CN101759655A - Conjugate of amino acid and pesticide, preparation method thereof and application as pesticide - Google Patents
Conjugate of amino acid and pesticide, preparation method thereof and application as pesticide Download PDFInfo
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Abstract
The invention relates to the field of pesticides, and discloses a conjugate of amino acid and a pesticide, a preparation method thereof and application as the pesticide. The preparation method comprises the following steps of: directly coupling the carboxyl of an amino acid compound and the amino or hydroxyl of pesticide molecules and then connecting the amino acid compound and the pesticide molecules through amide bonds and ester bonds so that a new compound is obtained, wherein the general formula of the compound is shown as the formula (I). The amino acid and the pesticide are coupled so that the conjugate of the amino acid and the pesticide is obtained, and therefore, the conjugate can be bidirectionally conducted at the phloem of a plant under the mediated guiding of the amino acid as a guiding radical in a plant body and present a certain growing point accumulation. The coupled pesticide has the activity similar to that of the non-coupled pesticide so that the conjugate can prevent and treating the plant diseases and insect pests of the roots and the vascular bundles of the plant through leaf surface-spraying application and is used for killing pests, pathogenic bacteria or other harmful organisms.
Description
The application is that name is called " coupling substance of amino acid and agricultural chemicals and preparation method thereof with as agricultural chemicals application ", and the applying date is on August 4th, 2006, and application number is 200610036936.5 divides an application
Technical field
The present invention relates to pesticide field, specifically, relate to the coupling substance and preparation method thereof of class of amino acid and agricultural chemicals and application as agricultural chemicals.
Background technology
Amino acid has consequence in the vital movement of plant, except play well-known effect in protein synthesis, also brought into play important function in the primary and secondary metabolism of plant.Some amino acid act on the assimilation and the source-Ku transhipment of nitrogenous source, and other then are the precursors of secondary metabolite (as hormone and plant defense related substances).As, L-glutamic acid, glutamine, aspartic acid and asparagine are mainly used in nitrogenous source from the transfer of source organ to the storehouse tissue, store nitrogen simultaneously under the competent condition of nitrogenous source, in order to plant materials growth, defence and breeding need.Simultaneously, can enter plant metabolism immediately, the synthetic nitrogenous source that provides of nucleic acid, amino acid and other nitrogenous compound is provided with the nitrogen that changes into L-glutamic acid and glutamine.In addition, the nitrogen that is assimilated in L-glutamic acid and the glutamine also can be incorporated in aspartic acid and the asparagine, and the reaction that participates in for a lot of transaminases provides nitrogen.Tryptophane is the precursor compound of synthetic auxin IAA, and arginine is the important as precursors of synthetic polyamine, and phenylalanine then is and disease resistance of plant and defensive raction amino acid in close relations, is the main precursor compound of Whitfield's ointment synthetic.
The conduction of amino acid between the different tissues organ of plant finished by conduit and screen casing, and amino acid whose content is generally between 5～40g/L in the transudate of phloem, and amino acid whose content only has only 0.1～2g/L in the transudate of xylem.This shows that amino acid whose running mainly is the screen casing by phloem, specific carrier is finished on this process need plasma membrane.Amino acid whose carrier can be divided into two classes according to the specificity of substrate and affinity and in the intravital phraseology of plant.That is to say that the existing certain specificity of these carriers has certain broad spectrum again.Most of regulatory genes of these carrier proteinss are positioned at present, and carry out the research of the physiological function of many clone genes with the plant of these carrier proteins genetically deficient bodies.
Summary of the invention
The coupling substance that the purpose of this invention is to provide class of amino acid and agricultural chemicals.
Another object of the present invention provides the preparation method of above-mentioned coupling substance.
Further purpose of the present invention provides above-mentioned coupling substance as the application in the agricultural chemicals.
To achieve these goals, the present invention is based on specificity, broad spectrum and the diversity of amino acid carrier system, amino acid and pesticide molecule are carried out combination, do not shielding under the prerequisite of function binding site separately, obtaining the new compound molecule (coupling substance of amino acid and agricultural chemicals) that to be transported by amino acid carrier.
The present invention directly carries out lotus root with the amino of the carboxyl of amino acids and pesticide molecule or hydroxyl and closes, and both is linked to each other with ester bond by amido linkage, obtains new compound, and its general formula is as (I) formula:
Wherein:
R1 is except that the residue behind the decarboxylate in the amino acid molecular;
R2 has in the pesticide molecule of amino, imino-or hydroxyl, removes deaminize hydrogen or imino-hydrogen or the later residue of hydroxyl hydrogen.
Above-mentioned amino acid is meant that optical configuration is the amino acid of L-configuration or the amino acid of L-configuration and D-form.
R1 is preferred following groups:
R2 is for being selected from following groups:
The preparation method of the coupling substance of above-mentioned amino acid and agricultural chemicals is: utilize amino acid to carry out lotus root with the pesticide molecule that contains amino or hydroxyl and close; before closing, lotus root to protect amino or other reactive group in the amino acid; close with the agricultural chemicals lotus root again, and then slough blocking group, obtain described compound.
Compared with prior art, the present invention has following beneficial effect: the present invention carries out coupling with amino acid and agricultural chemicals, obtain the coupling substance of amino acid and agricultural chemicals, it can be under the mediation of homing device at amino acid in plant materials, in the two-way transporting of the phloem of plant, and show certain vegetative point accumulation property.Agricultural chemicals after lotus root is closed has and the similar activity of agricultural chemicals before lotus root is closed, and so can pass through the foliar spray dispenser, prevents and treats plant root and vascular disease insect pest, is used for kill pests, germ or other harmful organism.
Embodiment
The lotus root of embodiment 1 L-Ala and hymexazo is closed, that is: 2-alanine-5 '-methyl-isoxazole-3 '-Ji-ester is synthetic.
Concrete steps are: the NaHCO that 8.9g L-L-Ala is dissolved in 200mL 2mol/L
3In the solution, 0 ℃ adds the 18.9g benzyl chloroformate down, reaction 10h, with 20mL ether washing 2 times, water is transferred about pH to 2 with the HCl of 6mol/L, with ethyl acetate extraction 50mL * 3, combined ethyl acetate layer, use anhydrous sodium sulfate drying, concentrate, separate out white crystals, get compd A, the heavy 16.8g of product, productive rate 75.3%.
In stink cupboard, the compd A of 0.01mol and sulfur oxychloride and the 2mL tetracol phenixin of 0.05mol (3.7mL) are joined in the 50mL Kjeldahl flask, add condensation and drying plant, be back to no gas and emit, boil off solvent to not having HCl and 8O
2Emit, add exsiccant methylene dichloride 10mL again, boil off solvent again, get compd B, directly enter next step reaction.
， is dissolved in the former medicine sample of hymexazo 0.01mol in the methylene dichloride that heavily steamed of 15mL in the Kjeldahl flask of 100mL, logical exsiccant nitrogen, and the exsiccant triethylamine of adding 1.1mL, gradation drips the compd B of 0.01mol on a small quantity in the ice bath.40 ℃ of backflow 3h are cooled to room temperature, reaction 10h, and thin-layer chromatography is followed the tracks of reaction process.After question response finishes, add the methylene dichloride dilution of 50mL again, mixture is washed with 15mL, the HCl solution washing of 15mL0.5mol/L, 15mLNaHCO
3The saturated solution washing washes with water to neutrality again.Organic phase MgSO
4Drying boils off solvent, column chromatography purification, and moving phase is sherwood oil and ethyl acetate gradient elution.Product is a white solid, i.e. Compound C, and productive rate is 54%.
In the round-bottomed flask of 50mL, add Compound C 0.01mol, the glacial acetic acid solution 10mL that adds HBr, normal-temperature reaction 2h, concentrating under reduced pressure evaporate HBr and Glacial acetic acid, add the 10mL water dissolution, the NaOH solution that adds 1mol/L to pH be 9, with ethyl acetate extraction 3 times, drying is sloughed solvent, get colorless liquid product D, productive rate is 67%.
Target compound C's
1HNMR (400MHz, DCl, D
2O) δ: 1.49 (d, J=7.1,3H, CH
3-C-N), 2.31 (s, 3H, CH
3-isoxazol), and 3.81-3.85 (m, 1H, CH-N), 5.55 (s, 1H, CH (in isoxazol)).
Synthesizing of the coupling substance of embodiment 2 L-glutamic acid and amicarthiazol, that is: 2-amino-5-(4 '-methyl-5 '-(benzoylamino)-thiazol-2-yl-amino)-5-carbonyl valeric acid is synthetic.
Concrete steps are: the NaHCO that adds 0.375mol (31.5g) in the three-necked flask of 500mL
3, and be dissolved in the H of 200mL
2Among the O, electric mixer is joined thermometer, dropping funnel and reflux.Slowly add 0.1mol (14.7g) L-glutamic acid under the room temperature, the limit edged stirs.Place 0 ℃ of water-bath then, slowly drip 0.11mol (18.9g) benzyl chloroformate, temperature is controlled at 0～5 ℃, dropwise and slowly rise to room temperature, reaction 24h, water is washed with the 30mL ether, HCl with 6mol/L is acidified to pH=2 then, with ethyl acetate extraction 3 times, each 50mL, the anhydrous MgSO of extracting solution
4Drying boils off solvent, and product A is a white solid, heavy 25g, productive rate 89%.
In the Kjeldahl flask of 500mL, the compd A of 0.04mol is dissolved in the toluene of 200mL, be equipped with Dean-Stark and divide water distilling apparatus and reflux condensing tube, add 0.08mol (2.4g) Paraformaldehyde 96 and 0.0024mol (0.46g) tosic acid.Mixture refluxes about 3h to azeotrope separation end.After the cooling, add the ethyl acetate of 50mL, separate organic phase, with the K of 4mL 0.3mol/L
2CO
3Solution washing washes MgSO again with water 3 times
4Drying boils off solvent, gets compd B, and product is a viscous liquid, productive rate 81%.
In stink cupboard, the compd B of 0.01mol and sulfur oxychloride and the 2mL tetracol phenixin of 0.05mol (3.7mL) are joined in the 50mL Kjeldahl flask, add condensation and drying plant, be back to no gas and emit, boil off solvent to not having HCl and SO
2Emit, add exsiccant methylene dichloride 10mL again, boil off solvent again, get Compound C, directly enter next step reaction.
In the Kjeldahl flask of 100mL, with the former medicine sample of amicarthiazol 0.01mol (2.33g) be dissolved in 25mL in the dry tetrahydrofuran (THF) of crossing of sodium Metal 99.5, logical exsiccant nitrogen adds 1.1mL exsiccant triethylamine, gradation drips the Compound C of 0.01mol on a small quantity in the ice bath.60 ℃ of backflow 3h are cooled to room temperature, reaction 15h, and thin-layer chromatography is followed the tracks of reaction process.After question response finishes, the pressure reducing and steaming tetrahydrofuran (THF), system is dissolved in the methylene dichloride of 50mL, and mixture is washed with 15mL, the HCl solution washing of 15mL0.5mol/L, 15mL NaHCO
3The saturated solution washing washes with water to neutrality again.Organic phase MgSO
4Drying boils off solvent, column chromatography purification, and moving phase is sherwood oil and ethyl acetate gradient elution.Product is a white solid, i.e. Compound D, and productive rate is 76%.
In the round-bottomed flask of 50mL, add Compound D 0.01mol, add the glacial acetic acid solution 10mL of HBr, normal-temperature reaction 2h, concentrating under reduced pressure evaporates HBr and Glacial acetic acid, and behind the adding dissolve with methanol, revaporization is to doing, add a small amount of 5% acetate dissolution, dropwise add with 2% NaOH solution then, to pH=7, this moment, precipitation can occur in a large number, filtered 2 washing precipitations of 10mL moisture, dry, use recrystallizing methanol, get white solid E, productive rate 88%.
Target product E,
1HNMR (400MHz, DCl, D
2O) δ: 1.89-2.11 (m, 2H, OOC-C-CH2), 2.50 (s, 3H, CH3-thiazol), 2.53-2.66 (m, 2H, OC-CH2-), 3.34-3.39 (m, 1H, OOC-CH-C), 7.05-7.66 (m, 5H ,-C6H5), 12.41 (s, 1H ,-COOH);
13CNMR (400MHz, DCl, D
2O) δ: 17.2,21.5,22.4,25.0,26.2,30.5,31.4,51.3,119.0,120.5 (2C), 123.7,128.6 (2C), 138.9,151.3,157.2,160.7,170.5,170.7; MS m/z:725.2[2M+H]
+, 363[M+H]
+, 234.0[M-C5H8NO3]
+.
The lotus root of embodiment 3 γ-An Jidingsuans and fluorine worm nitrile is closed, that is: 4-amino-N-[3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-trifluoromethyl sulphinyl base-1H-pyrazoles-5-yl] butyramide synthetic
Concrete steps: in being equipped with the 100mL there-necked flask of agitator, thermometer, drying tube and heating unit, add Tetra hydro Phthalic anhydride respectively, aminobutyric acid, triethylamine (mol ratio is 1: 1: 1.5) and toluene, reflux 5h, be cooled to room temperature, pour in the cold water, have precipitation to separate out, filtration drying gets white solid A.
Dropping into compd A and thionyl chloride (heavily steaming before the use) mol ratio in the 100mL there-necked flask is 1: 1.2, loads onto agitator, reflux condensing tube (having drying tube) and thermometer, and the backflow stirring reaction does not have gas evolution, needs 5h approximately.The gas of emitting in the reaction process absorbs with the aqueous solution of sodium hydroxide, and final body is faint yellow settled solution.After being cooled to room temperature, it is transferred in the 100mL single necked round bottom flask, steam excessive thionyl chloride with the water pump decompression earlier, the residual solution that stays is used the oil pump underpressure distillation again, obtains faint yellow solid B.
Be equipped with agitator, thermometer, dropping funnel and heating, add fluorine worm nitrile in the 100mL there-necked flask of refrigerating unit respectively, triethylamine, 4-N, N dimethylamine yl pyridines (mol ratio is 1: 1.3: 0.1) and an amount of trichloromethane are under 0 ℃, slowly splash into 1.2 normal compd Bs, naturally rise to room temperature, reflux 10h is chilled to room temperature, with 2 * 20mL1% dilute hydrochloric acid washing organic layer, use 2 * 30mL distilled water wash again, organic layer anhydrous sodium sulfate drying, precipitation, obtain thick liquid, with ethyl acetate and sherwood oil is solvent, and the gradient elution column chromatography for separation obtains Compound C.
Add an amount of methyl alcohol and Compound C respectively in being equipped with the 50mL there-necked flask of agitator, dropping funnel, drying tube and heating unit, slowly splashing into hydrazine hydrate (mol ratio is 1: 2), stirring at room is up to reacting completely.Use dichloromethane extraction, the organic phase anhydrous sodium sulfate drying, precipitation gets white solid, is solvent with ethyl acetate and sherwood oil, and the gradient elution column chromatography for separation obtains target compound D.Product is a white solid, fusing point 149.1-149.3 ℃, and productive rate 36.9%.
1H NMR (400MHz, CDCl
3) δ: 8.87 (1H, s, NH), 7.75,7.73 (each 1H, s, H-3 ' and H-5 '), 3.54 (2H, m, H
2-1 "), 2.59 (2H, m, H
2-3 "), 2.12 (2H, m, H
2-2 ").
Embodiment 4 conductivity experiment 1
With the coupling substance of L-glutamic acid and amicarthiazol concentration according to 200mg/L, after tobacco is coated with leaf and water planting respectively and handles, utilize the content of liquid chromatography for measuring at each position coupling substance of plant, as shown in table 1.
The content (the bright sample of μ g/g) at each position of plant behind the coupling substance processing tobacco seedling of table 1 amicarthiazol and L-glutamic acid
Presentation of results in the table 1, after amicarthiazol is handled tobacco leaf, the content of amicarthiazol reaches peak value at 48h in the processed blade, and the content of amicarthiazol also increases gradually in the apical growing point, the content of amicarthiazol does not have clear regularity in the stem, does not detect the existence of amicarthiazol at root.Compare with amicarthiazol, handle blade with the coupling substance of L-glutamic acid after, the content of coupling substance reaches maximum value at 24h in the blade of processing, and the leaf intensive amount just reaches 9.45 μ g/g (fresh weight) rapidly when 12h, quickly fallen to 6.2 μ g/g during 36h again, during 48h, slightly descended subsequently.Corresponding, at apical growing point, 24h also reaches the maximum value of absorption, reaches 3.73 μ g/g, and at the processing initial stage, the plant that the content of vegetative point coupling substance is handled apparently higher than amicarthiazol.In stem, the content of coupling substance all stage of measuring all about 1 μ g/g, but at root, the content of coupling substance reaches maximum value at 36h, and the content that has surpassed apical growing point and stem shows that this compound can absorb by plant leaf, moves and accumulates to vegetative point through phloem.
Embodiment 5 conductivity experiment 2
With the coupling substance of aminobutyric acid and fluorine worm nitrile concentration according to 200mg/L, after cabbage mustard is coated with leaf and water planting respectively and handles, utilize the content of liquid chromatography for measuring at each position coupling substance of plant, as shown in table 2.
Table 2 aminobutyric acid and fluorine worm nitrile coupling substance water planting are handled after the cabbage mustard Determination on content result in each position of plant
The coupling substance of table 3 aminobutyric acid and fluorine worm nitrile is coated with behind the leaf in each position Determination on content result of cabbage mustard
The presentation of results of table 2, the coupling substance of fluorine worm cyanogen and γ-An Jidingsuan can conduct in the cabbage mustard plant from bottom to top through water planting, and this conduction reduces with the distance of root, stem and leaf exsolution liquid.As known from Table 3, the coupling substance of fluorine worm cyanogen and γ-An Jidingsuan is coated with the content that the leaf method is handled each position after the cabbage mustard, behind processing 12,24,36 and the 48h, be untreated and all detected a certain amount of coupling substance in blade and the stem and exist, content reaches maximum at 24h, so fluorine worm cyanogen and γ-An Jidingsuan lotus root have had the characteristic of two-way conduction after closing.
Embodiment 6 conductivity experiment 3
The conductivity test of the coupling substance of glycine and acetamiprid on tobacco plant is coated with leaf with the coupling substance 200mg/L concentration of glycine and acetamiprid to the blade of the tobacco plant middle part of 10～13 leaf phases and handles, and the liquid chromatography for measuring different time is handled blade and the content of coupling substance in the blade at position up and down thereof.The results are shown in table 4.Presentation of results in the table 4 after acetamiprid and glycine lotus root are closed, has the trend of strengthening to the growing tips of the plant conduction, can conduct downwards again.
The content of coupling substance in the different sites blade behind the coupling substance processing tobacco plant of table 4 glycine and acetamiprid
Embodiment 7 conductivity experiment 4
The conductivity test of the coupling substance of L-Ala and acetamiprid on tobacco plant is coated with leaf with the coupling substance 200mg/L concentration of L-Ala and acetamiprid to the blade of the tobacco plant middle part of 10～13 leaf phases and handles, and the liquid chromatography for measuring different time is handled the content of coupling substance in blade and the top and the bottom bit organization thereof.The results are shown in table 5.Presentation of results in the table 5 after acetamiprid and L-Ala lotus root are closed, can conduct to root downwards again to the conduction of plant top.
The content of different sites coupling substance behind the coupling substance processing tobacco plant of table 5 L-Ala and acetamiprid
Embodiment 8 conductivity experiment 5
The conductivity test of the coupling substance of Xie Ansuan and acetamiprid on tobacco plant is coated with leaf with the coupling substance 250mg/L concentration of Xie Ansuan and acetamiprid to the blade of the tobacco plant middle part of 10～13 leaf phases and handles, and the liquid chromatography for measuring different time is handled blade and the content of coupling substance in the blade at position up and down thereof.The results are shown in table 6.Presentation of results in the table 6 after acetamiprid and Xie Ansuan lotus root are closed, has the trend of strengthening to the growing tips of the plant conduction, can conduct downwards again.
The content of coupling substance in the different sites blade behind the coupling substance processing tobacco plant of table 6 Xie Ansuan and acetamiprid
Embodiment 9 conductivity experiment 6
The conductivity test of the coupling substance of Methionin and acetamiprid on tobacco plant is coated with leaf with the coupling substance 200mg/L concentration of Methionin and acetamiprid to the blade of the tobacco plant middle part of 10～13 leaf phases and handles, and the liquid chromatography for measuring different time is handled blade and the content of coupling substance in the blade at position up and down thereof.The results are shown in table 7.After acetamiprid and Methionin lotus root are closed, have the trend of strengthening to the growing tips of the plant conduction, can conduct downwards again.
The content of coupling substance in the different sites blade behind the coupling substance processing tobacco plant of table 7 Methionin and acetamiprid
Embodiment 10 conductivity experiment 7
Glycine and the ferimzone coupling substance conductivity test on tobacco plant: the coupling substance 200mg/L concentration of glycine and ferimzone is coated with leaf to the blade of the tobacco plant middle part of 10～13 leaf phases handles, liquid chromatography for measuring different time processing blade and the content of coupling substance in the blade at position up and down thereof.The results are shown in Table 8.After glycine and ferimzone lotus root are closed, have the trend of strengthening to the growing tips of the plant conduction, can conduct downwards again.
The content of coupling substance in the different sites blade behind the coupling substance processing tobacco plant of table 8 glycine and ferimzone
Embodiment 11 conductivity experiment 8
The conductivity test of the coupling substance of L-Ala and ferimzone on tobacco plant: the coupling substance 200mg/L concentration of L-Ala and ferimzone is coated with leaf to the blade of the tobacco plant middle part of 10～13 leaf phases handles, liquid chromatography for measuring different time processing blade and the content of coupling substance in the blade at position up and down thereof.The results are shown in Table 9.After L-Ala and ferimzone lotus root are closed, have the trend of strengthening to the growing tips of the plant conduction, can conduct downwards again.
The content of coupling substance in the different sites blade behind the coupling substance processing tobacco plant of table 9 L-Ala and ferimzone
Embodiment 12 conductivity experiment 9
The conductivity test of the coupling substance of phenylalanine and ferimzone on tobacco plant is coated with leaf with the coupling substance 200mg/L concentration of phenylalanine and ferimzone to the blade of the tobacco plant middle part of 10～13 leaf phases and handles the content of coupling substance in liquid chromatography for measuring different time processing blade and other position of plant.The results are shown in table 10.After ferimzone and phenylalanine lotus root are closed, have the trend of strengthening to the growing tips of the plant conduction, can conduct to the root of plant again downwards.
The content of different sites coupling substance behind the coupling substance processing tobacco plant of table 10 phenylalanine and ferimzone
Embodiment 13 conductivity experiment 10
The conductivity test of the coupling substance of Xie Ansuan and ferimzone on tobacco plant: the coupling substance 200mg/L concentration of Xie Ansuan and ferimzone is coated with leaf to the blade of the tobacco plant middle part of 10～13 leaf phases handles, liquid chromatography for measuring different time processing blade and the content of coupling substance in the blade at position up and down thereof.The results are shown in Table 11.After Xie Ansuan and ferimzone lotus root are closed, have the trend of strengthening to the growing tips of the plant conduction, can conduct downwards again.
The content of coupling substance in the different sites blade behind the coupling substance processing tobacco plant of table 11 Xie Ansuan and ferimzone
Embodiment 14 conductivity experiment 11
The conductivity test of the coupling substance of proline(Pro) and ferimzone on tobacco plant is coated with leaf with the coupling substance 200mg/L concentration of proline(Pro) and ferimzone to the blade of the tobacco plant middle part of 10～13 leaf phases and handles, liquid chromatography for measuring different time processing blade and the content of coupling substance in the blade at position up and down thereof.The results are shown in table 12.After proline(Pro) and ferimzone lotus root are closed, can both direction conduction up and down in plant.
The content of coupling substance in the different sites blade behind the coupling substance processing tobacco plant of table 12 proline(Pro) and ferimzone
Embodiment 15 conductivity experiment 12
The conductivity test of the coupling substance of leucine and ferimzone on tobacco plant: the coupling substance 200mg/L concentration of leucine and ferimzone is coated with leaf to the blade of the tobacco plant middle part of 10～13 leaf phases handles, liquid chromatography for measuring different time processing blade and the content of coupling substance in the blade at position up and down thereof.The results are shown in Table 13.After leucine and ferimzone lotus root are closed, have the trend of strengthening to the growing tips of the plant conduction, can conduct downwards again.
The content of coupling substance in the different sites blade behind the coupling substance processing tobacco plant of table 13 leucine and ferimzone
Embodiment 16 conductivity experiment 13
The conductivity test of the coupling substance of aspartic acid and ferimzone on tobacco plant is coated with leaf with the coupling substance 200mg/L concentration of aspartic acid and ferimzone to the blade of the tobacco plant middle part of 10～13 leaf phases and handles the content of coupling substance in liquid chromatography for measuring different time processing blade and other position of plant.The results are shown in table 14.After aspartic acid and ferimzone lotus root are closed, can be in the plant body both direction conduction up and down, and can to a certain degree accumulation be arranged at vegetative point.
The content of different sites coupling substance behind the coupling substance processing tobacco plant of table 14 aspartic acid and ferimzone
Embodiment 17 conductivity experiment 14
The conductivity test of the coupling substance of glycine and triadimenol on tobacco plant: the coupling substance 200mg/L concentration of glycine and triadimenol is coated with leaf to the blade of the tobacco plant middle part of 10～13 leaf phases handles, liquid chromatography for measuring different time processing blade and the content of coupling substance in the blade at position up and down thereof.The results are shown in table 15.After glycine and triadimenol lotus root are closed, can be in the plant body both direction conduction up and down, can only be thereby changed triadimenol to the characteristic of top conductive.
The content of coupling substance in the different sites blade behind the coupling substance processing tobacco plant of table 15 glycine and triadimenol
Embodiment 18 conductivity experiment 15
The conductivity test of the coupling substance of L-glutamic acid and triadimenol on tobacco plant is coated with leaf with the coupling substance 200mg/L concentration of L-glutamic acid and ferimzone to the blade of the tobacco plant middle part of 10～13 leaf phases and handles the content of coupling substance in liquid chromatography for measuring different time processing blade and other position of plant.The results are shown in table 16.After triadimenol and L-glutamic acid lotus root are closed, changed triadimenol at the intravital transport properties of plant, and can be in the plant body both direction conduction up and down, and can to a certain degree accumulation be arranged at vegetative point.
The content of different sites coupling substance behind the coupling substance processing tobacco plant of table 16 L-glutamic acid and triadimenol
Embodiment 19 conductivity experiment 16
The conductivity test of the coupling substance of Serine and alkene azoles alcohol on tobacco plant is coated with leaf with the coupling substance 200mg/L concentration of Serine and alkene azoles alcohol to the blade of the tobacco plant middle part of 10～13 leaf phases and handles the content of coupling substance in liquid chromatography for measuring different time processing blade and other position of plant.The results are shown in table 17.After Serine and alkene azoles alcohol lotus root are closed, can both direction conduction up and down in the plant body.
The content of coupling substance in the different sites blade behind the coupling substance processing tobacco plant of table 17 Serine and alkene azoles alcohol
Embodiment 20 conductivity experiment 17
Threonine Yu the conductivity test of the coupling substance of hymexazo on tobacco plant with Threonine Yu the coupling substance 200mg/L concentration of hymexazo is coated with leaf to the blade of the tobacco plant middle part of 10～13 leaf phases handles, the liquid chromatography for measuring different time is handled the content of coupling substance in blade and other position of plant.The results are shown in table 18.After Threonine and hymexazo lotus root are closed, can both direction conduction up and down in the plant body.
Table 18 Threonine is Yu the coupling substance of hymexazo is handled behind the tobacco plant content of coupling substance in the different sites blade
Embodiment 21 conductivity experiment 18
Tryptophane Yu the conductivity test of the coupling substance of hymexazo on tobacco plant with tryptophane Yu the coupling substance 200mg/L concentration of hymexazo is coated with leaf to the blade of the tobacco plant middle part of 10～13 leaf phases handles, the liquid chromatography for measuring different time is handled the content of coupling substance in blade and other blade of plant.The results are shown in table 19.After tryptophane and hymexazo lotus root are closed, can both direction conduction up and down in the plant body.
Table 19 tryptophane is Yu the coupling substance of hymexazo is handled behind the tobacco plant content of coupling substance in the different sites blade
Embodiment 22 conductivity experiment 19
L-Ala Yu the conductivity test of the coupling substance of hymexazo on tobacco plant with L-Ala Yu the coupling substance 200mg/L concentration of hymexazo is coated with leaf to the blade of the tobacco plant middle part of 10～13 leaf phases handles, the liquid chromatography for measuring different time is handled the content of coupling substance in blade and other blade of plant.The results are shown in table 20.After L-Ala and hymexazo lotus root are closed, can both direction conduction up and down in the plant body.
Table 20 L-Ala is Yu the coupling substance of hymexazo is handled behind the tobacco plant content of coupling substance in the different sites blade
Embodiment 23 insecticidal tests 1
γ-An Jidingsuan and fluorine worm nitrile coupling substance are tested small cabbage moth 3 instar larvae toxic actions: choose clean fresh cabbage leaves (avoiding master pulse).According to the definite toxicity test concentration range of prerun test, will be for 5～6 concentration of the former medicinal acetone solution of examination, take out after blade floods about 5 seconds in soup and dry, put into and be lined with the filter paper of preserving moisture, diameter is in the culture dish of 7.5cm, inserts small cabbage moth 3 instar larvaes of the same size, places [temperature: 26 ~ 28 ℃ in the insectary then, relative humidity: 70 ~ 80%, illumination: 14h: 10h (L: D)].If solvent is contrast, fluorine worm nitrile is the medicament contrast, and each handles 4 repetitions, 10 examinations of every repetition worm.Check dead borer population behind processing 24 and the 48h.Calculate mortality ratio and corrected mortality, obtain LC according to the linear regression straight line equation
50Value and LC
5095% fiducial interval.As can be seen from Table 21, the biological activity of fluorine worm nitrile and γ-An Jidingsuan coupling substance is higher than fluorine worm nitrile.
Table 21 fluorine worm nitrile and γ-An Jidingsuan coupling substance and fluorine worm nitrile are to small cabbage moth 3 instar larvae toxicity tests
Embodiment 24 insecticidal tests 2
Glycine and carbofuran coupling substance are tested the cytotoxicity of adult housefly: accurately taking by weighing earlier the 1g white sugar is 2.5cm, high in the test tube of 7.5cm in diameter, then with the sample acetone solution, get the 1mL sample solution in the test tube of white sugar, shake up, make sample dry up standby with fan equably attached on the white sugar.Select the housefly of the back 3 ~ 4d neat and consistent of sprouting wings, behind etherization, in every pipe, insert 10 boss flies rapidly.3 concentration are established in determination of activity: 50,25 and 12.5 μ gmL
-1, 3 repetitions are established in every processing, and every repetition 10 cephalonts make blank and do the medicament contrast with the carbofuran under the same concentrations with acetone.After handling 24h, observe the reaction of examination worm, and write down dead borer population, calculate mortality ratio and corrected mortality.Obtain LC according to the linear regression straight line equation
50Value and LC
5095% fiducial interval.Carbofuran and glycine coupling substance are to biological activity ratio's carbofuran height of adult housefly as can be seen from Table 22.
Table 22 carbofuran and glycine coupling substance and carbofuran are to the adult housefly toxicity test
Embodiment 25 sterilization experiments 1
Adopt mycelial growth rate to suppress method, Ce is Dinged hymexazo and the indoor bacteriostatic activity of L-glutamic acid coupling substance respectively, and the former powder of Bing Yong hymexazo calculates the inhibiting rate of soup to mycelial growth in contrast, and the calculating medicament is to the EC of Rhizoctonia solani Kuhn
50The biological activity of ， hymexazo and L-glutamic acid coupling substance is Yu hymexazo is suitable as can be seen from Table 23.
Table 23 hymexazo and L-glutamic acid coupling substance are with the fungicidal activity measurement result of hymexazo
Embodiment 26 sterilization experiments 2
Adopt mycelial growth rate to suppress method, measure amicarthiazol and the indoor bacteriostatic activity of glycine coupling substance respectively, and with the former powder of amicarthiazol in contrast, the calculating soup is to the inhibiting rate of mycelial growth, the calculating medicament is to the EC of Rhizoctonia solani Kuhn
50As can be seen from Table 24, the biological activity and the amicarthiazol of amicarthiazol and glycine coupling substance are suitable.
The fungicidal activity measurement result of table 24 amicarthiazol and glycine coupling substance and amicarthiazol
Claims (3)
1. the coupling substance of amino acid and agricultural chemicals, general formula are as (I) formula:
Wherein:
R1 is except that the residue behind the decarboxylate in the amino acid molecular;
R2 has in the pesticide molecule of imino-, removes the later residue of imino-;
R1 is for being selected from following groups:
R2 is for being selected from following groups:
2. coupling substance as claimed in claim 1 is characterized in that described amino acid is meant that optical configuration is the amino acid of L-configuration or the amino acid of L-configuration and D-form.
3. claim 1 or 2 described coupling substances are as the application in sterilant or the sterilant.
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| CN111567541B (en) * | 2020-05-26 | 2021-05-07 | 华南农业大学 | Preparation method and application of nano pesticide for conduction of plant phloem |
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