CN106608873A - Pyrazole amide compound, and preparation method and application thereof - Google Patents
Pyrazole amide compound, and preparation method and application thereof Download PDFInfo
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- CN106608873A CN106608873A CN201510704893.2A CN201510704893A CN106608873A CN 106608873 A CN106608873 A CN 106608873A CN 201510704893 A CN201510704893 A CN 201510704893A CN 106608873 A CN106608873 A CN 106608873A
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- pyrazoles
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- 0 CC[C@](C)C(CC(CC(*C(C)[C@@](C)C(C)C(C1=CCC(C(OCC)=C)=**1)I(CC1CC2)C1/C=*(\C(C)C)/C=C2/*=N)=*)=*)=O Chemical compound CC[C@](C)C(CC(CC(*C(C)[C@@](C)C(C)C(C1=CCC(C(OCC)=C)=**1)I(CC1CC2)C1/C=*(\C(C)C)/C=C2/*=N)=*)=*)=O 0.000 description 2
- BAXQALVEQWAEIA-UHFFFAOYSA-N CC(C)c1cc(C(C)=O)n[n]1C Chemical compound CC(C)c1cc(C(C)=O)n[n]1C BAXQALVEQWAEIA-UHFFFAOYSA-N 0.000 description 1
- ORUOMSOGLOFVHA-UHFFFAOYSA-N NCc1c[s]c(C2=CC=CCC=C2)n1 Chemical compound NCc1c[s]c(C2=CC=CCC=C2)n1 ORUOMSOGLOFVHA-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
Abstract
The invention discloses a pyrazole amide compound represented by the formula (I), and a preparation method and an application thereof, wherein R, R1, R2 and W have the definitions indicated in the specification. The compound represented by the formula (I) has bactericidal, insecticidal or acaricidal biological activities, and specially has quite high activity on pathogenic bacteria such as sphaerotheca fuliginea, botrytis cinerea, melampsora lini and the like.
Description
Technical field
The invention belongs to kill insects mites, antibacterial field, and in particular to the pyrazole amide for killing insects mites, sterilization biological activity
Class compound and preparation method thereof, killing insects mites, microbicide compositions and use these compounds containing the compound
Control evil insects mites, the purposes of harmful levels of pathogens and method.
Background technology
Pyrazol acid amide compounds have and kill insects mites and bactericidal activity, and have the acaricide-tebufenpyrad shown in D1
(tebufenpyrad) and shown in D2 kill insects mites agent-Tolfenpyrad (tolfenpyrad) etc. by succession exploitation be parasite killing,
Acaricide.
Tebufenpyrad (EP289879) has speed as Mitochondria In Developing Flight Muscle of Insects respiration inhibitor to the development full period of various mite class and demodicid mite
Effect and efficiently effect.Tolfenpyrad (EP365925) is used as the analog of tebufenpyrad, and its activity profile is wider, it to Lepidoptera,
Semiptera, beetle mesh, Hymenoptera, Diptera and mite class are effective.
High efficiency, high selectivity, high Environmental compatibility and economy are the characteristics of modern should possess.To be lived
Property spectrum is wider, activity is higher and/or more economical pyrazol acid amide compounds, the minor structures such as thiazole introduce pyrazoles by inventor
In amide structure, design and synthesize and a series of have no document report and with the broad spectrum of activity such as excellent insecticidal/demodicid mite and/or sterilization
Pyrazol acid amide compounds.Compare with D1 with D2, the compounds of this invention has more wide spectrum and efficient biological activity,
Such as compound 7 is far superior to D2 to the bactericidal activity of powdery mildew, gray mold etc., can with commercialization antibacterial Fluoxastrobin,
Boscalid compares favourably；Compound 10 then has the insecticidal activity suitable with D2.
The content of the invention
The invention provides shown in formula (I) with the pyrazol acid amide for murdering the biological activitys such as insects mites, harmful levels of pathogens
Compound：
Wherein：
R represents C1-C12Alkyl, C2-C12Alkenyl, C2-C12Alkynyl group, C3-C8Cycloalkyl or phenyl；
R1Represent C1-C12Alkyl, C2-C12Alkenyl, C2-C12Alkynyl group, C3-C8Cycloalkyl or phenyl；
R2Represent hydrogen, halogen, C1-C12Alkyl, C2-C12Alkenyl, C2-C12Alkynyl group or C3-C8Cycloalkyl；
R、R1And R2Middle hydrogen atom partly or entirely can be selected from it is following in identical or different substituent group replace：Halogen
Element, C1-C6Alkyl, C1-C6Alkoxyl, C1-C6Alkylthio group, C1-C6Alkyl amine group, C2-C6Alkenyl, C2-C6Chain
Thiazolinyl epoxide, C2-C6Alkenyl thio, C2-C6Alkenyl amido, C2-C6Alkynyl group, C2-C6Alkynyl group epoxide, C2-C6
Alkynyl group sulfenyl, C2-C6Alkynyl group amido, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3-C8Cycloalkylsulfanyl,
C3-C8Cycloalkyl amido, C6-C12Aryl or the band up to heteroaryl of 10 carbon atoms, C6-C12Aryloxy or band are more
To heteroaryl epoxide, the C of 10 carbon atoms6-C12Artyl sulfo or the band up to Heteroarylthio of 10 carbon atoms, C6-C12
Heteroaryl amido, the C of up to 10 carbon atoms of arylamine group or band6-C12Up to 10 carbon atoms of aryl or band
Heteroarylaryl, C6-C12The heteroarylheteroaryl of aryl heteroaryl or band up to 10 carbon atoms；
R1And R2Can be connected to each other, with two carbon of pyrazole ring C is formed4-C8Cycloalkane structure；
W represents oxygen or sulfur；
And R=R1=CH3, during W=O, R2H is not represented；
In the definition of compound (I) given above, no matter term used is used alone also being used in compound word, represent
Following substituent group：
Halogen：Refer to fluorine, chlorine, bromine, iodine；
Alkyl：Refer to straight or branched alkyl；
Haloalkyl：Refer to straight or branched alkyl, hydrogen moiety on these alkyl or all replaced by halogen atom；
Cycloalkyl：Refer to saturation or unsaturation ring alkyl；
Heterocyclylalkyl：Refer to saturation or unsaturated heterocycle alkyl, at least 1 N, O and/or S in formula；
Halogenated cycloalkyl：Refer to saturation or unsaturation ring alkyl, and hydrogen moiety therein or all replaced by halogen atom；
Alkenyl；Refer to straight or branched alkyl, and double bond can be there are on any position；
Halogenated alkenyl：Refer to straight or branched alkyl, and double bond, and hydrogen atom therein can be there are on any position
Partly or entirely replaced by halogen atom；
Alkynyl group；Refer to straight or branched alkyl, and three keys can be there are on any position；
Halo alkynyl：Refer to straight or branched alkyl, and three keys, and hydrogen atom portion therein can be there are on any position
Point or all replaced by halogen atom；
C6-C12Aryl means phenyl and by its derivative ring aryl phenyl or polyaromatic naphthyl, xenyl, anthryl,
Phenanthryl；
The heteroaryl of band up to 10 carbon atoms refers to a ring heteroaryl or polyheteroaromatic, at least 1 N in formula, O and
/ or S, such as thiazolyl, pyrazolyl, thiadiazolyl group, pyridine radicals, thienyl, benzothienyl, furyl, benzo
Furyl, pyrrole radicals, benzopyrrole base, indyl, benzindole base, imidazole radicals, benzimidazolyl, quinolyl,
Pyranose, pyrazinyl, pyrimidine radicals, pyridazinyl, benzopyranyl, benzopyrazines base, benzo pyrimidine radicals, benzo pyridazine
Ji ， oxazolyl ， isoxazolyls, benzoxazolyl, benzoisoxazole base, benzothiazolyl, isothiazolyl, benzisoxa
Thiazolyl, pyrimido triazolyl.
Currently preferred compound is compound shown in formula (I), wherein：R represents C1-C12Alkyl or phenyl；R1
Represent C1-C12Alkyl；R2Represent hydrogen, halogen or C1-C12Alkyl；And R, R1And R2The part of middle hydrogen atom is complete
Portion can be selected from it is following in identical or different substituent group replace：Halogen, C1-C6Alkyl, C1-C6Alkoxyl；R1With
R2Can be connected to each other, with two carbon of pyrazole ring C is formed5-C6Cycloalkane structure；W represents oxygen or sulfur.
The further preferred compound of the present invention is compound shown in formula (I), wherein：R represents C1-C6Alkyl；R1Generation
Table C1-C6Alkyl；R2Represent hydrogen, halogen, C1-C6Alkyl；And R, R1And R2The part or all of of middle hydrogen atom can
Be selected from it is following in identical or different substituent group replace：Halogen, C1-C3Alkyl, C1-C3Alkoxyl；W represents oxygen.
Compound specifically preferred according to the invention is compound shown in formula (I), wherein：R represents methyl or ethyl；R1Represent
C1-C6Alkyl；R2Represent hydrogen, halogen, C1-C3Alkyl；And R, R1And R2The part or all of of middle hydrogen atom can be with
Be selected from it is following in identical or different substituent group replace：Halogen, methyl, ethyl, methoxyl group；W represents oxygen.
Concrete preferred formula (I) compound of the invention is following compounds：
1,3,4- trimethyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (4)；
The chloro- 1,3- dimethyl-N -s of 4- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (6)；
3- ethyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (7)；
3- ethyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- carbothioic acid amides (8)；
3- ethyl -1,4- dimethyl-N -s [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (9)；
The chloro- 3- ethyls -1- methyl-N- of 4- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (10)；
The bromo- 3- ethyls -1- methyl-N- of 4- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (11)；
1- methyl -3- propyl group -- N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (12)；
3- isopropyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (13)；
3- cyclopropyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (14)；
3- butyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (20)；
2- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -2,4,5,6- tetrahydro cyclopentyls alkane simultaneously [c] pyrazoles -3- benzoic acid amides (23)；
2- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -4,5,6,7- tetrahydrochysene -2H- Yin rattle away azoles -3- benzoic acid amides (24)
1- ethyl -3- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (25)；
The chloro- 1- ethyls -3- methyl-N- of 4- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (27)；
The chloro- 1,3- diethyl-N- of 4- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (30)；
3- methyl isophthalic acids-phenyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (31)；
3- methyl isophthalic acids-(4- chlorphenyls)-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (35)；
1- methyl -5- propyl group-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -3- benzoic acid amides (50)；
5- isopropyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -3- benzoic acid amides (52).
The invention further relates to a kind of pest control/demodicid mite, (I) compound of the formula containing biologic effective dose of harmful levels of pathogens and at least
A kind of other compositionss selected from surfactant, solid diluent and liquid diluent.
The invention further relates to a kind of pest control/demodicid mite, (I) compound of the formula containing biologic effective dose of harmful levels of pathogens and effectively
At least one other bioactive compound of amount or the compositionss of preparation.
The invention further relates to a kind of pest control/demodicid mite, the method for harmful levels of pathogens, including formula (I) chemical combination by biologic effective dose
Thing contact evil insects mites, harmful levels of pathogens or its environment.Such a evil insects mites, harmful levels of pathogens prevention and controls are also related to,
Do harm to formula (I) compound of insects mites, harmful levels of pathogens or its environment biologic effective dose or containing formula (I) compound and biology
At least one other compound of effective dose or the mixture of preparation carry out contact and come pest control/demodicid mite, harmful levels of pathogens.
Formula (I) compound of the present invention has broad spectrum of activity：Some compounds can be used for pest control/demodicid mite, it may also be used for anti-
Control harmful levels of pathogens.And the compound having has very high biological activity to some evil insects mites and/or harmful levels of pathogens so that
Good effect is obtained with very low concentrations.
Currently preferred compositionss are the compositionss containing above-mentioned preferred compound.It is preferable that with it is above-mentioned preferably
The method of compound.
Further illustrate the present invention with the part formula (I) compound listed in 1～table of table 2 below, but do not limit this
Invention.Fusing point is not calibrated given in the present invention；When formula (I) compound synthesized by the present invention is viscous liquid, have
A little viscous liquid refrigerators can solidify after placing, and when synthesized formula (I) compound of invention is viscous solid, some viscosity are consolidated
Body refrigerator can be cured as non-tacky solids after placing；All compounds are in LC-MS (APCI, Pos) (Agilent in table 1
1100Series LC/MSD) or GC-MS (Agilent 7890-5975C) in its molecular ion peak can be observed；Table 1
Middle compound1H NMR (Varian INOVA-300spectrometer) make internal standard with tetramethylsilane (TMS),
Deuterochloroform (CDCl3) or deuterated dimethyl sulfoxide (DMSO) make solvent.
Table 1
Table 2
Compound shown in the formula (I) of the present invention can be obtained by reaction equation 1 shown below；(II) in reaction equation 1
Can be obtained by reaction equation 2 shown below；(III) in reaction equation 1 can be obtained by reaction equation 3；Reaction
(IV) in formula 2 can be obtained by purchase or reaction equation 4-1 or 4-2；Z in reaction equation 1 to reaction equation 3 is
Leaving group, such as chlorine, bromine, other substituent groups are outer unless specified otherwise to be limited as front.
Reaction equation 1：
Reaction equation 2：
Reaction equation 3：
Reaction equation 4：
The compound of formula (I) can be prepared so (reaction equation 1)：Suitable solvent for example tetrahydrofuran, acetonitrile,
In dichloromethane, dichloroethanes, toluene or dimethylbenzene, in -10 DEG C～system reflux temperature, without alkali or in appropriate base
Such as in the presence of triethylamine, pyridine, sodium hydride, sodium hydroxide or potassium hydroxide, with the compound shown in formula (II W=O)
React with the compound shown in formula (III), obtain formula (I W=O) compound, add catalyst such as 4- dimethylamino pyridines
Carry out etc. reaction can be accelerated；The sulfide such as P that compound ECDC shown in formula (I W=O) is fitted2S5Process to obtain formula (I W=S)
Compound.
The compound of formula (II) can be prepared so (reaction equation 2)：Solvent-free or suitable solvent such as dichloroethanes,
In dichloromethane or toluene, in 15 DEG C～system reflux temperature, with the compound shown in formula (IV W=O) and with it is suitable
Halide reagent such as thionyl chloride, phosgene or oxalyl chloride etc. react to obtain formula (II W=O) compound.
The compound of formula (III) can be prepared via a method which (reaction equation 3)：In suitable solvent such as ethanol, tetrahydrochysene
In the mixture of furan, ethanol and tetrahydrofuran, in 25 DEG C～system reflux temperature, 1.3 dihalo-s (chlorine or bromine) acetone
4- chloromethyl -2- phenyl thiazoles are reacted to obtain with Aminothiocarbonylbenzene；4- chloromethyls -2- phenyl thiazoles ammonia treatment or 4- chloromethanes
Base -2- phenyl thiazoles react the chemical combination that the solid thing product hydrazine hydrate process of gained obtains final product formula (III) with potassium phthalimide
Thing.
The compound of formula (IV W=O) can be prepared (reaction equation 4) by purchase or following method：In suitable solvent
Such as in ethanol, methanol, propanol, butanol or water, in the presence of suitable alkali such as Sodium ethylate, Feldalat NM or sodium hydroxide,
It is anti-with oxalate diester such as ethyl oxalate with the compound shown in formula (V) or (V ') in -15 DEG C～system reflux temperature
Should, obtain formula (VI) or the compound shown in (VI ')；The compound of formula (VI) or (VI ') Jing after conventional post processing,
Again with hydrazine hydrate cyclization, the compound of formula (VII) or (VII ') is obtained；In suitable solvent such as N,N-dimethylformamide
In, under the conditions of 30 DEG C～100 DEG C, the compound and alkylating reagent such as dimethyl sulfate of formula (VII) or (VII '),
Dithyl sulfate or iodomethane etc. react to obtain formula (VIII) or (VIII ') compound；Or formula (VI) or (VI ')
Compound, with replacement hydrazine cyclization, obtains formula (VIII) or (VIII ') compound Jing after conventional post processing；Shown in (VIII ')
Compound Jing halogenating reactions or the respective reaction such as alkylation obtain compound shown in formula (VIII)；In suitable solvent such as
In water, ethanol, the mixed solvent of the single solvent of methanol or water and ethanol, water and methanol, in appropriate base such as sodium hydroxide
Or in the presence of potassium hydroxide, under 50 DEG C～system reflux temperature, (VIII) compound Jing after routine hydrolysis reaction, with dilute
Hydrochloric acid solution process formula (IV) compound.
Concrete synthetic method has in the following embodiments more detailed elaboration.
With reference to embodiments the invention will be further described, but the present invention is only limitted to absolutely not these embodiments, embodiment
In yield it is not optimized.
Formula (I) compound that the present invention is provided has broad-spectrum biological activity under 15～2250 grams of effective ingredient/hectare consumption,
Can be not only used for pest control/demodicid mite, it may also be used for preventing and treating harmful levels of pathogens, some compounds have evil insects mites well and/or have
Fall ill bacterium preventive and therapeutic effect, good effect is obtained with very low concentrations.
Formula (I) compound that the present invention is provided, with biological activity and the compound that has has good biological activity.It is special
It is not to show activity in terms of agricultural, gardening, flowers and sanitary insect pest, the preventing and treating of pathogenic bacteria.Harmful life described here
Thing include but not limited to this, also never limits the present invention.
Evil insects mites：
Homoptera such as leafhopper, plant hopper, aphid, Lepidoptera such as oriental armyworm, snout moths larva, Prodenia litura, diamondback moth, Radix Betae
Noctuid, cabbage looper, Pieris rapae etc., Hymenoptera such as sawfly larva etc., Diptera such as yellow-fever mosquito, culex, fly etc., acarian
Mesh such as cotton spider mites, Zhu disturb by making noise tetranychid, the full melon demodicid mite of mandarin orange, Shenmu-Yanan railway, apple tetranychus, citrus rust mite, Rhizoglyphus hyacinthi,
T.urticae Koch etc..
Especially, formula (I) compound is led to homoptera pest such as aphid and lepidoptera pest such as mythimna separata etc., in low concentration
Under still there is well activity.
Harmful disease：
Oomycetes diseases, such as downy mildew, white rust, damping off, pythium rot, epidemic disease, late blight；
It is Fungi Imperfecti disease, such as droop, root rot, damping-off, anthrax, verticillium wilt, scab, gray mold, brown
Pinta, melasma, spot blight, early blight, ring spot, leaf blight, base rot disease etc.；
Load fungus diseases, such as rust, smut；
Ascomycetess disease, such as powdery mildew, sclerotiniose (Caulis et Folium Lini sclerotiniose, sclerotinia rot of colza, soybean sclerotinia crown rot, Semen arachidis hypogaeae bacterium
Core disease, Nicotiana tabacum L. sclerotiniose, Fructus Capsici sclerotiniose, Fructus Solani melongenae sclerotiniose, bean sclerotinia rot, Semen Pisi sativi sclerotiniose, cucumber timberrot,
Fructus Momordicae charantiae sclerotiniose, wax gourd sclerotinia, Citrullus vulgariss sclerotiniose, Herba Apii graveolentis sclerotiniose), scab etc.；
Especially, the compounds of this invention still has activity well to powdery mildew, gray mold, rust etc. under low concentration.
Due to its positive characteristic, above-claimed cpd is advantageously used for the important crop of protecting agriculture and horticulture, domestic animal
And breeding stock, and the environment that often goes of the mankind avoids the injury of insect, pathogenic bacteria.
To obtain ideal effect, the consumption of compound changes because of various factors, for example compound used therefor, pre- protection,
The type of harmful organism, gradient of infection, weather conditions, application method, the dosage form of employing.
Present invention additionally comprises using logical parasite killing, bactericidal composition of the formula (I) compound as active component.The parasite killing, sterilization
The weight percentage of active component is between 0.5-99% in compositionss.In the parasite killing, bactericidal composition also include agricultural,
Acceptable carrier in forestry, health.
It is effective to controlling insect, pathogenic bacteria when formula (I) compound of the present invention is used alone, they can also be with it
Allogene chemical substance is used together, and these biochemicals include other insecticides, antibacterial, herbicide, plant
Growth regulator, acaricide or fertilizer etc., and thus can produce additional advantage and effect.
Using formula (I) compound of present invention offer as the preparation of active ingredient, desired any agent can be made
Type, such as dry compressing grains, easily flow intermixture, granule, wettable powder, water dispersible granules, emulsible concentration
Thing, powder, powdery concentrate, microemulsion, suspending agent, cream, aqueous emulsion, soluble liquid, water preparation, dispersible
Liquor, suitable auxiliary agent includes carrier (diluent) and other adjuvant such as spreader-sticker, emulsifying agent, wetting agent, dispersion
Agent, sticker and distintegrant.Contain in these preparations mixed with the acceptable solid of inert, pharmacology or liquid diluent
The compound of the present invention is closed.
The compositionss example of the present invention can also make desired any dosage form, such as dry compressing grains, easily flowing
Intermixture, granule, wettable powder, water dispersible granules, emulsifiable concentrate, powder, powdery concentrate, microemulsion
Glue, suspending agent, cream, aqueous emulsion, soluble liquid, water preparation, dispersible agent, suitable auxiliary agent includes that carrier is (dilute
Release agent) and other adjuvant such as spreader-sticker, emulsifying agent, wetting agent, dispersant, sticker and distintegrant.These preparations
In containing with the acceptable solid of inert, pharmacology or liquid diluent be mixed with the present invention compound.
It should be appreciated that, in scope defined by the claims of the present invention, various conversion and change can be carried out.
With reference to embodiments the invention will be further described, and the yield in embodiment is not optimized.
Specific embodiment
Embodiment 1 this example demonstrates that in table 1 compound 4 preparation
3- methylpyrazole -5- Ethyl formates under -15～-5 DEG C and stirring condition, by acetone (0.30mol) and oxalic acid two
The mixed solution of ethyl ester (0.32mol) is added drop-wise in the ethanol of 96% Sodium ethylate (0.45mol) (300mL) solution.
After completion of dropping, continue to react after 2-4 hours, reactant liquor is poured in frozen water, with dilute hydrochloric acid its PH=4, acetic acid are adjusted
Ethyl ester is extracted, and after washing, anhydrous sodium sulfate drying obtains acetopyruvic acid ethylester 46.5g to gained organic faciess after concentrating under reduced pressure.
Under -10～-5 DEG C and stirring condition, in 1-2 hours, 80% hydrazine hydrate (0.38mol) is added drop-wise to into above-mentioned acetyl
In ethanol (300mL) solution of ethyl pyruvate.After completion of dropping, continue insulation reaction 1-2hr.Removed under reduced pressure is big
After partial solvent, ethyl acetate extraction, after washing, anhydrous sodium sulfate drying, concentrating under reduced pressure must be marked gained organic faciess
Topic compound 31.5g.
1,3- dimethyl pyrazoles -5- Ethyl formates 3- methylpyrazoles -5- Ethyl formates (65mmol) and dimethyl sulfate (78
Mmol) in DMF (DMF, 120mL), in 60-70 DEG C of stirring reaction 2-4 hour.Reaction
It is extracted with ethyl acetate after liquid cooling, gained organic faciess Jing washing, anhydrous sodium sulfate drying, concentrating under reduced pressure obtains titled
Compound 9.0g.
1,3,4- trimethylpyrazol -5- Ethyl formates under room temperature and stirring condition, by 1,3- dimethyl pyrazole -5- Ethyl formates
(50mmol) paraformaldehyde (100mmol), concentrated hydrochloric acid (100mmol) and concentrated sulphuric acid (5mmol) are added in batches
In 1,4- dioxane (100mL) solution.4-6 hours are reacted under counterflow conditions, cooling, removed under reduced pressure part is molten
Pour into after agent in frozen water, ethyl acetate extraction, gained organic faciess Jing washing, anhydrous sodium sulfate drying, concentrating under reduced pressure obtains 1,3-
Dimethyl -4- chloromethyl pyrazole-5-ethyl formate 9.0g.Under nitrogen protection, by 1,3- dimethyl -4- chloromethyl pyrazoles -5- first
During acetoacetic ester (40mmol) is transferred to pressure bottle, and methanol (50mL) is added, water (10mL) and 5%Pd/C are urged
Agent (50% moisture, 0.4g).After stirring, hydrogen exchange 5 times is passed through, 8-10 hours are reacted under room temperature.Cross
Filter reactant liquor, adds water (100mL), ethyl acetate extraction, the washing of gained organic faciess Jing, anhydrous sodium sulfate in filtrate
It is dried, concentrating under reduced pressure obtains title thing 4.6g.
1,3,4- trimethylpyrazols -5- formic acid 1,3,4- trimethylpyrazols -5- Ethyl formates (25mmol), sodium hydroxide (75
), mmol water (60mL) and ethanol (10mL) react 3-5 hours under backflow simultaneously stirring condition.Reactant liquor is cooled down
Afterwards, ethyl acetate extraction, gained water dilute hydrochloric acid is acidified to faintly acid (PH=5-6), stands, and filters consolidating for precipitation
Body, obtains title compound 2.6g.
The trimethylpyrazol -5- formic acid (15mmol) of 1,3,4- trimethylpyrazol -5- formic acid acyl chlorides 1,3,4-, thionyl chloride (35
Mmol) and 1,2- dichloroethanes (25mL) in backflow and stirring condition under react 3-5 hours.After cooling, removed under reduced pressure
The thionyl chloride of solvent and excess, obtains title compound 2.2g.
The dichloroacetone (170mmol) of 4- chloromethyl -2- phenyl thiazoles 1.3, Aminothiocarbonylbenzene (150mmol), second
Alcohol (150mL) and THF (75mL) are reacted after 5-8 hours in backflow and under stirring condition.The most of solvent of removing,
Cooling, reactant liquor is poured in frozen water, ethyl acetate extraction, washes organic faciess, and anhydrous sodium sulfate drying, decompression is sloughed molten
Agent obtains yellow liquid title thing 28g.
4- aminomethyls -2- phenyl thiazoles (III) 4- chloromethyls -2- phenyl thiazoles (45mmol), phthalimide
It is little that potassium (50mmol) and N,N-dimethylformamide (DMF, 100mL) react 2-5 under 60-80 DEG C and stirring condition
Shi Hou, is cooled to room temperature, and reactant liquor is poured in frozen water, separates out solid.Filter separated out solid and hydrazine hydrate (100
Mmol), ethanol (200mL) is reacted after 3-5 hours in backflow and under stirring condition, and cooling is filtered.Filtrate removes
After most of ethanol, ethyl acetate extraction, the washing of organic faciess Jing, anhydrous sodium sulfate drying, removed under reduced pressure solvent obtain title
Compound 6.0g.
1,3,4- trimethyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (compound 4 in table 1) ice
Under water-bath cooling and stirring condition, by 1 in 1 hour, the tetrahydrochysene furan of 3,4- trimethylpyrazols -5- formic acid acyl chlorides (10mmol)
(THF, 5mL) solution of muttering drops to 4- aminomethyls -2- phenyl thiazoles (10mmol), triethylamine (20mmol)
In THF (25mL) mixture of 4- dimethylamino pyridines (catalytic amount).After completion of dropping, continue to react
Night.Reactant mixture is extracted with ethyl acetate, the washing of organic faciess Jing, anhydrous sodium sulfate drying, removed under reduced pressure solvent, institute
Obtain crude product Jing column chromatography (petrol ether/ethyl acetate=10:1～5:1) purification, obtains the title thing 2.1g of off-white powder.
Embodiment 2 this example demonstrates that in table 1 compound 7 preparation
Under -10～-5 DEG C of 3- ethylpyrazol -5- Ethyl formates and stirring condition, in 1-2 hours by butanone (0.30mol) and
The ethanol (300mL) that the mixed solution of ethyl oxalate (0.32mol) is added drop-wise to 96% Sodium ethylate (0.45mol) is molten
In liquid.After completion of dropping, continue stirring reaction 2-4 hour.Under control temperature -5～0 DEG C and stirring condition, successively will
Acetic acid (0.30mol) and 80% hydrazine hydrate (0.38mol) drop to above-mentioned reactant mixture.After completion of dropping, continue
Reaction 1-2 hours.Water (200mL), ethyl acetate extraction, gained organic faciess Jing are added after gained reactant concentrating under reduced pressure
After washing, anhydrous sodium sulfate drying, concentrating under reduced pressure obtains title compound 29.6g.
3- ethyls -1- methylpyrazoles -5- Ethyl formates 3- ethylpyrazols -5- Ethyl formates (100mmol) and dimethyl sulfate
Ester (120mmol) reacts 3-4 hours in DMF (150mL), under 60-70 DEG C and stirring condition.Reactant liquor
It is extracted with ethyl acetate after cooling, gained organic faciess Jing washing, anhydrous sodium sulfate drying, concentrating under reduced pressure obtains title compound
Thing 15.0g.
3- ethyls -1- methylpyrazoles -5- formic acid 3- ethyls -1- methylpyrazoles -5- Ethyl formates (50mmol), sodium hydroxide
(150mmol), water (120mL) and ethanol (20mL) react 4-5 hours under backflow simultaneously stirring condition.Reaction
After liquid cooling, ethyl acetate extraction, gained water dilute hydrochloric acid is acidified to faintly acid (PH=5-6), stands, and filters analysis
The solid for going out, obtains title compound 4.8g.
3- ethyls -1- methylpyrazoles -5- formic acid acyl chlorides 3- ethyls -1- methyl pyrazole formic acid (10mmol), thionyl chloride (25
Mmol) and 1,2- dichloroethanes (15mL) in backflow and stirring condition under react 3-4 hours.After cooling, reduce pressure bar
The thionyl chloride of desolvation and excess under part, obtains title compound 1.3g.
3- ethyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (compound 7 in table 1)
In ice-water bath cooling and under stirring condition, by the tetrahydrofuran of 1- methyl -3- ethylpyrazols -5- formic acid acyl chlorides (7.5mmol)
(THF, 5mL) solution drops to 4- aminomethyls -2- phenyl thiazoles (7.5mmol), triethylamine (15mmol) and
In THF (15mL) mixture of 4- dimethylamino pyridines (catalytic amount).After completion of dropping, continue to react overnight.
Reactant mixture is extracted with ethyl acetate, desolvation under the washing of organic faciess Jing, anhydrous sodium sulfate drying, reduced pressure,
Gained crude product Jing column chromatography (petrol ether/ethyl acetate=10:1～5:1) purification, obtains off-white powder title thing 1.5g.
Embodiment 3 this example demonstrates that in table 1 compound 8 preparation
3- ethyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- carbothioic acid amides (compound in table 1
8) 3- ethyls -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (2.5mmol) and five sulfur
Change two phosphorus (7.5mmol) after back flow reaction 2-3 hour in tetrahydrofuran (50mL), add the sulfuration of second batch five two
Phosphorus (7.5mmol), after continuing back flow reaction 2-3 hour, adds the 3rd batch of phosphorus pentasulfide (7.5mmol), is further continued for
Back flow reaction 2-3 hour.Reactant mixture Jing is cooled down, and is concentrated under reduced pressure.Saturated aqueous common salt is added in concentrate,
Ethyl acetate is extracted, the washing of organic faciess Jing, anhydrous sodium sulfate drying, removed under reduced pressure solvent, gained crude product Jing column chromatography
(petrol ether/ethyl acetate=10:1～5:1) purification, obtains the title thing 0.7g of yellow solid.
Embodiment 4 this example demonstrates that in table 1 compound 10 preparation
The chloro- 3- ethyls -1- methylpyrazoles -5- Ethyl formates of 4- are cooled down and under stirring condition in ice-water bath, by chlorination sulfone (55
Mmol the 1,2- dichloroethanes (100mL) for) being added drop-wise to 3- ethyls -1- methylpyrazoles -5- Ethyl formates (50mmol) are molten
In liquid.Completion of dropping reacts 3-4 hours under counterflow conditions, is extracted with ethyl acetate after reactant liquor cooling, and gained has
Machine phase Jing is washed, and anhydrous sodium sulfate drying, concentrating under reduced pressure obtains title compound 7.9g.
Preparation of the chloro- 3- ethyls -1- methylpyrazoles -5- formic acid of 4- with reference to 3- ethyl -1- methylpyrazole -5- formic acid in embodiment 2
Method, with 4- chlorine 3- ethyl -1- methylpyrazole -5- Ethyl formates 3- ethyl -1- methylpyrazole -5- Ethyl formates are replaced, can be with
Prepare the chloro- 3- ethyls -1- methylpyrazoles -5- formic acid of 4-.
The chloro- 3- ethyls -1- methylpyrazoles -5- formic acid acyl chlorides of 4- is with reference to 3- ethyl -1- methylpyrazole -5- formic acid acyls in embodiment 2
The preparation method of chlorine, with 4- chlorine 3- ethyl -1- methylpyrazole -5- formic acid 3- ethyl -1- methylpyrazole -5- formic acid is replaced, can be with
Prepare the chloro- 3- ethyls -1- methylpyrazoles -5- formic acid acyl chlorides of 4-.
The chloro- 3- ethyls -1- methyl-N- of 4- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (compound in table 1
10) with reference to the preparation method of 3- ethyl -1- methylpyrazole -5- benzoic acid amides in embodiment 2, with 4- chlorine 3- ethyl -1- first
Base pyrazoles -5- formic acid acyl chlorides replaces 3- ethyl -1- methylpyrazole -5- formic acid acyl chlorides, can prepare the chloro- 3- ethyls -1- methyl of 4-
- N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides.
Embodiment 5 this example demonstrates that in table 1 compound 13 and 52 preparation
3- isopropyl -1- methylpyrazole -5- formic acid and 5- isopropyl -1- methylpyrazole -3- formic acid are with reference to 3- second in embodiment 2
The preparation method of base -1- methylpyrazole -5- formic acid, with 3- methyl -2-butanone butanone is replaced, and 3- isopropyl -1- methyl can be obtained
The mixture of pyrazoles -5- formic acid and 5- isopropyl -1- methylpyrazole -3- formic acid.
3- isopropyls -1- methylpyrazoles -5- formic acid acyl chlorides and 5- isopropyl -1- methylpyrazole -3- formic acid acyl chlorides are with reference to embodiment
The preparation method of 3- ethyls -1- methylpyrazoles -5- formic acid acyl chlorides in 2, with above-mentioned 3- isopropyls -1- methylpyrazole -5- formic acid and
The mixture of 5- isopropyl -1- methylpyrazole -3- formic acid replaces 3- ethyl -1- methylpyrazole -5- formic acid, can prepare 3- isopropyls
The mixture of base -1- methylpyrazoles -5- formic acid acyl chlorides and 5- isopropyl -1- methylpyrazole -3- formic acid acyl chlorides.
3- isopropyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (compound 13 in table 1)
With 5- isopropyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -3- benzoic acid amides (compound 52 in table 1)
With reference to the preparation method of 3- ethyl -1- methylpyrazole -5- benzoic acid amides in embodiment 2, with 3- isopropyl -1- methylpyrazole -5-
The mixture of formic acid acyl chlorides and 5- isopropyl -1- methylpyrazole -3- formic acid acyl chlorides replaces 3- ethyl -1- methylpyrazole -5- formic acid acyls
Chlorine, can prepare 3- isopropyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (in table 1
Compound 13) and 5- isopropyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -3- benzoic acid amides (tables 1
Middle compound 52) mixture, Jing column chromatographies (petrol ether/ethyl acetate=10:1～5:1) isolate and purify, respectively obtain
Off-white powder title thing 13 and 52.
Embodiment 6 this example demonstrates that in table 1 compound 24 preparation
Replace butanone with cyclohexanone, with reference to the correlation method in embodiment 2,2- methyl-N- [(2- phenyl thiazoles can be prepared
- 4- bases) methyl] -4,5,6,7- tetrahydrochysene -2H- Yin rattle away azoles -3- benzoic acid amides (compound 24 in table 1).
Other compounds of the invention are referred to embodiment 1 and prepare to embodiment 6 and relevant references method.
The preparation of the cream of embodiment 7
Formula (I) compound of the appropriate present invention is proportionally weighed, pesticide used additives and solvent etc. are put into reactor.First plus
Enter a certain amount of solvent and defoamer and stir 10～30min, add the components such as stabilizer, synergist, continue to stir 10～
30min, then the solvent of effective dose is put in kettle, blowing after stirring.
3- ethyl -1- methyl-the N- of embodiment 8 [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides (are changed in table 1
Compound 7) cream preparation：Weigh formula (I) compound that the present invention of appropriate (by required percentage by weight) is provided：
3- ethyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides, appropriate solvent such as N, N- diformazans
Base Methanamide, acetone, ethyl acetate or dimethylbenzene, appropriate pesticide use emulsifier such as Tween80 and other pesticide
Used additives are put into reactor, are initially charged a certain amount of defoamer and stir 10～30min, add appropriate stabilizer, increase
The components such as effect agent, penetrating agent, continue to stir 10～30min, adjust pH value, then the solvent of effective dose is put in kettle,
Blowing is obtained final product needed for 3- ethyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides after stirring
Percentage by weight cream.
Biological activity determination embodiment
The compounds of this invention is carried out sterilizing and insects mites activity test has been killed, the compound for as a result showing the present invention has had very well
Sterilization and/or kill insects mites activity, part of test results is as follows：
Bactericidal activity (pot-culture method) of the embodiment 9 to wheat powdery mildew (Erisiphe griminis)
Method is as follows：Testing compound is dissolved in suitable solvent such as DMF (DMF), then with containing 0.2%
The sterilized water of Tween80 emulsifying agents is diluted to desired concn；The basin alms bowl of cut-off stem 15cm or so, per alms bowl, sowing Semen Tritici aestivi is satisfied
20 full healthy and strong, seed, is wholeheartedly for experiment afterwards wait two leaves are grown；Take ready wheat seedling plant Jing finite concentrations
Reagent spray process, pathogenic bacteria inoculation is carried out after one day.3 repetitions are often processed, the blank without testing compound is separately set
For blank, commercialization antibacterial Fluoxastrobin is commercial References；The culture of moisturizing thermophilic is checked to blank morbidity
Lesion area, calculates pharmacy control efficacy.Activity in percentage, is divided into A, B, C, D level Four relative to blank,
100%≤Fang Xiao≤90% be A levels, 90% ＞ Fang Xiao≤70% be B levels, 70% ＞ Fang Xiao≤50% be C levels, 50%
＞ Fang Xiao≤0% is D levels.As a result the compound for showing the present invention has prevention effect, and the change having to wheat powdery mildew
Compound still has at very low concentrations very high activity.To compare the compounds of this invention with D2 to wheat powdery mildew
Active height, selection the compounds of this invention 7 is representative, is tested by control of D2, as a result shows of the present inventionization
Compound 7 is much better than activity of the D2 to wheat powdery mildew to the activity of wheat powdery mildew.Partial results are as follows：
Under 500mg/L concentration, the compounds of this invention 1,4,7,8,13,14,23 etc. and Fluoxastrobin are to wheat powdery mildew
With A levels preventing and treating activity；
Under 100mg/L concentration, there is A levels to prevent and treat to wheat powdery mildew for the compounds of this invention 1,7,13 etc. and Fluoxastrobin
Activity；4th, 14 etc. have B levels preventing and treating activity to wheat powdery mildew；9 and 11 etc. there is C levels to prevent and treat to wheat powdery mildew
Activity；
Under 25mg/L concentration, the compounds of this invention 7 and Fluoxastrobin etc. still have A levels preventing and treating activity to wheat powdery mildew；1
Still there is B levels preventing and treating activity to wheat powdery mildew with 13 grades；D2 is B levels to the activity of wheat powdery mildew；
Further to compare activity height of the compounds of this invention with D2 to wheat powdery mildew, the compounds of this invention 7 is selected
To represent, by control of D2 deep screening, partial results such as table 3. are carried out
The prevention effect (%) of the compounds of this invention 7 of table 3 and D2 to wheat powdery mildew
Prevention effect of the embodiment 10 to powdery mildew of cucumber (Sphaerotheca fuliginea)
For further activity of the checking the compounds of this invention to Powdery Mildew, selection the compounds of this invention 7 is representative, with Huang
Melon powdery mildew is target, and Fluoxastrobin is comparison medicament, has carried out the drug effect examination that the compounds of this invention 7 prevents and treats powdery mildew of cucumber
Test.Result of the test shows that the compounds of this invention 7 has excellent prevention effect to powdery mildew of cucumber, and its preventive effect is better than equal
The preventive effect of comparison medicament Fluoxastrobin under dosage.Partial results are as follows：
7 days after 2 medicines, in 225g a.i./hm2、281.25g a.i./hm2、337.5g a.i./hm2Under dosage, the present invention
Compound 718%EC is respectively 82.30%, 85.84% and 87.35% to the prevention effect of powdery mildew of cucumber；Comparison medicine
Agent Fluoxastrobin 250g/L SC are in 281.25g a.i./hm2It is 83.15% to the prevention effect of powdery mildew of cucumber under dosage.
Bactericidal activity (pot-culture method) of the embodiment 11 to botrytis cinerea pers (Botrytis cinerea)
Method：Testing compound is dissolved in suitable solvent such as DMF (DMF), then with containing 0.2%
The sterilized water of Tween80 emulsifying agents is diluted to desired concn；4 repetitions are often processed, the sky without testing compound is separately set
It is in vain blank, commercialization antibacterial Boscalid is commercial References；Gray mold of cucumber opportunistic pathogen is gone to into PDA plate to live
Change and gone in PD culture medium after culture, water bath with thermostatic control culture 4 days；Cultured mycelium pellet refiner is crushed and is used in combination
Clear water is allocated to certain density bacteria suspension；Whne Fructus Cucumidis sativi length to flatten two panels true leaf when, spray the medicinal liquid of testing compound, 1
Bacteria suspension is sprayed after it to seedling surface, moisturizing culture simultaneously observes seedling incidence；When control treatment morbidity is obvious, open
Begin the incidence for recording each process, calculates pharmacy control efficacy.Activity relative to blank in percentage, be divided into A,
B, C, D level Four, 100%≤Fang Xiao≤90% be A levels, 90% ＞ Fang Xiao≤70% be B levels, 70% ＞ Fang Xiao≤50%
For C levels, 50% ＞ Fang Xiao≤0% is D levels.As a result the compound for showing the present invention has preventing and treating effect to gray mold of cucumber
Really, and the compound that has still has at very low concentrations very high activity.To compare the compounds of this invention with D2 to Huang
The activity height of melon gray mold, selection the compounds of this invention 7 is representative, is tested by control of D2, as a result table
Bright the compounds of this invention 7 is much better than activity of the D2 to gray mold of cucumber to the activity of gray mold of cucumber.Partial results are as follows：
Under 500mg/L concentration, the compounds of this invention 1,4,7,20,52 etc. and Boscalid have to gray mold of cucumber
A levels preventing and treating activity, 12,14,30 etc. have B levels preventing and treating activity to gray mold of cucumber；
Under 100mg/L concentration, the compounds of this invention 1,4,7,20 etc. and Boscalid have A levels to gray mold of cucumber
Preventing and treating activity；
Under 25mg/L concentration, the compounds of this invention 1,4,7,20 etc. and Boscalid still have A to gray mold of cucumber
Level preventing and treating activity；
To compare activity height of the compounds of this invention with D2 to botrytis cinerea pers, the compounds of this invention 7 is selected to be generation
Table, by control of D2 deep screening has been carried out, and as a result shows that the compounds of this invention 7 is remote to the activity of botrytis cinerea pers
Better than activity of the D2 to botrytis cinerea pers, partial results such as table 4.
The prevention effect (%) of the compounds of this invention 7 of table 4 and D2 to gray mold of cucumber
Bactericidal activity (pot-culture method) of the embodiment 12 to corn rust (Puccinia Polysora)
Testing compound is dissolved in suitable solvent such as DMF (DMF), then with containing 0.2%Tween80
The sterilized water of emulsifying agent is diluted to desired concn；4 repetitions are often processed, if the blank without testing compound is control,
With D2 as control；Morbidity maize leaf is cut, is washed with 0.05%Tween80 or other suitable surfactant aqueous solutions
Lower spore, and with 2～4 layers of filtered through gauze, concentration is made for 1 × 105The suspension of individual spore/mL；Treat Semen Maydiss length to 2
The heart of leaf 1 sprays the medicinal liquid of testing compound, spore suspension spray inoculation after 1 day, moisturizing cabinet is moved to after inoculation (relative
Humidity more than 95%, 20 DEG C～22 DEG C of temperature), (intensity of illumination 5000Lux～10000Lux) training under low light condition
Support 15～24 hours；When blank disease leaf rate is up to more than 50%, the incidence of each process is investigated, calculate medicament
Preventive effect.Activity in percentage, is divided into A, B, C, D level Four relative to blank, and 100%≤Fang Xiao≤90% is
A levels, 90% ＞ Fang Xiao≤70% is B levels, and 70% ＞ Fang Xiao≤50% is C levels, and 50% ＞ Fang Xiao≤0% is D levels.
As a result show that the compounds of this invention has prevention effect to corn rust, and the compound having still has at very low concentrations
Prevention effect, is listed below partial results：
Under 500mg/L concentration, the compounds of this invention 1,7,9,12,13,20,30,31 and 52 etc. becomes rusty to Semen Maydiss
Disease has A levels preventing and treating activity；6th, 11 and 50 etc. have B levels preventing and treating activity to corn rust；
Under 100mg/L concentration, the compounds of this invention 1 and 13 etc. has A levels activity to corn rust, and 9 and 11 etc. is right
Corn rust has B levels activity, and 30 grades have C levels activity to corn rust, and D2 is to the activity of corn rust less than C
Level；
Under 50mg/L concentration, the grade of the compounds of this invention 13 still has A levels activity to corn rust, and D2 is to corn rust
Activity is not shown.
Bactericidal activity of the embodiment 13 to Sclerotinia sclerotiorum (Sclerotonia sclerotiorum)
Method：Testing compound is dissolved in suitable solvent such as DMF (DMF), then with containing 0.2%
The sterilized water of Tween80 emulsifying agents is diluted to desired concn；The addition of 3mL medicinal liquids is cooled to 45 DEG C 27 are taken with pipet
Culture dish is poured into after shaking up in mL potato agar culture mediums (PDA) and fully；With Inoculating needle from culture 7 after cooling
It Sclerotinia sclerotiorum colony edge takes 6mm diameter mycelia blocks, moves to culture dish central authorities, and mycelia faces down, while
If the blank without testing compound is control, 4 repetitions are often processed；Culture dish is placed in into 28 DEG C of constant temperature after being disposed
Cultivate in biochemical cultivation case, mycelial growth diameter is measured after 4 days, bacterium is analyzed and calculated using EXCEL statistical softwares
Silk growth inhibition ratio (%).Simultaneously with D2 as control.Activity relative to blank in percentage, be divided into A, B,
C, D level Four, 100%≤Fang Xiao≤90% be A levels, 90% ＞ Fang Xiao≤70% be B levels, 70% ＞ Fang Xiao≤50%
For C levels, 50% ＞ Fang Xiao≤0% is D levels.As a result show that the compounds of this invention has to Sclerotinia sclerotiorum substantially living
Property.Partial results are listed below：
Under 25mg/L concentration, the compounds of this invention 4,13,31 and 52 etc. has A levels activity to Sclerotinia sclerotiorum,
9th, 10,27 and 35 etc. have B levels activity to Sclerotinia sclerotiorum, and D2 is to the active less than 20% of Sclerotinia sclerotiorum.
Evaluated biological activity of the embodiment 14 to mythimna separata (Mythimna separata)
Potter nebulizations：Testing compound is dissolved in suitable solvent as in DMF (DMF), then with containing
The clear water of 0.2%Tween80 emulsifying agents is diluted to desired concn, if the blank without testing compound is control.Take fresh and tender
Leaf of Semen Maydis be cut into the basically identical fragment of size, be put into and be lined with advance in the culture dish of filter paper (Ф 90mm).Then exist
3 instar larvae of mythimna separata 10 is accessed in ware, being put under Potter spray towers carries out metered dose, spray liquid measure 1ml, per dense
3 repetitions of degree.It is disposed, covers ware lid, be placed in recovery indoor cultivation, routine observation was checked after 72 hours
And test worm death condition is recorded, calculate mortality rate, results averaged.As a result show that the compounds of this invention has to mythimna separata
Remarkable activity, such as under 500mg/L concentration, the compounds of this invention 7 and 10 etc. has 100% activity to mythimna separata.
Insecticidal Activity of the embodiment 15 to aphid (Aphis fabae)
To evaluate activity of the compounds of this invention to homoptera pest, selection aphid is object, is surveyed using infusion process indoors
Activity of the compounds of this invention to aphid is determined.
Infusion process：Testing compound is dissolved in suitable solvent such as DMF (DMF), then with containing 0.2%
The clear water of Tween80 emulsifying agents is diluted to desired concn, if the blank without testing compound is control, often processes 3 times
Repeat.Black bean aphid is connected on just unearthed bean seedlings, per plant connects more than 20, is then dipped in bean seedlings together with test worm
In formula (I) medicinal liquid that the present invention is provided, take out after 5 seconds, suck unnecessary medicinal liquid, in inserting the sponge of water suction, use glass
Shroud is lived, and survival and dead borer population, results averaged are checked after 24 hours.Active (mortality rate) is right relative to blank
According in percentage, being divided into A, B, C, D level Four, 100%≤Fang Xiao≤90% is A levels, 90% ＞ Fang Xiao≤70%
For B levels, 70% ＞ Fang Xiao≤50% is C levels, and 50% ＞ Fang Xiao≤0% is D levels.As a result the compounds of this invention pair is shown
Aphid is active, and the compound having still has at very low concentrations high activity, and partial results are listed below：
Under 500mg/L concentration, the compounds of this invention 1,4,6,7,9,10,11,12,13,20,24 and 50
Deng aphid is had A levels activity；8th, 14,23 and 25 etc. have B levels activity to aphid；
Under 50mg/L concentration, the compounds of this invention 4,6,7,9,10 and 11 etc. is respectively provided with A levels activity to aphid；
Under 12.5mg/L concentration, the grade of the compounds of this invention 10 still has A levels activity to aphid.
Acaricidal activity evaluation of the embodiment 16 to two-spotted spider mite (Tetranychus urticae)
Method：Testing compound is dissolved in suitable solvent such as DMF (DMF), then with containing 0.2%
The water of Tween80 emulsifying agents is diluted to desired concn, if the blank without testing compound is blank, often processes 3
Secondary repetition；The bean seedlings inoculation red spider that selection is grown fine, there is 100-200 demodicid mite on every plant of bean seedlings, treat that red spider colonizes
Afterwards, band demodicid mite bean seedlings are cut and is impregnated 10 seconds in the medicinal liquid of formula (I) compound that the present invention for preparing is provided, take out
Unnecessary medicinal liquid is sucked with filter paper, is inserted in and is filled with water in beaker, in observation indoor cultivation, survival and death are checked after 48 hours
Demodicid mite number, results averaged.As a result the compound for showing the present invention has remarkable activity to red spider, and such as 500mg/L is dense
Under degree, the compounds of this invention 6,7,14,24 and 52 etc. has A levels activity, 1,12,13,35 and to red spider
50 grades have B levels activity to red spider.
Claims (10)
1. pyrazol acid amide compounds, it is characterised in that represent pyrazol acid amide compounds with logical formula (I)：
Wherein：
R represents C1-C12Alkyl, C2-C12Alkenyl, C2-C12Alkynyl group, C3-C8Cycloalkyl or phenyl；
R1Represent C1-C12Alkyl, C2-C12Alkenyl, C2-C12Alkynyl group, C3-C8Cycloalkyl or phenyl；
R2Represent hydrogen, halogen, C1-C12Alkyl, C2-C12Alkenyl, C2-C12Alkynyl group or C3-C8Cycloalkyl；
R、R1And R2Middle hydrogen atom partly or entirely can be selected from it is following in identical or different substituent group replace：Halogen,
C1-C6Alkyl, C1-C6Alkoxyl, C1-C6Alkylthio group, C1-C6Alkyl amine group, C2-C6Alkenyl, C2-C6Alkenyl oxy,
C2-C6Alkenyl thio, C2-C6Alkenyl amido, C2-C6Alkynyl group, C2-C6Alkynyl group epoxide, C2-C6Alkynyl group sulfenyl,
C2-C6Alkynyl group amido, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3-C8Cycloalkylsulfanyl, C3-C8Cycloalkyl amido,
C6-C12Aryl or the band up to heteroaryl of 10 carbon atoms, C6-C12The heteroaryl of aryloxy or band up to 10 carbon atoms
Epoxide, C6-C12Artyl sulfo or the band up to Heteroarylthio of 10 carbon atoms, C6-C12Up to 10, arylamine group or band
The heteroaryl amido of carbon atom, C6-C12Aryl or the band up to Heteroarylaryl of 10 carbon atoms, C6-C12Aryl heteroaryl
The heteroarylheteroaryl of base or band up to 10 carbon atoms；
R1And R2Can be connected to each other, with two carbon of pyrazole ring C is formed4-C8Cycloalkanes；
W represents oxygen or sulfur；
And R=R1=CH3, during W=O, R2H is not represented；
In the definition of compound (I) given above, no matter term used is used alone also being used in compound word, represent as follows
Substituent group：
Halogen：Refer to fluorine, chlorine, bromine, iodine；
Alkyl：Refer to straight or branched alkyl；
Haloalkyl：Refer to straight or branched alkyl, hydrogen moiety on these alkyl or all replaced by halogen atom；
Cycloalkyl：Refer to saturation or unsaturation ring alkyl；
Heterocyclylalkyl：Refer to saturation or unsaturated heterocycle alkyl, at least 1 N, O and/or S in formula；
Halogenated cycloalkyl：Refer to saturation or unsaturation ring alkyl, and hydrogen moiety therein or all replaced by halogen atom；
Alkenyl；Refer to straight or branched alkyl, and double bond can be there are on any position；
Halogenated alkenyl：Refer to straight or branched alkyl, and double bond, and hydrogen moiety therein can be there are on any position
Or all replaced by halogen atom；
Alkynyl group；Refer to straight or branched alkyl, and three keys can be there are on any position；
Halo alkynyl：Refer to straight or branched alkyl, and three keys can be there are on any position, and hydrogen moiety therein or
All replaced by halogen atom；
C6-C12Aryl means phenyl and by its derivative naphthyl, xenyl, anthryl or phenanthryl；
The heteroaryl of band up to 10 carbon atoms refers to thiazolyl, pyrazolyl, thiadiazolyl group, pyridine radicals, thienyl, benzothiophene
Base, furyl, benzofuranyl, pyrrole radicals, benzopyrrole base, indyl, benzindole base, imidazole radicals, benzimidazole
Base, quinolyl, pyranose, pyrazinyl, pyrimidine radicals, pyridazinyl, benzopyranyl, benzopyrazines base, benzo pyrimidine radicals,
Benzo pyridazinyl ， oxazolyl ， isoxazolyls, benzoxazolyl, benzoisoxazole base, benzothiazolyl, isothiazolyl, benzene
And isothiazolyl or pyrimido triazolyl.
2. pyrazol acid amide compounds according to claim 1, it is characterised in that in compound shown in logical formula (I)：
R represents C1-C12Alkyl or phenyl；R1Represent C1-C12Alkyl；R2Represent hydrogen, halogen or C1-C12Alkyl；And R,
R1And R2Middle hydrogen atom partly or entirely can be selected from it is following in identical or different substituent group replace：Halogen, C1-C6Alkane
Base, C1-C6Alkoxyl；R1And R2Can be connected to each other, with two carbon of pyrazole ring C is formed5-C6Cycloalkane structure；W generations
Epoxy or sulfur.
3. pyrazol acid amide compounds according to claim 1, it is characterised in that in compound shown in logical formula (I)：
R represents C1-C6Alkyl；R1Represent C1-C6Alkyl；R2Represent hydrogen, halogen, C1-C6Alkyl；And R, R1And R2
Middle hydrogen atom partly or entirely can be selected from it is following in identical or different substituent group replace：Halogen, C1-C3Alkyl, C1-C3
Alkoxyl；W represents oxygen.
4. pyrazol acid amide compounds according to claim 1, it is characterised in that in compound shown in logical formula (I)：
R represents methyl or ethyl；R1Represent C1-C6Alkyl；R2Represent hydrogen, halogen, C1-C3Alkyl；And R, R1And R2
Middle hydrogen atom partly or entirely can be selected from it is following in identical or different substituent group replace：Halogen, methyl, ethyl, first
Epoxide；W represents oxygen.
5. pyrazol acid amide compounds according to claim 1, it is characterised in that compound shown in logical formula (I) is：
1,3- dimethyl-N -s [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
1,3,4- trimethyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
The chloro- 1,3- dimethyl-N -s of 4- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
3- ethyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
3- ethyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- carbothioic acid amides；
3- ethyl -1,4- dimethyl-N -s [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
The chloro- 3- ethyls -1- methyl-N- of 4- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
The bromo- 3- ethyls -1- methyl-N- of 4- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
1- methyl -3- propyl group -- N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
3- isopropyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
3- cyclopropyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
3- butyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
2- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -2,4,5,6- tetrahydro cyclopentyls alkane simultaneously [c] pyrazoles -3- benzoic acid amides；
2- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -4,5,6,7- tetrahydrochysene -2H- Yin rattle away azoles -3- benzoic acid amides；
1- ethyl -3- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
The chloro- 1- ethyls -3- methyl-N- of 4- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
The chloro- 1,3- diethyl-N- of 4- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
3- methyl isophthalic acids-phenyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
3- methyl isophthalic acids-(4- chlorphenyls)-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -5- benzoic acid amides；
1- methyl -5- propyl group-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -3- benzoic acid amides；
5- isopropyl -1- methyl-N- [(2- phenyl thiazole -4- bases) methyl] -1H- pyrazoles -3- benzoic acid amides.
6. the preparation method of pyrazol acid amide compounds according to claim 1, it is characterised in that the change shown in formula (I)
Compound is prepared by reaction shown below,
Reaction equation 1：
Reaction equation 2：
Reaction equation 3：
Reaction equation 4：
In solvents tetrahydrofurane, acetonitrile, dichloromethane, dichloroethanes, toluene or dimethylbenzene, in -10 DEG C～system backflow temperature
Degree, in no alkali or in the presence of triethylamine, pyridine, sodium hydride, sodium hydroxide, potassium hydroxide, with formula (II W=O) institute
Compound reaction shown in the compound for showing and formula (III), obtains formula (I W=O) compound, adds catalyst 4- dimethylamino
Pyridine can accelerate reaction to carry out；Compound Jing sulfide P shown in formula (I W=O)2S5Process to obtain formula (I W=S) compound
(reaction equation 1)；
Solvent-free or in solvent dichloroethanes, dichloromethane or toluene, in 15 DEG C～system reflux temperature, with formula (IV W=O)
Shown compound and react to obtain formula (II W=O) compound (reaction equation 2) with halide reagent thionyl chloride, phosgene or oxalyl chloride；
In the mixture of etoh solvent, tetrahydrofuran or ethanol and tetrahydrofuran, in 25 DEG C～system reflux temperature, 1.3 2
Chlroacetone or 1.3 dibromoacetones and Aminothiocarbonylbenzene react to obtain 4- chloromethyl -2- phenyl thiazoles；4- chloromethyl -2- phenyl thiazoles are used
Ammonia treatment or 4- chloromethyl -2- phenyl thiazoles are processed with the solid thing product hydrazine hydrate of potassium phthalimide reaction gained and obtain final product formula
(III) compound (reaction equation 3)；
In etoh solvent, methanol, propanol, butanol or water, in the presence of alkali Sodium ethylate, Feldalat NM or sodium hydroxide, in -15 DEG C～
System reflux temperature, is reacted with the compound shown in formula (V) or (V ') and ethyl oxalate, obtains formula (VI) or (VI ')
Shown compound；The compound of formula (VI) or (VI ') Jing after conventional post processing, then with hydrazine hydrate cyclization, obtain formula (VII)
Or the compound of (VII ')；In solvent DMF, under the conditions of 30 DEG C～100 DEG C, formula (VII) or (VII ')
Compound and alkylating reagent dimethyl sulfate, dithyl sulfate or iodomethane reaction obtain formula (VIII) or (VIII ') chemical combination
Thing；Or the compound of formula (VI) or (VI ') is Jing after conventional post processing, with replacement hydrazine cyclization, formula (VIII) or (VIII ') are obtained
Compound；Compound Jing respective reactions shown in (VIII ') obtain the compound shown in formula (VIII)；In aqueous solvent, ethanol, first
In the single solvent or water of alcohol and the mixed solvent of ethanol, water and methanol, in the presence of alkali sodium hydroxide or potassium hydroxide, in
Under 50 DEG C～system reflux temperature, (VIII) compound processes to obtain formula (IV) Jing after routine hydrolysis reaction with dilute hydrochloric acid solution
Compound (reaction equation 4)；
R, R in formula1、R2, W have given in claim 1 define, Z is leaving group chlorine or bromine.
7. the purposes of the pyrazol acid amide compounds according to any one of Claims 1 to 5, it is characterised in that 15～5000
There is sterilization, parasite killing or mite killing biological activity under gram effective ingredient/hectare consumption.
8. the pyrazol acid amide compounds according to any one of Claims 1 to 5 are used to prepare with sterilization, parasite killing or mite killing
The purposes of the medicine of activity.
9. a kind of sterilization, parasite killing or miticide composition, it is characterised in that：Containing as active component such as Claims 1 to 5
Pyrazol acid amide compounds described in any one, the weight percentage of active component is 0.5-99% in compositionss.
10. a kind of preventing and treating pathogen, the method for insect or evil mite, it is characterised in that：Effective dose such as Claims 1 to 5 is appointed
Pyrazol acid amide compounds described in one are imposed on the pathogen, insect, evil mite or its somatomedin.
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