CN110066270A - Multiamide class compound and the preparation method and application thereof - Google Patents

Multiamide class compound and the preparation method and application thereof Download PDF

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CN110066270A
CN110066270A CN201810068406.1A CN201810068406A CN110066270A CN 110066270 A CN110066270 A CN 110066270A CN 201810068406 A CN201810068406 A CN 201810068406A CN 110066270 A CN110066270 A CN 110066270A
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base
bromo
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formamide
pyrazoles
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CN110066270B (en
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柳爱平
任叶果
张再
汤非易
刘卫东
刘民华
李建明
刘兴平
胡礼
朱有为
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Hunan Research Institute of Chemical Industry
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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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

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  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses multiamide class compounds and the preparation method and application thereof shown in formula (I).Ar, R, R in formula1、R2、R3、R4And R5With definition given in specification.Formula (I) compound of the present invention has desinsection, mite killing bioactivity, especially has very high activity to pest such as aphid, mythimna separata etc..

Description

Multiamide class compound and the preparation method and application thereof
Technical field
The invention belongs to kill insects mites agent field, and in particular to have kill insects mites bioactivity multiamide class compound and its Preparation method, containing the compound kill insects mites agent composition and with these compounds control evil insects mites purposes with Method.
Background technique
Amides compound has broad spectrum of activity, well known to have adjacent amido benzamides in field of pesticides Compound has significant insecticidal activity.Adjacent amido benzamide compound as insecticide commercialization successively has chlorantraniliprole (D1), cyanogen insect amide (D2) and ring bromine insect amide (D3) etc., the govern-house-variety that chlorantraniliprole (D1) is prevented and treated as lepidoptera pest, Although its Time To Market, less than 10 years, sales volume early has reached 1,500,000,000 dollars, and row's insecticide sells the umber one.Adjacent amido benzene first Amide insecticides are with their own characteristics, each has something to recommend him.Chlorantraniliprole (D1) has excellent effect to lepidoptera pest, but to Homoptera Pest is helpless, and cyanogen insect amide (D2) and ring bromine insect amide (D3), which have homoptera pest activity compared with chlorantraniliprole, significantly to be mentioned Height, but chlorantraniliprole (D1) is defeated by lepidoptera pest effect.
To obtain the wider array of amides compound of active higher or activity profile, acyl group etc. is introduced adjacent amido benzene first by inventor In amide structure, design and synthesize it is a series of have no document report and have kill the multiamide class chemical combination of the broad spectrum of activity such as insects mites Object.Compared with D1, D2 and D3, the compounds of this invention is active to compose the wider or more high unique bioactivity feature of activity.
Summary of the invention
The present invention provides the multiamide class compounds and its isomery shown in formula (I) with bioactivity such as evil insects mites Body:
Wherein:
I.Ar represents a) C6-C12The heteroaryl of up to 10 carbon atoms of aryl or band, wherein some or all of hydrogen atom It can be replaced by identical or different substituent group in following: halogen, nitro, cyano, C1-C12Alkyl, C1-C12Alkoxy, C1-C12Alkylthio group, C1-C12Alkoxy carbonyl group, C1-C12Alkyl carbonyl epoxide, C1-C12Alkyl amine group, C2-C12Alkenyl, C2-C12Chain Alkenyl oxygroup, C2-C12Alkenyl thio, C2-C12Alkenyloxycarbonyl, C2-C12Alkenyl amido, C2-C12Alkynyl group, C2- C12Alkynyl group oxygroup, C2-C12Alkynyl group sulfenyl, C2-C12Alkynyl group Epoxide carbonyl, C2-C12Alkynyl group amido, C3-C8Naphthenic base, C3-C8Cycloalkyl oxy, C3-C8Cycloalkylsulfanyl, C3-C8Cycloalkyloxycarbonyl, C3-C8Naphthenic base amido, C6-C12Aryl or Heteroaryl, the C of up to 10 carbon atoms of band6-C12The heteroaryl oxygroup of up to 10 carbon atoms of aryloxy or band, C6-C12Virtue Heteroarylthio, the C of up to 10 carbon atoms of base sulfenyl or band6-C12Aryloxycarbonyl or band up to 10 carbon atoms it is miscellaneous Aryloxycarbonyl, C6-C12The heteroaryl amido, C of up to 10 carbon atoms of arylamine group or band6-C12Aryl methyl or with more Hetervaromatic methyl, C to 10 carbon atoms6-C12Heteroarylaryl, the C of up to 10 carbon atoms of aryl or band6-C12Virtue The heteroarylheteroaryl of up to 10 carbon atoms of base heteroaryl or band；B) such as in I.a) in identified meaning, wherein hydrogen atom Some or all of can be replaced by identical or different substituent group in following: halogen, nitro, cyano, C1-C12Alkyl, C1-C12Halogenated alkyl, C1-C12Alkoxy, C1-C12Halogenated alkoxy, C1-C12Alkyloxycarbonyl, C1-C12Alkyl amine group, C2- C12Alkenyl, C2-C12Halogenated alkenyl, C2-C12Alkenyl oxy, C2-C12Alkynyl group, C2-C12Haloalkynyl group, C2-C12Chain Alkynyl oxygroup, C3-C8Naphthenic base, C3-C8Halogenated cycloalkyl, C3-C8Cycloalkyl oxy, C6-C12Aryl or band up to 10 carbon originals Heteroaryl, the C of son6-C12The heteroaryl oxygroup of up to 10 carbon atoms of aryloxy or band；
II.R represents hydrogen, C1-C12Alkyl or C3-C8Naphthenic base；
III.R1、R2And R3It is same or different, and represents hydrogen, halogen, cyano, nitro, C1-C12Alkyl；
IV.R4Represent hydrogen or C1-C12Alkyl-carbonyl；
V.R4When representing hydrogen, R5Represent C1-C12Alkyl-carbonyl, CNCH2(CH3)2C、NH2COCH2(CH3)2C、CNCH2CH3CH Or NH2COCH2CH3CH；R4Represent C1-C12When alkyl-carbonyl, R5Represent C1-C12Alkyl, C3-C8Naphthenic base, C3-C8Heterocyclylalkyl, C1-C12Alkyl-carbonyl；
II., hydrogen atom can be partly or entirely selected from down in alkyl, naphthenic base or Heterocyclylalkyl in III., IV. and V. Identical or different substituent group replaces in column: halogen, cyano, C1-C6Alkyl, C1-C6Alkenyl, C1-C6Alkynyl group, C1-C6Alcoxyl Base, C3-C6Naphthenic base, C3-C6Heterocyclylalkyl, C1-C6Alkyl-carbonyl, C1-C6Alkoxy carbonyl, amino-carbonyl, C1-C6Alkylthio group Or C1-C6Alkyl amine group；
It is given above in the definition of formula (I), no matter term used exclusive use is also used in compound word, representative takes as follows Dai Ji:
Halogen: refer to fluorine, chlorine, bromine, iodine；
Alkyl: refer to linear or branched alkyl group；
Halogenated alkyl: referring to linear or branched alkyl group, hydrogen moiety on these alkyl or is all replaced by halogen atom；
Naphthenic base: refer to saturation or unsaturated ring alkyl；
Halogenated cycloalkyl: referring to saturation or unsaturated ring alkyl, and hydrogen moiety therein or is all replaced by halogen atom；
Alkenyl；Refer to linear or branched alkyl group, and can in any position on there are double bonds；
Halogenated alkenyl: referring to linear or branched alkyl group, and can in any position on there are double bond, and hydrogen atom therein Partly or entirely replaced by halogen atom；
Alkynyl group；Refer to linear or branched alkyl group, and can in any position on there are three keys；
Halo alkynyl: referring to linear or branched alkyl group, and can in any position on there are three keys, and hydrogen atom portion therein Divide or is all replaced by halogen atom；
Heterocyclylalkyl: the naphthenic base of at least 1 N, O and/or S in formula, such as tetrahydrofuran base；
Alkyl-carbonyl: referring to acyl group, such as methyl carbonyl, that is, acetyl group CH3CO, ethylcarbonyl group refer to propiono CH3CH2CO etc.；
C6-C12Aryl means phenyl or by its derivative cyclophane base or polyaromatic, such as naphthalene, xenyl；
The heteroaryl of up to 10 carbon atoms of band refers to a ring heteroaryl or polyheteroaromatic, in formula at least 1 N, O or/ And S, such as thiazolyl, pyrazolyl, thiadiazolyl group, pyridyl group, thienyl, benzothienyl, furyl, benzofuranyl, pyrroles Base, benzopyrrole base, indyl, benzindole base, imidazole radicals, benzimidazolyl, quinolyl, pyranose, pyrazinyl, pyrimidine Base, pyridazinyl, benzopyranyl, benzopyrazines base, benzo pyrimidine radicals, benzo pyridazinyl, oxazolyl, isoxazolyl, benzo are disliked Oxazolyl, benzo isoxazolyl, benzothiazolyl, isothiazolyl, benzisothia oxazolyl, pyrimido triazolyl, triazolyl or tetrazolium Base etc.；
Except the definition of compound given above (I), formula (I) compound also represents R=CH in formula (I)3；R5=CH2CH3 Formula (IA-1) compound, Ar, R in formula (IA-1)1、R2、R3And R4With the definition in above-mentioned formula (I) compound,
Currently preferred compound is compound shown in formula (I), in which:
I.Ar is selected from Ar-1~Ar-30 as follows:
II.R represents hydrogen, C1-C12Alkyl or C3-C8Naphthenic base；
III.R1、R2And R3It is same or different, and represents hydrogen, halogen, cyano, nitro, C1-C12Alkyl；
IV.R4Represent hydrogen or C1-C12Alkyl-carbonyl；
V.R4When representing hydrogen, R5Represent C1-C12Alkyl-carbonyl, CNCH2CH3CH、NH2COCH2CH3CH CNCH2(CH3)2C or NH2COCH2(CH3)2C；R4Represent C1-C12When alkyl-carbonyl, R5Represent C1-C12Alkyl, C3-C8Naphthenic base, C3-C8Heterocyclylalkyl, C1-C12Alkyl-carbonyl；
II., hydrogen atom can be partly or entirely chosen in alkyl, naphthenic base or Heterocyclylalkyl in III., IV. and V. Identical or different substituent group replaces in following: halogen, cyano or amino-carbonyl；
Except preferred formula (I) compound given above, preferred formula (I) compound also represents R=CH in formula (I)3；R4 =H；R5=CH2CH3Preferred formula (IA-2) compound, Ar, R in preferred formula (IA-2) compound1、R2And R3With above-mentioned Definition in preferred formula (I) compound,
The further preferred compound of the present invention is R in compound shown in formula (I)1、R2And R3Be it is same or different, And formula (IB-1) as follows~(IB-16) compound selected from methyl, cyano, nitro or halogen:
In compound shown in formula (IB-1)~(IB-16):
I.Ar is selected from Ar-1~Ar-30 as follows:
II.R represents hydrogen, C1-C12Alkyl or C3-C8Naphthenic base；
III.R4Represent hydrogen or C1-C12Alkyl-carbonyl；
IV.R4When representing hydrogen, R5Represent C1-C12Alkyl-carbonyl, CNCH2(CH3)2C、NH2COCH2(CH3)2C、CNCH2CH3CH Or NH2COCH2CH3CH；R4Represent C1-C12When alkyl-carbonyl, R5Represent C1-C12Alkyl, C3-C8Naphthenic base or C1-C12Alkyl oxycarbonyl Base；
Except above-mentioned further preferred formula (I) compound, further preferred formula (I) compound also represents R=in formula (I) CH3；R3=R4=H；R5=CH2CH3Further preferred following formula (IA-3)~(IA-10) compound, formula (IA-3)~ (IA-10) Ar in compound has the definition in above-mentioned formula (I) compound,
Compound specifically preferred according to the invention is R in compound shown in formula (I)1、R2And R3It is same or different, and Selected from methyl, cyano, nitro or halogen；R is selected from hydrogen, CNCH2(CH3)2C、NH2COCH2(CH3)2C、CNCH2CH3CH、 NH2COCH2CH3CH、CH3、CH3CH2、CH3CH2CH2、(CH3)2CH、CH3CH2CH2CH2、(CH3)2CHCH2、CH3CH2CH3CH、 CH3CH2(CH3)2C、(CH3)3C、(CH3)3CCH2、(CH3)3CCH2CH2Cyclopropyl or cyclopenta；R4Selected from hydrogen, CH3CO or CH3CH2CO；R4When selected from hydrogen, R5Selected from CH3CO、CH3CH2CO、(CH3)2CHCO、CH3CH2CH2CO、CNCH2(CH3)2C、 NH2COCH2(CH3)2C、CNCH2CH3CH or NH2COCH2CH3CH；R4Selected from CH3CO or CH3CH2When CO, R5Selected from C1-C6Alkyl, Such as CH3、CH3CH2、CH3CH2CH2、(CH3)2CH、CH3CH2CH2CH2、(CH3)2CHCH2、CH3CH2CH3CH、CH3CH2(CH3)2C、 (CH3)3C、(CH3)3CCH2、(CH3)3CCH2CH2、CH3OCH2CH2CH2、CH3OCH2CH2、CH3CO、CH3CH2CO、(CH3)2CHCO、 CH3CH2CH2CO、CNCH2(CH3)2C、NH2COCH2(CH3)2C、CNCH2CH3CH or NH2COCH2CH3Formula (IC-1)~(IC- of CH 256) compound:
Ar in compound shown in formula (IC-1)~(IC-256) is selected from Ar-1~Ar-30 as follows:
Specifically preferred formula (I) compound is following compounds to the present invention:
N- (the chloro- 6- of 2,4- bis- (ethyl (methyl) amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- base) -1H- Pyrazoles -5- formamide (05)；
N- (the chloro- 2- of 4- ((1- cyano -2- methylpropane -2- base) amido formacyl) -6- aminomethyl phenyl) bromo- 1- (3- of -3- Chloropyridine -2- base) -1H- pyrazoles -5- formamide (10)；
N- (4- cyano -2- ((1- cyano -2- methylpropane -2- base) amido formacyl) -6- aminomethyl phenyl) bromo- 1- of -3- (3- chloropyridine -2- base) -1H- pyrazoles -5- formamide (12)；
N- (the chloro- 6- of 2,4- bis- ((1- cyano -2- methylpropane -2- base) amido formacyl) phenyl) -3- bromo- 1- (3- chlorine Pyridine -2- base) -1H- pyrazoles -5- formamide (14)；
N- (the chloro- 2- of 4- ((1- dicyanopropane -2- base) amido formacyl) -6- aminomethyl phenyl) -3- bromo- 1- (3- chloropyridine - 2- yl) -1H- pyrazoles -5- formamide (28)；
N- (the bromo- 2- of 4- ((1- dicyanopropane -2- base) amido formacyl) -6- aminomethyl phenyl) -3- bromo- 1- (3- chloropyridine - 2- yl) -1H- pyrazoles -5- formamide (29)；
N- (4- cyano -2- ((1- dicyanopropane -2- base) amido formacyl) -6- aminomethyl phenyl) the bromo- 1- of -3- (3- chlorine pyrrole Pyridine -2- base) -1H- pyrazoles -5- formamide (30)；
N- (the chloro- 6- of 2,4- bis- ((1- dicyanopropane -2- base) amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide (32)；
N- (the chloro- 6- of the bromo- 2- of 4- ((1- dicyanopropane -2- base) amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide (33)；
N- (the chloro- 6- of the bromo- 4- of 2- ((1- dicyanopropane -2- base) amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide (35)；
N- (2- ((4- amido -4- oxygen butane -2- base) amido formacyl) the chloro- 6- aminomethyl phenyl of -4-) -3- bromo- 1- (3- chlorine Pyridine -2- base) -1H- pyrazoles -5- formamide (37)；
N- (2- ((4- amido -4- oxygen butane -2- base) amido formacyl) -4,6- dichlorophenyl) the bromo- 1- of -3- (3- chlorine pyrrole Pyridine -2- base) -1H- pyrazoles -5- formamide (41)；
N- acetyl group-N- (2- chloro- 4- methyl -6- (methylamino formoxyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide (82)；
N- acetyl group-N- (2- bromo- 4- methyl -6- (methylamino formoxyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide (83)；
N- acetyl group-N- (the bromo- 4- of 2- chloro- 6- (Ethylcarbamoyl) phenyl) bromo- 1- of -3- (3- chloropyridine -2- base) - 1H- pyrazoles -5- formamide (125)；
N- acetyl group-N- (2,4- bis- chloro- 6- (isopropyl amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide (194)；
N- acetyl group-N- (the chloro- 6- of the bromo- 2- of 4- (cyclopropyl amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide (375)；
N- acetyl group-N- (the chloro- 6- of the bromo- 2- of 4- (cyclopenta amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide (411)；
N- acetyl group-N- (the chloro- 6- of the bromo- 4- of 2- (cyclopenta amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide (413)；
N- acetyl group-N- (2- (acetyl group (methyl) amido formacyl) the chloro- 6- aminomethyl phenyl of -4-) -3- bromo- 1- (3- chlorine Pyridine -2- base) -1H- pyrazoles -5- formamide (730)；
N- acetyl group-N- (2- (acetyl group (methyl) amido formacyl) the bromo- 6- aminomethyl phenyl of -4-) -3- bromo- 1- (3- chlorine Pyridine -2- base) -1H- pyrazoles -5- formamide (731)；
N- acetyl group-N- (2- (acetyl group (methyl) amido formacyl) -4,6- dichlorophenyl) the bromo- 1- of -3- (3- chlorine pyrrole Pyridine -2- base) -1H- pyrazoles -5- formamide (734)；
N- acetyl group-N- (2- (acetyl group (methyl) amido formacyl) the bromo- 4- chlorphenyl of -6-) the bromo- 1- of -3- (3- chlorine pyrrole Pyridine -2- base) -1H- pyrazoles -5- formamide (738)；
N- acetyl group-N- (2- (acetyl group (ethyl) amido formacyl) the bromo- 4- chlorphenyl of -6-) the bromo- 1- of -3- (3- chlorine pyrrole Pyridine -2- base) -1H- pyrazoles -5- formamide (774)；
N- acetyl group-N- (2- (acetyl group (isopropyl) amido formacyl) -4,6- dichlorophenyl) the bromo- 1- of -3- (3- chlorine pyrrole Pyridine -2- base) -1H- pyrazoles -5- formamide (843)；
N- acetyl group-N- (2- (acetyl group (cyclopropyl) amido formacyl) -4,6- dichlorophenyl) the bromo- 1- of -3- (3- chlorine pyrrole Pyridine -2- base) -1H- pyrazoles -5- formamide (951)；
N- acetyl group-N- (2- (acetyl group (cyclopropyl) amido formacyl) the bromo- 4- chlorphenyl of -6-) -3- bromo- 1- (3- chlorine Pyridine -2- base) -1H- pyrazoles -5- formamide (954)；
N- acetyl group-N- (2- (acetyl group (cyclopenta) amido formacyl) -4,6- dichlorophenyl) the bromo- 1- of -3- (3- chlorine pyrrole Pyridine -2- base) -1H- pyrazoles -5- formamide (987)；
N- acetyl group-N- (2- (acetyl group (cyclopenta) amido formacyl) the bromo- 6- chlorphenyl of -4-) -3- bromo- 1- (3- chlorine Pyridine -2- base) -1H- pyrazoles -5- formamide (988)；
N- acetyl group-N- (2,4- bis- chloro- 6- (dimethyl amido formoxyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide (1023)；
N- acetyl group-N- (the chloro- 6- of the bromo- 4- of 2- (dimethyl amido formoxyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide (1026)；
N- acetyl group-N- (the chloro- 6- of 2,4- bis- (ethyl (methyl) amido formacyl) phenyl) -3- bromo- 1- (3- chloropyridine - 2- yl) -1H- pyrazoles -5- formamide (1059)；
N- acetyl group-N- (the chloro- 6- of the bromo- 4- of 2- (ethyl (methyl) amido formacyl) phenyl) -3- bromo- 1- (3- chloropyridine - 2- yl) -1H- pyrazoles -5- formamide (1062)；
N- acetyl group-N- (2,4- bis- chloro- 6- (diethyl amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide (1068)；
N- (the chloro- 2- of 4- ((1- cyano -2- methylpropane -2- base) amido formacyl) -6- aminomethyl phenyl) bromo- 1- of -3- (3, 5- dichloropyridine -2- base) -1H- pyrazoles -5- formamide (1784)；
N- (the chloro- 4- cyano -6- of 2- ((1- cyano -2- methylpropane -2- base) amido formacyl) phenyl) bromo- 1- of -3- (3, 5- dichloropyridine -2- base) -1H- pyrazoles -5- formamide (1790)；
N- (the chloro- 2- of 4- ((1- dicyanopropane -2- base) amido formacyl) -6- aminomethyl phenyl) -3- bromo- 1- (3,5- dichloro Pyridine -2- base) -1H- pyrazoles -5- formamide (1791)；
N- (4- cyano -2- ((1- cyano -2- methylpropane -2- base) amido formacyl) -6- aminomethyl phenyl) -3- methoxy Base -1- (3,5- dichloropyridine -2- base) -1H- pyrazoles -5- formamide (1979).
The compound of the present invention can exist in the form of one or more isomers.Isomers includes enantiomter, non- Enantiomter, geometric isomer.Formula (I) compound represented of the present invention, since carbon-to-carbon double bond therein connects different take Dai Ji and geometric isomer can be formed, different configurations is indicated with Z and E respectively, the present invention includes Z-type isomers and E type The mixture of isomers and their any ratios.Formula (I) compound represented of the present invention, due to connecting on wherein same carbon atom It connects four different substituent groups and forms stereoisomer, different configurations is indicated with R and S respectively, the present invention includes that R type is different The mixture of structure body and S type isomers and R isomers and any ratio of S isomers.
The invention further relates to formula (I) compound containing biologic effective dose and at least one of a kind of pest control/mite are another The outer composition selected from surfactant, solid diluent and liquid diluent.
The invention further relates to a kind of formula (I) compound containing biologic effective dose of pest control/mite and it is a effective amount of extremely The composition of few a kind of other bioactive compound or preparation.
The invention further relates to a kind of methods of pest control/mite, including formula (I) compound of biologic effective dose is contacted evil Insects mites or its environment.Also relate to such a pest/acarid control method, evil insects mites or its environment biologic effective dose The mixture of formula (I) compound or at least one other compound or preparation containing formula (I) compound and biologic effective dose It is contacted and carrys out pest control/mite.
Formula (I) compound of the invention has broad spectrum of activity: these compounds can be used for pest control/mite.And have Compound has very high bioactivity to certain harmful insects mites, so that being obtained with good effect at very low concentrations.
Currently preferred composition is the composition containing above-mentioned preferred compound.It is preferable that with above-mentioned excellent The method for selecting compound.
The present invention is further illustrated with the part formula (I) compound listed in 1~table of table 2 below, but does not limit this Invention.Fusing point given in the present invention is not calibrated；(I) compound of formula synthesized by the present invention is viscous liquid or viscous solid When, non-tacky solids can be cured as after some viscous liquids or the placement of viscous solid refrigerator；All compounds are in LC-MS in table 1 Its molecular ion peak can be observed in (APCI, Pos) (Agilent 1100Series LC/MSD)；Compound in table 11H NMR (Varian INOVA-300spectrometer or Varian INOVA-500spectrometer) with Tetramethylsilane (TMS) makees internal standard, deuterated chloroform (CDCl3) or deuterated dimethyl sulfoxide (DMSO) make solvent.
Table 1
Table 2
Formula (I) compound of the present invention can be obtained by reaction equation 1 shown below；(II) in reaction equation 1-1 can lead to Reaction equation 2 shown below is crossed to obtain；(VI) in reaction equation 1-2 can be obtained by reaction equation 3 shown below；In reaction equation 2 (VII) can be obtained by reaction equation 4 shown below；(VII) in reaction equation 3 can be obtained by reaction equation 4 shown below It arrives；(III), (VI), (VIII), (IX), (X) of the reaction equation 1 into reaction equation 4 can be by purchases or referring to related to (XI) Document synthesizes to obtain.The substituent group into reaction equation 4 of reaction equation 1 is outer unless specified otherwise to be limited as preceding, and wherein L is leaving group Such as chlorine or bromine.
Reaction equation 1:
Reaction equation 2:
Reaction equation 3:
Reaction equation 4:
The compound of formula (I) can be prepared in this way: suitable solvent for example tetrahydrofuran, 1,4- dioxane, toluene, In dimethylbenzene or n,N-Dimethylformamide, in -15 DEG C~system reflux temperature, in suitable alkali such as triethylamine, pyridine, hydrogen-oxygen In the presence of changing sodium, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide or sodium bicarbonate, the chemical combination shown in formula (II) Object and the reaction of formula (III) compound represented, obtain compound (reaction equation 1-1) shown in formula (I).
The compound of formula (I) is it is also possible that prepare: in suitable solvent such as tetrahydrofuran, 1,4- dioxane, first In benzene, dimethylbenzene or n,N-Dimethylformamide, in -15~system reflux temperature, in suitable alkali such as triethylamine, pyridine, hydrogen In the presence of sodium oxide molybdena, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide or sodium bicarbonate, change shown in formula (IV) Object and the reaction of formula (III) compound represented are closed, compound shown in formula (V) is obtained；Under similarity condition, formula (V) compound represented It is reacted again with formula (VI) compound represented, obtains compound (reaction equation 1-2) shown in formula (I).
The compound of formula (II) can be prepared in this way: in suitable solvent such as tetrahydrofuran, 1,4- dioxane, first In benzene, dimethylbenzene, acetone, methylene chloride, dichloroethanes or n,N-Dimethylformamide, in -15 DEG C~system reflux temperature, use Formula (VII) compound represented and the reaction of formula (VIII) compound represented, obtain compound (reaction equation 2) shown in formula (II).
The compound of formula (IV) can be prepared in this way: in suitable solvent such as tetrahydrofuran, 1,4- dioxane, first In benzene, dimethylbenzene, acetone, methylene chloride, dichloroethanes or n,N-Dimethylformamide, in -15 DEG C~system reflux temperature, use Formula (VII) compound represented and the reaction of formula (IX) compound represented, obtain compound (reaction equation 3) shown in formula (IV).
The compound of formula (VII) can be prepared in this way: in suitable solvent such as tetrahydrofuran, 1,4- dioxane, first In benzene, dimethylbenzene, acetone, acetonitrile, methylene chloride, dichloroethanes or n,N-Dimethylformamide, flow back in -15 DEG C~system warm Degree handles compound shown in formula (X) and formula (XI) with methylsufonyl chloride in the presence of suitable alkali such as pyridine or picoline Mixture obtains compound (reaction equation 4) shown in formula (VII).
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, can be not only used for pest control/mite, it may also be used for prevention and treatment disinfect pathogen, some compounds have well evil insects mites and/or Disinfect pathogen preventive and therapeutic effect is obtained with good effect at very low concentrations.
Formula (I) compound provided by the invention, with bioactivity and the compound that has has good bioactivity.It is special Be not agricultural, gardening, flowers and sanitary insect pest, germ prevention and treatment in terms of show activity.Harmful organism packet described here It includes, but is not limited only to this, also never limit the present invention.
Pest, harmful mite:
Homoptera pest such as leafhopper, plant hopper, aphid, lepidoptera pest for example oriental armyworm, snout moth's larva, prodenia litura, diamondback moth, Beet armyworm, cabbage looper, cabbage caterpillar etc., Hymenoptera pest such as sawfly larva etc., Diptera pest such as yellow-fever mosquito, culex, fly etc., Acarina such as cotton spider mites, Zhu are disturbed by making noise tetranychid, the full melon mite of citrus, Shenmu-Yanan railway, apple tetranychus, citrus rust mite, Rhizoglyphus hyacinthi, 2 points Tetranychid etc..
Particularly, lead to formula (I) compound to homoptera pest such as aphid, plant hopper etc. and lepidoptera pest such as mythimna separata etc., Still there is activity well under low concentration.
Harmful disease:
Oomycetes diseases, such as downy mildew, white rust, samping off, pythium rot, epidemic disease, late blight；
Fungi Imperfecti disease, as wilt disease, root rot, damping-off, anthracnose, verticillium wilt, scab, gray mold, brown spot, Black spot, spot blight, early blight, ring spot, leaf blight, base rot disease etc.；
Load fungus diseases, such as rust, smut；
Sac fungus disease, such as powdery mildew, sclerotiniose (flax sclerotiniose, sclerotinia sclerotiorum, soybean sclerotinia crown rot, peanut sclerotium Disease, tobacco sclerotiniose, capsicum sclerotiniose, eggplant sclerotiniose, bean sclerotinia rot, pea sclerotiniose, cucumber timberrot, balsam pear sclerotium Disease, wax gourd sclerotinia, watermelon sclerotiniose, celery sclerotiniose), scab etc.；
Particularly, the compounds of this invention still has corn rust, rice sheath blight disease etc. living well under low concentration Property.
Due to its positive characteristic, above compound is advantageously used for protection agricultural and the important crop of horticulture, family Injury of the environment that poultry and breeding stock and the mankind often go from evil insects mites, germ.
To obtain ideal effect, the dosage of compound changes because of various factors, for example, compound used therefor, pre- protection, Type, gradient of infection, weather conditions, application method, the dosage form of use of harmful organism.
The invention also includes to lead to formula (I) compound as desinsection/acaricidal composition of active component.This kills insects mites combination The weight percentage of active component is between 0.5-99% in object.Further include agricultural in the desinsection/acaricidal composition, forestry, defend Acceptable carrier in life.
When formula of the invention (I) compound is used alone, to control evil insects mites, germ be it is effective, they can also be with Other biological chemical substance is used together, these biochemicals include other insecticides, fungicide, herbicide, plant life Long regulator, acaricide or fertilizer etc., and thus can produce additional advantage and effect.
With (I) compound provided by the invention, as the preparation of effective ingredient, desired any agent can be made Such as dry compressed particle of type, 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 auxiliary agent packet Include carrier (diluent) and other adjuvants such as spreader-sticker, emulsifier, wetting agent, dispersing agent, sticker and distintegrant.These systems Contain in agent and is mixed with the compound of the present invention with the acceptable solid of inert, pharmacology or liquid diluent.
Such as dry compressed particle of 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.
It should be appreciated that various transformation and change can be carried out in scope defined by the claims of the present invention.
The invention will be further described with reference to embodiments, and the yield in embodiment is not optimized.
Specific embodiment
Embodiment 1 this example demonstrates that in table 1 compound 05 preparation
Chloro- 4H- benzo [d] [1,3] oxazines-of 2- (the bromo- 1- of 3- (3- chloropyridine -2- base) -1H- pyrazoles -5- base) -6,8- two Methylsufonyl chloride (2ml) is added to 2- amino -3,5- dichlorobenzoic acid in batches under -10~0 DEG C and stirring condition by 4- ketone (10mmol), the bromo- 1- of 3- (3- chloropyridine -2- base) -1H- pyrazoles -5- carboxylic acid (10mmol), pyridine (4ml) and acetonitrile (50mL) Mixture in.Then insulation reaction 3-5h gives free rein to be warming up to room temperature reaction 1-2h.Brine ice is added, filters precipitation Solid, washing, drying, obtains title compound faint yellow solid 4.25g, is directly used in and synthesizes in next step.
N- (the chloro- 6- of 2,4- bis- (ethyl (methyl) amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- base) -1H- Pyrazoles -5- formamide drips tetrahydrofuran (2mL) solution of N- methyl ethyl-amine (12mmol) under -10~0 DEG C and stirring condition Add to chloro- 4H- benzo [d] [1,3] oxazines -4- ketone of 2- (the bromo- 1- of 3- (3- chloropyridine -2- base) -1H- pyrazoles -5- base) -6,8- two In tetrahydrofuran (THF, the 8mL) solution of (5mmol).Then insulation reaction 3-5h gives free rein to be warming up to room temperature reaction 1-2h. Brine ice is added, filters the crude product of precipitation.Crude product is pure through column chromatography (V petrol ether/ethyl acetate=10:1~5:1) separation Change to obtain title object white solid 0.85g.
Embodiment 2 this example demonstrates that in table 1 compound 10 preparation
The chloro- 8- methyl -4H- benzo [d] [1,3] of 2- (the bromo- 1- of 3- (3- chloropyridine -2- base) -1H- pyrazoles -5- base) -6- is disliked Methylsufonyl chloride (2ml) is added to 2- amino -3- methyl-5-chloro benzene in batches under -10~0 DEG C and stirring condition by piperazine -4- ketone Formic acid (10mmol), the bromo- 1- of 3- (3- chloropyridine -2- base) -1H- pyrazoles -5- carboxylic acid (10mmol), pyridine (4ml) and acetonitrile In the mixture of (50mL).Then insulation reaction 3-5h gives free rein to be warming up to room temperature reaction 1-2h.Brine ice, filtering is added The solid of precipitation, washing, drying, obtains title compound off-white powder 3.50g, is directly used in and synthesizes in next step.
N- (the chloro- 2- of 4- ((1- cyano -2- methylpropane -2- base) amido formacyl) -6- aminomethyl phenyl) bromo- 1- (3- of -3- Chloropyridine -2- base) -1H- pyrazoles -5- formamide (10) is under -10~0 DEG C and stirring condition, by 3- amido -3- methylbutyronitrile Tetrahydrofuran (2mL) solution of (2.2mmol) is added dropwise to 2- (the bromo- 1- of 3- (3- chloropyridine -2- base) -1H- pyrazoles -5- base) -6- In tetrahydrofuran (THF, 5mL) solution of chloro- 8- methyl -4H- benzo [d] [1,3] oxazines -4- ketone (2mmol).Insulation reaction 3- Then 5h gives free rein to be warming up to room temperature reaction 1-2h.Brine ice is added, filters the crude product of precipitation.Crude product is chromatographed through column (V petrol ether/ethyl acetate=10:1~5:1) isolates and purifies to obtain title object white solid 0.48g.
Embodiment 3 this example demonstrates that in table 1 compound 29 preparation
The bromo- 8- methyl -4H- benzo [d] [1,3] of 2- (the bromo- 1- of 3- (3- chloropyridine -2- base) -1H- pyrazoles -5- base) -6- is disliked Methylsufonyl chloride (2ml) is added to 2- amino -3- methyl -5- bromobenzene in batches under -10~0 DEG C and stirring condition by piperazine -4- ketone Formic acid (10mmol), the bromo- 1- of 3- (3- chloropyridine -2- base) -1H- pyrazoles -5- carboxylic acid (10mmol), pyridine (4ml) and acetonitrile In the mixture of (50mL).Then insulation reaction 3-5h gives free rein to be warming up to room temperature reaction 1-2h.Brine ice, filtering is added The solid of precipitation, washing, drying, obtains title compound off-white powder 3.62g, is directly used in and synthesizes in next step.
N- (the bromo- 6- of 2- methyl -4- ((1- cyanopropyl -2- base) amido formacyl)) phenyl) the bromo- 1- of -3- (3- chlorine pyrrole Pyridine -2- base) -1H- pyrazoles -5- formamide is under -10~0 DEG C and stirring condition, by the tetrahydro furan of 3- amido butyronitrile (2.2mmol) (2mL) solution of muttering is added dropwise to 2- (the bromo- 1- of 3- (3- chloropyridine -2- base) -1H- pyrazoles -5- base) bromo- 8- methyl -4H- benzo of -6- In tetrahydrofuran (THF, 5mL) solution of [d] [1,3] oxazines -4- ketone (2mmol).Then insulation reaction 3-5h gives free rein to rise Warm to room temperature reaction 1-2h.Brine ice is added, filters the crude product of precipitation.Crude product chromatographs (V petrol ether/ethyl acetate through column =10:1~5:1) isolate and purify to obtain title object white solid 0.50g.
Embodiment 4 this example demonstrates that in table 1 compound 738 preparation
The chloro- 4H- benzo [d] [1,3] of the bromo- 2- of 8- (the bromo- 1- of 3- (3- chloropyridine -2- base) -1H- pyrazoles -5- base) -6- is disliked Methylsufonyl chloride (2ml) is added to the bromo- 5- chlorobenzene first of 2- amino -3- in batches under -10~0 DEG C and stirring condition by piperazine -4- ketone Acid (10mmol), the bromo- 1- of 3- (3- chloropyridine -2- base) -1H- pyrazoles -5- carboxylic acid (10mmol), pyridine (4ml) and acetonitrile In the mixture of (50mL).Then insulation reaction 3-5h gives free rein to be warming up to room temperature reaction 1-2h.Brine ice, filtering is added The solid of precipitation, washing, drying, obtains title compound faint yellow solid 4.10g, is directly used in and synthesizes in next step.
N- (the chloro- 6- of the bromo- 4- of 2- (methylamino formoxyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- base) -1H- pyrazoles - The aqueous solution (15mmol) of methylamine is added dropwise to the bromo- 2- of the 8- (bromo- 1- (3- of 3- under -10~0 DEG C and stirring condition by 5- formamide Chloropyridine -2- base) -1H- pyrazoles -5- base) chloro- 4H- benzo [d] [1,3] oxazines -4- ketone (5mmol) of -6- tetrahydrofuran In (THF, 10mL) solution.Then insulation reaction 3-5h gives free rein to be warming up to room temperature reaction 1-2h.Brine ice, filtering is added The solid of precipitation, washing, drying, obtains title compound off-white powder 1.69g, is directly used in and synthesizes in next step.
N- acetyl group-N- (2- (acetyl group (methyl) amido formacyl) the bromo- 4- chlorphenyl of -6-) the bromo- 1- of -3- (3- chlorine pyrrole Pyridine -2- base) acetic anhydride (10mmol) in -10~0 DEG C and under stirring condition, is added dropwise to N- by -1H- pyrazoles -5- formamide (738) (the chloro- 6- of the bromo- 4- of 2- (methylamino formoxyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- base) -1H- pyrazoles -5- formamide In N,N-dimethylformamide (DMF, 8mL) solution of (2mmol) and sodium hydride (60%, 10mmol).Insulation reaction 4-6h, so After be allowed to warm naturally to room temperature reaction 1-2h.Brine ice is added, filters the crude product of precipitation.Crude product chromatographs (V petroleum through column Ether/ethyl acetate=10:1~5:1) isolate and purify to obtain title object white solid 0.39g.
Embodiment 5 this example demonstrates that in table 1 compound 843 preparation
Chloro- 4H- benzo [d] [1,3] oxazines-of 2- (the bromo- 1- of 3- (3- chloropyridine -2- base) -1H- pyrazoles -5- base) -6,8- two Methylsufonyl chloride (2ml) is added to 2- amino -3,5- dichlorobenzoic acid in batches under -10~0 DEG C and stirring condition by 4- ketone (10mmol), the bromo- 1- of 3- (3- chloropyridine -2- base) -1H- pyrazoles -5- carboxylic acid (10mmol), pyridine (4ml) and acetonitrile (50mL) Mixture in.Then insulation reaction 3-5h gives free rein to be warming up to room temperature reaction 1-2h.Brine ice is added, filters precipitation Solid, washing, drying, obtains title compound faint yellow solid 3.80g, is directly used in and synthesizes in next step.
N- (2,4- bis- chloro- 6- (isopropyl amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- base) -1H- pyrazoles - Tetrahydrofuran (2mL) solution of isopropylamine (12mmol) is added dropwise to 2- (3- under -10~0 DEG C and stirring condition by 5- formamide Bromo- 1- (3- chloropyridine -2- base) -1H- pyrazoles -5- base) two chloro- 4H- benzo [d] [1,3] oxazines -4- ketone (5mmol) of -6,8- In tetrahydrofuran (THF, 8mL) solution.Then insulation reaction 3-5h gives free rein to be warming up to room temperature reaction 1-2h.Cryosel is added Water, filters the solid of precipitation, and washing, drying obtain title compound off-white powder 1.82g, be directly used in and synthesize in next step.
N- acetyl group-N- (2- (acetyl group (isopropyl) amido formacyl) -4,6- dichlorophenyl) the bromo- 1- of -3- (3- chlorine pyrrole Pyridine -2- base) -1H- pyrazoles -5- formamide is in -10 DEG C~0 DEG C and under stirring condition, by acetic anhydride (10mmol) be added dropwise to N- (2, 4- bis- chloro- 6- (isopropyl amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- base) -1H- pyrazoles -5- formamide In N,N-dimethylformamide (DMF, 6mL) solution of (2mmol) and sodium hydride (60%, 10mmol).Insulation reaction 4-6h, so After be allowed to warm naturally to room temperature reaction 1-2h.Brine ice is added, filters the crude product of precipitation.Crude product chromatographs (V petroleum through column Ether/ethyl acetate=10:1~6:1) isolate and purify to obtain white solid title object 0.35g.
Embodiment 6 this example demonstrates that in table 1 compound 1059 preparation
N- (the chloro- 6- of 2,4- bis- (ethyl (methyl) amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- base) -1H- Pyrazoles -5- formamide is synthesized referring to above-described embodiment 1.
N- acetyl group-N- (2- (ethyl (methyl) amido formacyl) -4,6- dichlorophenyl) -3- bromo- 1- (3- chloropyridine - 2- yl) chloroacetic chloride (2.2mmol) in -10~0 DEG C and under stirring condition, is added dropwise to N- (2,4- bis- by -1H- pyrazoles -5- formamide Chloro- 6- (isopropyl amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- base) -1H- pyrazoles -5- formamide (2mmol) and In tetrahydrofuran (THF, 8mL) solution of sodium hydride (60%, 4mmol).Then insulation reaction 4-6h gives free rein to be warming up to room Temperature reaction 1-2h.Brine ice is added, filters the crude product of precipitation.Crude product chromatographs (V petrol ether/ethyl acetate=10:1 through column ~5:1) isolate and purify to obtain title object white solid 0.52g.
The other compounds of the present invention are referred to the method and relevant references preparation of 1~embodiment of embodiment 6.
Biological activity determination embodiment
The compounds of this invention is carried out to kill insects mites and bactericidal activity test, the results showed that the compound of the present invention is shown Kill insects mites activity well out, part of test results is as follows:
Biological evaluation of the embodiment 7 to mythimna separata (Mythimna separata)
Potter spray-on process: untested compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing The clear water of 0.2%Tween80 emulsifier is diluted to required concentration, if the blank without untested compound is control.It takes fresh and tender Maize leaves are cut into the almost the same segment of size, are put into and are lined in the culture dish (Ф 90mm) of filter paper in advance.Then it is connect in ware Enter 3 instar larvae of mythimna separata 10, be put under Potter spray tower and carry out metered dose, spray liquid measure 1ml, 3 repetitions of every concentration.Place Reason finishes, and covers ware lid, is placed in culture, routine observation in recovery room and test worm death condition is checked and recorded after 72 hours, count The death rate is calculated, results are averaged.Active (death rate) in percentage with respect to blank control, divides A, B, C, D level Four, 100 >= The death rate (%) >=90 is A grades, and 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 mythimna separata, and the compound having is very low dense Still there is high activity under degree, partial results are listed below:
Under 500mg/L concentration, the compounds of this invention 12,10,14,28,29,30,32,33,34,35,37,41,82,83, 194、374、375、411、413、730、731、734、738、843、951、954、987、988、1026、1073、1784、1787、 1791,1979 and 1982 etc. A grades of activity are all had to mythimna separata with D1, D2 and D3.
Under 50mg/L concentration, the compounds of this invention 10,12,14,28,29,30,32,35,37,41,82,83,730,738, 843,1026,1784 and 1791 etc. A grades of activity are all had to mythimna separata with D1, D2 and D3.
Under 12.5mg/L concentration, 10,12,14,28,29,30,32,35,37,82,730,738 and of the compounds of this invention 1791 equal and D1 and D2 all have A grades of activity to mythimna separata；41,843 and 954 etc. have B grades of activity to mythimna separata with D3.
Further screening shows that the compounds of this invention such as 10,28,29 and 738 etc. shows very high activity to mythimna separata, 10, it 28,29 and 738 etc. can compare favourably with activity of the chlorantraniliprole to mythimna separata to the activity of mythimna separata.
Compound whether can be improved to the activity of mythimna separata for research acylation, while comparing 738 and its non-acylate (N- (the chloro- 6- of the bromo- 4- of 2- (methylamino formoxyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- base) -1H- pyrazoles -5- formamide) it is right The activity of mythimna separata, the results showed that the activity of 738 pairs of mythimna separatas is apparently higher than its non-acylate, to the LC of mythimna separata 73850Value is its non-acyl Compound LC50The nearly one third of value, that is, the activity of 738 pairs of mythimna separatas is high compared with its non-acylate.
Insecticidal Activity of the embodiment 8 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 point 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 Grade, 50 > death rate (%) >=0 are D grades.The result shows that the compounds of this invention has activity, and the chemical combination having well to aphid Object still has high activity at very low concentrations, and partial results are listed below:
Under 500mg/L concentration, the compounds of this invention 05,10,12,14,28,29,30,32,33,34,35,37,41,125, 194、374、375、411、413、731、734、738、774、843、951、954、987、988、1023、1026、1059、1062、 1068,1784,1790,1791 and 1979 etc. have A grades of activity to aphid with D1, D2 and D3.
Under 50mg/L concentration, the compounds of this invention 05,12,32,33,35,41,125,194,375,411,413,738, 774,843,951,954,987,988,1023,1026,1059,1062,1068,1784,1790 and 1979 etc. with D2 and D3 couples Aphid all has A grades of activity；14,28,30,731 and 734 etc. have B grades of activity to aphid；D1 has D grades of activity to aphid.
Under 12.5mg/L concentration, the compounds of this invention 05,32,35,125,375,413,738,843,951,988,1023 A grades of activity are all had to aphid with 1790 equal and D2；12,30,33,41,194,411,731,734,954,987,1059, 1068,1784 and 1979 etc. have B grades of activity to aphid；D3 has C grades of activity to aphid.
Further to compare the compounds of this invention and D2 to the activity of aphid, select the compounds of this invention 05,194,738, 843, it 1059 and 1068 carries out going deep into screening simultaneously for representative and D2, the results showed that 05,194,738,843,1059 and of the present invention The 1068 equal LC to aphid50Value is lower than 2.0mg/L, LC of the D2 to aphid50Value is higher than 2.0mg/L.
The selection result shows the compounds of this invention such as 738 and 843 etc. to the activity of aphid better than D1, D2 and D2.
Compound whether can be improved to the activity of aphid for research acylation, while comparing 738 and its non-acylate (N- (the chloro- 6- of the bromo- 4- of 2- (methylamino formoxyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- base) -1H- pyrazoles -5- formamide) it is right The activity height of aphid, the results showed that the activity of 738 pairs of aphids is significantly higher than its non-acylate.
Embodiment 9 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 D2 as standard control.Active (death rate) in percentage, divides A, B, C, D level Four relative to blank control, 100 >=dead Dying 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 compound of the present invention has activity well to red spider, and the compound having is very low dense Still there is high activity under degree, partial results are listed below:
Under 500mg/L concentration, the compounds of this invention 10,33,194,375,734,843,1059 and 1791 etc. is to red spider All have A grades of activity；28,29,34,374,954 and 1790 etc. B grades of activity are all had to red spider；14,411,413,730 and 738 etc. all have C grades of activity to red spider；D3 does not show activity to red spider.
Under 200mg/L concentration, the compounds of this invention 194 and 734 etc. has A grades of activity to red spider；374 and 954 etc. pairs Red spider has B grades of activity.
According to the selection result and literature survey, D1, D2 and D3 do not show apparent acaricidal activity.

Claims (10)

1. multiamide class compound, it is characterised in that indicate multiamide class compound and its isomers with logical formula (I):
I.Ar represents a) C6-C12The heteroaryl of up to 10 carbon atoms of aryl or band, wherein some or all of hydrogen atom can be with Replaced by identical or different substituent group in following: halogen, nitro, cyano, C1-C12Alkyl, C1-C12Alkoxy, C1-C12 Alkylthio group, C1-C12Alkoxy carbonyl group, C1-C12Alkyl carbonyl epoxide, C1-C12Alkyl amine group, C2-C12Alkenyl, C2-C12Alkenyl Oxygroup, C2-C12Alkenyl thio, C2-C12Alkenyloxycarbonyl, C2-C12Alkenyl amido, C2-C12Alkynyl group, C2-C12Chain Alkynyl oxygroup, C2-C12Alkynyl group sulfenyl, C2-C12Alkynyl group Epoxide carbonyl, C2-C12Alkynyl group amido, C3-C8Naphthenic base, C3-C8 Cycloalkyl oxy, C3-C8Cycloalkylsulfanyl, C3-C8Cycloalkyloxycarbonyl, C3-C8Naphthenic base amido, C6-C12Aryl or with more Heteroaryl, C to 10 carbon atoms6-C12The heteroaryl oxygroup of up to 10 carbon atoms of aryloxy or band, C6-C12Aryl sulphur Heteroarylthio, the C of up to 10 carbon atoms of base or band6-C12The heteroaryl of up to 10 carbon atoms of aryloxycarbonyl or band Epoxide carbonyl, C6-C12The heteroaryl amido, C of up to 10 carbon atoms of arylamine group or band6-C12Aryl methyl or band up to 10 Hetervaromatic methyl, the C of a carbon atom6-C12Heteroarylaryl, the C of up to 10 carbon atoms of aryl or band6-C12Aryl is miscellaneous The heteroarylheteroaryl of up to 10 carbon atoms of aryl or band；B) such as in I.a) in identified meaning, the wherein portion of hydrogen atom Point or can all be replaced by identical or different substituent group in following: halogen, nitro, cyano, C1-C12Alkyl, C1-C12 Halogenated alkyl, C1-C12Alkoxy, C1-C12Halogenated alkoxy, C1-C12Alkyloxycarbonyl, C1-C12Alkyl amine group, C2-C12Chain Alkenyl, C2-C12Halogenated alkenyl, C2-C12Alkenyl oxy, C2-C12Alkynyl group, C2-C12Haloalkynyl group, C2-C12Alkynyl group Oxygroup, C3-C8Naphthenic base, C3-C8Halogenated cycloalkyl, C3-C8Cycloalkyl oxy, C6-C12Aryl or band up to 10 carbon atoms Heteroaryl, C6-C12The heteroaryl oxygroup of up to 10 carbon atoms of aryloxy or band；
II.R represents hydrogen, C1-C12Alkyl or C3-C8Naphthenic base；
III.R1、R2And R3It is same or different, and represents hydrogen, halogen, cyano, nitro or C1-C12Alkyl；
IV.R4Represent hydrogen or C1-C12Alkyl-carbonyl；
V.R4When representing hydrogen, R5Represent C1-C12Alkyl-carbonyl, CNCH2(CH3)2C、NH2COCH2(CH3)2C、CNCH2CH3CH or NH2COCH2CH3CH；R4Represent C1-C12When alkyl-carbonyl, R5Represent C1-C12Alkyl, C3-C8Naphthenic base, C3-C8Heterocyclylalkyl, C1-C12Alkyl-carbonyl；
II., hydrogen atom can be partly or entirely by following in alkyl, naphthenic base or Heterocyclylalkyl in III., IV. and V. Identical or different substituent group replaces: halogen, cyano, C1-C6Alkyl, C1-C6Alkenyl, C1-C6Alkynyl group, C1-C6Alkoxy, C3-C6Naphthenic base, C3-C6Heterocyclylalkyl, C1-C6Alkyl-carbonyl, amino-carbonyl or C1-C6Alkyl amine group；
It is given above in the definition of formula (I), no matter term used exclusive use is also used in compound word, represents following replace Base:
Halogen: refer to fluorine, chlorine, bromine or iodine；
Alkyl: refer to linear or branched alkyl group；
Halogenated alkyl: referring to linear or branched alkyl group, hydrogen moiety on these alkyl or is all replaced by halogen atom；
Naphthenic base: refer to saturation or unsaturated ring alkyl；
Halogenated cycloalkyl: referring to saturation or unsaturated ring alkyl, and hydrogen moiety therein or is all replaced by halogen atom；
Alkenyl；Refer to linear or branched alkyl group, and can in any position on there are double bonds；
Halogenated alkenyl: referring to linear or branched alkyl group, and can in any position on there are double bond, and hydrogen moiety therein Or all replaced by halogen atom；
Alkynyl group；Refer to linear or branched alkyl group, and can in any position on there are three keys；
Halo alkynyl: referring to linear or branched alkyl group, and can in any position on there are three keys, and hydrogen moiety therein or All replaced by halogen atom；
Heterocyclylalkyl: the naphthenic base of at least 1 N, O and/or S, such as tetrahydrofuran base in formula；
Alkyl-carbonyl: referring to acyl group, such as methyl carbonyl, that is, acetyl group CH3CO, ethylcarbonyl group refer to propiono CH3CH2CO；
C6-C12Aryl means phenyl or by its derivative cyclophane base or polyaromatic, such as naphthalene, xenyl；
The heteroaryl of up to 10 carbon atoms of band refers to a ring heteroaryl or polyheteroaromatic, at least 1 N, O or/and S in formula, Such as thiazolyl, pyrazolyl, thiadiazolyl group, pyridyl group, thienyl, benzothienyl, furyl, benzofuranyl, pyrrole radicals, benzene And pyrrole radicals, indyl, benzindole base, imidazole radicals, benzimidazolyl, quinolyl, pyranose, pyrazinyl, pyrimidine radicals, pyridazine Base, benzopyranyl, benzopyrazines base, benzo pyrimidine radicals, benzo pyridazinyl, oxazolyl, isoxazolyl, benzoxazolyl, benzene And isoxazolyl, benzothiazolyl, isothiazolyl, benzisothia oxazolyl, pyrimido triazolyl, triazolyl or tetrazole radical；
Except the definition of compound given above (I), formula (I) compound also represents R=CH in formula (I)3；R5=CH2CH3Formula (IA-1) compound, Ar, R in formula (IA-1)1、R2、R3And R4With the definition in above-mentioned formula (I) compound,
2. multiamide class compound according to claim 1, it is characterised in that in compound shown in logical formula (I):
I.Ar is selected from Ar-1~Ar-30 as follows:
II.R represents hydrogen, C1-C12Alkyl or C3-C8Naphthenic base；
III.R1、R2And R3It is same or different, and represents hydrogen, halogen, cyano, nitro or C1-C12Alkyl；
IV.R4Represent hydrogen or C1-C12Alkyl-carbonyl；
V.R4When representing hydrogen, R5Represent C1-C12Alkyl-carbonyl, CNCH2CH3CH、NH2COCH2CH3CH CNCH2(CH3)2C or NH2COCH2(CH3)2C；R4Represent C1-C12When alkyl-carbonyl, R5Represent C1-C12Alkyl, C3-C8Naphthenic base, C3-C8Heterocyclylalkyl, C1-C12Alkyl-carbonyl；
II., hydrogen atom can be partly or entirely selected from down in alkyl, naphthenic base or Heterocyclylalkyl in III., IV. and V. Identical or different substituent group replaces in column: halogen, cyano or amino-carbonyl；
Except above-mentioned formula (I) compound, formula (I) compound also represents R=CH in formula (I)3；R4=H；R5=CH2CH3Formula (IA-2) Compound, Ar, R in formula (IA-2)1、R2And R3With the definition in above-mentioned formula (I) compound,
3. multiamide class compound according to claim 1, it is characterised in that compound shown in logical formula (I) is R in formula (I)1、 R2And R3It is same or different, and formula (IB-1)~(IB-16) as follows selected from methyl, cyano, nitro or halogen Compound:
In compound shown in formula (IB-1)~(IB-16):
I.Ar is selected from Ar-1~Ar-30 as follows:
II.R represents hydrogen, C1-C12Alkyl or C3-C8Naphthenic base；
III.R4Represent hydrogen or C1-C12Alkyl-carbonyl；
IV.R4When representing hydrogen, R5Represent C1-C12Alkyl-carbonyl, CNCH2(CH3)2C、NH2COCH2(CH3)2C、CNCH2CH3CH or NH2COCH2CH3CH；R4Represent C1-C12When alkyl-carbonyl, R5Represent C1-C12Alkyl, C3-C8Naphthenic base or C1-C12Alkyl-carbonyl；
Except above-mentioned formula (I) compound, formula (I) compound also represents R=CH in formula (I)3；R3=R4=H；R5=CH2CH3It is following Formula (IA-3)~(IA-10) compound, wherein Ar has the definition in above-mentioned formula (I) compound,
4. multiamide class compound according to claim 1, it is characterised in that compound shown in logical formula (I) is formula (I) institute Show R in compound1、R2And R3It is same or different, and is selected from methyl, cyano, nitro or halogen；R is selected from hydrogen, CNCH2 (CH3)2C、NH2COCH2(CH3)2C、CNCH2CH3CH、NH2COCH2CH3CH、CH3、CH3CH2、CH3CH2CH2、(CH3)2CH、 CH3CH2CH2CH2、(CH3)2CHCH2、CH3CH2CH3CH、CH3CH2(CH3)2C、(CH3)3C、(CH3)3CCH2、(CH3)3CCH2CH2Ring Propyl or cyclopenta；R4Selected from hydrogen, CH3CO or CH3CH2CO；R4When selected from hydrogen, R5Selected from CH3CO、CH3CH2CO、(CH3)2CHCO、 CH3CH2CH2CO、CNCH2(CH3)2C、NH2COCH2(CH3)2C、CNCH2CH3CH or NH2COCH2CH3CH；R4Selected from CH3CO or CH3CH2When CO, R5Selected from CH3、CH3CH2、CH3CH2CH2、(CH3)2CH、CH3CH2CH2CH2、(CH3)2CHCH2、CH3CH2CH3CH、 CH3CH2(CH3)2C、(CH3)3C、(CH3)3CCH2、(CH3)3CCH2CH2、CH3OCH2CH2CH2、CH3OCH2CH2、CH3CO、 CH3CH2CO、(CH3)2CHCO、CH3CH2CH2CO、CNCH2(CH3)2C、NH2COCH2(CH3)2C、CNCH2CH3CH or NH2COCH2CH3The formula (IC-1) of CH~(IC-256) compound:
Ar in compound shown in formula (IC-1)~(IC-256) is selected from Ar-1~Ar-30 as follows:
5. multiamide class compound according to claim 1, it is characterised in that compound shown in logical formula (I) is:
N- (the chloro- 6- of 2,4- bis- (ethyl (methyl) amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- base) -1H- pyrazoles - 5- formamide；
N- (the chloro- 2- of 4- ((1- cyano -2- methylpropane -2- base) amido formacyl) -6- aminomethyl phenyl) the bromo- 1- of -3- (3- chlorine pyrrole Pyridine -2- base) -1H- pyrazoles -5- formamide；
N- (4- cyano -2- ((1- cyano -2- methylpropane -2- base) amido formacyl) -6- aminomethyl phenyl) -3- bromo- 1- (3- chlorine Pyridine -2- base) -1H- pyrazoles -5- formamide；
N- (the chloro- 6- of 2,4- bis- ((1- cyano -2- methylpropane -2- base) amido formacyl) phenyl) -3- bromo- 1- (3- chloropyridine - 2- yl) -1H- pyrazoles -5- formamide；
N- (the chloro- 2- of 4- ((1- dicyanopropane -2- base) amido formacyl) -6- aminomethyl phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide；
N- (the bromo- 2- of 4- ((1- dicyanopropane -2- base) amido formacyl) -6- aminomethyl phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide；
N- (4- cyano -2- ((1- dicyanopropane -2- base) amido formacyl) -6- aminomethyl phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide；
N- (the chloro- 6- of 2,4- bis- ((1- dicyanopropane -2- base) amido formacyl) phenyl) bromo- 1- of -3- (3- chloropyridine -2- base) - 1H- pyrazoles -5- formamide；
N- (the chloro- 6- of the bromo- 2- of 4- ((1- dicyanopropane -2- base) amido formacyl) phenyl) bromo- 1- of -3- (3- chloropyridine -2- base) - 1H- pyrazoles -5- formamide；
N- (the chloro- 6- of the bromo- 4- of 2- ((1- dicyanopropane -2- base) amido formacyl) phenyl) bromo- 1- of -3- (3- chloropyridine -2- base) - 1H- pyrazoles -5- formamide；
N- (2- ((4- amido -4- oxygen butane -2- base) amido formacyl) the chloro- 6- aminomethyl phenyl of -4-) the bromo- 1- of -3- (3- chlorine pyrrole Pyridine -2- base) -1H- pyrazoles -5- formamide；
N- (2- ((4- amido -4- oxygen butane -2- base) amido formacyl) -4,6- dichlorophenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide；
N- acetyl group-N- (2- chloro- 4- methyl -6- (methylamino formoxyl) phenyl) bromo- 1- of -3- (3- chloropyridine -2- base) - 1H- pyrazoles -5- formamide；
N- acetyl group-N- (2- bromo- 4- methyl -6- (methylamino formoxyl) phenyl) bromo- 1- of -3- (3- chloropyridine -2- base) - 1H- pyrazoles -5- formamide；
N- acetyl group-N- (the bromo- 4- of 2- chloro- 6- (Ethylcarbamoyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- base) -1H- Pyrazoles -5- formamide；
N- acetyl group-N- (2,4- bis- chloro- 6- (isopropyl amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- base) -1H- Pyrazoles -5- formamide；
N- acetyl group-N- (the chloro- 6- of the bromo- 2- of 4- (cyclopropyl amido formacyl) phenyl) bromo- 1- of -3- (3- chloropyridine -2- base) - 1H- pyrazoles -5- formamide；
N- acetyl group-N- (the chloro- 6- of the bromo- 2- of 4- (cyclopenta amido formacyl) phenyl) bromo- 1- of -3- (3- chloropyridine -2- base) - 1H- pyrazoles -5- formamide；
N- acetyl group-N- (the chloro- 6- of the bromo- 4- of 2- (cyclopenta amido formacyl) phenyl) bromo- 1- of -3- (3- chloropyridine -2- base) - 1H- pyrazoles -5- formamide；
N- acetyl group-N- (2- (acetyl group (methyl) amido formacyl) the chloro- 6- aminomethyl phenyl of -4-) -3- bromo- 1- (3- chloropyridine - 2- yl) -1H- pyrazoles -5- formamide；
N- acetyl group-N- (2- (acetyl group (methyl) amido formacyl) the bromo- 6- aminomethyl phenyl of -4-) -3- bromo- 1- (3- chloropyridine - 2- yl) -1H- pyrazoles -5- formamide；
N- acetyl group-N- (2- (acetyl group (methyl) amido formacyl) -4,6- dichlorophenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide；
N- acetyl group-N- (2- (acetyl group (methyl) amido formacyl) the bromo- 4- chlorphenyl of -6-) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide；
N- acetyl group-N- (2- (acetyl group (ethyl) amido formacyl) the bromo- 4- chlorphenyl of -6-) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide；
N- acetyl group-N- (2- (acetyl group (isopropyl) amido formacyl) -4,6- dichlorophenyl) -3- bromo- 1- (3- chloropyridine - 2- yl) -1H- pyrazoles -5- formamide；
N- acetyl group-N- (2- (acetyl group (cyclopropyl) amido formacyl) -4,6- dichlorophenyl) -3- bromo- 1- (3- chloropyridine - 2- yl) -1H- pyrazoles -5- formamide；
N- acetyl group-N- (2- (acetyl group (cyclopropyl) amido formacyl) the bromo- 4- chlorphenyl of -6-) -3- bromo- 1- (3- chloropyridine - 2- yl) -1H- pyrazoles -5- formamide；
N- acetyl group-N- (2- (acetyl group (cyclopenta) amido formacyl) -4,6- dichlorophenyl) -3- bromo- 1- (3- chloropyridine - 2- yl) -1H- pyrazoles -5- formamide；
N- acetyl group-N- (2- (acetyl group (cyclopenta) amido formacyl) the bromo- 6- chlorphenyl of -4-) -3- bromo- 1- (3- chloropyridine - 2- yl) -1H- pyrazoles -5- formamide；
N- acetyl group-N- (2,4- bis- chloro- 6- (dimethyl amido formoxyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- base) -1H- Pyrazoles -5- formamide；
N- acetyl group-N- (the chloro- 6- of the bromo- 4- of 2- (dimethyl amido formoxyl) phenyl) bromo- 1- of -3- (3- chloropyridine -2- base) - 1H- pyrazoles -5- formamide；
N- acetyl group-N- (the chloro- 6- of 2,4- bis- (ethyl (methyl) amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide；
N- acetyl group-N- (the chloro- 6- of the bromo- 4- of 2- (ethyl (methyl) amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- Base) -1H- pyrazoles -5- formamide；
N- acetyl group-N- (2,4- bis- chloro- 6- (diethyl amido formacyl) phenyl) the bromo- 1- of -3- (3- chloropyridine -2- base) -1H- Pyrazoles -5- formamide；
N- (the chloro- 2- of 4- ((1- cyano -2- methylpropane -2- base) amido formacyl) -6- aminomethyl phenyl) the bromo- 1- of -3- (3,5- bis- Chloropyridine -2- base) -1H- pyrazoles -5- formamide；
N- (the chloro- 4- cyano -6- of 2- ((1- cyano -2- methylpropane -2- base) amido formacyl) phenyl) the bromo- 1- of -3- (3,5- bis- Chloropyridine -2- base) -1H- pyrazoles -5- formamide；
N- (the chloro- 2- of 4- ((1- dicyanopropane -2- base) amido formacyl) -6- aminomethyl phenyl) -3- bromo- 1- (3,5- dichloropyridine - 2- yl) -1H- pyrazoles -5- formamide；
N- (4- cyano -2- ((1- cyano -2- methylpropane -2- base) amido formacyl) -6- aminomethyl phenyl) -3- methoxyl group -1- (3,5- dichloropyridine -2- base) -1H- pyrazoles -5- formamide.
6. the preparation method of multiamide class compound according to claim 1, it is characterised in that formula (I) compound represented It is prepared by reaction shown below,
Reaction equation 1:
Reaction equation 2:
Reaction equation 3:
Reaction equation 4:
In solvents tetrahydrofurane, Isosorbide-5-Nitrae-dioxane, toluene, dimethylbenzene or n,N-Dimethylformamide, in -15 DEG C~system Reflux temperature, in alkali triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide or carbonic acid It in the presence of hydrogen sodium, is reacted with formula (II) compound represented and formula (III) compound represented, it is (anti-to obtain compound shown in formula (I) Answer formula 1-1)；Or
In solvents tetrahydrofurane, Isosorbide-5-Nitrae-dioxane, toluene, dimethylbenzene or n,N-Dimethylformamide, returned in -15~system Temperature is flowed, in alkali triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydride, sodium methoxide or bicarbonate In the presence of sodium, is reacted with formula (IV) compound represented and formula (III) compound represented, obtain compound shown in formula (V)；Equally Under the conditions of, formula (V) compound represented is reacted with formula (VI) compound represented again, obtains compound (reaction equation 1- shown in formula (I) 2)；
In solvents tetrahydrofurane, 1,4- dioxane, toluene, dimethylbenzene, acetone, methylene chloride, dichloroethanes or N, N- diformazan In base formamide, in -15 DEG C~system reflux temperature, with formula (VII) compound represented and formula (VIII) compound represented Reaction, obtains compound (reaction equation 2) shown in formula (II)；
In solvents tetrahydrofurane, 1,4- dioxane, toluene, dimethylbenzene, acetone, methylene chloride, dichloroethanes or N, N- diformazan It is anti-with formula (VII) compound represented and formula (IX) compound represented in -15 DEG C~system reflux temperature in base formamide It answers, obtains compound (reaction equation 3) shown in formula (IV)；
In solvents tetrahydrofurane, 1,4- dioxane, toluene, dimethylbenzene, acetone, acetonitrile, methylene chloride, dichloroethanes or N, N- In dimethylformamide, in -15 DEG C~system reflux temperature, in the presence of alkali pyridine or picoline, at methylsufonyl chloride The mixture of compound shown in reason formula (X) and formula (XI) obtains compound (reaction equation 4) shown in formula (VII)；
(III) and (VI) in (III), reaction equation 1-2 in reaction equation 1-1, (VIII) in reaction equation 2, in reaction equation 3 (IX) (X) and (XI) and in reaction equation 4 can synthesize to obtain by purchase or referring to pertinent literature；
Ar, R, R in formula1、R2、R3、R4And R5With defining given in claim 1, L is leaving group chlorine or bromine.
7. the purposes of described in any item multiamide class compounds according to claim 1~5, it is characterised in that at 15~5000 grams There is desinsection or mite killing bioactivity under effective component/hectare dosage.
8. described in any item multiamide class compounds are used to prepare with desinsection or acaricidal activity according to claim 1~5 The purposes of drug.
9. a kind of desinsection or miticide composition, it is characterised in that: containing as active component such as any one of Claims 1 to 5 The multiamide class compound, the weight percentage of active component is 0.5-99% in composition.
10. a kind of method of pest control or harmful mite, it is characterised in that: by a effective amount of as described in any one of Claims 1 to 5 Multiamide class compound impose on the pest, harmful mite or its somatomedin.
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