CN103833735B - A kind of compound preventing and treating downy mildew of garpe and apply its compositions - Google Patents
A kind of compound preventing and treating downy mildew of garpe and apply its compositions Download PDFInfo
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- CN103833735B CN103833735B CN201410065333.2A CN201410065333A CN103833735B CN 103833735 B CN103833735 B CN 103833735B CN 201410065333 A CN201410065333 A CN 201410065333A CN 103833735 B CN103833735 B CN 103833735B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
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Abstract
The invention provides a kind of organic compound preventing and treating downy mildew of garpe and compositions thereof, it can prepare into the dosage forms such as soluble liquid, microemulsion, aqueous emulsion, suspension emulsion, seed coat agent, wettable powder granule, sustained-release granular formulation, controlled release granule, water dispersible granules, dry suspension emulsion, or the granule directly used.Described compositions is used for preventing and treating downy mildew of garpe.
Description
Technical field
The present invention relates to agricultural chemical compound and compositions field thereof, prevent and treat downy mildew of garpe compound and compositions thereof particularly to one.
Background technology
Downy mildew of garpe is that pathogenic bacteria is primary on the amur grape of eastern North America by fungus-caused a kind of worldwide disease.19 th century later, plant Fructus Vitis viniferae to whole world introducing and planting with Europe, and downy mildew of garpe propagates all vinegrowing districts, the whole world, and the chemical bactericide Bordeaux mixture as invented the earliest is aiming at this disease and occurs and find.All there is generation each grape growing region of China, and disease mainly infects the tender organ of children of plant, harm blade, the tender tip and young fruit.If preventing and treating is not in time, downy mildew is very big on Fructus Vitis viniferae tree vigo(u)r and yield thereof and quality impact.More almost all there is distribution downy mildew of garpe each viny region.Downy mildew of garpe main harm blade, also can infect the tender tissues such as young sprout young fruit.Blade is killed, the fleck that nascent faint yellow water stain shape blur margin is clear, expands as the irregular shape of brown or polygon scab gradually later, and number speckle is connected and becomes the big speckle of irregular shape.During wet weather, produce white downy mildew shape thing in the scab back side, i.e. the sporangiophore of pathogenic bacteria and Sporangium.Serious seasonal disease leaf of falling ill is early withered caducous, and the tender tip is injured, and forms water soaked spots, after become the slightly concave sunken scab of brown, time moist, scab also produces white downy mildew.Young sprout distortion time seriously ill, growth stops, even withered.Tendril, cob, petiole sometimes also can be killed, and its symptom is similar to the tender tip.Young fruit is killed, fades in disease portion, hardening sagging, and upper raw white downy mildew, very easy atrophy comes off.Being injured when fruit grain is medium-sized, disease portion brown is to dark-coloured, and soft corruption is caducous.No longer infect after fruit color.
Pathogenic bacteria survives the winter in diseased tissues or with invalid body with oospore in soil, can survive 1～2 year.Green sprouting in next year produces sporangium, sporangium produces zoospore, propagate on host's blade by means of wind and rain, invaded by pore, mycelia spreads at intercellular substance, and grows cone haustorium and stretch and draw nutriment in people's host cell, then stretches out sporangiophore from pore, produce Sporangium, infect again by means of wind and rain.The incubation period of disease only has 4～13 days in susceptible variety, and disease-resistant variety then needs 20 days.Autumn end pathogenic bacteria coordinates through oogonium and pollinodium in diseased tissues, forms oospore and survives the winter.
Weather conditions are very big on morbidity and popular impact.Occurring in the fall more than this disease, be grape growth later stage disease, the weather of the humidity that cools favorably is fallen ill.Pathogenic bacteria Germination of Oospores temperature range 13～33 DEG C, preference temperature 25 DEG C, there are moisture or the rain and dew of abundance simultaneously.Sporangium Germination Temperature scope 5～27 DEG C, preference temperature 10～15 DEG C, and to have free water to exist.Sporangium formation temperature 13～28 DEG C, about 15 DEG C formation Sporangiums are maximum, it is desirable to relative humidity 95～100%.Zoospore output temperature range 12～30 DEG C, preference temperature 18～24 DEG C, water droplet must be had to exist.Test shows: when Sporangium has rain and dew to exist, and sprouts 40-50% for 21 DEG C, sprouts 95% when 10 DEG C；Sporangium can be survived 4～6 days in high temperature drying condition, can survive at low temperatures 14～16 days；Zoospore can invade spire when relative humidity 70～80%, and relative humidity Lao Ye when 80～100% just can be injured.Therefore autumn low temperature, rainy easily cause the popular of this disease.
For a long time, controlling downy mildew of garpe and rely primarily on chemical agent such as lime sulfur, auspicious poison mancozeb wettable powder, AL-PHOSETHYL aluminum tris(ethyl phosphite) wettable powder, ridomil, Mancozeb, metalaxyl, M 9834, Sandofan etc., developing medicament recently has dimethomorph, flumorph, cymoxanil etc..In recent years, due to long-term single use, pathogenic bacteria produces Drug resistance in various degree, and metalaxyl almost loses preventive effect in the old producing region of Fructus Vitis viniferae, and the systemic fungicide preventive effect such as AL-PHOSETHYL aluminum tris(ethyl phosphite), the many Mils of thunder is gradually lowered.
Summary of the invention
Present invention aim at providing a kind of organic compound preventing and treating downy mildew of garpe and compositions thereof, to be solved technical problem is that prevents and treats downy mildew of garpe.
The described organic compound preventing and treating downy mildew of garpe, it has following chemical structural formula
Preferably, it is crystal, and described crystal belongs to orthorhombic system, and its space group is P21, β=89.5°。
Described organic compound auxiliary agent acceptable with on pesticide, surfactant, solvent prepare into composition pesticide with carrier；
Described auxiliary agent and surfactant are preferably one or more in dispersing agent NNO, sodium lauryl sulphate, dispersing agent MF, sodium lignin sulfonate, agriculture breast 600#, fatty alcohol-polyoxyethylene ether, naphthalene sulfonic acid formaldehyde condensation polymer, ammonium sulfate, emulsifying agent 603#, calcium dodecyl benzene sulfonate 500#；One or more in the preferred isopropanol of described solvent, dimethylformamide, Ketohexamethylene, ethyl acetate, dimethylbenzene；One or more in the preferred white carbon of described carrier, Kaolin, water, potter's clay.
Described compositions can be prepared for soluble liquid, microemulsion, aqueous emulsion, suspension emulsion, seed coat agent, wettable powder granule, sustained-release granular formulation, controlled release granule, water dispersible granules, dry suspension emulsion, or the granule directly used；
Described compositions can prevent and treat downy mildew of garpe.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic spectrum that the present invention prepares embodiment 1 compound
Detailed description of the invention
The invention will be further described by the examples below.It should be understood that preparation method described in the embodiment of the present invention is only used for illustrating the present invention rather than limitation of the present invention, under the concept thereof of the present invention, the simple modifications of preparation method of the present invention is broadly fallen into the scope of protection of present invention.The all raw materials used in embodiment and solvent are all purchased from SigmaBiochemicalandOrganicCompoundsforResearchandDiagnos ticClinicalReagents company.
Preparation embodiment 1
Synthesis step:
(1) in being furnished with the reaction bulb of mechanical agitation and reflux condensing tube, fluoro-4 toluene bromides of 0.4mol2-and 14.4g benzoyl peroxide are added, the lower heating of stirring is to backflow, by bromo-for 0.4mol2-2,5-pyrroledione (NBS) was dividedly in some parts reaction bulb in 20 minutes, it is heated to reflux 2 hours, reaction yield 65% (GC).Reactant liquor adds sodium carbonate and neutralizes, concentration, dissolves with industry anhydrous ethanol (1g:1mL) backflow, is cooled to-15 DEG C and carries out recrystallization, purity about 90% (GC).Repeatedly obtain white crystal product, its purity after recrystallization > 99%.
(2), under nitrogen protection, in being furnished with the reaction bulb of mechanical agitation and reflux condensing tube, 0.05mol carbazole, 100mLDMF are added; ice bath is cooled to 5 DEG C, is slowly added dropwise phosphorus oxychloride 0.1mol under stirring, after being added dropwise to complete; remove ice bath, after 1 hour, rise to room temperature.It is heated to reflux 12 hours.Reactant liquor adds 100mL water, then divides 4 times by 400mL ethyl acetate and extract, and organic facies merges, and is washed to neutrality, and anhydrous magnesium sulfate dries, after removing ethyl acetate, and silica gel chromatography, obtain white solid, isolated yield 62%.
(3) under nitrogen protection, adding 0.03mol step (1) product, 0.09mol NSC 5284 in being furnished with the reaction bulb of mechanical agitation and reflux condensing tube, the lower heating of stirring, to backflow, is reacted 1 hour.After reaction stops, decompression distills out excessive NSC 5284.After having distilled, it is cooled to room temperature, with ice bath cooling down reaction temperature to 5 DEG C.Keeping reaction temperature is 5 DEG C, is dividedly in some parts 0.03mol potassium tert-butoxide in 20 minutes, after reacting 1 hour, the dropping THF solution 35mL containing 0.03mol step (2) product, reacts 2 hours.Reactant liquor adds 100mL water and 100mL dichloromethane, separatory, and aqueous phase uses 100mL dichloromethane extraction again, after merging organic facies and being washed till neutrality with water and a small amount of dilute hydrochloric acid, anhydrous magnesium sulfate dries, and removes dichloromethane, silica gel chromatography, obtains yellow solid, isolated yield 45%.
(4) under nitrogen protection; the reaction bulb being furnished with mechanical agitation, reflux condensing tube adds 0.01mol step (3) product; 0.012mol2-(tributyl tinbase) triazole; 3%mol tetra-(triphenylphosphinyl) palladium; 50mL toluene; stirring, heating, to backflow, is reacted 48 hours.Reactant liquor dries under vacuo, adds 100mL dichloromethane and dissolves, divides three washings with 6M hydrochloric acid 60mL, aqueous phase under the state of cooling with in 10% ammonia and, use 100mL dichloromethane extraction again, merge organic facies, add 50mL water and with 10% ammonia scrubbing to neutral.Collect organic facies, dry, cross silica gel column chromatography and purify, obtain yellow solid, isolated yield 43%.
Structural Identification:
1HNMR (DMSO-d6): δ (ppm), 11.66 (s, 1H, NH), 8.19 (d, 1H, CH), 8.12 (d, 1H, CH), 7.63 (s, 1H, CH), 7.62 (d, 1H, CH), 7.56 (d, 1H, CH), 7.22 (d, 1H, H), 6.78 (s, 1H, H), 4.22 (m, 2H, CH2), 2.30 (s, 1H, NH).
Elementary analysis: actual measurement C:74.14, N:15.72, H:4.81, F:5.33:
After measured, the fusing point of this material is 171-172 DEG C.
Preparation embodiment 2
Organic compound prepared by above-mentioned (4th) step is placed in quartz ampoule (quartzampoule).At temperature 100 DEG C, by this compound vacuum dehydration prepared.This pipe is disengaged, and is placed in crystal growing furnace.By Bridgman (Bridgman) method growth crystal in the dual stove (doublefurnace) have isolating membrane.Finally, colourless web crystal is obtained.This crystal is carried out Advances in crystal X-ray diffraction crystallographic analysis, and its crystallographic parameter is as follows: for orthorhombic system, its space group is P21, β=89.5°。
Preparation embodiment 3
Above raw materials etc. join after weighing by proportioning in shearing tank, shear and within 30 minutes, make mixing of materials uniform, open recirculated water, and by material ball milling with a certain amount of flow, temperature controls less than 40 degree, and fineness crosses 325 mesh sieves, after grinding 1.5h, obtains uniform emulsion liquid.
Preparation embodiment 4
Each raw material is added mix and blend in double worm mixer, pulverizes then through jet mill, mix by again passing by double worm mixer after 325 mesh sieves and obtain product.
Preparation embodiment 5
Each raw material being added mix and blend in double worm mixer, pulverizes then through jet mill, by again passing by double worm mixer mixing after 325 mesh sieves, rear addition pinches mixture granulation, the mixture pelleting of gained, is drying to obtain product.
Preparation embodiment 6
By said mixture Homogeneous phase mixing, comminution by gas stream, add suitable quantity of water and also mediate, the mixture pelleting of gained, be drying to obtain product.The addition of the auxiliary agents such as naphthalene sulfonic acid formaldehyde condensation polymer, sodium lauryl sulphate, ammonium sulfate, potter's clay, had both made for dosage form and had provided safeguard, and can make again the dispersibility that product maintenance is good, and the tack of target surface is relatively good.
BIOLOGICAL ACTIVITY EXAMPLES 1:
The PPAR δ activity of the compound represented by Formulas I of the present invention confirms by transfecting detection.It addition, the selectivity for PPAR hypotype PPAR α and PPAR γ is also carried out inspection.Test cell toxicity is detected, by animal experiment study activity in vivo by MTT.
This detection uses CV-1 cell.Described cell is seeded in 96 orifice plates containing the DMEM being added with 10%FBS, DBS (DBS, through defat) and 1% penicillin/streptomycin, and at 37 DEG C, 5%CO2Incubator in cultivate.Test and carry out according to the step of inoculation, transfection, sample administration and confirmation.Specifically, CV-1 cell is seeded to 96 orifice plates (5000 cells/well), transfects after 24 hours.By total length PPAR plasmid DNA, can confirm that because having uciferase activity PPAR activity reporter dna, provide the beta galactosidase DNA about transfection efficiency information and transfection reagent to be used for transfecting.Dissolve a sample in dimethyl sulfoxide (DMSO), by medium, it is administered in cell with variable concentrations.Incubator is cultivated cell after 24 hours, by using lysis buffer to make lysis.Photometer and microplate reader is used to measure uciferase activity and betagalactosidase activity.Use the value of the luciferase of the value correction acquisition of beta galactosidase.Utilize these value graphings, and calculate EC50。
| Compound | hPPARδ | hPPARα | hPPARγ |
| I | 2.5nM | ia | ia |
The compound of the present invention has high selectivity for PPAR δ as can be seen here.
Perform the cytotoxicity that MTT detection is the compound represented by formula (I) in order to test the present invention.MTT is dissolved in the yellow substance of water, but can become, by the dehydrogenase in mitochondrion, the crystal that purple is insoluble when it is introduced in living cells.Can pass through to measure OD550 after being dissolved in dimethyl sulfoxide by MTT and confirm cytotoxicity.Experiment is carried out as follows.
CV-1 cell is inoculated in 96 orifice plates (5000 cells/well).At 37 DEG C, 5%CO2Incubator in cultivate described cell 24 hours, and it is used the sample of variable concentrations.Then, again described cell is cultivated 24 hours, be added thereto to MTT reagent.After cultivating 15 minutes, the purple crystals of generation is dissolved in dimethyl sulfoxide.Microplate reader is used to measure optical density, to confirm cytotoxicity.
As a result, formula (I) compound represented is identified does not have cytotoxicity for PPAR, even if being EC in its concentration50Value 100 times～1000 times time also such.
BIOLOGICAL ACTIVITY EXAMPLES 2:
Reagent agent: preparation embodiment 3 emulsion.
For studying thing: Fructus Vitis viniferae, kind HONGTI.
Experimental field: test and Selection is in cowboying village, Huaxi District, Guiyang City, Guizhou Province, and experimental field physical features is smooth, soil property is well loam, and rich water quality management is consistent, and vine body growing way is uniformly neat, the age of tree 3 years, experimental field natural occurrence.
EXPERIMENTAL DESIGN: test sets a chemicals treatment district altogether.Process A: preparation embodiment 3 emulsion；B: clear water blank.
Adopting random alignment between district's group, repeat 3 times, amount to 18 communities, every community takes 5 strain vine investigation, the strain of whole test survey Fructus Vitis viniferae 90.
Spraying time, number of times and method: when grape branch middle and lower part starts morbidity, carry out Fructus Vitis viniferae spraying medicine for the first time, and dispenser adopts workers and peasants 16 type back of the body formula hand sprayer, and medicine liquid spray is uniformly thoughtful, and spouting liquid is 40ml/800m2.Interval sprays 1 time for 7 days, executes 3 times altogether.
Disease investigation method: investigation takes at random every time, 10, every community young sprout, and every tip investigates 15 leaves from top to bottom, records sick level respectively, by grade scale record, calculates disease index and prevention effect.
Downy mildew blade stage division:
0 grade: without scab；
1 grade: lesion area accounts for less than the 10% of whole leaf area；
3 grades: lesion area accounts for the 11%～25% of whole leaf area；
5 grades: lesion area accounts for the 26%～40% of whole leaf area；
7 grades: lesion area accounts for the 41%～65% of whole leaf area；
9 grades: lesion area accounts for more than the 65% of whole leaf area.
Drug effect computing formula:
Result and analysis:
Can be seen that the compound of embodiment 1 has good anti-downy mildew of garpe activity.
Claims (5)
1. the organic compound preventing and treating downy mildew of garpe, it is characterised in that represent with following chemical structural formula:
2. organic compound according to claim 1, it is characterised in that it is crystal, described crystal belongs to orthorhombic system, and its space group is P21, β=89.5 °.
3. a composition pesticide, it is characterised in that it includes acceptable auxiliary agent on the arbitrary described organic compound of claim 1-2 and pesticide.
4. the compositions described in claim 3, it can be made into soluble liquid, microemulsion, aqueous emulsion, suspension emulsion, seed coat agent, wettable powder granule, sustained-release granular formulation, controlled release granule, water dispersible granules.
5. the purposes in preventing and treating downy mildew of garpe of the compositions described in claim 3.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083810A (en) * | 1992-08-19 | 1994-03-16 | 道伊兰科公司 | 4-[2-(4-(2-pyridine oxygen) phenyl) oxyethyl group] quinazoline and analogue thereof |
| CN1335748A (en) * | 1998-12-22 | 2002-02-13 | 阿方蒂农科股份有限公司 | Synergic fungicide composition comprising a compound analogue of strobilurin |
| EP1997804A1 (en) * | 2006-03-03 | 2008-12-03 | Shionogi & Co., Ltd. | Mmp-13-selective inhibitor |
| CN101423514A (en) * | 2008-12-09 | 2009-05-06 | 云南民族大学 | Heterocycle substituted triazole compound and synthetic method thereof |
| CN101486902A (en) * | 2009-03-02 | 2009-07-22 | 西安近代化学研究所 | Organic electroluminescent blue luminescence compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60156745A (en) * | 1984-01-27 | 1985-08-16 | Asahi Glass Co Ltd | Electrically-conductive material of organic high polymer |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083810A (en) * | 1992-08-19 | 1994-03-16 | 道伊兰科公司 | 4-[2-(4-(2-pyridine oxygen) phenyl) oxyethyl group] quinazoline and analogue thereof |
| CN1335748A (en) * | 1998-12-22 | 2002-02-13 | 阿方蒂农科股份有限公司 | Synergic fungicide composition comprising a compound analogue of strobilurin |
| EP1997804A1 (en) * | 2006-03-03 | 2008-12-03 | Shionogi & Co., Ltd. | Mmp-13-selective inhibitor |
| CN101423514A (en) * | 2008-12-09 | 2009-05-06 | 云南民族大学 | Heterocycle substituted triazole compound and synthetic method thereof |
| CN101486902A (en) * | 2009-03-02 | 2009-07-22 | 西安近代化学研究所 | Organic electroluminescent blue luminescence compound |
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