CN102030803A - Theasaponin derivative as well as preparation method and application thereof - Google Patents
Theasaponin derivative as well as preparation method and application thereof Download PDFInfo
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- CN102030803A CN102030803A CN 201010515876 CN201010515876A CN102030803A CN 102030803 A CN102030803 A CN 102030803A CN 201010515876 CN201010515876 CN 201010515876 CN 201010515876 A CN201010515876 A CN 201010515876A CN 102030803 A CN102030803 A CN 102030803A
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Abstract
The invention relates to a theasaponin derivative as well as a preparation method and application thereof. The theasaponin derivative has a structure shown in the formula I and is prepared by the following steps of: (1) reacting triphenylchloromethane with theasaponin, and then adding bromobenzyl to react with the theasaponin; (2) reacting phosphorus tribromide with sugar, and then reacting with the bromobenzyl; (3) mixing the theasaponin obtained in the step (1) with the sugar obtained in the step (2), and then adding tritylation deprotective agents to react; and then adding phenmethyl deprotective agents in the presence of catalysts to obtain the theasaponin derivative shown in the formula I after the reaction. The preparation method has the advantages that the process is simple, the reaction conditions are easy to control, and the preparation method can be used for the commercial production. The prepared theasaponin derivative can be used as a surface active agent, the foaming power and the foam stabilization are stronger in high-salt and high-temperature environments, and the problem of poor foam stabilization in the high-salt and high-temperature environments of the traditional theasaponin is solved.
Description
Technical field
The present invention relates to the tensio-active agent field, be specifically related to a kind of theasaponin derivative and preparation method thereof, with and as the application of hydrophilic nonionic bio-surfactant in agricultural chemicals, material of construction, daily use chemicals articles for washing.
Background technology
Tensio-active agent have dispersion, infiltration, solubilising, emulsification, wetting, bubble, performance such as lubricated, sterilization, be widely used in fields such as food, medicine, agricultural chemicals, weaving, chemical industry, tamanori, ore dressing, oil field chemical, papermaking, leather, sensitive materials, articles for washing, makeup, its kind and consumption increase day by day.But for a long time, people use artificial synthetic tensio-active agent always.A large amount of uses of synthetic surfactant can cause environmental pollution and safety issue.Bio-surfactant nontoxic, easy degraded more and more is subject to people's attention.Many natural compoundss have surfactivity, and as saponins compound, but than synthetic surfactant, its surfactivity is still on the low side.
Modern study shows that double type (Gemini) tensio-active agent has more superior surfactivity, and micelle-forming concentration is low, foaming power is strong, foam stability is good.This surfactant structure has the feature of double end and two tails as dimeric polymer.
Theasaponin is to be present in a kind of main pentacyclic triterpene compound in tea seed or the tea seed, is made up of sapogenin, sugared body and organic acid three parts.Be that a class has surface-active compound, it has the advantages that foaming power is strong, foam is little, dispersion force is strong.Yet find in the practical application that foam stability can be still relatively poor in high salt hot environment for theasaponin.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of surface-active theasaponin derivative of superior salt tolerant heatproof that has with not enough.
Another object of the present invention is to provide the preparation method of above-mentioned theasaponin derivative.
A further object of the present invention is to provide above-mentioned theasaponin derivative as hydrophilic nonionic Application of biosurfactant.
Purpose of the present invention is achieved through the following technical solutions:
A kind of theasaponin derivative, its structure is suc as formula shown in the I:
(formula I)
Wherein, R is the sugar of tool hemiacetal hydroxyl, preferred glucose, fructose, pectinose, maltose.
The preparation method of above-mentioned theasaponin derivative may further comprise the steps:
(1) get the reaction of triphenylmethyl chloride and theasaponin, purpose is that the primary hydroxyl on the theasaponin C28 is protected; Then, add the reaction of bromobenzyl and theasaponin, benzyl is connected on the secondary hydroxyl of theasaponin;
(2) get phosphorus tribromide and sugar reaction, the sugar replaced hemiacetal hydroxyl of bromine atoms; With the bromobenzyl reaction, benzyl is connected on the hydroxyl of sugar again;
(3) get the sugar that theasaponin that step (1) prepares and step (2) prepare and mix, add the trityl deprotection agent again, reaction; Reaction result is that the primary hydroxyl on the theasaponin C28 is gone protection, and the primary hydroxyl on the theasaponin C28 is connected with the bromination carbon atom of sugar then; Then, under the situation that catalyzer exists, add the benzyl deprotection agent, reaction; Reaction result is the benzyl of having sloughed on theasaponin and the sugar, obtains suc as formula the theasaponin derivative shown in the I.
The consumption of described triphenylmethyl chloride is 1~1.5 times of molar mass of theasaponin, and temperature of reaction is 25~50 ℃, reaction times 8~16h; Preferred 11~13h of reaction times.
In the step (1), the consumption of described bromobenzyl is 12~14 times of molar masss of theasaponin, 120~140 ℃ of temperature of reaction, reaction times 6~8h.
Described sugar is any in glucose, fructose, pectinose, the maltose, sugared consumption be theasaponin etc. molar mass.
In the step (2), described phosphorus tribromide consumption is 1/3 molar mass of sugar, 20~30 ℃ of reaction 3~5h; The consumption of bromobenzyl is 4~7 times of molar masss of sugar, 120~140 ℃ of temperature of reaction, reaction times 6~8h.
Described trityl deprotection agent is the tosic acid pyridinium salt, its consumption be triphenylmethyl chloride etc. molar mass; Molar masss such as described sugar and theasaponin are are participated in reaction, and reaction time of esterification is 3~5h.
Described benzyl deprotection agent is a hydrogen, and catalyst system therefor is 10% palladium carbon, 20~30 ℃ of temperature of reaction, reaction times 3~6h.
The application of above-mentioned theasaponin derivative is characterized in that: described sugared theasaponin is directly used in oil-water emulsifiers, gas concrete air entrapment agent, suds-stabilizing agent, biological pesticide, biological pesticide auxiliary agent, cleaning product as hydrophilic nonionic bio-surfactant.
The present invention has following advantage and effect with respect to prior art:
(1) the present invention be raw material with the theasaponin through with sugared grafting after the tensio-active agent that obtains, foaming power and foam stability can be stronger in high salt and hot environment.
(2) theasaponin derivative tensio-active agent of the present invention is nontoxic all from natural matter, easily degraded.
(3) preparation method's technology of theasaponin derivative of the present invention is simple; Adopt full hydroxyl protection, intermediate need not to make with extra care, and reaction conditions is easy to control, can be used for suitability for industrialized production.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) with theasaponin 100g, join in the pyridine of 300mL, be heated to 50 ℃ and make it dissolving.The triphenylmethyl chloride (23g) of adding and theasaponin equimolar amount keeps 50 ℃ of stirring reaction 8h; Add the potassium hydroxide (4.6g) of triphenylmethyl chloride 1/5 quality, be warming up to 80 ℃, stir 1h, pressure reducing and steaming moisture and pyridine.Add the dissolving of 500mL toluene again, be warming up to 120 ℃, slowly dripping is the bromobenzyl (170g) of 12 times of molar weights of theasaponin, and stirring reaction 8h, reaction solution are called A liquid;
(2) get glucose (14.8g) with tea soap unit equimolar amount in addition, add 100mL toluene, 30 ℃ drip phosphorus tribromides (7.4g) down, reaction 3h is warming up to 120 ℃, and slowly dripping is the bromobenzyl (56g) of 4 times of molar weights of glucose, stirring reaction 8h, reaction solution are called B liquid;
(3) A liquid is mixed with B liquid, add p-methyl benzenesulfonic acid pyridinium salt 21g, reflux water-dividing 5h places pressure reaction still, is catalyzer with 10% palladium/carbon, 30 ℃, feeds hydrogen 3h.Use the 600mL alcohol extraction, get product 72g behind the recovery ethanol.
Structural analysis to product shows that MS:m/z 1378; Elementary compositionly be: C56.59%, H7.45%, O35.95%, its molecular formula is C
65H
102O
31,
1H-NMR with
13The hydrogen of C-NMR is identical with theasaponin and glucose with the carbon signal displacement.Its structure is as follows:
Embodiment 2
(1) with theasaponin 100g, join in the pyridine of 300mL, (25 ℃) make it dissolving under the room temperature.Press 1.5 times of molar weights of theasaponin and add triphenylmethyl chloride (34.5g), stirring reaction 16h; Add the potassium hydroxide (6.9g) of triphenylmethyl chloride 1/5 quality again, be warming up to 80 ℃, stir 1h, pressure reducing and steaming moisture and pyridine; Add the dissolving of 500mL toluene, be warming up to 140 ℃, slowly drip the bromobenzyl (200g) of 14 times of molar weights of theasaponin, stirring reaction 6h, reaction solution are called A liquid;
(2) get fructose (14.8g) with the theasaponin equimolar amount in addition, add 100mL toluene, 20 ℃ drip phosphorus tribromides (7.4g) down, and reaction 5h is warming up to 140 ℃, slowly drips the bromobenzyl (70g) of 5 times of molar weights of fructose, and stirring reaction 6h, reaction solution are called B liquid;
(3) A liquid is mixed with B liquid, add p-methyl benzenesulfonic acid pyridinium salt 31g, reflux water-dividing 3h places pressure reaction still, is catalyzer with 10% palladium/carbon, 20 ℃, feeds hydrogen 5h.Use the 600mL alcohol extraction, get product 86g behind the recovery ethanol.
Structural analysis to product shows that MS:m/z 1378; Elementary compositionly be: C56.59%, H7.45%, O35.95%, its molecular formula is C
65H
102O
31,
1H-NMR with
13The hydrogen of C-NMR is identical with theasaponin and fructose with the carbon signal displacement.Its structure is as follows:
(formula III)
Embodiment 3
(1) with theasaponin 100g, join in the pyridine of 300mL, be heated to 40 ℃ and make it dissolving.Press 1.2 times of molar weights of theasaponin and add triphenylmethyl chloride (27.6g), insulated and stirred reaction 12h; Add the potassium hydroxide (5.5g) of triphenylmethyl chloride 1/5 quality again, be warming up to 80 ℃, stir 1h, pressure reducing and steaming moisture and pyridine; Add the dissolving of 500mL toluene again, be warming up to 130 ℃, slowly drip the bromobenzyl (183g) of 13 times of molar weights of theasaponin, stirring reaction 7h, reaction solution are called A liquid;
(2) get pectinose (12.3g) with the theasaponin equimolar amount in addition, add 100mL toluene, 25 ℃ drip phosphorus tribromides (7.4g) down, reaction 4h is warming up to 130 ℃, slowly drips the bromobenzyl (56g) of 4 times of molar weights of pectinose, stirring reaction 7h, reaction solution are called B liquid;
(3) A liquid is mixed with B liquid, add p-methyl benzenesulfonic acid pyridinium salt 25g, reflux water-dividing 4h places pressure reaction still, is catalyzer with 10% palladium/carbon, 25 ℃, feeds hydrogen 4h.Use the 600mL alcohol extraction, get product 82g behind the recovery ethanol.
Structural analysis to product shows that MS:m/z 1364; Elementary compositionly be: C56.29%, H7.38%, O36.32%, its molecular formula is C
64H
100O
31,
1H-NMR with
13The hydrogen of C-NMR is identical with theasaponin and pectinose with the carbon signal displacement.Its structure is as follows:
Embodiment 4
(1) with theasaponin 100g, join in the pyridine of 300mL, be heated to 30 ℃ and make it dissolving.The triphenylmethyl chloride (23g) of adding and theasaponin equimolar amount keeps 30 ℃ of stirring reaction 10h; Add the potassium hydroxide (4.6g) of triphenylmethyl chloride 1/5 quality, be warming up to 80 ℃, stir 1h, pressure reducing and steaming moisture and pyridine.Add the dissolving of 500mL toluene again, be warming up to 120 ℃, slowly dripping is the bromobenzyl (170g) of 12 times of molar weights of theasaponin, and stirring reaction 8h, reaction solution are called A liquid;
(2) get maltose (28.2g) with tea soap unit equimolar amount in addition, add 100mL toluene, 30 ℃ drip phosphorus tribromides (7.4g) down, reaction 3h is warming up to 120 ℃, and slowly dripping is the bromobenzyl (98g) of 7 times of molar weights of maltose, stirring reaction 8h, reaction solution are called B liquid;
(3) A liquid is mixed with B liquid, add p-methyl benzenesulfonic acid pyridinium salt 21g, reflux water-dividing 5h places pressure reaction still, is catalyzer with 10% palladium/carbon, 20 ℃, feeds hydrogen 6h.Use the 600mL alcohol extraction, get product 78g behind the recovery ethanol.
Structural analysis to product shows that MS:m/z 1540; Elementary compositionly be: C55.32%, H7.32%, O37.36%, its molecular formula is C
71H
112O
36,
1H-NMR with
13The hydrogen of C-NMR is identical with theasaponin and maltose with the carbon signal displacement.Its structure is as follows:
Embodiment 5
Employing standard GB/T 22237-2008 " the capillary mensuration of tensio-active agent " and GB/T13173.6-2000 " mensuration of washing composition foaming power " are as follows to the The performance test results of the theasaponin derivative that embodiment 1-4 prepares:
Surface tension :≤30 milli ox/rice
Foaming height (1.0% concentration, starting altitude): 〉=180mm
Foam lost rate (1.0% concentration, 24%NaCl+1%CaCl
2, 80 ℃, 5 minutes) :≤40%
PH value (1.0% concentration): 8.0-8.5
Above presentation of results theasaponin derivative of the present invention has superior salt tolerant heatproof surfactivity.
Embodiment 6
The theasaponin derivative is as the gas concrete air entrapment agent.It is as follows to fill a prescription:
Cement 350kg, sandstone 1500kg, water 150kg after the mixing, adds theasaponin derivative 140g (account for cement amount 0.04%), air content 3.5%, water-reducing rate is greater than 6%, and bleeding rate is less than 50%.Compressive strength rate was greater than 95% in 28 days.Product reaches national sector standard (JC 943-2004 " concrete perforated brick ") acceptable end product standard.
Embodiment 7
The theasaponin derivative is as inert ingredient.It is as follows to fill a prescription:
Glyphosate 100g, theasaponin derivative 20g, thin up is to 1000g.Liquor is dispersed and emulsifying property is good, and stability meets national standard (GB/T 1603-2001 " agricultural chemicals stability of emulsion measuring method ").Can be used for the orchard weeding, effective.
Embodiment 8
The theasaponin derivative is as the shampoo additive.It is as follows to fill a prescription:
AES 80g, theasaponin derivative 50g, 6501 15g, CMC, sodium-chlor, essence, each 0.1g of citric acid add water to 1000mL.Sample thermotolerance and winter hardiness are good, and physical and chemical index meets national light industry standard (QB-T 1974-2004 " shampoo (cream) ").Use the easy rinsing of back hair, easily unclog and readjust, no hair quality damage, comfort is strong.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. theasaponin derivative, it is characterized in that: described theasaponin derivative has suc as formula the structure shown in the I:
(formula I)
Wherein, described R is the sugar of tool hemiacetal hydroxyl.
2. theasaponin derivative according to claim 1 is characterized in that: described R is a kind of in glucose, fructose, pectinose or the maltose.
3. the preparation method of claim 1 or 2 described theasaponin derivatives is characterized in that may further comprise the steps:
(1) get the reaction of triphenylmethyl chloride and theasaponin, purpose is that the primary hydroxyl on the theasaponin C28 is protected; Then, add the reaction of bromobenzyl and theasaponin, benzyl is connected on the secondary hydroxyl of theasaponin;
(2) get phosphorus tribromide and sugar reaction, the sugar replaced hemiacetal hydroxyl of bromine atoms; With the bromobenzyl reaction, benzyl is connected on the hydroxyl of sugar again;
(3) get the sugar that theasaponin that step (1) prepares and step (2) prepare and mix, add the trityl deprotection agent again, reaction; Reaction result is that the primary hydroxyl on the theasaponin C28 is gone protection, and the primary hydroxyl on the theasaponin C28 is connected with the bromination carbon atom of sugar then; Then, under the situation that catalyzer exists, add the benzyl deprotection agent, reaction; Reaction result is the benzyl of having sloughed on theasaponin and the sugar, obtains suc as formula the theasaponin derivative shown in the I.
4. according to the preparation method of the described theasaponin derivative of claim 3, it is characterized in that: the consumption of described triphenylmethyl chloride is 1~1.5 times of molar mass of theasaponin, and temperature of reaction is 25~50 ℃, and the reaction times is 8~16h.
5. according to the preparation method of the described theasaponin derivative of claim 3, it is characterized in that: in the step (1), the consumption of described bromobenzyl is 12~14 times of molar masss of theasaponin, 120~140 ℃ of temperature of reaction, reaction times 6~8h.
6. according to the preparation method of the described theasaponin derivative of claim 3, it is characterized in that: the consumption of described sugar be theasaponin etc. molar mass.
7. according to the preparation method of the described theasaponin derivative of claim 3, it is characterized in that: in the step (2), described phosphorus tribromide consumption is 1/3 molar mass of sugar, 20~30 ℃ of reaction 3~5h; The consumption of bromobenzyl is 4~7 times of molar masss of sugar, 120~140 ℃ of temperature of reaction, reaction times 6~8h.
8. according to the preparation method of the described theasaponin derivative of claim 3, it is characterized in that:
Described trityl deprotection agent is the tosic acid pyridinium salt, its consumption be triphenylmethyl chloride etc. molar mass;
Molar masss such as described sugar and theasaponin are are participated in reaction, and reaction time of esterification is 3~5h.
9. according to the preparation method of the described theasaponin derivative of claim 3, it is characterized in that: described benzyl deprotection agent is a hydrogen, and catalyst system therefor is 10% palladium carbon, 20~30 ℃ of temperature of reaction, reaction times 3~6h.
10. the application of claim 1 or 2 described theasaponin derivatives is characterized in that: described theasaponin derivative is directly used in gas concrete air entrapment agent, inert ingredient, cleaning product additive as hydrophilic nonionic bio-surfactant.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102408200A (en) * | 2011-08-22 | 2012-04-11 | 青田中野天然植物科技有限公司 | Camellia saponin modified compound concrete air-entraining agent |
CN102731608A (en) * | 2012-06-29 | 2012-10-17 | 浙江大学 | Preparation method of tea saponin ester succinate surfactant and product thereof |
CN104974868A (en) * | 2014-04-13 | 2015-10-14 | 海南大学 | Pollution-free vegetable and fruit pesticide residue removal agent |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101392015A (en) * | 2008-07-22 | 2009-03-25 | 沈阳药科大学 | Triterpene saponin in camellia seeds, preparation method and medical use thereof |
CN101824059A (en) * | 2010-03-25 | 2010-09-08 | 大连工业大学 | Low-sugar-chain high-activity new tea saponin and biotransformation method thereof |
-
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101392015A (en) * | 2008-07-22 | 2009-03-25 | 沈阳药科大学 | Triterpene saponin in camellia seeds, preparation method and medical use thereof |
CN101824059A (en) * | 2010-03-25 | 2010-09-08 | 大连工业大学 | Low-sugar-chain high-activity new tea saponin and biotransformation method thereof |
Non-Patent Citations (2)
Title |
---|
《Journal of Pharmacological Sciences》 20041231 Zhong-Fang Lai, et al. Effects of Sasanquasaponin on Ischemia and Reperfusion Injury in Mouse Hearts 313-324 1-10 第94卷, * |
《茶叶科学》 20061231 杨钟鸣 等 茶皂甙合成聚醚反应机理及其衍生物结构表征 91-94,107 1-10 第26卷, 第2期 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102408200A (en) * | 2011-08-22 | 2012-04-11 | 青田中野天然植物科技有限公司 | Camellia saponin modified compound concrete air-entraining agent |
CN102731608A (en) * | 2012-06-29 | 2012-10-17 | 浙江大学 | Preparation method of tea saponin ester succinate surfactant and product thereof |
CN104974868A (en) * | 2014-04-13 | 2015-10-14 | 海南大学 | Pollution-free vegetable and fruit pesticide residue removal agent |
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