CN104327130A - Method for preparing sucralose-6-acetate - Google Patents
Method for preparing sucralose-6-acetate Download PDFInfo
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- CN104327130A CN104327130A CN201410682179.3A CN201410682179A CN104327130A CN 104327130 A CN104327130 A CN 104327130A CN 201410682179 A CN201410682179 A CN 201410682179A CN 104327130 A CN104327130 A CN 104327130A
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Abstract
The invention discloses a method for preparing sucralose-6-acetate. The method comprises the following steps: adding sucrose, trimethyl orthoacetate and a sulfonated cage-type mesoporous carbon catalyst in a reaction vessel, carrying out a C-6 hydroxy protection reaction of sucrose, and after the reaction is completed, dropwise adding a Vilsmeier reagent for carrying out a chlorination reaction; after the reaction is completed, adding ethyl acetate, and vigorously stirring; adding alkali liquor for adjusting the pH value of the obtained mixture to 9-10, and vigorously stirring for 1 h; and dropwise adding a small amount of glacial acetic acid for adjusting the pH value of the obtained mixture to 6-7, carrying out suction filtration, washing by using ethyl acetate, carrying out activated carbon decoloration, and carrying out condensing and crystallization on the obtained product, so that a sucralose-6-acetate product is obtained. The method disclosed by the invention has the characteristics of simple technological operation, good technical performance, less 'three wastes', convenient aftertreatment, and reusable reaction system, therefore, the method is an economical and practical green and environmental protection technology.
Description
Technical field
The present invention relates to a kind of method preparing sucralose-6-acetic ester.
Background technology
Sucralose is Sucralose again, and be called for short TGS, chemical name is 4,1', chloro-4,1', the 6'-tri-deoxidation sucralose of 6'-tri-, it is a kind of white powder product, very easily water-soluble, the solubleness in 20 DEG C of water is 28.2g/dL, and chemical stability is high in an acidic solution, and pass through the severe test such as pharmacology, toxicity, physiology physics and chemistry of long-term (10 years), prove that Sucralose is safe to people.Because sweet taste is pure, pole is similar to natural product sucrose, is 600 times of sweetness of cane sugar, and the unhappy aftertaste not having other sweeting agent to bring; Be not absorbed by the body, do not produce heat energy, and metabolism discord Regular Insulin is had an effect, and diabetics, adiposis patient and the elderly etc. can be supplied edible; Dental caries can not be caused to become, contribute to the advantages such as dental health, there is wide application advantage.Sucralose synthesized successfully in 1976 by Tate & Lyle company of Britain, put goods on the market in 1988, performance characteristics due to its excellence is considered to the high-intensity sweetener of a kind of most competitive power that the mankind have up to now developed, be included China to use as sweeting agent at more than 40 interior state approval, be widely used in dairy products, beverage, pickles, compound seasoner, assembled alcoholic drinks, ice cream, cake, fruit can, bake and in the food such as jelly, be one of study hotspot of current high-intensity sweetener.Therefore, the traditional technology of this series products is improved there is good economic benefit and important social benefit.
The preparation method of current Sucralose has radical protection method, enzyme-chemically integrated process, monoesters method, raffinose method etc. four kinds.Current domestic production producer many employings monoesters method is produced, and the production process of general the synthesis of Sucralose by using monoesterification is: sucrose → cane sugar-6-acetic ester → sucralose-6-acetic ester-Sucralose.This critical technological point is in second step chlorination reaction, domestic technique majority makes solvent with DMF, chlorinating agent carries out chlorination, temperature of reaction requires high, long reaction time, owing to producing hydrogenchloride and sulfur dioxide gas in reaction process, if can not timely and effectively get rid of, can cause product carbonization, operation strengthens.Therefore, traditional technology is undergone technological transformation there is important using value.
Cascade reaction technology is the one very promising methodology of organic synthesis of tool.Polycomponent cascade reaction is compared tool with traditional stepwise synthesis and is had an enormous advantage, and can reduce reactions steps greatly, saves a lot of complicated loaded down with trivial details sepn process.From raw material relatively simple and easy to get, without the separation of intermediate, directly obtain baroque molecule.This reaction technology starting raw material is cheap and easy to get, and reaction scheme is short, and synthesis cycle reduces, and separation and purification is simple, and ratio defective product is high, and reaction is efficient, obviously economically with environmental friendliness on advantageously, be beneficial to scale operation.
Summary of the invention
The object of the invention is to provide and is a kind ofly suitable for the industrialized method preparing sucralose-6-acetic ester, namely adopts series process reaction technology to complete the separation and purification of the esterification of sucrose C-6 hydroxyl, the chlorination of carboxylate and sucralose-6-acetic ester.
For achieving the above object, the present invention adopts following technical scheme:
A kind of method preparing sucralose-6-acetic ester, comprise: in reaction vessel, add sucrose, trimethyl orthoacetate and sulfonation cage modle gold/mesoporous carbon catalyst, the C-6 position hydroxyl protection reaction of sucrose is carried out under DMF exists, drip Vilsmeier reagent after reacting completely and carry out chlorination reaction, add ethyl acetate after completion of the reaction, vigorous stirring, add lye pH adjustment=9-10, vigorous stirring 1h, drip a small amount of Glacial acetic acid and adjust pH=6-7, suction filtration, washs by ethyl acetate, activated carbon decolorizing, condensing crystal obtains sucralose-6-acetic ester product;
Sulfonation cage modle gold/mesoporous carbon catalyst of the present invention is solid acid catalyst, its preparation method is: take F127 as structure directing agent, tetraethoxy is silicon source, through 150 DEG C of Hydrothermal Synthesiss, in retort furnace, calcine away structure directing agent obtain mesoporous silicon oxide KIT-5-150, with ordered mesoporous silicon KIT-5-150 for silicon template, sucrose is carbon source, repeatedly in silicon template, pour into sucrose 2 times, through thermopolymerization, being formed is situated between sees phase, then carbonization in nitrogen atmosphere, finally go out silicon template by hydrofluoric acid dips, obtain cage modle mesoporous carbon CKT-3 (A); CKT-3 (A), Isopentyl nitrite and Sulphanilic Acid are added to the water, at 80 DEG C and under stirring, the sulfonic group phenyl radical produced with Isopentyl nitrite and Sulphanilic Acid reaction and mesoporous carbon CKT-3 (A) carry out reaction and realize surface-functionalized, obtain with sulfonic cage modle mesoporous carbon S-CKT.
The quality consumption of sulfonation cage modle gold/mesoporous carbon catalyst of the present invention is the 10-30% of sucrose quality, is preferably 12-16%.
The mass ratio that feeds intake of sucrose of the present invention and sulfonation cage modle gold/mesoporous carbon catalyst, phthalate group cation germini surfactant is 1:0.1 ~ 0.3:2 ~ 10.
The mass ratio that feeds intake of sucrose of the present invention and sulfonation cage modle gold/mesoporous carbon catalyst, phthalate group cation germini surfactant is 1:0.12 ~ 0.16:5 ~ 6.
Hydroxyl protection of the present invention reaction is carried out under the temperature condition of room temperature ~ 45 DEG C.
Hydroxyl protection of the present invention reaction first 35 ~ 45 DEG C of reactions 4 ~ 6 hours, then room temperature reaction 2 ~ 5 hours.
Chlorination reaction of the present invention is carried out under the temperature condition of 90 ~ 120 DEG C, 1 ~ 10 hour reaction times.
Chlorination reaction of the present invention is carried out under the temperature condition of 100 ~ 110 DEG C, 3 ~ 6 hours reaction times.
The concrete preparation method of Vilsmeier reagent of the present invention is: the DMF that 40mL heavily steams, and proceeds to low-temp reaction device, drips 13mL SOCl
2, control to drip speed and make interior temperature be no more than 20 DEG C, dropwise low temperature and stir 1h, 50 DEG C are stirred 2h, then revolve except SO in 50 DEG C
2, until there is a small amount of DMF to be screwed out, reaction solution is proceeded to low-temp reaction device, occurs the needle-like crystal that a large amount of white is easily stirred and Vilsmeier reagent, by for subsequent use for its DMF suspension cryopreservation.
Compared with prior art, the invention has the beneficial effects as follows that the present invention is in reaction process, polycomponent being carried out cascade reaction, has that technological operation is simple, technological performance, the three wastes are few, the reusable feature of convenient post-treatment, reaction system, is economical and practical green environmental protection technique.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited to this.
Embodiment one
The preparation of sulfonation cage modle mesoporous carbon
Take F127 as structure directing agent, tetraethoxy is silicon source, through 150 DEG C of Hydrothermal Synthesiss, calcines away structure directing agent and obtain mesoporous silicon oxide KIT-5-150 in retort furnace, with ordered mesoporous silicon KIT-5-150 for silicon template, sucrose is carbon source, repeatedly in silicon template, pours into sucrose, through thermopolymerization 2 times, being formed is situated between sees phase, then carbonization in nitrogen atmosphere, finally goes out silicon template by hydrofluoric acid dips, obtains cage modle mesoporous carbon CKT-3 (A); CKT-3 (A), Isopentyl nitrite and Sulphanilic Acid are added to the water, at 80 DEG C and under stirring, the sulfonic group phenyl radical produced with Isopentyl nitrite and Sulphanilic Acid reaction and mesoporous carbon CKT-3 (A) carry out reaction and realize surface-functionalized, obtain with sulfonic cage modle mesoporous carbon S-CKT.
The preparation of Vilsmeier reagent
The DMF that 40mL heavily steams, proceeds to low-temp reaction device, drips 13mL SOCl
2, control to drip speed and make interior temperature be no more than 20 DEG C, dropwise low temperature and stir 1h, 50 DEG C are stirred 2h, then revolve except SO in 50 DEG C
2, until there is a small amount of DMF to be screwed out, reaction solution is proceeded to low-temp reaction device, occurs the needle-like crystal that a large amount of white is easily stirred and Vilsmeier reagent, by for subsequent use for its DMF suspension cryopreservation.
The preparation of sucralose-6-acetic ester
In 250 milliliters of there-necked flasks, add 50mL DMF, sucrose 34.2 grams (0.1 mole), trimethyl orthoacetate 12 grams (0.1 mole) and embodiment 1 sulfonation cage modle gold/mesoporous carbon catalyst 3 grams, 40 DEG C of stirring reactions 5 hours, stirring at room temperature 2 hours, drip Vilsmeier reagent obtained in excessive embodiment 2 and carry out chlorination reaction, add ethyl acetate after completion of the reaction, vigorous stirring, add lye pH adjustment=9-10, vigorous stirring 1h, drip a small amount of Glacial acetic acid and adjust pH=6-7, suction filtration, wash by ethyl acetate, activated carbon decolorizing, condensing crystal obtains sucralose-6-acetic ester product 22.3 grams.Fusing point: 75 ~ 76 DEG C; Product detects purity through HPLC and reaches more than 98.0%.
Embodiment two
The difference of the present embodiment and embodiment one is the preparation of sucralose-6-acetic ester.
In 250 milliliters of there-necked flasks, add 50mL DMF, sucrose 34.2 grams (0.1 mole), trimethyl orthoacetate 12 grams (0.1 mole) and embodiment 1 sulfonation cage modle gold/mesoporous carbon catalyst 3 grams, 40 DEG C of stirring reactions 5 hours, stirring at room temperature 2 hours, drip Vilsmeier reagent obtained in excessive embodiment 2 and carry out chlorination reaction, add ethyl acetate after completion of the reaction, vigorous stirring, add lye pH adjustment=9-10, vigorous stirring 1h, drip a small amount of Glacial acetic acid and adjust pH=6-7, suction filtration, wash by ethyl acetate, activated carbon decolorizing, condensing crystal obtains sucralose-6-acetic ester product 21.8 grams.Fusing point: 75 ~ 76 DEG C; Product detects purity through HPLC and reaches more than 98.0%.
Those skilled in the art can carry out various change and modification to invention and not depart from the spirit and scope of the present invention.Like this, if these amendments of the present invention and modification belong within the scope of the claims in the present invention and equivalent technologies thereof, then the present invention is also intended to comprise these change and modification.
Claims (7)
1. prepare the method for sucralose-6-acetic ester for one kind; comprise: in reaction vessel, add sucrose, trimethyl orthoacetate and sulfonation cage modle gold/mesoporous carbon catalyst; the C-6 position hydroxyl protection reaction of sucrose is carried out under DMF exists; drip Vilsmeier reagent after reacting completely and carry out chlorination reaction; add ethyl acetate after completion of the reaction; vigorous stirring; add lye pH adjustment=9-10; vigorous stirring 1h; drip a small amount of Glacial acetic acid to adjust between pH to 6-7, suction filtration, washs by ethyl acetate; activated carbon decolorizing, condensing crystal obtains sucralose-6-acetic ester product.
2. prepare the method for sucralose-6-acetic ester as claimed in claim 1, it is characterized in that: the mass ratio that feeds intake of described sucrose and sulfonation cage modle gold/mesoporous carbon catalyst, Vilsmeier reagent is 1:(0.1 ~ 0.3): (2 ~ 10).
3. prepare the method for sucralose-6-acetic ester as claimed in claim 2, it is characterized in that: the mass ratio that feeds intake of described sucrose and sulfonation cage modle gold/mesoporous carbon catalyst, Vilsmeier reagent is 1:(0.12 ~ 0.16): (5 ~ 6).
4. the method preparing sucralose-6-acetic ester as described in one of claims 1 to 3, is characterized in that: described hydroxyl protection reaction is carried out under the temperature condition of 25 DEG C ~ 45 DEG C.
5. prepare the method for sucralose-6-acetic ester as claimed in claim 4, it is characterized in that: described hydroxyl protection reaction first 35 ~ 45 DEG C of reactions 4 ~ 6 hours, then room temperature reaction 2 ~ 5 hours.
6. the method preparing sucralose-6-acetic ester as described in one of claims 1 to 3, is characterized in that: described chlorination reaction is carried out under the temperature condition of 90 DEG C ~ 120 DEG C, 1 ~ 10 hour reaction times.
7. prepare the method for sucralose-6-acetic ester as claimed in claim 5, it is characterized in that: described chlorination reaction is carried out under the temperature condition of 100 DEG C ~ 110 DEG C, 3 ~ 6 hours reaction times.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171088A (en) * | 2020-01-07 | 2020-05-19 | 广东省石油与精细化工研究院 | Catalytic selective synthesis method of fatty acid oligosaccharide monoester |
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- 2014-11-24 CN CN201410682179.3A patent/CN104327130A/en active Pending
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| CN1526716A (en) * | 2003-09-23 | 2004-09-08 | 李宝才 | Monoester process of synthesizing trichlorosucrose |
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| WO2009016646A1 (en) * | 2007-08-01 | 2009-02-05 | Council Of Scientific & Industrial Research | Novel glycerol-based heterogeneous solid acid catalysts useful for the esterification of fatty acids, a process and use thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171088A (en) * | 2020-01-07 | 2020-05-19 | 广东省石油与精细化工研究院 | Catalytic selective synthesis method of fatty acid oligosaccharide monoester |
| CN111171088B (en) * | 2020-01-07 | 2021-05-04 | 广东省石油与精细化工研究院 | Catalytic selective synthesis method of fatty acid oligosaccharide monoester |
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