CN102627674A - Preparation method of thioglycoside compound - Google Patents
Preparation method of thioglycoside compound Download PDFInfo
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- CN102627674A CN102627674A CN2012101146270A CN201210114627A CN102627674A CN 102627674 A CN102627674 A CN 102627674A CN 2012101146270 A CN2012101146270 A CN 2012101146270A CN 201210114627 A CN201210114627 A CN 201210114627A CN 102627674 A CN102627674 A CN 102627674A
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Abstract
The invention provides a preparation method of a thioglycoside compound. The preparation method comprises the following steps of: (a) dissolving halogenated acetylated sugar and thiourea into a first organic solvent and reacting under a heating condition to obtain S-glycosyl isothiourea halide; and (b) reacting the S-glycosyl isothiourea halide and halothane in mixed solution of a second organic solvent and organic amine to obtain the thioglycoside compound. In the entire reaction process, the thiourea and the halothane are mainly selected and used as reactants, ethanethiol with offensive odor and toxicity is not required to be selected and used, and the hazard caused to human health and environment is effectively avoided. In addition, according to the method provided by the invention, an obtained product is extremely easy to separate crystals, the pH is not required to be adjusted, and the post-treatment operation is simple.
Description
Technical field
The present invention relates to the sugar compounds field, relate in particular to a kind of preparation method of thio glycoside compound.
Background technology
Saccharide compound is to contain the general name that can generate a compounds of poly-hydroxy aldehyde or polyhydroxyketone after poly-hydroxy aldehyde or polyhydroxyketone and the hydrolysis.Saccharide compound is the organic cpds that distributed in nature is the most extensive, quantity is maximum, is one of moity of food, also is the photosynthetic direct product of green plants.Saccharide compound accounts for 3/4 in the natural biological substance, from the bacterium to the higher animal, all contains saccharide compound.Simultaneously saccharide compound also is the earn a bare living main source of activity institute energy requirement of organism, is the basic raw material of synthetic other compounds, is the primary structure composition of organism.Therefore saccharide compound is one of particularly important organic cpds.
Glucosides is the principal mode that sugar exists at nature; Extensively be present in the organism; Wherein a lot of glucosides are being undertaken important biological function owing to having special biological activity; Many glucosides also are natural pigment and pigments simultaneously, so glucosides class material medically with in the industry all has very big use value.Dry out son or other micromolecular compound of the semi-acetal hydroxyl of glucosides sugar and hydroxyl, amino or thiol etc. in another molecular compound forms; For example; Sugar generates the aminoglycoside compound with the amine reaction, and sugar generates the thio glycoside compound with thiol reactant.
In thio glycoside compound synthetic, prior art directly adopts BFEE and sulfur alcohol to prepare the thio glycoside compound.This method prepares the thio glycoside compound need use sulfur alcohol; Strong to have, the lasting and pungency garlic odour flavor of this reactant and well-known; It is the most smelly material of including in the version Guiness World Records in 2000, and when containing sulfur alcohol 1/50000000000th concentration in the air, its stink just can be perceiveed; And this material is a kind of high poisonous substance, and is very big to HUMAN HEALTH and environmental hazard.In addition, adopt also more complicated of subsequent disposal work that BFEE and sulfur alcohol prepare the thio glycoside compound, also want neutralization solution adjusting pH value at last through repeatedly extraction, operation steps is more loaded down with trivial details.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of method that adopts poisonous material to prepare the thio glycoside compound.
In view of this, the invention provides a kind of preparation method of thio glycoside compound, may further comprise the steps:
A) halo acetylize sugar compounds and thiocarbamide are dissolved in first organic solvent, reaction obtains S-glycosyl isothiourea halides under heating condition;
B) said S-glycosyl isothiourea halides and halogen ethane react in the mixing solutions of second organic solvent and organic amine, obtain the thio glycoside compound.
Preferably, said halo acetylize sugar compounds is reacted in hydrogen halide solution by the acetylize sugar compounds and obtains.
Preferably, said hydrogen halide solution is an ACIDITY OF THE HYDROGEN HALIDS solution.
Preferably, said hydrogen halide is a hydrogen bromide.
Preferably, said first organic solvent is acetonitrile, methylene dichloride or ETHYLE ACETATE; Said second organic solvent is acetonitrile, methylene dichloride or ETHYLE ACETATE.
Preferably, the Heating temperature of said heating is 60 ℃～80 ℃.
Preferably, said organic amine is monoethylamine, diethylamine or triethylamine.
Preferably, step b) is specially:
In said S-glycosyl isothiourea halides, add second organic solvent and organic amine, regulating and controlling temperature adds halogen ethane subsequently for the first time, and regulating and controlling temperature obtains the thio glycoside compound after the reaction end for the second time.
Preferably, said first time, the TR of regulating and controlling temperature was 5 ℃～15 ℃, and said second time, the TR of regulating and controlling temperature was no more than 20 ℃.
Preferably, said halogen ethane is monobromethane.
The invention provides a kind of preparation method of thio glycoside compound, may further comprise the steps:
A) halo acetylize sugar compounds and thiocarbamide are dissolved in first organic solvent, reaction obtains S-glycosyl isothiourea halides under heating condition; B) said S-glycosyl isothiourea halides and halogen ethane react in the mixing solutions of second organic solvent and organic amine, obtain the thio glycoside compound.The present invention with halo acetylize sugar compounds and thiocarbamide reaction, changes into S-glycosyl isothiourea halides earlier in the preparation process of thio glycoside compound; Halogen ethane and S-glycosyl isothiourea halides reaction then obtains the thio glycoside compound.In entire reaction course, mainly selecting thiocarbamide and halogen ethane for use is reactant, need not to have selected for use bad smell and toxic sulfur alcohol, has avoided the harm to HUMAN HEALTH and environment effectively.According to method provided by the invention, the product that obtains is easy to just can separate out crystal, need not to regulate pH in addition, and aftertreatment work is simple.
Description of drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the sulfo-fucoside compound of embodiment 4 preparations;
Fig. 2 is the carbon-13 nmr spectra figure of the sulfo-fucoside compound of embodiment 4 preparations.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of preparation method of thio glycoside compound, may further comprise the steps:
A) halo acetylize sugar compounds and thiocarbamide are dissolved in first organic solvent, reaction obtains S-glycosyl isothiourea halides under heating condition;
B) said S-glycosyl isothiourea halides and halogen ethane react in the mixing solutions of second organic solvent and organic amine, obtain the thio glycoside compound.
Step a) is halo acetylize sugar compounds and thiocarbamide reaction, obtains intermediate product S-glycosyl isothiourea halides.Above-mentioned first organic solvent as the reaction medium, just play the effect of solvent at this, its as reaction medium not with raw material reaction.Above-mentioned first organic solvent is preferably acetonitrile, methylene dichloride or ETHYLE ACETATE, more preferably acetonitrile.Above-mentioned reaction must just can react under heating condition, and the Heating temperature of above-mentioned heating is preferably 60 ℃～80 ℃, more preferably 65 ℃～75 ℃.Above-mentioned halo acetylize sugar compounds is unstable, very easily transforms, and as preferred version, said halo acetylize sugar compounds is reacted in hydrogen halide solution by the acetylize sugar compounds and obtains.For the acetylize sugar compounds is fully reacted, above-mentioned hydrogen halide solution is preferably ACIDITY OF THE HYDROGEN HALIDS solution, more preferably the hydrogen halide acetum.Above-mentioned hydrogen halide solution is preferably hydrogen fluoride solution, hydrogen chloride solution, hydrogen bromide solution and hydrogen iodide solution, more preferably hydrogen bromide solution.
Step b) is S-glycosyl isothiourea halides and the reaction of halogen ethane, obtains the thio glycoside compound.The effect of above-mentioned organic amine provides the needed weak base environment of reaction, and this is reflected at pH >=7 and o'clock just can carries out, and above-mentioned organic amine is preferably monoethylamine, diethylamine or triethylamine, more preferably triethylamine.Above-mentioned second organic solvent is preferably acetonitrile, methylene dichloride or ETHYLE ACETATE.As preferred version, above-mentioned steps b) be specially: in said S-glycosyl isothiourea halides, add second organic solvent and organic amine, regulating and controlling temperature adds halogen ethane subsequently for the first time, and regulating and controlling temperature obtains the thio glycoside compound after the reaction end for the second time.Above-mentioned first time, the TR of regulating and controlling temperature was preferably 5 ℃～15 ℃; More preferably 10 ℃, above-mentioned second time, the TR of regulating and controlling temperature was no more than 20 ℃, and partial reaction is thermopositive reaction in this step reaction; And temperature is bigger to the influence of reaction; Productive rate to reaction too high or too low for temperature all can be influential, even other chemical transformation can take place, and therefore the temperature of reaction regulated and control.
The present invention with halo acetylize sugar compounds and thiocarbamide reaction, changes into S-glycosyl isothiourea halides earlier in the preparation process of thio glycoside compound; Halogen ethane and S-glycosyl isothiourea halides reaction then obtains the thio glycoside compound.In entire reaction course, mainly selecting thiocarbamide and halogen ethane for use is reactant, has not selected bad smell and virose sulfur alcohol for use, has avoided the harm to HUMAN HEALTH and environment effectively.According to method provided by the invention, the product that obtains is easy to just can separate out crystal, need not to regulate pH in addition, and aftertreatment work is simple, and has improved the productive rate of thio glycoside compound.
In order further to understand the present invention, below in conjunction with embodiment the preparation method of thio glycoside compound provided by the invention is described in detail, protection scope of the present invention is not limited by the following examples.
A) to 160g tetra-acetylated-add acetic acid/HBr solution 162ml of 33wt% in the L-arabinose, stir and make its dissolving, react about 1.5h, TLC point board test reaction process; Raw material point disappears and thinks that promptly reaction finishes; In reaction solution, add the 500ml methylene dichloride then, add the Na of 5wt% again
2CO
3With pH value to 7, organic phase is told in stirring among the solution 200ml, organic phase with anhydrous sodium sulfate drying after at 40 ℃ of following evaporates to dryness, obtain bromo tetra-acetylated-L-arabinose, output is 639g;
B) with above-mentioned 165g bromo tetra-acetylated-L-arabinose adds the 630ml acetonitrile makes its dissolving, is heated to 60 ℃; Beginning slowly adds the 36.5g thiocarbamide in reaction solution, and when refluxing beginning, the adularescent floss generates; After thiocarbamide adds, react behind about 30min, disappear up to raw material point with TLC point board test reaction process; After reaction is accomplished, reaction solution is placed on 0 ℃ stirs 3h～4h down, all products are better separated out; Suction filtration goes out solid, and solid is placed and dried, and the 150g that weighs is S-glycosyl isothiourea bromo-derivative.
C) above-mentioned 150gS-glycosyl isothiourea bromo-derivative is joined in the there-necked flask, add 534ml acetonitrile and 135ml triethylamine under the room temperature successively, control to about 10 ℃; Begin to drip the 43.5ml monobromethane, temperature is no more than 20 ℃, after dropwising, places stirring at room, reacts about 1h and can accomplish; Reaction solution is first at 40 ℃ of left and right sides evaporates to dryness, and then adds 100ml methylene dichloride steaming 2～3 times, is half-dried Off-white solid behind the evaporate to dryness; Use dichloromethane extraction again, the organic phase that extracts is at 40 ℃ of following evaporates to dryness; Add the isohexane crystallization then, obtain white solid, be sulfo-pectinose glycoside compound, about 95g weighs.
A) to 450g tetra-acetylated-add acetic acid/HBr solution 478ml of 33wt% in the L-arabinose, stir and make its dissolving, react about 1.5h, TLC point board test reaction process; Raw material point disappears and thinks that promptly reaction finishes; In reaction solution, add the 1.5L methylene dichloride then, add the Na of 5wt% again
2CO
3With pH value to 7, organic phase is told in stirring among the solution 600ml, organic phase with anhydrous sodium sulfate drying after at 40 ℃ of following evaporates to dryness, obtain bromo tetra-acetylated-L-arabinose, theoretical yield is 480g.
B) above-mentioned 480g bromo acetylize sugar compounds is added the 1.86L acetonitrile and make its dissolving, be heated to 75 ℃; Beginning slowly adds the 107.6g thiocarbamide in reaction solution, when refluxing beginning, can generate by the adularescent floss; After thiocarbamide adds, react behind about 30min, disappear up to raw material point with TLC point board test reaction process; After reaction is accomplished, reaction solution is placed on 0 ℃ stirs 3h～4h down, all products are better separated out; Suction filtration goes out solid, and solid is placed and dried, and the 450g that weighs is S-glycosyl isothiourea bromo-derivative.
C) above-mentioned 450gS-glycosyl isothiourea bromo-derivative is joined in the there-necked flask, add 1.6L acetonitrile and 405ml triethylamine under the room temperature successively, control to about 10 ℃; Beginning dripping bromine ethane 130.5ml, temperature is no more than 20 ℃, after dropwising, places stirring at room, reacts about 1h and can accomplish; Reaction solution is first at 40 ℃ of left and right sides evaporates to dryness, and then adds 300ml methylene dichloride steaming 2～3 times, is half-dried Off-white solid behind the evaporate to dryness; Use dichloromethane extraction again, the organic phase that extracts is at 40 ℃ of following evaporates to dryness; Add the isohexane crystallization then, obtain white solid, be sulfo-pectinose glycoside compound, about 304g weighs.
Embodiment 3
A) to 93g tetra-acetylated-add acetic acid/HBr solution 104ml of 33wt% in the L-arabinose, stir and make its dissolving, react about 1.5h, TLC point board test reaction process; Raw material point disappears and thinks that promptly reaction finishes; In reaction solution, add the 176ml methylene dichloride then, add the Na of 5wt% again
2CO
3With pH value to 7, organic phase is told in stirring among the solution 175ml, organic phase with anhydrous sodium sulfate drying after at 40 ℃ of following evaporates to dryness, obtain bromo tetra-acetylated-L-arabinose, theoretical yield is 98g.
B) with above-mentioned 98g bromo tetra-acetylated-L-arabinose adds the 392ml acetonitrile makes its dissolving, is heated to 65 ℃; In reaction solution, begin slowly to add the 22.5g thiocarbamide, when refluxing beginning, can generate by the adularescent floss; After thiocarbamide adds, react behind about 30min, disappear up to raw material point with TLC point board test reaction process; After reaction is accomplished, reaction solution is placed on 0 ℃ stirs 3h～4h down, all products are better separated out; Suction filtration goes out solid, and solid is placed and dried, and the 95g that weighs is S-glycosyl isothiourea bromo-derivative.
C) above-mentioned 95gS-glycosyl isothiourea bromo-derivative is joined in the there-necked flask, add 340ml acetonitrile and 83.4ml triethylamine under the room temperature successively, control to about 10 ℃; Beginning dripping bromine ethane 27.5ml, temperature is no more than 20 ℃, after dropwising, places stirring at room, reacts about 1h and can accomplish; Reaction solution is first at 40 ℃ of left and right sides evaporates to dryness, and then adds 65ml methylene dichloride steaming 2～3 times, is half-dried Off-white solid behind the evaporate to dryness; Use dichloromethane extraction again, the organic phase that extracts is at 40 ℃ of following evaporates to dryness; Add the isohexane crystallization then, obtain white solid, be sulfo-pectinose glycoside compound, about 100g weighs.
The reaction formula of embodiment 1～embodiment 3 preparation sulfo-pectinose glycoside compounds is as follows:
A) acetic acid/HBr solution 640ml of adding 33wt% in 607g acetylize Fucose stirs and makes its dissolving, reacts about 1.5h, TLC point board test reaction process; Raw material point disappears and thinks that promptly reaction finishes; In reaction solution, add the 1.9L methylene dichloride then, add the Na of 5wt% again
2CO
3With pH value to 7, organic phase is told in stirring among the solution 863ml, organic phase with anhydrous sodium sulfate drying after at 40 ℃ of following evaporates to dryness, obtain bromo acetylize Fucose, theoretical yield is 645g.
B) above-mentioned 480g bromo acetylize Fucose is added the 2.5L acetonitrile and make its dissolving, be heated to 70 ℃; Beginning slowly adds the 144.5g thiocarbamide in reaction solution, when refluxing beginning, can generate by the adularescent floss; After thiocarbamide adds, react behind about 30min, disappear up to raw material point with TLC point board test reaction process; After reaction is accomplished, reaction solution is placed on 0 ℃ stirs 3h～4h down, all products are better separated out; Suction filtration goes out solid, and solid is placed and dried, and the 570g that weighs is S-glycosyl isothiourea bromo-derivative.
C) above-mentioned 570gS-glycosyl isothiourea bromo-derivative is joined in the there-necked flask, add acetonitrile 2L and 513ml triethylamine under the room temperature successively, control to about 10 ℃; Beginning dripping bromine ethane 165.3ml, temperature is no more than 20 ℃, after dropwising, places stirring at room, reacts about 1h and can accomplish; Reaction solution is earlier at 40 ℃ of left and right sides evaporates to dryness, and then the 380ml steaming 2～3 times that adds methylene chloride, and is half-dried Off-white solid behind the evaporate to dryness; Use dichloromethane extraction again, the organic phase that extracts is at 40 ℃ of following evaporates to dryness; Add the isohexane crystallization then, obtain white solid, be sulfo-fucoside compound, about 304g weighs.Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of sulfo-fucoside compound, and Fig. 2 is the carbon-13 nmr spectra figure of sulfo-fucoside compound, can know that with Fig. 2 sulfo-fucoside compound can successfully prepare by 1.
The reaction formula of embodiment 4 preparation sulfo-fucoside compounds is as follows:
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. the preparation method of a thio glycoside compound is characterized in that, may further comprise the steps:
A) halo acetylize sugar compounds and thiocarbamide are dissolved in first organic solvent, reaction obtains S-glycosyl isothiourea halides under heating condition;
B) said S-glycosyl isothiourea halides and halogen ethane react in the mixing solutions of second organic solvent and organic amine, obtain the thio glycoside compound.
2. preparation method according to claim 1 is characterized in that, said halo acetylize sugar compounds is reacted in hydrogen halide solution by the acetylize sugar compounds and obtains.
3. preparation method according to claim 2 is characterized in that, said hydrogen halide solution is an ACIDITY OF THE HYDROGEN HALIDS solution.
4. preparation method according to claim 2 is characterized in that, said hydrogen halide is a hydrogen bromide.
5. preparation method according to claim 1 is characterized in that, said first organic solvent is acetonitrile, methylene dichloride or ETHYLE ACETATE; Said second organic solvent is acetonitrile, methylene dichloride or ETHYLE ACETATE.
6. preparation method according to claim 1 is characterized in that, the Heating temperature of said heating is 60 ℃～80 ℃.
7. preparation method according to claim 1 is characterized in that, said organic amine is monoethylamine, diethylamine or triethylamine.
8. preparation method according to claim 1 is characterized in that step b) is specially:
In said S-glycosyl isothiourea halides, add second organic solvent and organic amine, regulating and controlling temperature adds halogen ethane subsequently for the first time, and regulating and controlling temperature obtains the thio glycoside compound after the reaction end for the second time.
9. preparation method according to claim 8 is characterized in that, said first time, the TR of regulating and controlling temperature was 5 ℃～15 ℃, and said second time, the TR of regulating and controlling temperature was no more than 20 ℃.
10. preparation method according to claim 1 is characterized in that, said halogen ethane is monobromethane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102942598A (en) * | 2012-11-28 | 2013-02-27 | 济南圣泉唐和唐生物科技有限公司 | Post-treatment method for acetyl sugar halogenating reaction |
| CN103087121A (en) * | 2013-01-12 | 2013-05-08 | 江西师范大学 | Synthetic method for isopropyl-beta-D-thiogalactoside |
| CN103342725A (en) * | 2013-07-26 | 2013-10-09 | 济南卡博唐生物科技有限公司 | Method for separating and purifying beta-end-group thio-glycoside compound |
| CN103980330A (en) * | 2014-04-04 | 2014-08-13 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of isothiourea dihydrobromide |
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2012
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| E. S. H. EL ASHRY ET AL: "Microwave Irradiation for Accelerating the Synthesis of Thioglycosides", 《SYNTHETIC COMMUNICATIONS》 * |
| YU ZHIQIANG ET AL: "One-pot synthesis of hyperbranched poly(amido amine) clicked with a sugar shell via Michael addition polymerization and thiol click reaction", 《SCI CHINA CHEM》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942598A (en) * | 2012-11-28 | 2013-02-27 | 济南圣泉唐和唐生物科技有限公司 | Post-treatment method for acetyl sugar halogenating reaction |
| CN103087121A (en) * | 2013-01-12 | 2013-05-08 | 江西师范大学 | Synthetic method for isopropyl-beta-D-thiogalactoside |
| CN103087121B (en) * | 2013-01-12 | 2018-01-30 | 江西师范大学 | The synthetic method of isopropyl ss D thiogalactosides |
| CN103342725A (en) * | 2013-07-26 | 2013-10-09 | 济南卡博唐生物科技有限公司 | Method for separating and purifying beta-end-group thio-glycoside compound |
| CN103342725B (en) * | 2013-07-26 | 2016-09-14 | 济南尚博生物科技有限公司 | A kind of process for separation and purification of β end group thio glycoside compound |
| CN103980330A (en) * | 2014-04-04 | 2014-08-13 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of isothiourea dihydrobromide |
| CN103980330B (en) * | 2014-04-04 | 2017-02-01 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of isothiourea dihydrobromide |
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Effective date of registration: 20211224 Address after: 250204 2F, building 24, Shengquan Industrial Park, Diao Town Industrial Development Zone, Zhangqiu District, Jinan City, Shandong Province Patentee after: CARBOTANG BIOTECH CO.,LTD. Address before: 250204 Shengquan Industrial Park, Diaozhen Industrial Development Zone, Zhangqiu City, Jinan City, Shandong Province Patentee before: HEALTANG BIOTECH Co.,Ltd. |
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Address after: 250204 Diaozhen Street Chemical Industrial Park, Zhangqiu District, Jinan City, Shandong Province Patentee after: Jinan Carbotang Biotech Co.,Ltd. Address before: 250204 2F, building 24, Shengquan Industrial Park, Diao Town Industrial Development Zone, Zhangqiu District, Jinan City, Shandong Province Patentee before: CARBOTANG BIOTECH CO.,LTD. |