CN1943341B - Coupling substance of amino acid and pesticide and its preparing method and use as pesticide - Google Patents

Coupling substance of amino acid and pesticide and its preparing method and use as pesticide Download PDF

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CN1943341B
CN1943341B CN2006100369365A CN200610036936A CN1943341B CN 1943341 B CN1943341 B CN 1943341B CN 2006100369365 A CN2006100369365 A CN 2006100369365A CN 200610036936 A CN200610036936 A CN 200610036936A CN 1943341 B CN1943341 B CN 1943341B
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conjugate
blade
plant
amino acid
content
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CN1943341A (en
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徐汉虹
李俊凯
江定心
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South China Agricultural University
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Abstract

The invention discloses a pesticide compound prepared by coupling the carboxy of amino acid derivations and the amino or hydroxyl of the molecular of pesticide through amide and ester bond. The compound is used as agrochemical to prevent and treat root and vascular bundle diseases of plants, and other fungous diseases.

Description

Conjugate of amino acid and agricultural chemicals and preparation method thereof and application as agricultural chemicals
Technical field
The present invention relates to pesticide field, specifically, relate to the conjugate 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 in protein synthesis, playing well-known effect, in the primary and secondary metabolism of plant, also brought into play important function.Some amino acid act on the assimilation and the source-Ku transhipment of nitrogenous source, and other then are the precursors of secondary metabolite (like hormone and plant defense related substances).As, glutamic acid, glutamine, asparatate and asparagine are mainly used in nitrogenous source from the transfer of source organ to the storehouse tissue, under the sufficient condition of nitrogenous source, store nitrogen simultaneously, in order to plant corpus growth, defence and breeding need.Simultaneously, can get into plant metabolism immediately, be the synthetic nitrogenous source that provides of nucleic acid, amino acid and other nitrogen-containing compound with the nitrogen that changes into glutamic acid and glutamine.In addition, the nitrogen that is assimilated in glutamic acid and the glutamine also can be incorporated in asparatate and the asparagine, and the reaction of participating in for a lot of aminotransferases provides nitrogen.Tryptophan is the precursor compound of synthetic auxin IAA, and arginine is the important as precursors of synthetic polyamine, and phenyl alanine then is and disease resistance of plant and defense reaction amino acid in close relations, is the synthetic main precursor compound of salicylic acid.
The conduction of amino acid between the different tissues organ of plant accomplished through conduit and screen casing, and content of amino acids is generally between 5～40g/L in the diffusate of phloem, and content of amino acids only has 0.1～2g/L in the diffusate of xylem.This shows that amino acid whose running mainly is the screen casing through phloem, specific carrier is accomplished on this process need plasma membrane.Amino acid whose carrier can be divided into two types according to the specificity of substrate and affinity and the expression way in plant corpus.That is to say that the existing certain selectivity of these carriers has certain broad spectrum activity again.Most of controlling genes of these carrier proteins are positioned at present, and carry out the research of the physiological function of many clone genes with the plant of these carrier protein gene delection bodies.
Summary of the invention
The conjugate 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 conjugate.
Further purpose of the present invention provides above-mentioned conjugate as the application in the agricultural chemicals.
To achieve these goals; The present invention is based on selectivity, broad spectrum activity and the diversity of amino acid carrier system; Amino acid and pesticide molecule are combined; Do not shielding under the prerequisite of function binding site separately, having obtained can be by the new compound molecule (conjugate of amino acid and agricultural chemicals) of amino acid carrier transhipment.
The present invention directly carries out lotus root with the amino or hydroxyl of the carboxyl of amino acids and pesticide molecule and closes, and both is linked to each other with ester bond through amido link, obtains new compound, and its general formula is like (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 group or hydroxyl, removes deaminize hydrogen or imino group 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-configuration.
R1 is preferred following groups:
Figure DEST_PATH_S06136936520060823D000031
R2 is preferred following groups:
Figure DEST_PATH_S06136936520060823D000032
Figure DEST_PATH_S06136936520060823D000041
Figure DEST_PATH_S06136936520060823D000081
Figure DEST_PATH_S06136936520060823D000091
Figure DEST_PATH_S06136936520060823D000121
Figure DEST_PATH_S06136936520060823D000141
Figure DEST_PATH_S06136936520060823D000161
Figure DEST_PATH_S06136936520060823D000171
Figure DEST_PATH_S06136936520060823D000181
The preparation method of the conjugate 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 conjugate of amino acid and agricultural chemicals; It can be under the mediation of homing device at amino acid in plant corpus, in the two-way transporting of the phloem of plant, and shows certain growing 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 pest.
Embodiment
The lotus root of embodiment 1 alanine 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-alanine is dissolved in 200mL 2mol/L 3In the solution, 0 ℃ adds the 18.9g benzyl chloroformate down, and reaction 10h is 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, and the 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 fume hood, the compd A of 0.01mol and thionyl chloride and the 2mL carbon tetrachloride of 0.05mol (3.7mL) are joined in the 50mL kieldahl flask, add condensation and drying equipment, be back to no gas and emit, boil off solvent to not having HCl and SO 2Emit, add dry carrene 10mL again, boil off solvent again, get compd B, directly get into next step reaction.
Figure S06136936520061128D000041
， is dissolved in the former medicine sample of hymexazo 0.01mol in the carrene that heavily steamed of 15mL in the kieldahl flask of 100mL, logical dry nitrogen, and the triethylamine of the drying 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 carrene dilution of 50mL again, mixture is washed with 15mL, the HCl solution washing of 15mL 0.5mol/L, 15mL NaHCO 3The saturated solution washing, water is washed till neutrality again.Organic facies is used MgSO 4Drying boils off solvent, column chromatography purification, and flowing phase is benzinum 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, add the glacial acetic acid solution 10mL of HBr, normal-temperature reaction 2h; Concentrating under reduced pressure evaporates HBr and glacial acetic acid, adds that 10mL is water-soluble to be separated, 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 conjugate of embodiment 2 glutamic acid and Seedvax, that is: 2-amino-5-(4 '-methyl-5 '-(benzamido)-thiazol-2-yl-amino)-5-carbonyl valeric acid is synthetic.
Concrete steps are: the NaHCO that in the three-neck flask of 500mL, adds 0.375mol (31.5g) 3, and be dissolved in the H of 200mL 2Among the O, electric mixer is joined thermometer, dropping funel and reflux.Slowly add 0.1mol (14.7g) 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, extract is used anhydrous MgSO 4Drying boils off solvent, and product A is a white solid, heavy 25g, productive rate 89%.
In the kieldahl flask of 500mL, the compd A of 0.04mol is dissolved in the toluene of 200mL, be equipped with Dean-Stark and divide water distillation apparatus and reflux condensing tube, add 0.08mol (2.4g) paraformaldehyde and 0.0024mol (0.46g) p-methyl benzenesulfonic acid.Mixture refluxes about 3h to azeotropic mixture separation end.After the cooling, add the ethyl acetate of 50mL, separate organic facies, with the K of 4mL 0.3mol/L 2CO 3Solution washing is again with washing 3 times, MgSO 4Drying boils off solvent, gets compd B, and product is a viscous liquid, productive rate 81%.
In fume hood, the compd B of 0.01mol and thionyl chloride and the 2mL carbon tetrachloride of 0.05mol (3.7mL) are joined in the 50mL kieldahl flask, add condensation and drying equipment, be back to no gas and emit, boil off solvent to not having HCl and SO 2Emit, add dry carrene 10mL again, boil off solvent again, get Compound C, directly get into next step reaction.
In the kieldahl flask of 100mL, with the former medicine sample of Seedvax 0.01mol (2.33g) be dissolved in 25mL in the dry oxolane of crossing of sodium metal, logical dry nitrogen adds the dry triethylamine of 1.1mL, 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 oxolane, system is dissolved in the carrene of 50mL, and mixture is washed with 15mL, the HCl solution washing of 15mL 0.5mol/L, 15mL NaHCO 3The saturated solution washing, water is washed till neutrality again.Organic facies is used MgSO 4Drying boils off solvent, column chromatography purification, and flowing phase is benzinum 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 evaporate HBr and glacial acetic acid; After adding dissolve with methanol, be evaporated to driedly again, add a small amount of 5% acetate dissolution, dropwise add with 2% NaOH solution then; To pH=7, this moment, deposition can occur in a large number, filtered 2 washing precipitations of 10mL moisture; Drying is used recrystallizing methanol, gets 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 GABAs and fluorine worm nitrile is closed, that is: 4-amino-N-[3-cyanic acid-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-trifluoromethyl sulphinyl base-1H-pyrazoles-5-yl] butyramide is synthetic
Concrete steps: in being equipped with the 100mL there-necked flask of agitator, thermometer, drying tube and heater, add phthalic anhydride respectively, reanal, triethylamine (mol ratio is 1: 1: 1.5) and toluene; Reflux 5h; Be cooled to room temperature, pour in the cold water, have deposition to separate out; Filtration drying gets white solid A.
In the 100mL there-necked flask, dropping into compd A and thionyl chloride (heavily steaming before the use) mol ratio is 1: 1.2, loads onto agitator, reflux condensing tube (having drying tube) and thermometer, and the no gas of refluxing and stirring reaction is overflowed, and needs 5h approximately.The gas of emitting in the course of reaction absorbs with the aqueous solution of sodium hydroxide, and final system 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 decompression distillation again, obtains faint yellow solid B.
In being equipped with the 100mL there-necked flask of agitator, thermometer, dropping funel and heating, cooling device, add fluorine worm nitrile respectively, triethylamine, 4-N, TMSDMA N dimethylamine yl pyridines (mol ratio is 1: 1.3: 0.1) and an amount of chloroform are under 0 ℃; Slowly splash into the compd B of 1.2 equivalents, rise to room temperature, reflux 10h naturally; Be chilled to room temperature,, use 2 * 30mL distilled water wash again with 2 * 20mL, 1% watery hydrochloric acid washing organic layer; Organic layer is used anhydrous sodium sulfate drying, and precipitation obtains thick liquid; Use ethyl acetate and benzinum to be solvent, the gradient elution column chromatography for separation obtains Compound C.
Figure S06136936520061128D000071
In being equipped with the 50mL there-necked flask of agitator, dropping funel, drying tube and heater, add an amount of methyl alcohol and Compound C respectively, slowly splash into hydrazine hydrate (mol ratio is 1: 2), stirring at room is up to reacting completely.Use dichloromethane extraction, organic facies is used anhydrous sodium sulfate drying, and precipitation gets white solid, uses ethyl acetate and benzinum to be solvent, 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%. 1HNMR (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 conjugate of glutamic acid and Seedvax 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 conjugate of plant, as shown in table 1.
The content (the bright appearance of μ g/g) at each position of plant behind the conjugate processing tobacco seedling of table 1 Seedvax and glutamic acid
Figure S06136936520061128D000081
Presentation of results in the table 1; After Seedvax is handled tobacco leaf; The content of Seedvax reaches peak value at 48h in the blade that is processed; And the content of Seedvax also increases gradually in the apical growing point, and the content of Seedvax does not have clear regularity in the stem, does not detect the existence of Seedvax at root.Compare with Seedvax, handle blade with the conjugate of glutamic acid after, the content of conjugate reaches maximum 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 of absorption, reaches 3.73 μ g/g, and at the processing initial stage, the plant that the content of growing point conjugate is handled apparently higher than Seedvax.In stem, the content of conjugate all stage of measuring all about 1 μ g/g, but at root; The content of conjugate reaches maximum at 36h; And the content that has surpassed apical growing point and stem shows that this compound can absorb through plant leaf blade, moves and accumulates to growing point through phloem.
Embodiment 5 conductivity experiment 2
With the conjugate of reanal 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 conjugate of plant, as shown in table 2.
Table 2 reanal and fluorine worm nitrile conjugate water planting are handled after the cabbage mustard Determination on content result in each position of plant
The conjugate of table 3 reanal 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 conjugate of fluorine worm cyanogen and GABA can conduct in the cabbage mustard plant through water planting from bottom to top, and this conduction reduces with the distance of root, stem and leaf exsolution liquid.Can know from table 3; The conjugate of fluorine worm cyanogen and GABA 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; Being untreated has all detected a certain amount of conjugate in blade and the stem and has existed, and content reaches maximum at 24h, so fluorine worm cyanogen and GABA lotus root have had the characteristic of two-way conduction after closing.
Embodiment 6 conductivity experiment 3
The conductivity test of the conjugate of glycine and Acetamiprid on tobacco plant is coated with leaf with the conjugate 200mg/L concentration of glycine and Acetamiprid 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 conjugate in the blade at position up and down thereof.The result lists 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 conjugate in the different parts blade behind the conjugate processing tobacco plant of table 4 glycine and Acetamiprid
Figure S06136936520061128D000101
Embodiment 7 conductivity experiment 4
The conductivity test of the conjugate of alanine and Acetamiprid on tobacco plant is coated with leaf with the conjugate 200mg/L concentration of alanine and Acetamiprid to the blade of the tobacco plant middle part of 10～13 leaf phases and handles the content of conjugate in liquid chromatography for measuring different time processing blade and the top and the bottom bit organization thereof.The result lists in table 5.Presentation of results in the table 5 after Acetamiprid and alanine lotus root are closed, can conduct to root downwards again to the conduction of plant top.
The content of different parts conjugate behind the conjugate processing tobacco plant of table 5 alanine and Acetamiprid
Figure S06136936520061128D000111
Embodiment 8 conductivity experiment 5
The conductivity test of the conjugate of valine and Acetamiprid on tobacco plant is coated with leaf with the conjugate 250mg/L concentration of valine and Acetamiprid 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 conjugate in the blade at position up and down thereof.The result lists in table 6.Presentation of results in the table 6 after Acetamiprid and valine lotus root are closed, has the trend of strengthening to the growing tips of the plant conduction, can conduct downwards again.
The content of conjugate in the different parts blade behind the conjugate processing tobacco plant of table 6 valine and Acetamiprid
Figure S06136936520061128D000112
Embodiment 9 conductivity experiment 6
The conductivity test of the conjugate of lysine and Acetamiprid on tobacco plant is coated with leaf with the conjugate 200mg/L concentration of lysine and Acetamiprid 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 conjugate in the blade at position up and down thereof.The result lists in table 7.After Acetamiprid and lysine lotus root are closed, have the trend of strengthening to the growing tips of the plant conduction, can conduct downwards again.
The content of conjugate in the different parts blade behind the conjugate processing tobacco plant of table 7 lysine and Acetamiprid
Embodiment 10 conductivity experiment 7
Glycine and the ferimzone conjugate conductivity test on tobacco plant: the conjugate 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 conjugate in the blade at position up and down thereof.The result sees 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 conjugate in the different parts blade behind the conjugate processing tobacco plant of table 8 glycine and ferimzone
Embodiment 11 conductivity experiment 8
The conductivity test of the conjugate of alanine and ferimzone on tobacco plant: the conjugate 200mg/L concentration of alanine 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 conjugate in the blade at position up and down thereof.The result sees table 9.After alanine 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 conjugate in the different parts blade behind the conjugate processing tobacco plant of table 9 alanine and ferimzone
Figure S06136936520061128D000122
Embodiment 12 conductivity experiment 9
The conductivity test of the conjugate of phenyl alanine and ferimzone on tobacco plant is coated with leaf with the conjugate 200mg/L concentration of phenyl alanine and ferimzone to the blade of the tobacco plant middle part of 10～13 leaf phases and handles the content of conjugate in liquid chromatography for measuring different time processing blade and other position of plant.The result lists in table 10.After ferimzone and phenyl alanine 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 parts conjugate behind the conjugate processing tobacco plant of table 10 phenyl alanine and ferimzone
Figure S06136936520061128D000131
Embodiment 13 conductivity experiment 10
The conductivity test of the conjugate of valine and ferimzone on tobacco plant: the conjugate 200mg/L concentration of valine 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 conjugate in the blade at position up and down thereof.The result sees table 11.After valine 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 conjugate in the different parts blade behind the conjugate processing tobacco plant of table 11 valine and ferimzone
Figure S06136936520061128D000132
Embodiment 14 conductivity experiment 11
The conductivity test of the conjugate of proline and ferimzone on tobacco plant is coated with leaf with the conjugate 200mg/L concentration of proline 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 conjugate in the blade at position up and down thereof.The result lists in table 12.After proline and ferimzone lotus root are closed, can be to both direction conduction up and down in plant.
The content of conjugate in the different parts blade behind the conjugate processing tobacco plant of table 12 proline and ferimzone
Embodiment 15 conductivity experiment 12
The conductivity test of the conjugate of leucine and ferimzone on tobacco plant: the conjugate 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 conjugate in the blade at position up and down thereof.The result sees 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 conjugate in the different parts blade behind the conjugate processing tobacco plant of table 13 leucine and ferimzone
Figure S06136936520061128D000142
Embodiment 16 conductivity experiment 13
The conductivity test of the conjugate of asparatate and ferimzone on tobacco plant is coated with leaf with the conjugate 200mg/L concentration of asparatate and ferimzone to the blade of the tobacco plant middle part of 10～13 leaf phases and handles the content of conjugate in liquid chromatography for measuring different time processing blade and other position of plant.The result lists in table 14.After asparatate and ferimzone lotus root are closed, can be in the plant body to both direction conduction up and down, and can accumulation to a certain degree be arranged at growing point.
The content of different parts conjugate behind the conjugate processing tobacco plant of table 14 asparatate and ferimzone
Embodiment 17 conductivity experiment 14
The conductivity test of the conjugate of glycine and Triadimenol on tobacco plant: the conjugate 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 conjugate in the blade at position up and down thereof.The result lists in table 15.After glycine and Triadimenol lotus root are closed, can be in the plant body to both direction conduction up and down, can only be thereby changed Triadimenol to the characteristic of top conductive.
The content of conjugate in the different parts blade behind the conjugate processing tobacco plant of table 15 glycine and Triadimenol
Embodiment 18 conductivity experiment 15
The conductivity test of the conjugate of glutamic acid and Triadimenol on tobacco plant is coated with leaf with the conjugate 200mg/L concentration of glutamic acid and ferimzone to the blade of the tobacco plant middle part of 10～13 leaf phases and handles the content of conjugate in liquid chromatography for measuring different time processing blade and other position of plant.The result lists in table 16.After Triadimenol and glutamic acid lotus root are closed, changed the transport properties of Triadimenol in the plant body, and can be in the plant body to both direction conduction up and down, and can accumulation to a certain degree be arranged at growing point.
The content of different parts conjugate behind the conjugate processing tobacco plant of table 16 glutamic acid and Triadimenol
Figure S06136936520061128D000161
Embodiment 19 conductivity experiment 16
The conductivity test of the conjugate of serine and alkene azoles alcohol on tobacco plant is coated with leaf with the conjugate 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 conjugate in liquid chromatography for measuring different time processing blade and other position of plant.The result lists in table 17.After serine and alkene azoles alcohol lotus root are closed, can be to both direction conduction up and down in the plant body.
The content of conjugate in the different parts blade behind the conjugate processing tobacco plant of table 17 serine and alkene azoles alcohol
Figure S06136936520061128D000162
Embodiment 20 conductivity experiment 17
Threonine Yu the conductivity test of the conjugate of hymexazo on tobacco plant with threonine Yu the conjugate 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 conjugate in blade and other position of plant.The result lists in table 18.After threonine and hymexazo lotus root are closed, can be to both direction conduction up and down in the plant body.
Table 18 threonine is Yu the conjugate of hymexazo is handled behind the tobacco plant content of conjugate in the different parts blade
Figure S06136936520061128D000163
Figure S06136936520061128D000171
Embodiment 21 conductivity experiment 18
Tryptophan Yu the conductivity test of the conjugate of hymexazo on tobacco plant with tryptophan Yu the conjugate 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 conjugate in blade and other blade of plant.The result lists in table 19.After tryptophan and hymexazo lotus root are closed, can be to both direction conduction up and down in the plant body.
Table 19 tryptophan is Yu the conjugate of hymexazo is handled behind the tobacco plant content of conjugate in the different parts blade
Embodiment 22 conductivity experiment 19
Alanine Yu the conductivity test of the conjugate of hymexazo on tobacco plant with alanine Yu the conjugate 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 conjugate in blade and other blade of plant.The result lists in table 20.After alanine and hymexazo lotus root are closed, can be to both direction conduction up and down in the plant body.
Table 20 alanine is Yu the conjugate of hymexazo is handled behind the tobacco plant content of conjugate in the different parts blade
Embodiment 23 insecticidal tests 1
GABA and fluorine worm nitrile conjugate are tested diamond-back moth 3 instar larvae toxic actions: choose clean fresh cabbage leaves (avoiding master pulse).According to the toxicity test concentration range that the prerun test is confirmed, will supply 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 diamond-back moth 3 instar larvaes of the same size, places [temperature: 26～28 ℃ in the insectary then; Relative moisture: 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.The dead borer population of inspection behind processing 24 and the 48h.Calculate lethality and corrected mortality, obtain LC according to the linear regression straight line equation 50Value and LC 5095% confidence interval.Can find out that by table 21 biologically active of fluorine worm nitrile and GABA conjugate is higher than fluorine worm nitrile.
Table 21 fluorine worm nitrile and GABA conjugate and fluorine worm nitrile are to diamond-back moth 3 instar larvae toxicity tests
Figure S06136936520061128D000181
Embodiment 24 insecticidal tests 2
Glycine and carbofuran conjugate are tested the cytotoxicity of adult housefly: accurately taking by weighing earlier the 1g white granulated sugar is 2.5cm, high in the test tube of 7.5cm in diameter; Then sample is used acetone solution; Get the 1mL sample solution in the test tube of white granulated sugar; Shake up, make sample dry up subsequent use with fan equably attached on the white granulated 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 lethality and corrected mortality.Obtain LC according to the linear regression straight line equation 50Value and LC 5095% confidence interval.Can find out that by table 22 carbofuran and glycine conjugate are high to biological activity ratio's carbofuran of adult housefly.
Table 22 carbofuran and glycine conjugate and carbofuran are to the adult housefly toxicity test
Figure S06136936520061128D000191
Embodiment 25 sterilization experiments 1
Adopt mycelial growth rate to suppress method, Ce is Dinged hymexazo and the indoor bacteriostatic activity of glutamic acid conjugate respectively, and the former powder of Bing Yong hymexazo calculates the inhibiting rate of soup to mycelial growth as contrast, and the calculating medicament is to the EC of Rhizoctonia solani Kuhn 50The biologically active that can find out ， hymexazo and glutamic acid conjugate by table 23 is Yu hymexazo is suitable.
Table 23 hymexazo and glutamic acid conjugate are with the bactericidal activity of hymexazo is measured the result
Embodiment 26 sterilization experiments 2
Adopt mycelial growth rate to suppress method, measure Seedvax and the indoor bacteriostatic activity of glycine conjugate respectively, and with the former powder of Seedvax as contrast, the calculating soup is to the inhibiting rate of mycelial growth, the calculating medicament is to the EC of Rhizoctonia solani Kuhn 50Can find out that by table 24 biologically active and the Seedvax of Seedvax and glycine conjugate are suitable.
The bactericidal activity of table 24 Seedvax and glycine conjugate and Seedvax is measured the result

Claims (3)

1. the conjugate of amino acid and agricultural chemicals, general formula are like (I) formula:
Figure FC20016314200610036936501C00011
Wherein:
R1 is except that the residue behind the decarboxylate in the amino acid molecular;
R2 has in the pesticide molecule of hydroxyl, removes the later residue of hydroxyl hydrogen;
R1 is for being selected from following groups:
R2 is for being selected from following groups:
Figure FC20016314200610036936501C00022
Figure FC20016314200610036936501C00041
2. conjugate as claimed in claim 1 is characterized in that said 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 said conjugates are as the application in insecticide or the bactericide.
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US10717703B2 (en) 2017-08-21 2020-07-21 Celgene Corporation Processes for the preparation of (S)-tert-butyl 4,5-diamino-5-oxopentanoate
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