CN102718890A - Alpha-aminophenylpyridine ether phosphate derivatives and preparation method thereof - Google Patents
Alpha-aminophenylpyridine ether phosphate derivatives and preparation method thereof Download PDFInfo
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- CN102718890A CN102718890A CN2011103789538A CN201110378953A CN102718890A CN 102718890 A CN102718890 A CN 102718890A CN 2011103789538 A CN2011103789538 A CN 2011103789538A CN 201110378953 A CN201110378953 A CN 201110378953A CN 102718890 A CN102718890 A CN 102718890A
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Abstract
The invention belongs to the technical field of ocean chemical engineering and especially relates to alpha-aminophenylpyridine ether phosphate derivatives and a preparation method thereof. The alpha-aminophenylpyridine ether phosphate derivatives have a general formula I and in the general formula I, R represents alkyl or aryl and n is in a range of 4 to 4000. Alpha-aminophosphonate groups are introduced into a chitosan structure and the alpha-aminophosphonate groups and the chitosan structure have synergistic effects and thus a bacteriostatic activity of chitosan is improved obviously. The prepared alpha-aminophosphonate derivatives of chitosan has good dissolvability, can be dissolved in a plurality of solvents, and has a wide application scope and a potential application value in the field of pesticides.
Description
Technical field
The invention belongs to the marine chemical industry engineering, be specifically related to a kind of alpha-amino group benzene pyrimidine ether phosphonates verivate and preparation method thereof.
Background technology
Too much use the chemical pesticide can be to ecotope is had a negative impact, as: the part agricultural chemicals produces poisoning; Production process discharges pollutants; The part persistent pesticide remains in the agricultural-food, influences agricultural product quality; Riskiest pesticide kind such as SRA-5172, thiophos, parathion-methyl, phosphamidon, SD-9129 cause poisoning in manufacturing, use; Part agricultural chemicals and a large amount of aromatic hydrocarbons get into environment with other solvent in the use, and only aromatic hydrocarbons such as the toluene of the annual entering of China environment, YLENE just reach about 260,000 tons.Therefore the requirement of substitute of seeking chemical pesticide is more and more urgent.
Chitin (chitin) is the polysaccharide of N-ethanoyl-D-glycamine with β-1,4 key be combined into, is the cell wall constituent of the mushroom such as exoskeleton and mushroom of crustaceans such as crab, shrimp, beetle etc., extensively is present in nature.Chitosan (chitosan) is the product of chitin deacetylate, and safety non-toxic has good bio-compatibility, with human body cell good affinity is arranged, and non-immunogenicity has anticancer and antineoplastic action.Chitosan and verivate thereof have the function of broad-spectrum antimicrobial to various bacteria, fungi because of its peculiar biological activity.
α-An Jilinsuan fat is as the analogue of natural amino acid; In the sheep body, separated more than 50 year so far in the 1950's from chemist Horguchi; Its compound method and biological activity receive scientist's extensive concern, and its changeable structure type is laid a good foundation for continuous synthetic new compound. discover that it has multiple biological activitys such as Antiphytoviral, weeding, plant growth regulating, inhibitory enzyme activity, sterilization, anticancer, anti-oxidant activity.
Summary of the invention
The object of the invention is to provide a kind of novel structure, chitosan alpha-amino-benzene pyrimidine ether phosphonates verivate that bacteriostatic activity is good and preparation method thereof.
In order to realize above-mentioned purpose of the present invention, the present invention adopts following technical scheme to be:
A kind of alpha-amino group benzene pyrimidine ether phosphonates verivate, its general formula be suc as formula shown in the I,
Among the formula I, R is alkyl or aromatic base; N=4-4000.R is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, phenyl or substituted-phenyl.
The preparation method of alpha-amino group benzene pyrimidine ether phosphonates verivate; To be dissolved in Chitosan Schiff-base and dialkyl phosphite in the solvent; Reacted 6-10 hour down at 60-100 ℃, and the after-filtration filter cake promptly obtains chitosan derivatives alpha-amino group benzene pyrimidine ether phosphonates verivate through the washing after drying; Wherein the volume ratio of the quality of Chitosan Schiff-base and dialkyl phosphite is 1: 1-10.
Being prepared as of said Chitosan Schiff-base: will be dissolved in chitosan and 4-pyrimidyl-2-oxygen base-phenyl aldehyde in the solvent under acid catalysis with 60-100 ℃, react and generated Chitosan Schiff-base in 6-10 hour; Wherein, the volume of solvent is 10-300 with the chitosan mass ratio: 1; The mol ratio of chitosan and 4-pyrimidyl-2-oxygen base-phenyl aldehyde is 1: 1-3; Acid is 1 with the volume ratio of solvent: 10-100.Said acid catalysis adopts one or more in formic acid, acetate, the propionic acid.Said solvent is methyl alcohol, ethanol, water, N, one or more in the dinethylformamide.Said dialkyl phosphite is dimethylphosphite or phosphorous acid diethyl ester.The solvent load of said dissolving Chitosan Schiff-base is that the volume of solvent is 10-300 with the chitosan mass ratio: 1.Said solvent is benzene, toluene, N, one or both in the dinethylformamide.The solvent that is used to wash extract during said filter is ethanol or acetone.
The present invention adopts active substructure splicing principle, the bio-active group of α-An Jilinsuan fat verivate is incorporated in the natural product chitosan skeleton, i.e. 4-pyrimidyl-2-oxygen base-phenyl aldehyde and chitosan C
2On the position-NH
2The generation Chitosan Schiff-base reacts; React with dialkyl phosphite afterwards and generate alpha-amino group benzene pyrimidine ether phosphonates verivate; The verivate of gained is confirmed its structure through IR spectroscopy, and chitosan combines to generate α-An Jilinsuan fat verivate effectively with the group of access.Principle: contain in the Chitosan Schiff-base structure-C=N, can a type mannich reaction take place with dialkyl phosphite and in chitosan structure, introduce α-An Jilinsuan fat reactive group, and then produce synergy, significantly improve the biological activity of verivate with chitosan.
Advantage of the present invention:
1. the present invention introduces α-An Jilinsuan fat group in chitosan structure, and both produce synergistic function, have significantly improved the bacteriostatic activity of chitosan.
2. the chitosan α-An Jilinsuan fat verivate of the present invention's preparation has good solubility, dissolves in multiple solvent, has enlarged its Application Areas, at pesticide field the potential using value is arranged.
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): 1595,896.
The infrared spectrogram of the chitosan derivatives 1 that Fig. 2 provides for the embodiment of the invention, its infrared signature absorbs (cm
-1): 3423,1670,1521,1403,1182,1051,993,833,761,671.
The infrared spectrogram of the chitosan derivatives 2 that Fig. 3 provides for the embodiment of the invention, its infrared signature absorbs (cm-1): 3466,2890,1648,1535,1386,1182,1162,1066,998,808,665.
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 3.22 gram molecular weights is that 230,000 chitosan, 3.68 gram 4-pyrimidyl-2-oxygen base-phenyl aldehydes join in the 60mL absolute ethyl alcohol, stir down and drip 0.4mL acetate, back flow reaction 10 hours to it; Be cooled to room temperature; The reactant suction filtration, absolute ethanol washing, 60 ℃ are dry down; Get faint yellow toner end, be Chitosan Schiff-base.Perhaps the preparation of Chitosan Schiff-base can be with reference to following document: ZhanyongGuo; R.X., Song Liu, Zhimei Zhong; Xia Ji; Lin Wang, Pengcheng Li (2007). " Antifungal properties of Schiff bases of chitosan, N-substituted chitosan and quaternized chitosan. "
Carbohydrate Research342 (10): 1329-1332.
1.50 gram Chitosan Schiff-base, 5mL dimethylphosphites are joined in the 30mL toluene, and 80 ℃ of reactions 10 hours down are cooled to room temperature, the reactant suction filtration, absolute ethanol washing, 60 ℃ dry down, yellow toner end, be chitosan derivatives 1.Structure is seen general formula I (R is a methyl).
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; 1670,1403cm
-1Be the charateristic avsorption band of C=N and C-N, 1521cm
-1Be the characteristic absorbance of phenyl ring, 1182,1051,833cm
-1For the charateristic avsorption band of P=O, P-O-C and P-C; Proof order verivate 1 synthesizes successfully.
The preparation of embodiment 2 verivates 2
1.50 gram Chitosan Schiff-base, 5mL diethyl phosphites are joined in the 30mL toluene, and 80 ℃ of reactions 10 hours down are cooled to room temperature, the reactant suction filtration, absolute ethanol washing, 60 ℃ dry down, yellow toner end, be chitosan derivatives 2.Structure is seen general formula I (R is an ethyl).
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; 1648,1386cm
-1Be the charateristic avsorption band of C=N and C-N, 1535cm
-1Be the characteristic absorbance of phenyl ring, 1162,1066,808cm
-1For the charateristic avsorption band of P=O, P-O-C and P-C; Proof order verivate 1 synthesizes successfully.
Bacteriostatic activity is measured
Adopt the bacteriostatic activity of growth rate method working sample to the former bacterium of black rot of pear.Test is in the inhibition effect of 3 sample concentrations to pears wheels line, 3 sample concentrations promptly: 125 μ g/mL, 250 μ g/mL, 500 μ g/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
| Compound | Concentration ((μ g/mL) | To pears wheel line bacteriostasis rate (%) |
| 1 | 125 | 42.3 |
| 250 | 46.9 | |
| 500 | 75.6 | |
| 2 | 125 | 43.9 |
| 250 | 51.1 | |
| 500 | 78.2 | |
| Good general oligosaccharides | 125 | 32.2 |
| 250 | 53.7 | |
| 500 | 56.0 | |
| Chitosan | 125 | 20.8 |
| 250 | 25.7 | |
| 500 | 31.6 |
Claims (10)
1. an alpha-amino group benzene pyrimidine ether phosphonates verivate is characterized in that, its general formula is suc as formula shown in the I,
Among
formula I, R is alkyl or aromatic base; N=4-4000.
2. alpha-amino group benzene pyrimidine ether phosphonates verivate according to claim 1 is characterized in that R is methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, phenyl or substituted-phenyl.
3. the preparation method of the described alpha-amino group benzene of claim 1 a pyrimidine ether phosphonates verivate; It is characterized in that; To be dissolved in Chitosan Schiff-base and dialkyl phosphite in the solvent; Reacted 6-10 hour down at 60-100 ℃, and the after-filtration filter cake promptly obtains chitosan derivatives alpha-amino group benzene pyrimidine ether phosphonates verivate through the washing after drying; Wherein the volume ratio of the quality of Chitosan Schiff-base and dialkyl phosphite is 1: 1-10.
4. the preparation method of alpha-amino group benzene pyrimidine ether phosphonates verivate according to claim 3; It is characterized in that; Being prepared as of said Chitosan Schiff-base: will be dissolved in chitosan and 4-pyrimidyl-2-oxygen base-phenyl aldehyde in the solvent under acid catalysis with 60-100 ℃, react and generated Chitosan Schiff-base in 6-10 hour; Wherein, the volume of solvent is 10-300 with the chitosan mass ratio: 1; The mol ratio of chitosan and 4-pyrimidyl-2-oxygen base-phenyl aldehyde is 1: 1-3; Acid is 1 with the volume ratio of solvent: 10-100.
5. the preparation method of alpha-amino group benzene pyrimidine ether phosphonates verivate according to claim 4 is characterized in that, said acid catalysis adopts one or more in formic acid, acetate, the propionic acid.
6. the preparation method of alpha-amino group benzene pyrimidine ether phosphonates verivate according to claim 4 is characterized in that said solvent is methyl alcohol, ethanol, water, N, one or more in the dinethylformamide.
7. the preparation method of alpha-amino group benzene pyrimidine ether phosphonates verivate according to claim 3 is characterized in that said dialkyl phosphite is dimethylphosphite or phosphorous acid diethyl ester.
8. according to the preparation method of claim 3 or 4 described alpha-amino group benzene pyrimidine ether phosphonates verivates, it is characterized in that the solvent load of said dissolving Chitosan Schiff-base is that the volume of solvent is 10-300 with the chitosan mass ratio: 1.
9. the preparation method of alpha-amino group benzene pyrimidine ether phosphonates verivate according to claim 3 is characterized in that said solvent is benzene, toluene, N, one or both in the dinethylformamide.
10. the preparation method of alpha-amino group benzene pyrimidine ether phosphonates verivate according to claim 3 is characterized in that, the solvent that is used to wash extract during said filter is ethanol or acetone.
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| 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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 |
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Application publication date: 20121010 |