CN111848429A - Method for selectively synthesizing N-alkyl amino dipropionate solution - Google Patents
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- C07—ORGANIC CHEMISTRY
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- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
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Abstract
The invention belongs to the technical field of organic synthesis, and particularly discloses a method for selectively synthesizing an N-alkyl amino dipropionate solution. The invention can obtain high-purity N-alkyl amino dipropionate, and the impurity content can be reduced to below 5 percent; and does not need high temperature and high pressure and complicated crystallization purification steps, thus being simple and easy to operate; the used raw materials and the solvent can be recycled, so that the energy is saved and the environment is protected.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for selectively synthesizing an N-alkyl amino dipropionate solution.
Background
N-alkyl aminopropionates and N-alkyl aminopropionates are two very useful classes of surfactants, widely used as cleaning agents, emulsifiers, flotation agents, and plating additives, among others. At present, the two compounds are synthesized by basically converting aliphatic amine and alpha, beta-unsaturated acid, nitrile or ester under certain conditions, but the reaction products are mixed with N-alkyl amino propionate and N-alkyl amino dipropionate, and the two substances with high purity are required to be selectively prepared due to the difference of hydrophilic and lipophilic properties of the N-alkyl amino propionate and the N-alkyl amino dipropionate and the wide application in daily chemicals such as household detergents, cosmetics and the like.
There is no method for producing high purity N-alkylaminopropionates or N-alkylaminopropionates, and selective production of N-alkylaminopropionates has been studied (e.g., US2468012, US 2816911); U.S. Pat. No. 5,5922909 describes a method of adjusting the ratio of N-alkylaminopropionate to N-alkylaminopropionate by controlling the pH of the reaction, but the adjustment range is not so large that an absolute advantage cannot be obtained. Therefore, it is difficult to obtain N-alkylaminodipropionic acid salts singly by the conventional synthetic method.
Disclosure of Invention
In order to solve the problems, the invention provides a method for selectively synthesizing the solution of the N-alkyl amino dipropionate, which can obtain the high-purity N-alkyl amino dipropionate and has simple process.
A method for selectively synthesizing a solution of an N-alkylaminodipropionic acid salt, comprising the steps of:
s1: dissolving acrylic ester in an organic solvent to prepare an acrylic ester solution;
s2: dropwise adding 1 molar equivalent of alkyl primary amine into 2-5 molar equivalents of acrylate solution; after the dropwise addition is finished, reacting for 10-48 hours at the temperature of 10-100 ℃;
s3: adding 2.0-4.0 molar equivalent of 0.5-2.0 mol/L alkali metal hydroxide solution into the reaction solution, and reacting at 10-100 ℃ for 10-48 hours;
s4: adding pure water with the mass 5-20 times of that of the primary alkylamine into the reaction liquid, and then carrying out reduced pressure distillation at the temperature of 30-80 ℃ and the pressure of 0-0.03 MPa until the weight content of the N-alkyl amino dipropionate is 10-50%.
Note: the molar equivalents are a relative term, specifically referring to primary alkyl amines in the present invention: acrylate ester: the molar ratio of alkali metal hydroxide is 1: (2-5): (2.0-4.0).
Preferably, the acrylate refers to the formula CH2Compounds of formula i = CHCOOR1 wherein R1 denotes methyl, ethyl or propyl.
Preferably, the alkyl primary amine is represented by the formula RNH2Wherein R denotes an alkane group consisting of from 6 to 24 carbon atoms.
Preferably, in step S1, the organic solvent is an ester, an ether, an alcohol or a halogenated alkane. Wherein: esters such as ethyl acetate, butyl acetate, etc., ethers such as diethyl ether, methyl t-butyl ether, etc., alcohols such as methanol, ethanol, etc., halogenated alkanes such as methylene chloride, chloroform, etc.
Preferably, in the step S1, the concentration of the acrylate solution is 1 to 4 mol/l.
Preferably, in step S2, 1 molar equivalent of primary alkylamine is added dropwise to 2.0 to 2.5 molar equivalents of acrylate solution; after the dropwise addition is finished, the reaction is carried out for 15-24 hours at the temperature of 20-40 ℃.
Preferably, in step S2, the dropping rate of the primary alkylamine is controlled to be 0.5 to 2 hours after the completion of the dropping.
Preferably, in step S3, an alkali metal hydroxide solution having a concentration of 0.8 to 1.2 mol/l is added to the reaction solution in an amount of 2.0 to 2.2 mol equivalents, and the reaction is carried out at a temperature of 20 to 60 ℃ for 15 to 24 hours.
Preferably, in step S3, the alkali metal hydroxide aqueous solution is a sodium hydroxide solution or a potassium hydroxide solution.
Preferably, in step S4, pure water with the mass 10-15 times that of the alkyl primary amine is added into the reaction solution, and then the mixture is subjected to reduced pressure distillation at the temperature of 40-80 ℃ and the pressure of 0-0.03 MPa until the weight content of the N-alkyl amino dipropionate is 10-30%.
The method comprises the steps of taking primary alkyl amine and acrylic ester as raw materials, dissolving the acrylic ester in an organic solvent to prepare an acrylic ester solution, then dropwise adding the primary alkyl amine into the acrylic ester solution to enable the reaction to proceed in the direction of generating N-alkyl amino dipropionate, then adding an alkali metal hydroxide aqueous solution to convert the N-alkyl amino dipropionate into N-alkyl amino dipropionate, and then removing the organic solvent through reduced pressure distillation to realize the selective synthesis of the N-alkyl amino dipropionate.
The invention has the following beneficial effects:
1. the acrylic ester is firstly dissolved in the organic solvent, and then the alkyl primary amine is dripped into the acrylic ester solution, so that the reaction is carried out in the direction of generating the N-alkyl amino dipropionate, the generation of the N-alkyl amino propionate is obviously reduced, and the purity is improved.
2. The N-alkyl amino dipropionate is converted into N-alkyl amino dipropionate by adding the alkali metal hydroxide aqueous solution, and simultaneously, the reaction of the acrylate and the alkyl primary amine is more thorough, so that the conversion rate is improved (the N-alkyl amino propionic acid is quickly transferred from an organic phase to the alkali metal hydroxide aqueous solution while the alkali metal hydroxide aqueous solution is added, so that the residual raw materials in the organic phase can be continuously reacted). More optimally, the alkali metal hydroxide is strong alkaline sodium hydroxide or potassium hydroxide, so that the hydrolysis speed can be accelerated, and the conversion efficiency can be improved.
3. The yield of the N-alkyl amino dipropionate is improved by adding pure water before the reduced pressure distillation. The product N-alkyl amino dipropionate after the hydrolysis process has stronger hydrophilicity but also has hydrophobic groups, so that the product N-alkyl amino dipropionate can be distributed in a water phase and an organic phase, and the N-alkyl amino dipropionate is completely separated from the organic phase by adding pure water with the mass 5-20 times of that of alkyl primary amine, so that the entrainment of an organic reagent is reduced, the product loss in the subsequent reduced pressure distillation process is reduced, the yield is effectively improved, and the purity of the product is not influenced.
4. The invention can obtain high-purity N-alkyl amino dipropionate, and the impurity content can be reduced to below 5 percent; and does not need high temperature and high pressure and complicated crystallization purification steps, thus being simple and easy to operate; the used raw materials and the solvent can be recycled, so that the energy is saved and the environment is protected.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
A method for selectively synthesizing a solution of an N-alkylaminodipropionic acid salt, comprising the steps of:
s1: 103 g of methyl acrylate (1.2 mol) was dissolved in 500 ml of methyl t-butyl ether to prepare a methyl acrylate solution;
s2: 93 g of dodecylamine (0.5 mol) is dripped into the methyl acrylate solution, and the dripping is finished within 1 hour; then reacting for 20 hours at the temperature of 30 ℃;
s3: 1100 ml of 1.0 mol/l potassium hydroxide solution was added to the reaction solution and reacted at 40 ℃ for 18 hours;
s4: 1.2L of pure water was added to the reaction solution, and then distilled under reduced pressure at 50 ℃ and 0.02MPa to 800 g, to obtain a solution containing 24.4% of potassium N-alkylaminodipropionate and having a purity of 98%.
Example 2
A method for selectively synthesizing a solution of an N-alkylaminodipropionic acid salt, comprising the steps of:
s1: 215 g of methyl acrylate (2.5 mol) is dissolved in 1000 ml of methyl tert-butyl ether to prepare a methyl acrylate solution;
s2: 93 g of dodecylamine (0.5 mol) is dropwise added into the methyl acrylate solution, and the dropwise addition is finished within 1.5 hours; then reacting for 12 hours at the temperature of 55 ℃;
s3: adding 750 ml of 2.0 mol/L potassium hydroxide solution into the reaction solution, and reacting for 14 hours at the temperature of 55 ℃;
s4: 1.8L of pure water was added to the reaction solution, and then the mixture was distilled under reduced pressure at a temperature of 85 ℃ and a pressure of 0.01MPa to 800 g, whereby the obtained solution had a potassium N-alkylaminodipropionate content of 22.7% and a purity of 97%.
Example 3
A method for selectively synthesizing a solution of an N-alkylaminodipropionic acid salt, comprising the steps of:
s1: 86 g of methyl acrylate (1 mol) is dissolved in 500 ml of methyl tert-butyl ether to prepare a methyl acrylate solution;
s2: 93 g of dodecylamine (0.5 mol) is dripped into the methyl acrylate solution, and the dripping is finished within 0.5 hour; then reacting for 30 hours at the temperature of 18 ℃;
s3: adding 2.0L of 0.5 mol/L potassium hydroxide solution into the reaction solution, and reacting at 15 ℃ for 25 hours;
s4: 500 ml of pure water was added to the reaction solution, and then the mixture was distilled under reduced pressure at a temperature of 35 ℃ and a pressure of 0.03MPa to 800 g, whereby the content of potassium N-alkylaminodipropionate in the resulting solution was 20.5% and the purity was 96%.
Example 4
A method for selectively synthesizing a solution of an N-alkylaminodipropionic acid salt, comprising the steps of:
s1: 215 g of methyl acrylate (2.5 mol) is dissolved in 1000 ml of ethanol to prepare methyl acrylate solution;
s2: 93 g of dodecylamine (0.5 mol) is dropwise added into the methyl acrylate solution, and the dropwise addition is finished within 1.5 hours; then reacting for 12 hours at the temperature of 70 ℃;
s3: adding 2.0L of 1.0 mol/L potassium hydroxide solution into the reaction solution, and reacting at the temperature of 40 ℃ for 12 hours;
s4: 1L of pure water was added to the reaction solution, and then the mixture was distilled under reduced pressure at a temperature of 80 ℃ and a pressure of 0.01MPa to 820 g, whereby the content of potassium N-alkylaminodipropionate in the resulting solution was 23.7% and the purity was 96%.
Example 5
S1: dissolving 100 g of ethyl acrylate (1 mol) in 800 ml of methanol to prepare an ethyl acrylate solution;
s2: 107 g of tetradecylamine (0.5 mol) is dropwise added into the ethyl acrylate solution, and the dropwise addition is finished within 1.2 hours; then reacting for 15 hours at the temperature of 40 ℃;
s3: adding 1000 ml of 1.0 mol/L sodium hydroxide solution into the reaction solution, and reacting for 10 hours at the temperature of 25 ℃;
s4: 1L of pure water was added to the reaction solution, and then the solution was distilled under reduced pressure at 50 ℃ and 0.03MPa to 1000 g, whereby the content of sodium N-alkylaminodipropionate in the resulting solution was 19.7% and the purity was 98%.
Comparative example 1
A process for the selective synthesis of a solution of an N-alkylaminodipropionic acid salt, substantially as described in example 1, with the only difference that: methyl acrylate was not dissolved using an organic solvent, methyl tert-butyl ether, but dodecylamine was directly added dropwise to methyl acrylate.
The content of the obtained liquid potassium N-alkyl amino dipropionate is 15.1 percent, and the purity is 78 percent. Therefore, the acrylic ester is dissolved in the organic solvent to react, which plays an important role in controlling the reaction direction of the N-alkyl amino dipropionate, and greatly influences the purity of the product.
Comparative example 2
A process for the selective synthesis of a solution of an N-alkylaminodipropionic acid salt, substantially as described in example 1, with the only difference that: in step S2, dodecylamine is added to the acrylate solution at one time, i.e., without a dropwise addition.
The content of the obtained liquid potassium N-alkyl amino dipropionate is 11.5 percent, and the purity is 70 percent. Therefore, the method for dropwise adding the alkyl primary amine plays an important role in controlling the reaction direction for generating the N-alkyl amino dipropionate, and greatly influences the purity of the product. Comparative example 3
A process for the selective synthesis of a solution of an N-alkylaminodipropionic acid salt, substantially as described in example 1, with the only difference that: in step S4, the distillation was carried out under reduced pressure without adding pure water.
The resulting solution had a solid content of 10.8% and a purity of 65%. Therefore, the pure water is added in the step S4 and then the distillation under reduced pressure is carried out, so that the yield of the product N-alkyl amino dipropionate can be obviously improved, and the high purity of the product after the distillation is ensured.
Note: in each example, the content and purity of the product N-alkylaminodipropionic acid salt solution were calculated according to the NMR method.
This detailed description is to be construed as illustrative only and is not to be taken as limiting the invention, as any changes that may be made by a person skilled in the art after reading the present specification will be protected by the patent laws within the scope of the appended claims.
Claims (10)
1. A method for selectively synthesizing a solution of N-alkylaminodipropionic acid salts is characterized in that: the method comprises the following steps:
s1: dissolving acrylic ester in an organic solvent to prepare an acrylic ester solution;
s2: dropwise adding 1 molar equivalent of alkyl primary amine into 2-5 molar equivalents of acrylate solution; after the dropwise addition is finished, reacting for 10-48 hours at the temperature of 10-100 ℃;
s3: adding 2.0-4.0 molar equivalent of 0.5-2.0 mol/L alkali metal hydroxide solution into the reaction solution, and reacting at 10-100 ℃ for 10-48 hours;
s4: adding pure water with the mass 5-20 times of that of the primary alkylamine into the reaction liquid, and then carrying out reduced pressure distillation at the temperature of 30-80 ℃ and the pressure of 0-0.03 MPa until the weight content of the N-alkyl amino dipropionate is 10-50%.
2. The process for the selective synthesis of a solution of N-alkylaminodipropionic acid salts according to claim 1, characterized in that: the acrylate refers to a molecular formula of CH2Compounds of formula i = CHCOOR1 wherein R1 denotes methyl, ethyl or propyl.
3. The process for the selective synthesis of a solution of N-alkylaminodipropionic acid salts according to claim 1 or 2, characterized in that: the alkyl primary amine refers to the molecular formula of RNH2Wherein R denotes an alkane group consisting of from 6 to 24 carbon atoms.
4. The process for the selective synthesis of a solution of N-alkylaminodipropionic acid salts according to claim 1, characterized in that: in step S1, the organic solvent is an ester, an ether, an alcohol, or a halogenated alkane.
5. The process for the selective synthesis of a solution of N-alkylaminodipropionic acid salts according to claim 1, characterized in that: in step S1, the concentration of the acrylate solution is 1-4 mol/L.
6. The process for the selective synthesis of a solution of N-alkylaminodipropionic acid salts according to claim 1, characterized in that: in step S2, 1 molar equivalent of alkyl primary amine is added into 2.0-2.5 molar equivalent of acrylate solution; after the dropwise addition is finished, the reaction is carried out for 15-24 hours at the temperature of 20-40 ℃.
7. The process for the selective synthesis of a solution of N-alkylaminodipropionic acid salts according to claim 1 or 6, characterized in that: in step S2, the dropping speed of the primary alkyl amine is controlled to be 0.5-2 hours after the dropping is finished.
8. The process for the selective synthesis of a solution of N-alkylaminodipropionic acid salts according to claim 1, characterized in that: in step S3, an alkali metal hydroxide solution having a concentration of 0.8 to 1.2 mol/liter is added to the reaction solution in an amount of 2.0 to 2.2 mol equivalents, and the reaction is carried out at a temperature of 20 to 60 ℃ for 15 to 24 hours.
9. The process for the selective synthesis of a solution of N-alkylaminodipropionic acid salts according to claim 1 or 8, characterized in that: in step S3, the alkali metal hydroxide aqueous solution is a sodium hydroxide solution or a potassium hydroxide solution.
10. The process for the selective synthesis of a solution of N-alkylaminodipropionic acid salts according to claim 1, characterized in that: in the step S4, pure water with the mass 10-15 times of that of the alkyl primary amine is added into the reaction liquid, and then the mixture is subjected to reduced pressure distillation at the temperature of 40-80 ℃ and the pressure of 0-0.03 MPa until the weight content of the N-alkyl amino dipropionate is 10-30%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110296746A1 (en) * | 2010-06-03 | 2011-12-08 | Instituto Mexicano Del Petroleo | Amino and imino propionic acids, process of preparation and use |
| CN108675936A (en) * | 2018-06-22 | 2018-10-19 | 陕西科技大学 | N- lauryls-(alpha-alkyl)-Beta-alanine amphoteric surfactant and the preparation method and application thereof of pH responses |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110296746A1 (en) * | 2010-06-03 | 2011-12-08 | Instituto Mexicano Del Petroleo | Amino and imino propionic acids, process of preparation and use |
| CN108675936A (en) * | 2018-06-22 | 2018-10-19 | 陕西科技大学 | N- lauryls-(alpha-alkyl)-Beta-alanine amphoteric surfactant and the preparation method and application thereof of pH responses |
Non-Patent Citations (1)
| Title |
|---|
| BRAHIM BETTAYEB ET AL.: "Pure N-Alkylaminopropionic Acid and N-Alkylaminodipropionic Acid Sodium Salts: Synthesis, Characterization, and Physicochemical Properties", 《J SURFACT DETERG》 * |
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Address after: 325000 No.1, Jinlian Road, Yongzhong street, Longwan District, Wenzhou City, Zhejiang Province Patentee after: Wenzhou Research Institute of Guoke (Wenzhou Institute of biomaterials and Engineering) Address before: 325000 enterprise development headquarters building, science and Technology City, 156 Wenchang Road, high tech Zone, Wenzhou City, Zhejiang Province Patentee before: Wenzhou Research Institute of Chinese Academy of Sciences (Wenzhou Institute of Biomaterials and Engineering) |