WO2014187297A1 - N-pyridine(hetero)aromatic amide compound and preparation method and use thereof - Google Patents

N-pyridine(hetero)aromatic amide compound and preparation method and use thereof Download PDF

Info

Publication number
WO2014187297A1
WO2014187297A1 PCT/CN2014/077821 CN2014077821W WO2014187297A1 WO 2014187297 A1 WO2014187297 A1 WO 2014187297A1 CN 2014077821 W CN2014077821 W CN 2014077821W WO 2014187297 A1 WO2014187297 A1 WO 2014187297A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
nitropyridin
carboxamide
amino
trifluoromethylthiazole
Prior art date
Application number
PCT/CN2014/077821
Other languages
French (fr)
Chinese (zh)
Inventor
王晓光
柳爱平
刘兴平
何莲
欧晓明
雷满香
胡礼
高岗
余一平
左金江
Original Assignee
湖南化工研究院有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 湖南化工研究院有限公司 filed Critical 湖南化工研究院有限公司
Publication of WO2014187297A1 publication Critical patent/WO2014187297A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • 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
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • 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
    • C07D213/72—Nitrogen atoms
    • C07D213/76—Nitrogen atoms to which a second hetero atom is attached
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • 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
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • 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
    • C07D401/12—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 linked by a chain containing hetero atoms as chain links
    • 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
    • C07D401/14—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 three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • N-pyridine (hetero) aramid compound N-pyridine (hetero) aramid compound and preparation method and application thereof
  • the present invention relates to an N-pyridine (hetero) aromatic amide compound having bactericidal, herbicidal, insecticidal/industrial activity, a process for the preparation thereof, a bactericidal, herbicidal, insecticidal/sputum composition containing the compound, and the use thereof
  • N-pyridine (hetero) aromatic amide compound having bactericidal, herbicidal, insecticidal/industrial activity
  • a process for the preparation thereof a bactericidal, herbicidal, insecticidal/sputum composition containing the compound, and the use thereof
  • the use and method of compounds to control harmful germs, weeds, pests/cockroaches The use and method of compounds to control harmful germs, weeds, pests/cockroaches.
  • Amide compounds are an important class of compounds in medicinal chemistry. They have a broad spectrum of biological activities, and there are many reports on biologically active amide compounds. Also, heterocyclic compounds, particularly pyridine heterocyclic compounds, are also an important class of compounds in medicinal chemistry, and they also have a broad spectrum of biological activities, and there are many reports on biologically active pyridine heterocyclic compounds. However, it is difficult to find related literature reports on biologically active N-pyridine (hetero) aramid compounds.
  • the present invention provides an N-pyridine (hetero) arylamide compound having the biological activity of bacteria, weeds, pests, cockroaches and the like and an isomer thereof represented by the formula (I):
  • C1-C12 C1-C12 C1-C12 C1-C12 II (Ci-Ci 2 )3 ⁇ 43 ⁇ 43 ⁇ 4 Amino, C 2 -C 12 alkenyl, C 2 -C 12 alkenyl group, C 2 -C 12 alkenyl group, C 2 -C 12 alkenyl sulfonyl group, C 2 -C 12 Alkenylsulfinyl, c 2 -c 12 alkenylcarbonyl, c 2 -c 12 alkenyloxycarbonyl, c 2 -c 12 alkenylcarbonyloxy, C 2 -C 12 alkenylamine , c 2 -c 12 alkenylamino, c 2 -c 12 alkynyl, c 2 -c 12 alkynyloxy, c 2 -c 12 alkynylthio, c 2 -c 12 Alkynylsulfonyl, c 2 -c 12
  • R 1 and R 2 , R 3 are the same or different and represent
  • alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl groups described in I. b) and II. are unsubstituted or alkyl groups as described in L b) and II.
  • the hydrogen atom in the cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl group is partially or wholly substituted with the same or different substituents selected from the group consisting of halogen, nitro, cyano, amine, hydroxy, a mercapto group, a carboxyl group, an aldehyde group, a hydrazine group, a hydrazone group, dC 12 alkyl, dC 12 alkyloxy, dC 12 alkylthio, dC 12 alkylsulfonyl, alkylsulfinyl 12, dC 12 alkyl Carbocarbonyl, 12 alkyloxycarbonyl, 12 alkylcarbonyloxy, Ci-Ci 2 alkylamino, bis(d-Cu)alkylamino, c 2 -c 12 alkenyl, c 2 -c 12 alkenyloxy group, c 2 -c 12 alkenyl
  • aryl and heteroaryl groups identified in I. and II. and 1) may be partially or fully hydrogenated, one of which or
  • Two CH 2 groups can be substituted by CO;
  • Halogen means fluorine, chlorine, bromine, iodine
  • Alkyl means a straight or branched alkyl group
  • Cycloalkyl refers to saturated and unsaturated cycloalkyl
  • Alkenyl means straight or branched and may have a double bond at any position
  • Alkenyl means straight or branched and may have a triple bond at any position
  • C 6 -C 12 aryl means phenyl and a cyclic aryl or polycyclic aryl group derived therefrom, such as naphthyl, biphenyl, etc.; heteroaryl group having up to 10 carbon atoms means a ring hetero An aryl or polycyclic heteroaryl group having at least one N, 0, S, P and/or Se in the ring, such as thiazolyl, pyrazolyl, thiadiazolyl, pyridyl, thienyl, benzothienyl , furyl, benzofuranyl, pyrrolyl, benzopyrrolyl, fluorenyl, benzofluorenyl, imidazolyl, benzimidazolyl, quinolyl, pyranyl, pyrazinyl, pyrimidinyl, Pyridazinyl, benzopyranyl, benzopyrazinyl, benzopyrimidinyl, benzoxazinyl,
  • the C 6 -C 12 aryl group and the heteroaryl group having up to 10 carbon atoms may be partially or fully hydrogenated, wherein one or two CH 2 are substituted by CO, such as a cyclohexenyl group, a cyclohexanedione group or the like.
  • Preferred compounds of the invention are: In formula (I):
  • alkyl, cycloalkyl, alkenyl, alkynyl, or hydrogen atom in the phenyl group is partially or completely substituted by the same or different substituents selected from the group consisting of halogen, dC 6 alkyl, dC 6 Alkyloxy, dC 6 alkylthio, dC 6 alkylamino, bis(CrC 6 )alkylamino, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, C 2- C 6 alkenylthio, C 2 -C 6 alkenylamino, di C 2 -C 6 alkenylamino, C 2 -C 6 alkynyl, C 2 -C 6 alkynyl Oxy, C 2 -C 6 alkynylthio, C 2 -C 6 alkynylamino, di c 2 -c 6 alkynylamino, c 3 -c 6 cycloalkyl,
  • an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or a hydrogen atom in the phenyl group in 1) may also be substituted by the same or different substituents selected from the group consisting of hydrogen, halogen, dC 6 Alkyl, dC 6 alkyloxy, dC 6 alkylthio, dC 6 alkylamino, bis(CrC 6 )alkylamino, C 2 -C 6 alkenyl, C 2 -C 6 alkene alkoxy group, C 2 -C 6 alkenyl group, C 2 -C 6 alkenyl group, di-C 2 -C 6 alkenyl group, C 2 -C 6 alkynyl group, C 2 - C 6 alkynyloxy, C 2 -C 6 alkynylthio, c 2 -c 6 alkynylamino, di c 2 -c 6 alkynyla
  • the compounds of the invention may exist in the form of one or more isomers. Isomers include enantiomers, diastereomers, geometric isomers.
  • the compound of the formula (I) of the present invention can form geometric isomers (different configurations are represented by Z and E, respectively) due to the carbon-carbon double bond linking different substituents therein, and the present invention includes Z-isomers and E-isomers and mixtures thereof in any ratio.
  • the compound of the formula (I) of the present invention since one of the carbon atoms is bonded to four different substituents to form a stereoisomer (respectively represented by R and S, respectively;), the present invention includes R-isomers and S-isomers and mixtures thereof in any ratio.
  • the invention further relates to a biologically effective amount of a compound of formula (I) and at least one additional composition selected from the group consisting of surfactants, solid diluents and liquid diluents for controlling harmful germs, weeds, pests/caries.
  • the invention further relates to a composition
  • a composition comprising a biologically effective amount of a compound of formula (I) and an effective amount of at least one additional biologically active compound or formulation for controlling harmful bacteria, weeds, pests/cockroaches.
  • the invention further relates to a method of controlling harmful germs, weeds, pests, mites, which comprises contacting a biologically effective amount of a compound of formula (I) with harmful germs, weeds, mites or their environment. Also relates to such a harmful pathogen, weed, pest control method, harmful bacteria, weeds, pests or their environmentally effective amounts of a compound of formula (I) or a compound of formula (I) and a biologically effective amount At least one additional compound or mixture of formulations is contacted to control harmful germs, weeds, pests.
  • the compounds of the formula (I) of the present invention have a broad spectrum of activity: some compounds are useful for controlling harmful bacteria, and can also be used for controlling pests/caries; and some compounds are useful for controlling harmful weeds. Moreover, some compounds have high biological activity against certain target bacteria, so that good results can be obtained at very low doses.
  • the scooping group of the present invention is not a square shed secondary bile method containing a 3 ⁇ 4 medullary biliary group.
  • the invention will be further illustrated by the following formula (I) of the formulae listed in Tables 1 to 2, but does not limit the invention.
  • the melting point given in the present invention is uncorrected.
  • the compound of the formula (I) synthesized by the present invention is a viscous solid, some of the viscous solid refrigerators are solidified into a non-tacky solid after being placed, and the compound of the formula (I) synthesized by the present invention is In the case of viscous liquids, some viscous liquids will solidify when placed in the refrigerator.
  • the compound of the formula (I) of the present invention can be obtained by the reaction formula 1 (1-1 or 1-2) shown below; (II) and (V) in the reaction formula 1 can be reacted by the reaction shown below.
  • the compound of the formula (I) can be produced by the following reaction (reaction formula 1): in a suitable solvent such as dichloromethane or toluene, dichloroethane, hydrazine, hydrazine-dimethylformamide (DMF), tetrahydrofuran, dioxane In the ring, at -10 ° C ⁇ solvent reflux temperature, in the presence of a suitable base such as triethylamine or pyridine, sodium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, The compound represented by the formula (II) is reacted with the corresponding compound represented by the formula (III) or the formula (IV), or the compound represented by the formula (V) and the corresponding compound represented by the formula (VI) are reacted. (I) The compound shown. The addition of a suitable catalyst such as 4-dimethylaminopyridine (DMAP) or potassium iodide accelerates the reaction or increases the yield of the reaction.
  • the compound of the formula ( ⁇ ) and the formula (V) can be produced by the following (reaction formula 2): in a solvent-free or suitable solvent such as dichloroethane or dichloromethane, toluene, at a temperature of from 15 ° C to the reflux temperature of the system,
  • the compound of the formula (VII) is reacted with thionyl chloride or p-methylbenzenesulfonyl chloride to obtain a compound of the formula ( ⁇ ), and a catalyst amount of ruthenium, dimethyl-dimethylformamidine (DMF) is added.
  • the reaction can be accelerated or the reaction yield can be improved; and the compound represented by the formula (V) can be reacted with an amine water to obtain a compound represented by the formula (V).
  • the compounds of the formula ( ⁇ ) and the formula (IV) can be prepared by the following reaction (reaction formula 3): in a suitable solvent such as water or tetrahydrofuran, an alcohol, toluene, dichloroethane or dichloromethane at 0 ° C. ⁇ system reflux temperature, in the presence of a suitable base such as potassium carbonate or sodium carbonate, triethylamine, pyridine, sodium hydride, sodium hydroxide, potassium hydroxide, the reaction of the compound of formula (vm) and R 2 H A compound represented by the formula (VI) is obtained.
  • a suitable solvent such as water or tetrahydrofuran, an alcohol, toluene, dichloroethane or dichloromethane at 0 ° C. ⁇ system reflux temperature
  • the compound of the formula (VI) or the compound of the formula (IV) can be obtained by reacting the compound of the formula (VI) with aqueous ammonia or RM ⁇ in tetrahydrofuran and/or water at a reflux temperature of from 0 ° C to the reflux temperature of the system.
  • the compound of the formula (VII) can be produced in the same manner (Reaction formula 4): According to the structure of (VII) and possible starting materials, a suitable route in the reaction formula 4 is selected, and a compound of the formula (VII) can be obtained by a corresponding synthesis method.
  • the compound of the formula (VIII) can be produced by the following formula (reaction formula 5): a substituted 2-aminopyridine, which is nitrated with a mixed acid of sulfuric acid and nitric acid to give a substituted 2-aminonitropyridine, a substituted 2-amino group.
  • the nitropyridine is subjected to conventional diazotization, chlorination to give R-substituted 2-chloronitropyridine, and N-oxidation, chlorination to obtain a compound of the formula (VIII).
  • the compound of the formula (I) provided by the present invention has a broad spectrum of biological activity at a dosage of 3.75 to 2250 g of active ingredient per hectare, and can be used for controlling bacteria and for controlling weeds or harmful insects. Some compounds have good pathogen control effects and can achieve good results at very low doses.
  • the compound of the formula (I) provided by the present invention has biological activity and some compounds have excellent biological activity. Especially, it exhibits activity in the control of agriculture, horticulture, flower and hygienic bacteria, weeds, and pests.
  • the pests described here include, but are not limited to:
  • Gramineous weeds crabgrass, valerian, foxtail, hard grass, valerian, brome, amethyst, stalked wheat, sodic grass, star grass, wild oats, ryegrass;
  • weeds Broadleaf weeds: ramie, sorghum, sylvestris, scorpion, scorpion scorpion, scorpion scorpion, scorpion, etc.;
  • Orthoptera such as striata, pteridoptera such as cotton scorpion horse, rice scorpion horse, melon scorpion horse, Homoptera such as spider mites, locusts, locusts, lepidoptera such as oriental armyworm, Spodoptera litura, side dish Moth, beet armyworm, Spodoptera litura, Pieris rapae, Hymenoptera such as leaf bee larvae, Diptera such as Aedes, Culex, fly;
  • Harmful pathogens Phytophthora species, white powder species, Gibberella species, species of the genus Verticillium, species of Sclerotinia, Rhizoctonia species, Botrytis species, Pyriculara species, Fusarium species, such as rice blast (cM/ar a oryzae); wheat stripe rust (Puccinia striiformis), leaf rust (Puccinia recondita) and other Rust; barley stripe rust (Puccinia striiformis) leaf rust Puccinia recondita) and other rust; barley and wheat powdery mildew (Erysiphe graminis), cucumber powdery mildew (Sphaerotheca fuligenea), apple powdery mildew Podosphaera / ewcotr c rar) Powdery mildew (Poi/io p Mera leucotrichar); wheat sheath blight and Septoria
  • Anthrax on cucumber, apple scab, cucumber downy mildew, grape downy mildew, potato and tomato disease, monochae Thanatephorus cucumeris on rice and other hosts Such as wheat and barley, other Rhizoctonia on vegetables; Sclerotionia sclerotiorum; Gibberella zeae; Phytophythora capsici.
  • the compound of the formula (I) of the present invention When used alone, it is effective for controlling pathogens, weeds, and pests, and they can also be used together with other biochemical substances including other fungicides, herbicides, and insecticides. .
  • the agricultural preparation of the compound (I) provided by the present invention as an active ingredient can be prepared into any desired dosage form such as dry compressed granules, a flowable mixture, granules, wettable powders, water-dispersible granules, Emulsifying concentrates, powders, powder concentrates, microemulsions, suspending agents, emulsifiable concentrates, aqueous emulsions, soluble liquids, aqueous solutions, dispersible agents, suitable adjuvants including carriers (diluents) and others Adjuvants such as spreading agents, emulsifiers, wetting agents, dispersing agents, adhesives and decomposers.
  • These formulations contain the compound of the present invention in admixture with an inert, pharmacologically acceptable solid or liquid diluent.
  • the wettable powders, powders and powder concentrates of the present invention can be prepared by milling about 5-30% by weight of a compound of formula (I) with about 5-30% by weight of a solid anionic surfactant.
  • a solid anionic surfactant is the dioctyl ester of sodium sulfosuccinate.
  • Inorganic solid diluents such as talc, kaolin, diatomaceous earth, limestone, silicates and the like are also used in these formulations in an amount of from 40% to 90% by weight.
  • the compressed granules are prepared by milling approximately equal amounts of, for example, 5 to 30 parts of the compound of formula (I) with a solid surfactant and from about 40 to 90 parts of gypsum, and the mixture is then compressed to about 10-100 mesh (1.676- 0.152 mm) particles of size or larger.
  • the solid surfactants used in the formulations of the present invention are not only anionic sodium dioctyl phenyl succinate, but also block polymers of nonionic ethylene oxide and propylene oxide.
  • the flowable agent can be applied in situ with the aqueous solution.
  • Solid preparation can be used in combination with other fungicides or herbicides and insecticides, and can be used as a multi-component mixture. Use, or use sequentially.
  • liquid preparation of the formula (I) can also be used in combination with other bactericides or herbicides, insecticides, and can be mixed in a container or sequentially in the form of a liquid spray.
  • the liquid spray formulation of the present invention should contain from about 10-5000 ppm of a compound of formula (I).
  • composition of the present invention may also be wettable powders, powders, granules and liquids, emulsifiable concentrates, emulsions, suspension concentrates, aerosols and aerosols.
  • Wettable powders usually contain 15, 25, 50 parts by weight of active ingredient, and usually contain 3-10% by weight of dispersing agent in addition to the solid inert carrier, and if necessary, 0-10% by weight of stabilizer and/or other additives such as infiltration may be added.
  • the powder can usually be formed into a powder concentrate having a composition similar to that of a wettable powder but without a dispersing agent.
  • Granules are typically made to have a size of 10-100 mesh (1.676-0.152 mm) and can be prepared by agglomeration or infusion techniques.
  • the granules contain 0.5 to 50% by weight of the active ingredient and 0 to 10% by weight of an additive such as a stabilizer, a surfactant, and a sustained release modifier.
  • the emulsifiable concentrate may contain a cosolvent, 1-50% W/V active ingredient, 2-20% W/V emulsifier and 0-20% W/V other additives such as stabilizer, penetrant, in addition to solvent.
  • suspension concentrates usually contain 10-75% by weight of active ingredient, 0.5-15% by weight of dispersant, 0.1-10% by weight of other additives such as antifoaming agent, corrosion inhibitor, stabilizer, penetrant And adhesives.
  • Aqueous dispersions and emulsions for example compositions obtained by diluting a wettable powder or concentrate according to the invention with water, are also included in the scope of the invention.
  • the emulsions referred to include both water-in-oil and oil-in-water.
  • EXAMPLE 1 This example illustrates the preparation of compound 14 in Table 1.
  • 2-Chloro-3-nitropyridine Add 2-amino-3-nitropyridine (0.07 mol) and water (200 mL) in a 250 mL three-necked flask equipped with a magnetic stirrer and a constant pressure dropping funnel. Concentrated sulfuric acid (50 mL) was added dropwise, cooled to below 0 °C in an ice bath, and an aqueous solution of sodium nitrite (0.15 mol) was added dropwise. After the dropwise addition, the mixture was slowly warmed to room temperature for 2 hr, and refluxed for 3-5 hr.
  • 2,6-Dichloro-3-pinopyridine In a 500 mL three-necked flask equipped with a magnetic stirrer, a constant pressure dropping funnel and a drying tube, 2-chloro-3-nitropyridine (0.03 mol), dichloro Methane (250 mL) was added with urea peroxide (6.2 g, 0.06 mol) in portions under ice-cooling. After stirring for 0.5 hr, trifluoroacetic anhydride (0.03 mol) was added dropwise over 0.5 hr. Slowly rise to room temperature for 2 d.
  • 2,6-difluorobenzoyl chloride in a three-necked flask (500 mL) with a magnetic stirring and drying device, adding 2,6-difluorobenzoic acid (0.1 mol), 1,2-dichloroethane (100) (mL), slowly add dropwise thionyl chloride (0.13 mol) at 10-20 ° C and stirring. After the completion of the dropwise addition, the temperature is raised to reflux for 5-6 hours until the reaction is complete (GC detection), and the excess is removed under reduced pressure. The thionyl chloride and the solvent gave red 2,6-difluorobenzoyl chloride 16.2 g.
  • N,N'-(5-nitropyridine-2,6-diyl)-bis(2,6-difluorobenzamide) (14 in Table 1) was added to a 100 mL three-neck bottle
  • N-(6-Amino-5-nitropyridin-2-yl)-2,6-difluorobenzamide (52 in Table 1) 2,6-diamino-3-nitro group in a 100 mL three-necked flask Pyridine (10 mmol), toluene (50 mL), triethylamine (0.2 g), 4-dimethylaminopyridine (0.1 g), slowly added 2,6-di at 10-20 °C under stirring A solution of fluorobenzoyl chloride (10 mmol) in toluene (10 mL) was added and the mixture was warmed to reflux for 4-6 hours until the reaction was complete (LC traced). After cooling, the reaction mixture was poured into ice water, EtOAc (EtOAc) The title compound was obtained as a yellow solid, 1.16 g, m.
  • EXAMPLE 5 This example illustrates the preparation of the compound 151 in Table 1.
  • 2-Chloro-4-trifluoromethylthiazole-5-carboxylic acid ethyl ester was added dropwise to a solution of sodium nitrite (3.4 g) and water (40.0 g) in 2-amino-4-trifluoromethyl under ice cooling.
  • the mixture of thiazole-5-carboxylate (8.0 g) and 36% hydrochloric acid (80 mL) was added dropwise and allowed to react at room temperature for 3-4 hours. After cooling, the reaction solution was poured into ice water and filtered to give y.
  • N-(6-Amino-5-nitropyridin-2-yl)-2-methoxy-4-trifluoromethylthiazole-5-carboxamide (151 in Table 1) in a three-necked magnetic stir bar
  • the reaction solution was slowly poured into ice water, extracted with ethyl acetate, and washed with water, organic The organic phase was dried over sodium sulfate and evaporated to dryness to give crude. Purification by column chromatography gave the title compound as a yellow solid. Content 92% (HPLC), melting point 148.2 ⁇ 149.6 °C.
  • EXAMPLE 6 This example illustrates the preparation of compound 163 in Table 1.
  • 2-ethyl-4-trifluoromethylthiazole-5-formyl chloride 2-ethyl-4-trifluoromethyl-thiazole-5-carboxylic acid (16.8 g) was added to a three-necked flask equipped with a magnetic stir bar. And 1,2-dichloroethane (150 mL), adding thionyl chloride (11.8 g) dropwise at room temperature, refluxing for 4 to 5 hours after the addition, removing excess solvent and dichlorosulfoxide to obtain a brown liquid under reduced pressure.
  • the title of the object is 18.0 g.
  • DMF hydrazine-dimethylformamide
  • 2,6-diamino-3-nitropyridine 3.0 g
  • 2-ethyl-4-trifluoromethyl-thiazole-5-formyl chloride (8.6 g;) was added dropwise.
  • Pentanamide replaced by propionamide may be prepared N- (6- amino-5-nitropyridin-2-yl) - 2 - butyl-4-trifluoromethyl-thiazol-5 - Formic acid amide sticky solid. (168 in Table 1).
  • Ethyl propionylpyruvate A mixed solution of diethyl oxalate (0.05 mol) and 2-butanone (0.05 mol) was added dropwise to a sodium ethoxide (0.06 mol) in toluene (150 mL) under ice cooling. After the reaction is continued at room temperature for 1-3 hr, the reaction solution is poured into ice water, the pH is adjusted to about 3 with hydrochloric acid, the oil layer is separated, the aqueous layer is extracted with toluene, and the organic layer is combined, dried over anhydrous sodium sulfate and evaporated. Solvent to obtain oily liquid ethyl propionylpyruvate 7.5 g
  • a certain proportion of water, surfactant, antifreeze, antifoaming agent, ⁇ thickener and preservative are mixed together to form a uniform aqueous phase, and then the compound, solvent and emulsifier of the formula provided by the present invention, The co-emulsifier is mixed to make it a homogeneous oil phase. Finally, the homogeneous oil phase is mixed with the water phase under high-speed stirring to prepare a concentrated emulsion. Dilute with water to the desired concentration of fti.
  • a certain proportion of water, surfactant, antifreeze, antifoaming agent, ⁇ Zengduqi U and preservative are mixed together to form a uniform aqueous phase, and then the compound, solvent and emulsifier of the formula provided by the invention are provided.
  • the co-emulsifier is mixed to make it a homogeneous oil phase.
  • the homogeneous oil phase is mixed with the water phase under high-speed stirring to prepare a concentrated emulsion. Dilute with water to the desired concentration of fti.
  • Example 12 Preparation of emulsifiable concentrate: 10 (by weight) of the compound (I) provided by the present invention, 80 release agent such as xylene and 10 auxiliaries can be uniformly mixed to prepare an emulsifiable concentrate, which can be applied by dilution with water (active compound content is 10 %).
  • Example 13 Preparation of a wettable powder: 20 parts by weight of the thiazolylmethine pyridine compound provided by the present invention, 53 parts of clay, 20 parts of white carbon black, 5 parts of lignin silicate and 2 parts of polyoxygen
  • a wettable powder (active compound content of 20%) can be obtained by mixing and grinding an ethyl alkyl ether into a fine powder.
  • the synthesized compounds were tested for bactericidal, insecticidal, acaricidal and herbicidal activities, and some of the experimental results are as follows.
  • test compound is dissolved in a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF), and then diluted to the desired concentration with sterile water containing 0.1% Tween 80 emulsifier; 3 mL of the drug is taken with a pipette
  • PDA potato agar medium
  • PDA potato agar medium
  • a 6 mm diameter hyphae was taken from the edge of the bacterial colony for 7 days with an inoculating needle, and moved to In the center of the culture dish, the hyphae face down, and the blank containing no test compound is used as a control, and each treatment is repeated 4 times.
  • the culture dish is placed in a constant temperature biochemical incubator at 28 °C.
  • the mycelial growth diameter was measured after 4 days, and analyzed by EXCEL statistical software and the mycelial growth inhibition rate (%) was calculated.
  • Activity is divided into A, B, C, and D levels in percentages relative to the blank control, 100% ⁇ inhibition rate ⁇ 90% is grade A, 90% > inhibition rate ⁇ 70% is grade B, 70% > inhibition rate ⁇ 50% is C grade, 50% > inhibition rate ⁇ 0% is D grade.
  • Example 16 Bactericidal activity against Rhizoctonia solanO (ex vivo leaf culture method) The method is as follows: The test compound is dissolved in a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF), and 0.1 The sterile water of % TweenSO emulsifier is diluted to the required concentration; the leaves of fresh and young broad bean seedlings are treated with a certain concentration of the drug and placed in a petri dish coated with aqueous filter paper. The leaves and filter paper are made with homemade perforation. The iron frames are separated. After drying the leaves, connect the fresh hyphae with a diameter of 6 mm and culture for 2 to 3 days.
  • a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF), and 0.1
  • the sterile water of % TweenSO emulsifier is diluted to the required concentration; the leaves of fresh and young broad bean seedlings are treated with a
  • the method is as follows: The test compound is dissolved in a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF), and diluted with a sterile water containing 0.1% TweenSO emulsifier to the desired concentration; Potted oysters, 15 seeds of full-bodied and vigorous seeds per rice, to be tested after growing two leaves and one heart; the prepared rice seedling plants are sprayed with a certain concentration of the drug, and the disease suspension is inoculated one day later. Each treatment was repeated 3 times, and a blank containing no test compound was set as a control. After moisturizing and warming culture until the onset of the blank control, the area of the lesion was examined, and the drug control effect was calculated.
  • a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF), and diluted with a sterile water containing 0.1% TweenSO emulsifier to the desired concentration
  • Potted oysters 15 seeds of full-bodied and vigorous
  • the compound of the present invention has a control effect against rice sheath blight, and is superior to the commercial fungicide Jinggangmycin at the same dose.
  • the concentrations of 100 mg/L and 200 mg/L the control effect of compound 168 on rice sheath blight was more than 80%, and the control effect of Jinggangmycin on rice sheath blight was below 80%.
  • Example 18 Bactericidal activity against wheat white powder pathogen (Erisiphe griminis) (pot method)
  • the method is as follows: The test compound is dissolved in a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF), and diluted with a sterile water containing 0.1% TweenSO emulsifier to the desired concentration; Potted oysters, 20 seeds of wheat full and healthy seeds per sputum, to be tested after growing two leaves and one heart; the prepared wheat seedling plants are sprayed with a certain concentration of the drug, and the bacteria are inoculated one day later. Each treatment was repeated 3 times, and a blank containing no test compound was set as a control. After moisturizing and warming culture until the onset of the blank control, the area of the lesion was examined, and the drug control effect was calculated.
  • a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF), and diluted with a sterile water containing 0.1% TweenSO emulsifier to the desired concentration
  • Potted oysters 20 seeds of wheat full and healthy
  • the activity is divided into A, B, C, and D levels based on the percentage of the blank control, 100% ⁇ control effect 90% is A grade, 90%> control effect ⁇ 70% Grade B, 70%> Control effect ⁇ 50% is C grade, 50% > Control effect ⁇ 0% is D grade.
  • the results show that the compound of the present invention has a control effect against wheat powdery mildew, and some of the results are shown in Table 7.
  • the method is as follows: (1) Quantitatively compacting the soil in a plastic pot with a cross-sectional area of 64 cm 2 and placing it in a stainless steel pot. Select seeds with full grain size and uniform size, and divide the monocotyledon weeds [Digitaria sanguinalis X ⁇ ] Grass (Echinochloa crus-galliX foxtail (Setaria viridis ⁇ ⁇ ⁇ ⁇ Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab
  • Control effect (%) 100 (control plant height - treated plant height) I control plant height; (7) According to control effect Herbicidal activity classification: 100% ⁇ Control effect 90% A grade, 90%> Control effect 75% B grade, 75%> Control effect 50% C grade, 50%> Control effect 25% D Grade, 25%>control effect ⁇ 0% is grade E.
  • the compounds of the invention are active against weeds, such as compounds 40, 49, 67, etc. at a concentration of 2250 g ai/ha against broadleaf weeds, ramie
  • Both the treatment and the stem and leaf treatment have A-level herbicidal activity; the compounds 40, 49, 67, etc. have A-level herbicidal activity on the broad-leaved weeds and alfalfa soil at 2250 g ai/ha, 49 at 2250 g ai/
  • the concentration of ha also has a class A herbicidal activity on broadleaf weed ramie soil treatment; compound 49 et al.
  • the treatment still has Class A herbicidal activity, and still has Class A herbicidal activity for broadleaf weeds and alfalfa soil treatment.
  • Some compounds show activity against monocotyledonous weeds, such as 59 at 2250 g ai/ha
  • the concentration has a class A herbicidal activity on the treatment of monocotyledonous weed crabgrass, valerian and foxtail stems and leaves.
  • Potter spray method Weigh the appropriate amount of the N-pyridine (hetero) aramid compound provided by the invention, dissolve it with N, N-dimethylformamide, add a small amount of Tween 80 emulsifier, stir evenly, add quantitative water, Formulated to the required concentration, set clear water as a control. Take the fresh corn leaves and cut them into pieces of the same size, and put them into the filter paper with the filter paper in advance. In the dish ( ⁇ K90mm). Then, 10 pieces of 3rd instar larvae of the armyworm were placed in the dish, and placed under the Potter spray tower for quantitative spraying. The amount of the spray liquid was 1 ml, and the concentration was repeated 3 times.
  • the lid was placed, placed in a recovery chamber, and observed regularly. After 72 hours, the death of the test insects was recorded, and the mortality (%) was calculated. The results were averaged. Activity is divided into A, B, C, and D levels in percentages relative to the blank control, 100% ⁇ mortality ⁇ 90% is grade A, 90% > mortality ⁇ 70% is grade B, 70% > mortality ⁇ 50% for grade C, 50% > mortality ⁇ 0% for grade D.
  • the results indicate that the compound of the present invention has insecticidal activity against armyworms, for example, at a concentration of 1000 mg/L, compounds 179 and 218 have class A activity against armyworm, and compound 80 has class B activity against armyworm.
  • the method is as follows: Weigh an appropriate amount of the compound of the formula (I) provided by the present invention, dissolve it in a suitable solvent such as N, N-dimethylformamide, add a small amount of Tween 80 emulsifier, stir evenly, add quantitative water, and prepare a solution. The concentration is required, and the water is set as the control.
  • the soybean meal is attached to the newly unearthed bean seedlings, and each plant is connected with more than 20 heads. Then, the bean seedlings are immersed together with the test insects in the liquid medicine of the formula (I) provided by the present invention, and taken out after 5 seconds, sucked.
  • Example 22 Acaricidal activity against the cotton red spider Tetranychus urticae
  • the method is as follows: Weigh an appropriate amount of the compound of the formula (I) provided by the present invention, dissolve it in a suitable solvent such as N, N-dimethylformamide, add a small amount of Tween 80 emulsifier, stir evenly, add quantitative water, and prepare a solution. The concentration is required, and the water is set as the control. Choose a good bean sprout to inoculate red spider. After the spider is colonized, cut the bean seedlings into the prepared liquid for 10 seconds. Remove the excess liquid from the filter paper and insert it into the water beaker. In the observation room culture, the number of survival and death sputum was checked after 24 hours, and there were 100-200 cockroaches per bean seedling. The experiment was repeated three times. The results were averaged.
  • a suitable solvent such as N, N-dimethylformamide
  • Activity is divided into A, B, C, and D levels in percentages relative to the blank control, 100% ⁇ mortality ⁇ 90% is grade A, 90% > mortality ⁇ 70% is grade B, 70% > mortality ⁇ 50% for grade C, 50% > mortality ⁇ 0% for grade D.
  • the results indicate that the compound of the present invention is active against cotton spider mites, for example, at a concentration of 500 mg/L, compounds 06 and 187 have class B activity against cotton red spiders, and compounds 09 and 10 have class C activity against cotton spider mites.

Abstract

Disclosed in the present invention is a N-pyridine(hetero)aromatic amide compound of formula (I) and a preparation method and use thereof In the formula, Ar, R1, R2, R3, m and X have definitions as given in the description. The compound of formula (I) of the present invention has fungicidal and/or phytocidal, insecticidal and acaricidal bioactivities.

Description

N-吡啶 （杂） 芳酰胺类化合物及其制备方法与应用  N-pyridine (hetero) aramid compound and preparation method and application thereof
【技术领域】  [Technical Field]
本发明涉及具有杀菌、 除草、 杀虫 /螨生物活性的 N-吡啶 （杂） 芳酰胺类化合物及其 制备方法、 含有所述化合物的杀菌、 除草、 杀虫 /螨剂组合物、 以及用这些化合物控制有害 病菌、 杂草、 害虫 /螨的用途与方法。  The present invention relates to an N-pyridine (hetero) aromatic amide compound having bactericidal, herbicidal, insecticidal/industrial activity, a process for the preparation thereof, a bactericidal, herbicidal, insecticidal/sputum composition containing the compound, and the use thereof The use and method of compounds to control harmful germs, weeds, pests/cockroaches.
【背景技术】  【Background technique】
病菌、杂草、 害 螨的防治在实现高效农业的过程中非常重要。 同时病菌、杂草、 害 螨的防 治在林、 牧、 畐 iJ、 渔以及公共卫生中也很重要。 虽然市场上已有很多病菌、 杂草、 害 螨防治剂， 但是由于市场的不断扩大以 卜来的病菌、杂草、 害 螨和病菌、杂草、 害 螨的抗性、药物的使 用 及药物的经济性等问题和人们对环境的日益籠， 需要科学家们不断研究， 进而开发出新的 高效、 安全、 经济、 环境相容和具有不同作用方式的杀菌、 除草、 杀 i!/螨剂新品种。  The control of germs, weeds, and mites is very important in achieving efficient agriculture. At the same time, the prevention of germs, weeds, and mites is also important in forestry, animal husbandry, 畐iJ, fishing, and public health. Although there are many germs, weeds, and pest control agents on the market, the market continues to expand the pests, weeds, pests and germs, weeds, pest resistance, drug use and drugs. The economics and other issues and the increasing cages of the environment require scientists to continuously research and develop new efficient, safe, economical, environmentally compatible and different ways of sterilization, weeding, killing! Variety.
酰胺类化合物在药物化学中是一类重要化合物， 它们具有广谱的生物活性， 有关具有生物 活性的酰胺类化合物的报道很多。 同样， 杂环化合物特别是吡啶杂环化合物在药物化学中也是 一类重要化合物， 它们也具有广谱的生物活性， 关于具有生物活性的吡啶杂环化合物的报道也 很多。 但对于具有生物活性的 N-吡啶 （杂）芳酰胺类化合物却难以找到相关文献报道。  Amide compounds are an important class of compounds in medicinal chemistry. They have a broad spectrum of biological activities, and there are many reports on biologically active amide compounds. Also, heterocyclic compounds, particularly pyridine heterocyclic compounds, are also an important class of compounds in medicinal chemistry, and they also have a broad spectrum of biological activities, and there are many reports on biologically active pyridine heterocyclic compounds. However, it is difficult to find related literature reports on biologically active N-pyridine (hetero) aramid compounds.
为获得具有独特作用机制的高效、 广谱生物活性物质， 我们设计并合成未见文献报道 的具有式 （I) 所示的具有病菌、 杂草、 害虫 /螨活性的 N-吡啶 （杂） 芳酰胺类化合物。 【发明内容】  In order to obtain a highly efficient, broad-spectrum biologically active substance with a unique mechanism of action, we designed and synthesized N-pyridine (hetero) aromatics with pathogen, weed, pest/螨 activity as shown in formula (I). An amide compound. [Summary of the Invention]
本发明提供了式 （I) 所示的具有病菌、 杂草、 害虫 /螨等生物活性的 N-吡啶 （杂） 芳 酰胺类化合物及其异构体：
Figure imgf000003_0001
The present invention provides an N-pyridine (hetero) arylamide compound having the biological activity of bacteria, weeds, pests, cockroaches and the like and an isomer thereof represented by the formula (I):
Figure imgf000003_0001
其中：  among them:
I. Ar代表  I. Ar representative
(a) C6-C12芳基或带多至 10个碳原子的杂芳基， 或 (a) a C 6 -C 12 aryl group or a heteroaryl group having up to 10 carbon atoms, or
(b) 如在 I. a)中所确定的含义， 其中氢原子部分或全部被选自下列中相同或不同的取 代基取代： 氢、 卤素、 硝基、 氰基、 胺基、 羟基、 巯基、 羧基、 醛基、 肼基、 腙基、 d-C12 院基、 d-C12烷基氧基、 d-C12烷基硫基、 d-C12烷基磺酰基、 12烷基亚磺酰基、 Ci-Ci2 (b) as defined in I. a), wherein some or all of the hydrogen atoms are substituted by the same or different substituents selected from the group consisting of: hydrogen, halogen, nitro, cyano, amine, hydroxy, fluorenyl , a carboxyl group, an aldehyde group, a hydrazine group, a hydrazone group, group homes 12 dC, dC 12 alkyloxy, dC 12 alkylthio, alkylsulfonyl dC 12, 12 alkylsulfinyl, Ci-Ci 2
C1-C12 C1-C12 C1-C12 二 (Ci-Ci2)¾¾¾ 胺基、 C2-C12链烯基、 C2-C12链烯基氧基、 C2-C12链烯基硫基、 C2-C12链烯基磺酰基、 C2-C12 链烯基亚磺酰基、 c2-c12链烯基羰基、 c2-c12链烯基氧基羰基、 c2-c12链烯基羰基氧基、 C2-C12链烯基胺基、 二 c2-c12链烯基胺基、 c2-c12链炔基、 c2-c12链炔基氧基、 c2-c12链炔 基硫基、 c2-c12链炔基磺酰基、 c2-c12链炔基亚磺酰基、 c2-c12链炔基羰基、 c2-c12链炔基 氧基羰基、 C2-C12链炔基羰基氧基、 C2-C12链炔基胺基、 二 C2-C12链炔基胺基、 C3-C8环烷 基、 c3-c8环烷基氧基、 c3-c8环烷基羰基、 c3-c8环烷基羰基氧基、 c3-c8环烷基氧基羰基、C1-C12 C1-C12 C1-C12 II (Ci-Ci 2 )3⁄43⁄43⁄4 Amino, C 2 -C 12 alkenyl, C 2 -C 12 alkenyl group, C 2 -C 12 alkenyl group, C 2 -C 12 alkenyl sulfonyl group, C 2 -C 12 Alkenylsulfinyl, c 2 -c 12 alkenylcarbonyl, c 2 -c 12 alkenyloxycarbonyl, c 2 -c 12 alkenylcarbonyloxy, C 2 -C 12 alkenylamine , c 2 -c 12 alkenylamino, c 2 -c 12 alkynyl, c 2 -c 12 alkynyloxy, c 2 -c 12 alkynylthio, c 2 -c 12 Alkynylsulfonyl, c 2 -c 12 alkynylsulfinyl, c 2 -c 12 alkynylcarbonyl, c 2 -c 12 alkynyloxycarbonyl, C 2 -C 12 alkynylcarbonyloxy , C 2 -C 12 alkynylamino, di C 2 -C 12 alkynylamino, C 3 -C 8 cycloalkyl, c 3 -c 8 cycloalkyloxy, c 3 -c 8 Cycloalkylcarbonyl, c 3 -c 8 cycloalkylcarbonyloxy, c 3 -c 8 cycloalkyloxycarbonyl,
C3-C8环烷基硫基、 C3-C8环烷基亚磺酰基、 C3-C8环烷基磺酰基、 C3-C8环烷基胺基、二 C3-C8 环烷基胺基、 C6-C12芳基或带多至 10个碳原子的杂芳基、 C6-C12芳基氧基或带多至 10个 碳原子的杂芳基氧基、 C6-C12芳基硫基或带多至 10个碳原子的杂芳基硫基、 c6-c12芳基磺 酰基或带多至 10个碳原子的杂芳基磺酰基、 C6-C12芳基亚磺酰基或带多至 10个碳原子的 杂芳基亚磺酰基、 C6-C12芳基羰基或带多至 10个碳原子的杂芳基羰基、 c6-c12芳基氧基羰 基或带多至 10个碳原子的杂芳基氧基羰基、 C6-C12芳基羰基氧基或带多至 10个碳原子的 杂芳基羰基氧基、 C6-C12芳基胺基或带多至 10个碳原子的杂芳基胺基、二 c6-c12芳基胺基 或带多至 10个碳原子的二杂芳基胺基、 C6-C12芳基芳基或带多至 10个碳原子的杂芳基芳 基、 C6-C12芳基杂芳基或带多至 10个碳原子的杂芳基杂芳基； C 3 -C 8 cycloalkylthio, C 3 -C 8 cycloalkylsulfinyl, C 3 -C 8 cycloalkylsulfonyl, C 3 -C 8 cycloalkylamino, di C 3 -C 8 -cycloalkylamino, C 6 -C 12 aryl or heteroaryl with up to 10 carbon atoms, C 6 -C 12 aryloxy or heteroaryloxy with up to 10 carbon atoms a C 6 -C 12 arylthio group or a heteroarylthio group having up to 10 carbon atoms, a c 6 -c 12 arylsulfonyl group or a heteroarylsulfonyl group having up to 10 carbon atoms, C a 6- C 12 arylsulfinyl group or a heteroarylsulfinyl group having up to 10 carbon atoms, a C 6 -C 12 arylcarbonyl group or a heteroarylcarbonyl group having up to 10 carbon atoms, c 6 - a c 12 aryloxycarbonyl group or a heteroaryloxycarbonyl group having up to 10 carbon atoms, a C 6 -C 12 arylcarbonyloxy group or a heteroarylcarbonyloxy group having up to 10 carbon atoms, C 6- C 12 arylamino group or heteroarylamino group having up to 10 carbon atoms, di c 6 -c 12 arylamino group or diheteroarylamino group having up to 10 carbon atoms, C aryl-heteroaryl 6 -C 12 aryl group or an aryl group with up to 10 carbon atoms, C 6 -C 12 aryl or heteroaryl heteroaryl with up to 10 carbon atoms, Heteroaryl;
II. R1和 R2、 R3是相同的或不同的， 并代表 II. R 1 and R 2 , R 3 are the same or different and represent
氢、 卤素、 硝基、 氰基、 胺基、 羟基、 巯基、 羧基、 醛基、 肼基、 腙基、 d-C12烷基、 CrC12烷基氧基、 d-C12烷基硫基、 d-C12烷基磺酰基、 12烷基亚磺酰基、 d-C12烷基 羰基、 12烷基氧基羰基、 12烷基羰基氧基、 d-C12烷基胺基、二 （d-C12)烷基胺基、 c2-c12链烯基、 c2-c12链烯基氧基、 c2-c12链烯基硫基、 c2-c12链烯基磺酰基、 c2-c12链烯 基亚磺酰基、 C2-C12链烯基羰基、 C2-C12链烯基氧基羰基、 C2-C12链烯基羰基氧基、 C2-C12 链烯基胺基、 二 c2-c12链烯基胺基、 c2-c12链炔基、 c2-c12链炔基氧基、 c2-c12链炔基硫 基、 c2-c12链炔基磺酰基、 c2-c12链炔基亚磺酰基、 c2-c12链炔基羰基、 c2-c12链炔基氧基 羰基、 c2-c12链炔基羰基氧基、 c2-c12链炔基胺基、 二 c2-c12链炔基胺基、 ^ 8环烷基、 C3-C8环烷基氧基、 C3-C8环烷基羰基、 C3-C8环烷基羰基氧基、 C3-C8环烷基氧基羰基、 C3-C8 环烷基硫基、 C3-C8环烷基亚磺酰基、 C3-C8环烷基磺酰基、 C3-C8环烷基胺基、 二 C3-C8 环烷基胺基、 C6-C12芳基或带多至 10个碳原子的杂芳基、 C6-C12芳基氧基或带多至 10个 碳原子的杂芳基氧基、 C6-C12芳基硫基或带多至 10个碳原子的杂芳基硫基、 c6-c12芳基磺 酰基或带多至 10个碳原子的杂芳基磺酰基、 C6-C12芳基亚磺酰基或带多至 10个碳原子的 杂芳基亚磺酰基、 C6-C12芳基羰基或带多至 10个碳原子的杂芳基羰基、 C6-C12芳基氧基羰 基或带多至 10个碳原子的杂芳基氧基羰基、 C6-C12芳基羰基氧基或带多至 10个碳原子的 杂芳基羰基氧基、 C6-C12芳基胺基或带多至 10个碳原子的杂芳基胺基、二 c6-c12芳基胺基 或带多至 10个碳原子的二杂芳基胺基、 C6-C12芳基芳基或带多至 10个碳原子的杂芳基芳 基、 C6-C12芳基杂芳基或带多至 10个碳原子的杂芳基杂芳基； Hydrogen, halogen, nitro, cyano, amine, hydroxy, decyl, carboxy, aldehyde, decyl, decyl, dC 12 alkyl, CrC 12 alkyloxy, dC 12 alkylthio, dC 12 alkane Sulfonyl, 12 alkylsulfinyl, dC 12 alkylcarbonyl, 12 alkyloxycarbonyl, 12 alkylcarbonyloxy, dC 12 alkylamino, di(dC 12 )alkylamino, c 2 -c 12 alkenyl, c 2 -c 12 alkenyloxy, c 2 -c 12 alkenyl group, c 2 -c 12 alkenyl sulfonyl group, c 2 -c 12 alkenyl methylsulfoximide Acyl, C 2 -C 12 alkenylcarbonyl, C 2 -C 12 alkenyloxycarbonyl, C 2 -C 12 alkenylcarbonyloxy, C 2 -C 12 alkenylamino, di c 2 -c 12 alkenylamino, c 2 -c 12 alkynyl, c 2 -c 12 alkynyloxy, c 2 -c 12 alkynylthio, c 2 -c 12 alkynylsulfonyl , c 2 -c 12 alkynylsulfinyl, c 2 -c 12 alkynylcarbonyl, c 2 -c 12 alkynyloxycarbonyl, c 2 -c 12 alkynylcarbonyloxy, c 2 - c 12 alkynylamino, di c 2 -c 12 alkynylamino, ^ 8 cycloalkyl, C 3 -C 8 cycloalkyloxy, C 3 -C 8 cycloalkylcarbonyl, C 3 -C 8 cycloalkylcarbonyloxy, C 3 -C 8 cycloalkyloxycarbonyl, C 3 -C 8 cycloalkylthio, C 3 -C 8 cycloalkylsulfinyl, C 3 -C 8 Cycloalkylsulfonyl, C 3 -C 8 cycloalkylamino, di-C 3 -C 8 cycloalkylamino, C 6 -C 12 aryl or heteroaryl with up to 10 carbon atoms, C 6- C 12 aryloxy or heteroaryloxy having up to 10 carbon atoms, C 6 -C 12 arylthio or heteroarylthio having up to 10 carbon atoms, c 6 - a c 12 arylsulfonyl group or a heteroarylsulfonyl group having up to 10 carbon atoms, a C 6 -C 12 arylsulfinyl group or a heteroarylsulfinyl group having up to 10 carbon atoms, C 6 - a C 12 arylcarbonyl group or a heteroarylcarbonyl group having up to 10 carbon atoms, a C 6 -C 12 aryloxycarbonyl group or a heteroaryloxycarbonyl group having up to 10 carbon atoms, C 6 -C 12 An arylcarbonyloxy group or a band of up to 10 carbon atoms a heteroarylcarbonyloxy group, a C 6 -C 12 arylamino group or a heteroarylamino group having up to 10 carbon atoms, a di c 6 -c 12 arylamino group or having up to 10 carbon atoms Diheteroarylamino, C 6 -C 12 arylaryl or heteroarylaryl with up to 10 carbon atoms, C 6 -C 12 arylheteroaryl or up to 10 carbon atoms Heteroarylheteroaryl;
III. X代表 C， S或 so;  III. X stands for C, S or so;
IV. m代表 0， 1或 2， 且  IV. m stands for 0, 1 or 2, and
1) I. b) 和 II. 中所述烷基、 环烷基、 链烯基、 链炔基、 芳基、 杂芳基为未取代的或 者 L b) 和 II. 中所述烷基、 环烷基、 链烯基、 链炔基、 芳基、 杂芳基中氢原子部分或全部 被选自下列中相同或不同的取代基取代： 卤素、 硝基、 氰基、 胺基、 羟基、 巯基、 羧基、 醛基、 肼基、 腙基、 d-C12烷基、 d-C12烷基氧基、 d-C12烷基硫基、 d-C12烷基磺酰基、 12烷基亚磺酰基、 d-C12烷基羰基、 12烷基氧基羰基、 12烷基羰基氧基、 Ci-Ci2 烷基胺基、 二 （d-Cu)烷基胺基、 c2-c12链烯基、 c2-c12链烯基氧基、 c2-c12链烯基硫基、 c2-c12链烯基磺酰基、 c2-c12链烯基亚磺酰基、 c2-c12链烯基羰基、 c2-c12链烯基氧基羰基、1) The alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl groups described in I. b) and II. are unsubstituted or alkyl groups as described in L b) and II. The hydrogen atom in the cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl group is partially or wholly substituted with the same or different substituents selected from the group consisting of halogen, nitro, cyano, amine, hydroxy, a mercapto group, a carboxyl group, an aldehyde group, a hydrazine group, a hydrazone group, dC 12 alkyl, dC 12 alkyloxy, dC 12 alkylthio, dC 12 alkylsulfonyl, alkylsulfinyl 12, dC 12 alkyl Carbocarbonyl, 12 alkyloxycarbonyl, 12 alkylcarbonyloxy, Ci-Ci 2 alkylamino, bis(d-Cu)alkylamino, c 2 -c 12 alkenyl, c 2 -c 12 alkenyloxy group, c 2 -c 12 alkenyl group, c 2 -c 12 alkenyl sulfonyl group, c 2 -c 12 alkenylsulfinyl group, c 2 -c 12 alkenyl carbonyl group , c 2 -c 12 alkenyloxycarbonyl,
C2-C12链烯基羰基氧基、 C2-C12链烯基胺基、 二 C2-C12链烯基胺基、 C2-C12链炔基、 C2-C12 链炔基氧基、 c2-c12链炔基硫基、 C2-C12链炔基磺酰基、 C2-C12链炔基亚磺酰基、 C2-C12 链炔基羰基、 C2-C12链炔基氧基羰基、 C2-C12链炔基羰基氧基、 C2-C12链炔基胺基、二 C2-C12 链炔基胺基、 ^ 8环烷基、 c3-c8环烷基氧基、 c3-c8环烷基羰基、 c3-c8环烷基羰基氧基、 C3-C8环烷基氧基羰基、 c3-c8环烷基硫基、 c3-c8环烷基亚磺酰基、 ^ 8环烷基磺酰基、 C3-C8环烷基胺基、二 C3-C8环烷基胺基、 C6-C12芳基或带多至 10个碳原子的杂芳基、 C6-C12 芳基氧基或带多至 10个碳原子的杂芳基氧基、 C6-C12芳基硫基或带多至 10个碳原子的杂 芳基硫基、 C6-C12芳基磺酰基或带多至 10个碳原子的杂芳基磺酰基、 C6-C12芳基亚磺酰基 或带多至 10个碳原子的杂芳基亚磺酰基、 C6-C12芳基羰基或带多至 10个碳原子的杂芳基 羰基、 C6-C12芳基氧基羰基或带多至 10个碳原子的杂芳基氧基羰基、 c6-c12芳基羰基氧基 或带多至 10个碳原子的杂芳基羰基氧基、 C6-C12芳基胺基或带多至 10个碳原子的杂芳基 胺基、二 C6-C12芳基胺基或带多至 10个碳原子的二杂芳基胺基、 c6-c12芳基芳基或带多至 10个碳原子的杂芳基芳基、 C6-C12芳基杂芳基或带多至 10个碳原子的杂芳基杂芳基；且 1 ) 中所述烷基、 环烷基、 链烯基、 链炔基、 苯基中氢原子部分或全部同样可被选自下列中相 同或不同的取代基取代： 氢、 卤素、 d-C6烷基、 d-C6烷基氧基、 d-C6烷基硫基、 d-C6 烷基胺基、二 （d- )烷基胺基、 C2-C6链烯基、 C2-C6链烯基氧基、 C2-C6链烯基硫基、 C2-C6 链烯基胺基、 二 c2-c6链烯基胺基、 c2-c6链炔基、 c2-c6链炔基氧基、 c2-c6链炔基硫基、 c2-c6链炔基胺基、 二 c2-c6链炔基胺基、 c3-c6环烷基、 c3-c6环烷基氧基、 c3-c6环烷基 硫基、 c3-c6环烷基胺基、 二 c3-c6环烷基胺基； 2) I. 和 II. 以及 1 )中所述取代基的 2个代表甲二氧基或乙二氧基， 甲二氧基或乙二 氧基有时带 1个或 2个相同或不同的选自卤素和 d-C6烷基的取代基； C 2 -C 12 alkenylcarbonyloxy, C 2 -C 12 alkenylamino, di C 2 -C 12 alkenylamino, C 2 -C 12 alkynyl, C 2 -C 12 chain Alkynyloxy, c 2 -c 12 alkynylthio, C 2 -C 12 alkynylsulfonyl, C 2 -C 12 alkynylsulfinyl, C 2 -C 12 alkynylcarbonyl, C 2 -C 12 alkynyl group, a carbonyl group, C 2 -C 12 alkynyl group, a carbonyl group, C 2 -C 12 alkynyl group, di-C 2 -C 12 alkynyl group, a cycloalkyl ^ 8 , c 3 -c 8 cycloalkyloxy, c 3 -c 8 cycloalkylcarbonyl, c 3 -c 8 cycloalkylcarbonyloxy, C 3 -C 8 cycloalkyloxycarbonyl, c 3 - c 8 cycloalkylthio, c 3 -c 8 cycloalkylsulfinyl, ^ 8 cycloalkylsulfonyl, C 3 -C 8 cycloalkylamino, di C 3 -C 8 cycloalkylamino , C 6 -C 12 aryl or heteroaryl group having up to 10 carbon atoms, C 6 -C 12 aryloxy group or heteroaryloxy group having up to 10 carbon atoms, C 6 -C 12 An arylthio group or a heteroarylthio group having up to 10 carbon atoms, a C 6 -C 12 arylsulfonyl group or a heteroarylsulfonyl group having up to 10 carbon atoms, a C 6 -C 12 aryl group Sulfonyl or heteroaryl with up to 10 carbon atoms Heteroaryloxy sulfinyl, C 6 -C 12 arylcarbonyl or with up to 10 carbon atoms, hetero arylcarbonyl group, C 6 -C 12 aryloxy carbonyl group or with up to 10 carbon atoms, Carbonyl, c 6 -c 12 arylcarbonyloxy or heteroarylcarbonyloxy with up to 10 carbon atoms, C 6 -C 12 arylamine or heteroarylamine with up to 10 carbon atoms a di-C 6 -C 12 arylamino group or a diheteroarylamino group having up to 10 carbon atoms, a c 6 -c 12 arylaryl group or a heteroaryl aryl group having up to 10 carbon atoms a C 6 -C 12 arylheteroaryl group or a heteroarylheteroaryl group having up to 10 carbon atoms; and the alkyl group, cycloalkyl group, alkenyl group, alkynyl group, benzene in 1) Part or all of the hydrogen atom in the group may likewise be substituted by the same or different substituents selected from the group consisting of: hydrogen, halogen, dC 6 alkyl, dC 6 alkyloxy, dC 6 alkylthio, dC 6 alkylamine group, di (D-) alkylamino, C 2 -C 6 alkenyl, C 2 -C 6 alkenyl group, C 2 -C 6 alkenyl group, C 2 -C 6 alkenyl Amino group, di c 2 -c 6 alkenylamino group, c 2 -c 6 alkynyl group, c 2 -c 6 alkynyloxy group, c 2 -c 6 alkynylthio, c 2 -c 6 alkynylamino, di c 2 -c 6 alkynylamino, c 3 -c 6 cycloalkyl, c 3 -c 6 cycloalkyloxy, a c 3 -c 6 cycloalkylthio group, a c 3 -c 6 cycloalkylamino group, a di c 3 -c 6 cycloalkylamino group; 2) Two of the substituents described in I. and II. and 1) represent methylenedioxy or ethylenedioxy, and methylenedioxy or ethylenedioxy sometimes has one or two identical or different choices. a substituent from a halogen and a dC 6 alkyl group;
3) I. 和 II. 以及 1 )中确定了含义的芳基和杂芳基可以部分或全部氢化， 其中 1个或 3) The aryl and heteroaryl groups identified in I. and II. and 1) may be partially or fully hydrogenated, one of which or
2个 CH2基团能被 CO取代； Two CH 2 groups can be substituted by CO;
上面给出的化 勿 (I)的定义中，所用术语不论单独棚还是用在复合词中，代表如下取代基: 卤素： 指氟、 氯、 溴、 碘；  In the definitions given above (I), the terms used, whether used alone or in compound words, represent the following substituents: Halogen: means fluorine, chlorine, bromine, iodine;
烷基： 指直链或支链烷基；  Alkyl: means a straight or branched alkyl group;
环烷基： 指饱和和不饱和的环烷基；  Cycloalkyl: refers to saturated and unsaturated cycloalkyl;
链烯基； 指直链或支链并可在任何位置上存在有双键；  Alkenyl; means straight or branched and may have a double bond at any position;
链炔基； 指直链或支链并可在任何位置上存在有三键；  Alkenyl; means straight or branched and may have a triple bond at any position;
C6-C12芳基指苯基和由它派生出的一环芳基或多环芳基， 如萘基， 联苯基等； 带多至 10个碳原子的杂芳基指一环杂芳基或多环杂芳基， 环中至少有 1个 N， 0， S， P 和 /或 Se， 如噻唑基， 吡唑基， 噻二唑基， 吡啶基， 噻吩基， 苯并噻吩基， 呋喃基， 苯并呋喃 基， 吡咯基， 苯并吡咯基， 吲哚基， 苯并吲哚基， 咪唑基， 苯并咪唑基， 喹啉基， 吡喃基， 吡 嗪基， 嘧啶基， 哒嗪基， 苯并吡喃基， 苯并吡嗪基， 苯并嘧啶基， 苯并哒嗪基， 噁唑基， 异噁C 6 -C 12 aryl means phenyl and a cyclic aryl or polycyclic aryl group derived therefrom, such as naphthyl, biphenyl, etc.; heteroaryl group having up to 10 carbon atoms means a ring hetero An aryl or polycyclic heteroaryl group having at least one N, 0, S, P and/or Se in the ring, such as thiazolyl, pyrazolyl, thiadiazolyl, pyridyl, thienyl, benzothienyl , furyl, benzofuranyl, pyrrolyl, benzopyrrolyl, fluorenyl, benzofluorenyl, imidazolyl, benzimidazolyl, quinolyl, pyranyl, pyrazinyl, pyrimidinyl, Pyridazinyl, benzopyranyl, benzopyrazinyl, benzopyrimidinyl, benzoxazinyl, oxazolyl, isomer
P坐基， 苯并噁唑基， 苯并异噁唑基， 苯并噻唑基， 异噻唑基， 苯并异噻唑基， 嘧啶并***基等；P-based, benzoxazolyl, benzoisoxazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, pyrimidotriazolyl, etc.;
C6-C12芳基和带多至 10个碳原子的杂芳基可以部分或全部氢化， 其中 1个或 2个 CH2 被 CO取代， 如环已烯基， 环已二酮基等。 本发明优选的化合物为： 式 （I) 中： The C 6 -C 12 aryl group and the heteroaryl group having up to 10 carbon atoms may be partially or fully hydrogenated, wherein one or two CH 2 are substituted by CO, such as a cyclohexenyl group, a cyclohexanedione group or the like. Preferred compounds of the invention are: In formula (I):
I. Ar代表  I. Ar representative
(a) 苯基、 噻唑基、 吡唑基、 噻二唑基、 吡啶基， 或  (a) phenyl, thiazolyl, pyrazolyl, thiadiazolyl, pyridyl, or
(b) 如在 I. a)中所确定的含义， 其中氢原子部分或全部被选自下列中相同或不同的取 代基取代： 氢、 卤素、 胺基、 羟基、 巯基、 d-C6烷基、 d-C6烷基氧基、 d-C6烷基硫基、 Ci-C6烷基胺基、 二 （CrC6)烷基胺基、 C2-C6链烯基、 C2-C6链烯基氧基、 C2-C6链烯基硫 基、 C2-C6链烯基胺基、 二 C2-C6链烯基胺基、 C2-C6链炔基、 C2-C6链炔基氧基、 C2-C6链 炔基硫基、 C2-C6链炔基胺基、二 C2-C6链炔基胺基、 C3-C6环烷基、 C3-C6环烷基氧基、 C3-C6 环烷基硫基、 C3-C6环烷基胺基、 二 C3-C6环烷基胺基、 苯基、 苯基氧基、 苯基硫基、 苯基胺基； II. R1和 R2是相同的或不同的， 并代表 (b) as defined in I. a), wherein some or all of the hydrogen atoms are substituted by the same or different substituents selected from the group consisting of: hydrogen, halogen, amine, hydroxy, decyl, dC 6 alkyl, dC 6 alkyloxy, dC 6 alkylthio, Ci-C 6 alkylamino, bis(CrC 6 )alkylamino, C 2 -C 6 alkenyl, C 2 -C 6 alkenyl alkoxy, C 2 -C 6 alkenyl group, C 2 -C 6 alkenyl group, di-C 2 -C 6 alkenyl group, C 2 -C 6 alkynyl group, C 2 -C 6 alkynyloxy, C 2 -C 6 alkynylthio, C 2 -C 6 alkynylamino, di C 2 -C 6 alkynylamino, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyloxy, C 3 -C 6 cycloalkylthio, C 3 -C 6 cycloalkylamino, di C 3 -C 6 cycloalkylamino, phenyl, phenyl Oxyl, phenylthio, phenylamino; II. R 1 and R 2 are the same or different and represent
氢、 卤素、 胺基、 羟基、 巯基、 肼基、 腙基、 d-C12烷基、 d-C12烷基氧基、 d-C12 烷基硫基、 d-C12烷基胺基、 二 （CrC12)烷基胺基、 C2-C12链烯基、 C2-C12链烯基氧基、Hydrogen, halogen, amine, hydroxy, decyl, decyl, decyl, dC 12 alkyl, dC 12 alkyloxy, dC 12 alkylthio, dC 12 alkylamino, bis(CrC 12 )alkyl Amino, C 2 -C 12 alkenyl, C 2 -C 12 alkenyloxy,
C2-C12链烯基硫基、 c2-c12链烯基胺基、 二 c2-c12链烯基胺基、 c2-c12链炔基、 c2-c12链炔 基氧基、 C2-C12链炔基硫基、 C2-C12链炔基胺基、二 C2-C12链炔基胺基、 ^ 8环烷基、 C3-C8 环烷基氧基、 c3-c8环烷基硫基、 c3-c8环烷基胺基、 二 c3-c8环烷基胺基； C 2 -C 12 alkenylthio, c 2 -c 12 alkenylamino, di c 2 -c 12 alkenylamino, c 2 -c 12 alkynyl, c 2 -c 12 alkyne Alkoxy, C 2 -C 12 alkynylthio, C 2 -C 12 alkynylamino, di C 2 -C 12 alkynylamino, ^ 8 cycloalkyl, C 3 -C 8 ring An alkyloxy group, c 3 -c 8 cycloalkylthio group, c 3 -c 8 cycloalkylamino group, di c 3 -c 8 cycloalkylamino group;
III. X代表 C;  III. X stands for C;
VI. m代表 0， 且  VI. m stands for 0, and
1) L b) 和 II. 中所述烷基、 环烷基、 链烯基、 链炔基、 苯基为未取代的或者 L b) 和 1) The alkyl, cycloalkyl, alkenyl, alkynyl, phenyl groups in L b) and II. are unsubstituted or L b) and
II. 中所述烷基、环烷基、链烯基、链炔基、 苯基中氢原子部分或全部被选自下列中相同或 不同的取代基取代： 卤素、 d-C6烷基、 d-C6烷基氧基、 d-C6烷基硫基、 d-C6烷基胺基、 二 （CrC6)烷基胺基、 C2-C6链烯基、 C2-C6链烯基氧基、 C2-C6链烯基硫基、 C2-C6链烯基 胺基、 二 C2-C6链烯基胺基、 C2-C6链炔基、 C2-C6链炔基氧基、 C2-C6链炔基硫基、 C2-C6 链炔基胺基、 二 c2-c6链炔基胺基、 c3-c6环烷基、 c3-c6环烷基氧基、 c3-c6环烷基硫基、 C3-C6环烷基胺基、 二 c3-c6环烷基胺基、 苯基、 苯基氧基、 苯基硫基、 苯基胺基； The alkyl, cycloalkyl, alkenyl, alkynyl, or hydrogen atom in the phenyl group is partially or completely substituted by the same or different substituents selected from the group consisting of halogen, dC 6 alkyl, dC 6 Alkyloxy, dC 6 alkylthio, dC 6 alkylamino, bis(CrC 6 )alkylamino, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, C 2- C 6 alkenylthio, C 2 -C 6 alkenylamino, di C 2 -C 6 alkenylamino, C 2 -C 6 alkynyl, C 2 -C 6 alkynyl Oxy, C 2 -C 6 alkynylthio, C 2 -C 6 alkynylamino, di c 2 -c 6 alkynylamino, c 3 -c 6 cycloalkyl, c 3 -c 6 cycloalkyloxy, c 3 -c 6 cycloalkylthio, C 3 -C 6 cycloalkylamino, di c 3 -c 6 cycloalkylamino, phenyl, phenyloxy, benzene Thiothio group, phenylamine group;
且 1 ) 中所述烷基、 环烷基、 链烯基、 链炔基、 苯基中氢原子部分或全部同样可被选 自下列中相同或不同的取代基取代： 氢、 卤素、 d-C6烷基、 d-C6烷基氧基、 d-C6烷基 硫基、 d-C6烷基胺基、 二 （CrC6)烷基胺基、 C2-C6链烯基、 C2-C6链烯基氧基、 C2-C6链 烯基硫基、 C2-C6链烯基胺基、二 C2-C6链烯基胺基、 C2-C6链炔基、 C2-C6链炔基氧基、 C2-C6 链炔基硫基、 c2-c6链炔基胺基、 二 c2-c6链炔基胺基、 c3-c6环烷基、 c3-c6环烷基氧基、 C3-C6环烷基硫基、 c3-c6环烷基胺基、 二 c3-c6环烷基胺基。 And an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or a hydrogen atom in the phenyl group in 1) may also be substituted by the same or different substituents selected from the group consisting of hydrogen, halogen, dC 6 Alkyl, dC 6 alkyloxy, dC 6 alkylthio, dC 6 alkylamino, bis(CrC 6 )alkylamino, C 2 -C 6 alkenyl, C 2 -C 6 alkene alkoxy group, C 2 -C 6 alkenyl group, C 2 -C 6 alkenyl group, di-C 2 -C 6 alkenyl group, C 2 -C 6 alkynyl group, C 2 - C 6 alkynyloxy, C 2 -C 6 alkynylthio, c 2 -c 6 alkynylamino, di c 2 -c 6 alkynylamino, c 3 -c 6 cycloalkyl , c 3 -c 6 cycloalkyloxy, C 3 -C 6 cycloalkylthio, c 3 -c 6 cycloalkylamino, di c 3 -c 6 cycloalkylamino.
本发明特别优选的式 （I) 化合物是：  Particularly preferred compounds of formula (I) according to the invention are:
N-(3-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺；  N-(3-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N-乙基 -N-(6-氯 -3-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺；  N-ethyl-N-(6-chloro-3-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N-(6—甲氧基―3—硝基吡啶―2—基)― 二氯苯甲酰胺； N-( 6 -methoxy- 3 -pyridin- 2 -yl)-dichlorobenzamide;
ΛΚ6-氨基 -3-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺；  ΛΚ6-Amino-3-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N-乙基 - N- (6-甲氧基 -3-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺；  N-ethyl-N-(6-methoxy-3-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N，N'-(5-硝基吡啶 -2,6-二基) -双 (2,6-二氯苯甲酰胺)；  N,N'-(5-nitropyridine-2,6-diyl)-bis(2,6-dichlorobenzamide);
N，N'-(5-硝基吡啶 -2,6-二基) -双 (2,6-二氟苯甲酰胺)；  N,N'-(5-nitropyridine-2,6-diyl)-bis(2,6-difluorobenzamide);
N-(6—甲氧基―3—硝基吡啶―2—基)― 二氟苯甲酰胺； N-( 6 -methoxy- 3 -pyridin- 2 -yl)-difluorobenzamide;
N-(6—甲氧基―3—硝基吡啶―2—基)―2—氯苯甲酰胺； N-( 6 -methoxy- 3 -pyridin- 2 -yl) -2 -chlorobenzamide;
N-(6-乙硫基 -3-硝基吡啶 -2-基) -2-氯苯甲酰胺；  N-(6-ethylthio-3-nitropyridin-2-yl)-2-chlorobenzamide;
N-(6-乙氧基 -3-硝基吡啶 -2-基) -2-三氟甲基苯甲酰胺；  N-(6-ethoxy-3-nitropyridin-2-yl)-2-trifluoromethylbenzamide;
N-(6-氯 -5-硝基吡啶 -2-基;) -2,6-二氯苯甲酰胺；  N-(6-chloro-5-nitropyridin-2-yl;)-2,6-dichlorobenzamide;
N-乙基 -N-(6-氯 -5-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺； N-(6—甲氧基―5—硝基吡啶―2—基)― 二氯苯甲酰胺；N-ethyl-N-(6-chloro-5-nitropyridin-2-yl)-2,6-dichlorobenzamide; N-( 6 -methoxy- 5 -nitropyridine- 2 -yl)-dichlorobenzamide;
^甲基 -N-(6-甲氧基 -3-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺； ^Methyl-N-(6-methoxy-3-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N-(6-甲胺基 -5-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺； N- (6 - methylamino --5-- nitropyridine - 2 - yl) - 2, 6 - dichloro-benzamide;
N-乙基 -N-(6-乙胺基 -5-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺； N-ethyl-N-(6-ethylamino-5-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N-(6-乙胺基 -5-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺；  N-(6-ethylamino-5-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N-(6-二甲胺基 -5-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺； N- (6 - dimethylamino --5-- nitropyridine - 2 - yl) - 2, 6 - dichloro-benzamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2,6-二氟苯甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2,6-difluorobenzamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -3,5-双三氟甲基苯甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-3,5-bistrifluoromethylbenzamide;
N-(6-乙胺基 -5-硝基吡啶 -2-基) -2-氯苯甲酰胺； N-(6-ethylamino-5-nitropyridin-2-yl)-2-chlorobenzamide;
N-甲基 -N-(6-甲氧基 -5-硝基吡啶 -2-基) -2-三氟甲基苯甲酰胺； N-methyl-N-(6-methoxy-5-nitropyridin-2-yl)-2-trifluoromethylbenzamide;
-(6-氯 -5-硝基吡啶 -2-基) -2-三氟甲基苯甲酰胺；  -(6-chloro-5-nitropyridin-2-yl)-2-trifluoromethylbenzamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-三氟甲基苯甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-trifluoromethylbenzamide;
N-(6-乙胺基 -5-硝基吡啶 -2-基； )-2-三氟甲基苯甲酰胺；  N-(6-ethylamino-5-nitropyridin-2-yl;)-2-trifluoromethylbenzamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-甲基苯甲酰胺； N-( 6 -Amino- 5 -nitropyridin- 2 -yl) -2 -methylbenzamide;
N-(6-乙胺基 -5-硝基吡啶 -2-基) -2,6-二氟苯甲酰胺；  N-(6-ethylamino-5-nitropyridin-2-yl)-2,6-difluorobenzamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-氯苯甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-chlorobenzamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -4-甲基苯磺酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-4-methylbenzenesulfonamide;
N-(6-乙胺基 -5-硝基吡啶 -2-基) -4-甲基苯磺酰胺；  N-(6-ethylamino-5-nitropyridin-2-yl)-4-methylbenzenesulfonamide;
N-(6-乙胺基 -5-硝基吡啶 -2-基) -2,6-二氯苯磺酰胺；N-(6-ethylamino-5-nitropyridin-2-yl)-2,6-dichlorobenzenesulfonamide;
(6-羟基 -3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； -(6-溴 -3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； -(6-甲基 -3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； (6-Hydroxy-3-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide; -(6-bromo-3-nitropyridin-2-yl) -2-methyl-4-trifluoromethylthiazole-5-carboxamide; -(6-methyl-3-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole- 5-carboxamide;
N-(6-甲氨基 -3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N，N'-(5-硝基吡啶 -2,6-二基) -双 (2-甲基 -4-三氟甲基噻唑 -5-甲酰胺)；N-(6-Methylamino-3-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide; N,N'-(5-nitropyridine-2 ,6-diyl)-bis(2-methyl-4-trifluoromethylthiazole-5-carboxamide);
N-(6-甲氧基 -3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺；N-(6-methoxy-3-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-乙氧基 -3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺；N-(6-ethoxy-3-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(3-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-甲胺基 -5-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-丁胺基 -5-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-Methylamino-5-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide; N-(6-butylamino-5-nitrate Pyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-甲酰胺基 -3-硝基吡啶 -2-基； )-2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-乙酰胺基 -3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-carboxamido-3-nitropyridin-2-yl; )-2-methyl-4-trifluoromethylthiazole-5-carboxamide; N-(6-acetamido-3-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-甲氧基 -5-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-methoxy-5-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-二甲胺基 -5-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-dimethylamino-5-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(5-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(5-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-环丙基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-Amino-5-nitropyridin-2-yl)-2-cyclopropyl-4-trifluoromethylthiazole-5-carboxamide;
N- :6-环丙基硫代甲酰胺基 -5-硝基吡啶 -2-基； )-2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N- :6-环已基 -5-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺；  N-: 6-cyclopropylthiocarboxamido-5-nitropyridin-2-yl; )-2-methyl-4-trifluoromethylthiazole-5-carboxamide; N-: 6-ring Benzyl-5-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N- :6-胺基 -3-硝基吡啶 -2-基-2-甲氧基 -4-三氟甲基噻唑 -5-甲酰胺； N-: 6-Amino-3-nitropyridine-2-yl-2-methoxy-4-trifluoromethylthiazole-5-carboxamide;
N- :6-胺基 -5-硝基吡啶 -2-基 '-2-乙氧基 -4-三氟甲基噻唑 -5-甲酰胺； N-: 6-amino-5-nitropyridin-2-yl '-2-ethoxy-4-trifluoromethylthiazole-5-carboxamide;
N- :6-胺基 -5-硝基吡啶 -2-基-2-録丙氧基 -4-三氟甲基噻唑 -5-甲酰胺; N- : 6 -amino-5-nitropyridin-2-yl-2-propoxy-4-trifluoromethylthiazole-5-carboxamide;
N- :6-胺基 -5-硝基吡啶 -2-基-2-丁氧基 -4-三氟甲基噻唑 -5-甲酰胺； N- : 6 -amino-5-nitropyridine- 2 -yl-2-butoxy-4-trifluoromethylthiazole-5-carboxamide;
N- :6-胺基 -5-硝基吡啶 -2-基 '-2-甲硫基 -4-三氟甲基噻唑 -5-甲酰胺； N-: 6-amino-5-nitropyridin-2-yl '-2-methylthio-4-trifluoromethylthiazole-5-carboxamide;
N- :6-胺基 -5-硝基吡啶 -2-基 2-丙硫基 -4-三氟甲基噻唑 -5-甲酰胺； N- : 6 -amino-5-nitropyridine- 2 -yl-2-propylthio-4-trifluoromethylthiazole-5-carboxamide;
N- :6-胺基 -5-硝基吡啶 -2-基-2-异丙氧基 -4-三氟甲基噻唑 -5-甲酰胺; N-: 6-amino-5-nitropyridine-2-yl-2-isopropoxy-4-trifluoromethylthiazole-5-carboxamide;
N- :6-胺基 -5-硝基吡啶 -2-基 -溴—4-三氟甲基噻唑—5-甲酰胺； N-: 6-amino-5-nitropyridin-2-yl-bromo-4-trifluoromethylthiazole-5-carboxamide;
N- :6-胺基 -5-硝基吡啶 -2-基-2-甲氧基 -4-三氟甲基噻唑 -5-甲酰胺； N- : 6 -amino-5-nitropyridin-2-yl-2-methoxy-4-trifluoromethylthiazole-5-carboxamide;
N- :6-胺基 -5-硝基吡啶 -2-基 '-2-乙胺基 -4-三氟甲基噻唑 -5-甲酰胺； N-: 6-Amino-5-nitropyridin-2-yl '-2-ethylamino-4-pyridylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基 '-2-二乙胺基 -4-三氟甲基噻唑 -5-甲酰胺; N-(6-Amino-5-nitropyridin-2-yl '-2-diethylamino-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基 μ2—乙基—4-三氟甲基噻唑 -5-甲酰胺； N-(6-Amino-5-nitropyridin-2-yl μ2 -ethyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基-2-异丙基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-Amino-5-nitropyridin-2-yl-2-isopropyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基 丙基—4-三氟甲基噻唑 -5-甲酰胺； N-(6-Amino-5-nitropyridin-2-ylpropyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基-2-甲胺基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-Amino-5-nitropyridin-2-yl-2-methylamino-4-pyrofluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基 丁基—4-三氟甲基噻唑 -5-甲酰胺； N-(6-Amino-5-nitropyridin-2-ylbutyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基 '-2-环已基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-Amino-5-nitropyridin-2-yl '-2-cyclohexyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基 '-2-环丙基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl '-2-cyclopropyl-4-trifluoromethylthiazole-5-carboxamide;
N- ' -硝基吡啶 -2-基) -2-乙基 -4-三氟甲基噻唑 -5-甲酰胺；  N- '-nitropyridine-2-yl)-2-ethyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6 -胺基 -5-硝基吡啶 -2-基 )-2—氯—4-三氟甲基噻唑—5-甲酰胺； N-(6-Amino-5-nitropyridin-2-yl)-2-chloro-4-trifluoromethylthiazole-5-carboxamide;
Ν,Ν' -(5-硝基吡啶 -2,6-二基卜双 (2-氯 -4-三氟甲基噻唑 -5-甲酰胺)； Ν,Ν'-(5-nitropyridine-2,6-diylbu-bis(2-chloro-4-trifluoromethylthiazole-5-carboxamide);
Ν-(6 .氯-3-硝基吡啶 -2-基) -2-氯吡啶 -3-甲酰胺； Ν-(6.Chloro- 3 -nitropyridine- 2 -yl) -2 -chloropyridine- 3 -carbamide;
Ν-(6•乙硫基 -3-硝基吡啶 -2-基) -2-氯吡啶 -3-甲酰胺； Ν-(6•ethylthio-3-nitropyridin-2-yl)-2-chloropyridine-3-carboxamide;
Ν-(6■胺基 -5-硝基吡啶 -2-基) -6-氯吡啶 -3-甲酰胺； N-(6-胺基 -5-硝基吡啶 -2-基) -2-氯吡啶 -3-甲酰胺； Ν-(6-Amino-5-nitropyridin-2-yl)-6-chloropyridine-3-carboxamide; N-( 6 -Amino- 5 -nitropyridin- 2 -yl) -2 -chloropyridine- 3 -carbamide;
N-(6-乙胺基 -5-硝基吡啶 -2-基) -2-(3-三氟甲基苯氧基)吡啶 -3-甲酰胺；  N-(6-ethylamino-5-nitropyridin-2-yl)-2-(3-trifluoromethylphenoxy)pyridine-3-carboxamide;
N-乙基 -N (6-甲氧基 -5-硝基吡啶 -2-基) -6-氯吡啶 -3-甲酰胺)；  N-ethyl-N (6-methoxy-5-nitropyridin-2-yl)-6-chloropyridine-3-carboxamide);
N，N'-(5-硝基吡啶 -2,6-二基) -双 (4-甲基噻二唑 -5-甲酰胺)；  N,N'-(5-nitropyridine-2,6-diyl)-bis(4-methylthiadiazole-5-carboxamide);
N—(6-胺基 -5-硝基吡啶 -2-基) -4-甲基噻二唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-4-methylthiadiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -4-甲基噻二唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-4-methylthiadiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -1-甲基 -3-乙基 -4-氯吡唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide;
N，N'-(5-硝基吡啶 -2,6-二基) -双 (1-甲基 -3-乙基 -4-氯吡唑 -5-甲酰胺)。  N,N'-(5-Nitropyridine-2,6-diyl)-bis(1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide).
本发明的化合物可以一种或多种异构体的形式存在。 异构体包括对映异构体、 非对映 异构体、 几何异构体。 如本发明的式（I)所示的化合物， 由于其中的碳一碳双键连接不同 的取代基而可以形成几何异构体 (分别以 Z和 E来表示不同的构型)， 本发明包括 Z型异构 体和 E型异构体以及它们任何比例的混合物。 本发明的式（I)所示的化合物， 由于其中的 一个碳原子上连接四个不同的取代基而形成立体异构体 （分别以 R和 S来表示不同的构 型；)， 本发明包括 R型异构体和 S型异构体以及它们任何比例的混合物。  The compounds of the invention may exist in the form of one or more isomers. Isomers include enantiomers, diastereomers, geometric isomers. The compound of the formula (I) of the present invention can form geometric isomers (different configurations are represented by Z and E, respectively) due to the carbon-carbon double bond linking different substituents therein, and the present invention includes Z-isomers and E-isomers and mixtures thereof in any ratio. The compound of the formula (I) of the present invention, since one of the carbon atoms is bonded to four different substituents to form a stereoisomer (respectively represented by R and S, respectively;), the present invention includes R-isomers and S-isomers and mixtures thereof in any ratio.
本发明还涉及一种防治有害病菌、 杂草、 害虫 /螨的含有生物有效量的式 （I) 化合物 和至少一种另外的选自表面活性剂、 固体稀释剂和液体稀释剂的组合物。  The invention further relates to a biologically effective amount of a compound of formula (I) and at least one additional composition selected from the group consisting of surfactants, solid diluents and liquid diluents for controlling harmful germs, weeds, pests/caries.
本发明还涉及一种防治有害病菌、 杂草、 害虫 /螨的含有生物有效量的式 （I) 化合物 和有效量的至少一种另外的生物活性化合物或制剂的组合物。  The invention further relates to a composition comprising a biologically effective amount of a compound of formula (I) and an effective amount of at least one additional biologically active compound or formulation for controlling harmful bacteria, weeds, pests/cockroaches.
本发明还涉及一种防治有害病菌、 杂草、 害 /螨的方法， 包括将生物有效量的式 （I)化合 物接触有害病菌、 杂草、 害 螨或其环境。 同时也涉及这样一种有害病菌、 杂草、 害 螨防治 方法， 有害病菌、 杂草、 害 螨或其环境用生物有效量的式（I)化合物或含有式 (I)化合物和 生物有效量的至少一种另外的化合物或制剂的混合物进行接触来防治有害病菌、 杂草、 害 螨。  The invention further relates to a method of controlling harmful germs, weeds, pests, mites, which comprises contacting a biologically effective amount of a compound of formula (I) with harmful germs, weeds, mites or their environment. Also relates to such a harmful pathogen, weed, pest control method, harmful bacteria, weeds, pests or their environmentally effective amounts of a compound of formula (I) or a compound of formula (I) and a biologically effective amount At least one additional compound or mixture of formulations is contacted to control harmful germs, weeds, pests.
本发明的式（I)化合物具有广谱活性： 有的化合物可用于防治有害病菌， 还可用于防 治有害虫 /螨； 有的化合物可用于防治有害杂草。而且有的化合物对某些靶标病菌具有很高 的生物活性， 使得在很低的剂量下就可以获得很好的效果。  The compounds of the formula (I) of the present invention have a broad spectrum of activity: some compounds are useful for controlling harmful bacteria, and can also be used for controlling pests/caries; and some compounds are useful for controlling harmful weeds. Moreover, some compounds have high biological activity against certain target bacteria, so that good results can be obtained at very low doses.
本发明删勺组 勿是含有 ¾髓化 膽组 的方 棚 继化 膽方法。 下面用表 1〜表 2中列出的部分式 （I)化合物来进一步说明本发明， 但并不限定本发明。 本发明中所给熔点均未经校正， 本发明所合成的式（I)化合物为粘性固体时， 有些粘性固体冰 箱放置后会固化为非粘性固体， 本发明所合成的式（I)化合物为粘性液体时， 有些粘性液体冰 箱放置后会固化， 表 1中所有化合物在 LC-MS (APCI, Pos) (Agilent 1100 Series LC/MSD)中均可 观察到其分子离子峰。 表 1 中化合物的 1H NMR (Varian INOVA-300 spectrometer)以 tetramethylsilane (TMS)作内标， 氘代氯仿 （CDC13)或氘代二甲基亚砜 (DMSO)作溶剂。 The scooping group of the present invention is not a square shed secondary bile method containing a 3⁄4 medullary biliary group. The invention will be further illustrated by the following formula (I) of the formulae listed in Tables 1 to 2, but does not limit the invention. The melting point given in the present invention is uncorrected. When the compound of the formula (I) synthesized by the present invention is a viscous solid, some of the viscous solid refrigerators are solidified into a non-tacky solid after being placed, and the compound of the formula (I) synthesized by the present invention is In the case of viscous liquids, some viscous liquids will solidify when placed in the refrigerator. All of the compounds in Table 1 can be observed in LC-MS (APCI, Pos) (Agilent 1100 Series LC/MSD). The 1H NMR (Varian INOVA-300 spectrometer) of the compound in Table 1 is tetramethylsilane (TMS) as internal standard, deuterochloroform (CDC1 3) or deuterated dimethyl sulfoxide (DMSO) as solvent.
Figure imgf000011_0001
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
IZ LLO/nOZSLJ/Ud OAV
Figure imgf000018_0001
IZ LLO/nOZSLJ/Ud OAV
Figure imgf000018_0001
TZ8..0/M0ZN3/X3d
Figure imgf000019_0001
TZ8..0/M0ZN3/X3d
Figure imgf000019_0001
IZ LLO/nOZSLJ/Ud OAV
Figure imgf000020_0001
Figure imgf000021_0001
IZ LLO/nOZSLJ/Ud OAV
Figure imgf000020_0001
Figure imgf000021_0001
TZ8..0/M0ZN3/X3d
Figure imgf000022_0001
1H, Py H), 11.176 (s, 1H, NH), 11.504 (s, 1H, NH). TZ8..0/M0ZN3/X3d
Figure imgf000022_0001
1H, Py H), 11.176 (s, 1H, NH), 11.504 (s, 1H, NH).
219 黄色固体。 Ή NMR 5(CDC13) 1.213(t, J=7.5 Hz, 3H, CH3), 2.587 (q, J=7.5 Hz, 2H, CH2), 3.919 (s: 219 yellow solid. NMR NMR 5(CDC1 3 ) 1.213 (t, J = 7.5 Hz, 3H, CH 3 ), 2.587 (q, J = 7.5 Hz, 2H, CH 2 ), 3.919 (s:
3H, CH3),3.941 (s, 3H, CH3), 7.986 (s, 1H, pyrazole H), 8.421 (d, J=9.3 Hz, 1H, Py H), 8.626 (d: J=9.0 Hz, 1H, Py H), 9.625 (s, 1H, NH), 11.412 (s, 1H, NH). 3H, CH 3 ), 3.941 (s, 3H, CH 3 ), 7.986 (s, 1H, pyrazole H), 8.421 (d, J=9.3 Hz, 1H, Py H), 8.626 (d : J=9.0 Hz, 1H, Py H), 9.625 (s, 1H, NH), 11.412 (s, 1H, NH).
本发明的式 （I)所示的化合物可以通过下面所示的反应式 1 ( 1-1或 1-2)得到； 反应 式 1中的（II)和（V)可以通过下面所示的反应式 2得到； 反应式 1中的（III)和（IV)、 (VI) 可以通过反应式 3得到； 反应式 2中的 （VII) 可以通过购买或反应式 4中的方法 得到； 反应式 3中的 （VIII) 可以通过购买或反应式 5中的方法得到； 反应式 1至反应式 5中的 Z为离去基团， 如氯、 溴、磺酸酯等， 反应式 1至反应式 5中的 L为离去基团如氯、 溴等， 其它取代基除特别指明外均如前所限定。  The compound of the formula (I) of the present invention can be obtained by the reaction formula 1 (1-1 or 1-2) shown below; (II) and (V) in the reaction formula 1 can be reacted by the reaction shown below. (Formula 2) (III) and (IV), (VI) can be obtained by the reaction formula 3; (VII) in the reaction formula 2 can be obtained by purchasing or reacting the method of the formula 4; (VIII) can be obtained by purchasing or reacting the method of the formula 5; Z in the reaction formula 1 to the reaction formula 5 is a leaving group such as chlorine, bromine, sulfonate or the like, and the reaction formula 1 to the reaction formula 5 L in the group is a leaving group such as chlorine, bromine, etc., and other substituents are as defined above unless otherwise specified.
反应式 1 : （1-"  Reaction formula 1 : (1-"
Figure imgf000023_0001
Figure imgf000023_0001
反应式 2:  Reaction 2:
A NH2 ( 2 ) A NH 2 ( 2 )
Figure imgf000023_0002
Figure imgf000023_0002
反应式 3 :
Figure imgf000023_0003
Reaction 3:
Figure imgf000023_0003
反应式 4:  Reaction 4:
ArCH2OH or ArCHO ArCH 2 OH or ArCHO
[ O ] ArX ArCN o ArCOR' ( 4 ) [ O ] ArX ArCN o ArCOR' ( 4 )
Figure imgf000023_0004
Figure imgf000023_0004
Figure imgf000023_0005
Figure imgf000023_0005
式 （I) 的化合物可以这样来制备 （反应式 1 ) : 在合适的溶剂如二氯甲烷或甲苯、 二 氯乙烷、 Ν,Ν-二甲基甲酰胺 （DMF)、 四氢呋喃、 二氧六环中， 于 -10°C〜溶剂回流温度， 在合适的碱如三乙胺或吡啶、 氢化钠、 氢氧化钠、 氢氧化钾、 碳酸钾、 碳酸钠存在下， 用 式 （II) 所示的化合物和相应的式 （III) 或式 （IV) 所示的化合物反应， 或用式 （V) 所 示的化合物和相应的式 （VI) 所示的化合物反应得式 （I) 所示的化合物。 加入合适的催 化剂如 4-二甲胺基吡啶 （DMAP) 或碘化钾可加快反应或提高反应收率。 The compound of the formula (I) can be produced by the following reaction (reaction formula 1): in a suitable solvent such as dichloromethane or toluene, dichloroethane, hydrazine, hydrazine-dimethylformamide (DMF), tetrahydrofuran, dioxane In the ring, at -10 ° C ~ solvent reflux temperature, in the presence of a suitable base such as triethylamine or pyridine, sodium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, The compound represented by the formula (II) is reacted with the corresponding compound represented by the formula (III) or the formula (IV), or the compound represented by the formula (V) and the corresponding compound represented by the formula (VI) are reacted. (I) The compound shown. The addition of a suitable catalyst such as 4-dimethylaminopyridine (DMAP) or potassium iodide accelerates the reaction or increases the yield of the reaction.
式（Π)和式（V) 的化合物可以这样来制备 （反应式 2): 在无溶剂或合适的溶剂如二氯乙 烷或二氯甲烷、 甲苯中， 于 15°C〜体系回流温度， 用式（VII)所示的化合物和与氯化亚砜、 对 甲基苯磺酰氯反应即得式 (Π)所示的化合物， 加入催化剂量的 Ν,Ν-二甲基甲酉纖 (DMF)可以 加快反应或提高反应收率； 用式（Π)所示的化合物与胺水反应可得式（V )所示的化合物。  The compound of the formula (Π) and the formula (V) can be produced by the following (reaction formula 2): in a solvent-free or suitable solvent such as dichloroethane or dichloromethane, toluene, at a temperature of from 15 ° C to the reflux temperature of the system, The compound of the formula (VII) is reacted with thionyl chloride or p-methylbenzenesulfonyl chloride to obtain a compound of the formula (Π), and a catalyst amount of ruthenium, dimethyl-dimethylformamidine (DMF) is added. The reaction can be accelerated or the reaction yield can be improved; and the compound represented by the formula (V) can be reacted with an amine water to obtain a compound represented by the formula (V).
式（ΠΙ)和式（IV) 的化合物可以这样来制备 （反应式 3 ): 在合适的溶剂如水或四氢呋 喃、 〜^的醇、 甲苯、 二氯乙烷、 二氯甲烷中， 于 0°C〜体系回流温度， 在合适的碱如碳 酸钾或碳酸钠、 三乙胺、 吡啶、 氢化钠、 氢氧化钠、 氢氧化钾存在下， 用式 （vm) 所示的 化合物和 R2H反应即得式 （VI)所示的化合物。 在四氢呋喃和 /或水中， 于 0°C〜体系回流温 度下， 用式 （VI)所示的化合物与氨水或 R M^反应即得式 （III) 或式 （IV) 的化合物。 The compounds of the formula (ΠΙ) and the formula (IV) can be prepared by the following reaction (reaction formula 3): in a suitable solvent such as water or tetrahydrofuran, an alcohol, toluene, dichloroethane or dichloromethane at 0 ° C. ~ system reflux temperature, in the presence of a suitable base such as potassium carbonate or sodium carbonate, triethylamine, pyridine, sodium hydride, sodium hydroxide, potassium hydroxide, the reaction of the compound of formula (vm) and R 2 H A compound represented by the formula (VI) is obtained. The compound of the formula (VI) or the compound of the formula (IV) can be obtained by reacting the compound of the formula (VI) with aqueous ammonia or RM^ in tetrahydrofuran and/or water at a reflux temperature of from 0 ° C to the reflux temperature of the system.
式 （VII) 的化合物可以这样来制备 （反应式 4): 根据 （VII) 的结构及可能的原料， 选择反应式 4中的合适路线， 通过相应的合成方法可得式 （VII) 的化合物。  The compound of the formula (VII) can be produced in the same manner (Reaction formula 4): According to the structure of (VII) and possible starting materials, a suitable route in the reaction formula 4 is selected, and a compound of the formula (VII) can be obtained by a corresponding synthesis method.
式 （VIII) 的化合物可以这样来制备 （反应式 5 ): 取代的 2-胺基吡啶， 用硫酸和 硝酸混合酸硝化得 ΚΛ„取代的 2-胺基硝基吡啶， 取代的 2-胺基硝基吡啶经过常规的重 氮化、 氯化得 R 取代的 2-氯硝基吡啶， 再 N-氧化， 氯化可得式 （VIII) 的化合物。  The compound of the formula (VIII) can be produced by the following formula (reaction formula 5): a substituted 2-aminopyridine, which is nitrated with a mixed acid of sulfuric acid and nitric acid to give a substituted 2-aminonitropyridine, a substituted 2-amino group. The nitropyridine is subjected to conventional diazotization, chlorination to give R-substituted 2-chloronitropyridine, and N-oxidation, chlorination to obtain a compound of the formula (VIII).
具体合成方法在下面的实施例中有更详细的阐述。  Specific synthetic methods are set forth in more detail in the examples below.
本发明提供的式（I)化合物在 3.75〜2250克有效成分 /公顷用量下具有广谱生物活性， 既可用于防治病菌， 还可用于防治杂草， 或有害昆虫。 有的化合物具有很好的病菌防治作 用， 在很低的剂量下就可以获得很好的效果。  The compound of the formula (I) provided by the present invention has a broad spectrum of biological activity at a dosage of 3.75 to 2250 g of active ingredient per hectare, and can be used for controlling bacteria and for controlling weeds or harmful insects. Some compounds have good pathogen control effects and can achieve good results at very low doses.
本发明提供的式（I)化合物， 具有生物活性且有的化合物具有很好的生物活性. 特别 是在农业、 园艺、 花卉和卫生病菌、 杂草、 害虫的防治方面表现出活性。 这里所述的有害 生物包括， 但不仅限于此：  The compound of the formula (I) provided by the present invention has biological activity and some compounds have excellent biological activity. Especially, it exhibits activity in the control of agriculture, horticulture, flower and hygienic bacteria, weeds, and pests. The pests described here include, but are not limited to:
禾本科杂草： 马唐、 稗草、 狗尾草、 硬草、 茼草、 雀麦、 看麦娘、 节节麦、 碱茅、 星 星草、 野燕麦、 黑麦草；  Gramineous weeds: crabgrass, valerian, foxtail, hard grass, valerian, brome, amethyst, stalked wheat, sodic grass, star grass, wild oats, ryegrass;
阔叶杂草： 苘麻、 繁缕、 龙葵、 藜、 凹头苋、 反枝苋、 剌苋等；  Broadleaf weeds: ramie, sorghum, sylvestris, scorpion, scorpion scorpion, scorpion scorpion, scorpion, etc.;
昆虫： 直翅目如蜚蠊， 缨翅目如棉蓟马、 稻蓟马、 瓜蓟马， 同翅目如叶蝉、 飞虱、 蚜 虫， 鳞翅目如东方粘虫、 斜纹夜蛾、 小菜蛾、 甜菜夜蛾、 粉纹夜蛾， 菜青虫， 膜翅目如叶 蜂幼虫， 双翅目如伊蚊、 库蚊、 蝇；  Insects: Orthoptera such as striata, pteridoptera such as cotton scorpion horse, rice scorpion horse, melon scorpion horse, Homoptera such as spider mites, locusts, locusts, lepidoptera such as oriental armyworm, Spodoptera litura, side dish Moth, beet armyworm, Spodoptera litura, Pieris rapae, Hymenoptera such as leaf bee larvae, Diptera such as Aedes, Culex, fly;
有害病原菌： 疫霉属种类， 白粉属种类， 赤霉属种类， 黑星菌属种类， 核盘菌属种类， 丝核菌属种类，葡萄孢属种类，梨孢属种类，镰孢属种类,如水稻稻瘟病 ( cM/ar a oryzae ) ; 小麦条锈病 (Puccinia striiformis) , 叶锈病 (Puccinia recondita) 禾口其它锈病； 大麦条锈病 ( Puccinia striiformis ) 叶锈病 Puccinia recondita ) 禾口其它锈病； 大麦禾口小麦白粉病 ( Erysiphe graminis )、 黄瓜白粉病 ( Sphaerotheca fuligenea )、 苹果白粉病 Podosphaera /ewcotr c rar)禾口葡萄白粉病 (Poi/io p Mera leucotrichar)； 小麦纹枯病禾口颖枯病 ( Septoria nodorum ) . 谷物上的长蠕孢、 嘴孢霉、 壳针孢属病、 核球壳菌属病、 Pseudocercosporella herpotrichoides 禾口小麦全 t虫病 ( Gaeumannomyces graminis 。 花生揭斑病 ( Cercospora arachidicola) 禾口花生黑斑病 ( Cercosporidium per sonata) 苹果轮纹病菌 (Botryosphaeria berengriana f.sp piricolaX 苹果腐烂病菌 (Cytospora sp. 甜菜、 大豆和稻谷上的其尾孢 霉属病。 番茄、 黄瓜、 葡萄灰霉病 (Mrytis ci a 蔬菜 （如黄瓜） 上的铰链孢属病。 黄瓜上的炭疽病， 苹果黑星病， 黄瓜霜霉病， 葡萄霜霉病， 马铃薯和番茄上的疫病， 稻谷 上的单子菌 Thanatephorus cucumeris以及其他宿主如小麦和大麦、 蔬菜上的其它丝核菌； 油菜菌核病 ( Sclerotonia sclerotiorum )； 小麦赤霉病 ( Gibberella zeae )； 辣椒疫霉病 Phytophythora capsici)。 Harmful pathogens: Phytophthora species, white powder species, Gibberella species, species of the genus Verticillium, species of Sclerotinia, Rhizoctonia species, Botrytis species, Pyriculara species, Fusarium species, such as rice blast (cM/ar a oryzae); wheat stripe rust (Puccinia striiformis), leaf rust (Puccinia recondita) and other Rust; barley stripe rust (Puccinia striiformis) leaf rust Puccinia recondita) and other rust; barley and wheat powdery mildew (Erysiphe graminis), cucumber powdery mildew (Sphaerotheca fuligenea), apple powdery mildew Podosphaera / ewcotr c rar) Powdery mildew (Poi/io p Mera leucotrichar); wheat sheath blight and Septoria nodorum. Helminthosporium, M. oxysporum, Helminthosporium, Helicobacter genus, Pseudocercosporella Herpotrichoides and wheat t-bug disease (Gaeumannomyces graminis. Cercospora arachidicola and Cercosporidium per sonata) Apple rot pathogen (Botryosphaeria berengriana f.sp piricolaX apple rot pathogen (Cytospora sp. beet) , Solanum spp. on soybeans and rice. Tomato, cucumber, grape gray mold (Mrytis ci a vegetable Hysterospores on vegetables (eg cucumber). Anthrax on cucumber, apple scab, cucumber downy mildew, grape downy mildew, potato and tomato disease, monochae Thanatephorus cucumeris on rice and other hosts Such as wheat and barley, other Rhizoctonia on vegetables; Sclerotionia sclerotiorum; Gibberella zeae; Phytophythora capsici.
单独使用本发明的式（I)化合物时， 对控制病菌、 杂草、 害虫是有效的， 它们也可以 与其他生物化学物质一起使用， 这些生物化学物质包括其他杀菌剂和除草剂、 杀虫剂。  When the compound of the formula (I) of the present invention is used alone, it is effective for controlling pathogens, weeds, and pests, and they can also be used together with other biochemical substances including other fungicides, herbicides, and insecticides. .
以本发明提供的 （I)化合物， 作为有效成份的农用制剂， 可以制成所希望的任何一种剂 型如干的压缩颗粒、 易流动混合剂、 粒剂、 可湿性粉剂、 水分散粒剂、 可乳化的浓缩物、 粉 齐 U、 粉状浓缩物、 微乳胶、 悬浮剂、 乳油、 水乳剂、 可溶性液剂、 水剂、 可分散液剂， 适宜 的助剂包括载体 （稀释剂）和其它辅助剂如展着剂、 乳化剂、 湿润剂、 分散剂、 粘着剂和分 解剂。这些制剂中含有同惰性的、 药理学可接受的固体或液体稀释剂混合了本发明的化合物。  The agricultural preparation of the compound (I) provided by the present invention as an active ingredient can be prepared into any desired dosage form such as dry compressed granules, a flowable mixture, granules, wettable powders, water-dispersible granules, Emulsifying concentrates, powders, powder concentrates, microemulsions, suspending agents, emulsifiable concentrates, aqueous emulsions, soluble liquids, aqueous solutions, dispersible agents, suitable adjuvants including carriers (diluents) and others Adjuvants such as spreading agents, emulsifiers, wetting agents, dispersing agents, adhesives and decomposers. These formulations contain the compound of the present invention in admixture with an inert, pharmacologically acceptable solid or liquid diluent.
例如： 本发明的可湿性粉剂、 粉剂和粉末浓缩物， 可以通过将重量约 5-30%的式 （I) 化合物， 同重量约 5-30%的固体阴离子表面活性剂一起碾磨而制备。 一种合适的阴离子表 面活性剂是磺基琥珀酸钠的二辛基酯。 这些制剂中也使用重量 40%-90%的惰性固体稀释 剂， 如滑石、 高岭土、 硅藻土、 石灰石、 硅酸盐等。  For example: The wettable powders, powders and powder concentrates of the present invention can be prepared by milling about 5-30% by weight of a compound of formula (I) with about 5-30% by weight of a solid anionic surfactant. One suitable anionic surfactant is the dioctyl ester of sodium sulfosuccinate. Inorganic solid diluents such as talc, kaolin, diatomaceous earth, limestone, silicates and the like are also used in these formulations in an amount of from 40% to 90% by weight.
压缩颗粒的制备是将大约等量的如 5-30份式 (I)化合物和固体表面活性剂以及约 40-90份 的石膏一起碾磨， 然后混合物再压缩为约 10-100目 （1.676-0.152mm)大小或更大的颗粒。  The compressed granules are prepared by milling approximately equal amounts of, for example, 5 to 30 parts of the compound of formula (I) with a solid surfactant and from about 40 to 90 parts of gypsum, and the mixture is then compressed to about 10-100 mesh (1.676- 0.152 mm) particles of size or larger.
本发明配方中所使用的固体表面活性剂不仅有阴离子的磺基琥珀酸钠的二辛基苯酯， 还有非离子型环氧乙烷和环氧丙烷的嵌段聚合物。  The solid surfactants used in the formulations of the present invention are not only anionic sodium dioctyl phenyl succinate, but also block polymers of nonionic ethylene oxide and propylene oxide.
易流动剂可就地与水溶液一起施用。  The flowable agent can be applied in situ with the aqueous solution.
式（I) 固体制剂可以同其它杀菌剂或除草剂、 杀虫剂结合使用， 可以作为多组分混合 物使用， 或者顺序地使用。 Formula (I) Solid preparation can be used in combination with other fungicides or herbicides and insecticides, and can be used as a multi-component mixture. Use, or use sequentially.
同理， 式（I) 的液体制剂也可以同其它杀菌剂或除草剂、 杀虫剂结合使用， 可以在容 器中混合或以液体喷雾剂方式分别依次施用。本发明的液体喷洒剂配方中应含有约 10-5000 ppm 的式 （I) 化合物。  Similarly, the liquid preparation of the formula (I) can also be used in combination with other bactericides or herbicides, insecticides, and can be mixed in a container or sequentially in the form of a liquid spray. The liquid spray formulation of the present invention should contain from about 10-5000 ppm of a compound of formula (I).
本发明的组合物的实例也可以是可湿性粉剂、粉剂、颗粒剂和液剂， 可乳化的浓缩剂、 乳剂、 悬浮浓缩剂、 气雾剂和烟雾剂。 可湿性粉剂通常含 15， 25， 50 重量活性成分， 且 通常除固体惰性载体外， 还含有 3-10%重量分散剂， 必要时可加入 0-10%重量稳定剂和 /或 其它添加剂如渗透剂和粘着剂。 粉剂通常可成型为具有与可湿性粉剂相似的组成但没有分 散剂的粉剂浓缩剂。 粒剂通常制成具有 10-100 目 （1.676-0.152mm) 大小， 且可用成团或 注入技术制备。 通常， 粒剂含 0.5-50%重量的活性成分和 0-10%重量添加剂如稳定剂、 表 面活性剂、 缓释改良剂。 可乳化浓缩剂除溶剂外， 必要时可含有共溶剂， 1-50%W/V活性 成分， 2-20%W/V乳化剂和 0-20%W/V其它添加剂如稳定剂、 渗透剂和腐蚀抑制剂， 悬浮 浓缩剂通常含有 10-75%重量的活性成分、 0.5-15%重量的分散剂、 0.1-10%重量的其它添加 剂如消泡剂、 腐蚀抑制剂、 稳定剂、 渗透剂和粘着剂。  Examples of the composition of the present invention may also be wettable powders, powders, granules and liquids, emulsifiable concentrates, emulsions, suspension concentrates, aerosols and aerosols. Wettable powders usually contain 15, 25, 50 parts by weight of active ingredient, and usually contain 3-10% by weight of dispersing agent in addition to the solid inert carrier, and if necessary, 0-10% by weight of stabilizer and/or other additives such as infiltration may be added. Agents and adhesives. The powder can usually be formed into a powder concentrate having a composition similar to that of a wettable powder but without a dispersing agent. Granules are typically made to have a size of 10-100 mesh (1.676-0.152 mm) and can be prepared by agglomeration or infusion techniques. Usually, the granules contain 0.5 to 50% by weight of the active ingredient and 0 to 10% by weight of an additive such as a stabilizer, a surfactant, and a sustained release modifier. The emulsifiable concentrate may contain a cosolvent, 1-50% W/V active ingredient, 2-20% W/V emulsifier and 0-20% W/V other additives such as stabilizer, penetrant, in addition to solvent. And corrosion inhibitors, suspension concentrates usually contain 10-75% by weight of active ingredient, 0.5-15% by weight of dispersant, 0.1-10% by weight of other additives such as antifoaming agent, corrosion inhibitor, stabilizer, penetrant And adhesives.
水分散剂和乳剂， 例如通过用水稀释按照本发明的可湿性粉剂或浓缩物得到的组合 物， 也列入本发明的范围。 所指乳剂包括油包水和水包油两种。  Aqueous dispersions and emulsions, for example compositions obtained by diluting a wettable powder or concentrate according to the invention with water, are also included in the scope of the invention. The emulsions referred to include both water-in-oil and oil-in-water.
以下结合实施例对本发明作进一步说明， 实施例中的收率均未经优化。  The invention is further illustrated by the following examples in which the yields in the examples are not optimized.
【具体实施方式】  【detailed description】
实施例 1 本实施例说明表 1中化合物 14的制备方法  EXAMPLE 1 This example illustrates the preparation of compound 14 in Table 1.
^ _ ^ pi ,, NOi _ ^ N _ , ^ Ν。 _ ^ QrF fYN°2 ^ _ ^ pi ,, NO i _ ^ N _ , ^ Ν . _ ^ Qr F fY N ° 2
° 14  ° 14
2_氨基 -3-硝基吡啶 在配有磁力搅拌器、温度计和恒压滴液漏斗的 250 mL三口瓶中加 入浓硫酸（80 mL)禾口 2-氨基吡啶（0.10 mol)，冰浴冷却至 0°C以下， 滴加发烟硝酸 (0.11 mol)的 浓硫酸（10 mL)溶液， 0.5 hr内滴完， 反应温度升至常温后继续反应 1-2 hr。 将反应液倒入冰水 中， 用氨水调节溶液 PH值至中性， 过滤， 用水洗三次， 干燥， 得 2-氨基 -3-硝基-吡啶和 2-氨基 -5- 硝基-吡啶的混合物， 经纯化分离， 分别得 2-氨基 -3-硝基-吡啶和 2-氨基 -5-硝基-吡啶。 2 _Amino-3-nitropyridine In a 250 mL three-necked flask equipped with a magnetic stirrer, thermometer and constant pressure dropping funnel, concentrated sulfuric acid (80 mL) and 2-aminopyridine (0.10 mol) were added and cooled in an ice bath. To a temperature below 0 °C, a solution of fuming nitric acid (0.11 mol) in concentrated sulfuric acid (10 mL) was added dropwise, and the mixture was dropped in 0.5 hr. The reaction temperature was raised to normal temperature and the reaction was continued for 1-2 hr. Pour the reaction solution into ice water, adjust the pH of the solution to neutral with ammonia water, filter, wash three times with water, and dry to obtain a mixture of 2-amino-3-nitro-pyridine and 2-amino-5-nitro-pyridine. Purified and isolated to give 2-amino-3-nitro-pyridine and 2-amino-5-nitro-pyridine, respectively.
2-氯 -3-硝基吡啶 在配有磁力搅拌器和恒压滴液漏斗的 250 mL三口烧瓶中加入 2-氨 基 -3-硝基吡啶 （0.07 mol)和水（200 mL)， 搅拌下滴加浓硫酸 (50 mL)， 冰浴冷却至 0°C以 下， 滴加亚硝酸钠水溶液 (0.15 mol)， 滴毕后， 缓慢升至室温反应 2 hr后， 回流 3-5 hr， 将 反应液倒入冰水中， 用碳酸钠水溶液调节溶液 PH值至弱酸性， 过滤， 用水洗三次， 干燥， 得淡黄色固体 2-羟基 -3-硝基吡啶 （0.04 mol)。 2-羟基 -3-硝基 -4甲基吡啶 （0.04 mol) 和三 氯氧磷 （40 mL)， 加热回流 5-8 hr， 冷却， 减压蒸熘除去三氯氧磷后倒入水中， 用碳酸钠 水溶液调节溶液 pH至弱碱性， 乙酸乙酯萃取， 水洗有机相， 无水硫酸钠干燥有机相， 脱 溶， 得棕褐色固体 2-氯 -3-硝基吡啶 （0.03 mol)。 2-Chloro-3-nitropyridine Add 2-amino-3-nitropyridine (0.07 mol) and water (200 mL) in a 250 mL three-necked flask equipped with a magnetic stirrer and a constant pressure dropping funnel. Concentrated sulfuric acid (50 mL) was added dropwise, cooled to below 0 °C in an ice bath, and an aqueous solution of sodium nitrite (0.15 mol) was added dropwise. After the dropwise addition, the mixture was slowly warmed to room temperature for 2 hr, and refluxed for 3-5 hr. The solution was poured into ice water, the pH of the solution was adjusted to weakly acidic with aqueous sodium carbonate, filtered, washed three times with water, and dried to give a pale yellow solid 2-hydroxy-3-nitropyridine (0.04 mol). 2-hydroxy-3-nitro-4methylpyridine (0.04 mol) and three Phosphorus oxychloride (40 mL), heated to reflux for 5-8 hr, cooled, distilled under reduced pressure to remove phosphorus oxychloride, poured into water, adjusted to pH with alkaline sodium carbonate solution, extracted with ethyl acetate, washed with organic The organic phase was dried over anhydrous sodium sulfate and evaporated to give a brown solid, 2-chloro-3-nitropyridine (0.03 mol).
2,6—二氯 -3—銷基吡啶 在配有磁力搅拌器、恒压滴液漏斗和干燥管的 500 mL三口烧瓶中加 入 2-氯 -3-硝基吡啶 (0.03 mol), 二氯甲烷 (250 mL), 冰浴冷却下分批加入过氧化尿素 (6.2 g, 0.06 mol) ， 搅拌 0.5 hr后， 滴加三氟乙酸酐（0.03 mol) ， 在 0.5 hr内。 缓慢升至常温反应 2 d。 滴 加亚硫酸钠饱和水溶液（40 mL)，搅拌 2 hr后，加饱和碳酸氢钠水溶液， 使反应混合液至碱性， 分液， 二氯甲烷萃取， 水洗有机相， 无水硫酸钠干燥， 脱溶， 得淡黄色固体 2-氯 -3-硝基吡啶 -N- 氧化物 (0.014 mol)。在 150 mL三口烧瓶中加入上述 2-氯 -3-硝基吡啶 -N-氧化物和三氯氧磷（40 mL), 加热回流 5-8 hr, 冷却， 减压蒸熘除去三氯氧磷， 后倒入水中， 用碳酸钠水溶液， 调节 反应液 pH至弱碱性， 乙酸乙酯萃取， 水洗有机相， 无水硫酸钠干燥有机相， 脱溶， 经柱层析 纯化得淡黄色固体 2,6-二氯 -3-硝基吡啶 （5.2 mmol)。  2,6-Dichloro-3-pinopyridine In a 500 mL three-necked flask equipped with a magnetic stirrer, a constant pressure dropping funnel and a drying tube, 2-chloro-3-nitropyridine (0.03 mol), dichloro Methane (250 mL) was added with urea peroxide (6.2 g, 0.06 mol) in portions under ice-cooling. After stirring for 0.5 hr, trifluoroacetic anhydride (0.03 mol) was added dropwise over 0.5 hr. Slowly rise to room temperature for 2 d. Add a saturated aqueous solution of sodium sulfite (40 mL), stir for 2 hr, then add a saturated aqueous solution of sodium hydrogencarbonate, and then let the mixture mixture to basic, partitioned, extracted with dichloromethane, washed with water, dried over anhydrous sodium sulfate and evaporated. , a pale yellow solid 2-chloro-3-nitropyridine-N-oxide (0.014 mol). The above 2-chloro-3-nitropyridine-N-oxide and phosphorus oxychloride (40 mL) were added to a 150 mL three-necked flask, heated under reflux for 5-8 hr, cooled, and distilled under reduced pressure to remove phosphorus oxychloride. After pouring into water, the pH of the reaction solution is adjusted to be weakly alkaline with an aqueous solution of sodium carbonate, extracted with ethyl acetate, and the organic phase is washed with water. The organic phase is dried over anhydrous sodium sulfate, evaporated, and purified by column chromatography. , 6-Dichloro-3-nitropyridine (5.2 mmol).
2,6-二胺基 -3-硝基吡啶 2,6-二氨基 -3-硝基吡啶 （19.2 g)， 25%氨水 （30.0g) 和四氢 呋喃 （40 mL), 密闭反应器并加热至回流条件下反应至完全 （LC检测至无原料） 。 冷却 后将反应液倒入大量水中， 过滤， 得黄色固体 14.5 g， 含量 96% (LC)， 收率 95%。  2,6-Diamino-3-nitropyridine 2,6-diamino-3-nitropyridine (19.2 g), 25% aqueous ammonia (30.0 g) and tetrahydrofuran (40 mL), sealed reactor and heated to The reaction was complete under reflux conditions (LC detected to no starting material). After cooling, the reaction solution was poured into a large amount of water and filtered to give a yellow solid, 14.5 g, 96% (LC), yield 95%.
2,6-二氟苯甲酰氯 在带有磁力搅拌和干燥装置的三口瓶 （500 mL) 中， 加入 2,6-二氟 苯甲酸 （0.1 mol) ， 1,2-二氯乙烷 （lOO mL), 于 10-20°C和搅拌条件下缓慢滴加氯化亚砜 ( 0.13 mol) ， 滴毕后， 升温至回流反应 5-6小时至反应完全 （GC检测）， 减压脱去过量 的氯化亚砜和溶剂， 得红色 2,6-二氟苯甲酰氯 16.2 g。  2,6-difluorobenzoyl chloride in a three-necked flask (500 mL) with a magnetic stirring and drying device, adding 2,6-difluorobenzoic acid (0.1 mol), 1,2-dichloroethane (100) (mL), slowly add dropwise thionyl chloride (0.13 mol) at 10-20 ° C and stirring. After the completion of the dropwise addition, the temperature is raised to reflux for 5-6 hours until the reaction is complete (GC detection), and the excess is removed under reduced pressure. The thionyl chloride and the solvent gave red 2,6-difluorobenzoyl chloride 16.2 g.
N，N'-(5-硝基吡啶 -2,6-二基) -双 (2,6-二氟苯甲酰胺）（表 1中 14) 100 mL三口瓶中加入 N,N'-(5-nitropyridine-2,6-diyl)-bis(2,6-difluorobenzamide) (14 in Table 1) was added to a 100 mL three-neck bottle
2,6-二氨基 -3-硝基吡啶 (10 mmol)， 甲苯 (50 mL)， 三乙胺 (0.5 g)， 4-二甲胺基吡啶 ( 0.2 g) ， 于 10-20°C和搅拌条件下缓慢滴加 2,6-二氟苯甲酰氯 （25 mmol) 的甲苯 （10 mL) 溶液， 滴加完毕后升温至回流反应 6-8小时至反应完全 （LC跟踪检测）。 冷却后将反应液倒入冰 水中， 乙酸乙酯萃取， 水洗， 无水硫酸钠干燥， 减压脱去溶剂， 得粗产物， 经柱层析 （V 石油醚 /乙酸乙酯 = 6/1 )得黄色固体标题化合物 2.26 g， 熔点 203.2〜204.8°C， 收率 52.0%。 2,6-diamino-3-nitropyridine (10 mmol), toluene (50 mL), triethylamine (0.5 g), 4-dimethylaminopyridine (0.2 g) at 10-20 ° C and A solution of 2,6-difluorobenzoyl chloride (25 mmol) in toluene (10 mL) was slowly added dropwise with stirring, and the mixture was warmed to reflux for 6-8 hours until the reaction was complete (LC tracking). After cooling, the reaction mixture was poured into ice water, EtOAc (EtOAc) The title compound was obtained as a yellow solid, 2.26 g, m.
的制备方法（方法 A )
Figure imgf000027_0001
Preparation method (method A)
Figure imgf000027_0001
ΛΚ6-乙氨基 -5-硝基吡啶 -2-基) -2,6-二氯苯甲酸酰胺 （表 1中 49) 在 100 mL反应瓶中 加入 2-乙氨基 -6-氨基 -3-硝基吡啶 (5 mmol), 四氢呋喃 (50 m L)， KI ( 0.2 g)， 氢化钠 (15 mmol),冰浴下搅拌 10 min, 滴加 2,6-二氯苯甲酰氯（ 5 mmol)的四氢呋喃（THF )溶液（10 ml), 搅拌并自然升温至室温反应 2-6 hr， 倒入冰水中， 乙酸乙酯萃取， 水洗， 干燥， 脱溶， 柱层析得目标物黄色固体 1.65 g， 产率 93.0%， 熔点 166.7〜168.1 °C。 的制备方法 （方法 B)
Figure imgf000028_0001
ΛΚ6-Ethylamino-5-nitropyridin-2-yl)-2,6-dichlorobenzoic acid amide (49 in Table 1) 2-ethylamino-6-amino-3-nitrate was added to a 100 mL reaction flask Pyridine (5 mmol), tetrahydrofuran (50 m L), KI (0.2 g), sodium hydride (15 mmol), stirred for 10 min in ice bath, and 2,6-dichlorobenzoyl chloride (5 mmol) Tetrahydrofuran (THF) solution (10 Mg), stirred and naturally warmed to room temperature for 2-6 hr, poured into ice water, extracted with ethyl acetate, washed with water, dried, and then evaporated, and then purified by column chromatography to yield 1.65 g of the title compound as a yellow solid, yield 93.0%, melting point 166.7 ~168.1 °C. Preparation method (method B)
Figure imgf000028_0001
N-(6-乙氨基 -5-硝基吡啶 -2-基) -2,6-二氯苯甲酸酰胺（表 1中 49) 在 100 mL反应瓶中加入 2,6-二氯苯甲酰胺（ 5 mmol), 氢氧化钠（ 10 mmol)和 DMF(40 mL), 冰浴条件下搅拌 10 min, 滴 加 6-氯 -2-乙胺基 -3-硝基吡啶 C5 mmol)的 DMFC15 mL)， 加毕后室温反应 4-8 hr， 倒入水中， 调节 pH至中性， 乙酸乙酯萃取， 水洗， 干燥， 脱溶， 柱层析得目标物 0.37 g， 产率 21%。 实施例 4 本实施例说明表 1中化合物 52的制备方法  N-(6-Ethylamino-5-nitropyridin-2-yl)-2,6-dichlorobenzoic acid amide (49 in Table 1) 2,6-dichlorobenzamide was added to a 100 mL reaction flask (5 mmol), sodium hydroxide (10 mmol) and DMF (40 mL), stirred for 10 min under ice-cooling, and then added dropwise chloroform 15 mL of 6-chloro-2-ethylamino-3-nitropyridine C5 mmol) After the addition, the reaction was carried out at room temperature for 4-8 hr, poured into water, the pH was adjusted to neutrality, extracted with ethyl acetate, washed with water, dried, and then evaporated, and then subjected to column chromatography to obtain the target compound (0.37 g, yield 21%). EXAMPLE 4 This example illustrates the preparation of compound 52 in Table 1.
Η2ΝΗ 2 Ν
Figure imgf000028_0002
Figure imgf000028_0002
N-(6-氨基 -5-硝基吡啶 -2-基) -2,6-二氟苯甲酰胺（表 1中 52) 100 mL三口瓶中加入 2,6- 二氨基 -3-硝基吡啶 (10 mmol), 甲苯 (50 mL)， 三乙胺 (0.2 g)， 4-二甲胺基吡啶 ( 0.1 g) ， 于 10-20 °C和搅拌条件下缓慢滴加 2,6-二氟苯甲酰氯（10 mmol) 的甲苯（10 mL)溶液， 滴加 完毕后升温至回流反应 4-6小时至反应完全（LC跟踪检测）。冷却后将反应液倒入冰水中， 乙酸乙酯萃取， 水洗， 无水硫酸钠干燥， 减压脱去溶剂， 得粗产物， 经柱层析 （V石油醚 / 乙酸乙酯 = 4/1 ) 得黄色固体标题化合物 1.16 g， 熔点 244.0〜244.8°C， 收率 39.5%。  N-(6-Amino-5-nitropyridin-2-yl)-2,6-difluorobenzamide (52 in Table 1) 2,6-diamino-3-nitro group in a 100 mL three-necked flask Pyridine (10 mmol), toluene (50 mL), triethylamine (0.2 g), 4-dimethylaminopyridine (0.1 g), slowly added 2,6-di at 10-20 °C under stirring A solution of fluorobenzoyl chloride (10 mmol) in toluene (10 mL) was added and the mixture was warmed to reflux for 4-6 hours until the reaction was complete (LC traced). After cooling, the reaction mixture was poured into ice water, EtOAc (EtOAc) The title compound was obtained as a yellow solid, 1.16 g, m.
实施例 5 本实施例说明表 1中化合物 151的制备方法  EXAMPLE 5 This example illustrates the preparation of the compound 151 in Table 1.
― " ―厂 s COOC COOC2H5 S .COOH ― " ―Factory s COOC COOC 2 H 5 S .COOH
« ^、。—— NlCF3 ——"、 3 \" 「3 « ^,. —— N l CF3 ——", 3 \" ” 3
Figure imgf000028_0003
Figure imgf000028_0003
2-氨基 -4-三氟甲基噻唑 -5-甲酸乙酯 2-氯三氟乙酸乙酯 (21.8 g)，硫脲 (7.6 g)和乙醇（200 mL) 于回流 下反应 4-5小时。 冷却后将反应液倒入冰水中， 过滤， 得白色固体 22.0 g。  2-Amino-4-trifluoromethylthiazole-5-carboxylate ethyl 2-chlorotrifluoroacetate (21.8 g), thiourea (7.6 g) and ethanol (200 mL) were reacted under reflux for 4-5 hours . After cooling, the reaction solution was poured into ice water and filtered to give a white solid (22.0 g).
2-氯 -4-三氟甲基噻唑 -5-甲酸乙酯 冰浴冷却下， 滴加亚硝酸钠 （3.4 g)和水 （40.0 g) 的溶液入 2-氨基 -4-三氟甲基噻唑 -5-甲酸乙酯 （8.0 g) 和 36%的盐酸 （80 mL) 混合液中， 滴加完毕， 室温反应 3-4小时。 冷却， 将反应液倒入冰水中， 过滤， 得黄色固体 7.8 g。  2-Chloro-4-trifluoromethylthiazole-5-carboxylic acid ethyl ester was added dropwise to a solution of sodium nitrite (3.4 g) and water (40.0 g) in 2-amino-4-trifluoromethyl under ice cooling. The mixture of thiazole-5-carboxylate (8.0 g) and 36% hydrochloric acid (80 mL) was added dropwise and allowed to react at room temperature for 3-4 hours. After cooling, the reaction solution was poured into ice water and filtered to give y.
2-甲氧基 -4-三氟甲基噻唑 -5-甲酸 缓慢滴加氢氧化钠 (4.0 g)和水（20.0 g) 的溶液入 2-氯 -4-三氟甲基噻唑 -5-甲酸乙酯 （13.0 g) 的甲醇 （300 mL)溶液中， 回流条件下反应 4-5小时。 冷 却后将反应液倒入冰水中， 用稀盐酸调至 PH至 〜 2， 过滤， 得黄色固体 10.0 g。  2-Methoxy-4-trifluoromethylthiazole-5-carboxylic acid was slowly added dropwise to a solution of sodium hydroxide (4.0 g) and water (20.0 g) in 2-chloro-4-trifluoromethylthiazole-5- Ethyl formate (13.0 g) in methanol (300 mL) was reacted under reflux for 4-5 hours. After cooling, the reaction solution was poured into ice water, adjusted to pH ~ 2 with dilute aqueous hydrochloric acid, and filtered to yield 10.0 g.
2-甲氧基 -4-三氟甲基噻唑 -5-甲酰氯 在装有磁力搅拌子的 250ml三口瓶中加入 2-甲氧 基—4-三氟甲基噻唑 -5-甲酸（11.4 g)和 1,2-二氯乙烷 (150mL)，室温下滴加二氯亚砜 (14.2 g)， 加毕后回流反应 4〜5小时， 减压脱去过量溶剂和二氯亚砜得黄色液体的标题物 11.5 g。2-methoxy-4-trifluoromethylthiazole-5-formyl chloride 2-methoxy-4-trifluoromethylthiazole-5-carboxylic acid (11.4 g) in a 250 ml three-necked flask equipped with a magnetic stir bar And 1,2-dichloroethane (150 mL), adding thionyl chloride (14.2 g) at room temperature, After the addition, the reaction was refluxed for 4 to 5 hours, and the title compound (11.5 g, m.
N-(6-氨基 -5-硝基吡啶 -2-基) -2-甲氧基 -4-三氟甲基噻唑 -5-甲酰胺 （表 1中 151) 在装有 磁力搅拌子的三口瓶中加入 NaH (60% 2.2 g) 和 DMF ( 80 mL)， 搅拌 5 min后分批加入 2,6-二氨基 -3-硝基吡啶 (3.0 g)， 室温搅拌 30 min后， 滴加 2-甲氧基 -4-三氟甲基 -噻唑 -5- 甲酸酰氯（9.5 g)， 室温搅拌 2-5 hr后， 将反应液缓慢倾入冰水中， 乙酸乙酯萃取， 水洗有 机相， 无水硫酸钠干燥有机相， 减压脱溶， 得粗产物。 经柱层析纯化得标题化合物黄色固 体 1.10 g。 含量 92% (HPLC), 熔点 148.2〜149.6°C。 N-(6-Amino-5-nitropyridin-2-yl)-2-methoxy-4-trifluoromethylthiazole-5-carboxamide (151 in Table 1) in a three-necked magnetic stir bar Add NaH (60% 2.2 g) and DMF (80 mL) to the bottle, stir for 5 min, then add 2,6-diamino-3-nitropyridine (3.0 g) in portions, stir at room temperature for 30 min, then add 2 -Methoxy-4-trifluoromethyl-thiazole-5-carboxylic acid chloride (9.5 g), after stirring at room temperature for 2-5 hr, the reaction solution was slowly poured into ice water, extracted with ethyl acetate, and washed with water, organic The organic phase was dried over sodium sulfate and evaporated to dryness to give crude. Purification by column chromatography gave the title compound as a yellow solid. Content 92% (HPLC), melting point 148.2~149.6 °C.
实施例 6 本实施例说明表 1中化合物 163的制备方法
Figure imgf000029_0001
EXAMPLE 6 This example illustrates the preparation of compound 163 in Table 1.
Figure imgf000029_0001
硫代丙酰胺 室温下，分批加入五硫化二磷 (55.5 g)至丙酰胺 (36.5 g)和无水*** (500mL)中， 加完后继续室温反应 3-4小时， 过滤， 减压脱去滤液， 得黄色油状液体 37.0 g， 收率 83%。  Thiopropanamide was added in portions to a solution of phosphorus pentasulfide (55.5 g) to propionamide (36.5 g) and anhydrous diethyl ether (500 mL) at room temperature. After the addition, the reaction was continued at room temperature for 3-4 hours, filtered, and the filtrate was evaporated under reduced pressure. A yellow oily liquid was obtained in 37.0 g, yield 83%.
2-氯 -三氟乙酰乙酸乙酯 于 -5〜- 10°C， 缓慢通入氯气至三氟乙酰乙酸乙酯 (37.0 g)和 四氯化碳 （300 mL) 的溶液中， GC跟踪至反应完毕， 减压脱去溶剂得浅红色液体 40.7 g。  Ethyl 2-chloro-trifluoroacetoacetate at -5 to -10 ° C, slowly pass chlorine to a solution of ethyl trifluoroacetoacetate (37.0 g) and carbon tetrachloride (300 mL), GC traced to After completion of the reaction, the solvent was removed under reduced pressure to give a pale red liquid, 40.7 g.
2—乙基—4-三氟甲基噻唑 -5-甲酸乙酯 2-氯 -三氟乙酰乙酸乙酯 (21.8 g)， 硫代乙酰胺 (9.0 g)和乙醇 （200 mL) 于回流条件下反应 4-5小时。 冷却后， 将反应液倒入冰水中， 乙酸乙 酯萃取， 水洗， 无水硫酸钠干燥， 减压脱去溶剂， 得黄色液体 22.0 g。  2-ethyl-4-trifluoromethylthiazole-5-carboxylic acid ethyl ester 2-chloro-trifluoroacetoacetate ethyl ester (21.8 g), thioacetamide (9.0 g) and ethanol (200 mL) under reflux The next reaction is 4-5 hours. After cooling, the reaction solution was poured into ice water, ethyl acetate was evaporated, washed with water, dried over anhydrous sodium sulfate and evaporated
2-乙基 -4-三氟甲基噻唑 -5-甲酸 2-乙基 -4-三氟甲基噻唑 -5-甲酸乙酯 (49.0 g)溶于 300 ml乙醇中， 于室温缓慢滴加氢氧化钠 （15.4 g)和水 （78.0 g) 的溶液， 加毕后升温至回流 条件下反应 2-3小时， 冷却， 用稀盐酸调至 PH至 1〜2， 乙酸乙酯萃取， 水洗， 无水硫酸 钠干燥， 减压脱去溶剂， 得黄色液体 37.0g。  Ethyl 2-ethyl-4-trifluoromethylthiazole-5-carboxylate 2-ethyl-4-trifluoromethylthiazole-5-carboxylate (49.0 g) was dissolved in 300 ml of ethanol and slowly added dropwise at room temperature. A solution of sodium hydroxide (15.4 g) and water (78.0 g) is added. After the addition, the mixture is heated to reflux for 2-3 hours, cooled, adjusted to pH 1 to 2 with dilute hydrochloric acid, extracted with ethyl acetate and washed with water. After drying over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure to give 37.0 g.
2—乙基 -4—三氟甲基噻唑 -5—甲酰氯 在装有磁力搅拌子的三口瓶中加入 2-乙基 -4-三氟 甲基 -噻唑 -5-羧酸 （16.8 g) 和 1,2-二氯乙烷 (150mL)， 室温下滴加二氯亚砜 (11.8 g), 加毕 后回流反应 4〜5小时， 减压脱去过量溶剂和二氯亚砜得棕色液体的标题物 18.0 g。  2-ethyl-4-trifluoromethylthiazole-5-formyl chloride 2-ethyl-4-trifluoromethyl-thiazole-5-carboxylic acid (16.8 g) was added to a three-necked flask equipped with a magnetic stir bar. And 1,2-dichloroethane (150 mL), adding thionyl chloride (11.8 g) dropwise at room temperature, refluxing for 4 to 5 hours after the addition, removing excess solvent and dichlorosulfoxide to obtain a brown liquid under reduced pressure. The title of the object is 18.0 g.
N-(6-氨基 -5-硝基吡啶 -2-基) -2-乙基 -4-三氟甲基噻唑 -5-甲酰胺 （表 1中 163) 在装有磁 力搅拌子的三口瓶中加入 NaH (60% 2.0 g)和 Ν,Ν-二甲基甲酰胺（DMF) ( 80 mL), 搅拌 5 min后分批加入 2,6-二氨基 -3-硝基吡啶 (3.0 g), 室温搅拌 30 min后， 滴加 2-乙基 -4-三氟 甲基 -噻唑 -5-甲酰氯 (8.6 g；)， 室温搅拌 2-3 hr后， 将反应液倾入冰水中， 乙酸乙酯萃取， 水 洗有机相， 无水硫酸钠干燥有机相， 减压脱溶， 得黄色粘性固体， 经柱层析纯化得标题化 合物棕色固体 2.1 g。 含量 95%， 熔点 163.4-165.9°C。 实施例 7 本实施例说明表 1中化合物 168的制备方法
Figure imgf000030_0001
N-(6-Amino-5-nitropyridin-2-yl)-2-ethyl-4-trifluoromethylthiazole-5-carboxamide (163 in Table 1) in a three-necked flask equipped with a magnetic stir bar Add NaH (60% 2.0 g) and hydrazine, hydrazine-dimethylformamide (DMF) (80 mL), and stir for 5 min, then add 2,6-diamino-3-nitropyridine (3.0 g) in portions. After stirring at room temperature for 30 min, 2-ethyl-4-trifluoromethyl-thiazole-5-formyl chloride (8.6 g;) was added dropwise. After stirring at room temperature for 2-3 hr, the reaction solution was poured into ice water, acetic acid. The ethyl acetate was extracted, and the organic layer was evaporated. The content is 95%, and the melting point is 163.4-165.9 °C. EXAMPLE 7 This example illustrates the preparation of compound 168 in Table 1.
Figure imgf000030_0001
用戊酰胺代替丙酰胺，参照实施例 6中的相应方法，可以制备 N-(6-氨基 -5-硝基吡啶 -2- 基 )-2-丁基 -4-三氟甲基噻唑 -5-甲酸酰胺粘性固体。 （表 1中 168)。 Pentanamide replaced by propionamide, corresponding method of Reference Example 6, may be prepared N- (6- amino-5-nitropyridin-2-yl) - 2 - butyl-4-trifluoromethyl-thiazol-5 - Formic acid amide sticky solid. (168 in Table 1).
实施例 8 本实施例说明表 1中化合物 213的制备方法 、 Ji  EXAMPLE 8 This example illustrates the preparation of compound 213 in Table 1, Ji
Y 。
Figure imgf000030_0002
Y.
Figure imgf000030_0002
丙酰丙酮酸乙酯 冰水浴冷却条件下滴加草酸二乙酯（0.05 mol)和 2-丁酮（0.05 mol) 的混合溶液入乙醇钠 （0.06 mol) 的甲苯 （150 mL) 中。 滴毕继续于室温反应 1-3 hr后， 将反应液倒入冰水中， 盐酸调节 pH为 3左右， 分出油层， 水层用甲苯萃取， 合并有机层， 无水硫酸钠干燥， 减压脱去溶剂得油状液体丙酰丙酮酸乙酯 7.5 g  Ethyl propionylpyruvate A mixed solution of diethyl oxalate (0.05 mol) and 2-butanone (0.05 mol) was added dropwise to a sodium ethoxide (0.06 mol) in toluene (150 mL) under ice cooling. After the reaction is continued at room temperature for 1-3 hr, the reaction solution is poured into ice water, the pH is adjusted to about 3 with hydrochloric acid, the oil layer is separated, the aqueous layer is extracted with toluene, and the organic layer is combined, dried over anhydrous sodium sulfate and evaporated. Solvent to obtain oily liquid ethyl propionylpyruvate 7.5 g
1-甲基 -3-乙基 -1H-吡唑 -5-甲酸乙酯 冰浴冷却条件下， 滴力口 40%的甲基肼 (6.9 g)入丙酰丙 酮酸乙酯（7.5 g) 的无水乙醇 （50 mL)溶液中， 滴加完毕后于室温反应至完全。 反应液倾入冰 水中， 乙酸乙酯萃取， 水洗， 有机相用无水硫酸钠干燥， 减压脱溶， 得标题物 6.8 g  Ethyl 1-methyl-3-ethyl-1H-pyrazole-5-carboxylate under ice cooling conditions, 40% methylhydrazine (6.9 g) was added to ethyl propionylpyruvate (7.5 g) In a solution of absolute ethanol (50 mL), the reaction was completed at room temperature until completion. The reaction mixture was poured into ice water, ethyl acetate was evaporated, evaporated, evaporated, evaporated.
1-甲基 -3-乙基 -4-氯 -1H-吡唑 -5-甲酸乙酯 冰浴冷却条件下， 滴加磺酰氯（5.4 g)入 1- 甲基 -3-乙基 -1H-吡唑 -5-甲酸乙酯 （6.8 g) 的氯仿 （100 mL)溶液中， 滴毕， 缓慢升温至回 流条件反应 0.5-2.0 hr。 冷却后， 反应液倾入冰水中， 分出有机层， 水层用氯仿萃取， 合并 有机层， 无水硫酸钠干燥后， 减压脱去氯仿， 得标题物 6. 4 g  1-methyl-3-ethyl-4-chloro-1H-pyrazole-5-carboxylic acid ethyl ester was added dropwise with sulfonyl chloride (5.4 g) in 1-methyl-3-ethyl-1H under ice cooling. -Pyrazole-5-carboxylic acid ethyl ester (6.8 g) in chloroform (100 mL) was added dropwise, and the temperature was slowly raised to reflux conditions for 0.5-2.0 hr. After cooling, the reaction mixture was poured into ice water, the organic layer was separated, and the aqueous layer was evaporated, evaporated, evaporated, evaporated.
1-甲基 -3-乙基 -4-氯 -1H-吡唑 -5-甲酸 1-甲基 -3-乙基 -4-氯 -1H-吡唑 -5-甲酸乙酯 （6.4 g) 在 20%的 NaOH水溶液 C25 mL)回流反应 0.5-1.0 hr。 冷却后， 将反应液中倒入冰水中， 用 稀盐酸调节 pH为 3左右， 有固体析出， 过滤， 水洗， 干燥， 得固体标题物 5.1 g  1-methyl-3-ethyl-4-chloro-1H-pyrazole-5-carboxylic acid 1-methyl-3-ethyl-4-chloro-1H-pyrazole-5-carboxylic acid ethyl ester (6.4 g) The reaction was refluxed in a 20% aqueous NaOH solution (25 mL) for 0.5-1.0 hr. After cooling, the reaction solution was poured into ice water, and the pH was adjusted to about 3 with dilute hydrochloric acid. A solid precipitated, filtered, washed with water and dried to give a solid title product: 5.1 g
1-甲基 -3-乙基 -4-氯 -1H-吡唑 -5-甲酸酰氯 参照实施例 1中合成酰氯的方法进行合成。 N-(6-氨基 -5-硝基吡啶 -2-基) - 1-甲基 -3-乙基 -4-氯 -1H-吡唑 -5-甲酸酰胺 （(表 1中 213) ) 在 100 mL三口瓶中加入 2,6-二氨基 -3-硝基吡啶 （10 mmol) 和四氢呋喃 (50 mL), 搅拌条 件下分批加入 NaH (25 mmol)， 室温搅拌 30 min后， 冷却至 0 5 °C， 滴加 1-甲基 -3-乙基 -4-氯 -1H-吡唑 -5-甲酰氯 （lO mmol), 滴毕， 室温反应 2-4 hr后， 停止反应。 反应液倒入冰 水中， 乙酸乙酯萃取， 水洗， 有机层用无水硫酸钠干燥， 减压脱去溶剂， 得粗产物。 经柱 层析纯化得标题化合物淡黄色固体 1.06 g。 熔点 189.9 190.5 °C  1-Methyl-3-ethyl-4-chloro-1H-pyrazole-5-carboxylic acid chloride The synthesis was carried out by the method of synthesizing an acid chloride in Example 1. N-(6-Amino-5-nitropyridin-2-yl)-1-methyl-3-ethyl-4-chloro-1H-pyrazole-5-carboxylic acid amide ((213 in Table 1)) Add 2,6-diamino-3-nitropyridine (10 mmol) and tetrahydrofuran (50 mL) to a 100 mL three-necked flask. Add NaH (25 mmol) in portions, stir at room temperature for 30 min, then cool to 0. At 5 ° C, 1-methyl-3-ethyl-4-chloro-1H-pyrazole-5-formyl chloride (10 mmol) was added dropwise, and the reaction was stopped after 2-4 hr at room temperature. The reaction mixture was poured into ice water, ethyl acetate was evaporated and evaporated. The title compound was obtained as a pale yellow solid. Melting point 189.9 190.5 °C
实施例 9 制备悬浮剂  Example 9 Preparation of Suspending Agent
先将 2-6%的润湿分散剂稀释于 4-10%的防冻剂中， 并向该溶液中缓缓加入一定量的 水， 然后在高速剪切刀搅拌下， 依次加入 5-80%的本发明提供的式 （I) 活性化合物， 0.01-0.05%防腐剂， 0.01-0.05%消泡剂和增稠剂等。最后倾入砂磨机中进行碾磨， 再加入溶 剂至体积。 使用时可用水稀释至所需任何浓度。 First dilute 2-6% of the wetting and dispersing agent in 4-10% antifreeze, and slowly add a certain amount to the solution. Water, then, under stirring with a high speed shearing knife, 5-80% of the active compound of the formula (I) provided by the present invention, 0.01-0.05% preservative, 0.01-0.05% antifoaming agent and thickener, and the like are sequentially added. Finally, it is poured into a sand mill for milling, and then the solvent is added to the volume. Dilute with water to any concentration required.
实施例 10 制备浓缩乳剂  Example 10 Preparation of a concentrated emulsion
先将一定配比的水、 表面活性剂、 抗冻剂、 消泡剂、 ±曾稠剂和防腐剂混合在一起组成均一水 相， 然后将本发明提供的式 )化合物、 溶剂以及乳化剂、 共乳化剂混合使其成为均匀油相。 最后在高速搅拌下将均匀油相与水相混合即可制成浓缩乳剂。使用时可用水稀释至所需 fti可浓度。  First, a certain proportion of water, surfactant, antifreeze, antifoaming agent, ± thickener and preservative are mixed together to form a uniform aqueous phase, and then the compound, solvent and emulsifier of the formula provided by the present invention, The co-emulsifier is mixed to make it a homogeneous oil phase. Finally, the homogeneous oil phase is mixed with the water phase under high-speed stirring to prepare a concentrated emulsion. Dilute with water to the desired concentration of fti.
实施例 11 制备可湿性粉剂  Example 11 Preparation of a wettable powder
先将一定配比的水、 表面活性剂、 抗冻剂、 消泡剂、 ±曾稠齐 U和防腐剂混合在一起组成均一水 相， 然后将本发明提供的式 )化合物、 溶剂以及乳化剂、 共乳化剂混合使其成为均匀油相。 最后在高速搅拌下将均匀油相与水相混合即可制成浓缩乳剂。使用时可用水稀释至所需 fti可浓度。  First, a certain proportion of water, surfactant, antifreeze, antifoaming agent, ±Zengduqi U and preservative are mixed together to form a uniform aqueous phase, and then the compound, solvent and emulsifier of the formula provided by the invention are provided. The co-emulsifier is mixed to make it a homogeneous oil phase. Finally, the homogeneous oil phase is mixed with the water phase under high-speed stirring to prepare a concentrated emulsion. Dilute with water to the desired concentration of fti.
实施例 12 制备乳油： 将 10 (重量计） 本发明提供的 （I) 化合物， 80释剂如二甲苯 和 10宜助剂均匀混合即可制备乳油， 用水稀释即可施用 (活性化合物含量为 10%)。  Example 12 Preparation of emulsifiable concentrate: 10 (by weight) of the compound (I) provided by the present invention, 80 release agent such as xylene and 10 auxiliaries can be uniformly mixed to prepare an emulsifiable concentrate, which can be applied by dilution with water (active compound content is 10 %).
实施例 13 制备可湿性粉剂： 将 20份 （以重量计） 本发明提供的噻唑甲胺基吡啶类 化合物， 53份粘土， 20份白炭黑， 5份木素硅酸盐和 2份聚氧乙基烷基醚混合磨成细粉即 可制得可湿性粉剂 (活性化合物含量为 20%)。  Example 13 Preparation of a wettable powder: 20 parts by weight of the thiazolylmethine pyridine compound provided by the present invention, 53 parts of clay, 20 parts of white carbon black, 5 parts of lignin silicate and 2 parts of polyoxygen A wettable powder (active compound content of 20%) can be obtained by mixing and grinding an ethyl alkyl ether into a fine powder.
实施例 14 N-(6-氨基 -5-硝基吡啶 -2-基) -2-乙基 -4-三氟甲基噻唑 -5-甲酰胺 10%浮油制备 称取适量 （按重量百分比 10%) 的本发明提供的式 （I) 化合物： N-(6-氨基 -5-硝基吡 啶 -2-基;) -2-乙基 -4-三氟甲基噻唑 -5-甲酰胺、 适量的助溶剂 （乙酸乙酯）、 适量的农药用助 剂及溶剂 （甲苯）等放入反应釜， 先加入一定量的溶剂 （甲苯）和消泡剂搅拌 10〜30min， 再加入适量的稳定剂、 增效剂、 穿透剂等组分， 继续搅拌 10〜30min， 调节 PH值， 再将 有效量的溶剂投入釜内，搅拌均匀后放料即得 N-(6-氨基 -5-硝基吡啶 -2-基) -2-乙基 -4-三氟甲 基噻唑 -5-甲酸酰胺 10%乳油。  Example 14 Preparation of N-(6-amino-5-nitropyridin-2-yl)-2-ethyl-4-trifluoromethylthiazole-5-carboxamide 10% slick oil. 10%) of the compound of formula (I) provided by the present invention: N-(6-amino-5-nitropyridin-2-yl;)-2-ethyl-4-trifluoromethylthiazole-5-carboxamide Add appropriate amount of cosolvent (ethyl acetate), appropriate amount of pesticide auxiliary and solvent (toluene) to the reaction kettle, first add a certain amount of solvent (toluene) and defoamer for 10~30min, then add appropriate amount Stabilizer, synergist, penetrant and other components, continue to stir for 10~30min, adjust the PH value, then put an effective amount of solvent into the kettle, stir evenly and then release the material to get N-(6-amino-5- Nitropyridin-2-yl)-2-ethyl-4-trifluoromethylthiazole-5-carboxylic acid amide 10% emulsifiable concentrate.
生测实施例  Biometric example
对所合成化合物进行了杀菌、 杀虫、 杀螨和除草活性试验， 部分实验结果如下。  The synthesized compounds were tested for bactericidal, insecticidal, acaricidal and herbicidal activities, and some of the experimental results are as follows.
实施例 15 对小麦赤霉病菌 Gibberella薩 的杀菌活性  Example 15 Bactericidal activity against Gibberella sinensis
方法如下： 待测化合物溶于适宜溶剂如 Ν,Ν-二甲基甲酰胺 （DMF) 中， 再用含 0.1% Tween80乳化剂的无菌水稀释至所需浓度；用移液管取 3mL药液加入冷却至 45 °C的 27mL 的马铃薯琼脂培养基 （PDA) 中并充分摇匀后倒入培养皿； 冷却后用接种针从培养 7天的 病菌菌落边缘取 6mm直径菌丝块， 移至培养皿中央， 菌丝面朝下， 同时设不含待测化合 物的空白为对照， 每处理 4次重复； 处理完毕后将培养皿置于 28°C的恒温生化培养箱中培 养， 4天后测量菌丝生长直径，采用 EXCEL统计软件进行分析并计算菌丝生长抑制率(％)。 活性相对于空白对照以百分比计， 分为 A、 B、 C、 D四级， 100% ^抑制率 ^ 90%为 A级， 90% >抑制率^ 70%为 B级， 70% >抑制率^ 50%为 C级， 50% >抑制率^ 0%为 D级。 The method is as follows: The test compound is dissolved in a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF), and then diluted to the desired concentration with sterile water containing 0.1% Tween 80 emulsifier; 3 mL of the drug is taken with a pipette The solution was added to 27 mL of potato agar medium (PDA) cooled to 45 ° C and shaken well, then poured into a Petri dish; after cooling, a 6 mm diameter hyphae was taken from the edge of the bacterial colony for 7 days with an inoculating needle, and moved to In the center of the culture dish, the hyphae face down, and the blank containing no test compound is used as a control, and each treatment is repeated 4 times. After the treatment, the culture dish is placed in a constant temperature biochemical incubator at 28 °C. The mycelial growth diameter was measured after 4 days, and analyzed by EXCEL statistical software and the mycelial growth inhibition rate (%) was calculated. Activity is divided into A, B, C, and D levels in percentages relative to the blank control, 100% ^ inhibition rate ^ 90% is grade A, 90% > inhibition rate ^ 70% is grade B, 70% > inhibition rate ^ 50% is C grade, 50% > inhibition rate ^ 0% is D grade.
采用上述测定方法，分别测定了所合成化合物对辣椒疫霉病菌 (/^ytop/^/zora ca/A«'c 、 烟草赤星病菌 (.Alternaria alternata ) 黄瓜灰霉病菌 (.Botrytis cinerea )^ 油菜菌核病菌 ( Sclerotonia sclerotiorum ) 苹果轮纹病菌 (Botryosphaeria berengrianaf.sp piricola )、苹果 腐烂病菌 fQyto^ora ^. J的杀菌活性。 部分测试结果见表 3〜表 5。  Using the above determination method, the synthesized compounds were tested for Phytophthora capsici (/^ytop/^/zora ca/A«'c, Tobacco brown spot disease (.Alternaria alternata), Botrytis cinerea, rapeseed The bactericidal activity of Sclerotonia sclerotiorum (Botryosphaeria berengrianaf.sp piricola) and apple rot pathogen fQyto^ora ^. J. Some test results are shown in Table 3 to Table 5.
表 3 部分化合物在 25 mg/L浓度下对小麦赤霉病菌和辣椒疫霉病菌等的活性 化合物 06 10 11 14 16 18 23 37 39 41 43 44 48 小麦赤霉病菌 D D A A C D D A D D D A D 辣椒疫霉病菌 B D A D D D D A C D A B D 烟草赤星病菌 D D D D D D D D D D D D D 黄瓜灰霉病菌 D B C D D D B D D C C D D 油菜菌核病菌 B C C D C C A C C B B D C 化合物 49 52 54 57 61 62 64 66 68 76 78 79 80 小麦赤霉病菌 A A D D A A D A A D D D A 辣椒疫霉病菌 A A D D A A D A B D D C C 烟草赤星病菌 D D D D D D D D D D D C D 黄瓜灰霉病菌 D D B D D D C D D D C B D 油菜菌核病菌 B D A C D C B D D B B A B 化合物 83 85 89 90 115 116 134 135 139 140 141 143 146 小麦赤霉病菌 D B D A D D C A D A A D B 辣椒疫霉病菌 D D D A D D c A D A D D D 烟草赤星病菌 D D D D D D D D D D D C D 黄瓜灰霉病菌 D D D D C C D C D D D D D 油菜菌核病菌 C D A B D D D A B A D B D 化合物 148 150 151 152 154 155 156 157 158 159 160 161 163 小麦赤霉病菌 A A A A A A B D B A D C A 辣椒疫霉病菌 D D B D D C A B C A D c A 烟草赤星病菌 D D D D D D D D D D D D D 黄瓜灰霉病菌 C D D D D D D D D D D D C 油菜菌核病菌 A D A B B B D D C B C C A 化合物 164 165 167 168 169 170 189 192 193 199 206 213 214 小麦赤霉病菌 A A A A A B D D A D A A B 辣椒疫霉病菌 D A A A B D D D D D A A C 烟草赤星病菌 D D D D D B D D D C D D D 黄瓜灰霉病菌 D C D C C B D D C B D D D 油菜菌核病菌 B B B B A B B B B A C D D  Table 3 Active compounds of some compounds against Fusarium graminearum and Phytophthora capsici at 25 mg/L 06 10 11 14 16 18 23 37 39 41 43 44 48 Fusarium graminearum DDAACDDADDDAD Phytophthora capsici BDADDDDACDABD Tobacco red star Pathogen DDDDDDDDDDDDD Botrytis cinerea DBCDDDBDDCCDD Sclerotinia sclerotiorum BCCDCCACCBBDC Compound 49 52 54 57 61 62 64 66 68 76 78 79 80 Fusarium oxysporum AADDAADAADDDA Phytophthora capsici AADDAADABDDCC Tobacco brown spot disease DDDDDDDDDDDCD Cucumber botrytis DDBDDDCDDDCBD Brassica sclerotium BDACDCBDDBBAB Compound 83 85 89 90 115 116 134 135 139 140 141 143 146 Fusarium graminearum DBDADDCADAADB Phytophthora capsici DDDADD c ADADDD Tobacco brown spot disease DDDDDDDDDDDCD Cucumber botrytis DDDDCCDCDDDDD Sclerotinia sclerotiorum CDABDDDABADBD Compound 148 150 151 152 154 155 156 157 158 159 160 161 163 Wheat Red AAAAAABDBADCA Phytophthora capsici DDBDDCABCAD c A Tobacco brown spot disease DDDDDDDDDDDDD Cucumber gray mold pathogen CDDDDDDDDDDDC Sclerotinia sclerotiorum ADABBBDDCBCCA Compound 164 165 168 168 169 170 189 192 193 199 206 213 214 Fusarium oxysporum AAAAABDDADAAB Phytophthora capsici DAAABDDDDDAAC Tobacco brown spot DDDDDBDDDCDDD Cucumber gray mold DCDCCBDDCBDDD Brassica sclerotium BBBBABBBBACDD
表 4 部分化合物在 2.5 mg/L浓度下对小麦赤霉病菌和辣椒疫霉病菌的活性 化合物 11 52 62 66 68 135 148 151 小麦赤霉病菌 A A A A A A A A 辣椒疫霉病菌 D D A A D A D B 化合物 159 163 165 167 168 169 213  Table 4 Active compounds of some compounds against Fusarium oxysporum and Phytophthora capsici at a concentration of 2.5 mg/L 11 52 62 66 68 135 148 151 Fusarium oxysporum AAAAAAAA Phytophthora capsici DDAADADB Compound 159 163 165 167 168 169 213
小麦赤霉病菌 B A B A A A A  Fusarium graminearum B A B A A A A
辣椒疫霉病菌 A A A A C C A 表 5 部分化合物在 2.5 mg/L浓度下对苹果轮纹病菌等的活性 小麦赤霉病菌 A A APhytophthora capsici AAAACCA Table 5 Active Scab AAA of some compounds against apple ringworm at 2.5 mg/L
―、、、、靈、 謹、、、、、、、、、— ―^^^^^^^ ―,,,,,,,,,,,,,,,,,,, ——^^^^^^^
实施例 16 对稻纹枯病菌 Rhizoctonia solanO 的杀菌活性 （离体叶片培养法） 方法如下： 待测化合物溶于适宜溶剂如 Ν,Ν-二甲基甲酰胺 （DMF ) 中， 再用含 0.1% TweenSO乳化剂的无菌水稀释至所需浓度； 取新鲜、 幼嫩的蚕豆幼苗植株叶片经一定浓度 的药剂处理后平放在铺有含水滤纸的培养皿内， 叶片与滤纸用自制打孔铁架相隔。 叶片晾 干后接上直径为 6mm， 培养 2~3天的新鲜菌丝块。每处理 3次重复， 另设不含待测化合物 的空白为对照， 保湿适温培养至空白对照发病后， 检查病斑面积， 计算药剂防效。 活性相 对于空白对照以百分比计， 分为 A、 B、 C、 D四级， 100% ^防效^ 90%为 A级， 90%> 防效^ 70%为 B级， 70%>防效^ 50%为 C级， 50%>防效^ 0%为 D级。 结果表明本发明 的化合物对水稻纹枯病具有防治效果， 部分结果如表 6。  Example 16 Bactericidal activity against Rhizoctonia solanO (ex vivo leaf culture method) The method is as follows: The test compound is dissolved in a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF), and 0.1 The sterile water of % TweenSO emulsifier is diluted to the required concentration; the leaves of fresh and young broad bean seedlings are treated with a certain concentration of the drug and placed in a petri dish coated with aqueous filter paper. The leaves and filter paper are made with homemade perforation. The iron frames are separated. After drying the leaves, connect the fresh hyphae with a diameter of 6 mm and culture for 2 to 3 days. Each treatment was repeated 3 times, and a blank containing no test compound was set as a control. After moisturizing and warming culture until the onset of the blank control, the area of the lesion was examined and the drug control effect was calculated. The activity is divided into A, B, C, and D levels according to the percentage of the blank control, 100% ^ control effect 90% is A grade, 90% > control effect ^ 70% is grade B, 70% > control effect ^ 50% is C grade, 50%> control effect ^ 0% is D grade. The results show that the compound of the present invention has a control effect against rice sheath blight, and some of the results are shown in Table 6.
表 6 部分化合物在 500 mg/L浓度下对水稻纹枯病的防效  Table 6 Effect of some compounds on rice sheath blight at a concentration of 500 mg/L
化合物 18 61 136 151 159 166 168 活性级别 A C C C C C A  Compound 18 61 136 151 159 166 168 Activity level A C C C C C A
实施例 17 对稻纹枯病菌 Rhizoctonia solan 的杀菌活性 （盆栽法）  Example 17 Bactericidal activity against Rhizoctonia solana (potted method)
方法如下： 待测化合物溶于适宜溶剂如 Ν,Ν-二甲基甲酰胺 （DMF ) 中， 再用含 0.1% TweenSO乳化剂的无菌水稀释至所需浓度； 取直茎 15 cm左右的盆钵， 每钵播种水稻饱满健 壮的种子 15粒， 待长出二叶一心后供试验用； 取准备好的水稻幼苗植株经一定浓度的药剂喷 雾处理， 一天后进行病菌悬浮液接种。 每处理 3次重复， 另设不含待测化合物的空白为对照， 保湿适温培养至空白对照发病后， 检查病斑面积， 计算药剂防效。 为便于比较设商品化杀菌 剂井岗霉素为对照药剂进行对照。 结果表明本发明的化合物对水稻纹枯病具有防治效果， 且 优于同等剂量下的商品化杀菌剂井岗霉素。 如在 100 mg/L和 200 mg/L浓度下， 化合物 168 对水稻纹枯病的防效均大于 80%， 而井岗霉素对水稻纹枯病的防效均在 80%以下。  The method is as follows: The test compound is dissolved in a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF), and diluted with a sterile water containing 0.1% TweenSO emulsifier to the desired concentration; Potted oysters, 15 seeds of full-bodied and vigorous seeds per rice, to be tested after growing two leaves and one heart; the prepared rice seedling plants are sprayed with a certain concentration of the drug, and the disease suspension is inoculated one day later. Each treatment was repeated 3 times, and a blank containing no test compound was set as a control. After moisturizing and warming culture until the onset of the blank control, the area of the lesion was examined, and the drug control effect was calculated. In order to compare and compare the commercial bactericide jinggangmycin as a control agent for comparison. The results show that the compound of the present invention has a control effect against rice sheath blight, and is superior to the commercial fungicide Jinggangmycin at the same dose. For example, at the concentrations of 100 mg/L and 200 mg/L, the control effect of compound 168 on rice sheath blight was more than 80%, and the control effect of Jinggangmycin on rice sheath blight was below 80%.
实施例 18 对小麦白粉病菌 （Erisiphe griminis ) 的杀菌活性 （盆栽法）  Example 18 Bactericidal activity against wheat white powder pathogen (Erisiphe griminis) (pot method)
方法如下： 待测化合物溶于适宜溶剂如 Ν,Ν-二甲基甲酰胺 （DMF ) 中， 再用含 0.1% TweenSO乳化剂的无菌水稀释至所需浓度； 取直茎 15 cm左右的盆钵， 每钵播种小麦饱满 健壮的种子 20粒， 待长出二叶一心后供试验用； 取准备好的小麦幼苗植株经一定浓度的 药剂喷雾处理， 一天后进行病菌接种。 每处理 3次重复， 另设不含待测化合物的空白为对 照， 保湿适温培养至空白对照发病后， 检查病斑面积， 计算药剂防效。 活性相对于空白对 照以百分比计， 分为 A、 B、 C、 D四级， 100% ^防效^ 90%为 A级， 90%>防效^ 70%为 B级， 70%>防效^ 50%为 C级， 50%>防效^ 0%为 D级。 结果表明本发明的化合物对小 麦白粉病具有防治效果， 部分结果如表 7。 The method is as follows: The test compound is dissolved in a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF), and diluted with a sterile water containing 0.1% TweenSO emulsifier to the desired concentration; Potted oysters, 20 seeds of wheat full and healthy seeds per sputum, to be tested after growing two leaves and one heart; the prepared wheat seedling plants are sprayed with a certain concentration of the drug, and the bacteria are inoculated one day later. Each treatment was repeated 3 times, and a blank containing no test compound was set as a control. After moisturizing and warming culture until the onset of the blank control, the area of the lesion was examined, and the drug control effect was calculated. The activity is divided into A, B, C, and D levels based on the percentage of the blank control, 100% ^ control effect 90% is A grade, 90%> control effect ^ 70% Grade B, 70%> Control effect ^ 50% is C grade, 50% > Control effect ^ 0% is D grade. The results show that the compound of the present invention has a control effect against wheat powdery mildew, and some of the results are shown in Table 7.
表 7 部分化合物在 500 mg/L浓度下对小麦白粉病的防效  Table 7 Effect of some compounds on wheat powdery mildew at 500 mg/L
化合物 09 23 29 61 68 89 136 139 活性级别 C B B A A B C B 化合物 140 141 142 144 145 146 147 152 活性级别 C C B C C B C B 实施例 19 除草活性评价  Compound 09 23 29 61 68 89 136 139 Activity Level C B B A A B C B Compound 140 141 142 144 145 146 147 152 Activity Level C C B C C B C B Example 19 Evaluation of Herbicidal Activity
方法如下： （1 ) 在截面积 64cm2的塑料盆钵中定量装土压平， 置于不锈钢盆中， 选取 籽粒饱满、大小一致的种子，分单子叶杂草【马唐 (Digitaria sanguinalis X稗草 ( Echinochloa crus-galliX 狗尾草 (Setaria viridis Ά禾口双子叶杂草【苘麻 (Abutilon theophrasti )、 朿 lj苋 (Amaranthus spinosus )、 藜 (Chenopodium album \分鉢播禾中， 各占鉢面禾只的 1/3 , 覆 1cm 厚细土， 从塑料盆钵底部加水至上层土壤浸润， 置于温室培养， 待试材长至所需叶龄进行试验 处理； （2)称取适量本发明提供的具有生物活性的 N-吡啶 （杂） 芳酰胺类化合物， 以 N， N- 二甲基甲酰胺溶解， 再加入少量吐温 80乳化剂， 搅拌均匀， 加入定量清水， 配制成所需浓度， 设相应溶剂和清水为对照； （3 )处理方式： 试材播种次日进行苗前土壤处理， 单子叶试材长至 1叶 1心期、 双子叶试材长至 2片真叶期进行苗后茎叶处理； （4)按设置剂量定量移取药液进 行茎叶喷雾和土壤喷雾处理，分别以喷雾溶剂和清水为对照； （5 )处理试材置于温室培养； (6) 处理 15-25天后目测地上部生长情况，根据调查结果，按以下公式计算各化合物对杂草的防效: 防效（％) =100 (对照株高 -处理株高） I对照株高； （7)根据防效进行除草活性分级： 100% ^ 防效^ 90%为 A级， 90%>防效^ 75%为 B级， 75%>防效^ 50%为 C级， 50%>防效^ 25% 为 D级， 25%>防效^ 0%为 E级。结果表明本发明化合物对杂草具有活性， 如化合物 40、 49、 67等在 2250 g a.i./ha浓度对阔叶杂草苘麻、 剌苋和藜茎叶处理均具有 A级除草活性； 化合物 40、 49、 67等在 2250 g a.i./ha浓度对阔叶杂草剌苋和藜土壤处理均具有 A级除草活性， 49在 2250 g a.i./ha浓度对阔叶杂草苘麻土壤处理也具有 A级除草活性； 化合物 49等在 375 g a.i./ha 浓度下对阔叶杂草苘麻、 剌苋和藜茎叶处理仍均具有 A级除草活性， 对阔叶杂草剌苋和藜土 壤处理仍均具有 A级除草活性。 有的化合物则对单子叶杂草表现出活性， 如 59等在 2250 g a.i./ha浓度对单子叶杂草马唐、 稗草和狗尾草茎叶处理均具有 A级除草活性。 The method is as follows: (1) Quantitatively compacting the soil in a plastic pot with a cross-sectional area of 64 cm 2 and placing it in a stainless steel pot. Select seeds with full grain size and uniform size, and divide the monocotyledon weeds [Digitaria sanguinalis X稗] Grass (Echinochloa crus-galliX foxtail (Setaria viridis 双 口 双 双 Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab Ab 1/3, covering 1cm thick fine soil, adding water from the bottom of the plastic pot to the upper layer of soil infiltration, placed in the greenhouse for cultivation, and the test material is grown to the required leaf age for testing; (2) Weighing the appropriate amount of the present invention Biologically active N-pyridine (hetero) aramid compound, dissolved in N, N-dimethylformamide, add a small amount of Tween 80 emulsifier, stir evenly, add quantitative water, prepare the desired concentration, set The corresponding solvent and clean water are used as a control; (3) Treatment method: The soil material is pre-emergence on the next day of the test material sowing. The monocotyledonous test material grows to 1 leaf 1 heart stage, and the dicotyledon test material grows to 2 true leaf stage for post-emergence Stem and leaf (4) Quantitatively take the liquid medicine according to the set dose for stem and leaf spray and soil spray treatment, respectively, with spray solvent and water as the control; (5) Treat the test material in greenhouse culture; (6) Visually after 15-25 days of treatment According to the survey results, the control effect of each compound on weeds was calculated according to the following results: Control effect (%) = 100 (control plant height - treated plant height) I control plant height; (7) According to control effect Herbicidal activity classification: 100% ^ Control effect 90% A grade, 90%> Control effect 75% B grade, 75%> Control effect 50% C grade, 50%> Control effect 25% D Grade, 25%>control effect^0% is grade E. The results show that the compounds of the invention are active against weeds, such as compounds 40, 49, 67, etc. at a concentration of 2250 g ai/ha against broadleaf weeds, ramie Both the treatment and the stem and leaf treatment have A-level herbicidal activity; the compounds 40, 49, 67, etc. have A-level herbicidal activity on the broad-leaved weeds and alfalfa soil at 2250 g ai/ha, 49 at 2250 g ai/ The concentration of ha also has a class A herbicidal activity on broadleaf weed ramie soil treatment; compound 49 et al. at 375 g ai/ha concentration on broadleaf weeds ramie, alfalfa and stalk leaves The treatment still has Class A herbicidal activity, and still has Class A herbicidal activity for broadleaf weeds and alfalfa soil treatment. Some compounds show activity against monocotyledonous weeds, such as 59 at 2250 g ai/ha The concentration has a class A herbicidal activity on the treatment of monocotyledonous weed crabgrass, valerian and foxtail stems and leaves.
实施例 20 对粘虫 Mythimna separated 的生物活性评价  Example 20 Evaluation of Biological Activity of Mythimna separated Mythimna
Potter 喷雾法： 称取适量本发明提供的 N-吡啶 （杂） 芳酰胺类化合物， 以 N， N- 二甲基甲酰胺溶解， 再加入少量吐温 80 乳化剂， 搅拌均匀， 加入定量清水， 配制成所需 浓度， 设清水为对照。 取鲜嫩的玉米叶剪成大小基本一致的片段， 放入事先垫有滤纸的培 养皿 （<K90mm) 中。 然后在皿中接入粘虫 3龄幼虫 10头， 放到 Potter喷雾塔下进行定量 喷雾， 喷药液量 lml， 每浓度 3次重复。 处理完毕， 盖上皿盖， 置于恢复室内培养， 定期 观察， 于 72小时后检查记录试虫死亡情况， 计算死亡率 （％)， 结果取平均值。 活性相对 于空白对照以百分比计， 分为 A、 B、 C、 D四级， 100% ^死亡率 ^ 90%为 A级， 90%> 死亡率 ^ 70%为 B级， 70%>死亡率 ^ 50%为 C级， 50%>死亡率 ^ 0%为 D级。 结果表明 本发明的化合物对粘虫具有杀虫活性， 如在 1000 mg/L浓度， 化合物 179和 218等对粘虫 具有 A级活性， 化合物 80等对粘虫具有 B级活性。 Potter spray method: Weigh the appropriate amount of the N-pyridine (hetero) aramid compound provided by the invention, dissolve it with N, N-dimethylformamide, add a small amount of Tween 80 emulsifier, stir evenly, add quantitative water, Formulated to the required concentration, set clear water as a control. Take the fresh corn leaves and cut them into pieces of the same size, and put them into the filter paper with the filter paper in advance. In the dish (<K90mm). Then, 10 pieces of 3rd instar larvae of the armyworm were placed in the dish, and placed under the Potter spray tower for quantitative spraying. The amount of the spray liquid was 1 ml, and the concentration was repeated 3 times. After the treatment was completed, the lid was placed, placed in a recovery chamber, and observed regularly. After 72 hours, the death of the test insects was recorded, and the mortality (%) was calculated. The results were averaged. Activity is divided into A, B, C, and D levels in percentages relative to the blank control, 100% ^ mortality ^ 90% is grade A, 90% > mortality ^ 70% is grade B, 70% > mortality ^ 50% for grade C, 50% > mortality ^ 0% for grade D. The results indicate that the compound of the present invention has insecticidal activity against armyworms, for example, at a concentration of 1000 mg/L, compounds 179 and 218 have class A activity against armyworm, and compound 80 has class B activity against armyworm.
实施例 21 对豆蚜 （Aphis fabae) 的杀虫活性评价  Example 21 Evaluation of insecticidal activity against soybean meal (Aphis fabae)
方法如下： 称取适量本发明提供的式（I)化合物， 以合适溶剂如 N， N-二甲基甲酰胺 溶解， 再加入少量吐温 80 乳化剂， 搅拌均匀， 加入定量清水， 配制成所需浓度， 设清水 为对照。 将豆蚜接于刚出土的豆苗上， 每株接 20头以上， 然后将豆苗连同试虫一起浸于 本发明提供的式 （I) 药液药液中， 5秒钟后取出， 吸去多余药液， ***吸水的海棉中， 用 玻管罩住， 24小时后检查存活和死亡虫数。 重复 3次， 结果取平均值。 活性相对空白对照 以百分比计， 分为 A、 B、 C、 D四级， 100% ^死亡率 ^ 90%为 A级， 90%>死亡率 ^ 70% 为 B级， 70%>死亡率 ^ 50%为 C级， 50%>死亡率 ^ 0%为 D级。 结果表明本发明的化合 物对豆蚜具有活性， 部分结果见表 8。  The method is as follows: Weigh an appropriate amount of the compound of the formula (I) provided by the present invention, dissolve it in a suitable solvent such as N, N-dimethylformamide, add a small amount of Tween 80 emulsifier, stir evenly, add quantitative water, and prepare a solution. The concentration is required, and the water is set as the control. The soybean meal is attached to the newly unearthed bean seedlings, and each plant is connected with more than 20 heads. Then, the bean seedlings are immersed together with the test insects in the liquid medicine of the formula (I) provided by the present invention, and taken out after 5 seconds, sucked. Remove the excess liquid, insert it into the absorbent sponge, cover it with a glass tube, and check the number of surviving and dead insects after 24 hours. Repeat 3 times and the results are averaged. Activity relative to blank control, divided into A, B, C, D, 4%, 100% ^ mortality ^ 90% for grade A, 90% > mortality ^ 70% for grade B, 70% > mortality ^ 50% is C grade, 50%> mortality ^ 0% is grade D. The results showed that the compounds of the present invention were active against soybean meal, and some of the results are shown in Table 8.
部分化合物在 500 mg/L浓度下对豆蚜的杀虫的活性 (％)  Insecticidal activity of some compounds against soybean meal at a concentration of 500 mg/L (%)
化合物 01 04 37 44 78 82 114 136 142 活性级别 C C B B B C C A C 化合物 148 149 150 159 160 167 187 201  Compound 01 04 37 44 78 82 114 136 142 Activity level C C B B B C C A C Compound 148 149 150 159 160 167 187 201
活性级别 C B C B C A B A  Activity level C B C B C A B A
实施例 22 对棉红蜘蛛 Tetranychus urticae 的杀螨活性  Example 22 Acaricidal activity against the cotton red spider Tetranychus urticae
方法如下： 称取适量本发明提供的式（I)化合物， 以合适溶剂如 N， N-二甲基甲酰胺 溶解， 再加入少量吐温 80 乳化剂， 搅拌均匀， 加入定量清水， 配制成所需浓度， 设清水 为对照。 选择长势良好的豆苗接种红蜘蛛， 待红蜘蛛定殖后， 将带螨豆苗剪下于配制好的 药液中浸渍 10秒， 取出用滤纸吸去多余的药液， 插于盛水烧杯中， 于观察室内培养， 24 小时后检查存活和死亡螨数， 每株豆苗上有 100-200个螨。 实验重复 3次。 结果取平均值。 活性相对于空白对照以百分比计， 分为 A、 B、 C、 D四级， 100% ^死亡率 ^ 90%为 A级， 90% >死亡率 ^ 70%为 B级， 70% >死亡率 ^ 50%为 C级， 50%>死亡率 ^ 0%为 D级。 结 果表明本发明的化合物对棉红蜘蛛具有活性， 如在 500 mg/L浓度下， 化合物 06和 187等 对棉红蜘蛛具 B级活性， 化合物 09和 10对棉红蜘蛛具有 C级活性。  The method is as follows: Weigh an appropriate amount of the compound of the formula (I) provided by the present invention, dissolve it in a suitable solvent such as N, N-dimethylformamide, add a small amount of Tween 80 emulsifier, stir evenly, add quantitative water, and prepare a solution. The concentration is required, and the water is set as the control. Choose a good bean sprout to inoculate red spider. After the spider is colonized, cut the bean seedlings into the prepared liquid for 10 seconds. Remove the excess liquid from the filter paper and insert it into the water beaker. In the observation room culture, the number of survival and death sputum was checked after 24 hours, and there were 100-200 cockroaches per bean seedling. The experiment was repeated three times. The results were averaged. Activity is divided into A, B, C, and D levels in percentages relative to the blank control, 100% ^ mortality ^ 90% is grade A, 90% > mortality ^ 70% is grade B, 70% > mortality ^ 50% for grade C, 50% > mortality ^ 0% for grade D. The results indicate that the compound of the present invention is active against cotton spider mites, for example, at a concentration of 500 mg/L, compounds 06 and 187 have class B activity against cotton red spiders, and compounds 09 and 10 have class C activity against cotton spider mites.

Claims

权 利 要 求 Rights request
1、 N-吡啶 （杂） 芳酰胺类化合物， 其特征在于用通式 （I) 表示：
Figure imgf000036_0001
1. An N-pyridine (hetero) aramid compound characterized by the formula (I):
Figure imgf000036_0001
其中：  among them:
I. Ar代表  I. Ar representative
(a) C6-C12芳基或带多至 10个碳原子的杂芳基， 或 (a) a C 6 -C 12 aryl group or a heteroaryl group having up to 10 carbon atoms, or
(b) 如在 I. a)中所确定的含义， 其中氢原子部分或全部被选自下列中相同或不同的取 代基取代： 氢、 卤素、 硝基、 氰基、 胺基、 羟基、 巯基、 羧基、 醛基、 肼基、 腙基、 d-C12 烷基、 d-C12烷基氧基、 d-C12烷基硫基、 d-C12烷基磺酰基、 12烷基亚磺酰基、 Ci-Ci2 (b) as defined in I. a), wherein some or all of the hydrogen atoms are substituted by the same or different substituents selected from the group consisting of: hydrogen, halogen, nitro, cyano, amine, hydroxy, fluorenyl , carboxy, aldehyde, decyl, decyl, dC 12 alkyl, dC 12 alkyloxy, dC 12 alkylthio, dC 12 alkylsulfonyl, 12 alkylsulfinyl, Ci-Ci 2
C1-C12 C1-C12 C1-C12 二 (Ci-Ci2)¾¾¾ 胺基、 C2-C12链烯基、 C2-C12链烯基氧基、 C2-C12链烯基硫基、 C2-C12链烯基磺酰基、 C2-C12 链烯基亚磺酰基、 c2-c12链烯基羰基、 c2-c12链烯基氧基羰基、 c2-c12链烯基羰基氧基、 C2-C12链烯基胺基、 二 c2-c12链烯基胺基、 c2-c12链炔基、 c2-c12链炔基氧基、 c2-c12链炔 基硫基、 c2-c12链炔基磺酰基、 c2-c12链炔基亚磺酰基、 c2-c12链炔基羰基、 c2-c12链炔基 氧基羰基、 c2-c12链炔基羰基氧基、 c2-c12链炔基胺基、 二 c2-c12链炔基胺基、 c3-c8环焼 基、 c3-c8环烷基氧基、 c3-c8环烷基羰基、 c3-c8环烷基羰基氧基、 c3-c8环烷基氧基羰基、C1-C12 C1-C12 C1-C12 bis(Ci-Ci 2 )3⁄43⁄43⁄4 amino group, C 2 -C 12 alkenyl group, C 2 -C 12 alkenyloxy group, C 2 -C 12 alkenylthio group , C 2 -C 12 alkenylsulfonyl, C 2 -C 12 alkenylsulfinyl, c 2 -c 12 alkenylcarbonyl, c 2 -c 12 alkenyloxycarbonyl, c 2 -c 12 alkenylcarbonyloxy, C 2 -C 12 alkenylamino, di c 2 -c 12 alkenylamino, c 2 -c 12 alkynyl, c 2 -c 12 alkynyloxy , c 2 -c 12 alkynylthio, c 2 -c 12 alkynylsulfonyl, c 2 -c 12 alkynylsulfinyl, c 2 -c 12 alkynylcarbonyl, c 2 -c 12 Alkynyloxycarbonyl, c 2 -c 12 alkynylcarbonyloxy, c 2 -c 12 alkynylamino, di c 2 -c 12 alkynylamino, c 3 -c 8 cyclodecyl , c 3 -c 8 cycloalkyloxy, c 3 -c 8 cycloalkylcarbonyl, c 3 -c 8 cycloalkylcarbonyloxy, c 3 -c 8 cycloalkyloxycarbonyl,
C3-C8环烷基硫基、 C3-C8环烷基亚磺酰基、 C3-C8环烷基磺酰基、 C3-C8环烷基胺基、二 C3-C 8 环烷基胺基、 C6-C12芳基或带多至 10个碳原子的杂芳基、 C6-C12芳基氧基或带多至 10 水 碳原子的杂芳基氧基、 C6-C12芳基硫基或带多至 10个碳原子的杂芳基硫基、 c6-c12芳基磺 酰基或带多至 10个碳原子的杂芳基磺酰基、 C6-C12芳基亚磺酰基或带多至 10个碳原子的 杂芳基亚磺酰基、 C6-C12芳基羰基或带多至 10个碳原子的杂芳基羰基、 c6-c12芳基氧基羰 基或带多至 10个碳原子的杂芳基氧基羰基、 C6-C12芳基羰基氧基或带多至 10个碳原子的 杂芳基羰基氧基、 C6-C12芳基胺基或带多至 10个碳原子的杂芳基胺基、二 c6-c12芳基胺基 或带多至 10个碳原子的二杂芳基胺基、 C6-C12芳基芳基或带多至 10个碳原子的杂芳基芳 基、 C6-C12芳基杂芳基或带多至 10个碳原子的杂芳基杂芳基； C 3 -C 8 cycloalkylthio, C 3 -C 8 cycloalkylsulfinyl, C 3 -C 8 cycloalkylsulfonyl, C 3 -C 8 cycloalkylamino, di C 3 -C 8 cycloalkylamino, C 6 -C 12 aryl or heteroaryl with up to 10 carbon atoms, C 6 -C 12 aryloxy or heteroaryloxy with up to 10 water carbon atoms a C 6 -C 12 arylthio group or a heteroarylthio group having up to 10 carbon atoms, a c 6 -c 12 arylsulfonyl group or a heteroarylsulfonyl group having up to 10 carbon atoms, C a 6- C 12 arylsulfinyl group or a heteroarylsulfinyl group having up to 10 carbon atoms, a C 6 -C 12 arylcarbonyl group or a heteroarylcarbonyl group having up to 10 carbon atoms, c 6 - a c 12 aryloxycarbonyl group or a heteroaryloxycarbonyl group having up to 10 carbon atoms, a C 6 -C 12 arylcarbonyloxy group or a heteroarylcarbonyloxy group having up to 10 carbon atoms, C 6- C 12 arylamino group or heteroarylamino group having up to 10 carbon atoms, di c 6 -c 12 arylamino group or diheteroarylamino group having up to 10 carbon atoms, C aryl-heteroaryl 6 -C 12 aryl group or an aryl group with up to 10 carbon atoms, C 6 -C 12 aryl or heteroaryl heteroaryl with up to 10 carbon atoms, Heteroaryl group;
II. R1和 R2、 R3是相同的或不同的， 并代表 II. R 1 and R 2 , R 3 are the same or different and represent
氢、 卤素、 硝基、 氰基、 胺基、 羟基、 巯基、 羧基、 醛基、 肼基、 腙基、 d-C12烷基、 CrC12烷基氧基、 d-C12烷基硫基、 d-C12烷基磺酰基、 12烷基亚磺酰基、 d-C12烷基 羰基、 12烷基氧基羰基、 12烷基羰基氧基、 d-C12烷基胺基、二 （d-C12)烷基胺基、 C2-C12链烯基、 c2-c12链烯基氧基、 c2-c12链烯基硫基、 c2-c12链烯基磺酰基、 c2-c12链烯 基亚磺酰基、 C2-C12链烯基羰基、 C2-C12链烯基氧基羰基、 C2-C12链烯基羰基氧基、 C2-C12 链烯基胺基、 二 c2-c12链烯基胺基、 c2-c12链炔基、 c2-c12链炔基氧基、 c2-c12链炔基硫 基、 c2-c12链炔基磺酰基、 c2-c12链炔基亚磺酰基、 c2-c12链炔基羰基、 c2-c12链炔基氧基 羰基、 C2-C12链炔基羰基氧基、 C2-C12链炔基胺基、 二 C2-C12链炔基胺基、 ^ 8环烷基、 C3-C8环烷基氧基、 C3-C8环烷基羰基、 C3-C8环烷基羰基氧基、 C3-C8环烷基氧基羰基、 C3-C8 环烷基硫基、 C3-C8环烷基亚磺酰基、 C3-C8环烷基磺酰基、 C3-C8环烷基胺基、 二 C3-C8 环烷基胺基、 C6-C12芳基或带多至 10个碳原子的杂芳基、 C6-C12芳基氧基或带多至 10个 碳原子的杂芳基氧基、 C6-C12芳基硫基或带多至 10个碳原子的杂芳基硫基、 c6-c12芳基磺 酰基或带多至 10个碳原子的杂芳基磺酰基、 C6-C12芳基亚磺酰基或带多至 10个碳原子的 杂芳基亚磺酰基、 C6-C12芳基羰基或带多至 10个碳原子的杂芳基羰基、 c6-c12芳基氧基羰 基或带多至 10个碳原子的杂芳基氧基羰基、 C6-C12芳基羰基氧基或带多至 10个碳原子的 杂芳基羰基氧基、 C6-C12芳基胺基或带多至 10个碳原子的杂芳基胺基、二 c6-c12芳基胺基 或带多至 10个碳原子的二杂芳基胺基、 C6-C12芳基芳基或带多至 10个碳原子的杂芳基芳 基、 C6-C12芳基杂芳基或带多至 10个碳原子的杂芳基杂芳基； Hydrogen, halogen, nitro, cyano, amine, hydroxy, decyl, carboxy, aldehyde, decyl, decyl, dC 12 alkyl, CrC 12 alkyloxy, dC 12 alkylthio, dC 12 alkane Sulfonyl, 12 alkylsulfinyl, dC 12 alkylcarbonyl, 12 alkyloxycarbonyl, 12 alkylcarbonyloxy, dC 12 alkylamino, di(dC 12 )alkylamino, C 2 -C 12 alkenyl, c 2 -c 12 alkenyloxy, c 2 -c 12 alkenyl group, c 2 -c 12 alkenyl sulfonyl group, c 2 -c 12 alkenyl group Sulfonyl, C 2 -C 12 alkenylcarbonyl, C 2 -C 12 alkenyloxycarbonyl, C 2 -C 12 alkenylcarbonyloxy, C 2 -C 12 alkenylamino, two c 2 -c 12 alkenylamino, c 2 -c 12 alkynyl, c 2 -c 12 alkynyloxy, c 2 -c 12 alkynylthio, c 2 -c 12 alkynyl Sulfonyl, c 2 -c 12 alkynylsulfinyl, c 2 -c 12 alkynylcarbonyl, c 2 -c 12 alkynyloxycarbonyl, C 2 -C 12 alkynylcarbonyloxy, C 2 -C 12 alkynyl group, di-C 2 -C 12 alkynyl group, ^ 8 cycloalkyl, C 3 -C 8 cycloalkyloxy, C 3 -C 8 cycloalkylcarbonyl, C 3- C 8 cycloalkylcarbonyloxy, C 3 -C 8 cycloalkyloxycarbonyl, C 3 -C 8 cycloalkylthio, C 3 -C 8 cycloalkylsulfinyl, C 3 -C 8 -cycloalkylsulfonyl, C 3 -C 8 cycloalkylamino, di-C 3 -C 8 cycloalkylamino, C 6 -C 12 aryl or heteroaryl with up to 10 carbon atoms, heteroaryloxy C 6 -C 12 aryl group or a group with up to 10 carbon atoms, , Heteroarylthio C 6 -C 12 aryl group or a group with up to 10 carbon atoms, C 6 -c 12 hetero aryl group or a sulfonyl group with up to 10 carbon atoms, arylsulfonyl, C a 6- C 12 arylsulfinyl group or a heteroarylsulfinyl group having up to 10 carbon atoms, a C 6 -C 12 arylcarbonyl group or a heteroarylcarbonyl group having up to 10 carbon atoms, c 6 - a c 12 aryloxycarbonyl group or a heteroaryloxycarbonyl group having up to 10 carbon atoms, a C 6 -C 12 arylcarbonyloxy group or a heteroarylcarbonyloxy group having up to 10 carbon atoms, C 6- C 12 arylamino group or heteroarylamino group having up to 10 carbon atoms, di c 6 -c 12 arylamino group or diheteroarylamino group having up to 10 carbon atoms, C a 6- C 12 arylaryl group or a heteroarylaryl group having up to 10 carbon atoms, a C 6 -C 12 arylheteroaryl group or a heteroarylheteroaryl group having up to 10 carbon atoms;
III. X代表 C， S或 so;  III. X stands for C, S or so;
IV. m代表 0， 1或 2， 且  IV. m stands for 0, 1 or 2, and
1) I. b) 和 II. 中所述烷基、 环烷基、 链烯基、 链炔基、 芳基、 杂芳基为未取代的或 者 L b) 和 II. 中所述烷基、 环烷基、 链烯基、 链炔基、 芳基、 杂芳基中氢原子部分或全部 被选自下列中相同或不同的取代基取代： 卤素、 硝基、 氰基、 胺基、 羟基、 巯基、 羧基、 醛基、 肼基、 腙基、 d-C12烷基、 d-C12烷基氧基、 d-C12烷基硫基、 d-C12烷基磺酰基、 ^烷基亚磺酰基、 d-C12烷基羰基、 12烷基氧基羰基、 12烷基羰基氧基、 Ci-Ci2 烷基胺基、 二 （d-Cu)烷基胺基、 c2-c12链烯基、 c2-c12链烯基氧基、 c2-c12链烯基硫基、 c2-c12链烯基磺酰基、 c2-c12链烯基亚磺酰基、 c2-c12链烯基羰基、 c2-c12链烯基氧基羰基、 C2-C12链烯基羰基氧基、 C2-C12链烯基胺基、 二 C2-C12链烯基胺基、 C2-C12链炔基、 C2-C12 链炔基氧基、 c2-c12链炔基硫基、 C2-C12链炔基磺酰基、 C2-C12链炔基亚磺酰基、 C2-C12 链炔基羰基、 c2-c12链炔基氧基羰基、 c2-c12链炔基羰基氧基、 c2-c12链炔基胺基、二 c2-c12 链炔基胺基、 ^ 8环烷基、 c3-c8环烷基氧基、 c3-c8环烷基羰基、 c3-c8环烷基羰基氧基、 C3-C8环烷基氧基羰基、 c3-c8环烷基硫基、 c3-c8环烷基亚磺酰基、 ^ 8环烷基磺酰基、 C3-C8环烷基胺基、二 C3-C8环烷基胺基、 C6-C12芳基或带多至 10个碳原子的杂芳基、 C6-C12 芳基氧基或带多至 10个碳原子的杂芳基氧基、 C6-C12芳基硫基或带多至 10个碳原子的杂 芳基硫基、 C6-C12芳基磺酰基或带多至 10个碳原子的杂芳基磺酰基、 c6-c12芳基亚磺酰基 或带多至 10个碳原子的杂芳基亚磺酰基、 C6-C12芳基羰基或带多至 10个碳原子的杂芳基 羰基、 C6-C12芳基氧基羰基或带多至 10个碳原子的杂芳基氧基羰基、 c6-c12芳基羰基氧基 或带多至 10个碳原子的杂芳基羰基氧基、 C6-C12芳基胺基或带多至 10个碳原子的杂芳基 胺基、二 C6-C12芳基胺基或带多至 10个碳原子的二杂芳基胺基、 C6-C12芳基芳基或带多至 10个碳原子的杂芳基芳基、 C6-C12芳基杂芳基或带多至 10个碳原子的杂芳基杂芳基；且 1 ) 中所述烷基、 环烷基、 链烯基、 链炔基、 苯基中氢原子部分或全部同样可被选自下列中相 同或不同的取代基取代： 氢、 卤素、 d-C6烷基、 d-C6烷基氧基、 d-C6烷基硫基、 d-C6 烷基胺基、二 （d- )烷基胺基、 C2-C6链烯基、 C2-C6链烯基氧基、 C2-C6链烯基硫基、 C2-C6 链烯基胺基、 二 c2-c6链烯基胺基、 c2-c6链炔基、 c2-c6链炔基氧基、 c2-c6链炔基硫基、 C2-C6链炔基胺基、 二 c2-c6链炔基胺基、 c3-c6环烷基、 c3-c6环烷基氧基、 c3-c6环烷基 硫基、 c3-c6环烷基胺基、 二 c3-c6环烷基胺基； 1) The alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl groups described in I. b) and II. are unsubstituted or alkyl groups as described in L b) and II. The hydrogen atom in the cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl group is partially or wholly substituted with the same or different substituents selected from the group consisting of halogen, nitro, cyano, amine, hydroxy, Sulfhydryl, carboxyl, aldehyde, decyl, decyl, dC 12 alkyl, dC 12 alkyloxy, dC 12 alkylthio, dC 12 alkylsulfonyl, alkylsulfinyl, dC 12 alkyl Carbonyl, 12 alkyloxycarbonyl, 12 alkylcarbonyloxy, Ci-Ci 2 alkylamino, bis(d-Cu)alkylamino, c 2 -c 12 alkenyl, c 2 -c 12 alkenyloxy group, c 2 -c 12 alkenyl group, c 2 -c 12 alkenyl sulfonyl group, c 2 -c 12 alkenylsulfinyl group, c 2 -c 12 alkenyl carbonyl group, c 2 -c 12 alkenyloxycarbonyl, C 2 -C 12 alkenylcarbonyloxy, C 2 -C 12 alkenylamino, di C 2 -C 12 alkenylamino, C 2 - C 12 alkynyl group, C 2 -C 12 alkynyl group, c 2 -c 12 alkynyl group, C 2 -C 12 alkynyl Sulfonyl, C 2 -C 12 alkynyl alkylsulfinyl, C 2 -C 12 alkynyl carbonyl, c 2 -c 12 alkynyl group butoxycarbonyl, c 2 -c 12 alkynyl-carbonyl group, c 2 -c 12 alkynylamino, di c 2 -c 12 alkynylamino, ^ 8 cycloalkyl, c 3 -c 8 cycloalkyloxy, c 3 -c 8 cycloalkylcarbonyl, c 3- c- 8 cycloalkylcarbonyloxy, C 3 -C 8 cycloalkyloxycarbonyl, c 3 -c 8 cycloalkylthio, c 3 -c 8 cycloalkylsulfinyl, ^ 8 naphthenic Sulfonyl, C 3 -C 8 cycloalkylamino, di C 3 -C 8 cycloalkylamino, C 6 -C 12 aryl or heteroaryl with up to 10 carbon atoms, C 6 - a C 12 aryloxy group or a heteroaryloxy group having up to 10 carbon atoms, a C 6 -C 12 arylthio group or a heterocyclic group having up to 10 carbon atoms Arylthio, C 6 -C 12 arylsulfonyl or heteroarylsulfonyl having up to 10 carbon atoms, c 6 -c 12 arylsulfinyl or heteroaryl having up to 10 carbon atoms a sulfinyl group, a C 6 -C 12 arylcarbonyl group or a heteroarylcarbonyl group having up to 10 carbon atoms, a C 6 -C 12 aryloxycarbonyl group or a heteroaryloxy group having up to 10 carbon atoms Carbonyl group, c 6 -c 12 arylcarbonyloxy group or heteroarylcarbonyloxy group having up to 10 carbon atoms, C 6 -C 12 arylamino group or heteroaryl group having up to 10 carbon atoms Amino, di-C 6 -C 12 arylamine or diheteroarylamine having up to 10 carbon atoms, C 6 -C 12 arylaryl or heteroaryl having up to 10 carbon atoms An aryl group, a C 6 -C 12 arylheteroaryl group or a heteroarylheteroaryl group having up to 10 carbon atoms; and the alkyl group, cycloalkyl group, alkenyl group, alkynyl group, 1) Part or all of the hydrogen atom in the phenyl group may likewise be substituted by the same or different substituents selected from the group consisting of: hydrogen, halogen, dC 6 alkyl, dC 6 alkyloxy, dC 6 alkylthio, dC 6 alkyl Amino, bis(d-)alkylamino, C 2 -C 6 alkenyl, C 2 -C 6 chain Alkenyloxy, C 2 -C 6 alkenyl group, C 2 -C 6 alkenyl group, di-c 2 -c 6 alkenyl group, c 2 -c 6 alkynyl group, c 2 -c 6 alkynyloxy, c 2 -c 6 alkynylthio, C 2 -C 6 alkynylamino, di c 2 -c 6 alkynylamino, c 3 -c 6 naphthenic a c 3 -c 6 cycloalkyloxy group, a c 3 -c 6 cycloalkylthio group, a c 3 -c 6 cycloalkylamino group, a di c 3 -c 6 cycloalkylamino group;
2) I. 和 II. 以及 1 )中所述取代基的 2个代表甲二氧基或乙二氧基， 甲二氧基或乙二 氧基有时带 1个或 2个相同或不同的选自卤素和 d-C6烷基的取代基； 2) Two of the substituents described in I. and II. and 1) represent methylenedioxy or ethylenedioxy, and methylenedioxy or ethylenedioxy sometimes has one or two identical or different choices. a substituent from a halogen and a dC 6 alkyl group;
3) I. 和 II. 以及 1 )中确定了含义的芳基和杂芳基可以部分或全部氢化， 其中 1个或 3) The aryl and heteroaryl groups identified in I. and II. and 1) may be partially or fully hydrogenated, one of which or
2个 CH2基团能被 CO取代； Two CH 2 groups can be substituted by CO;
上面给出的化合物（I) 的定义中， 所用术语不论单独使用还是用在复合词中， 代表如 下取代基：  In the definition of the compound (I) given above, the terms used, whether used alone or in a compound, represent the following substituents:
卤素： 指氟、 氯、 溴、 碘；  Halogen: means fluorine, chlorine, bromine, iodine;
烷基： 指直链或支链烷基；  Alkyl: means a straight or branched alkyl group;
环烷基： 指饱和和不饱和的环烷基；  Cycloalkyl: refers to saturated and unsaturated cycloalkyl;
链烯基； 指直链或支链并可在任何位置上存在有双键；  Alkenyl; means straight or branched and may have a double bond at any position;
链炔基； 指直链或支链并可在任何位置上存在有三键；  Alkenyl; means straight or branched and may have a triple bond at any position;
C6-C12芳基指苯基和由它派生出的一环芳基或多环芳基； C 6 -C 12 aryl means phenyl and a cyclic aryl or polycyclic aryl derived therefrom;
带多至 10个碳原子的杂芳基指一环杂芳基或多环杂芳基， 环中至少有 1个 N， 0， S， A heteroaryl group having up to 10 carbon atoms means a monocyclic heteroaryl group or a polycyclic heteroaryl group having at least one N, 0, S in the ring.
P禾口 /或 Se; P and / or Se ;
C6-C12芳基和带多至 10个碳原子的杂芳基可以部分或全部氢化， 其中 1个或 2个 CH2 被 CO取代， 如环已烯基， 环已二酮基。 The C 6 -C 12 aryl group and the heteroaryl group having up to 10 carbon atoms may be partially or fully hydrogenated, wherein one or two CH 2 are substituted by CO, such as a cyclohexenyl group, a cyclohexanedione group.
2、 根据权利要求 1所述的 N-吡啶 （杂） 芳酰胺类化合物， 其特征在于通式 （I) 所示 化合物中：  The N-pyridine (hetero) arylamide compound according to claim 1, which is characterized by the compound of the formula (I):
C6-C12芳基指苯基和由它派生出的萘基或联苯基； 带多至 10个碳原子的杂芳基指嚜唑基， 吡唑基， 嚜二唑基， 吡啶基， 嚜吩基， 苯并 噻吩基， 呋喃基， 苯并呋喃基， 吡咯基， 苯并吡咯基， 吲哚基， 苯并吲哚基， 咪唑基， 苯 并咪唑基， 喹啉基， 吡喃基， 吡嗪基， 嘧啶基， 哒嗪基， 苯并吡喃基， 苯并吡嗪基， 苯并 嘧啶基， 苯并哒嗪基， 噁唑基， 异噁唑基， 苯并噁唑基， 苯并异噁唑基， 苯并噻唑基， 异 噻唑基， 苯并异噻唑基， 嘧啶并***基。 C 6 -C 12 aryl means phenyl and naphthyl or biphenyl derived therefrom; Heteroaryl group having up to 10 carbon atoms means carbazolyl, pyrazolyl, oxadiazolyl, pyridyl, porphinyl, benzothienyl, furyl, benzofuranyl, pyrrolyl, benzo Pyrrolyl, fluorenyl, benzofluorenyl, imidazolyl, benzimidazolyl, quinolyl, pyranyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzopyranyl, benzopyrazine Benzopyrimidinyl, benzoxazinyl, oxazolyl, isoxazolyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, Pyrimidin and triazolyl.
3、 根据权利要求 1或 2所述的 N-吡啶 （杂） 芳酰胺类化合物， 其特征在于通式 （I) 所示化合物中： The N-pyridine (hetero) aryl amide compound according to claim 1 or 2, which is characterized by the compound of the formula (I):
I. Ar代表  I. Ar representative
(a) 苯基、 噻唑基、 吡唑基、 噻二唑基、 吡啶基， 或  (a) phenyl, thiazolyl, pyrazolyl, thiadiazolyl, pyridyl, or
(b)如在 I. a)中所确定的含义， 其中氢原子部分或全部被选自下列中相同或不同的取代基 取代： 氢、 卤素、 胺基、 羟基、 巯基、 d-C6烷基、 d-C6烷基氧基、 d-C6焼基硫基、 d-C6 烷基胺基、 二（d-C6)烷基胺基、 C2-C6链烯基、 C2-C6链烯基氧基、 C2-C6链烯基硫基、 C2-C6 链烯基胺基、二 C2-C6链烯基胺基、 C2-C6链炔基、 C2-C6链炔基氧基、 C2-C6链炔基硫基、 C2-C6 链炔基胺基、二 C2-C6链炔基胺基、 C3-C6环烷基、 C3-C6环烷基氧基、 C3-C6环烷基硫基、 C3-C6 环焼基胺基、 二 C3-C6环烷基胺基、 苯基、 苯基氧基、 苯基硫基、 苯基胺基； (b) as defined in I. a), wherein the hydrogen atom is partially or completely substituted with the same or different substituents selected from the group consisting of: hydrogen, halogen, amine, hydroxy, decyl, dC 6 alkyl, dC 6 alkyloxy, firing dC 6-yl group, dC 6 alkylamino, di (dC 6) alkylamino, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy group , C 2 -C 6 alkenylthio, C 2 -C 6 alkenylamino, di C 2 -C 6 alkenylamino, C 2 -C 6 alkynyl, C 2 -C 6 chain Alkynyloxy, C 2 -C 6 alkynylthio, C 2 -C 6 alkynylamino, di C 2 -C 6 alkynylamino, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyloxy, C 3 -C 6 cycloalkylthio, C 3 -C 6 cyclodecylamino, di C 3 -C 6 cycloalkylamino, phenyl, phenyloxy , phenylthio group, phenylamine group;
II. R1和 R2是相同的或不同的， 并代表 II. R 1 and R 2 are the same or different and represent
氢、 卤素、 胺基、 羟基、 巯基、 肼基、 腙基、 d-C12烷基、 d-C12烷基氧基、 d-C12 烷基硫基、 d-C12烷基胺基、 二 （CrC12)烷基胺基、 C2-C12链烯基、 C2-C12链烯基氧基、Hydrogen, halogen, amine, hydroxy, decyl, decyl, decyl, dC 12 alkyl, dC 12 alkyloxy, dC 12 alkylthio, dC 12 alkylamino, bis(CrC 12 )alkyl Amino, C 2 -C 12 alkenyl, C 2 -C 12 alkenyloxy,
C2-C12链烯基硫基、 c2-c12链烯基胺基、 二 c2-c12链烯基胺基、 c2-c12链炔基、 c2-c12链炔 基氧基、 C2-Ci2链炔基硫基、 C2-Ci2链炔基胺基、二 C2-C12链炔基胺基、 C3-C8环烷基、 C3-C8 环烷基氧基、 c3-c8环烷基硫基、 c3-c8环烷基胺基、 二 c3-c8环烷基胺基； C 2 -C 12 alkenylthio, c 2 -c 12 alkenylamino, di c 2 -c 12 alkenylamino, c 2 -c 12 alkynyl, c 2 -c 12 alkyne yloxy, C 2 -Ci 2 alkynyl group, C 2 -Ci 2 alkynyl group, di-C 2 -C 12 alkynyl group, C 3 -C 8 cycloalkyl, C 3 - C 8 cycloalkyloxy, c 3 -c 8 cycloalkylthio, c 3 -c 8 cycloalkylamino, di c 3 -c 8 cycloalkylamino;
III. X代表 C;  III. X stands for C;
VI. m代表 0， 且  VI. m stands for 0, and
1) L b) 和 II. 中所述烷基、 环烷基、 链烯基、 链炔基、 苯基为未取代的或者 L b) 和 II. 中所述烷基、环烷基、链烯基、链炔基、 苯基中氢原子部分或全部被选自下列中相同或 不同的取代基取代： 卤素、 d-C6烷基、 d-C6烷基氧基、 d-C6烷基硫基、 d-C6烷基胺基、 二 （CrC6)烷基胺基、 C2-C6链烯基、 C2-C6链烯基氧基、 C2-C6链烯基硫基、 C2-C6链烯基 胺基、 二 C2-C6链烯基胺基、 C2-C6链炔基、 C2-C6链炔基氧基、 C2-C6链炔基硫基、 C2-C6 链炔基胺基、 二 C2-C6链炔基胺基、 C3-C6环烷基、 C3-C6环烷基氧基、 C3-C6环烷基硫基、 C3-C6环烷基胺基、 二 C3-C6环烷基胺基、 苯基、 苯基氧基、 苯基硫基、 苯基胺基； 1) The alkyl, cycloalkyl, alkenyl, alkynyl, phenyl group in L b) and II. is unsubstituted or alkyl, cycloalkyl, chain as described in L b) and II. The alkenyl group, the alkynyl group, or a hydrogen atom in the phenyl group is partially or wholly substituted with the same or different substituents selected from the group consisting of halogen, dC 6 alkyl, dC 6 alkyloxy, dC 6 alkylthio, dC 6 alkylamino, bis(CrC 6 )alkylamino, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy, C 2 -C 6 alkenylthio, C 2 - C 6 alkenylamino, di C 2 -C 6 alkenylamino, C 2 -C 6 alkynyl, C 2 -C 6 alkynyloxy, C 2 -C 6 alkynylthio , C 2 -C 6 alkynylamino, di C 2 -C 6 alkynylamino, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyloxy, C 3 -C 6 ring An alkylthio group, a C 3 -C 6 cycloalkylamino group, a di-C 3 -C 6 cycloalkylamino group, a phenyl group, a phenyloxy group, a phenylthio group, a phenylamino group;
且 1 ) 中所述烷基、 环烷基、 链烯基、 链炔基、 苯基中氢原子部分或全部同样可被选 自下列中相同或不同的取代基取代： 氢、 卤素、 d-C6烷基、 d-C6烷基氧基、 d-C6烷基 硫基、 d-C6烷基胺基、 二 （CrC6)烷基胺基、 C2-C6链烯基、 C2-C6链烯基氧基、 C2-C6链 烯基硫基、 C2-C6链烯基胺基、二 C2-C6链烯基胺基、 C2-C6链炔基、 C2-C6链炔基氧基、 C2-C6 链炔基硫基、 c2-c6链炔基胺基、 二 c2-c6链炔基胺基、 c3-c6环烷基、 c3-c6环烷基氧基、 C3-C6环烷基硫基、 C3-C6环烷基胺基、 二 C3-C6环烷基胺基。 And the alkyl, cycloalkyl, alkenyl, alkynyl, or a hydrogen atom in the phenyl group in 1) may also be selected Substituted from the same or different substituents in the following: hydrogen, halogen, dC 6 alkyl, dC 6 alkyloxy, dC 6 alkylthio, dC 6 alkylamino, bis(CrC 6 )alkylamino , C 2 -C 6 alkenyl, C 2 -C 6 alkenyl group, C 2 -C 6 alkenyl group, C 2 -C 6 alkenyl group, di-C 2 -C 6 chain Alkenylamino, C 2 -C 6 alkynyl, C 2 -C 6 alkynyloxy, C 2 -C 6 alkynylthio, c 2 -c 6 alkynylamino, di c 2 -c 6 alkynylamino, c 3 -c 6 cycloalkyl, c 3 -c 6 cycloalkyloxy, C 3 -C 6 cycloalkylthio, C 3 -C 6 cycloalkylamino , a C 3 -C 6 cycloalkylamino group.
4、 根据权利要求 1或 2所述的 N-吡啶 （杂） 芳酰胺类化合物， 其特征在于通式 （I) 所示化合物是：  The N-pyridine (hetero) arylamide compound according to claim 1 or 2, wherein the compound of the formula (I) is:
N-(3-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺；  N-(3-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N-乙基 -N-(6-氯 -3-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺；  N-ethyl-N-(6-chloro-3-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N-(6-甲氧基 -3-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺； N- (6 - methoxy - 3 - nitropyridine - 2 - yl) - 2, 6 - dichloro-benzamide;
ΛΚ6-氨基 -3-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺；  ΛΚ6-Amino-3-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N-乙基 - N- (6-甲氧基 -3-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺；  N-ethyl-N-(6-methoxy-3-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N，N'-(5-硝基吡啶 -2,6-二基) -双 (2,6-二氯苯甲酰胺)；  N,N'-(5-nitropyridine-2,6-diyl)-bis(2,6-dichlorobenzamide);
N，N'-(5-硝基吡啶 -2,6-二基) -双 (2,6-二氟苯甲酰胺)；  N,N'-(5-nitropyridine-2,6-diyl)-bis(2,6-difluorobenzamide);
N-(6-甲氧基 -3-硝基吡啶 -2-基) -2,6-二氟苯甲酰胺；  N-(6-methoxy-3-nitropyridin-2-yl)-2,6-difluorobenzamide;
N-(6—甲氧基―3—硝基吡啶―2—基)―2—氯苯甲酰胺； N-( 6 -methoxy- 3 -pyridin- 2 -yl) -2 -chlorobenzamide;
N-(6-乙硫基 -3-硝基吡啶 -2-基) -2-氯苯甲酰胺；  N-(6-ethylthio-3-nitropyridin-2-yl)-2-chlorobenzamide;
N-(6-乙氧基 -3-硝基吡啶 -2-基) -2-三氟甲基苯甲酰胺；  N-(6-ethoxy-3-nitropyridin-2-yl)-2-trifluoromethylbenzamide;
W-(6—氯―5—硝基吡啶―2—基)― 二氯苯甲酰胺； W-( 6 -chloro- 5 -nitropyridine- 2 -yl)-dichlorobenzamide;
N-乙基 -N-(6-氯 -5-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺；  N-ethyl-N-(6-chloro-5-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N-(6—甲氧基―5—硝基吡啶―2—基)― 二氯苯甲酰胺； N-( 6 -methoxy- 5 -nitropyridine- 2 -yl)-dichlorobenzamide;
^甲基 -N-(6-甲氧基 -3-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺；  ^Methyl-N-(6-methoxy-3-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N-(6-甲胺基 -5-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺； N- (6 - methylamino --5-- nitropyridine - 2 - yl) - 2, 6 - dichloro-benzamide;
N-乙基 -N-(6-乙胺基 -5-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺；  N-ethyl-N-(6-ethylamino-5-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N-(6-乙胺基 -5-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺；  N-(6-ethylamino-5-nitropyridin-2-yl)-2,6-dichlorobenzamide;
N-(6-二甲胺基 -5-硝基吡啶 -2-基) -2,6-二氯苯甲酰胺； N- (6 - dimethylamino --5-- nitropyridine - 2 - yl) - 2, 6 - dichloro-benzamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2,6-二氟苯甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2,6-difluorobenzamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -3,5-双三氟甲基苯甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-3,5-bistrifluoromethylbenzamide;
N-(6-乙胺基 -5-硝基吡啶 -2-基) -2-氯苯甲酰胺；  N-(6-ethylamino-5-nitropyridin-2-yl)-2-chlorobenzamide;
N-甲基 -N-(6-甲氧基 -5-硝基吡啶 -2-基) -2-三氟甲基苯甲酰胺； iV—(6—氯 -5—硝基吡啶—2—基 )—2—三氟甲基苯甲酰胺； N-methyl-N-(6-methoxy-5-nitropyridin-2-yl)-2-trifluoromethylbenzamide; iV— (6 -chloro-5-nitropyridine-2-yl)-2-pyrofluoromethylbenzamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-三氟甲基苯甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-trifluoromethylbenzamide;
N-(6-乙胺基 -5-硝基吡啶 -2-基) -2-三氟甲基苯甲酰胺； N-(6-ethylamino-5-nitropyridin-2-yl)-2-trifluoromethylbenzamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-甲基苯甲酰胺； N-(6-Amino-5-nitropyridin-2-yl)-2-methylbenzamide;
N-(6-乙胺基 -5-硝基吡啶 -2-基) -2,6-二氟苯甲酰胺； N-(6-ethylamino-5-nitropyridin-2-yl)-2,6-difluorobenzamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-氯苯甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-chlorobenzamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -4-甲基苯磺酰胺； N-(6-Amino-5-nitropyridin-2-yl)-4-methylbenzenesulfonamide;
N-(6-乙胺基 -5-硝基吡啶 -2-基) -4-甲基苯磺酰胺； N-(6-ethylamino-5-nitropyridin-2-yl)-4-methylbenzenesulfonamide;
N-(6-乙胺基 -5-硝基吡啶 -2-基) -2,6-二氯苯磺酰胺； N-(6-ethylamino-5-nitropyridin-2-yl)-2,6-dichlorobenzenesulfonamide;
N-(6-羟基 -3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺；N-(6-Hydroxy-3-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
(6—溴—3—硝基吡啶—2—基)—2—甲基—4-三氟甲基噻唑 -5-甲酰胺；  (6-bromo-3-nitropyridine-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-甲基 -3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-methyl-3-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-甲氨基 -3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-methylamino-3-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N，N'-(5-硝基吡啶 -2,6-二基) -双 (2-甲基 -4-三氟甲基噻唑 -5-甲酰胺)； N,N'-(5-nitropyridine-2,6-diyl)-bis(2-methyl-4-trifluoromethylthiazole-5-carboxamide);
N—(6-甲氧基 -3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-methoxy-3-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-乙氧基 -3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-ethoxy-3-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(3-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-甲胺基 -5-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-Methylamino-5-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-丁胺基 -5-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-butylamino-5-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-甲酰胺基 -3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-carboxamido-3-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-乙酰胺基 -3-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-acetamido-3-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-甲氧基 -5-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-methoxy-5-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-二甲胺基 -5-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-dimethylamino-5-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(5-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(5-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-环丙基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-Amino-5-nitropyridin-2-yl)-2-cyclopropyl-4-trifluoromethylthiazole-5-carboxamide;
Λ/_(6—环丙基硫代甲酰胺基—5—硝基吡啶 -2-基 )-2—甲基—4_三氟甲基噻唑 -5-甲酰胺；Λ/_( 6 -cyclopropylthiocarboxamido-5-nitropyridin-2-yl)-2-methyl- 4 _trifluoromethylthiazole- 5 -carboxamide;
N-(6-环已基 -5-硝基吡啶 -2-基) -2-甲基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-cyclohexyl-5-nitropyridin-2-yl)-2-methyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -3-硝基吡啶 -2-基) -2-甲氧基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-Amino-3-nitropyridin-2-yl)-2-methoxy-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-乙氧基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-Amino-5-nitropyridin-2-yl)-2-ethoxy-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-烯丙氧基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-Amino-5-nitropyridin-2-yl)-2-allyloxy-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-丁氧基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-胺基 -5-硝基吡啶 -2-基) -2-甲硫基 -4-三氟甲基噻唑 -5-甲酰胺； N-(6-Amino-5-nitropyridin-2-yl)-2-butoxy-4-trifluoromethylthiazole-5-carboxamide; N-(6-Amino-5-nitropyridin-2-yl)-2-methylthio-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-丙硫基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-propanethio-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基； )-2-异丙氧基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl;)-2-isopropoxy-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-溴 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-bromo-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-甲氧基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-methoxy-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-乙胺基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-ethylamino-4-pyridylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-二乙胺基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-diethylamino-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-乙基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-ethyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-异丙基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-isopropyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-丙基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-propyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-甲胺基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-methylamino-4-fluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-丁基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-butyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-环已基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-cyclohexyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-环丙基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-cyclopropyl-4-trifluoromethylthiazole-5-carboxamide;
N-(3-硝基吡啶 -2-基) -2-乙基 -4-三氟甲基噻唑 -5-甲酰胺；  N-(3-nitropyridin-2-yl)-2-ethyl-4-trifluoromethylthiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-氯 -4-三氟甲基噻唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-2-chloro-4-trifluoromethylthiazole-5-carboxamide;
N，N'-(5-硝基吡啶 -2,6-二基) -双 (2-氯 -4-三氟甲基噻唑 -5-甲酰胺)；  N,N'-(5-nitropyridine-2,6-diyl)-bis(2-chloro-4-trifluoromethylthiazole-5-carboxamide);
K6-氯 -3-硝基吡啶 -2-基;) -2-氯吡啶 -3-甲酰胺；  K6-chloro-3-nitropyridin-2-yl;)-2-chloropyridine-3-carboxamide;
N-(6-乙硫基 -3-硝基吡啶 -2-基) -2-氯吡啶 -3-甲酰胺；  N-(6-ethylthio-3-nitropyridin-2-yl)-2-chloropyridine-3-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -6-氯吡啶 -3-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-6-chloropyridine-3-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -2-氯吡啶 -3-甲酰胺； N-( 6 -Amino- 5 -nitropyridin- 2 -yl) -2 -chloropyridine- 3 -carbamide;
N-(6-乙胺基 -5-硝基吡啶 -2-基) -2-(3-三氟甲基苯氧基)吡啶 -3-甲酰胺；  N-(6-ethylamino-5-nitropyridin-2-yl)-2-(3-trifluoromethylphenoxy)pyridine-3-carboxamide;
N-乙基 -N (6-甲氧基 -5-硝基吡啶 -2-基) -6-氯吡啶 -3-甲酰胺)；  N-ethyl-N (6-methoxy-5-nitropyridin-2-yl)-6-chloropyridine-3-carboxamide);
N，N'-(5-硝基吡啶 -2,6-二基) -双 (4-甲基噻二唑 -5-甲酰胺)；  N,N'-(5-nitropyridine-2,6-diyl)-bis(4-methylthiadiazole-5-carboxamide);
N—(6-胺基 -5-硝基吡啶 -2-基) -4-甲基噻二唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-4-methylthiadiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -4-甲基噻二唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-4-methylthiadiazole-5-carboxamide;
N-(6-胺基 -5-硝基吡啶 -2-基) -1-甲基 -3-乙基 -4-氯吡唑 -5-甲酰胺；  N-(6-Amino-5-nitropyridin-2-yl)-1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide;
N，N'-(5-硝基吡啶 -2,6-二基) -双 (1-甲基 -3-乙基 -4-氯吡唑 -5-甲酰胺） 。  N,N'-(5-Nitropyridine-2,6-diyl)-bis(1-methyl-3-ethyl-4-chloropyrazole-5-carboxamide).
5、 根据权利要求 1所述的 N-吡啶 （杂） 芳酰胺类化合物的制备方法， 其特征在于式 ( I ) 所示的化合物通过下面所示的反应制备得到，  The process for producing an N-pyridine (hetero) arylamide compound according to claim 1, wherein the compound represented by the formula (I) is produced by the reaction shown below.
反应式 1 : r ( 1-1 )
Figure imgf000043_0001
Figure imgf000043_0002
Reaction formula 1: r ( 1-1 )
Figure imgf000043_0001
Figure imgf000043_0002
反应式 3 :
Figure imgf000043_0003
Reaction 3:
Figure imgf000043_0003
反应式 4:  Reaction 4:
ArCH2OH or ArCHO ArCH 2 OH or ArCHO
[ O ]  [ O ]
[ H20 ] [ H 2 0 ]
ArCN or ArCOR' ( 4 )ArCN or ArCOR' ( 4 )
Figure imgf000043_0004
Figure imgf000043_0004
反应式 5  Reaction formula 5
¾  3⁄4
( 5 ) (5)
N' NH N NH- 在溶剂二氯甲烷或甲苯、 二氯乙烷、 Ν,Ν-二甲基甲酰胺 （DMF)、 四氢呋喃、 二氧六 环中， 于 -10°C〜溶剂回流温度， 在碱三乙胺或吡啶、 氢化钠、 氢氧化钠、 氢氧化钾、 碳酸 钾、 碳酸钠存在下， 用式 （Π) 所示的化合物和相应的式 （III) 或式 （IV) 所示的化合物 反应， 或用式 （V) 所示的化合物和相应的式 （VI) 所示的化合物反应得式 （I) 所示的化 合物， 加入催化剂 4-二甲胺基吡啶或碘化钾可以加快反应或提高反应收率 （反应式 1 ) ； 在无溶剂或溶剂二氯乙烷、 二氯甲烷、 甲苯中， 于 15°C〜体系回流温度， 用式 （VII) 所示的化合物和与氯化亚砜或对甲基苯磺酰氯反应即得式 （Π) 所示的化合物， 加入催化 剂量的 Ν,Ν-二甲基甲酰胺可以加快反应或提高反应收率； 用式 （II) 所示的化合物与胺水 反应可得式 （V ) 所示的化合物 （反应式 2) ； N 'NH N NH- in the solvent dichloromethane or toluene, dichloroethane, hydrazine, hydrazine-dimethylformamide (DMF), tetrahydrofuran, dioxane, at -10 ° C ~ solvent reflux temperature, In the presence of alkali triethylamine or pyridine, sodium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, using a compound of the formula (III) and the corresponding formula (III) or formula (IV) The compound is reacted, or a compound represented by the formula (V) and the corresponding compound represented by the formula (VI) are reacted to obtain a compound represented by the formula (I), and a catalyst such as 4-dimethylaminopyridine or potassium iodide may be added to accelerate the reaction. Or increase the reaction yield (Reaction formula 1); in the solvent-free or solvent dichloroethane, dichloromethane, toluene, at 15 ° C ~ system reflux temperature, using the compound of formula (VII) and with chlorination The reaction of sulfoxide or p-methylbenzenesulfonyl chloride gives the compound of the formula (Π), and the addition of a catalyst amount of hydrazine, hydrazine-dimethylformamide can accelerate the reaction or increase the reaction yield; The compound is reacted with an amine water to obtain a compound represented by the formula (V) (Reaction formula 2);
在溶剂水或四氢呋喃、 〜^的醇、 甲苯、 二氯乙烷、 二氯甲烷中， 于 0°C〜体系回 流温度， 在碱碳酸钾或碳酸钠、 三乙胺、 吡啶、 氢化钠、 氢氧化钠、 氢氧化钾存在下， 用 式 (VIII)所示的化合物和 R2H反应得式 （VI)所示的化合物； 在四氢呋喃和 /或水中， 于 0°C〜体系回流温度下，用式（VI)所示的化合物与氨水或 R^ t反应得式（III)或式（IV) 的化合物 （反应式 3 ) ； In solvent water or tetrahydrofuran, ~^ alcohol, toluene, dichloroethane, dichloromethane, at 0 ° C ~ system reflux temperature, in alkali potassium carbonate or sodium carbonate, triethylamine, pyridine, sodium hydride, hydrogen In the presence of sodium oxide or potassium hydroxide, a compound of the formula (VIII) and R 2 H are reacted to obtain a compound of the formula (VI); in tetrahydrofuran and/or water, at a reflux temperature of from 0 ° C to the system. The compound represented by the formula (VI) is reacted with aqueous ammonia or R^t to obtain the formula (III) or the formula (IV). Compound (Reaction formula 3);
根据（VII)的结构及原料，选择反应式 4中的合适路线，通过相应的合成方法得式（VII) 的化合物 （反应式 4) ；  According to the structure and raw materials of (VII), a suitable route in Reaction Scheme 4 is selected, and a compound of the formula (VII) is obtained by a corresponding synthesis method (Reaction formula 4);
取代的 2-胺基吡啶， 用硫酸和硝酸混合酸硝化得 R 取代的 2-胺基硝基吡啶， 取代的 2-胺基硝基吡啶经过常规的重氮化、 氯化得 R 取代的 2-氯硝基吡啶， 再 N-氧化， 氯化可得式 （VIII) 的化合物 （反应式 5 ) ；  Substituted 2-aminopyridine, nitrated with a mixed acid of sulfuric acid and nitric acid to give R-substituted 2-amino nitropyridine, substituted 2-amino nitropyridine by conventional diazotization, chlorination to give R substituted 2 -Chloronitropyridine, N-oxidized, chlorinated to obtain a compound of formula (VIII) (Scheme 5);
式中 Ar、 R R2、 R3、 m、 X具有权利要求 1中所给定义， Z为离去基团氯或溴、 磺 酸酯， L为离去基团氯或溴。 Wherein Ar, RR 2 , R 3 , m, X have the definitions given in claim 1, Z is a leaving group chlorine or bromine, a sulfonate, and L is a leaving group chlorine or bromine.
6、根据权利要求 1所述的 N-吡啶（杂）芳酰胺类化合物的用途，其特征在于在 3.75〜 The use of the N-pyridine (hetero) aryl amide compound according to claim 1, which is characterized in that
2250克有效成分 /公顷用量下具有杀菌和 /或除草、 杀虫、 杀螨生物活性。 2250 grams of active ingredient / hectare has bactericidal and / or weeding, insecticidal, acaricidal biological activity.
7、 根据权利要求 1所述的 N-吡啶 （杂） 芳酰胺类化合物用于制备具有杀菌活性和 /或 除草活性、 杀虫活性、 杀螨活性的药物的用途。  The use of the N-pyridine (hetero) arylamide compound according to claim 1 for the preparation of a medicament having bactericidal activity and/or herbicidal activity, insecticidal activity, acaricidal activity.
PCT/CN2014/077821 2013-05-20 2014-05-19 N-pyridine(hetero)aromatic amide compound and preparation method and use thereof WO2014187297A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310187115.1 2013-05-20
CN201310187115.1A CN104163791B (en) 2013-05-20 2013-05-20 N-pyridine (hetero) aryl amide compound and preparation method and application thereof

Publications (1)

Publication Number Publication Date
WO2014187297A1 true WO2014187297A1 (en) 2014-11-27

Family

ID=51907794

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/077821 WO2014187297A1 (en) 2013-05-20 2014-05-19 N-pyridine(hetero)aromatic amide compound and preparation method and use thereof

Country Status (2)

Country Link
CN (1) CN104163791B (en)
WO (1) WO2014187297A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017202768A1 (en) * 2016-05-24 2017-11-30 Basf Se Herbicidal uracilpyrid
US9951069B1 (en) 2017-01-11 2018-04-24 Rodin Therapeutics, Inc. Bicyclic inhibitors of histone deacetylase
US10421756B2 (en) 2015-07-06 2019-09-24 Rodin Therapeutics, Inc. Heterobicyclic N-aminophenyl-amides as inhibitors of histone deacetylase
US10919902B2 (en) 2015-07-06 2021-02-16 Alkermes, Inc. Hetero-halo inhibitors of histone deacetylase
US11168068B2 (en) 2016-07-18 2021-11-09 Janssen Pharmaceutica Nv Tau PET imaging ligands
US11225475B2 (en) 2017-08-07 2022-01-18 Alkermes, Inc. Substituted pyridines as inhibitors of histone deacetylase

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106608873B (en) * 2015-10-26 2019-05-24 湖南化工研究院有限公司 Pyrazol acid amide compounds and the preparation method and application thereof
CN106608872B (en) * 2015-10-26 2019-04-19 湖南化工研究院有限公司 5- pyrazol acid amide compounds and the preparation method and application thereof
CN111662283B (en) * 2019-03-07 2021-11-16 湖南化工研究院有限公司 Imidazopyridine compound and intermediate, preparation method and application thereof
CN114685448A (en) * 2020-12-25 2022-07-01 江苏天士力帝益药业有限公司 Synthesis method of zopiclone impurity pyrazine-2-carboxylic acid (5-chloro-pyridin-2-yl) -amide
CN116354902A (en) * 2023-04-06 2023-06-30 广东禾康精细化工有限公司 Green and environment-friendly process for synthesizing 2-methyl-4-trifluoromethyl-5-thiazole formic acid

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN87103542A (en) * 1986-05-17 1988-02-03 先灵农业化学品公司 Herbicide
WO1997003976A1 (en) * 1995-07-21 1997-02-06 Nissan Chemical Industries, Ltd. Semicarbazone derivatives and pesticides
WO2002054867A1 (en) * 2001-01-16 2002-07-18 Sumitomo Chemical Takeda Agro Company, Limited Sulfonamide derivative-containing agricultural and horticultural composition
US20040023938A1 (en) * 1999-04-28 2004-02-05 Takanori Tabuchi Sulfonamide derivatives
US20070066617A1 (en) * 2004-03-05 2007-03-22 Nissan Chemical Industries, Ltd. Isoxazoline-substituted benzamide compound and pesticide
JP2008239611A (en) * 2007-02-27 2008-10-09 Nissan Chem Ind Ltd Isoxazoline-substituted benzamide compound and pesticide
JP2009073818A (en) * 2007-08-29 2009-04-09 Mitsui Chemicals Inc Isoxazole carboxylic acid derivative and method for producing the same, and microbicide
US20090233962A1 (en) * 2005-06-21 2009-09-17 Mitsui Chemicals, Inc. Amide derivative and insecticide containing the same
US20110105532A1 (en) * 2009-10-27 2011-05-05 Bayer Cropscience Ag Haloalkyl-substituted amides as insecticides and acaricides
US7951828B1 (en) * 2005-09-02 2011-05-31 Nissan Chemical Industries, Ltd. Isoxazoline-substituted benzamide compound and pesticide
CN102942565A (en) * 2012-11-06 2013-02-27 江西天人生态股份有限公司 3,4-dichloro isothiazole derivatives, their preparation method and application

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN87103542A (en) * 1986-05-17 1988-02-03 先灵农业化学品公司 Herbicide
WO1997003976A1 (en) * 1995-07-21 1997-02-06 Nissan Chemical Industries, Ltd. Semicarbazone derivatives and pesticides
US20040023938A1 (en) * 1999-04-28 2004-02-05 Takanori Tabuchi Sulfonamide derivatives
WO2002054867A1 (en) * 2001-01-16 2002-07-18 Sumitomo Chemical Takeda Agro Company, Limited Sulfonamide derivative-containing agricultural and horticultural composition
US20070066617A1 (en) * 2004-03-05 2007-03-22 Nissan Chemical Industries, Ltd. Isoxazoline-substituted benzamide compound and pesticide
US20090233962A1 (en) * 2005-06-21 2009-09-17 Mitsui Chemicals, Inc. Amide derivative and insecticide containing the same
US7951828B1 (en) * 2005-09-02 2011-05-31 Nissan Chemical Industries, Ltd. Isoxazoline-substituted benzamide compound and pesticide
JP2008239611A (en) * 2007-02-27 2008-10-09 Nissan Chem Ind Ltd Isoxazoline-substituted benzamide compound and pesticide
JP2009073818A (en) * 2007-08-29 2009-04-09 Mitsui Chemicals Inc Isoxazole carboxylic acid derivative and method for producing the same, and microbicide
US20110105532A1 (en) * 2009-10-27 2011-05-05 Bayer Cropscience Ag Haloalkyl-substituted amides as insecticides and acaricides
CN102942565A (en) * 2012-11-06 2013-02-27 江西天人生态股份有限公司 3,4-dichloro isothiazole derivatives, their preparation method and application

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 1139866-47-9P *
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 1299481-66-5P *
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 187932-34-9P *
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 917921-44-9P *
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 928786-17-8P *
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 930108-24-0P *
GUCMA, M. ET AL.: "Synthesis and fungicidal activity of substituted isoxazolecarboxamides", PESTYCYDY, vol. 1, no. 4, 31 December 2010 (2010-12-31), pages 21 - 31 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10919902B2 (en) 2015-07-06 2021-02-16 Alkermes, Inc. Hetero-halo inhibitors of histone deacetylase
US10421756B2 (en) 2015-07-06 2019-09-24 Rodin Therapeutics, Inc. Heterobicyclic N-aminophenyl-amides as inhibitors of histone deacetylase
US11858939B2 (en) 2015-07-06 2024-01-02 Alkermes, Inc. Hetero-halo inhibitors of histone deacetylase
JP2019516755A (en) * 2016-05-24 2019-06-20 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Uracil pyridine herbicide
WO2017202768A1 (en) * 2016-05-24 2017-11-30 Basf Se Herbicidal uracilpyrid
JP7195932B2 (en) 2016-05-24 2022-12-26 ビーエーエスエフ ソシエタス・ヨーロピア Uracilpyridine herbicide
KR102420191B1 (en) 2016-05-24 2022-07-12 바스프 에스이 Herbicidal uracilpyrid
US11247980B2 (en) 2016-05-24 2022-02-15 Basf Se Herbicidal uracilpyrid
KR20190008960A (en) * 2016-05-24 2019-01-25 바스프 에스이 First-aid Ura Saphire Lead
US11168068B2 (en) 2016-07-18 2021-11-09 Janssen Pharmaceutica Nv Tau PET imaging ligands
US10519149B2 (en) 2017-01-11 2019-12-31 Rodin Therapeutics, Inc. Bicyclic inhibitors of histone deacetylase
US11225479B2 (en) 2017-01-11 2022-01-18 Alkermes, Inc. Bicyclic inhibitors of histone deacetylase
US11286256B2 (en) 2017-01-11 2022-03-29 Alkermes, Inc. Bicyclic inhibitors of histone deacetylase
US10793567B2 (en) 2017-01-11 2020-10-06 Rodin Therapeutics, Inc. Bicyclic inhibitors of histone deacetylase
US10696673B2 (en) 2017-01-11 2020-06-30 Rodin Therapeutics, Inc. Bicyclic inhibitors of histone deacetylase
US9951069B1 (en) 2017-01-11 2018-04-24 Rodin Therapeutics, Inc. Bicyclic inhibitors of histone deacetylase
US11912702B2 (en) 2017-08-07 2024-02-27 Alkermes, Inc. Substituted pyridines as inhibitors of histone deacetylase
US11225475B2 (en) 2017-08-07 2022-01-18 Alkermes, Inc. Substituted pyridines as inhibitors of histone deacetylase

Also Published As

Publication number Publication date
CN104163791A (en) 2014-11-26
CN104163791B (en) 2017-05-03

Similar Documents

Publication Publication Date Title
RU2751642C1 (en) M-diamide based compound, method of synthesis and application thereof
WO2014187297A1 (en) N-pyridine(hetero)aromatic amide compound and preparation method and use thereof
WO2015000392A1 (en) N-(aryl alkyl) aryloxy phenoxy carboxylic acid amide compound and preparation method and application thereof
WO2014187298A1 (en) N-pyridine amide compound, preparation method therefor, and application thereof
WO2012003748A1 (en) N-oxo-aryloxyphenoxycarboxylic acid amide compounds with biological activities, preparation method and application thereof
CN105315199B (en) N-pyridine aryloxy phenoxy carboxylic acid derivative and preparation method and application thereof
CN111662269B (en) 1-pyridyl pyrazole amide compound and preparation method and application thereof
WO2013097518A1 (en) Thiazole methylamino pyridine compounds and preparation method therefor
CN112661665B (en) Amide compound and preparation method and application thereof
CN108117529B (en) N-phenylthiazole amide compound and preparation method and application thereof
CN111662283B (en) Imidazopyridine compound and intermediate, preparation method and application thereof
CN110878081B (en) Pyridinyl ring substituted pyridazinol compounds and derivatives thereof, preparation method, weeding composition and application
CN107629012B (en) Phenazine-1-carboxylic acid bisamide compound and application thereof
JP2004269515A (en) Substituted heterocyclic amide derivative, its intermediate, agricultural and horticultural agent and method for using them
CN111662282B (en) Aza-and pyridine compounds and intermediates thereof
EP1110956B1 (en) The use of 5-carboxanilido-2,4-bis-trifluoromethylthiazoles to control rice blast
CN109232534B (en) Heterocyclic diarylamine-containing pyrazole formamide compound and preparation method and application thereof
CN109553615B (en) Pyrimidine salt compound and application thereof
CN108117518B (en) N-2, 4-substituted phenyl bisamide compound and preparation method and application thereof
CN114516868B (en) N-heteroaryl methyl difluoromethyl pyrimidine amine compound, and preparation method and application thereof
WO2019128976A1 (en) Pyridine sulfone, derivatives thereof, preparation method therefor, and application thereof
CN114516841B (en) N-aryloxy/thiobenzyl difluoromethyl pyrilamine compound, and preparation method and application thereof
CN107298652B (en) Dihalopropene ether compound, preparation and application thereof
CN113754636B (en) Quinazoline-containing aza-ether compounds
CN108912114B (en) 1,2, 4-oxadiazole insecticide containing o-benzoylsulfonylimido

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14801397

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14801397

Country of ref document: EP

Kind code of ref document: A1