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WO1999044992A1 - Composes d'anilide et herbicide - Google Patents

Composes d'anilide et herbicide Download PDF

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Publication number
WO1999044992A1
WO1999044992A1 PCT/JP1999/001048 JP9901048W WO9944992A1 WO 1999044992 A1 WO1999044992 A1 WO 1999044992A1 JP 9901048 W JP9901048 W JP 9901048W WO 9944992 A1 WO9944992 A1 WO 9944992A1
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WO
WIPO (PCT)
Prior art keywords
group
alkyl
phenyl
hydrogen atom
alkyl group
Prior art date
Application number
PCT/JP1999/001048
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English (en)
Japanese (ja)
Inventor
Shigeaki Akiyama
Yasuo Kondo
Michiaki Adachi
Takashi Mizukoshi
Shigeomi Watanabe
Chiaki Akiyoshi
Tooru Ohki
Kunimitsu Nakahira
Original Assignee
Nissan Chemical Industries, Ltd.
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 Nissan Chemical Industries, Ltd. filed Critical Nissan Chemical Industries, Ltd.
Priority to AU27458/99A priority Critical patent/AU2745899A/en
Publication of WO1999044992A1 publication Critical patent/WO1999044992A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/30—Halogen atoms or nitro radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines

Definitions

  • the present invention relates to an anilide compound and a herbicide containing the compound as an active ingredient.
  • Japanese Patent Application Laid-Open No. 63-198670 discloses that certain pyrimidine-15-carboxylic acid anilide compounds have a plant growth inhibitory action. However, it does not disclose a pyrimidine-15-carboxylic acid anilide compound having, for example, an ester group, an amide group, a cyano group, an acyl group, or the like as a substituent at the 4-position of the pyrimidine ring.
  • Japanese Patent Application Laid-Open No. Hei 9-232394 discloses that a certain pyridine 3-carboxyanilide compound has a herbicidal action. However, it does not disclose a pyridine 3-carboxylate compound having a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, or the like as a substituent on the 2-position of the pyridine ring.
  • the present inventors have conducted intensive studies on the herbicidal activity of the novel acid anilide compound, and as a result, have found that the compound of the present invention represented by the following formula has an excellent herbicidal activity, thereby completing the present invention.
  • the present invention provides a compound represented by the formula (I):
  • R 1 , R 2 , R 22 and R 23 may be the same or different; a hydrogen atom, a C 1 to C 6 alkyl group, a C 3 to Cs cycloalkyl group, a C 1 to C 6 haloalkyl group A C 3 -C 6 cycloalkyl group, a C 2 -C 6 alkenyl group, a C 2 -C 6 haloalkenyl group, a C 2 -C 6 alkynyl group, a C 2 -C 6 cycloalkynyl group, substituted with A An optionally substituted phenyl group, a phenyl C, -C 4 alkyl group in which a phenyl group may be substituted with A, a phenyl C 2 -C 4 alkenyl group, in which a phenyl group may be substituted with A, A phenyl group in which the phenyl group may be substituted with A phenyl C 2
  • R 5 ) R fi )-N (R 8 ) R 9 groups one (C (R 5 ) R 6 ) — N (R s ) R 9 groups, — L one R 10 groups, C 1, to C (; an alkylcarbonyl group, a phenyl group which may be substituted with A, phenyl (! To alkyl alkyl carbonyl group, C i to (: 6 dialkyl rubamoyl group,
  • R 3 is a hydrogen atom, a C! Cs alkyl group, or a phenyl group which may be substituted with A phenyl C! ! ⁇ Ji alkyl group, C C s alkyl group, downy phenyl group may be substituted by A Nzoiru group, C, ⁇ C 6 alkoxy C> - (: 6 alkyl group or a C, - C 6 alkoxycarbonyl Represents a radical,
  • A is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a C 1 -C 6 alkyl group, a C i Cs haloalkyl group, a C i -C 6 alkoxy group, a C 1 -C 6 , a mouth alkoxy group, a C 6 alkoxy carbonyl groups, C, ⁇ (6 alkylcarbonyl group, phenyl group, phenoxy group, a benzyl group, c alkylcarbonyl ⁇ Mi amino group, c, to c 4 ⁇ alkoxycarbonyl ⁇ Mi Roh groups, C alkylthio group and a C, ⁇ (Represents one or more identical or different groups selected from 6 alkylsulfonyl groups,
  • R 4 is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a C i -C 6 alkyl group, a C 1 -C 6 haloalkyl group, a C! Cs alkoxy group, a C 1 -C 6 haloalkoxy group,
  • ⁇ C 6 alkoxycarbonyl group, c, ⁇ c 6 alkylcarbonyl group, phenyl group, phenoxy group, benzyl group, C! Represents the same or different one or more groups selected from an alkylcarbonylamino group, a C! Calkoxycarbonylamino group, a Calkylthio group and a C, ⁇ ⁇ alkylsulfonyl group,
  • R 5 and R 6 may be the same or different, and represent a hydrogen atom or a C, to (
  • R 7 represents a hydrogen atom, a C alkyl group or a C 6 cycloalkyl group
  • R 8 and R 9 may be the same or different, and represent a hydrogen atom.
  • C alkenyl represents groups, phenylene Le group phenyl optionally substituted with a C, -C 4 alkynyl, C, ⁇ alkylsulfonyl group or C, and -C 4 dialkyl sulfamoyl group,
  • R 8 and R 9 may form a 3- to 9-membered ring together with the nitrogen atom to be bonded, or may form a 5- to 8-membered ring containing 1 or 2 oxygen atoms or 1 or 2 sulfur atoms. Often,
  • L represents an oxygen atom or a zeo atom
  • R 1 C is hydrogen, C C s alkyl group, C C s haloalkyl group, (;!! A cycloalkyl group, c 2 -C 6 alkenyl group, C 2 -C 6 haloalkenyl group, C 2 -C 6 !
  • alkynyl group C 2 -C 6 haloalkynyl group, ( ⁇ Ji Arukokishi Ji ⁇ ⁇ Aruki Le group, C t C ⁇ alkylthio C '-C 4 alkyl groups, - C 0 2 R 7 group, one (C (R 5 ) R 6 ) 1 C0 2 R 7 groups, 1 (C (R 5 ) R 6 ) 2 — C0 2 R 7 groups,-(C (R 5 ) R 6 ) 3 -C 0 2 R 7 groups,- (C (R 5) R 6 ) - C 0 2 R 7 group, optionally substituted with A Hue group, phenyl optionally substituted by A C I ⁇ C alkyl group, Shiano C, -C 4 alkyl groups, —CON (R 8 ) R 9 groups, one (C (R 5 ) R 6 ) -CON (R s ) R s groups.
  • R 11 is a hydrogen atom, an alkyl group, C, -C 6 haloalkyl group, C 3 -C 6 cyclo alkyl group, C 2 -C 6 alkenyl group, C 2 ⁇ C 6 haloalkenyl, C 2 -C 6 alkynyl Group, C 2 -C 6 haloalkynyl group, phenyl group optionally substituted with A, phenyl C 1 -C 4 alkyl group optionally substituted with A, or C alkoxycarbonyl C, -C 4 Represents an alkyl group,
  • R 12 , R 13 , R 14 and R 15 may be the same or different, and represent a hydrogen atom, C, -C,.
  • Alkyl group, C 2 ⁇ C! Alkenyl group, C 2 ⁇ C! .
  • Alkynyl group, C! C! O cutting edge alkyl group, C 2 ⁇ C].
  • Haloalkenyl, C 2 ⁇ C! Haloalkynyl group, C 3 ⁇ C 10 cycloalkyl group, C 3 ⁇ C,. .!!!
  • Halocycloalkyl group human Dorokishi (, ⁇ ⁇ alkyl group, C Cs alkoxy C Ce alkyl group, C -C (; alkylthio C i ⁇ C 6 alkyl group, C, -C alkyl group, C, ⁇ C4 alkoxycarbonyl group, phenyl group in which phenyl group may be substituted with A, C ⁇ 4C4 alkylcarbonyl group, cyano group, phenyl group which may be substituted in A, phenyl group in A Optionally substituted phenyl C i Cj alkyl group, phenyl group optionally substituted with A, ⁇ C 4 alkenyl group, phenyl group optionally substituted with A, phenyl C, ⁇ C 4 Alkynyl group, C alkylsulfonyl group or C! ⁇
  • R 12 and R 13 may form a 3- to 9-membered ring together with the nitrogen atom or oxygen atom to be bonded, and form a 5- to 8-membered ring containing one or two oxygen atoms or two sulfur atoms. May be
  • R 16 and R 17 may be the same or different, and represent a hydrogen atom, C, A phenyl group which may be substituted with A, a phenyl group in which the phenyl group may be substituted with A, (: a 4 alkyl group or a C, ⁇ C 4 alkylthio C, ⁇ C 4 alkyl group,
  • R 16 and R 17 may form a 4- to 9-membered ring with the carbon atom to which they are attached,
  • R 18 represents a hydrogen atom or a C! -C 4 alkyl group
  • R 19 is a hydrogen atom, a C! CG alkyl group, a C 3 -C 6 cycloalkyl group, a C Cs haloalkyl group, a c 2 -C 6 alkenyl group, a C 2- (: 6 alkynyl group, even if substituted with A A good phenyl group or a phenyl C, which may be substituted with A, a C 4 alkyl group;
  • R 2 ° represents a hydrogen atom, (:, to ((; alkyl group, C 2 to C 6 alkenyl group, C 2 to C 6 haloalkenyl group, C 2 to C 6 alkynyl group, cyano C, to C 6 alkyl group , C! Cs ⁇ alkoxy C, -C 6 alkyl or C! Ce alkylthio C alkyl group table eagle,
  • G is a structure of G (a), G (b), G (c) or G (d)
  • R 2 represents a hydrogen atom, a C 1, to ( 6 alkyl group or a C, to C 6 cycloalkyl group.
  • a novel anilide compound hereinafter referred to as the compound of the present invention
  • the present invention relates to salts and pesticides characterized by containing them as an active ingredient, particularly to herbicides, provided that when the above compounds have optical isomers, diastereomers, and geometric isomers, It includes both mixtures and isolated forms (the best mode for carrying out the invention).
  • R ′, R 2 , R 22 and R 23 represent a hydrogen atom, methyl group, ethyl group, propyl group, i-propyl group, i-butyl group, t-butyl group, cyclopropyl group, cyclopentyl group, cyclopentyl group Hexyl, trichloromethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl, fluoromethyl, fluoroethyl, trifluoroethyl, fluoropropyl, vinyl, acryl, crotyl, metharyl Group, 3-chloroallyl group, ethynyl group, propargyl group,
  • R 3 is a hydrogen atom, methyl group, ethyl group, isopropyl group, benzyl group, acetyl group, bivaloyl group, benzoyl group, 4-methoxybenzoyl group, methoxymethyl group, ethoxymethyl group, methoxycarbonyl Or an ethoxycarbonyl group, preferably a hydrogen atom, a bivaloyl group, or a 4-methoxybenzoyl group. ⁇ or an ethoxycarbonyl group.
  • ⁇ includes a hydrogen atom, a chlorine atom, a fluorine atom, a bromine atom, an iodine atom, a nitro group, a cyano group, a methyl group, an ethyl group, a propyl group, an i-propyl group, an i-butyl group, and a t- Butyl group, trichloromethyl group, trifluoromethyl group, difluoromethyl group, methoxy group, ethoxy group, trifluoromethoxy group, difluoromethoxy group, methoxycarbonyl group, ethoxycarbonyl group, acetyl group, phenyl group, phenoxy group A benzyl group, an acetylamino group, a methoxycarbonylamino group, an ethoxycarbonylamino group, a methylthio group or a methanesulfonyl group, preferably a hydrogen atom
  • substitution position of A examples include the 2-, 3-, and 4-positions with respect to the position to which the phenyl group is bonded, and preferably the 2- or 4-position.
  • the number to be substituted for A is an integer of 1 to 5, preferably 1, 2 or 3.
  • Mono-substituted R includes, for example, hydrogen atom, chlorine atom, fluorine atom, bromine atom, iodine atom, nitro group, cyano group, methyl group, ethyl group, propyl group, i-propyl group, t-propyl group —Butyl, trichloromethyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methoxycarbonyl, ethoxycarbonyl, acetyl, phenyl Group, a phenoxy group, a benzyl group, an acetylamino group, a methoxycarbonylamino group, an ethoxycarbonylamino group, a methylthio group or a methanesulfonyl group, preferably a hydrogen atom, a chlorine atom, or a fluorine atom.
  • Atom bromine atom, iodine atom, nitro group, cyano group, methyl group, ethyl group, propyl group i monopropyl group, t-butyl group, trifluoromethyl group, difluoromethyl group, methoxy group, ethoxy group, difluoromethoxy group, trifluoromethoxy group, methoxycarbonyl group, ethoxycarbonyl group, acetyl group, phenyl Group, phenoxy group, benzyl group, acetylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, methylthio group or methanesulfonyl group.
  • R 4 may be substituted at the 2-, 3- or 4-position to the anilide bond. And preferably in the 2- or 4-position.
  • Examples of the 2-substituted to 5-substituted R 4 include the following.
  • Is an R 5 and R 6, a hydrogen atom, a methyl group, Echiru group or an isopropyl group is ani Gerare, favored properly can be mentioned a hydrogen atom or a methyl group.
  • R 7 includes a hydrogen atom, a methyl group, an ethyl group, a propyl group, a cyclopropyl group or a cyclopentyl group, preferably a methyl group or an ethyl group.
  • R 8 and R 9 include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a vinyl group, an aryl group, a methallyl group, a crotyl group, an ethynyl group, a propargyl group, a 1-methylpropargyl group, and a 3-methyl Propargyl group, trichloromethyl group, difluoromethyl group, difluorochloromethyl group, trifluoroethyl group, 3-chloroaryl group, 3-chloropropargyl group, cyclopropyl group, cyclopentyl group, 2,2-dichlorocyclopropyl Group, methoxymethyl group, ethoxymethyl group, methoxymethyl group, ethoxymethyl group, methylthiomethyl group, ethylthiomethyl group, acetyl group, propionyl group, methoxycarbonyl group, ethoxycarbonyl group,
  • L represents an oxygen atom or a zeo atom, and preferably an oxygen atom.
  • R 1 ′ includes a hydrogen atom, a methyl group, an ethyl group, a trichloromethyl group, a trifluoromethyl group, a trifluoroethyl group, a cyclopropyl group, an aryl group, and a prono group.
  • examples thereof include a lugyl group, a phenyl group, a benzyl group and an ethoxycarbonylmethyl group, and preferably a hydrogen atom, a methyl group or an ethyl group.
  • R 12 and R 13 are a hydrogen atom, a methyl group, an ethyl group, a propyl group, an i-butyl group, a butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a pentyl group Group, hexyl group, heptyl group, octyl group, aryl group, methallyl group, crotyl group, 3-methyl-12-butenyl group, 1-methyl-12-propenyl group, 1,1-dimethylpropyl Nyl, propargyl, 1-methylpropargyl, 1,1-dimethylpropargyl, 2-butynyl, homopropargyl, difluoromethyl, trifluoroethyl, chloroethyl, chloropropyl, bromopropyl, fluoropropyl Group, 2-chloroallyl group, 3-chloroallyl group, 3,
  • R 12 and R 13 has decreased together (CH 2) - group, one (CH 2) 5 - group -.
  • R 14 includes a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, an aryl group, a phenyl group or a benzyl group, and preferably a hydrogen atom, an isopropyl group or an aryl group.
  • R 15 includes a hydrogen atom, a methyl group or an ethyl group, and preferably a hydrogen atom.
  • R 16 and R 17 include a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a benzyl group or a methylthioethyl group, preferably a hydrogen atom, a methyl group, an ethyl group or an isopropyl group.
  • R 16 and R 17 taken together include a (CH 2 ) 4 — group or a (CH 2 ) 5 — group.
  • R 18 includes a hydrogen atom, a methyl group or an ethyl group, and preferably a methyl group or an ethyl group.
  • Is a R 19 a hydrogen atom, a methyl group, Echiru group, Application Benefits Furuoromechiru group, Application Benefits click Roromechiru group, Ariru group, propargyl group, is exemplified et been Fuweniru group or base Njiru group, preferably a hydrogen atom or a methyl group Is mentioned.
  • R 2 ° examples include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isobutyl group, an aryl group, a 3-chloroallyl group, a propargyl group, a cyanomethyl group, a methoxymethyl group, and a methylthiomethyl group.
  • Examples include an atom, a methyl group, an ethyl group or an aryl group.
  • G is G (a), G (b), G (c) or G (d)
  • R 21 examples include a hydrogen atom, a methyl group, an ethyl group, a cyclopropyl group, and an evenly-butyl group.
  • the compound of the present invention can be synthesized, for example, by the methods shown in Schemes 1 to 9.
  • RR 2 , R 3 , R 4 , R, R 12 , R 13 , R 1 ′, R 15 , R 16 , R 17 , R 18 , R 22 , R 23 , G and L in Schemes 1 to 9 are each as defined above. Represents the same meaning as, Le represents a halogen group, and Q represents 0, 1, 2, or 3.
  • Pyrimidine mono-, 5-dicarboxylic diester (II) is hydrolyzed to dicarboxylic acid (III), and then dehydrated again to obtain dicarboxylic anhydride (IV). Next, it is reacted with an aniline compound (VII) to give an anilide compound (V), and is again subjected to dehydration ring closure to give an N-phenylimido compound (VI).
  • Solvents that can be used in the hydrolysis reaction from compound (II) to compound (III) include, for example, alcohols such as methanol and ethanol, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and benzene.
  • Aromatic hydrocarbons such as toluene, xylene, polar non-proton solvents such as acetonitril, N, N-dimethylformamide, ethers such as getyl ether, tetrahydrofuran, dioxane, acetic acid, Examples include organic acids such as trifluoroacetic acid and the like, ketones such as acetone and methylethyl ketone, and preferably alcohols such as methanol and ethanol. These solvents can be used alone or as a mixture.
  • hydrolysis catalyst examples include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, hydrochloric acid, sulfuric acid, etc. And sodium hydroxide and potassium hydroxide can be preferably used.
  • the amount of these catalysts to be used is preferably 0.1 to equimolar to excess mole, and more preferably 2 to 2.5 moles, per mole of compound (II).
  • the reaction temperature may be selected from the range of 110 ° C. to the boiling point of the inert solvent, and preferably from room temperature to 120 ° C.
  • the reaction time is not fixed depending on the reaction temperature, the reaction scale and the like, but may be in the range of several minutes to 48 hours, preferably 30 minutes to 5 hours.
  • the desired product can be purified by isolation means such as extraction, recrystallization, distillation, etc., if necessary. The product can be directly used for the next reaction without purification. You.
  • Solvents that can be used in the dehydration ring-closing reaction from compound (III) to compound (IV) are preferably those that do not inhibit the progress of the reaction.
  • halogenated hydrocarbons such as dichloromethane and chloroform, benzene, toluene, and xylene
  • non-protonic polar solvents such as N, N-dimethylformamide
  • organic acetic acids such as acetic acid and trifluoroacetic acid.
  • a dehydrating agent exemplified below may be used as it is as a solvent.
  • dehydrating agent for example, dehydrating agents such as acetic anhydride, trifluoroacetic anhydride, thionyl chloride, phosphorus oxychloride, and dicyclohexylcarbodiimide can be used. It may be used in a molar amount or an excess molar amount, and may be used as a solvent.
  • the reaction temperature may be selected from the room temperature or the boiling point range of the solvent.
  • the reaction time is not fixed depending on the reaction temperature and the reaction scale, but may be in the range of several minutes to 48 hours. Preferably, the range is 30 minutes to 5 hours.
  • the reaction is completed, isolate the target compound and, if necessary, purify the target compound by purification means such as recrystallization, distillation, or column chromatography.
  • purification means such as recrystallization, distillation, or column chromatography.
  • the desired product may be subjected to the next reaction without isolation.
  • Examples of the solvent that can be used in the synthesis reaction from compound (IV) to compound (V) into an anilide compound are exemplified by the synthesis reaction from compound (II) to compound (III).
  • pyridine can be used if necessary.
  • the aniline compound of the compound (VII) can be used in an equimolar amount or an excess molar amount with respect to the compound (IV). Preferably it is in the range of equimolar to 2 times molar.
  • a salt of an aniline compound may be used.
  • the base that can be used for example, in addition to the inorganic bases exemplified in the synthesis reaction from compound (II) to compound (III), for example, hydrogen Metal hydrides such as sodium hydride, organic bases such as pyridine, triethylamine, 1, S-diazabicyclo [5,4,0] -17-indene, and alkoxides such as sodium methoxide.
  • a reaction may be performed.
  • the reaction temperature may be appropriately selected from the range of 10 ° C. to the boiling point of the inert solvent, and is preferably in the range of 0 ° C. to 150 ° C.
  • the target compound can be isolated and, if necessary, purified by recrystallization, distillation, column chromatography, or other purification means, but the target compound can be used in the next reaction without isolation. You may.
  • dehydration ring closure reaction from compound (V) to compound (VI) can be similarly carried out according to the conditions exemplified above for the dehydration ring closure reaction from compound (III) to compound (IV). .
  • halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride
  • Aromatic hydrocarbons such as benzene, toluene and xylene, polar non-proton solvents such as acetonitrile, N, N-dimethylformamide, ethers such as getyl ether, tetrahydrofuran, dioxane, and acetone And ketones such as methylethyl ketone, preferably halogenated hydrocarbons such as dichloromethane and chloroform, and aromatic hydrocarbons such as benzene and toluene.
  • solvents can be used alone or as a mixture.
  • a halogenating agent exemplified below may be used as a solvent as it is.
  • the reaction temperature may be selected from the range of 110 ° C. to the boiling point of the inert solvent, and preferably from room temperature to 120 ° C.
  • the reaction time may be varied within a range of several minutes to 48 hours, and may be varied within a range of several minutes to 48 hours, preferably 30 minutes to 5 hours.
  • the desired product can be purified by an isolation means such as extraction, recrystallization, or distillation, if necessary. However, it can be directly used for the next reaction without purification, and the halogenating agent used is, for example, thionyl chloride. Examples thereof include phosphorus oxychloride, oxalic acid dichloride, phosphorous trichloride and phosphorous pentachloride, and preferred is thiol chloride.
  • inert solvent that can be used in the reaction from compound (X) to compound (XI)
  • pyridines are used in addition to the solvents exemplified in the synthesis reaction from compound (IX) to compound (X) in Scheme 2 I can do it.
  • the reaction temperature may be selected from the range of 110 ° C. to the boiling point range of the inert solvent, and preferably from room temperature to 120 ° C.
  • the reaction time is not fixed depending on the reaction temperature, the reaction scale and the like, but may be in the range of several minutes to 48 hours, preferably 30 minutes to 5 hours. Also, is the target substance capable of being purified by isolation means such as extraction, recrystallization, distillation, and column chromatography if necessary? The product can be directly used for the next reaction without purification.
  • aniline (VII) can be used in an equimolar amount or an excess molar amount relative to compound (X). Preferably it is in the range of equimolar to 2 times molar.
  • the reaction may be performed using an appropriate base.
  • Examples of usable bases include, in addition to the inorganic bases exemplified in the synthesis reaction from compound (II) to compound (III), metal hydrides such as sodium hydride, pyridine, triethylamine, 1,8—
  • the reaction may be carried out by adding an organic base such as diazabicyclo [5,4,0] -17-decene or an alkoxide such as sodium methoxide.
  • the base in the reaction, can be used in an equimolar amount or an excess molar amount with respect to compound (X). Preferably it is in the range of equimolar to 2 times molar.
  • the reaction can be carried out in the same manner, for example, under the conditions used in the hydrolysis of compound (II) to compound (III) in Scheme 1.
  • the target product can be purified by a purification means such as extraction, recrystallization, column chromatography or the like, if necessary.
  • the same reaction can be carried out under the conditions used for the reaction from compound (X) to compound (XI) in Scheme 2. come.
  • ammonia can be used in an equimolar amount or an excess amount with respect to compound (X). Preferably it is in the range of equimolar to 3 molar times.
  • the target compound can be purified by an isolation means such as extraction, recrystallization, distillation, column chromatography or the like, if necessary, but can be directly used in the next reaction without purification.
  • the dehydration reaction from compound (XII) to compound (XIII) can be carried out in the same manner, for example, under the conditions used for the dehydration reaction from compound (II) to compound (IV) in Scheme 1.
  • phosphorus halides such as phosphorus trichloride and phosphorus pentachloride
  • organic acids such as para-toluenesulfonic acid
  • mineral acids such as hydrochloric acid and sulfuric acid
  • the amount thereof can be used in an equimolar amount or an excess molar amount with respect to compound (XI).
  • a dehydrating agent can be used as it is as a solvent.
  • the reaction temperature may be selected from the range of 110 ° C. to the boiling point range of the inert solvent, and preferably from room temperature to 120 ° C.
  • the reaction time is not fixed depending on the reaction temperature, the reaction scale and the like, but may be in the range of several minutes to 48 hours.
  • the target compound After completion of the reaction, the target compound can be isolated and, if necessary, the target compound can be purified by recrystallization distillation, column chromatography, or other purification means.
  • the hydrolysis reaction from compound (XIII) to compound (XIV) can be carried out, for example, under the conditions used in the hydrolysis of compound (II) to compound (III) in Scheme 1.
  • the reaction can be carried out in the same manner under the conditions used for the synthesis reaction from compound (IX) to compound (XI).
  • the desired product can be purified by an isolation means such as extraction, recrystallization, distillation, column chromatography or the like, if necessary.
  • reaction in the synthesis reaction from compound (XVI) to an anilide compound of compound (XVII), for example, the reaction can be carried out in the same manner under the conditions used in the synthesis reaction from compound (IV) to compound (V) in Scheme 1. .
  • the target compound is isolated and, if necessary, purified by recrystallization, distillation, column chromatography, etc., to purify the target compound. Good.
  • the synthesis reaction from the compound (XVII) to the target compound (I) can be similarly carried out according to the conditions exemplified for the reaction from the compound (V) to the target compound (I) in Scheme 1. .
  • R 3 H (Scheme 5)
  • acetic acid organic acids such as trifluoroacetic acid, etc.
  • the oxidizing agent to be used is, for example, peracetic acid, m-monoperoxybenzoic acid, etc.
  • Organic peroxides or peroxides such as hydrogen peroxide can be used. It is preferable to use an equimolar amount or an excess molar amount with respect to the amount, and preferably to use an equimolar to 1.5-fold molar amount.
  • the reaction can be carried out by adding an acid or a base.
  • the acid to be used include mineral acids such as hydrochloric acid and sulfuric acid, and organic acids such as acetic acid and trifluoroacetic acid.
  • the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, and potassium hydrogencarbonate.
  • the reaction temperature may be selected from the range of 110 ° C. to the boiling point of the inert solvent, preferably from 0 ° C. to room temperature.
  • the reaction time is not fixed depending on the reaction temperature, reaction scale, etc., but it takes several minutes to 48 hours.
  • the treatment may be performed within the range, preferably within 30 minutes to 5 hours.
  • the target compound can be purified by an isolation means such as extraction, recrystallization, distillation, column chromatography or the like, if necessary, but can be directly used in the next reaction without purification.
  • Solvents that can be used in the halogenation of compound (XIX) to compound (XX) include, for example, halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride; and aromatic hydrocarbons such as benzene, toluene, and xylene.
  • Acetonitrile, polar non-proton solvents such as N, N-dimethylformamide, ethers such as getyl ether, tetrahydrofuran, and dioxane; ketones such as acetone and methyl ethyl ketone. Tons, preferably dichloromethane and black form.
  • solvents can be used alone or as a mixture.
  • the reaction may be performed in a solvent-free solvent.
  • the halogenating agent to be used includes, for example, sulfuryl chloride, phosphorus trichloride, phosphorus oxychloride or phosphorus pentachloride, and preferably phosphorus oxychloride.
  • the reaction temperature may be selected from the range of 110 ° C. to the boiling point range of the inert solvent, and preferably from room temperature to 120 ° C.
  • the reaction time may be in the range of a few minutes to 48 hours, which is not constant depending on the reaction temperature, the reaction scale, and the like, and is preferably 30 minutes to 5 hours.
  • the desired product can be purified by isolation means such as extraction, recrystallization, distillation, etc., if necessary.The product can be directly used for the next reaction without purification.o
  • Solvents that can be used in the reaction of compound (XX) with compound (XVIII) with a nucleophilic reagent include, for example, alcohols such as methanol and ethanol, and halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride.
  • Aromatic hydrocarbons such as benzene, toluene and xylene, polar non-proton solvents such as acetonitrile, N, N-dimethylformamide, ethers such as getyl ether, tetrahydrofuran, and dioxane And organic acids such as acetic acid and trifluoroacetic acid; ketones such as acetone and methylethylketone; and N, N-dimethylformamide. These solvents can be used alone or as a mixture.
  • a nucleophilic reagent may be used in an equimolar amount or an excess molar amount relative to compound (XX). Preferably it is in the range of equimolar to 2 times molar.
  • a base that can be used,
  • metal hydrides such as sodium hydride, pyridine, triethylamine, 1,8 —Diazabicyclo [5,4,0] -17—Organic bases such as pendecene and alkoxides such as sodium methoxide may be added to carry out the reaction.
  • the reaction temperature may be appropriately selected from the range of 110 ° C. or the boiling point of the inert solvent, and is preferably not 0 but may be in the range of 150.
  • the target compound After completion of the reaction, the target compound is isolated, and if necessary, the target compound can be purified by purification means such as recrystallization, distillation, or column chromatography.However, the target compound is not isolated and used for the reaction as it is. Is also good.
  • purification means such as recrystallization, distillation, or column chromatography.However, the target compound is not isolated and used for the reaction as it is. Is also good.
  • the synthesis reaction from the compound (XVIII) to the compound (I) is performed according to the conditions exemplified for the reaction from the compound (IV) to the compound (V) in Scheme 1, and the compound (X) is converted to the target compound (I). Can be led.
  • Solvents that can be used in the hydrolysis reaction of compound (XXI) to compound (XXII) include, for example, alcohols such as methanol and ethanol, halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride, benzene, and toluene. , Xylene and other aromatic hydrocarbons, acetonitrile, polar non-proton solvents such as N, N-dimethylformamide, etc., ethers such as getyl ether, tetrahydrofuran, dioxane, acetone, methylethylketone, etc. And preferably alcohols such as methanol and ethanol. These solvents can be used alone or as a mixture.
  • hydrolysis catalyst examples include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and mineral acids such as hydrochloric acid and sulfuric acid.
  • inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and mineral acids such as hydrochloric acid and sulfuric acid.
  • sodium hydroxide and potassium hydroxide can be used.
  • the amount of these catalysts to be used is preferably 0.1 to equimolar to excess mole, and more preferably 2 to 2.5 moles, per mole of Compound (XXI).
  • the reaction temperature may be selected from the range of 110 ° C. to the boiling point of the inert solvent, and preferably from room temperature to 120 ° C.
  • the reaction time is not fixed depending on the reaction temperature, the reaction scale and the like, but may be in the range of several minutes to 48 hours, preferably 30 minutes to 5 hours.
  • the desired product can be purified by isolation means such as extraction, recrystallization, distillation, etc., if necessary. The product can be directly used for the next reaction without purification.
  • Compound (XXI) is, for example, J. Heterocyclic Chem.
  • Solvents that can be used in the dehydration ring closure reaction from compound (XXII) to compound (XXIII) include, for example, halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride; and aromatic hydrocarbons such as benzene, toluene, and xylene. And non-proton solvents such as acetonitrile and N, N-dimethylformamide; ethers such as getyl ether, tetrahydrofuran and dioxane; and ketones such as acetone and methylethyl ketone. And preferably dichloromethane, chloroform, benzene, toluene or xylene.
  • halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride
  • aromatic hydrocarbons such as benzene, toluene, and xylene.
  • non-proton solvents
  • dehydrating agent examples include acetic anhydride, trifluoroacetic anhydride, thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, dicyclohexyl chloride, and preferably thionyl chloride.
  • the amount of these reagents to be used is preferably equimolar to excess mol, more preferably equimolar to 2.5 equivalents, relative to compound (XXII). Further, it may be used as a solvent itself.
  • the reaction temperature may be selected from the range of 110 ° C. to the boiling point range of the inert solvent, and preferably from room temperature to 120 ° C.
  • the reaction time may be in the range of several minutes to 48 hours, with a force 5 ′ that is not constant depending on the reaction temperature, reaction scale, and the like, and is preferably 30 minutes to 5 hours.
  • the target product can be purified by an isolation means such as extraction, recrystallization, or distillation, if necessary, but can be directly used in the next reaction without purification.
  • Solvents that can be used in the reaction from compound (XXIII) to compound (XXIV) include, for example, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and aromatic hydrocarbons such as benzene, toluene, and xylene.
  • Acetonitrile, polar non-proton solvents such as N, N-dimethylformamide, ethers such as getyl ether, tetrahydrofuran, and dioxane; organic acids such as acetic acid and trifluoroacetic acid; acetone and methyl ethyl ketone; Ketones may be mentioned, and preferably dichloromethane, chloroform, benzene, toluene or xylene.
  • the reaction is preferably carried out by reacting the aniline compound of the compound (VII) with the compound (XXIII). It can be carried out using from about 1 mole to an excess, more preferably from about 1 mole to 2 equivalents.
  • the reaction temperature may be selected from the range of 110 ° C. to the boiling point of the inert solvent, and preferably from room temperature to 120 ° C.
  • the reaction time is not fixed depending on the reaction temperature, the reaction scale and the like, but may be in the range of several minutes to 4 S hours, preferably 30 minutes to 5 hours.
  • the desired product can be purified by an isolation means such as extraction, recrystallization, or distillation, if necessary. The product can be directly used for the next reaction without purification.
  • reaction in the synthesis reaction from compound (XXIV) to compound (I), the reaction can be carried out in the same manner, for example, under the conditions used in the synthesis reaction from compound (V) to compound (I) in Scheme 1.
  • the target compound After completion of the reaction, the target compound is isolated, and if necessary, the target compound can be purified by purification means such as recrystallization, distillation, or column chromatography.
  • Solvents that can be used in the reaction from compound (XXVI) to compound (I) include, for example, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and benzene.
  • Aromatic hydrocarbons such as benzene, toluene, and xylene; polar non-proton solvents such as atsenitrile; N, N-dimethylformamide; ethers such as getylether, tetrahydrofuran, and dioxane;
  • Examples thereof include organic acids such as acetic acid and trifluoroacetic acid, and ketones such as acetone and methyl ethyl ketone, and preferably include dichloromethane, chloroform, benzene, toluene and xylene.
  • Examples of the dehydrating agent include acetic anhydride, trifluoroacetic anhydride, thionyl chloride, phosphorus oxychloride, pentachloroaniline, dicyclohexylcarbodiimide, and 11- (3-methylaminopropyl) -13-ethylcarboimide. And preferably 11- (3-dimethylaminopropyl) -13-ethylcarbodiimide.
  • the amount of these reagents to be used is preferably an excess mole, more preferably equimolar to 2 equivalents, relative to compound (XXVI).
  • the reaction temperature may be selected from the range of from 110 to the boiling point of the inert solvent, and preferably from room temperature to 120 ° C.
  • the reaction time may be in the range of several minutes to 48 hours, which is not fixed depending on the reaction temperature, reaction scale, etc., and is preferably 30 minutes to 5 hours.
  • the desired product can be purified by an isolation means such as extraction, recrystallization, distillation, column chromatography or the like, if necessary.
  • the target compound can be isolated and, if necessary, the target compound can be purified by purification means such as recrystallization, distillation, and column chromatography.
  • the pyridazine-1,3-dicarboxylic acid of the compound (XXVII) can be synthesized by referring to, for example, J. Heterocyc 1ic Chem., 30, 1597 (1993). .
  • Solvents that can be used in the reaction from compound (XXXI) to compound (I) include, for example, halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride; and aromatic hydrocarbons such as benzene, toluene, and xylene.
  • halogenated hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride
  • aromatic hydrocarbons such as benzene, toluene, and xylene.
  • Non-proton solvents such as acetonitrile, N, N-dimethylformamide, ethers such as diethyl ether, tetrahydrofuran, and dioxane
  • organic acids such as acetic acid and trifluoroacetic acid
  • acetone And ketones such as methylethyl ketone.
  • dichloromethane chloroform, benzene, toluene or xylene power is used.
  • the dehydrating agent include acetic anhydride, trifluoroacetic anhydride, thionyl chloride, phosphorus oxychloride, 5-chloroaniline, dicyclohexylcarpoimide, and 11- (3-dimethylaminopropyl) 13- O- (3-dimethylaminopropyl), preferably 3-ethylethyl carbodiimide.
  • the amount of these reagents to be used is preferably an excess mole, more preferably equimolar to 2 equivalents, relative to compound (XXXI).
  • the reaction temperature may be selected from the range of 110 ° C. to the boiling point of the inert solvent, and preferably from room temperature to 120 ° C.
  • the reaction time may be varied within a range of a few minutes to 48 hours, depending on the reaction temperature, the reaction scale, etc., preferably 30 minutes to 5 hours.
  • the target product can be purified by an isolation means such as extraction, recrystallization, distillation, or column chromatography as required.
  • the black-mouthed form layer was washed with diluted hydrochloric acid and saturated saline, and dried with anhydrous sodium sulfate.
  • the solvent was distilled off under reduced pressure to obtain 14.97 g (55 mm 01) of 2-methylthiopyridin-1,4-dicarboxylate getyl. This diester was used for the next reaction as it was.
  • 6-Chloro-N- (3-chloro-2,6-getylphenyl) pyridin-13,4-dicarboxyimide 500 mg was dissolved in dimethylformamide 3 ml in a methylmercaptanadium aqueous solution. (15% aqueous solution, 0.75 ml) was added slowly at 0 ° C, and the reaction was carried out for 1 hour. After confirming the disappearance of the starting compounds, water was added, and the target substance was extracted from the reaction system with ethyl acetate. After extraction and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the obtained residue was washed with a small amount of ether to obtain 300 mg of the intended product. This was used for the next reaction as it was.
  • Pyridazine-1,4-dicarboxylic acid (1.4 g, 8.3 mm 01) was suspended in benzene (20 ml), and thionyl chloride (10 ml) was added, followed by heating under reflux for 1 hour. After standing to cool, the solvent was distilled off under reduced pressure to obtain pyridazine-1,4-dicarboxylic anhydride.
  • 2-Methylthio-6- (3-chloro-2,6-getylphenylaminocarbonyl) pyrimidine-5-carboxylic acid 0.5 g (1.3 mm 01), isoptylamine 0.
  • a mixture of 15 g (2 mm 01), 4-dimethylaminopyridine (catalytic amount) and 1 O ml of toluene was heated to 70 ° C.
  • WSC 1-ethyl-3- (3-dimethylaminopropyl) monocarposimid hydrochloride
  • the chloroform layer and the aqueous layer were separated, and the aqueous layer was extracted with black hole form, combined with the previous black hole form layer, washed with saturated saline, and dried over anhydrous sodium sulfate.
  • the solvent was distilled off under reduced pressure, and a mixed solution of ethyl ether and hexane was added to remove insolubles.
  • the solvent was distilled off under reduced pressure to obtain 1.8 g (4.7 mmol) of an imido compound. This was used for the next reaction as it was.
  • Tables 1 to 8 show the structural formulas and physical properties of the compounds of the present invention synthesized according to the above Examples, including the above Examples.
  • P h (R 4 ) represents a structure shown below.
  • H 3IAIH0 H3 Z H3 0 H
  • H 3 ⁇ 4 d H 3 H3 0 H
  • H 3 H 3 2 H 3
  • H lE 0 UD z UO ⁇ d 3 ⁇ 0 2 H0 H
  • H 0 H 3 2 HD 9 ⁇ 0 ⁇ ( Z H3) 0 H
  • H3 H3 Z H 3 ⁇ aO s H3 0 H

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Abstract

L'invention concerne des composés de formule (I) ou leurs sels qui sont utilisés comme herbicide, dans laquelle le noyau Z désigne une pyridine substituée en 3,4, une pyrimidine ou une pyrazine qui sont éventuellement substituées par un alkyle, etc.; R3 désigne H, alkyle C¿1-6?, phénylalkyle (substitué), etc.; R?4¿ désigne H, halogéno, nitro, cyano, alkyle C¿1-6?, etc.; et X désigne un alcoxycarbonyle, alkylaminoaminocarbonyle, cyano, alkylcarbonyle, oxydiazolyle (substitué), etc.
PCT/JP1999/001048 1998-03-05 1999-03-04 Composes d'anilide et herbicide WO1999044992A1 (fr)

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WO2001000575A1 (fr) * 1999-06-24 2001-01-04 Nihon Nohyaku Co., Ltd. Derives de diamide d'acide dicarboxylique heterocycliques, insecticides pour l'agriculture/l'horticulture, et procede d'utilisation
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JP2001064258A (ja) * 1999-06-24 2001-03-13 Nippon Nohyaku Co Ltd 複素環ジカルボン酸ジアミド誘導体及び農園芸用殺虫剤並びにその使用方法
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US6747041B1 (en) 1999-06-24 2004-06-08 Nihon Nohyaku Co., Ltd. Heterocyclic dicarboxylic acid diamide derivatives, agricultural/horticultural insecticides and method of using the same
WO2001000575A1 (fr) * 1999-06-24 2001-01-04 Nihon Nohyaku Co., Ltd. Derives de diamide d'acide dicarboxylique heterocycliques, insecticides pour l'agriculture/l'horticulture, et procede d'utilisation
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US11866434B2 (en) 2020-11-06 2024-01-09 Incyte Corporation Process for making a PD-1/PD-L1 inhibitor and salts and crystalline forms thereof
US11780836B2 (en) 2020-11-06 2023-10-10 Incyte Corporation Process of preparing a PD-1/PD-L1 inhibitor
US12084443B2 (en) 2020-11-06 2024-09-10 Incyte Corporation Process of preparing a PD-1/PD-L1 inhibitor
US11760756B2 (en) 2020-11-06 2023-09-19 Incyte Corporation Crystalline form of a PD-1/PD-L1 inhibitor
US12404272B2 (en) 2020-11-06 2025-09-02 Incyte Corporation Process for making a PD-1/PD-L1 inhibitor and salts and crystalline forms thereof

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