CN109970653A - Methoxy acrylate derivative and its preparation method and application of the one kind containing difluoromethyl pyrazole - Google Patents
Methoxy acrylate derivative and its preparation method and application of the one kind containing difluoromethyl pyrazole Download PDFInfo
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- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or 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
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Abstract
Methoxy acrylate derivative the present invention provides one kind containing difluoromethyl pyrazole and its preparation method and application, the methoxy acrylate derivative the present invention relates to one kind containing difluoromethyl pyrazole, general formula of the chemical structure are shown in formula III:
Description
Technical field
Technical solution of the present invention is related to the methoxyacrylate compound containing difluoromethyl pyrazole, and in particular to 1- first
Base -3- difluoromethyl pyrazole class methoxy acrylate derivative.
Background technique
It successfully developed a kind of novel fungicide product using natural products Strobilurin A as lead compound
Kind --- methoxy acrylic bactericide, such fungicide have the characteristics that high-efficiency low-toxicity wide spectrum and absorbability are strong.It is made
Mainly pass through the electron transmission inhibited between cytochrome b and c1 with mechanism, prevents the synthesis of cellular energy, and then inhibit its line
Plastochondria respiration is mitochondrial respiratory chain inhibitor.
Pyrazole derivatives have efficiently, low toxicity, wide spectrum biological activity, its in methoxy acrylic bactericide
Middle pyraclostrobin, the disease that (Zhang Kai waits, modern, 2018 (2): 8-11) generates the phytopathogen in various crop
Evil, such as melon and fruit powdery mildew, downy mildew, anthracnose, leaf spot, scab, spike rot, brown spot disease are with preferable anti-
Effect, the medical instrument have the features such as dosage is few, and good drug efficacy, effect is fast, environmentally friendly.The succinic acid to put goods on the market in nearly 20 years is de-
There are about 70% or more in hydrogen enzyme inhibitor class fungicide kind all to contain a pyrazole heterocycle.Existing pyrazole amide reported in the literature
Targeting compounds mitochondrial respiratory chain Complex II be also known as succinate dehydrogenase (Du Shijie, waits, Pesticide Science journal, 2018 (5):
It 545-556), is the fungicide of a kind of wide spectrum.Fungicide containing pyrazole heterocycle is various in style, has excellent bactericidal activity.
Pyrazole compound has wide research space, and the derivative containing pyrrazole structure improves tool to the activity of fungicide
It plays an important role.The popular research side that pyrazole group is China and foreign countries scientific research institutions and agro-chemical companies is introduced in pesticide molecule design
To.The sterilization that the multifarious methoxy acrylate derivative containing difluoromethyl pyrazole of construction structure improves target molecule is living
Property, it is mainly used for the prevention and treatment of corn rust and wheat powdery mildew, has to the fungicide with broad-spectrum disease resistance for researching and developing novel
There is important more practical value.
To find and finding more efficient, wide spectrum, low toxicity, low ecological risk and the agriculture of without cross-resistance with existing fungicides
Methoxy acrylate pharmacophore and pyrazole group are introduced same MOLECULE DESIGN and have synthesized one kind by medicine lead compound, the present invention
Methoxy acrylate derivative containing difluoromethyl pyrazole, while the screening and evaluation of the bioactivity of system have been carried out, with
Phase finds more high activities, low resistance risk and the high environment friendly agricultural candidate kind of Environmental compatibility.
Summary of the invention
The technical problems to be solved by the present invention are: it is derivative to provide a kind of methoxy acrylate containing difluoromethyl pyrazole
The synthetic method of object, provide this kind of compound modulates agricultural, gardening and health and forestry plant pathogen bioactivity and
Its measuring method, while these compounds answering in agriculture field, horticultural field, field of forestry and health field being provided
With.
The present invention solves technical solution used by the technical problem: having agriculture field, horticultural field, field of forestry
The general formula of the chemical structure of a kind of methoxy acrylate derivative containing difluoromethyl pyrazole of bactericidal activity is shown in formula III:
N is 0 or 1, and X is N or CH, and Y is N or O；
R1、R2It is selected from: hydrogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy, C2-C6Alkene
Base, C2-C6Halogenated alkenyl, C2-C6Alkynyl, C2-C6Halo alkynyl, hydroxyl, C3-C6Naphthenic base, is taken substituted piperidin-1-yl
The phenyl or C that the morpholine -1- base in generation, substituted nafoxidine -1- base, phenyl or halogen replace1-C6Alkyl-substituted benzene
Base or C1-C6The phenyl or C that halogenated alkyl replaces3-C6The phenyl or C that the phenyl or nitro that naphthenic base replaces replace2-C6Alkenyl
Substituted phenyl or C2-C6The phenyl or C that halogenated alkenyl replaces3-C6The phenyl or C that cycloalkenyl replaces2-C6Alkynyl substituted
Phenyl or C2-C6The phenyl or C that halo alkynyl replaces3-C6The pyridine that phenyl, pyridyl group or the halogen that cycloalkynyl radical replaces replace
Base or C1-C6Alkyl-substituted pyridyl group or C1-C6The pyridyl group or C that halogenated alkyl replaces3-C6The pyridine that naphthenic base replaces
The pyridyl group or C that base or nitro replace2-C6The pyridyl group or C that alkenyl replaces2-C6The pyridyl group or C that halogenated alkenyl replaces3-
C6The pyridyl group or C that cycloalkenyl replaces2-C6The pyridyl group or C of alkynyl substituted2-C6The pyridyl group or C that halo alkynyl replaces3-C6
The pyrimidine radicals or C that pyridyl group, pyrimidine radicals or the halogen that cycloalkynyl radical replaces replace1-C6Alkyl-substituted pyrimidine radicals or C1-C6Halogen
The pyrimidine radicals or C that substituted alkyl replaces3-C6The pyrimidine radicals or C that the pyrimidine radicals or nitro that naphthenic base replaces replace2-C6Alkenyl takes
The pyrimidine radicals or C in generation2-C6The pyrimidine radicals or C that halogenated alkenyl replaces3-C6The pyrimidine radicals or C that cycloalkenyl replaces2-C6Alkynyl takes
The pyrimidine radicals or C in generation2-C6The pyrimidine radicals or C that halo alkynyl replaces3-C6Cycloalkynyl radical replace pyrimidine radicals, it is substituted contain 1 or
Five yuan of 2 N atoms or six membered heteroaryl, substituted five yuan containing 1 or 2 S atom or six membered heteroaryl contain 1 or 2
Substituted five yuan of a O atom or six membered heteroaryl, substituted five yuan or hexa-atomic miscellaneous containing 1 N atom and 1 S atom
Aryl, substituted five yuan or six membered heteroaryl, the quilt containing 2 N atoms and 1 S atom containing 1 N atom and 1 O atom
Five yuan or the six membered heteroaryl, substituted five yuan or six membered heteroaryl containing 2 N atoms and 1 O atom replaced；Above-mentioned five
Member or six membered heteroaryl are selected from: substituted furyl, thienyl, pyrrole radicals, imidazole radicals, pyrazolyl, thiazolyl, isothiazole
Base, oxazolyl, isoxazolyl, oxadiazoles base, thiadiazolyl group, pyridyl group, pyridazinyl, pyrimidine radicals, pyrazinyl, triazine radical, tetrazine
Base, indyl, benzothienyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazole base, benzothiazolyl, benzo
Thiadiazolyl group, benzoxazolyl, the quinolyl of isomerization, the isoquinolyl of isomerization, phthalazinyl, quinoxalinyl, quinazolyl,
The silicon substrate that cinnoline base or naphthyridines base, alkyl or alkenyl replace；
Halogen is fluorine, chlorine, bromine or iodine in above-mentioned definition；
The alkyl, alkenyl or alkynyl are straight chain or branch alkyl；Alkyl itself or portion as other substituent groups
It is selected from methyl, ethyl, propyl, butyl, amyl, hexyl and its isomers, isomers is selected from isopropyl, isobutyl group, Zhong Ding
Base, tert-butyl, isopentyl or tertiary pentyl；
The halogenated alkyl group is selected from the group containing one or more identical or different halogen atoms, the alkyl halide
Base is selected from CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CF3CH2、CH3CF2、CF3CF2Or CCl3CCl2；
Described naphthenic base itself or as other substituent groups part be selected from cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl；
Described alkenyl itself or as other substituent groups part be selected from vinyl, allyl, 1- acrylic, butene-2-
Base, butylene -3- base, amylene -1- base, amylene -3- base, hexene -1- base or 4- methyl-3-pentenyl；
Described alkynyl itself or as other substituent groups part be selected from acetenyl, propine -1- base, propine -2- base, fourth
Alkynes -1- base, crotonylene-base, 1- methyl -2- butynyl, hexin -1- base or 1- ethyl -2- butynyl.
R1It preferably is selected from: methyl, methoxyl group, allyl, propargyl, 2- butine, methylene cyclopropyl, allyloxy, alkynes third
Oxygroup, methylene cyclopropyl oxygroup；R2 preferably is selected from: methyl, cyclopropyl；N is 0 or 1, and X is N or CH, and Y is N or O.
The synthetic method of the methoxy acrylate derivative of difluoromethyl pyrazole of the invention is as follows:
Wherein, substituent R1、R2It is defined as described above；R1It preferably is selected from: methyl, methoxyl group, allyl, propargyl, 2- fourth
Alkynes, methylene cyclopropyl, allyloxy, propynyloxy base, methylene cyclopropyl oxygroup；R2It preferably is selected from: methyl, cyclopropyl；N be 0 or
1, X is N or CH, and Y is N or O.
The synthesis of methoxy acrylate derivative containing difluoromethyl pyrazole of the invention and biological activity determination
Specific method is divided into following steps:
A. the preparation of compound II and IIIc:
5 mMs of compound I, 1- (3- dimethylamino-propyl) -3- ethyl carbon are added in 250 milliliters of twoport round-bottomed flasks
Diimmonium salt hydrochlorate (EDCI) is 6 mMs, and I-hydroxybenzotriazole (HOBT) is 5.13 mMs, is dissolved in methylene chloride
In (100 milliliters) solution, stirred 15 minutes in ice bath.Methylene chloride (25 milliliters) solution of amine is added into reaction system,
Then 6 mMs of Et is added3Reaction 16 hours is stirred at room temperature in reaction mixture by N.After the reaction was completed, water (2 is successively used
× 60 milliliters) washing and (80 milliliters) washing organic layers of saturated brine, organic layer is dry with MgSO4 and that removing is concentrated under reduced pressure is extra
Solvent, residue purify to obtain compound II and IIIc through 100~200 mesh silica gel column chromatographies, and eluant, eluent is 60~90 degrees Celsius
Petroleum ether: ethyl acetate, according to the difference of product, volume ratio 8: 1-2: 1；The amount of the preparation of compound II and IIIc and anti-
Volume of a container is answered to expand or shrink by corresponding proportion.
B. the preparation of compound IIIa and IIId:
4 mMs of compounds II or IIIc are added in 50 milliliters of single necked round bottom flask, add 10 milliliters of dry N,
4.8 mM 60% of sodium hydride is added into reaction, stirs 30 minutes, 4.8 mmoles are added for dinethylformamide, ice bath
That halogenated hydrocarbons, is then slowly raised to room temperature, is stirred at room temperature 4-12 hours, end of reaction, and TLC monitors reaction solution, and discovery raw material is
It is reacted complete, stop reaction.30 milliliters of water are added, is then extracted with ethyl acetate, organic layer, organic layer saturation are isolated
Sodium chloride is washed one time, and anhydrous sodium sulfate is dry, is filtered, solvent is removed under reduced pressure, residue is pure through 100~200 mesh silica gel column chromatographies
Change to obtain compound IIIa and IIId, the petroleum ether that eluant, eluent is 60~90 degrees Celsius: ethyl acetate, according to the difference of product,
Volume ratio is 10: 1-4: 1, yield 38-89%；The amount of compound IIIa and IIId preparation and the volume of reaction vessel are by corresponding ratio
Example is expanded or shunk.
C. the preparation of compound IIIb and IIIe:
3 mMs of compound IIIa, IIIc and IIId are added in 100 milliliters of single necked round bottom flask；It is added 30 milliliters
15 mMs of triethylamines and 9 mMs of amine is added in methanol solution, and temperature is slowly increased to flow back, and it is small to stir 6 at a reflux temperature
When；After contact plate monitors fully reacting, first it is concentrated under reduced pressure, removes extra amine and methanol solution.Residue is through 100~200 mesh silicon
It is gel column chromatography eluting to obtain compound IIIb and IIIe, the petroleum ether that eluant, eluent is 60~90 degrees Celsius: ethyl acetate, according to production
The difference of object, volume ratio 10: 1-4: 1, yield 38-89%；The amount of compound III preparation and the volume of reaction vessel press phase
Ratio is answered to expand or shrink.
D. the measurement of the bactericidal activity of the methoxy acrylate derivative III of the invention containing difluoromethyl pyrazole:
The sterilization of methoxy acrylate derivative III containing difluoromethyl pyrazole of the invention or bacteriostatic activity use bacterium
The measurement of body growth rate method, specific steps are as follows: take 1.8 milligrams of samples to be dissolved in 2 drop n,N-Dimethylformamide, then with containing
The aqueous solution of a certain amount of polysorbas20 emulsifier is diluted to the medicament of 500 mcg/mls, and reagent agent is aseptically respectively inhaled
1 milliliter is taken in culture dish, then is separately added into 9 milliliters of PDA culture mediums, 50 mcg/ml drug containing tablets are made after shaking up, to add
Add the plate of 1 milliliter of aqua sterilisa to do blank control, cuts bacterium disk along mycelia outer rim with 4 millimeters of diameter of punch, move to drug containing
In equilateral triangle to put on plate, every processing is repeated 3 times, and culture dish is placed on training in 24 ± 1 degrees Celsius of constant incubators
It supports, each processing bacterium disk extension diameter is investigated after compareing colony diameter and being extended to more than 2 centimetres, is averaged, with blank control
Compare the opposite bacteriostasis rate of calculating, is most of typical plant pathogen that field actually occurs in China's agricultural production for examination strain
Kind, code name and title be as follows: AS: tomato early blight bacterium, latin name are as follows: Alternariasolani, BC: cucumber ash
Mildew bacterium, latin name are as follows: Botrytis cinerea, CA: peanut Cercospora bacteria, latin name are as follows:
Cercosporaarachidicola, GZ: fusarium graminearum, latin name are as follows: Gibberellazeae, PI: potato evening
Epidemic disease bacterium, latin name are as follows: Phytophthorainfestans (Mont.) de Bary, PP: Botryosphaeria berengeriana f. sp, Latin
Name are as follows: Physalosporapiricola, PS: Rhizoctonia solani Kuhn, latin name are as follows: Pelliculariasasakii, RC:
Rhizoctonia cerealis, latin name are as follows: Rhizoctoniacerealis, SS: Sclerotinia sclerotiorum, latin name are as follows:
Sclerotiniasclerotiorum。
E. the living body Antibacterial Activity of the methoxy acrylate derivative III of the invention containing difluoromethyl pyrazole:
The living body Screening of Antibacterial Activities method of methoxy acrylate derivative III containing difluoromethyl pyrazole of the invention
It is specific as follows: it weighs 0.01 gram of compound of test and is dissolved in 0.5 milliliter of DMF, it is then dilute with water (Tween 80 containing 0.1%)
It releases to 100 mcg/mls, then by configured medicine liquid spray in plant leaf surface, two hours are small to naturally dry, then through 24
Fungi is seeded on plant by Shi Hou.Each test designs blank control, blank control VAcetone∶VMethanol∶VWater=1: 1: 2 it is molten
Liquid sprays plant, and fungi is seeded to plant after 24 hours.Compared with blank control, calculate Disease management percentage, 0 indicate without
Activity, 100 indicate complete inhibition, and the plant disease of test has cucumber downy mildew, wheat powdery mildew, corn rust, cucumber anthracnose
Disease.
The beneficial effects of the present invention are: having carried out elder generation to the methoxy acrylate derivative III containing difluoromethyl pyrazole
Optimization is led, and the screening of bacteriostatic activity has been carried out to the methoxy acrylate derivative III containing difluoromethyl pyrazole.
The present invention passes through specific preparation and more specific first of the explanation containing difluoromethyl pyrazole of biological activity determination embodiment
The synthesis of oxygroup acrylate derivative III and bioactivity and application, the embodiment be only used for illustrating the present invention and
The unrestricted present invention, especially bioactivity are merely illustrative of, rather than limit this patent, and specific embodiment is as follows:
Embodiment 1: the preparation of compound II:
5 mMs of compound I-1,1- (3- dimethylamino-propyl) -3- ethyls are added in 250 milliliters of twoport round-bottomed flasks
Carbodiimide hydrochloride (EDCI) is 6 mMs, and I-hydroxybenzotriazole (HOBT) is 5.13 mMs, is dissolved in methylene chloride
In solution, stirred 15 minutes in ice bath.Methylene chloride (50 milliliters) solution of amine is added into reaction system, is then added 6
MM Et3Reaction 16 hours is stirred at room temperature in reaction mixture by N.After the reaction was completed, water (2 × 60 milliliters) successively are used
Simultaneously (80 milliliters) washing organic layers of saturated brine are washed, organic layer is dry with MgSO4 and removing excess of solvent is concentrated under reduced pressure, remaining
Object purifies to obtain compound II-1, the petroleum ether that eluant, eluent is 60~90 degrees Celsius: acetic acid second through 100~200 mesh silica gel column chromatographies
Ester, volume ratio 2: 1, yield 58%；White solid, fusing point 110-111%, the following II-1 of the nuclear magnetic data of the compound:1H NMR (400MHz, Chloroform-d) δ 9.99 (s, 1H), 8.07 (d, J=2.3Hz, 1H), 7.04 (t, J=54.1Hz,
1H), 3.93 (s, 3H), the amount of the preparation of 3.81 (s, 3H) compound II-1 and the volume of reaction vessel are expanded by corresponding proportion
Or it reduces.
Embodiment 2: the preparation of compound IIIa-1:
4 mMs of compound II-1 are added in 50 milliliters of single necked round bottom flask, add 10 milliliters of dry N, N- bis-
4.8 mM 60% of sodium hydride is added into reaction, stirs 30 minutes, 4.8 mMs of halogen is added for methylformamide, ice bath
For hydrocarbon, it is then slowly raised to room temperature, is stirred at room temperature 8 hours, end of reaction, TLC monitors reaction solution, and discovery raw material is reacted complete
Entirely, stop reaction.30 milliliters of water are added, is then extracted with ethyl acetate, isolates organic layer, organic layer is washed with saturated sodium-chloride
One time, anhydrous sodium sulfate is dry, filters, solvent is removed under reduced pressure, residue purifies to obtain chemical combination through 100~200 mesh silica gel column chromatographies
Object IIIa-1, the petroleum ether that eluant, eluent is 60~90 degrees Celsius: ethyl acetate, volume ratio 6: 1, yield 77%；White is solid
Body, fusing point 163-164%, the following II-1 of the nuclear magnetic data of the compound:1H NMR (400MHz, Chloroform-d) δ δ 7.88
(s, 1H), 7.49-7.27 (m, 4H), 7.19-7.12 (m, 1H), 4.78 (s, 2H), 4.04 (s, 3H), 3.93 (s, 3H), 3.83
(s, 3H), the amount of 3.53 (s, 3H) compound IIIa-1 preparation and the volume of reaction vessel are expanded or shunk by corresponding proportion.
Embodiment 3: the preparation of compound IIIb-1:
3 mMs of compound IIIa-1 is added in 100 milliliters of single necked round bottom flask；30 ml methanol solution are added,
15 mMs of triethylamines and 9 mMs of methylamine is added, temperature is slowly increased to flow back, and stirs 6 hours at a reflux temperature；Contact plate
After monitoring fully reacting, first it is concentrated under reduced pressure, removes extra amine and methanol solution.Residue is through 100~200 mesh silica gel column chromatographies
Purifying obtains compound IIIb-1, the petroleum ether that eluant, eluent is 60~90 degrees Celsius: ethyl acetate, volume ratio 5: 1, yield
46%-90%；Yield 87%；White solid, fusing point 128-129%, the compound1HNMR (400MHz, CDCl3): δ δ 7.88
(d, J=1.4Hz, 1H), 7.47-7.16 (m, 5H), 6.85 (d, J=5.2Hz, 1H), 4.80 (s, 2H), 3.96 (s, 3H),
3.95 (s, 3H), 3.48 (s, 3H), the amount of 2.79 (d, J=5.0Hz, 3H) compound IIIb-1 preparation and the body of reaction vessel
Product is expanded or shunk by corresponding proportion.The physical and chemical parameter and structural parameters of compound III is shown in Table 1.
Embodiment 4: the bactericidal activity measurement of the methoxy acrylate derivative III of the invention containing difluoromethyl pyrazole
As a result:
The frequently seen plants disease fungus code name and title that the present invention tests are as follows: AS: tomato early blight bacterium, latin name
Are as follows: Alternariasolani, BC: botrytis cinerea pers, latin name are as follows: Botrytis cinerea, CA: the cercospora brown spot of peanut
Bacterium, latin name are as follows: Cercosporaarachidicola, GZ: fusarium graminearum, latin name are as follows:
Gibberellazeae, PI: phytophthora infestans, latin name are as follows: Phytophthorainfestans (Mont.) de
Bary, PP: Botryosphaeria berengeriana f. sp, latin name are as follows: Physalosporapiricola, PS: Rhizoctonia solani Kuhn, latin name
Are as follows: Pelliculariasasakii, RC: Rhizoctonia cerealis, latin name are as follows: Rhizoctoniacerealis, SS: Sclerotina Sclerotiorum in Winter Rape
Core germ, latin name are as follows: Sclerotiniasclerotiorum, these strains represent what field in agricultural production occurred
The kind of most of pathogen.
Thalli growth rate method measurement result is shown in Table 2, and table 2 shows majority of compounds of the invention in 50 mcg/ml
In vitro has certain bacteriostatic activity to the thallus of test.Chemical combination is shown to the Activity Results of tomato early blight bacterium
Object ydy01-99 is up to 50% to the growth inhibitory effect of tomato early blight bacterium, with existing commercial high activity kind trifloxystrobin
(inhibiting rate to tomato early blight bacterium is 53%) is suitable.Compound ydy01- is shown to the Activity Results of botrytis cinerea pers
62, ydy01-195 is respectively 56%, 57% and existing commercial high activity kind to the growth inhibitory effect of botrytis cinerea pers
Trifloxystrobin is suitable.To the Activity Results of peanut Cercospora asparagagas show compound ydy01-99, ydy01-157, ydy01-196,
33% or more, activity is higher by the (inhibition to the cercospora brown spot of peanut of commercial varieties trifloxystrobin for ydy01-198, inhibitory activity
Rate is 12%) 20% or more.Part of compounds, which shows, to be shown to the active testing of fusarium graminearum and phytophthora infestans
Certain activity out.Show the active testing of Botryosphaeria berengeriana f. sp the antibacterial work of ydy01-82, ydy01-99, ydy01-102
Property 64% or more, activity is high with trifloxystrobin (inhibiting rate to Botryosphaeria berengeriana f. sp is 64%).Work to Rhizoctonia solani Kuhn
Property test show that part of compounds shows certain activity.Compound ydy01- is shown to the active testing of Rhizoctonia cerealis
For 73 bacteriostatic activity 90%, activity is higher than trifloxystrobin (inhibiting rate to Rhizoctonia cerealis is 87%).To Sclerotinia sclerotiorum
Active testing show the bacteriostatic activity of compound ydy01-99 92%, activity and the trifloxystrobin (suppression to Sclerotinia sclerotiorum
Rate processed is 91%) suitable.
Embodiment 5: the living body bacteriostatic activity of the methoxy acrylate derivative III of the invention containing difluoromethyl pyrazole
Measurement result:
The live plant disease that the present invention tests has cucumber downy mildew, wheat powdery mildew, corn rust, cucumber anthracnose.
Living body measurement the results are shown in Table 3.Under the concentration of 200 mcg/mls, measurement result is listed in table 3, for wheat powdery mildew,
There is the control efficiency of 17 compounds to reach 100%, it is suitable with positive control drug trifloxystrobin.For corn rust, there are 7
The control efficiency of compound reaches 90% or more, and activity is suitable with positive control drug trifloxystrobin.
Embodiment 6: the methoxy acrylate derivative III and its intermediate of the invention containing difluoromethyl pyrazole is being made
Application in standby composition pesticide:
Of the invention methoxy acrylate derivative III and its intermediate containing difluoromethyl pyrazole can prepare pesticide
Composition, the composition include this methoxy acrylate derivative III of the invention containing difluoromethyl pyrazole and among it
Body is 0.1% to 99.9% weight, the solid or liquid of 99.9% to 0.1% weight as active constituent, the content of active constituent
The surfactant of body auxiliary agent and optional 0 to 50% weight.
Embodiment 7: the methoxy acrylate derivative III and its intermediate of the invention containing difluoromethyl pyrazole is being made
Application in standby pesticide complex composition:
Of the invention methoxy acrylate derivative III and its intermediate containing difluoromethyl pyrazole can be with other quotient
Product pesticide, i.e. insecticide, acaricide, fungicide, antivirotic or activating plants agent compounding preparation pesticide complex composition, this is multiple
It include the methoxy acrylate derivative III and its intermediate of the invention containing difluoromethyl pyrazole and other quotient with composition
As active constituent, of the invention contains difluoro for product pesticide, i.e. insecticide, acaricide, fungicide, antivirotic or activating plants agent
The methoxy acrylate derivative III and its intermediate and other commercially available agricultural chemicals of methylpyrazole, i.e. insecticide, kill at acaricide
The ratio of microbial inoculum, antivirotic or activating plants agent is mass percent 1%: 99% to 99%: 1%, the content of active constituent
For 0.1% to 99.9% weight, the table of the solid or liquid adjuvants of 99.9% to 0.1% weight and optional 0 to 50% weight
Face activating agent.
Embodiment 8: the methoxy acrylate derivative III and insecticide composition of the invention containing difluoromethyl pyrazole exists
Application in prevention and treatment agricultural and forestry and gardening plant insect pest:
Appointing in all methoxy acrylate derivative IIIs containing difluoromethyl pyrazole and commodity insecticide of the invention
The one or two kinds of combinations of meaning form Pesticidal combination for preventing and treating agricultural and forestry and gardening plant insect pest, the commodity desinsection
Agent is selected from: ground Asia Nong, Acetamiprid, emamectin benzoate, milbemectin, avermectin, pleocidin, cypermethrin, efficiently
Cypermethrin, Cyhalothrin, decis, Fenpropathrin, Beta- cyfloxylate, Lambda- Cyhalothrin,
Permethrin, permethrin, allethrin, Biphenthrin, Permethrin, ethofenprox, flumethrin, penta chrysanthemum of chlorine fluorine amine cyanogen
Ester, Nitenpyram, imidaclothiz, thiacloprid, Diacloden, clothianidin, dinotefuran, clothianadin, Da Tenan, diflubenzuron, goes out at imidacloprid
Young urea, Teflubenzuron, deinsectization be grand, flubenzuron, flufenoxuron, pyridine worm are grand, lufenuron, poisonous insect urea, penfluron, flucycloxuron, chlorfluazuron, piperazine
Worm urea, tebufenozide, chlorine tebufenozide, methoxyfenozide, ring tebufenozide, flolimat, DDVP, quinalphos, is rattled away at furan tebufenozide
Piperazine sulphur phosphorus, isoprocarb, sevin, Aphox, MTMC, Mobucin, cartap, Bassa, leaf disperse, carbaryl, rosickyite gram
Budweiser, carbosulfan, cartap, fenisobromolate, Hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, pyrrole aphid
Ketone, Envidor, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azacyclotin, Buprofezin, Cupric sulfate, dimehypo, chlorantraniliprole, fluorine
Insect amide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, chlorfenapyr, pyrazinones, etoxazole, tebufenpyrad, young ketone of rattling away, pyrrole third
Ether, emaricin；Methoxy acrylate derivative III containing difluoromethyl pyrazole of the invention is in the Pesticidal combination
Mass percentage be 1%-90%, the solid or liquid adjuvants of 99% to 10% weight and optional 0 to 50% weight
Surfactant, the methoxy acrylate derivative III of the invention containing difluoromethyl pyrazole and aforementioned commodity insecticide
Ratio is mass percent 1%: 99% to 99%: 1%；The dosage form of the Pesticidal combination processing is selected from: seed treatment emulsion,
Aqueous emulsion, big granula, microemulsion, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, blocky poison bait,
Sustained-release block, dense poison bait, CG/Encapsulated granule, micro-capsule suspension, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, water
It is packet oil emu, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog stick, seed treatment suspending agent, smog piece, smog ball, granular
Poison bait, medicine paint, fine granule, oil suspending agent, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkles and pours agent, seed coat agent, painting thermal fog
Smear agent, suspended emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspending agent, tracking pulvis,
Any one in ultra low volume liquids, wet-mixing kind water-dispersible powder；The insect pest of the plant of the Pesticidal combination prevention and treatment is selected from:
Red spider, Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, Oriental burmeister, rice thrips, onion thrips,
Greenhouse thrips, haplothrips aculeatus, Mai Jianguan thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, chlorita biguttula, spot clothing
The flat angle plant hopper of plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, sugarcane, cotten aphid, green bugs, grain aphid, black peach aphid, kaoliang aphid,
Radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, banana net
Stinkbug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, green rice bug, green plant bug, alfalfa plant bug, in
It is black fleahopper, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, oriental moth, brown slug moth, thosea siensis, gelechiid, pink bollworm, sweet
Potato gelechiid, diamondback moth, small heart-eating peach worm, eating-core bean worm, apple Spilonota lechriaspis, brown belt length leaf roller, Adoxophyes cyrtosema,
Striped rice borer, bean-pod borer, corn borer, yellow rice borer, Oeobia undalis, rice leaf roller, snout moth's larva, Notarchaderogata, dichocrocis punctiferalis, armyworm, twill
Noctuid, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point spark, black cutworm, big cutworm, Huang Di
Tiger steals poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight grain rice hesperiidae, pelopidas mathias, Papilio xuthus, Common Mormon, dish
White butterfly, pyrameis indica, a ramie Huang a kind of butterfly harmful to crop plants, beans blister beetle, Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, thin chest gold
The small buprestid beetle of needle worm, khapra beetle, attagenus piceus, citrus, golden edge buprestid beetle, yellow meal worm, dark mealworm, red flour beetle, confused flour beetle,
Verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori, pink neck longicorn, big ape leaf
Worm, daicon leaf beetle, aulacophora femoralis, phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pears are real
Bee, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm hang cocoon ichneumon wasp, Campoletis chlorideae, snout moth's larva stain wart ichneumon wasp, mosquito, horsefly, Mai Hong
Suction pulp worm, contarinia tritici, citrus fruit fly, melonfly, wheat leaf ash dive fly, Americal rice leaf miner, Soybean stem borer, frit fly,
Hylemyia Platura Meigen, onion fly, radish fly, full skirt Exorista civilis, corn borer is strict posts fly；The plant of Pesticidal combination prevention and treatment is selected from: paddy, small
Wheat, barley, oat, corn, sorghum, sweet potato, potato, cassava, soybean, garden pea, semen viciae fabae, pea, mung bean, red bean, cotton,
Silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp,
Tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tuber, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, mandarin orange
Tangerine, peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape.
Embodiment 9: the methoxy acrylate derivative III and antimicrobial combination of the invention containing difluoromethyl pyrazole exists
Application in prevention and treatment agricultural and forestry and gardening plant disease:
Appointing in all methoxy acrylate derivative IIIs containing difluoromethyl pyrazole and commodity fungicide of the invention
The one or two kinds of combinations of meaning form bactericidal composition for preventing and treating agricultural and forestry and gardening plant disease, the commodity sterilization
Agent is selected from: diazosulfide, tiadinil, is abbreviated as TDL, tisocromide, first thiophene and is lured amine, 4- methyl-1,2,3- thiadiazoles -5- first
Acid, 4- methyl-1,2,3- thiadiazoles -5- sodium formates, 4- methyl-1,2,3- thiadiazoles -5- Ethyl formates, DL- beta-aminobutyric acid,
Isotianil, English common name are as follows: isotianil, 3,4-, bis- chloroisothiazole -5- formic acid, 3,4-, bis- chloroisothiazole -5- formic acid
Sodium, 3,4-, bis- chloroisothiazole -5- Ethyl formate, virazole, antofine, Ningnanmycin or salicylic acid, cymoxanil, thiram, good fortune
U.S. zinc, Mancozeb, aliette, thiophanate-methyl, Bravo, enemy can pine, procymidone, fenpropidin, thiophanate methyl, Tobes
Saliva, Metalaxyl-M, flumorph, dimethomorph, mefenoxam, benalaxyl-M, double chlorine zarilamid, flusulfamide, first flusulfamide,
Thiophene fluorine bacterium amine, flutolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr,
Pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, iprodione, Fluoxastrobin, dimoxystrobin, fluorine are phonetic
Bacterium ester, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, pyraclostrobin, trifloxystrobin, Enestroburin, alkene oxime amine, oxygen ring
Azoles, bromuconazole, Cyproconazole, difenoconazole, olefin conversion, efficient olefin conversion, epoxiconazole, benzoxazole, Fluquinconazole, Flusilazole,
Flutriafol, hexaconazole, glyoxalin, kind bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, simeconazoles, penta azoles
Alcohol, tetraconazole, Triadimenol, triticonazole, bitertanol, probenazole, furidazol, imazalil, efficient imazalil, Prochloraz,
Fluorine bacterium azoles, Fenamidone, dislike imidazoles, pefurazoate, Famoxate, oxazole, hymexazol, Wakil, thiazole bacterium at cyazofamid
Amine, Grandox fumigant, octhilinone, benthiozole, dodemorph, butadiene morpholine, tridemorph, fenpiclonil, fludioxonil, fluazinam,
It is pyrifenox, ring pyridine bacterium amine, Boscalid, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic
Mould amine, Fenarimol, nuarimol, chinomethionat, dithianon, ethoxyquin, oxyquinoline, the third oxygen quinoline, benzene oxygen quinoline
Quinoline, diethofencarb, iprovalicarb, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, different rice blast net, pyrazophos, tolelofos-methyl,
Blasticidin-S, kasugarnycin, polyoxin, Polyoxin, valida, jinggangmeisu, streptomysin, metalaxyl, furalaxyl, benzene frost
Spirit, ofurace, mebenil, carbendazim, benomyl, thiophanate-methyl, triazolone, bupirimate, dimethirimol, second are phonetic
Phenol, difoltan, captan, folpet, vinclozolin, fluoromide, dimethachlon, Bravo, Isoprothiolane, kitazine, leaf
Withered azoles, pentachloronitrobenzene, Propineb, phosethyl-Al, sulphur, Bordeaux mixture, copper sulphate, copper oxychloride, cuprous oxide, hydrogen-oxygen
Change copper, metrafenone, Pencycuron, diclomezin, Rabcide, pyroquilon, volution bacterium amine, tricyclazole, triforine, more fruit pyridines, biguanides
Pungent salt, iminoctadine, botran, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bromine nitre
Alcohol, iodomethane, metham-sodium, enemy line ester, dazomet, nemamort, lythidathion, fensulfothion, thionazin, dichlofenthion, fosthietan,
Oxamyl, vikane, dichloropropylene, dichloro-isonicotinic acid, allyl isothiazole；Methoxy propyl containing difluoromethyl pyrazole of the invention
Total mass percentage of the olefin(e) acid ester derivant III in the bactericidal composition is 1%-90%, 99% to 10% weight
Solid or liquid adjuvants and optional 0 to 50% weight surfactant, the methoxy of the invention containing difluoromethyl pyrazole
The ratio of base acrylate derivative III and aforementioned commodity fungicide is mass percent 1%: 99% to 99%: 1%；It is described
The dosage form of bactericidal composition processing is selected from: seed treatment emulsion, aqueous emulsion, big granula, microemulsion, water-soluble granule, solubility
Dense dose, it is water-dispersible granules, poison grain, aerosol, blocky poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, micro-capsule suspension, dry
Seed dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, cigarette
Mist stick, seed treatment suspending agent, smog piece, smog ball, granular poison bait, thermal fog, medicine paint, fine granule, oil suspending agent, oil-dispersing property
Pulvis, sheet poison bait, dense jelly, sprinkle pour agent, seed coat agent, liniment, suspended emulsion, film forming finish, soluble powder, at seed
Manage water solube powder, ultra-low volume suspending agent, tracking pulvis, ultra low volume liquids, any in wet-mixing kind water-dispersible powder
It is a kind of；The plant disease of the bactericidal composition prevention and treatment is selected from: seedling blight of rice, tomato root rot, the late blight of potato, tobacco
Balck shank, millet powdery mildew, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose；The bactericidal composition
Applicable plant is selected from: paddy, wheat, barley, oat, corn, sorghum, sweet potato, potato, cassava, soybean, garden pea, silkworm
Beans, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, shellfish
Mother, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tuber, green onion, garlic, watermelon,
Muskmelon, "Hami" melon, pawpaw, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid,
Potted landscape.
Embodiment 10: the methoxy acrylate derivative III and Antiphytoviral of the invention containing difluoromethyl pyrazole
Application of the agent combination in prevention and treatment agricultural and forestry and gardening plant virus disease:
In all methoxy acrylate derivative IIIs containing difluoromethyl pyrazole and commodity antiviral agent of the invention
The combination of any one or two kinds form antiviral composition for preventing and treating agricultural and forestry and gardening plant virus disease, institute
State commodity antiviral agent to be selected from: diazosulfide, tiadinil are abbreviated as TDL, isotianil, English common name are as follows:
Isotianil, 4- methyl-1,2,3- thiadiazoles -5- formic acid, 4- methyl-1,2,3- thiadiazoles -5- sodium formates, 4- methyl-1,2,
3- thiadiazoles -5- Ethyl formate, 3,4-, bis- chloroisothiazole -5- formic acid, 3,4-, bis- chloroisothiazole -5- sodium formate, 3,4- dichloro are different
Thiazole -5- Ethyl formate, DL- beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lure amine or salicylic acid
, cytosintetidemycin, dichloro-isonicotinic acid, allyl isothiazole, well ridge azanol, jinggangmeisu；Of the invention contains difluoromethyl
Total mass percentage of the methoxy acrylate derivative III of pyrazoles in the antiviral composition is 1%-
90%, the surfactant of the solid or liquid adjuvants of 99% to 10% weight and optional 0 to 50% weight is of the invention
The ratio of methoxy acrylate derivative III and aforementioned commodity anti-plant virus agent containing difluoromethyl pyrazole is quality percentage
Than 1%: 99% to 99%: 1%；The dosage form of the antiviral composition processing is selected from: seed treatment emulsion, aqueous emulsion, big grain
Agent, microemulsion, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, blocky poison bait, sustained-release block, dense poison
Bait, CG/Encapsulated granule, micro-capsule suspension, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil in water emulsion, cigarette
Mist tank, granula subtilis, smoke candle, smoke cartridge, smog stick, seed treatment suspending agent, smog piece, smog ball, granular poison bait, hot mist
Agent, fine granule, oil suspending agent, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkles and pours agent, seed coat agent, liniment, suspension medicine paint
Emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspending agent, tracking pulvis, ultra-low volume
Any one in liquor, wet-mixing kind water-dispersible powder；The virus disease of the antiviral composition prevention and treatment is selected from: rice is short
Contracting disease, yellow dwarf, stripe virus disease, fern leaf of tomato viral disease, Tomato yellow mosaic virus, pepper mosaic virus disease viral disease, tobacco arteries and veins are bad
Dead virosis, maize dwarf mosaic, cauliflower mosaic virus, citrus virosis, cymbidium mosaic virus, cybidium ring spot virus；Institute
State antiviral composition for prevention and treatment plant be selected from: paddy, wheat, barley, oat, corn, sorghum, sweet potato, potato, wood
Potato, soybean, garden pea, semen viciae fabae, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane,
Coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, squeezing
Dish, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper,
Banana, papaya, orchid, potted landscape.
Embodiment 11: the methoxy acrylate derivative III of the invention containing difluoromethyl pyrazole is combined with acaricide
Application in prevention and treatment agricultural and forestry and gardening plant mite evil:
Appointing in all methoxy acrylate derivative IIIs containing difluoromethyl pyrazole and commodity acaricide of the invention
The one or two kinds of combinations of meaning form miticide composition for preventing and treating agricultural and forestry and gardening plant mite evil, the commodity mite killing
Agent is selected from: azacyclotin, plictran, fenbutatin oxide, three phosphor tins, chlorfenviphos, dimethylvinphos, crotoxyphos, heptenophos, Menite, two
Bromine phosphorus, Diothyl, imino-formyl chloride sulphur phosphorus, omethoate, dioxathion, Ethodan, methacrifos, Phosalone, methylpyrimidine sulphur phosphorus, quinoline
Sulphur phosphorus, Kilval, propetamphos, dialifos, phosmet, acrinathrin, Biphenthrin, lambda-cyhalothrin, the efficient chlorine of essence
Flucythrinate, Fenpropathrin, flucythrinate, flumethrin, taufluvalinate, brofluthrinate, Bifenazate, fenothiocarb,
Butocarboxim, Talcord, thiofanox, benomyl, sok, carbosulfan, MTMC, promacyl, Carzol, single carbonamidine,
Medimeform, Amitraz, Ergol, fenisobromolate, cyflumetofen, acequinocyl, Nissol, flufenoxuron, macro tetrolide, worm mite are mould
Element, thuringiensin, tetranactin, avermectin, doractin, eprinomectin, ivermectin, selamectin, moxidectin,
Pyrethrin, nicotine, matrine, nimbin, rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, Hexythiazox,
Envidor, fluacrypyrim, chlorfenizon, propargite, pyridaben；Methoxy acrylate containing difluoromethyl pyrazole of the invention is derivative
Total mass percentage of the object III in the miticide composition is 1%-90%, the solid or liquid of 99% to 10% weight
The surfactant of body auxiliary agent and optional 0 to 50% weight, the methoxy acrylate of the invention containing difluoromethyl pyrazole
Derivative III and the acaricidal ratio of the commodity are mass percent 1%: 99% to 99%: 1%；The miticide composition
The dosage form of processing is selected from: seed treatment emulsion, aqueous emulsion, big granula, microemulsion, water-soluble granule, soluble thick agent, water dispersion
Property granula, poison grain, aerosol, blocky poison bait, sustained-release block, dense poison bait, CG/Encapsulated granule, micro-capsule suspension, Waterless Seed Dressing pulvis, cream
Oil, electrostatic spray agent, water-in-oil emulsion, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog stick, at seed
Manage suspending agent, smog piece, smog ball, granular poison bait, thermal fog, medicine paint, fine granule, oil suspending agent, oil-dispersing property pulvis, sheet poison
Bait, dense jelly sprinkle and pour agent, seed coat agent, liniment, suspended emulsion, film forming finish, soluble powder, seed treatment water soluble powder
Agent, ultra-low volume suspending agent, tracking pulvis, ultra low volume liquids, any one in wet-mixing kind water-dispersible powder；It is described to kill
The mite evil of acaricidal composition prevention and treatment is selected from: mite evil is selected from Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae, tetranychus telarius category, Eriophyidae
Harmful mite, these harmful mites are worldwide Agricultural Mites, forestry harmful mites, gardening harmful mite and hygienic harmful mite；The miticide composition is used
Be selected from the plant of prevention and treatment: paddy, wheat, barley, oat, corn, sorghum, sweet potato, potato, cassava, soybean, garden pea,
Semen viciae fabae, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria,
Rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tuber, rape, green onion, garlic, west
Melon, muskmelon, "Hami" melon, pawpaw, apple, citrus, peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid
Flower, potted landscape.
The chemical structure of the methoxy acrylate derivative III of the invention containing difluoromethyl pyrazole of table 1. and physical and chemical ginseng
Number
The chemistry knot of the methoxy acrylate derivative III and its intermediate of the invention containing difluoromethyl pyrazole of table 1.
Structure and physical and chemical parameter (Continued)
The antibacterial work of the methoxy acrylate derivative III and its intermediate of the invention containing difluoromethyl pyrazole of table 2.
Property (inhibiting rate/% of 50 mcg/mls)
| Serial number | Compound number | AS | BC | CA | GZ | PI | PP | PS | RC | SS |
| 1 | 01-62 | 27 | 56 | 5 | 0 | 0 | 21 | 25 | 2 | 39 |
| 2 | 01-66 | 27 | 0 | 0 | 0 | 17 | 25 | 10 | 2 | 16 |
| 3 | 01-67 | 27 | 0 | 14 | 0 | 17 | 21 | 14 | 33 | 16 |
| 4 | 01-71 | 19 | 8 | 5 | 3 | 9 | 35 | 6 | 38 | 16 |
| 5 | 01-73 | 19 | 0 | 5 | 0 | 22 | 35 | 18 | 38 | 16 |
| 6 | 01-82 | 19 | 28 | 14 | 0 | 9 | 65 | 37 | 90 | 48 |
| 7 | 01-83 | 12 | 0 | 10 | 0 | 11 | 42 | 6 | 2 | 48 |
| 8 | 01-99 | 50 | 42 | 48 | 42 | 43 | 67 | 29 | 0 | 92 |
| 9 | 01-102 | 19 | 14 | 5 | 0 | 0 | 71 | 18 | 5 | 32 |
| 10 | 01-103 | 12 | 28 | 14 | 0 | 17 | 35 | 6 | 5 | 16 |
| 11 | 01-157 | 26 | 33 | 36 | 16 | 0 | 13 | 30 | 78 | 33 |
| 12 | 01-158 | 32 | 39 | 18 | 18 | 21 | 13 | 23 | 43 | 70 |
| 13 | 01-193 | 26 | 41 | 15 | 12 | 0 | 15 | 18 | 45 | 54 |
| 14 | 01-194 | 26 | 33 | 0 | 24 | 18 | 23 | 23 | 47 | 74 |
| 15 | 01-195 | 32 | 57 | 21 | 24 | 18 | 26 | 18 | 53 | 78 |
| 16 | 01-196 | 29 | 41 | 33 | 14 | 26 | 9 | 27 | 43 | 78 |
| 17 | 01-197 | 32 | 41 | 0 | 14 | 18 | 19 | 27 | 45 | 83 |
| 18 | 01-198 | 29 | 37 | 52 | 20 | 18 | 9 | 18 | 47 | 74 |
| 19 | Trifloxystrobin | 52 | 63 | 12 | 72 | 84 | 64 | 86 | 87 | 91 |
AS: tomato early blight bacterium, latin name are as follows: Alternaria solani, BC: botrytis cinerea pers, latin name
Are as follows: Botrytis cinerea, CA: peanut Cercospora bacteria, latin name are as follows: Cercospora arachidicola, GZ: small
Wheat gibberellic hypha, latin name are as follows: Gibberella zeae, PI: phytophthora infestans, latin name are as follows:
Phytophthora infestans (Mont.) de Bary, PP: Botryosphaeria berengeriana f. sp, latin name are as follows: Physalospora
Piricola, PS: Rhizoctonia solani Kuhn, latin name are as follows: Pellicularia sasakii, RC: Rhizoctonia cerealis, Latin
Name are as follows: Rhizoctonia cerealis, SS: Sclerotinia sclerotiorum, latin name are as follows: Sclerotinia
sclerotiorum.
The living body bacteriostatic activity (200 of the methoxy acrylate derivative III of the invention containing difluoromethyl pyrazole of table 3.
Inhibiting rate/% of mcg/ml)
Claims (9)
1. a kind of methoxy acrylate derivative containing difluoromethyl pyrazole, it is characterised in that: have and tied as shown in formula III
Structure general formula:
Wherein:
N is 0 or 1, and X is N or CH, and Y is N or O；
R1、R2It is selected from: hydrogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy, C2-C6Alkenyl, C2-
C6Halogenated alkenyl, C2-C6Alkynyl, C2-C6Halo alkynyl, hydroxyl, C3-C6It is naphthenic base, substituted piperidin-1-yl, substituted
The phenyl or C that morpholine -1- base, substituted nafoxidine -1- base, phenyl or halogen replace1-C6Alkyl-substituted phenyl or
C1-C6The phenyl or C that halogenated alkyl replaces3-C6The phenyl or C that the phenyl or nitro that naphthenic base replaces replace2-C6Alkenyl replaces
Phenyl or C2-C6The phenyl or C that halogenated alkenyl replaces3-C6The phenyl or C that cycloalkenyl replaces2-C6The phenyl of alkynyl substituted
Or C2-C6The phenyl or C that halo alkynyl replaces3-C6Pyridyl group that phenyl that cycloalkynyl radical replaces, pyridyl group or halogen replace or
C1-C6Alkyl-substituted pyridyl group or C1-C6The pyridyl group or C that halogenated alkyl replaces3-C6Naphthenic base replace pyridyl group or
The pyridyl group or C that nitro replaces2-C6The pyridyl group or C that alkenyl replaces2-C6The pyridyl group or C that halogenated alkenyl replaces3-C6Ring
The pyridyl group or C that alkenyl replaces2-C6The pyridyl group or C of alkynyl substituted2-C6The pyridyl group or C that halo alkynyl replaces3-C6Cycloalkyne
The pyrimidine radicals or C that pyridyl group, pyrimidine radicals or the halogen that base replaces replace1-C6Alkyl-substituted pyrimidine radicals or C1-C6Alkyl halide
The pyrimidine radicals or C that base replaces3-C6The pyrimidine radicals or C that the pyrimidine radicals or nitro that naphthenic base replaces replace2-C6What alkenyl replaced
Pyrimidine radicals or C2-C6The pyrimidine radicals or C that halogenated alkenyl replaces3-C6The pyrimidine radicals or C that cycloalkenyl replaces2-C6Alkynyl substituted
Pyrimidine radicals or C2-C6The pyrimidine radicals or C that halo alkynyl replaces3-C6Pyrimidine radicals that cycloalkynyl radical replaces substituted contains 1 or 2 N
Five yuan of atom or six membered heteroaryl, substituted five yuan containing 1 or 2 S atom or six membered heteroaryl contain 1 or 2 O
Substituted five yuan of atom or six membered heteroaryl, substituted five yuan or hexa-atomic heteroaryl containing 1 N atom and 1 S atom
Base, substituted five yuan containing 1 N atom and 1 O atom or six membered heteroaryl, being taken containing 2 N atoms and 1 S atom
Five yuan of generation or six membered heteroaryl, substituted five yuan or six membered heteroaryl containing 2 N atoms and 1 O atom；Above-mentioned five yuan
Or six membered heteroaryl is selected from: substituted furyl, thienyl, pyrrole radicals, imidazole radicals, pyrazolyl, thiazolyl, isothiazolyl,
Oxazolyl, isoxazolyl, oxadiazoles base, thiadiazolyl group, pyridyl group, pyridazinyl, pyrimidine radicals, pyrazinyl, triazine radical, tetrazine base,
Indyl, benzothienyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazole base, benzothiazolyl, benzo thiophene two
Oxazolyl, benzoxazolyl, the quinolyl of isomerization, the isoquinolyl of isomerization, phthalazinyl, quinoxalinyl, quinazolyl, cinnolines
The silicon substrate that base or naphthyridines base, alkyl or alkenyl replace；
Halogen is fluorine, chlorine, bromine or iodine in above-mentioned definition；
The alkyl, alkenyl or alkynyl are straight chain or branch alkyl；Alkyl itself or as other substituent groups part select
From methyl, ethyl, propyl, butyl, amyl, hexyl and its isomers, isomers is selected from isopropyl, isobutyl group, sec-butyl, uncle
Butyl, isopentyl or tertiary pentyl；
The halogenated alkyl group is selected from the group containing one or more identical or different halogen atoms, the halogenated alkyl choosing
From CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CF3CH2、CH3CF2、CF3CF2Or CCl3CCl2；
Described naphthenic base itself or as other substituent groups part be selected from cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl；
Described alkenyl itself or as other substituent groups part be selected from vinyl, allyl, 1- acrylic, butene-2-base, fourth
Alkene -3- base, amylene -1- base, amylene -3- base, hexene -1- base or 4- methyl-3-pentenyl；
Described alkynyl itself or as other substituent groups part be selected from acetenyl, propine -1- base, propine -2- base, butine -1-
Base, crotonylene-base, 1- methyl -2- butynyl, hexin -1- base or 1- ethyl -2- butynyl.
2. the methoxy acrylate derivative III containing difluoromethyl pyrazole according to claim 1, R1It preferably is selected from: methyl,
Methoxyl group, allyl, propargyl, 2- butine, methylene cyclopropyl, allyloxy, propynyloxy base, methylene cyclopropyl oxygroup；R2
It preferably is selected from: methyl, cyclopropyl；N is 0 or 1, and X is N or CH, and Y is N or O.
3. according to claim 1 with the tool of the methoxy acrylate derivative III described in claim 2 containing difluoromethyl pyrazole
Body synthetic route and method are as follows:
The definition of the substituent group is as described in claim 1, and the definition of preferred substituents is as claimed in claim 2；Specific synthesis
Method is divided into following steps:
A. the preparation of intermediate II and compound IIIc:
Intermediate II and compound IIIc are by starting material I and different amine in condensing agent EDCI and HOBT in methylene chloride
In be stirred to react preparation, the wherein definition such as claim 1 of starting material I and intermediate II and the substituent group in compound IIIc
Described, the definition of preferred substituents is as claimed in claim 2；
B. the preparation of compound IIIa and compound IIId:
Compound IIIa and compound IIId under alkaline condition, are stirred by intermediate II and compound IIIc and halogenated hydrocarbons in room temperature
Reaction preparation is mixed, wherein the definition of the substituent group in compound IIIa and compound IIId is as described in claim 1, preferably replaces
The definition of base is as claimed in claim 2；
C. the preparation of compound IIIb and compound IIIe:
Compound IIIb and compound IIIe is by compound IIIa, IIIc or IIId and amine in Et3Return stirring is anti-in methyl alcohol by N
It should prepare, wherein the definition of the substituent group in compound IIIa, IIIb, IIIc, IIId or IIIe is as described in claim 1, excellent
Select the definition of substituent group as claimed in claim 2.
4. prepared by claim 1 and the methoxy acrylate derivative III as claimed in claim 2 containing difluoromethyl pyrazole
Purposes in agricultural fungicidal agent.
5. a kind of composition pesticide, it includes claims 1 and the methoxy propyl as claimed in claim 2 containing difluoromethyl pyrazole
Olefin(e) acid ester derivant III can prepare pesticide close object, the composition include claim 1 and it is as claimed in claim 2 contain difluoro
The methoxy acrylate derivative III of methylpyrazole is 0.1 to 99.9% weight as active constituent, the content of active constituent
Amount, the surfactant of the solid or liquid adjuvants of 99.9 to 0.1% weight and optional 0 to 50% weight.
6. a kind of pesticide complex composition, it includes claims 1 and the methoxy as claimed in claim 2 containing difluoromethyl pyrazole
Base acrylate derivative III and its intermediate can prepare pesticide complex composition, which includes claim 1
With the methoxy acrylate derivative III as claimed in claim 2 containing difluoromethyl pyrazole and its intermediate and commodity agriculture
Medicine is 0.1% to 99.9% weight, the solid or liquid of 99.9% to 0.1% weight as active constituent, the content of active constituent
The surfactant of body auxiliary agent and optional 0 to 50% weight.
7. a kind of agricultural bactericidal complex composition, it includes claims 1 and as claimed in claim 2 containing difluoromethyl pyrazole
Methoxy acrylate derivative III and other bactericide compounded as active constituent, methoxy propyls containing difluoromethyl pyrazole
The ratio of olefin(e) acid ester derivant III and other fungicide is mass percent 1%: 99% to 99%: 1%, and active constituent contains
Amount is 1% to 99% weight, the solid or liquid adjuvants of 99% to 1% weight.
8. a kind of agricultural insecticidal, mite killing complex composition, it includes claim 1 and as claimed in claim 2 contain difluoromethyl
The methoxy acrylate derivative III of pyrazoles and other Insecticidal and acaricidal agents compounding are used as active constituent, contain difluoromethyl pyrazole
Methoxy acrylate derivative III and the ratios of other fungicide be mass percent 1%: 99% to 99%: 1%, it is living
Property ingredient content be 1 to 99% weight, the solid or liquid adjuvants of 99 to 1% weight.
9. a kind of anti-plant virus agent complex composition, it includes claims 1 and pyrrole containing difluoromethyl as claimed in claim 2
The methoxy acrylate derivative III I of azoles and other anti-plant virus agents compounding are used as active constituent, contain difluoromethyl pyrazole
Methoxy acrylate derivative III and other anti-plant virus agents ratio be mass percent 1%: 99% to 99%:
1%, the content of active constituent is 1 to 99% weight, the solid or liquid adjuvants of 99 to 1% weight.
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| CN111410638A (en) * | 2020-03-18 | 2020-07-14 | 天津农学院 | Benzothiadiazine methoxyl acrylate derivatives, and preparation method and application thereof |
| CN112358444A (en) * | 2020-11-02 | 2021-02-12 | 南开大学 | Oxime ether heterocyclic formamide derivatives, and preparation method and application thereof |
| CN113408849A (en) * | 2021-05-13 | 2021-09-17 | 柳州东风容泰化工股份有限公司 | Method and system for evaluating pesticide effect of mixture of fenpyroximate and pesticide |
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| CN112358444A (en) * | 2020-11-02 | 2021-02-12 | 南开大学 | Oxime ether heterocyclic formamide derivatives, and preparation method and application thereof |
| CN113408849A (en) * | 2021-05-13 | 2021-09-17 | 柳州东风容泰化工股份有限公司 | Method and system for evaluating pesticide effect of mixture of fenpyroximate and pesticide |
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