CN108117518A - N-2,4- substituted-phenyl bisamide class compounds and preparation method and application - Google Patents

N-2,4- substituted-phenyl bisamide class compounds and preparation method and application Download PDF

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CN108117518A
CN108117518A CN201611084347.4A CN201611084347A CN108117518A CN 108117518 A CN108117518 A CN 108117518A CN 201611084347 A CN201611084347 A CN 201611084347A CN 108117518 A CN108117518 A CN 108117518A
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alkyl
compound
phenyl
formula
formamides
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CN108117518B (en
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刘卫东
柳爱平
刘兴平
龙楚云
于红
项军
雷满香
李中
张再
闫忠忠
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Hunan Research Institute of Chemical Industry
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group; Thio analogues thereof
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/90—Carboxylic acid amides having nitrogen atoms of carboxamide groups further acylated
    • C07C233/92—Carboxylic acid amides having nitrogen atoms of carboxamide groups further acylated with at least one carbon atom of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
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    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/62—Compounds containing any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylcarbamates
    • C07C271/64—Y being a hydrogen or a carbon atom, e.g. benzoylcarbamates
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • 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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Abstract

The invention discloses 2,4 substituted-phenyl bisamide class compounds of N shown in formula (I) and preparation method and application.R, Ar, R in formula1、R2、R3Have with n and defined given in specification.Formula (I) compound of the present invention has desinsection and/or sterilization bioactivity, especially active to pests such as homoptera pest such as aphids.

Description

N-2,4- substituted-phenyl bisamide class compounds and preparation method and application
Technical field
The invention belongs to desinsection, fungicide fields, and in particular to have desinsection, the N-2 for sterilizing bioactivity, 4- substituted-phenyls Bisamide class compound and preparation method thereof, the desinsection containing the compound, microbicide compositions and with these compounds Control pest, the purposes and method of harmful levels of pathogens.
Background technology
Pest, the prevention of harmful levels of pathogens are extremely important during high-efficiency agriculture is realized.Pest, harmful levels of pathogens simultaneously Prevention woods, herd, in the fields such as secondary, fishing and public health it is also critically important.Although have many pests in the market, harmful levels of pathogens is prevented Control medicament, but the continuous expansion due to market, external pest and harmful levels of pathogens, the resistance to the action of a drug of pest and harmful levels of pathogens, drug The problems such as service life, Pharmacoeconomic and people to the pay attention to day by day of environment, it is necessary to scientists are constantly studied, Jin Erkai Send compatible new efficient, safety, economy, environment and desinsection with the different modes of action, fungicide new varieties.
Bisamide class compound is a kind of important compound in pharmaceutical chemistry, they have wide spectrum biological activity.Make For the prior art of the present invention, WO2007020986 reports below formula pyrazol acid amide compounds with acaricidal activity, and Embodiment compound with such as lower structure is as acaricide commercialization, and general entitled Pyflubumide, it is also unique business The pyrazoles bisamide class acaricide of product, Pyflubumide have excellent activity, LC to evil mite50Value 1-3mg/L, but Pyflubumide is to diseases such as the insect pests such as aphid and powdery mildews without apparent activity.
To obtain with more economical, more efficient, more broad-spectrum biological activity and/or the new amides chemical combination of novel mechanism of action Object, the work based on pertinent literature He our early periods, we design and synthesize have not been reported with shown in formula (I) with killing Worm, the N-2,4- substituted-phenyl bisamide class compounds of bactericidal activity.The compounds of this invention is shown compared with WO2007020986 chemical combination The higher insecticidal activities of object such as Pyflubumide and bactericidal activity.
The content of the invention
The present invention provides the N-2,4- substituted benzenes with bioactivity such as pest control, harmful levels of pathogens shown in formula (I) Base bisamide class compound and its isomers：
Wherein：
I.R represents C1-C12Alkyl, C1-C12Alkoxy, C2-C12Alkenyl, C2-C12Alkenyl oxygroup, C2-C12Alkynyl, C2-C12 Alkynyl oxygroup, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3-C8Heterocyclylalkyl, C3-C8Heterocyclylalkyl oxygroup, phenyl, benzene oxygen Base, xenyl, pyrazolyl, thiadiazolyl group, pyridyl group, thienyl, benzothienyl, furyl, benzofuranyl, pyrrole radicals, Benzopyrrole base, indyl, imidazole radicals, benzimidazolyl, quinolyl, pyranose, pyrazinyl, pyrimidine radicals, are rattled away at benzindole base Piperazine base, benzopyranyl, benzopyrazines base, benzo pyrimidine radicals, benzo pyridazinyl, benzoxazolyl, benzoxazine, benzo Thiazolyl, isothiazolyl, benzisothia oxazolyl, pyrimido triazolyl；
II.Ar represent phenyl, xenyl, pyrazolyl, thiadiazolyl group, pyridyl group, thienyl, benzothienyl, furyl, Benzofuranyl, pyrrole radicals, benzopyrrole base, indyl, benzindole base, imidazole radicals, benzimidazolyl, quinolyl, pyrans Base, pyrazinyl, pyrimidine radicals, pyridazinyl, benzopyranyl, benzopyrazines base, benzo pyrimidine radicals, benzo pyridazinyl, benzoxazole Base, benzoxazine, benzothiazolyl, isothiazolyl, benzisothia oxazolyl, pyrimido triazolyl；
III.R1And R2It is same or different, and represents halogen, cyano, nitro, C1-C12Alkyl, C1-C12Alkoxy, C1-C12Alkyl-carbonyl or C1-C12Alkyl sulphonyl；
IV.R3Represent hydrogen, halogen, cyano, nitro, C1-C12Alkyl or C1-C12Alkoxy；
V.n represents 0,1,2 or 3 integer；And
1) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen atom is not take Generation；Or 2) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen moiety or whole It can be substituted by identical or different substituent group in following：Halogen, nitro, cyano, C1-C12Alkyl, C1-C12Alkyl halide Base, C1-C12Alkoxy, C1-C12Halogenated alkoxy, C1-C12Alkylthio group, C1-C12Alkyl sulphonyl, C1-C12Alkyl sulphinyl, C1-C12Alkoxy carbonyl group, C1-C12Alkyl carbonyl epoxide, C1-C12Alkyl amine group, C2-C12Alkenyl, C2-C12Alkenyl oxy, 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-C8Cycloalkyl, C3-C8Cycloalkyloxy group Base, C3-C8Cycloalkylsulfanyl, C3-C8Cycloalkyloxycarbonyl, C3-C8Cycloalkyl amido, C3-C8Heterocyclylalkyl, C3-C8Heterocycle alkane Base oxygroup, C3-C8Heterocyclylalkyl sulfenyl, C3-C8Heterocyclylalkyl Epoxide carbonyl, C3-C8Heterocyclylalkyl amido, phenyl, by halogen, C1-C6Alkyl and/or C1-C6Alkoxy substitution phenyl, phenoxy group, by halogen, C1-C6Alkyl and/or C1-C6Alkoxy substitutes Phenoxy group；
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 or iodine；
Alkyl：Refer to straight or branched alkyl；
Cycloalkyl：Refer to saturation or unsaturation ring alkyl；
Alkenyl；Refer to linear chain or branch chain alkenyl, and can there are double bonds on any position；
Alkynyl group；Refer to linear chain or branch chain alkynyl, and can there are three keys on any position；
It is halogenated：Refer to hydrogen moiety therein or all substituted by halogen atom.
Currently preferred compound is：In formula (I)：
I.R represents C1-C12Alkyl, C2-C12Alkenyl, C2-C12Alkynyl, C3-C8Cycloalkyl, C3-C8Heterocyclylalkyl, C1-C12Alkane Oxygroup, C2-C12Alkenyl oxygroup, C2-C12Alkynyl oxygroup, C3-C8Cycloalkyl oxy, C3-C8Heterocyclylalkyl oxygroup, phenyl, pyrazolyl Or pyridyl group；
II.Ar represents phenyl, pyrazolyl, thiadiazolyl group, pyridyl group, thienyl, benzothienyl, furyl, benzo furan It mutters base, pyrrole radicals, benzopyrrole base, indyl, benzindole base, imidazole radicals, benzimidazolyl, quinolyl, pyranose, pyrazine Base, pyrimidine radicals, pyridazinyl, benzopyranyl, benzopyrazines base, benzo pyrimidine radicals, benzo pyridazinyl, benzoxazolyl, benzo Isoxazolyl, benzothiazolyl, isothiazolyl, benzisothia oxazolyl, pyrimido triazolyl；
III.R1And R2It is same or different, and represents halogen, cyano, nitro, C1-C12Alkyl, C1-C12Alkoxy, C1-C12Alkyl-carbonyl or C1-C12Alkyl sulphonyl；
IV.R3Represent hydrogen, halogen, cyano, nitro, C1-C12Alkyl or C1-C12Alkoxy；
V.n represents 0,1,2 or 3 integer；And
1) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen atom is not take Generation；Or 2) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen moiety or whole It can be substituted by identical or different substituent group in following：Halogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alcoxyl Base, C1-C6Halogenated alkoxy, C1-C6Alkylthio group, C1-C6Alkyl sulphonyl, C1-C6Alkyl sulphinyl, C1-C6Alkyl amine group, C2-C6Alkenyl, C2-C6Alkenyl oxy, C2-C6Alkenyl thio, C2-C6Alkenyl amido, C2-C6Alkynyl group, C2-C6Alkyne Base oxygroup, C2-C6Alkynyl group sulfenyl, C2-C6Alkynyl group amido, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3-C8Cycloalkyl sulphur Base, C3-C8Cycloalkyl amido, phenyl, by halogen, C1-C6Alkyl and/or C1-C6Alkoxy substitution phenyl, phenoxy group, by halogen Element, C1-C6Alkyl and/or C1-C6The phenoxy group of alkoxy substitution.
The further preferred compound of the present invention is：In formula (I)：
I.R represents C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C8Cycloalkyl, C3-C8Heterocyclylalkyl, C1-C6Alcoxyl Base, C2-C6Alkenyl oxygroup, C3-C6Alkynyl oxygroup, C3-C8Cycloalkyl oxy, C3-C8Heterocyclylalkyl oxygroup, phenyl, pyrazolyl or pyrrole Piperidinyl；
II.Ar represents phenyl, pyrazolyl or pyridyl group；
III.R1And R2It is same or different, and represents halogen, cyano, nitro, C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkyl-carbonyl or C1-C6Alkyl sulphonyl；
IV.R3Represent hydrogen, halogen, cyano, nitro, C1-C6Alkyl or C1-C6Alkoxy；
V.n represents 0,1,2 or 3 integer；And
1) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen atom is not take Generation；Or 2) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen moiety or whole It can be substituted by identical or different substituent group in following：Halogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alcoxyl Base, C1-C6Halogenated alkoxy, C1-C6Alkylthio group, C1-C6Alkyl amine group, C2-C6Alkenyl, C2-C6Alkenyl oxy, C2-C6Chain Enylsulfanyl, C2-C6Alkenyl amido, C2-C6Alkynyl group, C2-C6Alkynyl group oxygroup, C2-C6Alkynyl group sulfenyl, C2-C6Alkynyl group Amido, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3-C8Cycloalkylsulfanyl, C3-C8Cycloalkyl amido, phenyl, by halogen and/ Or C1-C6Alkyl-substituted phenyl.
Compound specifically preferred according to the invention is：In formula (I)：
I.R represents C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C8Cycloalkyl, C3-C8Heterocyclylalkyl, C1-C6Alcoxyl Base, C2-C6Alkenyl oxygroup, C3-C6Alkynyl oxygroup, C3-C8Cycloalkyl oxy, C3-C8Heterocyclylalkyl oxygroup, phenyl, pyrazolyl or pyrrole Piperidinyl；
II.Ar represents phenyl, pyrazolyl or pyridyl group；
III.R1And R2It is same or different, and represents halogen, cyano, nitro, C1-C6Alkyl, C1-C6Alkoxy；
IV.R3Represent hydrogen, halogen, cyano, nitro, C1-C6Alkyl or C1-C6Alkoxy；
V.n represents 0,1,2 or 3 integer；And
1) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen atom is not take Generation；Or 2) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen moiety or whole It can be substituted by identical or different substituent group in following：Halogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alcoxyl Base, C1-C6Halogenated alkoxy, phenyl, by halogen and/or C1-C6Alkyl-substituted phenyl.
Especially preferred formula (I) compound of the present invention is following compound：
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-) -1,3- dimethyl pyrazole -5- formamides (01)；
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -1,3- dimethyl pyrazole -5- formamides (02)；
N- isobutyryls-N- (bis- chloro- 4- cyano-phenyls of 2,6-) -1,3- dimethyl pyrazole -5- formamides (04)；
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-) -1- methyl -3- ethylpyrazol -5- formamides (07)；
N- propionos-N- (2,6- dichlor-4-trifluoromethyls phenyl) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides (09)；
N- bytyries-N- (2,6- dimethyl -4- nitrobenzophenones) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides (10)；
N- bytyries-N- (the bromo- 4- nitrobenzophenones of the chloro- 6- of 2-) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides (11)；
N- bytyries-N- (bis- chloro- 4- cyano-phenyls of 2,6-) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides (12).
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides (16)；
N- isobutyryls-N- (2,6- dimethyl -4- nitrobenzophenones) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides (17)；
N- isobutyryls-N- (2,6- dichlor-4-trifluoromethyls phenyl) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formyls Amine (19)；
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -1- (3- chloropyridine -2- bases) -3- bromine pyrazoles -5- formyls Amine (20)；
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-) -1,4,5- trimethylpyrazol -3- formamides (23)；
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -1,4,5- trimethylpyrazol -3- formamides (24)；
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-) -1,3- dimethyl pyrazole -4- formamides (25)；
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -1,3- dimethyl pyrazole -4- formamides (26)；
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-)-Niacinamide (29)；
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -2- chloropyridine -3- formamides (31)；
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-) -2- chloropyridine -3- formamides (32)；
N- bytyries-N- (bis- bromo- 4- cyano-phenyls of 2,6-) -2- chloropyridine -3- formamides (33)；
N- bytyries-N- (bis- chloro- 4- cyano-phenyls of 2,6-) -2- chloropyridine -3- formamides (34)；
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-) -2,6- dichloropyridine -3- formamides (35)；
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -2,6- dichloropyridine -3- formamides (36)；
N- bytyries-N- (bis- bromo- 4- cyano-phenyls of 2,6-) -2,6- dichloropyridine -3- formamides (37)；
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-) -2- trifluoromethyl benzamides (39)；
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -2- trifluoromethyl benzamides (40).
The compound of the present invention can the forms of one or more isomers exist.Isomers includes enantiomter, non- Enantiomter, geometric isomer and cis-trans-isomer.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 (representing different configurations respectively with Z and E), and the present invention includes The mixture of Z-type isomers and E-isomer and their any ratios.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 represented with R and S respectively), The present invention includes R types isomers and S types isomers and the mixture of their any ratios.Chemical combination shown in formula (I) of the present invention Object forms cis-trans-isomer (respectively with cis due to connecting the substituent group of 2 or more on cycloalkyl therein or Heterocyclylalkyl The configuration different with trans expressions), the present invention includes cis types isomers and trans types isomers and their any ratios Mixture.
The invention further relates to a kind of pest control, formula (I) compounds containing biologic effective dose of harmful levels of pathogens and at least A kind of other composition selected from surfactant, solid diluent and liquid diluent.
The invention further relates to a kind of pest control, harmful levels of pathogens formula (I) compound containing biologic effective dose and effectively At least one other bioactive compound of amount or the composition of preparation.
The invention further relates to a kind of method of pest control, harmful levels of pathogens, including by formula (I) compound of biologic effective dose Contact pest, harmful levels of pathogens or its environment.Such a pest, harmful levels of pathogens control method are also related to, pest has and falls ill The formula of bacterium or its environment biologic effective dose (I) compound or at least one containing formula (I) compound and biologic effective dose are another Outer compound or the mixture of preparation, which are contacted, comes pest control, harmful levels of pathogens.
Formula (I) compound of the present invention has broad spectrum of activity：Some compounds can be used for preventing harmful levels of pathogens, it may also be used for Pest control；And the compound having has very high bioactivity to some target pest germs so that in very low dosage Under be obtained with good effect.
Currently preferred composition is the composition containing above-mentioned preferred compound.It is preferable that with above-mentioned excellent The method for selecting compound.
The part formula (I) compound listed below with table 1 further illustrates the present invention, but does not limit the present invention.This Fusing point is not calibrated given in invention, and when formula (I) compound synthesized by the present invention is viscous solid, some viscous solids are put Non-tacky solids can be cured as by postponing, and when formula (I) compound synthesized by the present invention is viscous liquid, some viscous liquids are placed After can cure, all compounds are considerable in LC-MS (APCI, Pos) (Agilent 1100Series LC/MSD) in table 1 Observe its molecular ion peak.Compound in table 11H NMR (Varian INOVA-300spectrometer) with Tetramethylsilane (TMS) makees internal standard, deuterochloroform (CDCl3) or deuterated dimethyl sulfoxide (DMSO) make solvent.
Table 1：
Table 2
Formula (I) compound represented of the present invention can be obtained by reaction equation 1 or reaction equation 2 shown below；Reaction equation 1 Or (II), (III) or (V) in reaction equation 2 can be synthesized by purchase or with reference to pertinent literature；L generations in reaction equation Table chlorine, bromine, iodine, sulphonic acid ester, hydroxyl etc., other substituent groups are outer unless specified otherwise to be limited as preceding.
Reaction equation 1：
Reaction equation 2：
The compound of formula (I) can so be prepared (reaction equation 1)：Suitable solvent for example dichloromethane, dichloroethanes, In toluene, dimethylbenzene, n,N-Dimethylformamide (DMF), tetrahydrofuran, acetonitrile or dioxane etc., flow back in 0 DEG C~system Temperature, in suitable alkali such as triethylamine, pyridine, sodium hydride, sodium methoxide, potassium hydroxide, potassium carbonate, potassium tert-butoxide, sodium hydroxide Or in the presence of sodium carbonate etc., formula (IV) compound is reacted to obtain with the compound of formula (II) and the compound of formula (III)；Suitable Solvent such as dichloromethane, dichloroethanes, toluene, dimethylbenzene, N,N-dimethylformamide (DMF), tetrahydrofuran, acetonitrile or dioxy In six rings etc., in 0 DEG C~system reflux temperature, suitable alkali for example triethylamine, pyridine, sodium hydride, sodium methoxide, potassium hydroxide, In the presence of potassium carbonate, potassium tert-butoxide, sodium hydroxide or sodium carbonate etc., reacted with the compound of formula (IV) and the compound of formula (V) Obtain formula (I) compound.
The compound of formula (I) is it is also possible that prepare (reaction equation 2)：In suitable solvent such as dichloromethane, two chloroethenes In alkane, toluene, dimethylbenzene, n,N-Dimethylformamide (DMF), tetrahydrofuran, acetonitrile or dioxane etc., in 0 DEG C~system Reflux temperature, in suitable alkali such as triethylamine, pyridine, sodium hydride, sodium methoxide, potassium hydroxide, potassium carbonate, potassium tert-butoxide, hydrogen-oxygen In the presence of changing sodium or sodium carbonate etc., formula (VI) compound is reacted to obtain with the compound of formula (II) and the compound of formula (V)；Suitable Solvent such as dichloromethane, dichloroethanes, toluene, dimethylbenzene, N,N-dimethylformamide (DMF), tetrahydrofuran, acetonitrile or two In six ring of oxygen etc., in 0 DEG C~system reflux temperature, in suitable alkali such as triethylamine, pyridine, sodium hydride, sodium methoxide, hydroxide In the presence of potassium, potassium carbonate, potassium tert-butoxide, sodium hydroxide or sodium carbonate etc., with the compound of the compound and formula (III) of formula (VI) React to obtain formula (I) compound.
Formula (II), formula (III) and formula (V) compound can be by purchases or with reference to conventional synthesis process or coherent reference text Offer preparation.
Specific synthetic method has more detailed elaboration in the following embodiments.
Formula (I) compound provided by the invention under 15~2250 grams of active ingredients/hectare dosage there is broad-spectrum biological to live Property, it can be not only used for prevention harmful levels of pathogens, it may also be used for prevention harmful insect.Some compounds have good harmful insect or disease Bacterium preventive and therapeutic effect is obtained with good effect under very low dosage.
Formula (I) compound provided by the invention, with bioactivity and the compound that has it is special with good bioactivity Be not agricultural, gardening, flowers and sanitary insect pest, harmful levels of pathogens prevention in terms of show activity.Harmful life described here Object include but not limited to this：
Harmful pathogen：Phytophthora species, white powder category species, Gibberella species, Venturia species, Sclerotinia kind Class, Rhizoctonia species, Botrytis species, Pyricularia Sacc. species, Fusarium species.Such as rice blast (Pyricularia oryzae)；Stripe rust of wheat (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust Disease；Big wheat yellow rust (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust；Barley With wheat powdery mildew (Erysiphe graminis), powdery mildew of cucumber (Sphaerotheca fuligenea), apple mildew (Podosphaera leucotrichar) and uncinula necator (Podosphaera leucotrichar)；Wheat sharp eyespot and Glume blight (Septoria nodorum).The compacted spore of length on cereal, mouth spore is mould, Septoria is sick, caryosphere shell Pseudomonas disease, Pseudocercosporella herpotrichoides and take-all (Gaeumannomyces graminis).Peanut Brown spot (Cercospora arachidicola) and the cercospora black spot of peanut (Cercosporidium personata)；Apple wheel Line germ (Botryosphaeria berengriana f.sp piricola), Valsa mali (Cytospora sp.)； Its Cercospora disease on beet, soybean and paddy.Tomato, cucumber, grape grey mould (Botrytis cinerea).Vegetables Hinge spore on (such as cucumber) belongs to disease.Anthracnose on cucumber, scab of apple, cucumber downy mildew, downy mildew of garpe, potato With the epidemic disease on tomato, list bacterium Thanatephorus cucumeris and other hosts such as wheat and barley on paddy, Other rhizoctonias on vegetables；Sclerotinia sclerotiorum (Sclerotonia sclerotiorum)；Wheat scab (Gibberella zeae)；Phytophthora capsici disease (Phytophythora capsici).
Harmful insect：Lepidoptera pest such as oriental armyworm, prodenia litura, diamondback moth, beet armyworm, cabbage looper, dark greyish green Worm, Orthoptera such as blattaria, Thysanoptera such as cotton thrips, rice thrips, melon thrips, Homoptera such as leafhopper, plant hopper, aphid, Hymenoptera is such as Sawfly larva, Diptera such as yellow-fever mosquito, culex, fly；Acarina evil mite such as Jie-Li enzyme-SQ, cotton spider mites, T.urticae Koch etc..
It is effective to control pest, harmful levels of pathogens, they can also when formula (I) compound of the present invention is used alone It is used together with other biological chemical substance, these biochemicals include other insecticides, nematicide, acaricide and kill Microbial inoculum.
With formula provided by the invention (I) compound, as the Agrotechnical formulation of effective ingredient, can be made desirable any A kind of dosage form such as dry compressed particle easily flows intermixture, granula, wettable powder, water dispersible granules, emulsifiable concentration Object, pulvis, powdery concentrate, microemulsion, suspending agent, missible oil, aqueous emulsion, soluble liquid, aqua, dispersible agent, it is suitable Auxiliary agent include carrier (diluent) and other adjuvants such as spreader-sticker, emulsifier, wetting agent, dispersant, sticker and decomposition Agent.Contain in these preparations and be mixed with the compound of the present invention with the acceptable solid of inert, pharmacology or liquid diluent.
Desirable any dosage form such as dry compressed particle, easily flowing can also be made in the composition example of the present invention Intermixture, granula, wettable powder, water dispersible granules, emulsifiable concentrate, pulvis, powdery concentrate, microemulsion, suspension Agent, missible oil, aqueous emulsion, soluble liquid, aqua, dispersible agent, suitable auxiliary agent include carrier (diluent) and other auxiliary Auxiliary agent such as spreader-sticker, emulsifier, wetting agent, dispersant, sticker and distintegrant.Contain in these preparations with inert, pharmacology 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 10 preparation method (method one)
1- methyl -3- ethyl -4- chlorine pyrazoles -5- formyl chloride 1- methyl -3- ethyl -4- chlorine pyrazoles -5- formic acid (100mmol) ﹑ thionyl chlorides (150mmol) and 1,2- dichloroethanes (100mL) react 3- in 35 DEG C to system reflux temperature 5hr, removing solvent is up to title compound 15.8g.
N- (2,6- dimethyl -4- nitrobenzophenones) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamide 2,6- dimethyl - 4- nitroanilines be (50mmol) ﹑ 1- methyl -3- ethyl -4- chlorine pyrazoles -5- formyl chlorides (50mmol) and triethylamine (65mmol) Tetrahydrofuran (40mL) mixture reacts 2-6h in 10-60 DEG C to complete, and reaction mixture is poured into ice water, ethyl acetate extraction Take, organic layer washing after anhydrous sodium sulfate dry, remove solvent, through column chromatography or recrystallization purifying handle title object is faint yellow Solid 12.1g, purity 96.5%..
N- bytyries-N- (2,6- dimethyl -4- nitrobenzophenones) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides N- (2,6- dimethyl -4- nitrobenzophenones) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamide (25mmol) ﹑ butyl chlorides Tetrahydrofuran (40mL) mixture of (25mmol) and sodium hydride (60%, 25mmol) is stirred to react 2-6h in 25-60 DEG C to anti- It should be complete.Reaction mixture is poured into ice water, anhydrous sodium sulfate is dried after ethyl acetate extraction, organic layer washing, and removing is molten Agent, crude by column chromatography or recrystallization purifying handle to obtain title object faint yellow solid 6.6g, purity 98.1%.
Embodiment 2 this example demonstrates that in table 1 compound 10 preparation method (method two)
N- (2,6- dimethyl -4- nitrobenzophenones) butyramide 2,6- dimethyl -4- nitroaniline (100mmol) ﹑ butyric acid (50mmol), phosphorus oxychloride (100mmol) and acetonitrile (100mL) react 2-6h in 35 DEG C to system reflux temperature to the reaction was complete Afterwards, reaction mixture is poured into ice water, solid is precipitated, filter obtained solid and washed, it is dry, obtain title compound off-white color Solid 7.2g.
N- bytyries-N- (2,6- dimethyl -4- nitrobenzophenones) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides N- (2,6- dimethyl -4- nitrobenzophenones) butyramide (25mmol) ﹑ 1- methyl -3- ethyl -4- chlorine pyrazoles -5- formyl chlorides (25mmol) It is stirred to react with tetrahydrofuran (40mL) mixture of sodium hydride (60%, 25mmol) in 20-60 DEG C to the reaction was complete.It will reaction Mixture is poured into ice water, and anhydrous sodium sulfate is dried after ethyl acetate extraction, organic layer washing, removes solvent, column chromatography or again Crystallization purifying handles to obtain title object faint yellow solid 5.8g, purity 98.0%.
Other compounds of the present invention are referred to embodiment 1 or embodiment 2 is synthesized, if necessary, with reference to related text It offers.
Embodiment 3N- bytyries-N- (2,6- dimethyl -4- nitrobenzophenones) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- first The preparation of (10) 10% oil slick of amide
It weighs compound 10 in appropriate formula provided by the invention (I) compound of (by weight percentage 10%) such as table 1, fit Cosolvent (such as ethyl acetate or acetone), suitable pesticide used additives and the solvent (such as toluene, dimethyl) of amount are put into reaction Kettle first adds in a certain amount of solvent (such as toluene) and antifoaming agent and stirs 10~30min, add suitable stabilizer, synergist, The components such as penetrating agent continue 10~30min of stirring, adjust pH value, then a effective amount of solvent is put into kettle, are put after stirring evenly Expect up to N- bytyries-N- (2,6- dimethyl -4- nitrobenzophenones) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides (10) 10% missible oil.
It is raw to survey embodiment
Sterilization and insecticidal activity experiment are carried out to the compounds of this invention, part of test results is as follows.
Embodiment 4 is to the Insecticidal Activity of aphid (Aphis fabae)
It is to evaluate the compounds of this invention to the activity of homoptera pest, aphid is selected to be determined for object using infusion process The compounds of this invention is to the activity of aphid.
Infusion process：Testing compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.2% The clear water of Tween80 emulsifiers is diluted to required concentration, if the blank without testing compound is control, often handles 3 repetitions. Black bean aphid is connected on just unearthed bean seedlings, every plant connects 20 or more, and bean seedlings then are dipped in the present invention together with test worm carries In formula (I) liquid of confession, taken out after 5 seconds, suck extra liquid, be inserted into the sponge of water suction, covered with glass-tube, 24 it is small when after Check survival and dead borer population, results are averaged.Active (death rate) with respect to blank control in percentage, be divided into A, B, C, D level Four, 100 >=death rate (%) >=90 be A grades, 90>The death rate (%) >=70 be B grades, 70>The death rate (%) >=50 is C grades, 50>The death rate (%) >=0 is D grades.The result shows that the compounds of this invention is active to aphid, and the compound having is relatively low Under concentration still there is greater activity, partial results are listed below：
Under 500mg/L concentration, 10 and 29 grade of the compounds of this invention has aphid A grades of activity；16th, 19 and 31 etc. to aphid With B grades of activity；04th, 09,11,25,26,34 and 37 etc. have aphid C grades of activity；
Under 50mg/L concentration, the compounds of this invention 10 (78.39%) etc. has aphid B grades of activity；
Under 12.5mg/L concentration, the compounds of this invention 10 (65.94%) etc. has aphid C grades of activity.
Embodiment 5 is to the biological evaluation of mythimna separata (Mythimna separata)
Potter spray-on processes：Appropriate the compounds of this invention is weighed, is dissolved with n,N-Dimethylformamide, adds and spits on a small quantity Warm 80 emulsifiers, stir evenly, and add in quantitative clear water, are configured to required concentration, if clear water is control.Fresh and tender maize leaves is taken to cut The segment basically identical into size is put into and is lined in advance in the culture dish (Ф 90mm) of filter paper.Then 3 age of mythimna separata is accessed in ware Larva 10, is put under Potter spray towers and carries out metered dose, and spray liquid measure 1ml, per 3 repetitions of concentration.It is disposed, covers Upper ware lid, is placed in culture in recovery room, routine observation, when 72 is small after check and record the death condition of test worm, calculate dead Rate (%), results are averaged.Activity in percentage, is divided into A, B, C, D level Four, 100 >=death rate compared with blank control (%) >=90 be A grades, 90>The death rate (%) >=70 be B grades, 70>The death rate (%) >=50 be C grades, 50>The death rate (%) >=0 For D grades.The result shows that 16 and 20 grade of the compounds of this invention is active with more than 80% B grades to mythimna separata.
Embodiment 6 is to the control effect of rice sheath blight disease (Rhizoctonia solani)
Testing compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.2%Tween80 breasts The sterile water of agent is diluted to required concentration, if the blank without testing compound is control, often handles 4 repetitions；By rice Sheath blight the original bacterium is gone to after going to PDA plate activation culture in PD culture mediums, water bath with thermostatic control culture 4 days；By cultured mycelia Ball is crushed with refiner and allocated with clear water to certain density bacteria suspension；When cucumber is grown to flattening two panels true leaf, spray The liquid of testing compound is stated, bacteria suspension is sprayed after 1 day to seedling surface, moisturizing culture simultaneously observes seedling incidence, when right It is apparent according to processing morbidity, start to record the incidence of each processing, calculate disease index and pharmacy control efficacy.It is the result shows that of the invention Compound has good control effect to rice sheath blight disease.Such as under 500mg/L concentration, 09 and 39 grade pair of the compounds of this invention Rice sheath blight disease has more than 90% control effect；07th, 17,19,31 and 33 etc. there is 70-90% to prevent rice sheath blight disease Control effect.
Embodiment 7 is to the control effect of corn rust (Puccinia Polysora)
Method：Testing compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.2% The sterile water of Tween80 emulsifiers is diluted to required concentration, if the blank without testing compound is control, often handles 4 weights It is multiple；Morbidity maize leaf is cut, lower spore is washed with 0.05-0.2%Tween80 or other suitable surfactant aqueous solutions, and With 2~4 layers of filtered through gauze, concentration is made as 1 × 105The suspension of a spore/mL；It is above-mentioned to treat that corn length to 1 heart stage of 2 leaf sprays The liquid of testing compound, spore suspension spray inoculation after 1 day move to moisturizing cabinet (relative humidity more than 95%, temperature after inoculation 20 DEG C~22 DEG C of degree), the r of (intensity of illumination 5000Lux~10000Lux) culture 15 under low light condition~for 24 hours；Treat blank control disease When leaf rate is up to more than 50%, the incidence of each processing is investigated, calculates disease index and pharmacy control efficacy.The result shows that the present inventionization Close object has control effect to corn rust.Such as under 500mg/L concentration, the compounds of this invention 24,29 and 32 etc. becomes rusty to corn Disease has more than 70% control effect.
Embodiment 8 is to the bactericidal activity (pot-culture method) of wheat powdery mildew (Erisiphe griminis)
Method：Testing compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.2% The sterile water of Tween80 emulsifiers is diluted to required concentration；The basin alms bowl of cut-off stem 15cm or so sows the full stalwartness of wheat per alms bowl 20, seed, be for experiment after the first true leaf is grown；Ready wheat seedling plant is taken to be sprayed through certain density medicament Mist processing, carries out germ inoculation after one day.3 repetitions are often handled, separately set the blank without testing compound as blank control；It protects After wet thermophilic culture is fallen ill to blank control, lesion area is checked, calculate disease index and pharmacy control efficacy.It is the result shows that of the invention Compound has good control effect to wheat powdery mildew.Such as under 500mg/L concentration, the compounds of this invention 12,19 and 31 Deng the control effect to wheat powdery mildew with more than 90%；01st, 02,09,23,32,35,36 and 40 etc. have wheat powdery mildew There is more than 70% control effect.

Claims (10)

1.N-2,4- substituted-phenyl bisamide class compound and preparation method and application, it is characterised in that represented with logical formula (I) N-2,4- substituted-phenyls bisamide class compound and its isomers：
Wherein：
I.R represents C1-C12Alkyl, C1-C12Alkoxy, C2-C12Alkenyl, C2-C12Alkenyl oxygroup, C2-C12Alkynyl, C2-C12Alkynyl Oxygroup, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3-C8Heterocyclylalkyl, C3-C8Heterocyclylalkyl oxygroup, phenyl, phenoxy group, connection Phenyl, pyrazolyl, thiadiazolyl group, pyridyl group, thienyl, benzothienyl, furyl, benzofuranyl, pyrrole radicals, benzo pyrrole Cough up base, indyl, benzindole base, imidazole radicals, benzimidazolyl, quinolyl, pyranose, pyrazinyl, pyrimidine radicals, pyridazinyl, Benzopyranyl, benzopyrazines base, benzo pyrimidine radicals, benzo pyridazinyl, benzoxazolyl, benzoxazine, benzothiazole Base, isothiazolyl, benzisothia oxazolyl, pyrimido triazolyl；
II.Ar represents phenyl, xenyl, pyrazolyl, thiadiazolyl group, pyridyl group, thienyl, benzothienyl, furyl, benzo Furyl, pyrrole radicals, benzopyrrole base, indyl, benzindole base, imidazole radicals, benzimidazolyl, quinolyl, pyranose, pyrrole Piperazine base, pyrimidine radicals, pyridazinyl, benzopyranyl, benzopyrazines base, benzo pyrimidine radicals, benzo pyridazinyl, benzoxazolyl, benzene And isoxazolyl, benzothiazolyl, isothiazolyl, benzisothia oxazolyl, pyrimido triazolyl；
III.R1And R2It is same or different, and represents halogen, cyano, nitro, C1-C12Alkyl, C1-C12Alkoxy, C1- C12Alkyl-carbonyl or C1-C12Alkyl sulphonyl；
IV.R3Represent hydrogen, halogen, cyano, nitro, C1-C12Alkyl or C1-C12Alkoxy；
V.n represents 0,1,2 or 3 integer；And
1) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen atom is unsubstituted；Or 2) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen moiety all can be by The identical or different substituent group substitution in following：Halogen, nitro, cyano, C1-C12Alkyl, C1-C12Halogenated alkyl, C1-C12 Alkoxy, C1-C12Halogenated alkoxy, C1-C12Alkylthio group, C1-C12Alkyl sulphonyl, C1-C12Alkyl sulphinyl, C1-C12Alkane Oxygen carbonyl, C1-C12Alkyl carbonyl epoxide, C1-C12Alkyl amine group, C2-C12Alkenyl, C2-C12Alkenyl oxy, C2-C12Alkene Base sulfenyl, C2-C12Alkenyloxycarbonyl, C2-C12Alkenyl amido, C2-C12Alkynyl group, C2-C12Alkynyl group oxygroup, C2-C12 Alkynyl group sulfenyl, C2-C12Alkynyl group Epoxide carbonyl, C2-C12Alkynyl group amido, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3- C8Cycloalkylsulfanyl, C3-C8Cycloalkyloxycarbonyl, C3-C8Cycloalkyl amido, C3-C8Heterocyclylalkyl, C3-C8Heterocyclylalkyl oxygen Base, C3-C8Heterocyclylalkyl sulfenyl, C3-C8Heterocyclylalkyl Epoxide carbonyl, C3-C8Heterocyclylalkyl amido, phenyl, by halogen, C1-C6Alkane Base and/or C1-C6Alkoxy substitution phenyl, phenoxy group, by halogen, C1-C6Alkyl and/or C1-C6The benzene oxygen of alkoxy substitution Base；
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 or iodine；
Alkyl：Refer to straight or branched alkyl；
Cycloalkyl：Refer to saturation or unsaturation ring alkyl；
Alkenyl；Refer to linear chain or branch chain alkenyl, and can there are double bonds on any position；
Alkynyl group；Refer to linear chain or branch chain alkynyl, and can there are three keys on any position；
It is halogenated：Refer to hydrogen moiety therein or all substituted by halogen atom.
2. N-2 according to claim 1,4- substituted-phenyl bisamide class compound, it is characterised in that logical formula (I) compound In：
I.R represents C1-C12Alkyl, C2-C12Alkenyl, C2-C12Alkynyl, C3-C8Cycloalkyl, C3-C8Heterocyclylalkyl, C1-C12Alkoxy, C2-C12Alkenyl oxygroup, C2-C12Alkynyl oxygroup, C3-C8Cycloalkyl oxy, C3-C8Heterocyclylalkyl oxygroup, phenyl, pyrazolyl or pyrrole Piperidinyl；
II.Ar represent phenyl, pyrazolyl, thiadiazolyl group, pyridyl group, thienyl, benzothienyl, furyl, benzofuranyl, It is pyrrole radicals, benzopyrrole base, indyl, benzindole base, imidazole radicals, benzimidazolyl, quinolyl, pyranose, pyrazinyl, phonetic Piperidinyl, pyridazinyl, benzopyranyl, benzopyrazines base, benzo pyrimidine radicals, benzo pyridazinyl, benzoxazolyl, benzoisoxazole Base, benzothiazolyl, isothiazolyl, benzisothia oxazolyl, pyrimido triazolyl；
III.R1And R2It is same or different, and represents halogen, cyano, nitro, C1-C12Alkyl, C1-C12Alkoxy, C1- C12Alkyl-carbonyl or C1-C12Alkyl sulphonyl；
IV.R3Represent hydrogen, halogen, cyano, nitro, C1-C12Alkyl or C1-C12Alkoxy；
V.n represents 0,1,2 or 3 integer；And
1) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen atom is unsubstituted；Or 2) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen moiety all can be by The identical or different substituent group substitution in following：Halogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy, C1-C6 Halogenated alkoxy, C1-C6Alkylthio group, C1-C6Alkyl sulphonyl, C1-C6Alkyl sulphinyl, C1-C6Alkyl amine group, C2-C6Alkene Base, C2-C6Alkenyl oxy, C2-C6Alkenyl thio, C2-C6Alkenyl amido, C2-C6Alkynyl group, C2-C6Alkynyl group oxygroup, C2-C6Alkynyl group sulfenyl, C2-C6Alkynyl group amido, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3-C8Cycloalkylsulfanyl, C3-C8 Cycloalkyl amido, phenyl, by halogen, C1-C6Alkyl and/or C1-C6Alkoxy substitution phenyl, phenoxy group, by halogen, C1-C6 Alkyl and/or C1-C6The phenoxy group of alkoxy substitution.
3. N-2 according to claim 1,4- substituted-phenyl bisamide class compound, it is characterised in that logical formula (I) compound In：
I.R represents C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C8Cycloalkyl, C3-C8Heterocyclylalkyl, C1-C6Alkoxy, C2- C6Alkenyl oxygroup, C3-C6Alkynyl oxygroup, C3-C8Cycloalkyl oxy, C3-C8Heterocyclylalkyl oxygroup, phenyl, pyrazolyl or pyridyl group；
II.Ar represents phenyl, pyrazolyl or pyridyl group；
III.R1And R2It is same or different, and represents halogen, cyano, nitro, C1-C6Alkyl, C1-C6Alkoxy, C1-C6 Alkyl-carbonyl or C1-C6Alkyl sulphonyl；
IV.R3Represent hydrogen, halogen, cyano, nitro, C1-C6Alkyl or C1-C6Alkoxy；
V.n represents 0,1,2 or 3 integer；And
1) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen atom is unsubstituted；Or 2) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen moiety all can be by The identical or different substituent group substitution in following：Halogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy, C1-C6 Halogenated alkoxy, C1-C6Alkylthio group, C1-C6Alkyl amine group, C2-C6Alkenyl, C2-C6Alkenyl oxy, C2-C6Alkenyl sulphur Base, C2-C6Alkenyl amido, C2-C6Alkynyl group, C2-C6Alkynyl group oxygroup, C2-C6Alkynyl group sulfenyl, C2-C6Alkynyl group amido, C3-C8Cycloalkyl, C3-C8Cycloalkyl oxy, C3-C8Cycloalkylsulfanyl, C3-C8Cycloalkyl amido, phenyl, by halogen and/or C1- C6Alkyl-substituted phenyl.
4. N-2 according to claim 1,4- substituted-phenyl bisamide class compound, it is characterised in that logical formula (I) compound It is：
I.R represents C1-C6Alkyl, C2-C6Alkenyl, C2-C6Alkynyl, C3-C8Cycloalkyl, C3-C8Heterocyclylalkyl, C1-C6Alkoxy, C2- C6Alkenyl oxygroup, C3-C6Alkynyl oxygroup, C3-C8Cycloalkyl oxy, C3-C8Heterocyclylalkyl oxygroup, phenyl, pyrazolyl or pyridyl group；
II.Ar represents phenyl, pyrazolyl or pyridyl group；
III.R1And R2It is same or different, and represents halogen, cyano, nitro, C1-C6Alkyl, C1-C6Alkoxy；
IV.R3Represent hydrogen, halogen, cyano, nitro, C1-C6Alkyl or C1-C6Alkoxy；
V.n represents 0,1,2 or 3 integer；And
1) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen atom is unsubstituted；Or 2) identified meaning, R, Ar, R such as in I., II., III. or IV.1、R2And/or R3Middle hydrogen moiety all can be by The identical or different substituent group substitution in following：Halogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy, C1-C6 Halogenated alkoxy, phenyl, by halogen and/or C1-C6Alkyl-substituted phenyl.
5. N-2 according to claim 1,4- substituted-phenyl bisamide class compound, it is characterised in that leading to formula (I) compound is Following compound：
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-) -1,3- dimethyl pyrazole -5- formamides；
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -1,3- dimethyl pyrazole -5- formamides；
N- isobutyryls-N- (bis- chloro- 4- cyano-phenyls of 2,6-) -1,3- dimethyl pyrazole -5- formamides；
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-) -1- methyl -3- ethylpyrazol -5- formamides；
N- propionos-N- (2,6- dichlor-4-trifluoromethyls phenyl) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides；
N- bytyries-N- (2,6- dimethyl -4- nitrobenzophenones) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides；
N- bytyries-N- (the bromo- 4- nitrobenzophenones of the chloro- 6- of 2-) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides；
N- bytyries-N- (bis- chloro- 4- cyano-phenyls of 2,6-) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides.
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides；
N- isobutyryls-N- (2,6- dimethyl -4- nitrobenzophenones) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides；
N- isobutyryls-N- (2,6- dichlor-4-trifluoromethyls phenyl) -1- methyl -3- ethyl -4- chlorine pyrazoles -5- formamides；
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -1- (3- chloropyridine -2- bases) -3- bromine pyrazoles -5- formamides；
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-) -1,4,5- trimethylpyrazol -3- formamides；
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -1,4,5- trimethylpyrazol -3- formamides；
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-) -1,3- dimethyl pyrazole -4- formamides；
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -1,3- dimethyl pyrazole -4- formamides；
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-)-Niacinamide；
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -2- chloropyridine -3- formamides；
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-) -2- chloropyridine -3- formamides；
N- bytyries-N- (bis- bromo- 4- cyano-phenyls of 2,6-) -2- chloropyridine -3- formamides；
N- bytyries-N- (bis- chloro- 4- cyano-phenyls of 2,6-) -2- chloropyridine -3- formamides；
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-) -2,6- dichloropyridine -3- formamides；
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -2,6- dichloropyridine -3- formamides；
N- bytyries-N- (bis- bromo- 4- cyano-phenyls of 2,6-) -2,6- dichloropyridine -3- formamides；
N- bytyries-N- (bis- chloro-4 nitrophenyls of 2,6-) -2- trifluoromethyl benzamides；
N- isobutyryls-N- (bis- chloro-4 nitrophenyls of 2,6-) -2- trifluoromethyl benzamides.
6. the preparation method of N-2 according to claim 1,4- substituted-phenyl bisamide class compound, it is characterised in that formula (I) Compound represented is prepared by reaction shown below,
Reaction equation 1：
Reaction equation 2：
The compound of formula (I) can be prepared so：In methylene chloride, dichloroethanes, toluene, dimethylbenzene, N, N- diformazans In base formamide, tetrahydrofuran, acetonitrile or dioxane, in 0 DEG C~system reflux temperature, in alkali triethylamine, pyridine, hydrogenation In the presence of sodium, sodium methoxide, potassium hydroxide, potassium carbonate, potassium tert-butoxide, sodium hydroxide or sodium carbonate, with the compound of formula (II) with The compound of formula (III) reacts to obtain formula (IV) compound；In methylene chloride, dichloroethanes, toluene, dimethylbenzene, N, N- bis- In methylformamide, tetrahydrofuran, acetonitrile or dioxane, in 0 DEG C~system reflux temperature, in alkali triethylamine, pyridine, hydrogenation In the presence of sodium, sodium methoxide, potassium hydroxide, potassium carbonate, potassium tert-butoxide, sodium hydroxide or sodium carbonate, with the compound of formula (IV) with The compound of formula (V) reacts to obtain formula (I) compound (reaction equation 1)；
The compound of formula (I) is it is also possible that prepare：In methylene chloride, dichloroethanes, toluene, dimethylbenzene, N, N- bis- In methylformamide, tetrahydrofuran, acetonitrile or dioxane, in 0 DEG C~system reflux temperature, in alkali triethylamine, pyridine, hydrogenation In the presence of sodium, sodium methoxide, potassium hydroxide, potassium carbonate, potassium tert-butoxide, sodium hydroxide or sodium carbonate, with the compound of formula (II) with The compound of formula (V) reacts to obtain formula (VI) compound；In methylene chloride, dichloroethanes, toluene, dimethylbenzene, N, N- diformazans In base formamide, tetrahydrofuran, acetonitrile or dioxane, in 0 DEG C~system reflux temperature, in suitable alkali such as triethylamine, pyrrole In the presence of pyridine, sodium hydride, sodium methoxide, potassium hydroxide, potassium carbonate, potassium tert-butoxide, sodium hydroxide or sodium carbonate, with the change of formula (VI) It closes object and the compound of formula (III) reacts to obtain formula (I) compound (reaction equation 2)；
Formula (II), formula (III) and formula (V) compound can be by purchases or with reference to conventional synthesis process or relevant references system It is standby；
R, Ar, R in formula1、R2、R3Have with n and defined given in claim 1, L is leaving group chlorine, bromine, iodine, sulphonic acid ester, hydroxyl Base.
7. according to the purposes of Claims 1 to 5 any one of them N-2,4- substituted-phenyl bisamide class compound, feature exists In under 15~5000 grams of active ingredients/hectare dosage have desinsection and/or sterilization bioactivity.
It is killed 8. being used to prepare to have according to Claims 1 to 5 any one of them N-2,4- substituted-phenyl bisamide class compounds The purposes of the drug of worm and/or bactericidal activity.
9. a kind of desinsection and/or bactericidal composition, it is characterised in that：Containing as active component as Claims 1 to 5 is any N-2 described in, 4- substituted-phenyl bisamide class compounds, the weight percentage of active component is 0.5- in composition 99%.
10. a kind of pest control or the method for germ, it is characterised in that：By a effective amount of as described in any one of Claims 1 to 5 N-2,4- substituted-phenyl bisamide class compounds impose on the pest, germ or its growth medium.
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