CN103664795B - Pyridazinone compound and application thereof - Google Patents

Pyridazinone compound and application thereof Download PDF

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Publication number
CN103664795B
CN103664795B CN201210328143.6A CN201210328143A CN103664795B CN 103664795 B CN103664795 B CN 103664795B CN 201210328143 A CN201210328143 A CN 201210328143A CN 103664795 B CN103664795 B CN 103664795B
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formula
compound
alkyl
hydrogen
cucumber
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CN103664795A (en
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徐玉芳
赵振江
朱维平
韩景龙
李洪林
曹贤文
李宝聚
石延霞
钱旭红
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East China University of Science and Technology
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East China University of Science and Technology
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Priority to PCT/CN2013/082984 priority patent/WO2014036952A1/en
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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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

Abstract

The present invention relates to the pyridazinone compound of Formulas I and its it is used as the application in terms of Plant activator：In formula, R1‑R5It is independently selected from：Hydrogen, C1 C6 alkyl, C1 C6 alkoxies, halogen, halo C1 C6 alkyl, halo C1 C6 alkoxies, nitro, amino, CN, NCO, NCS, carboxyl, C1 C3 alkoxies formoxyl, C1 C3 amide groups；X is selected from oxygen, sulphur and nitrogen；R6For the substitution of H, optionally substituted C1 C3 alkyl and optionally substituted phenyl, 5 10 unit's heteroaryls；And R7For optional H, the C1 C3 alkyl and optionally substituted phenyl of substitution.

Description

Pyridazinone compound and application thereof
Technical field
The present invention relates to a kind of pyridazinone compound and application thereof.
Background technology
Agricultural chemicals (Pesticides) is primarily referred to as preventing various diseases (insect, evil mite, line in agriculture forest and husbandry production Worm, pathogen, weeds and muroid) and coordinate plant growth chemicals.Before the eighties, being mainly used in of agricultural chemicals does harm to thing " kill ", but since the eighties, the concept of agricultural chemicals has a very large change.Today, we do not focus on " killing ", but It is more concerned with regulation.Therefore, the objective of modern agricultural chemicals is that insect pest germ is efficiently prevented and treated, and non-target organism and environment are pacified Entirely.China is a large agricultural country, after liberation, and China's pesticide industry flourishes, and pesticide species and yield are doubled and redoubled, I State's agricultural chemicals yield is had been able to the need for meeting agricultural, and has a number of outlet, but kind is still not enough.China is annual Using pesticidal preparations up to 65 ~ 700,000 tons, active ingredient amount is up to 22 ~ 250,000 tons.The seldom of harmful organism can be really prevented, be there are about More than 90% agricultural chemicals, which is dissipated in farmland, pollutes environment, and particularly highly toxic pesticide pollution environment is more serious.
Agricultural chemicals has had the history of very long development in about 150 years in the world, and 70, the eighties, the scientific research of chemical pesticide, open Send out and produce unprecedentedly active, the novel agricultural chemicals new type of efficient, low toxicity, the mechanism of action, such as pyrethroid, pyrazoles, pyrrole Pyridine class, nicotinoids, pyroles, process for preparation of benzoylurea compounds；Carbamates, beta-methoxy acrylic ester, benzimidazole Class, triazole bactericidal agent；Imidazolone type, sulfonylurea herbicide etc. emerge in an endless stream, and promote chemical pesticide to step into and develop rapidly Fast traffic lane.But the negative effect that is brought to environment of the large-scale use of traditional agricultural chemicals and cause pathogenic microorganism and insect Drug resistance makes its application power have a greatly reduced quality, and harmful organism is unable to effectively preventing if lacking with agricultural chemicals, often results in agricultural and subtracts Production, directly influences the development of national economy, and the agricultural chemicals of 21 century progressively develops to the new ideas of biological regulation.
Since being delivered first on " the acquisition physiologic immunity of plant " text from Chester K. in 1933, some existing works Person is summarized it.System resume most study wherein on tobacco, different researchers are antiviral, antimycotic to its System research, such as tobacco resisting tobacco mosaic virus (TMV), anti-eye spot (Cercospora have been carried out with bacteria resistance Nicotianae), anti-balck shank (Phytophthora parasitica), downy mildew resistance (Peronospora tabacina), Antibacterium wildfire (Pseudomonas syrtngae pv.tabaci) etc., and find pathogenesis-related proteins and system is resisted Characteristic of disease gene coded protein.Eighties of last century beginning of the sixties, Ross researchs tobacco mosaic virus (TMV) proposes botanical system and obtains disease-resistant Property（Systemic acguired resistance, SAR）, i.e., when the induction bacterium of necrotic type pathogen or screening infects or some After chemicals induction processing, some plant can infect generation resistance to subsequent pathogen.And these can induce plant The biological and chemical agents for producing SAR are known as plant disease resistance inductor or activator.
Plant activator（Elicitor or plant activiator）Refer to compound in itself and its metabolin without Direct bactericidal activity, but the immune system of plant can be stimulated and plant generation system obtains the material of disease-resistant performance.This resistance With four characteristicses, i.e.,：Systematicness, SAR shows the non-induced factor treatment position of plant；Persistence, SAR can be held after producing Even some months in continuous a few weeks；Broad spectrum activity, SAR produces inhibitory action to disease caused by some fungies, bacterium, germ simultaneously；Safety Property, these derivants do not produce toxic action to germ in itself, but induction plant produces resistance, therefore environment is not produced Side effect.Therefore, the research and development of this series bactericidal agent have broad application prospects.
Pyridazine compound is that a class has efficient weeding, Insecticiding-miticiding, the heterocyclic compound of plant growth regulating isoreactivity Thing, the characteristics of many kinds also have low toxicity, low-residual.At present, pyridazine analog derivative has become important fragrant miscellaneous of a class Cycle compound, and pyridazinone compound is then a class more important in pyridyl derivatives.1949, Schoene and Hoffmann reports that 4- hydroxypyridazin ketone has the characteristic of strong inhibition plant cell division first, and is used as plant growth regulating Agent is applied in agricultural production.The features such as pyridazinone agricultural chemicals is active high, environmentally friendly, in integrated pest control and drop Played an important role in terms of low agricultural chemicals environmental pollution, be one of focus for studying both at home and abroad in recent years, it has good biological Activity, it has also become the heterocyclic compound of a class great exploitation potential and researching value.At present, existing many commercialized pyridazinones Class agricultural chemicals, including plant growth regulator, herbicide, bactericide, desinsection (mite killing) agent, insect growth regulator, IGR etc..
The research of Systemic Acquired Resistance In Plants is started late in China, about in the research of the sick mechanism of action of plant inducer impedance Hold the conduction mechanism for being concentrated mainly on resistance signal, the clone of Mechanism of Physiological and Biochemical and related disease-resistant gene and application upper, and The development of the disease-resistant activator of new plant is slower.The Plant activator of only minority is successfully opened so far Hair, the wherein more successful Plant activator of the commercialization such as NCI, BTH, TDL, can induce plant to bacterium, fungi and virus Deng the resistance for producing wide spectrum（MichikoYasuda.,J.Pestic.Sci.2004,29:46-49).
In consideration of it, the exploitation of Plant activator is causing extensive concern with initiative.
The content of the invention
The drug design of the present inventor's integrated use computer, pharmaceutical chemistry and molecular biology method and technology, design is simultaneously A series of pyridazinone compounds are synthesized, i.e., compound shown in formula I, and these compounds are suppressing agricultural and gardening and woods The bioactivity and the disease-resistant activity of induction plant generation and its assay method of industry disease fungus, while providing these compounds Application in agriculture field and horticultural field and field of forestry.
The pyridazinone compound of the present invention is compound shown in formula I：
In formula I, R1~R5It is respectively and independently selected from：Hydrogen, C1-C6 alkyl, C1-C6 alkoxies, halogen, halo C1-C6 alkyl, Halo C1-C6 alkoxies, nitro, amino, CN, NCO, NCS, carboxyl, C1-C3 alkoxy formoxyls, C1-C3 amide groups；X is selected from Oxygen, sulphur and nitrogen；R6For the substitution of H, optionally substituted C1-C3 alkyl and optionally substituted phenyl, 5-10 unit's heteroaryls；R7To be optional H, the C1-C3 alkyl and optionally substituted phenyl of substitution.
In a specific embodiment, R1And R5Each stand alone as H, halogen, halo C1-C6 alkyl and halo C1-C6 alcoxyls Base.
In a specific embodiment, R3And R4Each stand alone as H, halogen, halo C1-C6 alkyl and halo C1-C6 alcoxyls Base.
In a specific embodiment, R3Selected from H, halogen, C1-C6 alkoxies, halo C1-C6 alkyl, nitro, halo C1-C6 alkoxies and C1-C6 alkyl.
In a specific embodiment, R6For H.
In a specific embodiment, R7For H or C1-C6 alkyl.
In a specific embodiment, X is O.
In a specific embodiment, R1、R2、R4、R5And R6For H, R3Selected from H, halogen, C1-C6 alkoxies, halo C1- C6 alkyl, nitro, halo C1-C6 alkoxies and C1-C6 alkyl, X is O.
In a specific embodiment, R1、R3、R5And R6For H, R2And R4Selected from H, halogen and C 1-C6 alkoxies, X is O.
In a specific embodiment, the structure of compounds of formula I is as shown in formula II：
In formula, R1-R5Independently it preferably is selected from：Hydrogen, C1-C6 alkoxies, halogen, nitro and halo C1-C6 alkoxies.
In a specific embodiment, the structure of compounds of formula I is as shown in formula II：
In formula, R1-R5Independently it preferably is selected from：Hydrogen, C1-C6 alkoxies, halogen, nitro and halo C1-C6 alkoxies.
The invention further relates to application of the compound of Formula I as Plant activator.
In one embodiment, made the present invention relates to compound of Formula I with agriculturally acceptable carrier or auxiliary agent Purposes in standby Plant activator, anti-plant virus agent, insecticide, bactericide, plant growth regulator and herbicide.
In one embodiment, compound of Formula I of the present invention can suppress disease fungus and induce plant disease-resistant activity.Can The plant prevented and treated with compound of Formula I of the present invention include various agricultural plants, gardening plant and forestry plant, including but It is not limited to cucumber, tomato, paddy rice etc..
In one embodiment, the plant disease that can be prevented and treated with compound of Formula I of the present invention includes but is not limited to Cucumber blight dis-ease, Cucumber Target Leaf Spot, cucumber bacterial angular leaf spot, tomato late blight, rice sheath blight disease, gray mold of cucumber and cucumber Droop etc..
In one embodiment, the plant disease that can be prevented and treated with compound of Formula I of the present invention be tomato late blight, Cucumber Target Leaf Spot, cucumber blight dis-ease and rice sheath blight disease.
In one embodiment, can be with compound of Formula I of the present invention preventing and treating by muskmelon spherical cavity bacterium（Mycosphaerella melonis）, the withered bacterium of stem（Corynespora cassiicola）, pseudomonas syringae angular leaf spot of cucumber pathological form （Pseudomonas syringae pv.Lachrymans）, phytophthora infestans（Phytophthora infestans(Mont.) De Bary）, thanatephorus cucumeris(frank) donk（Thanatephorus cucumeris(Frank)Donk.）, Botrytis cinerea（Botrytis cinerea Pers.ex Fr.）And pinch outs cucumber specialized form (Fusarium oxysporum (Schl.) F.sp Cucumerinum Owen) etc. germ plant disease.
The invention further relates to the preparation of compound of Formula I.Specifically, preparation method of the invention includes：With substituted benzene Amine（Compound shown in formula A）For initiation material, hydrochloric acid and natrium nitrosum generation diazol are added, then the diazol of generation is dripped In the ethanol water for being added to 1,3- dimethyl acetone-1,3-dicarboxylates and sodium acetate, room temperature reaction（Such as 20min）, that is, obtain centre Body phenylhydrazone（Compound shown in formula B）.Intermediate B heating reflux reaction in o-dichlorohenzene（Such as about 2h）, obtain compound II；Intermediate B is dissolved in sodium hydrate aqueous solution（Such as 2M sodium hydrate aqueous solution）In, concentrated hydrochloric acid is added dropwise and separates out solid, Obtain compound III.
In formula, R1-R5As mentioned before.
Embodiment
In the application, " alkyl " includes side chain and straight chained alkyl, and long is usually 1-6 carbon atom, and preferably 1-4 carbon is former Son, more preferably 1-3 carbon atom.The example of alkyl includes but is not limited to methyl, ethyl, propyl group, butyl, the tert-butyl group, isobutyl group Deng.
" alkoxy " refers to " alkyl-O- " group, wherein, alkyl can be C1-C6 straight or branched alkyls, preferably C1-C4 Straight or branched alkyl.
In the present invention, the alkyl in alkyl or alkoxy is optionally replaced by halogen, hydroxyl etc..Haloalkyl or halo The example of alkoxy includes but is not limited to by one or several F, Cl and/or Br C1-C6 alkyl replaced or C1-C6 alkoxies, Specific example such as trifluoromethyl ,-O-CF3Deng.
" aryl " refers to the monocyclic, bicyclic or tricyclic aromatic group containing 6 to 14 carbon atoms, including phenyl, naphthyl, phenanthrene Base, anthryl, indenyl, Fluorene bases, tetrahydro naphthyl, indanyl etc..
Aryl is optionally by 1-5（For example, 1,2,3,4 or 5）Replace selected from following substituent：Halogen, C1-4Aldehyde Base, C1-6Straight or branched alkyl, cyano group, nitro, amino, hydroxyl, methylol, the alkyl of halogen substitution（Such as trifluoromethyl）、 The alkoxy of halogen substitution（Such as trifluoromethoxy）, carboxyl, C1-4Alkoxy, ethoxycarbonyl, N (CH3) and C1-4Acyl group.
For example, aryl can be selected from following substituent group by 1-5：Halogen ,-OH, C1-4Alkoxy, C1-4Alkyl chain ,- NO2,-NH2,-N (CH3)2, carboxyl, and ethoxycarbonyl etc..
" heteroaryl " used herein is that, containing 5-10 atom in finger ring, and have 6,10 or 14 electronics in ring body Fasten shared.And institute's ontaining annular atoms are carbon atoms and optional 1-3 hetero atom from oxygen, nitrogen, sulphur.
Useful heteroaryl include thienyl, furyl, pyranose, pyrrole radicals, imidazole radicals, pyrazolyl, pyridine radicals including But it is not restricted to 2- pyridine radicals, 3- pyridine radicals and 4- pyridine radicals, pyrazinyl, pyrimidine radicals etc..
Heteroaryl is optionally by 1-5（For example, 1,2,3,4 or 5）Replace selected from following substituent：Halogen, C1-4 Aldehyde radical, C1-6Straight or branched alkyl, cyano group, nitro, amino, hydroxyl, methylol, the alkyl of halogen substitution（Such as fluoroform Base）, halogen substitution alkoxy（Such as trifluoromethoxy）, carboxyl, C1-4Alkoxy, ethoxycarbonyl, N (CH3) and C1-4Acyl Base.Optionally, in addition to containing fluoro substituents, on aryl can also contain others discussed above substituent, such as Cl, Br ,- OH, C1-4Alkoxy, C1-4Alkyl chain ,-NO2,-NH2,-N (CH3)2, carboxyl, and ethoxycarbonyl etc..
The present invention also includes the composition pesticide containing compound of the present invention.
In one embodiment, composition pesticide of the invention is also containing acceptable carrier in Pesticide Science.And agricultural chemicals Acceptable carrier on.
The composition can contain by weight 0.01%~95% Formulas I of the invention or the II institute as active component The compound shown.
Acceptable carrier includes various solid carriers known in the art, liquid-carrier, gas load in the Pesticide Science Body etc..Solid carrier can be, for example, clay material for example kaolin, diatomite, synthetic hydrated silicon oxide, bentonite, The fine powder or particle of Fubasami clays and acid clay；All kinds of talcums, ceramic and other inorganic material for example sericite, quartz, Sulphur, activated carbon, the fine powder or particle of calcium carbonate and hydrated SiO 2；And chemical fertilizer for example ammonium sulfate, ammonium phosphate, ammonium nitrate, The fine powder or particle of urea and ammonium chloride.
Liquid-carrier can include for example, water；Alcohols such as methanol and ethanol；Ketone such as acetone and methyl ethyl ketone；Hydro carbons Such as hexane, hexamethylene, kerosene and light oil；Esters such as ethyl acetate and butyl acetate；Nitrile such as acetonitrile and isobutyronitrile；Ethers such as two Isopropyl ether is He dioxane；Amide-type such as DMF and DMA；Halogenated hydrocarbons such as dichloromethane, Trichloroethanes and carbon tetrachloride；Dimethyl sulfoxide (DMSO)；And vegetable oil such as soya-bean oil and cottonseed oil.
Carrier gas or propellant can include for example, Freon gas, butane gas, LPG (liquefied petroleum gas), two Methyl ether and carbon dioxide.
Surfactant, such as alkyl sulfate, alkylsulfonate, alkyl virtue can also be contained in the composition pesticide of the present invention Base sulfonate, alkyl aryl ether and their polyethylene oxide derivant, polyglycol ether, polyol ester and sugar alcohol derivant.
The present invention composition pesticide can also contain adjuvant such as fixative or dispersant, for example, casein, gelatin, Polysaccharide (such as starch, gum arabic, cellulose derivative and alginic acid), lignin derivative, bentonite, sugared and such as poly- second The synthetic polymers such as enol, polyvinylpyrrolidone and polyacrylic acid.
The composition pesticide of the present invention can be included for example, PAP (isopropyl acid phosphoric acid ester), BHT with stabilizer (2,6- di-tert-butyl -4- methylphenols), BHA (2- tert-butyl -4- metoxyphenols and 3- tert-butyl -4- methoxybenzenes The mixture of phenol), vegetable oil, mineral oil, surfactant, fitter acids and its ester.
The pesticide combination of the present invention can be mixed with each other and prepared by the various components in composition pesticide of the present invention Thing.
The composition pesticide of the invention so prepared can directly using or use after being diluted with water.In addition, it can With with other insecticides, nematicide, acaricide, bactericide, mould inhibitor, herbicide, plant growth regulator, synergist, fertilizer Material, soil conditioner and/or animal feed blending use or do not blend but while use.
Therefore, the present invention also includes a kind of method for preventing and treating crop disease, and application method includes such as sprinkling crop, granted The method such as root of crop in soil.
, can be according to including preparation type, number of times, place and administration side when the composition pesticide of the present invention is used for agricultural These conditions of method, pest species and the extent of damage, the appropriate amount of application of setting and concentration.
The present invention is further elaborated by the following examples, these embodiments be merely to illustrate the present invention and preferably Understand present disclosure, it is not in any way limit the scope of the present invention.
Embodiment 1
4- hydroxyl -6- oxos -1-（4- fluorophenyls）- 1,6- dihydrogen dazin -3- carboxylic acids（Compound D1）Preparation：
Weigh 4- fluoroanilines（555mg, 0.5mmol）In 25mL single port eggplant-shape bottles, 7.5mL4M aqueous hydrochloric acid solutions are added, Magnetic agitation under ice bath, sodium nitrite in aqueous solution is slowly added dropwise with constant pressure funnel（400mg natrium nitrosums and 4mL water）, drop Plus terminate, to reaction solution clarification, obtain reaction solution A.870mg 1,3- dimethyl acetone-1,3-dicarboxylates and 3g sodium acetates are taken in 100mL eggplants In shape bottle, 10mL water and 3mL ethanol, room temperature magnetic agitation are added, reaction solution B is obtained.Reaction solution A is slowly added dropwise to reaction solution B In, there is reaction after yellow mercury oxide precipitation, 10min to finish, suction filtration is washed, and is dried.Crude product is through silica gel column chromatography（Petroleum ether/acetic acid Ethyl ester=8/1, v/v）Isolated orange/yellow solid 1.2g, yield 80%.
More than 1.2g intermediates are weighed in 100mL eggplant-shape bottles, the 22mL 2M NaOH aqueous solution is added, question response liquid is clear Clearly, concentrated hydrochloric acid is slowly added dropwise, pH is to 5 for regulation, there is Precipitation, suction filtration is washed, dried.Crude product recrystallizing methanol, obtains 4- Hydroxyl -6- oxos -1-（4- fluorophenyls）The slightly yellow solid 750mg of -1,6- dihydrogen dazin -3- carboxylic acids, yield 75%.Fusing point 242 ~ 245°C。1H NMR(400MHz,DMSO-d6):δ7.52(dd,J1=5.2Hz,J2=8.8Hz,2H),7.27-7.32(m,2H), 5.76 (s, 1H) .HRMS (ESI) calculated values C11H7N2O4F[M+H]+251.0463, experiment value 251.0466.
Embodiment 2
4- hydroxyl -6- oxos -1-（4- fluorophenyls）- 1,6- dihydrogen dazin -3- carboxylate methyl esters（Compound D2）Preparation：
Weigh 4- fluoroanilines（555mg, 0.5mmol）In 25mL single port eggplant-shape bottles, 7.5mL4M aqueous hydrochloric acid solutions are added, Magnetic agitation under ice bath, sodium nitrite in aqueous solution is slowly added dropwise with constant pressure funnel（400mg natrium nitrosums and 4mL water）, drop Plus terminate, to reaction solution clarification, obtain reaction solution A.870mg 1,3- dimethyl acetone-1,3-dicarboxylates and 3g sodium acetates are taken in 100mL eggplants In shape bottle, 10mL water and 3mL ethanol, room temperature magnetic agitation are added, reaction solution B is obtained.Reaction solution A is slowly added dropwise to reaction solution B In, there is reaction after yellow mercury oxide precipitation, 10min to finish, suction filtration is washed, and is dried.Crude product is through silica gel column chromatography（Petroleum ether/acetic acid Ethyl ester=8/1, v/v）Isolated orange/yellow solid 1.2g, yield 80%.
More than 1.3g intermediates are weighed in 25mL eggplant-shape bottles, 8mL o-dichlorohenzenes are added, magnetic agitation is heated to 180 DEG C Backflow, reacts 2 hours, TLC tracks to raw material and converted completely.Room temperature is down to, rotary evaporation removes solvent, obtains slightly yellow solid. Crude product is through silica gel column chromatography（Petrol ether/ethyl acetate=1/1, v/v）, isolated 4- hydroxyls -6- oxos -1-（4- fluorophenyls）- 1,6- dihydrogen dazin -3- acid methyl esters white solid 92mg, yield 70%, 145 ~ 146 °C of fusing point.1H NMR(400MHz,CDCl3):δ 10.42(s,1H),7.58(dd,J1=5.2Hz,J2=8.8Hz, 2H), 7.17-7.22 (m, 2H), 6.41 (s, 1H), 4.05 (s, 3H) .HRMS (ESI) calculated values C12H9N2O4F[M+H]+265.0619, experiment value 265.0622.
Embodiment 3
4- hydroxyl -6- oxos -1-（4- methoxyphenyls）- 1,6- dihydrogen dazin -3- carboxylic acids（Compound D3）Preparation：
Divided by P-nethoxyaniline alternative embodiment 1 outside para-fluoroaniline, other conditions and step are same as Example 1, Obtain compound D3, yield 80%.232 ~ 234oC of fusing point.1H NMR(400MHz,DMSO-d6):δ7.41(d,J=8.8Hz,1H), (s, 3H) .HRMS (ESI) calculated values of 7.03 (d, J=8.8Hz, 1H), 6.18 (s, 1H), 3.81 C12H7N2O5[M+H]+ 263.0662, experiment value 263.0666.
Embodiment 4
4- hydroxyl -6- oxos -1-（4- methoxyphenyls）- 1,6- dihydrogen dazins -3- acid methyl esters（Compound D4）Preparation：
Divided by P-nethoxyaniline alternative embodiment 2 outside para-fluoroaniline, other conditions and step are same as Example 2, Obtain compound D4）, yield 67%, 184.1 ~ 184.5 °C of fusing point.1H NMR(400MHz,CDCl3):δ10.40(s,1H),7.50 (d,J=8.8Hz,2H),7.01(d,J=8.8Hz,2H),6.40(s,1H),4.04(s,3H),3.87(s,3H).HRMS(ESI) Calculated value C13H12N2O5[M+H]+277.0819, experiment value 277.0822.
Embodiment 5
4- hydroxyl -6- oxo -1- phenyl -1,6- dihydrogen dazin -3- carboxylic acids（Compound D5）Preparation：
Divided by aniline alternative embodiment 1 outside para-fluoroaniline, other conditions are same as Example 1 with step, obtain chemical combination Thing D5, yield 73%, 246.0 ~ 246.5 °C of fusing point.1H NMR(400MHz,DMSO-d6):δ7.42-7.51(m,5H),6.20(s, 1H) .HRMS (ESI) calculated values C11H8N2O4[M+H]+233.0557, experiment value 233.0577.
Embodiment 6
4- hydroxyl -6- oxos -1- (4- chlorphenyls) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D6）Preparation：
Divided by parachloroanilinum alternative embodiment 1 outside para-fluoroaniline, other conditions are same as Example 1 with step, obtain Compound D6, yield 80%, 248.1 ~ 248.5 °C of fusing point.1H NMR(400MHz,DMSO-d6):δ7.57(brs,4H),6.15 (s, 1H) .HRMS (ESI) calculated values C11H7N2O4Cl[M+H]+267.0167, experiment value 267.0184.
Embodiment 7
4- hydroxyl -6- oxos -1- (3,5- dichlorophenyls) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D7）Preparation：
Divided by 3,5- dichloroaniline alternative embodiment 1 outside para-fluoroaniline, other conditions and step are same as Example 1, Obtain compound D7, yield 74%, 263.4 ~ 263.6 °C of fusing point.1H NMR(400MHz,DMSO-d6):δ7.71(s,1H),7.7 (s, 2H), 6.14 (s, 1H) .HRMS (ESI) calculated values C11H6N2O4Cl2[M+H]+300.9777, experiment value 300.9778.
Embodiment 8
4- hydroxyl -6- oxos -1- (3,5- dichlorophenyls) -1,6- dihydrogen dazin -3- carboxylate methyl esters（Compound D8）System It is standby：
Divided by 3,5- dichloroaniline alternative embodiment 2 outside para-fluoroaniline, other conditions and step are same as Example 2, Obtain compound D8, yield 71%.1HNMR(400MHz,CDCl3):δ10.45(s,1H),7.57(d,J=1.6Hz,2H),7.45 (t,J=1.6Hz,1H),6.41(s,1H),4.08(s,3H)。
Embodiment 9
4- hydroxyl -6- oxos -1- (2,4 dichloro benzene base) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D9）Preparation：
Divided by 2,4- dichloroaniline alternative embodiment 1 outside para-fluoroaniline, other conditions and step are same as Example 1, Obtain compound D9, yield 72%, 236 ~ 237 °C of fusing point.1H NMR(400MHz,DMSO-d6):δ7.87（s,1H）,7.61(s, 2H), 6.13 (s, 1H) .HRMS (ESI) calculated values C11H6N2O4Cl2[M+H]+300.9777, experiment value 300.9773.
Embodiment 10
4- hydroxyl -6- oxos -1- (3,4- dichlorophenyls) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D10）Preparation：
Divided by 3,4-DCA alternative embodiment 1 outside para-fluoroaniline, other conditions and step are same as Example 1, Obtain compound D10, yield 77%, 268.1 ~ 268.3 °C of fusing point.1H NMR(400MHz,DMSO-d6):δ7.89(d,J= 2.4Hz,1H),7.78(d,J=8.8Hz,1H),7.59(dd,J1=2.4Hz,J2=8.8Hz,1H),6.14(s,1H).HRMS (ESI) calculated value C11H6N2O4Cl2[M+H]+300.9777, experiment value 300.9774.
Embodiment 11
4- hydroxyl -6- oxos -1- (3,4- dichlorophenyls) -1,6- dihydrogen dazin -3- carboxylate methyl esters（Compound D11）System It is standby：
Divided by 3,4-DCA alternative embodiment 2 outside para-fluoroaniline, other conditions and step are same as Example 2, Obtain compound D11, yield 81%, 179.1 ~ 179.3 °C of fusing point.1H NMR(400MHz,CDCl3):δ10.41(s,1H),7.76 (s, 1H), 7.57 (d, J=8.8Hz, 1H), 7.52 (d, J=8.8Hz, 1H), 6.39 (s, 1H) .HRMS (ESI) calculated values C12H8N2O4Cl2[M+H]+314.9934, experiment value 314.9940.
Embodiment 12
4- hydroxyl -6- oxos -1- (4- trifluoromethyls) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D12）System It is standby：
Divided by 4- 5-trifluoromethylanilines alternative embodiment 1 outside para-fluoroaniline, other conditions and step and the phase of embodiment 1 Together, compound D12, yield 71%, 255 ~ 256 °C of fusing point are obtained.1H NMR(400MHz,DMSO-d6):δ7.88(d,J=8.8Hz, 2H), 7.80 (d, J=8.8Hz, 2H), 6.16 (s, 1H) .HRMS (ESI) calculated values C12H7N2O4F3[M+H]+301.0431, experiment Value 301.0427.
Embodiment 13
4- hydroxyl -6- oxo -1- p-nitrophenyl -1,6- dihydrogen dazin -3- carboxylate methyl esters（Compound D13）Preparation：
Divided by paranitroanilinum alternative embodiment 2 outside para-fluoroaniline, other conditions are same as Example 2 with step, obtain To compound D13, yield yield 72%, 200 ~ 212 °C of fusing point.1H NMR(400MHz,CDCl3):δ10.47(s,1H),8.38 (d, J=9.2Hz, 2H), 7.90 (d, J=9.2Hz, 2H), 6.44 (s, 1H), 4.08 (s, 3H) .HRMS (ESI) calculated values C12H9N3O6[M+H]+292.0564, experiment value 292.0564.
Embodiment 14
4- hydroxyl -6- oxos -1- (4- trifluoromethyls) -1,6- dihydrogen dazin -3- carboxylate methyl esters（Compound D14）'s Prepare：
Divided by 4- 5-trifluoromethylanilines alternative embodiment 2 outside para-fluoroaniline, other conditions and step and the phase of embodiment 2 Together, compound D14, yield 69% are obtained.1HNMR(400MHz,CDCl3):δ7.57(dd,J1=4.8Hz,J2=8.8Hz,2H), 7.19(m,2H),6.42(s,1H),4.05(s,3H)。
Embodiment 15
4- hydroxyl -6- oxo -1- p-bromophenyl -1,6- dihydrogen dazin -3- carboxylic acids（Compound D15）Preparation：
Divided by 4- bromanilines alternative embodiment 1 outside para-fluoroaniline, other conditions are same as Example 1 with step, obtain Compound D15, yield 83%.1H NMR(400MHz,DMSO-d6):δ7.70(d,J=8.8Hz,2H),7.50(d,J=8.8Hz, 2H),6.17(s,1H)。
Embodiment 16
4- hydroxyl -6- oxo -1- p-bromophenyl -1,6- dihydrogen dazin -3- carboxylate methyl esters（Compound D16）Preparation：
Divided by 4- bromanilines alternative embodiment 2 outside para-fluoroaniline, other conditions are same as Example 2 with step, obtain Compound D16, yield 69%.1HNMR(400MHz,CDCl3):δ10.47(s,1H),8.38(d,J=9.2Hz,2H),7.90(d,J =9.2Hz,2H),6.44(s,1H),4.08(s,3H)。
Embodiment 17
4- hydroxyl -6- oxos -1- (3- trifluoromethyls) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D17）System It is standby：
Divided by 3- 5-trifluoromethylanilines alternative embodiment 1 outside para-fluoroaniline, other conditions and step and the phase of embodiment 1 Together, compound D17, yield 81% are obtained.1H NMR(400MHz,DMSO-d6):δ7.95(s,1H),7.87(d,J=8.0Hz, 1H),7.82(d,J=8.0Hz,1H),7.75(t,J=8.0Hz,1H),6.22(s,1H)。
Embodiment 18
4- hydroxyl -6- oxygen -1-（3- trifluoromethyls）- 1,6- dihydrogen dazin -3- carboxylate methyl esters（Compound D18）System It is standby：
Divided by 3- 5-trifluoromethylanilines alternative embodiment 2 outside para-fluoroaniline, other conditions and step and the phase of embodiment 2 Together, compound D18, yield 71% are obtained.1HNMR(400MHz,CDCl3):δ10.47(s,1H),7.88(s,1H),7.85(d,J= 8.0Hz,1H),7.72(d,J=7.6Hz,1H),7.62-7.67(m,1H),6.43(s,1H),4.08(s,3H)。
Embodiment 19
4- hydroxyl -6- oxos -1- (4- Trifluoromethoxyphen-ls) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D19）System It is standby：
Divided by 4- trifluoro-methoxyanilines alternative embodiment 1 outside para-fluoroaniline, other conditions and step and the phase of embodiment 1 Together, compound D19, yield 83% are obtained.1H NMR(400MHz,DMSO-d6):δ7.67(d,J=8.8Hz,2H),7.51(d,J= 8.8Hz,2H),6.17(s,1H)。
Embodiment 20
4- hydroxyl -6- oxos -1- (2- trifluoromethyls) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D20）System It is standby：
Divided by 2- 5-trifluoromethylanilines alternative embodiment 1 outside para-fluoroaniline, other conditions and step and the phase of embodiment 1 Together, compound D20, yield 85% are obtained.1H NMR(400MHz,DMSO-d6):δ7.93(d,J=7.6Hz,1H),7.87(t,J= 7.6Hz,1H),7.76(t,J=7.6Hz,1H),7.63(d,J=7.6Hz,1H),6.19(s,1H)。
Embodiment 21
4- hydroxyl -6- oxos -1- (3- methoxyphenyls) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D21）Preparation：
Divided by 3- aminoanisoles alternative embodiment 1 outside para-fluoroaniline, other conditions and step are same as Example 1, Obtain compound D21, yield 82%.1H NMR(400MHz,DMSO-d6):δ7.41(t,J=8.0Hz,1H),7.01-7.08(m, 3H),6.17(s,1H),3.79(s,3H)。
Embodiment 22
4- hydroxyl -6- oxos -1- (2- methoxyphenyls) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D22）Preparation：
Divided by 2- aminoanisoles alternative embodiment 1 outside para-fluoroaniline, other conditions and step are same as Example 1, Obtain compound D22, yield 86%.1H NMR(400MHz,DMSO-d6):δ7.46(t,J=7.6Hz,1H),7.30(d,J= 7.6Hz,1H),7.20(d,J=7.6Hz,1H),7.07(t,J=7.6Hz,1H),6.14(s,1H),3.75(s,3H)。
Embodiment 23
4- hydroxyl -6- oxos -1- (2- methoxyphenyls) -1,6- dihydrogen dazin -3- carboxylate methyl esters（Compound D23）System It is standby：
Divided by 2- aminoanisoles alternative embodiment 2 outside para-fluoroaniline, other conditions and step are same as Example 2, Obtain compound D23, yield 66%.1HNMR(400MHz,CDCl3):δ10.44(s,1H),7.46(t,J=7.6Hz,1H),7.31 (d,J=7.6Hz,1H),7.05-7.11(m,2H),6.41(s,1H),4.02(s,3H),3.84(s,3H)。
Embodiment 24
4- hydroxyl -6- oxos -1- (3,5- Dimethoxyphenyls) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D24）System It is standby：
Divided by 3,5- dimethoxyaniline alternative embodiment 1 outside para-fluoroaniline, other conditions and step and the phase of embodiment 1 Together, compound D24, yield 77% are obtained.1H NMR(400MHz,DMSO-d6):δ6.66(d,J=1.0Hz,2H),6.60(d,J= 1.0Hz,1H),6.17(s,1H),3.78(s,6H)。
Embodiment 25
4- hydroxyl -6- oxos -1- (3,5- Dimethoxyphenyls) -1,6- dihydrogen dazin -3- carboxylate methyl esters（Compound D25） Preparation：
Divided by 3,5- dimethoxyaniline alternative embodiment 2 outside para-fluoroaniline, other conditions and step and the phase of embodiment 2 Together, compound D25, yield 67% are obtained.1HNMR(400MHz,CDCl3):δ10.43(s,1H),6.69(d,J=2.4Hz,2H), 6.54(d,J=2.4Hz,1H),6.40(s,1H),4.04(s,3H),3.83(s,6H)。
Embodiment 26
4- hydroxyl -6- oxos -1- (3,4- difluorophenyls) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D26）Preparation：
Divided by 3,4- difluoroaniline alternative embodiment 1 outside para-fluoroaniline, other conditions and step are same as Example 1, Obtain compound D26, yield 78%.1H NMR(400MHz,DMSO-d6):δ7.39-7.46(m,3H),6.17(s,1H)。
Embodiment 27
4- hydroxyl -6- oxos -1- (the fluoro- 4- aminomethyl phenyls of 3-) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D27）System It is standby：
Divided by 3- fluorine open-chain crown ethers alternative embodiment 1 outside para-fluoroaniline, other conditions and step and the phase of embodiment 1 Together, compound D27, yield 77% are obtained.1H NMR(400MHz,DMSO-d6):δ7.62(d,J=2.0Hz,1H),7.48(d,J= 8.0Hz,1H),7.41(dd,J1=2.0Hz,J2=8.0Hz,1H),6.14(s,1H),2,39(s,3H)。
Embodiment 28
4- hydroxyl -6- oxos -1- (3- fluorophenyls) -1,6- dihydrogen dazin -3- carboxylate methyl esters（Compound D28）Preparation：
Divided by 3- fluoroanilines alternative embodiment 1 outside para-fluoroaniline, other conditions are same as Example 1 with step, obtain Compound D28, yield 79%.1H NMR(400MHz,DMSO-d6):δ7.52-7.59(m,1H),7.46(d,J=2.0Hz,1H), 7.40(d,J=8.0Hz,1H),7.31(dt,J1=2.0Hz,J2=8.0Hz,1H),6.16(s,1H)。
Embodiment 29
4- hydroxyl -6- oxos -1- (3- fluorophenyls) -1,6- dihydrogen dazin -3- carboxylate methyl esters（Compound D29）Preparation：
Divided by 4- 5-trifluoromethylanilines alternative embodiment 2 outside para-fluoroaniline, other conditions and step and the phase of embodiment 2 Together, compound D29, yield 66% are obtained.1HNMR(400MHz,CDCl3):δ10.43(s,1H),7.42-7.51(m,2H), 7.36-7.39(m,1H),7.13-7.19(m,1H),6.41(s,1H),4.06(s,1H)。
Embodiment 30
4- hydroxyl -6- oxos -1- (2- fluorophenyls) -1,6- dihydrogen dazin -3- carboxylate methyl esters（Compound D30）Preparation：
Divided by 2- fluoroanilines alternative embodiment 2 outside para-fluoroaniline, other conditions are same as Example 2 with step, obtain Compound D30, yield 59%.1HNMR(400MHz,CDCl3):δ10.46(s,1H),7.42(m,2H),7.32(d,J=7.6Hz, 1H),7.26(d,J=8.8Hz,1H),6.43(s,1H),4.05(s,1H)。
Embodiment 31
4- hydroxyl -6- oxos -1- (the fluoro- 3- trifluoromethyls of 4-) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D31） Preparation：
Divided by the fluoro- 3- 5-trifluoromethylanilines alternative embodiments 1 of 4- outside para-fluoroaniline, other conditions and step and embodiment 1 is identical, obtains compound D31, yield 78%.1H NMR(400MHz,DMSO-d6):δ7.65-8.02(m,3H),6.18(s, 1H)。
Embodiment 32
4- hydroxyl -6- oxos -1- (the chloro- 3- trifluoromethyls of 4-) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D32） Preparation：
Divided by the chloro- 3- 5-trifluoromethylanilines alternative embodiments 1 of 4- outside para-fluoroaniline, other conditions and step and embodiment 1 is identical, obtains compound D32, yield 78%.1H NMR(400MHz,DMSO-d6):δ8.09(d,J=2.0Hz,1H),7.87- 7.93(m,2H),6.17(s,1H)。
Embodiment 33
4- hydroxyl -6- oxos -1- (the chloro- 3- trifluoromethyls of 4-) -1,6- dihydrogen dazin -3- carboxylic acids（Compound D33） Preparation：
Divided by the bromo- 3- 5-trifluoromethylanilines alternative embodiments 1 of 4- outside para-fluoroaniline, other conditions and step and embodiment 1 is identical, obtains compound D33, yield 81%.1H NMR(400MHz,DMSO-d6):δ8.07(d,J=2.4Hz,1H),8.04(d, J=8.8Hz,1H),7.81(dd,J1=2.4Hz,J2=8.8Hz,1H),6.19(s,1H)。
Embodiment 34：Active testing
The compound that the present invention is provided is used as inhibition of the Plant activator to germ：
1st, experimental subjects：Anti-yellowing melon blight dis-ease, anti-Cucumber Target Leaf Spot, anti-cucumber bacterial angular leaf spot, anti-tomato late blight, Rice sheath blight disease, gray mold of cucumber, cucumber fusarium axysporum.
2nd, test concentrations：This test uses 100mg/L test concentrations.
3rd, method of testing：The good various crops of sowing in advance, and sample is quantitatively weighed, dissolved with DMF and add appropriate surface to live Property agent, is diluted with water to setting concentration.Using roll-back method 7 days before inoculation, 5 days, 3 days, 1 day, drug-treated is carried out in four times, Then it is disposable to be inoculated with pathogen simultaneously.Experiment is carried out using pot-culture method, is repeated 3 times.The calculating of disease index and protection effect Mode is as follows：Disease index=[∑ (the sick numbers of sheets at different levels × relative value of series) × 100]/(investigation total number of sheets × morbidity is at the highest level Representative numerical value), prevention effect (%)=[(check plot disease index-treatment region disease index) × 100]/check plot state of an illness refers to Number.
4th, experimental result
The present invention is employed above to 11 4- hydroxyl -6- oxo -1- phenyl -1,6- dihydrogen dazin -3- carboxylic acid derivates Methods described is tested to the inducing anti-disease activity of five kinds of diseases, in early stage compound test activity data such as following table 1 It is shown：
Preferred compound is as shown in table 2 below to the live body and in vitro inhibitory activity of several germs：
Note：Often the upper column number evidence of row is isolated activity, lower field live body activity.
Table 2

Claims (22)

1. the compound shown in formula I is being prepared for preventing and treating by muskmelon spherical cavity bacterium, the withered bacterium of stem, pseudomonas syringae cucumber angle Application in pinta pathological form or the composition pesticide of the microbial plant disease of phytophthora infestans：
In formula,
R1-R5It is independently selected from：Hydrogen, C1-C6 alkyl, C1-C6 alkoxies, halogen and halo C1-C6 alkyl；
X is oxygen；
R6For H；With
R7For H or C1-C3 alkyl.
2. application as claimed in claim 1, it is characterised in that the compound has the structure shown in formula II or III：
In formula, R1-R5It is independently selected from：Hydrogen, C1-C4 alkoxies, halogen and halo C1-C6 alkyl.
3. application as claimed in claim 1 or 2, it is characterised in that R1、R2、R4And R5For H, R3Selected from H, halogen, C1-C4 alkane Epoxide and halo C1-C4 alkyl.
4. application as claimed in claim 1 or 2, it is characterised in that R1、R3And R5For H, R2And R4Selected from H and halogen.
5. application as claimed in claim 1, it is characterised in that the compound is selected from：
6. application as claimed in claim 1, it is characterised in that the plant disease is cucumber blight dis-ease, Cucumber Target Leaf Spot, Huang Melon bacterial angular leaf spot or tomato late blight.
7. Formula Il or the compound shown in III are preparing the application in being used to prevent and treat the composition pesticide of rice sheath blight disease：
In Formula II or III,
R3For halogen, C1-C4 alkoxies or halo C1-C4 alkyl, R1、R2、R4And R5It is hydrogen；Or
R3For Cl, R1For Cl, R2、R4And R5For H；Or
R3For Cl, R2For Cl, R1、R4And R5For H.
8. application as claimed in claim 7, it is characterised in that the compound is selected from：
9. Formula Il or the compound shown in III are preparing the application in being used to prevent and treat the composition pesticide of gray mold of cucumber：
In Formula II, R3For halogen or C1-C4 alkoxies, R1、R2、R4And R5It is hydrogen；
In formula III, R3For halo C1-C4 alkyl or C1-C4 alkoxies, R1、R2、R4And R5It is hydrogen.
10. application as claimed in claim 9, it is characterised in that the compound is selected from：
11. the compound shown in Formula Il I is preparing the application in being used to prevent and treat the composition pesticide of cucumber fusarium axysporum：
In formula III, R1、R2、R3、R4And R5It is hydrogen；Or R1For hydrogen or Cl, R3For Cl, R2、R4And R5It is hydrogen.
12. a kind of method of controlling plant diseases, it is characterised in that methods described includes：By compounds of formula I or its agricultural chemicals Composition gives the plant, so as to prevent and treat the plant disease：
In formula,
R1-R5It is independently selected from：Hydrogen, C1-C6 alkyl, C1-C6 alkoxies, halogen and halo C1-C6 alkyl；
X is oxygen；
R6For H；With
R7For H or C1-C3 alkyl；
Wherein, the plant disease is by muskmelon spherical cavity bacterium, the withered bacterium of stem, pseudomonas syringae angular leaf spot of cucumber pathological form, cause Plant disease caused by sick phytophthora or thanatephorus cucumeris(frank) donk.
13. method as claimed in claim 12, it is characterised in that the compound has the structure shown in formula II or III：
In formula, R1-R5It is independently selected from：Hydrogen, C1-C4 alkoxies, halogen and halo C1-C6 alkyl.
14. the method as described in claim 12 or 13, it is characterised in that R1、R2、R4And R5For H, R3Selected from H, halogen, C1-C4 Alkoxy and halo C1-C4 alkyl.
15. the method as described in claim 12 or 13, it is characterised in that R1、R3And R5For H, R2And R4Selected from H and halogen.
16. method as claimed in claim 12, it is characterised in that the compound is selected from：
17. method as claimed in claim 12, it is characterised in that the plant disease be cucumber blight dis-ease, Cucumber Target Leaf Spot, Cucumber bacterial angular leaf spot or tomato late blight.
18. a kind of method for preventing and treating rice sheath blight disease, it is characterised in that methods described includes：By formula II or III compound Or its composition pesticide gives paddy rice, so as to prevent and treat the rice sheath blight disease：
In Formula II or III,
R3For halogen, C1-C4 alkoxies or halo C1-C4 alkyl, R1、R2、R4And R5It is hydrogen；Or
R3For Cl, R1For Cl, R2、R4And R5For H；Or
R3For Cl, R2For Cl, R1、R4And R5For H.
19. method as claimed in claim 18, it is characterised in that the compound is selected from：
20. a kind of method for preventing and treating gray mold of cucumber, it is characterised in that methods described includes：By formula II or III compound Or its composition pesticide gives cucumber, so as to prevent and treat the gray mold of cucumber：
In Formula II, R3For halogen or C1-C4 alkoxies, R1、R2、R4And R5It is hydrogen；
In formula III, R3For halo C1-C4 alkyl or C1-C4 alkoxies, R1、R2、R4And R5It is hydrogen.
21. method as claimed in claim 20, it is characterised in that the compound is selected from：
22. a kind of method for preventing and treating cucumber fusarium axysporum, it is characterised in that methods described includes：By compounds of formula III or its Composition pesticide gives cucumber, so as to prevent and treat the cucumber fusarium axysporum：
In formula III, R1、R2、R3、R4And R5It is hydrogen；Or R1For hydrogen or Cl, R3For Cl, R2、R4And R5It is hydrogen.
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