WO2024007903A1 - N-substituted aniline compound and use thereof - Google Patents

N-substituted aniline compound and use thereof Download PDF

Info

Publication number
WO2024007903A1
WO2024007903A1 PCT/CN2023/102975 CN2023102975W WO2024007903A1 WO 2024007903 A1 WO2024007903 A1 WO 2024007903A1 CN 2023102975 W CN2023102975 W CN 2023102975W WO 2024007903 A1 WO2024007903 A1 WO 2024007903A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkoxy
halogenated
alkyl
compound
alkylcarbonyl
Prior art date
Application number
PCT/CN2023/102975
Other languages
French (fr)
Chinese (zh)
Inventor
李慧超
芦志成
李思博
关爱莹
冯聪
班兰凤
李志念
孙芹
杨金龙
Original Assignee
沈阳中化农药化工研发有限公司
江苏扬农化工股份有限公司
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 沈阳中化农药化工研发有限公司, 江苏扬农化工股份有限公司 filed Critical 沈阳中化农药化工研发有限公司
Publication of WO2024007903A1 publication Critical patent/WO2024007903A1/en

Links

Classifications

    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
    • A01N33/18—Nitro compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/07—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms
    • C07C205/11—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings
    • C07C205/12—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings the six-membered aromatic ring or a condensed ring system containing that ring being substituted by halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
    • C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/76—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by nitration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C07C211/56—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups

Definitions

  • the invention belongs to the field of agricultural fungicides and bacteriostatic agents. Specifically, it relates to an N-substituted aniline compound and its use as a bactericide and fungicide.
  • Bacterial diseases are common diseases in agricultural production in my country. They occur in almost every crop and usually cause crop yield reductions of 20% to 30%. Their number and degree of damage have surpassed viruses and become the second most common disease after fungi. Large pathogens. Compared with the pesticides used to prevent and control fungal diseases, the pesticides currently registered in China for the prevention and treatment of bacterial diseases are very limited, mainly copper preparations (including organic or inorganic copper preparations) and antibiotics with large dosages. Therefore, the market needs new bacterial disease control agents that are efficient, low-toxic, and environmentally friendly.
  • the object of the present invention is to provide an N-substituted aniline compound and its use as a bactericide and fungicide.
  • N-substituted aniline compound as a bactericidal agent, the application of the N-substituted aniline compound shown in the general formula I in bactericidal
  • Y is selected from CH or N;
  • R 1 is selected from hydrogen, C 1 -C 12 alkyl, halo C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkylcarbonyl, halo C 1 -C 12 alkyl Carbonyl group, C 1 -C 12 alkoxycarbonyl group, C 1 -C 12 alkylaminocarbonyl group, C 1 -C 12 alkylthio group, halogenated C 1 -C 12 alkylthio group, C 1 -C 12 alkyl group Sulfonyl, C 1 -C 12 alkoxy C 1 -C 12 alkyl, C 1 -C 12 alkoxy C 1 -C 12 alkylcarbonyl, C 1 -C 12 alkoxycarbonyl C 1 -C 12 Alkyl, C 1 -C 12 alkylaminothio, C 2 -C 12 dialkylaminothio or CO-X-CO 2 R 3 , where X
  • p 1, 2, 3, 4, 5 or 6;
  • R 2 is selected from hydrogen, halogen, C 1 -C 12 alkyl, halogenated C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkoxy, halogenated C 1 -C 12 alkoxy, C 1 -C 12 alkylamino, halogenated C 1 -C 12 alkylamino, C 1 -C 12 alkylthio, halogenated C 1 -C 12 alkylthio, C 1 -C 3 Alkylcarbonylamino, C 1 -C 12 alkylsulfonyl, C 2 -C 12 dialkylamino, C 3 -C 12 alkenyloxy, halogenated C 3 -C 12 alkenyloxy, C 3 -C 12 Alkynyloxy, halogenated C 3 -C 12 alkynyloxy, C 1 -C 12 alkylcarbonyloxy, C 1 -C 12 alkylsul
  • R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 6 alkyl
  • R 5 is selected from halogen, nitro, cyano, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkyl Oxygen group, C 1 -C 6 alkylthio group, C 1 -C 6 alkylcarbonyl group, C 1 -C 6 alkoxycarbonyl group, C 2 -C 6 alkenyl group, halogenated C 2 -C 6 alkenyl group, C 3 -C 6 alkenyloxy, halogenated C 3 -C 6 alkenyloxy, C 2 -C 6 alkynyl, halogenated C 2 -C 6 alkynyl, C 3 -C 6 alkynyloxy, halogenated C 3 -C 6 alkynyloxy, halo C 1 -C 6 alkylthio, halo C 1 -C 6 alkylcarbonyl,
  • n 0, 1, 2, 3, 4 or 5;
  • Y is selected from CH or N;
  • R 1 is selected from hydrogen, C 1 -C 8 alkyl, halo C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 8 alkylcarbonyl, halo C 1 -C 8 alkyl Carbonyl, C 1 -C 8 alkylsulfonyl, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 1 -C 8 alkylcarbonyl, C 1 -C 8Alkoxycarbonyl C 1 -C 8 alkyl;
  • R 2 is selected from hydrogen, halogen, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, halogenated C 1 -C 8 alkyl, C 1 -C 8 alkoxy, halogenated C 1 -C 8 alkoxy, C 1 -C 8 alkylamino, halogenated C 1 -C 8 alkylamino, C 1 -C 8 alkylthio, halogenated C 1 -C 8 alkylthio , C 2 -C 8 dialkylamino, C 3 -C 8 alkenyloxy, halogenated C 3 -C 8 alkenyloxy, C 3 -C 8 alkynyloxy, halogenated C 3 -C 8 alkynyloxy;
  • R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 4 alkyl
  • R 5 is selected from halogen, nitro, cyano, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and halogenated C 1 -C 4 alkoxy;
  • n 0, 1, 2, 3, 4 or 5;
  • Y is selected from CH or N;
  • R 1 is selected from hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkylcarbonyl;
  • R 2 is selected from hydrogen, halogen, C 1 -C 4 alkoxy, halogenated C 1 -C 4 alkoxy, C 1 -C 4 alkylamino, C 1 -C 4 alkylthio, C 2 -C 4 dialkylamino;
  • R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 4 alkyl
  • R 5 is selected from halogen and halogenated C 1 -C 4 alkyl
  • n 0, 1, 2, 3 or 4;
  • Y is selected from CH or N;
  • R 1 is selected from hydrogen, methyl, and acetyl
  • R 2 is selected from hydrogen, fluorine, chlorine, methoxy, isopropoxy, trifluoroethoxy, methylamino, methylthio, and dimethylamino;
  • R is selected from fluorine, chlorine, bromine, iodine, cyano, nitro, carboxyl, CONH 2 , CONHCH 3 , methyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy, difluoromethyl Oxygen, trifluoromethoxy, methylcarbonyl, methoxycarbonyl, OCF 2 OCF 3 , phenoxycarbonyl or 3-chloro-5trifluoromethylpyridin-2-yloxy;
  • n 0, 1, 2, 3 or 4;
  • the bacteria are fruit spot, leaf spot, bacterial wilt, bacterial blight, canker, soft rot, bacterial angular spot, bacterial stripe, leaf blight, bacterial blight, and wildfire. or bacterial scab.
  • a bactericidal composition contains a compound of general formula I as an active component and an agriculturally acceptable carrier.
  • the weight percentage of the active component in the composition is 0.5-90%.
  • N-substituted aniline compound the N-substituted aniline compound is represented by the general formula Ia:
  • R 1 is selected from hydrogen, C 1 -C 12 alkyl, halo C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkylcarbonyl, halo C 1 -C 12 alkyl Carbonyl group, C 1 -C 12 alkoxycarbonyl group, C 1 -C 12 alkylaminocarbonyl group, C 1 -C 12 alkylthio group, halogenated C 1 -C 12 alkylthio group, C 1 -C 12 alkyl group Sulfonyl, C 1 -C 12 alkoxy C 1 -C 12 alkyl, C 1 -C 12 alkoxy C 1 -C 12 alkylcarbonyl, C 1 -C 12 alkoxycarbonyl C 1 -C 12 Alkyl, C 1 -C 12 alkylaminothio, C 2 -C 12 dialkylaminothio or CO-X-CO 2 R 3 , where X
  • p 1, 2, 3, 4, 5 or 6;
  • R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 6 alkyl
  • R 5 is selected from halogen, nitro, cyano, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 3 -C 6 alkenyloxy, halogenated C 3 -C 6 alkenyloxy, C 2 -C 6 alkynyl, halogenated C 2 -C 6 alkynyl, C 3 -C 6 alkynyloxy, halogenated C 3 -C 6 Alkynyloxy, halogenated C 1 -C 6 alkylthio, halogenated C 1 -C 6 alkylcarbonyl, C 1 -C 6 al
  • n 0, 1, 2, 3, 4 or 5;
  • R 1 is selected from hydrogen, C 1 -C 8 alkyl, halo C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 8 alkylcarbonyl, halo C 1 -C 8 alkyl Carbonyl, C 1 -C 8 alkylsulfonyl, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 1 -C 8 alkylcarbonyl, C 1 -C 8Alkoxycarbonyl C 1 -C 8 alkyl;
  • R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 4 alkyl
  • R 5 is selected from halogen, nitro, cyano, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and halogenated C 1 -C 4 alkoxy;
  • n 0, 1, 2, 3, 4 or 5;
  • R 1 is selected from hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkylcarbonyl;
  • R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 4 alkyl
  • R 5 is selected from halogen and halogenated C 1 -C 4 alkyl
  • n 0, 1, 2, 3 or 4;
  • the compound of formula Ia is:
  • R 1 is selected from hydrogen and acetyl
  • R is selected from fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, trifluoromethyl, heptafluoroisopropyl, methoxy, difluoromethoxy, trifluoromethoxy, methylcarbonyl , methoxycarbonyl;
  • n 0, 1, 2 or 3;
  • a fungicidal composition contains a compound of general formula Ia as an active component and an agriculturally acceptable carrier.
  • the weight percentage of the active component in the composition is 0.5-90%.
  • Halogen refers to fluorine, chlorine, bromine or iodine.
  • Alkyl A straight or branched chain alkyl group such as methyl, ethyl, propyl, isopropyl or tert-butyl.
  • Cycloalkyl A substituted or unsubstituted cyclic alkyl group such as cyclopropyl, cyclopentyl or cyclohexyl. Substituents such as methyl, halogen, etc.
  • Haloalkyl straight-chain or branched alkyl, the hydrogen atoms on these alkyl groups can be partially or completely replaced by halogen, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl Methyl, trifluoromethyl, etc.
  • Alkoxy A straight or branched alkyl group bonded to the structure through an oxygen atom.
  • Haloalkoxy straight-chain or branched alkoxy, the hydrogen atoms on these alkoxy groups may be partially or fully replaced by halogen.
  • halogen for example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, etc.
  • Alkylthio A straight or branched chain alkyl group bonded to the structure via a sulfur atom.
  • Haloalkylthio group straight chain or branched chain alkylthio group, the hydrogen atoms on these alkylthio groups can be partially or completely replaced by halogen atoms.
  • halogen atoms for example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, etc.
  • Alkylamino A straight or branched chain alkyl group bonded to the structure via a nitrogen atom.
  • Haloalkylamino linear or branched chain alkylamino, the hydrogen atoms on these alkylamino groups can be partially or completely replaced by halogen.
  • Aryl groups and aryl moieties in aralkyl, aryloxy and aryloxyalkyl groups include phenyl or naphthyl groups and the like.
  • Heteroaryl groups are five- or six-membered rings containing one or more N, O, and S heteroatoms.
  • Table 1 and Table 2 respectively list the specific substituents of Rn and R 1 in some general formulas.
  • Ph represents phenyl and Py represents pyridine. alkylinyl.
  • the compounds of the present invention are represented by the general formula I', and some specific compounds are shown in Table 3; when Y in the general formula I is N, the compounds of the present invention are represented by the general formula IB, Some specific compounds are shown in Table 4.
  • the compounds in the present invention can be illustrated by the specific compounds listed in Table 3 and Table 4, but are not limited thereto.
  • M and W are selected from halogen atoms or amino groups respectively, but cannot be selected from halogen atoms or amino groups at the same time;
  • Z is selected from halogen atoms;
  • Y, R 2 , R, and n are respectively as described above;
  • R 1 is as described above , but R 1 ⁇ H.
  • Suitable bases may be selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide or sodium tert-butoxide.
  • the reaction is carried out in a suitable solvent, and the suitable solvent can be selected from the group consisting of tetrahydrofuran, acetonitrile, toluene, xylene, benzene, N,N-dimethylformamide, dimethyl sulfoxide, acetone or butanone, etc.
  • the reaction temperature can be between the ice bath and the boiling point temperature of the solvent, usually 0 to 100°C.
  • the reaction time is 30 minutes to 20 hours, usually 1 to 10 hours.
  • Intermediate III can be prepared according to known methods, for example, by referring to the method introduced in JP2003292476.
  • the compound of the general formula I of the present invention can be prepared from a substituted diphenylamine intermediate through nitration.
  • the nitro group-containing general formula can be obtained by nitrating the compounds of the general formula IV and the general formula V.
  • Compound I for preparation methods, see US4041172, etc.).
  • the compound of general formula I containing a halogen atom in Rn can also be obtained by halogenating a substituted diphenylamine compound containing no halogen atom in Rn of general formula I.
  • the compound represented by the general formula I of the present invention is used to control plant bacterial diseases, and can be used to prevent and treat a variety of plant bacterial diseases, such as fruit spot (such as melon fruit spot, etc.), leaf spot (such as tomato bacterial disease) leaf spot, etc.), bacterial wilt (such as tomato bacterial wilt, potato bacterial wilt, etc.), bacterial diseases, canker diseases (such as citrus canker, kiwi canker, etc.), soft rot (such as Chinese cabbage soft rot) rot, etc.), bacterial angular leaf spot (such as cucumber bacterial angular leaf spot, etc.), bacterial stripe disease (such as rice bacterial stripe, etc.), leaf blight, bacterial blight (such as rice white leaf blight, etc.) blight, etc.), wildfire disease and bacterial scab, etc.
  • plant bacterial diseases such as fruit spot (such as melon fruit spot, etc.), leaf spot (such as tomato bacterial disease) leaf
  • the compounds of the general formula Ia of the present invention show excellent activity against a variety of fungi in agriculture or other fields. Therefore, the technical solution of the present invention also includes the application of compounds of general formula Ia in preventing and treating pathogenic bacteria in agriculture or other fields.
  • the examples of diseases mentioned below are only used to illustrate the present invention, but in no way limit the present invention.
  • Oomycete diseases such as downy mildew (cucumber downy mildew, rape downy mildew Diseases, soybean downy mildew, beet downy mildew, sugarcane downy mildew, tobacco downy mildew, pea downy mildew, luffa downy mildew, winter melon downy mildew, melon downy mildew, cabbage downy mildew, spinach downy mildew Mildew, radish downy mildew, grape downy mildew, onion downy mildew), white rust (rapeseed white rust, cabbage white rust), damping-off disease (rape damping-off, tobacco damping-off, tomato damping-off diseases, pepper damping-off, eggplant damping-off, cucumber damping-off, cotton seedling damping-off), cotton rot (pepper cotton rot, luffa cotton rot, winter melon cotton rot
  • the dosage of the compound varies depending on various factors, such as the compound used, the crop protected, the type of pest, the degree of infection, climatic conditions, application method, dosage form used.
  • the object of the present invention also relates to a method for controlling phytopathogenic bacteria in crops important for agriculture and horticulture and/or in environments frequented by livestock and breeding animals and/or by humans by applying compounds of the general formula I.
  • the dosage of the compound varies from 10 g to 5 kg per hectare.
  • Another object of the invention also relates to the control of agriculturally and horticulturally important crops and/or Methods for phytopathogenic fungi in environments frequented by livestock and breeding stock and/or humans.
  • the dosage of the compound varies from 10 g to 5 kg per hectare.
  • compositions containing one or more compounds of the general formula For practical applications in agriculture it is often advantageous to use compositions containing one or more compounds of the general formula.
  • the technical solution of the present invention also includes a bactericidal composition containing a compound of general formula I as an active component and an agriculturally acceptable carrier.
  • the weight percentage of the active component in the composition is 0.5-90%.
  • Another technical solution of the present invention also includes a fungicidal composition containing a compound of general formula Ia as an active component and an agriculturally acceptable carrier.
  • the weight percentage of the active component in the composition is 0.5-90. %.
  • reaction solution was filtered, and the filtrate was evaporated under reduced pressure and purified by column chromatography (the eluent was ethyl acetate and petroleum ether (boiling range 60-90°C), the volume ratio was 1:20) to obtain the compound. 2. 1.37g of yellow solid, melting point 136-137°C.
  • Compound 183 was prepared according to the method of Example 3, yellow solid, melting point 112-114°C.
  • Compound 78 melting point 204-206°C. ⁇ (300MHz,DMSO):10.40(s,1H),8.86(s,1H),8.73(s,1H),7.03(s,1H),2.32(s,3H).
  • Compound 150 black solid, melting point 123-125°C. ⁇ (600MHz, CDCl 3 ): 9.53 (s, 1H), 9.00 (d, 1H), 7.78 (d, 2H), 1.73 (d, 3H).
  • Example 7 Determination of bactericidal activity
  • the compounds of the present invention have been used to determine the control effectiveness against various plant bacterial diseases.
  • the test methods are as follows:
  • Test method for in vivo control effectiveness of melon bacterial fruit spot, cucumber bacterial angular spot, Chinese cabbage soft rot, and tomato bacterial wilt Dissolve the compound to be tested with a small amount of dimethyl sulfoxide and dilute it to the required concentration. Also set a blank control. When spraying, ensure that the front and back of the leaves are evenly coated. Adjust the cultured pathogenic bacterial liquid to the required concentration, and spray the plant leaves to inoculate the pathogenic bacteria. The treated plants were placed in an artificial climate chamber, and then transferred to a greenhouse for normal cultivation. After the onset of the disease, the control effect of the pesticide was investigated using the blank control.
  • the compound to be tested is treated with a small amount of dimethyl Dissolve methyl sulfoxide and prepare a mother solution with the concentration required for the test, and set a blank control at the same time.
  • the cultured pathogenic bacteria liquid is adjusted to the required concentration and the required amount of compound stock solution for the test is mixed and cultured in a microwell plate. Investigate by judging the control effectiveness using a microplate reader.
  • compounds 138, 183, 185, and IB-18 have a preventive effect greater than 60%; compounds 117, 234, 237, 246, 247, 521, IB-27, and IB- have a preventive effect greater than 50%.
  • IB-46, IB-78; those with control effects greater than 40% include compounds 41, 47, 61, 79, 81, 242, 244, 278, IB-1, IB-4, IB-20, and IB-64.
  • compounds 5, 37, 91, 138, 183, 185, 525, and IB-1 have a preventive effect greater than 60%; compounds 4, 79, 81, 277, and IB- have a preventive effect greater than 50%. 4.
  • compound 37 has a preventive effect greater than 60%; compounds 138, 183, and 525 have a preventive effect greater than 50%.
  • the compounds with 100% activity include compounds 45, 62, 88, 89, 96, 97, 117, 185, 234, 236, 237, 245, 246, IB-24, IB-70, and IB-71 , IB-102; compounds 42, 61, 63, 78, 666, and IB-68 have an activity of 80%.
  • compounds 42, 61, 234, 235, 666, IB-70, and IB-71 had 100% activity; compounds 89, 96, 237, 245, and 246 had 80% activity.
  • compounds 42, 117, 235, 666, and IB-70 had 100% activity; compounds 43, 61, 234, and IB-71 had 80% activity.
  • compounds 42, 43, 235, 666, and IB-70 had 100% activity; compounds 61 and IB-71 had 80% activity.
  • compounds 42, 89, 234, 235, 245, 246, 666, IB-70, and IB-71 had 100% activity; compounds 62, 96, and 237 had 80% activity.
  • compounds 42, 43, 117, 235, 666, IB-70, and IB-71 had 100% activity; compound 246 had 80% activity.
  • compounds 43 and IB-71 had 100% activity; compounds 42, 117, 235, and 666 had 80% activity.
  • compounds 234, IB-70, and IB-71 had 100% activity; compounds 42, 62, 88, 89, 96, 235, 666, and IB-68 had 80% activity.
  • compounds 43, IB-70, and IB-71 had 100% activity; compounds 117 and 235 had 80% activity.
  • the compounds with 100% activity include compounds 42, 61, 62, 63, 88, 96, 234, 235, 237, 245, 246, 666, IB-68, IB-70, and IB-71; activity Compounds 89, 91, and 236 accounted for 80%.
  • compounds 42, 43, 61, 117, 234, 235, 237, 245, 246, 666, IB-70, and IB-71 have 100% activity; compounds 62, 63, 88, 91, 96, 236.
  • compounds 42, 45, 61, 62, 63, 78, 88, 89, 91, 96, 97, 183, 234, 235, 236, 237, 245, 246, 666 have 100% activity.
  • compounds 42, 43, 45, 61, 62, 63, 78, 88, 89, 91, 96, 97, 117, 183, 234, 235, 236, 237, 245 have 100% activity.
  • 246, 666, IB-24, IB-68, IB-70, IB-71, IB-102; compounds 144 and 243 have an activity of 80%.
  • the compounds with 100% activity include compounds 42, 43, 61, 62, 78, 88, 89, 91, 96, 97, 235, 237, 245, 246, IB-70, and IB-71; Compounds 63 and 236 have an activity of 80%.
  • compounds 42, 61, 62, 63, 88, 89, 96, 234, 235, 236, 237, 246, 666, IB-70, and IB-71 have an activity of 100%; the activity is 80 % include compounds 78, 91, 243, and IB-68.
  • compounds 42, 43, 61, 62, 63, 89, 96, 117, 235, 236, 237, 246, 666, IB-70, and IB-71 have an activity of 100%; the activity is 80 % include compounds 234 and 243.
  • compounds 42, 43, 117, and IB-70 had 100% activity; compounds 61, 235, 236, 246, 666, and IB-71 had 80% activity.
  • compounds 42, 61, 62, 63, 88, 89, 96, 234, 235, 237, 245, 246, 666, IB-70, and IB-71 have an activity of 100%; the activity is 80 % has compound IB-68.
  • compounds 42, 43, 61, 62, 63, 89, 117, 234, 235, 237, 245, 246, 666, IB-70, and IB-71 have an activity of 100%; the activity is 80 % has compound 96.
  • Example 8 Determination of fungicidal activity
  • the method for determining rice blast and cucumber gray mold is as follows: using a high-throughput screening method, that is, using a suitable solvent for the sample of the compound to be tested (types of solvents such as acetone, methanol, DMF, etc., and selecting them based on their ability to dissolve the sample) ) to dissolve and prepare the test solution with the required concentration.
  • a suitable solvent for the sample of the compound to be tested types of solvents such as acetone, methanol, DMF, etc., and selecting them based on their ability to dissolve the sample
  • a suitable solvent for the sample of the compound to be tested types of solvents such as acetone, methanol, DMF, etc., and selecting them based on their ability to dissolve the sample
  • a suitable solvent for the sample of the compound to be tested types of solvents such as acetone, methanol, DMF, etc., and selecting them based on their ability to dissolve the sample
  • the determination methods of cucumber downy mildew, cucumber anthracnose, and corn rust are as follows: using the living potted plant determination method, that is, using a small amount of solvent (types of solvents such as acetone, methanol, DMF, etc.) to the compound to be tested, and based on its ability to dissolve the sample. Select (the volume ratio of the solvent amount to the spray liquid amount is equal to or less than 0.05) to dissolve, dilute with water containing 0.1% Tween 80, and prepare the test liquid with the required concentration. On the crop sprayer, spray the liquid to be tested on the disease host plant (the host plant is a standard potted seedling cultured in a greenhouse), and perform disease inoculation 24 hours later.
  • solvent types of solvents such as acetone, methanol, DMF, etc.
  • the diseased plants that require temperature-controlled and moisturizing cultivation are inoculated and cultured in an artificial climate chamber. After the disease has completed the infection, they are moved to the greenhouse for cultivation.
  • the diseased plants that do not require moisturizing and cultivating are directly inoculated and cultivated in the greenhouse.
  • Set up a blank control which is processed as above but does not contain the sample to be tested or other active compounds. After the blank control has fully developed disease (usually one week), the disease prevention effect of the compound is evaluated.
  • compounds 132, 138, 144, 150, 151, 185, 213, 215, 216, 223, 224, 225, 234, 235, 236, 237, 240, 242, 243, 244, 245, 246 , 247, and 277 have an inhibitory rate of 100% against rice blast fungus; compounds 143 and 278 have an inhibitory rate of 80% against rice blast fungus.
  • compounds 216, 234, 235, 236, 237, 242, 243, 245, 246, and 247 have an inhibitory rate of 100% against rice blast fungus; compounds 185, 213, and 240 have a 100% inhibitory rate against rice blast fungus.
  • the inhibition rate is 80%.
  • the inhibitory rate of compounds 216, 234, 235, 237, 242, 245, 246, and 247 against cucumber Botrytis cinerea was 100%; the inhibition rate of compounds 185, 236, and 243 against cucumber Botrytis cinerea was 80%. %.
  • the inhibitory rate of compounds 216, 224, 235, 237, 242, 245, 246, and 247 against cucumber Botrytis cinerea was 100%.
  • the in vivo protective activity of compounds 137, 143, 183, 185, 200, 216, 240, 245, and 247 against cucumber downy mildew is 100%; the in vivo protective activity of compounds 278 and 364 against cucumber downy mildew is 100%. is 80-90%.
  • the in vivo protective activity of compounds 150, 234, 235, 236, 237, 242, 243, and 244 against cucumber downy mildew is 100%; the in vivo protective activity of compounds 200, 215, 224, and 245 against cucumber downy mildew is 100%.
  • Protective activity is 80-90%.
  • the in vivo protective activity of compound 200 against cucumber anthracnose is 100%; the in vivo protective activity of compounds 210 and 225 against cucumber anthracnose is 80-90%.
  • the in vivo protective activity of compounds 234, 235, 242, and 246 against cucumber anthracnose is 100%; the in vivo protective activity of compounds 215 and 236 against cucumber anthracnose is 90-95%.
  • the in vivo protective activity of compound 242 against cucumber anthracnose was 100%; the in vivo protective activity of compound 235 against cucumber anthracnose was 95%.
  • WO2011116671 discloses that the compound of the general formula has fungicidal activity.
  • Table 4 lists the activity comparison results of compounds 44 (CK1) and 45 (CK2) in WO2011116671 and the compound of the general formula Ia of the present application. The results show that the compound has fungicidal activity.
  • Compounds of general formula Ia are claimed to have better fungicidal activity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Microbiology (AREA)
  • Mycology (AREA)
  • Agronomy & Crop Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention belongs to the field of agricultural fungicides and bactericide, and specifically relates to an N-substituted aniline compound, and the uses thereof as a bactericide and a fungicide. The N-substituted aniline compound is represented by general formula (I), and the definition of each substituent in the formula is shown in the specification. The compound represented by general formula (I) shows good activity on various bacteria in the agricultural field, and particularly has excellent activity on diseases such as napa cabbage soft rot, muskmelon bacterial fruit blotch, cucumber bacterial angular leaf spot, tomato bacterial wilt, citrus canker, kiwi fruit canker, grape root cancer, rice bacterial leaf stripe, and tomato canker. In addition, the compound has low raw material cost, high cost performance and wide application prospect.

Description

一种N取代苯胺类化合物及其用途An N-substituted aniline compound and its use 技术领域Technical field
本发明属农用杀真菌剂、细菌剂领域。具体地涉及一种N取代苯胺类化合物，及其用作杀细菌剂、杀真菌剂中的用途。The invention belongs to the field of agricultural fungicides and bacteriostatic agents. Specifically, it relates to an N-substituted aniline compound and its use as a bactericide and fungicide.
背景技术Background technique
现代农业生产需要不断开发出结构新颖、性能优异的新农药。虽然现有杀真菌剂品种较多，但由于抗性等问题，仍需要不断更新换代，解决生产使用中遇到的问题。Modern agricultural production requires the continuous development of new pesticides with novel structures and excellent performance. Although there are many varieties of fungicides, due to problems such as resistance, they still need to be constantly updated to solve problems encountered in production and use.
细菌性病害是我国农业生产中的常发性病害，几乎每种作物都有发生，通常会造成作物减产20％～30％，其数量和危害程度已经超越病毒，成为仅次于真菌的第二大病原物。与防治真菌性病害的药剂相比，目前国内登记用于防治细菌性病害的农药十分有限，主要为用量较大的铜制剂(包括有机或无机铜制剂)和抗生素。因此，市场需要高效、低毒、环境友好的新型细菌性病害防治药剂。Bacterial diseases are common diseases in agricultural production in my country. They occur in almost every crop and usually cause crop yield reductions of 20% to 30%. Their number and degree of damage have surpassed viruses and become the second most common disease after fungi. Large pathogens. Compared with the pesticides used to prevent and control fungal diseases, the pesticides currently registered in China for the prevention and treatment of bacterial diseases are very limited, mainly copper preparations (including organic or inorganic copper preparations) and antibiotics with large dosages. Therefore, the market needs new bacterial disease control agents that are efficient, low-toxic, and environmentally friendly.
发明内容Contents of the invention
本发明的目的是提供一种N取代苯胺类化合物，及其用作杀细菌剂、杀真菌剂中的用途。The object of the present invention is to provide an N-substituted aniline compound and its use as a bactericide and fungicide.
为实现上述目的，本发明采用技术方案为：In order to achieve the above object, the technical solution adopted by the present invention is:
一种N取代苯胺类化合物作为杀细菌剂的用途，通式I所示N取代苯胺类化合物在杀细菌中的应用
The use of an N-substituted aniline compound as a bactericidal agent, the application of the N-substituted aniline compound shown in the general formula I in bactericidal
式中：In the formula:
Y选自CH或N；Y is selected from CH or N;
R1选自氢、C1-C12烷基、卤代C1-C12烷基、C3-C12环烷基、C1-C12烷基羰基、卤代C1-C12烷基羰基、C1-C12烷氧基羰基、C1-C12烷基氨基羰基、C1-C12烷硫基、卤代C1-C12烷硫基、C1-C12烷基磺酰基、C1-C12烷氧基C1-C12烷基、C1-C12烷氧基C1-C12烷基羰基、C1-C12烷氧基羰基C1-C12烷基、C1-C12烷基氨基硫基、C2-C12二烷基氨基硫基或CO-X-CO2R3，其中X选自(CHR3)p、CR3＝CR4或C6H4；R 1 is selected from hydrogen, C 1 -C 12 alkyl, halo C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkylcarbonyl, halo C 1 -C 12 alkyl Carbonyl group, C 1 -C 12 alkoxycarbonyl group, C 1 -C 12 alkylaminocarbonyl group, C 1 -C 12 alkylthio group, halogenated C 1 -C 12 alkylthio group, C 1 -C 12 alkyl group Sulfonyl, C 1 -C 12 alkoxy C 1 -C 12 alkyl, C 1 -C 12 alkoxy C 1 -C 12 alkylcarbonyl, C 1 -C 12 alkoxycarbonyl C 1 -C 12 Alkyl, C 1 -C 12 alkylaminothio, C 2 -C 12 dialkylaminothio or CO-X-CO 2 R 3 , where X is selected from (CHR 3 )p, CR 3 =CR 4 or C 6 H 4 ;
p＝1、2、3、4、5或6；p=1, 2, 3, 4, 5 or 6;
R2选自氢、卤素、C1-C12烷基、卤代C1-C12烷基、C3-C12环烷基、C1-C12烷氧基、卤代C1-C12烷氧基、C1-C12烷基氨基、卤代C1-C12烷基氨基、C1-C12烷硫基、卤代C1-C12烷硫基、C1-C3烷基羰基氨基、C1-C12烷基磺酰基、C2-C12二烷基氨基、C3-C12烯氧基、卤代C3-C12烯氧基、C3-C12炔氧基、卤代C3-C12炔氧基、C1-C12烷基羰基氧基、C1-C12烷基磺酰基氧基、C1-C12烷氧基C1-C12烷氧基、C1-C12烷氧基羰基C1-C12烷氧基、未取代的或被1-5个R5取代的芳基氨基、杂芳基氨基、芳氧基、杂芳基氧基、芳甲基氧基或芳甲基氨基；R 2 is selected from hydrogen, halogen, C 1 -C 12 alkyl, halogenated C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkoxy, halogenated C 1 -C 12 alkoxy, C 1 -C 12 alkylamino, halogenated C 1 -C 12 alkylamino, C 1 -C 12 alkylthio, halogenated C 1 -C 12 alkylthio, C 1 -C 3 Alkylcarbonylamino, C 1 -C 12 alkylsulfonyl, C 2 -C 12 dialkylamino, C 3 -C 12 alkenyloxy, halogenated C 3 -C 12 alkenyloxy, C 3 -C 12 Alkynyloxy, halogenated C 3 -C 12 alkynyloxy, C 1 -C 12 alkylcarbonyloxy, C 1 -C 12 alkylsulfonyloxy, C 1 -C 12 alkoxy C 1 -C 12 alkoxy, C 1 -C 12 alkoxycarbonyl C 1 -C 12 alkoxy, unsubstituted or arylamino substituted by 1-5 R 5 , heteroarylamino, aryloxy, hetero Aryloxy, arylmethyloxy or arylmethylamino;
R选自卤素、氰基、硝基、羧基、C(＝O)NR3R4、C1-C12烷基、卤代C1-C12烷基、C1-C12烷氧基、卤代C1-C12烷氧基、C1-C12烷基氨基、卤代C1-C12烷基氨基、C1-C12烷硫基、卤代C1-C12烷硫基、C2-C12烯基、C2-C12炔基、C1-C12烷基磺酰基、C1-C12烷基羰基、C1-C12烷氧基羰基、C1-C12烷氧基C1-C12烷基、C1-C12烷氧基羰基C1-C12烷基、C1-C12烷基羰基氧基、C1-C12烷氧基羰基氧基、C1-C12烷基氨基羰基氧基、C1-C12烷基磺酰基氧基、C1-C12烷氧基C1-C12烷氧基、卤代C1-C12烷氧基卤代C1-C12烷氧基、C1-C12烷氧基羰基C1-C12烷氧基、未取代的或被1-5个R5取代的芳基、芳甲基、芳基羰基、芳甲基羰基、芳基氨基、芳氧基、杂芳基氧基、芳氧基羰基或芳基氨基羰基；R is selected from halogen, cyano, nitro, carboxyl, C(=O)NR 3 R 4 , C 1 -C 12 alkyl, halogenated C 1 -C 12 alkyl, C 1 -C 12 alkoxy, Halogenated C 1 -C 12 alkoxy, C 1 -C 12 alkylamino, halogenated C 1 -C 12 alkylamino, C 1 -C 12 alkylthio, halogenated C 1 -C 12 alkylthio , C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 1 -C 12 alkylsulfonyl, C 1 -C 12 alkylcarbonyl, C 1 -C 12 alkoxycarbonyl, C 1 -C 12 alkoxy C 1 -C 12 alkyl, C 1 -C 12 alkoxycarbonyl C 1 -C 12 alkyl, C 1 -C 12 alkylcarbonyloxy, C 1 -C 12 alkoxycarbonyloxy group, C 1 -C 12 alkylaminocarbonyloxy group, C 1 -C 12 alkylsulfonyloxy group , C 1 -C 12 alkoxy group, C 1 -C 12 alkoxy group , halogenated C 1 -C 12 Alkoxy halo C 1 -C 12 alkoxy, C 1 -C 12 alkoxycarbonyl C 1 -C 12 alkoxy, unsubstituted or aryl substituted by 1-5 R 5 , arylmethyl base, arylcarbonyl, arylmethylcarbonyl, arylamino, aryloxy, heteroaryloxy, aryloxycarbonyl or arylaminocarbonyl;
R3、R4可相同或不同，分别选自氢或C1-C6烷基；R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 6 alkyl;
R5选自卤素、硝基、氰基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷 氧基、C1-C6烷硫基、C1-C6烷基羰基、C1-C6烷氧基羰基、C2-C6烯基、卤代C2-C6烯基、C3-C6烯氧基、卤代C3-C6烯氧基、C2-C6炔基、卤代C2-C6炔基、C3-C6炔氧基、卤代C3-C6炔氧基、卤代C1-C6烷硫基、卤代C1-C6烷基羰基、C1-C6烷基氨基、卤代C1-C6烷基氨基、C2-C8二烷基氨基、C1-C6烷基羰基氨基、卤代C1-C6烷基羰基氨基、C1-C6烷基氨基羰基或卤代C1-C6烷基氨基羰基；R 5 is selected from halogen, nitro, cyano, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkyl Oxygen group, C 1 -C 6 alkylthio group, C 1 -C 6 alkylcarbonyl group, C 1 -C 6 alkoxycarbonyl group, C 2 -C 6 alkenyl group, halogenated C 2 -C 6 alkenyl group, C 3 -C 6 alkenyloxy, halogenated C 3 -C 6 alkenyloxy, C 2 -C 6 alkynyl, halogenated C 2 -C 6 alkynyl, C 3 -C 6 alkynyloxy, halogenated C 3 -C 6 alkynyloxy, halo C 1 -C 6 alkylthio, halo C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylamino, halo C 1 -C 6 alkylamino, C 2 -C 8 dialkylamino, C 1 -C 6 alkylcarbonylamino, halogenated C 1 -C 6 alkylcarbonylamino, C 1 -C 6 alkylaminocarbonyl or halogenated C 1 -C 6 alkyl Aminocarbonyl;
n＝0、1、2、3、4或5；n=0, 1, 2, 3, 4 or 5;
或通式I化合物的盐。Or salts of compounds of general formula I.
优选，所述通式I中，Preferably, in the general formula I,
Y选自CH或N；Y is selected from CH or N;
R1选自氢、C1-C8烷基、卤代C1-C8烷基、C3-C8环烷基、C1-C8烷基羰基、卤代C1-C8烷基羰基、C1-C8烷基磺酰基、C1-C8烷氧基C1-C8烷基、C1-C8烷氧基C1-C8烷基羰基、C1-C8烷氧基羰基C1-C8烷基；R 1 is selected from hydrogen, C 1 -C 8 alkyl, halo C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 8 alkylcarbonyl, halo C 1 -C 8 alkyl Carbonyl, C 1 -C 8 alkylsulfonyl, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 1 -C 8 alkylcarbonyl, C 1 -C 8Alkoxycarbonyl C 1 -C 8 alkyl;
R2选自氢、卤素、C1-C8烷基、C3-C8环烷基、卤代C1-C8烷基、C1-C8烷氧基、卤代C1-C8烷氧基、C1-C8烷基氨基、卤代C1-C8烷基氨基、C1-C8烷硫基、卤代C1-C8烷硫基、C2-C8二烷基氨基、C3-C8烯氧基、卤代C3-C8烯氧基、C3-C8炔氧基、卤代C3-C8炔氧基；R 2 is selected from hydrogen, halogen, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, halogenated C 1 -C 8 alkyl, C 1 -C 8 alkoxy, halogenated C 1 -C 8 alkoxy, C 1 -C 8 alkylamino, halogenated C 1 -C 8 alkylamino, C 1 -C 8 alkylthio, halogenated C 1 -C 8 alkylthio , C 2 -C 8 dialkylamino, C 3 -C 8 alkenyloxy, halogenated C 3 -C 8 alkenyloxy, C 3 -C 8 alkynyloxy, halogenated C 3 -C 8 alkynyloxy;
R选自卤素、氰基、硝基、羧基、C(＝O)NR3R4、C1-C8烷基、卤代C1-C8烷基、C1-C8烷氧基、卤代C1-C8烷氧基、C1-C8烷基氨基、卤代C1-C8烷基氨基、C1-C8烷硫基、卤代C1-C8烷硫基、C1-C8烷基磺酰基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷氧基C1-C8烷基、C1-C8烷基羰基氧基、C1-C8烷氧基羰基氧基、C1-C8烷氧基C1-C8烷氧基、卤代C1-C8烷氧基卤代C1-C8烷氧基、C1-C8烷氧基羰基C1-C8烷氧基、未取代的或被1-3个R5取代的苯基氨基、苯氧基、吡啶基氧基、苯氧基羰基或苯基氨基羰基；R is selected from halogen, cyano, nitro, carboxyl, C(=O)NR 3 R 4 , C 1 -C 8 alkyl, halogenated C 1 -C 8 alkyl, C 1 -C 8 alkoxy, Halogenated C 1 -C 8 alkoxy, C 1 -C 8 alkylamino, halogenated C 1 -C 8 alkylamino, C 1 -C 8 alkylthio, halogenated C 1 -C 8 alkylthio , C 1 -C 8 alkylsulfonyl, C 1 -C 8 alkylcarbonyl, C 1 -C 8 alkoxycarbonyl, C 1 -C 8 alkoxy C 1 -C 8 alkyl, C 1 -C 8Alkylcarbonyloxy , C 1 -C 8 alkoxycarbonyloxy, C 1 -C 8 alkoxy C 1 -C 8 alkoxy, halogenated C 1 -C 8 alkoxy halogenated C 1 -C 8 alkoxy, C 1 -C 8 alkoxycarbonyl, C 1 -C 8 alkoxy, unsubstituted or phenylamino substituted by 1-3 R 5 , phenoxy, pyridyloxy , phenoxycarbonyl or phenylaminocarbonyl;
R3、R4可相同或不同，分别选自氢或C1-C4烷基；R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 4 alkyl;
R5选自卤素、硝基、氰基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基；R 5 is selected from halogen, nitro, cyano, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and halogenated C 1 -C 4 alkoxy;
n＝0、1、2、3、4或5；n=0, 1, 2, 3, 4 or 5;
或通式I化合物的盐。Or salts of compounds of general formula I.
进一步优选，所述通式I中，Further preferably, in the general formula I,
Y选自CH或N；Y is selected from CH or N;
R1选自氢、C1-C4烷基、C1-C4烷基羰基；R 1 is selected from hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkylcarbonyl;
R2选自氢、卤素、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷基氨基、C1-C4烷硫基、C2-C4二烷基氨基；R 2 is selected from hydrogen, halogen, C 1 -C 4 alkoxy, halogenated C 1 -C 4 alkoxy, C 1 -C 4 alkylamino, C 1 -C 4 alkylthio, C 2 -C 4 dialkylamino;
R选自卤素、氰基、硝基、羧基、C(＝O)NR3R4、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷氧基C1-C4烷氧基、卤代C1-C4烷氧基卤代C1-C4烷氧基、未取代的或被1-2个R5取代的苯氧基、吡啶基氧基；R is selected from halogen, cyano, nitro, carboxyl, C(=O)NR 3 R 4 , C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 4 alkoxy, Halo C 1 -C 4 alkoxy, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkoxy C 1 -C 4 alkoxy, halo C 1 -C 4 alkoxy halo C 1 -C 4 alkoxy, unsubstituted or phenoxy substituted by 1-2 R 5 , pyridyloxy;
R3、R4可相同或不同，分别选自氢或C1-C4烷基；R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 4 alkyl;
R5选自卤素、卤代C1-C4烷基；R 5 is selected from halogen and halogenated C 1 -C 4 alkyl;
n＝0、1、2、3或4；n=0, 1, 2, 3 or 4;
或通式I化合物与盐酸、硫酸、磷酸、甲酸、乙酸、三氟乙酸、甲磺酸、对甲苯磺酸、苹果酸或柠檬酸形成的盐。Or salts of compounds of general formula I with hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, malic acid or citric acid.
更优选，通式I中More preferably, in general formula I
Y选自CH或N；Y is selected from CH or N;
R1选自氢、甲基、乙酰基；R 1 is selected from hydrogen, methyl, and acetyl;
R2选自氢、氟、氯、甲氧基、异丙氧基、三氟乙氧基、甲基氨基、甲硫基、二甲基氨基；R 2 is selected from hydrogen, fluorine, chlorine, methoxy, isopropoxy, trifluoroethoxy, methylamino, methylthio, and dimethylamino;
R选自氟、氯、溴、碘、氰基、硝基、羧基、CONH2、CONHCH3、甲基、叔丁基、三氟甲基、七氟异丙基、甲氧基、二氟甲氧基、三氟甲氧基、甲基羰基、甲氧基羰基、OCF2OCF3、苯氧基羰基或3-氯-5三氟甲基吡啶-2-基氧基； R is selected from fluorine, chlorine, bromine, iodine, cyano, nitro, carboxyl, CONH 2 , CONHCH 3 , methyl, tert-butyl, trifluoromethyl, heptafluoroisopropyl, methoxy, difluoromethyl Oxygen, trifluoromethoxy, methylcarbonyl, methoxycarbonyl, OCF 2 OCF 3 , phenoxycarbonyl or 3-chloro-5trifluoromethylpyridin-2-yloxy;
n＝0、1、2、3或4；n=0, 1, 2, 3 or 4;
或通式I化合物与盐酸、硫酸、磷酸、三氟乙酸、甲磺酸或对甲苯磺酸形成的盐。Or salts of compounds of formula I with hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, methanesulfonic acid or p-toluenesulfonic acid.
所述细菌为果斑病、叶斑病、青枯病、细菌性疫病、溃疡病、软腐病、细菌性角斑病、细菌性条斑病、叶枯病、白叶枯病、野火病或细菌性疮痂病。The bacteria are fruit spot, leaf spot, bacterial wilt, bacterial blight, canker, soft rot, bacterial angular spot, bacterial stripe, leaf blight, bacterial blight, and wildfire. or bacterial scab.
一种杀细菌组合物，含有作为活性组分的通式I化合物和农业上可接受的载体，组合物中活性组分的重量百分含量为0.5-90％。A bactericidal composition contains a compound of general formula I as an active component and an agriculturally acceptable carrier. The weight percentage of the active component in the composition is 0.5-90%.
一种N取代苯胺类化合物，所述N取代苯胺类化合物如通式Ia所示：
An N-substituted aniline compound, the N-substituted aniline compound is represented by the general formula Ia:
式中：In the formula:
R1选自氢、C1-C12烷基、卤代C1-C12烷基、C3-C12环烷基、C1-C12烷基羰基、卤代C1-C12烷基羰基、C1-C12烷氧基羰基、C1-C12烷基氨基羰基、C1-C12烷硫基、卤代C1-C12烷硫基、C1-C12烷基磺酰基、C1-C12烷氧基C1-C12烷基、C1-C12烷氧基C1-C12烷基羰基、C1-C12烷氧基羰基C1-C12烷基、C1-C12烷基氨基硫基、C2-C12二烷基氨基硫基或CO-X-CO2R3，其中X选自(CHR3)p、CR3＝CR4或C6H4；R 1 is selected from hydrogen, C 1 -C 12 alkyl, halo C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkylcarbonyl, halo C 1 -C 12 alkyl Carbonyl group, C 1 -C 12 alkoxycarbonyl group, C 1 -C 12 alkylaminocarbonyl group, C 1 -C 12 alkylthio group, halogenated C 1 -C 12 alkylthio group, C 1 -C 12 alkyl group Sulfonyl, C 1 -C 12 alkoxy C 1 -C 12 alkyl, C 1 -C 12 alkoxy C 1 -C 12 alkylcarbonyl, C 1 -C 12 alkoxycarbonyl C 1 -C 12 Alkyl, C 1 -C 12 alkylaminothio, C 2 -C 12 dialkylaminothio or CO-X-CO 2 R 3 , where X is selected from (CHR 3 )p, CR 3 =CR 4 or C 6 H 4 ;
p＝1、2、3、4、5或6；p=1, 2, 3, 4, 5 or 6;
R3、R4可相同或不同，分别选自氢或C1-C6烷基；R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 6 alkyl;
R选自卤素、氰基、硝基、羧基、C(＝O)NR3R4、C1-C12烷基、卤代C1-C12烷基、C1-C12烷氧基、卤代C1-C12烷氧基、C1-C12烷基氨基、卤代C1-C12烷基氨基、C1-C12烷硫基、卤代C1-C12烷硫基、C2-C12烯基、C2-C12炔基、C1-C12烷基磺酰基、C1-C12烷基羰基、C1-C12烷氧基羰基、C1-C12烷氧基C1-C12烷基、C1-C12烷氧基羰基C1-C12烷基、C1-C12烷基羰基氧基、C1-C12烷氧基羰基氧基、C1-C12烷基氨基羰基氧基、C1-C12烷基磺酰基氧基、C1-C12烷氧基C1-C12烷氧基、卤代C1-C12烷氧基卤代C1-C12烷氧基、C1-C12烷氧基羰基C1-C12烷氧基、未取代的或被1-5个R5取代的芳基、芳甲基、芳基羰基、芳甲基羰基、芳基氨基、芳氧基、杂芳基氧基、芳氧基羰基或芳基氨基羰基；R is selected from halogen, cyano, nitro, carboxyl, C(=O)NR 3 R 4 , C 1 -C 12 alkyl, halogenated C 1 -C 12 alkyl, C 1 -C 12 alkoxy, Halogenated C 1 -C 12 alkoxy, C 1 -C 12 alkylamino, halogenated C 1 -C 12 alkylamino, C 1 -C 12 alkylthio, halogenated C 1 -C 12 alkylthio , C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 1 -C 12 alkylsulfonyl, C 1 -C 12 alkylcarbonyl, C 1 -C 12 alkoxycarbonyl, C 1 -C 12 alkoxy C 1 -C 12 alkyl, C 1 -C 12 alkoxycarbonyl C 1 -C 12 alkyl, C 1 -C 12 alkylcarbonyloxy, C 1 -C 12 alkoxycarbonyloxy group, C 1 -C 12 alkylaminocarbonyloxy group, C 1 -C 12 alkylsulfonyloxy group , C 1 -C 12 alkoxy group, C 1 -C 12 alkoxy group , halogenated C 1 -C 12 Alkoxy halo C 1 -C 12 alkoxy, C 1 -C 12 alkoxycarbonyl C 1 -C 12 alkoxy, unsubstituted or aryl substituted by 1-5 R 5 , arylmethyl base, arylcarbonyl, arylmethylcarbonyl, arylamino, aryloxy, heteroaryloxy, aryloxycarbonyl or arylaminocarbonyl;
R5选自卤素、硝基、氰基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷硫基、C1-C6烷基羰基、C1-C6烷氧基羰基、C2-C6烯基、卤代C2-C6烯基、C3-C6烯氧基、卤代C3-C6烯氧基、C2-C6炔基、卤代C2-C6炔基、C3-C6炔氧基、卤代C3-C6炔氧基、卤代C1-C6烷硫基、卤代C1-C6烷基羰基、C1-C6烷基氨基、卤代C1-C6烷基氨基、C2-C8二烷基氨基、C1-C6烷基羰基氨基、卤代C1-C6烷基羰基氨基、C1-C6烷基氨基羰基或卤代C1-C6烷基氨基羰基；R 5 is selected from halogen, nitro, cyano, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 3 -C 6 alkenyloxy, halogenated C 3 -C 6 alkenyloxy, C 2 -C 6 alkynyl, halogenated C 2 -C 6 alkynyl, C 3 -C 6 alkynyloxy, halogenated C 3 -C 6 Alkynyloxy, halogenated C 1 -C 6 alkylthio, halogenated C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylamino, halogenated C 1 -C 6 alkylamino, C 2 -C 8 dialkylamino, C 1 -C 6 alkylcarbonylamino, halogenated C 1 -C 6 alkylcarbonylamino, C 1 -C 6 alkylaminocarbonyl or halogenated C 1 -C 6 alkylaminocarbonyl;
n＝0、1、2、3、4或5；n=0, 1, 2, 3, 4 or 5;
或通式Ia化合物的盐。Or salts of compounds of general formula Ia.
优选，所述通式Ia中Preferably, in the general formula Ia
R1选自氢、C1-C8烷基、卤代C1-C8烷基、C3-C8环烷基、C1-C8烷基羰基、卤代C1-C8烷基羰基、C1-C8烷基磺酰基、C1-C8烷氧基C1-C8烷基、C1-C8烷氧基C1-C8烷基羰基、C1-C8烷氧基羰基C1-C8烷基；R 1 is selected from hydrogen, C 1 -C 8 alkyl, halo C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 8 alkylcarbonyl, halo C 1 -C 8 alkyl Carbonyl, C 1 -C 8 alkylsulfonyl, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 1 -C 8 alkylcarbonyl, C 1 -C 8Alkoxycarbonyl C 1 -C 8 alkyl;
R选自卤素、氰基、硝基、羧基、C(＝O)NR3R4、C1-C8烷基、卤代C1-C8烷基、C1-C8烷氧基、卤代C1-C8烷氧基、C1-C8烷基氨基、卤代C1-C8烷基氨基、C1-C8烷硫基、卤代C1-C8烷硫基、C1-C8烷基磺酰基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷氧基C1-C8烷基、C1-C8烷基羰基氧基、C1-C8烷氧基羰基氧基、C1-C8烷氧基C1-C8烷氧基、卤代C1-C8烷氧基卤代C1-C8烷氧基、C1-C8烷氧基羰基C1-C8烷氧基、未取代的或被1-3个R5取代的苯基氨基、苯氧基、吡啶基氧基、苯氧基羰基或苯基氨基羰基；R is selected from halogen, cyano, nitro, carboxyl, C(=O)NR 3 R 4 , C 1 -C 8 alkyl, halogenated C 1 -C 8 alkyl, C 1 -C 8 alkoxy, Halogenated C 1 -C 8 alkoxy, C 1 -C 8 alkylamino, halogenated C 1 -C 8 alkylamino, C 1 -C 8 alkylthio, halogenated C 1 -C 8 alkylthio , C 1 -C 8 alkylsulfonyl, C 1 -C 8 alkylcarbonyl, C 1 -C 8 alkoxycarbonyl, C 1 -C 8 alkoxy C 1 -C 8 alkyl, C 1 -C 8Alkylcarbonyloxy , C 1 -C 8 alkoxycarbonyloxy, C 1 -C 8 alkoxy C 1 -C 8 alkoxy, halogenated C 1 -C 8 alkoxy halogenated C 1 -C 8 alkoxy, C 1 -C 8 alkoxycarbonyl, C 1 -C 8 alkoxy, unsubstituted or phenylamino substituted by 1-3 R 5 , phenoxy, pyridyloxy , phenoxycarbonyl or phenylaminocarbonyl;
R3、R4可相同或不同，分别选自氢或C1-C4烷基； R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 4 alkyl;
R5选自卤素、硝基、氰基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基；R 5 is selected from halogen, nitro, cyano, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and halogenated C 1 -C 4 alkoxy;
n＝0、1、2、3、4或5；n=0, 1, 2, 3, 4 or 5;
或通式Ia化合物的盐。Or salts of compounds of general formula Ia.
进一步优选，通式Ia中Further preferably, in the general formula Ia
R1选自氢、C1-C4烷基、C1-C4烷基羰基；R 1 is selected from hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkylcarbonyl;
R选自卤素、氰基、硝基、羧基、C(＝O)NR3R4、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷氧基C1-C4烷氧基、卤代C1-C4烷氧基卤代C1-C4烷氧基；R is selected from halogen, cyano, nitro, carboxyl, C(=O)NR 3 R 4 , C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 4 alkoxy, Halo C 1 -C 4 alkoxy, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkoxy C 1 -C 4 alkoxy, halo C 1 -C 4 alkoxy halo C 1 -C 4 alkoxy;
R3、R4可相同或不同，分别选自氢或C1-C4烷基；R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 4 alkyl;
R5选自卤素、卤代C1-C4烷基；R 5 is selected from halogen and halogenated C 1 -C 4 alkyl;
n＝0、1、2、3或4；n=0, 1, 2, 3 or 4;
或通式Ia化合物与盐酸、硫酸、磷酸、甲酸、乙酸、三氟乙酸、甲磺酸、对甲苯磺酸、苹果酸或柠檬酸形成的盐。Or salts of compounds of general formula Ia with hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, malic acid or citric acid.
更优选，通式Ia化合物为：More preferably, the compound of formula Ia is:
R1选自氢、乙酰基；R 1 is selected from hydrogen and acetyl;
R选自氟、氯、溴、碘、氰基、硝基、甲基、三氟甲基、七氟异丙基、甲氧基、二氟甲氧基、三氟甲氧基、甲基羰基、甲氧基羰基；R is selected from fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, trifluoromethyl, heptafluoroisopropyl, methoxy, difluoromethoxy, trifluoromethoxy, methylcarbonyl , methoxycarbonyl;
n＝0、1、2或3；n=0, 1, 2 or 3;
或通式Ia化合物与盐酸、硫酸、磷酸、三氟乙酸、甲磺酸或对甲苯磺酸形成的盐。Or salts of compounds of general formula Ia with hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, methanesulfonic acid or p-toluenesulfonic acid.
所述通式Ia化合物的应用，所述的通式Ia化合物在农业或其他领域中防治真菌病害的应用。The application of the compound of general formula Ia, the application of the compound of general formula Ia in preventing and treating fungal diseases in agriculture or other fields.
一种杀真菌组合物，含有作为活性组分的通式Ia化合物和农业上可接受的载体，组合物中活性组分的重量百分含量为0.5-90％。A fungicidal composition contains a compound of general formula Ia as an active component and an agriculturally acceptable carrier. The weight percentage of the active component in the composition is 0.5-90%.
上面给出的通式化合物的定义中，汇集所用术语一般代表如下取代基：In the definitions of compounds of the general formula given above, the terms used in the collection generally represent the following substituents:
卤素：指氟、氯、溴或碘。Halogen: refers to fluorine, chlorine, bromine or iodine.
烷基：直链或支链烷基，例如甲基、乙基、丙基、异丙基或叔丁基。Alkyl: A straight or branched chain alkyl group such as methyl, ethyl, propyl, isopropyl or tert-butyl.
环烷基：取代或未取代的环状烷基，例如环丙基、环戊基或环己基。取代基如甲基、卤素等。Cycloalkyl: A substituted or unsubstituted cyclic alkyl group such as cyclopropyl, cyclopentyl or cyclohexyl. Substituents such as methyl, halogen, etc.
卤代烷基：直链或支链烷基，在这些烷基上的氢原子可部分或全部被卤素所取代，例如，氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基等。Haloalkyl: straight-chain or branched alkyl, the hydrogen atoms on these alkyl groups can be partially or completely replaced by halogen, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl Methyl, trifluoromethyl, etc.
烷氧基：直链或支链烷基，经氧原子键连接到结构上。Alkoxy: A straight or branched alkyl group bonded to the structure through an oxygen atom.
卤代烷氧基：直链或支链烷氧基，在这些烷氧基上的氢原子可部分或全部被卤素所取代。例如，氯甲氧基、二氯甲氧基、三氯甲氧基、氟甲氧基、二氟甲氧基、三氟甲氧基、氯氟甲氧基、三氟乙氧基等。Haloalkoxy: straight-chain or branched alkoxy, the hydrogen atoms on these alkoxy groups may be partially or fully replaced by halogen. For example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, etc.
烷硫基：直链或支链烷基，经硫原子键连接到结构上。Alkylthio: A straight or branched chain alkyl group bonded to the structure via a sulfur atom.
卤代烷硫基：直链或支链烷硫基，在这些烷硫基上的氢原子可部分或全部被卤原子所取代。例如，氯甲硫基、二氯甲硫基、三氯甲硫基、氟甲硫基、二氟甲硫基、三氟甲硫基、氯氟甲硫基等。Haloalkylthio group: straight chain or branched chain alkylthio group, the hydrogen atoms on these alkylthio groups can be partially or completely replaced by halogen atoms. For example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, etc.
烷基氨基：直链或支链烷基，经氮原子键连接到结构上。Alkylamino: A straight or branched chain alkyl group bonded to the structure via a nitrogen atom.
卤代烷基氨基：直链或支链烷基氨基，在这些烷基氨基上的氢原子可部分或全部被卤素所取代。Haloalkylamino: linear or branched chain alkylamino, the hydrogen atoms on these alkylamino groups can be partially or completely replaced by halogen.
芳基以及芳烷基、芳氧基和芳氧基烷基中的芳基部分包括苯基或萘基等。Aryl groups and aryl moieties in aralkyl, aryloxy and aryloxyalkyl groups include phenyl or naphthyl groups and the like.
杂芳基是含1个或多个N、O、S杂原子的五元环或六元环。例如吡啶基、呋喃基、嘧啶基、吡嗪基、哒嗪基、三嗪基、喹啉基、吡唑基、噻唑基等。Heteroaryl groups are five- or six-membered rings containing one or more N, O, and S heteroatoms. For example, pyridyl, furyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolyl, pyrazolyl, thiazolyl, etc.
表1和表2分别列举了部分通式中Rn和R1具体取代基，表中Ph代表苯基，Py代表吡 啶基。Table 1 and Table 2 respectively list the specific substituents of Rn and R 1 in some general formulas. In the table, Ph represents phenyl and Py represents pyridine. alkylinyl.
表1

Table 1

表2
Table 2
当通式I中的Y为CH时，本发明化合物如通式I’所示，部分具体化合物见表3；当通式I中的Y为N时，本发明化合物如通式IB所示，部分具体化合物见表4。本发明中的化合物可以用表3、表4中列出的具体化合物来说明，但并不被其限定。
When Y in the general formula I is CH, the compounds of the present invention are represented by the general formula I', and some specific compounds are shown in Table 3; when Y in the general formula I is N, the compounds of the present invention are represented by the general formula IB, Some specific compounds are shown in Table 4. The compounds in the present invention can be illustrated by the specific compounds listed in Table 3 and Table 4, but are not limited thereto.
表3

















table 3

















表4


Table 4


通式I化合物的制备方法如下：
The preparation method of the compound of general formula I is as follows:
式中：M和W分别选自卤原子或氨基，但不能同时选自卤原子或氨基；Z选自卤原子；Y、R2、R、n分别如前所述；R1如前所述，但R1≠H。In the formula: M and W are selected from halogen atoms or amino groups respectively, but cannot be selected from halogen atoms or amino groups at the same time; Z is selected from halogen atoms; Y, R 2 , R, and n are respectively as described above; R 1 is as described above , but R 1 ≠H.
适宜的碱可选自如氢氧化钾、氢氧化钠、碳酸钠、碳酸钾、碳酸氢钠、三乙胺、吡啶、甲醇钠、乙醇钠、氢化钠、叔丁醇钾或叔丁醇钠等。Suitable bases may be selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium tert-butoxide or sodium tert-butoxide.
按照以上制备方法，中间体Ⅱ和中间体Ⅲ在碱性条件下反应得到通式I中R1＝H的化合物Ⅰ-a；将其与卤代烃或酰卤等反应，即可制得R1≠H的通式化合物I。According to the above preparation method, intermediate II and intermediate III are reacted under alkaline conditions to obtain compound I-a with R 1 =H in general formula I; by reacting it with a halogenated hydrocarbon or acid halide, R can be obtained Compound I of the general formula 1 ≠H.
反应在适宜的溶剂中进行，适宜的溶剂可选自如四氢呋喃、乙腈、甲苯、二甲苯、苯、N,N-二甲基甲酰胺、二甲亚砜、丙酮或丁酮等。The reaction is carried out in a suitable solvent, and the suitable solvent can be selected from the group consisting of tetrahydrofuran, acetonitrile, toluene, xylene, benzene, N,N-dimethylformamide, dimethyl sulfoxide, acetone or butanone, etc.
反应温度可在冰浴至溶剂沸点温度之间，通常为0～100℃。The reaction temperature can be between the ice bath and the boiling point temperature of the solvent, usually 0 to 100°C.
反应时间为30分钟至20小时，通常1～10小时。The reaction time is 30 minutes to 20 hours, usually 1 to 10 hours.
中间体Ⅱ多为市售商品，也可以按公知方法制备，例如参照文献Indian Journal of Chemistry,Section B:Organic Chemistry Including Medicinal Chemistry,45B(4),972-975；2006中介绍的方法或者文献Tetrahedron Letters,44(21),4085-4088；2003报道的方法，以及波兰专利PL174903中的方法等制得。Intermediate II is mostly commercially available and can also be prepared according to known methods. For example, refer to the method introduced in the literature Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 45B(4), 972-975; 2006 or the literature Tetrahedron It was prepared by the method reported in Letters, 44(21), 4085-4088; 2003, and the method in Polish patent PL174903.
中间体Ⅲ可以按公知方法制备，例如参照JP2003292476介绍的方法得到。Intermediate III can be prepared according to known methods, for example, by referring to the method introduced in JP2003292476.
还可以采用其他方法制备本发明的通式I化合物，例如：可以由取代二苯胺中间体通过硝化来制得，如对通式Ⅳ、通式Ⅴ化合物进行硝化均可得到含硝基的通式I化合物(制备方法参见US4041172等)。
Other methods can also be used to prepare the compound of the general formula I of the present invention. For example, it can be prepared from a substituted diphenylamine intermediate through nitration. For example, the nitro group-containing general formula can be obtained by nitrating the compounds of the general formula IV and the general formula V. Compound I (for preparation methods, see US4041172, etc.).
式中：R1、R2、R分别如前所述；n＝1-5。
In the formula: R 1 , R 2 and R are as described above respectively; n=1-5.
式中：R1、R2、R分别如前所述；m＝1-4，n＝2-5；Rn中有1-3个取代基选自NO2。In the formula: R 1 , R 2 and R are as described above; m=1-4, n=2-5; Rn has 1-3 substituents selected from NO 2 .
还可以将通式I的Rn中不含卤原子的取代二苯胺类化合物，通过卤化得到Rn中含卤原子的通式I化合物。The compound of general formula I containing a halogen atom in Rn can also be obtained by halogenating a substituted diphenylamine compound containing no halogen atom in Rn of general formula I.
本发明通式I所示的化合物用于控制植物细菌性病害的用途，可用于防治多种植物细菌性病害，例如果斑病(如甜瓜果斑病等)、叶斑病(如番茄细菌性叶斑病等)、青枯病(如番茄青枯病、马铃薯青枯病等)、细菌性疫病、溃疡病(如柑橘溃疡病、猕猴桃溃疡病等)、软腐病(如大白菜软腐病等)、细菌性角斑病(如黄瓜细菌性角斑病等)、细菌性条斑病(如水稻细菌性条斑病等)、叶枯病、白叶枯病(如水稻白叶枯病等)、野火病和细菌性疮痂病等。The compound represented by the general formula I of the present invention is used to control plant bacterial diseases, and can be used to prevent and treat a variety of plant bacterial diseases, such as fruit spot (such as melon fruit spot, etc.), leaf spot (such as tomato bacterial disease) leaf spot, etc.), bacterial wilt (such as tomato bacterial wilt, potato bacterial wilt, etc.), bacterial diseases, canker diseases (such as citrus canker, kiwi canker, etc.), soft rot (such as Chinese cabbage soft rot) rot, etc.), bacterial angular leaf spot (such as cucumber bacterial angular leaf spot, etc.), bacterial stripe disease (such as rice bacterial stripe, etc.), leaf blight, bacterial blight (such as rice white leaf blight, etc.) blight, etc.), wildfire disease and bacterial scab, etc.
本发明通式Ia化合物对农业或其他领域中的多种真菌显示出优异的活性。因此，本发明的技术方案还包括通式Ia化合物在农业或其他领域中防治病菌的应用，下面提及的病害的例子仅用来说明本发明，但绝不限定本发明。The compounds of the general formula Ia of the present invention show excellent activity against a variety of fungi in agriculture or other fields. Therefore, the technical solution of the present invention also includes the application of compounds of general formula Ia in preventing and treating pathogenic bacteria in agriculture or other fields. The examples of diseases mentioned below are only used to illustrate the present invention, but in no way limit the present invention.
通式Ia化合物可用于防治下列病害：卵菌纲病害，如霜霉病(黄瓜霜霉病、油菜霜霉 病、大豆霜霉病、甜菜霜霉病、甘蔗霜霉病、烟草霜霉病、豌豆霜霉病、丝瓜霜霉病、冬瓜霜霉病、甜瓜霜霉病、白菜类霜霉病、菠菜霜霉病、萝卜霜霉病、葡萄霜霉病、葱霜霉病)，白锈菌(油菜白锈病、白菜类白锈病)，猝倒病(油菜猝倒病、烟草猝倒病、番茄猝倒病、辣椒猝倒病、茄子猝倒病、黄瓜猝倒病、棉苗猝倒病)，绵腐病(辣椒绵腐病、丝瓜绵腐病、冬瓜绵腐病)，疫病(蚕豆疫病、黄瓜疫病、南瓜疫病、冬瓜疫病、西瓜疫病、甜瓜疫病、辣椒疫病、韭菜疫病、大蒜疫病、棉花疫病)，晚疫病(马铃薯晚疫病、番茄晚疫病)等；半知菌病害，如枯萎病(甘薯枯萎病、棉花枯萎病、芝麻枯萎病、蓖麻枯萎病、番茄枯萎病、菜豆枯萎病、黄瓜枯萎病、丝瓜枯萎病、南瓜枯萎病、冬瓜枯萎病、西瓜枯萎病、甜瓜枯萎病、辣椒枯萎病、蚕豆枯萎病、油菜枯萎病、大豆枯萎病)，根腐病(辣椒根腐病、茄子根腐病、菜豆根腐病、黄瓜根腐病、苦瓜根腐病、棉黑根腐病、蚕豆根腐病)，立枯病(棉苗立枯病、芝麻立枯病、辣椒立枯病、黄瓜立枯病、白菜立枯病)，炭疽病(高粱炭疽病、棉花炭疽病、红麻炭疽病、黄麻炭疽病、亚麻炭疽病、烟草炭疽病、桑炭疽病、辣椒炭疽病、茄子炭疽病、菜豆炭疽病、黄瓜炭疽病、苦瓜炭疽病、西葫芦炭疽病、冬瓜炭疽病、西瓜炭疽病、甜瓜炭疽病、荔枝炭疽病)，黄萎病(棉花黄萎病、向日葵黄萎病、番茄黄萎病、辣椒黄萎病、茄子黄萎病)，黑星病(西葫芦黑星病、冬瓜黑星病、甜瓜黑星病)，灰霉病(棉铃灰霉病、红麻灰霉病、番茄灰霉病、辣椒灰霉病、菜豆灰霉病、芹菜灰霉病、菠菜灰霉病、猕猴桃灰霉病)，褐斑病(棉花褐斑病、黄麻褐斑病、甜菜褐斑病、花生褐斑病、辣椒褐斑病、冬瓜褐斑病、大豆褐斑病、向日葵褐斑病、豌豆褐斑病、蚕豆褐斑病)，黑斑病(亚麻假黑斑病、油菜黑斑病、芝麻黑斑病、向日葵黑斑病、蓖麻黑斑病、番茄黑斑病、辣椒黑斑病、茄子黑斑病、菜豆黑斑病、黄瓜黑斑病、芹菜黑斑病、胡萝卜黑腐病、胡萝卜黑斑病、苹果黑斑病、花生黑斑病)，斑枯病(番茄斑枯病、辣椒斑枯病、芹菜斑枯病)，早疫病(番茄早疫病、辣椒早疫病、茄子早疫病、马铃薯早疫病、芹菜早疫病)，轮纹病(大豆轮纹病、芝麻轮纹病、菜豆轮纹病)，叶枯病(芝麻叶枯病、向日葵叶枯病、西瓜叶枯病、甜瓜叶枯病)，茎基腐病(番茄茎基腐病、菜豆茎基腐病)，及其他(玉米圆斑病、红麻腰折病、稻瘟病、栗黑鞘病、甘蔗眼斑病、棉铃曲霉病、花生冠腐病、大豆茎枯病、大豆黑点病、甜瓜大斑病、花生网斑病、茶赤叶斑病、辣椒白星病、冬瓜叶斑病、芹菜黑腐病、菠菜心腐病、红麻叶霉病、红麻斑点病、黄麻茎斑病、大豆紫斑病、芝麻叶斑病、蓖麻灰斑病、茶褐色叶斑病、茄子褐色圆星病、菜豆红斑病、苦瓜白斑病、西瓜斑点病、黄麻枯腐病、向日葵根茎腐病、菜豆炭腐病、大豆靶点病、茄子棒孢叶斑病、黄瓜靶斑病、番茄叶霉病、茄子叶霉病、蚕豆赤斑病等)等；担子菌病害，如锈病(小麦条锈病、小麦杆锈病、小麦叶锈病、花生锈病、向日葵锈病、甘蔗锈病、韭菜锈病、葱锈病、栗锈病、大豆锈病)，黑穗病(玉米丝黑穗病、玉米黑粉病、高粱丝黑穗病、高粱散黑穗病、高粱坚黑穗病、高梁柱黑粉病、栗粒黑穗病、甘蔗黑穗病、菜豆锈病)及其他(如小麦纹枯病、水稻纹枯病等)等；子囊菌病害，如白粉病(小麦白粉病、油菜白粉病、芝麻白粉病、向日葵白粉病、甜菜白粉病、茄子白粉病、豌豆白粉病、丝瓜白粉病、南瓜白粉病、西葫芦白粉病、冬瓜白粉病、甜瓜白粉病、葡萄白粉病、蚕豆白粉病)，菌核病(亚麻菌核病、油菜菌核病、大豆菌核病、花生菌核病、烟草菌核病、辣椒菌核病、茄子菌核病、菜豆菌核病、豌豆菌核病、黄瓜菌核病、苦瓜菌核病、冬瓜菌核病、西瓜菌核病、芹菜菌核病)，黑星病(苹果黑星病、梨黑星病)等。特别地，对黄瓜霜霉病、水稻稻瘟病和蔬菜灰霉病等，在较低剂量下仍具有很好的防治效果。Compounds of general formula Ia can be used to control the following diseases: Oomycete diseases, such as downy mildew (cucumber downy mildew, rape downy mildew Diseases, soybean downy mildew, beet downy mildew, sugarcane downy mildew, tobacco downy mildew, pea downy mildew, luffa downy mildew, winter melon downy mildew, melon downy mildew, cabbage downy mildew, spinach downy mildew Mildew, radish downy mildew, grape downy mildew, onion downy mildew), white rust (rapeseed white rust, cabbage white rust), damping-off disease (rape damping-off, tobacco damping-off, tomato damping-off diseases, pepper damping-off, eggplant damping-off, cucumber damping-off, cotton seedling damping-off), cotton rot (pepper cotton rot, luffa cotton rot, winter melon cotton rot), diseases (broad bean blight, cucumber Blight, pumpkin blight, winter melon blight, watermelon blight, melon blight, pepper blight, leek blight, garlic blight, cotton blight), late blight (potato late blight, tomato late blight), etc.; Deuteromicrobial diseases, such as Fusarium wilt (sweet potato) Fusarium wilt, cotton wilt, sesame wilt, castor wilt, tomato wilt, bean wilt, cucumber wilt, luffa wilt, pumpkin wilt, winter melon wilt, watermelon wilt, melon wilt, pepper wilt Diseases, faba bean wilt, rapeseed wilt, soybean wilt), root rot (pepper root rot, eggplant root rot, kidney bean root rot, cucumber root rot, bitter melon root rot, cotton black root rot, Broad bean root rot), blight (cotton blight, sesame blight, pepper blight, cucumber blight, cabbage blight), anthracnose (sorghum anthracnose, cotton anthracnose, kenaf Anthracnose, jute anthracnose, flax anthracnose, tobacco anthracnose, mulberry anthracnose, pepper anthracnose, eggplant anthracnose, bean anthracnose, cucumber anthracnose, bitter melon anthracnose, zucchini anthracnose, winter melon anthracnose, watermelon anthracnose , melon anthracnose, lychee anthracnose), Verticillium wilt (cotton Verticillium wilt, sunflower Verticillium wilt, tomato Verticillium wilt, pepper Verticillium wilt, eggplant Verticillium wilt), scab (zucchini scab, winter melon Scab, melon scab), gray mold (cotton boll gray mold, kenaf gray mold, tomato gray mold, pepper gray mold, bean gray mold, celery gray mold, spinach gray mold, Kiwi gray mold), brown spot diseases (cotton brown spot, jute brown spot, sugar beet brown spot, peanut brown spot, pepper brown spot, winter melon brown spot, soybean brown spot, sunflower brown spot, Pea brown spot, broad bean brown spot), black spot (flax pseudoblack spot, rape black spot, sesame black spot, sunflower black spot, castor black spot, tomato black spot, pepper black spot Diseases, eggplant black spot, bean black spot, cucumber black spot, celery black spot, carrot black rot, carrot black spot, apple black spot, peanut black spot), spotted blight (tomato spot blight diseases, pepper leaf blight, celery leaf blight), early blight (tomato early blight, pepper early blight, eggplant early blight, potato early blight, celery early blight), ring disease (soybean ring disease, sesame ring disease , Bean ring blight), leaf blight (sesame leaf blight, sunflower leaf blight, watermelon leaf blight, melon leaf blight), stem rot (tomato stem rot, bean stem rot), and others (corn round spot, kenaf shank blight, rice blast, chestnut black sheath disease, sugarcane eye spot, cotton boll aspergillosis, peanut crown rot, soybean stem blight, soybean black spot, melon leaf spot , peanut net spot, tea red leaf spot, pepper white spot, winter melon leaf spot, celery black rot, spinach heart rot, kenaf leaf mold, kenaf spot, jute stem spot, soybean purple spot , sesame leaf spot, castor gray spot, tea brown leaf spot, eggplant brown spot, bean red spot, bitter melon white spot, watermelon spot, jute blight, sunflower root rot, bean charcoal rot, Soybean target spot disease, eggplant corynespora leaf spot, cucumber target spot, tomato leaf mold, eggplant leaf mold, broad bean red spot, etc.); basidiomycete diseases, such as rust (wheat stripe rust, wheat stem rust, Wheat leaf rust, peanut rust, sunflower rust, sugarcane rust, leek rust, onion rust, chestnut rust, soybean rust), smut (corn head smut, corn smut, sorghum head smut, sorghum black Ear diseases, sorghum smut, sorghum smut, chestnut smut, sugarcane smut, bean rust) and others (such as wheat sheath blight, rice sheath blight, etc.); ascomycete diseases, Such as powdery mildew (wheat powdery mildew, rape powdery mildew, sesame powdery mildew, sunflower powdery mildew, beet powdery mildew, eggplant powdery mildew, pea powdery mildew, luffa powdery mildew, pumpkin powdery mildew, zucchini powdery mildew, winter melon powdery mildew, melon powdery mildew diseases, grape powdery mildew, broad bean powdery mildew), sclerotinia (linen sclerotinia, rapeseed sclerotinia, soybean sclerotinia, peanut sclerotinia, tobacco sclerotinia, pepper sclerotinia, eggplant sclerotinia, Bean Sclerotinia, Pea Sclerotinia, Cucumber Sclerotinia, Momordica Sclerotinia, Winter Melon Sclerotinia, Watermelon Sclerotinia, Celery Sclerotinia), Scab (Apple Scab, Pear Scab) wait. In particular, it still has good control effects at lower doses against cucumber downy mildew, rice blast and vegetable gray mold.
为获得理想效果，化合物的用量因各种因素而改变，例如所用化合物、保护的作物、有害生物的类型、感染程度、气候条件、施药方法、采用的剂型。To obtain the desired effect, the dosage of the compound varies depending on various factors, such as the compound used, the crop protected, the type of pest, the degree of infection, climatic conditions, application method, dosage form used.
每公顷10克－5公斤的化合物剂量能提供充分的防治。Doses of 10 grams to 5 kilograms of compound per hectare provide adequate control.
本发明的目的还涉及通过施用通式I化合物，防治农业和园艺业重要的作物和/或家畜和种畜和/或人类常去的环境中的植物致病性细菌的方法。尤其是，化合物的用量在每公顷10克－5公斤内变化。The object of the present invention also relates to a method for controlling phytopathogenic bacteria in crops important for agriculture and horticulture and/or in environments frequented by livestock and breeding animals and/or by humans by applying compounds of the general formula I. In particular, the dosage of the compound varies from 10 g to 5 kg per hectare.
本发明的另一目的还涉及通过施用通式Ia化合物，防治农业和园艺业重要的作物和/或 家畜和种畜和/或人类常去的环境中的植物致病性真菌的方法。尤其是，化合物的用量在每公顷10克－5公斤内变化。Another object of the invention also relates to the control of agriculturally and horticulturally important crops and/or Methods for phytopathogenic fungi in environments frequented by livestock and breeding stock and/or humans. In particular, the dosage of the compound varies from 10 g to 5 kg per hectare.
为了实际应用于农业，使用含一种或多种通式化合物的组合物通常是有益的。For practical applications in agriculture it is often advantageous to use compositions containing one or more compounds of the general formula.
因此，本发明的技术方案还包括一种杀细菌组合物，含有作为活性组分的通式I化合物和农业上可接受的载体，组合物中活性组分的重量百分含量为0.5-90％。本发明的另外一种技术方案还包括一种杀真菌组合物，含有作为活性组分的通式Ia化合物和农业上可接受的载体，组合物中活性组分的重量百分含量为0.5-90％。Therefore, the technical solution of the present invention also includes a bactericidal composition containing a compound of general formula I as an active component and an agriculturally acceptable carrier. The weight percentage of the active component in the composition is 0.5-90%. . Another technical solution of the present invention also includes a fungicidal composition containing a compound of general formula Ia as an active component and an agriculturally acceptable carrier. The weight percentage of the active component in the composition is 0.5-90. %.
具体实施方式Detailed ways
以下具体实施例用来进一步说明本发明，但本发明绝非限于这些例子。The following specific examples are used to further illustrate the present invention, but the present invention is by no means limited to these examples.
合成实施例Synthesis Example
实例1：化合物2的制备
Example 1: Preparation of Compound 2
将0.81g(0.005mol)2,4-二氯苯胺分批加入到0.4g(0.01mol)60％的氢化钠的20mL四氢呋喃悬浮液中，加完后室温搅拌30min，向其中滴入1.56g(0.006mol)2,6-二氯-3,5-二硝基甲苯的30mL四氢呋喃溶液，约30min滴加完，继续室温搅拌5小时。TLC监测反应完毕后，将反应液过滤，滤液减压脱溶，柱层析(洗脱剂为乙酸乙酯与石油醚(沸程60-90℃)，体积比为1:20)纯化得化合物2，黄色固体1.37g，熔点136-137℃。Add 0.81g (0.005mol) 2,4-dichloroaniline in batches to a suspension of 0.4g (0.01mol) 60% sodium hydride in 20mL tetrahydrofuran. After the addition is completed, stir at room temperature for 30min, and drop into it 1.56g ( 0.006 mol) of 30 mL of tetrahydrofuran solution of 2,6-dichloro-3,5-dinitrotoluene was added dropwise in about 30 minutes, and continued stirring at room temperature for 5 hours. After the reaction was monitored by TLC, the reaction solution was filtered, and the filtrate was evaporated under reduced pressure and purified by column chromatography (the eluent was ethyl acetate and petroleum ether (boiling range 60-90°C), the volume ratio was 1:20) to obtain the compound. 2. 1.37g of yellow solid, melting point 136-137°C.
1H-NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):8.93(s,1H),8.68(s,1H),7.49(s,1H),7.17(d,1H),6.53(d,1H),2.14(s,3H)。 1 H-NMR (300MHz, internal standard TMS, solvent CDCl 3 ) δ (ppm): 8.93 (s, 1H), 8.68 (s, 1H), 7.49 (s, 1H), 7.17 (d, 1H), 6.53 ( d,1H),2.14(s,3H).
实例2：化合物38的制备
Example 2: Preparation of compound 38
将0.56g(0.0015mol)化合物2溶于5mL浓硫酸(96％，下同)中并冷却至0℃，将0.15g发烟硝酸(95％)和3mL浓硫酸混合均匀后加入反应瓶，继续搅拌5min，TLC监测反应完毕，将反应液倒入冰水中，有固体析出，过滤，用水冲洗滤饼，干燥，得化合物38，棕色固体0.59g，熔点156-158℃。Dissolve 0.56g (0.0015mol) of compound 2 in 5mL of concentrated sulfuric acid (96%, the same below) and cool to 0°C. Mix 0.15g of fuming nitric acid (95%) and 3mL of concentrated sulfuric acid and add it to the reaction bottle. Continue Stir for 5 minutes. TLC monitors that the reaction is completed. Pour the reaction solution into ice water. If solid precipitates, filter, rinse the filter cake with water, and dry to obtain compound 38, 0.59 g of brown solid, melting point 156-158°C.
1H-NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):9.75(s,1H),8.60(s,1H),8.01(s,1H),7.66(s,1H),2.09(s,3H)。 1 H-NMR (300MHz, internal standard TMS, solvent CDCl 3 ) δ (ppm): 9.75 (s, 1H), 8.60 (s, 1H), 8.01 (s, 1H), 7.66 (s, 1H), 2.09 ( s,3H).
实例3：化合物43的制备
Example 3: Preparation of compound 43
将0.83g(0.004mol)2,6-二氯-4-硝基苯胺分批加入到0.32g(0.008mol)60％的氢化钠的10mL N’N-二甲基甲酰胺(DMF)悬浮液中，加完后室温下搅拌30min，然后在30min内分批加入1.20g(0.0048mol)2,6-二氯-3,5-二硝基甲苯，室温下继续反应3小时。TLC监测反应完毕后，将反应液倒入50mL饱和食盐水中，乙酸乙酯萃取，萃取液用无水硫酸镁干燥减压 脱溶，柱层析(洗脱剂为乙酸乙酯与石油醚(沸程60-90℃)，体积比为1:10)纯化得化合物43，黄色固体1.20g，熔点157-158℃。0.83g (0.004mol) 2,6-dichloro-4-nitroaniline was added in portions to a suspension of 0.32g (0.008mol) 60% sodium hydride in 10mL N'N-dimethylformamide (DMF) After the addition, stir at room temperature for 30 minutes, then add 1.20g (0.0048mol) 2,6-dichloro-3,5-dinitrotoluene in batches within 30 minutes, and continue the reaction at room temperature for 3 hours. After TLC monitoring of the reaction is completed, pour the reaction solution into 50 mL of saturated saline, extract with ethyl acetate, and dry the extract over anhydrous magnesium sulfate under reduced pressure. After desolvation and column chromatography (eluent: ethyl acetate and petroleum ether (boiling range 60-90°C), volume ratio 1:10), compound 43 was purified, 1.20 g of yellow solid, melting point 157-158°C.
1H-NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):8.95(s,1H),8.65(s,1H),8.29(s,2H),2.02(s,3H)。 1 H-NMR (300MHz, internal standard TMS, solvent CDCl 3 ) δ (ppm): 8.95 (s, 1H), 8.65 (s, 1H), 8.29 (s, 2H), 2.02 (s, 3H).
实例4：化合物183的制备
Example 4: Preparation of Compound 183
取2,6-二氯-4-硝基苯胺5.02g(0.02mol)于反应瓶中，加50mL N,N-二甲基甲酰胺(DMF)搅拌，加入无水氟化钾3.48g(0.06mol)和催化量18冠6，然后在80至90℃保温反应，TLC检测无原料剩余，冷却至室温。加入适量水，乙酸乙酯萃取(50mL×3)，有机相用无水硫酸镁干燥后减压脱溶，柱层析(洗脱剂为乙酸乙酯与石油醚(沸程60-90℃)，体积比为1:10)纯化得中间体D，淡黄色固体2.65g。
Take 5.02g (0.02mol) of 2,6-dichloro-4-nitroaniline in the reaction bottle, add 50mL of N,N-dimethylformamide (DMF), stir, and add 3.48g of anhydrous potassium fluoride (0.06 mol) and a catalytic amount of 18 Crown 6, and then insulate the reaction at 80 to 90°C. TLC detects that there is no remaining raw material, and cool to room temperature. Add an appropriate amount of water, extract with ethyl acetate (50mL , volume ratio is 1:10) and purified to obtain intermediate D, 2.65g of light yellow solid.
按照实例3的方法制备化合物183，黄色固体，熔点112-114℃。Compound 183 was prepared according to the method of Example 3, yellow solid, melting point 112-114°C.
1H-NMR(600MHz，内标TMS，溶剂CDCl3)δ(ppm):9.12(s,1H),8.94(d,1H),7.76(d,1H),7.45(dd,1H),6.70(d,1H),2.02(d,3H)。 1 H-NMR (600MHz, internal standard TMS, solvent CDCl 3 ) δ (ppm): 9.12 (s, 1H), 8.94 (d, 1H), 7.76 (d, 1H), 7.45 (dd, 1H), 6.70 ( d,1H),2.02(d,3H).
实例5：化合物290的制备
Example 5: Preparation of compound 290
将0.38g(0.001mol)化合物2加入到0.10g(0.0025mol)60％的氢化钠的10mL DMF悬浮液中，搅拌1小时，加入0.43g(0.003mol)碘甲烷，反应5小时。TLC监测反应完毕后，将反应液倒入50mL饱和食盐水中，乙酸乙酯萃取，萃取液用无水硫酸镁干燥，减压脱溶，柱层析(洗脱剂为乙酸乙酯与石油醚(沸程60-90℃)，体积比为1:10)纯化得化合物290，黄色固体0.15g，熔点142-144℃。Add 0.38g (0.001mol) compound 2 to 0.10g (0.0025mol) 60% sodium hydride suspension in 10mL DMF, stir for 1 hour, add 0.43g (0.003mol) methyl iodide, and react for 5 hours. After TLC monitoring of the reaction, pour the reaction solution into 50 mL of saturated brine, extract with ethyl acetate, dry the extract with anhydrous magnesium sulfate, elute under reduced pressure, and perform column chromatography (the eluent is ethyl acetate and petroleum ether ( (boiling range 60-90°C), volume ratio 1:10) was purified to obtain compound 290, 0.15g yellow solid, melting point 142-144°C.
1H-NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):8.04(s,1H),7.25(d,2H),7.09(d,1H),3.31(s,3H),2.54(s,3H)。 1 H-NMR (300MHz, internal standard TMS, solvent CDCl 3 ) δ (ppm): 8.04 (s, 1H), 7.25 (d, 2H), 7.09 (d, 1H), 3.31 (s, 3H), 2.54 ( s,3H).
实例6：化合物521的制备
Example 6: Preparation of compound 521
取0.42g化合物43(0.001mol)于微波反应瓶中，用2.5mL的二甲基亚砜(DMSO)将其溶解，加入25％的甲胺水溶液1mL后盖上盖子，放入Biotage微波合成仪中，在150℃下反 应40min。将反应液倒入50mL饱和食盐水中，乙酸乙酯萃取，萃取液用无水硫酸镁干燥，减压脱溶，柱层析(洗脱剂为乙酸乙酯与石油醚(沸程60-90℃)，体积比为1:20)纯化得化合物521，黄色固体0.25g，熔点218-219℃。Take 0.42g of compound 43 (0.001mol) in a microwave reaction bottle, dissolve it with 2.5mL of dimethyl sulfoxide (DMSO), add 1mL of 25% methylamine aqueous solution, close the lid, and put it into the Biotage microwave synthesizer. Medium, reverse at 150℃ Should be 40min. Pour the reaction solution into 50 mL saturated brine, extract with ethyl acetate, dry the extract with anhydrous magnesium sulfate, elute under reduced pressure, and perform column chromatography (eluent is ethyl acetate and petroleum ether (boiling range 60-90°C) ), volume ratio is 1:20) and purified compound 521, 0.25 g of yellow solid, melting point 218-219°C.
1H-NMR(300MHz，内标TMS，溶剂CDCl3)δ(ppm):9.58(s,1H),9.12(s,1H),8.31(s,2H),8.25(d,1H),3.09(d,3H),1.70(s,3H)。 1 H-NMR (300MHz, internal standard TMS, solvent CDCl 3 ) δ (ppm): 9.58 (s, 1H), 9.12 (s, 1H), 8.31 (s, 2H), 8.25 (d, 1H), 3.09 ( d,3H),1.70(s,3H).
本发明的其他化合物可以参照以上实例制备。Other compounds of the present invention can be prepared with reference to the above examples.
部分化合物的物性数据及核磁数据(1H NMR，内标TMS，ppm)如下：The physical property data and nuclear magnetic data ( 1H NMR, internal standard TMS, ppm) of some compounds are as follows:
化合物1：熔点136-138℃。δ(300MHz,CDCl3):9.00(s,1H),8.72(s,1H),7.26(m,1H),7.21(m,2H),2.12(s,3H)。Compound 1: melting point 136-138°C. δ (300MHz, CDCl 3 ): 9.00 (s, 1H), 8.72 (s, 1H), 7.26 (m, 1H), 7.21 (m, 2H), 2.12 (s, 3H).
化合物3：熔点122-123℃。δ(300MHz,CDCl3):8.84(s,1H),8.65(s,1H),7.28(d,1H,J＝8.7Hz),6.42(d,1H,J＝8.7Hz),2.17(s,3H)。Compound 3: melting point 122-123°C. δ (300MHz, CDCl 3 ): 8.84 (s, 1H), 8.65 (s, 1H), 7.28 (d, 1H, J = 8.7Hz), 6.42 (d, 1H, J = 8.7Hz), 2.17 (s, 3H).
化合物4：熔点142-143℃。δ(300MHz,CDCl3):8.80(s,1H),8.67(s,1H),7.58(s,1H),6.59(s,1H),2.20(s,3H)。Compound 4: melting point 142-143°C. δ (300MHz, CDCl 3 ): 8.80 (s, 1H), 8.67 (s, 1H), 7.58 (s, 1H), 6.59 (s, 1H), 2.20 (s, 3H).
化合物5：熔点160-162℃。δ(300MHz,CDCl3):9.19(s,1H),8.72(s,1H),7.41(s,2H),1.95(s,3H)。Compound 5: melting point 160-162°C. δ (300MHz, CDCl 3 ): 9.19 (s, 1H), 8.72 (s, 1H), 7.41 (s, 2H), 1.95 (s, 3H).
化合物7：熔点184-186℃。δ(300MHz,CDCl3):8.93(s,1H),8.66(s,1H),7.62(d,2H),6.87(d,2H),2.22(s,3H)。Compound 7: melting point 184-186°C. δ (300MHz, CDCl 3 ): 8.93 (s, 1H), 8.66 (s, 1H), 7.62 (d, 2H), 6.87 (d, 2H), 2.22 (s, 3H).
化合物8：熔点172-174℃。δ(300MHz,DMSO):9.49(s,1H),8.64(s,1H),8.06(d,2H),6.83(d,2H),2.34(s,3H)。Compound 8: melting point 172-174°C. δ(300MHz,DMSO):9.49(s,1H),8.64(s,1H),8.06(d,2H),6.83(d,2H),2.34(s,3H).
化合物9：熔点185-186℃。δ(300MHz,CDCl3):10.59(s,1H),9.23(s,1H),8.52(s,1H),8.31(d,1H),6.56(d,1H),2.41(s,3H)。Compound 9: melting point 185-186°C. δ (300MHz, CDCl 3 ): 10.59 (s, 1H), 9.23 (s, 1H), 8.52 (s, 1H), 8.31 (d, 1H), 6.56 (d, 1H), 2.41 (s, 3H).
化合物10：红色油状物。δ(300MHz,CDCl3):10.93(s,1H),9.09(s,2H),8.52(s,1H),2.27(s,3H)。Compound 10: red oil. δ (300MHz, CDCl 3 ): 10.93 (s, 1H), 9.09 (s, 2H), 8.52 (s, 1H), 2.27 (s, 3H).
化合物12：熔点91-94℃。δ(300MHz,CDCl3):9.20(s,1H),8.71(s,1H),7.21(d,2H),6.91(d,2H),2.14(s,3H)。Compound 12: melting point 91-94°C. δ (300MHz, CDCl 3 ): 9.20 (s, 1H), 8.71 (s, 1H), 7.21 (d, 2H), 6.91 (d, 2H), 2.14 (s, 3H).
化合物14：熔点107-109℃。δ(300MHz,CDCl3):9.42(s,1H),8.74(s,1H),6.89(m,4H),3.82(s,3H),2.06(s,3H)。Compound 14: melting point 107-109°C. δ (300MHz, CDCl 3 ): 9.42 (s, 1H), 8.74 (s, 1H), 6.89 (m, 4H), 3.82 (s, 3H), 2.06 (s, 3H).
化合物20：熔点206-208℃。δ(300MHz,CDCl3):9.08(s,1H),8.69(s,1H),7.95(d,2H,J＝8.4Hz),6.87(d,2H,J＝8.4Hz),2.59(s,3H),2.19(s,3H)。Compound 20: melting point 206-208°C. δ (300MHz, CDCl 3 ): 9.08 (s, 1H), 8.69 (s, 1H), 7.95 (d, 2H, J = 8.4Hz), 6.87 (d, 2H, J = 8.4Hz), 2.59 (s, 3H),2.19(s,3H).
化合物28：熔点158-160℃。δ(300MHz,CDCl3):8.56(s,1H),7.34(m,4H),7.12(m,2H),6.83(d,4H),2.10(s,3H)。Compound 28: melting point 158-160°C. δ (300MHz, CDCl 3 ): 8.56 (s, 1H), 7.34 (m, 4H), 7.12 (m, 2H), 6.83 (d, 4H), 2.10 (s, 3H).
化合物31：熔点106-108℃。δ(300MHz,CDCl3):8.87(s,1H),8.65(s,1H),7.75(s,1H),7.43(d,1H),6.55(d,1H),2.22(s,3H)。Compound 31: melting point 106-108°C. δ (300MHz, CDCl 3 ): 8.87 (s, 1H), 8.65 (s, 1H), 7.75 (s, 1H), 7.43 (d, 1H), 6.55 (d, 1H), 2.22 (s, 3H).
化合物32：熔点191-193℃。δ(300MHz,CDCl3):8.79(s,1H),8.62(s,1H),8.41(s,1H),8.06(d,1H),6.48(d,1H),2.29(s,3H)。Compound 32: melting point 191-193°C. δ (300MHz, CDCl 3 ): 8.79 (s, 1H), 8.62 (s, 1H), 8.41 (s, 1H), 8.06 (d, 1H), 6.48 (d, 1H), 2.29 (s, 3H).
化合物33：熔点206-208℃。δ(300MHz,CDCl3):8.80(s,1H),8.62(s,1H),7.77(s,1H),7.47(d,1H),6.48(d,1H),2.25(s,3H)。Compound 33: melting point 206-208°C. δ (300MHz, CDCl 3 ): 8.80 (s, 1H), 8.62 (s, 1H), 7.77 (s, 1H), 7.47 (d, 1H), 6.48 (d, 1H), 2.25 (s, 3H).
化合物34：熔点121-123℃。δ(300MHz,CDCl3):9.03(s,1H),8.74(s,1H),7.27(s,1H),7.10(d,1H),6.53(d,1H),2.40(s,3H),2.02(s,3H)。Compound 34: melting point 121-123°C. δ(300MHz, CDCl 3 ):9.03(s,1H),8.74(s,1H),7.27(s,1H),7.10(d,1H),6.53(d,1H),2.40(s,3H), 2.02(s,3H).
化合物36：熔点204-205℃。δ(300MHz,CDCl3):10.36(s,1H),8.54(s,1H),8.26(s,1H),7.43(d,1H),6.48(d,1H),2.31(s,3H)。Compound 36: melting point 204-205°C. δ (300MHz, CDCl 3 ): 10.36 (s, 1H), 8.54 (s, 1H), 8.26 (s, 1H), 7.43 (d, 1H), 6.48 (d, 1H), 2.31 (s, 3H).
化合物39：熔点148-150℃。δ(300MHz,CDCl3):8.97(s,1H),8.71(s,1H),7.72(s,1H),7.53(s,1H),2.07(s,3H)。Compound 39: melting point 148-150°C. δ (300MHz, CDCl 3 ): 8.97 (s, 1H), 8.71 (s, 1H), 7.72 (s, 1H), 7.53 (s, 1H), 2.07 (s, 3H).
化合物41：熔点154-156℃。δ(300MHz,CDCl3):9.94(s,1H),8.59(s,1H),7.80(m,1H),7.20(m,1H),2.21(s,3H)。Compound 41: melting point 154-156°C. δ (300MHz, CDCl 3 ): 9.94 (s, 1H), 8.59 (s, 1H), 7.80 (m, 1H), 7.20 (m, 1H), 2.21 (s, 3H).
化合物42：熔点140-142℃。δ(300MHz,CDCl3):8.94(s,1H),8.71(s,1H),7.19(d,2H),2.17(s, 3H)。Compound 42: melting point 140-142°C. δ(300MHz, CDCl 3 ):8.94(s,1H),8.71(s,1H),7.19(d,2H),2.17(s, 3H).
化合物44：熔点143-144℃。δ(300MHz,CDCl3):9.10(s,1H),8.70(s,1H),7.66(s,2H),1.98(s,3H)。Compound 44: melting point 143-144°C. δ (300MHz, CDCl 3 ): 9.10 (s, 1H), 8.70 (s, 1H), 7.66 (s, 2H), 1.98 (s, 3H).
化合物45：熔点180-182℃。δ(300MHz,CDCl3):9.00(s,1H),8.67(s,1H),7.69(s,2H),1.99(s,3H)。Compound 45: melting point 180-182°C. δ (300MHz, CDCl 3 ): 9.00 (s, 1H), 8.67 (s, 1H), 7.69 (s, 2H), 1.99 (s, 3H).
化合物47：熔点241-243℃。δ(300MHz,CDCl3):9.11(s,1H),8.69(s,1H),7.83(s,2H),1.97(s,3H)。Compound 47: melting point 241-243°C. δ (300MHz, CDCl 3 ): 9.11 (s, 1H), 8.69 (s, 1H), 7.83 (s, 2H), 1.97 (s, 3H).
化合物51：熔点259-261℃。δ(300MHz,CDCl3):10.51(s,1H),8.62(s,1H),8.50(s,1H),7.70(d,1H),6.54(d,1H),2.38(s,3H)。Compound 51: melting point 259-261°C. δ (300MHz, CDCl 3 ): 10.51 (s, 1H), 8.62 (s, 1H), 8.50 (s, 1H), 7.70 (d, 1H), 6.54 (d, 1H), 2.38 (s, 3H).
化合物52：熔点171-173℃。δ(300MHz,CDCl3):10.60(s,1H),8.87(s,1H),8.53(s,1H),8.07(d,1H,J＝9.0Hz),6.53(d,1H,J＝9.0Hz),2.63(s,3H),2.37(s,3H)。Compound 52: melting point 171-173°C. δ (300MHz, CDCl 3 ): 10.60 (s, 1H), 8.87 (s, 1H), 8.53 (s, 1H), 8.07 (d, 1H, J = 9.0Hz), 6.53 (d, 1H, J = 9.0 Hz),2.63(s,3H),2.37(s,3H).
化合物61：熔点160-162℃。δ(300MHz,CDCl3):9.97(s,1H),8.55(s,1H),8.32(d,1H),7.88(d,1H),2.18(s,3H)。Compound 61: melting point 160-162°C. δ (300MHz, CDCl 3 ): 9.97 (s, 1H), 8.55 (s, 1H), 8.32 (d, 1H), 7.88 (d, 1H), 2.18 (s, 3H).
化合物62：熔点169-171℃。δ(300MHz,CDCl3):10.14(s,1H),8.99(s,1H),8.50(d,2H),2.26(s,3H)。Compound 62: melting point 169-171°C. δ (300MHz, CDCl 3 ): 10.14 (s, 1H), 8.99 (s, 1H), 8.50 (d, 2H), 2.26 (s, 3H).
化合物63：熔点204-206℃。δ(300MHz,CDCl3):10.00(s,1H),8.51(s,1H),8.38(s,1H),7.87(s,1H),2.23(s,3H)。Compound 63: melting point 204-206°C. δ (300MHz, CDCl 3 ): 10.00 (s, 1H), 8.51 (s, 1H), 8.38 (s, 1H), 7.87 (s, 1H), 2.23 (s, 3H).
化合物67：熔点187-190℃。δ(300MHz,CDCl3):10.39(s,1H),8.57(s,1H),8.23(s,2H),2.18(s,3H)。Compound 67: melting point 187-190°C. δ (300MHz, CDCl 3 ): 10.39 (s, 1H), 8.57 (s, 1H), 8.23 (s, 2H), 2.18 (s, 3H).
化合物69：熔点93-95℃。δ(300MHz,CDCl3):10.42(s,1H),8.56(s,1H),8.14(s,2H),2.19(s,3H)。Compound 69: melting point 93-95°C. δ (300MHz, CDCl 3 ): 10.42 (s, 1H), 8.56 (s, 1H), 8.14 (s, 2H), 2.19 (s, 3H).
化合物77：橘红色油状物。δ(300MHz,DMSO):9.54(s,1H),6.92(d,1H),8.63(s,1H),7.78(d,1H),7.26(s,1H),2.33(s,3H)。Compound 77: orange-red oil. δ(300MHz,DMSO):9.54(s,1H),6.92(d,1H),8.63(s,1H),7.78(d,1H),7.26(s,1H),2.33(s,3H).
化合物78：熔点204-206℃。δ(300MHz,DMSO):10.40(s,1H),8.86(s,1H),8.73(s,1H),7.03(s,1H),2.32(s,3H)。Compound 78: melting point 204-206°C. δ(300MHz,DMSO):10.40(s,1H),8.86(s,1H),8.73(s,1H),7.03(s,1H),2.32(s,3H).
化合物79：熔点125-127℃。δ(300MHz,CDCl3):9.29(s,1H),8.75(s,1H),7.53(s,2H),1.94(s,3H)。Compound 79: melting point 125-127°C. δ (300MHz, CDCl 3 ): 9.29 (s, 1H), 8.75 (s, 1H), 7.53 (s, 2H), 1.94 (s, 3H).
化合物81：熔点160-161℃。δ(300MHz,CDCl3):8.96(s,1H),8.68(s,1H),7.19(d,1H),6.40(d,1H),2.54(s,3H),2.13(s,3H)。Compound 81: melting point 160-161°C. δ (300MHz, CDCl 3 ): 8.96 (s, 1H), 8.68 (s, 1H), 7.19 (d, 1H), 6.40 (d, 1H), 2.54 (s, 3H), 2.13 (s, 3H).
化合物83：熔点110-112℃。δ(300MHz,CDCl3):9.06(s,1H),8.73(s,1H),7.24(d,1H),7.05(t,1H),6.50(d,1H),2.50(s,3H),2.03(s,3H)。Compound 83: melting point 110-112°C. δ(300MHz, CDCl 3 ):9.06(s,1H),8.73(s,1H),7.24(d,1H),7.05(t,1H),6.50(d,1H),2.50(s,3H), 2.03(s,3H).
化合物84：熔点133-135℃。δ(300MHz,CDCl3):9.08(s,1H),8.74(s,1H),7.21(d,1H),7.06(t,1H),6.53(d,1H),2.50(s,3H),2.03(s,3H)。Compound 84: melting point 133-135°C. δ(300MHz, CDCl 3 ):9.08(s,1H),8.74(s,1H),7.21(d,1H),7.06(t,1H),6.53(d,1H),2.50(s,3H), 2.03(s,3H).
化合物86：熔点158-161℃。δ(300MHz,CDCl3):8.85(s,1H),8.69(s,1H),7.67(d,1H),6.47(d,1H),2.61(s,3H),2.16(s,3H)。Compound 86: melting point 158-161°C. δ (300MHz, CDCl 3 ): 8.85 (s, 1H), 8.69 (s, 1H), 7.67 (d, 1H), 6.47 (d, 1H), 2.61 (s, 3H), 2.16 (s, 3H).
化合物88：熔点172-175℃。δ(300MHz,DMSO):9.50(s,1H),8.68(s,2H),8.49(s,1H),2.32(s,3H)。Compound 88: melting point 172-175°C. δ(300MHz,DMSO):9.50(s,1H),8.68(s,2H),8.49(s,1H),2.32(s,3H).
化合物89：熔点136-138℃。δ(300MHz,CDCl3):10.10(s,1H),8.72(s,1H),8.50(s,1H),2.41(s,3H)。Compound 89: melting point 136-138°C. δ (300MHz, CDCl 3 ): 10.10 (s, 1H), 8.72 (s, 1H), 8.50 (s, 1H), 2.41 (s, 3H).
化合物90：熔点127-129℃。δ(300MHz,CDCl3):10.31(s,1H),8.54(s,1H),8.40(s,1H),6.55(s,1H),2.36(s,3H)。Compound 90: melting point 127-129°C. δ (300MHz, CDCl 3 ): 10.31 (s, 1H), 8.54 (s, 1H), 8.40 (s, 1H), 6.55 (s, 1H), 2.36 (s, 3H).
化合物91：熔点169-171℃。δ(300MHz,CDCl3):8.62(s,1H),8.60(s,1H),8.20(s,1H),6.42(s,1H),2.32(s,3H)。Compound 91: melting point 169-171°C. δ (300MHz, CDCl 3 ): 8.62 (s, 1H), 8.60 (s, 1H), 8.20 (s, 1H), 6.42 (s, 1H), 2.32 (s, 3H).
化合物96：熔点159-162℃。δ(300MHz,CDCl3):8.91(s,1H),8.63(s,1H),8.23(s,1H),2.16(s,3H)。Compound 96: melting point 159-162°C. δ (300MHz, CDCl 3 ): 8.91 (s, 1H), 8.63 (s, 1H), 8.23 (s, 1H), 2.16 (s, 3H).
化合物97：熔点133-135℃。δ(300MHz,CDCl3):9.22(s,1H),8.69(s,1H),7.70(s,1H),2.07(s, 3H)。Compound 97: melting point 133-135°C. δ(300MHz, CDCl 3 ):9.22(s,1H),8.69(s,1H),7.70(s,1H),2.07(s, 3H).
化合物101：熔点96-97℃。δ(300MHz,CDCl3):8.78(s,1H),8.66(s,1H),7.49(s,1H),6.59(s,1H),2.21(s,3H)。Compound 101: melting point 96-97°C. δ (300MHz, CDCl 3 ): 8.78 (s, 1H), 8.66 (s, 1H), 7.49 (s, 1H), 6.59 (s, 1H), 2.21 (s, 3H).
化合物102：熔点192-194℃。δ(300MHz,CDCl3):9.43(s,1H),9.07(s,1H),8.22(s,1H),8.04(s,1H),7.05(s,2H),2.20(s,3H)。Compound 102: melting point 192-194°C. δ (300MHz, CDCl 3 ): 9.43 (s, 1H), 9.07 (s, 1H), 8.22 (s, 1H), 8.04 (s, 1H), 7.05 (s, 2H), 2.20 (s, 3H).
化合物103：熔点132-134℃。δ(300MHz,CDCl3):9.34(s,1H),8.74(s,1H),7.35(t,2H,J＝8.1Hz),7.18(t,1H,J＝8.1Hz),6.90(d,2H),2.11(s,3H)。Compound 103: melting point 132-134°C. δ (300MHz, CDCl 3 ): 9.34 (s, 1H), 8.74 (s, 1H), 7.35 (t, 2H, J = 8.1Hz), 7.18 (t, 1H, J = 8.1Hz), 6.90 (d, 2H),2.11(s,3H).
化合物104：熔点150-151℃。δ(300MHz,CDCl3):9.02(s,1H),8.69(s,1H),7.48(dd,1H,3J＝7.8Hz,4J＝1.5Hz),7.14-7.19(m,1H),7.04-7.10(m,1H),6.61(d,1H,J＝8.1Hz),2.13(s,3H)。Compound 104: melting point 150-151°C. δ(300MHz, CDCl 3 ):9.02(s,1H),8.69(s,1H),7.48(dd,1H, 3 J＝7.8Hz, 4 J＝1.5Hz),7.14-7.19(m,1H), 7.04-7.10(m,1H),6.61(d,1H,J=8.1Hz),2.13(s,3H).
化合物105：熔点120-122℃。δ(300MHz,CDCl3):9.09(s,1H),8.68(s,1H),7.24-7.29(m,1H),7.12(d,1H,J＝7.5Hz),6.88(s,1H),6.76(d,1H,J＝8.1Hz),2.16(s,3H3)。Compound 105: melting point 120-122°C. δ (300MHz, CDCl 3 ): 9.09 (s, 1H), 8.68 (s, 1H), 7.24-7.29 (m, 1H), 7.12 (d, 1H, J = 7.5Hz), 6.88 (s, 1H), 6.76 (d, 1H, J = 8.1Hz), 2.16 (s, 3H 3 ).
化合物106：熔点120-122℃。δ(300MHz,CDCl3):δ9.17(s,1H),8.70(s,1H),7.31(d,2H,J＝9.0Hz),6.83(d,2H,J＝9.0Hz),2.13(s,3H)。Compound 106: melting point 120-122°C. δ (300MHz, CDCl 3 ): δ9.17 (s, 1H), 8.70 (s, 1H), 7.31 (d, 2H, J = 9.0Hz), 6.83 (d, 2H, J = 9.0Hz), 2.13 ( s,3H).
化合物107：熔点183-185℃。δ(300MHz,CDCl3):9.37(s,1H),8.75(s,1H),7.35(d,2H,J＝8.7Hz),6.85(d,2H,J＝8.4Hz),2.10(s,3H),1.32(s,9H3)。Compound 107: melting point 183-185°C. δ (300MHz, CDCl 3 ): 9.37 (s, 1H), 8.75 (s, 1H), 7.35 (d, 2H, J = 8.7Hz), 6.85 (d, 2H, J = 8.4Hz), 2.10 (s, 3H),1.32(s,9H 3 ).
化合物108：熔点158-160℃。δ(300MHz,CDCl3):8.90(s,1H),8.66(s,1H),7.22(d,1H,J＝8.1Hz),7.11(t,1H,J＝7.8Hz),2.16(s,3H)。Compound 108: melting point 158-160°C. δ (300MHz, CDCl 3 ): 8.90 (s, 1H), 8.66 (s, 1H), 7.22 (d, 1H, J = 8.1Hz), 7.11 (t, 1H, J = 7.8Hz), 2.16 (s, 3H).
化合物109：熔点166-168℃。δ(300MHz,CDCl3):9.29(s,1H),8.73(s,1H),7.40(d,2H,J＝8.1Hz),7.19(t,1H,J＝8.1Hz),1.94(s,3H)。Compound 109: melting point 166-168°C. δ (300MHz, CDCl 3 ): 9.29 (s, 1H), 8.73 (s, 1H), 7.40 (d, 2H, J = 8.1Hz), 7.19 (t, 1H, J = 8.1Hz), 1.94 (s, 3H).
化合物110：熔点106-108℃。δ(300MHz,CDCl3):9.04(s,1H),8.69(s,1H),7.39(d,1H,J＝7.8Hz),6.98(s,1H),6.72(dd,1H,3J＝8.4Hz,4J＝2.4Hz),2.17(s,3H)。Compound 110: melting point 106-108°C. δ (300MHz, CDCl 3 ): 9.04 (s, 1H), 8.69 (s, 1H), 7.39 (d, 1H, J = 7.8Hz), 6.98 (s, 1H), 6.72 (dd, 1H, 3 J = 8.4Hz, 4 J＝2.4Hz), 2.17 (s, 3H).
化合物111：熔点148-150℃。δ(300MHz,CDCl3):8.91(s,1H),8.70(s,1H),7.12(s,1H),6.73(s,2H),2.21(s,3H)。Compound 111: melting point 148-150°C. δ (300MHz, CDCl 3 ): 8.91 (s, 1H), 8.70 (s, 1H), 7.12 (s, 1H), 6.73 (s, 2H), 2.21 (s, 3H).
化合物112：熔点178-180℃。δ(300MHz,CDCl3):8.88(s,1H),8.64(s,1H),8.08(s,1H),7.77(d,1H,J＝8.4Hz),6.51(d,1H,J＝8.4Hz),2.58(s,3H),2.23(s,3H)。Compound 112: melting point 178-180°C. δ (300MHz, CDCl 3 ): 8.88 (s, 1H), 8.64 (s, 1H), 8.08 (s, 1H), 7.77 (d, 1H, J = 8.4Hz), 6.51 (d, 1H, J = 8.4 Hz),2.58(s,3H),2.23(s,3H).
化合物115：熔点163-164℃。δ(300MHz,CDCl3):8.94(s,1H),8.87(s,1H),6.88(s,2H),2.22(s,3H)。Compound 115: melting point 163-164°C. δ (300MHz, CDCl 3 ): 8.94 (s, 1H), 8.87 (s, 1H), 6.88 (s, 2H), 2.22 (s, 3H).
化合物116：熔点151-153℃。δ(300MHz,CDCl3):9.00(s,1H),8.66(s,1H),8.47(d,1H),8.31(d,1H),1.99(s,3H)。Compound 116: melting point 151-153°C. δ (300MHz, CDCl 3 ): 9.00 (s, 1H), 8.66 (s, 1H), 8.47 (d, 1H), 8.31 (d, 1H), 1.99 (s, 3H).
化合物117：熔点151-154℃。δ(300MHz,CDCl3):9.03(s,1H),8.68(s,1H),8.49(s,2H),1.97(s,3H)。Compound 117: melting point 151-154°C. δ (300MHz, CDCl 3 ): 9.03 (s, 1H), 8.68 (s, 1H), 8.49 (s, 2H), 1.97 (s, 3H).
化合物118：熔点132-134℃。δ(300MHz,CDCl3):9.13(s,1H),8.70(s,1H),8.05(s,2H),3.96(s,3H),1.95(s,3H)。Compound 118: melting point 132-134°C. δ (300MHz, CDCl 3 ): 9.13 (s, 1H), 8.70 (s, 1H), 8.05 (s, 2H), 3.96 (s, 3H), 1.95 (s, 3H).
化合物119：熔点135-137℃。δ(300MHz,CDCl3):8.82(s,1H),8.63(s,1H),8.26(t,1H),7.95(dd,1H),2.16(s,3H)。Compound 119: melting point 135-137°C. δ (300MHz, CDCl 3 ): 8.82 (s, 1H), 8.63 (s, 1H), 8.26 (t, 1H), 7.95 (dd, 1H), 2.16 (s, 3H).
化合物120：熔点131-132℃。δ(300MHz,CDCl3):8.98(s,1H),8.72(s,1H),7.17(m,1H),6.99(t,2H),2.10(s,3H)。Compound 120: melting point 131-132°C. δ (300MHz, CDCl 3 ): 8.98 (s, 1H), 8.72 (s, 1H), 7.17 (m, 1H), 6.99 (t, 2H), 2.10 (s, 3H).
化合物121：熔点148-150℃。δ(300MHz,CDCl3):8.87(s,1H),8.70(s,1H),7.04(d,2H),2.12(s,3H)。Compound 121: melting point 148-150°C. δ (300MHz, CDCl 3 ): 8.87 (s, 1H), 8.70 (s, 1H), 7.04 (d, 2H), 2.12 (s, 3H).
化合物122：δ(300MHz,CDCl3):9.14(s,1H),8.70(s,1H),7.78(s,2H),3.03(d,3H),1.94(s,3H)。Compound 122: δ (300MHz, CDCl 3 ): 9.14 (s, 1H), 8.70 (s, 1H), 7.78 (s, 2H), 3.03 (d, 3H), 1.94 (s, 3H).
化合物123：熔点216-219℃。δ(300MHz,CDCl3):8.85(s,1H),8.48(s,1H),7.88(s,2H),2.30(s,3H)。Compound 123: melting point 216-219°C. δ (300MHz, CDCl 3 ): 8.85 (s, 1H), 8.48 (s, 1H), 7.88 (s, 2H), 2.30 (s, 3H).
化合物124：熔点146-148℃。δ(300MHz,CDCl3):9.52(s,1H),8.80(s,1H),7.28(m,1H),7.18(m,2H),2.40(s,3H),1.86(s,3H)。 Compound 124: melting point 146-148°C. δ (300MHz, CDCl 3 ): 9.52 (s, 1H), 8.80 (s, 1H), 7.28 (m, 1H), 7.18 (m, 2H), 2.40 (s, 3H), 1.86 (s, 3H).
化合物125：熔点137-139℃。δ(300MHz,CDCl3):9.20(s,1H),8.73(s,1H),8.21(s,1H),8.10(s,1H),2.31(s,3H),1.91(s,3H)。Compound 125: melting point 137-139°C. δ (300MHz, CDCl 3 ): 9.20 (s, 1H), 8.73 (s, 1H), 8.21 (s, 1H), 8.10 (s, 1H), 2.31 (s, 3H), 1.91 (s, 3H).
化合物126：棕色固体，熔点70-72℃。δ(600MHz,CDCl3):9.58(s,1H),9.00(d,1H),7.40–7.34(dt,2H),7.24–7.18(t,1H),7.02–6.95(dd,2H),1.89(d,3H)。Compound 126: brown solid, melting point 70-72°C. δ(600MHz, CDCl 3 ):9.58(s,1H),9.00(d,1H),7.40–7.34(dt,2H),7.24–7.18(t,1H),7.02–6.95(dd,2H),1.89 (d,3H).
化合物132：褐色固体，熔点131-133℃。δ(600MHz,CDCl3):9.15(s,1H),8.94(d,1H),7.13(d,1H),6.75(d,1H),6.63(dd,1H),1.98(d,3H)。Compound 132: brown solid, melting point 131-133°C. δ (600MHz, CDCl 3 ): 9.15 (s, 1H), 8.94 (d, 1H), 7.13 (d, 1H), 6.75 (d, 1H), 6.63 (dd, 1H), 1.98 (d, 3H).
化合物137：黄色固体，熔点147-149℃。δ(600MHz,CDCl3):9.10(s,1H),8.96(d,1H),7.59(s,1H),6.77(s,1H),2.00(d,3H)。Compound 137: yellow solid, melting point 147-149°C. δ (600MHz, CDCl 3 ): 9.10 (s, 1H), 8.96 (d, 1H), 7.59 (s, 1H), 6.77 (s, 1H), 2.00 (d, 3H).
化合物138：黄色固体，熔点163-165℃。δ(600MHz,CDCl3):9.47(s,1H),9.01(d,1H),7.43(s,2H),1.75(d,3H)。Compound 138: yellow solid, melting point 163-165°C. δ (600MHz, CDCl 3 ): 9.47 (s, 1H), 9.01 (d, 1H), 7.43 (s, 2H), 1.75 (d, 3H).
化合物143：黄色固体。δ(600MHz,CDCl3):9.23(s,1H),8.99(d,J＝7.9Hz,1H),7.23(td,J＝8.4,4.2Hz,1H),7.05–6.95(m,2H),1.88(d,J＝3.1Hz,3H)。Compound 143: yellow solid. δ(600MHz, CDCl 3 ):9.23(s,1H),8.99(d,J＝7.9Hz,1H),7.23(td,J＝8.4,4.2Hz,1H),7.05–6.95(m,2H), 1.88(d,J=3.1Hz,3H).
化合物144：红褐色固体，熔点126-128℃。δ(600MHz,CDCl3):9.20(s,1H),8.98(d,1H),6.98(m,1H),6.69(m,1H),1.94(d,3H)。Compound 144: reddish brown solid, melting point 126-128°C. δ (600MHz, CDCl 3 ): 9.20 (s, 1H), 8.98 (d, 1H), 6.98 (m, 1H), 6.69 (m, 1H), 1.94 (d, 3H).
化合物150：黑色固体，熔点123-125℃。δ(600MHz,CDCl3):9.53(s,1H),9.00(d,1H),7.78(d,2H),1.73(d,3H)。Compound 150: black solid, melting point 123-125°C. δ (600MHz, CDCl 3 ): 9.53 (s, 1H), 9.00 (d, 1H), 7.78 (d, 2H), 1.73 (d, 3H).
化合物151：褐色油状物。δ(600MHz,CDCl3):9.28(s,1H),8.98(d,1H),7.96–7.87(dd,1H),7.35–7.28(dt,1H),7.00–6.89(dt,1H),6.75(dd,1H),1.84(d,3H)。Compound 151: brown oil. δ(600MHz, CDCl 3 ):9.28(s,1H),8.98(d,1H),7.96–7.87(dd,1H),7.35–7.28(dt,1H),7.00–6.89(dt,1H),6.75 (dd,1H),1.84(d,3H).
化合物185：黄色固体。δ(600MHz,CDCl3):9.03(s,1H),8.92(d,J＝7.6Hz,1H),7.78(d,J＝1.8Hz,1H),7.49(dd,J＝8.4,1.8Hz,1H),6.61(d,J＝8.4Hz,1H),2.06(d,J＝3.2Hz,3H)。Compound 185: yellow solid. δ (600MHz, CDCl 3 ): 9.03 (s, 1H), 8.92 (d, J = 7.6Hz, 1H), 7.78 (d, J = 1.8Hz, 1H), 7.49 (dd, J = 8.4, 1.8Hz, 1H), 6.61 (d, J = 8.4Hz, 1H), 2.06 (d, J = 3.2Hz, 3H).
化合物200：黄色固体，熔点146-148℃。δ(600MHz,CDCl3):10.66(s,1H),8.86(d,1H),8.57(d,1H),7.71(dd,1H),6.67(d,1H),2.20(d,3H)。Compound 200: yellow solid, melting point 146-148°C. δ (600MHz, CDCl 3 ): 10.66 (s, 1H), 8.86 (d, 1H), 8.57 (d, 1H), 7.71 (dd, 1H), 6.67 (d, 1H), 2.20 (d, 3H).
化合物210：褐色油状物。δ(600MHz,CDCl3):11.44(s,1H),8.89(d,1H),7.23(m,2H),6.71(d,1H),2.35(d,3H),2.20(s,3H)。Compound 210: brown oil. δ (600MHz, CDCl 3 ): 11.44 (s, 1H), 8.89 (d, 1H), 7.23 (m, 2H), 6.71 (d, 1H), 2.35 (d, 3H), 2.20 (s, 3H).
化合物213：橙黄色固体，熔点134-136℃。δ(600MHz,CDCl3):9.55(s,1H),8.95(d,1H),7.37(t,1H),7.32(dd,1H),6.68(d,1H),1.99(d,3H)。Compound 213: orange-yellow solid, melting point 134-136°C. δ (600MHz, CDCl 3 ): 9.55 (s, 1H), 8.95 (d, 1H), 7.37 (t, 1H), 7.32 (dd, 1H), 6.68 (d, 1H), 1.99 (d, 3H).
化合物215：橙黄色固体，熔点151-153℃。δ(600MHz,CDCl3):9.16(s,1H),8.98(d,1H),7.94(d,1H),7.67(d,1H),7.43(s,1H),2.04(d,3H)。Compound 215: orange-yellow solid, melting point 151-153°C. δ (600MHz, CDCl 3 ): 9.16 (s, 1H), 8.98 (d, 1H), 7.94 (d, 1H), 7.67 (d, 1H), 7.43 (s, 1H), 2.04 (d, 3H).
化合物216：黄色固体，熔点118-120℃。δ(600MHz,CDCl3):9.21(s,1H),8.98(d,1H),7.44(dd,1H),7.31(t,1H),7.09(m,1H),1.97(d,3H)。Compound 216: yellow solid, melting point 118-120°C. δ (600MHz, CDCl 3 ): 9.21 (s, 1H), 8.98 (d, 1H), 7.44 (dd, 1H), 7.31 (t, 1H), 7.09 (m, 1H), 1.97 (d, 3H).
化合物223：红色固体，熔点127-129℃。δ(600MHz,CDCl3):9.66(s,1H),9.00(d,1H),6.82(d,1H),6.60(d,1H),6.55(d,1H),3.90(s,3H),3.87(s,3H),1.88(d,3H)。Compound 223: red solid, melting point 127-129°C. δ(600MHz, CDCl 3 ):9.66(s,1H),9.00(d,1H),6.82(d,1H),6.60(d,1H),6.55(d,1H),3.90(s,3H), 3.87(s,3H),1.88(d,3H).
化合物224：黄色固体，熔点152-154℃。δ(600MHz,CDCl3):9.11(s,1H),8.95(d,1H),7.80(d,1H),7.23(d,1H),7.03(dd,1H),2.07(d,3H)。Compound 224: yellow solid, melting point 152-154°C. δ (600MHz, CDCl 3 ): 9.11 (s, 1H), 8.95 (d, 1H), 7.80 (d, 1H), 7.23 (d, 1H), 7.03 (dd, 1H), 2.07 (d, 3H).
化合物225：黄色固体，熔点104-106℃。δ(600MHz,CDCl3):9.36(s,1H),8.99(d,1H),7.51(d,1H),7.28(d,1H),7.02(dd,1H),1.94(d,3H)。Compound 225: yellow solid, melting point 104-106°C. δ (600MHz, CDCl 3 ): 9.36 (s, 1H), 8.99 (d, 1H), 7.51 (d, 1H), 7.28 (d, 1H), 7.02 (dd, 1H), 1.94 (d, 3H).
化合物234：黄色固体。δ(600MHz,CDCl3):9.01–8.91(m,2H),8.03–7.89(m,2H),2.02(d,J＝3.0Hz,3H)。Compound 234: yellow solid. δ (600MHz, CDCl 3 ): 9.01–8.91 (m, 2H), 8.03–7.89 (m, 2H), 2.02 (d, J = 3.0Hz, 3H).
化合物235：黄色固体，熔点141-142℃。δ(600MHz,CDCl3):9.27(s,1H),8.96(d,J＝7.7Hz,1H),8.31(s,2H),1.80(d,J＝2.8Hz,3H)。Compound 235: yellow solid, melting point 141-142°C. δ (600MHz, CDCl 3 ): 9.27 (s, 1H), 8.96 (d, J = 7.7 Hz, 1H), 8.31 (s, 2H), 1.80 (d, J = 2.8 Hz, 3H).
化合物236：黄色固体。δ(600MHz,CDCl3):9.40(s,1H),8.99(d,J＝7.8Hz,1H),7.68(s,2H),1.76(d,J＝2.9Hz,3H)。Compound 236: yellow solid. δ (600MHz, CDCl 3 ): 9.40 (s, 1H), 8.99 (d, J = 7.8 Hz, 1H), 7.68 (s, 2H), 1.76 (d, J = 2.9 Hz, 3H).
化合物237：黄色固体。δ(600MHz,CDCl3):9.29(s,1H),8.96(d,J＝7.7Hz,1H),7.71(s,2H),1.78(d,J＝2.6Hz,3H)。Compound 237: yellow solid. δ (600MHz, CDCl 3 ): 9.29 (s, 1H), 8.96 (d, J = 7.7 Hz, 1H), 7.71 (s, 2H), 1.78 (d, J = 2.6 Hz, 3H).
化合物240：黄色固体。δ(600MHz,CDCl3):9.41(s,1H),8.98(d,J＝7.8Hz,1H),8.07(s,2H),1.74(d,J＝2.9Hz,3H)。 Compound 240: yellow solid. δ (600MHz, CDCl 3 ): 9.41 (s, 1H), 8.98 (d, J = 7.8 Hz, 1H), 8.07 (s, 2H), 1.74 (d, J = 2.9 Hz, 3H).
化合物242：黄色固体，熔点199-200℃。δ(600MHz,CDCl3):9.35(s,1H),8.98(d,J＝7.7Hz,1H),8.51(s,2H),1.76(d,J＝2.8Hz,3H)。Compound 242: yellow solid, melting point 199-200°C. δ (600MHz, CDCl 3 ): 9.35 (s, 1H), 8.98 (d, J = 7.7 Hz, 1H), 8.51 (s, 2H), 1.76 (d, J = 2.8 Hz, 3H).
化合物243：黄色固体，熔点126-128℃。δ(600MHz,CDCl3):9.50(s,1H),9.01(d,1H),7.90(d,2H),1.74(d,3H)。Compound 243: yellow solid, melting point 126-128°C. δ (600MHz, CDCl 3 ): 9.50 (s, 1H), 9.01 (d, 1H), 7.90 (d, 2H), 1.74 (d, 3H).
化合物244：黄色固体。δ(600MHz,CDCl3):9.58(s,1H),9.02(d,J＝7.8Hz,1H),7.54(s,2H),1.73(d,J＝2.7Hz,3H)。Compound 244: yellow solid. δ (600MHz, CDCl 3 ): 9.58 (s, 1H), 9.02 (d, J = 7.8 Hz, 1H), 7.54 (s, 2H), 1.73 (d, J = 2.7 Hz, 3H).
化合物245：黄色固体。δ(600MHz,CDCl3):9.09(s,1H),8.93(d,J＝7.6Hz,1H),8.30–8.23(m,1H),7.98(dd,J＝10.6,2.4Hz,1H),1.95(d,J＝3.0Hz,3H)。Compound 245: yellow solid. δ(600MHz, CDCl 3 ):9.09(s,1H),8.93(d,J＝7.6Hz,1H),8.30–8.23(m,1H),7.98(dd,J＝10.6,2.4Hz,1H), 1.95(d,J=3.0Hz,3H).
化合物246：黄色固体，熔点109-111℃。δ(600MHz,CDCl3):9.31(s,1H),8.97(d,J＝7.7Hz,1H),8.48(d,J＝2.5Hz,1H),8.33(d,J＝2.5Hz,1H),1.78(d,J＝2.9Hz,3H)。Compound 246: yellow solid, melting point 109-111°C. δ (600MHz, CDCl 3 ): 9.31 (s, 1H), 8.97 (d, J = 7.7Hz, 1H), 8.48 (d, J = 2.5Hz, 1H), 8.33 (d, J = 2.5Hz, 1H) ,1.78(d,J=2.9Hz,3H).
化合物247：黄色固体。δ(600MHz,CDCl3):9.49(s,1H),9.01(d,J＝7.8Hz,1H),8.22(d,J＝2.4Hz,1H),8.11(d,J＝2.1Hz,1H),2.37(s,3H),1.70(d,J＝2.9Hz,3H)。Compound 247: yellow solid. δ(600MHz, CDCl 3 ):9.49(s,1H),9.01(d,J＝7.8Hz,1H),8.22(d,J＝2.4Hz,1H),8.11(d,J＝2.1Hz,1H) ,2.37(s,3H),1.70(d,J＝2.9Hz,3H).
化合物277：黄色固体，熔点109-111℃。δ(600MHz,CDCl3):9.60(s,1H),8.89(d,1H),7.29(d,1H),7.19(d,1H),2.42(s,3H),2.35(d,3H)。Compound 277: yellow solid, melting point 109-111°C. δ (600MHz, CDCl 3 ): 9.60 (s, 1H), 8.89 (d, 1H), 7.29 (d, 1H), 7.19 (d, 1H), 2.42 (s, 3H), 2.35 (d, 3H).
化合物278：黄色固体，熔点118-120℃。δ(600MHz,CDCl3):9.16(s,1H),8.96(d,1H),6.94(s,2H),6.17–5.94(m,1H),2.05(d,3H)。Compound 278: yellow solid, melting point 118-120°C. δ (600MHz, CDCl 3 ): 9.16 (s, 1H), 8.96 (d, 1H), 6.94 (s, 2H), 6.17–5.94 (m, 1H), 2.05 (d, 3H).
化合物293：熔点138-140℃。δ(300MHz,CDCl3):8.08(s,1H),7.57(d,1H),7.48(s,1H),7.23(d,1H),3.37(s,3H),2.58(s,3H)。Compound 293: melting point 138-140°C. δ (300MHz, CDCl 3 ): 8.08 (s, 1H), 7.57 (d, 1H), 7.48 (s, 1H), 7.23 (d, 1H), 3.37 (s, 3H), 2.58 (s, 3H).
化合物304：熔点140-142℃。δ(300MHz,CDCl3):8.57(s,2H),8.38(s,1H),3.30(s,3H),2.58(s,3H)。Compound 304: melting point 140-142°C. δ (300MHz, CDCl 3 ): 8.57 (s, 2H), 8.38 (s, 1H), 3.30 (s, 3H), 2.58 (s, 3H).
化合物364：红色固体，熔点90-92℃。δ(600MHz,CDCl3):8.87(s,1H),7.22(d,1H),7.09(dd,1H),6.94(d,1H),2.17(d,3H),1.73(s,3H)。Compound 364: red solid, melting point 90-92°C. δ (600MHz, CDCl 3 ): 8.87 (s, 1H), 7.22 (d, 1H), 7.09 (dd, 1H), 6.94 (d, 1H), 2.17 (d, 3H), 1.73 (s, 3H).
化合物413：熔点134-136℃。δ(300MHz,CDCl3):9.18(s,1H),8.74(s,1H),8.29(s,2H),3.96(s,3H),1.79(s,3H)。Compound 413: melting point 134-136°C. δ (300MHz, CDCl 3 ): 9.18 (s, 1H), 8.74 (s, 1H), 8.29 (s, 2H), 3.96 (s, 3H), 1.79 (s, 3H).
化合物438：棕色油状物。δ(600MHz,CDCl3):8.85(s,1H),8.69(s,1H),7.72(d,1H),7.39(d,1H),6.55(d,1H),4.41(m,1H),2.07–2.01(s,3H),1.40–1.34(m,6H)。Compound 438: brown oil. δ(600MHz, CDCl 3 ):8.85(s,1H),8.69(s,1H),7.72(d,1H),7.39(d,1H),6.55(d,1H),4.41(m,1H), 2.07–2.01(s,3H),1.40–1.34(m,6H).
化合物485：熔点132-134℃。δ(300MHz,CDCl3):8.95(s,1H),8.47(s,1H),8.29(s,2H),2.39(s,3H),2.11(s,3H)。Compound 485: melting point 132-134°C. δ (300MHz, CDCl 3 ): 8.95 (s, 1H), 8.47 (s, 1H), 8.29 (s, 2H), 2.39 (s, 3H), 2.11 (s, 3H).
化合物525：熔点216-218℃。δ(300MHz,CDCl3):9.58(s,1H),9.13(s,1H),8.18(s,1H),7.80(s,2H),3.04(m,6H),1.56(s,3H)。Compound 525: melting point 216-218°C. δ (300MHz, CDCl 3 ): 9.58 (s, 1H), 9.13 (s, 1H), 8.18 (s, 1H), 7.80 (s, 2H), 3.04 (m, 6H), 1.56 (s, 3H).
化合物558：熔点178-180℃。δ(300MHz,CDCl3):9.45(s,1H),8.66(s,1H),8.29(s,2H),2.86(s,6H),1.71(s,3H)。Compound 558: melting point 178-180°C. δ (300MHz, CDCl 3 ): 9.45 (s, 1H), 8.66 (s, 1H), 8.29 (s, 2H), 2.86 (s, 6H), 1.71 (s, 3H).
化合物583：熔点178-180℃。δ(600MHz,CDCl3):9.02(s,1H),8.85(s,1H),7.78–7.71(dd,1H),7.44(d,1H),6.62(d,1H),4.46(q,2H),2.06(s,3H)。Compound 583: melting point 178-180°C. δ(600MHz, CDCl 3 ):9.02(s,1H),8.85(s,1H),7.78–7.71(dd,1H),7.44(d,1H),6.62(d,1H),4.46(q,2H ),2.06(s,3H).
化合物594：熔点126-128℃。δ(300MHz,CDCl3):9.20(s,1H),8.85(s,1H),8.30(s,2H),4.42(q,2H),1.83(s,3H)。Compound 594: melting point 126-128°C. δ (300MHz, CDCl 3 ): 9.20 (s, 1H), 8.85 (s, 1H), 8.30 (s, 2H), 4.42 (q, 2H), 1.83 (s, 3H).
本发明其它化合物可参照专利CN103539681、CN102827072等进行制备。Other compounds of the present invention can be prepared with reference to patents CN103539681, CN102827072, etc.
生物活性测定Bioactivity assay
实施例7：杀细菌活性测定Example 7: Determination of bactericidal activity
用本发明的化合物对多种植物细菌性病害进行了防效测定，针对不同的细菌性病害，试验方法如下：The compounds of the present invention have been used to determine the control effectiveness against various plant bacterial diseases. For different bacterial diseases, the test methods are as follows:
甜瓜细菌性果斑病、黄瓜细菌性角斑病、大白菜软腐病、番茄青枯病活体防效测试方法：将待测化合物用少量二甲基亚砜溶解，稀释至所需要的浓度，同时设置空白对照。喷雾时确保叶片正反面均匀着药。将培养的病原细菌菌液调至所需浓度，对植株叶片喷雾接种病菌。将处理好的植株放入人工气候室，后转至温室通常培养，空白对照发病后，对药剂的防治效果进行调查。 Test method for in vivo control effectiveness of melon bacterial fruit spot, cucumber bacterial angular spot, Chinese cabbage soft rot, and tomato bacterial wilt: Dissolve the compound to be tested with a small amount of dimethyl sulfoxide and dilute it to the required concentration. Also set a blank control. When spraying, ensure that the front and back of the leaves are evenly coated. Adjust the cultured pathogenic bacterial liquid to the required concentration, and spray the plant leaves to inoculate the pathogenic bacteria. The treated plants were placed in an artificial climate chamber, and then transferred to a greenhouse for normal cultivation. After the onset of the disease, the control effect of the pesticide was investigated using the blank control.
甘蓝黑腐病、大白菜软腐病、葡萄根癌病、水稻细条病、烟草野火病、柑橘溃疡病、猕猴桃溃疡病、水稻白叶枯病、水稻细菌性基腐病、核桃黑斑病、桃细菌性穿孔病、番茄青枯病、甜瓜细菌性果斑病、黄瓜细菌性角斑病、番茄溃疡病离体防效测试方法：运用离体高通量方法，将待测化合物用少量二甲基亚砜溶解，配制成试验所需浓度的母液，同时设置空白对照。将培养的病原细菌菌液调至所需浓度与试验所需量的化合物母液在微孔板中混合培养。通过酶标仪判断防效进行调查。Cabbage black rot, Chinese cabbage soft rot, grape root cancer, rice stripe disease, tobacco wildfire, citrus canker, kiwi canker, rice bacterial blight, rice bacterial root rot, walnut black spot, Test method for in vitro control effectiveness of peach bacterial perforation, tomato bacterial wilt, melon bacterial fruit spot, cucumber bacterial angular spot, and tomato canker: Using an in vitro high-throughput method, the compound to be tested is treated with a small amount of dimethyl Dissolve methyl sulfoxide and prepare a mother solution with the concentration required for the test, and set a blank control at the same time. The cultured pathogenic bacteria liquid is adjusted to the required concentration and the required amount of compound stock solution for the test is mixed and cultured in a microwell plate. Investigate by judging the control effectiveness using a microplate reader.
部分化合物对大白菜软腐病活体防效：The in vivo control effects of some compounds on Chinese cabbage soft rot:
600mg/L剂量下，防效大于60％的有化合物138、183、185、IB-18；防效大于50％的有化合物117、234、237、246、247、521、IB-27、IB-28、IB-46、IB-78；防效大于40％的有化合物41、47、61、79、81、242、244、278、IB-1、IB-4、IB-20、IB-64。At the dose of 600 mg/L, compounds 138, 183, 185, and IB-18 have a preventive effect greater than 60%; compounds 117, 234, 237, 246, 247, 521, IB-27, and IB- have a preventive effect greater than 50%. 28. IB-46, IB-78; those with control effects greater than 40% include compounds 41, 47, 61, 79, 81, 242, 244, 278, IB-1, IB-4, IB-20, and IB-64.
300mg/L剂量下，防效大于60％的有化合物138、183、185。At the dose of 300 mg/L, compounds 138, 183, and 185 had a control effect greater than 60%.
部分化合物对黄瓜角斑病活体防效：Some compounds have in vivo control effects on cucumber angular leaf spot:
600mg/L剂量下，防效大于60％的有化合物5、37、91、138、183、185、525、IB-1；防效大于50％的有化合物4、79、81、277、IB-4、IB-10、IB-11、IB-17、IB-18、IB-20、IB-27、IB-28、IB-57、IB-70、IB-78、IB-95。At the dose of 600 mg/L, compounds 5, 37, 91, 138, 183, 185, 525, and IB-1 have a preventive effect greater than 60%; compounds 4, 79, 81, 277, and IB- have a preventive effect greater than 50%. 4. IB-10, IB-11, IB-17, IB-18, IB-20, IB-27, IB-28, IB-57, IB-70, IB-78, IB-95.
300mg/L剂量下，防效大于60％的有化合物37；防效大于50％的有化合物138、183、525。At the dose of 300 mg/L, compound 37 has a preventive effect greater than 60%; compounds 138, 183, and 525 have a preventive effect greater than 50%.
部分化合物对柑橘溃疡病离体活性：In vitro activity of some compounds against citrus canker:
25mg/L剂量下，活性为100％的有化合物45、62、88、89、96、97、117、185、234、236、237、245、246、IB-24、IB-70、IB-71、IB-102；活性为80％的有化合物42、61、63、78、666、IB-68。At the dose of 25mg/L, the compounds with 100% activity include compounds 45, 62, 88, 89, 96, 97, 117, 185, 234, 236, 237, 245, 246, IB-24, IB-70, and IB-71 , IB-102; compounds 42, 61, 63, 78, 666, and IB-68 have an activity of 80%.
2mg/L剂量下，活性为100％的有化合物42、45、61、63、89、96、97、117、234、236、237、245、246、666、IB-70、IB-71；活性为80％的有化合物62。At the dose of 2 mg/L, compounds 42, 45, 61, 63, 89, 96, 97, 117, 234, 236, 237, 245, 246, 666, IB-70, and IB-71 have 100% activity; 80% had compound 62.
0.2mg/L剂量下，活性为80％的有化合物42、246、IB-70。At the dose of 0.2 mg/L, compounds 42, 246, and IB-70 had an activity of 80%.
部分化合物对甜瓜果斑病离体活性：In vitro activity of some compounds against melon fruit spot disease:
20mg/L剂量下，活性为100％的有化合物42、61、234、235、666、IB-70、IB-71；活性为80％的有化合物89、96、237、245、246。At the dose of 20 mg/L, compounds 42, 61, 234, 235, 666, IB-70, and IB-71 had 100% activity; compounds 89, 96, 237, 245, and 246 had 80% activity.
4mg/L剂量下，活性为100％的有化合物42、117、235、666、IB-70；活性为80％的有化合物43、61、234、IB-71。At a dose of 4 mg/L, compounds 42, 117, 235, 666, and IB-70 had 100% activity; compounds 43, 61, 234, and IB-71 had 80% activity.
部分化合物对黄瓜角斑病离体活性：In vitro activity of some compounds against cucumber angular leaf spot:
20mg/L剂量下，活性为100％的有化合物42、61、234、235、237、245、666、IB-70、IB-71。At the dose of 20 mg/L, compounds 42, 61, 234, 235, 237, 245, 666, IB-70, and IB-71 had 100% activity.
4mg/L剂量下，活性为100％的有化合物42、43、235、666、IB-70；活性为80％的有化合物61、IB-71。At a dose of 4 mg/L, compounds 42, 43, 235, 666, and IB-70 had 100% activity; compounds 61 and IB-71 had 80% activity.
部分化合物对猕猴桃溃疡病离体活性：In vitro activity of some compounds against kiwi canker:
20mg/L剂量下，活性为100％的有化合物42、89、234、235、245、246、666、IB-70、IB-71；活性为80％的有化合物62、96、237。At the dose of 20 mg/L, compounds 42, 89, 234, 235, 245, 246, 666, IB-70, and IB-71 had 100% activity; compounds 62, 96, and 237 had 80% activity.
4mg/L剂量下，活性为100％的有化合物42、43、117、235、666、IB-70、IB-71；活性为80％的有化合物246。At the dose of 4 mg/L, compounds 42, 43, 117, 235, 666, IB-70, and IB-71 had 100% activity; compound 246 had 80% activity.
部分化合物对水稻白叶枯病离体活性：In vitro activity of some compounds against rice bacterial blight:
20mg/L剂量下，活性为100％的有化合物42、234、235、666、IB-70、IB-71；活性为80％的有化合物96。At the dose of 20 mg/L, compounds 42, 234, 235, 666, IB-70, and IB-71 had 100% activity; compound 96 had 80% activity.
4mg/L剂量下，活性为100％的有化合物43、IB-71；活性为80％的有化合物42、117、235、666。At a dose of 4 mg/L, compounds 43 and IB-71 had 100% activity; compounds 42, 117, 235, and 666 had 80% activity.
部分化合物对水稻细菌性基腐病离体活性：In vitro activity of some compounds against rice bacterial root rot:
20mg/L剂量下，活性为100％的有化合物234、IB-70、IB-71；活性为80％的有化合物42、62、88、89、96、235、666、IB-68。 At the dose of 20 mg/L, compounds 234, IB-70, and IB-71 had 100% activity; compounds 42, 62, 88, 89, 96, 235, 666, and IB-68 had 80% activity.
4mg/L剂量下，活性为100％的有化合物43、IB-70、IB-71；活性为80％的有化合物117、235。At a dose of 4 mg/L, compounds 43, IB-70, and IB-71 had 100% activity; compounds 117 and 235 had 80% activity.
部分化合物对甘蓝黑腐病离体活性：In vitro activity of some compounds against cabbage black rot:
20mg/L剂量下，活性为100％的有化合物42、61、62、63、88、96、234、235、237、245、246、666、IB-68、IB-70、IB-71；活性为80％的有化合物89、91、236。At the dose of 20 mg/L, the compounds with 100% activity include compounds 42, 61, 62, 63, 88, 96, 234, 235, 237, 245, 246, 666, IB-68, IB-70, and IB-71; activity Compounds 89, 91, and 236 accounted for 80%.
4mg/L剂量下，活性为100％的有化合物42、43、61、117、234、235、237、245、246、666、IB-70、IB-71；活性为80％的有化合物62、63、88、91、96、236。At the dose of 4 mg/L, compounds 42, 43, 61, 117, 234, 235, 237, 245, 246, 666, IB-70, and IB-71 have 100% activity; compounds 62, 63, 88, 91, 96, 236.
0.8mg/L剂量下，活性为100％的有化合物43、61、117、246、IB-70、IB-71；活性为80％的有化合物235。At the dose of 0.8 mg/L, compounds 43, 61, 117, 246, IB-70, and IB-71 had 100% activity; compound 235 had 80% activity.
部分化合物对番茄溃疡病离体活性：In vitro activity of some compounds against tomato canker:
20mg/L剂量下，活性为100％的有化合物42、45、61、62、63、78、88、89、91、96、97、183、234、235、236、237、245、246、666、IB-24、IB-68、IB-70、IB-71、IB-95、IB-102；活性为80％的有化合物144、243、277。At the dose of 20mg/L, compounds 42, 45, 61, 62, 63, 78, 88, 89, 91, 96, 97, 183, 234, 235, 236, 237, 245, 246, 666 have 100% activity. , IB-24, IB-68, IB-70, IB-71, IB-95, IB-102; compounds 144, 243, and 277 with an activity of 80%.
4mg/L剂量下，活性为100％的有化合物42、43、45、61、62、63、78、88、89、91、96、97、117、183、234、235、236、237、245、246、666、IB-24、IB-68、IB-70、IB-71、IB-102；活性为80％的有化合物144、243。At the dose of 4 mg/L, compounds 42, 43, 45, 61, 62, 63, 78, 88, 89, 91, 96, 97, 117, 183, 234, 235, 236, 237, 245 have 100% activity. , 246, 666, IB-24, IB-68, IB-70, IB-71, IB-102; compounds 144 and 243 have an activity of 80%.
0.16mg/L剂量下，活性为100％的有化合物42、43、61、62、78、88、89、91、96、97、235、237、245、246、IB-70、IB-71；活性为80％的有化合物63、236。At the dose of 0.16 mg/L, the compounds with 100% activity include compounds 42, 43, 61, 62, 78, 88, 89, 91, 96, 97, 235, 237, 245, 246, IB-70, and IB-71; Compounds 63 and 236 have an activity of 80%.
部分化合物对核桃黑斑病离体活性：In vitro activity of some compounds against walnut black spot:
20mg/L剂量下，活性为100％的有化合物42、61、62、63、88、89、96、234、235、236、237、246、666、IB-70、IB-71；活性为80％的有化合物78、91、243、IB-68。At the dose of 20 mg/L, compounds 42, 61, 62, 63, 88, 89, 96, 234, 235, 236, 237, 246, 666, IB-70, and IB-71 have an activity of 100%; the activity is 80 % include compounds 78, 91, 243, and IB-68.
4mg/L剂量下，活性为100％的有化合物42、43、61、62、63、89、96、117、235、236、237、246、666、IB-70、IB-71；活性为80％的有化合物234、243。At the dose of 4 mg/L, compounds 42, 43, 61, 62, 63, 89, 96, 117, 235, 236, 237, 246, 666, IB-70, and IB-71 have an activity of 100%; the activity is 80 % include compounds 234 and 243.
0.8mg/L剂量下，活性为100％的有化合物42、43、117、IB-70；活性为80％的有化合物61、235、236、246、666、IB-71。At the dose of 0.8 mg/L, compounds 42, 43, 117, and IB-70 had 100% activity; compounds 61, 235, 236, 246, 666, and IB-71 had 80% activity.
部分化合物对桃细菌性穿孔病离体活性：In vitro activity of some compounds against bacterial perforation of peach:
20mg/L剂量下，活性为100％的有化合物42、61、62、63、88、89、96、234、235、237、245、246、666、IB-70、IB-71；活性为80％的有化合物IB-68。At the dose of 20 mg/L, compounds 42, 61, 62, 63, 88, 89, 96, 234, 235, 237, 245, 246, 666, IB-70, and IB-71 have an activity of 100%; the activity is 80 % has compound IB-68.
4mg/L剂量下，活性为100％的有化合物42、43、61、62、63、89、117、234、235、237、245、246、666、IB-70、IB-71；活性为80％的有化合物96。At the dose of 4 mg/L, compounds 42, 43, 61, 62, 63, 89, 117, 234, 235, 237, 245, 246, 666, IB-70, and IB-71 have an activity of 100%; the activity is 80 % has compound 96.
表5部分化合物对大白菜软腐病、甜瓜细菌性果斑病进一步活体筛选结果


注：“/”表示无数据，下同。Table 5 Results of further in vivo screening of some compounds against Chinese cabbage soft rot and melon bacterial fruit spot


Note: "/" means no data, the same below.
表6化合物183对番茄青枯病活体防治结果
Table 6 The results of in vivo control of tomato bacterial wilt by compound 183
部分化合物与对照化合物氟啶胺、K1、K2、K3、K4的对比试验结果见表7-表11。
The comparative test results of some compounds and the reference compounds fluazinam, K1, K2, K3, and K4 are shown in Tables 7 to 11.
表7对番茄青枯病离体试验比较结果
Table 7 Comparative results of in vitro experiments on tomato bacterial wilt
表8对大白菜软腐病离体试验比较结果
Table 8 Comparative results of in vitro tests on Chinese cabbage soft rot
表9对葡萄根癌病离体试验比较结果
Table 9 Comparative results of in vitro tests on grape root cancer
表10对水稻细条病离体试验比较结果
Table 10 Comparative results of in vitro tests on rice thin streak disease
表11对烟草野火病离体试验比较结果
Table 11 Comparative results of in vitro tests on tobacco wildfire disease
实例8：杀真菌活性测定Example 8: Determination of fungicidal activity
水稻稻瘟病、黄瓜灰霉病测定方法如下：采用高通量筛选方法，即将待测化合物样品用适合的溶剂(溶剂的种类如丙酮、甲醇、DMF等，并且依据其对样品的溶解能力而选择)溶解，配制成所需浓度待测液。在超净工作环境下，将待测液加入到96孔培养板的微孔中，再将病原菌繁殖体悬浮液加入其中，处理后的培养板放置在恒温培养箱中培养。设空白对照， 处理同上但不含待测样品或其他活性化合物。24小时后进行调查，调查时目测病原菌繁殖体萌发或生长情况，并根据空白对照处理的萌发或生长情况，评价化合物抑菌活性。The method for determining rice blast and cucumber gray mold is as follows: using a high-throughput screening method, that is, using a suitable solvent for the sample of the compound to be tested (types of solvents such as acetone, methanol, DMF, etc., and selecting them based on their ability to dissolve the sample) ) to dissolve and prepare the test solution with the required concentration. In an ultra-clean working environment, add the liquid to be tested into the microwells of a 96-well culture plate, then add the pathogenic bacteria propagule suspension into it, and place the treated culture plate in a constant-temperature incubator for culture. Set a blank control, Process as above but without the sample to be tested or other active compounds. An investigation was conducted after 24 hours. During the investigation, the germination or growth of the pathogenic bacteria propagules was visually observed, and the antibacterial activity of the compound was evaluated based on the germination or growth of the blank control treatment.
黄瓜霜霉病、黄瓜炭疽病、玉米锈病测定方法如下：采用活体盆栽测定方法，即将待测化合物样品用少量溶剂(溶剂的种类如丙酮、甲醇、DMF等，并且依据其对样品的溶解能力而选择，溶剂量与喷液量的体积比等于或小于0.05)溶解，用含有0.1％吐温80的水稀释，配制成所需浓度待测液。在作物喷雾机上，将待测液喷施于病害寄主植物上(寄主植物为在温室内培养的标准盆栽苗)，24小时后进行病害接种。依据病害特点，将需要控温保湿培养的病害植物接种后放在人工气候室中培养，待病害完成侵染后，移入温室培养，将不需要保湿培养的病害植物直接在温室内接种并培养。设空白对照，处理同上但不含待测样品或其他活性化合物。待空白对照充分发病后(通常为一周时间)进行化合物防病效果评估。The determination methods of cucumber downy mildew, cucumber anthracnose, and corn rust are as follows: using the living potted plant determination method, that is, using a small amount of solvent (types of solvents such as acetone, methanol, DMF, etc.) to the compound to be tested, and based on its ability to dissolve the sample. Select (the volume ratio of the solvent amount to the spray liquid amount is equal to or less than 0.05) to dissolve, dilute with water containing 0.1% Tween 80, and prepare the test liquid with the required concentration. On the crop sprayer, spray the liquid to be tested on the disease host plant (the host plant is a standard potted seedling cultured in a greenhouse), and perform disease inoculation 24 hours later. According to the characteristics of the disease, the diseased plants that require temperature-controlled and moisturizing cultivation are inoculated and cultured in an artificial climate chamber. After the disease has completed the infection, they are moved to the greenhouse for cultivation. The diseased plants that do not require moisturizing and cultivating are directly inoculated and cultivated in the greenhouse. Set up a blank control, which is processed as above but does not contain the sample to be tested or other active compounds. After the blank control has fully developed disease (usually one week), the disease prevention effect of the compound is evaluated.
部分化合物对水稻稻瘟病菌的抑制率：Inhibition rates of some compounds against rice blast fungus:
25mg/L剂量下，化合物132、138、144、150、151、185、213、215、216、223、224、225、234、235、236、237、240、242、243、244、245、246、247、277对水稻稻瘟病菌的抑制率为100％；化合物143、278对水稻稻瘟病菌的抑制率为80％。At the dose of 25mg/L, compounds 132, 138, 144, 150, 151, 185, 213, 215, 216, 223, 224, 225, 234, 235, 236, 237, 240, 242, 243, 244, 245, 246 , 247, and 277 have an inhibitory rate of 100% against rice blast fungus; compounds 143 and 278 have an inhibitory rate of 80% against rice blast fungus.
8.3mg/L剂量下，化合物132、138、144、150、185、213、215、216、224、225、234、235、236、237、240、242、243、244、245、246、247、277对水稻稻瘟病菌的抑制率为100％；化合物151、223对水稻稻瘟病菌的抑制率为80％。At the dose of 8.3mg/L, compounds 132, 138, 144, 150, 185, 213, 215, 216, 224, 225, 234, 235, 236, 237, 240, 242, 243, 244, 245, 246, 247, The inhibitory rate of 277 against rice blast fungus was 100%; the inhibitory rate of compounds 151 and 223 against rice blast fungus was 80%.
0.9mg/L剂量下，化合物216、234、235、236、237、242、243、245、246、247对水稻稻瘟病菌的抑制率为100％；化合物185、213、240对水稻稻瘟病菌的抑制率为80％。At a dose of 0.9 mg/L, compounds 216, 234, 235, 236, 237, 242, 243, 245, 246, and 247 have an inhibitory rate of 100% against rice blast fungus; compounds 185, 213, and 240 have a 100% inhibitory rate against rice blast fungus. The inhibition rate is 80%.
部分化合物对黄瓜灰霉病菌的抑制率：Inhibition rates of some compounds against cucumber Botrytis cinerea:
25mg/L剂量下，化合物216、234、235、237、242、245、246、247对黄瓜灰霉病菌的抑制率为100％；化合物185、236、243对黄瓜灰霉病菌的抑制率为80％。At the dose of 25 mg/L, the inhibitory rate of compounds 216, 234, 235, 237, 242, 245, 246, and 247 against cucumber Botrytis cinerea was 100%; the inhibition rate of compounds 185, 236, and 243 against cucumber Botrytis cinerea was 80%. %.
8.3mg/L剂量下，化合物216、224、235、237、242、245、246、247对黄瓜灰霉病菌的抑制率为100％。At a dose of 8.3 mg/L, the inhibitory rate of compounds 216, 224, 235, 237, 242, 245, 246, and 247 against cucumber Botrytis cinerea was 100%.
0.9mg/L剂量下，化合物234、235、237、242、245、246、247对黄瓜灰霉病菌的抑制率为100％。At a dose of 0.9 mg/L, the inhibition rate of compounds 234, 235, 237, 242, 245, 246, and 247 against cucumber Botrytis cinerea was 100%.
部分化合物对黄瓜霜霉病的活体保护活性：In vivo protective activity of some compounds against cucumber downy mildew:
400mg/L剂量下，化合物137、143、183、185、200、216、240、245、247对黄瓜霜霉病的活体保护活性为100％；化合物278、364对黄瓜霜霉病的活体保护活性为80-90％。At the dose of 400 mg/L, the in vivo protective activity of compounds 137, 143, 183, 185, 200, 216, 240, 245, and 247 against cucumber downy mildew is 100%; the in vivo protective activity of compounds 278 and 364 against cucumber downy mildew is 100%. is 80-90%.
25mg/L剂量下，化合物150、234、235、236、237、242、243、244对黄瓜霜霉病的活体保护活性为100％；化合物200、215、224、245对黄瓜霜霉病的活体保护活性为80-90％。At the dose of 25 mg/L, the in vivo protective activity of compounds 150, 234, 235, 236, 237, 242, 243, and 244 against cucumber downy mildew is 100%; the in vivo protective activity of compounds 200, 215, 224, and 245 against cucumber downy mildew is 100%. Protective activity is 80-90%.
3.125mg/L剂量下，化合物235、236、237、242、244对黄瓜霜霉病的活体保护活性为100％。3. At the dose of 125 mg/L, the in vivo protective activity of compounds 235, 236, 237, 242, and 244 against cucumber downy mildew was 100%.
部分化合物对黄瓜炭疽病的活体保护活性：In vivo protective activity of some compounds against cucumber anthracnose:
400mg/L剂量下，化合物200对黄瓜炭疽病的活体保护活性为100％；化合物210、225对黄瓜炭疽病的活体保护活性为80-90％。At a dose of 400 mg/L, the in vivo protective activity of compound 200 against cucumber anthracnose is 100%; the in vivo protective activity of compounds 210 and 225 against cucumber anthracnose is 80-90%.
100mg/L剂量下，化合物234、235、242、246对黄瓜炭疽病的活体保护活性为100％；化合物215、236对黄瓜炭疽病的活体保护活性为90-95％。At a dose of 100 mg/L, the in vivo protective activity of compounds 234, 235, 242, and 246 against cucumber anthracnose is 100%; the in vivo protective activity of compounds 215 and 236 against cucumber anthracnose is 90-95%.
25mg/L剂量下，化合物242对黄瓜炭疽病的活体保护活性为100％；化合物235对黄瓜炭疽病的活体保护活性为95％。At a dose of 25 mg/L, the in vivo protective activity of compound 242 against cucumber anthracnose was 100%; the in vivo protective activity of compound 235 against cucumber anthracnose was 95%.
部分化合物对玉米锈病的活体保护活性：In vivo protective activity of some compounds against corn rust:
400mg/L剂量下，化合物126对玉米锈病的活体保护活性为100％。At a dose of 400 mg/L, the in vivo protective activity of compound 126 against corn rust was 100%.
现有技术WO2011116671中公开了其通式化合物具有杀真菌活性，表4列出了WO2011116671中的化合物44(CK1)和45(CK2)与本申请通式Ia化合物的活性对比结果，结果表明，本申请通式Ia化合物具有更好的杀真菌活性。
The prior art WO2011116671 discloses that the compound of the general formula has fungicidal activity. Table 4 lists the activity comparison results of compounds 44 (CK1) and 45 (CK2) in WO2011116671 and the compound of the general formula Ia of the present application. The results show that the compound has fungicidal activity. Compounds of general formula Ia are claimed to have better fungicidal activity.
表4本申请通式Ia化合物与WO2011116671中化合物对黄瓜霜霉病活性比较结果
Table 4 Comparative results of the activity of compounds of general formula Ia of the present application and compounds in WO2011116671 against cucumber downy mildew

Claims (10)

  1. 一种N取代苯胺类化合物作为杀细菌剂的用途，其特征在于：通式I所示N取代苯胺类化合物在杀细菌中的应用
    The use of an N-substituted aniline compound as a bactericidal agent, which is characterized in that: the application of the N-substituted aniline compound shown in the general formula I in bactericidal
    式中：In the formula:
    Y选自CH或N；Y is selected from CH or N;
    R1选自氢、C1-C12烷基、卤代C1-C12烷基、C3-C12环烷基、C1-C12烷基羰基、卤代C1-C12烷基羰基、C1-C12烷氧基羰基、C1-C12烷基氨基羰基、C1-C12烷硫基、卤代C1-C12烷硫基、C1-C12烷基磺酰基、C1-C12烷氧基C1-C12烷基、C1-C12烷氧基C1-C12烷基羰基、C1-C12烷氧基羰基C1-C12烷基、C1-C12烷基氨基硫基、C2-C12二烷基氨基硫基或CO-X-CO2R3，其中X选自(CHR3)p、CR3＝CR4或C6H4；R 1 is selected from hydrogen, C 1 -C 12 alkyl, halo C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkylcarbonyl, halo C 1 -C 12 alkyl Carbonyl group, C 1 -C 12 alkoxycarbonyl group, C 1 -C 12 alkylaminocarbonyl group, C 1 -C 12 alkylthio group, halogenated C 1 -C 12 alkylthio group, C 1 -C 12 alkyl group Sulfonyl, C 1 -C 12 alkoxy C 1 -C 12 alkyl, C 1 -C 12 alkoxy C 1 -C 12 alkylcarbonyl, C 1 -C 12 alkoxycarbonyl C 1 -C 12 Alkyl, C 1 -C 12 alkylaminothio, C 2 -C 12 dialkylaminothio or CO-X-CO 2 R 3 , where X is selected from (CHR 3 )p, CR 3 =CR 4 or C 6 H 4 ;
    p＝1、2、3、4、5或6；p=1, 2, 3, 4, 5 or 6;
    R2选自氢、卤素、C1-C12烷基、卤代C1-C12烷基、C3-C12环烷基、C1-C12烷氧基、卤代C1-C12烷氧基、C1-C12烷基氨基、卤代C1-C12烷基氨基、C1-C12烷硫基、卤代C1-C12烷硫基、C1-C3烷基羰基氨基、C1-C12烷基磺酰基、C2-C12二烷基氨基、C3-C12烯氧基、卤代C3-C12烯氧基、C3-C12炔氧基、卤代C3-C12炔氧基、C1-C12烷基羰基氧基、C1-C12烷基磺酰基氧基、C1-C12烷氧基C1-C12烷氧基、C1-C12烷氧基羰基C1-C12烷氧基、未取代的或被1-5个R5取代的芳基氨基、杂芳基氨基、芳氧基、杂芳基氧基、芳甲基氧基或芳甲基氨基；R 2 is selected from hydrogen, halogen, C 1 -C 12 alkyl, halogenated C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkoxy, halogenated C 1 -C 12 alkoxy, C 1 -C 12 alkylamino, halogenated C 1 -C 12 alkylamino, C 1 -C 12 alkylthio, halogenated C 1 -C 12 alkylthio, C 1 -C 3 Alkylcarbonylamino, C 1 -C 12 alkylsulfonyl, C 2 -C 12 dialkylamino, C 3 -C 12 alkenyloxy, halogenated C 3 -C 12 alkenyloxy, C 3 -C 12 Alkynyloxy, halogenated C 3 -C 12 alkynyloxy, C 1 -C 12 alkylcarbonyloxy, C 1 -C 12 alkylsulfonyloxy, C 1 -C 12 alkoxy C 1 -C 12 alkoxy, C 1 -C 12 alkoxycarbonyl C 1 -C 12 alkoxy, unsubstituted or arylamino substituted by 1-5 R 5 , heteroarylamino, aryloxy, hetero Aryloxy, arylmethyloxy or arylmethylamino;
    R选自卤素、氰基、硝基、羧基、C(＝O)NR3R4、C1-C12烷基、卤代C1-C12烷基、C1-C12烷氧基、卤代C1-C12烷氧基、C1-C12烷基氨基、卤代C1-C12烷基氨基、C1-C12烷硫基、卤代C1-C12烷硫基、C2-C12烯基、C2-C12炔基、C1-C12烷基磺酰基、C1-C12烷基羰基、C1-C12烷氧基羰基、C1-C12烷氧基C1-C12烷基、C1-C12烷氧基羰基C1-C12烷基、C1-C12烷基羰基氧基、C1-C12烷氧基羰基氧基、C1-C12烷基氨基羰基氧基、C1-C12烷基磺酰基氧基、C1-C12烷氧基C1-C12烷氧基、卤代C1-C12烷氧基卤代C1-C12烷氧基、C1-C12烷氧基羰基C1-C12烷氧基、未取代的或被1-5个R5取代的芳基、芳甲基、芳基羰基、芳甲基羰基、芳基氨基、芳氧基、杂芳基氧基、芳氧基羰基或芳基氨基羰基；R is selected from halogen, cyano, nitro, carboxyl, C(=O)NR 3 R 4 , C 1 -C 12 alkyl, halogenated C 1 -C 12 alkyl, C 1 -C 12 alkoxy, Halogenated C 1 -C 12 alkoxy, C 1 -C 12 alkylamino, halogenated C 1 -C 12 alkylamino, C 1 -C 12 alkylthio, halogenated C 1 -C 12 alkylthio , C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 1 -C 12 alkylsulfonyl, C 1 -C 12 alkylcarbonyl, C 1 -C 12 alkoxycarbonyl, C 1 -C 12 alkoxy C 1 -C 12 alkyl, C 1 -C 12 alkoxycarbonyl C 1 -C 12 alkyl, C 1 -C 12 alkylcarbonyloxy, C 1 -C 12 alkoxycarbonyloxy group, C 1 -C 12 alkylaminocarbonyloxy group, C 1 -C 12 alkylsulfonyloxy group , C 1 -C 12 alkoxy group, C 1 -C 12 alkoxy group , halogenated C 1 -C 12 Alkoxy halo C 1 -C 12 alkoxy, C 1 -C 12 alkoxycarbonyl C 1 -C 12 alkoxy, unsubstituted or aryl substituted by 1-5 R 5 , arylmethyl base, arylcarbonyl, arylmethylcarbonyl, arylamino, aryloxy, heteroaryloxy, aryloxycarbonyl or arylaminocarbonyl;
    R3、R4可相同或不同，分别选自氢或C1-C6烷基；R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 6 alkyl;
    R5选自卤素、硝基、氰基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷硫基、C1-C6烷基羰基、C1-C6烷氧基羰基、C2-C6烯基、卤代C2-C6烯基、C3-C6烯氧基、卤代C3-C6烯氧基、C2-C6炔基、卤代C2-C6炔基、C3-C6炔氧基、卤代C3-C6炔氧基、卤代C1-C6烷硫基、卤代C1-C6烷基羰基、C1-C6烷基氨基、卤代C1-C6烷基氨基、C2-C8二烷基氨基、C1-C6烷基羰基氨基、卤代C1-C6烷基羰基氨基、C1-C6烷基氨基羰基或卤代C1-C6烷基氨基羰基；R 5 is selected from halogen, nitro, cyano, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 3 -C 6 alkenyloxy, halogenated C 3 -C 6 alkenyloxy, C 2 -C 6 alkynyl, halogenated C 2 -C 6 alkynyl, C 3 -C 6 alkynyloxy, halogenated C 3 -C 6 Alkynyloxy, halogenated C 1 -C 6 alkylthio, halogenated C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylamino, halogenated C 1 -C 6 alkylamino, C 2 -C 8 dialkylamino, C 1 -C 6 alkylcarbonylamino, halogenated C 1 -C 6 alkylcarbonylamino, C 1 -C 6 alkylaminocarbonyl or halogenated C 1 -C 6 alkylaminocarbonyl;
    n＝0、1、2、3、4或5；n=0, 1, 2, 3, 4 or 5;
    或通式I化合物的盐。Or salts of compounds of general formula I.
  2. 按权利要求1所述的N取代苯胺类化合物作为杀细菌剂的用途，其特征在于：所述通式I中，The use of N-substituted aniline compounds as bactericides according to claim 1, characterized in that: in the general formula I,
    Y选自CH或N；Y is selected from CH or N;
    R1选自氢、C1-C8烷基、卤代C1-C8烷基、C3-C8环烷基、C1-C8烷基羰基、卤代C1-C8 烷基羰基、C1-C8烷基磺酰基、C1-C8烷氧基C1-C8烷基、C1-C8烷氧基C1-C8烷基羰基、C1-C8烷氧基羰基C1-C8烷基；R 1 is selected from hydrogen, C 1 -C 8 alkyl, halo C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 8 alkylcarbonyl, halo C 1 -C 8 Alkylcarbonyl, C 1 -C 8 alkylsulfonyl, C 1 -C 8 alkoxy C 1 -C 8 alkyl, C 1 -C 8 alkoxy C 1 -C 8 alkylcarbonyl, C 1 - C 8 alkoxycarbonyl C 1 -C 8 alkyl;
    R2选自氢、卤素、C1-C8烷基、C3-C8环烷基、卤代C1-C8烷基、C1-C8烷氧基、卤代C1-C8烷氧基、C1-C8烷基氨基、卤代C1-C8烷基氨基、C1-C8烷硫基、卤代C1-C8烷硫基、C2-C8二烷基氨基、C3-C8烯氧基、卤代C3-C8烯氧基、C3-C8炔氧基、卤代C3-C8炔氧基；R 2 is selected from hydrogen, halogen, C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, halogenated C 1 -C 8 alkyl, C 1 -C 8 alkoxy, halogenated C 1 -C 8 alkoxy, C 1 -C 8 alkylamino, halogenated C 1 -C 8 alkylamino, C 1 -C 8 alkylthio, halogenated C 1 -C 8 alkylthio , C 2 -C 8 dialkylamino, C 3 -C 8 alkenyloxy, halogenated C 3 -C 8 alkenyloxy, C 3 -C 8 alkynyloxy, halogenated C 3 -C 8 alkynyloxy;
    R选自卤素、氰基、硝基、羧基、C(＝O)NR3R4、C1-C8烷基、卤代C1-C8烷基、C1-C8烷氧基、卤代C1-C8烷氧基、C1-C8烷基氨基、卤代C1-C8烷基氨基、C1-C8烷硫基、卤代C1-C8烷硫基、C1-C8烷基磺酰基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷氧基C1-C8烷基、C1-C8烷基羰基氧基、C1-C8烷氧基羰基氧基、C1-C8烷氧基C1-C8烷氧基、卤代C1-C8烷氧基卤代C1-C8烷氧基、C1-C8烷氧基羰基C1-C8烷氧基、未取代的或被1-3个R5取代的苯基氨基、苯氧基、吡啶基氧基、苯氧基羰基或苯基氨基羰基；R is selected from halogen, cyano, nitro, carboxyl, C(=O)NR 3 R 4 , C 1 -C 8 alkyl, halogenated C 1 -C 8 alkyl, C 1 -C 8 alkoxy, Halogenated C 1 -C 8 alkoxy, C 1 -C 8 alkylamino, halogenated C 1 -C 8 alkylamino, C 1 -C 8 alkylthio, halogenated C 1 -C 8 alkylthio , C 1 -C 8 alkylsulfonyl, C 1 -C 8 alkylcarbonyl, C 1 -C 8 alkoxycarbonyl, C 1 -C 8 alkoxy C 1 -C 8 alkyl, C 1 -C 8Alkylcarbonyloxy , C 1 -C 8 alkoxycarbonyloxy, C 1 -C 8 alkoxy C 1 -C 8 alkoxy, halogenated C 1 -C 8 alkoxy halogenated C 1 -C 8 alkoxy, C 1 -C 8 alkoxycarbonyl, C 1 -C 8 alkoxy, unsubstituted or phenylamino substituted by 1-3 R 5 , phenoxy, pyridyloxy , phenoxycarbonyl or phenylaminocarbonyl;
    R3、R4可相同或不同，分别选自氢或C1-C4烷基；R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 4 alkyl;
    R5选自卤素、硝基、氰基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基；R 5 is selected from halogen, nitro, cyano, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and halogenated C 1 -C 4 alkoxy;
    n＝0、1、2、3、4或5；n=0, 1, 2, 3, 4 or 5;
    或通式I化合物的盐。Or salts of compounds of general formula I.
  3. 按权利要求2所述的N取代苯胺类化合物作为杀细菌剂的用途，其特征在于：所述通式I中，The use of N-substituted aniline compounds as bactericides according to claim 2, characterized in that: in the general formula I,
    Y选自CH或N；Y is selected from CH or N;
    R1选自氢、C1-C4烷基、C1-C4烷基羰基；R 1 is selected from hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkylcarbonyl;
    R2选自氢、卤素、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷基氨基、C1-C4烷硫基、C2-C4二烷基氨基；R 2 is selected from hydrogen, halogen, C 1 -C 4 alkoxy, halogenated C 1 -C 4 alkoxy, C 1 -C 4 alkylamino, C 1 -C 4 alkylthio, C 2 -C 4 dialkylamino;
    R选自卤素、氰基、硝基、羧基、C(＝O)NR3R4、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷氧基C1-C4烷氧基、卤代C1-C4烷氧基卤代C1-C4烷氧基、未取代的或被1-2个R5取代的苯氧基、吡啶基氧基；R is selected from halogen, cyano, nitro, carboxyl, C(=O)NR 3 R 4 , C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 4 alkoxy, Halo C 1 -C 4 alkoxy, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkoxy C 1 -C 4 alkoxy, halo C 1 -C 4 alkoxy halo C 1 -C 4 alkoxy, unsubstituted or phenoxy substituted by 1-2 R 5 , pyridyloxy;
    R3、R4可相同或不同，分别选自氢或C1-C4烷基；R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 4 alkyl;
    R5选自卤素、卤代C1-C4烷基；R 5 is selected from halogen and halogenated C 1 -C 4 alkyl;
    n＝0、1、2、3或4；n=0, 1, 2, 3 or 4;
    或通式I化合物与盐酸、硫酸、磷酸、甲酸、乙酸、三氟乙酸、甲磺酸、对甲苯磺酸、苹果酸或柠檬酸形成的盐。Or salts of compounds of general formula I with hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, malic acid or citric acid.
  4. 按权利要求1-3任意一项所述的N取代苯胺类化合物作为杀细菌剂的用途，其特征在于：所述细菌为果斑病、叶斑病、青枯病、细菌性疫病、溃疡病、软腐病、细菌性角斑病、细菌性条斑病、叶枯病、白叶枯病、野火病或细菌性疮痂病。The use of N-substituted aniline compounds as bactericides according to any one of claims 1 to 3, characterized in that: the bacteria are fruit spot, leaf spot, bacterial wilt, bacterial disease, and canker , soft rot, bacterial angular spot, bacterial streak, leaf blight, bacterial blight, wildfire or bacterial scab.
  5. 一种杀细菌组合物，其特征在于：含有作为活性组分的通式I化合物和农业上可接受的载体，组合物中活性组分的重量百分含量为0.5-90％。A bactericidal composition is characterized in that it contains a compound of general formula I as an active component and an agriculturally acceptable carrier, and the weight percentage of the active component in the composition is 0.5-90%.
  6. 一种N取代苯胺类化合物，其特征在于：N取代苯胺类化合物如通式Ia所示：
    An N-substituted aniline compound is characterized in that: the N-substituted aniline compound is represented by the general formula Ia:
    式中：In the formula:
    R1选自氢、C1-C12烷基、卤代C1-C12烷基、C3-C12环烷基、C1-C12烷基羰基、卤代C1-C12烷基羰基、C1-C12烷氧基羰基、C1-C12烷基氨基羰基、C1-C12烷硫基、卤代C1-C12烷硫基、C1-C12烷基磺酰基、C1-C12烷氧基C1-C12烷基、C1-C12烷氧基C1-C12烷基羰基、C1-C12烷氧 基羰基C1-C12烷基、C1-C12烷基氨基硫基、C2-C12二烷基氨基硫基或CO-X-CO2R3，其中X选自(CHR3)p、CR3＝CR4或C6H4；R 1 is selected from hydrogen, C 1 -C 12 alkyl, halo C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkylcarbonyl, halo C 1 -C 12 alkyl Carbonyl group, C 1 -C 12 alkoxycarbonyl group, C 1 -C 12 alkylaminocarbonyl group, C 1 -C 12 alkylthio group, halogenated C 1 -C 12 alkylthio group, C 1 -C 12 alkyl group Sulfonyl, C 1 -C 12 alkoxy C 1 -C 12 alkyl, C 1 -C 12 alkoxy C 1 -C 12 alkylcarbonyl, C 1 -C 12 alkoxy Carbonyl C 1 -C 12 alkyl, C 1 -C 12 alkylaminothio, C 2 -C 12 dialkylaminothio or CO-X-CO 2 R 3 , where X is selected from (CHR 3 ) p, CR 3 =CR 4 or C 6 H 4 ;
    p＝1、2、3、4、5或6；p=1, 2, 3, 4, 5 or 6;
    R3、R4可相同或不同，分别选自氢或C1-C6烷基；R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 6 alkyl;
    R选自卤素、氰基、硝基、羧基、C(＝O)NR3R4、C1-C12烷基、卤代C1-C12烷基、C1-C12烷氧基、卤代C1-C12烷氧基、C1-C12烷基氨基、卤代C1-C12烷基氨基、C1-C12烷硫基、卤代C1-C12烷硫基、C2-C12烯基、C2-C12炔基、C1-C12烷基磺酰基、C1-C12烷基羰基、C1-C12烷氧基羰基、C1-C12烷氧基C1-C12烷基、C1-C12烷氧基羰基C1-C12烷基、C1-C12烷基羰基氧基、C1-C12烷氧基羰基氧基、C1-C12烷基氨基羰基氧基、C1-C12烷基磺酰基氧基、C1-C12烷氧基C1-C12烷氧基、卤代C1-C12烷氧基卤代C1-C12烷氧基、C1-C12烷氧基羰基C1-C12烷氧基、未取代的或被1-5个R5取代的芳基、芳甲基、芳基羰基、芳甲基羰基、芳基氨基、芳氧基、杂芳基氧基、芳氧基羰基或芳基氨基羰基；R is selected from halogen, cyano, nitro, carboxyl, C(=O)NR 3 R 4 , C 1 -C 12 alkyl, halogenated C 1 -C 12 alkyl, C 1 -C 12 alkoxy, Halogenated C 1 -C 12 alkoxy, C 1 -C 12 alkylamino, halogenated C 1 -C 12 alkylamino, C 1 -C 12 alkylthio, halogenated C 1 -C 12 alkylthio , C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 1 -C 12 alkylsulfonyl, C 1 -C 12 alkylcarbonyl, C 1 -C 12 alkoxycarbonyl, C 1 -C 12 alkoxy C 1 -C 12 alkyl, C 1 -C 12 alkoxycarbonyl C 1 -C 12 alkyl, C 1 -C 12 alkylcarbonyloxy, C 1 -C 12 alkoxycarbonyloxy group, C 1 -C 12 alkylaminocarbonyloxy group, C 1 -C 12 alkylsulfonyloxy group , C 1 -C 12 alkoxy group, C 1 -C 12 alkoxy group , halogenated C 1 -C 12 Alkoxy halo C 1 -C 12 alkoxy, C 1 -C 12 alkoxycarbonyl C 1 -C 12 alkoxy, unsubstituted or aryl substituted by 1-5 R 5 , arylmethyl base, arylcarbonyl, arylmethylcarbonyl, arylamino, aryloxy, heteroaryloxy, aryloxycarbonyl or arylaminocarbonyl;
    R5选自卤素、硝基、氰基、C1-C6烷基、卤代C1-C6烷基、C1-C6烷氧基、卤代C1-C6烷氧基、C1-C6烷硫基、C1-C6烷基羰基、C1-C6烷氧基羰基、C2-C6烯基、卤代C2-C6烯基、C3-C6烯氧基、卤代C3-C6烯氧基、C2-C6炔基、卤代C2-C6炔基、C3-C6炔氧基、卤代C3-C6炔氧基、卤代C1-C6烷硫基、卤代C1-C6烷基羰基、C1-C6烷基氨基、卤代C1-C6烷基氨基、C2-C8二烷基氨基、C1-C6烷基羰基氨基、卤代C1-C6烷基羰基氨基、C1-C6烷基氨基羰基或卤代C1-C6烷基氨基羰基；R 5 is selected from halogen, nitro, cyano, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkoxycarbonyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 3 -C 6 alkenyloxy, halogenated C 3 -C 6 alkenyloxy, C 2 -C 6 alkynyl, halogenated C 2 -C 6 alkynyl, C 3 -C 6 alkynyloxy, halogenated C 3 -C 6 Alkynyloxy, halogenated C 1 -C 6 alkylthio, halogenated C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylamino, halogenated C 1 -C 6 alkylamino, C 2 -C 8 dialkylamino, C 1 -C 6 alkylcarbonylamino, halogenated C 1 -C 6 alkylcarbonylamino, C 1 -C 6 alkylaminocarbonyl or halogenated C 1 -C 6 alkylaminocarbonyl;
    n＝0、1、2、3、4或5；n=0, 1, 2, 3, 4 or 5;
    或通式Ia化合物的盐。Or salts of compounds of general formula Ia.
  7. 根据权利要求5所述的N取代苯胺类化合物，其特征在于：通式Ia中N-substituted aniline compounds according to claim 5, characterized in that: in the general formula Ia
    R1选自氢、C1-C8烷基、卤代C1-C8烷基、C3-C8环烷基、C1-C8烷基羰基、卤代C1-C8烷基羰基、C1-C8烷基磺酰基、C1-C8烷氧基C1-C8烷基、C1-C8烷氧基C1-C8烷基羰基、C1-C8烷氧基羰基C1-C8烷基；R 1 is selected from hydrogen, C 1 -C 8 alkyl, halo C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 1 -C 8 alkylcarbonyl, halo C 1 -C 8 alkyl Carbonyl, C 1 -C 8 alkylsulfonyl, C 1 -C 8 alkoxy, C 1 -C 8 alkyl, C 1 -C 8 alkoxy, C 1 -C 8 alkylcarbonyl, C 1 -C 8Alkoxycarbonyl C 1 -C 8 alkyl;
    R选自卤素、氰基、硝基、羧基、C(＝O)NR3R4、C1-C8烷基、卤代C1-C8烷基、C1-C8烷氧基、卤代C1-C8烷氧基、C1-C8烷基氨基、卤代C1-C8烷基氨基、C1-C8烷硫基、卤代C1-C8烷硫基、C1-C8烷基磺酰基、C1-C8烷基羰基、C1-C8烷氧基羰基、C1-C8烷氧基C1-C8烷基、C1-C8烷基羰基氧基、C1-C8烷氧基羰基氧基、C1-C8烷氧基C1-C8烷氧基、卤代C1-C8烷氧基卤代C1-C8烷氧基、C1-C8烷氧基羰基C1-C8烷氧基、未取代的或被1-3个R5取代的苯基氨基、苯氧基、吡啶基氧基、苯氧基羰基或苯基氨基羰基；R is selected from halogen, cyano, nitro, carboxyl, C(=O)NR 3 R 4 , C 1 -C 8 alkyl, halogenated C 1 -C 8 alkyl, C 1 -C 8 alkoxy, Halogenated C 1 -C 8 alkoxy, C 1 -C 8 alkylamino, halogenated C 1 -C 8 alkylamino, C 1 -C 8 alkylthio, halogenated C 1 -C 8 alkylthio , C 1 -C 8 alkylsulfonyl, C 1 -C 8 alkylcarbonyl, C 1 -C 8 alkoxycarbonyl, C 1 -C 8 alkoxy C 1 -C 8 alkyl, C 1 -C 8Alkylcarbonyloxy , C 1 -C 8 alkoxycarbonyloxy, C 1 -C 8 alkoxy C 1 -C 8 alkoxy, halogenated C 1 -C 8 alkoxy halogenated C 1 -C 8 alkoxy, C 1 -C 8 alkoxycarbonyl, C 1 -C 8 alkoxy, unsubstituted or phenylamino substituted by 1-3 R 5 , phenoxy, pyridyloxy , phenoxycarbonyl or phenylaminocarbonyl;
    R3、R4可相同或不同，分别选自氢或C1-C4烷基；R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 4 alkyl;
    R5选自卤素、硝基、氰基、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基；R 5 is selected from halogen, nitro, cyano, C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 4 alkoxy, and halogenated C 1 -C 4 alkoxy;
    n＝0、1、2、3、4或5；n=0, 1, 2, 3, 4 or 5;
    或通式Ia化合物的盐。Or salts of compounds of general formula Ia.
  8. 根据权利要求6所述的N取代苯胺类化合物，其特征在于：通式Ia中N-substituted aniline compounds according to claim 6, characterized in that: in the general formula Ia
    R1选自氢、C1-C4烷基、C1-C4烷基羰基；R 1 is selected from hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkylcarbonyl;
    R选自卤素、氰基、硝基、羧基、C(＝O)NR3R4、C1-C4烷基、卤代C1-C4烷基、C1-C4烷氧基、卤代C1-C4烷氧基、C1-C4烷基羰基、C1-C4烷氧基羰基、C1-C4烷氧基C1-C4烷氧基、卤代C1-C4烷氧基卤代C1-C4烷氧基；R is selected from halogen, cyano, nitro, carboxyl, C(=O)NR 3 R 4 , C 1 -C 4 alkyl, halogenated C 1 -C 4 alkyl, C 1 -C 4 alkoxy, Halo C 1 -C 4 alkoxy, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl, C 1 -C 4 alkoxy C 1 -C 4 alkoxy, halo C 1 -C 4 alkoxy halo C 1 -C 4 alkoxy;
    R3、R4可相同或不同，分别选自氢或C1-C4烷基；R 3 and R 4 may be the same or different, and are respectively selected from hydrogen or C 1 -C 4 alkyl;
    R5选自卤素、卤代C1-C4烷基；R 5 is selected from halogen and halogenated C 1 -C 4 alkyl;
    n＝0、1、2、3或4；n=0, 1, 2, 3 or 4;
    或通式Ia化合物与盐酸、硫酸、磷酸、甲酸、乙酸、三氟乙酸、甲磺酸、对甲苯磺酸、苹果酸或柠檬酸形成的盐。 Or salts of compounds of general formula Ia with hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid, malic acid or citric acid.
  9. 根据权利要求6所述的化合物的应用，其特征在于：所述的通式Ia化合物在农业或其他领域中防治真菌病害的应用。The application of the compound according to claim 6, characterized in that the compound of general formula Ia is used to prevent and treat fungal diseases in agriculture or other fields.
  10. 一种杀真菌组合物，其特征在于：含有作为活性组分的通式Ia化合物和农业上可接受的载体，组合物中活性组分的重量百分含量为0.5-90％。 A fungicidal composition is characterized in that it contains a compound of general formula Ia as an active component and an agriculturally acceptable carrier, and the weight percentage of the active component in the composition is 0.5-90%.
PCT/CN2023/102975 2022-07-04 2023-06-28 N-substituted aniline compound and use thereof WO2024007903A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210785392.1A CN117378607A (en) 2022-07-04 2022-07-04 N-substituted aniline compound and application thereof
CN202210785392.1 2022-07-04

Publications (1)

Publication Number Publication Date
WO2024007903A1 true WO2024007903A1 (en) 2024-01-11

Family

ID=89437894

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/102975 WO2024007903A1 (en) 2022-07-04 2023-06-28 N-substituted aniline compound and use thereof

Country Status (2)

Country Link
CN (1) CN117378607A (en)
WO (1) WO2024007903A1 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01186849A (en) * 1988-01-19 1989-07-26 Sumitomo Chem Co Ltd Diphenylamine derivative, production thereof and harmful organism controller comprising said derivative as active ingredient
JPH11209205A (en) * 1998-01-22 1999-08-03 Nissan Chem Ind Ltd Industrial antibacterial and antifungal agent, algicidal agent and anti-biofouling agent containing n-pyridylanilines
CN102199095A (en) * 2010-03-22 2011-09-28 中国中化股份有限公司 Substituted diphenylamine compounds and preparation and application thereof
CN102827072A (en) * 2011-06-17 2012-12-19 中国中化股份有限公司 Substituted nitroaniline compound and its application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01186849A (en) * 1988-01-19 1989-07-26 Sumitomo Chem Co Ltd Diphenylamine derivative, production thereof and harmful organism controller comprising said derivative as active ingredient
JPH11209205A (en) * 1998-01-22 1999-08-03 Nissan Chem Ind Ltd Industrial antibacterial and antifungal agent, algicidal agent and anti-biofouling agent containing n-pyridylanilines
CN102199095A (en) * 2010-03-22 2011-09-28 中国中化股份有限公司 Substituted diphenylamine compounds and preparation and application thereof
CN102827072A (en) * 2011-06-17 2012-12-19 中国中化股份有限公司 Substituted nitroaniline compound and its application

Also Published As

Publication number Publication date
CN117378607A (en) 2024-01-12

Similar Documents

Publication Publication Date Title
EP2551258B1 (en) Substituted diphenylamine compounds, preparation method and use thereof
KR19980018703A (en) SUBSTITUTED CARBOXYLIC ACID ANILIDE DERIVATIVES AND PREVENTIVE AND EXTERMINATOR OF BLIGHT COMPRISING THE DERIVATIVE AS ACTIVE INGREDINET
CN113045561B (en) Diarylamine derivatives as fungicides
CN107200712A (en) One class yl pyrimidines aryl containing substitution amidine compound, its preparation method and application
RU2475490C1 (en) N-ACYLATED 3-AMINO-4,6-DIMETHYLTHIENO[2,3-b]PYRIDINE-2-CARBOXAMIDES AS ANTIDOTES OF 2,4-D ON SUNFLOWER
WO2024007903A1 (en) N-substituted aniline compound and use thereof
CN111377870A (en) 2, 4-dioxoimidazolines cyclohexane sulfonamide compounds, process for their preparation and their use as fungicides or bactericides
CN108059613B (en) Pyrazole amide compound and application thereof
EP0751120A2 (en) Hydroxylamine derivatives and fungicides containing the same
WO2020156297A1 (en) Malononitrile compound and application thereof
CN110963963A (en) Pyridine amide compound and sterilization application thereof
CN110804019A (en) Amide compound and preparation method and application thereof
WO2024104344A1 (en) Quinolinecarboxylic acid derivative and use thereof
CN102464618A (en) Pyrazolecarboxamide compound and application thereof
CN112745260B (en) Amide compound containing substituted acetophenone structural fragment and preparation method and application thereof
CN108610283B (en) Secondary amine compound and preparation and application thereof
CN114560826B (en) Thiazole amide compound containing diphenyl ether group and preparation method and application thereof
US11390602B2 (en) N-alkyl-N-cyanoalkylbenzamide compound and use thereof
JP2012201640A (en) Benzene-2-carboxamide derivative and fungicide containing the same as active ingredient
RU2356892C1 (en) N1-(3-fluorophenyl)-2-(4,6-dimethyl-5-chloro-3-cyano-2-pyridylsulfanil)-acetamide as antidote of 2,4-d on sunflower
CN108976167B (en) Substituted phenylhydrazine compound and application thereof
JP2584807B2 (en) Maleimide derivative, process for producing the same, and agricultural / horticultural fungicide containing the same as an active ingredient
EP1364951B1 (en) Triazoquinolone derivatives as pest controllers
CN115872901A (en) Imine compound and application thereof
KR100295819B1 (en) New quinoline sulfonium salt derivatives

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: 23834671

Country of ref document: EP

Kind code of ref document: A1