CN101824102B - N-(ethylamino) inulin and preparation and application thereof - Google Patents
N-(ethylamino) inulin and preparation and application thereof Download PDFInfo
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- CN101824102B CN101824102B CN201010163998.9A CN201010163998A CN101824102B CN 101824102 B CN101824102 B CN 101824102B CN 201010163998 A CN201010163998 A CN 201010163998A CN 101824102 B CN101824102 B CN 101824102B
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Abstract
The invention relates to the field of daily health products and the pharmaceutical industry, in particular to an N-(ethylamino) inulin and preparation and application thereof. The N-(ethylamino) inulin is as shown in a formula (1), wherein the average value of n ranges from 10 to 35. The preparation method comprises the following steps of: halogenating or esterifying the inulin with sulfonic acid chloride; then reacting the inulin for 8 to 24 hours at the temperature of 40 to 90 DEG C; and purifying the inulin to obtain the N-(ethylamino) inulin, wherein the molar weight of the anhydrous ethylenediamine is 30 to 40 times the weight of the inulin. The obtained compound can be used as an antioxidant. The preparation has the advantages of simple synthetic process, easy popularization and easily available needed equipment and raw materials. The product obtained by the invention can be widely applied to the fields of biology, medicament, foods, chemical industry and the like.
Description
Technical field
The present invention relates to household chemicals field and pharmaceutical industries, is specifically a kind of N-(ethylamino) synanthrin and preparation and application.
Background technology
Synanthrin (Inulin) is called again inulin, is a kind of biological polyoses.By D-fructofuranose molecule, with β-(2,1) glycosidic link, connected and generate, each synanthrin molecule end connects a glucosyl residue with α-(1,2) glycosidic link, and the polymerization degree is generally 2～60, and mean polymerisation degree is 10.
Synanthrin is widespread in nature in some microorganisms and fungus body.But be mainly still present in the body of plant, as jerusalem artichoke, witloof, salsify, Garden Dahlia stem tuber etc., wherein jerusalem artichoke is the main raw material source that synanthrin is produced.Jerusalem artichoke is commonly called as Jerusalem artichoke, Jerusalem artichoke, originates in North America, is per nnial herb, and China generally cultivates various places, and its stem tuber is rich in synanthrin, and total synanthrin content is generally 14～17%, and source is abundant, and cost is lower.
Synanthrin is as the margin of energy material of the plants such as jerusalem artichoke, it is the vegetable polysaccharides that a kind of safety non-toxic is easy to get, its high-valued exploitation, a large amount of functional products will be provided for us, its the high-valued enthusiasm that raising people are planted to littoral zone halophytes jerusalem artichoke of while, thus the life of seashore salt promoted with the reparation of environment.Yet the report about the utilization of this renewable resources is considerably less.Particularly when comparing compared with the polysaccharide of good utilisation degree with having of other.Such as: chitosan.Causing this renewable resources to utilize one of less reason is exactly there is no comparatively active group on the molecular structure of synanthrin.The exploitation of the several functions product of chitosan, makes us recognize that on synanthrin molecule, can have an amino is a very valuable compound intermediate.Can the improving by modification degree of the higher value application of synanthrin after introducing more active amino, such as forming hydrophilic quaternary ammonium salt, Schiff alkali by amino, the higher value application degree of the raising such as acid amides synanthrin.
Summary of the invention
In order to provide a kind of, modify, utilize the N-that degree is higher (ethylamino) synanthrin and preparation and application.
For achieving the above object, the technical solution adopted in the present invention is:
N-(ethylamino) synanthrin, is characterized in that: shown in (1),
The preparation of N-(ethylamino) synanthrin: synanthrin is reacted to 8-24h with anhydrous ethylenediamine after halo or SULPHURYL CHLORIDE esterification under 40-90 ℃ of condition, purified, obtain N-(ethylamino) synanthrin, the molar weight of described anhydrous ethylenediamine is 30 to 40 times of synanthrin.When reacting with anhydrous ethylenediamine, described synanthrin after halo or SULPHURYL CHLORIDE esterification reacts under the system as solvent at methyl-sulphoxide (DMSO).Describedly take methyl-sulphoxide during as solvent, described in to add the molar weight of anhydrous ethylenediamine be 2 to 4 times of synanthrin.Described halo is bromo or iodo, and described SULPHURYL CHLORIDE esterification is benzene sulfonyl esterification, tolysulfonyl esterification or the esterification of fluoroform sulphonyl.Described halo refers to: synanthrin and lithiumbromide, N-bromo-succinimide (NBS) and triphenylphosphine react the purified and freeze-dried back of 2-12h at 40-70 ℃.Described SULPHURYL CHLORIDE esterification refers to: synanthrin reacts 10-36h with SULPHURYL CHLORIDE in stirring at room, purified and freeze-dried back.Described purifying finishes after product by reaction separates out with acetone, then uses successively ether, washing with acetone, and then vacuum lyophilization, obtains N-(ethylamino) synanthrin.
Application: described N-(ethylamino) synanthrin has oxidation-resistance, and it can be used as antioxidant.
The present invention has advantages of:
(1) compare this compound with synanthrin and have following advantage: after introducing more active amino, the reactive behavior of product improves greatly, such as forming hydrophilic quaternary ammonium salt, Schiff alkali by amino, acid amides etc. improve the higher value application degree of synanthrin.
(2) on polysaccharide, modifying amino is a kind of important modification sugar, and organism is comprised to the mankind are vital.Such as: they play a crucial role in the structure of glycoprotein biologically and function; Many microbiotic are as aminoglycoside, and the realization of the antibacterial of Macrolide is all inseparable with function amino in polysaccharide.In addition containing amino polysaccharide, in application aspect, play an important role.Such as the exploitation of chitosan functional product, mostly by its amino of 2.
(3) on synthesis technique, this synthetic method has following advantage: synthesis step of the present invention is simple, and cost is lower, required equipment and raw material are easy to get.The substitution value of gained compound of the present invention is high, can reach 100%.The present invention is simultaneously connected to amino on synanthrin by stable C-N key, for Liao Yitiaoxin road is opened up in the research and development that synanthrin higher value application is modified.
Figure of description
Fig. 1 is the infrared spectrogram of synanthrin.
Fig. 2 is N-of the present invention (ethylamino) synanthrin infrared spectrogram.
Fig. 3 is N-of the present invention (ethylamino) synanthrin nuclear magnetic spectrogram.
Embodiment
N-(ethylamino) synanthrin is the compound shown in formula (1).
The preparation of N-(ethylamino) synanthrin: 1.62g synanthrin and 1.90g Tosyl chloride are dissolved in 30mL nitrogen dimethylformamide, at room temperature stirs companion's reaction 10h.After reaction finishes, reaction solution is inclined to 150mL acetone, separate out precipitation.Precipitation is through acetone, the lyophilize of tetrahydrofuran (THF) washing final vacuum, standby.Made product is tosylation synanthrin, obtains 3.2g, is dissolved in 22mL anhydrous ethylenediamine, and reacts 12h at 50 ℃.Reaction finishes with 100mL acetone, product to be separated out afterwards, uses respectively after ether, washing with acetone product, and-50 ℃ of vacuum-dryings obtain product.Products obtained therefrom is off-white powder, soluble in water, and its infrared spectrum is referring to Fig. 1 and Fig. 2, its with
13c NMR spectrum is shown in Fig. 3.
Wherein synanthrin (Inulin) by D-fructofuranose molecule with β-(2,1) glycosidic link connects generation, each synanthrin molecule end is with α-(1,2) glycosidic link connects a glucosyl residue, the polymerization degree is generally 10～35, mean polymerisation degree is 10, and the mean value of molecule is more lower slightly than starch, 4000-5000 left and right.Compare with synanthrin raw material as can be seen from Figure 2, the 1589cm-1 newly increasing and 1473 absorption peak are respectively the charateristic avsorption band of primary amino, and the methylene radical absorption peak newly increasing (Guo Chuzhen. carbohydrate chemistry [M]. Beijing: the 2005.106-108 of Chemical Industry Press).In synanthrin molecule, the stretching vibration of O-H obviously weakens in the INFRARED SPECTRUM of N-(ethylamino) synanthrin near the broad peak occurring 3386cm-1, be due to amino replace make hydroxyl reduce (Wei Lingyun. the separation and purification process of synanthrin is studied with functional product. Zhejiang University's doctorate paper).The chemical shift that is arranged in the C-6 of 60.1ppm from the known synanthrin raw material of figure tri-spectrum disappears at product, and in product, there is 42.3ppm, 56.4ppm, 49.7ppm, prove the OH quilt-NH-CH on the C-6 of synanthrin
2-CH
2-NH
2institute replaces (Liu, C., & Baumann, H. (2002) .Exclusive and complete introduction of amino groups and theirN-sulfo and N-carboxymethyl groups into the 6-position of cellulosewithout the use of protecting groups.Carbohydrate Research, 337 (14), 1297-1307).
Embodiment 2
Difference from Example 1 is:
(1) synanthrin, lithiumbromide are dried through 100 ℃, vacuum, 8h.Get 1.62g synanthrin, 0.86g lithiumbromide adds in the nitrogen dimethylformamide after 20mL purifying under the protection of nitrogen; be warming up to synanthrin, lithiumbromide dissolves completely, question response liquid temp adds 3.5g N-bromo-succinimide (NBS) in above-mentioned reaction solution while being down to room temperature.Take 5.2g triphenylphosphine dissolved to 10mL nitrogen dimethylformamide.This solution is at room temperature dropped in reaction solution. at room temperature after reaction solution reaction 30min, temperature of reaction system is warming up to 70 ℃. reaction is carried out after 3h, by reaction solution impouring 150mL acetone, separating out precipitation at 70 ℃.Precipitation, after suction filtration, washing with acetone, tetrahydrofuran (THF) washing, obtains bromo synanthrin 1.92g after-50 ℃ of vacuum lyophilizations, standby.
(2) the product bromo synanthrin 1.92g of step (1) gained is dissolved in 25mL anhydrous ethylenediamine, and reacts 10h at 70 ℃.Reaction finishes with 100mL acetone, product to be separated out afterwards, uses respectively after ether, washing with acetone product suction filtration, and-50 ℃ of vacuum-dryings obtain product.
Embodiment 3
Difference from Example 1 is: 1.62g synanthrin and 1.90g Tosyl chloride are dissolved in 30mL nitrogen dimethylformamide, under the catalysis of 3.7mL triethylamine, at room temperature stirs companion's reaction 6h.After reaction finishes, reaction solution is inclined to 150mL acetone, separate out precipitation.Precipitation obtains tolysulfonyl esterification synanthrin 3.0g through acetone, the lyophilize of tetrahydrofuran (THF) washing final vacuum.Made product is dissolved in 27mL anhydrous ethylenediamine, and reacts 10h at 70 ℃.Reaction finishes with 100mL acetone, product to be separated out afterwards, uses respectively after ether, washing with acetone product, and-50 ℃ of vacuum-dryings obtain product.
Embodiment 4
Difference from Example 1 is: by the step of embodiment one (1), prepare after tosylation synanthrin; be dissolved in the methyl-sulphoxide of 20mL; question response temperature adds 5mL anhydrous ethylenediamine after rising to 75 ℃, and reacts 18h at this temperature.Reaction finishes with 100mL acetone, product to be separated out afterwards, uses respectively after ether, washing with acetone product, and-50 ℃ of vacuum-dryings obtain product.
Above-described embodiment is preferably embodiment of the present invention; but the present invention is not all restricted to the described embodiments; change, the modification of making in the consistent situation of other any and the present invention essence, principle, substitute, combination all should be equivalent replacement mode, within being included in protection scope of the present invention.
Application examples is removed the mensuration of hydroxy radical qiao resistance of oxidation:
Measure respectively the ability of the N-(ethylamino) of synthesized and the removal hydroxy radical qiao of synanthrin and contrast: N-prepared by embodiment 1-3 (ethylamino) synanthrin and experiment use synanthrin vacuum lyophilization to constant weight, prepare respectively desired concn in table one, get prepared solution 1mL, phosphoric acid buffer 1mL (preparation phosphoric acid buffer: get respectively 41.58gNa
2hPO
412H
2o, 5.2887gNaH
2pO
42H
2o, adds water and is dissolved to 1000ml.), the sarranine 1ml of 360ug/m, 2mmol/LEDTA-Fe 0.5ml, sample liquid 1.0ml, 3% hydrogen peroxide 1ml, in test tube, mix, in 37 degree water-baths, react after 30min, working sample is in the absorbancy at 520nm place, and blank group 1ml distilled water substitutes test sample, control group 1.0ml distilled water and 1ml phosphoric acid buffer substitute sample and hydrogen peroxide (note: sample all surveys twice, averages).
Remove hydroxyl radicals (%) [(the blank 520nm of A sample 520nm-A)/(the blank 520nm of A contrast 520nm-A)] * 100
Experimental result: the removal hydroxyl radicals of the N-of synthesized (ethylamino) synanthrin and synanthrin is as shown in table 1, the removal hydroxyl radicals of synthesized N-(ethylamino) is obviously better than synanthrin
Table 1, the ability (%) of the removal hydroxy radical qiao of 0-(amino-ethyl) synanthrin and synanthrin
Claims (6)
1. N-(ethylamino) synanthrin, is characterized in that: shown in (1),
wherein the average span of n is 10-35.
2. the preparation method by N-claimed in claim 1 (ethylamino) synanthrin, it is characterized in that: synanthrin is reacted to 8-24h with anhydrous ethylenediamine after halo or SULPHURYL CHLORIDE esterification under 40-90 ℃ of condition, purified, obtain N-(ethylamino) synanthrin, the molar weight of described anhydrous ethylenediamine is 30 to 40 times of synanthrin;
Described halo refers to: synanthrin and lithiumbromide, N-bromo-succinimide and triphenylphosphine react the purified and freeze-dried back of 2-12h at 40-70 ℃;
Described SULPHURYL CHLORIDE esterification refers to: synanthrin reacts 10-36h with SULPHURYL CHLORIDE in stirring at room, purified and freeze-dried back.
3. by the preparation method of N-claimed in claim 2 (ethylamino) synanthrin, it is characterized in that: described synanthrin after halo or SULPHURYL CHLORIDE esterification reacts under the system as solvent at methyl-sulphoxide while reacting with anhydrous ethylenediamine.
4. by the preparation method of N-claimed in claim 3 (ethylamino) synanthrin, it is characterized in that: describedly take methyl-sulphoxide during as solvent, described in to add the molar weight of anhydrous ethylenediamine be 2 to 4 times of synanthrin.
5. by the preparation method of N-claimed in claim 2 (ethylamino) synanthrin, it is characterized in that: described purifying finishes after product by reaction and separates out with acetone, then use successively ether, washing with acetone, then vacuum lyophilization, obtains N-(ethylamino) synanthrin.
6. by an application for N-claimed in claim 1 (ethylamino) synanthrin, it is characterized in that: described N-(ethylamino) synanthrin is as antioxidant.
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| CN102060942B (en) * | 2010-11-22 | 2013-03-27 | 中国科学院烟台海岸带研究所 | 6-amino-6-deoxyinulin as well as preparation and application thereof |
| CN102500974B (en) * | 2011-11-23 | 2015-01-28 | 芜湖瑞创叉车有限公司 | Fixture for circumferential weld |
| CN102952208B (en) * | 2012-11-06 | 2014-11-19 | 中国科学院烟台海岸带研究所 | Amphiphilic amido inulin and preparation method thereof |
| CN108676040A (en) * | 2018-06-28 | 2018-10-19 | 中国科学院烟台海岸带研究所 | A kind of preparation method and application of 1,2,3- triazoles diphenyl phosphate synanthrin derivative |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367880A (en) * | 2008-09-05 | 2009-02-18 | 烟台海岸带可持续发展研究所 | Inulin quaternary ammonium salt, preparation and uses thereof |
| CN101366686A (en) * | 2008-09-05 | 2009-02-18 | 烟台海岸带可持续发展研究所 | Application of compound carboxymethyl inulin |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367880A (en) * | 2008-09-05 | 2009-02-18 | 烟台海岸带可持续发展研究所 | Inulin quaternary ammonium salt, preparation and uses thereof |
| CN101366686A (en) * | 2008-09-05 | 2009-02-18 | 烟台海岸带可持续发展研究所 | Application of compound carboxymethyl inulin |
Non-Patent Citations (3)
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| 栗衍华等.菊粉硫酸酯的制备及其抑真菌活性研究.《中国生化药物杂志》.2007,第28卷(第01期),14-16. * |
| 王争昱等.菊粉提取及羧甲基菊粉钠的制备.《郑州大学学报(医学版)》.2009,第44卷(第01期),192-194. * |
| 胡娟等.改性菊糖的制备及表面特性.《食品科学》.2007,第28卷(第11期),109-112. * |
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