CN102617390A - Preparation method of epsilon-N-lauroyl lysine - Google Patents
Preparation method of epsilon-N-lauroyl lysine Download PDFInfo
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- CN102617390A CN102617390A CN2012100705840A CN201210070584A CN102617390A CN 102617390 A CN102617390 A CN 102617390A CN 2012100705840 A CN2012100705840 A CN 2012100705840A CN 201210070584 A CN201210070584 A CN 201210070584A CN 102617390 A CN102617390 A CN 102617390A
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Abstract
The invention relates to a preparation method of epsilon-N-lauroyl lysine. In the method, lysine or a salt thereof and lauroyl chloride are taken as raw materials. The method comprises the following steps of: making lysine or a salt thereof and a divalent metal ion form a chelate for protecting alpha-amino and carboxyl; undergoing an amidization reaction on the chelate and lauroyl chloride; and damaging a chelate structure through acid hydrolysis, and deprotecting alpha-amino and carboxyl to obtain the epsilon-N-lauroyl lysine. According to the method disclosed by the invention, an entire operating process is simple and convenient, reaction directional property is definite, a small quantity of side products are produced, high-purity epsilon-N-lauroyl lysine (more than or equal to 98.5 percent) can be obtained, and the obtained product can be applied in the field of cosmetics.
Description
Technical field
The present invention relates to the preparation method of a kind of ε-N-lauryl Methionin.
Background technology
At present the preparation method of ε-N-lauryl Methionin mainly contains LAURIC ACID 99 MIN and Methionin hot method altogether, behind LAURIC ACID 99 MIN and the Methionin formation double salt in high boiling dehydration of organic solvent method, and lauroyl chloride and the direct amidation of Methionin etc.Above-mentioned several method all exists numerous adverse factors; Wherein: the lauryl Methionin that common hot method is obtained is mixture; Wherein contain ε-N-lauryl Methionin, α-N-lauryl Methionin, N, N-two replaces Methionin etc., therefore is difficult to obtain the qualified ε of purity-N-lauryl Methionin; Make use range limited, can't be applied in the cosmetic industry.The deficiency of dehydration of organic solvent method is to have used high boiling hazardous solvent in the building-up process, so just certainly exists residues of harmful substances in the product, makes use range limited equally.What the direct amidated maximum deficiency of Methionin was to obtain is the mixture of several compounds, and side reaction is many, and aftertreatment is pretty troublesome, and yield is very low, can't or be difficult to obtain high-quality ε-N-lauryl Methionin.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that overcomes prior art, and a kind of preparation method of easy high purity ε-N-lauryl Methionin is provided
For solving above technical problem, the present invention takes following technical scheme:
The preparation method of a kind of ε-N-lauryl Methionin; With Methionin or its salt, lauroyl chloride is raw material, and said method at first makes Methionin or its salt and divalent-metal ion form inner complex, to form the protection to alpha-amino group and carboxyl; Make this inner complex and lauroyl chloride carry out amidate action then; Destroy chelate structure through acidolysis at last, make alpha-amino group and carboxyl deprotection, get ε-N-lauryl Methionin.
According to the present invention, said divalent-metal ion can include but not limited to Ca for the various ions that can form chelate structure with Methionin
2+, Mg
2+, Cu
2+, Fe
2+, Zn
2+Deng.According to a concrete aspect, said inner complex by L-Methionin or L lysine HCL and the salt that contains said divalent-metal ion in pH6.5～11, temperature-20 ℃～80 ℃ down reaction obtain.The salt of said divalent-metal ion comprises the salt of salt, metal and organic acid formation that metal and inorganic acid radical form etc., and wherein, inorganic acid radical can be for example Cl
-, SO
4 2-Organic acid is COO for example
-The salt of typical divalent-metal ion has CaCl
2, ZnCl
2, MgCl
2, ZnCl
2, ZnSO
4, FeSO
4, CuSO
4Deng.
Preferably, being reflected under 20 ℃～30 ℃ of the pH 8.0～9.0, temperature of preparation inner complex carried out.The reaction times of preparation inner complex is 2～24 hours, is preferably 8 hours.
According to an aspect of the present invention, said amidate action is carried out under pH 6.5～12.5, temperature-20 ℃～50 ℃, and lauroyl chloride and inner complex in molar ratio 1～10: 1 feeds intake.Preferably, amidate action is carried out under pH 9.0～10.0, temperature-5 ℃～5 ℃.Lauroyl chloride and inner complex in molar ratio 1～2: 1 feeds intake.The time of amidate action is 1～24 hour, is preferably 8 hours.
According to another aspect of the invention, said acidolysis can be carried out under pH 1～6.5, temperature-20 ℃～80 ℃, preferably under 40 ℃～50 ℃ of pH 2～3, temperature, carries out.Acidolysis can be used the aqueous solution of various suitable mineral acid, organic acid and hydrogen salt, preferably salt acid solution and sulphuric acid soln.The reaction times of acidolysis was generally 0.5～24 hour, preferred 4～5 hours.In addition, also can use suitable organic solvent, particular methanol, ethanol in the acidolysis process.
Salt as the Methionin of raw material can be for example hydrochloride etc.
Because the employing of technique scheme, the present invention compared with prior art has the following advantages:
Method of the present invention, the entire operation process is easy, and the Direction of Reaction property is clear and definite, and by product is few, can obtain the ε-N-lauryl Methionin of high purity (more than or equal to 98.5%), and products obtained therefrom can be used in cosmetic field.
Embodiment
Main invention thinking of the present invention is: 1) a kind of new synthetic route is provided; Promptly at first make Methionin or its salt combine to form inner complex with divalent-metal ion; Utilize chelate structure that the alpha-amino group and the carboxyl of Methionin are protected; After this inner complex and lauroyl chloride carry out amidate action,, get ε-N-lauryl lysine salt again through the acidolysis deprotection; 2) to the 1st) in preparation and the method for acidolysis of the inner complex mentioned be optimized design.
According to the present invention, the preparation of ε-N-lauryl Methionin mainly comprises following three steps:
1. the preparation of inner complex:
The available chemical equation of the preparation of inner complex is represented as follows:
In the above-mentioned formula, M
2+The expression divalent-metal ion can be Ca
2+, Mg
2+, Cu
2+, Fe
2+, Zn
2+Deng.Formula I compound is inner complex.
2. the inner complex represented of formula I and lauroyl chloride carry out amidate action and obtain formula II compound.
3. the acidolysis of formula II compound generates ε-N-lauryl Methionin (formula III compound).
Below in conjunction with concrete embodiment the present invention is done further detailed explanation.
Embodiment 1
In the reaction flask of whisking appliance is housed, add CaCl
2111g (1mol) and water, stirring and dissolving adds L-Methionin 292g (2mol) then in batches; Stirred 3 hours, transferring pH is 8.0, and the vial material is cooled to about-10 ℃ with the salt water dissolution; Begin to drip lauroyl chloride 218g (1mol); Drip off in 2 hours, drip off the back and under this temperature, continue reaction 6 hours, get white solid.
Above-mentioned gained white solid is added in the hydrochloric acid soln of 30wt%, stirred 4 hours under the room temperature, cross and filter bullion, wash this bullion three times with purified water, oven dry at last gets refined prod, surveys 229～230 ℃ of fusing points, and ε-N-lauryl Methionin purity is 98.6%.
Embodiment 2
In the reaction flask of whisking appliance is housed, add MgCl
295g (1mol) and water, stirring and dissolving adds L-Methionin 146g (1mol) then in batches; Stirred 3 hours, transferring pH is 7.5, and the vial material is cooled to about-5 ℃ with the salt water dissolution; Begin to drip lauroyl chloride 218g (1mol); Drip off in 2 hours, drip off the back and under this temperature, continue reaction 8 hours, get white solid.
The gained white solid is added in the hydrochloric acid soln of 30wt%, stirred 5 hours under the room temperature, cross and filter bullion, wash this bullion three times with purified water, oven dry at last gets refined prod, surveys 229～230 ℃ of fusing points, and ε-N-lauryl Methionin purity is 98.7%.
Embodiment 3
In the reaction flask of whisking appliance is housed, add ZnSO
4161g (1mol) and water, stirring and dissolving adds L-Methionin 219g (1.5mol) then in batches; Stirred 3 hours, transferring pH is 9.0, and the vial material is cooled to about 25 ℃ with the salt water dissolution; Begin to drip lauroyl chloride 436g (2mol); Drip off in 2 hours, drip off the back and under this temperature, continue reaction 7 hours, get white solid.
The gained white solid is added in the sulphuric acid soln of 30wt%, stirred 4 hours under the room temperature, cross and filter bullion, wash this bullion three times with purified water, oven dry at last gets refined prod, surveys 229～230 ℃ of fusing points, and ε-N-lauryl Methionin purity is 98.9%.
Embodiment 4
In the reaction flask of whisking appliance is housed, add CuSO
4159g (1mol) and water, stirring and dissolving adds L-Methionin 146g (1mol) then in batches; Stirred 3 hours, transferring pH is 8.5, and the vial material is cooled to about-10 ℃ with the salt water dissolution; Begin to drip lauroyl chloride 436g (2mol); Drip off in 2 hours, drip off the back and under this temperature, continue reaction 10 hours, get blue solid.
The gained blue solid is added in the sulphuric acid soln of 30wt%, stirred 5 hours under the room temperature, cross and filter bullion, wash this bullion three times with purified water, oven dry at last gets refined prod, surveys 229～230 ℃ of fusing points, and ε-N-lauryl Methionin purity is 99.1%.
Embodiment 5
In the reaction flask of whisking appliance is housed, add FeSO
4152g (1mol) and water, stirring and dissolving adds L-Methionin 219g (1.5mol) then in batches; Stirred 3 hours, transferring pH is 9.0, and the vial material is cooled to about-10 ℃ with the salt water dissolution; Begin to drip lauroyl chloride 218g (1mol); Drip off in 2 hours, drip off the back and under this temperature, continue reaction 6 hours, get the light green solid.
Gained light green solid is added in the sulphuric acid soln of 30wt%, stirred 4 hours under the room temperature, cross and filter bullion, wash this bullion three times with purified water, oven dry at last gets refined prod, surveys 229～230 ℃ of fusing points, and ε-N-lauryl Methionin purity is 98.6%.
Embodiment 6
In the reaction flask of whisking appliance is housed, add ZnCl
2136g (1mol) and water, stirring and dissolving adds L-Methionin 146g (1mol) then in batches; Stirred 3 hours, transferring pH is 8.0, and the vial material is cooled to about-10 ℃ with the salt water dissolution; Begin to drip lauroyl chloride 436g (2mol); Drip off in 2 hours, drip off the back and under this temperature, continue reaction 8 hours, get white solid.
The gained white solid is added in the hydrochloric acid soln of 30wt%, stirred 5 hours under the room temperature, cross and filter bullion, wash this bullion three times with purified water, oven dry at last gets refined prod, surveys 229～230 ℃ of fusing points, and ε-N-lauryl Methionin purity is 98.8%.
Embodiment 7
In the reaction flask of whisking appliance is housed, add ZnCl
2136g (1mol) and water, stirring and dissolving adds L lysine HCL 182g (1mol) then in batches; Stirred 3 hours, transferring pH is 9.0, and the vial material is cooled to about-10 ℃ with the salt water dissolution; Begin to drip lauroyl chloride 436g (2mol); Drip off in 2 hours, drip off the back and under this temperature, continue reaction 6 hours, get white solid.
The gained white solid is added in the hydrochloric acid soln of 30wt%, stirred 4 hours under the room temperature, cross and filter bullion, wash this bullion three times with purified water, oven dry at last gets refined prod, surveys 229～230 ℃ of fusing points, and ε-N-lauryl Methionin purity is 98.7%.
Embodiment 8
In the reaction flask of whisking appliance is housed, add CuSO
4159g (1mol) and water, stirring and dissolving adds lysine hydrochloride 364g (2mol) then in batches; Stirred 3 hours, transferring pH is 8.5, and the vial material is cooled to about-10 ℃ with the salt water dissolution; Begin to drip lauroyl chloride 218g (1mol); Drip off in 2 hours, drip off the back and under this temperature, continue reaction 6 hours, get blue solid.
The gained blue solid is added in the sulphuric acid soln of 30wt%, stirred 4 hours under the room temperature, cross and filter bullion, wash this bullion three times with purified water, get refined prod, survey 229～230 ℃ of fusing points, ε-N-lauryl Methionin purity is 98.9%.
The foregoing description only is explanation technical conceive of the present invention and characteristics; Its purpose is to let the personage who is familiar with this technology can understand content of the present invention and enforcement according to this; Can not limit protection scope of the present invention with this; All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (10)
1. the preparation method of ε-Ν-lauryl Methionin; With Methionin or its salt, lauroyl chloride is raw material, it is characterized in that: said method at first makes Methionin or its salt and divalent-metal ion form inner complex, to form the protection to alpha-amino group and carboxyl; Make this inner complex and lauroyl chloride carry out amidate action then; Destroy chelate structure through acidolysis at last, make alpha-amino group and carboxyl deprotection, get ε-Ν-lauryl Methionin.
2. the preparation method of ε-Ν according to claim 1-lauryl Methionin is characterized in that: said divalent-metal ion is Ca
2+, Mg
2+, Cu
2+, Fe
2+Or Zn
2+
3. the preparation method of ε-Ν according to claim 1 and 2-lauryl Methionin is characterized in that: said inner complex by L-Methionin or L lysine HCL and the salt that contains said divalent-metal ion pH 6.5 ~ 11, temperature-20 ℃ ~ 80 ℃ down reaction obtain.
4. the preparation method of ε-Ν according to claim 3-lauryl Methionin is characterized in that: being reflected under 20 ℃ ~ 30 ℃ of the pH 8.0 ~ 9.0, temperature of preparation inner complex carried out.
5. the preparation method of ε-Ν according to claim 1-lauryl Methionin is characterized in that: said amidate action is carried out under pH 6.5 ~ 12.5, temperature-20 ℃ ~ 50 ℃, and lauroyl chloride and inner complex in molar ratio 1 ~ 10:1 feed intake.
6. the preparation method of ε-Ν according to claim 5-lauryl Methionin is characterized in that: said amidate action is carried out under pH 9.0 ~ 10.0, temperature-5 ℃ ~ 5 ℃.
7. the preparation method of ε-Ν according to claim 5-lauryl Methionin is characterized in that: lauroyl chloride and inner complex 1 ~ 2:1 in molar ratio feed intake.
8. the preparation method of ε-Ν according to claim 1-lauryl Methionin is characterized in that: said acidolysis is carried out under pH 1 ~ 6.5, temperature-20 ℃ ~ 80 ℃.
9. the preparation method of ε-Ν according to claim 8-lauryl Methionin is characterized in that: said acidolysis is carried out under 40 ℃ ~ 50 ℃ of pH 2 ~ 3, temperature.
10. according to Claim 8 or the preparation method of 9 described ε-Ν-lauryl Methionin, it is characterized in that: said acidolysis is also carried out in the presence of methyl alcohol or alcoholic acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718275A (en) * | 2020-07-21 | 2020-09-29 | 江南大学 | Preparation method of N-lauroyl lysine |
| CN115160173A (en) * | 2022-09-01 | 2022-10-11 | 烟台海川化学制品有限公司 | N ε Process for producing dodecasyllysine |
Citations (1)
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|---|---|---|---|---|
| EP1314717A1 (en) * | 2001-11-26 | 2003-05-28 | Ajinomoto Co., Inc. | Method for preparing N-long chain acyl neutral amino acid |
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2012
- 2012-03-16 CN CN 201210070584 patent/CN102617390B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1314717A1 (en) * | 2001-11-26 | 2003-05-28 | Ajinomoto Co., Inc. | Method for preparing N-long chain acyl neutral amino acid |
Non-Patent Citations (5)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718275A (en) * | 2020-07-21 | 2020-09-29 | 江南大学 | Preparation method of N-lauroyl lysine |
| CN115160173A (en) * | 2022-09-01 | 2022-10-11 | 烟台海川化学制品有限公司 | N ε Process for producing dodecasyllysine |
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