CN105131152B - A kind of marine polysaccharide copper composition and prepare and as the application of disinfectant use in agriculture - Google Patents
A kind of marine polysaccharide copper composition and prepare and as the application of disinfectant use in agriculture Download PDFInfo
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Abstract
The invention belongs to marine chemical industry engineering technology, and in particular to a kind of marine polysaccharide copper composition and prepare and as the application of disinfectant use in agriculture.Marine polysaccharide copper composition is O carboxymethyl chitosan acetylacetone,2,4-pentanedione amino benzoic Acid Schiff's base copper composition derivants, and shown in formula I, in Formulas I, X is carboxyl, the simultaneously-substituted phenyl of methyl, the simultaneously-substituted phenyl of carboxyl, halogen or carboxyl phenyl to its formula；N=1000 8000.O carboxymethyl chitosan acetylacetone,2,4-pentanedione amino benzoic Acid Schiff's base copper composition derivants prepared by the present invention have good dissolubility, dissolve in multi-solvents, heavy metal ion be also avoid while fungistatic effect is improved to remain in soil, its application is expanded, has potential using value in pesticide field.
Description
Technical field
The invention belongs to marine chemical industry engineering technology, and in particular to a kind of marine polysaccharide copper composition and preparation and work
For the application of disinfectant use in agriculture.
Background technology
Copper agent is as which is cheap, using method is simple, obtain long-term many advantages, such as be not likely to produce Drug resistance
Extensively apply.Which is broadly divided into inorganic and organic two types.By discharge in copper ion and pathogenic bacteria vivo protein-
SH、-NH2,-COOH, the group such as-OH work, cause pathogenic bacteria dead.But traditional copper agent improper use easily produces poisoning simultaneously
The outburst of induction mite class.Therefore, the content and releasability of copper ion is the principal element for determining copper agent sterilizing disease-preventing effect,
It is also to determine its key factor to crop safety height simultaneously.
Shitosan is the good ocean aminopolysaccharide of a kind of renewable, nontoxic, biocompatibility and degradability.Shitosan pair
Various plants pathogenic fungi has inhibitory action, in agricultural can prevent and treat soil-borne disease as soil conditioner, as kind of a clothing
Agent prevents and treats seed-borne disease, preserving fruit and vegetable utilizing control postharvest disease etc., and it is novel sea biogenic pesticide to be developed, undoubtedly with wide
Wealthy application prospect.But shitosan is directly asked using having that drug effect is poor, consumption is big, cost is high etc. as single-activity component
Topic, thus Difficulty.
The content of the invention
The present invention is aiming at the problems referred to above, there is provided a kind of structure is novel, the marine polysaccharide copper that bacteriostatic activity is good
Complex and prepare and as the application of disinfectant use in agriculture.
In order to realize the above-mentioned purpose of the present invention, the present invention is adopted the following technical scheme that：
A kind of marine polysaccharide copper composition, marine polysaccharide copper composition are O-CMC acetylacetone,2,4-pentanedione
Amino benzoic Acid Schiff's base copper composition derivant, its formula shown in formula I,
In Formulas I, X is carboxyl, the simultaneously-substituted phenyl of methyl, the simultaneously-substituted phenyl of carboxyl, halogen or carboxyl phenyl；n
=1000-8000.
In the Formulas I, X is carboxyl and methyl or the simultaneously-substituted phenyl of halogen.
A kind of preparation method of marine polysaccharide copper composition：
(1) amino benzoic Acid is dissolved in solvent, reaction generation single cropping amine is carried out in the case where being heated to reflux with acetylacetone,2,4-pentanedione and is matched somebody with somebody
Body；Wherein, the volume of solvent and amino benzoic Acid mass ratio are 30-300:1；Amino benzoic Acid with the mol ratio of acetylacetone,2,4-pentanedione is
1:1-3；
(2) full chitosan is dissolved in solvent, carries out reaction with single cropping amine ligand and generate shitosan under acid catalysiss
Acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives, generate O-CMC acetylacetone,2,4-pentanedione with chloroacetate reaction after reaction again
Amino benzoic Acid Schiff base derivatives；Wherein, the volume of solvent and full chitosan mass ratio are 50-300:1；Take off full second
Acyl shitosan is 1 with the mass ratio of single cropping amine ligand:4-10；Full chitosan is 1 with chloroacetic mass ratio:5-10；
(3) O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives are dissolved in solvent, are existed with copper acetate
Reaction under heated and stirred generates O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff's base copper composition shown in Formulas I and derives
Thing；Wherein, the volume of solvent and O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives mass ratio are 100-
300:1；O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives are 1 with the mass ratio of copper acetate:3-5；Instead
Temperature is answered for 60-80 DEG C, the response time is 6-12 hours；Filter cake is washed with solvent, is dried at 50-60 DEG C, after being dried
Obtain Chitosan Schiff-base copper composition derivant.
The step (1) is dissolved in amino benzoic Acid in solvent, reacts 6-12 with acetylacetone,2,4-pentanedione little under 60-80 DEG C of backflow
Shi Shengcheng single cropping amine ligands；Wherein, solvent is methanol and/ethanol.
The amino benzoic Acid is 4-Amino-3-methylbenzoic acid, 4- amino-2-methyl benzoic acid, 3- amino-2-methyls
Benzoic acid, 3- amino -4- ar-Toluic acids, 3- amino -4- chlorobenzoic acids or 4- amino -2- chlorobenzoic acids；Solvent be methanol and/
Ethanol.
Step (2) step is that full chitosan is dissolved in solvent, is reacted at 60-80 DEG C with single cropping amine ligand
6-12 hours generate shitosan acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives, anti-at 60-80 DEG C with monoxone again after reaction
Answer 6-12 hours to react, then filter filter cake organic solvent washing, be dried at 50-60 DEG C, after being dried, obtain O- carboxylics
Methyl chitosan acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives；Wherein, solvent is alcohol and water, and alcohol is methanol and/ethanol；Have
Machine solvent is ethanol or acetone.
Step (3) the O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives are dissolved in solvent, with
Copper acetate reacts 6-12 hours under 60-80 DEG C of stirring, filters filter cake and uses ethanol, water washing successively, at 50-60 DEG C after reaction
It is dried, the amino benzoic Acid Schiff's base of O-CMC acetylacetone,2,4-pentanedione shown in Formulas I copper composition is obtained after being dried and is derived
Thing；Wherein, solvent is alcohol and water, and alcohol is methanol and/ethanol.
A kind of application of marine polysaccharide copper composition, polysaccharide copper composition shown in the Formulas I is in agricultural, forestry and defends
It is used as the application of antibacterial in raw field.
Principle：Contain-NH in chitosan structure2, can be with single cropping amine ligand generation schiff base reaction in chitosan structure
Amino benzoic Acid is introduced, then is coordinated copper ions with two N in amino benzoic Acid with shitosan, that is, be increased number of amino groups, increase
Strong biological activity it is strong, and then produce synergism with shitosan, significantly improve the biological activity of derivant.
Specifically, in the present invention, amino benzoic Acid is reacted with acetylacetone,2,4-pentanedione and generates single cropping amine ligand, single cropping amine ligand
With full chitosan C2- NH on position2React generation Chitosan Schiff-base, and reacted generation afterwards with monoxone
O-CMC derivant, C on the chitosan derivatives2The copper of-N=, the connected-NH- of phenyl ring on position and copper acetate from
Son coordination generates O-CMC copper composition derivant, and the derivant Jing infrared spectrum analysiss of gained determine its structure,
Shitosan is effectively combined generation O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff's base copper with the group for accessing and is combined
Thing derivant.
Advantages of the present invention：
1. aminobenzoic acid groups and copper ion are introduced in chitosan structure of the present invention, and three produces synergistic function,
Significantly improve the bacteriostatic activity of shitosan.
2. the O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff's base copper composition derivant tool that prepared by the present invention
There is good dissolubility, dissolve in multi-solvents, heavy metal ion is also avoid in soil while fungistatic effect is improved
Residual, expands its application, has potential using value in pesticide field.
Description of the drawings
Fig. 1 is the infrared spectrogram of full chitosan, and its infrared signature absorbs (cm-1)：1556,1069.
Fig. 2 is the infrared spectrogram of chitosan derivatives provided in an embodiment of the present invention 1, and its infrared signature absorbs (cm-1)：
3426,3345,2922,1682,1596,1541,1434,1320,1280,1247。
Fig. 3 is the infrared spectrogram of chitosan derivatives provided in an embodiment of the present invention 2, and its infrared signature absorbs (cm-
1)：3426,3337,2923,1682,1596,1541,1434,1320,1280,1246.
Fig. 4 is the infrared spectrogram of chitosan derivatives provided in an embodiment of the present invention 3, and its infrared signature absorbs (cm-
1)：3422,3335,1672,1595,1542,1418,1320,1279,1246.
Fig. 5 is the infrared spectrogram of chitosan derivatives provided in an embodiment of the present invention 4, and its infrared signature absorbs (cm-
1)：3311,2877,1556,1397,1314.
Fig. 6 is the infrared spectrogram of chitosan derivatives provided in an embodiment of the present invention 5, and its infrared signature absorbs (cm-
1)：3422,3336,1683,1596,1542,1418,1317.
Fig. 7 is the infrared spectrogram of chitosan derivatives provided in an embodiment of the present invention 6, and its infrared signature absorbs (cm-
1)：3422,3336,2926,1683,1595,1542,1419,1318,1279,1246.
Specific embodiment
With reference to Figure of description, the invention will be further described, and protection scope of the present invention is not only limited to
Following examples.
The bio-active group of amino benzoic Acid Schiff base derivatives is drawn by the present invention using active substructure splicing principle
Enter in natural product shitosan skeleton, using the amino complex copper ion in molecule, prepare antibacterial and inducing anti-disease activity
The chitosan derivative that improves, is to develop novel biopesticide to open new way.
The preparation of 1 derivant 1 of embodiment
2.5 grams of 4-Amino-3-methylbenzoic acids, 1.66 grams of acetylacetone,2,4-pentanediones are added in 70mL dehydrated alcohol, 60 DEG C anti-
Answer 12 hours, reactant revolving, cold ethanol are washed, and be dried, obtain final product single cropping amine ligand at 60 DEG C.
The full chitosan that 0.5 gram-molecular weight is 1,300,000 is added in 20mL dehydrated alcohol and 25mL water, is stirred
It is lower to its Deca 0.5mL acetic acid；2.0 grams of single cropping amine ligands are added in 50mL dehydrated alcohol, are added drop-wise in reaction system, 60 DEG C
Reaction 12 hours；2.5 grams of monoxones are added in 10mL dehydrated alcohol, are added drop-wise in reaction system, 60 DEG C are reacted 6 hours,
Room temperature is cooled to, dehydrated alcohol precipitation is added, sucking filtration is precipitated, absolute ethanol washing is dried at 60 DEG C, obtains pale yellow powder, i.e.,
For O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives.
0.3 gram of O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives is dissolved in 30mL water, 0.5 gram
Cu(OAc)2·2H2O is dissolved in 50mL water, acetic acid copper liquor is added drop-wise in Schiff aqueous alkali under 70 DEG C of stirrings, reaction 6
Hour, room temperature being cooled to, is centrifuged, washing, 60 DEG C of dryings obtain dark green powder, and as shown in Formulas I, O-CMC copper is multiple
Compound derivant 1, wherein X be 2- methyl -4- carboxyl phenyls, n=1000-8000.
Infrared spectrum shows：The infrared spectrum (Fig. 2) of O-CMC copper composition derivant 1 and complete deacetylated shell
The infrared spectrum (Fig. 1) of polysaccharide is compared, positioned at 1556cm-1NH characteristic absorption peak weaken, show NH2Have occurred and that reaction；
1596,1434cm-1For the characteristic absorption peak of C=N and C-N；1541cm-1For the characteristic absorption of phenyl ring；Prove that mesh derivant 1 is closed
Into success.
The preparation of 2 derivant 2 of embodiment
2.5 grams of 4- amino-2-methyl benzoic acid, 1.66 grams of acetylacetone,2,4-pentanediones are added in 70mL dehydrated alcohol, 60 DEG C anti-
Answer 12 hours, reactant revolving, cold ethanol are washed, and be dried, obtain final product single cropping amine ligand at 60 DEG C.
The full chitosan that 0.5 gram-molecular weight is 1,300,000 is added in 20mL dehydrated alcohol and 25mL water, is stirred
It is lower to its Deca 0.5mL acetic acid；2.0 grams of single cropping amine ligands are added in 50mL dehydrated alcohol, are added drop-wise in reaction system, 60 DEG C
Reaction 12 hours；2.5 grams of monoxones are added in 10mL dehydrated alcohol, are added drop-wise in reaction system, 60 DEG C are reacted 6 hours,
Room temperature is cooled to, dehydrated alcohol precipitation is added, sucking filtration is precipitated, absolute ethanol washing is dried at 60 DEG C, obtains faint yellow color powder,
As O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives.
0.3 gram of O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives is dissolved in 30mL water, 0.5 gram
Cu(OAc)2·2H2O is dissolved in 50mL water, acetic acid copper liquor is added drop-wise in Schiff aqueous alkali under 70 DEG C of stirrings, reaction 6
Hour, room temperature being cooled to, is centrifuged, washing, 60 DEG C of dryings obtain dark green powder, and as shown in Formulas I, O-CMC copper is multiple
Compound derivant 1, wherein X be 3- methyl -4- carboxyl phenyls, n=1000-8000.
Infrared spectrum shows：The infrared spectrum (Fig. 3) of O-CMC derivant 2 is red with full chitosan
Outer spectrogram (Fig. 1) is compared, positioned at 1556cm-1NH characteristic absorption peak weaken, show NH2Have occurred and that reaction；1596,
1434cm-1For the characteristic absorption peak of C=N and C-N；1541cm-1For the characteristic absorption of phenyl ring；Prove mesh derivant it is 2-in-1 into into
Work(.
The preparation of 3 derivant 3 of embodiment
2.5 grams of 3- amino-2-methyl benzoic acid, 1.66 grams of acetylacetone,2,4-pentanediones are added in 70mL dehydrated alcohol, 60 DEG C anti-
Answer 12 hours, reactant revolving, cold ethanol are washed, and be dried, obtain final product single cropping amine ligand at 60 DEG C.
The full chitosan that 0.5 gram-molecular weight is 1,300,000 is added in 20mL dehydrated alcohol and 25mL water, is stirred
It is lower to its Deca 0.5mL acetic acid；2.0 grams of single cropping amine ligands are added in 50mL dehydrated alcohol, are added drop-wise in reaction system, 60 DEG C
Reaction 12 hours；2.5 grams of monoxones are added in 10mL dehydrated alcohol, are added drop-wise in reaction system, 60 DEG C are reacted 6 hours,
Room temperature is cooled to, dehydrated alcohol precipitation is added, sucking filtration is precipitated, absolute ethanol washing is dried at 60 DEG C, obtains faint yellow color powder,
As O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives.
0.3 gram of O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives is dissolved in 30mL water, 0.5 gram
Cu(OAc)2·2H2O is dissolved in 50mL water, acetic acid copper liquor is added drop-wise in Schiff aqueous alkali under 70 DEG C of stirrings, reaction 6
Hour, room temperature being cooled to, is centrifuged, washing, 60 DEG C of dryings obtain dark green powder, and as shown in Formulas I, O-CMC copper is multiple
Compound derivant 1, wherein X be 2- methyl -3- carboxyl phenyls, n=1000-8000.
Infrared spectrum shows：The infrared spectrum (Fig. 4) of O-CMC derivant 3 is red with full chitosan
Outer spectrogram (Fig. 1) is compared, positioned at 1556cm-1NH characteristic absorption peak weaken, show NH2Have occurred and that reaction；1595,
1418cm-1For the characteristic absorption peak of C=N and C-N；1541cm-1For the characteristic absorption of phenyl ring；Prove that mesh derivant 3 synthesizes into
Work(.
The preparation of 4 derivant 4 of embodiment
2.5 grams of 3- amino -4- ar-Toluic acids, 1.66 grams of acetylacetone,2,4-pentanediones are added in 70mL dehydrated alcohol, 60 DEG C anti-
Answer 12 hours, reactant revolving, cold ethanol are washed, and be dried, obtain final product single cropping amine ligand at 60 DEG C.
The full chitosan that 0.5 gram-molecular weight is 1,300,000 is added in 20mL dehydrated alcohol and 25mL water, is stirred
It is lower to its Deca 0.5mL acetic acid；2.0 grams of single cropping amine ligands are added in 50mL dehydrated alcohol, are added drop-wise in reaction system, 60 DEG C
Reaction 12 hours；2.5 grams of monoxones are added in 10mL dehydrated alcohol, are added drop-wise in reaction system, 60 DEG C are reacted 6 hours,
Room temperature is cooled to, dehydrated alcohol precipitation is added, sucking filtration is precipitated, absolute ethanol washing is dried at 60 DEG C, obtains faint yellow color powder,
As O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives 4.
0.3 gram of O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives is dissolved in 30mL water, 0.5 gram
Cu(OAc)2·2H2O is dissolved in 50mL water, acetic acid copper liquor is added drop-wise in Schiff aqueous alkali under 70 DEG C of stirrings, reaction 6
Hour, room temperature being cooled to, is centrifuged, washing, 60 DEG C of dryings obtain dark green powder, and as shown in Formulas I, O-CMC copper is multiple
Compound derivant 1, wherein X be 2- methyl -5- carboxyl phenyls, n=1000-8000.
Infrared spectrum shows：The infrared spectrum (Fig. 5) of O-CMC derivant 4 is red with full chitosan
Outer spectrogram (Fig. 1) is compared, positioned at 1556cm-1NH characteristic absorption peak weaken, show NH2Have occurred and that reaction；1556cm-1For
The characteristic absorption of phenyl ring；Prove that mesh derivant 4 synthesizes successfully.
The preparation of 5 derivant 5 of embodiment
2.5 grams of 3- amino -4- chlorobenzoic acids, 1.66 grams of acetylacetone,2,4-pentanediones are added in 70mL dehydrated alcohol, 60 DEG C of reactions
12 hours, reactant revolving, cold ethanol were washed, and be dried, obtain final product single cropping amine ligand at 60 DEG C.
The full chitosan that 0.5 gram-molecular weight is 1,300,000 is added in 20mL dehydrated alcohol and 25mL water, is stirred
It is lower to its Deca 0.5mL acetic acid；2.0 grams of single cropping amine ligands are added in 50mL dehydrated alcohol, are added drop-wise in reaction system, 60 DEG C
Reaction 12 hours；2.5 grams of monoxones are added in 10mL dehydrated alcohol, are added drop-wise in reaction system, 60 DEG C are reacted 6 hours,
Room temperature is cooled to, dehydrated alcohol precipitation is added, sucking filtration is precipitated, absolute ethanol washing is dried at 60 DEG C, obtains faint yellow color powder,
As O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives.
0.3 gram of O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives is dissolved in 30mL water, 0.5 gram
Cu(OAc)2·2H2O is dissolved in 50mL water, acetic acid copper liquor is added drop-wise in Schiff aqueous alkali under 70 DEG C of stirrings, reaction 6
Hour, room temperature being cooled to, is centrifuged, washing, 60 DEG C of dryings obtain dark green powder, and as shown in Formulas I, O-CMC copper is multiple
Compound derivant 1, wherein X be 3- carboxyl -5- chlorphenyls, n=1000-8000.
Infrared spectrum shows：The infrared spectrum (Fig. 6) of O-CMC derivant 5 is red with full chitosan
Outer spectrogram (Fig. 1) is compared, positioned at 1556cm-1NH characteristic absorption peak weaken, show NH2Have occurred and that reaction；1596,
1418cm-1For the characteristic absorption peak of C=N and C-N；1542cm-1For the characteristic absorption of phenyl ring；Prove that mesh derivant 5 synthesizes into
Work(.
The preparation of 6 derivant 6 of embodiment
2.5 grams of 4- amino -2- chlorobenzoic acids, 1.66 grams of acetylacetone,2,4-pentanediones are added in 70mL dehydrated alcohol, 60 DEG C of reactions
12 hours, reactant revolving, cold ethanol were washed, and be dried, obtain final product single cropping amine ligand at 60 DEG C.
The full chitosan that 0.5 gram-molecular weight is 1,300,000 is added in 20mL dehydrated alcohol and 25mL water, is stirred
It is lower to its Deca 0.5mL acetic acid；2.0 grams of single cropping amine ligands are added in 50mL dehydrated alcohol, are added drop-wise in reaction system, 60 DEG C
Reaction 12 hours；2.5 grams of monoxones are added in 10mL dehydrated alcohol, are added drop-wise in reaction system, 60 DEG C are reacted 6 hours,
Room temperature is cooled to, dehydrated alcohol precipitation is added, sucking filtration is precipitated, absolute ethanol washing is dried at 60 DEG C, obtains faint yellow color powder,
As O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives.
0.3 gram of O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives is dissolved in 30mL water, 0.5 gram
Cu(OAc)2·2H2O is dissolved in 50mL water, acetic acid copper liquor is added drop-wise in Schiff aqueous alkali under 70 DEG C of stirrings, reaction 6
Hour, room temperature being cooled to, is centrifuged, washing, 60 DEG C of dryings obtain dark green powder, and as shown in Formulas I, O-CMC copper is multiple
Compound derivant 1, wherein X be 4- carboxyl -3- chlorphenyls, n=1000-8000.
Infrared spectrum shows：The infrared spectrum (Fig. 7) of O-CMC derivant 6 is red with full chitosan
Outer spectrogram (Fig. 1) is compared, positioned at 1556cm-1NH characteristic absorption peak weaken, show NH2Have occurred and that reaction；1595,
1419cm-1For the characteristic absorption peak of C=N and C-N；1542cm-1For the characteristic absorption of phenyl ring；Prove that mesh derivant 6 synthesizes into
Work(.
Antibacterial Activity
Using bacteriostatic activity of the growth rate method determination sample to Phytophthora capsici pathogen.Test is under 3 sample concentrations
I.e.：The inhibition of 100 μ g/mL, 200 μ g/mL, 400 μ g/mL to Phytophthora capsici.
Test with the good general oligosaccharide medicament (commercially available is 2% water preparation) and Thiodiazole-copper of same concentrations that (commercially available is 20% to hang
Floating agent) medicament be positive control, with distilled water as negative control.Culture medium is uniformly poured into the culture dish of 1 a diameter of 9cm
In, after solidifying completely, the bacteria cake of 3 pieces of a diameter of 5mm is inoculated with each culture dish.After cultivating 72 hours at 27 DEG C, survey
Amount colony diameter, calculates the bacteriostasis rate of sample.1 culture dish of setting per treatment, is inoculated with 3 bacterium colonies, to each bacterium colony per ware
Determine maximum gauge (Dmax) and minimum diameter (Dmin), average as sample antibacterial circle diameter DSample, total Test repetition one
It is secondary.Bacteriostasis rate (table 1) is calculated according to following formula.
Bacteriostasis rate (%)=(DBlank-DSample)/(DBlank-5)×100
Test result indicate that O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff's base copper composition derivant is to peppery
Green pepper phytophthora generally has good fungistatic effect, is considerably better than now existing good general oligosaccharide and Thiodiazole-copper product.
Inhibitory activity of 1 partial Formula of table, 1 chitosan derivatives to Phytophthora capsici
| Compound | Concentration (μ g/mL) | To Phytophthora capsici suppression ratio (%) |
| 2 | 100 | 28.6 |
| 200 | 63.3 | |
| 400 | 73.5 | |
| 3 | 100 | 38.0 |
| 200 | 100.0 | |
| 400 | 100.0 | |
| 4 | 100 | 28.6 |
| 200 | 100.0 | |
| 400 | 100.0 | |
| 5 | 100 | 22.9 |
| 200 | 83.7 | |
| 400 | 100.0 | |
| 6 | 100 | 24.1 |
| 200 | 73.1 | |
| 400 | 100.0 | |
| Good general oligosaccharide | 100 | 45.7 |
| 200 | 58.0 | |
| 400 | 75.5 | |
| Thiodiazole-copper | 100 | -1.6 |
| 200 | -9.0 | |
| 400 | 35.9 | |
| Shitosan | 100 | 14.3 |
| 200 | 16.3 | |
| 400 | 42.0 |
Claims (8)
1. a kind of marine polysaccharide copper composition, it is characterised in that：Marine polysaccharide copper composition is O- carboxymethyl chitosans
Sugared acetylacetone,2,4-pentanedione amino benzoic Acid Schiff's base copper composition derivant, its formula shown in formula I,
In Formulas I, X is the replacement simultaneously of carboxyl, methyl, and carboxyl, halogen replace simultaneously or carboxyl replaces；N=1000-8000.
2. marine polysaccharide copper composition according to claim 1, it is characterised in that：In the Formulas I, X be carboxyl with
Methyl or halogen replace simultaneously.
3. the preparation method of the marine polysaccharide copper composition described in a kind of claim 1, it is characterised in that：
(1) amino benzoic Acid is dissolved in solvent, reaction is carried out in the case where being heated to reflux with acetylacetone,2,4-pentanedione and generates single cropping amine ligand；Its
In, volume and the amino benzoic Acid mass ratio of solvent are 30-300:1；Amino benzoic Acid is 1 with the mol ratio of acetylacetone,2,4-pentanedione:1-
3；
(2) full chitosan is dissolved in solvent, reaction is carried out under acid catalysiss with single cropping amine ligand and generates shitosan second
Acyl acetone amino benzoic Acid Schiff base derivatives, generate O-CMC acetylacetone,2,4-pentanedione ammonia with chloroacetate reaction after reaction again
Yl benzoic acid Schiff base derivatives；Wherein, the volume of solvent and full chitosan mass ratio are 50-300:1；It is complete deacetylated
Shitosan is 1 with the mass ratio of single cropping amine ligand:4-10；Full chitosan is 1 with chloroacetic mass ratio:5-10；
(3) O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives are dissolved in solvent, are being added with copper acetate
Reaction under thermal agitation generates O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff's base copper composition derivant shown in Formulas I；
Wherein, the volume of solvent and O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives mass ratio are 100-300:
1；O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives are 1 with the mass ratio of copper acetate:3-5；Reaction temperature
Spend for 60-80 DEG C, the response time is 6-12 hours；Filter cake is washed with solvent, is dried at 50-60 DEG C, is obtained after being dried
Chitosan Schiff-base copper composition derivant.
4. the preparation method of marine polysaccharide copper composition according to claim 3, it is characterised in that：The step
(1) amino benzoic Acid is dissolved in solvent, 6-12 hours generation single cropping amine is reacted under 60-80 DEG C of backflow with acetylacetone,2,4-pentanedione and is matched somebody with somebody
Body；Wherein, solvent is methanol and/or ethanol.
5. the preparation method of the marine polysaccharide copper composition according to claim 3 or 4, it is characterised in that：The ammonia
Yl benzoic acid be 4-Amino-3-methylbenzoic acid, 4- amino-2-methyl benzoic acid, 3- amino-2-methyl benzoic acid, 3- amino-
4- ar-Toluic acids, 3- amino -4- chlorobenzoic acids or 4- amino -2- chlorobenzoic acids；Solvent is methanol and/or ethanol.
6. the preparation method of marine polysaccharide copper composition according to claim 3, it is characterised in that：The step
(2) step is that full chitosan is dissolved in solvent, reacts 6-12 hours with single cropping amine ligand and generate shell at 60-80 DEG C
Polysaccharide acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives, react 6-12 hour at 60-80 DEG C with monoxone after reaction, then again
Filter cake organic solvent washing is filtered, is dried at 50-60 DEG C, after being dried, obtain O-CMC acetylacetone,2,4-pentanedione ammonia
Yl benzoic acid Schiff base derivatives；Wherein, solvent is alcohol and water；Organic solvent is ethanol or acetone.
7. the preparation method of marine polysaccharide copper composition according to claim 3, it is characterised in that：The step
(3) O-CMC acetylacetone,2,4-pentanedione amino benzoic Acid Schiff base derivatives are dissolved in solvent, are stirred at 60-80 DEG C with copper acetate
Lower reaction 6-12 hours are mixed, filter cake is filtered after reaction and is used ethanol, water washing successively, be dried at 50-60 DEG C, after being dried
To the amino benzoic Acid Schiff's base copper composition derivant of O-CMC acetylacetone,2,4-pentanedione shown in Formulas I；Wherein, solvent be alcohol and
Water.
8. the application of the marine polysaccharide copper composition described in a kind of claim 1, it is characterised in that：It is many shown in the Formulas I
Sugared copper composition is used as the application of antibacterial in agricultural, forestry and health field.
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