CN106187936B - Acrylonitrile compound and application thereof - Google Patents
Acrylonitrile compound and application thereof Download PDFInfo
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- CN106187936B CN106187936B CN201510228782.9A CN201510228782A CN106187936B CN 106187936 B CN106187936 B CN 106187936B CN 201510228782 A CN201510228782 A CN 201510228782A CN 106187936 B CN106187936 B CN 106187936B
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- BNJIEXPNNOUZHP-UHFFFAOYSA-N CCCCC(CC(CN=C)=C)C(C)(C)C Chemical compound CCCCC(CC(CN=C)=C)C(C)(C)C BNJIEXPNNOUZHP-UHFFFAOYSA-N 0.000 description 1
- 0 CCOC(C(C(C)(C)[Fl]=C1C)=C1Cl)=O Chemical compound CCOC(C(C(C)(C)[Fl]=C1C)=C1Cl)=O 0.000 description 1
Abstract
The invention discloses acrylonitrile compounds and the preparation method and application thereof shown in formula (I).Ar in formula1、Ar2、R、R1、R2, X, Y and n have specification given in define.Formula (I) compound of the present invention has desinsection, mite killing or sterilization bioactivity, especially has very high activity to for example red spider of pest such as aphid, mythimna separata and evil mite and disease such as corn rust and rice sheath blight disease etc..
Description
Technical field
The invention belongs to kill insects mites, fungicide field, and in particular to have the vinyl cyanide for killing insects mites, sterilizing bioactivity
Compound and preparation method thereof, containing the compound kill insects mites, microbicide compositions and with these compounds control
Evil insects mites, the purposes of harmful levels of pathogens and method.
Background technology
Acrylonitrile compound, which has, kills insects mites activity, and three acrylonitrile compounds are by success shown in D1~D3
To kill insects mites agent, D2 and D3 have visibly different structure feature compared with D1 for exploitation.Thiapronil is in 600mg/L shown in D1
Under concentration, the activity to aphid, Tetranychus cinnabarinus and mythimna separata is respectively 95.1%, 70.6% and 100%【Finely with special chemistry
Product.2012,20 (1), p45-47】；Cyenopyrafen shown in D2 has excellent activity to mite, and is significantly higher than thiapronil；
NC510 shown in D3 has excellent activity to aphid, and is significantly higher than thiapronil.Acrylonitrile compound honeybee multipair greatly and fish
Equal non-target organisms safety.
High efficiency, highly selective, high Environmental compatibility and economy are the characteristics of modern should have.To be lived
The wider and/or more economical acrylonitrile compound of property higher, activity profile, inventor draw the hetero atoms such as sulphur, halogen, nitrogen or oxygen
Enter in acrylonitrile structure, designs and synthesizes and a series of have no document report and with killing the propylene of the broad spectrum of activity such as insects mites, sterilization
Nitrile compounds.Compared with D1~D3, the compounds of this invention has more wide spectrum and efficient bioactivity.
Invention content
The present invention provides the acrylonitrile compounds shown in formula (I) with bioactivity such as evil insects mites, harmful levels of pathogens
And its isomers：
Wherein：
I.Ar1And Ar2It is same or different, and represents
a)C6-C12The heteroaryl of up to 10 carbon atoms of aryl or band, or
B) such as in I.a) in identified meaning, wherein some or all of hydrogen atom can by identical in following or
Different substituent group substitutions：Halogen, nitro, cyano, C1-C12Alkyl, C1-C12Alkoxy, C1-C12Alkylthio group, C1-C12Alcoxyl carbonyl
Base, C1-C12Alkyl carbonyl epoxide, C1-C12Alkyl amine group, C2-C12Alkenyl, C2-C12Alkenyl oxy, C2-C12Alkenyl sulphur
Base, C2-C12Alkenyloxycarbonyl, C2-C12Alkenyl amido, C2-C12Alkynyl group, C2-C12Alkynyl group oxygroup, C2-C12Alkyne
Base sulfenyl, C2-C12Alkynyl group Epoxide carbonyl, C2-C12Alkynyl group amido, C3-C8Naphthenic base, C3-C8Cycloalkyl oxy, C3-C8Ring
Alkyl sulfenyl, C3-C8Cycloalkyloxycarbonyl, C3-C8Naphthenic base amido, C6-C12The heteroaryl of up to 10 carbon atoms of aryl or band
Base, C6-C12The heteroaryl oxygroup of up to 10 carbon atoms of aryloxy or band, C6-C12Artyl sulfo or band up to 10 carbon originals
Heteroarylthio, the C of son6-C12Heteroaryloxycarbonyl, the C of up to 10 carbon atoms of aryloxycarbonyl or band6-C12Aryl
The heteroaryl amido, C of up to 10 carbon atoms of amido or band6-C12The heteroaryl virtue of up to 10 carbon atoms of aryl or band
Base, C6-C12The heteroarylheteroaryl of up to 10 carbon atoms of aryl heteroaryl or band；
C) such as in I.b) in identified meaning, wherein some or all of hydrogen atom can by identical in following or
Different substituent group substitutions：Halogen, nitro, cyano, C1-C12Alkyl, C1-C12Halogenated alkyl, C1-C12Alkoxy, C1-C12It is halogenated
Alkoxy, C1-C12Alkyloxycarbonyl, C1-C12Alkyl amine group, C2-C12Alkenyl, C2-C12Halogenated alkenyl, C2-C12Alkene
Base oxygroup, C2-C12Alkynyl group, C2-C12Haloalkynyl group, C2-C12Alkynyl group oxygroup, C3-C8Naphthenic base, C3-C8Halogenated cycloalkanes
Base, C3-C8Cycloalkyl oxy, C6-C12Heteroaryl, the C of up to 10 carbon atoms of aryl or band6-C12Aryloxy or band up to 10
The heteroaryl oxygroup of a carbon atom；
II.R and R1、R2It is same or different, and represents hydrogen, C1-C12Alkyl, C1-C12Halogenated alkyl, C2-C12Alkene
Base, C2-C12Halogenated alkenyl, C2-C12Alkynyl group, C2-C12Haloalkynyl group, C3-C8Naphthenic base, C3-C8Halogenated cycloalkyl, C6-
C12Heteroaryl, the C of up to 10 carbon atoms of aryl or band6-C12The haloheteroaryl of up to 10 carbon atoms of halogenated aryl or band；
III.X represents S, halogen, SO, SO2, O, NH or NHC1-C3Alkyl；
IV.Y represents O or S；
V.n represents 0,1 or 2；
And R1=R2=CH3, n=1, X=Cl or R1=R2=H, n=0, when X=Cl, Ar2Following substituent group is not represented：
In the definition of compound (I) given above, no matter term used exclusive use is also used in compound word, represent
Following substituent group：
Halogen：Refer to fluorine, chlorine, bromine, iodine；
Alkyl：Refer to linear or branched alkyl group；
Halogenated alkyl：Refer to linear or branched alkyl group, hydrogen moiety on these alkyl or is all replaced by halogen atom；
Naphthenic base：Refer to saturation or unsaturation ring alkyl；
Halogenated cycloalkyl：Refer to saturation or unsaturation ring alkyl, and hydrogen moiety therein or is all replaced by halogen atom；
Alkenyl；Refer to linear or branched alkyl group, and can in any position on there are double bonds；
Halogenated alkenyl：Refer to linear or branched alkyl group, and can in any position on there are double bond, and hydrogen atom therein
Partly or entirely replaced by halogen atom；
Alkynyl group；Refer to linear or branched alkyl group, and can in any position on there are three keys；
Halo alkynyl：Refer to linear or branched alkyl group, and can in any position on there are three keys, and hydrogen atom portion therein
Divide or is all replaced by halogen atom；
C6-C12Aryl means phenyl and by its derivative cyclophane base or polyaromatic, such as naphthalene, xenyl；
The heteroaryl of up to 10 carbon atoms of band refers to a ring heteroaryl or polyheteroaromatic, at least 1 N in formula, O and/
Or S, such as thiazolyl, pyrazolyl, thiadiazolyl group, pyridyl group, thienyl, benzothienyl, furyl, benzofuranyl, pyrroles
Base, benzopyrrole base, indyl, benzindole base, imidazole radicals, benzimidazolyl, quinolyl, pyranose, pyrazinyl, pyrimidine
Base, pyridazinyl, benzopyranyl, benzopyrazines base, benzo pyrimidine radicals, benzo pyridazinyl , oxazolyl , isoxazolyls, Ben Bing Evil
Oxazolyl, benzoxazine, benzothiazolyl, isothiazolyl, benzisothia oxazolyl, pyrimido triazolyl.
Currently preferred compound is compound shown in formula (I), wherein：
Ar1Represent Ar1- 1 or Ar1-2；Ar2Represent Ar2-1、Ar2-2、Ar2- 3 or Ar2-4；R and R1、R2It is identical or not
With, and represent hydrogen, C1-C12Alkyl, C2-C12Alkenyl, C2-C12Alkynyl group, C3-C8Naphthenic base, phenyl, halogenophenyl, C1-
C6Alkyl phenyl, C1-C6Haloalkylphenyl；X represents S or chlorine；Y represents oxygen；N represents 0 or 1；
Ar1And Ar2Middle R ', R3~R9It is same or different, and represents hydrogen, halogen, C1-C12Alkyl, C1-C12It is halogenated
Alkyl, C1-C12Alkoxy, C1-C12Alkylthio group, C1-C12Alkylamino radical, C1-C12Halogenated alkoxy, phenyl, halogenophenyl, C1-C6Alkane
Base phenyl, C1-C6Haloalkylphenyl；Z represents S or O.
The further preferred compound of the present invention is compound shown in formula (I), wherein：
Ar1Represent Ar1- 1a or Ar1-2；Ar2Represent Ar2-1a、Ar2-2a、Ar2- 3 or Ar2-4；R and R1、R2It is identical
Or it is different, and represent hydrogen, C1-C6Alkyl, C1-C6Halogenated alkyl；X represents S or chlorine；Y represents oxygen；N represents 0 or 1；
Ar1And Ar2Middle R ', R3~R9It is same or different, and represents hydrogen, halogen, C1-C6Alkyl, C1-C6Alkoxy,
C1-C6Halogenated alkyl；Z represents S or O.
Compound specifically preferred according to the invention is compound shown in formula (I), wherein：
Ar1Represent Ar1- 1a or Ar1-2；Ar2Represent Ar2-1a、Ar2-2a、Ar2- 3 or Ar2-4；R and R1、R2It is identical
Or it is different, and represent hydrogen or C1-C6Alkyl；X represents S or chlorine；Y represents oxygen；N represents 0 or 1；
Ar1Middle R ' represents hydrogen, tertiary butyl, and Z represents S；Ar2Middle R3~R9Same or different, and represent hydrogen, halogen,
C1-C6Alkyl, C1-C6Alkoxy, trifluoromethyl.
Specifically preferred formula (I) compound is the Z-type of following compounds, E types or Z-type and any ratio of E types to the present invention
Mixture：
(Z) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2-
Methylmercaptan ethyl acid esters；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2-
Methylmercaptan ethyl acid esters；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2-
Methyl mercapto propionic ester；
(Z) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2-
Methyl mercapto propionic ester；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2-
Ethylmercapto group propionic ester；
(Z) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2-
Ethylmercapto group propionic ester；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2-
Rosickyite base propionic ester；
(Z) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2-
Rosickyite base propionic ester；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2-
Methyl -3- methyl mercapto propionic esters；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2,4- dimethylthiazole -5- bases) vinyl 2- methyl mercaptos
Propionic ester；
(Z) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2,4- dimethylthiazole -5- bases) vinyl 2- methyl mercaptos
Propionic ester；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2,
2- dimethyl -3- chloropropionates；
(Z) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2,
2- dimethyl -3- chloropropionates；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2-
Bromo-propionic acid ester；
(Z) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2-
Bromo-propionic acid ester；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (the chloro- 4- methylthiazols -5- bases of 2-) vinyl 2,2- diformazans
Base -3- chloropropionates；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- trifluoromethyls) vinyl 2- methyl mercapto propionic acid
Ester；
(Z) -2- cyano -2- (4- tert-butyl-phenyls) -1- (1,3,4- trimethyl -1H- pyrazoles -5- bases) vinyl 2- first sulphur
Base propionic ester；
(E) -2- cyano -2- (4- tert-butyl-phenyls) -1- (1,3,4- trimethyl -1H- pyrazoles -5- bases) vinyl 2- first sulphur
Base propionic ester；
(E) -2- cyano -2- (4- tert-butyl-phenyls) -1- (1,3,4- trimethyl -1H- pyrazoles -5- bases) vinyl 2,2- bis-
Methyl -3- methyl mercapto propionic esters；
(E) -2- cyano -2- (4- tert-butyl-phenyls) -1- (1- ethyl -3- methyl-1 H- pyrazoles -5- bases) vinyl 2- first
Thiohydracrylic acid ester；
(E) -2- cyano -2- (4- tert-butyl-phenyls) -1- (1- ethyl -3- methyl-1 H- pyrazoles -5- bases) vinyl 2- second
Thiohydracrylic acid ester；
(E) -2- cyano -2- (4- tert-butyl-phenyls) -1- (the chloro- 1H- pyrazoles -5- bases of 1- ethyl -3- methyl -4-) vinyl
2,2- dimethyl -3- methyl mercapto propionic esters；
(E) -2- cyano -2- (4- tert-butyl-phenyls) -1- (the chloro- 1H- pyrazoles -5- bases of 1,3- dimethyl -4-) vinyl 2-
Methyl mercapto propionic ester；
(Z) -2- cyano -2- (4- tert-butyl-phenyls) -1- (the chloro- 1H- pyrazoles -5- bases of 1,3- dimethyl -4-) vinyl 2-
Methyl mercapto propionic ester；
(E) -2- cyano -2- (4- tert-butyl-phenyls) -1- (the chloro- 1H- pyrazoles -5- bases of 1- ethyl -3- methyl -4-) vinyl
2- methyl mercapto propionic esters；
(E) -2- cyano -2- (4- tert-butyl-phenyls) -1- (the chloro- 1H- pyrazoles -5- bases of 1,3- dimethyl -4-) vinyl 2,
2- dimethyl -3- chloropropionates；
(Z) -2- cyano -2- (4- tert-butyl-phenyls) -1- (the chloro- 1H- pyrazoles -5- bases of 1,3- dimethyl -4-) vinyl 2,
2- dimethyl -3- chloropropionates.
The compound of the present invention can exist in the form of one or more isomers.Isomers includes enantiomter, non-
Enantiomter, geometric isomer.Formula (I) compound represented of the present invention, since carbon-to-carbon double bond therein connects different take
Geometric isomer can be formed for base, respectively with Z and E come to indicate different configurations, the present invention include Z-type isomers and E types
The mixture of isomers and their any ratios.Formula (I) compound represented of the present invention, due to connecting on wherein same carbon atom
It connects four different substituent groups and forms stereoisomer, respectively with R and S come to indicate different configurations, the present invention include that R types are different
The mixture of structure body and S types isomers and R isomers and any ratio of S isomers.
The invention further relates to a kind of pest control/mite, formula (I) compounds containing biologic effective dose of harmful levels of pathogens and extremely
A kind of few other composition selected from surfactant, solid diluent and liquid diluent.
The invention further relates to a kind of pest control/mite, harmful levels of pathogens formula (I) compound containing biologic effective dose and have
The composition of at least one other bioactive compound or preparation of effect amount.
Include changing the formula (I) of biologic effective dose the invention further relates to a kind of pest control/mite, the method for harmful levels of pathogens
Close object contact evil insects mites, harmful levels of pathogens or its environment.Such a harmful insects mites, harmful levels of pathogens control method are also related to,
Evil insects mites, formula (I) compound of harmful levels of pathogens or its environment biologic effective dose contain formula (I) compound and biologically effective
The mixture of at least one other compound or preparation of amount, which is contacted, comes pest control/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/mite, it may also be used for
Prevent harmful levels of pathogens.And the compound having has very high bioactivity to certain harmful insects mites and/or harmful levels of pathogens so that
It is obtained with good effect at very low concentrations.
Currently preferred composition is the composition containing above-mentioned preferred compound.It is preferable that with above-mentioned excellent
The method for selecting compound.
It is further illustrated the present invention below with the part formula (I) compound listed in 1~table of table 2, but does not limit this
Invention.Fusing point given in the present invention is not calibrated；When formula (I) compound synthesized by the present invention is viscous solid, some are viscous
Property solid refrigerator place after can be cured as non-tacky solids；All compounds are in LC-MS (APCI, Pos) (Agilent in table 1
1100Series LC/MSD) in its molecular ion peak can be observed；Compound in table 11H NMR(Varian INOVA-
Internal standard, deuterochloroform (CDCl 300spectrometer) are made with tetramethylsilane (TMS)3) or deuterated dimethyl Asia
Sulfone (DMSO) makees solvent.
Table 1
*E indicates that E-isomer, Z indicate Z-type isomers
Table 2
Formula (I) compound represented of the present invention can be obtained by reaction equation 1 shown below；(II) in reaction equation 1
It can be obtained by reaction equation 2 shown below, (III) in reaction equation 1 can be obtained by reaction equation 3 shown below.
Substituent group is outer unless specified otherwise in reaction equation 1 to reaction equation 3 limits as preceding.
Reaction equation 1：
Reaction equation 2：
Reaction equation 3：
The compound of formula (I) can be prepared in this way：In suitable solvent such as tetrahydrofuran, dichloromethane, toluene, dichloro
In ethane or chloroform, in 0~60 DEG C, in suitable alkali such as triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid
It in the presence of potassium or sodium bicarbonate, is reacted, is obtained shown in formula (I) with formula (II) compound represented and formula (III) compound represented
Compound (reaction equation 1).
The compound of formula (II) can be prepared in this way：In suitable solvent such as normal heptane, normal hexane, thiacyclohexane, oil
In ether, tetrahydrofuran, toluene, dichloromethane or dichloroethanes, under reaction system reflux temperature, in suitable alkali such as methanol
In the presence of sodium, sodium ethoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium carbonate or carbonic acid, it is added or is added without glycol ether,
With the compound reaction of the compound and formula (V) of formula (IV), acidification obtains the compound (2-1) of formula (II)；
Or in suitable solvent such as tetrahydrofuran, toluene, dichloromethane or dichloroethanes, in -10.0 DEG C~room temperature,
In the presence of appropriate base such as potassium tert-butoxide, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide, sodium carbonate or carbonic acid, formula is used
(IV) the compound reaction of compound and formula (VI), acidification obtain the compound (2-2) of formula (II).
The compound of formula (III) can be prepared in this way：Suitable solvent for example chloroform, toluene, dichloromethane or
In dichloroethanes, formula (VII) compound represented and acylating reagent such as thionyl chloride, phosgene, oxalyl chloride or phosphorus trichloride etc. are anti-
It should be up to compound (reaction equation 3) shown in formula (III)；
Specific synthetic method has more detailed elaboration in the following embodiments.
Formula (I) compound provided by the invention under 15~2250 grams of active ingredients/hectare dosage there is broad-spectrum biological to live
Property, can be not only used for pest control/mite, it may also be used for prevention harmful levels of pathogens, some compounds have well evil insects mites and/or
Harmful levels of pathogens preventive and therapeutic effect is obtained with good effect at very low concentrations.
Formula (I) compound provided by the invention, with bioactivity and the compound that has is with good bioactivity.It is special
Be not agricultural, gardening, flowers and sanitary insect pest, germ prevention in terms of show activity.Harmful organism packet described here
It includes, but is not limited only to this, also never limit the present invention.
Pest, evil mite：
Homoptera pest such as leafhopper, plant hopper, aphid, lepidoptera pest for example oriental armyworm, snout moth's larva, prodenia litura, diamondback moth,
Beet armyworm, cabbage looper, cabbage caterpillar etc., Hymenoptera pest such as sawfly larva etc., Diptera pest such as yellow-fever mosquito, culex, fly etc.,
Acarina such as cotton spider mites, Zhu disturb by making noise tetranychid, the full melon mite of citrus, Shenmu-Yanan railway, apple tetranychus, citrus rust mite, Rhizoglyphus hyacinthi, 2 points
Tetranychid etc..
Particularly, lead to formula (I) compound to homoptera pest such as aphid, plant hopper etc. and lepidoptera pest such as mythimna separata etc.,
Still there is activity well under low concentration.
Harmful disease：
Oomycetes diseases, such as downy mildew, white rust, samping off, pythium rot, epidemic disease, late blight；
Fungi Imperfecti disease, as droop, root rot, damping-off, anthracnose, verticillium wilt, scab, gray mold, brown spot,
Black spot, spot blight, early blight, ring spot, leaf blight, base rot disease etc.；
Load fungus diseases, such as rust, smut；
Sac fungus disease, such as powdery mildew, sclerotiniose (flax sclerotiniose, sclerotinia sclerotiorum, soybean sclerotinia crown rot, peanut sclerotium
Disease, tobacco sclerotiniose, capsicum sclerotiniose, eggplant sclerotiniose, bean sclerotinia rot, pea sclerotiniose, cucumber timberrot, balsam pear sclerotium
Disease, wax gourd sclerotinia, watermelon sclerotiniose, celery sclerotiniose), scab etc.；
Particularly, the compounds of this invention still has corn rust, rice sheath blight disease etc. under low concentration and lives well
Property.
Due to its positive characteristic, above compound is advantageously used for protection agricultural and the important crop of horticulture, family
Injury of the environment that poultry and breeding stock and the mankind often go from evil insects mites, germ.
To obtain ideal effect, the dosage of compound changes because of various factors, for example, compound used therefor, pre- protection,
Type, gradient of infection, weather conditions, application method, the dosage form of use of harmful organism.
The invention also includes kill insects mites, bactericidal composition as active component using logical formula (I) compound.The desinsection/
The weight percentage of active component is between 0.5-99% in mite, bactericidal composition.This is killed in insects mites, bactericidal composition also
Including acceptable carrier in agricultural, forestry, health.
It is effective to control evil insects mites, germ, they can also be with when formula (I) compound of the present invention is used alone
Other biological chemical substance is used together, these biochemicals include other insecticides, fungicide, herbicide, plant life
Long conditioning agent, acaricide or fertilizer etc., and thus can generate additional advantage and effect.
Desirable any type agent can be made as the preparation of effective ingredient with (I) compound provided by the invention
Such as dry compressed particle of type, easily flow intermixture, granula, wettable powder, water dispersible granules, emulsifiable concentrate, pulvis,
Powdery concentrate, microemulsion, suspending agent, missible oil, aqueous emulsion, soluble liquid, aqua, dispersible agent, suitable auxiliary agent packet
Include carrier (diluent) and other adjuvants such as spreader-sticker, emulsifier, wetting agent, dispersant, sticker and distintegrant.These systems
Contain in agent and is mixed with the compound of the present invention with the acceptable solid of inert, pharmacology or liquid diluent.
Such as dry compressed particle of desirable any type dosage form, easily flowing can also be made in the composition example of the present invention
Intermixture, granula, wettable powder, water dispersible granules, emulsifiable concentrate, pulvis, powdery concentrate, microemulsion, suspension
Agent, missible oil, aqueous emulsion, soluble liquid, aqua, dispersible agent, suitable auxiliary agent include carrier (diluent) and other auxiliary
Auxiliary agent such as spreader-sticker, emulsifier, wetting agent, dispersant, sticker and distintegrant.Containing with inert, pharmacology in these preparations
It learns acceptable solid or liquid diluent is mixed with the compound of the present invention.
It should be appreciated that in scope defined by the claims of the present invention, various transformation and change can be carried out.
The invention will be further described with reference to embodiments, and the yield in embodiment is not optimized.
Specific implementation mode
Embodiment 1 this example demonstrates that in table 1 compound 3 and 11 preparation (method A)
1.3 dichloroacetone (220mmol) of 4- chloromethyl -2- phenyl thiazoles, thiobenzamide (200mmol), ethyl alcohol
It after (400mL) and THF (200mL) react 4-6hr under counterflow condition, is cooled to room temperature, reaction solution pours into ice water, acetic acid second
Ester extracts, and washes organic phase, and anhydrous sodium sulfate is dried, and sloughing solvent under reduced pressure obtains liquid title object 38.0g.
2- (2- phenyl thiazole -4- bases) acetonitrile 4- chloromethyl -2- phenyl azoles thiophenes (100mmol), Cymag (115mmol) and
After catalytic amount 18 crown ether reacts 4-6hr in acetonitrile (150mL) under counterflow condition, it is cooled to room temperature, reaction solution pours into ice water
In, organic phase, anhydrous sodium sulfate drying are washed in ethyl acetate extraction, and decompression sloughs solvent, obtains liquid title object 16.7g.
3- hydroxyls -3- (2- methyl -4- trifluoromethyl thiazole -5- bases) -2- (2- phenyl thiazole -4- bases) acrylonitrile equipped with
Magnetic stirring apparatus, thermometer, water knockout drum and condenser pipe reaction bulb in 2- (2- phenyl thiazole -4- bases) acetonitrile is added
(50mmol), 2- methyl -4- trifluoromethyl thiazole -5- Ethyl formates (52.5mmol), glycol ether (4.0mL) and normal heptane
200mL is warming up to after reacting 1.0hr under counterflow condition, and the methanol solution (100mmol) of 28% sodium methoxide is slowly added dropwise, and drop finishes
Continue to react 4-6hr under counterflow condition afterwards.It after reaction solution cooling, is poured into ice water, ether extraction, ether layer discards, institute
It obtaining water phase and is acidified to PH=3~4 with dilute hydrochloric acid, ether layer, anhydrous sodium sulfate drying are washed in ether extraction, and solvent is sloughed in decompression,
Gained crude product is through column chromatography (petrol ether/ethyl acetate=20:1~10:1) it purifies, obtains title object 7.0g.
Under 2- methyl mercapto propionyl chloride room temperatures and stirring condition, thionyl chloride (220mL) is slowly added dropwise and arrives 2- methyl mercapto propionic acid
After in 1,2- dichloroethanes (120mL) solution of (200mmol), after being added dropwise, it is warming up to reflux and reacts 4-6hr.It is cooling
Afterwards, solvent and excessive thionyl chloride are removed under reduced pressure, obtains title object 23.6g, are directly used in lower step synthesis.
2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2- first sulphur
Base propionic ester is slowly added dropwise 2- methyl mercaptos propionyl chloride (4.3mmol) and arrives 3- hydroxyls -3- under ice-water bath cooling and stirring condition
(2- methyl -4- trifluoromethyl thiazole -5- bases) -2- (2- phenyl thiazole -4- bases) acrylonitrile (3.1mmol) and triethylamine
In tetrahydrofuran (THF25mL) solution of (4.3mmol), after being added dropwise, in room temperature reaction 3-5hr.Reaction solution is poured into ice water
In, ethyl acetate extraction is washed, and solvent is sloughed in anhydrous sodium sulfate drying, decompression, and gained crude product is through column chromatography (petroleum ether/second
Acetoacetic ester=40:1~30:1) it purifies, obtains E- titles object (3) 0.46g of tacky yellowish solid and the Z- title objects of yellow solid
(11)0.30g。
Embodiment 2 this example demonstrates that in table 1 compound 3 and 11 preparation (method B)
Under (2- methyl -4- trifluoromethyl thiazole -5- bases) (1H- pyrazol-1-yls) ketone room temperature and stirring condition, by chlorination
Sulfoxide (250mmol) is added drop-wise to the 1,2- dichloroethanes of 2- methyl -4- trifluoromethyl thiazole -5- formic acid (23.1g, 100mmol)
It in (120mL) solution, is warming up to after being added dropwise after reacting 4-6hr under counterflow condition, removes solvent and excessive thionyl chloride,
Obtain brown liquid.Dichloromethane (150mL) is added in above-mentioned brown liquid, pyrazoles (160mmol) is added portionwise, reacts at room temperature
After 2-4hr, reaction solution is poured into water, and separates dichloromethane layer, and water phase is extracted 2 times with dichloromethane, merges organic phase, anhydrous sulphur
Sour sodium drying, removing solvent obtain title object crude product 22.3g, are directly used in and react in next step.
3- hydroxyls -3- (2- methyl -4- trifluoromethyl thiazole -5- bases) -2- (2- phenyl thiazole -4- bases) acrylonitrile is in -5.0
Under~5.0 DEG C and stirring condition, 2- (2- phenyl thiazole -4- bases) acetonitrile is added portionwise in potassium tert-butoxide (55mmol)
The anhydrous tetrahydrochysene furan of (50mmol) and (2- methyl -4- trifluoromethyl thiazole -5- bases) (1H- pyrazol-1-yls) ketone (50mmol)
It mutters in (200mL) solution, room temperature reaction is warmed naturally to after finishing overnight.After reaction solution removes part tetrahydrofuran, water is poured into
In, after 2N HCl adjusting pH value to 2~3, ethyl acetate is extracted twice, and merges organic phase, and anhydrous sodium sulfate drying removes molten
Agent obtains title object 15.0g, is directly used in and reacts in next step.
2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2- first sulphur
Base propionic ester is slowly added dropwise 2- methyl mercaptos propionyl chloride (4.3mmol) and arrives 3- hydroxyls -3- under ice-water bath cooling and stirring condition
(2- methyl -4- trifluoromethyl thiazole -5- bases) -2- (2- phenyl thiazole -4- bases) acrylonitrile (3.1mmol) and triethylamine
In tetrahydrofuran (THF25mL) solution of (4.3mmol), after being added dropwise, in room temperature reaction 3-5hr.Reaction solution is poured into ice water
In, ethyl acetate extraction is washed, and solvent is sloughed in anhydrous sodium sulfate drying, decompression, and gained crude product is through column chromatography (petroleum ether/second
Acetoacetic ester=40:1~30:1) it purifies, obtains E- titles object (3) 0.49g of tacky yellowish solid and the Z- title objects of yellow solid
(11)0.35g。
Embodiment 3 this example demonstrates that in table 1 compound 89 preparation
3- hydroxyls -3- (the chloro- 1H- pyrazoles -5- bases of 1,3- dimethyl -4-) -2- (4- tert-butyl-phenyls) acrylonitrile equipped with
Magnetic stirring apparatus, thermometer, water knockout drum and condenser pipe reaction bulb in the chloro- 1H- pyrazoles -5- formic acid of 1,3- dimethyl -4- is added
Ethyl ester (0.045mol), to tert-butyl benzene acetonitrile (0.045mol), glycol ether (4.00mL) and normal heptane (150mL), room temperature
0.5hr is stirred, reflux temperature stirs 1~2hr, and the methanol solution (0.06mol) of 30% sodium methoxide is added dropwise, continues after being added dropwise
5~6hr of back flow reaction.Reaction solution is cooled to room temperature, and is poured into ice water, and ethyl acetate extraction discards ethyl acetate layer, gained water
Mutually with after 2N HCl adjusting pH value to 3~4, ethyl acetate is extracted twice, and merges organic phase, and anhydrous sodium sulfate is dried, and removing is molten
Agent obtains title object 7.6g, is directly used in and reacts in next step.
2- cyano -2- (4- tert-butyl-phenyls) -1- (the chloro- 1H- pyrazoles -5- bases of 1,3- dimethyl -4-) vinyl 2,2- bis-
Chloro- 2, the 2- dimethylpropionic acid chlorides (6mmol) of 3- are slowly added dropwise under ice-water bath cooling and stirring condition in methyl -3- chloropropionates
To 3- hydroxyls -3- (the chloro- 1H- pyrazoles -5- bases of 1,3- dimethyl -4-) -2- (4- tert-butyl-phenyls) acrylonitrile (5mmol), three second
In the solution of amine (5mmol) and tetrahydrofuran (30mL), after being added dropwise, warm naturally to react 4~6hr under room temperature.
Reaction solution pours into ice water, ethyl acetate extraction, and after washing organic phase, anhydrous sodium sulfate drying, removed under reduced pressure solvent, which obtains, slightly to be produced
Product are through column chromatography (petrol ether/ethyl acetate=30:1~20:1) it purifies, obtains faint yellow viscous solid E- titles object (89)
0.56g。
The other compounds of the present invention are referred to the method for 1~embodiment of embodiment 4 and prepared by relevant references.
Biological activity determination embodiment
The compounds of this invention is carried out to kill insects mites and bactericidal activity experiment, the results showed that the compound of the present invention is shown
Go out and kill insects mites, bactericidal activity well, part of test results is as follows：
Biological evaluation of the embodiment 4 to mythimna separata (Mythimna separata)
Potter spray-on processes：Untested compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing
The clear water of 0.2%Tween80 emulsifiers is diluted to required concentration, if the blank without untested compound is control.It takes fresh and tender
Maize leaves are cut into the almost the same segment of size, are put into and are lined in the culture dish (Ф 90mm) of filter paper in advance.Then it is connect in ware
Enter 3 instar larvae of mythimna separata 10, be put under Potter spray towers and carry out metered dose, spray liquid measure 1ml, per 3 repetitions of concentration.Place
Reason finishes, and covers ware lid, is placed in culture, routine observation in recovery room and test worm death condition is checked and recorded after 72 hours, count
The death rate is calculated, results are averaged.Active (death rate) in percentage with respect to blank control, divides A, B, C, D level Four, 100 >=
The death rate (%) >=90 is A grades, and the 90 ＞ death rates (%) >=70 are B grades, and the 70 ＞ death rates (%) >=50 are C grades, and 50 ＞ are dead
Rate (%) >=0 is D grades.The result shows that the compound of the present invention has activity well to mythimna separata, and the compound having is very low
Concentration under still have high activity, partial results are listed below：
Under 200mg/L concentration, the compounds of this invention 1,3,11,33,35,47,52,53,54,55,56,58,60,62,68,
70,71 etc. and D3 all has A grades of activity to mythimna separata；D2 does not show mythimna separata apparent activity.
Under 50mg/L concentration, the compounds of this invention 3,11,33,58,60,62,68 etc. all has A grades of activity to mythimna separata.
Just select the compounds of this invention 3 and 11 for representative the active of mythimna separata with D3 to compare the compounds of this invention, with
D3 is that control has carried out deep screening, the results showed that the activity of the compounds of this invention 3 and 11 pairs of mythimna separatas is above D3 (table 3).
3 the compounds of this invention of table gos deep into screen fraction result to mythimna separata
| Compound | Regression equation (Y=a+bx) | Related coefficient (r) | LC50(mg/L) |
| 3 | Y=-6.5947+11.3471x | 0.9319 | 10.52 |
| 11 | Y=2.3108+2.7462x | 0.959 | 9.45 |
| D3 | Y=-5.3067+9.2977x | 0.9691 | 12.84 |
Insecticidal Activity of the embodiment 5 to aphid (Aphis fabae)
It is to evaluate the compounds of this invention to the activity of homoptera pest, selects aphid for object, use infusion process indoors
Determine activity of the compounds of this invention to aphid.
Infusion process：Untested compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.2%
The clear water of Tween80 emulsifiers is diluted to required concentration, if the blank without untested compound is control, often handles 3 repetitions.
Black bean aphid is connected on just unearthed bean seedlings, every plant connects 20 or more, and bean seedlings are then dipped in the present invention together with test worm carries
In formula (I) liquid of confession, is taken out after 5 seconds, suck extra liquid, be inserted into the sponge of water suction, covered with glass-tube, after 24 hours
Check survival and dead borer population, results are averaged.Active (death rate) in percentage with respect to blank control, be divided into A, B, C,
D level Four, 100 >=death rate (%) >=90 are A grades, and the 90 ＞ death rates (%) >=70 are B grades, and the 70 ＞ death rates (%) >=50 are C
Grade, the 50 ＞ death rates (%) >=0 are D grades.The result shows that the compounds of this invention has activity, and the chemical combination having well to aphid
Object still has high activity at very low concentrations, and partial results are listed below：
Under 500mg/L concentration, the compounds of this invention 1,3,11,33,35,47,48,49,50,51,52,53,54,55,56,
58,60,62,63,64,65,66,67,68,70,71,73,80 etc. and D3 all has A grades of activity to aphid；Work of the D2 to aphid
Property is less than A grades.
Under 12.5mg/L concentration, the compounds of this invention 1,3,11,33,35,47,56,58 etc. and D3 all have A grades to aphid
Activity.
Further deeply screening shows the LC of the compound to aphid mostly such as present invention 1,3,11,33,35,5850Value is all
Less than 5.0mg/L.
To compare activity height of the compounds of this invention with D3 to aphid, select the compounds of this invention 35 for representative, with D3
Deep screening has been carried out for control, the results showed that the LC of the compounds of this invention 35 and D3 to aphid50Value is in 1.0-1.5mg/L models
In enclosing, it is in same activity level.
Embodiment 6 evaluates the acaricidal activity of two-spotted spider mite (Tetranychus urticae)
Method：Untested compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.2%
The water of Tween80 emulsifiers is diluted to required concentration, if the blank without untested compound is blank control, often handles 3 weights
It is multiple；Select the bean seedlings to grow fine inoculation red spider that will be cut with mite bean seedlings in the prepared present invention after red spider colonizes
It being impregnated 10 seconds in the liquid of formula (I) compound of offer, taking-up sucks extra liquid with filter paper, inserts in and is filled with water in beaker, in
It is cultivated in observation ward, survival and dead mite number is checked after 48 hours, has 100-200 mite on every plant of bean seedlings.Results are averaged.
Simultaneously using D2 as standard control.Active (death rate) in percentage, divides A, B, C, D level Four relative to blank control, 100 >=dead
It is A grades to die rate (%) >=90, and the 90 ＞ death rates (%) >=70 are B grades, and the 70 ＞ death rates (%) >=50 are C grades, the 50 ＞ death rates
(%) >=0 is D grades.The result shows that the compound of the present invention has activity well to red spider, and the compound having is very low
Concentration under still have high activity, partial results are listed below：
Under 500mg/L concentration, the compounds of this invention 1,3,11,33,35,47,48,49,50,52,53,55,89,83,56,
58,60,62,68,70,71,72,73,76,77,78,79,80,81,82,83,84,88,89,95 etc. and D2 has red spider
There are A grades of activity.
Under 12.5mg/L concentration, the compounds of this invention 11,73,76,77,79,80,82,83,84,88,89 etc. and D2 are to red
Spider all has A grades of activity.
Further deeply screening shows most chemical combination such as the compounds of this invention 73,77,78,79,80,82,83,88,89
The LC of object and D2 to red spider50Value is below 2.0mg/L, LCs of the D3 to red spider50Value is 7.92mg/L, and D3 is to red spider
Activity is far below the compounds of this invention and D2.
To compare activity height of the compounds of this invention with D2 to red spider, select the compounds of this invention 83 and 89 for generation
Table is that control has carried out deep screening with D2, the results showed that LCs of 83, the 89 and D2 of the compounds of this invention to red spider50Value exists
Within the scope of 0.2-0.3mg/L, it is in same activity level.
Bactericidal activity of the embodiment 7 to Sclerotinia sclerotiorum (Sclerotonia sclerotiorum)
Method is as follows：Untested compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.1%
The sterile water of Tween80 emulsifiers is diluted to required concentration；The 27mL Ma Ling that the addition of 3mL liquids is cooled to 45 DEG C are taken with pipette
Culture dish is poured into after shaking up in potato agar medium (PDA) and fully；Use transfer needle from the sclerotinia sclerotiorum of culture 7 days after cooling
Bacterium colony edge takes 6mm diameter mycelia blocks, moves to culture dish center, mycelia is face-down, while setting the sky without untested compound
White is control, often handles 4 repetitions；Culture dish is placed in 28 DEG C of constant temperature biochemical cultivation cases after being disposed and is cultivated, is surveyed after 4 days
Mycelia growth diameter is measured, mycelial growth inhibition rate (%) is analyzed and calculated using EXCEL statistical softwares, activity is relative to sky
White control is in percentage.Simultaneously using D2 and D3 as standard control.The result shows that the compounds of this invention has Sclerotinia sclerotiorum
There is apparent activity.Partial results are listed below：
Under 25mg/L concentration, the compounds of this invention 1,11 and 47 etc. is respectively 84.1% to the activity of Sclerotinia sclerotiorum,
87.0% and 82.1% etc.；D3 is 81.1% to the activity of Sclerotinia sclerotiorum；D2 does not show Sclerotinia sclerotiorum bright
Aobvious activity.
Embodiment 8 is to fusarium graminearum (Gibberella zeae) and P. capsici (phytophythora
Capsici bactericidal activity)
With reference to the active assay method of Sclerotinia sclerotiorum, test the compounds of this invention is to fusarium graminearum and capsicum
The activity of phytophthora germ.The result shows that the compounds of this invention is active to fusarium graminearum and P. capsici, part
As a result as follows：
Under 25mg/L concentration, equal to fusarium graminearum compound 11 with 75.0% activity, D2 does not show bright
The activity of aobvious activity, D3 is 42.6%；Under 25mg/L concentration, P. capsici compound 1 is waited with 86.2% activity,
D2 does not show apparent activity, and the activity of D3 is 64.1%.
Bactericidal activity of the embodiment 9 to corn rust (Puccinia Polysora)
Pot-culture method：Untested compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.2%
The sterile water of Tween80 emulsifiers is diluted to required concentration, if the blank without untested compound is control, often handles 4 weights
It is multiple；Morbidity maize leaf is cut, lower spore is washed with 0.05%Tween80 or other suitable surfactant aqueous solutions, it is used in combination 2~
4 layers of filtered through gauze, are made a concentration of 1 × 105The suspension of a spore/mL；Wait for corn grow to 1 heart stage of 2 leaf spray it is above-mentioned to be measured
The liquid of compound, spore suspension spray inoculation after 1 day move to moisturizing cabinet (95% or more relative humidity, temperature 20 after inoculation
DEG C~22 DEG C), the r of (intensity of illumination 5000Lux~10000Lux) culture 15 under low light condition~for 24 hours；Wait for blank control disease leaf rate
When up to 50% or more, the incidence of each processing is investigated, calculates pharmacy control efficacy.Simultaneously using D2 and D3 as standard control.As a result table
Bright the compound of the present invention has good control effect to corn rust, and the compound having still has at very low concentrations
Excellent prevention fruit, is listed below partial results：
Under 500mg/L concentration, the compounds of this invention 3,11,35,56,58,73,83,89 etc. and D3 prevent corn rust
Effect is all higher than 95%；1,33,60,72,77,78,80,81,82,88 etc. 90% is all higher than to the preventive effect of corn rust；65,79 etc.
80% is all higher than to the preventive effect of corn rust；Control effect unobvious of the D2 to corn rust.
Under 100mg/L concentration, the compounds of this invention 3,11,35,56,58,83,89 etc. and D3 are equal to the preventive effect of corn rust
More than 90%.
To compare the compounds of this invention and D3 to the control effect of corn rust, select the compounds of this invention 89 for representative,
It is that control has carried out deep screening with D3, the results showed that the compounds of this invention 89 becomes rusty to corn down under 1.56mg/L concentration
The preventive effect of disease is still up to 95.20%, and D3 has dropped to 90% hereinafter, being 87.98% to the preventive effect of corn rust.
Bactericidal activity of the embodiment 10 to rice sheath blight disease (Rhizoctonia solani)
Pot-culture method：Untested compound is dissolved in suitable solvent such as n,N-Dimethylformamide, with containing 0.1%Tween80 breasts
The sterile water of agent is diluted to required concentration；Rice banded sclerotial blight pathogen goes to after going to PDA plate activation culture in PD culture mediums,
After water bath with thermostatic control culture 4 days, cultured mycelium pellet is crushed with refiner and is allocated to certain density bacteria suspension with clear water；
When cucumber is grown to flattening two panels cotyledon, above-mentioned liquid is sprayed, sprays bacteria suspension after r for 24 hours to seedling surface；Moisturizing culture is simultaneously observed
Seedling incidence starts the incidence for recording each processing when blank control processing morbidity is apparent, calculate disease index and
Control effect, activity relative to blank control in percentage.Simultaneously using D2 and D3 as standard control.The result shows that of the present inventionization
Close object has good control effect to rice sheath blight disease, and the compound having still has high activity at very low concentrations, under
List partial results in face：
Under 500mg/L concentration, the compounds of this invention 3,33,35,50,51,58,60 etc. is big to the preventive effect of rice sheath blight disease
In 90%；1,3 etc. 80% is all higher than to the preventive effect of rice sheath blight disease；54,62,73,79,80 etc. and D3 prevents rice sheath blight disease
Effect is all higher than 70%；Control effect unobvious of the D2 to rice sheath blight disease.
Under 100mg/L concentration, the compounds of this invention 3,58 etc. is more than 75% to the preventive effect of rice sheath blight disease；D3 is to rice line
The preventive effect of blight is 65%.
Claims (9)
1. acrylonitrile compound, it is characterised in that indicate acrylonitrile compound and its geometric isomer with logical formula (I)：
Wherein：
I.Ar1And Ar2It is same or different, and Ar1Represent Ar1- 1 or Ar1-2；Ar2Represent Ar2-1、Ar2-2、Ar2-3
Or Ar2-4；Ar1And Ar2Middle R ', R3、R4、R5、R6、R7、R8And R9It is same or different, and represents hydrogen, halogen, C1-C12Alkane
Base, C1-C12Halogenated alkyl, C1-C12Alkoxy, C1-C12Halogenated alkoxy, phenyl, halogenophenyl, C1-C6Alkyl phenyl, C1-C6
Haloalkylphenyl；Z represents sulphur or oxygen；
II.R、R1And R2It is same or different, and represents hydrogen, C1-C12Alkyl, C1-C12Halogenated alkyl, C3-C8Naphthenic base or
C3-C8Halogenated cycloalkyl；
III.X represents S；
IV.Y represents O or S；
V.n represents 0,1 or 2；
In the definition of compound (I) given above, no matter term used exclusive use is also used in compound word, represent as follows
Substituent group：
Halogen：Refer to fluorine, chlorine, bromine, iodine；
Alkyl：Refer to linear or branched alkyl group；
Halogenated alkyl：Refer to linear or branched alkyl group, hydrogen moiety on these alkyl or is all replaced by halogen atom；
Naphthenic base：Refer to saturation or unsaturation ring alkyl；
Halogenated cycloalkyl：Refer to saturation or unsaturation ring alkyl, and hydrogen moiety therein or is all replaced by halogen atom.
2. acrylonitrile compound according to claim 1, it is characterised in that logical formula (I) compound represented includes geometry
The mixture of isomers E formulas and Z formulas and E formulas and Z formulas.
3. acrylonitrile compound according to claim 1, it is characterised in that in compound shown in logical formula (I)：
Ar1Represent Ar1- 1a or Ar1-2；Ar2Represent Ar2-1a、Ar2-2a、Ar2- 3 or Ar2-4；R and R1、R2It is identical or different
, and represent hydrogen or C1-C6Alkyl；X represents S；Y represents oxygen；N represents 0 or 1；
Ar1Middle R ' represents hydrogen, tertiary butyl, and Z represents S；Ar2Middle R3~R9It is same or different, and represents hydrogen, halogen, C1-C6
Alkyl, C1-C6Alkoxy, trifluoromethyl.
4. acrylonitrile compound according to claim 1, it is characterised in that compound is shown in logical formula (I)：
(Z) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2- first sulphur
Yl acetate；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2- first sulphur
Yl acetate；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2- first sulphur
Base propionic ester；
(Z) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2- first sulphur
Base propionic ester；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2- second sulphur
Base propionic ester；
(Z) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2- second sulphur
Base propionic ester；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2- rosickyite
Base propionic ester；
(Z) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2- rosickyite
Base propionic ester；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- methyl -4- trifluoromethyl thiazole -5- bases) vinyl 2- first
Base -3- methyl mercapto propionic esters；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2,4- dimethylthiazole -5- bases) vinyl 2- methyl mercapto propionic acid
Ester；
(Z) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2,4- dimethylthiazole -5- bases) vinyl 2- methyl mercapto propionic acid
Ester；
(E) -2- cyano -2- (2- phenyl thiazole -4- bases) -1- (2- trifluoromethyls) vinyl 2- methyl mercapto propionic esters；
(Z) -2- cyano -2- (4- tert-butyl-phenyls) -1- (1,3,4- trimethyl -1H- pyrazoles -5- bases) vinyl 2- methyl mercaptos third
Acid esters；
(E) -2- cyano -2- (4- tert-butyl-phenyls) -1- (1,3,4- trimethyl -1H- pyrazoles -5- bases) vinyl 2- methyl mercaptos third
Acid esters；
(E) -2- cyano -2- (4- tert-butyl-phenyls) -1- (1,3,4- trimethyl -1H- pyrazoles -5- bases) vinyl 2,2- diformazans
Base -3- methyl mercapto propionic esters；
(E) -2- cyano -2- (4- tert-butyl-phenyls) -1- (1- ethyl -3- methyl-1 H- pyrazoles -5- bases) vinyl 2- methyl mercaptos
Propionic ester；
(E) -2- cyano -2- (4- tert-butyl-phenyls) -1- (1- ethyl -3- methyl-1 H- pyrazoles -5- bases) vinyl 2- ethylmercapto groups
Propionic ester；
(E) -2- cyano -2- (4- tert-butyl-phenyls) -1- (the chloro- 1H- pyrazoles -5- bases of 1- ethyl -3- methyl -4-) vinyl 2,2-
Dimethyl -3- methyl mercapto propionic esters；
(E) -2- cyano -2- (4- tert-butyl-phenyls) -1- (the chloro- 1H- pyrazoles -5- bases of 1,3- dimethyl -4-) vinyl 2- first sulphur
Base propionic ester；
(Z) -2- cyano -2- (4- tert-butyl-phenyls) -1- (the chloro- 1H- pyrazoles -5- bases of 1,3- dimethyl -4-) vinyl 2- first sulphur
Base propionic ester；
(E) -2- cyano -2- (4- tert-butyl-phenyls) -1- (the chloro- 1H- pyrazoles -5- bases of 1- ethyl -3- methyl -4-) vinyl 2- first
Thiohydracrylic acid ester.
5. the preparation method of acrylonitrile compound according to claim 1, it is characterised in that formula (I) compound represented
It is prepared by reaction shown below,
Reaction equation 1：
Reaction equation 2：
Reaction equation 3：
In solvents tetrahydrofurane, dichloromethane, toluene, dichloroethanes or chloroform, in alkali triethylamine, pyridine, sodium hydroxide, hydrogen
In the presence of potassium oxide, sodium carbonate, potassium carbonate or sodium bicarbonate, in 0~60 DEG C, with formula (II) compound represented and formula (III institutes
The compound shown react formula (I) compound；
In solvent n-heptane, normal hexane, thiacyclohexane, petroleum ether, tetrahydrofuran, toluene, dichloromethane or dichloroethanes, in anti-
It answers under system reflux temperature, is deposited in alkali sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium carbonate or carbonic acid
Under, it is added or is added without glycol ether, after the compound reaction with the compound and formula (V) of formula (IV), acidification obtains formula
(II) compound；
Or in solvents tetrahydrofurane, toluene, dichloromethane or dichloroethanes, in -10.0 DEG C~room temperature, in the alkali tert-butyl alcohol
In the presence of potassium, sodium methoxide, sodium ethoxide, sodium hydroxide, potassium hydroxide, sodium carbonate or carbonic acid, with the compound and formula of formula (IV)
(VI) after compound reaction, acidification obtains the compound of formula (II)；
In solvent chloroform, toluene, dichloromethane or dichloroethanes, formula (VII) compound represented and acylating reagent chlorine
Change sulfoxide, phosgene, oxalyl chloride or phosphorus trichloride reaction, obtains compound shown in formula (III)；
Ar in formula1、Ar2、R、R1、R2, X, Y and n have claim 1 given in define.
6. according to the purposes of Claims 1 to 4 any one of them acrylonitrile compound, it is characterised in that at 15~5000 grams
There is desinsection, mite killing or sterilization bioactivity under active ingredient/hectare dosage.
It lives with desinsection, mite killing or sterilization 7. being used to prepare according to Claims 1 to 4 any one of them acrylonitrile compound
The purposes of the drug of property.
8. a kind of desinsection, mite killing or bactericidal composition, it is characterised in that：Containing as active component such as Claims 1 to 4 times
Acrylonitrile compound described in one, the weight percentage of active component is 0.5-99% in composition.
9. a kind of pest control, evil mite or the method for pathogen, it is characterised in that：By a effective amount of as Claims 1 to 4 is any
Acrylonitrile compound described in imposes on the pest, evil mite, pathogen or growth medium.
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| CN103833669A (en) * | 2012-11-23 | 2014-06-04 | 中国中化股份有限公司 | Thiazolyl acrylonitrile compound and application thereof |
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| CN104649997A (en) * | 2013-11-25 | 2015-05-27 | 中国中化股份有限公司 | 2,4-dimethylthiazole acrylonitrile compound and application thereof |
| CN104650063A (en) * | 2013-11-25 | 2015-05-27 | 中国中化股份有限公司 | 2,4-dimethyl oxazole acrylonitrile compound and application thereof |
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| CN1247530A (en) * | 1997-02-14 | 2000-03-15 | 石原产业株式会社 | Acrylonitrile compounds, process for their prodn. and pesticides containing them |
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