CN102863555A - Chitosan sulfate schiff base and synthetic method thereof - Google Patents
Chitosan sulfate schiff base and synthetic method thereof Download PDFInfo
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- CN102863555A CN102863555A CN2012103620539A CN201210362053A CN102863555A CN 102863555 A CN102863555 A CN 102863555A CN 2012103620539 A CN2012103620539 A CN 2012103620539A CN 201210362053 A CN201210362053 A CN 201210362053A CN 102863555 A CN102863555 A CN 102863555A
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Abstract
The invention relates to the daily use chemical filed and the pharmaceuticals industry, in particular to chitosan sulfate schiff base and a synthetic method of chitosan sulfate schiff base. Chitosan sulfate schiff base is obtained by carrying sulfuric acid esterification on chitosan, and reacting amino in product obtained after sulfuric acid esterification with protocatechualdehyde to obtain chitosan sulfate schiff base shown in a formula (1), the obtained chitosan sulfate schiff base is soluble to water, strengthens biological activity of chitosan, has synergistic effects, expands application scope of chitosan and can be widely used in the daily use chemical filed such as medicines.
Description
Technical field
The present invention relates to household chemicals field and pharmaceutical industries, specifically a kind of sulfated chitosan schiff bases and synthetic method thereof.
Background technology
Chitosan (Chitosan) be a kind of extensively be present in occurring in nature renewable, have no side effect, the natural glycosaminoglycan that biocompatibility and degradation property are good, himself and derivative thereof have physiology, the pharmacological function character of many uniquenesses, are widely used in the multiple industry fields such as medicine, food, agricultural, daily use chemicals, environmental protection.The structure that chitosan itself is special and character have sterilization, bacteriostatic activity, and nontoxic, free of contamination characteristic, can be used as the object of modification to developing the secondary lead compound.Sulfated chitosan is compared with chitosan except having multiple better biological activity, also have extraordinary water-soluble, but the product that seldom has pair sulfated chitosan further to modify.So, chitosan is further modified, have very large DEVELOPMENT PROSPECT.
Rancinamycin IV is a kind of active compound that contains phenolic hydroxyl group that mainly extracts from plant, and good antibacterial, anti-oxidant isoreactivity is arranged.Can widespread use in food, medicine, the industry of change shape product.But because molecular weight is low, so that the rancinamycin IV poor stability.Existing bibliographical information can improve its stability with on the small molecule active compound access macromolecular compound, plays synergism, enlarges its range of application.
Chitosan also has certain oxidation-resistance as polyol itself simultaneously, and sulfated chitosan is compared with chitosan except having better oxidation-resistance, also has these characteristics of good aqueous solubility.For the oxidation-resistance of Tri-methyl Quaternary Ammonium Salt of Chitosan, access has the active group of good oxidation resistance, is expected to obtain more highly active chitosan derivatives.
Summary of the invention
The object of the invention is to provide a kind of sulfated chitosan schiff bases and synthetic method and application.
For achieving the above object, the technical solution used in the present invention is:
A kind of sulfated chitosan schiff bases, sulfated chitosan schiff bases are by the chitosan sulfate esterification, and amino reacts gained with rancinamycin IV behind the sulphating, as the formula (1),
The synthetic method of sulfated chitosan schiff bases, at first chitosan carries out sulphating, amino and rancinamycin IV are to react 1-8h under with 20-60 ℃ of conditions in the 20%-100% ethanolic soln in excessive concentration on the sulphating after product, namely get the sulfated chitosan schiff bases behind the purifying; The molar weight of described rancinamycin IV is 1-3 times of sulfated chitosan.
In the building-up process; at first chitosan 2 bit aminos are protected through Tetra hydro Phthalic anhydride; with excessive esterifying agent with 3 of chitosan with 6 whole sulphatings of hydroxyl; secondly the sulphating after product is removed the protection of 2 bit aminos; to remove at last sulphating after product and the rancinamycin IV reaction of the protection of 2 bit aminos, namely get the sulfated chitosan schiff bases.
Described chitosan molecule amount is between 1-70 ten thousand, and deacetylation is 80-100%.
The advantage that the present invention has is: gained compound sulfated chitosan schiff bases of the present invention is compared with chitosan, and its oxidation-resistance is greatly improved.Because rancinamycin IV is exactly that good oxidation-resistance is just arranged, and its access during sulfated chitosan, is not destroyed active function groups-phenolic hydroxyl group that it mainly plays oxidation-resistance, so can put forward the oxidation-resistance of doing chitosan.More than strengthened the chitosan biological activity, and the water capacity, play synergism, enlarged its Application Areas, can be in household chemicals field widespread uses such as food, change shape product.
Simultaneously simple in synthesis technique step of the present invention, cost is lower, required equipment and raw material are easy to get.
Description of drawings
The synthetic route chart that Fig. 1 provides for the embodiment of the invention.
The infrared spectrogram of the chitosan that Fig. 2 provides for the embodiment of the invention.
Fig. 3 provides the sulfated chitosan infrared spectrogram for the embodiment of the invention.
Fig. 4 provides the infrared spectrogram of sulfated chitosan rancinamycin IV schiff bases for the embodiment of the invention.
Embodiment
The invention will be further described with way of example again for the below, provides implementation detail of the present invention, but be not intended to limit protection scope of the present invention.
Sulfated chitosan rancinamycin IV schiff bases is compound shown in (formula 1)
Synthetic route
The present embodiment is by the synthetic target compound of above synthetic route.
(1) synthetic compound (): under nitrogen protection, 5g chitosan and 10g phthalic acid are intoxicated with 120mL 95%N, react 8h in the N-dimethylformamide solvent, and temperature of reaction is 120 ℃.Reaction in reaction solution impouring 1000mL mixture of ice and water, is separated out product after finishing.Products therefrom is after using dehydrated alcohol soxhlet extraction purifying 72h, and 60 ℃ of vacuum-dryings get compound () 8.5g.
(2) synthetic compound (two): 10m L chlorsulfonic acid is added dropwise in the 60mL pyridine, and reaction is after 40 minutes in ice-water bath, and reacting liquid temperature is increased to 100 ℃.Get 5g compound () again and add to wherein, and react 3h under 100 ℃ of conditions, reaction is cooled to room temperature after finishing.In the reaction solution impouring 200mL water, behind the abundant mixing of question response liquid and water, gained solution is poured in the 500mL dehydrated alcohol, compound (two) separate out.Products therefrom is after washing twice with dehydrated alcohol, and 60 ℃ of vacuum-dryings get compound (two) 7.3g.
(3) synthetic compound (three): 5g compound (two) is dissolved in that (commercially available water ammonia hydrazine solution is 85% in the 100mL 20% hydrazine hydrate solution; after diluting 4.25 times; get final product); under the protection of nitrogen; under 100 ℃ of conditions, react 4h; after reaction finished, in the reaction solution impouring 400mL dehydrated alcohol, product was separated out.Products therefrom is after using dehydrated alcohol soxhlet extraction purifying 72h, and 60 ℃ of vacuum-dryings get compound (three) 2.4g.
(4) synthetic compound sulfated chitosan rancinamycin IV schiff bases: 2g compound (three) is scattered in the 100mL10% ethanolic soln with the 1.5g rancinamycin IV, under 25 ℃ of conditions, react 2h, after the reaction end, in the reaction solution impouring 500mL dehydrated alcohol, product is separated out.Products therefrom is after using dehydrated alcohol soxhlet extraction purifying 72h, and 60 ℃ of vacuum-dryings get product 2.6g.Products made thereby is buff powder, and is soluble in water.
Fig. 2 is that deacetylation is that 90% chitosan: 3421.10cm-1 is the stretching vibration absorption peak of O-H and N-H, 2881.13cm-1 be the absorption peak of C-H stretching vibration, 1600.63cm-1 be the flexural vibration absorption peak of NH2,1076.09cm-1 with 1153.22cm-1 be the absorption peak of C-O stretching vibration, 898.85cm-1 for stretching vibration absorption peak Fig. 3 of chitosan six-ring is the infrared spectrogram of sulfated chitosan: compared to Figure 1 1253cm-1 is the sulfuric acid vibration and receives the peak, and 786cm-1 is C-O-S vibration absorption peak and 1608 amino vibration peak are kept.Fig. 4 is that the infrared spectrogram of sulfated chitosan rancinamycin IV schiff bases: 1639.20cm-1 is the charateristic avsorption band of schiff bases.1519.92cm
-1, 690.25cm
-1Charateristic avsorption band for benzene.The formation of above proof target compound.
Embodiment 2
Difference from Example 1 is:
Synthetic compound sulfated chitosan rancinamycin IV schiff bases: 2g compound (three) and 2g rancinamycin IV are scattered in 100mL 30% ethanolic soln, react 3h under 30 ℃ of conditions, wait reaction to finish after, in the reaction solution impouring 500mL dehydrated alcohol, product is separated out.Products therefrom is after using dehydrated alcohol soxhlet extraction purifying 72h, and 60 ℃ of vacuum-dryings get product 2.6g.
Embodiment 3
Difference from Example 1 is:
Synthetic compound sulfated chitosan rancinamycin IV schiff bases: 2g compound (three) is scattered in 100mL 100% ethanolic soln with the 2.5g rancinamycin IV, under 25 ℃ of conditions, react 3h, after the reaction end, in the reaction solution impouring 500mL dehydrated alcohol, product is separated out.Products therefrom is after using dehydrated alcohol soxhlet extraction purifying 72h, and 60 ℃ of vacuum-dryings get product 2.6g.
Application examples
Remove the mensuration of hydroxy radical qiao resistance of oxidation:
Measure respectively the gallic acid chitosan trimethylammonium quaternary amine synthesized and chitosan trimethylammonium quaternary amine the removal hydroxy radical qiao ability and do contrast:
The product of embodiment 1-3 preparation and Tri-methyl Quaternary Ammonium Salt of Chitosan vacuum lyophilization to constant weight, are prepared respectively desired concn in the table one, get the solution 1mL, the phosphoric acid buffer 1mL(that prepare and prepare 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-Fe0.5ml, 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 test sample, control group 1.0ml distilled water and 1ml phosphoric acid buffer substitute sample and hydrogen peroxide (annotate: 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: above-described embodiment the removal hydroxyl radicals of synthetic sulfated chitosan rancinamycin IV schiff bases and chitosan as shown in table 1, the removal hydroxyl radicals of the sulfated chitosan rancinamycin IV schiff bases of being synthesized obviously is better than chitosan.
Table 1, the ability (%) of the removal hydroxy radical qiao of chitosan and sulfated chitosan rancinamycin IV schiff bases
Claims (3)
1. sulfated chitosan schiff bases is characterized in that: the sulfated chitosan schiff bases is by the chitosan sulfate esterification, amino and rancinamycin IV reaction gained behind the sulphating, as the formula (1),
2. the synthetic method of a sulfated chitosan schiff bases claimed in claim 1, it is characterized in that: at first chitosan carries out sulphating, amino and rancinamycin IV are to react 1-8h under with 20-60 ℃ of conditions in the 20%-100% ethanolic soln in excessive concentration behind the sulphating, namely get the sulfated chitosan schiff bases behind the purifying; The molar weight of described rancinamycin IV is 1-3 times of sulfated chitosan.
3. by the synthetic method of sulfated chitosan schiff bases claimed in claim 2, it is characterized in that: described chitosan molecule amount is between 1-70 ten thousand, and deacetylation is 80-100%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231112A (en) * | 2014-04-29 | 2014-12-24 | 深圳大学 | Synthesis method of 6-O-carboxymethyl chitosan sulfuric sulfation product |
| CN104530259A (en) * | 2015-01-14 | 2015-04-22 | 皖西学院 | Chitosan type Schiff base, preparing method thereof and feather cleaning deodorant based on same |
| CN106832058A (en) * | 2017-03-07 | 2017-06-13 | 陕西科技大学 | A kind of O succinic acid Chitosan Schiff-base and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104231112A (en) * | 2014-04-29 | 2014-12-24 | 深圳大学 | Synthesis method of 6-O-carboxymethyl chitosan sulfuric sulfation product |
| CN104231112B (en) * | 2014-04-29 | 2016-03-23 | 深圳大学 | A kind of synthetic method of CARB OXYMETHYL-CHITOSAN sulfation product |
| CN104530259A (en) * | 2015-01-14 | 2015-04-22 | 皖西学院 | Chitosan type Schiff base, preparing method thereof and feather cleaning deodorant based on same |
| CN104530259B (en) * | 2015-01-14 | 2017-01-11 | 皖西学院 | Chitosan type Schiff base, preparing method thereof and feather cleaning deodorant based on same |
| CN106832058A (en) * | 2017-03-07 | 2017-06-13 | 陕西科技大学 | A kind of O succinic acid Chitosan Schiff-base and preparation method thereof |
| CN106832058B (en) * | 2017-03-07 | 2019-06-07 | 陕西科技大学 | A kind of O- succinic acid Chitosan Schiff-base and preparation method thereof |
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