CN102516413A - Furyl alpha-aminophosphonate chitosan derivative and its preparation method - Google Patents
Furyl alpha-aminophosphonate chitosan derivative and its preparation method Download PDFInfo
- Publication number
- CN102516413A CN102516413A CN2011104105117A CN201110410511A CN102516413A CN 102516413 A CN102516413 A CN 102516413A CN 2011104105117 A CN2011104105117 A CN 2011104105117A CN 201110410511 A CN201110410511 A CN 201110410511A CN 102516413 A CN102516413 A CN 102516413A
- Authority
- CN
- China
- Prior art keywords
- furyl
- chitosan
- ester
- preparation
- jilinsuan
- 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
- 0 CC([C@](C1O)NC(c2ccc[o]2)P(O*)(O*)=O)OC(CO)[C@]1OC Chemical compound CC([C@](C1O)NC(c2ccc[o]2)P(O*)(O*)=O)OC(CO)[C@]1OC 0.000 description 1
Images
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
Belonging to ocean chemical engineering technologies, the invention specifically relates to a furyl alpha-aminophosphonate chitosan derivative and its preparation method. The general formula of the derivative is shown as formula I, wherein, R is an alkyl group and n=4-4000. The preparation method comprises: taking chitosan as a matrix, which is mixed with dialkyl phosphite and furfural, and conducting reaction at a temperature of 0-120DEG C and under microwave power of 10-1000W for 1-60min, immersing the reactant with a solvent, then conducting pumping filtration, washing the filter cake with the solvent, and carrying out drying so as to obtain the furyl alpha-amidophosphonate chitosan derivative. Specifically, the chitosan, the dialkyl phosphite and the furfural are in a molar ratio of 1:1-3:1-3. In the invention, furyl alpha-aminophosphonate is introduced into a chitosan structure, and the two generate synergistic effects, thus significantly improving the antibacterial activity of chitosan.
Description
Technical field
The invention belongs to the marine chemical industry engineering, be specifically related to a kind of furyl α-An Jilinsuan ester chitosan derivatives and preparation method thereof.
Background technology
The advantage of chemical pesticide is that control is timely, and remarkably productive, easy to use, use cost is low.But shortcoming is also very obvious, mainly is the target poor selectivity, and toxicity is high, and is big to environmental influence, is easy to generate resistance, and the unreasonable use owing to chemical pesticide has caused certain detrimentally affect in addition, thereby chemical pesticide has been proposed stricter requirement.Impel the more friendly biological pesticide of people's development environment, to satisfy the demand of agriculture prodn.
Chitosan is the alkaline polysaccharide that occurring in nature exists, its good biocompatibility, nontoxic, the easy degraded, thereby receive extensive concern in many fields such as food, medicine, agriculturals.But chitosan is water insoluble and OOS, causes its range of application to receive than limitations, so improve the important directions that its solvability is the chitosan application and development.And contain-NH in the chitosan molecule structure
2With-OH, have bigger structural modification space.
The microwave current synthetic technology is widely used at chemical field.Compare with traditional heating mode, the fast and homogeneous heating of microwave heating speed has shortened and has handled the used time of material, has saved the energy, and experimental installation is simple, safety, environmental protection.
α-An Jilinsuan fat is as the analogue of natural amino acid, discovers that it has multiple biological activitys such as Antiphytoviral, weeding, plant growth regulating, inhibitory enzyme activity, sterilization, anticancer, anti-oxidant activity, has caused the many concerns of People more and more.
Summary of the invention
The present invention is exactly to the problems referred to above, and a kind of good water solubility, novel structure, a kind of furyl α-An Jilinsuan ester chitosan derivatives that bacteriostatic activity is good and preparation method thereof are provided.
To achieve these goals, the technical scheme of the present invention's employing is:
A kind of furyl α-An Jilinsuan ester chitosan derivatives, its general formula be suc as formula shown in the I,
Among the formula I, R is an alkyl; N=4-4000.
R is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, amyl group.The preparation method of furyl α-An Jilinsuan ester chitosan derivatives; With the chitosan is parent, mixes with dialkyl phosphite and furfural, at 0-120 ℃; The 10-1000W microwave power reacted 1-60 minute down; Reactant is suction filtration behind solvent soaking, and filter cake is used solvent wash, obtains furyl α-An Jilinsuan ester chitosan derivatives after the drying; Wherein, the mol ratio of chitosan and dialkyl phosphite, furfural is 1: 1-3: 1-3.
Said dialkyl phosphite is dimethylphosphite, diethyl phosphite, phosphorous acid di ester, phosphorous acid diisopropyl ester, phosphorous acid di-n-butyl ester, phosphorous acid diisobutyl ester, phosphorous acid diamyl ester.
The solvent of said immersion reactant and the solvent of washing leaching cake are one or more in acetone, ethanol, the methyl alcohol.
Said washing back filter cake carries out drying under 50-60 ℃.
The advantage that the present invention had:
On dialkyl phosphite, furfural and the chitosan C2 position-NH
2React and generate a type mannich reaction generation furyl α-An Jilinsuan ester chitosan derivatives; The verivate of gained is confirmed its structure through IR spectroscopy, and chitosan combines to generate furyl α-An Jilinsuan ester derivative verivate effectively with the group of access.
2. introduce furyl α-An Jilinsuan ester group in the chitosan structure of the present invention, both produce synergistic function, have significantly improved the bacteriostatic activity of chitosan.
3. the chitosan furyl α-An Jilinsuan ester derivative of the present invention's preparation has good solubility, dissolves in multiple solvent, has solved the poorly soluble problem of chitosan, has enlarged its Application Areas, at pesticide field the potential using value is arranged.
4. the present invention adopts solvent-free microwave to synthesize chitosan furyl α-An Jilinsuan ester derivative, has avoided the use of organic solvent, and simultaneously microwave method is compared chemical method and had shorter, more save energy, the characteristics of environmental protection more of reaction times.
Description of drawings
The infrared spectrogram of the chitosan that Fig. 1 provides for the embodiment of the invention, its infrared signature absorbs (cm
-1): 3363,2883,1656,1595,1150,1075,1027,892.
The infrared spectrogram of the chitosan derivatives 1 that Fig. 2 provides for the embodiment of the invention, its infrared signature absorbs (cm
-1): 3434,1650,1538,1384,1201,1060,989,892,777.
The infrared spectrogram of the chitosan derivatives 2 that Fig. 3 provides for the embodiment of the invention, its infrared signature absorbs (cm
-1): 3425,1648,1535,1388,1155,1070,1022,993,921.
Embodiment
Below in conjunction with Figure of description the present invention is described further, and protection scope of the present invention not only is confined to following examples.
The preparation of embodiment 1 verivate 1
With 10 mmole molecular weight is that 230,000 chitosan, 10 mmole dimethylphosphites and 10 mmole furfurals join in the agate mortar, and ground and mixed is even, in microwave reactor; Down reaction 3 minutes of 200W, reaction product is with alcohol immersion 1 hour, suction filtration, absolute ethanol washing; 60 ℃ dry down, gets brown powder, is chitosan furyl α-An Jilinsuan methyl esters; Be verivate 1, structural formula is referring to general formula I.
Ir spectra shows: the infrared spectrum of chitosan derivatives 1 (Fig. 2) is compared with the infrared spectrum (Fig. 1) of chitosan, is positioned at 1595cm
-1The charateristic avsorption band of NH disappear, show NH
2React; 1538,1384cm
-1Be the charateristic avsorption band of N-H and C-N, 1201,1060,989cm
-1Charateristic avsorption band for P=O, P-O-C and P-C; Proof verivate 1 synthesizes successfully.
The preparation of embodiment 2 verivates 2
With 10 mmole molecular weight is that 230,000 chitosan, 10 mmole diethyl phosphites, 10 mmole furfurals join in the agate mortar, and ground and mixed is even, in microwave reactor; Down reaction 3 minutes of 200W, reaction product is with alcohol immersion 1 hour, suction filtration, absolute ethanol washing; 60 ℃ dry down, gets brown powder, is chitosan furyl α-An Jilinsuan ethyl ester; Be verivate 2, structural formula is referring to general formula I.
Ir spectra shows: the infrared spectrum of chitosan derivatives 2 (Fig. 3) is compared with the infrared spectrum (Fig. 1) of chitosan, is positioned at 1595cm
-1The charateristic avsorption band of NH disappear, show NH
2React; 1535,1388cm
-1Be the charateristic avsorption band of N-H and C-N, 1155,1070,993cm
-1Charateristic avsorption band for P=O, P-O-C and P-C; Proof verivate 2 synthesizes successfully.
Bacteriostatic activity is measured
Adopt growth rate method to measure the foregoing description and prepare the bacteriostatic activity of the verivate sample of gained the former bacterium of black rot of pear.Test prepares under the derivatives concentration of gained the inhibition effect to the black rot of pear bacterium at 3 the foregoing descriptions.3 sample concentrations are: 125 μ g/mL, 250g/mL, 500g/mL.
Experiment is with the positive contrast of the good general oligosaccharides medicament of same concentrations (commercially available be 2% aqua), with the negative contrast of zero(ppm) water.Evenly pouring substratum into 2 diameters is in the petridish of 9cm, after treating to solidify fully, and 2 bacterium cakes that diameter is 5mm of inoculation in each petridish.After cultivating 72 hours under 27 ℃, measure colony diameter, the bacteriostasis rate of calculation sample.The each processing is provided with 2 petridish, and 2 bacterium colonies of every ware inoculation are measured maximum diameter (D to each bacterium colony
Max) and minimum diameter (D
Min), averaging is sample antibacterial circle diameter D
Sample, Total Test repeats once.According to computes bacteriostasis rate (referring to table 2).Bacteriostasis rate (%)=(D
Blank-D
Sample)/(D
Blank-5) * 100
Table 2 part general formula 1 chitosan derivatives is active to the inhibition of pears wheel line
Claims (6)
2. furyl α-An Jilinsuan ester chitosan derivatives according to claim 1 is characterized in that R is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, amyl group.
3. the preparation method of the described furyl α-An Jilinsuan of claim 1 an ester chitosan derivatives is characterized in that, is parent with the chitosan; Mix with dialkyl phosphite and furfural; At 0-120 ℃, the 10-1000W microwave power reacted 1-60 minute down, reactant suction filtration behind solvent soaking; Filter cake is used solvent wash, obtains furyl α-An Jilinsuan ester chitosan derivatives after the drying; Wherein, the mol ratio of chitosan and dialkyl phosphite, furfural is 1: 1-3: 1-3.
4. the preparation method of furyl α-An Jilinsuan ester chitosan derivatives according to claim 3; It is characterized in that said dialkyl phosphite is dimethylphosphite, diethyl phosphite, phosphorous acid di ester, phosphorous acid diisopropyl ester, phosphorous acid di-n-butyl ester, phosphorous acid diisobutyl ester, phosphorous acid diamyl ester.
5. the preparation method of furyl α-An Jilinsuan ester chitosan derivatives according to claim 3 is characterized in that, the solvent of said immersion reactant and the solvent of washing leaching cake are one or more in acetone, ethanol, the methyl alcohol.
6. the preparation method of furyl α-An Jilinsuan ester chitosan derivatives according to claim 3 is characterized in that, said washing back filter cake carries out drying under 50-60 ℃.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201110410511.7A CN102516413B (en) | 2011-12-09 | 2011-12-09 | Furyl alpha-aminophosphonate chitosan derivative and its preparation method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201110410511.7A CN102516413B (en) | 2011-12-09 | 2011-12-09 | Furyl alpha-aminophosphonate chitosan derivative and its preparation method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102516413A true CN102516413A (en) | 2012-06-27 |
CN102516413B CN102516413B (en) | 2014-02-12 |
Family
ID=46287522
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201110410511.7A Active CN102516413B (en) | 2011-12-09 | 2011-12-09 | Furyl alpha-aminophosphonate chitosan derivative and its preparation method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102516413B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113667038A (en) * | 2021-08-30 | 2021-11-19 | 中南大学 | Water-soluble phosphorylated chitosan and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1283100A (en) * | 1997-12-22 | 2001-02-07 | 西巴特殊化学品控股有限公司 | Use of polyanionic and polyanionically-derivatised natural polysaecharides for inhibiting alkaline phosphatase |
WO2006092057A1 (en) * | 2005-03-04 | 2006-09-08 | Laboratoires Mauves Inc. | Amine-based and imine-based polymers, uses and preparation thereof |
CN101157734A (en) * | 2007-09-07 | 2008-04-09 | 中国科学院海洋研究所 | Chitosan alpha-aminoalkyl phosphonate ester derivative and preparation method thereof |
CN101863933A (en) * | 2010-06-21 | 2010-10-20 | 河南农业大学 | Chitosan oligosaccharide Schiff base phosphonate as well as preparation method and application thereof |
-
2011
- 2011-12-09 CN CN201110410511.7A patent/CN102516413B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1283100A (en) * | 1997-12-22 | 2001-02-07 | 西巴特殊化学品控股有限公司 | Use of polyanionic and polyanionically-derivatised natural polysaecharides for inhibiting alkaline phosphatase |
WO2006092057A1 (en) * | 2005-03-04 | 2006-09-08 | Laboratoires Mauves Inc. | Amine-based and imine-based polymers, uses and preparation thereof |
CN101157734A (en) * | 2007-09-07 | 2008-04-09 | 中国科学院海洋研究所 | Chitosan alpha-aminoalkyl phosphonate ester derivative and preparation method thereof |
CN101863933A (en) * | 2010-06-21 | 2010-10-20 | 河南农业大学 | Chitosan oligosaccharide Schiff base phosphonate as well as preparation method and application thereof |
Non-Patent Citations (2)
Title |
---|
《Journal of Tetrahedron Letters》 20060213 Xue-Jun Mu et al Microwave-assisted solvent-free and catalyst-free kabachnik-fields reactions for alpha-amino phosphonates 第1125-1127页 3-6 第47卷, 第7期 * |
XUE-JUN MU ET AL: "Microwave-assisted solvent-free and catalyst-free kabachnik-fields reactions for α-amino phosphonates", 《JOURNAL OF TETRAHEDRON LETTERS》, vol. 47, no. 7, 13 February 2006 (2006-02-13), pages 1125 - 1127 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113667038A (en) * | 2021-08-30 | 2021-11-19 | 中南大学 | Water-soluble phosphorylated chitosan and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN102516413B (en) | 2014-02-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102584448B (en) | Compound fertilizer | |
CN101033264B (en) | Chitosan biguanide hydrochloride, preparation method and use thereof | |
CN107032886B (en) | Selenium-rich natural multifunctional foliar fertilizer and preparation method thereof | |
CN105237655A (en) | Marine organism polysaccharide Schiff base derivative, preparation method thereof, and application thereof as agricultural bactericide | |
CN101423854A (en) | Method for preparing algin oligosacchride by using algin lyase | |
CN109912675B (en) | Ferrous sucrose and preparation method thereof | |
CN101058522A (en) | Leaf surface fertilizer for composite amino acid chelate complex | |
CN102976855A (en) | Polydopamine coated controlled-release fertilizer | |
CN102924179B (en) | Application of chitosan-oligosaccharide containing composition in production of edible fungi | |
CN103804076A (en) | Method for separating humic acid in pH mode and application thereof | |
CN105131152A (en) | Marine organism polysaccharide copper compound, preparation thereof and application of marine organic polysaccharide copper compound serving as agricultural bactericide | |
CN111171086B (en) | Wheat stress-resistant preparation and application thereof | |
CN102153674A (en) | Chitosan ester p-aminobenzoate and preparation method thereof | |
CN102417425B (en) | Novel ecological slow release carbamide compound, and preparation method and application thereof in production of agriculture or forestry | |
CN103664385B (en) | Polymalic acid is or/and salt is in the application prepared in fertilizer and obtained product thereof and preparation method | |
CN107793262A (en) | A kind of water soluble fertilizer and preparation method thereof | |
CN101406203A (en) | Plant growth regulator and production thereof | |
CN107736373B (en) | Method for improving activity of antioxidase of cucumber seedlings | |
CN102718888A (en) | Novel dithiocarbamate derivative of chitosan and preparation method thereof | |
CN102516413B (en) | Furyl alpha-aminophosphonate chitosan derivative and its preparation method | |
CN106135263B (en) | Composition and application thereof containing organic zinc | |
CN102718886A (en) | Novel 1,2,4-triazole derivative of chitosan and preparation method thereof | |
CN108101707B (en) | Total nutrient microbial amino acid water-soluble fertilizer and preparation method thereof | |
CN116199542A (en) | Humic acid-containing liquid fertilizer based on kitchen biogas slurry, preparation method and application | |
CN109180387A (en) | A kind of granular urea preparation method containing alginic acid synergistic carrier suitable for rice top dressing |
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 |