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WO1997012884A1 - Derives de la 6-heterocyclyl-indazole, comme herbicides - Google Patents

Derives de la 6-heterocyclyl-indazole, comme herbicides Download PDF

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WO1997012884A1
WO1997012884A1 PCT/US1996/015963 US9615963W WO9712884A1 WO 1997012884 A1 WO1997012884 A1 WO 1997012884A1 US 9615963 W US9615963 W US 9615963W WO 9712884 A1 WO9712884 A1 WO 9712884A1
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alkyl
compound
alkoxy
methyl
haloalkyl
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Lester L. Maravetz
George Theodoridis
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FMC Corp
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FMC Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
    • C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—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
    • 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
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues 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
    • C07D403/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom 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
    • C07D413/14—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

Definitions

  • the present invention relates generally to novel herbicidal
  • the present invention relates to novel 6-heterocyclic indazole derivatives and their use as herbicides.
  • Herbicides are useful for controlling unwanted vegetation which may otherwise cause significant damage to crops such as wheat, corn, soybeans and cotton, to name a few.
  • crops such as wheat, corn, soybeans and cotton
  • selective herbicides are desired which can control the weeds without damaging the crop.
  • crops are said to exhibit tolerance to the herbicide.
  • it is desirable to use herbicides that provide complete vegetation control such as in areas around railroad tracks and other structures. While many
  • JP 224431 (Enomoto et al.) discloses herbicidal indazoles of formula:
  • R is alkyl, alkenyl, alkynyl, alkyloxyalkyl, or haloalkyl; and X is H or halogen.
  • n 1 or 2; and R 9 is variously substituted.
  • EP 640600 Al discloses herbicidal heterocyclic
  • R 1 is H or halogen
  • R 2 and R 3 are variously substituted
  • E is or ;
  • Q is O or S; and
  • R 7 is H or optionally substituted alkyl.
  • certain 6-heterocyclic indazole derivatives have good activity as pre- and post-emergence herbicides.
  • certain compounds of the present invention exhibit varying levels of selectivity favorable to soybean, corn or wheat in pre- or post-emergence applications.
  • Certain compounds of the present invention are be especially useful as pre-emergence herbicides for soybean and corn. Others are especially useful as very active non-selective herbicides, in both pre- and post-emergence applications.
  • novel 6-heterocyclic indazole derivatives of the present invention have the following generic structure:
  • T is H, alkyl, cycloalkyl, alkoxyalkyl, cyanoalkyl, phenylalkyl, alkenyl, haloalkyl, alkenyloxycarbonyl, alkoxycarbonylalkenyl, haloalkenyl, alkadienyl, alkynyl, alkylcarbonyl, (dialkylamino)thiocarbonyl,
  • dialkylaminocarbonyl haloalkylcarbonyl, alkylsulfonyl, haloalkylsulfonyl, alkylaminosulfonyl, cyanothioalkylcarbonyl, dialkylaminosulfonyl, phenylalkylsulfonyl, oxacycloalkylmethyl, tetrahydrofuran-2-on-3-yl, 3-halo-5-haloalkyl-2-pyridyl,
  • U is H, halogen, alkyl, and nitro; V is H, halogen; W is H, Na, amino, alkyl, and haloalkyl; X is O or S; Y is alkyl or haloalkyl; Z is H or halogen; R is halogen; R 1 is haloalkoxy; R 2 is alkyl; R 3 is H or methyl; R 4 is OH, ONa, OK, ONH 4 , O-alkylammonium, O-dialkylammonium, alkoxy, haloalkoxy, nitroalkoxy, cyanoalkoxy, propargyloxy, NH2, NH-phenyl, NHCH 2 Ph, N(alkyl) 2 , NH-alkyl, N(alkyl)(alkoxy), NH-alkynyl; NHCH 2 (halophenyl), NHCH 2 (nitrophenyl), NHSO 2 -alkyl, NHSO 2
  • R 5 represents one or two substituents selected from alkyl, halogen, and nitro.
  • alkyl alone or as part of a larger moiety, includes straight or branched chain alkyl groups of 1 to 6 carbon atoms, while the term
  • alkoxy alone or as part of a larger moiety, includes straight or branched chain alkoxy groups of 1 to 6 carbon atoms
  • DBU deoxy
  • THF tetrahydrofuran
  • NCS N-chlorosuccinimide
  • Halogen refers to fluorine, chlorine or bromine.
  • Halo when used as a prefix, such as in haloalkyl or haloalkoxy, indicates that the group contains one or more halogen atoms.
  • the term "Ph” when used as part of a larger moiety means phenyl.
  • dialkylaminocarbonyl alkylaminosulfonyl, dialkylaminosulfonyl, cyanoalkyl, or alkylsulfonyl, or
  • R 4 is alkoxy, haloalkoxy, S-Et, NHSO 2 -alkyl, NH-alkyl, N(alkyl) 2 , NHCH 2 Ph, or N(alkyl)(alkoxy).
  • the compounds of the present invention may be prepared by one of two general approaches.
  • the indazole nucleus is formed before the first approach.
  • the nitroaniline A may be cyclized with a diazotizing agent such as sodium nitrite in the presence of a suitable acid such as acetic acid using the method of Porter et al. (Org. Syn., 20(72), Coll. Vol. III, p. 660), yielding the indazole B.
  • B in turn may be treated with a variety of T-X where X is a good leaving group such as Cl or Br to provide compounds having substitution in the 1-position of the indazole ring (the T group), as in C.
  • a suitable T group at this stage of the synthesis is one that is generally stable during the subsequent steps of pyrimidinedione ring construction and /or indazole ring modification.
  • either B or C may be halogenated with an N-halosuccinimide such as NCS to give, for example, D.
  • the nitro group of D may be reduced with iron powder to give the corresponding aniline E.
  • aniline E 1,1-dimethylethyl 2-(6-amino-3-chloroindazol-1-yl)propanoate is halogenated using NCS in DMF as previously described, 1,1-dimethylethyl 2-(6-amino-3,7-dichloroindazol-1-yl)propanoate is obtained rather than the intended 1,1-dimethylethyl 2-(6-amino-3,5-dichloroindazol-1-yl)propanoate.
  • the amino group of E may be converted to an isocyanate group by treatment with trichloromethyl chloroformate in ethyl acetate to give F.
  • F is then cyclized with 3-amino-4,4,4-trifluoro-2-butenoate in the presence of an appropriate base in an inert solvent to form the corresponding 3-(1-substituted-indazol-6-yl)-1- unsubstituted-6-trifluoromethyl-2,4-(1H,3H)-pyrimidinedione (IIa), isolated either as the free pyrimidinedione or as the sodium salt (W is Na).
  • bases examples include organic bases such as triethylamine, pyridine, and N,N-diethylamine, and inorganic bases such as sodium hydride and potassium carbonate.
  • inert solvents examples include aromatic hydrocarbons such as benzene and toluene, halogenated
  • reaction temperature is preferably about 20° - 80 °C.
  • the construction of the pyrimidinedione ring from aniline E may also be acheived by the methods described in US Patent 5,169,431, incorporated herein by reference. According to this reference, E may also be converted to an alkyl carbamate to give F' where Q is NHCO-alkyl. F' is treated in generally the same manner as F to obtain Ila except that the reaction temperature is preferably about 80° - 120 °C when using F'.
  • the indazolylpyrimidinedione may be used as an intermediate for obtaining other compounds of the present invention.
  • treatment of Ha with methyl iodide and potassium carbonate in acetone provides IIb.
  • treatment of Ea with 1-aminooxysulfonyl-2,4,6-trimethylbenzene in THF provides IIc.
  • T is an unsaturated group reduction conditions may be used to obtain the corresponding saturated group, as in the reduction of 3-[3-chloro-1-(2-methylprop-2-enyl)indazol-6- yl]-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione sodium salt, with hydrogen in the presence of 10% palladium on carbon, to provide the corresponding 1-isobutylindazole.
  • T is represented by an ester group
  • such a group may be converted to various amides or other ester groups.
  • ethyl 2-[3-optionally substituted-6-[6-trifluoromethyl-2,4(1H,3H)-pyrimidinedion-3-yl]indazol-1-yl]propanoate sodium salt reacts with ammonia or a substituted amine to yield the corresponding (indazol-1-yl)propanamides.
  • Compounds Ila-c where T is an alkanamide may also be obtained by hydrolysis of the corresponding ester to an acid, conversion of the acid to an acid chloride, and treatment of the acid chloride with an amine.
  • the intermediate acid chloride may alternatively be treated with various alcohols to provide other compounds of the present invention where T is an ester group.
  • T is an ester group.
  • Detailed descriptions of how these reactions are conducted are provided in Examples 1, 4, 6, 7, 9, and 10, and many of these basic transformations are well-known to one skilled in the art.
  • Scheme 2 illustrates a preparation of pyrazole-containing compounds of the present invention.
  • the indazole ring is prepared before construction of the pyrazole ring.
  • the aniline G may be cyclized with a diazotizing agent such as an alkylnitrite, preferably isopentyl nitrite, using the method of C. Ruchardt et al. (Leibigs Ann. Chem. pp. 908-927 (1980)), yielding the corresponding 6-acetylindazole H, which in turn is halogenated with an N-halosuccinimide, as previously described, providing a 3-halo-6- acetylindazole J.
  • a diazotizing agent such as an alkylnitrite, preferably isopentyl nitrite
  • J may be treated with a variety of alkylating agents to provide compounds having substitution at position 1 of the indazole ring, as in K.
  • K Treatment of K with diethyl carbonate under basic conditions, affords the corresponding ⁇ -ketoester L. Cyclization of an alkyl ⁇ -ketoester such as L with hydrazine or a substituted hydrazine, such as an alkylhydrazine (e.g., methylhydrazine in ethanol), yields the pyrazole M.
  • the pyrazole ring in M is amenable to further substitution to provide additional compounds of the present invention.
  • the OH group may be alkylated with a haloalkane in the presence of DMF and a base.
  • alkylation of M with chlorodifluoromethane provides N.
  • Treatment of N with an N-halosuccinimide introduces a halogen substituent in position 4 of the pyrazole ring (where R is attached), as in III.
  • the indazole nucleus may be formed after the pyrimidinedione ring is already in place, as depicted below in Scheme 3.
  • the chemistry used to obtain the intermediate O as well as the chemistry used to convert Ha to compounds of the present invention is similar to that previously discussed.
  • the indazole nucleus may also be formed after the pyrazole ring is already in place. Using chemistry previously discussed P may be obtained and converted to the indazole M (Scheme 4).
  • U is H, CH 3 , Br or Cl
  • Q is NO 2 , NH 2 , NCO, or NHCO 2 -alkyl
  • V is H, F, or Cl
  • T is H, alkyl, cycloalkyl, alkoxyalkyl, cyanoalkyl, phenylalkyl, alkenyl, haloalkyl, alkenyloxycarbonyl, alkoxycarbonylalkenyl, haloalkenyl, alkadienyl, alkynyl, alkylcarbonyl, (dialkylamino)thiocarbonyl,
  • dialkylaminocarbonyl haloalkylcarbonyl, alkylsulfonyl, haloalkylsulfonyl, alkylaminosulfonyl, cyanothioalkykarbonyl, dialkylaminosulfonyl, phenylalkylsulfonyl, oxacycloalkylmethyl, tetrahydrofuran-2-on-3-yl, 3-halo-5-haloalkyl-2-pyridyl,
  • X is O or S; R 3 is H or methyl; R 4 is OH, ONa, OK, ONH 4 , O-alkylammonium, O-dialkylammonium, alkoxy, haloalkoxy, nitroalkoxy, cyanoalkoxy, propargyloxy, NH 2 , NH-phenyl, NHCH 2 Ph, N(alkyl) 2 , NH-alkyl, N(alkyl)(alkoxy), NH-alkynyl; NHCH 2 (halophenyl),
  • NHCH 2 (nitrophenyl), NHSO 2 -alkyl, NHSO 2 -haloalkyl, NHSO 2 -phenyl, NHOCH 2 Ph, CH 2 SCN, S-alkyl, CH 2 S-alkyl, nitroalkoxy, OCH 2 Ph,
  • R 5 represents one or two substituents selected from alkyl, halogen, and nitro.
  • R 5 represents one or two substituents selected from alkyl, halogen, and nitro.
  • V is H, F, or Cl
  • W is H, CH 3
  • A is H, NO 2 or NH 2
  • Y is CH 3 or CF 3
  • Z is H, provided that when A is H, V is F.
  • V is H, F, or Cl
  • A is NH 2 or NO 2
  • R is Cl
  • R 1 is haloalkoxy
  • R 2 is alkyl
  • reaction mixture Upon completion of addition, the reaction mixture was allowed to warm to ambient temperature where it stirred for about 18 hours. After this time the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure to a residual solid. The solid was triturated with diethyl ether and collected by filtration, yielding 2.2 grams of title compound, mp >200°C. The NMR spectrum was consistent with the proposed structure.
  • This compound was prepared in a manner analogous to that of Step A of Example 1, using 25.0 grams (0.20 mole) of 2-fluoro-4-methylaniline and 26.5 mL (0.22 mole) of trichloromethyl chloroformate in about 375 mL of ethyl acetate. The yield of title compound was about 28.0 grams. The NMR spectrum was consistent with the proposed structure.
  • Step B 3-(2-fluoro-4-methylphenyl)-6-trifluoromethyl-2,4(1H,3H)- pyrimidinedione
  • This compound was prepared in a manner analogous to that of Step B of Example 1, using 24.5 grams (0.16 mole) of 2-fluoro-4-methylphenyl isocyanate, 32.7 grams (0.18 mole) of ethyl 3-amino-4,4,4-trifluoro-2-butenoate, and 7.8 grams (0.20 mole) of 60% sodium hydride in 600 mL of THF.
  • This procedure differed from Step B of Example 1 in that the free amine (rather than the sodium salt) was collected by first pouring the reaction mixture into 1000 mL of aqueous 2N hydrochloric acid, then extracting the mixture with 500 mL of ethyl acetate. The extract was dried with magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure, yielding 45.2 grams of title compound.
  • the NMR spectrum was consistent with the proposed structure.
  • reaction mixture was stirred for 15 minutes. The reaction mixture was then allowed to warm to ambient temperature where the reaction was quenched by the addition of ice. The mixture was then poured into 400 mL of water. The organic layer was separated, dried with magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, yielding 36.2 grams of title
  • Step E 3-(5-amino-2-fluoro-4-methylphenyl)-1-methyl-6-trifluoro methyl-2,4(1H,3H)-pyrimidinedione
  • This compovmd was prepared using 35.0 grams (0.101 mole) of 3-(2-fluoro-4-methyl-5-mtrophenyl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione, 17.0 grams (0.304 mole) of iron powder, 6.0 grams (0.112 mole) of ammonium chloride, and 300 mL of water in 600 mL of ethanol. After vigorous stirring at about 80°C for one hour, the mixture was filtered through diatomaceous earth, and the filtrate was concentrated under reduced pressure. Residual water was removed as a toluene /water azeotrope. The yield of title compound was 30.2 grams. The NMR spectrum was consistent with the proposed structure.
  • Step F 3-(5-fluoro-1-methylcarbonylindazol-6-yl)-1-methyl-6- trifluoromethyl-2,4(1H,3H)-pyrimidinedione
  • This compound was prepared by adding 6.5 grams (0.049 mole) of N-chlorosuccinimide to a solution of 14.3 grams (0.044 mole) of 3-(5-fluoroindazol-6-yl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione in 100 mL of N,N-dimethylformamide.
  • the reaction mixture was stirred for one hr at about 150 °C, cooled and poured into a saturated sodium chloride solution. The precipitate was collected and washed with water and hexanes to provide Compound 23 (13.3 grams).
  • the NMR spectrum was consistent with the proposed structure.
  • Step I 1,1-dimethylethyl 2-[3-chloro-5-fluoro-6-[1-methyl-6-trifluoro methyl-2,4(1H,3H)-pyrimidinedion-3-yl]indazol-1- yl]propanoate (Compound 132) This compound was prepared in a manner analogous to that of Step
  • Example 9 using 7.8 grams (0.022 mole) of 3-(3-chloro-5-fluoroindazol-6-yl)-1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione, 5.0 gram (0.024 mole) of tert.-butyl 2-bromopropanoate [prepared by the method of M. S. Newman et al. JACS, 77, 946-7, (1955)], and 3.6 grams (0.024 mole) of DBU in 200 mL of acetonitrile. The residue was subjected to column chromatography on silica gel, using methylene chloride as the eluant. The product-containing fractions were combined and concentrated under reduced pressure, yielding 2.0 grams of Compound 132, mp 58-60 °C. The NMR spectrum was consistent with the proposed structure.
  • Step K 2-[3-chloro-5-fluoro-6-[1-methyl-6-trifluoromethyl-2,4(1H,3H)- pyrimidinedion-3-yl]indazol-1-yl]propanecarboxylic acid chloride
  • Oxalyl chloride (0.5 mL) was added in one portion to a stirred solution of 1.0 gram (0.0024 mole) of 2-[3-chloro-5-fluoro-6-[1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedion-3-yl]indazol-1-yl]propanecarboxylic acid in 50 mL of toluene.
  • the reaction mixture was warmed to reflux where it stirred for about four hours.
  • the reaction mixture was cooled and concentrated under reduced pressure, yielding 1.0 gram title compound.
  • the NMR spectrum was consistent with the proposed structure.
  • reaction mixture was stirred at ambient temperature for about 18 hours. After this time the reaction mixture was poured into 50 mL of an aqueous solution saturated with sodium chloride. The mixture was shaken with ethyl acetate, and the organic layer was separated. The organic layer was washed with two 50 mL portions of an aqueous solution saturated with sodium chloride, then stirred with magnesium sulfate and decolorizing carbon. The mixture was filtered, and the filtrate concentrated under reduced pressure to a residue. The residue was subjected to column chromatography on silica gel, using 40% ethyl acetate in hexanes as the eluant. The product-containing fractions were combined and concentrated under reduced pressure, yielding 0.3 gram of title compound, mp 195-197 °C. The NMR spectrum was consistent with the proposed structure.
  • This compound was prepared in a manner analogous to that of Step H of Example 2, using 1.3 grams (0.003 mole) of 2-[6-[1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedion-3-yl]indazol-1-yl]propanamide and 0.5 gram (0.0049 mole) of N-chlorosuccinimide in 10 mL of N,N-dimethylformamide. The yield of title compound was about 0.2 gram. The NMR spectrum was consistent with the proposed structure.
  • This compound was prepared in a manner analogous to that of Step B of Example 1 using 1.8 grams (0.045 mole) of 60% sodium hydride, 5.4 grams (0.030 mole) of ethyl 3-amino-4,4,4-trifluoro-2-butenoate, and 7.5 grams (0.027 mole) of [3-bromo-1-(prop-2-enyl)indazol-6-yl]isocyanate in 300 mL of THF. The yield of title compound was 9.0 grams, mp >200°C. The NMR spectrum was consistent with the proposed structure.
  • This compound was prepared in a manner analogous to that of Step J of Example 2, using 3.8 grams (0.008 mole) of 1,1-dimethylethyl 2-[3-chloro-6-[1-methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedion-3-yl]indazol-1-yljpropanoate and 13 mL (excess) of trifluoroacetic acid in 13 mL of methylene chloride. The yield of title compound was 3.2 grams. The NMR spectrum was consistent with the proposed structure.
  • reaction mixture was cooled to ambient temperature, and 0.3 gram (0.002 mole) of 1-methylethylsulfonylamine was added in one portion.
  • reaction mixture was stirred for about 10 minutes, and a solution of 0.4 gram (0.002 mole) of DBU in about 2.0 mL of THF was added during a five minute period.
  • reaction mixture was stirred at ambient temperature for about two hours. After this time, the reaction mixture was quenched by pouring it into 100 mL of aqueous 10% hydrochloric acid. The mixture was diluted further with 300 mL of water, and the resultant gummy mixture was extracted with methylene chloride.
  • the extract was washed with water, dried with magnesium sulfate, and filtered.
  • the filtrate was concentrated under reduced pressure to a residue.
  • the residue was subjected to column chromatography on silica gel, using 5% methanol in methylene chloride and then 1:1:1 methylene chloride, methanol, and ethyl acetate.
  • the product-containing fractions were combined and concentrated under reduced pressure, yielding 0.6 gram of title compound, mp 211-215°C.
  • the NMR spectrum was consistent with the proposed structure.
  • This compound was prepared in a manner analogous to that of Step H of Example 2, using 21.0 grams (0.131 mole) of 6-methylcarbonylindazole and 20.0 grams (0.015 mole) of N-chlorosuccinimide in 200 mL of N,N-dimethylformamide. The yield of title compound was 25.0 grams, mp 95-98°C. The NMR spectrum was consistent with the proposed structure.
  • Step D 3-chloro-1-methyl-6-methylcarbonylindazole
  • a mixture of 25.0 grams (0.129 mole) of 3-chloro-6-methylcarbonylindazole and 19.6 grams (0.129 mole) of DBU in 200 mL of acetonitrile was stirred for ten minutes and 8.0 mL (0.129 mole) of methyl iodide was added portionwise.
  • the reaction mixture was stirred for three hours, then poured into water yielding a solid.
  • the solid was collected and dissolved in methylene chloride.
  • the solution was dried over magnesium sulfate, filtered and concentrated to a solid residue.
  • This compound was prepared in a manner analogous to that of Step E of Example 9, using 25.0 grams (0.186 mole) of 4-methylcarbonyltoluene and 15.0 grams (0.375 mole) of 60% sodium hydride in 100 mL of diethyl carbonate. The yield of title compound was 40.0 grams. The NMR spectrum was consistent with the proposed structure.
  • This compound was prepared in a manner analogous to that of Step F of Example 9, using 20.0 grams (0.097 mole) of ethyl (4-methylphenyloxo)acetate and 6.5 mL (0.125 mole) of methyl hydrazine in 250 mL of ethanol. The yield of title compound was 9.0 grams. The NMR spectrum was consistent with the proposed structure.
  • This compound was prepared in a manner analogous to that of Step H of Example 2, using 2.0 grams (0.008 mole) of 3-(4-methylphenyl)-5-difluoromethoxy-1-methylpyrazole and 1.3 grams (0.009 mole) of N-chlorosuccinimide in 50 mL of N,N-dimethylformamide.
  • the yield of 3-(4-methylphenyl)-4-chloro-5-difluoromethoxy-1-methylpyrazole was 2.0 grams.
  • the NMR spectrum was consistent with the proposed structure.
  • the 2.0 grams of pyrazole was combined with 5.7 grams of 3-(4-methylphenyl)-4-chloro-5-difluoromethoxy-1-methylpyrazole from another run of this reaction.
  • Step E 3-(4-methyl-3-nitrophenyl)-4-chloro-5-difluoromethoxy-1- methylpyrazole
  • Step F 3-(3-amino-4-methylphenyl)-4-chloro-5-difluoromethoxy-1- methylpyrazole
  • This compound was prepared in a manner analogous to that of Step E of Example 2, using 4.8 grams (0.015 mole) of 3-(4-methyl-3-nitrophenyl)-4-chloro-5-difluoromethoxy-1-methylpyrazole, 1.0 gram (0.019 mole) of ammonium chloride, 5.0 grams (0.090 mole) of iron powder, and 50 mL of water in 100 mL of ethanol. The yield of title compound was 3.4 grams. The NMR spectrum was consistent with the proposed structure.
  • This compound was prepared in a manner analogous to that of C. Ruchardt et al. (Leibigs Ann. Chem. 1980, 908-927), using 3.4 grams (0.012 mole) of 3-(3-amino-4-methylphenyl)-4-chloro-5-difluoromethoxy-1-methylpyrazole, 1.3 grams (0.013 mole) of potassium acetate, 4.0 mL (0.042 mole) of acetic anhydride, and 3.0 mL (0.022 mole) of isopentyl nitrite in toluene. The yield of title compound was 2.1 grams, mp 138-141 °C. The NMR spectrum was consistent with the proposed structure.
  • This compound was prepared in a manner analogous to that of Step H of Example 2, using 1.9 grams (0.006 mole) of 3-(indazol-6-yl)-4-chloro-5-difluoromethoxy-1-methylpyrazole and 1.0 gram (0.008 mole) of N-chlorosuccinimide in 25 mL of N,N-dimethylformamide. The yield of title compound was 0.5 gram. The NMR spectrum was consistent with the proposed structure.
  • This compound was prepared in a manner analogous to that of Step D of Example 9, using 0.4 gram (0.001 mole) of 3-(3-chloroindazol-6-yl)-4-chloro-5-difluoromethoxy-1-methylpyrazole, 0.2 gram (0.002 mole) of 1-bromo-2-propyne, and 0.2 gram (0.001 mole) of DBU in 25 mL of acetonitrile. The yield of title compound was about 0.1 gram, mp 136-138°C. The NMR spectrum was consistent with the proposed structure.
  • the 6-indazole derivatives of the present invention were tested for pre- and postemergence herbicidal activity using a variety of crops and weeds.
  • the test plants included soybean (Glycine max var. Winchester), field corn (Zea mays var. Pioneer 3732), wheat (Triticum aestivum var. Lew), morning glory (Ipomea lacunosa or Ipomea hederacea), velvetleaf (Abutilon theophrasti), green foxtail (Setaria viridis), Johnsongrass (Sorghum
  • two disposable fiber flats (8 cm ⁇ 15 cm ⁇ 25 cm) for each rate of application of each candidate herbicide were filled to an approximate depth of 6.5 cm with steam-sterilized sandy loam soil.
  • the soil was leveled and impressed with a template to provide five evenly spaced furrows 13 cm long and 0.5 cm deep in each flat. Seeds of soybean, wheat, corn, green foxtail, and johnsongrass were planted in the furrows of the first flat, and seeds of velvetleaf, morningglory, common chickweed, cocklebur, and blackgrass were planted in the furrows of the second flat.
  • the five-row template was employed to firmly press the seeds into place.
  • a topping soil of equal portions of sand and sandy loam soil was placed uniformly on top of each flat to a depth of approximately 0.5 cm.
  • Flats for postemergence testing were prepared in the same manner except that they were planted 9-14 days prior to the preemergence flats and were placed in a greenhouse and watered, thus allowing the seeds to germinate and the foliage to develop.
  • a stock solution of the candidate herbicide was prepared by dissolving 0.27g of the compound in 20 mL of water/acetone (50/50) containing 0.5% v/v sorbitan monolaurate. For an application rate of 3000 g/ha of herbicide a 10 mL portion of the stock solution was diluted with water /acetone (50/50) to 45 mL.
  • the volumes of stock solution and diluent used to prepare solutions for lower application rates are shown in the following table:
  • the preemergence flats were initially subjected to a light water spray.
  • the four flats were placed two by two along a conveyor belt (i.e., the two preemergence followed by the two postemergence flats).
  • the conveyor belt fed under a spray nozzle mounted about ten inches above the postemergent foliage.
  • the preemergent flats were elevated on the belt so that the soil surface was at the same level below the spray nozzle as the foliage canopy of the postemergent plants.
  • the spray of herbicidal solution was commenced and once stabilized, the flats were passed under the spray at a speed to receive a coverage equivalent of 1000L/ha. At this coverage the application rates are those shown in the above table for the individual herbicidal solutions.
  • the preemergence flats were watered immediately thereafter, placed in the greenhouse and watered regularly at the soil surface.
  • the postemergence flats were immediately placed in the green-house and not watered until 24 hours after treatment with the test solution. Thereafter they were regularly watered at ground level. After 12-17 d the plants were examined, and phytotoxicity data was recorded.
  • Herbicidal activity data at selected application rates are given for various compounds of the present invention in Tables 2 and 3.
  • the test compounds are identified by numbers which correspond to those in Table 1.
  • Phytotoxicity data are taken as percent control. Percent control is determined by a method similar to the 0 to 100 rating system disclosed in "Research Methods in Weed Science,” 2 nd ed., B. Truelove, Ed. (Southern Weed Science Society; Auburn University,
  • Herbicidal compositions are prepared by combining herbicidally effective amounts of the active compounds with adjuvants and carriers normally employed in the art for facilitating the dispersion of active ingredients for the particular utility desired, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the material in a given application.
  • the present herbicidal compounds may be formulated as granules of relatively large particle size, as water-soluble or water-dispersible granules, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, or as any of several other known types of formulations, depending on the desired mode of application. It is to be understood that the amounts specified in this specification are intended to be approximate only, as if the word "about” were placed in front of the amounts specified.
  • herbicidal compositions may be applied either as water-diluted sprays, or dusts, or granules to the areas in which suppression of vegetation is desired. These formulations may contain as little as 0.1%, 0.2% or 0.5% to as much as 95% or more by weight of active ingredient.
  • Dusts are free flowing admixtures of the active ingredient with finely divided solids such as talc, natural clays, kieselguhr, flours such as walnut shell and cottonseed flours, and other organic and inorganic solids which act as dispersants and carriers for the toxicant; these finely divided solids have an average particle size of less than about 50 microns.
  • a typical dust formulation useful herein is one containing 1.0 part or less of the herbicidal compound and 99.0 parts of talc.
  • Wettable powders also useful formulations for both pre- and postemergence herbicides, are in the form of finely divided particles which disperse readily in water or other dispersant.
  • the wettable powder is ultimately applied to the soil either as a dry dust or as an emulsion in water or other liquid.
  • Typical carriers for wettable powders include Fuller's earth, kaolin clays, silicas, and other highly absorbent, readily wet inorganic diluents
  • Wettable powders normally are prepared to contain about 5-80% of active ingredient, depending on the absorbency of the carrier, and usually also contain a small amount of a wetting, dispersing or emulsifying agent to facilitate dispersion.
  • a useful wettable powder formulation contains 80.0 parts of the herbicidal compound, 17.9 parts of Palmetto clay, and 1.0 part of sodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester as wetting agents. Additional wetting agent and /or oil will frequently be added to the tank mix for postemergence application to facilitate dispersion on the foliage and absorption by the plant.
  • ECs emulsifiable concentrates
  • ECs emulsifiable concentrates
  • ECs emulsifiable concentrates
  • these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated.
  • the percentage by weight of the essential active ingredient may vary according to the manner in which the
  • composition is to be applied, but in general comprises 0.5 to 95% of active ingredient by weight of the herbicidal composition.
  • Flowable formulations are similar to ECs except that the active ingredient is suspended in a liquid carrier, generally water.
  • Flowables like ECs, may include a small amount of a surfactant, and will typically contain active ingredients in the range of 0.5 to 95%, frequently from 10 to 50%, by weight of the composition.
  • flowables may be diluted in water or other liquid vehicle, and are normally applied as a spray to the area to be treated.
  • Typical wetting, dispersing or emulsifying agents used in agricultural formulations include, but are not limited to, the alkyl and alkylphenyl sulfonates and sulfates and their sodium salts; alkylphenyl polyether alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addition product of longChain mercaptans and ethylene oxide.
  • Many other types of useful surface-active agents are available in commerce. Surface-active agents, when used, normally comprise 1 to 15% by weight of the composition.
  • compositions include suspensions of the active ingredient in a relatively non-volatile solvent such as water, corn oil, kerosene, propylene glycol, or other suitable solvents.
  • Still other useful formulations for herbicidal applications include simple solutions of the active ingredient in a solvent in which it is
  • Granular formulations wherein the toxicant is carried on relative coarse particles, are of particular utility for aerial distribution or for penetration of cover crop canopy.
  • Pressurized sprays typically aerosols wherein the active ingredient is dispersed in finely divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freon fluorinated hydrocarbons, may also be used.
  • a low boiling dispersant solvent carrier such as the Freon fluorinated hydrocarbons
  • Water-soluble or water-dispersible granules are free-flowing, non-dusty, and readily water-soluble or water-miscible.
  • the soluble or dispersible granvdar formulations described in US 3,920,442 are useful herein with the present herbicidal compounds.
  • the granular formulations, emulsifiable concentrates, flowable concentrates, solutions, etc. may be diluted with water to give a concentration of active ingredient in the range of say 0.1% or 0.2% to 1.5% or 2%.
  • Sample herbicidal compositions of the present invention are shown below, and can be prepared in accordance with techniques known to those skilled in the art.
  • the active herbicidal compounds of this invention may be formulated and /or applied with insecticides, fungicides, nematicides, plant growth regulators, fertilizers, or other agricultural chemicals and may be used as effective soil sterilants as well as selective herbicides in agriculture.
  • an effective amount and concentration of the active compound is of course employed; the amount may be as low as, e.g. about 1 to 250 g/ha, preferably about 4 to 30 g/ha.
  • higher application rates e.g., four times the rates mentioned above may be employed.
  • the active herbicidal compounds of the present invention may also be used in combination with other herbicides.
  • herbicides include, for example: N-(phosphonomethyl) glycine ("glyphosate”); aryloxyalkanoic acids such as (2,4-dichlorophenoxy)acetic acid (“2,4-D"), (4-chloro-2-methylphenoxy)acetic acid (“MCPA”), (+/-)-2-(4-chloro-2-methylphenoxy)propanoic acid (MCPP); ureas such as N,N-dimethyl-N'-[4-(1-methylethyl)phenyl]urea (“isoproturon”); imidazolinones such as 2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-pyridinecarboxylic acid (“imazapyr”), a reaction product comprising (+/-)-2-[4,5-dihydr
  • hydroxybenzonitriles such as 4-hydroxy-3,5-diiodobenzonitrile ("ioxynil”) and 3,5-dibromo-4-hydroxybenzonitrile (“bromoxynil”); sulfonylureas such as 2-[[[[(4-CHLoro-6-methoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoic acid (“chlorimuron”), 2-chloro-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]-carbonyl]benzenesulfonamide (“chlorsulfuron”), 2-[[[[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]methyl]benzoic acid
  • dicamba pyridyloxyacetic acids
  • fluroxypyr pyridyloxyacetic acids

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Abstract

L'invention concerne de nouveaux composés herbicides, des compositions les contenant et des procédés permettant leur préparation, ainsi que leur utilisation pour éliminer les mauvaises herbes. Les nouveaux composés herbicides sont des indazoles ayant la formule (1). Dans cette formule, Q a la formule (2) ou (3); T est H, cycloalkyle, alcoxyalkyle, cyanoalkyle, phénylalkyle, alcényle, haloalkyle, alcényloxycarbonyle, alcoxycarbonylalcényle, haloalcényle, alcadiényle, alcynyle, alkylcarbonyle, (dialkylamino)thiocarbonyle, dialkylaminocarbonyle, haloalkylcarbonyle, alkylsulfonyle, haloalkylsulfonyle, alkylaminosulfonyle, cyanothioalkylcarbonyle, dialkylaminosulfonyle, phénylalkylsulfonyle, oxacycloalkylméthyle, tétrahydrofuran-2-one-3-yle, 3-halo-5-haloalkyl-2-pyridyle, ou T peut avoir la formule (4), (5), (6) ou (7); U est un H, halogéno, alkyle ou nitro; V et un H ou halogène; W est H, Na, amino, alkyle et haloalkyle; X est O ou S; Y est un alkyle ou un haloalkyle; Z est H ou halogéno; R est un halogéno; R<1> est un haloalcoxy; R<2> est un alkyle; R<3> est un H ou méthyle; R<4> est un OH, ONa, OK, ONH4, O-alkylammonium, O-dialkylammonium, alcoxy, haloalcoxy, nitroalcoxy, cyanoalcoxy, propargyloxy, NH2, NH-phényle, NHCH2Ph, N(alkyl)2, NH-alkyle, N(alkyl)(alcoxy), NH-alcynyle, NHCH2-halophényle, NHCH2-nitrophényle, NHSO2-alkyle, NHSO2-haloalkyle, NHSO2-phényle, NHOCH2Ph, CH2SCN, S-alkyle, CH2S-alkyle, nitroalcoxy, OCH2Ph, OCH2CO2-alkyle, SCH2Ph, SCH2CO2-alkyle, cycloalkylalcoxy ou oxacycloalkylalcoxy; et R<5> représente un ou deux substituants choisis parmi alkyle, halogène et nitro.
PCT/US1996/015963 1995-10-04 1996-10-03 Derives de la 6-heterocyclyl-indazole, comme herbicides Ceased WO1997012884A1 (fr)

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Cited By (9)

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WO1998027083A1 (fr) * 1996-12-17 1998-06-25 Bayer Aktiengesellschaft Heterocyclyluraciles
WO2000015633A1 (fr) * 1998-09-10 2000-03-23 Sumitomo Chemical Company, Limited Composes heterocycliques condenses et herbicides les contenant
WO2000028822A3 (fr) * 1998-11-16 2000-11-16 Basf Ag 3-[benz(ox/thi)azol-7-yl]-1h-pyrimidin-2,4-diones
US6914069B2 (en) 2000-05-19 2005-07-05 Applied Research Systems Ars Holding N.V. Pharmaceutically active compounds and methods of use
WO2005064006A1 (fr) * 2003-12-31 2005-07-14 Schering Aktiengesellschaft ?-hydroxy esters heteroaromatiques actifs sur le plan optique, procedes de preparation de ceux-ci a partir de ?-ceto esters et procedes de preparation de ces ?-ceto esters
US7626035B2 (en) 2005-01-03 2009-12-01 Bayer Schering Pharma Ag Optically active, heteroaromatic β-hydroxy esters and processes for their preparation from β-keto esters and processes for the preparation of these β-keto esters
US7723348B2 (en) * 2004-10-15 2010-05-25 Memory Pharmaceuticals Corporation Phosphodiesterase 4 inhibitors
US8268868B2 (en) 2007-01-10 2012-09-18 Albany Molecular Research, Inc. 5-pyridinone substituted indazoles
US8273770B2 (en) 2007-07-21 2012-09-25 Albany Molecular Research, Inc. 5-pyridinone substituted indazoles

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998027083A1 (fr) * 1996-12-17 1998-06-25 Bayer Aktiengesellschaft Heterocyclyluraciles
WO2000015633A1 (fr) * 1998-09-10 2000-03-23 Sumitomo Chemical Company, Limited Composes heterocycliques condenses et herbicides les contenant
US6586368B1 (en) 1998-09-10 2003-07-01 Sumitomo Chemical Company, Limited Condensed heterocylic compounds and herbicides containing them
WO2000028822A3 (fr) * 1998-11-16 2000-11-16 Basf Ag 3-[benz(ox/thi)azol-7-yl]-1h-pyrimidin-2,4-diones
US6624119B1 (en) 1998-11-16 2003-09-23 Basf Aktiengesellschaft 3-[Benz(ox/thi)azol-7-yl]-1h-pyrimidine-2,4-diones
US7456201B2 (en) 2000-05-19 2008-11-25 Laboratoires Serono Sa Pharmaceutically active compounds and methods of use
US6914069B2 (en) 2000-05-19 2005-07-05 Applied Research Systems Ars Holding N.V. Pharmaceutically active compounds and methods of use
WO2005064006A1 (fr) * 2003-12-31 2005-07-14 Schering Aktiengesellschaft ?-hydroxy esters heteroaromatiques actifs sur le plan optique, procedes de preparation de ceux-ci a partir de ?-ceto esters et procedes de preparation de ces ?-ceto esters
JP2007516999A (ja) * 2003-12-31 2007-06-28 バイエル・シエーリング・ファーマ アクチエンゲゼルシャフト 複素芳香族β−ヒドロキシエステルの光学活性化、β−ケトエステルからのこれらの製造方法、およびこれらのβ−ケトエステルの製造方法
US7935827B2 (en) 2003-12-31 2011-05-03 Bayer Schering Pharma Ag Optically active, heteroaromatic β-hydroxy esters and processes for their preparation from β-keto esters and processes for the preparation of these β-keto esters
US7723348B2 (en) * 2004-10-15 2010-05-25 Memory Pharmaceuticals Corporation Phosphodiesterase 4 inhibitors
US7626035B2 (en) 2005-01-03 2009-12-01 Bayer Schering Pharma Ag Optically active, heteroaromatic β-hydroxy esters and processes for their preparation from β-keto esters and processes for the preparation of these β-keto esters
US8268868B2 (en) 2007-01-10 2012-09-18 Albany Molecular Research, Inc. 5-pyridinone substituted indazoles
US8273770B2 (en) 2007-07-21 2012-09-25 Albany Molecular Research, Inc. 5-pyridinone substituted indazoles

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