CN1663947A - Process for preparing L-cysteic acid and its ester - Google Patents
Process for preparing L-cysteic acid and its ester Download PDFInfo
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- CN1663947A CN1663947A CN 200410021950 CN200410021950A CN1663947A CN 1663947 A CN1663947 A CN 1663947A CN 200410021950 CN200410021950 CN 200410021950 CN 200410021950 A CN200410021950 A CN 200410021950A CN 1663947 A CN1663947 A CN 1663947A
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- cysteic acid
- ester
- recrystallization
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Abstract
The invention discloses a process for preparing L-cysteic acid and L-cysteic acid ester, which is prepared from L- cysteine and chlorine as raw material through mixing L- cysteine with a predetermined amount of water or corresponding alcohol, letting in chlorine for oxidization, finally carrying out concentration or recrystallization to obtain the final product.
Description
One, affiliated field
The invention belongs to medical technical field.Relate more specifically to a kind of preparation method of compound, relating to a kind of is raw material with L-Gelucystine and chlorine, prepares the method for L-cysteic acid or L-cysteic acid ester in water or alcohol.
Two, background technology
The L-cysteic acid is a kind of important biochemical reagents, and physiological action is widely arranged in animal body, and is increasingly extensive in the application of industries such as medicine, makeup, washing composition.But with it is the medicine of raw material synthesizing anti-AIDS poison (HIV I), Herpes Simplex I virus, coccus and bacillus; But the diffusion of poly-cysteic acid anticancer and without any side effects to non-infected cells; The hair care agent that contains cysteic acid can keep hair elasticity and humidity, and the setting agent and the hair dye that contain cysteic acid can prevent hair damage, also can repair the hair that has damaged and improve hair quality; Be main raw material synthetic ethyl aspartic acid cysteic acid (EAC) and be the substitute products of the raw material synthetic sulfo group third ammonia succinate with cysteic acid, ethylene dibromide and aspartic acid as the washing auxiliary detergent tripoly phosphate sodium STPP with cysteic acid, alkyl maleic acid ester, have concurrently biodegradable and strong detergency two big advantages, because of the multiple metal ion of complexing, antirust, antiscale, anti-corrosion performance excellence can be widely used in industry and life with aspects such as washing composition and oil-field water processing, modified cements.
At present, the preparation method of L-cysteic acid makees oxygenant with bromine by the L-Gelucystine to make in hydrochloric acid medium.Directly make oxygenant, not only cost an arm and a leg, cost height but also seriously corroded, also have problem of environmental pollutions such as discharging of waste liquid with the liquid bromine.Also have at present and use the synthetic method of methyl-sulphoxide as oxygenant, but long reaction time, impurity many, make with extra care difficult.Also have in addition and use superoxide as oxygenant preparation, its reaction conditions requires high temperature, complicated operation.Particularly the preparation of L-cysteic acid ester all is to make in two steps, promptly earlier makes the L-cysteic acid by the L-Gelucystine, is got by the esterification of L-cysteic acid again.
Three, summary of the invention
At above problem, the objective of the invention is to disclose a kind of is raw material with L-Gelucystine and chlorine, makes the L-cysteic acid of solvent or the preparation method of its ester with water or corresponding alcohol.
The present invention can be achieved in the following manner: with L-Gelucystine and a certain amount of water or corresponding alcohol mixing, between 0～100 ℃, feed chlorine and carry out oxidation, the reaction back is if system L-cysteic acid then is concentrated into reaction solution certain volume recrystallization then; If system L-cysteic acid ester, then react the after-filtration solid and with solvent wash, be drying to obtain or again the recrystallization after drying make corresponding L-cysteic acid ester.
More specifically, at room temperature chlorine is fed in the mixed solution of L-Gelucystine and excessive water, the sign that its reaction is carried out is the feeding with chlorine, and the L-Gelucystine is dissolving gradually in water; All the dissolving back continues to feed chlorine 10 minutes in reaction solution.Reaction finishes, and reaction solution is concentrated into 1/5～1/4 of original volume, places refrigerator (about 0 ℃) crystallization promptly, and the solvent that crystallization is adopted is the mixed solution of water or water and ethanol arbitrary proportion (not containing straight alcohol).The reaction optimum temps is 20-30 ℃.
The present invention is that L-Gelucystine and corresponding alcohol is mixed when preparation L-cysteic acid ester, stir, then at 0～100 ℃, feed chlorine, after reaction finishes, cross filter solid and with solvent wash, be drying to obtain or recrystallization, drying then again, obtain L-cysteic acid ester at last, the general formula of its corresponding alcohol is:
ROH，R＝H?or
Wherein R1, R2, R3 are one or more in the substituting group substituting groups such as hydrogen, alkyl (straight chained alkyl, branched-chain alkyl, cycloalkyl), aryl.
More particularly at room temperature chlorine is fed in L-Gelucystine and the excessive corresponding alcohol, the sign that its reaction is carried out is the feeding with chlorine, and the L-Gelucystine is dissolving gradually in alcohol; All chlorine is continued to feed until all separating out with solid form again in the dissolving back in reaction solution, and filtration washing or recrystallization get final product then.The solvent that washing is adopted can be ether, ethyl acetate, ethanol or its miscellany; If recrystallization, the solvent that is adopted can be water, methyl alcohol, ethanol or its miscellany, and the best is a methyl alcohol.When the L-cysteic acid ester of four carbon of preparation and above alcohol thereof, need recrystallization.The temperature of recrystallization-20～40 ℃, the temperature of suitable recrystallization is 0～20 ℃.
Adopt the present invention to prepare L-cysteic acid or its ester preparation method than before, not only reaction temperature and, temperature of reaction is wide, and is easy to control, reaction times is short, and side reaction is few, and is easy to operate, and aftertreatment is simple and direct, and simple to the production unit requirement, cost is low, is more suitable for suitability for industrialized production.The particularly preparation of L-cysteic acid ester, single stage method can high yield obtain especially, has reduced step, has reduced cost.
Four, embodiment
The inventive method will further be described by following examples.
Embodiment 1:
Add 200 gram L-Gelucystines, 2500 ml deionized water in 5000 milliliters of reaction flasks, stir, feed chlorine then under 25 ℃, tail gas is with 5% NaOH aqueous solution absorption.When solution becomes gets transparent clarification, continued logical chlorine 30 minutes, continued stirring at room thereafter 3 hours.Reaction finishes, and reaction mixture is concentrated into 600 milliliters, in 0 ℃ of crystallization, and filtration, dry that L-cysteic acid 198 restrains (70.3%).
The L-cysteic acid is characterised in that:
CF: white crystal
Fusing point: 245-248 ℃
Specific rotation :+5.9 (c5.1, H
2O)
Infrared spectra: main key band is positioned at 3157,2585,1767,1616,1576,1505,1417,1364,1239,1132,1081,1062and1029cm
-1
Mass spectrum: (ESI (-)): 168 (M-H)
-
Proton nmr spectra (600MHz, D
2O, δ in ppm and TMS as internal standard): δ 4.36 (1H, dd, J=3.3,8.4Hz), 3.46 (1H, dd, J=3.3,15.1Hz), 3.34 (1H, dd, J=8.4,15.1Hz)
Embodiment 2:
In 2500 milliliters of reaction flasks, add 100 gram L-Gelucystines, 1500 milliliters of anhydrous methanols, stir, feed chlorine then, tail gas absorbs with 5% the NaOH aqueous solution, after L-Gelucystine solid all dissolves, continues to feed chlorine to reaction solution and all solidifies, filter and wash with ether, dry that L-cysteic acid methyl esters 142 restrains (93.1%).
L-cysteic acid methyl esters is characterised in that:
CF: white powder
Fusing point: 220-224 ℃
Specific rotation :+17.3 (c2.6, H
2O)
Infrared spectra: main key band is positioned at 3177,3023,2919,1748,1595,1496,1441,1424,1373,1334,1290,1272,1179,1139,1101and1032cm
-1
Mass spectrum: (ESI (+)): 184 (M+H)
+
(ESI(-))：182(M-H)
-
Proton nmr spectra (600MHz, D
2O, δ in ppm and TMS as internal standard): δ 4.58 (1H, dd, J=3.8,7.1Hz), 3.85 (3H, s), 3.55 (1H, dd, J=3.8,15.1Hz), 3.49 (1H, dd, J=7.1,15.1Hz)
Carbon-13 nmr spectra (600MHz, D
2O, δ in ppm and TMS as internal standard): δ 168.8,54.3, and 50.0,49.2
Embodiment 3:
In 2500 milliliters of reaction flasks, add 100 gram L-Gelucystines, 1500 milliliters of n-hexyl alcohols, stir, feed chlorine then, tail gas absorbs with 5% the NaOH aqueous solution, when the dissolving of L-Gelucystine solid, continue to feed chlorine to reaction soln and become thick solid again, filter, filtrate discards, filter residue with dissolve with methanol after a small amount of insolubles of elimination, concentrated filtrate, crystallization promptly get the just own ester of L-cysteic acid 169 grams (productive rate 80.2%).
The just own ester of L-cysteic acid is characterised in that:
CF: white crystal
Fusing point: 194-196 ℃
Specific rotation :-4.0 (c8.2, MeOH: H
2O=1: 5)
Infrared spectra: main key band is positioned at 3470,2595,2860,1745,1602,1535,1469,1421,1397,1376,1341,1222,1150,1090,1070and1039cm
-1
Mass spectrum: (ESI (+)): 254 (M+H)
+
(ESI(-))：252(M-H)
-
Proton nmr spectra (600MHz, D
2O, δ in ppm and TMS as internal standard): δ 4.48 (1H, dd, J=3.8,7.3Hz), 4.20 (2H, m), 3.48 (1H, dd, J=3.8,15.1Hz), 3.42 (1H, dd, J=7.3,15.1Hz), 1.62 (2H, m), 1.30 (2H, m), 0.79 (3H, t, J=7.1Hz)
Carbon-13 nmr spectra (600MHz, D
2O, δ in ppm and TMS as internal standard): δ 168.4,68.3, and 50.0,49.2,30.8,27.7,24.9,22.1,13.5
Embodiment 4:
Add 100 gram L-Gelucystines in 2500 milliliters reaction flask, 1500 milliliters of isopropylcarbinols stir, and feed chlorine then 1 hour, and tail gas absorbs with 5% the NaOH aqueous solution, stirs thereafter 2 hours; Feeding chlorine again 1 hour, is yellow thick solid at this moment, and stirring at room 3 hours gets Off-white solid.Cross filter solid, filter residue first alcohol and water (1: 1) recrystallization gets L-cysteic acid isobutyl ester 142 grams (75.8%).
L-cysteic acid isobutyl ester is characterised in that:
CF: white crystal
Fusing point: 268-270 ℃
Specific rotation :-7.9 (c5.0, MeOH: H
2O=1: 5)
Infrared spectra: main key band is positioned at 3468,3116,2958,1748,1582,1505,1471,1422,1402,1388,1373,1289and1074cm
-1
Mass spectrum: (ESI (+)): 226 (M+H)
+
(ESI(-))：224(M-H)
-
Proton nmr spectra (600MHz, D
2O, δ in ppm and TMS as internal standard): δ 4.51 (1H, dd, J=4.0,7.1Hz), 3.98 (2H, m), 3.48 (1H, dd, J=4.0,15.1Hz), 3.44 (1H, dd, J=7.1,15.1Hz), 1.92 (1H, m), 0.86 (6H, d, J=6.8Hz) carbon-13 nmr spectra (600MHz, D
2O, δ in ppm and TMS as internal standard): δ 168.4,73.9, and 50.0,49.2,27.2,18.3.
Claims (7)
1, a kind of method for preparing L-cysteic acid and ester thereof, it is characterized in that: with L-Gelucystine and a certain amount of water or corresponding alcohol mixing, feed chlorine and carry out oxidation between 0～100 ℃, the reaction back is if system L-cysteic acid then is concentrated into reaction solution certain volume recrystallization then; If system L-cysteic acid ester, then react the after-filtration solid and with solvent wash, be drying to obtain or again the recrystallization after drying make corresponding L-cysteic acid ester.
2, the method for preparing L-cysteic acid and ester thereof according to claim 1 is characterized in that: the general formula of its corresponding alcohol is:
ROH，R＝H?or
Wherein R1, R2, R3 are one or more in the substituting group substituting groups such as hydrogen, alkyl (straight chained alkyl, branched-chain alkyl, cycloalkyl), aryl.
3, the method for preparing L-cysteic acid and ester thereof according to claim 1 is characterized in that: the sign that reaction is carried out is the feeding with chlorine, and the L-Gelucystine dissolves gradually.
4, the method for preparing L-cysteic acid and ester thereof according to claim 1 is characterized in that: the reaction optimum temps is 20-30 ℃.
5, according to claim 1 or the 2 or 3 described methods that prepare L-cysteic acid and ester thereof, it is characterized in that: during system L-cysteic acid ester, reaction feeds chlorine L-Gelucystine and all dissolves the back and continue to feed chlorine until all separating out with solid form again in reaction solution, then filtration washing or recrystallization get final product L-cysteic acid ester.
6, the method for preparing L-cysteic acid and ester thereof according to claim 4 is characterized in that: the solvent that washing is adopted can be ether, ethyl acetate, ethanol or its miscellany; If recrystallization, the solvent that is adopted can be water, methyl alcohol, ethanol or its miscellany, and the best is a methyl alcohol.
7, the method for preparing L-cysteic acid and ester thereof according to claim 4, it is characterized in that: when the L-cysteic acid ester of four carbon of preparation and above alcohol thereof, need recrystallization, the temperature of recrystallization-20～40 ℃, the temperature of suitable recrystallization is 0～20 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100219509A CN1309707C (en) | 2004-03-02 | 2004-03-02 | Process for preparing L-cysteic acid and its ester |
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|---|---|---|---|
| CNB2004100219509A CN1309707C (en) | 2004-03-02 | 2004-03-02 | Process for preparing L-cysteic acid and its ester |
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| Publication Number | Publication Date |
|---|---|
| CN1663947A true CN1663947A (en) | 2005-09-07 |
| CN1309707C CN1309707C (en) | 2007-04-11 |
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| CNB2004100219509A Expired - Fee Related CN1309707C (en) | 2004-03-02 | 2004-03-02 | Process for preparing L-cysteic acid and its ester |
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