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WO1994017059A1 - Derive heterocyclique - Google Patents

Derive heterocyclique Download PDF

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Publication number
WO1994017059A1
WO1994017059A1 PCT/JP1994/000109 JP9400109W WO9417059A1 WO 1994017059 A1 WO1994017059 A1 WO 1994017059A1 JP 9400109 W JP9400109 W JP 9400109W WO 9417059 A1 WO9417059 A1 WO 9417059A1
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WIPO (PCT)
Prior art keywords
ome
substituted
alkyl
bruno
compound
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PCT/JP1994/000109
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English (en)
Japanese (ja)
Inventor
Yasuyuki Miyazawa
Yoshihiko Hara
Akiyoshi Ueda
Masami Koguchi
Kazuyuki Tomida
Takashi Kawana
Original Assignee
Nippon Soda Co., Ltd.
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Priority to AU58914/94A priority Critical patent/AU5891494A/en
Publication of WO1994017059A1 publication Critical patent/WO1994017059A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • 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
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—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
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to a novel heterocyclic derivative, a method for producing the same, and a herbicide containing the derivative as an active ingredient.
  • Herbicides are being used. However, there is a need for the development of drugs that can be used safely and safely at lower doses because they cause phytotoxicity, remain in the environment, and pollute crops.
  • rr 2 is a lower alkyl group, a lower alkoxy group, etc.
  • r 3 is a lower alkyl group, etc.
  • X 2 is 0 or S
  • a! Is CH or N
  • y 1, y 2 and y 3 are H, etc.
  • bi is CH or N.
  • An object of the present invention is to provide a herbicide which can be synthesized industrially advantageously, is effective at a lower dose, has high safety, and has high crop selectivity.
  • the present invention has the general formula (1)
  • A represents a nitrogen atom or a carbon atom substituted by R 3 ;
  • B represents a nitrogen atom or a carbon atom substituted by hydrogen or X;
  • Z represents oxygen, optionally oxidized sulfur, optionally substituted nitrogen, or optionally substituted carbon atom,
  • Q represents a 5- to 6-membered heterocyclic ring containing 1 to 4 nitrogen, oxygen or sulfur, and is bonded to a benzene or pyridin ring at the carbon atom of Q;
  • R, R 2 are each independently hydrogen, d-4 alkyl, d-4 alkoxy, C, - 4 haloalkoxy, haloalkyl, C, - 4 Arukiruami Bruno, current events ⁇ alkyl Ruami Bruno, C, - 4 alkylthio, Represents a halogen or cyano group,
  • R 3 represents hydrogen, d-alkyl, halogen, nitro, formyl, or acyl; R 2 and R 3 may be taken together to form a ring;
  • X, Y are each independently hydrogen, CI- e alkyl, C 3 - 7 cycloalkyl, C 2 - e ⁇ alkenyl, C haloalkyl, C 2 - 6 alkynyl, halogen, nitro, ⁇ Mi Roh, C Arukiruami Bruno, Ashiruami Bruno, CI- 6 alkylsulfonyl ⁇ Mi Bruno, formyl, Ashiru, Shiano, carboxyl, 'I Mi Bruno, human Dorokishiru, Ci - 6 an alkoxy carbonyl, C -!
  • Examples of the 5- to 6-membered heterocyclic ring containing 1 to 4 nitrogen, oxygen, or sulfur of Q include, for example, imidazole, isoxazole, oxazole, oxaziazole, pyrrol, pyrazole, thiazol, thiadiazole, and tereazole.
  • Examples include tolazole, triaryl, dithiazole, pyrimidine, pyridine, pyrazine, oxazine, pyridazine, pyrone, triazine, and dihydro forms of these heterocycles.
  • Y, ⁇ 55 is hydrogen, d-alkyl, C 3 - 7 cycloalkyl, C 2 one 6 alkenyl, haloalkyl, C 2 _ 6 alkynyl, halogen, two Toro, amino, Arukiruami Bruno, Ashiruami Bruno , d alkylsulfonyl ⁇ Mi Bruno, formyl, Ashiru, Shiano, carboxyl, I Mi Bruno, human Dorokishiru, C i-6 alkoxide aryloxycarbonyl, C alkoxy, which may be substituted Benjiruokishi, C 2 - 6 Arukeniruokishi, C i haloalkoxy, C 2 -alkynyloxy, optionally substituted phenoxy, optionally substituted benzyl, aminoxy, C 6 alkylthio, optionally substituted phenyl, alkylsulfonyl, optionally substituted Fuweniruchio,
  • two ⁇ , to Y 55 may form a carbocyclic or heterocyclic ring. ] And so on. And, preferably, Q-Upsilon eta,
  • D 2 When D, is N, D 2 represents NY or 0,
  • Q is particularly preferably an oxazole-5-yl or 2-oxazoline-5-yl group.
  • benzyloxy, phenoxy, benzyl, phenyl, phenylthio, benzoyl, phenylsulfonyl, heterocyclic-oxy, and heterocyclic monothio groups may be substituted by de alkoxy, C, -s alkyl, Halogen, nitro
  • the compound of the present invention can be produced by the following method.
  • the 0-heterocyclic-substituted phenol (or hydroxypyridin) derivative [3] as a raw material in the above reaction can be produced by the method described below.
  • solvents used in the following reactions include alcohols such as methanol, ethanol, and isopropyl alcohol, aromatic hydrocarbons such as benzene and toluene, dichloromethane, and chloroform.
  • C such as mouth holm Hydrogenated hydrocarbons, ethers such as getyl ether and THF, ketones such as acetone and MEK, esters such as methyl acetate and ethyl acetate, non-protonic polar solvents such as DMF and DMS 0,
  • ethers such as getyl ether and THF
  • ketones such as acetone and MEK
  • esters such as methyl acetate and ethyl acetate
  • non-protonic polar solvents such as DMF and DMS 0
  • Examples include nitriles such as cetonitrile, water and the like.c.
  • Examples of the base used include sodium carbonate, carbonate such as carbonated carbonate, sodium hydroxide, hydroxylated phosphate and the like.
  • Metal hydroxides such as sodium hydroxide, sodium methylate, sodium methylate, etc., metal hydrides such as sodium hydride, alkyl metals such as butyl lithium, lithium diisopropylamide, lithium bismuth Examples thereof include lithium amides such as rimethylsilylamide, and organic bases such as triethylamine and DBU.
  • the acid to be used include mineral acids such as hydrochloric acid, nitric acid, and sulfuric acid, organic acids such as formic acid and acetic acid, and Lewis acids such as aluminum chloride and boronant fluoridated getyl ether.
  • the reaction temperature may be from 190 ° C. to the boiling point of the solvent or lower. (Hereinafter, X, m, and B represent the same meaning as described above.)
  • a compound in which Q is imidazole-41-yl can be produced by reacting imine [7] with Tos MIC (p-toluenesulfonylmethyl isocyanide) in the presence of a base.
  • Tos MIC p-toluenesulfonylmethyl isocyanide
  • the compound [3f] in which Q is 1,3,4-triazol_2-2-yl is obtained by converting the compound [8] to acid chloride or an acid anhydride in DMF at 0 to 120 ° C. It can be produced by reacting with.
  • R 5 represents an alkyl, aryl or CF 3 group.
  • 3-position substitution-1,3,4_triazole-2-yl derivative [3g] is the teaching of J. 0rg. Chem. 4 Volume 4, 4160 pages (1977) Then, the amide [9] is reacted with dimethylformamide and dimethylacetal to synthesize N-[(dimethylamino) methylene] amide [10]. Hydrazines react with [10] To induce Triazole [11]. When L 2 is a methoxymethoxy or benzyloxy group, [11] is treated with an acid, or [3 g] is obtained by a hydrogenolysis reaction using palladium carbon or the like as a catalyst.
  • [3h] is obtained by reacting tin azide with [13] according to the method described in J. Org. Chem. 56, pp. 2395 (1991). Can also be manufactured.
  • a derivative in which Q is thiazol-2-yl is synthesized as follows.
  • the thioamide [15] and the promotone [16] are reacted in an alcohol at 25 to 80 ° C for 1 to 20 hours to synthesize [17].
  • [3i] is produced by performing the same reaction as in the production method of [17] to [3g].
  • R 8 represents alkyl, ⁇ reel, CF 3 group
  • R g represents hydrogen, alkyl, COOR 10 group
  • R 10 represents alkyl group
  • L 2 and RT have the same meanings as above. Represents.
  • the derivative [3j] of Q is thiazole-4-yl is obtained by reacting [19] with the promotone [18] in an alcohol at 25 to 80 for 1 to 20 hours to form a thiazole ring. After being formed, it is produced by performing the same reaction as in the production method of [3 g].
  • R 12 represents alkyl, aryl, R 13 NH group
  • R 13 represents hydrogen, alkyl, aryl group
  • L 2 , R 7 and R 10 represent the same meaning as described above.
  • the derivative [3k] of thiazol-5-yl for Q can also be produced by the same method as described above.
  • R 14 represents hydrogen or an alkyl group
  • L 2 , R 7 , and R 12 represent the same meaning as described above.
  • the derivative [31] of Q is oxazole-2-yl is obtained by reacting the amide [9] with the promoketone [23] at 50 to 160 ° C for 1 to 48 hours with [24]. After that, the reaction can be carried out in the same manner as in the production method of [3 g].
  • R 15 represents a hydrogen, alkyl, phenyl or CF 3 group
  • R 16 represents a hydrogen, an alkyl or phenyl group
  • L 2 and R 7 have the same meanings as described above.
  • oxazole-4-yl Derivative of oxazole-4-yl is also obtained by the same reaction as (31) .c Compound (27) and amide (28) are reacted at 50 to 160 ° C for 1 to 48 hours. After obtaining the oxazole derivative [29], [3n] can be produced by performing the same reaction as in the production method of [3g] from [29].
  • L 3 represents halogen
  • R 17 represents hydrogen, methyl, ethyl group, COOR 10
  • R 18 represents hydrogen, alkyl, phenyl group
  • L 2 , R 7 , R 10 Represents the same meaning as described above.
  • R 22 H, Alkyl, CH 2 Ph or Nitro
  • the derivative [3r] of Q is oxazole-5-yl can also be produced by the following method. That is, by reacting isonitrile [38] with aldehyde [37] in the presence of a base such as sodium carbonate hydride at 25 to 100 for 0.5 to 8 hours. [9], followed by the same reaction as in [3 g].
  • a base such as sodium carbonate hydride
  • R 22 represents a hydrogen, an alkyl, or a benzyl group
  • L 2 and R 7 represent the same meaning as described above.
  • R 23 H, Alkyl, Halogen
  • the derivative [3s] of Q is a condensed oxazole-2-yl is prepared by reacting compound [40] with thiominophenol [41] to give compound [4 2] via compound [42]. It is produced by performing the same reaction as described above.
  • R 23 represents hydrogen, an alkyl group, or halogen, and L 2 and R 7 have the same meanings as described above.
  • Derivative [3x] of Q isoxazole-4-yl is obtained by converting compound [44] into formylolate to form [45], cyclizing with hydroxylamine, and finally phenol. It is produced by removing the protecting group. References for this reaction include Pharmaceutical Journal, Vol. 79, p. 623 (1959). (In the formula, R 24 represents a hydrogen, alkyl, or funinyl group.)
  • (3y) can be produced by reacting benzofuran [47] with hydroxylamine in alcohol at 25 to 80 ° C for 0.5 to 8 hours,
  • 1,2,4-oxaziazol-5-yl derivative [3z] is obtained by converting [34] and amidoxime [48] in the presence of a base in the range of 1 to 8 at 0 to 140 ° C. After reacting for 4 hours to obtain [49], the same reaction as in the production method of [3 g] is performed, It is.
  • R 25 represents hydrogen, alkyl, benzyl, aryl, haloalkyl, alkoxyalkyl, or alkylthioalkyl, and L 2 and R 7 have the same meanings as described above.
  • the derivative of pyrrolyl-3-yl [3c '] is obtained by converting ketone [52] to oxime [53], and then cyclizing it with an acetylene compound to form a pyrrole ring. And then performing the same reaction as in the production method of [3 g].
  • R 26 and R 27 each represent a CN, COORio> phenyl group, and L 2 and R 10 have the same meaning as described above.
  • ketone [55] By reacting ketone [55] with glyoxylic acid and hydrazine, a derivative of 3-pyridazinone-6-yl [3d '] can be produced.
  • the compound represented by the general formula [1] can also be produced by the following method.
  • the compound can be produced by a method similar to the method for synthesizing compound [3] described above. That is, this is a method for producing [1] by reacting a compound represented by the general formula [56] with an appropriate condensing agent shown in the production method of the above [3].
  • R 29 H, Alkyl, CH 2 Ph, Aryl, C00R IO , represents the group shown in Tos. L ⁇ LS. R ⁇ . RU. R. R. R ⁇ has the same meaning as described above.
  • the compound represented by the general formula [57] and sodium azide are mixed in a suitable solvent, preferably using DMF, at a temperature from room temperature to a temperature lower than the boiling point of the solvent, preferably 80 to 120 to 1-. Manufactured by reacting for 24 hours. (Hereinafter, in the formula, R,, R 2 , A, B, Z, X, and m have the above meanings.) N /: i ⁇
  • Examples of the solvent used for this reaction include alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform; Ethers such as ether, THF, etc., ketones such as acetate, MEK, etc., esters such as methyl acetate, ethyl acetate, non-protonic polar solvents such as DMF and DMS 0, acetonitrile, water, etc.
  • Bases used in this reaction include carbonates such as sodium carbonate and potassium carbonate, sodium hydroxide, metal hydroxides such as hydroxylating lime, sodium methylate and sodium ethylate.
  • Metal hydrides such as sodium hydride, hydrogen hydride, lithium amides such as lithium diisopropylamide, lithium bistrimethylsilylamide, triethylamine, DBU, etc. Organic bases and the like.
  • the compound represented by the general formula (60) is reacted with T 0 s MIC in a suitable solvent in a suitable solvent at a temperature from room temperature to a temperature lower than the boiling point of the solvent for 1 to 24 hours. It is manufactured by having
  • solvent used in this reaction examples include alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform; Ethers, ethers such as THF, ketones such as acetone, MEK, methyl acetate., Ethyl acetate 109
  • Esters such as 27, non-protonic polar solvents such as DMF and DMS 0, and acetonitrile-water.
  • the base used in this reaction include sodium carbonate, carbonate such as sodium carbonate, sodium hydroxide, metal hydroxide such as sodium hydroxide, sodium methylate, and sodium hydroxide.
  • Metal alcohols such as lithium ethylate; metal hydrides such as sodium hydride and potassium hydride; lithium amides such as lithium diisopropylamide and lithium bistrimethylsilyl amide;
  • Organic bases such as triethylamine and DBU are exemplified.
  • the compound represented by the general formula [61] is reacted with a hydrazine in the presence or absence of a suitable base in a suitable solvent at a temperature from room temperature to a temperature lower than the boiling point of the solvent for 1 to 24 hours.
  • a suitable base in a suitable solvent at a temperature from room temperature to a temperature lower than the boiling point of the solvent for 1 to 24 hours.
  • the solvent used in this reaction include alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene and toluene; and halogenated hydrocarbons such as dichloromethane and chloroform.
  • Ethers such as getyl ether and THF, ketones such as acetone and MEK, esters such as methyl acetate and ethyl acetate, non-protonic polar solvents such as DMF and DMSO, acetonitrile, and water And the like.
  • the base used in this reaction include sodium carbonate, carbonate such as carbonated lime, sodium hydroxide, metal hydroxide such as hydroxylated lime, sodium methylate and sodium methacrylate.
  • Metal hydrides such as sodium hydride, hydrogen hydride, etc .; lithium amides such as lithium diisopropylamide and lithium bistrimethylsilyl amide; and triethylamid And organic bases such as DBU.
  • the compound represented by the general formula [62] and the promoketone [16] are reacted with a suitable base in the presence or absence of a suitable base in a suitable solvent at a temperature from room temperature to a temperature lower than the boiling point of the solvent, from 1 to 24. It is manufactured by reacting for hours.
  • Examples of the solvent used in this reaction include alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform; Examples include ethers such as THF, ketones such as acetone and MEK, esters such as methyl acetate and ethyl acetate, non-protonic polar solvents such as DMF and DMSO, and acetonitrile.
  • the base used in this reaction includes sodium carbonate, carbonated carbonate and the like, sodium hydroxide-hydroxide hydroxide and other metal hydroxides, and sodium methyler.
  • Metal alkoxides such as sodium and sodium hydride, metal hydrides such as sodium hydride and hydrogen hydride, lithium amides such as lithium diisopropylamide, and organic bases such as triethylamine and DBU. And the like. (In the formula, R 8. R 8 represents the same meaning as described above.)
  • the aldehyde represented by the general formula [63] and the isonitrinole [38] are reacted with the aldehyde in the presence of at least two equivalents of a suitable base in a suitable solvent at room temperature to below the boiling point of the solvent. It is produced by reacting at a temperature for 1 to 24 hours.
  • Solvents used in this reaction include, for example, alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chloroform; dimethyl ether; Examples include ethers such as THF, non-protonic polar solvents such as DMF and DMS0, and acetonitrile.
  • Examples of the base used in this reaction include carbonates such as sodium carbonate and potassium carbonate, metal hydroxides such as sodium hydroxide and hydroxide rim, sodium methylate, sodium methylate and the like.
  • Solvents used in this reaction include, for example, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, ethers such as getyl ether and THF, DMF, DM Non-protonic polar solvents such as S0 and acetonitril.
  • the base used in this reaction includes sodium carbonate, sodium carbonate and the like, sodium hydroxide, metal hydroxide such as sodium hydroxide, sodium hydride, hydrogen hydride and the like.
  • Metal hydrides such as lithium, lithium amides such as lithium diisopropylamide and lithium pristylmethylsilylamide, organic salts such as triethylamine and DBU, and the like. (Wherein, R 20 represents the same meaning as described above.)
  • the aldehyde represented by the general formula [63] and isonitrile [38] are reacted in a suitable solvent in the presence of a suitable base in an amount equivalent to the aldehyde at a temperature of 0 ° C to room temperature.
  • [1j] is produced by reacting for 1 to 2 hours.
  • the solvent used in this reaction include alcohols such as methanol, ethanol, and isopropanol; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as dichloromethane and chromatoform; and dimethyl ether.
  • ethers such as THF, non-protonic polar solvents such as DMF and DMSO, and acetonitrile.
  • Examples of the base used in this reaction include carbonates such as sodium carbonate and potassium carbonate, metal hydroxides such as sodium hydroxide and hydrating power, sodium hydride, potassium hydride and the like.
  • acylimidazole represented by the general formula [64] and the amide oxime [48] are reacted in a suitable solvent in the presence of a suitable base at a temperature of 15 to 140 ° C for 1 to 24 hours. This produces [lk].
  • Solvents used in this reaction include, for example, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as dichloromethane and chloroform, ethers such as getyl ether and THF, DMF, Non-protonic polar solvents such as DMSO, acetonitril, and the like.
  • Examples of the base used in this reaction include carbonates such as sodium carbonate and potassium carbonate, metal hydroxides such as sodium hydroxide and hydroxide hydroxide, sodium hydride, and hydrogen.
  • Metal hydrides such as potassium iodide, and lithium such as lithium diisopropylamide Examples include amides, triethylamine, and organic bases such as DBU. (Wherein, R 25 has the same meaning as described above.)
  • the compound represented by the general formula [1 '] is reacted with a suitable base or acid in the absence of a solvent or in a suitable solvent at a temperature of from 178 ° C to a temperature lower than the boiling point of the solvent, according to a method known in the literature.
  • (11) is produced by reacting the compound of the general formula (1j) with (65) in the presence of a suitable base in a suitable solvent at a temperature of 15-25 for 1 to 24 hours.
  • c is a solvent used in this reaction, for example, alcohols such as methanol, ethanol and isoprene Robanoru, benzene, aromatic hydrocarbons such as toluene, dichloroethylene Rorometan, halogenated hydrocarbons such as black hole Holm , Jettlätel, TH
  • ethers such as F
  • ketones such as acetone and MEK
  • esters such as methyl acetate and ethyl acetate
  • non-protonic polar solvents such as DMF and DMS 0, acetonitrile, and water.
  • Examples of the base used in this reaction include sodium carbonate, carbonates such as carbonated lime, sodium hydroxide, metal hydroxides such as hydroxylated lime, sodium methylate, and sodium methylate.
  • Metal alcohols such as triethyl ethylate; metal hydrides such as sodium hydride and potassium hydride; lithium amides such as lithium diisopropyl amide and lithium p-methylsilyl amide
  • organic bases such as triethylamine and DBU.
  • a compound of the general formula [2] (wherein, R,, R 2 , A and L represent the same meaning as described above); and a compound of the general formula [66] (where B, Q, X, Y, m and n represent the same meaning as described above.) in an organic solvent in the presence of a base.
  • a base include metal hydrides such as sodium hydride, carbonates such as potassium carbonate, and organic bases such as triethylamine.
  • the solvent include DMF, DMS0, THF, and DME.
  • the 0-heterocyclic-substituted thiol (or mercapto pyridine) derivative [66] as the raw material in the above reaction can be produced by the method described below.
  • solvents used in the following reactions include alcohols such as methanol, ethanol, and isopropyl alcohol, aromatic hydrocarbons such as benzene and toluene, dichloromethane, and chloroform.
  • Halo such as mouth form Genated hydrocarbons, ethers such as getyl ether and THF, ketones such as acetone and MEK, esters such as methyl acetate and ethyl acetate, and non-protonic polar solvents such as DMF and DMS O And nitriles such as acetonitril, and water.
  • the base to be used include carbonates such as sodium carbonate and carbonated carbonate, sodium hydroxide, metal hydroxides such as hydroxided sodium, sodium methylate, and sodium ethylate.
  • Metal alcohols such as metal, hydrogenated metals such as sodium hydride, alkyl metals such as butyllithium, lithium amides such as lithium diisopropylamide and lithium bistrimethylsilylamide And organic bases such as triethylamine, DBU and the like.
  • the acid used include mineral acids such as hydrochloric acid, nitric acid and sulfuric acid, organic acids such as formic acid and acetic acid, aluminum chloride, and Lewis acids such as boron trifluoride dodecyl ether.
  • the reaction temperature is, for example, a temperature of 190 ° C to 250 ° C. (Hereinafter, Q, X, Y, m, n, and B represent the same meaning as described above.)
  • Compound (66) can be produced by reacting a compound of the general formula (68) with sodium sulfide or thioperia, which can be produced by a method similar to the method for synthesizing compound (3) described above. I can do it. References for this reaction include Chemistry Letters, page 1307 (1985).
  • [66] is obtained by deriving the above-mentioned compound [3] to [69], and then applying the method described in J. 0 rg. Chem. 31 Volume 1, p. 398 (1966)
  • the compound can also be produced by hydrolyzing this as [70] by the Newman rearrangement reaction described in (1).
  • aniline derivative [71] was converted to 0 r g a n i c S y n t h e se s C o l
  • [66] can also be produced by applying the method described in 1 ect., Volume 3, page 809. (In the formula, L 4 represents halogen, preferably fluorine.)
  • a compound of the general formula [72] (wherein R,, R 2 , A and Z represent the same meaning as described above), and a compound of the general formula [68] (where B, Q, X, Y , m, n, L 4 is a compound of representing.) as defined above, is the presence coupling base in an organic solvent.
  • the base include metal hydrides such as sodium hydride, carbonates such as carbonated lime, and organic bases such as tritylamine.
  • the solvent include DMF, DMS O, THF, and DME. .
  • the reaction mixture is stirred at 0-90 ° C, optionally at 120 ° C, until the reaction is complete.
  • Examples of the salt of the compound represented by the general formula [1] include environmentally acceptable salts, for example, inorganic acid salts such as hydrochloric acid salt and hydrogen bromide salt, and organic acid salts such as acetate, oxalate, and formate. And alkaline metals, alkaline earth metals, ammonium salts and the like. These salts can be prepared in a conventional manner.
  • the structure of the compound of the present invention was determined from IR, NMR, MS and the like.
  • Triethylamine (0.07 g) was added to a methylene chloride solution of 0.15 g of 5- (2- (4,6-dimethoxypyrimidine-12-yloxy) -16-hydroxyphenyl) oxazole. The reaction was stirred at room temperature and after 15 minutes cyclohexyliso 0.08 g of cyanate was added. After stirring for 1.5 hours, water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the obtained oil was recrystallized from a mixed solvent of n-hexane and diethyl ether. Thus, 0.17 g of the desired product was obtained.
  • the compound of the present invention or a salt thereof exhibits a high herbicidal activity under any conditions of upland cropping in any of soil treatment and foliage treatment.
  • foliar spray treatment has a high efficacy against various field weeds such as mexican, california, strawberry, and inubu, and also contains compounds that have selectivity for crops such as corn, wheat, soybeans, and ivy.
  • the compound of the present invention or a salt thereof has an excellent herbicidal activity against weeds such as paddy field weeds such as Nobie, Tamagayari, Omodaka and Houyui, and also includes a compound showing selectivity to rice.
  • the compound of the present invention or a salt thereof can also be applied to the control of weeds in orchards, lawns, track ends, vacant lots and the like.
  • the compound of the present invention or a salt thereof includes those having a plant growth regulating action.
  • the herbicide of the present invention contains one or more of the compound represented by the general formula [1] or a salt thereof as an active ingredient, and has a form similar to that of a general pesticide. That is, the active ingredient compound is generally used in the form of a wettable powder, an emulsion, a granule, a water solvent, a flowable or the like by mixing an appropriate amount with a carrier.
  • the solid carrier include talc, white carbon (silicone force), bentonite, clay, and diatomaceous earth.
  • liquid carrier examples include water, alcohol, benzene, xylene, kerosene, mineral oil, cyclohexane, and the like. Cyclohexanone, dimethylformamide and the like are used. In these preparations, a surfactant may be added if necessary to obtain a uniform and stable form.
  • the active ingredient concentration in the herbicide of the present invention varies depending on the form of the preparation described above.
  • a wettable powder it is 5 to 90%, preferably 10 to 85%. %: 3 to 70%, preferably 5 to 30% in the emulsion: 0.01 to 30%, preferably 0.05 to 10% in the granule
  • the concentration is used.
  • the wettable powder and emulsion thus obtained are diluted with water to a predetermined concentration to form a suspension or emulsion, and the granules are directly sprayed or mixed before or after germination of the weeds. .
  • an appropriate amount of 0.1 g or more of the effective component per 10 is applied.
  • the herbicide of the present invention can also be used by mixing with known fungicides, insecticides, acaricides, herbicides, plant growth regulators and the like. In particular, it is possible to reduce the amount of drug used by mixing and using herbicides. In addition to saving labor, higher effects can be expected due to the synergistic action of the mixed drug. In that case, a combination with a plurality of known herbicides is also possible.
  • Suitable agents to be used in combination with the herbicide of the present invention include acid amides such as carbamate herbicides such as benthiocarb, molinate and dimepirate, tiocarbamate herbicides, butachlor, pretilachlor, mefenacet and the like.
  • Herbicides diphenyl ether herbicides such as chrometoxynil and bifenox; triazine herbicides such as atrazine and cyanadine; sulfonylurea herbicides such as chlorsulfuron and sulfometurone monomethyl; MCP, MCPB Carboxylic acid-based herbicides such as diclohop-methyl, etc., phenoxyphenoxypropionic acid-based herbicides such as diclohop-methyl, and pyridyloxy-benzooxypropionic acid-based herbicides such as fluazifop-butyl, and benzoylprop Benzyl, etc.
  • Minopropionic acid herbicides imidazoline and other imidazolinone herbicides, and other products such as piperophos, dimelone, benzozone, difenzocoat, nabroanilide, and HW-52 (4-ethoxyethoxybenz-1) 2,3-Dichloranilide), triazophenamide, kink-mouth lac, and cyclohexanedione-based herbicides such as sethoxydim and aroxydim-sodium. Vegetable oils and oil concentrates can also be added to these combinations.
  • the soil was filled in a pot of 200 cm 2 , and seedlings of Meishishiba, Karyarigusa and Inubu were sown on the surface layer, and after lightly covering the soil, they were grown in a greenhouse.
  • the emulsion of each test compound was diluted with water and adjusted to a concentration of 400 ppm. (equivalent to 400 g per a) and sprayed on the foliage of weeds with a small sprayer.
  • the weed herbicidal effect was investigated according to the following criteria, and the results are shown in Table 32 below. Survey criteria
  • the numbers 1, 3, 5 7 9 represent the intermediate values between 0, 22, and 4, 4 and 6, 6, 6, 8, 8, and 10, respectively.

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Abstract

Un composé, aux qualités herbicide et régulatrice de la croissance des plantes améliorées, est représenté par la formule générale (1): où A représente azote ou carbone substitué à R3; B représente azote ou carbone qui peut être substitué par X; Z représente oxygène ou soufre, azote ou carbone éventuellement oxydé; Q représente un hétérocycle à 5 ou 6 membres présentant de 1 à 4 atomes d'azote, d'oxygène ou de soufre, et lié au cycle benzène ou pyridine par son atome de carbone; R1 et R2 représentent chacun hydrogène, alkyle, alcoxy, haloalcoxy, haloalkyle, alkylamino, dialkylamino, alkylthio, halogène ou cyano; R3 représente hydrogène, alkyle, halogène, nitro, formyle ou acyle, ou bien R2 et R3 peuvent se combiner pour former un cycle; X et Y représentent chacun hydrogène, alkyle, cycloalkyle, alkényle, haloalkyle, alkynyle, halogène, nitro, amino, alkylamino, etc.; et m et n représentent chacun un nombre entier allant de 1 à 4.
PCT/JP1994/000109 1993-01-29 1994-01-27 Derive heterocyclique WO1994017059A1 (fr)

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Cited By (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996033994A1 (fr) * 1995-04-28 1996-10-31 Nippon Soda Co., Ltd. Derives amino-substitues, leur procede de preparation et herbicide
WO1996037491A1 (fr) * 1995-05-25 1996-11-28 Nippon Soda Co., Ltd. Derives heterocycliques ayant un groupe hydroxyalkyle phenyle et herbicides
US5633272A (en) * 1995-02-13 1997-05-27 Talley; John J. Substituted isoxazoles for the treatment of inflammation
EP0776894A4 (fr) * 1994-08-02 1997-11-05 Nippon Soda Co Derive d'oxazole, son procede de production et herbicide
WO1998056777A1 (fr) * 1997-06-10 1998-12-17 Nippon Soda Co., Ltd. Benzenes isoxazol-5-yl-substitues et leur procede de production
US5859257A (en) * 1995-02-13 1999-01-12 G. D. Searle & Co. Isoxazole compounds as cyclooxygenase inhibitors
EP1195375A4 (fr) * 1999-06-25 2002-11-27 Nihon Nohyaku Co Ltd Derives de benzamide, insecticides pour l'agriculture/l'horticulture, et utilisation
US6743815B2 (en) 1998-08-07 2004-06-01 Chiron Corporation Estrogen receptor modulators
US6759538B2 (en) 2001-11-02 2004-07-06 Rigel Pharmaceuticals, Inc. Substituted diphenyl heterocycles useful for treating HCV infection
MY120647A (en) * 2000-12-20 2005-11-30 Nihon Nohyaku Co Ltd Benzamide derivatives and agricultural and horticultural insecticides and method for using thereof.
US7115642B2 (en) 2003-05-02 2006-10-03 Rigel Pharmaceuticals, Inc. Substituted diphenyl isoxazoles, pyrazoles and oxadiazoles useful for treating HCV infection
US7157473B2 (en) 2002-08-23 2007-01-02 Rigel Pharmaceuticals, Inc. Pyridyl substituted heterocycles useful for treating or preventing HCV infection
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US7326790B2 (en) 2003-05-02 2008-02-05 Rigel Pharmaceuticals, Inc. Diphenylisoxazole compounds and hydro isomers thereof
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US7470715B2 (en) 2005-12-22 2008-12-30 Pfizer Inc. Estrogen modulators
US7498353B2 (en) 2005-05-02 2009-03-03 Rigel Pharmaceuticals, Inc. Heterocyclic anti-viral compounds comprising metabolizable moieties and their uses
US7514434B2 (en) 2004-02-23 2009-04-07 Rigel Pharmaceuticals, Inc. Heterocyclic compounds having an oxadiazole moiety and hydro isomers thereof
JP2011518841A (ja) * 2008-04-24 2011-06-30 ニューリンク ジェネティクス， インコーポレイテッド Ｉｄｏ阻害剤
US8969347B2 (en) 2008-06-03 2015-03-03 Intermune, Inc. Compounds and methods for treating inflammatory and fibrotic disorders
WO2015108779A1 (fr) 2014-01-16 2015-07-23 E. I. Du Pont De Nemours And Company Dérivés de pyrimidinyloxy benzène à utiliser en tant qu'herbicides
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US9359379B2 (en) 2012-10-02 2016-06-07 Intermune, Inc. Anti-fibrotic pyridinones
WO2016149315A1 (fr) * 2015-03-18 2016-09-22 E. I. Du Pont De Nemours And Company Dérivés de pyrimidinyloxy pyridine substitués utilisés comme herbicides
US9527816B2 (en) 2005-05-10 2016-12-27 Intermune, Inc. Method of modulating stress-activated protein kinase system
US9561231B2 (en) 2012-06-12 2017-02-07 Abbvie Inc. Pyridinone and pyridazinone derivatives
US9695155B2 (en) 2013-12-10 2017-07-04 E I Du Pont De Nemours And Company Herbicidal substituted pyrimidinyloxy benzene compounds
US10220027B2 (en) 2011-07-13 2019-03-05 Gilead Sciences, Inc. FXR (NR1H4) binding and activity modulating compounds
US10233195B2 (en) 2014-04-02 2019-03-19 Intermune, Inc. Anti-fibrotic pyridinones
US10329286B2 (en) 2016-06-13 2019-06-25 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US10421730B2 (en) 2016-06-13 2019-09-24 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US10485235B2 (en) 2015-07-13 2019-11-26 Fmc Corporation Aryloxypyrimidinyl ethers as herbicides
WO2020094524A1 (fr) 2018-11-05 2020-05-14 Syngenta Crop Protection Ag Composés herbicides
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WO2021074325A1 (fr) * 2019-10-17 2021-04-22 Syngenta Crop Protection Ag Composés herbicides
CN112739687A (zh) * 2018-09-18 2021-04-30 巴斯夫欧洲公司 二氨基三嗪化合物
US11053204B2 (en) 2015-06-05 2021-07-06 Fmc Corporation Pyrimidinyloxy benzene derivatives as herbicides
US11225473B2 (en) 2019-01-15 2022-01-18 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US11427549B2 (en) 2017-05-02 2022-08-30 Fmc Corporation Pyrimidinyloxy benzo-fused compounds as herbicides
US11524005B2 (en) 2019-02-19 2022-12-13 Gilead Sciences, Inc. Solid forms of FXR agonists
US11833150B2 (en) 2017-03-28 2023-12-05 Gilead Sciences, Inc. Methods of treating liver disease

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01305070A (ja) * 1988-04-07 1989-12-08 Shell Internatl Res Maatschappij Bv トリアジン除草剤
JPH03200784A (ja) * 1989-12-28 1991-09-02 Ishihara Sangyo Kaisha Ltd アジン系化合物、それらの製造方法及びそれらを含有する除草剤
JPH03232881A (ja) * 1989-12-26 1991-10-16 Mitsui Toatsu Chem Inc ピリジルオキシピリミジン誘導体、その製造法およびそれを有効成分とする除草剤
JPH04108777A (ja) * 1990-08-30 1992-04-09 Kumiai Chem Ind Co Ltd ピリミジン誘導体及び除草剤
JPH04342586A (ja) * 1991-04-17 1992-11-30 Ishihara Sangyo Kaisha Ltd アジン系化合物、それらの製造方法及びそれらを含有する除草剤

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01305070A (ja) * 1988-04-07 1989-12-08 Shell Internatl Res Maatschappij Bv トリアジン除草剤
JPH03232881A (ja) * 1989-12-26 1991-10-16 Mitsui Toatsu Chem Inc ピリジルオキシピリミジン誘導体、その製造法およびそれを有効成分とする除草剤
JPH03200784A (ja) * 1989-12-28 1991-09-02 Ishihara Sangyo Kaisha Ltd アジン系化合物、それらの製造方法及びそれらを含有する除草剤
JPH04108777A (ja) * 1990-08-30 1992-04-09 Kumiai Chem Ind Co Ltd ピリミジン誘導体及び除草剤
JPH04342586A (ja) * 1991-04-17 1992-11-30 Ishihara Sangyo Kaisha Ltd アジン系化合物、それらの製造方法及びそれらを含有する除草剤

Cited By (99)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0776894A4 (fr) * 1994-08-02 1997-11-05 Nippon Soda Co Derive d'oxazole, son procede de production et herbicide
US5633272A (en) * 1995-02-13 1997-05-27 Talley; John J. Substituted isoxazoles for the treatment of inflammation
US5859257A (en) * 1995-02-13 1999-01-12 G. D. Searle & Co. Isoxazole compounds as cyclooxygenase inhibitors
US5985902A (en) * 1995-02-13 1999-11-16 G.D. Searle & Co. Substituted isoxazole for the treatment of inflammation
WO1996033994A1 (fr) * 1995-04-28 1996-10-31 Nippon Soda Co., Ltd. Derives amino-substitues, leur procede de preparation et herbicide
WO1996037491A1 (fr) * 1995-05-25 1996-11-28 Nippon Soda Co., Ltd. Derives heterocycliques ayant un groupe hydroxyalkyle phenyle et herbicides
WO1998056777A1 (fr) * 1997-06-10 1998-12-17 Nippon Soda Co., Ltd. Benzenes isoxazol-5-yl-substitues et leur procede de production
US6743815B2 (en) 1998-08-07 2004-06-01 Chiron Corporation Estrogen receptor modulators
US6869969B2 (en) 1998-08-07 2005-03-22 Chiron Corporation Estrogen receptor modulators
EP1195375A4 (fr) * 1999-06-25 2002-11-27 Nihon Nohyaku Co Ltd Derives de benzamide, insecticides pour l'agriculture/l'horticulture, et utilisation
US6642379B1 (en) 1999-06-25 2003-11-04 Nihon Nohyaku Co., Ltd. Benzamide derivatives, insecticides for agricultural and horticultural use and usage thereof
MY120647A (en) * 2000-12-20 2005-11-30 Nihon Nohyaku Co Ltd Benzamide derivatives and agricultural and horticultural insecticides and method for using thereof.
US7153880B2 (en) 2001-11-02 2006-12-26 Rigel Pharmaceuticals, Inc. Substituted diphenyl heterocycles useful for treating HCV infection
US6759538B2 (en) 2001-11-02 2004-07-06 Rigel Pharmaceuticals, Inc. Substituted diphenyl heterocycles useful for treating HCV infection
US7157473B2 (en) 2002-08-23 2007-01-02 Rigel Pharmaceuticals, Inc. Pyridyl substituted heterocycles useful for treating or preventing HCV infection
US7115642B2 (en) 2003-05-02 2006-10-03 Rigel Pharmaceuticals, Inc. Substituted diphenyl isoxazoles, pyrazoles and oxadiazoles useful for treating HCV infection
US7326790B2 (en) 2003-05-02 2008-02-05 Rigel Pharmaceuticals, Inc. Diphenylisoxazole compounds and hydro isomers thereof
US7220745B2 (en) 2003-05-15 2007-05-22 Rigel Pharmaceuticals Heterocyclic compounds useful to treat HCV
US7410979B2 (en) 2003-11-19 2008-08-12 Rigel Pharmaceuticals, Inc. Synergistically effective combinations of dihaloacetamide compounds and interferon or ribavirin against HCV infections
US7514434B2 (en) 2004-02-23 2009-04-07 Rigel Pharmaceuticals, Inc. Heterocyclic compounds having an oxadiazole moiety and hydro isomers thereof
US7498353B2 (en) 2005-05-02 2009-03-03 Rigel Pharmaceuticals, Inc. Heterocyclic anti-viral compounds comprising metabolizable moieties and their uses
US9527816B2 (en) 2005-05-10 2016-12-27 Intermune, Inc. Method of modulating stress-activated protein kinase system
US10010536B2 (en) 2005-05-10 2018-07-03 Intermune, Inc. Method of modulating stress-activated protein kinase system
US7291643B2 (en) 2005-07-29 2007-11-06 Wyeth Cyanopyrrole-sulfonamide progesterone receptor modulators and uses thereof
US7470715B2 (en) 2005-12-22 2008-12-30 Pfizer Inc. Estrogen modulators
US8748469B2 (en) 2008-04-24 2014-06-10 Newlink Genetics Corporation IDO inhibitors
JP2011518841A (ja) * 2008-04-24 2011-06-30 ニューリンク ジェネティクス， インコーポレイテッド Ｉｄｏ阻害剤
US9174942B2 (en) 2008-04-24 2015-11-03 Newlink Genetics Corporation IDO inhibitors
US8969347B2 (en) 2008-06-03 2015-03-03 Intermune, Inc. Compounds and methods for treating inflammatory and fibrotic disorders
USRE47142E1 (en) 2008-06-03 2018-11-27 Intermune, Inc. Compounds and methods for treating inflammatory and fibrotic disorders
US9290450B2 (en) 2008-06-03 2016-03-22 Intermune, Inc. Compounds and methods for treating inflammatory and fibrotic disorders
US10220027B2 (en) 2011-07-13 2019-03-05 Gilead Sciences, Inc. FXR (NR1H4) binding and activity modulating compounds
US10485795B2 (en) 2011-07-13 2019-11-26 Gilead Sciences, Inc. FXR (NR1H4) binding and activity modulating compounds
US9221756B2 (en) 2011-12-05 2015-12-29 University Of Leicester Pyrrole derivatives
US9561231B2 (en) 2012-06-12 2017-02-07 Abbvie Inc. Pyridinone and pyridazinone derivatives
US10376497B2 (en) 2012-10-02 2019-08-13 Intermune, Inc. Anti-fibrotic pyridinones
US10898474B2 (en) 2012-10-02 2021-01-26 Intermune, Inc. Anti-fibrotic pyridinones
US9359379B2 (en) 2012-10-02 2016-06-07 Intermune, Inc. Anti-fibrotic pyridinones
US9675593B2 (en) 2012-10-02 2017-06-13 Intermune, Inc. Anti-fibrotic pyridinones
US9695155B2 (en) 2013-12-10 2017-07-04 E I Du Pont De Nemours And Company Herbicidal substituted pyrimidinyloxy benzene compounds
EP3094631B1 (fr) 2014-01-16 2019-01-09 FMC Corporation Dérivés de pyrimidinyloxy benzène à utiliser en tant qu'herbicides
WO2015108779A1 (fr) 2014-01-16 2015-07-23 E. I. Du Pont De Nemours And Company Dérivés de pyrimidinyloxy benzène à utiliser en tant qu'herbicides
US11447476B2 (en) 2014-01-16 2022-09-20 Fmc Corporation Pyrimidinyloxy benzene derivatives as herbicides
KR20210122878A (ko) * 2014-01-16 2021-10-12 에프엠씨 코포레이션 제초제로서의 피리미디닐옥시 벤젠 유도체
EA030009B1 (ru) * 2014-01-16 2018-06-29 Е.И.Дюпон Де Немур Энд Компани Пиримидинилоксибензольные производные в качестве гербицидов
CN105916849A (zh) * 2014-01-16 2016-08-31 纳幕尔杜邦公司 作为除草剂的嘧啶氧基苯衍生物
US10131652B2 (en) 2014-01-16 2018-11-20 E. I. Du Pont De Nemours And Company Pyrimidinyloxy benzene derivatives as herbicides
KR102381584B1 (ko) 2014-01-16 2022-04-04 에프엠씨 코포레이션 제초제로서의 피리미디닐옥시 벤젠 유도체
JP2017504624A (ja) * 2014-01-16 2017-02-09 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパ 除草剤としてのピリミジニルオキシベンゼン誘導体
KR102381581B1 (ko) 2014-01-16 2022-04-04 에프엠씨 코포레이션 제초제로서의 피리미디닐옥시 벤젠 유도체
AU2019226283B2 (en) * 2014-01-16 2021-07-01 Fmc Corporation Pyrimidinyloxy benzene derivatives as herbicides
US20190084972A1 (en) * 2014-01-16 2019-03-21 Fmc Corporation Pyrimidinyloxy benzene derivatives as herbicides
AU2021232774B2 (en) * 2014-01-16 2023-11-30 Fmc Corporation Pyrimidinyloxy benzene derivatives as herbicides
US10654840B2 (en) 2014-01-16 2020-05-19 Fmc Corporation Pyrimidinyloxy benzene derivatives as herbicides
TWI669295B (zh) * 2014-01-16 2019-08-21 美商艾佛艾姆希公司 作為除草劑的嘧啶氧基苯衍生物
US20160333000A1 (en) * 2014-01-16 2016-11-17 E. I. Du Pont De Nemours And Company Pyrimidinyloxy benzene derivatives as herbicides
CN111574510A (zh) * 2014-01-16 2020-08-25 Fmc 公司 作为除草剂的嘧啶氧基苯衍生物
KR20160107276A (ko) * 2014-01-16 2016-09-13 이 아이 듀폰 디 네모아 앤드 캄파니 제초제로서의 피리미디닐옥시 벤젠 유도체
CN105916849B (zh) * 2014-01-16 2020-07-07 Fmc公司 作为除草剂的嘧啶氧基苯衍生物
EP3094631B2 (fr) † 2014-01-16 2024-12-25 FMC Corporation Dérivés de pyrimidinyloxy benzène à utiliser en tant qu'herbicides
US10544161B2 (en) 2014-04-02 2020-01-28 Intermune, Inc. Anti-fibrotic pyridinones
US10233195B2 (en) 2014-04-02 2019-03-19 Intermune, Inc. Anti-fibrotic pyridinones
CN107001349A (zh) * 2014-09-24 2017-08-01 先正达参股股份有限公司 除草吡啶并/嘧啶并噻唑
US11470846B2 (en) 2014-09-24 2022-10-18 Syngenta Participations Ag Herbicidal pyridino-/pyrimidino-thiazoles
WO2016046078A1 (fr) * 2014-09-24 2016-03-31 Syngenta Participations Ag Pyridino/pyrimidino-thiazoles herbicides
CN107001349B (zh) * 2014-09-24 2021-07-02 先正达参股股份有限公司 除草吡啶并/嘧啶并噻唑
US11006631B2 (en) 2015-03-18 2021-05-18 Fmc Corporation Substituted pyrimidinyloxy pyridine derivatives as herbicides
WO2016149315A1 (fr) * 2015-03-18 2016-09-22 E. I. Du Pont De Nemours And Company Dérivés de pyrimidinyloxy pyridine substitués utilisés comme herbicides
AU2016233348B2 (en) * 2015-03-18 2020-04-30 Fmc Corporation Substituted pyrimidinyloxy pyridine derivatives as herbicides
CN107250134A (zh) * 2015-03-18 2017-10-13 杜邦公司 作为除草剂的取代的嘧啶氧基吡啶衍生物
US20180020664A1 (en) * 2015-03-18 2018-01-25 E. I. Du Pont De Nemours And Company Substituted pyrimidinyloxy pyridine derivatives as herbicides
RU2735278C2 (ru) * 2015-03-18 2020-10-29 ЭфЭмСи Корпорейшн Замещенные производные пиримидинилокси-пиридина в качестве гербицидов
CN115785000A (zh) * 2015-06-05 2023-03-14 Fmc公司 作为除草剂的2-(苯氧基或苯硫基)嘧啶衍生物、其组合物及用其控制不希望植被的方法
US11053204B2 (en) 2015-06-05 2021-07-06 Fmc Corporation Pyrimidinyloxy benzene derivatives as herbicides
US10485235B2 (en) 2015-07-13 2019-11-26 Fmc Corporation Aryloxypyrimidinyl ethers as herbicides
US10421730B2 (en) 2016-06-13 2019-09-24 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US11739065B2 (en) 2016-06-13 2023-08-29 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US10329286B2 (en) 2016-06-13 2019-06-25 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US10981881B2 (en) 2016-06-13 2021-04-20 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US10774054B2 (en) 2016-06-13 2020-09-15 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US11247986B2 (en) 2016-06-13 2022-02-15 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US12358903B2 (en) 2016-06-13 2025-07-15 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US11833150B2 (en) 2017-03-28 2023-12-05 Gilead Sciences, Inc. Methods of treating liver disease
US11427549B2 (en) 2017-05-02 2022-08-30 Fmc Corporation Pyrimidinyloxy benzo-fused compounds as herbicides
CN112739687A (zh) * 2018-09-18 2021-04-30 巴斯夫欧洲公司 二氨基三嗪化合物
WO2020094524A1 (fr) 2018-11-05 2020-05-14 Syngenta Crop Protection Ag Composés herbicides
CN111217762B (zh) * 2018-11-23 2021-08-20 华中师范大学 多卤代5-(2-羟基苯基)异噁唑类化合物及其制备方法和应用
CN111217762A (zh) * 2018-11-23 2020-06-02 华中师范大学 多卤代5-(2-羟基苯基)异噁唑类化合物及其制备方法和应用
JP2022513966A (ja) * 2018-12-18 2022-02-09 バイエル・アクチエンゲゼルシヤフト 置換ピリジニルオキシベンゼン類及びそれらの塩並びに除草剤としてのそれらの使用
WO2020126746A1 (fr) 2018-12-18 2020-06-25 Bayer Aktiengesellschaft Pyridinyloxybenzènes substitués, leurs sels et leur utilisation comme agents herbicides
US12052991B2 (en) 2018-12-18 2024-08-06 Bayer Aktiengesellschaft Substituted pyridinyloxybenzenes and salts thereof and use thereof as herbicidal agents
EP3670505A1 (fr) 2018-12-18 2020-06-24 Bayer AG Pyridinyloxy-benzènes substituées ainsi que leurs sels et leur utilisation en tant que substances actives herbicides
US11225473B2 (en) 2019-01-15 2022-01-18 Gilead Sciences, Inc. FXR (NR1H4) modulating compounds
US11524005B2 (en) 2019-02-19 2022-12-13 Gilead Sciences, Inc. Solid forms of FXR agonists
US12102625B2 (en) 2019-02-19 2024-10-01 Gilead Sciences, Inc. Solid forms of FXR agonists
WO2021028421A1 (fr) 2019-08-13 2021-02-18 Bayer Aktiengesellschaft (2-hétéroaryloxyphényle) isoxazolines substituées et leurs sels et leur utilisation en tant que substances actives herbicides
WO2021028419A1 (fr) 2019-08-13 2021-02-18 Bayer Aktiengesellschaft 3-(2-hétéroaryloxyphényle)isoxazolines substituées, leurs sels et leur utilisation en tant que substances actives herbicides
CN114555591A (zh) * 2019-10-17 2022-05-27 先正达农作物保护股份公司 除草化合物
WO2021074325A1 (fr) * 2019-10-17 2021-04-22 Syngenta Crop Protection Ag Composés herbicides

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