CN108003151B - N- hetervaromatic methyl pyrimidinamine compound and the preparation method and application thereof - Google Patents
N- hetervaromatic methyl pyrimidinamine compound and the preparation method and application thereof Download PDFInfo
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- CN108003151B CN108003151B CN201610959601.4A CN201610959601A CN108003151B CN 108003151 B CN108003151 B CN 108003151B CN 201610959601 A CN201610959601 A CN 201610959601A CN 108003151 B CN108003151 B CN 108003151B
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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
-
- 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 and the preparation method and application thereof shown in formula (I).R, R in formula1、R2、R3、R4, X and n have and define 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 pests such as homoptera pests such as aphid, plant hopper.
Description
Technical field
The invention belongs to kill insects mites, fungicide field, and in particular to have the N- heteroaryl 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 compounds control evil insects mites, the purposes of disinfect pathogen and method.
Background technique
Evil insects mites, the prevention and treatment of disinfect pathogen are extremely important during realizing high-efficiency agriculture.Evil insects mites, nocuousness simultaneously
The prevention and treatment of germ woods, herd, in the fields such as secondary, fishing and public health it is also critically important.Although have in the market many evil insects mites,
Disinfect pathogen pesticide control, but the continuous expansion due to market, external evil insects mites and disinfect pathogen, evil insects mites and having are fallen ill
The problems such as drug resistance of bacterium, drug service life, Pharmacoeconomic and people need scientists to the pay attention to day by day of environment
Constantly research, and then develop that new efficient, safety, economy, environment be compatible and killing insects mites, killing with different role mode
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), inhibits for Mitochondrial electron transmitting
Agent.Report that phonetic worm amine all has aphid and tetranychid higher based on document [pesticide: Vol 52, No.9,639-641,2013]
Activity, but phonetic worm amine is lower 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；In
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, be based on phase
Close the work of document and our early periods, we design and synthesize have not been reported with shown in formula (I) with killing insects mites, kill
The active N- hetervaromatic methyl pyrimidinamine compound of bacterium.The compounds of this invention shows living compared with the higher desinsection of imidacloprid (D2)
Property, while the compounds of this invention also has bactericidal activity.
Summary of the invention
The present invention provides the N- heteroaryl first with bioactivity such as pest control/mite, disinfect 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, C1-C12Alkyl, C1-C12Halogenated alkyl,
C2-C12Alkenyl, C2-C12Halogenated alkenyl, C2-C12Alkynyl, C2-C12Halo alkynyl, C3-C8Naphthenic base, 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 halogenated alkyl amido, phenyl, identical or different by 1-5
Halogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy replace phenyl, phenoxy group, by 1-5
A identical or different halogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy or C1-C6The benzene that halogenated alkoxy replaces
Oxygroup；
II.R1Represent C1-C12Alkyl, C1-C12Halogenated alkyl, C2-C12Alkenyl, C2-C12Halogenated alkenyl, C2-C12Alkynyl, C2-
C12Halo alkynyl, C3-C8Naphthenic base, C3-C8Halogenated cycloalkyl, C3-C8Heterocyclylalkyl, C3-C8Halogenated heterocycloalkyl, phenyl, quilt
1-5 identical or different halogens, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy or C1-C6What halogenated alkoxy replaced
Phenyl；
III.R2Represent hydrogen, C1-C12Alkyl, C1-C12Halogenated alkyl, C2-C12Alkenyl, C2-C12Halogenated alkenyl, C2-C12Alkynes
Base, C2-C12Halo alkynyl, C3-C8Naphthenic base, C3-C8Halogenated cycloalkyl, C3-C8Heterocyclylalkyl, C3-C8Halogenated heterocycloalkyl, benzene
Base, by the identical or different halogens of 1-5, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy or C1-C6Halogenated alkoxy
Substituted phenyl；
IV.R3And R4It is same or different, and represents hydrogen, halogen, C1-C12Alkyl, C1-C12Halogenated alkyl, C2-C12
Alkenyl, C2-C12Halogenated alkenyl, C2-C12Alkynyl, C2-C12Halo alkynyl, C3-C8Naphthenic base, C3-C8Halogenated cycloalkyl, C3-C8It is miscellaneous
Naphthenic base, C3-C8Halogenated heterocycloalkyl, C1-C12Alkoxy, C1-C12Alkoxyalkyl, C1-C12Alkyl acyl, phenyl, by 1-5
Identical or different halogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy or C1-C6The phenyl of halogenated alkoxy substitution,
Phenoxy group, by the identical or different halogens of 1-5, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy or C1-C6Alkyl halide
The phenoxy group that oxygroup replaces；
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, 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；
Naphthenic base: refer to saturated or unsaturated naphthenic base；
Heterocyclylalkyl: refer to saturation or unsaturated heterocycle alkyl, at least 1 N, O and/or S in formula；
It is halogenated: to refer to hydrogen moiety therein or all replaced by halogen atom.
Currently preferred compound are as follows: in formula (I):
I.R is same or different, and represents hydrogen, halogen, C1-C12Alkyl, C1-C12Halogenated alkyl, C2-C12Alkenyl,
C2-C12Halogenated alkenyl, C2-C12Alkynyl, C2-C12Halo alkynyl, C3-C8Naphthenic base, 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-C6Halogenated alkyl, C1-C6Alkoxy or C1-C6Phenyl, the benzene of halogenated alkoxy substitution
Oxygroup, by the identical or different halogens of 1-5, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy or C1-C6Haloalkoxy
The phenoxy group that base replaces；
II.R1Represent C1-C12Alkyl, C1-C12Halogenated alkyl, C2-C12Alkenyl, C2-C12Halogenated alkenyl, C2-C12Alkynyl, C2-
C12Halo alkynyl, C3-C8Naphthenic base, C3-C8Halogenated cycloalkyl, C3-C8Heterocyclylalkyl, C3-C8Halogenated heterocycloalkyl, phenyl, quilt
1-5 identical or different halogens, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy or C1-C6What halogenated alkoxy replaced
Phenyl；
III.R2Represent hydrogen, C1-C12Alkyl, C1-C12Halogenated alkyl, C2-C12Alkenyl, C2-C12Halogenated alkenyl, C2-C12Alkynes
Base, C2-C12Halo alkynyl, C3-C8Naphthenic base, C3-C8Halogenated cycloalkyl, C3-C8Heterocyclylalkyl, C3-C8Halogenated heterocycloalkyl, benzene
Base, by the identical or different halogens of 1-5, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy or C1-C6Halogenated alkoxy
Substituted phenyl；
IV.R3And R4It is same or different, and represents hydrogen, halogen, C1-C12Alkyl, C1-C12Halogenated alkyl, C2-C12
Alkenyl, C2-C12Halogenated alkenyl, C2-C12Alkynyl, C2-C12Halo alkynyl, C3-C8Naphthenic base, C3-C8Halogenated cycloalkyl, C3-C8It is miscellaneous
Naphthenic base, C3-C8Halogenated heterocycloalkyl, phenyl, by the identical or different halogens of 1-5, C1-C6Alkyl, C1-C6Halogenated alkyl,
C1-C6Alkoxy or C1-C6The phenyl that halogenated alkoxy replaces；
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 are as follows: in formula (I):
I.R is same or different, and represents hydrogen, halogen, C1-C12Alkyl or C1-C12Halogenated alkyl；
II.R1Represent C1-C12Alkyl, C1-C12Halogenated alkyl, C2-C12Alkenyl, C2-C12Halogenated alkenyl, C2-C12Alkynyl, C2-
C12Halo alkynyl, C3-C8Naphthenic base, C3-C8Halogenated cycloalkyl, phenyl, by the identical or different halogens of 1-5, C1-C6Alkyl,
C1-C6Halogenated alkyl, C1-C6Alkoxy or C1-C6The phenyl that halogenated alkoxy replaces；
III.R2Represent hydrogen, C1-C12Alkyl, C1-C12Halogenated alkyl, C2-C12Alkenyl, C2-C12Halogenated alkenyl, C2-C12Alkynes
Base, C2-C12Halo alkynyl, C3-C8Naphthenic base, C3-C8Halogenated cycloalkyl, phenyl, by the identical or different halogens of 1-5, C1-C6
Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy or C1-C6The phenyl that halogenated alkoxy replaces；
IV.R3And R4It is same or different, and represents hydrogen, halogen, C1-C12Alkyl or C1-C12Halogenated alkyl；
V.X represents oxygen or sulphur；
VI.n represents 0, an integer of 1 or 2.
Compound specifically preferred according to the invention are as follows: in formula (I):
I.R is same or different, and represents hydrogen, halogen, C1-C12Alkyl or C1-C12Halogenated alkyl；
II.R1Represent C1-C12Alkyl, C1-C12Halogenated alkyl or C3-C8Naphthenic base；
III.R2Represent hydrogen, C1-C12Alkyl, C1-C12Halogenated alkyl, C2-C12Alkenyl, C2-C12Halogenated alkenyl, C2-C12Alkynes
Base, C2-C12Halo alkynyl, C3-C8Naphthenic base or C3-C8Halogenated cycloalkyl；
IV.R3And R4It is same or different, and represents hydrogen, halogen, C1-C12Alkyl, C1-C12Halogenated alkyl；
V.X represents oxygen or sulphur；
VI.n represents 0, an integer of 1 or 2.
Formula (I) compound specifically preferred according to the invention is compound as follows:
The compound of the present invention can exist in the form of one or more isomers.Isomers includes enantiomter, non-
Enantiomter, geometric isomer and cis-trans-isomer.Such as formula (I) compound represented of the present invention, due to carbon-carbon therein
Double bond connects different substituent groups and can form geometric isomer (indicating 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.Formula (I) compound represented of the present invention, due to wherein
A carbon atom on connect four different substituent groups and form stereoisomer (different configurations is indicated with R and S respectively),
The present invention includes the mixture of R type isomers and S type isomers and their any ratios.Chemical combination shown in formula (I) of the present invention
Object forms cis-trans-isomer (respectively with cis due to connecting 2 or more substituent groups on naphthenic base therein or Heterocyclylalkyl
Different configurations is indicated with trans), the present invention includes cis type isomers and trans type isomers and their any ratios
Mixture.
The invention further relates to a kind of pest control/mites, formula (I) compound containing biologic effective dose of disinfect pathogen 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, disinfect pathogen formula (I) compound containing biologic effective dose and have
The composition of at least one other bioactive compound or preparation of effect amount.
The invention further relates to a kind of pest control/mites, the method for disinfect pathogen, including changing the formula (I) of biologic effective dose
It closes object and contacts evil insects mites, disinfect pathogen or its environment.Such a harmful insects mites, disinfect pathogen control method are also related to,
It does harm to formula (I) compound of insects mites, disinfect pathogen or its environment biologic effective dose or contains 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, disinfect pathogen.
Formula (I) compound of the invention has broad spectrum of activity: the compound having can be used for preventing and treating disinfect pathogen, it may also be used for
Pest control/mite；And the compound having has very high bioactivity to certain target pest germs, so that in very low agent
Good effect is obtained under 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 is to further illustrate the present invention, but restriction is of the invention.This
Fusing point given in invention is not calibrated, 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 solidify, 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, deuterated chloroform (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
It is 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 substituent groups are outer unless specified otherwise to be limited as preceding.
Reaction equation 1:
The compound of formula (I) can prepare in this way (reaction equation 1): suitable solvent for example methylene chloride, dichloroethanes,
The mixing of the single solvents such as toluene, N,N-dimethylformamide (DMF), tetrahydrofuran, dioxane or water or any the two 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) with the compound of formula (III).
The compound of formula (II) can prepare in this way (reaction equation 2): in suitable solvent such as methanol, ethyl alcohol, N, N- bis-
The in the mixed solvent of the single solvents such as methylformamide (DMF), tetrahydrofuran, dioxane or water or any the two, extremely in 0 DEG C
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 (V) compound with formula (IV) compound.
The compound of formula (III) can be prepared via a method which (reaction equation 3): in condition of no solvent or suitable
The in the mixed solvent of the single solvents such as solvent such as methanol, ethyl alcohol, tetrahydrofuran, dioxane or water or any the two, in 25 DEG C
To system reflux temperature, formula (IX) compound is reacted to obtain with the compound of formula (VII) with the compound of formula (VIII)；Formula (IX)
Compound AMMONIA TREATMENT or formula (IX) compound react the solid object product of gained with potassium phthalimide and are handled 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 has broad-spectrum biological living under 15~2250 grams of effective components/hectare dosage
Property, it can be not only used for prevention and treatment harmful insect or harmful mite, it may also be used for prevention and treatment disinfect pathogen.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 has good bioactivity special
Be not agricultural, gardening, flowers and sanitary insect pest/mite, disinfect pathogen prevention and treatment in terms of show activity.Nocuousness described here
Biology include but are 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 harmful mite such as Jie-Li enzyme-SQ, cotton spider mites, T.urticae Koch etc..
Harmful pathogen: Phytophthora type, white powder category type, Gibberella type, Venturia type, Sclerotinia kind
Class, Rhizoctonia type, Botrytis type, Pyricularia Sacc. type, Fusarium type.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)；Phytoph-thora capsici leonian (Phytophythora capsici).
It is effectively that they can also to control evil insects mites, disinfect pathogen when formula of the invention (I) compound 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, desired any one can be made
Such as dry compressed particle of kind of dosage form, Yi Liudong 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, emulsifier, wetting agent, dispersing agent, sticker and distintegrant.This
Contain in a little preparations 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 desired any dosage form, Yi Liudong can also be made in composition example of the 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, dispersing agent, 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.
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.
Specific embodiment
Embodiment 1 this example demonstrates that in table 1 compound 21 preparation method
1.3 dichloroacetone (170mmol) of 4- chloromethyl -2- (4- aminomethyl phenyl) thiazole, 4- methyl thiobenzamide
After (150mmol), ethyl alcohol (150mL) and THF (75mL) react 5-8 hours under reflux and stirring condition.Removing is most of molten
Agent, cooling, reaction solution pours into ice water, and organic phase is washed in ethyl acetate extraction, and anhydrous sodium sulfate is dry, and solvent is sloughed in decompression
Obtain yellow liquid title object 28g.
4- aminomethyl -2- (4- aminomethyl phenyl) thiazole 4- chloromethyl -2- (4- aminomethyl phenyl) thiazole (45mmol), adjacent benzene
Dicarboximide potassium (50mmol) and N,N-dimethylformamide (DMF, 100mL) react 2-5 under 60-80 DEG C and stirring condition
It after hour, is cooled to room temperature, reaction solution pours into ice water, and solid is precipitated.Filter solid and hydrazine hydrate be precipitated
(100mmol), cooling after ethyl alcohol (200mL) reacts 3-5 hours under reflux and stirring condition, filtering.Filtrate removing is most of
After ethyl alcohol, ethyl acetate extraction, organic phase obtains title object 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 methylene chloride of Propionylacetic acid ethyl ester (0.25mol)
In (100mL) solution, sulfonic acid chloride (0.25mol) slowly is added dropwise, drop finish after in room temperature reaction 12-15 hours to complete.Reaction solution
It pours into saturated brine, methylene chloride extraction, after organic phase is dried over anhydrous sodium sulfate, removed under reduced pressure solvent obtains glassy yellow liquid
Body title object 39.2g.
Under chloro- 0~5 DEG C of the 6- ethyl-pyrimidine of 2- methyl -4- hydroxyl -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) slowly is added dropwise, drips Bi Jixu
It after reacting 0.5-1.0h, is heated under counterflow condition and reacts 3-5h, cooling, filtering, it is light that filtrate methanol removal obtains title object
Yellow solid 30.8g.
The chloro- 6- ethyl-pyrimidine (0.06mol) of the chloro- 6- Ethyl-2-Methyl pyrimidine 2- methyl -4- hydroxyl -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) slowly is added dropwise.The reaction was continued
In room temperature reaction 12-15h to complete after 2-4h.Reaction solution pours into ice water, and methylene chloride extraction, organic phase is through anhydrous sodium sulfate
After drying, removed under reduced pressure solvent obtains title object viscous solid 6.2g.
The chloro- 6- Ethyl-2-Methyl-N- of 5- ((2- (4- aminomethyl phenyl) thiazole-4-yl) methyl) pyrimidine -4- amine (21) 4,5-
Two chloro- 6- Ethyl-2-Methyl pyrimidines (0.01mol), 4- aminomethyl -2- (4- aminomethyl phenyl) thiazole (0.01mol) and anhydrous
N,N-dimethylformamide (30mL) mixture of potassium carbonate (0.02mol) is in 60-100 DEG C of reaction 4-8h to complete.Reaction solution
It pours into saturated brine, ethyl acetate extraction, after organic phase is dried over anhydrous sodium sulfate, it is thick to obtain title object for removed under reduced pressure solvent
Product.Crude product is through silica gel column chromatography (VPetroleum ether/VEthyl acetate=25:1-15:1) title object yellow solid 1.6g, purity are obtained after purification
98.0%.
Embodiment 2 this example demonstrates that in table 1 compound 37 preparation method
Referring to the method for embodiment 1, the 4- methyl thio benzoyl in embodiment 1 is replaced with 2- methyl thiobenzamide
It is phonetic can to prepare the chloro- 6- Ethyl-2-Methyl-N- of compound 5- in table 1 ((2- (2- aminomethyl phenyl) thiazole-4-yl) methyl) for amine
Pyridine -4- amine (37).
Embodiment 3 this example demonstrates that in table 1 compound 273 preparation method
1.3 dichloroacetone (150mmol) of 4- chloromethyl -2- (2- aminomethyl phenyl) oxazole and 2- methyl benzamide
(120mmol) reacts 3-8 hours to viscous solid title object 24.9g is obtained completely under 60-120 DEG C and stirring condition, directly uses
In in next step.
4- aminomethyl -2- (2- aminomethyl phenyl) oxazole 4- chloromethyl -2- (2- aminomethyl phenyl) oxazole (120mmol), it is adjacent
Phthalimide potassium (150mmol) and N,N-dimethylformamide (DMF, 200mL) react under 60-80 DEG C and stirring condition
It after 6-10 hours, is cooled to room temperature, reaction solution pours into ice water, and solid is precipitated.Filter solid and hydrazine hydrate be precipitated
(250mmol), cooling after ethyl alcohol (200mL) reacts 3-5 hours under reflux and stirring condition, filtering.Filtrate removing is most of
After ethyl alcohol, ethyl acetate extraction, organic phase obtains title object 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 pyrimidine is referring to the chloro- 6- ethyl-pyrimidine of 2- methyl -4- hydroxyl -5- in embodiment 1
Synthetic method, replace chloro Propionylacetic acid ethyl ester with chloro ethyl acetoacetate, 2,6- dimethyl -4- hydroxyl-can be prepared
5- chlorine pyrimidine.
Synthesis of the chloro- 2,6- dimethyl pyrimidine of 4,5- bis- referring to the chloro- 6- ethyl-pyrimidine of 2- methyl -4,5- two in embodiment 1
Method replaces the chloro- 6- ethyl-pyrimidine of 2- methyl -4- hydroxyl -5- with 2,6- dimethyl -4- hydroxyl -5- chlorine pyrimidine, can prepare 2,
6- dimethyl -4,5- dichloro pyrimidine.
The chloro- 2,6- dimethyl-N-of 5- ((2- (2- aminomethyl phenyl) oxazole -4- base) methyl) pyrimidine -4- amine (273) 4,5- bis-
Chloro- 2,6- dimethyl pyrimidine (0.005mol), 4- aminomethyl -2- (2- aminomethyl phenyl) oxazole (0.005mol) and Carbon Dioxide
The tetrahydrofuran (10mL) and water (5mL) mixture of potassium (0.01mol) are in 60-100 DEG C of reaction 4-8h 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 object crude product.
Crude product is through silica gel column chromatography (VPetroleum ether/VEthyl acetate=15:1-5:1) title object white solid 1.1g, purity are obtained after purification
98.2%.
Other compounds of the invention are referred to embodiment 1-3 and are synthesized, and when necessary, reference may also be made to coherent reference text
It offers.
The chloro- 6- Ethyl-2-Methyl-N- of 4 5- of embodiment ((2- (4- aminomethyl phenyl) thiazole-4-yl) methyl) pyrimidine -4- amine
The preparation of (21) 10% oil slick
It weighs compound 21 in formula provided by the invention (I) compound such as table 1 of appropriate (by weight percentage 10%), fit
Cosolvent (such as ethyl acetate or acetone), suitable pesticide auxiliaries and the solvent (such as toluene) of amount are put into reaction kettle, first plus
Enter a certain amount of solvent (such as toluene) and defoaming agent stirs 10~30min, adds suitable stabilizer, synergist, penetrating agent
Etc. components, continue 10~30min of stirring, adjust pH value, then a effective amount of solvent is put into kettle, blowing after mixing evenly to obtain the final product
(21) 10% missible oil of the chloro- 6- Ethyl-2-Methyl-N- of 5- ((2- (4- aminomethyl phenyl) 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 test, part of test results is as follows.
Insecticidal Activity of the embodiment 5 to aphid (Aphis fabae)
It is evaluation the compounds of this invention to the activity of homoptera pest, selects aphid for object, use infusion process indoors
The compounds of this invention is determined to the activity of 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 emulsifier is diluted to required concentration, if the blank without untested compound is control, 3 repetitions of every processing.
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 and are mentioned
In formula (I) medical fluid of confession, is taken out after 5 seconds, suck extra medical fluid, 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 90 > death rate (%) >=70 is B grades, and 70 > death rate (%) >=50 is C grades,
50 > death rate (%) >=0 is D grades.The result shows that the compounds of this invention has activity well to aphid, and the compound having exists
Still there is high activity under lower 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,
279,280,289,298,306,314,346,355,387,523,524 etc. have A grades of activity to aphid；
Under 50mg/L concentration, 11,21,29,37,75,196,267,273,274,279,289,298,306,314,346,
355,387,524 etc. have A grades of activity to aphid；
Under 12.5mg/L concentration, 11,21,37,75,289,298,314,346 etc. have A grades of activity to aphid；
Further to study the compounds of this invention to the activity of aphid, select the compounds of this invention 11,21 and 289 etc. for generation
Table, while it is compared with imidacloprid to the active height of aphid.The result shows that the compounds of this invention 11,21,37,75 and 289
Activity be better than or be equivalent to imidacloprid.Under 10.0mg/L concentration, the compounds of this invention 11,21,37,289 and imidacloprid pair
Aphid all has 100% A grade activity；Under 2.5mg/L concentration, 11,21 and 37 pairs of aphids of the compounds of this invention have 90% or
The above A grade activity, 75,289 and B grade of the imidacloprid to aphid with 70-80% it is active；Under 0.625mg/L concentration, the present invention
For compound 37 to aphid with 80% B grade activity, 21 pairs of aphids are active with 60% or more C grade, 11 and 289 pairs of aphids tools
There is the D grade 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 process: appropriate the compounds of this invention is weighed, is dissolved with n,N-Dimethylformamide, adds and spits on a small quantity
Warm 80 emulsifiers, stir evenly, and quantitative clear water is added, is configured to required concentration, if clear water is control.Fresh and tender maize leaves are taken to cut
At the almost the same segment of size, it is put into and is lined in the culture dish (Ф 90mm) of filter paper in advance.Then 3 age of mythimna separata is accessed in ware
It larva 10, is put under Potter spray tower and carries out metered dose, spray liquid measure 1ml, 3 repetitions of every concentration.It is disposed, covers
Upper ware lid is placed in culture, routine observation in recovery room, test worm death condition is checked and recorded after 72 hours, calculates 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 is A grades, and 90 > death rate (%) >=70 is B grades, and 70 > death rate (%) >=50 is C grades, 50 > death rate (%) >=0
It is D grades.The result shows that the compounds of this invention has activity well to aphid, and the compound having still has under lower concentration
There is high activity, partial results be listed below:
Under 500mg/L concentration, the compounds of this invention 11,21,289,314 etc. has A grades of activity to mythimna separata.
Under 200mg/L concentration, the compounds of this invention 11,21,289 etc. has A grades of activity to mythimna separata.
Embodiment 7 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 emulsifier is diluted to required concentration, if the blank without untested compound is blank control, 3 weights of every processing
It is multiple；Select the bean seedlings to grow fine inoculation red spider that will cut with mite bean seedlings after red spider colonizes in the prepared present invention
It being impregnated 10 seconds in the medical fluid of formula (I) compound of offer, taking-up sucks extra medical fluid with filter paper, and it 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 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 is A grades, and 90 > death rate (%) >=70 is B grades, and 70 > death rate (%) >=50 is C grades, 50 > death rate
(%) >=0 is D grades.The result shows that the compounds of this invention has activity well to red spider, and the compound having is lower
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,
314,346,355,387,523,524 etc. have A grades of activity to red spider.
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 A grades of activity to red spider.
Under 12.5mg/L concentration, the compounds of this invention 289 is equal active with 95% or more A grade to red spider, and 21 and 355
Deng active with 80% or more B grade to red spider.
Bactericidal activity (pot-culture method) of the embodiment 8 to wheat powdery mildew (Erisiphe griminis)
Method: untested compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.05-0.2%
The sterile water of Tween80 emulsifier is diluted to required concentration；The basin alms bowl of cut-off stem 15cm or so, every alms bowl sow the full stalwartness of wheat
20, seed, wait grow two leaves wholeheartedly afterwards be for experiment；Ready wheat seedling plant is taken to spray through certain density medicament
Mist processing, carries out germ inoculation after one day.3 repetitions of every processing, set the blank without untested compound separately as blank control, quotient
Product fungicide Flusilazole is commercial References；After the onset of moisturizing thermophilic culture 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 of the invention
Compound has control efficiency to wheat powdery mildew, and the compound having still has good control efficiency 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 wait the control efficiency for having 90% or more to wheat powdery mildew, up to A grades of activity.
Control efficiency of the embodiment 9 to corn rust (Puccinia Polysora)
Method: untested compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.05-0.2%
The sterile water of Tween80 emulsifier is diluted to required concentration, if the blank without untested compound is control, 4 weights of every processing
It is multiple；Morbidity maize leaf is cut, washes lower spore with 0.05-0.2%Tween80 or other suitable surfactant aqueous solutions, and
With 2~4 layers of filtered through gauze, it is 1 × 10 that concentration, which is made,5The suspension of a spore/mL；To corn it is long spray to 1 heart stage of 2 leaf it is above-mentioned
The medical fluid of untested compound, spore suspension spray inoculation after 1 day, inoculation are moved back to moisturizing cabinet (95% or more relative humidity, temperature
20 DEG C~22 DEG C of degree), the r of (5 000Lux of intensity of illumination~10000Lux) culture 15 under low light condition~for 24 hours；To blank control disease
When leaf rate is up to 50% or more, 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 control efficiency.Under the conditions of 500mg/L, the compounds of this invention 11,21,279,289,298,346,387 etc. pair
Corn rust prevents and treats activity with 90% or more A grade.
Claims (7)
1.N- hetervaromatic methyl pyrimidinamine compound, it is characterised in that indicated with logical formula (I):
Wherein:
I.R is same or different, and represents hydrogen, halogen, C1-C12Alkyl, C1-C12Halogenated alkyl, C1-C12Alkoxy, C1-
C12Halogenated alkoxy；
II.R1Represent C1-C12Alkyl；
III.R2Represent C1-C12Alkyl, C1-C12Halogenated alkyl, C3-C8Naphthenic base；
IV.R3And R4It is same or different, and represents hydrogen, halogen；
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, 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；
It is halogenated: to refer to hydrogen moiety therein or all replaced by halogen atom.
2. N- hetervaromatic methyl pyrimidinamine compound according to claim 1, it is characterised in that logical formula (I) compound be as
Lower compound represented:
3. the preparation method of N- hetervaromatic methyl 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
The in the mixed solvent of agent or their any 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) with the compound of formula (III)；
In solvent methanol, ethyl alcohol, 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, (VI) chemical combination is reacted with formula (IV) compound with formula (V) compound
Object, formula (VI) compound obtain formula (II) compound through phosphorus oxychloride chlorination；
Solvent-free or in the single solvent of solvent methanol, ethyl alcohol, tetrahydrofuran, dioxane or water or they are both any
In the mixed solvent reacted under 25 DEG C to system reflux temperature with the compound of formula (VII) with the compound of formula (VIII)
Formula (IX) compound；Gained after formula (IX) compound AMMONIA TREATMENT or formula (IX) compound are reacted with potassium phthalimide
Solid object product the 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.
4. the purposes of N- hetervaromatic methyl pyrimidinamine compound according to claim 1 or 2, it is characterised in that 15~
There is desinsection, mite killing and/or sterilization bioactivity under 5000 grams of effective components/hectare dosage.
5. N- hetervaromatic methyl pyrimidinamine compound according to claim 1 or 2 is used to prepare with desinsection, mite killing
And/or the purposes of the drug of bactericidal activity.
6. a kind of desinsection, mite killing and/or bactericidal composition, it is characterised in that: containing as active component such as claim 1 or
N- hetervaromatic methyl pyrimidinamine compound described in 2, the weight percentage of active component is 0.5-99% in composition.
7. a kind of method of pest control/mite or germ, it is characterised in that: by a effective amount of N- as claimed in claim 1 or 2
Hetervaromatic methyl pyrimidinamine compound imposes on the harmful insects mites, germ or its somatomedin.
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| EP4085057A1 (en) * | 2020-01-02 | 2022-11-09 | Helmholtz-Zentrum für Infektionsforschung GmbH | Novel pqsr inverse agonists |
| JP2023043197A (en) * | 2020-03-04 | 2023-03-29 | 日本曹達株式会社 | Azinyl azole compound and pest control agent |
| 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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| US4352806A (en) * | 1981-11-13 | 1982-10-05 | Olin Corporation | Selected 2-trichloromethyl-4-pyrimidinyl carboxylic esters and their use as fungicides |
| CN103183669A (en) * | 2011-12-27 | 2013-07-03 | 湖南化工研究院 | Thiazole methylaminopyridine compounds and preparation method for same |
| CN103833667A (en) * | 2012-11-23 | 2014-06-04 | 中国中化股份有限公司 | Phenyl thiazolyl acrylonitrile compound and application thereof |
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| US4352806A (en) * | 1981-11-13 | 1982-10-05 | Olin Corporation | Selected 2-trichloromethyl-4-pyrimidinyl carboxylic esters and their use as fungicides |
| CN103183669A (en) * | 2011-12-27 | 2013-07-03 | 湖南化工研究院 | Thiazole methylaminopyridine compounds and preparation method for same |
| CN103833667A (en) * | 2012-11-23 | 2014-06-04 | 中国中化股份有限公司 | Phenyl thiazolyl acrylonitrile compound and application thereof |
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