06-26

Publications (1)

Publication Number Publication Date
WO1999000350A1 true WO1999000350A1 (fr) 1999-01-07

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Application Number Title Priority Date Filing Date
PCT/JP1998/002844 Ceased WO1999000350A1 (fr) 1997-06-26 1998-06-25 Procede de production d'acides libres a partir de carboxylates d'ammonium

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AU (1) AU7933798A (fr)
WO (1) WO1999000350A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006213635A (ja) * 2005-02-03 2006-08-17 Mitsubishi Rayon Co Ltd マンデル酸類の製造方法およびマンデル酸類結晶
JP2008101005A (ja) * 2002-05-10 2008-05-01 Mitsubishi Chemicals Corp アンモニウム塩の分解方法
JP2012518022A (ja) * 2009-02-19 2012-08-09 エボニック デグサ ゲーエムベーハー 遊離の有機酸のそのアンモニウム塩からの反応性抽出
JP2013524833A (ja) * 2010-04-30 2013-06-20 ビオアンブ，ソシエテ パ アクシオンス シンプリフィエ アジピン酸二アンモニウムを含む発酵培地からのアジピン酸の製造方法
JP2013524834A (ja) * 2010-04-30 2013-06-20 ビオアンブ，ソシエテ パ アクシオンス シンプリフィエ Ｎｈ４＋−ｏｏｃ−ｒ−ｃｏｏ−ｎｈ４＋化合物及び／又はｈｏｏｃ−ｒ−ｃｏｏｈ化合物の酸を含む発酵培地からのｎｈ４＋−ｏｏｃ−ｒ−ｃｏｏｈ化合物の製造方法、及びｎｈ４＋−ｏｏｃ−ｒ−ｃｏｏｈ化合物のｈｏｏｃ−ｒ−ｃｏｏｈ化合物の酸への変換
US8940934B2 (en) 2008-06-20 2015-01-27 Asahi Kasei Chemicals Corporation Production process of α-hydroxy acids
CN109232408A (zh) * 2018-10-24 2019-01-18 张刘兵 一种以烟酸铵为原料生产烟酸的方法
CN110590532A (zh) * 2019-08-14 2019-12-20 兄弟科技股份有限公司 一种芳香酸的绿色合成方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS612055B2 (fr) * 1978-02-25 1986-01-22 Nitto Chemical Industry Co Ltd
JPS6150937A (ja) * 1984-08-20 1986-03-13 Asahi Chem Ind Co Ltd カルボン酸アンモン水溶液からカルボン酸の製造法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS612055B2 (fr) * 1978-02-25 1986-01-22 Nitto Chemical Industry Co Ltd
JPS6150937A (ja) * 1984-08-20 1986-03-13 Asahi Chem Ind Co Ltd カルボン酸アンモン水溶液からカルボン酸の製造法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008101005A (ja) * 2002-05-10 2008-05-01 Mitsubishi Chemicals Corp アンモニウム塩の分解方法
JP2006213635A (ja) * 2005-02-03 2006-08-17 Mitsubishi Rayon Co Ltd マンデル酸類の製造方法およびマンデル酸類結晶
US8940934B2 (en) 2008-06-20 2015-01-27 Asahi Kasei Chemicals Corporation Production process of α-hydroxy acids
JP2012518022A (ja) * 2009-02-19 2012-08-09 エボニック デグサ ゲーエムベーハー 遊離の有機酸のそのアンモニウム塩からの反応性抽出
JP2013524833A (ja) * 2010-04-30 2013-06-20 ビオアンブ，ソシエテ パ アクシオンス シンプリフィエ アジピン酸二アンモニウムを含む発酵培地からのアジピン酸の製造方法
JP2013524834A (ja) * 2010-04-30 2013-06-20 ビオアンブ，ソシエテ パ アクシオンス シンプリフィエ Ｎｈ４＋−ｏｏｃ−ｒ−ｃｏｏ−ｎｈ４＋化合物及び／又はｈｏｏｃ−ｒ−ｃｏｏｈ化合物の酸を含む発酵培地からのｎｈ４＋−ｏｏｃ−ｒ−ｃｏｏｈ化合物の製造方法、及びｎｈ４＋−ｏｏｃ−ｒ−ｃｏｏｈ化合物のｈｏｏｃ−ｒ−ｃｏｏｈ化合物の酸への変換
CN109232408A (zh) * 2018-10-24 2019-01-18 张刘兵 一种以烟酸铵为原料生产烟酸的方法
CN110590532A (zh) * 2019-08-14 2019-12-20 兄弟科技股份有限公司 一种芳香酸的绿色合成方法

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Publication number Publication date
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