CN1907023A - Coupling compounds of bios and pesticides, their preparation process and use as pesticides - Google Patents
Coupling compounds of bios and pesticides, their preparation process and use as pesticides Download PDFInfo
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- CN1907023A CN1907023A CNA2006100369331A CN200610036933A CN1907023A CN 1907023 A CN1907023 A CN 1907023A CN A2006100369331 A CNA2006100369331 A CN A2006100369331A CN 200610036933 A CN200610036933 A CN 200610036933A CN 1907023 A CN1907023 A CN 1907023A
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Abstract
The invention discloses a coupling material and preparing method and application of bios and pesticide in the pesticide compound domain, which is characterized by the following: coupling carboxyl group of bios compound and amino group or hydroxyl group of pesticide molecule directly to connect through amido and ester bond to produce the product with general formula as formula (I); conducting the coupling material in the phloem of plant downwards to possess biological activity as similar as pesticide.
Description
Technical field
The present invention relates to the agricultural chemical compound field, specifically, relate to the conjugate and preparation method thereof of class growth hormone and agricultural chemicals and application as agricultural chemicals.
Background technology
Known growth hormone can conduct at phloem in plant corpus, but the conduction of most of agricultural chemicals in plant corpus all is by after the root absorption, by xylem to top conductive.Because the plant auxins material has the feature of conducting by plant corpus downwards, if with it as lead compound, splice with agricultural chemicals, gained splicing thing can be under the mediation of lead compound, in plant corpus, can conduct downwards, thereby reach by blade face medication control plant root and fascicular damage by disease and insect.
Summary of the invention
The conjugate that the purpose of this invention is to provide class growth hormone and pesticide molecule.
Another object of the present invention provides the preparation method of above-mentioned conjugate.
Further purpose of the present invention provides the application of above-mentioned conjugate as agricultural chemicals.
To achieve these goals, the present invention directly carries out lotus root with the amino of the carboxyl of auxins compound and pesticide molecule or hydroxyl and closes, and both is linked to each other with ester bond by amido link, obtains the conjugate of growth hormone and pesticide molecule, and its general formula is as (I) formula:
Wherein:
R1 is the residue of removing in the growth hormone molecule behind the carboxyethyl;
R2 is the pesticide molecule that has amino, imino group or hydroxyl, removes deaminize hydrogen or imino group hydrogen or the later residue of hydroxyl hydrogen.
R1 is preferred following groups:
R2 is preferred following groups:
But do not comprise the compound of array structure down:
The preparation method of the conjugate of above-mentioned growth hormone and agricultural chemicals carries out coupling with the amino of the carboxyl of auxins compound and pesticide molecule or hydroxyl, obtains the conjugate of growth hormone and agricultural chemicals.Concrete grammar is: with heteroauxin or methyl or phenoxy acetic acid or 2,4-dichlorphenoxyacetic acid or 3,4, the 5-trichlorophenoxyacetic acid is dissolved in the anhydrous methylene chloride, DMAP (the N that adds catalytic amount, the N-dimethyl aminopyridine), adds the equimolar agricultural chemicals that contains amino or hydroxyl then, add equimolar DCC (dicyclohexyl carbimide) at last, normal-temperature reaction 2～24 hours, filter after reacting completely, discard filter residue, filtrate is washed reaction system 2 times with watery hydrochloric acid and saturated sodium bicarbonate solution respectively, be washed to neutrality, precipitation, column chromatography purification gets product.
Compared with prior art, the present invention has following beneficial effect: the present invention utilizes the plant auxins material to have the feature of conducting by plant corpus downwards, and it is carried out coupling as lead compound and agricultural chemicals, obtains the conjugate of growth hormone and agricultural chemicals.The conjugate of gained growth hormone and agricultural chemicals can be under the mediation of homing device at growth hormone in plant corpus, and in the downward transporting of the phloem of plant, and agricultural chemicals has and the agricultural chemicals similar biologically active of lotus root before closing.So just can pass through the foliar spray dispenser, prevent and treat plant root and vascular disease insect pest, be used for kill pests, germ or other pest.
Embodiment
Embodiment 1: the lotus root of heteroauxin and alkene azoles alcohol is closed, that is: 2.2 2 '-and (1H-indol-3-yl) acetate-1-(2,4 dichloro benzene base)-4,4-dimethyl-2-(1H-1,2,4-triazol-1-yl)-3-penta-1-alkene-ester synthetic
Take by weighing heteroauxin crystal 1.76g (0.01mol) in the 50ml round-bottomed flask, add the 15ml anhydrous methylene chloride, dissolving.Add 0.2g DMAP, add the former medicine of 2.96g alkene azoles alcohol after the dissolving again, magnetic agitation places ice bath to be cooled to about 0 ℃ to dissolving fully.Take by weighing 2.81g (0.011mol) DCC, be dissolved in the carrene of 10ml, drop in the flask.Install drying tube, reaction 10h.Reaction system is filtered, and precipitation uses 20ml washed with dichloromethane, cleaning solution to change in the lump in the separatory funnel of 250ml, washs 2 times with the HCl solution of 0.5mol/L and saturated sodium bicarbonate solution respectively, is washed with water to neutrality, the anhydrous MgSO of dichloromethane layer
4Drying, rotary evaporator concentrate near doing.Sample is crossed post through silicagel column, and benzinum and ethyl acetate gradient elution purify, and weighs the heavy 3.07g of product, productive rate 67.8%.Product fusing point 109.3～117.1, ultraviolet maximum absorption wavelength 256nm,
1HNMR result is:
1HNMR (500MHz, CDCl
3) δ: 0.63 (s, 9H ,-C (CH
3)
3), 4.01,3.97 (each 1H, d, J=16.0Hz, CH
2), 5.83 (s, 1H, CH-tert-butayl), 7.12 (s, 1H, CH-(in indole H-2), 7.13-7.76 (m, 7H, C
6H
4, C
6H
3), 7.93 (s, 1H, CH-(in triazol H-5)), 8.66 (s, 1H, CH-(in triazol H-3)).
Embodiment 2: the lotus root of methyl and Triadimenol is closed, that is: 2 '-naphthyl-acetate-1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butyl ester synthetic
The concrete operations of test are identical with embodiment 1, and last product is a white solid, productive rate 57%, and fusing point 91.2～93.7, uv-absorption maximum wavelength 282nm, the proton nmr spectra result is:
1HNMR (500MHz, CDCl
3) δ: 0.76 (s, 9H, C (CH
3)
3), 4.20 (d, J=16.2,1H, naphthyl-CH
2 (a)-), 4.27 (d, J=16.2,1H, naphthyl-CH
2 (b)-), 5.25 (d, J=5.3,1H, CH-tert-butyl), 6.53 (d, J=5.25,1H,-CH-triazol), 7.33,6.91 (each 1H, d, J=8.0Hz, ph-4H), 7.32-7.51 (7H, m, naphthyl-7H), 8.07 (s, 1H ,-CH-(in triazol H-5), (8.78 s, 1H, CH-(in triazol H-3)), the mass spectrum result is: ESI-MS m/z:927[2M+H]
+, 949[2M+Na]
+, 502[M+K]
+, 486[M+Na]
+, 464[M+H]
+, 395[M-C2H2N3]
+
Embodiment 3:2,4, the lotus root of 5-T and fluorine worm cyanogen is closed, that is: 1-[3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-trifluoromethyl sulphinyl base-1H-pyrazoles-5-yl]-3-[2-(2,4, the 5-Trichlorophenoxy) acetyl group] urea synthetic
Drop into 2,4 in the 100mL there-necked flask, 5-trichlorophenoxyacetic acid and thionyl chloride (heavily steaming before the use) mol ratio is 1: 1.2, loads onto agitator, and reflux condensing tube (having drying tube) and thermometer, backflow stirring reaction do not have gas overflows, and needs 5h approximately.The gas of emitting in the course of reaction absorbs with the NaOH aqueous solution, 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 decompression distillation again, obtains weak yellow liquid.
Be equipped with agitator, thermometer, dropping funel and heating, add fluorine worm nitrile in the 100mL there-necked flask of cooling device respectively, triethylamine, N, N-dimethylamino naphthyridine (mol ratio is 1: 1.3: 0.1) and an amount of chloroform are under 0 ℃, slowly splash into the acyl chlorides of 1.2 equivalents, naturally rise to room temperature, add hot reflux 10h, be chilled to room temperature, with 2 * 20mL1% watery 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 benzinum is eluant, eluent, and the gradient elution column chromatography for separation obtains target compound.
Product is a white solid, productive rate 37.2%.
1H NMR (400MHz, CDCl3) δ: 10.87,8.85 (each 1H, s, NH * 2), 7.81,7.78 (each 1H, s, H-3 ' and H-5 '), 7.51 (1H, s, H-8 "), 6.97 (1H, s, H-11 "), 4.60 (2H, s, H2-4 ").
Embodiment 4:2, the lotus root of 4-D and carbofuran is closed, that is: N-[2-(2,4 dichloro benzene oxygen base) acetyl group]-N-methyl carbamic acid-2,2-dimethyl-2,3-Dihydrobenzofuranes-7-a base ester synthetic
In being equipped with the 50mL there-necked flask of agitator, thermometer, dropping funel, drying tube and heater, add carbofuran, sodium hydride (mol ratio is 1: 1) respectively, an amount of anhydrous tetrahydro furan, stirring at room 4h, ice bath is cooled to 0 ℃, slowly drip the tetrahydrofuran solution of 1.2 equivalent acyl chlorides, maintain the temperature at below 5 ℃, continue to stir 1h, be raised to room temperature naturally, stir 5h, in the impouring 30mL1% hydrochloric acid, with 3 * 30mL ethyl acetate extraction, combined ethyl acetate layer, with 2 * 20mL distilled water wash organic facies, anhydrous sodium sulfate drying, precipitation.With ethyl acetate and benzinum is solvent, and the gradient elution column chromatography for separation obtains target compound.
Embodiment 5: heteroauxin with hold up the lotus root of lucky amine to close, that is: N-(3-chloro-2,6-dinitro-4-trifluoromethyl) phenyl-N-(3-chloro-5-trifluoromethyl)-pyridine-2 '-Ji-2-(1H-indol-3-yl)-acetamide is synthetic:
Take by weighing heteroauxin crystal 1.76g (0.01mol) in the 50ml round-bottomed flask, add the 15ml anhydrous methylene chloride, dissolving.Add 0.2g DMAP, add 4.65g after the dissolving again and hold up the former medicine of lucky amine, magnetic agitation places ice bath to be cooled to about 0 ℃ to dissolving fully.Take by weighing 2.81g (0.011mol) DCC, be dissolved in the carrene of 10ml, drop in the flask.Install drying tube, reaction 10h.Reaction system is filtered, and precipitation uses 20ml washed with dichloromethane, cleaning solution to change in the lump in the separatory funnel of 250ml, washs 2 times with the HCl solution of 0.5mol/L and saturated sodium bicarbonate solution respectively, is washed with water to neutrality, the anhydrous MgSO of dichloromethane layer
4Drying, rotary evaporator concentrate near doing.Ethyl acetate and benzinum system column chromatography purification get white crystal 4.5g, productive rate 72.8%.Product
1HNMR is: 3.37 (s, 2H, CH
2-induo), and 6.5-8.8 (m, 8H, phenyl-, pyridinyl-).
Embodiment 6 conductivity experiment 1
With the conjugate of alkene azoles alcohol and methyl concentration according to 200mg/L, big bean seedlings are carried out respectively utilizing the content of liquid chromatography for measuring at each position conjugate of plant after foliar spray and water planting handle, as shown in table 1.
Presentation of results in the table after methyl and alkene azoles alcohol lotus root are closed, can upwards conduct, and also can conduct downwards.And alkene azoles alcohol be considered to the to make progress compound of unidirectional conduction itself.
Table 1 alkene azoles alcohol is handled the assay result of back at each position of plant with the conjugate of methyl to the soybean spraying
| Mode | Time (h) | The content at each position (μ gg -1) | ||
| Root | Stem | Leaf | ||
| The spraying water planting | 12 24 36 48 60 12 24 36 48 60 | 1.87 1.21 1.54 0.73 0.34 12.5 18.2 30.1 32.6 26.8 | 0.68 2.05 0.91 1.02 0.43 2.5 5.2 7.3 9.8 7.6 | 8.12 10.81 10.65 5.84 2.61 4.6 6.8 8.7 17.4 19.0 |
Embodiment 7 conductivity experiment 2
With 2, the conjugate of 4-D and fluorine worm cyanogen is according to the concentration of 100mg/L, after the processing of cabbage mustard water planting and being coated with the leaf processing, utilize the content of liquid chromatography for measuring at each position conjugate of plant and fluorine worm cyanogen, testing conditions is: flowing phase: acetonitrile: water=60: 40 (v/v); Detect wavelength: 295nm; Chromatographic column: C
18Post; Flow velocity: 1mLmin
-1Sample size: 10 μ L.The result is respectively shown in table 2 and table 3.
The presentation of results of table 2, fluorine worm cyanogen and 2,4, the conjugate of 5-T can conduction from bottom to top in the cabbage mustard plant through water planting.As known from Table 3, fluorine worm cyanogen and 2,4, the conjugate of 5-T is coated with the content that the leaf method is handled each position behind the cabbage mustard, handles 12,24,36 and 48h, and the conjugate content in the cabbage mustard blade that is untreated reaches maximum at 48h, and the prolongation along with the time is arranged, and content has the trend of increase; Handle between the 36-48h, the strongest from handling transporting in the blade to the ability in the amount blade not, and along with the prolongation of time, the transporting amount also has the trend that increases.Handle between the 36-48h, conjugate is the amount maximum of transporting in the stem from handle blade, and the prolongation along with the time is arranged, and the transporting amount has the trend of increase.Therefore fluorine worm cyanogen and 2,4 has had the characteristic of two-way conduction after the 5-T lotus root is closed.
Table 2 fluorine worm cyanogen and 2,4, the conjugate of 5-T is handled the back in each position assay result of plant to the cabbage mustard water planting
| Processing time (h) | Stem (μ gg -1) | Leaf (μ gg -1) | Root (μ gg -1) |
| 12 24 36 48 | 0.42 0.49 0.56 0.69 | 0.65 0.50 0.41 0.81 | 7.88 15.18 32.72 20.63 |
Table 3 fluorine worm cyanogen and 2,4, the conjugate of 5-T are sprayed to cabbage mustard and are handled the back in each position assay result of plant
| Processing time (h) | Leaf (μ gg is untreated -1) | Stem (μ gg -1) | Handle leaf (μ gg -1) |
| 12 24 36 48 | 1.63 1.65 2.59 3.56 | 0.50 1.33 1.91 7.32 | 26.03 34.16 41.42 47.14 |
Embodiment 8 conductivity experiment 3
The conductivity test of the conjugate of heteroauxin and probenazole in tobacco plant: with the conjugate of heteroauxin and probenazole concentration according to 200mg/L, after the intermediate blade of the tobacco plants of 10～13 leaf phases is coated with leaf and handles, utilize the content of liquid chromatography for measuring conjugate in each position blade of plant, as shown in table 4.
Presentation of results in the table 4 after methyl and probenazole lotus root are closed, can absorb to the bottom of plant conduction by blade.And probenazole itself does not have this conductivity.
The conductivity test of the conjugate of table 4 heteroauxin and probenazole in tobacco plant
| Processing time (h) | Handle upper blade (the μ gg of leaf -1) | Handle lower blade (the μ gg of leaf -1) | Handle leaf (μ gg -1) |
| 12 24 | 1.56 2.24 | 1.10 1.45 | 12.45 20.61 |
| 36 48 | 3.53 3.27 | 3.21 2.54 | 31.82 28.94 |
Embodiment 9 conductivity experiment 4
2, the conductivity test of the conjugate of 4-D and dimethyl bacterium amine in tobacco plant: with 2, the conjugate of 4-D and dimethyl bacterium amine is according to the concentration of 100mg/L, after the intermediate blade of the tobacco plants of 10～13 leaf phases is coated with leaf and handles, utilize the content of liquid chromatography for measuring conjugate in each position blade of plant, as shown in table 5.Presentation of results in the table 5,2, after 4-D and dimethyl bacterium amine lotus root are closed, can absorb to the top and the bottom of plant conduction by blade.
The conductivity test in tobacco plant of table 52, the conjugate of 4-D and dimethyl bacterium amine
| Processing time (h) | Handle upper blade (the μ gg of leaf -1) | Handle lower blade (the μ gg of leaf -1) | Handle leaf (μ gg -1) |
| 12 24 36 48 | 2.45 3.16 3.78 4.35 | 1.35 1.54 2.50 3.33 | 8.63 15.21 17.48 15.20 |
Embodiment 10 conductivity experiment 5
The conductivity test of the conjugate of methyl and Nitenpyram in tobacco plant: with the conjugate of methyl and Nitenpyram concentration according to 200mg/L, after the intermediate blade of the tobacco plants of 10～13 leaf phases is coated with leaf and handles, utilize the content of liquid chromatography for measuring conjugate in each position blade of plant, as shown in table 6.Table 6 presentation of results after methyl and Nitenpyram lotus root are closed, can absorb to the top and the bottom of plant conduction by blade.
The conductivity test of the conjugate of table 6 methyl and Nitenpyram in tobacco plant
| Processing time (h) | Handle upper blade (the μ gg of leaf -1) | Handle lower blade (the μ gg of leaf -1) | Handle leaf (μ gg -1) |
| 12 24 36 | 3.23 4.62 3.98 | 2.11 3.17 2.50 | 11.58 18.21 15.35 |
| 48 | 2.41 | 2.16 | 10.27 |
Embodiment 11 conductivity experiment 6
2,4, the conductivity test of the conjugate of 5-T and phonetic worm amine in tobacco plant: with 2,4, the conjugate of 5-T and phonetic worm amine is according to the concentration of 100mg/L, after the intermediate blade of the tobacco plants of 10～13 leaf phases is coated with leaf and handles, utilize the content of liquid chromatography for measuring conjugate in each position blade of plant, as shown in table 7.Presentation of results in the table 7,2,4, after 5-T and phonetic worm amine lotus root are closed, can absorb to the top and the bottom of plant conduction by blade.
The conductivity test in tobacco plant of table 72,4, the conjugate of 5-T and phonetic worm amine
| Processing time (h) | Handle upper blade (the μ gg of leaf -1) | Handle lower blade (the μ gg of leaf -1) | Handle leaf (μ gg -1) |
| 12 24 36 48 | 2.45 3.16 3.78 4.35 | 1.35 1.54 2.50 3.33 | 8.63 15.21 17.48 15.20 |
Embodiment 12 conductivity experiment 7
The conductivity test of the conjugate that heteroauxin and pleasure must be ploughed in soybean plant strain: the conjugate that heteroauxin and pleasure must be ploughed is according to the concentration of 100mg/L, after spraying of the soybean plant strains of 8～10 leaf phases handled, utilize the content of liquid chromatography for measuring at each position conjugate of plant, as shown in table 8.Presentation of results in the table 8, heteroauxin and pleasure must be ploughed after lotus root closes, and can conduct to root from top in soybean plant strain.
The conductivity test of the conjugate that table 8 heteroauxin and pleasure must be ploughed in soybean plant strain
| Processing time (h) | Leaf (μ gg -1) | Stem (μ gg -1) | Root (μ gg -1) |
| 12 24 36 48 | 21.12 23.46 22.87 15.34 | 1.05 1.24 2.50 1.33 | 0.63 1.21 1.48 1.20 |
Embodiment 13 conductivity experiment 8
2, the conductivity test of the conjugate of 4-D and ferimzone in tobacco plant: with 2, the conjugate of 4-D and ferimzone is according to the concentration of 200mg/L, after the intermediate blade of the tobacco plants of 10～13 leaf phases is coated with leaf and handles, utilize the content of liquid chromatography for measuring conjugate in each position blade of plant, as shown in table 9.Presentation of results in the table 9,2, after 4-D and ferimzone lotus root are closed, can absorb to the top and the bottom of plant conduction by blade.
The conductivity test in tobacco plant of table 92, the conjugate of 4-D and ferimzone
| Processing time (h) | Handle upper blade (the μ gg of leaf -1) | Handle lower blade (the μ gg of leaf -1) | Handle leaf (μ gg -1) |
| 12 24 36 48 | 2.61 3.15 4.25 3.51 | 2.71 3.82 2.48 2.10 | 12.52 20.49 25.17 19.93 |
Embodiment 14 conductivity experiment 9
2,4, the conductivity test of the conjugate of 5-T and unden in tobacco plant: with 2,4, the conjugate of 5-T and unden is according to the concentration of 200mg/L, after the intermediate blade of the tobacco plants of 10～13 leaf phases is coated with leaf and handles, utilize the content of liquid chromatography for measuring conjugate in each position blade of plant, as shown in table 10.Presentation of results in the table 10,2,4, after 5-T and unden lotus root are closed, can absorb to the top and the bottom of plant conduction by blade.
The conductivity test in tobacco plant of table 10 2,4, the conjugate of 5-T and unden
| Processing time (h) | Handle upper blade (the μ gg of leaf -1) | Handle lower blade (the μ gg of leaf -1) | Handle leaf (μ gg -1) |
| 12 24 36 48 | 1.48 1.99 2.16 1.65 | 3.24 4.25 5.13 3.97 | 35.12 37.51 28.34 25.66 |
Embodiment 15 conductivity experiment 10
Heteroauxin and the conductivity test of the conjugate of holding up lucky amine in tobacco plant: with heteroauxin with hold up the concentration of the conjugate of lucky amine according to 100mg/L, after the intermediate blade of the tobacco plants of 10～13 leaf phases is coated with leaf and handles, utilize the content of liquid chromatography for measuring conjugate in each position blade of plant, as shown in table 11.Presentation of results in the table 11, heteroauxin with hold up lucky amine lotus root to close after, can absorb to the top and the bottom of plant conduction by blade.
Table 11 heteroauxin and the conductivity test of the conjugate of holding up lucky amine in tobacco plant
| Processing time (h) | Handle upper blade (the μ gg of leaf -1) | Handle lower blade (the μ gg of leaf -1) | Handle leaf (μ gg -1) |
| 12 24 36 48 | 1.05 1.54 1.21 0.87 | 2.55 3.84 3.46 3.33 | 21.13 25.14 27.61 20.58 |
Embodiment 16 insecticidal tests 1
2,4 dichlorophenoxyacetic acid 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 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 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.Check dead borer population 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.As can be seen from Table 12, the biologically active of fluorine worm nitrile and 2,4 dichlorophenoxyacetic acid conjugate is higher than fluorine worm nitrile.
Table 12 fluorine worm nitrile and 2,4 dichlorophenoxyacetic acid conjugate and fluorine worm nitrile are to diamond-back moth 3 instar larvae toxicity tests
| Sample | Time (h) | Regression equation/(y=a+bx) | Correlation coefficient (r) | LC 50 (μg·mL -1) | LC 5095% confidence interval (μ gmL -1) |
| Fluorine worm nitrile and 2,4-dichlorphenoxyacetic acid conjugate fluorine worm nitrile | 24 24 | y＝2.6592+2.1286x y＝2.9391+1.4679x | 0.9999 0.9668 | 12.58 25.35 | 7.64～20.70 10.86～59.19 |
| 48 | y＝3.2688+1.5864x | 0.9423 | 12.34 | 8.14～18.70 |
Embodiment 17 insecticidal tests 2
2,4,5-trichlorophenoxyacetic acid 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 with the sample acetone solution, get the 1mL sample solution in the test tube of white granulated sugar, shake up, make sample dry up standby 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.Carbofuran and 2,4 as can be seen from Table 13,5-trichlorophenoxyacetic acid conjugate is suitable to the biologically active and the carbofuran of adult housefly.
Table 13 carbofuran and 2,4,5-trichlorophenoxyacetic acid conjugate and carbofuran are to the adult housefly toxicity test
| Sample | Time (h) | Regression equation/(y=a+bx) | Correlation coefficient (r) | LC 50 (μg·mL -1) | LC 5095% confidence interval (μ gmL -1) |
| Carbofuran carbofuran and 2,4,5-trichlorophenoxyacetic acid conjugate | 24 24 | y＝3.3123+1.3413x y＝0.3214+3.3858x | 0.9968 0.9783 | 18.13 24.09 | 10.53～31.21 19.65～29.54 |
Embodiment 18 bactericidal assay 1
Adopt mycelial growth rate to suppress method, measure Triadimenol and the indoor bacteriostatic activity of heteroauxin conjugate respectively, and with the former powder of Triadimenol in contrast, the calculating soup is to the inhibiting rate of mycelial growth, the calculating medicament is to the EC of Rhizoctonia solani Kuhn
50Triadimenol and heteroauxin conjugate are to the EC of Rhizoctonia solani Kuhn
50Be (2.33 ± 0.27) mg/L, Triadimenol is (1.61 ± 0.15) mg/L, shows that Triadimenol and heteroauxin conjugate are suitable to the biologically active and the Triadimenol of Rhizoctonia solani Kuhn.
Embodiment 19 bactericidal assay 2
Adopt mycelial growth rate to suppress method, measure alkene azoles alcohol and the indoor bacteriostatic activity of heteroauxin conjugate respectively, and with the former powder of alkene azoles alcohol in contrast, calculate the inhibiting rate of soup to mycelial growth, the calculating medicament is to the EC of Rhizoctonia solani Kuhn
50Alkene azoles alcohol and the EC of heteroauxin conjugate to Rhizoctonia solani Kuhn
50Be (1.08 ± 0.74) mg/L, Triadimenol is (0.72 ± 0.33) mg/L, shows that alkene azoles alcohol and heteroauxin conjugate are suitable with alkene azoles alcohol to the biologically active of Rhizoctonia solani Kuhn.
Claims (5)
1, the conjugate of growth hormone and agricultural chemicals, its general formula are as (I) formula:
Wherein:
R1 is the residue of removing in the growth hormone molecule behind the carboxyethyl;
R2 is the pesticide molecule that has amino, imino group or hydroxyl, removes deaminize hydrogen or imino group hydrogen or the later residue of hydroxyl hydrogen.
2, conjugate as claimed in claim 1 is characterized in that,
R1 is for being selected from following groups:
R2 is for being selected from following groups:
But do not comprise the compound of array structure down:
3, the preparation method of claim 1 or 2 described conjugates is characterized in that the carboxyl of auxins compound and the amino or the hydroxyl of pesticide molecule are carried out coupling, obtains the conjugate of growth hormone and agricultural chemicals.
4, preparation method as claimed in claim 3, it is characterized in that comprising the steps: with heteroauxin or methyl or phenoxy acetic acid or 2,4-dichlorphenoxyacetic acid or 2,4, the 5-trichlorophenoxyacetic acid is dissolved in the anhydrous methylene chloride, adds the N of catalytic amount, the N-dimethyl aminopyridine, add the equimolar agricultural chemicals that contains amino or hydroxyl then, add equimolar dicyclohexyl carbimide at last, normal-temperature reaction 2～24 hours, filter the back that reacts completely, discard filter residue, filtrate is washed reaction system with watery hydrochloric acid and saturated sodium bicarbonate solution respectively, is washed to neutrality, precipitation, column chromatography purification gets product.
5, conjugate described in the claim 1 or 2 is as the application in insecticide or the bactericide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100369331A CN100556896C (en) | 2006-08-04 | 2006-08-04 | Coupling substance of growth hormone and agricultural chemicals and preparation method thereof and application as agricultural chemicals |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100369331A CN100556896C (en) | 2006-08-04 | 2006-08-04 | Coupling substance of growth hormone and agricultural chemicals and preparation method thereof and application as agricultural chemicals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1907023A true CN1907023A (en) | 2007-02-07 |
| CN100556896C CN100556896C (en) | 2009-11-04 |
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| CNB2006100369331A Expired - Fee Related CN100556896C (en) | 2006-08-04 | 2006-08-04 | Coupling substance of growth hormone and agricultural chemicals and preparation method thereof and application as agricultural chemicals |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058943A (en) * | 2013-01-08 | 2013-04-24 | 河南师范大学 | Diniconazole-1,2,3-triazole compound having antibacterial activity, and its preparation method |
| CN107629005A (en) * | 2017-08-22 | 2018-01-26 | 王泊理 | Polysubstituted phenylpyrazole derivatives and its production and use |
| CN111978243A (en) * | 2019-05-24 | 2020-11-24 | 南开大学 | Synthesis and application of oxalic acid monoester derivative |
| CN111978244A (en) * | 2019-05-24 | 2020-11-24 | 南开大学 | Synthesis and application of nitenpyram acyl derivatives |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201410148A (en) * | 2012-06-07 | 2014-03-16 | Dow Agrosciences Llc | Methods of improving the yield of 2,4-D resistant crop plants |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058943A (en) * | 2013-01-08 | 2013-04-24 | 河南师范大学 | Diniconazole-1,2,3-triazole compound having antibacterial activity, and its preparation method |
| CN107629005A (en) * | 2017-08-22 | 2018-01-26 | 王泊理 | Polysubstituted phenylpyrazole derivatives and its production and use |
| CN111978243A (en) * | 2019-05-24 | 2020-11-24 | 南开大学 | Synthesis and application of oxalic acid monoester derivative |
| CN111978244A (en) * | 2019-05-24 | 2020-11-24 | 南开大学 | Synthesis and application of nitenpyram acyl derivatives |
| CN111978244B (en) * | 2019-05-24 | 2022-09-06 | 南开大学 | Synthesis and application of nitenpyram acyl derivatives |
| CN111978243B (en) * | 2019-05-24 | 2022-09-06 | 南开大学 | Synthesis and application of oxalic acid monoester derivative |
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| CN100556896C (en) | 2009-11-04 |
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