WO2014187297A1 - Composé de n-pyridine-amide (hétéro)aromatique et procédé pour le préparer et l'utiliser - Google Patents

Composé de n-pyridine-amide (hétéro)aromatique et procédé pour le préparer et l'utiliser Download PDF

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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
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group
nitropyridin
carboxamide
amino
trifluoromethylthiazole
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PCT/CN2014/077821
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English (en)
Chinese (zh)
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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
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湖南化工研究院有限公司
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Publication of WO2014187297A1 publication Critical patent/WO2014187297A1/fr

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    • 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.

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Abstract

Cette invention concerne un composé de N-pyridine-amide (hétéro)aromatique de formule (I) et un procédé pour le préparer et l'utiliser, Ar, R1, R2, R3, m et X dans la formule ayant les définitions indiquées dans la description. Le composé de formule (I) selon la présente invention a des bioactivités fongicides et/ou phytocides, insecticides et acaricides.
PCT/CN2014/077821 2013-05-20 2014-05-19 Composé de n-pyridine-amide (hétéro)aromatique et procédé pour le préparer et l'utiliser WO2014187297A1 (fr)

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US11858939B2 (en) 2015-07-06 2024-01-02 Alkermes, Inc. Hetero-halo inhibitors of histone deacetylase
US10919902B2 (en) 2015-07-06 2021-02-16 Alkermes, Inc. Hetero-halo inhibitors of histone deacetylase
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JP2019516755A (ja) * 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 ウラシルピリジン除草剤
WO2017202768A1 (fr) * 2016-05-24 2017-11-30 Basf Se Uracil-pyridines herbicides
JP7195932B2 (ja) 2016-05-24 2022-12-26 ビーエーエスエフ ソシエタス・ヨーロピア ウラシルピリジン除草剤
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