CN101972615A - Glycosyl-contained surface active agent as well as preparation method and measuring method thereof - Google Patents
Glycosyl-contained surface active agent as well as preparation method and measuring method thereof Download PDFInfo
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- CN101972615A CN101972615A CN2010105116769A CN201010511676A CN101972615A CN 101972615 A CN101972615 A CN 101972615A CN 2010105116769 A CN2010105116769 A CN 2010105116769A CN 201010511676 A CN201010511676 A CN 201010511676A CN 101972615 A CN101972615 A CN 101972615A
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- SPWBRFNVXCTZRA-BKKFENPESA-N CCCCCCCCCCCCCCCCCCNCCNC[C@@H]([C@H]([C@@H]([C@@H](CO)O)O)O)O Chemical compound CCCCCCCCCCCCCCCCCCNCCNC[C@@H]([C@H]([C@@H]([C@@H](CO)O)O)O)O SPWBRFNVXCTZRA-BKKFENPESA-N 0.000 description 1
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Abstract
The invention relates to a glycosyl-contained surface active agent as well as a preparation method and a measuring method thereof. The glycosyl-contained surface active agent has a structural formula shown in the specification and is characterized in poor water solubility and extremely good solubility in a dilute acetic acid solution. The invention mainly adopts the raw materials of long-chain fatty acid and glucose, which are favorable to the promotion of the application of natural products to the preparation of the surface active agent.
Description
Technical field
The present invention relates to natural products or natural products derivative is raw material, a kind of preparation and surface-active that contains the surfactant of glycosyl.
Background technology
As its name suggests, glycosyl surfactant active is meant a class surfactant that contains glycosyl in the molecular structure.Compare with pure ionic surface active agent, the existence of glycosyl makes the performance of surfactant gentle more, and this can be applied in and people's daily life and healthy cosmetics and food aspect in close relations it.Except more superior surface-active, also has the favorable biological degradability energy.Therefore in recent years, glycosyl surfactant active has obtained people's attention and has developed rapidly.
China has abundant oil tea resource, contains aliphatic acid such as oleic acid in the camellia seed meal after the oil expression, is the good raw material of preparation surfactant.Making full use of this resource and take synthetic surfactant, is the effective way that reduces environmental pollution.After oleic acid separated from camellia seed meal, through hydrogenation, processing such as reduction just can obtain to have more 18 alcohol of extensive use.Though short carbon chain alcohol is of many uses in the surfactant preparation, the less application of 18 alcohol.This is because its carbochain is long, and the hydration of common ion head base is not enough so that it dissolves in the water.
Summary of the invention
The present invention relates to contain in a kind of structure the preparation and the surface-active of the surfactant of glycosyl.As initiation material, the surfactant of acquisition has very high surface-active with the aliphatic acid of long-chain and glucose.
A kind of surfactant that contains glycosyl, structural formula is as follows:
A kind ofly prepare the described method that contains the surfactant of glycosyl, with 18 alcohol, ethylenediamine, glucose is raw material, four steps of reaction, reduction amination through pure bromination, bromoalkane and ethylenediamine prepare the described surfactant that contains glycosyl, and concrete reaction equation is as follows:
Described 18 alcohol are for commercially available or obtain with stearic acid reduction, described stearic acid be the fatty acid ester that from camellia seed meal, extracts through hydrogenation, separate and obtain.
In the bromination step of alcohol, be that the mol ratio of 18 alcohol, red phosphorus and bromine is 1: 0.05～0.1: 0.6～1 with 18 alcohol, red phosphorus and bromine reaction.
In the reaction of bromo-octadecane and ethylenediamine, the mol ratio of bromo-octadecane and ethylenediamine is 1: 2～10.
In the reduction amination, reaction condition is 45～80 ℃ to be descended 20～60 minutes.
In the reduction amination, used reducing agent is any one in sodium borohydride, potassium borohydride, the hydrogen.
Be mixed with acetum when measuring surface-active, be 1 according to the mol ratio of surfactant and acetic acid: n, wherein the ratio of n＞2 is soluble in water with them, is formulated as the acetum measurement according to a conventional method again of surfactant.
The present invention obtains following effect:
1. product stearic acid and the glucose of the present invention after with the oleic acid hydrogenation is raw material, through reduction, and bromination, aminolysis, reduction amination synthesizes a kind of long-chain surfactant that contains glycosyl.Explored the actual conditions of long-chain ammonium and glucose reduction amination, control rationally generates the reaction time and the reduction reaction conditions of imines, helps improving reaction yield, reduces the difficulty of final products purifying.
2. the surfactant of Huo Deing itself is water insoluble, but in the presence of with the acetate form, then has very high surface-active, and its critical micelle concentration is 2.34 * 10
-5Mol/L far below the critical micelle concentration value of conventional surfactants, has shown very strong ability of aggregation.
Be 37.7mN/m, pC20 is 5.17, and these data show that this surfactant has capillary ability of stronger reduction and efficient.
Description of drawings
Fig. 1 is target product 6-(2-(octadecylamine base) ethylamino-) hexane-1,2,3,4, the nuclear magnetic spectrogram of 5-amylalcohol.
Fig. 2 is the surface tension curve of surfactant in the time of 25 ℃.
The specific embodiment
A kind of surfactant that contains glycosyl, structural formula is as follows:
Contain two nitrogen-atoms in the molecule, increase when being beneficial to that it is water-soluble with the acetic acid salify.
Synthetic route is as follows:
With stearic acid, ethylenediamine, glucose is raw material, prepares the described surfactant that contains glycosyl through four steps of reaction, reduction amination of bromination, bromoalkane and the ethylenediamine of the reduction of percarboxylic acids, alcohol.
The reduction concrete grammar of carboxylic acid can reference literature (J.Org.Chem.1995,60, the 5314-5315) method in.Described stearic acid is that the fatty acid ester that extracts from camellia seed meal obtains through hydrogenation, separation.Perhaps directly react with 18 commercially available alcohol.
The bromination of alcohol is to react according to a conventional method with 18 alcohol, red phosphorus and bromine.The mol ratio of 18 alcohol, red phosphorus and bromine is 1: 0.05～0.1: 0.6～1.The eight alcohol fusings of rising temperature to ten behind the adding red phosphorus, slowly splash into bromine.Continue reaction two hours after dripping off again.Add benzinum, through the sodium sulfite solution washing, drying, decompression distillation gets bromo-octadecane.
The reaction of bromoalkane and ethylenediamine:
In the mol ratio of bromo-octadecane and ethylenediamine is 1: 2～10 ratio, and with bromo-octadecane, ethylenediamine and absolute ethyl alcohol stirred 48 hours at 50 ℃.System is cooled to 30 ℃, adds NaOH, continues to stir two hours again.Filter out salt and excessive sodium hydrate, ethanol is removed in decompression.Residue washes with water earlier, obtains product three times with ethanol and benzinum recrystallization again.In this reaction, if do not add NaOH, though can obtain product, productive rate is relatively low.
Reduction amination:
The N that the preceding step is obtained
1-octadecyl-1,2-ethylenediamine and DEXTROSE ANHYDROUS and 80ml ethanol are 60 ℃ of stirrings, and glucose dissolves in the system gradually.Continued stirring reaction again 30 minutes, reactant mixture is cooled off.Add benzinum, separate out a large amount of precipitations in the mixed liquor, filter and obtain little yellow solid.This solid is dropped in the 40ml methyl alcohol, with reducing agent or catalyst hydrogenation reduction.In the reduction amination, used reducing agent is any one in sodium borohydride, potassium borohydride, the hydrogen.For the catalyst hydrogenation reduction process, be that 0.5%～10% ratio feeds intake according to the mass ratio of the Pd/C catalyst of 5%wt and reactant.Reduzate treated with absolute ethyl alcohol be recrystallized target product.
When imines generated, the amine and the glucose that also have part were present in the system.Can cause in product containing a large amount of impurity if directly add the sodium borohydride reduction agent this moment, is difficult to purify.By obtaining the method that imines restores earlier, can effectively reduce the impurity in the finished product.
(18.9g, 0.5mol), (34g stirs in the oxolane after 0.25mol) adding 250ml dewaters and spends the night zinc chloride, obtains the sub-translucent solution of lightpink with sodium borohydride.
(71.3g 0.5mol) adds in the bottle, is warming up to the stearic acid fusing with stearic acid.The tetrahydrofuran solution of above-mentioned zinc borohydride is dropwise added slowly, have a large amount of hydrogen to produce.Make temperature remain on the oxolane reflux state, all add up to 130ml solution.Keep temperature to continue reaction 4 hours.System temperature is cooled to room temperature, adds the excessive zinc borohydride of a small amount of 1mol/L hydrochloric acid solution quencher.When no gas produces, add excessive Anhydrous potassium carbonate again.With the mixture standing over night, inclining organic layer, removes oxolane under the decompression and obtains 18 alcohol, is white solid.Productive rate: 86.3%
Embodiment 2
Add in the bottle through 18 alcohol (126g) and red phosphorus (4g) that reduction obtains above-mentioned, temperature is raised to 80 ℃ to 18 alcohol fusings.Stir down bromine (43.8g) is slowly splashed into.Continue reaction two hours after dripping off again.Reaction finishes the back and add the 50ml benzinum in system, filters out excessive red phosphorus.Filtrate with the washing of 50ml 3 sodium sulfite solutions, is used anhydrous magnesium sulfate drying earlier again.Benzinum is removed in decompression, and residue gets bromo-octadecane through decompression distillation, is light yellow transparency liquid, cooling back be waxy solid (186 ℃, 10mmHg).Productive rate: 78.5%
Comparing embodiment
Commercially available 18 alcohol (126g) and red phosphorus (3.8g) are added in the bottle.Temperature is raised to 80 ℃ to 18 alcohol fusings.Stir down bromine (44.5g) is slowly splashed into.Continue reaction two hours after dripping off again.Post-processing approach is with embodiment 2.186 ℃ of same collections, the 10mmHg cut.Productive rate: 82.6%
The present embodiment explanation, for the preparation of bromo-octadecane, 18 alcohol that the camellia seed meal extract makes have similar effect to the commercial reagent.
Embodiment 3
With bromo-octadecane (42.1g), ethylenediamine (36g) and 150ml absolute ethyl alcohol stirred 48 hours at 50 ℃.System is cooled to 30 ℃, adds NaOH (5g), continues to stir two hours again.Filter out salt and excessive sodium hydrate, ethanol is removed in decompression.Residue washes with water earlier, obtains product three times with ethanol and benzinum recrystallization again, is white solid.Productive rate: 42.7%
Mass spectrum ESI (M+1)
+: 313.3
Embodiment 4
With N
1-octadecyl-1, the 2-ethylenediamine (5g, 0.016mol), DEXTROSE ANHYDROUS (2.88g, 0.016mol) and 80ml ethanol 60 ℃ stir half an hour after, glucose dissolves in the system gradually.Continue again to stir 20 minutes, reactant mixture is cooled off.Most of ethanol is removed in decompression, adds benzinum, separates out a large amount of precipitations in the mixed liquor, filters and obtains little yellow solid.This solid is dropped in the 40ml methyl alcohol, and add sodium borohydride under condition of ice bath (1g 0.026mol), stirred 8 hours in batches.After reaction finished, regulating mixture pH value with dilute hydrochloric acid solution was that 9-10. removes must white solid after desolvating.Wash this solid 4-6 time with distilled water, dry back with absolute ethyl alcohol be recrystallized target product.Productive rate: 17.2%
Embodiment 5
With N
1-octadecyl-1, the 2-ethylenediamine (2.5g, 0.008mol), DEXTROSE ANHYDROUS (1.44g, 0.008mol) and 40ml methyl alcohol 60 ℃ stir half an hour after, glucose dissolves in the system gradually.Continue again to stir 10 minutes.Reactant is added in the 100ml hydrogenation still while hot, add the Pd/C catalyst of 0.25g 5% simultaneously.At 50 ℃, the 8atm Hydrogen Vapor Pressure reacted 24 hours down.With the reactant cooling, add an amount of diatomite, filter out solid.Filtrate is removed methyl alcohol, and residue gets target product with ethyl alcohol recrystallization.Productive rate: 26.5%
Embodiment 6
As Fig. 1 target product 6-(2-(octadecylamine base) ethylamino-) hexane-1,2,3,4, shown in the nuclear magnetic spectrogram of 5-amylalcohol:
1H NMR (400MHz, MeOD, Me
4Si)
3.95～3.60 (m, 5H, NCH
2(CHOH)
5), 2.82～2.64 (m, 8H, CH
3(CH
2)
16CH
2NCH
2CH
2NCH
2), 1.56～1.30 (m, 32H, CH
3(CH
2)
16), 0.92 (t, 3H, CH
3).
Unnecessary 1 signal that hydrogen is residual ethanol between the triplet at 1.19 places and 3.95～3.60 wherein.
Mass spectrum ESI (M+1)
+: 477.3
Embodiment 7
Be mixed with acetum when measuring surface-active, be 1 according to the mol ratio of surfactant and acetic acid: n, wherein the ratio of n＞2 is soluble in water with them, is formulated as the acetum measurement according to a conventional method again of surfactant.
6-(2-(octadecylamine base) ethylamino-) hexane-1,2,3,4, the mol ratio of 5-amylalcohol and acetic acid is 1: 3, adds an amount of redistilled water, at room temperature stirs to get settled solution after 6 hours, carries out capillary measurement then under 25 ℃, as shown in Figure 2.
The surface-active parameter of table 1 surfactant
Claims (8)
1. surfactant that contains glycosyl is characterized in that structural formula is as follows:
2. one kind prepares the described method that contains the surfactant of glycosyl of claim 1, it is characterized in that, with 18 alcohol, ethylenediamine, glucose is raw material, main four steps of reaction, reduction amination through pure bromination, bromoalkane and ethylenediamine prepare the described surfactant that contains glycosyl, and concrete reaction equation is as follows:
3. preparation according to claim 2 contains the method for the surfactant of glycosyl, it is characterized in that, described 18 alcohol are for commercially available or obtain with stearic acid reduction, described stearic acid be the fatty acid ester that from camellia seed meal, extracts through hydrogenation, separate and obtain.
4. preparation according to claim 2 contains the method for the surfactant of glycosyl, it is characterized in that, and in the bromination step of alcohol, be that the mol ratio of 18 alcohol, red phosphorus and bromine is 1: 0.05～0.1: 0.6～1 with 18 alcohol, red phosphorus and bromine reaction.
5. preparation according to claim 2 contains the method for the surfactant of glycosyl, it is characterized in that, in the reaction of bromo-octadecane and ethylenediamine, the mol ratio of bromo-octadecane and ethylenediamine is 1: 2～10.
6. preparation according to claim 2 contains the method for the surfactant of glycosyl, it is characterized in that, in the reduction amination, reaction condition is 45～80 ℃ to be descended 20～60 minutes.
7. preparation according to claim 2 contains the method for the surfactant of glycosyl, it is characterized in that, in the reduction amination, used reducing agent is any one in sodium borohydride, potassium borohydride, the hydrogen.
8. the described measuring method that contains the surfactant of glycosyl of claim 1, it is characterized in that, be mixed with acetum when measuring surface-active, mol ratio according to surfactant and acetic acid is 1: n, wherein the ratio of n＞2 is soluble in water with them, and the acetum that is formulated as surfactant is measured according to a conventional method again.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111620916A (en) * | 2020-06-29 | 2020-09-04 | 天津科技大学 | Synthesis method of alkyl amino glucoside |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH101423A (en) * | 1996-06-14 | 1998-01-06 | Kanebo Ltd | Hair-treatment agent |
| CN1775792A (en) * | 2005-12-13 | 2006-05-24 | 北京服装学院 | Gemini boric acid ester glucose acylamine compound, and its preparing method and use |
| CN101254436A (en) * | 2007-12-05 | 2008-09-03 | 天津理工大学 | Octadecanamide surfactant and synthetic method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH101423A (en) * | 1996-06-14 | 1998-01-06 | Kanebo Ltd | Hair-treatment agent |
| CN1775792A (en) * | 2005-12-13 | 2006-05-24 | 北京服装学院 | Gemini boric acid ester glucose acylamine compound, and its preparing method and use |
| CN101254436A (en) * | 2007-12-05 | 2008-09-03 | 天津理工大学 | Octadecanamide surfactant and synthetic method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111620916A (en) * | 2020-06-29 | 2020-09-04 | 天津科技大学 | Synthesis method of alkyl amino glucoside |
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