CN109970650A - Pyrazole phenyl formamide analog derivative and its preparation method and application - Google Patents
Pyrazole phenyl formamide analog derivative and its preparation method and application Download PDFInfo
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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- 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
- C07D231/12—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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Abstract
The present invention provides pyrazole phenyl formamide derivatives and its preparation method and application, and the present invention relates to pyrazole phenyl formamide derivative, general formula of the chemical structure is shown in Formula VII:
Description
Technical field
Technical solution of the present invention is related to pyrazole phenyl Carbox amide, and in particular to 2- pyrazoles yl-benzamide and
3- pyrazolyl benzamide derivatives.
Background technique
Heterocyclic compound heterocyclic compound has efficient, low toxicity, wide spectrum biological activity, and the biology of patent literature report is living
Property compound in, it is most of that there is heterocycle structure；Document report five member ring heterocyclic compound has activating plants agent, fungicide, plant
The activity (Chen Danping modern, 2014,14 (2): 5-10) of object growth regulator and insecticide, wherein pyrazole compound
It has a wide range of applications in pesticide, pyrazoles fungicide has the characteristics that wide spectrum, efficient, low toxicity and structure diversity, has
Wide Research Prospects (such as Liu Shaohua finely and specialty chemicals, 2016,24 (10): 25-27.).
Succinate dehydrogenase inhibitors class (Succinate Dehydrogenase Inhibitors, SDHIs) compound
It is the fungicide that one kind acts on pathogen mitochondrial succinate dehydrogenase (albumen composition II).Succinate dehydrogenase conduct
The important component of the tricarboxylic acid cycle of cell mitochondrial respiratory electron transport chain is the ideal target for developing new type bactericide
Mark.In the past few decades, the new type bactericide kind developed for succinate dehydrogenase for target, because of its distinctive sterilization
Mechanism of action and broad spectrum activity have become the important research hot spot of pesticide field.Past during the decade, more and more SDHIs classes
Fungicide obtains exploitation and application, especially pyrazole-4-carboxamide class fungicide, as fluxapyroxad (Fluxapyroxad),
Fluorine azoles ring bacterium amine (Sedaxane), isopyrazam (Isopyrazam), fluorine azoles bacterium aniline (Penflufen), furametpyr
(Furametpyr) etc. commercialization fungicide remains amido bond and pyrrazole structure, and carries out structural modification to aniline moiety,
It can be found that polycarboxylic acid moiety's reservation available better bacteriostatic activity of pyrrazole structure of SDHIs class fungicide, and arylamine
With certain changeability.
To find and finding more efficient, wide spectrum, low toxicity, low ecological risk and pesticide guide and the candidate of no interactions resistance
Phenyl ring is introduced into the guide structure of pyrazolecarboxamide by compound, the present invention, and design has synthesized pyrazole phenyl formamide
Derivative, and carried out the screening and evaluation of the bioactivity of system.
Summary of the invention
The technical problems to be solved by the present invention are: providing the synthetic method of pyrazole phenyl formamide derivative, mention
For this kind of compound modulates agricultural, the bioactivity and its measuring method of gardening and health and forestry plant pathogen, simultaneously
Application of these compounds in agriculture field, horticultural field, field of forestry and health field is provided.
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 the pyrazole phenyl formamide analog derivative of bactericidal activity is shown in Formula VII:
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.
R1It preferably is selected from: difluoromethyl, trifluoromethyl, methyl；R2It preferably is selected from: 3- aminomethyl phenyl, 3- bromophenyl, 2- fluoroform
Base phenyl, benzyl, 2- aminomethyl phenyl, 2- bromophenyl, 3- trifluoromethyl, 2,4- dibromo phenyl, 2- isopropyl phenyl.
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 pyrazole phenyl carboxamides derivatives of the invention is as follows:
Wherein, substituent R1、R2It is defined as described above；R1It preferably is selected from: difluoromethyl, trifluoromethyl, methyl；R2It preferably is selected from:
3- aminomethyl phenyl, 3- bromophenyl, 2- trifluoromethyl, benzyl, 2- aminomethyl phenyl, 2- bromophenyl, 3- trifluoromethyl, 2,
4- dibromo phenyl, 2- isopropyl phenyl.
The synthesis of pyrazole phenyl carboxamides derivatives and the specific method of biological activity determination of the invention is divided into following
Step:
A. the preparation of compound II:
N2Under protective condition, I, n,N-diisopropylethylamine and diphenyl phosphate azide (DPPA) are dissolved in the tert-butyl alcohol,
It is stirred at room temperature after ten minutes, is heated to reflux, after the reaction was completed, decompression filters, and filtrate concentration removes solvent, column chromatographic purifying, system
Compound II is obtained, the amount of compound II preparation and the volume of reaction vessel are expanded or shunk by corresponding proportion.
B. the preparation of compound III:
II is dissolved in methylene chloride, trifluoroacetic acid is added and is stirred at room temperature, after the reaction was completed, decompression filters, filtrate concentration
Solvent is removed, is diluted with water, adjusting pH with saturated sodium carbonate solution is 8, ethyl acetate extraction, and organic layer is dry with anhydrous sodium sulfate
It is dry.Decompression filters, and filtrate concentration removes solvent, and compound III, the amount and reaction of compound IV preparation is made in column chromatographic purifying
Volume of a container is expanded or shunk by corresponding proportion.
C. the preparation of compound IV:
10.20 mMs of III are added into 200 milliliters of single necked round bottom flask, are dissolved in 76.5 milliliter of 4 mol/L hydrochloric acid
In solution, it is cooled to 0 DEG C of stirring.13.25 mMs of sodium nitrites are dissolved in suitable quantity of water, are added dropwise in reaction system, 0
It is stirred 1 hour under the conditions of DEG C.30.59 mMs of potassium iodide are added in reaction system in batches, are vigorously stirred 30 minutes, with
It is gradually warming up to room temperature afterwards.After the reaction was completed, it with saturated sodium carbonate solution neutralization reaction, is extracted, is had with 30 milliliters of methylene chloride
Machine layer is washed twice (20 milliliters × 2) with saturated sodium thiosulfate solution, and twice of (10 milli is extracted with dichloromethane in separation water-yielding stratum
Rise × 2).Merge organic layer to be washed one time with 10mL saturated sodium chloride solution, separation water-yielding stratum is extracted with dichloromethane twice (10
Milliliter × 2).It is dry with anhydrous sodium sulfate to merge organic layer.Decompression filters, and filtrate concentration removes solvent.With petroleum ether/acetic acid second
Ester (16: 1, volume/volume) eluant, eluent column chromatographic purifying, obtains yellow liquid IV, yield 58%, the amount of compound IV preparation and
The volume of reaction vessel is expanded or shunk by corresponding proportion.
D. the preparation of compound V:
N2Under protective condition, by 1.94 mMs of IV, 2.33 mMs of 3- carbethoxyl group phenyl boric acids, 3.88 mMs of carbonic acid
Caesium and 0.1 mM 1,1 '-bis- Diphenyl phosphino ferrocene palladium chlorides be dissolved in 15 milliliters of Isosorbide-5-Nitrae-dioxane/water (10: 1, body
Product/volume) in the mixed solvent, heated overnight at reflux is cooled to room temperature after the reaction was completed under the conditions of 110 DEG C, with being covered with diatom
Soil funnel depressurize filter, ethyl acetate washing, filtrate concentration remove solvent, with petrol ether/ethyl acetate (8: 1, volume/body
Product) eluant, eluent column chromatographic purifying, obtain target product V, the amount of yield 63-89%, compound V preparation and the volume of reaction vessel
It is expanded or shunk by corresponding proportion.
E. the preparation of compound VI:
V is dissolved in 2N NaOH and the mixed solution of ethyl alcohol (4: 1, volume/volume), 80 DEG C of reflux 30 are gradually heated to
Minute.It is after the reaction was completed in clear solution.It is cooled to room temperature, reflection solution is poured into beaker, with 2 mol/L salt wait react
Target product VI, the amount of yield 87-93%, compound VI preparation and the body of reaction vessel is obtained by filtration in acid-conditioning solution pH=2
Product is expanded or shunk by corresponding proportion.
F. the preparation of compound VII:
0.24 mM of VI is dissolved in methylene chloride, 0.48 mM of oxalyl chloride and 3 drop n,N-Dimethylformamide is added,
It stirs 30 minutes under room temperature.After completion of the reaction, solvent is removed under reduced pressure, then is diluted with methylene chloride, under condition of ice bath, by phase
The dichloromethane solution of acyl chlorides is answered to be added drop-wise to 0.26 mM of R2-NH2With the dichloromethane of 0.71 mM of n,N-diisopropylethylamine
In alkane solution, it is stirred overnight at room temperature；After the reaction was completed, with 10mL water washing one time, separation water-yielding stratum is extracted with dichloromethane two
All over (5 milliliters × 2)；Merge organic layer to be washed one time with 10mL saturated sodium chloride solution, separation water-yielding stratum is extracted with dichloromethane
Twice (5 milliliters × 2)；It is dry with anhydrous sodium sulfate to merge organic layer.Decompression filter, filtrate concentration remove solvent, with petroleum ether/
Ethyl acetate (2: 1-4: 1, volume/volume) eluant, eluent column chromatographic purifying obtains respective objects product VII, yield: 10-96%,
The amount of compound VII preparation and the volume of reaction vessel are expanded or shunk by corresponding proportion.
G. the measurement of pyrazole phenyl carboxamides derivatives VII bactericidal activity of the invention:
The sterilization of pyrazole phenyl carboxamides derivatives VII of the invention or bacteriostatic activity are measured using thalli 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 newborn containing a certain amount of polysorbas20
The aqueous solution of agent is diluted to the medicament of 500 mcg/mls, and reagent agent is aseptically respectively drawn to 1 milliliter in culture
In ware, then 9 milliliters of PDA culture mediums are separately added into, 50 mcg/ml drug containing tablets are made after shaking up, to add 1 milliliter of aqua sterilisa
Plate do blank control, cut bacterium disk along mycelia outer rim with 4 millimeters of diameter of punch, move in drug containing tablet, in equilateral
Triangle is put, and every processing is repeated 3 times, and it is straight that culture dish is placed on culture, bacterium colony to be compareed in 24 ± 1 degrees Celsius of constant incubators
Diameter investigates each processing bacterium disk extension diameter after being extended to more than 2 centimetres, average, and calculates compared with blank control relatively antibacterial
Rate is the kind of most of typical plant pathogen that field actually occurs in China's agricultural production for examination strain, code name and
Title 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, GZ: fusarium graminearum, latin name are as follows: Gibberella zeae, PI: potato evening
Epidemic disease bacterium, 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 beneficial effects of the present invention are: having carried out guide's optimization to pyrazole phenyl carboxamides derivatives VII, and to pyrazoles benzene
Base carboxamides derivatives VII has carried out the screening of bacteriostatic activity.
The present invention illustrates that pyrazole phenyl formamide is derivative by the way that specific preparation and biological activity determination embodiment are more specific
The synthesis of object VII 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
It is that bioactivity is merely illustrative of, rather than limits this patent, specific embodiment is as follows:
Embodiment 1: the preparation of compound II-1:
N228.39 mMs of I-1,56.78 mMs of N are added under protective condition into 250 milliliters of neck round bottom flask,
N- diisopropylethylamine (DIPEA) and 56.78 mMs of diphenyl phosphate azides (DPPA) are dissolved in 100 milliliters of tert-butyl alcohols, room
Temperature stirring 10 minutes.80-90 degrees Celsius is then raised temperature to, is heated to reflux 4 hours, after the reaction was completed, decompression filters, filtrate concentration
It removes solvent and obtains white solid II-1 with petrol ether/ethyl acetate (4: 1, volume/volume) eluant, eluent column chromatographic purifying, receive
Rate 94%；Work as R1When for difluoromethyl, the nuclear magnetic data of the compound is as follows:1H NMR (400MHz, CDCl3) δ 7.86 (s,
1H), 6.70 (t, J=54.6Hz, 1H), 6.66 (s, 1H), 3.84 (s, 3H), 1.50 (s, 9H)13C NMR (101MHz,
CDCl3) δ 152.59,133.61 (t, J=29.1Hz), 122.53,119.91,112.64 (t, J=231.5Hz), 80.85,
39.38 28.20.The amount of compound II-1 preparation and the volume of reaction vessel are expanded or shunk by corresponding proportion.
Embodiment 2: the preparation of compound III-1:
25.52 mMs of II-1 are added in 250 milliliters of single necked round bottom flask to be dissolved in 50mL methylene chloride.25 millis are added
It rises trifluoroacetic acid and is stirred at room temperature 2.5 hours, after the reaction was completed, decompression filters, and filtrate concentration removes solvent, is diluted with water, with full
PH=8 is adjusted with sodium carbonate liquor, is extracted with a large amount of ethyl acetate, it is dry with anhydrous sodium sulfate to merge organic layer；Decompression filters,
Filtrate concentration removes solvent and obtains rufous with petrol ether/ethyl acetate (4: 1, volume/volume) eluant, eluent column chromatographic purifying
Liquid III-1；Yield 96%；Work as R1When for difluoromethyl, the nuclear magnetic data of the compound is as follows:1H NMR (400MHz,
CDCl3) δ 6.97 (s, 1H), 6.67 (t, J=54.7Hz, 1H), 3.77 (s, 3H), 3.30 (s, 2H).Compound III-1 preparation
Amount and the volume of reaction vessel expanded or shunk by corresponding proportion.
Embodiment 3: the preparation of compound IV-1:
10.20 mMs of III-1 are added into 200 milliliters of single necked round bottom flask, are dissolved in 76.5 milliliter of 4 mol/L salt
In acid solution, it is cooled under 0 degree Celsius and stirs；13.25 mMs of sodium nitrites are dissolved in suitable quantity of water, are added dropwise to anti-
It answers in system, is stirred 1 hour under 0 degrees celsius；30.59 mMs of potassium iodide are added to reactant in batches
In system, it is vigorously stirred 30 minutes, is then gradually warming up to room temperature.After the reaction was completed, it with saturated sodium carbonate solution neutralization reaction, uses
30 milliliters of methylene chloride extractions, organic layer are washed twice (20 milliliters × 2) with saturated sodium thiosulfate solution, and separation water-yielding stratum is used
Methylene chloride extracts twice of (10 milliliters × 2)；Merge organic layer to be washed one time with 10 milliliters of saturated sodium chloride solutions, separation water outlet
Layer is extracted with dichloromethane twice (10 milliliters × 2)；It is dry with anhydrous sodium sulfate to merge organic layer；Decompression filters, filtrate concentration
Remove solvent；With petrol ether/ethyl acetate (16: 1, volume/volume) eluant, eluent column chromatographic purifying, yellow liquid IV-1 is obtained,
Yield 58%；Work as R1When for difluoromethyl, the nuclear magnetic data of the compound is as follows:1H NMR (400MHz, CDCl3) δ 7.47 (s,
1H), 6.66 (t, J=53.8Hz, 1H), 3.92 (s, 3H).The amount of compound IV-1 preparation and the volume of reaction vessel are by corresponding
Ratio is expanded or shunk.
Embodiment 4: the preparation of compound V-1:
N2Under protective condition, by 1.94 mMs of IV-1,2.33 mMs of 3- carbethoxyl group phenyl boric acids, 3.88 mMs of carbon
Sour caesium and 0.1 mM 1,1 '-bis- Diphenyl phosphino ferrocene palladium chloride [Pd (dppf) Cl2] it is dissolved in 15 milliliters of Isosorbide-5-Nitrae-dioxies
The in the mixed solvent of six rings/water (10: 1, volume/volume)；Heated overnight at reflux under 110 degrees celsius.After the reaction was completed, cold
But it to room temperature, is depressurized and is filtered with the funnel for being covered with diatomite, ethyl acetate washing, filtrate concentration removes solvent, with petroleum ether/second
Acetoacetic ester (8: 1, volume/volume) eluant, eluent column chromatographic purifying, obtains target product V-1, yield 65%；Work as R1For difluoromethyl
When, the nuclear magnetic data of the compound is as follows:1H NMR (400MHz, CDCl3) δ 8.13 (s, 1H), 7.97 (d, J=7.8Hz, 1H),
7.68 (d, J=7.7Hz, 1H), 7.56 (s, 1H), 7.45 (t, J=7.7Hz, 1H), 6.76 (t, J=54.1Hz, 1H), 4.37
(q, J=7.1Hz, 2H), 3.93 (s, 3H), 1.39 (t, J=7.1Hz, 3H).The amount and reaction vessel of compound V-1 preparation
Volume is expanded or shunk by corresponding proportion.
Embodiment 5: the preparation of compound VI-1:
V-1 is dissolved in 2N NaOH and the mixed solution of ethyl alcohol (4: 1, volume/volume), 80 DEG C of reflux are gradually heated to
30 minutes.It is after the reaction was completed in clear solution.It is cooled to room temperature, reflection solution is poured into beaker, with 2 mol/Ls wait react
Target product VI-1, yield 87% is obtained by filtration in hydrochloric acid conditioning solution pH=2；Work as R1For difluoromethyl, pyrazoles is in benzamide
When meta position, the nuclear magnetic data of the compound is as follows:1H NMR (400MHz, DMSO) δ 13.06 (s, 1H), 8.24 (s, 1H), 8.10
(s, 1H), 7.88 (d, J=7.6Hz, 1H), 7.73 (d, J=7.6Hz, 1H), 7.55 (t, J=7.7Hz, 1H), 7.07 (t, J=
53.7Hz, 1H), 3.93 (s, 3H)；The amount of compound VI-1 preparation and the volume of reaction vessel are expanded or shunk by corresponding proportion.
Embodiment 6: the preparation of compound VII:
0.24 mM of VI-1 is dissolved in methylene chloride, 0.48 mM of oxalyl chloride and 3 drop N, N- dimethyl formyl is added
Amine stirs 30 minutes under room temperature.After completion of the reaction, solvent is removed under reduced pressure, then is diluted with methylene chloride.Under condition of ice bath,
The dichloromethane solution of corresponding acyl chlorides is added drop-wise to 0.26 mM of R2-NH2With the two of 0.71 mM of n,N-diisopropylethylamine
In chloromethanes solution, it is stirred overnight at room temperature.After the reaction was completed, with 10 milliliters water washing one time, separate water-yielding stratum methylene chloride
Extract twice of (5 milliliters × 2)；Merge organic layer to be washed one time with 10 milliliters of saturated sodium chloride solutions, separates water-yielding stratum dichloro
Methane extracts twice of (5 milliliters × 2)；It is dry with anhydrous sodium sulfate to merge organic layer.Decompression filters, and filtrate concentration removes solvent,
Respective objects product VII -1 is obtained with petrol ether/ethyl acetate (2: 1-4: 1, volume/volume) eluant, eluent column chromatographic purifying, is produced
Rate: 10-96%.Work as R1For difluoromethyl, pyrazoles is in benzamide meta position, R2When for methyl, the nuclear magnetic data of the compound is such as
Under:1H NMR (400MHz, CDCl3) δ 7.94 (s, 2H), 7.76 (d, J=7.8Hz, 1H), 7.67 (d, J=7.8Hz, 1H),
7.55 (s, 1H), 7.53-7.41 (m, 3H), 7.25 (t, J=7.8Hz, 1H), 6.97 (d, J=7.5Hz, 1H), 6.76 (t, J=
54.1Hz, 1H), 3.94 (s, 3H), 2.36 (s, 3H)；The amount of compound VII-1 preparation and the volume of reaction vessel are by corresponding ratio
Example is expanded or shunk；The physical and chemical parameter and structural parameters of compound VII is shown in Table 1.
Embodiment 7: the bactericidal activity measurement result of pyrazole phenyl carboxamides derivatives VII 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 in 50 mcg/ml, allization that the present invention synthesizes
Closing object has different degrees of bactericidal activity.For tomato early blight bacterium, the compound of the present invention YB02-178, YB02-
180, the inhibiting rate of YB03-115 and YB03-119 reaches 50% or more, and wherein the bactericidal activity of compound YB03-115 reaches
85.7%, it is higher by comparison medicine fluxapyroxad and thiophene methuroxam 10% and 20% or more respectively；For peanut Cercospora bacteria,
The bactericidal activity of compound YB02-180, YB03-115 and YB03-119 are 60% or more, and wherein compound YB03-115 presses down
Rate highest processed is suitable with comparison medicine thifluzamide up to 83.1%；Compound YB02- is shown for the activity of fusarium graminearum
178, the inhibiting rate of YB02-180 and YB03-119 is higher by comparison medicine fluxapyroxad and thiophene methuroxam 50% or more
10% or more；For Botryosphaeria berengeriana f. sp, the inhibiting rate of compound YB02-178 and YB03-119 are higher than 40% or more
Comparison medicine thiophene methuroxam, wherein the inhibiting rate highest of compound YB03-119, reaches 67.9%, is higher than comparison medicine fluorine azoles bacterium acyl
Amine；For botrytis cinerea pers, compound YB02-175, YB02-178, YB02-180, YB02-186, YB02-188 and
The inhibiting rate of YB03-119 is higher by comparison medicine thifluzamide 50% or more；For Sclerotinia sclerotiorum, compound
The bactericidal activity of YB02-175, YB02-178, YB02-176, YB02-180, YB03-115 and YB03-119 75% or more,
Wherein the bactericidal activity of compound YB02-178, YB02-176 and YB02-180 is higher by comparison medicine fluorine azoles 90% or more
Bacterium amide and thiophene methuroxam；For Rhizoctonia cerealis, compound YB02-175, YB02-178, YB02-180, YB03-115
For bactericidal activity with YB03-119 80% or more, bactericidal activity is higher by comparison medicine fluxapyroxad and thiophene methuroxam 30%
More than；The activity of Phytophthora infestans shows compound YB02-178, YB02-180, YB03-115 and YB03-119's
Bactericidal activity is higher by comparison medicine fluxapyroxad and 20% or more thiophene methuroxam 30% or more；For rice sheath blight disease
For bacterium, the bactericidal activity of compound YB02-178, YB02-180, YB02-188 and YB03-115 are in 30% or more, height
Comparison medicine fluxapyroxad and 20% or more thiophene methuroxam out；In conclusion compound YB02-180 has the sterilization of wide spectrum living
Property.
Embodiment 8: pyrazole phenyl carboxamides derivatives VII of the invention is preparing the application in composition pesticide:
Pyrazole phenyl carboxamides derivatives VII of the invention can prepare composition pesticide, and the composition includes the present invention
Pyrazole amide pyrazole derivatives VII and its intermediate as active constituent, the content of active constituent is 0.1% to 99.9% weight
Amount, the surfactant of the solid or liquid adjuvants of 99.9% to 0.1% weight and optional 0 to 50% weight.
Embodiment 9: the application of pyrazole phenyl carboxamides derivatives VII of the invention in preparation pesticide complex composition:
Pyrazole phenyl carboxamides derivatives VII of the invention and its intermediate can with other commercially available agricultural chemicals, i.e., insecticide,
Acaricide, fungicide, antivirotic or activating plants agent compounding preparation pesticide complex composition, which includes this hair
It is bright pyrazole phenyl carboxamides derivatives VII and its intermediate other commercially available agricultural chemicals, i.e. insecticide, acaricide, fungicide, disease-resistant
Toxic agent or activating plants agent are as active constituent, pyrazole phenyl carboxamides derivatives VII of the invention and its intermediate and other
Commercially available agricultural chemical, i.e. insecticide, acaricide, fungicide, antivirotic or activating plants agent ratio be mass percent 1%:
99% to 99%: 1%, the content of active constituent is 0.1% to 99.9% weight, the solid or liquid of 99.9% to 0.1% weight
The surfactant of body auxiliary agent and optional 0 to 50% weight.
Embodiment 10: pyrazole phenyl carboxamides derivatives VII and insecticide composition of the invention is in prevention and treatment agricultural and forestry
And the application in gardening plant insect pest:
All pyrazole phenyl carboxamides derivatives VII of the invention are combined with any one or two kinds in commodity insecticide
It forms Pesticidal combination and is selected from 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 cyfluthrins
Pyrethroids, decis, Fenpropathrin, Beta- cyfloxylate, Lambda- Cyhalothrin, permethrin, benzyl chloride
Pyrethroids, allethrin, Biphenthrin, Permethrin, ethofenprox, flumethrin, fluvalinate, imidacloprid, alkene pyridine worm
Amine, imidaclothiz, thiacloprid, Diacloden, clothianidin, dinotefuran, clothianadin, Da Tenan, diflubenzuron, d ichlorbenzuron, Teflubenzuron, deinsectization
Grand, flubenzuron, flufenoxuron, pyridine worm be grand, lufenuron, poisonous insect urea, penfluron, flucycloxuron, chlorfluazuron, piperazine worm urea, furan tebufenozide,
Tebufenozide, chlorine tebufenozide, methoxyfenozide, ring tebufenozide, flolimat, DDVP, quinalphos, pyridaphethione, isoprocarb, west
Denapon, Aphox, MTMC, Mobucin, cartap, Bassa, leaf disperse, carbaryl, Benfuracard micro, carbosulfan,
Cartap, 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；Of the invention
The mass percentage of pyrazole amide pyrazole derivatives VII and its intermediate in the Pesticidal combination is 1%-90%,
The surfactant of the solid or liquid adjuvants of 99% to 10% weight and optional 0 to 50% weight, pyrazoles benzene of the invention
The ratio of base carboxamides derivatives VII and aforementioned commodity insecticide is mass percent 1%: 99% to 99%: 1%；It is described to kill
The dosage form of worm composition 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, dry mixing
Kind 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, thermal fog, medicine paint, fine granule, oil suspending agent, oil-dispersing property powder
Agent, dense jelly, sprinkles and pours agent, seed coat agent, liniment, suspended emulsion, film forming finish, soluble powder, seed treatment sheet poison bait
It is water solube powder, ultra-low volume suspending agent, tracking pulvis, ultra low volume liquids, any one in wet-mixing kind water-dispersible powder
Kind；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, Japan are yellow
Ridge locust, 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 plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, the flat angle plant hopper of sugarcane,
Cotten aphid, green bugs, grain aphid, black peach aphid, kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, Chinese wax
Worm, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, banana lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, rice are brown
Stinkbug, scotinophora lurida, green rice bug, green plant bug, alfalfa plant bug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, Huang
Slug moth, brown slug moth, thosea siensis, gelechiid, pink bollworm, brachmia triannuella, diamondback moth, small heart-eating peach worm, eating-core bean worm, apple top
Tip leaf roller, brown belt length leaf roller, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, corn borer, yellow rice borer, Oeobia undalis, cnaphalocrocis
Snout moth's larva, snout moth's larva, Notarchaderogata, dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, cotton boll
Worm, black cutworm, big cutworm, yellow cutworm, steals poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight grain rice at ancient cooking vessel point spark
It hesperids, pelopidas mathias, Papilio xuthus, Common Mormon, cabbage butterfly, pyrameis indica, a ramie Huang a kind of butterfly harmful to crop plants, beans blister beetle, Venus step
First, wrinkle sheath ground beetle, wheat head ground beetle, pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, the small buprestid beetle of citrus, Jin Yuanji
Tintinnid, yellow meal worm, dark mealworm, red flour beetle, confused flour beetle, verdigris different beetle, H. parallela, holotrichia oblita, mulberry
Longicorn, longicorn beetle, nadezhdiella cantori, pink neck longicorn, big daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, phyllotreta striolata, Callosobruchus chinensis, pea
Bean weevil, broad bean weevil, sitophilus zea-mais, rice weevil, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm hang cocoon ichneumon wasp, cotton
Earworm tooth lip ichneumon wasp, snout moth's larva stain wart ichneumon wasp, mosquito, horsefly, wheat midge, contarinia tritici, citrus fruit fly, melonfly, Mai Ye
The latent fly of ash, 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, wheat, barley, oat, corn, sorghum, sweet potato, potato, wood writes,
Soybean, garden pea, semen viciae fabae, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee
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, peach, tea, wild vegetables, bamboo shoots, hops, pepper, perfume (or spice)
Any of several broadleaf plants, papaya, orchid, potted landscape.
Embodiment 11: pyrazole phenyl carboxamides derivatives VII and antimicrobial combination of the invention is in prevention and treatment agricultural and forestry
And the application in gardening plant disease:
All pyrazole phenyl carboxamides derivatives VII of the invention are combined with any one or two kinds in commodity fungicide
It forms bactericidal composition and is selected from for preventing and treating agricultural and forestry and gardening plant disease, the commodity fungicide: benzo thiophene two
Azoles, tiadinil are abbreviated as TDL, tisocromide, first thiophene and lure amine, 4- methyl-1,2,3- thiadiazoles -5- formic acid, 4- methyl-1, and 2,
3- thiadiazoles -5- sodium formate, 4- methyl-1,2,3- thiadiazoles -5- Ethyl formates, DL- beta-aminobutyric acid, isotianil, English
Literary common name are as follows: isotianil, 3,4-, bis- chloroisothiazole -5- formic acid, 3,4-, bis- chloroisothiazole -5- sodium formate, 3,4- dichloro are different
Thiazole -5- Ethyl formate, virazole, antofine, Ningnanmycin or salicylic acid, cymoxanil, thiram, ziram, Mancozeb,
Aliette, 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；Pyrazole phenyl carboxamides derivatives VII of the invention is in the sterilization
Total mass percentage in composition is 1%-90%, the solid or liquid adjuvants of 99% to 10% weight and optional 0
To the surfactant of 50% weight, the ratio of pyrazole phenyl carboxamides derivatives VII of the invention and aforementioned commodity fungicide
For mass percent 1%: 99% to 99%: 1%；The dosage form of the bactericidal composition processing is selected from: seed treatment emulsion, water and milk
Agent, 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, 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 plant disease of the bactericidal composition prevention and treatment is selected from: rice
Seedling pythium rot, tomato root rot, the late blight of potato, tobacco black shank, millet powdery mildew, downy mildew of garpe, downy mildew of lettuce,
Cucumber downy mildew, cucumber anthracnose；The applicable plant of the bactericidal composition is selected from: paddy, wheat, barley, oat, corn,
Sorghum, sweet work, potato, cassava, soybean, garden pea, semen viciae fabae, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame
Fiber crops, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, trailing plants
Fore-telling, cucumber, Chinese cabbage, celery, hot pickled mustard tuber, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus and peach, tea, hill
Dish, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape.
Embodiment 12: pyrazole phenyl carboxamides derivatives VII of the invention is combined with anti-plant virus agent in prevention and treatment agricultural
With the application in forestry and gardening plant virus disease:
Any one in all pyrazole phenyl carboxamides derivatives VII of the invention and commodity antiviral agent or two kinds
Combination forms antiviral composition for preventing and treating agricultural and forestry and gardening plant virus disease, the commodity antiviral agent
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- 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；Pyrazole phenyl carboxamides derivatives VII of the invention is described antiviral
Total mass percentage in composition is 1%-90%, the solid or liquid adjuvants of 99% to 10% weight and optional 0
To the surfactant of 50% weight, pyrazole phenyl carboxamides derivatives VII of the invention and aforementioned commodity anti-plant virus agent
Ratio be mass percent 1%: 99% to 99%: 1%；The dosage form of the antiviral composition processing is selected from: seed treatment
Emulsion, aqueous emulsion, big granula, microemulsion, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, bulk
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
Agent, oil in water emulsion, smoke candle, granula subtilis, smoke candle, smoke cartridge, smog stick, seed treatment suspending agent, smog piece, smog
Ball, thermal fog, medicine paint, fine granule, oil suspending agent, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkles and pours agent, kind granular poison bait
Clothing agent, suspended emulsion, film forming finish, soluble powder, seed treatment water solube powder, ultra-low volume suspending agent, chases after liniment
Track pulvis, ultra low volume liquids, any one in wet-mixing kind water-dispersible powder；The virus of the antiviral composition prevention and treatment
Disease is selected from: rice dwarf virus disease, yellow dwarf, stripe virus disease, fern leaf of tomato viral disease, Tomato yellow mosaic virus, capsicum floral leaf
Virosis, tobacco veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, citrus virosis, cymbidium mosaic virus,
Cybidium ring spot virus；Plant of the antiviral composition for prevention and treatment is selected from: paddy, wheat, barley, oat, corn, height
Fine strain of millet, 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 and peach, tea, wild vegetables,
Bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape.
Embodiment 13: pyrazole phenyl carboxamides derivatives VII of the invention is combined with acaricide in prevention and treatment agricultural and forestry
And the application in gardening plant mite evil:
All pyrazole phenyl carboxamides derivatives VII of the invention are combined with any one or two kinds in commodity acaricide
It forms miticide composition and is selected from for preventing and treating agricultural and forestry and gardening plant mite evil, the commodity acaricide: azacyclotin, three
Ring tin, fenbutatin oxide, three phosphor tins, chlorfenviphos, dimethylvinphos, crotoxyphos, heptenophos, Menite, 2-dichloroethylk dimethyl phosphate, Diothyl, chloromethane
Phosmet, 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 matter of pyrazole phenyl carboxamides derivatives VII of the invention in the miticide composition
Measuring percentage composition is 1%-90%, the surface of the solid or liquid adjuvants of 99% to 10% weight and optional 0 to 50% weight
Activating agent, pyrazole phenyl carboxamides derivatives VII of the invention and the acaricidal ratio of the commodity are mass percent 1%:
99% to 99%: 1%；The dosage form of the miticide composition processing is selected from: seed treatment emulsion, aqueous emulsion, big granula, micro emulsion
Agent, water-soluble granule, soluble thick agent, water-dispersible granules, poison grain, aerosol, blocky poison bait, sustained-release block, dense poison bait, capsule
It is granula, micro-capsule suspension, Waterless Seed Dressing pulvis, missible oil, electrostatic spray agent, water-in-oil emulsion, oil in water emulsion, smoke candle, thin
Granula, smoke candle, smoke cartridge, smog stick, seed treatment suspending agent, smog piece, smog ball, granular poison bait, thermal fog, medicine paint,
Fine granule, oil-dispersing property pulvis, sheet poison bait, dense jelly, sprinkles and pours agent, seed coat agent, liniment, suspended emulsion, film forming oil suspending agent
Finish, soluble powder, seed treatment water solube powder, ultra-low volume suspending agent, tracking pulvis, ultra low volume liquids, wet-mixing
Plant any one in water-dispersible powder；The mite evil of the miticide composition prevention and treatment is selected from: mite evil is selected from Tetranychidae, false spider mite
Section, 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；Plant of the miticide composition for prevention and treatment is selected from: paddy, wheat, barley, oat, corn, height
Fine strain of millet, sweet potato, potato, cassava, soybean, garden pea, semen viciae fabae, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, 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, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus, peach, tea, hill
Dish, bamboo shoots, hops, pepper, banana, papaya, orchid, potted landscape.
The bacteriostatic activity (inhibiting rate/% of 50 mcg/mls) of the pyrazole phenyl carboxamides derivatives VII of the invention of table 2.
| Serial number | Compound number | AS | BC | GZ | PI | PP | PS | RC | SS |
| 1 | YB02-175 | 41.3 | 71.4 | 38.5 | 41.2 | 19.6 | 16.7 | 27.3 | 84.4 |
| 2 | YB02-178 | 56.5 | 74.6 | 28.2 | 56.9 | 36.1 | 40.5 | 45.5 | 82.2 |
| 3 | YB02-184 | 10.9 | 34.9 | 7.7 | 33.3 | 7.2 | 2.4 | 15.2 | 22.2 |
| 4 | YB02-187 | 8.7 | 33.3 | 5.1 | 13.7 | 1.0 | 2.4 | 9.1 | 31.1 |
| 5 | YB02-190 | 13.0 | 28.6 | 17.9 | 5.9 | 1.0 | 7.1 | 15.2 | 16.7 |
| 6 | YB02-176 | 39.1 | 49.2 | 33.3 | 35.3 | 9.3 | 14.3 | 3.0 | 51.1 |
| 7 | YB02-180 | 71.7 | 74.6 | 66.7 | 56.9 | 46.4 | 27.4 | 42.4 | 94.4 |
| 8 | YB02-186 | 30.4 | 57.1 | 28.2 | 45.1 | 9.3 | 14.3 | 15.2 | 42.2 |
| 9 | YB02-188 | 30.4 | 58.7 | 28.2 | 17.6 | 19.6 | 9.5 | 39.4 | 64.4 |
| 10 | YB03-120 | 23.8 | 29.4 | 15.5 | 25.0 | 0 | 9.8 | 21.9 | 28.6 |
| 11 | YB03-113 | 28.6 | 36.1 | 15.5 | 17.9 | 0 | 4.9 | 15.6 | 28.6 |
| 12 | YB03-115 | 85.7 | 45.4 | 83.1 | 0 | 39.3 | 23.2 | 53.1 | 94.9 |
| 13 | YB03-119 | 63.0 | 74.5 | 65.7 | 56.8 | 40.4 | 67.9 | 32.7 | 90.8 |
| 14 | Fluxapyroxad | 73.9 | 87.3 | 100 | 41.2 | 13.4 | 47.6 | 15.2 | 41.1 |
| 15 | Thiophene methuroxam | 65.2 | 58.7 | 82.1 | 35.3 | 13.4 | 39.3 | 15.2 | 55.6 |
AS: tomato early blight bacterium, latin name are as follows: .Alternaria solani, BC: botrytis cinerea pers, Latin
Name are as follows: Botrytis cinerea, GZ: fusarium graminearum, latin name are as follows: Gibberella zeae, PI: potato evening
Epidemic disease bacterium, 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。
Claims (9)
1. pyrazole phenyl formamide analog derivative, it is characterised in that: have the general structure as shown in Formula VII:
Wherein:
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. pyrazole phenyl carboxamides derivatives VII according to claim 1, R1It preferably is selected from: difluoromethyl, trifluoromethyl, first
Base；R2It preferably is selected from: 3- aminomethyl phenyl, 3- bromophenyl, 2- trifluoromethyl, benzyl, 2- aminomethyl phenyl, 2- bromophenyl, 3- tri-
Trifluoromethylphenyl, 2,4- dibromo phenyl, 2- isopropyl phenyl.
3. according to claim 1 with the specific synthetic route of pyrazole phenyl carboxamides derivatives VII and side described in claim 2
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 compound II:
N2Under protective condition, compound II is by raw material I, n,N-diisopropylethylamine and diphenyl phosphate azide (DPPA) in tertiary fourth
It is stirred at room temperature in alcohol after ten minutes, heating reflux reaction is complete to be made, and purifying is carried out by column chromatography method, wherein starting material I
As described in claim 1 with the definition of the substituent group in intermediate II, the definition of preferred substituents is as claimed in claim 2；
B. the preparation of compound III:
Compound III, which is stirred at room temperature in dichloromethane solvent by compound II with trifluoroacetic acid, reacts preparation, and column chromatography is pure
Change to obtain sterling compound III, wherein the definition of compound II and the substituent group in compound III is as described in claim 1, preferably
The definition of substituent group is as claimed in claim 2；
C. the preparation of compound IV:
Compound IV is prepared by compound III and sodium nitrite in aqueous solution and hydrochloric acid and iodate nak response, and column chromatographic purifying obtains pure
Product compound IV, wherein the definition of compound III and the substituent group in compound IV is as described in claim 1, preferred substituents
Definition it is as claimed in claim 2；
D. the preparation of compound V:
For compound V by compound IV and carbethoxyl group phenyl boric acid, cesium carbonate and 1,1 '-bis- Diphenyl phosphino ferrocene palladium chlorides are molten
Solution obtains sterling compound V in Isosorbide-5-Nitrae-dioxane/water in the mixed solvent heating reflux reaction preparation, column chromatographic purifying, wherein
The definition of compound IV and the substituent group in compound V is as described in claim 1, the definition of preferred substituents such as claim 2
It is described；
E. the preparation of compound VI:
Compound VI is prepared by compound V and NaOH and ethyl alcohol heating reflux reaction, and column chromatographic purifying obtains sterling compound VI,
The definition of middle compound V and the substituent group in compound VI is as described in claim 1, the definition of preferred substituents such as claim
Described in 2；
F. the preparation of compound VII:
Compound VII, which is dissolved in reacting at room temperature in methylene chloride by compound VI and oxalyl chloride and n,N-Dimethylformamide, to be prepared,
Column chromatographic purifying obtains sterling compound VII, wherein the definition of compound VI and the substituent group in compound VII such as claim 1
Described, the definition of preferred substituents is as claimed in claim 2.
4. claim 1 and pyrazole phenyl carboxamides derivatives VII as claimed in claim 2 and its intermediate are preparing agricultural kill
Purposes in epiphyte pharmaceutical.
5. a kind of composition pesticide, it includes claims 1 and pyrazole phenyl carboxamides derivatives VII as claimed in claim 2
And intermediate prepares composition pesticide, the composition includes that claim 1 and pyrazole phenyl formamide as claimed in claim 2 spread out
As active constituent, the content of active constituent is 0.1% to 99.9% weight for biological VII and its intermediate, 99.9% to 0.1%
The surfactant of the solid or liquid adjuvants of weight and optional 0 to 50% weight.
6. a kind of pesticide complex composition, it includes claims 1 and pyrazole phenyl carboxamides derivatives as claimed in claim 2
VII and its intermediate can prepare pesticide complex composition, which includes described in claim 1 and claim 2
Pyrazole phenyl carboxamides derivatives VII and its intermediate and commercially available agricultural chemical as active constituent, the content of active constituent is
0.1% to 99.9% weight, the surface of the solid or liquid adjuvants of 99.9% to 0.1% weight and optional 0 to 50% weight
Activating agent.
7. a kind of agricultural bactericidal complex composition, it includes claims 1 and pyrazole phenyl formamide as claimed in claim 2 to spread out
Biological VII and its intermediate and other it is bactericide compounded be used as active constituent, pyrazole phenyl carboxamides derivatives VII and among it
The ratio of body and other fungicide is mass percent 1%: 99% to 99%: 1%, and the content of active constituent 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 claims 1 and pyrazole phenyl first as claimed in claim 2
Amide derivatives VII and its intermediate and other Insecticidal and acaricidal agents compounding are used as active constituent, pyrazole phenyl carboxamides derivatives
The ratio of VII and its intermediate and other Insecticidal and acaricidal agents is mass percent 1%: 99% to 99%: 1%, active constituent
Content is 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 pyrazole phenyl formyl as claimed in claim 2
Amine derivative VII and its intermediate and other anti-plant virus agents compounding are used as active constituent, pyrazole phenyl carboxamides derivatives
The ratio of VII and its intermediate and other anti-plant virus agents is mass percent 1%: 99% to 99%: 1%, active constituent
Content be 1% to 99% weight, the solid or liquid adjuvants of 99% to 1% weight.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111087345A (en) * | 2019-12-27 | 2020-05-01 | 华东理工大学 | Azobenzene heterocyclic amide derivative and preparation method and application thereof |
| CN111233768A (en) * | 2020-03-18 | 2020-06-05 | 徐州圣元化工有限公司 | Preparation method of 3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxylic acid ethyl ester |
| CN111303035A (en) * | 2020-03-18 | 2020-06-19 | 徐州圣元化工有限公司 | Preparation method of 3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxylic acid |
| CN111393429A (en) * | 2020-04-21 | 2020-07-10 | 南开大学 | Isothiazole oxadiazole biphenyl amide derivatives and preparation method and application thereof |
| CN114752065A (en) * | 2022-04-20 | 2022-07-15 | 南阳柯丽尔科技有限公司 | Iron-loaded tertiary amino monophosphonic acid resin for rare earth enrichment and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111087345A (en) * | 2019-12-27 | 2020-05-01 | 华东理工大学 | Azobenzene heterocyclic amide derivative and preparation method and application thereof |
| CN111233768A (en) * | 2020-03-18 | 2020-06-05 | 徐州圣元化工有限公司 | Preparation method of 3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxylic acid ethyl ester |
| CN111303035A (en) * | 2020-03-18 | 2020-06-19 | 徐州圣元化工有限公司 | Preparation method of 3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxylic acid |
| CN111393429A (en) * | 2020-04-21 | 2020-07-10 | 南开大学 | Isothiazole oxadiazole biphenyl amide derivatives and preparation method and application thereof |
| CN114752065A (en) * | 2022-04-20 | 2022-07-15 | 南阳柯丽尔科技有限公司 | Iron-loaded tertiary amino monophosphonic acid resin for rare earth enrichment and preparation method thereof |
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