CN110128346A - A kind of biaryl amide pyrazole derivatives and its preparation method and application - Google Patents
A kind of biaryl amide pyrazole derivatives and its preparation method and application Download PDFInfo
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- CN110128346A CN110128346A CN201910422284.6A CN201910422284A CN110128346A CN 110128346 A CN110128346 A CN 110128346A CN 201910422284 A CN201910422284 A CN 201910422284A CN 110128346 A CN110128346 A CN 110128346A
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- 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
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- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—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
- 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
The present invention provides a kind of biaryl amide pyrazole derivatives and its preparation method and application, and the present invention relates to a kind of biaryl amide pyrazole derivatives, general formula of the chemical structure is shown in Formula IV:
Description
Technical field
Technical solution of the present invention is related to the pyrazole compound of amide containing biaryl, and in particular to 1- methyl -3- difluoromethyl
Pyrazoles and 1- methyl-3-trifluoromethyl pyrazol analog derivative.
Background technique
Biphenyl structural unit skeleton occupies an important position in natural products and field of medicinal chemistry, and many contains this knot
The organic molecule of structure unit all shows good chemical characteristic and potential bioactivity.Biphenyl structural in medicine can be with
In the novel inhibition for being accredited as Hedgehog signal transduction path as microsomal triglyceride transfer protein (MTP) inhibitor
Agent.(Peukert S.et al./Bioorg.Med.Chem.Lett.2009 (19): 328-333), inhibit as apolipoprotein B
Agent (Takasugi, H.et al.WO 2003045921) is used for the treatment of diabetes, inhibits nicotinamide phosphoribosyl transferase
And other effects (Willardsen, Adam J.et al.WO 2011109441).On pesticide biphenyl structural widely exist with it is more
A fungicide kind, especially succinate dehydrogenase inhibitors fungicide kind.
Pyrazole derivatives have efficient, low toxicity, wide spectrum biological activity, the succinic acid to put goods on the market in nearly 20 years
There are about 70% or more in dehydrogenase inhibitor class fungicide kind all to contain a pyrazole heterocycle.Existing pyrazoles acyl reported in the literature
Amine compounds targetted mitochondria Respiratory Chain Complex I I be also known as succinate dehydrogenase (Du Shijie, waits, Pesticide Science journal, 2018
It (5): 545-556), is the fungicide of a kind of wide spectrum.Fungicide containing pyrazole heterocycle is various in style, living with excellent sterilization
Property.
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 design feature of comprehensive existing succinate dehydrogenase inhibitors introduces pyrazole group in pesticide molecule design
It is the popular research direction of scientific research institutions, China and foreign countries and agro-chemical companies.The multifarious biaryl amide pyrazole derivatives of construction structure improve
The bactericidal activity of target molecule is mainly used for the prevention and treatment of corn rust and rice sheath blight disease, and have novel to research and development is wide
Disease-resistant fungicide is composed with 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
Biphenyl structural and pyrazole group are introduced same MOLECULE DESIGN and have synthesized a kind of biaryl amide pyrazoles by medicine lead compound, the present invention
Derivative, while having carried out the screening and evaluation of the bioactivity of system, to find more high activities, low resistance risk and ring
The high environment friendly agricultural candidate kind of border compatibility.
Summary of the invention
The technical problems to be solved by the present invention are: providing the synthetic method of a kind of biaryl amide pyrazole derivatives, provide
This kind of compound modulates agricultural, the bioactivity and its measuring method of gardening and health and forestry plant pathogen, mention simultaneously
For application of these compounds in agriculture field, horticultural field, field of forestry and health field.
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 biaryl amide pyrazole derivatives of bactericidal activity is shown in Formula IV:
R1、R2、R3、R4、R5It is selected from: hydrogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy, C1-C6Haloalkoxy
Base, C2-C6Alkenyl, C2-C6Halogenated alkenyl, C2-C6Alkynyl, C2-C6Halo alkynyl, hydroxyl, C3-C6Naphthenic base, substituted piperazine
The phenyl or C that pyridine -1- base, substituted morpholine -1- base, substituted nafoxidine -1- base, phenyl or halogen replace1-C6
Alkyl-substituted phenyl or C1-C6The phenyl or C that halogenated alkyl replaces3-C6The benzene that the phenyl or nitro that naphthenic base replaces replace
Base or C2-C6The phenyl or C that alkenyl replaces2-C6The phenyl or C that halogenated alkenyl replaces3-C6Cycloalkenyl replace phenyl or
C2-C6The phenyl or C of alkynyl substituted2-C6The phenyl or C that halo alkynyl replaces3-C6Phenyl, pyridyl group or the halogen that cycloalkynyl radical replaces
The pyridyl group or C that element replaces1-C6Alkyl-substituted pyridyl group or C1-C6The pyridyl group or C that halogenated alkyl replaces3-C6Cycloalkanes
The pyridyl group or C that the pyridyl group or nitro that base replaces replace2-C6The pyridyl group or C that alkenyl replaces2-C6Halogenated alkenyl replaces
Pyridyl group or C3-C6The pyridyl group or C that cycloalkenyl replaces2-C6The pyridyl group or C of alkynyl substituted2-C6What halo alkynyl replaced
Pyridyl group or C3-C6The pyrimidine radicals or C that pyridyl group, pyrimidine radicals or the halogen that cycloalkynyl radical replaces replace1-C6It is alkyl-substituted phonetic
Piperidinyl or C1-C6The pyrimidine radicals or C that halogenated alkyl replaces3-C6The pyrimidine radicals for pyrimidine radicals or the nitro substitution that naphthenic base replaces,
Or C2-C6The pyrimidine radicals or C that alkenyl replaces2-C6The pyrimidine radicals or C that halogenated alkenyl replaces3-C6The pyrimidine radicals of cycloalkenyl substitution,
Or C2-C6The pyrimidine radicals or C of alkynyl substituted2-C6The pyrimidine radicals or C that halo alkynyl replaces3-C6Pyrimidine radicals, the quilt of cycloalkynyl radical substitution
Five yuan or the six membered heteroaryl, substituted five yuan or hexa-atomic miscellaneous containing 1 or 2 S atom containing 1 or 2 N atom replaced
It is aryl, substituted five yuan containing 1 or 2 O atom or six membered heteroaryl, substituted containing 1 N atom and 1 S atom
Five yuan or six membered heteroaryl, substituted five yuan containing 1 N atom and 1 O atom or six membered heteroaryl contain 2 N atoms and 1
Substituted five yuan of a S atom or six membered heteroaryl, substituted five yuan or hexa-atomic miscellaneous containing 2 N atoms and 1 O atom
Aryl；Above-mentioned five yuan or six membered heteroaryl are selected from: substituted furyl, thienyl, pyrrole radicals, imidazole radicals, pyrazolyl, thiazole
Base, isothiazolyl, oxazolyl, isoxazolyl, oxadiazoles base, thiadiazolyl group, pyridyl group, pyridazinyl, pyrimidine radicals, pyrazinyl, three
Piperazine base, tetrazine base, indyl, benzothienyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazole base, benzo thiophene
Oxazolyl, diazosulfide base, benzoxazolyl, the quinolyl of isomerization, the isoquinolyl of isomerization, phthalazinyl, quinoxalinyl,
The silicon substrate that quinazolyl, cinnoline base or naphthyridines base, alkyl or alkenyl replace.
R1It preferably is selected from: difluoromethyl, trifluoromethyl；R2It preferably is selected from: hydrogen, fluorine；R3It preferably is selected from: hydrogen, fluorine, chlorine；R4It preferably is selected from:
Hydrogen, fluorine, chlorine, methyl, trifluoromethyl, tert-butyl；R5It preferably is selected from: hydrogen, fluorine, chlorine.
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.
The synthetic method of biaryl amide pyrazole derivatives of the invention is as follows:
Wherein, substituent R1、R2、R3It is defined as described above；R1It preferably is selected from: trifluoromethyl, difluoromethyl；R2It preferably is selected from: hydrogen,
Fluorine；R3R4R5It preferably is selected from: hydrogen, methoxyl group, tert-butyl, fluorine, chlorine, methyl, trifluoromethyl.
The synthesis of biaryl amide pyrazole derivatives and the specific method of biological activity determination of the invention is divided into following step
It is rapid:
A. the preparation of compound II:
28.3 mMs of pyrazoles acid compound I are added in 250 milliliters of twoport round-bottomed flasks, pyrazoles acid is selected from: 1- methyl-
- 4 pyrazole carboxylic acid of 3- trifluoromethyl, -4 pyrazole carboxylic acid of 1- methyl -3- difluoromethyl；It is suspended in t-butanol solution, nitrogen protection
Under, 36.91 mMs of diphenyl phosphate azides and 56.78 mMs of n,N-diisopropylethylamine, reaction solution are added at room temperature
Half an hour is stirred at room temperature, rear slow heating heating is stirred 4 hours at 80~90 DEG C.After fully reacting, system is cooled into room
Temperature, is concentrated under reduced pressure and removes excess of solvent, and residue purifies to obtain compound II, eluant, eluent 60 through 100~200 mesh silica gel column chromatographies
~90 degrees Celsius of petroleum ether: ethyl acetate, according to the difference of product, volume ratio 10: 1-6: 1, yield 76-91%；Change
The volume of the amount and reaction vessel of closing object II preparation is expanded or shunk by corresponding proportion.
B. the preparation of compound III:
4 mMs of compound II are added in 50 milliliters of single necked round bottom flask, it is molten to add 8 milliliters of dry methylene chloride
4 milliliters of trifluoroacetic acids are added into reaction, are then stirred at room temperature 2 hours, end of reaction for liquid, and TLC monitors reaction solution, and discovery is former
Expect II fully reacting, stops reaction.Reaction solution is concentrated under reduced pressure, extra solvent and trifluoroacetic acid are removed.Water is added
40ml, saturated aqueous sodium carbonate washing neutralize, are then extracted with ethyl acetate, isolate organic layer, organic layer saturated carbon
Sour hydrogen sodium is washed, saturated sodium-chloride is respectively washed one time, and anhydrous sodium sulfate is dry, is filtered, solvent is removed under reduced pressure, residue is through 100~200
Mesh silica gel column chromatography purifies to obtain compound III, the petroleum ether that eluant, eluent is 60~90 degrees Celsius: ethyl acetate, according to product
Difference, volume ratio 4: 1-2: 1, yield 89-93%；The amount of compound III preparation and the volume of reaction vessel are by corresponding ratio
Example is expanded or shunk.
C. the preparation of compound VI:
3 mMs of biaryl acid IV is added in 100 milliliters of single necked round bottom flask, biaryl acid is selected from: 4 '-chloro- 5- are fluoro-
[1,1 '-biphenyl] -2- formic acid, 3 ', 4 '-two chloro- fluoro- [1,1 '-the biphenyl] -2- formic acid of 5-, fluoro- [1, the 1 '-connection of 4 '-tert-butyl -5-
Benzene] -2- formic acid, fluoro- [1,1 '-the biphenyl] -2- formic acid of 5-, 3 ', 4 ', 5 '-three fluoro- fluoro- [1,1 '-the biphenyl] -2- formic acid of 5-, 4 ' -
Chloro- [1,1 '-biphenyl] -2- formic acid, 4 '-trifluoromethyls-[1,1 '-biphenyl] -2- formic acid, 4 '-methyl-[1,1 '-biphenyl] -2- first
Acid, 3 ', 4 ', 5 '-three fluoro- [1,1 '-biphenyl] -2- formic acid, 3 ', 4 '-two chloro- [1,1 '-biphenyl] -2- formic acid；It is added 30 milliliters
Dichloromethane solution, ice-water bath, temperature are down to zero degree, and n,N-Dimethylformamide two is dripped, and it is molten that 6 mMs of oxalyl chlorides are slowly added dropwise
Liquid is added dropwise, and is slowly increased to room temperature, is stirred at room temperature 2 hours；It after contact plate monitors fully reacting, is first concentrated under reduced pressure, removes more
Remaining oxalyl chloride solution and methylene chloride.It is spare to obtain crude product V.The amount of compound V preparation and the volume of reaction vessel are by corresponding
Ratio is expanded or shunk.
3 mMs of compound III are added in 100 milliliters of single necked round bottom flask, it is molten with 30 milliliters of dry methylene chloride
6 mMs of triethylamine is added into reaction for solution, and ice bath stirring 10 minutes, are then added dropwise into reaction system after adding
With 3 mMs of compound V of 5 milliliters of dry methylene chloride dissolutions；Ice bath stirring 30 minutes after adding, after be stirred at room temperature 4
Hour, after reaction, 15 milliliters of water is added in reaction solution, and methylene chloride extracts three times, isolates organic layer, and organic layer is used full
It is washed one time with sodium chloride, anhydrous sodium sulfate is dry, filters, solvent is removed under reduced pressure, residue is through 100~200 mesh silica gel column chromatographies
Purifying obtains compound VI, the petroleum ether that eluant, eluent is 60~90 degrees Celsius: ethyl acetate, according to the difference of product, volume
Than being 10: 1-2: 1, yield 46%-90%；The amount of compound VI preparation and the volume of reaction vessel are expanded or are contracted by corresponding proportion
It is small.
D. the measurement of the bactericidal activity of biaryl amide pyrazole derivatives VI of the invention:
The sterilization of biaryl amide pyrazole derivatives VI of the invention or bacteriostatic activity are measured using thalli growth rate method, specifically
Step are as follows: take 1.8 milligrams of samples to be dissolved in 2 drop n,N-Dimethylformamide, then use and contain a certain amount of polysorbas20 emulsifier
Aqueous solution be diluted to the medicaments of 500 mcg/mls, reagent agent is aseptically respectively drawn to 1 milliliter in culture dish,
It is separately added into 9 milliliters of PDA culture mediums again, 50 mcg/ml drug containing tablets are made after shaking up, to add the flat of 1 milliliter of aqua sterilisa
Plate does blank control, cuts bacterium disk along mycelia outer rim with 4 millimeters of diameter of punch, moves in drug containing tablet, is in equilateral triangle
Shape is put, and every processing is repeated 3 times, and culture dish is placed on culture in 24 ± 1 degrees Celsius of constant incubators, colony diameter to be compareed expands
It opens up and investigates each processing bacterium disk extension diameter after being greater than 2 centimetres, average, opposite bacteriostasis rate is calculated compared with blank control,
It is the kind for most of typical plant pathogen that field actually occurs in China's agricultural production, code name and title for examination strain
It is as follows: 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: wheat is red
Mildew bacterium, 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.
E. the living body Antibacterial Activity of biaryl amide pyrazole derivatives VI of the invention:
The living body Screening of Antibacterial Activities method of biaryl amide pyrazole derivatives VI of the invention is specific as follows: weighing testization
It closes 0.01 gram of object to be dissolved in 0.5 milliliter of DMF, is then diluted to 100 mcg/mls with water (Tween 80 containing 0.1%), so
Afterwards by configured medicine liquid spray in plant leaf surface, fungi to naturally dry, then after 24 hours, is seeded to plant by two hours
On object.Each test designs blank control, blank control VAcetone∶VMethanol∶VWater=1: 1: 2 solution sprays plant, after 24 hours
Fungi is seeded to plant.Compared with blank control, Disease management percentage is calculated, 0 indicates inactive, and 100 indicate suppression completely
System, the plant disease of test have wheat powdery mildew, corn rust, rice sheath blight disease, gray mold of cucumber.
The beneficial effects of the present invention are: having carried out guide's optimization to biaryl amide pyrazole derivatives VI, and to biaryl amide
Pyrazole derivatives VI has carried out the screening of bacteriostatic activity.
The present invention is by specific preparation and biological activity determination embodiment is more specific illustrates biaryl amide pyrazole derivatives
The synthesis of VI and bioactivity and application, the embodiment, which is only used for illustrating the present invention, to be not intended to limit the present invention, especially
Bioactivity is merely illustrative of, rather than limits this patent, and specific embodiment is as follows:
Embodiment 1: the preparation of compound II:
28.3 mMs of pyrazoles acid compound I-1 are added in 250 milliliters of twoport round-bottomed flasks, pyrazoles acid is selected from: 1- first
- 4 pyrazole carboxylic acid of base -3- difluoromethyl；It is suspended in t-butanol solution, under nitrogen protection, 36.91 mMs is added at room temperature
Half an hour is stirred at room temperature in diphenyl phosphate azide and 56.78 mMs of n,N-diisopropylethylamine, reaction solution, and rear slow heating rises
Temperature stirs 4 hours at 80~90 DEG C.After fully reacting, system is cooled into room temperature, is concentrated under reduced pressure and removes excess of solvent, it is residual
Excess purifies to obtain compound II-1, the petroleum ether that eluant, eluent is 60~90 degrees Celsius: acetic acid through 100~200 mesh silica gel column chromatographies
Ethyl ester, volume ratio 8: 1, R1For difluoromethyl, yield 91%, white solid, fusing point 91-92%, the nuclear-magnetism of the compound
The following II-1 of data:1H NMR (400MHz, CDCl3) δ 6.91 (s, 1H), 6.64 (t, J=54.7Hz, 1H), 3.73 (t, J=
1.5Hz, 3H), 3.11 (s, 2H).R1For trifluoromethyl, eluant, eluent volume ratio is 10: 1, yield 76%, white solid, fusing point
111-112%, the following II-2 of the nuclear magnetic data of the compound:1H NMR (400MHz, CDCl3) δ 7.91 (s, 1H), 6.45 (s,
1H), 3.88 (s, 3H), 1.50 (s, 9H).The amount of compound II preparation and the volume of reaction vessel are expanded or are contracted by corresponding proportion
It is small.Compound II.
Embodiment 2: the preparation of compound III-1:
4 mMs of compound II-1 are added in 50 milliliters of single necked round bottom flask, add 8 milliliters of dry methylene chloride
4 milliliters of trifluoroacetic acids are added into reaction, are then stirred at room temperature 2 hours, end of reaction for solution, and TLC monitors reaction solution, discovery
The fully reacting of raw material II -1 stops reaction.Reaction solution is concentrated under reduced pressure, extra solvent and trifluoroacetic acid are removed.It is added
Water 40ml, saturated aqueous sodium carbonate washing are neutralized, are then extracted with ethyl acetate, and isolate organic layer, organic layer saturation
Sodium bicarbonate is washed, saturated sodium-chloride is respectively washed one time, and anhydrous sodium sulfate is dry, is filtered, and is removed under reduced pressure solvent, residue through 100~
200 mesh silica gel column chromatographies purify to obtain compound III-1, the petroleum ether that eluant, eluent is 60~90 degrees Celsius: ethyl acetate, volume
Than being 2: 1, yield 89%；Work as R1When for difluoromethyl, III-1 compound1H NMR (400MHz, CDCl3): δ 7.48-7.41
(m, 3H), 7.39-7.35 (m, 2H), 6.66 (s, 1H), 3.74 (s, 3H).R1For trifluoromethyl, eluant, eluent volume ratio is 4: 1,
Yield 93%, liquid, the following III-2 of the nuclear magnetic data of the compound:1H NMR (400MHz, CDCl3) δ δ 6.96 (s, 1H),
3.79 (s, 3H), 3.17 (s, 2H).The amount of compound III preparation and the volume of reaction vessel are expanded or shunk by corresponding proportion.
Embodiment 3: the preparation of compound VI:
3 mMs of biaryl acid IV-1 is added in 100 milliliters of single necked round bottom flask, biaryl acid is selected from: 3 ', 4 '-two is chloro-
Fluoro- [1,1 '-the biphenyl] -2- formic acid of 5-, is added 30 milliliters of dichloromethane solutions, ice-water bath, temperature is down to zero degree, N, N- dimethyl
Formamide 2 drips, and 6 mMs of oxalyl chloride solutions are slowly added dropwise, is added dropwise, is slowly increased to room temperature, are stirred at room temperature 2 hours；Point
After plate monitors fully reacting, first it is concentrated under reduced pressure, removes extra oxalyl chloride solution and methylene chloride.It is spare to obtain crude product V-1.Change
The volume of the amount and reaction vessel of closing object V-1 preparation is expanded or shunk by corresponding proportion.
3 mMs of compound III-1 are added in 100 milliliters of single necked round bottom flask, with 30 milliliters of dry methylene chloride
6 mMs of triethylamine is added into reaction for dissolution, after adding, ice bath stirring 10 minutes, then dripped into reaction system
3 mMs of compound V-1 with 5 milliliters of dry methylene chloride dissolutions are added；Ice bath stirring 30 minutes after adding, rear room temperature
15 milliliters of water is added in stirring 4 hours, after reaction, reaction solution, and methylene chloride extracts three times, isolates organic layer, organic
Layer is washed one time with saturated sodium-chloride, and anhydrous sodium sulfate is dry, is filtered, solvent is removed under reduced pressure, residue is through 100~200 mesh silica gel
Column chromatographic purifying obtains compound VI-1, the petroleum ether that eluant, eluent is 60~90 degrees Celsius: ethyl acetate, not according to product
Together, volume ratio 10: 1-2: 1, yield 46%-90%；Work as R1For difluoromethyl, R2For fluorine, R3For hydrogen, R4For chlorine, R5For chlorine
When, the compound1H NMR (400MHz, CDCl3): δ 8.16 (s, 1H), 7.77 (dd, J=8.6,5.6Hz, 1H), 7.51 (d,
J=2.1Hz, 1H), 7.46 (d, J=8.2Hz, 1H), 7.35 (s, 1H), 7.23-7.14 (m, 2H), 7.08 (dd, J=9.1,
2.6Hz, 1H), 6.55 (t, J=54.5Hz, 1H), 3.86 (s, 3H).The amount of compound VI preparation and the volume of reaction vessel are pressed
Corresponding proportion is expanded or shunk.The physical and chemical parameter and structural parameters of compound VI is shown in Table 1.
Embodiment 4: the bactericidal activity measurement result of biaryl amide pyrazole derivatives VI and its intermediate of the invention:
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: Alternaria solani, BC: botrytis cinerea pers, latin name are as follows: Botrytis cinerea, CA: peanut foxiness
Germ, latin name are as follows: Cercospora arachidicola, GZ: fusarium graminearum, latin name are as follows: Gibberella
Zeae, PI: phytophthora infestans, latin name are as follows: Phytophthora infestans (Mont.) de Bary, PP: apple
Fruit Target spot pathogen, 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: Sclerotina Sclerotiorum in Winter Rape
Core germ, latin name are as follows: Sclerotinia sclerotiorum, 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.Compound ydy02-2, ydy02-40 and ydy02-43 couple
The growth inhibitory effect of botrytis cinerea pers be up to 90%, 93% and 90% with existing commercial high activity kind Boscalid and
Fluxapyroxad is suitable.To the Activity Results of peanut Cercospora asparagagas show compound ydy02-9, ydy02-12, ydy02-41,
For the inhibitory activity of ydy02-50, ydy02-54, ydy02-55 63% or more, activity is higher by commercial varieties Boscalid
(inhibiting rate to the cercospora brown spot of peanut is 53%) 10% or more, activity is higher by fluxapyroxad (to the inhibiting rate of the cercospora brown spot of peanut
Be 50%) 13% or more, wherein compound ydy02-12, ydy02-41, ydy02-50, ydy02-54, to the cercospora brown spot of peanut
Activity is higher than 70%, and especially compound ydy02-50 is up to 80% activity to the activity of the cercospora brown spot of peanut and is higher by comparison medicine pyridine acyl bacterium
Amine 27%.To the active testing of fusarium graminearum show compound ydy02-1, ydy02-12, ydy02-40, ydy02-42,
Ydy02-43, ydy02-46, ydy02-47, ydy02-48, ydy02-49, ydy02-50, ydy02-51 bacteriostatic activity are 59%
More than, the bactericidal activity of above compound is higher by the commercialization acid amide fungicides Boscalid (inhibition to fusarium graminearum
57%) rate is.The active testing of Phytophthora infestans the result shows that, compound ydy02-12, ydy02-48, ydy02-
49, for the bacteriostatic activity of ydy02-51 55% or more, activity is higher by acid amide fungicides Boscalid (Phytophthora infestans
Inhibiting rate be 23%) 22% or more, wherein the bacteriostatic activity of compound ydy02-49 is in 70% or more, active highest
72%, activity is higher by fluxapyroxad (inhibiting rate of Phytophthora infestans is 54%) close to 20% or more.To rice line
The active testing of blight bacterium show ydy02-12, ydy02-42, ydy02-43, ydy02-48, ydy02-49, ydy02-50,
For the bacteriostatic activity of ydy02-51 60% or more, activity is higher by the (suppression to Rhizoctonia solani Kuhn of acid amide fungicides Boscalid
Rate processed be 22%) close to 40% or more, activity be higher by fluxapyroxad (inhibiting rate to Rhizoctonia solani Kuhn is 54%) 6% with
On, the bactericidal activity of compound ydy02-12, ydy02-48, ydy02-49, ydy02-50, ydy02-51 are above compound fluorine
10% or more azoles bacterium amide, wherein ydy02-12 and ydy02-49 can reach 70% or more to the inhibiting rate of Rhizoctonia solani Kuhn,
It is higher by 16% or more fluxapyroxad.To the active testing of Rhizoctonia cerealis show compound ydy02-12, ydy02-40,
The bacteriostatic activity of ydy02-42, ydy02-43, ydy02-48, ydy02-49, ydy02-50, ydy02-51 are lived 86% or more
Property be higher than acid amide fungicides Boscalid (being 35% to the inhibiting rate of Rhizoctonia cerealis) 51% or more, above compound
Ydy02-12, ydy02-40, ydy02-42, ydy02-43, ydy02-48, ydy02-50 are higher than the inhibiting rate of Rhizoctonia cerealis
90%, wherein compound ydy02-40, ydy02-43, ydy02-50 reaches 100% to the inhibiting rate of Rhizoctonia cerealis, and activity is high
In with fluxapyroxad (being 86% to the inhibiting rate of Rhizoctonia cerealis) 14% or more.To the active testing table of Sclerotinia sclerotiorum
It is bright, compound ydy02-12, ydy02-39, ydy02-47, ydy02-48, ydy02-49, ydy02-51, ydy02-54,
The bacteriostatic activity of ydy02-55 is 100%, and (inhibiting rate to Sclerotinia sclerotiorum is for activity and acid amide fungicides Boscalid
100%) and fluxapyroxad (inhibiting rate to Sclerotinia sclerotiorum is 100%) is suitable.
Embodiment 5: the living body Antibacterial Activity result of biaryl amide pyrazole derivatives VI of the invention:
The live plant disease that the present invention tests has wheat powdery mildew, corn rust, rice sheath blight disease, gray mold of cucumber.
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,
The control efficiency of compound ydy02-40, ydy02-44, ydy02-47, ydy02-54 reach 100%, with positive control drug pyridine acyl
Bacterium amine and fluxapyroxad are suitable；For wheat powdery mildew, compound ydy02-12 is to the preventive effect of wheat powdery mildew
100%, it is suitable with comparison medicine Boscalid and fluxapyroxad.For rice sheath blight disease, compound ydy02-12,
The control efficiency of ydy02-13, ydy02-42, ydy02-54 reach 90% or more, and activity is higher than positive control drug Boscalid
(80%) 10% or more, it is higher than (70%) 20% or more fluxapyroxad.
Embodiment 6: biaryl amide pyrazole derivatives VI and its intermediate of the invention is preparing answering in composition pesticide
With:
Biaryl amide pyrazole derivatives VI of the invention and its intermediate can prepare composition pesticide, and the composition includes
As active constituent, the content of active constituent arrives for 0.1% for this biaryl amide pyrazole derivatives VI of the invention and its intermediate
99.9% weight, the surfactant of the solid or liquid adjuvants of 99.9% to 0.1% weight and optional 0 to 50% weight.
Embodiment 7: biaryl amide pyrazole derivatives VI and its intermediate of the invention is in preparation pesticide complex composition
Application:
Biaryl amide pyrazole derivatives VI of the invention and its intermediate can with other commercially available agricultural chemicals, i.e., insecticide, kill
Mite agent, fungicide, antivirotic or activating plants agent compounding preparation pesticide complex composition, which includes the present invention
Biaryl amide pyrazole derivatives VI and its intermediate and other commercially available agricultural chemicals, i.e. insecticide, acaricide, fungicide, antiviral
Agent or activating plants agent are as active constituent, biaryl amide pyrazole derivatives VI of the invention and its intermediate and other commodity agricultures
Medicine, i.e. insecticide, acaricide, fungicide, antivirotic or activating plants agent ratio be that mass percent 1%: 99% arrives
99%: 1%, the content of active constituent is 0.1% to 99.9% weight, the solid or liquid adjuvants of 99.9% to 0.1% weight,
And the surfactant of optional 0 to 50% weight.
Embodiment 8: biaryl amide pyrazole derivatives VI and insecticide composition of the invention prevention and treatment agricultural and forestry and
Application in gardening plant insect pest:
All biaryl amide pyrazole derivatives VI of the invention combine shape with any one or two kinds in commodity insecticide
It is selected from Pesticidal combination for preventing and treating agricultural and forestry and gardening plant insect pest, the commodity insecticide: ground Asia Nong, pyridine worm
Amidine, emamectin benzoate, milbemectin, avermectin, pleocidin, cypermethrin, effective cypermethrin, three cyfluthrin chrysanthemums
Ester, decis, Fenpropathrin, Beta- cyfloxylate, Lambda- Cyhalothrin, permethrin, benzyl chloride chrysanthemum
Ester, allethrin, Biphenthrin, Permethrin, ethofenprox, flumethrin, fluvalinate, imidacloprid, Nitenpyram,
Imidaclothiz, thiacloprid, Diacloden, clothianidin, dinotefuran, clothianadin, Da Tenan, diflubenzuron, d ichlorbenzuron, Teflubenzuron, deinsectization be grand,
Flubenzuron, flufenoxuron, pyridine worm be grand, lufenuron, poisonous insect urea, penfluron, flucycloxuron, chlorfluazuron, piperazine worm urea, furan tebufenozide, worm
Hydrazides, chlorine tebufenozide, methoxyfenozide, ring tebufenozide, flolimat, DDVP, quinalphos, pyridaphethione, isoprocarb, west dimension
Cause, Aphox, MTMC, Mobucin, cartap, Bassa, leaf are dispersed, carbaryl, Benfuracard micro, carbosulfan, are killed
Snout moth's larva pellet, fenisobromolate, Hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, pymetrozine, Envidor, spiral shell worm ester, spiral shell
Worm ethyl ester, butene-fipronil, azacyclotin, Buprofezin, Cupric sulfate, dimehypo, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen
Insect amide, Tolfenpyrad, chlorfenapyr, pyrazinones, etoxazole, tebufenpyrad, rattle away young ketone, Nylar, emaricin；Connection of the invention
Mass percentage of the fragrant amide pyrazole derivatives VI in the Pesticidal combination is 1%-90%, 99% to 10% weight
The surfactant of solid or liquid adjuvants and optional 0 to 50% weight, biaryl amide pyrazole derivatives VI of the invention with
The ratio of aforementioned commodity insecticide is mass percent 1%: 99% to 99%: 1%；The dosage form choosing of the Pesticidal combination processing
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, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog stick, seed treatment suspending agent, cigarette
Mist piece, smog ball, granular poison bait, thermal fog, medicine paint, fine granule, oil suspending agent, oil-dispersing property pulvis, sheet poison bait, dense jelly,
It sprinkles and pours agent, seed coat agent, liniment, suspended emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume
Suspending agent, tracking pulvis, ultra low volume liquids, any one in wet-mixing kind water-dispersible powder；The Pesticidal combination is anti-
The insect pest of the plant controlled is selected from: red spider, Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, east mole cricket
Mqb, rice thrips, onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jianguan thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, smalt
Leafhopper, chlorita biguttula, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, the flat angle plant hopper of sugarcane, cotten aphid, green bugs, Mai Changguan
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,
It is pear lace bug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, green rice bug, green blind
Stinkbug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, oriental moth, brown slug moth, thosea siensis, wheat
Moth, pink bollworm, brachmia triannuella, diamondback moth, small heart-eating peach worm, eating-core bean worm, apple Spilonota lechriaspis, brown belt length leaf roll
Moth, 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, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point spark, small ground are old
Brave, big cutworm, steals poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight grain rice hesperiidae, pelopidas mathias, citrus at yellow cutworm
Swallowtail butterfly, Common Mormon, cabbage 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,
It is the small buprestid beetle of pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, citrus, golden edge buprestid beetle, yellow meal worm, dark mealworm, red
Quasi- ostomatid, confused flour beetle, verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori,
Pink neck longicorn, big daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice
As, dolerus tritici, pear fruit sawfly, 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, wheat midge, contarinia tritici, citrus fruit fly, melonfly, wheat leaf ash latent fly, Americal rice leaf miner, beans stalk
Black latent fly, frit fly, Hylemyia Platura Meigen, onion fly, radish fly, full skirt Exorista civilis, corn borer is strict posts fly；The plant of the Pesticidal combination prevention and treatment
Object is selected from: 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, 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, citrus, peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape.
Embodiment 9: biaryl amide pyrazole derivatives VI and antimicrobial combination of the invention prevention and treatment agricultural and forestry and
Application in gardening plant disease:
All biaryl amide pyrazole derivatives VI of the invention combine shape with any one or two kinds in commodity fungicide
It is selected from bactericidal composition for preventing and treating agricultural and forestry and gardening plant disease, the commodity fungicide: diazosulfide,
Tiadinil is abbreviated as TDL, tisocromide, first thiophene and lures amine, 4- methyl-1,2,3- thiadiazoles -5- formic acid, 4- methyl-1,2,3- thiophenes
Diazole -5- sodium formate, 4- methyl-1,2,3- thiadiazoles -5- Ethyl formates, DL- beta-aminobutyric acid, isotianil, English are logical
With name are as follows: isotianil, 3,4-, bis- chloroisothiazole -5- formic acid, 3,4-, bis- chloroisothiazole -5- sodium formate, the different thiophene of 3,4- dichloro
Azoles -5- Ethyl formate, virazole, antofine, Ningnanmycin or salicylic acid, cymoxanil, thiram, ziram, Mancozeb, second
Phosphorus aluminium, thiophanate-methyl, Bravo, enemy can pine, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, fluorine
Quinoline, 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, double alkynes acyls
Bacterium amine, zoxamide, fenfuram, carboxin, chlozolinate, iprodione, Fluoxastrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, benzene
Oxygen bacterium amine, orysastrobin, ZEN 90160, pyraclostrobin, trifloxystrobin, Enestroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, cyclopropyl
Azoles alcohol, difenoconazole, olefin conversion, efficient olefin conversion, epoxiconazole, benzoxazole, Fluquinconazole, Flusilazole, Flutriafol, hexaconazole,
Glyoxalin, kind bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, three
Azoles alcohol, triticonazole, bitertanol, probenazole, furidazol, imazalil, efficient imazalil, Prochloraz, fluorine bacterium azoles, cyazofamid,
Fenamidone dislikes imidazoles, pefurazoate, Famoxate, oxazole, hymexazol, Wakil, Guardian, Grandox fumigant, pungent thiophene
Ketone, benthiozole, dodemorph, butadiene morpholine, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium
Amine, Boscalid, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, pyrimethanil, chlorobenzene pyrimidine
Alcohol, nuarimol, chinomethionat, dithianon, ethoxyquin, oxyquinoline, the third oxygen quinoline, quinoxyfen, diethofencarb, isopropyl
Bacterium amine, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, different rice blast net, pyrazophos, tolelofos-methyl, blasticidin-S, spring thunder are mould
Element, Polyoxin, valida, jinggangmeisu, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, goes out at polyoxin
Become rusty amine, carbendazim, benomyl, thiophanate-methyl, triazolone, bupirimate, dimethirimol, ethirimol, difoltan, gram bacterium
Pellet, folpet, vinclozolin, fluoromide, dimethachlon, Bravo, Isoprothiolane, kitazine, Yekuzuo, pentachloro- nitro
Benzene, Propineb, phosethyl-Al, sulphur, Bordeaux mixture, copper sulphate, copper oxychloride, cuprous oxide, Kocide SD, metrafenone,
Pencycuron, diclomezin, Rabcide, pyroquilon, volution bacterium amine, tricyclazole, triforine, more fruit pyridines, the pungent salt of biguanides, biguanides are pungent
Amine, botran, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, iodomethane,
Metham-sodium, enemy line ester, dazomet, nemamort, lythidathion, fensulfothion, thionazin, dichlofenthion, fosthietan, oxamyl, sulphur
Acyl fluorides, dichloropropylene, dichloro-isonicotinic acid, allyl isothiazole；Biaryl amide pyrazole derivatives VI of the invention is in the sterilization group
The total mass percentage closed in object is 1%-90%, and the solid or liquid adjuvants of 99% to 10% weight and optional 0 are arrived
The ratio of the surfactant of 50% weight, biaryl amide pyrazole derivatives VI of the invention and aforementioned commodity fungicide is quality
Percentage 1%: 99% to 99%: 1%；The dosage form of bactericidal composition processing is selected from: seed treatment emulsion, aqueous emulsion, big
It is 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, oil in water emulsion,
Smoke candle, 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 plant disease of the bactericidal composition prevention and treatment is selected from: rice seedling is continuous rotten
Disease, tomato root rot, the late blight of potato, tobacco black shank, millet powdery mildew, downy mildew of garpe, downy mildew of lettuce, cucumber cream
Mildew, cucumber anthracnose；The applicable plant of the bactericidal composition is selected from: 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, rape, sesame, Xiang
Certain herbaceous plants with big flowers, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, Huang
Melon, Chinese cabbage, celery, hot pickled mustard tuber, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus and peach, tea, wild vegetables, bamboo
Bamboo shoot, hops, pepper, banana, papaya, orchid, potted landscape.
Embodiment 10: biaryl amide pyrazole derivatives VI of the invention is combined with anti-plant virus agent in prevention and treatment agricultural and woods
Application in industry and gardening plant virus disease:
Any one in all biaryl amide pyrazole derivatives VI and commodity antiviral agent of the invention or two kinds of groups
Conjunction forms antiviral composition for preventing and treating agricultural and forestry and gardening plant virus disease, the commodity antiviral agent choosing
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- formic acid second
Ester, 3,4-, bis- chloroisothiazole -5- formic acid, 3,4-, bis- chloroisothiazole -5- sodium formate, 3,4-, bis- chloroisothiazole -5- Ethyl formate,
DL- beta-aminobutyric acid, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lure amine or salicylic acid, cytosintetidemycin, dichloro different
Niacin, allyl isothiazole, well ridge azanol, jinggangmeisu；Biaryl amide pyrazole derivatives VI of the invention is at described antiviral group
The total mass percentage closed in object is 1%-90%, and the solid or liquid adjuvants of 99% to 10% weight and optional 0 are arrived
The surfactant of 50% weight, the ratio of biaryl amide pyrazole derivatives VI of the invention and aforementioned commodity anti-plant virus agent
For mass percent 1%: 99% to 99%: 1%；The dosage form of the antiviral composition processing is selected from: seed treatment emulsion, water
Emulsion, microemulsion, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, blocky poison bait, delays big granula
Release block, dense poison bait, CG/Encapsulated granule, micro-capsule suspension, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, Shui Bao
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, smearing thermal fog
Agent, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspending agent, tracking pulvis, surpasses suspended emulsion
Any one in low capacity liquor, wet-mixing kind water-dispersible powder；The virus disease of the antiviral composition prevention and treatment is selected from:
Rice dwarf virus disease, yellow dwarf, stripe virus disease, fern leaf of tomato viral disease, Tomato yellow mosaic virus, pepper mosaic virus disease viral disease, cigarette
Careless veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, citrus virosis, cymbidium mosaic virus, sword-leaved cymbidium ring spot
Poison；Plant of the antiviral composition for prevention and treatment is selected from: paddy, wheat, barley, oat, corn, sorghum, sweet potato, Ma Ling
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
Dish, 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 11: biaryl amide pyrazole derivatives VI of the invention combined with acaricide prevention and treatment agricultural and forestry and
Application in gardening plant mite evil:
All biaryl amide pyrazole derivatives VI of the invention combine shape with any one or two kinds in commodity acaricide
It is selected from miticide composition for preventing and treating agricultural and forestry and gardening plant mite evil, the commodity acaricide: azacyclotin, tricyclic
Tin, fenbutatin oxide, three phosphor tins, chlorfenviphos, dimethylvinphos, crotoxyphos, heptenophos, Menite, 2-dichloroethylk dimethyl phosphate, Diothyl, chloromethane are sub-
Amine sulphur phosphorus, omethoate, dioxathion, Ethodan, methacrifos, Phosalone, methylpyrimidine sulphur phosphorus, quinalphos, Kilval, amine third
Fear, dialifos, phosmet, acrinathrin, Biphenthrin, lambda-cyhalothrin, smart gamma cyhalothrin, first cyanogen chrysanthemum
Ester, flucythrinate, flumethrin, taufluvalinate, brofluthrinate, Bifenazate, fenothiocarb, butocarboxim, Talcord, long
Imitate prestige, benomyl, sok, carbosulfan, MTMC, promacyl, Carzol, single carbonamidine, medimeform, Amitraz, benzene
Benzyl formate, fenisobromolate, cyflumetofen, acequinocyl, Nissol, flufenoxuron, macro tetrolide, piericidin, thuringiensin, mite killing
Element, avermectin, doractin, eprinomectin, ivermectin, selamectin, moxidectin, pyrethrin, nicotine, hardship
Ginseng alkali, rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine, propargite, Hexythiazox, Envidor, fluacrypyrim, kills at nimbin
Mite ester, propargite, pyridaben；The total quality hundred of biaryl amide pyrazole derivatives VI of the invention in the miticide composition
Point content is 1%-90%, the surface-active of the solid or liquid adjuvants of 99% to 10% weight and optional 0 to 50% weight
Agent, biaryl amide pyrazole derivatives VI of the invention and the acaricidal ratio of the commodity are that mass percent 1%: 99% arrives
99%: 1%；The dosage form of miticide composition processing is selected from: seed treatment emulsion, aqueous emulsion, big granula, microemulsion, water-soluble
Property granula, 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, smoke candle, granula subtilis, cigarette
Mist candle, smoke cartridge, smog 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, can
Soluble powder, seed treatment water solube powder, ultra-low volume suspending agent, tracking pulvis, ultra low volume liquids, wet-mixing kind water dispersion
Any one in property pulvis；The mite evil of the miticide 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 be worldwide Agricultural Mites, forestry harmful mites, gardening harmful mite and
Hygienic harmful mite；The miticide composition for prevention and treatment plant be selected from: 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
Dish, hot pickled mustard tuber, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus, peach, tea, wild vegetables, bamboo shoots, beer
Flower, pepper, banana, papaya, orchid, potted landscape.
The chemical structure and physical and chemical parameter of the biaryl amide pyrazole derivatives VI of the invention of table 1.
The chemical structure and physical and chemical parameter (Continued) of the biaryl amide pyrazole derivatives VI of the invention of table 1. and its intermediate
Bacteriostatic activity (the suppression of 50 mcg/mls of the biaryl amide pyrazole derivatives VI of the invention of table 2. and its intermediate
Rate/% processed)
| Serial number | Compound number | AS | BC | CA | GZ | PI | PP | PS | RC | SS |
| 1 | ydy02-1 | 54 | 76 | 47 | 59 | 49 | 30 | 56 | 80 | 91 |
| 2 | ydy02-2 | 46 | 90 | 37 | 44 | 36 | 35 | 46 | 71 | 95 |
| 3 | ydy02-11 | 49 | 68 | 23 | 56 | 28 | 32 | 27 | 68 | 88 |
| 4 | ydy02-12 | 62 | 71 | 73 | 67 | 62 | 49 | 71 | 92 | 100 |
| 5 | ydy02-13 | 41 | 63 | 0 | 30 | 33 | 21 | 24 | 56 | 91 |
| 6 | ydy02-15 | 44 | 83 | 37 | 52 | 46 | 25 | 54 | 80 | 91 |
| 7 | ydy02-39 | 36 | 49 | 53 | 35 | 21 | 13 | 22 | 52 | 100 |
| 8 | ydy02-40 | 56 | 93 | 53 | 61 | 46 | 25 | 54 | 100 | 96 |
| 9 | ydy02-41 | 44 | 66 | 77 | 57 | 26 | 11 | 32 | 65 | 89 |
| 10 | ydy02-42 | 59 | 71 | 53 | 65 | 51 | 35 | 61 | 95 | 96 |
| 11 | ydy02-43 | 56 | 90 | 40 | 69 | 51 | 38 | 61 | 100 | 95 |
| 12 | ydy02-44 | 46 | 76 | 37 | 44 | 28 | 28 | 27 | 83 | 89 |
| 13 | ydy02-45 | 46 | 56 | 43 | 35 | 21 | 21 | 24 | 68 | 86 |
| 14 | ydy02-46 | 51 | 68 | 53 | 59 | 36 | 10 | 46 | 74 | 96 |
| 15 | ydy02-47 | 49 | 59 | 37 | 61 | 51 | 17 | 54 | 76 | 100 |
| 16 | ydy02-48 | 59 | 68 | 40 | 61 | 59 | 13 | 66 | 91 | 100 |
| 17 | ydy02-49 | 59 | 78 | 57 | 59 | 72 | 39 | 76 | 89 | 100 |
| 18 | ydy02-50 | 56 | 88 | 80 | 59 | 51 | 32 | 66 | 100 | 96 |
| 19 | ydy02-51 | 56 | 80 | 57 | 59 | 56 | 21 | 68 | 86 | 100 |
| 20 | ydy02-54 | 46 | 49 | 70 | 44 | 33 | 21 | 44 | 68 | 100 |
| 21 | ydy02-55 | 54 | 59 | 63 | 57 | 41 | 32 | 54 | 79 | 100 |
| 22 | Boscalid | 90 | 95 | 53 | 57 | 23 | 58 | 22 | 35 | 100 |
| 23 | Fluxapyroxad | 95 | 100 | 50 | 67 | 54 | 82 | 54 | 86 | 100 |
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.
Living body bacteriostatic activity (the inhibition of 200 mcg/mls of the biaryl amide pyrazole derivatives VI of the invention of table 3.
Rate/%)
| Serial number | Compound number | Wheat powdery mildew/% | Corn rust/% | Rice sheath blight disease/% | Gray mold of cucumber/% |
| 1 | ydy02-1 | 0 | 0 | 0 | 0 |
| 2 | ydy02-2 | 20 | 90 | 10 | 0 |
| 3 | ydy02-11 | 0 | 90 | 60 | 0 |
| 4 | ydy02-12 | 0 | 100 | 100 | 0 |
| 5 | ydy02-13 | 0 | 98 | 90 | 0 |
| 6 | ydy02-15 | 0 | 0 | 0 | 0 |
| 7 | ydy02-39 | 0 | 0 | 0 | 20 |
| 8 | ydy02-40 | 100 | 20 | 50 | 0 |
| 9 | ydy02-41 | 0 | 0 | 0 | 0 |
| 10 | ydy02-42 | 0 | 90 | 90 | 0 |
| 11 | ydy02-43 | 0 | 20 | 40 | 0 |
| 12 | ydy02-44 | 100 | 20 | 40 | 0 |
| 13 | ydy02-45 | 0 | 40 | 50 | 0 |
| 14 | ydy02-46 | 0 | 0 | 20 | 0 |
| 15 | ydy02-47 | 100 | 0 | 30 | 0 |
| 16 | ydy02-48 | 0 | 30 | 0 | 0 |
| 17 | ydy02-49 | 0 | 98+ | 0 | 0 |
| 18 | ydy02-50 | 0 | 20 | 50 | 0 |
| 19 | ydy02-51 | 0 | 20 | 80 | 0 |
| 20 | ydy02-54 | 100 | 0 | 100 | 0 |
| 21 | ydy02-55 | 90 | 30 | 50 | 0 |
| 22 | Boscalid | 100 | 100 | 80 | 45 |
| 23 | Fluxapyroxad | 100 | 100 | 70 | 0 |
Claims (9)
1. a kind of biaryl amide pyrazole derivatives, it is characterised in that: have the general structure as shown in Formula IV:
Wherein:
R1、R2、R3、R4、R5It 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-C6Naphthenic base, substituted piperidin-1-yl,
The phenyl or C that substituted morpholine -1- base, substituted nafoxidine -1- base, phenyl or halogen replace1-C6Alkyl replaces
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-C6
The phenyl or C that alkenyl replaces2-C6The phenyl or C that halogenated alkenyl replaces3-C6The phenyl or C that cycloalkenyl replaces2-C6Alkynyl takes
The phenyl or C in generation2-C6The phenyl or C that halo alkynyl replaces3-C6The pyrrole that phenyl, pyridyl group or the halogen that cycloalkynyl radical replaces replace
Piperidinyl or C1-C6Alkyl-substituted pyridyl group or C1-C6The pyridyl group or C that halogenated alkyl replaces3-C6The pyrrole that naphthenic base replaces
The pyridyl group or C that piperidinyl or nitro replace2-C6The pyridyl group or C that alkenyl replaces2-C6Halogenated alkenyl replace pyridyl group or
C3-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-
C6The pyrimidine radicals or C that pyridyl group, pyrimidine radicals or the halogen that cycloalkynyl radical replaces replace1-C6Alkyl-substituted pyrimidine radicals or C1-C6
The pyrimidine radicals or C that halogenated alkyl replaces3-C6The pyrimidine radicals or C that the pyrimidine radicals or nitro that naphthenic base replaces replace2-C6Alkenyl
Substituted 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 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 substituted five yuan or six membered heteroaryl, substituted five yuan or hexa-atomic containing 1 N atom and 1 S atom of 2 O atoms
Heteroaryl, substituted five yuan containing 1 N atom and 1 O atom or six membered heteroaryl, containing 2 N atoms and 1 S atom
Substituted five yuan or six membered heteroaryl, substituted five yuan or six membered heteroaryl containing 2 N atoms and 1 O atom；It is above-mentioned
Five yuan 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 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. biaryl amide pyrazole derivatives VI, R according to claim 11It preferably is selected from: trifluoromethyl, difluoromethyl；R2It is excellent
It is selected from: hydrogen, fluorine；R3It preferably is selected from: hydrogen, fluorine, chlorine；R4Preferably be selected from: trifluoromethyl, hydrogen, fluorine, chlorine, methoxyl group, tert-butyl,；R5It is preferred that
From: hydrogen, fluorine, chlorine.
3. according to claim 1 with the specific synthetic route and method of biaryl amide pyrazole derivatives VI described in claim 2
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:
Intermediate II is stirred in n,N-diisopropylethylamine and solvent tertiary butanol instead by starting material I and diphenyl phosphate azide
It should prepare, wherein the definition of starting material I and the substituent group in intermediate II is as described in claim 1, and preferred substituents are determined
It is adopted as claimed in claim 2；
B. the preparation of intermediate III:
Reaction preparation is stirred at room temperature by intermediate II and trifluoroacetic acid in intermediate III, wherein in intermediate II and intermediate III
Substituent group definition it is as described in claim 1, the definition of preferred substituents is as claimed in claim 2；
C. the preparation of biaryl amide pyrazoles VI:
Biaryl amide pyrazoles VI is by intermediate III and intermediate compound IV and methylene chloride and acid binding agent Et3N is stirred in room temperature
Mix reaction preparation, wherein the definition of intermediate III and intermediate compound IV and the substituent group in target product biaryl amide pyrazoles VI
As described in claim 1, the definition of preferred substituents is as claimed in claim 2.
4. claim 1 and biaryl amide pyrazoles VI as claimed in claim 2 are preparing the purposes in agricultural fungicidal agent.
5. a kind of composition pesticide, it includes claims 1 and biaryl amide pyrazoles VI as claimed in claim 2 to prepare
Pesticide closes object, and the composition includes claim 1 and biaryl amide pyrazoles VI as claimed in claim 2 as active constituent,
The content of active constituent is 0.1 to 99.9% weight, and the solid or liquid adjuvants of 99.9 to 0.1% weight and optional 0 are arrived
The surfactant of 50% weight.
6. a kind of pesticide complex composition, it includes claim 1 and biaryl amide pyrazoles VI as claimed in claim 2 and its
Intermediate can prepare pesticide complex composition, which includes claim 1 and biaryl acyl as claimed in claim 2
As active constituent, the content of active constituent is 0.1% to 99.9% weight for amine pyrazoles VI and its intermediate and commercially available agricultural chemical
Amount, the surfactant of the solid or liquid adjuvants of 99.9% to 0.1% weight and optional 0 to 50% weight.
7. a kind of agricultural bactericidal complex composition, it includes claims 1 and biaryl amide pyrazoles VI as claimed in claim 2
With other it is bactericide compounded be used as active constituent, the ratio of biaryl amide pyrazoles VI and other fungicide is mass percent
1%: 99% to 99%: 1%, the content of active constituent is 1% to 99% weight, and the solid or liquid of 99% to 1% weight help
Agent.
8. a kind of agricultural insecticidal, mite killing complex composition, it includes claims 1 and biaryl amide pyrrole as claimed in claim 2
Azole VI and other Insecticidal and acaricidal agents, which compound, is used as active constituent, and the ratio of biaryl amide pyrazoles VI and other fungicide is
Mass percent 1%: 99% to 99%: 1%, the content of active constituent are 1 to 99% weight, the solid of 99 to 1% weight or
Liquid adjuvants.
9. a kind of anti-plant virus agent complex composition, it includes claims 1 and biaryl amide pyrazoles as claimed in claim 2
Class VI and other anti-plant virus agents compounding are used as active constituent, the ratio of biaryl amide pyrazoles VI and other anti-plant virus agents
Example is mass percent 1%: 99% to 99%: 1%, and the content of active constituent is 1 to 99% weight, and 99 to 1% weight is consolidated
Body or liquid adjuvants.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113788790A (en) * | 2021-10-18 | 2021-12-14 | 华东理工大学 | Aromatic heterocyclic amide derivative and application thereof |
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