CN108003151A - N- hetervaromatic methyl pyrimidinamine compounds and preparation method and application - Google Patents
N- hetervaromatic methyl pyrimidinamine compounds and preparation method and application Download PDFInfo
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- CN108003151A CN108003151A CN201610959601.4A CN201610959601A CN108003151A CN 108003151 A CN108003151 A CN 108003151A CN 201610959601 A CN201610959601 A CN 201610959601A CN 108003151 A CN108003151 A CN 108003151A
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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
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
Abstract
The invention discloses N hetervaromatic methyl pyrimidinamine compounds shown in formula (I) and preparation method and application.R, R in formula1、R2、R3、R4, X and n have and defined given in specification.Formula (I) compound of the present invention, which has, kills insects mites and/or sterilization bioactivity, especially has very high activity to the homoptera pest such as pest such as aphid, plant hopper.
Description
Technical field
The invention belongs to kill insects mites, fungicide field, and in particular to have the N- heteroaryls for killing insects mites, sterilizing bioactivity
Methylpyrimidine aminated compounds and preparation method thereof, killing insects mites, microbicide compositions and use this containing the compound
A little compound control evil insects mites, the purposes of harmful levels of pathogens and methods.
Background technology
Evil insects mites, the prevention of harmful levels of pathogens are extremely important during high-efficiency agriculture is realized.Insects mites are done harm at the same time, are harmful to
The prevention of germ woods, herd, in the field such as secondary, fishing and public health it is also critically important.Although the existing many evil insects mites of in the market,
Harmful levels of pathogens pesticide control, but due to market it is continuous expand, external evil insects mites and harmful levels of pathogens, evil insects mites and having are fallen ill
The problems such as resistance to the action of a drug of bacterium, medicine service life, Pharmacoeconomic and people are to the pay attention to day by day of environment, it is necessary to scientists
Constantly research, and then develop that new efficient, safety, economy, environment be compatible and killing insects mites, killing with the different modes of action
Microbial inoculum new varieties.
Pyrimidines have broad-spectrum biological activity, as the outstanding representative of aminopyrimidine reactive compound, phonetic worm amine
(flufenerim, D1) is the new pyrimidine insecticides that Ube Industries Ltd. releases, and is now developed by Sumitomo Chemical.Phonetic worm amine tool
There are desinsection, acaricidal activity, thus it is speculated that the mechanism of action is similar with Tolfenpyrad (tolfenpyrad), suppresses for Mitochondrial electron transmission
Agent.Based on document【Pesticide:Vol 52,No.9,639-641,2013】Report, phonetic worm amine is respectively provided with aphid and tetranychid higher
Activity, but phonetic worm amine is less than imidacloprid (imidacloprid, D2) to the activity of aphid (black peach aphid), such as in 1.25mg/L concentration
Under, imidacloprid (D2) is 73% to the activity of black peach aphid, is much better than under Isodose phonetic worm amine (D1) to the activity 37% of black peach aphid；
Under 10mg/L concentration, phonetic worm amine (D1) is 73% to the activity of Tetranychus cinnabarinus, and when reducing concentration to 5mg/L, phonetic worm amine (D1) is right
The activity of Tetranychus cinnabarinus is 0%.
There is more economical, more efficient and/or more broad-spectrum biological activity new pyrimidine aminated compounds to obtain, based on phase
Close the work of document and our early periods, we design and synthesize have no report with shown in formula (I) with killing insects mites, kill
The N- hetervaromatic methyl pyrimidinamine compounds of bacterium activity.The compounds of this invention shows the desinsection work compared with imidacloprid (D2) higher
Property, while the compounds of this invention also has bactericidal activity.
The content of the invention
The present invention provides the N- heteroaryl first with bioactivity such as pest control/mite, harmful levels of pathogens shown in formula (I)
Yl pyrimidines aminated compounds and its isomers：
Wherein：
I.R is same or different, and represents hydrogen, halogen, nitro, cyano group, C1-C12Alkyl, C1-C12Haloalkyl,
C2-C12Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-
C8Heterocyclylalkyl, C3-C8Halogenated heterocycloalkyl, C1-C12Alkoxyalkyl, C1-C12Alkoxy, C1-C12Halogenated alkoxy, C1-C12Alkane
Sulfenyl, C1-C12Halogenated alkylthio, C1-C12Alkyl sulphinyl, C1-C12Alkylsulfinyl, C1-C12Alkyl sulphonyl,
C1-C12Halogenated alkyl sulfonyl, C1-C12Alkyl amine group, C1-C12It is haloalkyl amido, phenyl, identical or different by 1-5
Halogen, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy substitution phenyl, phenoxy group, by 1-5
A identical or different halogen, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6The benzene of halogenated alkoxy substitution
Epoxide；
II.R1Represent C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-
C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-C8Heterocyclylalkyl, C3-C8Halogenated heterocycloalkyl, phenyl, quilt
1-5 identical or different halogens, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6Halogenated alkoxy substitution
Phenyl；
III.R2Represent hydrogen, C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynes
Base, C2-C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-C8Heterocyclylalkyl, C3-C8Halogenated heterocycloalkyl, benzene
Base, by the identical or different halogens of 1-5, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6Halogenated alkoxy
Substituted phenyl；
IV.R3And R4It is same or different, and represents hydrogen, halogen, C1-C12Alkyl, C1-C12Haloalkyl, C2-C12
Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-C8It is miscellaneous
Cycloalkyl, C3-C8Halogenated heterocycloalkyl, C1-C12Alkoxy, C1-C12Alkoxyalkyl, C1-C12Alkyl acyl, phenyl, by 1-5
Identical or different halogen, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6The phenyl of halogenated alkoxy substitution,
Phenoxy group, by the identical or different halogens of 1-5, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6Alkyl halide
The phenoxy group of epoxide substitution；
V.X represents oxygen or sulphur；
VI.n represents 0,1,2,3,4 or 5 integer；
In the definition of compound (I) given above, also it is used in compound word, represents no matter term used is used alone
Following substituent：
Halogen：Refer to fluorine, chlorine, bromine, iodine；
Alkyl：Refer to straight or branched alkyl；
Cycloalkyl：Refer to saturation or undersaturated cycloalkyl；
Heterocyclylalkyl：Refer to saturation or unsaturated heterocycle alkyl, at least 1 N, O and/or S in formula；
Halo：Refer to hydrogen moiety therein or all substituted by halogen atom.
Currently preferred compound is：In formula (I)：
I.R is same or different, and represents hydrogen, halogen, C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl,
C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-C8Heterocycle alkane
Base, C3-C8Halogenated heterocycloalkyl, C1-C12Alkoxyalkyl, C1-C12Alkoxy, C1-C12Halogenated alkoxy, phenyl, by 1-5 phase
Same or different halogen, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6Phenyl, the benzene of halogenated alkoxy substitution
Epoxide, by the identical or different halogens of 1-5, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6Haloalkoxy
The phenoxy group of base substitution；
II.R1Represent C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-
C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-C8Heterocyclylalkyl, C3-C8Halogenated heterocycloalkyl, phenyl, quilt
1-5 identical or different halogens, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6Halogenated alkoxy substitution
Phenyl；
III.R2Represent hydrogen, C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynes
Base, C2-C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-C8Heterocyclylalkyl, C3-C8Halogenated heterocycloalkyl, benzene
Base, by the identical or different halogens of 1-5, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6Halogenated alkoxy
Substituted phenyl；
IV.R3And R4It is same or different, and represents hydrogen, halogen, C1-C12Alkyl, C1-C12Haloalkyl, C2-C12
Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-C8It is miscellaneous
Cycloalkyl, C3-C8Halogenated heterocycloalkyl, phenyl, by the identical or different halogens of 1-5, C1-C6Alkyl, C1-C6Haloalkyl,
C1-C6Alkoxy or C1-C6The phenyl of halogenated alkoxy substitution；
V.X represents oxygen or sulphur；
VI.n represents 0,1,2,3,4 or 5 integer.
The further preferred compound of the present invention is：In formula (I)：
I.R is same or different, and represents hydrogen, halogen, C1-C12Alkyl or C1-C12Haloalkyl；
II.R1Represent C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-
C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, phenyl, by the identical or different halogens of 1-5, C1-C6Alkyl,
C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6The phenyl of halogenated alkoxy substitution；
III.R2Represent hydrogen, C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynes
Base, C2-C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, phenyl, by the identical or different halogens of 1-5, C1-C6
Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6The phenyl of halogenated alkoxy substitution；
IV.R3And R4It is same or different, and represents hydrogen, halogen, C1-C12Alkyl or C1-C12Haloalkyl；
V.X represents oxygen or sulphur；
VI.n represents 0,1 or 2 integer.
Compound specifically preferred according to the invention is：In formula (I)：
I.R is same or different, and represents hydrogen, halogen, C1-C12Alkyl or C1-C12Haloalkyl；
II.R1Represent C1-C12Alkyl, C1-C12Haloalkyl or C3-C8Cycloalkyl；
III.R2Represent hydrogen, C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynes
Base, C2-C12Halo alkynyl, C3-C8Cycloalkyl or C3-C8Halogenated cycloalkyl；
IV.R3And R4It is same or different, and represents hydrogen, halogen, C1-C12Alkyl, C1-C12Haloalkyl；
V.X represents oxygen or sulphur；
VI.n represents 0,1 or 2 integer.
Formula (I) compound specifically preferred according to the invention is compound as follows：
The compound of the present invention can the forms of one or more isomers exist.Isomers includes enantiomter, non-
Enantiomter, geometric isomer and cis-trans-isomer.Compound as shown in formula (I) of the present invention, due to carbon-carbon therein
Double bond connects different substituents and can form geometric isomer (representing different configurations respectively with Z and E), and the present invention includes
The mixture of Z-type isomers and E-isomer and their any ratios.Compound shown in formula (I) of the present invention, due to wherein
A carbon atom on connect four different substituents and form stereoisomer (different configurations is represented with R and S respectively),
The present invention includes R types isomers and S types isomers and the mixture of their any ratios.Chemical combination shown in formula (I) of the present invention
Thing, cis-trans-isomer is formed (respectively with cis due to connecting the substituent of more than 2 on cycloalkyl therein or Heterocyclylalkyl
The configuration different with trans expressions), the present invention includes cis types isomers and trans types isomers and their any ratios
Mixture.
The invention further relates to a kind of pest control/mite, formula (I) compound 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.
Change the invention further relates to a kind of pest control/mite, the method for harmful levels of pathogens, including by the formula (I) of biologic effective dose
Compound 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
At least one other compound of amount or the mixture of preparation are contacted and come 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 preventing harmful levels of pathogens, it may also be used for
Pest control/mite；And the compound having has very high bioactivity to some target pest germs so that in very low agent
Good effect is obtained with amount.
Currently preferred composition is the composition containing above-mentioned preferred compound.It is preferable that with above-mentioned excellent
The method for selecting compound.
The part formula (I) compound listed below with table 1 further illustrates the present invention, but does not limit the present invention.This
Fusing point is not calibrated given in invention, and when formula (I) compound synthesized by the present invention is viscous solid, some viscous solids are put
Non-tacky solids can be cured as by postponing, and when formula (I) compound synthesized by the present invention is viscous liquid, some viscous liquids are placed
After can cure, all compounds are considerable in LC-MS (APCI, Pos) (Agilent 1100Series LC/MSD) in table 1
Observe its molecular ion peak.Compound in table 11H NMR (Varian INOVA-300spectrometer) with
Tetramethylsilane (TMS) makees internal standard, deuterochloroform (CDCl3) or deuterated dimethyl sulfoxide (DMSO) make solvent.
Table 1：
Table 2
Compound shown in formula (I) of the present invention can be obtained by reaction equation 1 shown below；(II) in reaction equation 1 can be with
Obtained by reaction equation 2 shown below；(III) in reaction equation 1 can be obtained by reaction equation 3 shown below；In reaction equation
L be leaving group, such as chlorine, bromine or sulphonic acid ester, other substituents are outer unless specified otherwise to be limited as preceding.
Reaction equation 1：
The compound of formula (I) can be prepared so (reaction equation 1)：Suitable solvent for example dichloromethane, dichloroethanes,
The single solvents such as toluene, N,N-dimethylformamide (DMF), tetrahydrofuran, dioxane or water or it is any the two mixing it is molten
In agent, in 60~120 DEG C, in suitable alkali such as triethylamine, pyridine, sodium hydride, potassium hydroxide, potassium carbonate, sodium hydroxide or carbon
In the presence of sour sodium etc., formula (I) compound is reacted to obtain with the compound of formula (II) and the compound of formula (III).
The compound of formula (II) can be prepared so (reaction equation 2)：In suitable solvent such as methanol, ethanol, N, N- bis-
The single solvents such as methylformamide (DMF), tetrahydrofuran, dioxane or water or any in the mixed solvent of the two, in 0 DEG C extremely
Under system reflux temperature, in suitable alkali such as sodium hydride, sodium methoxide, sodium ethoxide, potassium tert-butoxide, potassium hydroxide, potassium carbonate, hydrogen-oxygen
In the presence of changing sodium or sodium carbonate etc., formula (II) compound is reacted to obtain with formula (IV) compound and formula (V) compound.
The compound of formula (III) can be prepared via a method which (reaction equation 3)：In condition of no solvent or suitable
The solvent such as single solvent such as methanol, ethanol, tetrahydrofuran, dioxane or water or any in the mixed solvent of the two, in 25 DEG C
To system reflux temperature, formula (IX) compound is reacted to obtain with the compound of formula (VII) and the compound of formula (VIII)；Formula (IX)
Compound is handled with AMMONIA TREATMENT or formula (IX) compound with the solid thing product of potassium phthalimide reaction gained with hydrazine hydrate
Up to the compound of formula (X)；The compound of processing formula (X) obtains the compound of 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, it can be not only used for prevention harmful insect or evil mite, it may also be used for prevention harmful levels of pathogens.Some compounds have harmful elder brother well
Worm or control of pest mite effect, are obtained with good effect under very low dosage.
Formula (I) compound provided by the invention, with bioactivity and the compound that has it is special with good bioactivity
Be not agricultural, gardening, flowers and sanitary insect pest/mite, harmful levels of pathogens prevention in terms of show activity.Described here is harmful
Biology include but not limited to this：
Harmful insect：Lepidoptera pest such as oriental armyworm, prodenia litura, diamondback moth, beet armyworm, cabbage looper, dark greyish green
Worm, Orthoptera such as blattaria, Thysanoptera such as cotton thrips, rice thrips, melon thrips, Homoptera such as leafhopper, plant hopper, aphid, Hymenoptera is such as
Sawfly larva, Diptera such as yellow-fever mosquito, culex, fly；Acarina evil mite such as Jie-Li enzyme-SQ, cotton spider mites, T.urticae Koch etc..
Harmful pathogen：Phytophthora species, white powder category species, Gibberella species, Venturia species, Sclerotinia kind
Class, Rhizoctonia species, Botrytis species, Pyricularia Sacc. species, Fusarium species.Such as rice blast (Pyricularia
oryzae)；Stripe rust of wheat (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust
Disease；Big wheat yellow rust (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust；Barley
With wheat powdery mildew (Erysiphe graminis), powdery mildew of cucumber (Sphaerotheca fuligenea), apple mildew
(Podosphaera leucotrichar) and uncinula necator (Podosphaera leucotrichar)；Wheat sharp eyespot and
Glume blight (Septoria nodorum).The compacted spore of length on cereal, mouth spore is mould, Septoria is sick, caryosphere shell Pseudomonas disease,
Pseudocercosporella herpotrichoides and take-all (Gaeumannomyces graminis).Peanut
Brown spot (Cercospora arachidicola) and the cercospora black spot of peanut (Cercosporidium personata)；Apple wheel
Line germ (Botryosphaeria berengriana f.sp piricola), Valsa mali (Cytospora sp.)；
Its Cercospora disease on beet, soybean and paddy.Tomato, cucumber, grape grey mould (Botrytis cinerea).Vegetables
Hinge spore on (such as cucumber) belongs to disease.Anthracnose on cucumber, scab of apple, cucumber downy mildew, downy mildew of garpe, potato
With the epidemic disease on tomato, list bacterium Thanatephorus cucumeris and other hosts such as wheat and barley on paddy,
Other rhizoctonias on vegetables；Sclerotinia sclerotiorum (Sclerotonia sclerotiorum)；Wheat scab (Gibberella
zeae)；Phytophthora capsici disease (Phytophythora capsici).
It is effective to control evil insects mites, harmful levels of pathogens, they also may be used when formula (I) compound of the present invention is used alone
To be used together with other biological chemical substance, these biochemicals include other insecticides, nematicide, acaricide and
Fungicide.
With (I) compound provided by the invention, as the Agrotechnical formulation of effective ingredient, desirable any one can be made
Kind of formulation flowed such as dry compressed particle, easily 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 helps
Agent includes carrier (diluent) and other adjuvants such as spreader-sticker, emulsifying agent, wetting agent, dispersant, sticker and distintegrant.This
Contain the compound that the present invention is mixed with the acceptable solid of inert, pharmacology or liquid diluent in a little preparations.
Desirable any type formulation such as dry compressed particle, 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, emulsifying agent, wetting agent, dispersant, sticker and distintegrant.Contain in these preparations with inert, pharmacology
Learn the compound that acceptable solid or liquid diluent are mixed with the present invention.
The invention will be further described with reference to embodiments, and the yield in embodiment is not optimized, the present invention its
Its compound is referred to following embodiments and prepared by pertinent literature.
Embodiment
Embodiment 1 this example demonstrates that in table 1 compound 21 preparation method
1.3 dichloroacetone (170mmol) of 4- chloromethyls -2- (4- aminomethyl phenyls) thiazole, 4- methyl thiobenzamides
After (150mmol), ethanol (150mL) and THF (75mL) are when flowing back and reaction 5-8 is small under stirring condition.Removing is most of molten
Agent, cooling, reaction solution are poured into frozen water, ethyl acetate extraction, wash organic phase, anhydrous sodium sulfate drying, and solvent is sloughed in decompression
Obtain yellow liquid title thing 28g.
4- aminomethyls -2- (4- aminomethyl phenyls) thiazole 4- chloromethyls -2- (4- aminomethyl phenyls) thiazole (45mmol), adjacent benzene
Dicarboximide potassium (50mmol) and N,N-dimethylformamide (DMF, 100mL) react 2-5 under 60-80 DEG C and stirring condition
After hour, it is cooled to room temperature, reaction solution is poured into frozen water, separates out solid.Filtering separated out solid and hydrazine hydrate
(100mmol), after ethanol (200mL) is when flowing back and reaction 3-5 is small under stirring condition, cools down, filtering.Filtrate removing is most of
After ethanol, ethyl acetate extraction, organic phase obtains title thing 6.0g through washing, anhydrous sodium sulfate drying, removed under reduced pressure solvent.
Under 0~5 DEG C of chloro Propionylacetic acid ethyl ester and stirring condition, to the dichloromethane of Propionylacetic acid ethyl ester (0.25mol)
In (100mL) solution, sulfonic acid chloride (0.25mol) is slowly added dropwise, drop finishes after room temperature reaction 12-15 hours to complete.Reaction solution
Pour into saturated brine, dichloromethane extraction, after organic phase is dried over anhydrous sodium sulfate, removed under reduced pressure solvent, obtains glassy yellow liquid
Body title thing 39.2g.
Under chloro- 0~5 DEG C of the 6- ethyl-pyrimidines of 2- methyl -4- hydroxyls -5- and stirring condition, to ethenylamidine hydrochloride (0.20mol) and
In methanol (100mL) solution of sodium methoxide (0.20mol), chloro Propionylacetic acid ethyl ester (0.20mol) is slowly added dropwise, drips Bi Jixu
After reacting 0.5-1.0h, it is heated under counterflow condition and reacts 3-5h, cool down, filtering, it is light that filtrate methanol removal obtains title thing
Yellow solid 30.8g.
The chloro- 6- ethyl-pyrimidines (0.06mol) of the chloro- 6- Ethyl-2-Methyls pyrimidine 2- methyl -4- hydroxyls -5- of 4,5- bis- and three
After chlorethoxyfos (0.24mol) stir 0.5-1.0h under the conditions of 0~5 DEG C, triethylamine (0.24mol) is slowly added dropwise.The reaction was continued
2-4h is after room temperature reaction 12-15h to complete.Reaction solution is poured into frozen water, and dichloromethane extraction, organic phase is through anhydrous sodium sulfate
After drying, removed under reduced pressure solvent, obtains title thing viscous solid 6.2g.
The chloro- 6- Ethyl-2-Methyls-N- of 5- ((2- (4- aminomethyl phenyls) thiazole-4-yl) methyl) pyrimidine -4- amine (21) 4,5-
Two chloro- 6- Ethyl-2-Methyls pyrimidines (0.01mol), 4- aminomethyls -2- (4- aminomethyl phenyls) thiazole (0.01mol) and anhydrous
N,N-dimethylformamide (30mL) mixture of potassium carbonate (0.02mol) reacts 4-8h in 60-100 DEG C to complete.Reaction solution
Pour into saturated brine, ethyl acetate extraction, after organic phase is dried over anhydrous sodium sulfate, removed under reduced pressure solvent, it is thick to obtain title thing
Product.Crude product is through silica gel column chromatography (VPetroleum ether/VEthyl acetate=25:1-15:1) title thing yellow solid 1.6g, purity are obtained after purification
98.0%.
Embodiment 2 this example demonstrates that in table 1 compound 37 preparation method
With reference to the method for embodiment 1, the 4- methyl thio benzoyls in embodiment 1 are replaced with 2- methyl thiobenzamides
Amine, it is phonetic can to prepare the chloro- 6- Ethyl-2-Methyls-N- of compound 5- in table 1 ((2- (2- aminomethyl phenyls) thiazole-4-yl) methyl)
Pyridine -4- amine (37).
Embodiment 3 this example demonstrates that in table 1 compound 273 preparation method
4- chloromethyls -2- (1.3 dichloroacetone (150mmol) of 2- aminomethyl phenyl) oxazoles and 2- methyl benzamides
(120mmol), reacts 3-8 hours to viscous solid title thing 24.9g is obtained completely under 60-120 DEG C and stirring condition, directly uses
In in next step.
4- aminomethyls -2- (2- aminomethyl phenyl) oxazole 4- chloromethyls -2- (2- aminomethyl phenyl) oxazoles (120mmol), it is adjacent
Phthalimide potassium (150mmol) and N,N-dimethylformamide (DMF, 200mL) react under 60-80 DEG C and stirring condition
After when 6-10 is small, it is cooled to room temperature, reaction solution is poured into frozen water, separates out solid.Filtering separated out solid and hydrazine hydrate
(250mmol), after ethanol (200mL) is when flowing back and reaction 3-5 is small under stirring condition, cools down, filtering.Filtrate removing is most of
After ethanol, ethyl acetate extraction, organic phase obtains title thing 16.6g through washing, anhydrous sodium sulfate drying, removed under reduced pressure solvent.
The synthetic method of chloro Propionylacetic acid ethyl ester in chloro ethyl acetoacetate reference embodiment 1, with acetoacetate second
Ester replaces Propionylacetic acid ethyl ester, can prepare chloro ethyl acetoacetate.
5- chloro-4-hydroxyl -2,6- dimethyl pyrimidines are with reference to the chloro- 6- ethyl-pyrimidines of 2- methyl -4- hydroxyls -5- in embodiment 1
Synthetic method, replace chloro Propionylacetic acid ethyl ester with chloro ethyl acetoacetate, can prepare 2,6- dimethyl -4- hydroxyls -
5- chlorine pyrimidines.
Synthesis of the chloro- 2,6- dimethyl pyrimidines of 4,5- bis- with reference to two chloro- 6- ethyl-pyrimidines of 2- methyl -4,5- in embodiment 1
Method, replaces the chloro- 6- ethyl-pyrimidines of 2- methyl -4- hydroxyls -5- with 2,6- dimethyl -4- hydroxyl -5- chlorine pyrimidine, can prepare 2,
6- dimethyl -4,5- dichloro pyrimidines.
The chloro- 2,6- dimethyl-N -s of 5- ((2- (2- aminomethyl phenyl) oxazole -4- bases) methyl) pyrimidine -4- amine (273) 4,5- bis-
Chloro- 2,6- dimethyl pyrimidines (0.005mol), 4- aminomethyls -2- (2- aminomethyl phenyl) oxazoles (0.005mol) and Carbon Dioxide
The tetrahydrofuran (10mL) and water (5mL) mixture of potassium (0.01mol) react 4-8h in 60-100 DEG C to complete.Reaction solution pours into
In saturated brine, ethyl acetate extraction, after organic phase is dried over anhydrous sodium sulfate, removed under reduced pressure solvent, obtains title thing crude product.
Crude product is through silica gel column chromatography (VPetroleum ether/VEthyl acetate=15:1-5:1) title thing white solid 1.1g, purity are obtained after purification
98.2%.
Other compounds of the present invention are referred to embodiment 1-3 and are synthesized, and if necessary, reference may also be made to coherent reference text
Offer.
The chloro- 6- Ethyl-2-Methyls-N- of 4 5- of embodiment ((2- (4- aminomethyl phenyls) thiazole-4-yl) methyl) pyrimidine -4- amine
The preparation of (21) 10% oil slick
Weigh compound 21 in formula provided by the invention (I) compound of (by weight percentage 10%) in right amount such as table 1, fit
Cosolvent (such as ethyl acetate or acetone), suitable pesticide used additives and the solvent (such as toluene) of amount are put into reaction kettle, first add
Enter a certain amount of solvent (such as toluene) and defoamer stirs 10~30min, add suitable stabilizer, synergist, penetrating agent
Etc. component, continue 10~30min of stirring, adjust pH value, then a effective amount of solvent is put into kettle, stir evenly rear blowing to obtain the final product
(21) 10% missible oil of the chloro- 6- Ethyl-2-Methyls-N- of 5- ((2- (4- aminomethyl phenyls) thiazole-4-yl) methyl) pyrimidine -4- amine.
It is raw to survey embodiment
The compounds of this invention is carried out to kill insects mites and bactericidal activity experiment, part of test results is as follows.
Insecticidal Activity of the embodiment 5 to aphid (Aphis fabae)
Activity for evaluation the compounds of this invention to homoptera pest, it is object to select aphid, indoors using infusion process
Determine activity of the compounds of this invention to aphid.
Infusion process：Testing compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.2%
The clear water of Tween80 emulsifying agents is diluted to required concentration, if the blank without testing compound is control, often handles 3 repetitions.
Black bean aphid is connected on just unearthed bean seedlings, every plant connects more than 20, and bean seedlings then are dipped in the present invention together with test worm carries
In formula (I) liquid of confession, taken out after 5 seconds, suck unnecessary liquid, be inserted into the sponge of water suction, covered with glass-tube, 24 it is small when after
Check survival and dead borer population, results are averaged.Active (death rate) with respect to blank control in percentage, be divided into A, B, C,
D level Four, 100 >=death rate (%) >=90 be A grades, 90>The death rate (%) >=70 be B grades, 70>The death rate (%) >=50 is C grades,
50>The death rate (%) >=0 is D grades.The result shows that the compounds of this invention has activity, and the compound having exists well to aphid
Still there is high activity under relatively low concentration, partial results are listed below：
Under 200mg/L concentration, the compounds of this invention 11,15,16,21,29,37,75,196,267,272,273,274,
279th, 280,289,298,306,314,346,355,387,523,524 etc. have aphid A grades of activity；
Under 50mg/L concentration, 11,21,29,37,75,196,267,273,274,279,289,298,306,314,346,
355th, 387,524 etc. have aphid A grades of activity；
Under 12.5mg/L concentration, 11,21,37,75,289,298,314,346 etc. have aphid A grades of activity；
Activity for further research the compounds of this invention to aphid, selects the compounds of this invention 11,21 and 289 etc. as generation
Table, while compare its height with imidacloprid to aphid activity.The result shows that the compounds of this invention 11,21,37,75 and 289
Activity be better than or equivalent to imidacloprid.Under 10.0mg/L concentration, the compounds of this invention 11,21,37,289 and imidacloprid pair
Aphid is respectively provided with 100% A levels activity；Under 2.5mg/L concentration, 11,21 and 37 pairs of aphids of the compounds of this invention have 90% or
More than A levels activity, 75,289 and imidacloprid it is active to B level of the aphid with 70-80%；Under 0.625mg/L concentration, the present invention
Compound 37 is to aphid with 80% B levels activity, and 21 pairs of aphids are with more than 60% C levels activity, 11 and 289 pairs of aphid tools
There is the D levels activity of 40-50%, imidacloprid is to the active less than 30% of aphid.
Biological evaluation of the embodiment 6 to mythimna separata (Mythimna separata)
Potter spray-on processes：Appropriate the compounds of this invention is weighed, is dissolved with n,N-Dimethylformamide, adds and spits on a small quantity
Warm 80 emulsifying agents, stir evenly, and add quantitative clear water, are configured to required concentration, if clear water is control.Fresh and tender maize leaves are taken to cut
The fragment basically identical into size, is put into and is lined with advance in the culture dish (Ф 90mm) of filter paper.Then 3 age of mythimna separata is accessed in ware
Larva 10, is put under Potter spray towers and carries out metered dose, and spray liquid measure 1ml, per 3 repetitions of concentration.It is disposed, covers
Upper ware lid, is placed in culture in recovery room, routine observation, when 72 is small after check and record test worm death condition, calculate the death rate
(%), results are averaged.Activity in percentage, is divided into A, B, C, D level Four, 100 >=death rate relative to blank control
(%) >=90 be A grades, 90>The death rate (%) >=70 be B grades, 70>The death rate (%) >=50 be C grades, 50>The death rate (%) >=0
For D grades.The result shows that the compounds of this invention has activity, and the compound having still has under relatively low concentration well to aphid
There is high activity, partial results are listed below：
Under 500mg/L concentration, the compounds of this invention 11,21,289,314 etc. has mythimna separata A grades of activity.
Under 200mg/L concentration, the compounds of this invention 11,21,289 etc. has mythimna separata A grades of activity.
Embodiment 7 evaluates the acaricidal activity of two-spotted spider mite (Tetranychus urticae)
Method：Testing compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.2%
The water of Tween80 emulsifying agents is diluted to required concentration, if the blank without testing compound is blank control, often handles 3 weights
It is multiple；The bean seedlings inoculation red spider to grow fine is selected, after red spider colonizes, will be cut with mite bean seedlings in the prepared present invention
Being impregnated 10 seconds in the liquid of formula (I) compound of offer, taking-up sucks unnecessary liquid with filter paper, inserts in and is filled with water in beaker, in
Cultivated in observation ward, 48 it is small when after check survival and dead mite number, have 100-200 mite on every plant of bean seedlings.Results are averaged.
At the same time using K2 as standard control.Active (death rate) in percentage, is divided into A, B, C, D level Four relative to blank control, 100 >=
The death rate (%) >=90 be A grades, 90>The death rate (%) >=70 be B grades, 70>The death rate (%) >=50 be C grades, 50>The death rate
(%) >=0 is D grades.The result shows that the compounds of this invention has activity, and the compound having is relatively low well to red spider
Still there is high activity under concentration, partial results are listed below：
Under 500mg/L concentration, the compounds of this invention 11,21,37,75,272,273,274,280,289,298,306,
314th, 346,355,387,523,524 etc. have red spider A grades of activity.
Under 200mg/L concentration, the compounds of this invention 11,21,37,273,289,298,346,355 and 387 etc. is to red spider
With A grades of activity.
Under 50mg/L concentration, the compounds of this invention 21,289,346,355 and 387 etc. has red spider A grades of activity.
Under 12.5mg/L concentration, the grade of the compounds of this invention 289 is active with more than 95% A levels to red spider, and 21 and 355
Deng active with 80% or more B levels to red spider.
Bactericidal activity (pot-culture method) of the embodiment 8 to wheat powdery mildew (Erisiphe griminis)
Method：Testing compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.05-0.2%
The sterile water of Tween80 emulsifying agents is diluted to required concentration；The basin alms bowl of cut-off stem 15cm or so, the sowing full stalwartness of wheat per alms bowl
20, seed, wait grow two leaves wholeheartedly afterwards be for experiment；Ready wheat seedling plant is taken to be sprayed through certain density medicament
Mist processing, carries out germ inoculation after one day.3 repetitions are often handled, separately set the blank without testing compound as blank control, business
Product fungicide Flusilazole is commercial References；After the culture of moisturizing thermophilic is fallen ill to blank control, lesion area is checked, calculate medicament
Preventive effect.Activity in percentage, is divided into A, B, C, D level Four relative to blank control, and 100%≤Fang Xiao≤90% is A grades, and 90%
＞ Fang Xiao≤70% is B grades, and 70% ＞ Fang Xiao≤50% is C grades, and 50% ＞ Fang Xiao≤0% is D grades.The result shows that the present invention
Compound has wheat powdery mildew prevention effect, and the compound having still has good prevention effect at low concentrations.Such as
Under 500mg/L concentration, the compounds of this invention 11,21,37,196,272,273,274,289,306,314,346,355,387,
523 grades have wheat powdery mildew more than 90% prevention effect, up to A grades of activity.
Prevention effect of the embodiment 9 to corn rust (Puccinia Polysora)
Method：Testing compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.05-0.2%
The sterile water of Tween80 emulsifying agents is diluted to required concentration, if the blank without testing compound is control, often handles 4 weights
It is multiple；Morbidity maize leaf is cut, lower spore is washed with 0.05-0.2%Tween80 or other suitable surfactant aqueous solutions, and
With 2~4 layers of filtered through gauze, concentration is made as 1 × 105The suspension of a spore/mL；It is above-mentioned to treat that corn length to 1 heart stage of 2 leaf sprays
The liquid of testing compound, spore suspension spray inoculation after 1 day, moves to moisturizing cabinet (relative humidity more than 95%, temperature after inoculation
20 DEG C~22 DEG C of degree), (5 000Lux of intensity of illumination~10000Lux) cultivate 15~24hr under low light condition；Treat blank control disease
When leaf rate is up to more than 50%, the incidence of each processing is investigated, calculates pharmacy control efficacy.The result shows that the compound of the present invention is to jade
Rice rust has prevention effect.Under the conditions of 500mg/L, the compounds of this invention 11,21,279,289,298,346,387 etc. pair
Corn rust is with more than 90% A levels prevention activity.
Claims (10)
1.N- hetervaromatic methyl pyrimidinamine compounds and preparation method and application, it is characterised in that represent N- with logical formula (I)
Hetervaromatic methyl pyrimidinamine compound and its isomers：
Wherein：
I.R is same or different, and represents hydrogen, halogen, nitro, cyano group, C1-C12Alkyl, C1-C12Haloalkyl, C2-C12
Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-C8It is miscellaneous
Cycloalkyl, C3-C8Halogenated heterocycloalkyl, C1-C12Alkoxyalkyl, C1-C12Alkoxy, C1-C12Halogenated alkoxy, C1-C12Alkane sulphur
Base, C1-C12Halogenated alkylthio, C1-C12Alkyl sulphinyl, C1-C12Alkylsulfinyl, C1-C12Alkyl sulphonyl,
C1-C12Halogenated alkyl sulfonyl, C1-C12Alkyl amine group, C1-C12It is haloalkyl amido, phenyl, identical or different by 1-5
Halogen, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy substitution phenyl, phenoxy group, by 1-5
A identical or different halogen, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6The benzene of halogenated alkoxy substitution
Epoxide；
II.R1Represent C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-C12Halogen
For alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-C8Heterocyclylalkyl, C3-C8Halogenated heterocycloalkyl, phenyl, by 1-5
Identical or different halogen, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6The phenyl of halogenated alkoxy substitution；
III.R2Represent hydrogen, C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-
C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-C8Heterocyclylalkyl, C3-C8Halogenated heterocycloalkyl, phenyl, quilt
1-5 identical or different halogens, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6Halogenated alkoxy substitution
Phenyl；
IV.R3And R4It is same or different, and represents hydrogen, halogen, C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl,
C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-C8Heterocycle alkane
Base, C3-C8Halogenated heterocycloalkyl, C1-C12Alkoxy, C1-C12Alkoxyalkyl, C1-C12It is alkyl acyl, phenyl, identical by 1-5
Or different halogens, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6Phenyl, the benzene oxygen of halogenated alkoxy substitution
Base, by the identical or different halogens of 1-5, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6Halogenated alkoxy
Substituted phenoxy group；
V.X represents oxygen or sulphur；
VI.n represents 0,1,2,3,4 or 5 integer；
In the definition of compound (I) given above, also it is used in compound word, represents as follows no matter term used is used alone
Substituent：
Halogen：Refer to fluorine, chlorine, bromine, iodine；
Alkyl：Refer to straight or branched alkyl；
Cycloalkyl：Refer to saturation or undersaturated cycloalkyl；
Heterocyclylalkyl：Refer to saturation or unsaturated heterocycle alkyl, at least 1 N, O and/or S in formula；
Halo：Refer to hydrogen moiety therein or all substituted by halogen atom.
2. N- hetervaromatic methyls pyrimidinamine compound according to claim 1, it is characterised in that in logical formula (I) compound：
I.R is same or different, and represents hydrogen, halogen, C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl, C2-C12
Haloalkenyl group, C2-C12Alkynyl, C2-C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-C8Heterocyclylalkyl, C3-C8
Halogenated heterocycloalkyl, C1-C12Alkoxyalkyl, C1-C12Alkoxy, C1-C12It is halogenated alkoxy, phenyl, identical or different by 1-5
Halogen, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6Phenyl, phenoxy group, the quilt of halogenated alkoxy substitution
1-5 identical or different halogens, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6Halogenated alkoxy substitution
Phenoxy group；
II.R1Represent C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-C12Halogen
For alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-C8Heterocyclylalkyl, C3-C8Halogenated heterocycloalkyl, phenyl, by 1-5
Identical or different halogen, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6The phenyl of halogenated alkoxy substitution；
III.R2Represent hydrogen, C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-
C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-C8Heterocyclylalkyl, C3-C8Halogenated heterocycloalkyl, phenyl, quilt
1-5 identical or different halogens, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6Halogenated alkoxy substitution
Phenyl；
IV.R3And R4It is same or different, and represents hydrogen, halogen, C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl,
C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, C3-C8Heterocycle alkane
Base, C3-C8Halogenated heterocycloalkyl, phenyl, by the identical or different halogens of 1-5, C1-C6Alkyl, C1-C6Haloalkyl, C1-C6
Alkoxy or C1-C6The phenyl of halogenated alkoxy substitution；
V.X represents oxygen or sulphur；
VI.n represents 0,1,2,3,4 or 5 integer.
3. N- hetervaromatic methyls pyrimidinamine compound according to claim 1, it is characterised in that in logical formula (I) compound：
I.R is same or different, and represents hydrogen, halogen, C1-C12Alkyl or C1-C12Haloalkyl；
II.R1Represent C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-C12Halogen
For alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, phenyl, by the identical or different halogens of 1-5, C1-C6Alkyl, C1-C6
Haloalkyl, C1-C6Alkoxy or C1-C6The phenyl of halogenated alkoxy substitution；
III.R2Represent hydrogen, C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-
C12Halo alkynyl, C3-C8Cycloalkyl, C3-C8Halogenated cycloalkyl, phenyl, by the identical or different halogens of 1-5, C1-C6Alkyl,
C1-C6Haloalkyl, C1-C6Alkoxy or C1-C6The phenyl of halogenated alkoxy substitution；
IV.R3And R4It is same or different, and represents hydrogen, halogen, C1-C12Alkyl or C1-C12Haloalkyl；
V.X represents oxygen or sulphur；
VI.n represents 0,1 or 2 integer.
4. N- hetervaromatic methyls pyrimidinamine compound according to claim 1, it is characterised in that leading to formula (I) compound is：
I.R is same or different, and represents hydrogen, halogen, C1-C12Alkyl or C1-C12Haloalkyl；
II.R1Represent C1-C12Alkyl, C1-C12Haloalkyl or C3-C8Cycloalkyl；
III.R2Represent hydrogen, C1-C12Alkyl, C1-C12Haloalkyl, C2-C12Alkenyl, C2-C12Haloalkenyl group, C2-C12Alkynyl, C2-
C12Halo alkynyl, C3-C8Cycloalkyl or C3-C8Halogenated cycloalkyl；
IV.R3And R4It is same or different, and represents hydrogen, halogen, C1-C12Alkyl, C1-C12Haloalkyl；
V.X represents oxygen or sulphur；
VI.n represents 0,1 or 2 integer.
5. N- hetervaromatic methyls pyrimidinamine compound according to claim 1, it is characterised in that logical formula (I) compound be as
Lower shown compound：
6. the preparation method of N- hetervaromatic methyls pyrimidinamine compound according to claim 1, it is characterised in that formula (I) institute
The compound shown is prepared by reaction shown below,
Reaction equation 1：
Reaction equation 2：
Reaction equation 3：
It is single molten in methylene chloride, dichloroethanes, toluene, N,N-dimethylformamide, tetrahydrofuran, dioxane or water
Agent or their any in the mixed solvents of the two, in 60~120 DEG C, in alkali triethylamine, pyridine, sodium hydride, potassium hydroxide, carbonic acid
In the presence of potassium, sodium hydroxide or sodium carbonate, formula (I) compound is reacted to obtain with the compound of formula (II) and the compound of formula (III)；
In solvent methanol, ethanol, N,N-dimethylformamide, tetrahydrofuran, dioxane or water single solvent or they are any
The in the mixed solvent of the two, under 0 DEG C to system reflux temperature, in alkali sodium hydride, sodium methoxide, sodium ethoxide, potassium tert-butoxide, hydrogen-oxygen
In the presence of changing potassium, potassium carbonate, sodium hydroxide or sodium carbonate, formula (II) change is reacted to obtain with formula (IV) compound and formula (V) compound
Compound；
It is solvent-free or solvent methanol, ethanol, tetrahydrofuran, dioxane or the single solvent of water or they it is any the two
In the mixed solvent, under 25 DEG C to system reflux temperature, reacted with the compound of formula (VII) and the compound of formula (VIII)
Formula (IX) compound；Formula (IX) compound AMMONIA TREATMENT or formula (IX) compound and gained after potassium phthalimide reaction
Solid thing product compound up to formula (X) is handled with hydrazine hydrate；The compound of processing formula (X) obtains the compound of formula (III)；
R, R in formula1、R2、R3、R4, X and n have and defined given in claim 1, L is leaving group chlorine or bromine.
7. according to the purposes of Claims 1 to 5 any one of them N- hetervaromatic methyl pyrimidinamine compounds, it is characterised in that
There is desinsection, mite killing and/or sterilization bioactivity under 15~5000 grams of active ingredients/hectare dosage.
8. according to Claims 1 to 5 any one of them N- hetervaromatic methyl pyrimidinamine compounds be used to prepare with desinsection,
The purposes of the medicine of mite killing and/or bactericidal activity.
9. a kind of desinsection, mite killing and/or bactericidal composition, it is characterised in that：Containing as active component such as claim 1~
5 any one of them N- hetervaromatic methyl pyrimidinamine compounds, the weight percentage of active component is 0.5- in composition
99%.
10. a kind of pest control/mite or the method for germ, it is characterised in that：By a effective amount of such as any one of Claims 1 to 5
The N- hetervaromatic methyl pyrimidinamine compounds are imposed on the harmful insects mites, germ or its growth medium.
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| WO2020007938A1 (en) * | 2018-07-03 | 2020-01-09 | Helmholtz-Zentrum für Infektionsforschung GmbH | PqsR INVERSE AGONISTS |
| WO2021136805A1 (en) * | 2020-01-02 | 2021-07-08 | Helmholtz-Zentrum für Infektionsforschung GmbH | NOVEL PqsR INVERSE AGONISTS |
| WO2021177160A1 (en) * | 2020-03-04 | 2021-09-10 | 日本曹達株式会社 | Azinyl azole compound and pest control agent |
| CN114516868A (en) * | 2020-11-20 | 2022-05-20 | 湖南海利常德农药化工有限公司 | N-heteroaryl methyl difluoromethyl pyrimidinamine compound and preparation method and application thereof |
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| US20230286942A1 (en) * | 2020-01-02 | 2023-09-14 | Helmholtz-Zentrum Fur Infektionsforschung Gmbh | NEW PqsR INVERSE AGONISTS |
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| WO2020007938A1 (en) * | 2018-07-03 | 2020-01-09 | Helmholtz-Zentrum für Infektionsforschung GmbH | PqsR INVERSE AGONISTS |
| JP2021529203A (en) * | 2018-07-03 | 2021-10-28 | ヘルムホルツ−ツェントルム フュア インフェクツィオンスフォルシュンク ゲーエムベーハー | PqsR inverse agonist |
| JP7399898B2 (en) | 2018-07-03 | 2023-12-18 | ヘルムホルツ－ツェントルム フュア インフェクツィオンスフォルシュンク ゲーエムベーハー | PqsR inverse agonist |
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| CN114516868A (en) * | 2020-11-20 | 2022-05-20 | 湖南海利常德农药化工有限公司 | N-heteroaryl methyl difluoromethyl pyrimidinamine compound and preparation method and application thereof |
| CN114516868B (en) * | 2020-11-20 | 2024-02-27 | 湖南海利常德农药化工有限公司 | N-heteroaryl methyl difluoromethyl pyrimidine amine compound, and preparation method and application thereof |
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