CN101824102A - N-(ethylamino) inulin and preparation and application thereof - Google Patents
N-(ethylamino) inulin and preparation and application thereof Download PDFInfo
- Publication number
- CN101824102A CN101824102A CN 201010163998 CN201010163998A CN101824102A CN 101824102 A CN101824102 A CN 101824102A CN 201010163998 CN201010163998 CN 201010163998 CN 201010163998 A CN201010163998 A CN 201010163998A CN 101824102 A CN101824102 A CN 101824102A
- Authority
- CN
- China
- Prior art keywords
- synanthrin
- ethylamino
- preparation
- inulin
- esterification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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, specifically is a kind of N-(ethylamino) synanthrin and preparation and application.
Background technology
Synanthrin (Inulin) is called inulin again, is a kind of biological polyoses.Connect generation by D-fructofuranose molecule with β-(2,1) glycosidic link, 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 mainly still be 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, China's various places common cultivated, and its stem tuber is rich in synanthrin, and total synanthrin content is generally 14～17%, and the source is abundant, and cost is lower.
Synanthrin is as the margin of energy material of plants such as jerusalem artichoke, it is the vegetable polysaccharides that a kind of safety non-toxic is easy to get, its high-valued development and use, to provide a large amount of functional products for us, the high-valued of it will be improved the enthusiasm that people plant littoral zone halophytes jerusalem artichoke simultaneously, thereby promote the reparation that seashore salt is given birth to the band border.Yet the report about the utilization of this renewable resources is considerably less.Particularly when with other have than the polysaccharide of good utilisation degree relatively the time.Such as: chitosan.Causing this renewable resources to utilize one of less reason is exactly comparatively active group not on the molecular structure of synanthrin.The exploitation of the multiple functional product of chitosan makes us recognize that it is a very valuable compound intermediate that an amino can be arranged on the synanthrin molecule.But the modification degree at the higher value application of introducing more active amino back synanthrin improves, and such as passing through amino hydrophilic quaternary ammonium salt, the Schiff alkali of forming, acid amides etc. improve the higher value application degree of synanthrin.
Summary of the invention
Modify, utilize the higher N-of degree (ethylamino) synanthrin and preparation and application in order to provide a kind of.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of N-(ethylamino) synanthrin is characterized in that: as the formula (1),
Wherein the average span of n is 10-35.
The preparation of N-(ethylamino) synanthrin: synanthrin is through reacting 8-24h with anhydrous ethylenediamine under 40-90 ℃ of condition after halo or the SULPHURYL CHLORIDE esterification, purified, promptly obtain N-(ethylamino) synanthrin, the molar weight of described anhydrous ethylenediamine is 30 to 40 times of synanthrin.Described synanthrin and anhydrous ethylenediamine reaction after halo or SULPHURYL CHLORIDE esterification the time reacted under the system of methyl-sulphoxide (DMSO) as solvent.Described when being solvent with the methyl-sulphoxide, the molar weight of described adding anhydrous ethylenediamine is 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 is meant: synanthrin and lithiumbromide, N-bromo-succinimide (NBS) and triphenylphosphine are 40-70 ℃ of purified and freeze-dried back of reaction 2-12h.Described SULPHURYL CHLORIDE esterification is meant: synanthrin and SULPHURYL CHLORIDE are reacted 10-36h in stirring at room, purified and freeze-dried back.Described purifying will react the end after product separates out with acetone, then uses ether, washing with acetone successively, and then vacuum lyophilization gets N-(ethylamino) synanthrin.
Use: described N-(ethylamino) synanthrin has oxidation-resistance, and it can be used as antioxidant.
The advantage that the present invention had:
(1) compare this compound with synanthrin following advantage is arranged: after introducing more active amino, the reactive behavior of product improves greatly, and such as forming hydrophilic quaternary ammonium salt, Schiff alkali by amino, acid amides etc. improve the higher value application degree of synanthrin.
(2) modifying amino on the polysaccharide is a kind of important modification sugar, and organism is comprised that the mankind are vital.Such as: they play a crucial role in the structure of biologically glycoprotein and function; Many microbiotic such as aminoglycoside, the realization of the antibacterial of Macrolide are all inseparable with the function of amino in the polysaccharide.Containing amino polysaccharide in addition plays an important role in application facet.Such as the exploitation of chitosan functional product, mostly by its amino of 2.
(3) this synthetic method has following advantage on synthesis technique: synthesis step of the present invention is simple, and cost is lower, required equipment and raw material are easy to get.The substitution value height of gained compound of the present invention can reach 100%.The present invention simultaneously is connected to amino on the synanthrin by stable C-N key, for a new road has been opened up in the research and development that the 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
Embodiment 1
N-(ethylamino) synanthrin is the compound shown in the formula (1).
The preparation of N-(ethylamino) synanthrin: 1.62g synanthrin and 1.90g Tosyl chloride are dissolved in the 30mL nitrogen dimethylformamide, at room temperature stir companion's reaction 10h.Reaction is inclined reaction solution to 150mL acetone after finishing, and separates out precipitation.Precipitation is through acetone, the lyophilize of tetrahydrofuran (THF) washing final vacuum, and is standby.Made product is the tosylation synanthrin, gets 3.2g, it is dissolved in the 22mL anhydrous ethylenediamine, and reacts 12h down at 50 ℃.Reaction finishes the back separates out product with 100mL acetone, use ether, washing with acetone product respectively after ,-50 ℃ of vacuum-dryings promptly get product.Products obtained therefrom is off-white powder, and is soluble in water, and its infrared spectrum is referring to Fig. 1 and Fig. 2, its with
13C NMR spectrum is seen 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, about 4000-5000.Compare with the synanthrin raw material as can be seen from Figure 2,1589cm-1 that increases newly and 1473 absorption peak are respectively the charateristic avsorption band of primary amino and the methylene radical absorption peak that increases newly (Guo Chuzhen. carbohydrate chemistry [M]. Beijing: the 2005.106-108 of Chemical Industry Press).The stretching vibration of O-H obviously weakens in the INFRARED SPECTRUM of N-(ethylamino) synanthrin near the broad peak that occurs the 3386cm-1 in the synanthrin molecule, be since 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 figure three as can be known the synanthrin raw material spectrum disappears at product, and 42.3ppm appears in product, 56.4ppm, 49.7ppm, prove the OH quilt-NH-CH on the C-6 of synanthrin
2-CH
2-NH
2Replace (Liu, C. ， ﹠amp; 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 through 100 ℃ in vacuum, 8h drying.Get in the nitrogen dimethylformamide 1.62g synanthrin, 0.86g lithiumbromide add to the 20mL purifying under protection of nitrogen gas after; be warming up to synanthrin, lithiumbromide dissolves fully, the question response liquid temp adds 3.5g N-bromo-succinimide (NBS) to the above-mentioned reaction solution when reducing to room temperature.Take by weighing the 5.2g triphenylphosphine dissolved to the 10mL nitrogen dimethylformamide.This solution is at room temperature dropped in the reaction solution. at room temperature behind the reaction solution reaction 30min temperature of reaction system is warming up to 70 ℃. be reflected at and carry out under 70 ℃ behind the 3h separating out precipitation in the reaction solution impouring 150mL acetone.Precipitation gets bromo synanthrin 1.92g after-50 ℃ of vacuum lyophilizations after suction filtration, washing with acetone, tetrahydrofuran (THF) washing, standby.
(2) the product bromo synanthrin 1.92g with step (1) gained is dissolved in the 25mL anhydrous ethylenediamine, and reacts 10h down at 70 ℃.Reaction finishes the back separates out product with 100mL acetone, use ether, washing with acetone product and suction filtration respectively after ,-50 ℃ of vacuum-dryings promptly get product.
Embodiment 3
Difference from Example 1 is: 1.62g synanthrin and 1.90g Tosyl chloride are dissolved in the 30mL nitrogen dimethylformamide, under the catalysis of 3.7mL triethylamine, at room temperature stir companion's reaction 6h.Reaction is inclined reaction solution to 150mL acetone after finishing, and separates out precipitation.Precipitation gets tolysulfonyl esterification synanthrin 3.0g through acetone, the lyophilize of tetrahydrofuran (THF) washing final vacuum.Made product is dissolved in the 27mL anhydrous ethylenediamine, and reacts 10h down at 70 ℃.Reaction finishes the back separates out product with 100mL acetone, use ether, washing with acetone product respectively after ,-50 ℃ of vacuum-dryings promptly get product.
Embodiment 4
Difference from Example 1 is: after pressing step (1) the preparation tosylation synanthrin of embodiment one, it is dissolved in the methyl-sulphoxide of 20mL, adds the 5mL anhydrous ethylenediamine after the question response temperature rises to 75 ℃, and react 18h under this temperature.Reaction finishes the back separates out product with 100mL acetone, use ether, washing with acetone product respectively after ,-50 ℃ of vacuum-dryings promptly get product.
The foregoing description is a preferred implementation of the present invention; but the present invention all is not restricted to the described embodiments; change, the modification of being made under the consistent situation of other essence any and of the present invention, principle, substitute, combination all should be the equivalent replacement mode, be included within protection scope of the present invention.
Application examples is removed the mensuration of hydroxy radical qiao resistance of oxidation:
Measure respectively the synthetic N-of institute (ethylamino) and synanthrin the removal hydroxy radical qiao ability and do contrast: with N-(ethylamino) synanthrin of embodiment 1-3 preparation and experiment with the synanthrin vacuum lyophilization to constant weight, prepare desired concn in the table one respectively, get solution 1mL, phosphoric acid buffer 1mL (the preparation phosphoric acid buffer of being prepared: get 41.58gNa respectively
2HPO
412H
2O, 5.2887gNaH
2PO
42H
2O, it is fixed molten to 1000ml to add water.), the sarranine 1ml of 360ug/m, 2mmol/LEDTA-Fe 0.5ml, sample liquid 1.0ml, 3% hydrogen peroxide 1ml, mixing in test tube, behind the reaction 30min, working sample is in the absorbancy at 520nm place in 37 degree water-baths, and blank group 1ml distilled water substitutes for test agent, control group 1.0ml distilled water and 1ml phosphoric acid buffer substitute sample and hydrogen peroxide (annotate: sample all surveys twice, averages).
Remove hydroxy radical qiao ability (%) [(the blank 520nm of A sample 520nm-A)/(the blank 520nm of A contrast 520nm-A)] * 100
Experimental result: the removal hydroxy radical qiao ability of the synthetic N-of institute (ethylamino) synanthrin and synanthrin is as shown in table 1, synthesize N-(ethylamino) removal hydroxy radical qiao ability obviously be better than synanthrin
Table 1, the ability (%) of the removal hydroxy radical qiao of 0-(amino-ethyl) synanthrin and synanthrin
Claims (9)
1. a N-(ethylamino) synanthrin is characterized in that: as the formula (1),
2. preparation by the described N-of claim 1 (ethylamino) synanthrin, it is characterized in that: with synanthrin through under 40-90 ℃ of condition, reacting 8-24h with anhydrous ethylenediamine after halo or the SULPHURYL CHLORIDE esterification, purified, promptly obtain N-(ethylamino) synanthrin, the molar weight of described anhydrous ethylenediamine is 30 to 40 times of synanthrin.
3. by the preparation of the described N-of claim 2 (ethylamino) synanthrin, it is characterized in that: described synanthrin after halo or SULPHURYL CHLORIDE esterification reacts under the system of methyl-sulphoxide as solvent when reacting with anhydrous ethylenediamine.
4. by the preparation of the described N-of claim 3 (ethylamino) synanthrin, it is characterized in that: described when being solvent with the methyl-sulphoxide, the molar weight of described adding anhydrous ethylenediamine is 2 to 4 times of synanthrin.
5. by the preparation of claim 2 or 3 described N-(ethylamino) synanthrin, it is characterized in that: described halo is bromo or iodo, and described SULPHURYL CHLORIDE esterification is benzene sulfonyl esterification, tolysulfonyl esterification or the esterification of fluoroform sulphonyl.
6. by the preparation of the described N-of claim 5 (ethylamino) synanthrin, it is characterized in that: described halo is meant: synanthrin and lithiumbromide, N-bromo-succinimide (NBS) and triphenylphosphine are 40-70 ℃ of purified and freeze-dried back of reaction 2-12h.
7. by the preparation of the described N-of claim 5 (ethylamino) synanthrin, it is characterized in that: described SULPHURYL CHLORIDE esterification is meant: synanthrin and SULPHURYL CHLORIDE are reacted 10-36h in stirring at room, purified and freeze-dried back.
8. by the described N-of claim 2 (ethylamino) synanthrin preparation method, it is characterized in that: described purifying will react the end after product separates out with acetone, then uses ether, washing with acetone successively, and then vacuum lyophilization gets N-(ethylamino) synanthrin.
9. application by the described N-of claim 1 (ethylamino) synanthrin, it is characterized in that: described N-(ethylamino) synanthrin can be used as antioxidant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010163998.9A CN101824102B (en) | 2010-04-27 | 2010-04-27 | N-(ethylamino) inulin and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010163998.9A CN101824102B (en) | 2010-04-27 | 2010-04-27 | N-(ethylamino) inulin and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101824102A true CN101824102A (en) | 2010-09-08 |
| CN101824102B CN101824102B (en) | 2014-04-16 |
Family
ID=42688285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010163998.9A Active CN101824102B (en) | 2010-04-27 | 2010-04-27 | N-(ethylamino) inulin and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101824102B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060942A (en) * | 2010-11-22 | 2011-05-18 | 中国科学院烟台海岸带研究所 | 6-amino-6-deoxyinulin as well as preparation and application thereof |
| CN102500974A (en) * | 2011-11-23 | 2012-06-20 | 芜湖瑞创叉车有限公司 | Fixture for circumferential weld |
| CN102952208A (en) * | 2012-11-06 | 2013-03-06 | 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 |
-
2010
- 2010-04-27 CN CN201010163998.9A patent/CN101824102B/en active Active
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)
| Title |
|---|
| 《中国生化药物杂志》 20070330 栗衍华等 菊粉硫酸酯的制备及其抑真菌活性研究 14-16 1-9 第28卷, 第01期 2 * |
| 《郑州大学学报(医学版)》 20090120 王争昱等 菊粉提取及羧甲基菊粉钠的制备 192-194 1-9 第44卷, 第01期 2 * |
| 《食品科学》 20071115 胡娟等 改性菊糖的制备及表面特性 109-112 1-9 第28卷, 第11期 2 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060942A (en) * | 2010-11-22 | 2011-05-18 | 中国科学院烟台海岸带研究所 | 6-amino-6-deoxyinulin as well as preparation and application thereof |
| 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 |
| CN102500974A (en) * | 2011-11-23 | 2012-06-20 | 芜湖瑞创叉车有限公司 | Fixture for circumferential weld |
| CN102952208A (en) * | 2012-11-06 | 2013-03-06 | 中国科学院烟台海岸带研究所 | Amphiphilic amido inulin and preparation method thereof |
| WO2014071593A1 (en) * | 2012-11-06 | 2014-05-15 | 中国科学院烟台海岸带研究所 | Amphiphilic amino inulin and preparation method therefor |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101824102B (en) | 2014-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102060942B (en) | 6-amino-6-deoxyinulin as well as preparation and application thereof | |
| CN102952208B (en) | Amphiphilic amido inulin and preparation method thereof | |
| CN103360499B (en) | Simple synthesis process of cellulose sulfate | |
| CN102558568B (en) | Method for preparing chitosan bearing cyclodextrin derivative | |
| CN101824102B (en) | N-(ethylamino) inulin and preparation and application thereof | |
| CN111234047B (en) | Exopolysaccharide rich in fucose and preparation method and application thereof | |
| Ren et al. | Highly efficient synthesis and antioxidant activity of O-(aminoethyl) inulin | |
| Lim et al. | Enzymatic synthesis of amylose nanocomposite microbeads using amylosucrase from Deinococcus geothermalis | |
| Chen et al. | Synthesis and characterization of quaternized β-chitin | |
| CA2142437A1 (en) | Thermoplastic biodegradable polysaccharide derivatives, process for the manufacture thereof and use thereof | |
| CN102702362A (en) | Preparation method of bacterial cellulose sulfate ester | |
| CN103755841B (en) | A kind of Aminopyridine type acetyl synanthrin and preparation method thereof | |
| CN106496339B (en) | One kettle way prepares low viscosity, high-intensitive hydroxypropyl starch ether | |
| CN100384883C (en) | Method for preparing chitose graft polycaprolactone | |
| CN102942691B (en) | Synthetic method of hemicellulose graft polypropylene oxide | |
| CN101709096B (en) | O-(amino ethyl) inulin and preparation and application thereof | |
| CN103694377B (en) | A kind of amphipathic C-6-(4-(methylamino)-1,2,3-triazoles) deoxidation synanthrin derivative and Synthesis and applications thereof | |
| CN108676105A (en) | A kind of synanthrin triazolium salt and its preparation method and application | |
| JP2010013549A (en) | Carboxylethyl cellulose | |
| EP1497335A2 (en) | Chitosan production | |
| CN111548512B (en) | Method for preparing dendritic hydrogel based on cyclodextrin-based metal-organic framework | |
| US20170002389A1 (en) | Method of preparing seaweed-derived galactose using agarase | |
| WO2015182445A1 (en) | Method for producing saccharide derivative, modified saccharide derivative, and modified saccharide derivative composition | |
| CN102061000A (en) | Method for dissolving bacterial cellulose with high polymerization degree | |
| Suhaimi et al. | Synthesis and physicochemical characterization of cationic polymeric surfactant from Dioscorea pyrifolia Starch |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |