CN109794203A - Double glucose glutamate surfactants and its synthetic method - Google Patents
Double glucose glutamate surfactants and its synthetic method Download PDFInfo
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- CN109794203A CN109794203A CN201811633136.0A CN201811633136A CN109794203A CN 109794203 A CN109794203 A CN 109794203A CN 201811633136 A CN201811633136 A CN 201811633136A CN 109794203 A CN109794203 A CN 109794203A
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Abstract
A kind of double glucose glutamate surfactants and its synthetic method, by the way that Pidolidone and chain alkyl acyl chloride reaction are obtained N- long alkanoyl glutamic acid, and then with obtained after four acetyl glucosamine condensation reactions.The surfactant that the present invention is prepared combines the mild non-stimulated of glycosyl surfactant active, because of the advantages that its resource is renewable, environmentally protective, easily biological-degradable, it can be widely applied to food, daily-use chemical industry, weaving, medicine and other fields, it has broad application prospects, and the synthesis is fairly simple, and equipment requirement is low to have industrial production prospect.
Description
Technical field
The present invention relates to a kind of technology of chemical field, specifically a kind of double glucose glutamate surfactants
And its synthetic method.
Background technique
Glycosyl surfactant active be with renewable natural resources sugared (monosaccharide, disaccharides, polysaccharide) or its derivative polyalcohol (such as
Sorbierite) terminal polar group as surfactant, it is most representative one kind in natural surfactant, has excellent
Biological degradability, nontoxicity, to human body and environment higher-security.Currently, can satisfy glycosyl surfactant active low price, height
The sugarcane in glucose, sugarcane and beet that the terminal polar group raw material that quality and availability require mainly has Starch Hydrolysis to obtain
Sorbierite obtained by sugar, glucose hydrogenation etc..
Summary of the invention
The present invention for example, by using the hydroxyl of the protection glucose such as benzyl, finally needs to use in view of the shortcomings of the prior art
Removing is carried out to hydrogen and Pd-C and by-product is unfavorable to environment, and this condition all proposes the equipment of factory and safety in production
Higher requirement, then I proposes that a kind of double glucose glutamate surfactants and its synthetic method, feature are to use
Acetyl group protects the acetyl group of glucose hydroxyl and removing No. 1 position of glucose with mild condition selectivity, finally with honest and clean
The raw material that valence is easy to get removes all acetyl group, whole process requirement not harsh to mechanical equipment, and all intermediates can be with
It is purified by recrystallization, has industrial production prospect, the surfactant being prepared combines glycosyl surface-active
Agent it is mild non-stimulated, because of the advantages that its resource is renewable, environmentally protective, easily biological-degradable, can be widely applied to food, daily
Chemical industry, weaving, medicine and other fields, have broad application prospects, and the synthesis is fairly simple, and equipment requirement is low to have industry
Change prospect of production.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of double glucose glutamate surfactants, specially (N- lauroyl glutamate)-Portugal
Grape sugar ester, structure are as follows:
Wherein: group R is C9H19、C11H23、C13H27Or C15H31。
The present invention relates to the synthetic method of above-mentioned double glucose glutamate surfactants, by by Pidolidone and length
Alkyl group acyl chloride reaction obtains N- long alkanoyl glutamic acid, so with obtained after four acetyl glucosamine condensation reactions.
The N- long alkanoyl glutamic acid, by the way that chain alkyl acyl is added dropwise under alkaline environment to Pidolidone solution
Chlorine reacts to obtain.
The N- long alkanoyl glutamic acid, especially by passing through inorganic alkali solution after mixing Pidolidone with solvent
PH is adjusted up to 9~12, it is 9~12 that chain alkyl acyl chlorides, which is slowly added dropwise, and keeps pH of mixed, in room temperature condition after being added dropwise
Lower the reaction was continued 1~8h.
Preferably, make pH up to 1~2 and after being acidified 1h after which the mixed solution of concentrated hydrochloric acid and water is added after completion of the reaction, filter,
Filter cake is washed to neutrality, then three times with petroleum ether with a large amount of deionized waters.Petroleum ether recrystallizes to obtain white solid N- long-chain
Alkanoyl glutamic acid.
The reaction equation of the N- long alkanoyl glutamic acid is as follows:
Wherein: R C9H19、C11H23、C13H27Or C15H31。
Solute is NaOH, KOH, K in the inorganic alkali solution2CO3One of or combinations thereof, solvent be water, acetone,
One of acetonitrile, THF, DMF, DMAC or combinations thereof, concentration are mass percent 10%~30%.
Four acetyl glucosamines, ZnO, ZnCl to be added in five acetyl glucose solution2、Zn(OAc)2、Zn(OTf)2
One of or combinations thereof heating reaction after obtain.
Mixed solvent is added especially by by five acetyl glucose in four acetyl glucosamines, then be added ZnO,
ZnCl2、Zn(OAc)2、Zn(OTf)2One of or combinations thereof, 4~10h is reacted in 40~80 DEG C of heating.
The reaction equation of four acetyl glucosamines is as follows:
Wherein: R C9H19、C11H23、C13H27Or C15H31。
The mixed solvent are as follows: CH3OH and THF, volume ratio are 1:1~1:6.
The metal reagent is ZnO, ZnCl2、Zn(OAc)2、Zn(OTf)2One of or combinations thereof.
The condensation reaction, by by four acetyl glucosamines and N- long alkanoyl glutamic acid, with DCC, HBTU,
One of TBTU, HOBt, EDCHCl, EDCl or combinations thereof react to obtain as condensing agent.
The condensation reaction, especially by will in N- long alkanoyl glutamic acid, DMAP and condensing agent mix after be added
Four acetyl glucosamine of compound being added after dichloromethane solution stirring, 10-50 DEG C of 24~48h of reaction；Condensation product is added
Into three neck round bottom flask, solvent is added, the lye that 1mol/L is added after 35 DEG C of heat preservation 5min mixes dissolution, and 0 DEG C of heat preservation washes out
A large amount of crystal, are obtained by filtration crude product, and ethyl alcohol recrystallization obtains (N- lauroyl glutamate)-glucose ester.
After the condensation reaction is preferably washed three times with 10% sodium bicarbonate solution after the completion of reaction, evaporated under reduced pressure has
Solvent obtains crude product, and ethyl alcohol recrystallization obtains white solid.
The reaction equation of the condensation reaction is as follows:
Wherein: R C9H19、C11H23、C13H27Or C15H31。
The condensing agent is one of DCC, HBTU, TBTU, HOBt, EDCHCl, EDCl or combinations thereof.
The solvent be one of methanol, ethyl alcohol, isopropanol, n-butanol, DMF, DMAC, tetrahydrofuran, water or its
Combination.
The lye be one of sodium hydroxide solution, potassium hydroxide solution, sodium methoxide solution, methanol potassium solution or
A combination thereof.
Technical effect
The present invention for example, by using the hydroxyl of the protection glucose such as benzyl, finally needs to use in view of the shortcomings of the prior art
Removing is carried out to hydrogen and Pd-C and by-product is unfavorable to environment, and this condition all proposes the equipment of factory and safety in production
Higher requirement, then I proposes that a kind of double glucose glutamate surfactants and its synthetic method, feature are to use
Acetyl group protects the acetyl group of glucose hydroxyl and removing No. 1 position of glucose with mild condition selectivity, finally with honest and clean
The raw material that valence is easy to get removes all acetyl group, whole process requirement not harsh to mechanical equipment, and all intermediates can be with
It is purified by recrystallization, has industrial production prospect, double glucose glutamate series of tables that the present invention is prepared
Face activating agent HLB value is 8-14 or so；Possess low order of magnitude cmc value, shows excellent surface-active；With the liter of temperature
Height, cmc value increase, Ycmc and be worth reduction；With the increase of fatty acyl group chain length, with amino acid series sugar ester cmc value and
Ycmc value reduces；PC20Value increases with the growth of carbochain, illustrates have the sugar ester of longer hydrophobic chain reducing given surface
Required concentration is less when force value, has excellent some surface active property, and have certain pharmacological, because its resource can be again
The advantages that raw, environmentally protective, easily biological-degradable, can be widely applied to food, daily-use chemical industry, weaving, medicine and other fields, and should
Synthesize fairly simple, equipment requirement is low to have industrial production prospect
Detailed description of the invention
Fig. 1 is surface tension schematic diagram of (N- the lauroyl glutamate)-glucose ester under various concentration.
Specific embodiment
Embodiment 1
The present embodiment is related to a kind of double glucose glutamate surfactants, and structural formula is as follows:
Double glucose glutamate process for synthesizing surfactant the following steps are included:
The synthesis of step 1) N- lauroyl glutamate, synthetic route are as follows:
14.7g Pidolidone is added in three neck round bottom flask, 150mL water is added and stirs to dissolve, wherein dropwise
The aqueous solution of the sodium hydroxide of 35g 30% is added to pH value of solution up to 9~10 or so.5~15℃Under the conditions of, it is slowly added dropwise
20.7g lauroyl chloride, while 30% sodium hydrate aqueous solution is added dropwise, keeping pH of mixed is 9~10.After being added dropwise,
The reaction was continued under room temperature 3h.After completion of the reaction, concentrated hydrochloric acid and the mixed solution of water, which is added, makes pH up to 1~2 or so.It is acidified 1h
Afterwards, it filters, washs filter cake to neutrality, then three times with petroleum ether with a large amount of deionized waters.Petroleum ether recrystallizes white solid
Body N- lauroyl glutamate.
1HNMR(500MHz,DMSO)δ/ppm,12.42(s,2H,2×COOH),8.04-8.02(m,1H,NH),4.20-4.16
(m,1H,CH),2.27-2.24(m,2H,CH2),2.11-2.07(m,2H,CH2),1.97-1.92(m,1H,CH),1.77-1.73
(m,1H,CH),1.48-1.46(m,2H,CH2),1.27-1.23(m,16H,8×CH2), 0.85 (d, 3H, J=7.0Hz, CH3)；
The synthesis of four acetyl glucosamine of step 2), synthetic route are as follows:
39g five acetyl glucose is added in three neck round bottom flask, 320mL mixed solvent, volume ratio CH is added3OH/
Then each 2g ZnO/ZnCl of metal reagent is added in THF=1:42, 70℃Heating reaction, reaction time 5h locate after reaction
Reason, evaporated under reduced pressure organic solvent, washing, 5%NaHCO3 washing obtain crude product with ethyl alcohol recrystallization and obtain four acetyl of white solid
Base Portugal glucose compound 5.
1HNMR(500MHz,CDCl3), δ 5.54 (t, J=9.9Hz, 1H), 5.46 (d, J=2.8Hz, 1H), 5.09 (t, J
=9.4Hz, 1H), 4.8-4.9 (m, 1H), 4.22-4.29 (m, 2H), 4.10-4.16 (m, 1H), 2.10 (s, 3H), 2.08 (s,
3H),2.04(s,3H),2.02(s,3H)；
Four acetyl glucosamine of step 3) and the condensation of N- long alkanoyl glutamic acid, synthetic route are as follows:
32.9g N- lauroyl glutamate is added in three neck round bottom flask, 30g DMAP and 60g condensing agent HBTU
It is added in flask, 250mL dichloromethane solution is added, stir 30min, four acetyl grape of 34.8g compound 1- hydroxyl is added
Sugar, 30℃30h is reacted, TLC tracking stops reaction, standing is cooled to room temperature, with 10% sodium bicarbonate solution after fully reacting
After washing three times, evaporated under reduced pressure organic solvent obtains crude product, and ethyl alcohol recrystallization obtains white solid (N- lauroyl glutamate)-
Acetyl group-glucose ester
1HNMR(500MHz,DMSO)δ/ppm
8.16-8.14(m,1H,NH),5.36-5.34(m,1H,H-1’,H-1”),5.13-5.06(m,2H,C6’-OH,
C6”-OH),5.04-4.98(m,2H,4’-OH,4”-OH),4.99-4.93(m,2H,3’-OH,3”-OH),4.91-4.87(m,
2H, 2 '-OH, 2 "-OH), and 4.54 (dd, 1H, J=12.5,6.0Hz, CH), 4.27-4.24 (m, 2H, H-2 ', H-2 "), 3.64-
3.58(m,2H,H-6’a,H-6”a),3.58-3.53(m,2H,H-5’,H-5”),3.49-3.44(m,2H,H-6’b,H-6”b),
3.29-3.13(m,2H,H-3’,H-3”),3.07-2.99(m,2H,H-4’,H-4”),2.53-2.32(m,1H,CH2),2.21-
2.19(m,1H,CH2),2.10(s,6H),2.08(s,6H),2.04(s,6H),2.02(s,6H),1.98-1.94(m,1H,
CH2),1.81-1.79(m,2H,CH2),1.60-1.58(m,1H,CH2),1.27-1.23(m,16H,8xCH2),0.88-0.85
(m,3H,CH3)；
The synthesis of the double glucose glutamate surfactants of step 4), synthetic route are as follows:
50g condensation product is added in three neck round bottom flask, addition 400mL methanol, 35℃It is added after heat preservation 5min
The sodium methoxide of 100mL1mol/L, which mixes, dissolves stirring 1h, and 0℃Heat preservation, is precipitated a large amount of crystal, crude product, ethyl alcohol recrystallization is obtained by filtration
Obtain white solid (N- lauroyl glutamate)-glucose ester.
1HNMR(500MHz,DMSO)δ/ppm
8.16-8.14(m,1H,NH),5.36-5.34(m,1H,H-1’,H-1”),5.13-5.06(m,2H,C6’-OH,
C6”-OH),5.04-4.98(m,2H,4’-OH,4”-OH),4.99-4.93(m,2H,3’-OH,3”-OH),4.91-4.87(m,
2H, 2 '-OH, 2 "-OH), and 4.54 (dd, 1H, J=12.5,6.0Hz, CH), 4.27-4.24 (m, 2H, H-2 ', H-2 "), 3.64-
3.58(m,2H,H-6’a,H-6”a),3.58-3.53(m,2H,H-5’,H-5”),3.49-3.44(m,2H,H-6’b,H-6”b),
3.29-3.13(m,2H,H-3’,H-3”),3.07-2.99(m,2H,H-4’,H-4”),2.53-2.32(m,1H,CH2),2.21-
2.19(m,1H,CH2),1.98-1.94(m,1H,CH2),1.81-1.79(m,2H,CH2),1.60-1.58(m,1H,C H2),
1.27-1.23(m,16H,8xCH2),0.88-0.85(m,3H,CH3)。
It is computed and measures (N- lauroyl glutamate)-glucose ester HLB value 15.20, and with fatty acyl group chain length
Increase, the sugar ester HLB value of homologous series reduces, can be as O/W type emulsifier, solubilizer, detergent.(N- at different temperatures
Lauroyl glutamate)-glucose ester surface-active parameter is as follows:
Above-mentioned specific implementation can by those skilled in the art under the premise of without departing substantially from the principle of the invention and objective with difference
Mode carry out local directed complete set to it, protection scope of the present invention is subject to claims and not by above-mentioned specific implementation institute
Limit, each implementation within its scope is by the constraint of the present invention.
Claims (10)
1. a kind of double glucose glutamate surfactants, which is characterized in that be specially (N- lauroyl glutamate)-grape
Sugar ester, structure are as follows:
Wherein: group R is C9H19、C11H23、C13H27Or C15H31。
2. a kind of method for preparing described in claim 1 double glucose glutamate surfactants, which is characterized in that pass through by
Pidolidone and chain alkyl acyl chloride reaction obtain N- long alkanoyl glutamic acid, so with after four acetyl glucosamine condensation reactions
It obtains, reaction equation includes:
Wherein: R C9H19、C11H23、C13H27Or C15H31。
3. according to the method described in claim 2, it is characterized in that, the N- long alkanoyl glutamic acid, by L- paddy ammonia
Chain alkyl acyl chloride reaction is added dropwise under alkaline environment and obtains for acid solution.
4. according to the method in claim 2 or 3, characterized in that the N- long alkanoyl glutamic acid, especially by general
Pidolidone by inorganic alkali solution adjusts pH up to 9~12 after mixing with solvent, and chain alkyl acyl chlorides is slowly added dropwise and keeps mixed
Closing liquid pH is 9~12, the reaction was continued at room temperature after being added dropwise 1~8h.
5. according to the method described in claim 4, it is characterized in that, the mixed solution to which concentrated hydrochloric acid and water are added after completion of the reaction makes
PH is filtered up to 1~2 and after being acidified 1h, washs filter cake to neutrality, then three times with petroleum ether with a large amount of deionized waters.Petroleum
Ether recrystallizes to obtain white solid N- long alkanoyl glutamic acid.
6. according to the method described in claim 4, it is characterized in that, in the inorganic alkali solution solute be NaOH, KOH, K2CO3
One of or combinations thereof, solvent is one of water, acetone, acetonitrile, THF, DMF, DMAC or combinations thereof, and concentration is quality hundred
Divide ratio 10%~30%.
7. according to the method described in claim 2, it is characterized in that, the condensation reaction, by by four acetyl glucosamines and N-
Long alkanoyl glutamic acid, using one of DCC, HBTU, TBTU, HOBt, EDCHCl, EDCl or combinations thereof as condensing agent
Reaction obtains.
8. the method according to claim 2 or 7, characterized in that the condensation reaction, especially by by N- long alkane acyl
In base glutamic acid, four acetyl glucosamine of compound being added after dichloromethane solution stirring is added after the mixing of DMAP and condensing agent,
10-50 DEG C of 24~48h of reaction；Condensation product is added in three neck round bottom flask, solvent is added, is added after 35 DEG C of heat preservation 5min
The lye of 1mol/L mixes dissolution, and 0 DEG C of heat preservation washes out a large amount of crystal, crude product is obtained by filtration, ethyl alcohol recrystallization obtains (N- laurel
Acyl glutamic acid)-glucose ester.
9. according to the method described in claim 2, it is characterized in that, the mixed solvent are as follows: CH3OH and THF, volume ratio are
1:1~1:6；The metal reagent is ZnO, ZnCl2、Zn(OAc)2、Zn(OTf)2One of or combinations thereof.
10. according to the method described in claim 2, it is characterized in that, the condensing agent be DCC, HBTU, TBTU, HOBt,
One of EDCHCl, EDCl or combinations thereof.
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|---|---|---|---|---|
| US5767255A (en) * | 1995-05-29 | 1998-06-16 | Hoechst Aktiengesellschaft | Glucose- and sophorose-lipids, a process for their preparation and their use |
| CN104592321A (en) * | 2015-01-09 | 2015-05-06 | 武汉信嘉和诚药物化学有限公司 | Method for catalytic synthesis of salidroside |
| CN106831900A (en) * | 2017-02-24 | 2017-06-13 | 湘潭大学 | A kind of glucoside compound |
| CN108055846A (en) * | 2015-09-28 | 2018-05-18 | 陶氏环球技术有限责任公司 | Branched alcohol-based sugar surfactant |
-
2018
- 2018-12-29 CN CN201811633136.0A patent/CN109794203A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5767255A (en) * | 1995-05-29 | 1998-06-16 | Hoechst Aktiengesellschaft | Glucose- and sophorose-lipids, a process for their preparation and their use |
| CN104592321A (en) * | 2015-01-09 | 2015-05-06 | 武汉信嘉和诚药物化学有限公司 | Method for catalytic synthesis of salidroside |
| CN108055846A (en) * | 2015-09-28 | 2018-05-18 | 陶氏环球技术有限责任公司 | Branched alcohol-based sugar surfactant |
| CN106831900A (en) * | 2017-02-24 | 2017-06-13 | 湘潭大学 | A kind of glucoside compound |
Non-Patent Citations (3)
| Title |
|---|
| 应礼彪 等: "2,3,4,6-四-O-乙酰基-D-吡喃葡萄糖研究概述", 《浙江化工》 * |
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| 李鹏飞 等: "糖合成中羟基的保护和去护方法", 《化学研究》 * |
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Application publication date: 20190524 |