CN1187184A - Preparation of alkali metal acyl amino acids - Google Patents
Preparation of alkali metal acyl amino acids Download PDFInfo
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- CN1187184A CN1187184A CN96194561A CN96194561A CN1187184A CN 1187184 A CN1187184 A CN 1187184A CN 96194561 A CN96194561 A CN 96194561A CN 96194561 A CN96194561 A CN 96194561A CN 1187184 A CN1187184 A CN 1187184A
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- acid
- basic metal
- metal
- amino acids
- acyl amino
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Abstract
A process of preparing alkali metal N-acyl amino acids, especially sodium N-acyl sarcosinates. The process of the invention eliminates the use of phosphorus trichloride or thionyl chloride and carboxylic acid chlorides. The process involves reacting the alkali metal N-acyl amino acid directly with a fatty acid at elevated temperatures with constant removal of water generated in the reaction.
Description
Background of invention
Use the amino acid salts tensio-active agent in preparation soap, particularly the N-acyl sarcosinate is known.General sarcosinate is that sodium, potassium or the ammonium salt solution form with it used.The industrial N-acyl sarcosinate of producing is under the condition of careful control, adopts the sodium salt of sarkosine and suitable fatty acyl group chlorine to react through Schotten-Baumann:
After reaction is finished, thick sodium salt acidifying is discharged the N-acyl group sarkosine of separating from moisture by product.Then, its neutralization is obtained salt form.Sarcosinate is that HampshireChemical Corp is with HAMPOSYL as sodium N-lauroyl sarcosinate, coconut acyl group sodium sarcosinate and myristoyl sodium sarcosinate
Trade mark is commercially available.
The N-acyl sarcosinate is being used for many years aspect the nursing such as oral, skin and hair.Shown that they can reduce the infiltration that potential pungency solute such as sodium ion pass human body skin; And other tensio-active agent increases this infiltration (" clean-out system and tensio-active agent are to the infiltrative influence of corium ", Bettley, F.Ray, Brit.J.Dermatol., 77,98-100 (1965)).Fashionable when the N-acyl sarcosinate is added as cosurfactant, it also demonstrates and can reduce the general skin irritation (U.S.2,962,448) relevant with the clean-out system preparation.The N-acyl sarcosinate has lower toxicity to Mammals and fish, lower trend that causes stimulation and very fast biological degradation.
So people have required to simplifying to produce N-acyl sarcosinate and other N-acylamino acid method and eliminate the ordinary method environmental pollution.
Summary of the invention
The present invention has solved prior art problems, and it provides preparation basic metal N-acylamino acid, the particularly method of N-acyl group sodium sarcosinate.Method of the present invention is not used phosphorus trichloride or thionyl chloride and carboxyl acyl chloride.Generally speaking, this method comprises at high temperature directly basic metal N-acylamino acid and a kind of fatty acid response, constantly removes the water that dereaction produced simultaneously.The detailed description of invention
Concerning the inventive method, initial action reagent is lipid acid and the amino amino acid that is replaced by a hydrogen atom at least with general formula R COOH.Lipid acid and amino acid at high temperature reaction result have formed acylamino acid, but darker color and by product have also occurred, and beat all be the formation minimum of color and by product under the used reaction conditions of the present invention.
Suitable lipid acid comprises straight chain fatty acid, branched chain fatty acid, cyclic fatty acid, saturated and unsaturated, aromatics and fragrant heterocyclic carboxylic acid, as acetic acid, propionic acid, butyric acid, sad, caproic acid, n-nonanoic acid, 3,5, the 5-tri-methyl hexanoic acid, n-nonanoic acid, capric acid, undecanoic acid, lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, linolic acid, docosoic acid, 2-methyl-undecanoic acid, 2-butyl-sad, 2-ethyl-caproic acid, alkyl succinic acid, the alkylene succsinic acid, hexanodioic acid, cyclohexyl, phenylformic acid, chloro-phenylformic acid, nitrobenzoic acid, naphthenic acid, sylvic acid, nicotinic acid, the 2-pyridine-3-carboxylic acid, terephthalic acid, phthalic acid, C
8(EO)
2COOH and composition thereof.Preferred fatty acid comprises C
8-C
20Carboxylic acid is preferably used oleic acid (CH
3(CH
2)
7CH:CH (CH
2)
7-COOH), lauric acid (CH
3(CH
2)
10COOH), tetradecanoic acid (CH
3(CH
2)
12COOH) and coconut acid prepare oleoylsarcosine, lauroyl sarcosine, myristoyl sarkosine and coconut acyl group sarkosine respectively.
Suitable amino acid is those amino acid that amino has a commutable hydrogen atom at least.Preferred amino acids comprises these sour an alkali metal salts of sarkosine, glycine, imino-acetic acid, L-Ala, N-methylalanine, Beta-alanine, N-methyl-Beta-alanine, aspartic acid, N-methylaspartic acid, Xie Ansuan, leucine, Isoleucine, Gelucystine, methionine(Met), phenylalanine, L-glutamic acid, proline(Pro) and Methionin.Preferred especially sodium sarcosinate.
With lipid acid and 1: 1 ratio of alkali metal acyl amino acids, though how much reaction times can both obtain the product yield of 50-55%.And, because of excessive alkali metal acyl amino acids can not help to advance finishing of this reaction.So, preferably the acid of excess of ammonia base is joined in the reaction mixture of alkali metal acyl amino acids and lipid acid to come accelerated reaction and reach higher conversion.The present inventor has been found that the excessive amino acid of the monovalent that adding is as the criterion with lipid acid can obtain the transformation efficiency of 85-90% after 8-10 hour.Add two equivalents and can after 3-5 hour, obtain 90% conversion.Use amino acid how much to depend on required conversion and speed.This acid can add or once all add by increment.
Exercisable temperature of reaction is from about 100 ℃ to about 200 ℃.When being lower than about 170 ℃, it is too slow that this reaction is tending towards.So, preferred 170 ℃-190 ℃, wherein 170 ℃ preferred especially.
The dried shape alkali metal acyl amino acids initiator of preferred use.The thick reaction mixture that produces is handled by diluting in the aqueous solution of Virahol, and the ratio of preferred Virahol and water is 95: 5 to 5: 95.Preferably the amount of Virahol is dropped to minimum.Then this thick product solution being acidified to pH is 1, causes to be separated.Be used for the suitable acid of acidifying and comprise mineral acid and sulfuric acid, preferably sulfuric acid.Isolate lighter organic layer and evaporate and remove Virahol and water.
On the other hand, initial substance can be this amino acid, this amino acid can enough bucks such as the sodium hydroxide spraying drying that neutralizes then produce the exsiccant amino acid sodium.
For fear of the formation of band colour solid, importantly this oxidizing reaction is dropped to minimum or removal fully.This enough a kind of rare gas element of energy (as nitrogen) is cleaned or uses vacuum to finish.This also can be used for removing the water that forms in alkali metal acyl amino acids and the lipid acid condensation course.
The present invention also describes in detail with the following example, and it is to describe rather than be used for limiting the present invention in detail that these embodiment purposes are provided.
Embodiment 1
11.04g (0.124 mole) sarkosine is joined in the 104g methyl alcohol, add 26.8g (0.124 mole) 25% sodium methylate then.This mixture was refluxed 15 minutes, so that this solution becomes gets evenly.Add a oleic acid and distillation for removing methanol, removed methyl alcohol after, the temperature of this reaction mixture is brought up to 170 ℃.At 4.0,5.5 and 6.5 hours, add 2.8g (0.031 mole) sarkosine again and continue heating at 170 ℃.The total heating of this reaction 8.5 hours, and oleoylsarcosine sodium is 85: 15 (area metering with HPLC is measured) with oleic last ratio.
Embodiment 2
The reactor that is equipped with mechanical stirrer, heating sheathing, thermometer and nitrogen is charged into 35.04g (0.125 mole) oleic acid.This oleic acid is heated to 80 ℃ and add 13.8g (0.125 mole) solid sodium sarcosinate.This mixture heating up to 170 ℃ also continuous spray nitrogen.When this reaction mixture reaches 170 ℃, add 11.4g (0.125 mole) solid sarkosine.From this reaction mixture, take a sample after 10 hours at 170 ℃, be converted into 84.2% with what oleic acid was as the criterion.
Crude product mixture is dissolved in the Virahol and water of 60g 50/50 volume ratio.With sulfuric acid this solution being acidified to pH is 1.In case acidifying, this solution just is divided into two-layer.Separate the upper strata of containing product and concentrate and obtain the N-oleoylsarcosine.
Embodiment 3
The reactor that is equipped with mechanical stirrer, heating sheathing, thermometer and nitrogen is charged into 35.04g (0.125 mole) oleic acid.This oleic acid is heated to 80 ℃ and add 13.8g (0.125 mole) solid sodium sarcosinate.This mixture heating up to 170 ℃ while is constantly sprayed into nitrogen.When this reaction mixture reaches 170 ℃, add 22.8g (0.250 mole) solid sarkosine.After 5 hours, from this reaction mixture, take a sample, be converted into 92.5% with what oleic acid was as the criterion.
Embodiment 4
In three neck 500ml round-bottomed flasks of being furnished with mechanical stirrer, thermometer, nitrogen inlet and nitrogen outlet, charge into the lauric acid of 35.70g (0.175 mole).Lauric acid is heated to 160 ℃ constantly spraying under the nitrogen, and adds 19.40g Sodium glycocollate and 15.90g (0.175 mole) glycine as quickly as possible.Under constantly spraying into nitrogen, this mixture heating up to 170 ℃ is removed the water that forms in the reaction process then.Regularly sample thief is monitored lauric disappearance.After 7 hours, 93% lauric acid is converted into product.
Embodiment 5
In three neck 500ml round-bottomed flasks of being furnished with mechanical stirrer, thermometer, nitrogen inlet and nitrogen outlet, charge into 49.00g (0.175 mole) oleic acid.Oleic acid is heated to 160 ℃ and add 8.60g (0.088 mole) Sodium glycocollate and 6.60g (0.088 mole) glycine as quickly as possible constantly spraying under the nitrogen.Under constantly spraying into nitrogen, this mixture heating up to 170 ℃ is removed the water that forms in the reaction process then.Regularly sample thief is monitored oleic disappearance.3.5 after hour, 45.8% oleic acid is converted into product.
Embodiment 6
In three neck 500ml round-bottomed flasks of being furnished with mechanical stirrer, thermometer, nitrogen inlet and nitrogen outlet, charge into 34.76g (0.124 mole) oleic acid.Oleic acid is heated to 160 ℃ and add 13.78g (0.124 mole) sodium sarcosinate as quickly as possible constantly spraying under the nitrogen.Under constantly spraying into nitrogen, this mixture heating up to 170 ℃ is removed the water that forms in the reaction process then.Regular sample thief and monitor the process of this reaction with HPLC.After 6 hours, 55% oleic acid is converted into product.Being reflected at 170 ℃ of reheat 4 hours (10 hours altogether), transformation efficiency is 57%.
Embodiment 7
In three neck 500ml round-bottomed flasks of being furnished with mechanical stirrer, thermometer, nitrogen inlet and nitrogen outlet, charge into 42.05g (0.150 mole) oleic acid.Oleic acid is heated to 160 ℃ constantly spraying under the nitrogen, and adds 20.50g (0.23 mole) sarkosine as quickly as possible.Under constantly spraying into nitrogen, this mixture heating up to 160 ℃ is removed the water that forms in the reaction process then.Regular sample thief and monitor the process of this reaction with HPLC.After 5 hours, 75% oleic acid is converted into product.
Claims (18)
1. method for preparing basic metal N-acylamino acid, it comprises that (wherein R is C among the RCOOH having general formula R COOH
1Or higher hydrocarbon base substituting group) amino acid or the reaction of a kind of alkali metal acyl amino acids that a kind of lipid acid and a kind of amino are replaced by a hydrogen atom at least.
2. according to the process of claim 1 wherein that said reaction is to carry out in the presence of the acid of this amino acid or alkali metal acyl amino acids.
3. according to the process of claim 1 wherein that said lipid acid is selected from the group of being made up of oleic acid, lauric acid, tetradecanoic acid, coconut acid, stearic acid, n-nonanoic acid, capric acid and undeeanoic acid.
4. according to the method for claim 2, wherein said lipid acid is selected from the group of being made up of oleic acid, lauric acid, tetradecanoic acid, coconut acid, stearic acid, n-nonanoic acid, capric acid and undeeanoic acid.
5. according to the process of claim 1 wherein that said lipid acid is lauric acid.
6. according to the method for claim 2, wherein said lipid acid is lauric acid.
7. according to the method for claim 1, also be included in the water of ceaselessly removing when basic metal N-acylamino acid forms in the reaction medium.
8. according to the method for claim 2, also be included in the water of ceaselessly removing when basic metal N-acylamino acid forms in the reaction medium.
9. according to the method for claim 7, water is wherein removed by spraying into rare gas element.
10. method according to Claim 8, water is wherein removed by spraying into rare gas element.
11. according to the process of claim 1 wherein that said reaction is to carry out under 170 ℃ to 190 ℃ temperature.
12. according to the method for claim 2, wherein said reaction is to carry out under 170 ℃ to 190 ℃ temperature.
13. according to the process of claim 1 wherein that the acid of said this alkali metal acyl amino acids is that the amount of the monovalent surplus that is as the criterion with this lipid acid adds.
14. according to the method for claim 2, wherein the acid of said this alkali metal acyl amino acids is that the amount of the monovalent surplus that is as the criterion with this lipid acid adds.
15. according to the process of claim 1 wherein that the acid of said this alkali metal acyl amino acids is that the amount of the two equivalent surpluses that are as the criterion with this lipid acid adds.
16. according to the method for claim 2, wherein the acid of said this alkali metal acyl amino acids is that the amount of the two equivalent surpluses that are as the criterion with this lipid acid adds.
17. according to the process of claim 1 wherein that said alkali metal acyl amino acids is selected from the group of being made up of basic metal sarkosine, basic metal glycine, basic metal iminodiethanoic acid, basic metal L-Ala, basic metal N-methylalanine, basic metal beta Alanine, basic metal N-methyl-Beta-alanine, basic metal aspartic acid, basic metal N-methylaspartic acid, basic metal Xie Ansuan, basic metal leucine, basic metal Isoleucine, basic metal Gelucystine, basic metal methionine(Met), basic metal phenylalanine, basic metal L-glutamic acid, basic metal proline(Pro) and basic metal Methionin.
18. according to the method for claim 2, wherein said alkali metal acyl amino acids is selected from the group of being made up of basic metal sarkosine, basic metal glycine, basic metal iminodiethanoic acid, basic metal L-Ala, basic metal N-methylalanine, basic metal beta Alanine, basic metal N-methyl-Beta-alanine, basic metal aspartic acid, basic metal N-methylaspartic acid, basic metal Xie Ansuan, basic metal leucine, basic metal Isoleucine, basic metal Gelucystine, basic metal methionine(Met), basic metal phenylalanine, basic metal L-glutamic acid, basic metal proline(Pro) and basic metal Methionin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96194561A CN1187184A (en) | 1995-06-06 | 1996-05-31 | Preparation of alkali metal acyl amino acids |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/466,094 | 1995-06-06 | ||
| CN96194561A CN1187184A (en) | 1995-06-06 | 1996-05-31 | Preparation of alkali metal acyl amino acids |
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| Publication Number | Publication Date |
|---|---|
| CN1187184A true CN1187184A (en) | 1998-07-08 |
Family
ID=5128707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96194561A Pending CN1187184A (en) | 1995-06-06 | 1996-05-31 | Preparation of alkali metal acyl amino acids |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266737A (en) * | 2011-06-16 | 2011-12-07 | 北京工商大学 | Method for preparing N-fatty acyl amino acid type surfactant by fat |
| CN103664665A (en) * | 2013-12-13 | 2014-03-26 | 天津天成制药有限公司 | Solid sodium sarcosine preparation method |
| CN103772227A (en) * | 2014-01-13 | 2014-05-07 | 石家庄菠莉亚日用化工有限公司 | Preparation method for grease-based amino acid salt-series surfactant |
| CN103857653A (en) * | 2011-07-28 | 2014-06-11 | 荷兰联合利华有限公司 | General method for preparing fatty acyl amido based surfactants |
| CN110938023A (en) * | 2019-12-23 | 2020-03-31 | 张家港格瑞特化学有限公司 | Preparation method of fatty acyl taurine surfactant |
-
1996
- 1996-05-31 CN CN96194561A patent/CN1187184A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266737A (en) * | 2011-06-16 | 2011-12-07 | 北京工商大学 | Method for preparing N-fatty acyl amino acid type surfactant by fat |
| CN103857653A (en) * | 2011-07-28 | 2014-06-11 | 荷兰联合利华有限公司 | General method for preparing fatty acyl amido based surfactants |
| CN103857653B (en) * | 2011-07-28 | 2016-08-17 | 荷兰联合利华有限公司 | Prepare surfactant conventional method based on fatty acyl amino |
| CN103664665A (en) * | 2013-12-13 | 2014-03-26 | 天津天成制药有限公司 | Solid sodium sarcosine preparation method |
| CN103772227A (en) * | 2014-01-13 | 2014-05-07 | 石家庄菠莉亚日用化工有限公司 | Preparation method for grease-based amino acid salt-series surfactant |
| CN103772227B (en) * | 2014-01-13 | 2020-03-20 | 石家庄菠莉亚日用化工有限公司 | Preparation method of grease-based amino acid salt series surfactant |
| CN110938023A (en) * | 2019-12-23 | 2020-03-31 | 张家港格瑞特化学有限公司 | Preparation method of fatty acyl taurine surfactant |
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