WO1998005646A1 - 1,2-dihydroquinoline derivatives having fungicidal activity - Google Patents

1,2-dihydroquinoline derivatives having fungicidal activity Download PDF

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Publication number
WO1998005646A1
WO1998005646A1 PCT/US1997/013089 US9713089W WO9805646A1 WO 1998005646 A1 WO1998005646 A1 WO 1998005646A1 US 9713089 W US9713089 W US 9713089W WO 9805646 A1 WO9805646 A1 WO 9805646A1
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Prior art keywords
alkyl
halo
substituted
phenyl
formula
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PCT/US1997/013089
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French (fr)
Inventor
Mark E. Cracknell
Albert Duriatti
Neil Kirby
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Dow Agrosciences Llc
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Priority to AU40458/97A priority Critical patent/AU4045897A/en
Publication of WO1998005646A1 publication Critical patent/WO1998005646A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/20—Oxygen atoms
    • C07D215/22—Oxygen atoms attached in position 2 or 4
    • C07D215/233—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 4
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic 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
    • 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
    • A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
    • 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
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/18—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
    • C07D493/14—Ortho-condensed systems

Definitions

  • This invention provides novel compounds which are 1,2- dihydroquinoline derivatives having plant fungicidal activity.
  • This invention also provides compositions and combination products containing one or more compounds of this invention as the active ingredient. Some of the combination products exhibit synergistic activity against plant pathogens.
  • This invention also provides fungicidal methods .
  • This invention provides novel compounds of formula (1)
  • X is CR 5 , where R 5 is H, Cl or CH 3 ;
  • Y is CR 5 ' where R 5 ' is H, Cl, or Br;
  • Z is O, S, SO, S02, CH 2 , CH 2 CH 2 , NR 6 , C.-C 3 alkenyl, substituted C.-C, alkenyl, -CH 2 0-, -OCH 2 -, OCH.CH,-, or NR 6 CH 2 CH 2 , where R 6 is H, C1-C4 alkyl, C1-C4 acyl, CR 7 R 8 , where R 7 and R 8 are independently H, C1-C4 alkyl, C1-C4 alkenyl, C2-C4 alkynyl, C1-C4 acyl, CN, or OH, or R 7 and R 8 together combine to form a carbocyclic ring containing four to six carbon atoms; R 1 -R 4 are independently H, OH, N ⁇ 2 , halo, I, C1-C4 alkyl, C3-C4 branched alkyl, C3 .
  • R 1 and R ⁇ or R2 and R ⁇ together combine to form a carbocyclic ring containing four to six carbon atoms;
  • R 17 is H, C1-C4 alkyl, C1-C4 acyl, CR 7 R 8 , where R 7 and R 8 are independently H, C1-C4 alkyl, C ⁇ C4 alkenyl, C2-C4 alkynyl, or R 7 and R 8 together combine to form one or more optionally substituted carbocyclic rings containing four to six carbon atoms on each ring, and R * ° and R 21 are independently H, lower alkyl, cycloalkyl, optionally substituted phenyl, or NR " °R 21 together combine to form part of a saturated or unsaturated heterocyclic ring containing 1 to 3 nitrogen atoms; and
  • R 9 -R 13 are independently H, CN, NO 2 , OH, halo, C 1 -C4 alkyl, C 3 -C 4 branched alkyl, C 2 -C 4 alkanoyl, halo C 1 -C 7 alkyl, hydroxy C 1 -C 7 alkyl, C 1 -C7 alkoxy, halo C1-C7 alkoxy, C 1 -C 7 alkylthio, halo C 1 -C7 alkylthio, phenyl, substituted phenyl, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, phenyl C 1 -C 4 alkyl, substituted phenyl C 1 -C 4 alkyl, benzoyl, SiR 30 R 31 R 32 or OSiR 30 R 31 R 3 2, where R 30 ,R 31 , and R 32 are H, a C-.-C6 straight chain or branched alky
  • R 14 is H, halo, halomethyl, CN, NO2 , C1-C4 alkyl, C3-C4 branched alkyl, phenyl, or C1-C4 alkoxy;
  • R 15 is H, halo, halomethyl, CN, N02 , C1-C4 alkyl, C3-C4 branched alkyl, phenyl, or C1-C4 alkoxy;
  • R 16 is H, halo, halomethyl, CN, N02 , C1-C4 alkyl, C3-C4 branched alkyl, phenyl, substituted phenyl, or C1-C4 alkoxy
  • J is N or CH and G is O, NR 19 or CH, provided that either J is N or G is NR 19 , where R 19 is H, C1-C4 alkyl, C ⁇ C4 acyl, phenylsulfonyl , or substituted phenylsulfonyl ;
  • (1) a group selected from 1-naphthyl, substituted 1- naphthyl, 4-pyrazolyl, 3-methyl-4-pyrazolyl , 1,3- benzodioxolyl, tricyclo [3.3.1.1 (3 , 7 ) ] dec-2-yl , l-(3- chlorophenyl) -lH-tetrazol-5-yl, pyridyl, substituted pyridyl, or an ac d addition salt of a compound of formula (1), or an N-oxide of a compound of formula (1) where Y is CH.
  • halo used alone or in combination with other terms, refers to F, Cl, or Br .
  • alkyl refers to a straight chain alkyl radical .
  • branched alkyl refers to all alkyl isomers containing the designated number of carbon atoms, except the straight chain isomers.
  • alkoxy refers to a straight or branched chain alkoxy group .
  • halo alkyl refers to a straight or branched alkyl group, substituted with one or more halo atoms.
  • halo alkoxy refers to an alkoxy group, substituted with one or more halo atoms.
  • halo alkylthio refers to a straight or branched alkylthio group, substituted with one or more halo atoms .
  • acyl refers to straight or branched chain alkanol .
  • substituted phenyl refers to phenyl substituted with up to three groups selected from halo, Ci- Cio alkyl, branched C 3 -C 6 alkyl, halo C1-C7 alkyl, hydroxy C 1 -C 7 alkyl, C 1 -C 7 alkoxy, halo C 1 -C 7 alkoxy, phenoxy, phenyl, O 2 , OH, CN, C 1 -C 4 alkanoyloxy, or benzyloxy.
  • substituted phenoxy refers to a phenoxy group substituted with up to three groups selected from halo, C 1 -C 10 alkyl, branched C 3 -C6 alkyl, halo C1-C7 alkyl, hydroxy C 1 -C 7 alkyl, C 1 -C 7 alkoxy, halo C 1 -C 7 alkoxy, phenoxy, phenyl, NO2, OH, CN, C1-C 4 alkanoyloxy, or benzyloxy.
  • substituted phenylthio refers to a phenylthio group substituted with up to three groups selected from halo, C1-C1 0 alkyl, branched C3-C6 alkyl, halo C1-C7 alkyl, hydroxy C1-C7 alkyl, C 1 -C 7 alkoxy, halo C 1 -C 7 alkoxy, phenoxy, phenyl, NO2, OH, CN, C1-C4 alkanoyloxy, or benzyloxy.
  • substituted phenylsulfonyl refers to a phenylsulfonyl group substituted with up to three groups selected from halo, I, C1-C10 alkyl, C3-C6 branched alkyl, halo C1-C7 alkyl, hydroxy C1-C7 alkyl, C1-C7 alkoxy, halo- C1-C7 alkoxy, phenoxy, phenyl, NO2 , OH, CN, C1-C4 alkanoyloxy, or benzyloxy.
  • saturated hydrocarbon chain refers to a hydrocarbon chain containing one to three multiple bond sites .
  • carrier ring refers to a saturated or unsaturated ring of four to seven carbon atoms .
  • X is CR 5 wherein R is H
  • Y is CR 5 wherein R 5 is H
  • R'-R 4 are independently H, halo, or C,-C 4 alkyl, or more preferably halo;
  • B is Cr ⁇ R 17 or 0 OR 17 wherein R 17 is H, C1-C4 alkyl, CR 7 R 8 , where R 7 and R 8 are independently H, C1-C4 alkyl, C ⁇ C4 alkenyl, C2-C4 alkynyl, or R 7 and R 8 together combine to form one or more optionally substituted carbocyclic rings containing four to six carbon atoms in each ring; and
  • A is a phenyl group of formula (2), above, wherein R 9 R n are independently halo or C,-C 4 alkyl, or more preferably halo.
  • the compounds of formula (1) have been found to control fungi, particularly plant pathogens. When employed in the treatment or prevention of plant fungal diseases, the compounds are applied to seeds or plants in a disease- inhibiting and phytologically-acceptable amount.
  • concentration o£ compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like.
  • the compounds of this invention may also be used to protect stored grain and other non-plant loci from fungal infestation.
  • the compounds of the present invention have been found to control fungi, particularly plant pathogens.
  • the compounds When employed in the treatment of plant fungal diseases, the compounds are applied to the plants in a disease inhibiting and phytologically acceptable amount.
  • disease inhibiting and phytologically acceptable amount refers to an amount of a compound of the present invention which kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 1 to 1000 ppm, with 10 to 500 ppm being preferred.
  • the exact concentration of compound required varies with the fungal disease to be controlled, the type formulation employed, the method of application, the particular plant species, climate conditions and the like.
  • a suitable application rate is typically in the range from about 0.10 to about 4 lb/A.
  • the compounds of the invention may also be used to protect stored grain and other non-plant loci from fungal infestation.
  • test compounds were formulated for application by foliar spray.
  • the following plant pathogens and their corresponding plants were employed.
  • test inoculum for wheat powdery mildew E. graminis f. sp . tritici
  • the test plants were inoculated by dusting spores from stock plants on test plants 24 hours after spray application
  • After inoculation the test plants were kept in the greenhouse for seven days, until disease on the untreated control plants was fully developed. Seven days after inoculation, the disease incidence on the leaves was assessed visually.
  • the compounds of this invention are made using well known chemical procedures.
  • the required starting materials are commercially available, or readily synthesized utilizing standard procedures, several of which are disclosed in U.S. Patent 5,145,843.
  • the compounds of formula (1) are then prepared by reduction of the corresponding quinolines with suitable reducing agents, such as, for example, diisobutylaluminium hydride, in a suitable solvent, such as, for example, ether, and subsequent acylation.
  • compositions which are important embodiments of the invention, and which comprise one or more compounds of formula (1) with a phytologically-acceptable inert carrier.
  • the composition may optionally include fungicidal combinations which comprise at least 1% of one or more compounds of formula (1) with another fungicide.
  • compositions are either concentrated formulations which are dispersed in water for application, or are dust or granular formulations which are applied without further treatment.
  • the compositions are prepared according to procedures which are conventional in the agricultural chemical art, but which are novel and important because of the presence therein of the compounds of this invention. Some description of the formulation of the compositions will, however, be given to assure that agricultural chemists can readily prepare any desired composition.
  • the dispersions in which the compounds are applied are most often aqueous suspensions or emulsions prepared from concentrated formulations of the compounds.
  • Such water- soluble, water suspendable, or emulsifiable formulations are either solids usually known as wettable powders, or liquids usually known as emulsifiable concentrates or aqueous suspensions.
  • Wettable powders which may be compacted to form water dispersible granules, comprise an intimate mixture of the active compound, an inert carrier and surfactants.
  • the concentration of the active compound is usually from about 10% to 90%.
  • the inert carrier is usually chosen from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates.
  • Effective surfactants comprising from about 0.5% to about 10% of the wettable powder, are found among the sulfonated lignins, the naphthalenesulfonates, alkylbenzenesulfonates , the alkyl sulfates, and non-ionic surfactants, such as, for example, ethylene oxide adducts of alkyl phenols.
  • Emulsifiable concentrates of the compounds comprise a convenient concentration of a compound, such as from about 10% to about 50% of liquid, dissolved in an inert carrier, which is either a water miscible solvent or a mixture of water-immiscible organic solvents, and emulsifiers.
  • a compound such as from about 10% to about 50% of liquid, dissolved in an inert carrier, which is either a water miscible solvent or a mixture of water-immiscible organic solvents, and emulsifiers.
  • Useful organic solvents include aromatics, especially the high- boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclkohexanone, and complex alcohols, such as 2- ethoxyethanol .
  • Aqueous suspensions comprise suspensions of water- insoluble compounds of this invention, dispersed in an aqueous vehicle at a concentration in the range from about 5% to about 50%.
  • Suspensions are prepared by finely grinding the compound, and vigorously mixing it into a vehicle comprised of water and surfactants chosen from the same types discussed above.
  • Inert ingredients such as inorganic salts and synthetic or natural gums, may also be added, to increase the density and viscosity of the aqueous vehicle. It is often most effective to grind and mix the compound at the same time by preparing the aqueous mixture, and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogenizer.
  • the compounds may also be applied as granular compositions, which are particularly useful for applications to the soil.
  • Granular compositions usually contain from about 0.5% to about 10% of the compound, dispersed in an inert carrier which consists entirely of in large part of clay or a similar inexpensive substance.
  • Such compositions are usually prepared by dissolving the compound in a suitable solvent, and applying it to a granular carrier which a] has been pre-formed to the appropriate particle size, in the range of from about 0.5 to 3 mm.
  • Such compositions may also be formulated by making a dough or past of the carrier and compound, and crushing and drying to obtain the desired granular particle.
  • Dusts containing the compounds are prepared simply by intimately mixing the compound in powdered form with a suitable dusty agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% of the compound.
  • a suitable dusty agricultural carrier such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% of the compound.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

This invention provides compounds of formula (1) wherein X is CR5, where R5 is H, Cl or CH¿3?; Y is CR?5'¿ where R5' is H, Cl, or Br; Z is O, S, SO, SO¿2?, CH2, CH2CH2, NR?6¿; B is (i, ii, iii, iv, or v) wherein s is 1 or 2, R17 is H, C¿1?-C4 alkyl, C1-C4 acyl, CR?7R8¿, where R?7 and R8¿ are independently H, C¿1?-C4 alkyl, C1-C4 alkenyl, C2-C4 alkynyl, or R?7 and R8¿ together combine to form one or more optionally substituted carbocyclic rings containing four to six carbon atoms on each ring, and R?20 and R21¿ are independently H, lower alkyl, cycloalkyl, optionally substituted phenyl, or NR20R21 together combine to form part of a saturated or unsaturated heterocyclic ring containing 1 to 3 nitrogen atoms; and A is (a) a C¿1?-C18 saturated or unsaturated straight or branched hydrocarbon chain, optionally including a hetero atom selected from O, S, SO, or SO2, and optionally substituted with halo, halo C1-C4 alkoxy, OH, or C1-C4 acyl; (b) C3-C8 cycloalkyl or cycloalkenyl; (c) a phenyl group; (d) a furyl group; (e) a thienyl group; (f) a group of formula (5) or (5a); (g) a group selected from pyridyl or substituted pyridyl; (h) a group selected from pyrimidinyl or substituted pyrimidinyl; or (i) a group selected from 1-naphthyl, substituted 1- naphthyl, 4-pyrazolyl, 3-methyl-4-pyrazolyl, 1,3-benzodioxolyl, tricyclo[3.3.1.1(3,7)]dec-2-yl, 1-(3-chlorophenyl)-1H-tetrazol-5-yl, pyridyl, substituted pyridyl, or an acid addition salt of a compound of formula (1), or an N-oxide of a compound of formula (1) where Y is CH. The compounds of formula (1) are plant fungicides.

Description

1 , 2-DIHYDROQU NOLINE DERIVATIVES HAVING FUNGICIDAL ACTIVITY
Background of the Invention
This invention provides novel compounds which are 1,2- dihydroquinoline derivatives having plant fungicidal activity. This invention also provides compositions and combination products containing one or more compounds of this invention as the active ingredient. Some of the combination products exhibit synergistic activity against plant pathogens. This invention also provides fungicidal methods .
Summary of the Invention
This invention provides novel compounds of formula (1)
Figure imgf000003_0001
wherein
X is CR5, where R5 is H, Cl or CH3 ;
Y is CR5' where R5' is H, Cl, or Br;
Z is O, S, SO, S02, CH2, CH2CH2, NR6, C.-C3 alkenyl, substituted C.-C, alkenyl, -CH20-, -OCH2-, OCH.CH,-, or NR6CH2CH2, where R6 is H, C1-C4 alkyl, C1-C4 acyl, CR7R8, where R7 and R8 are independently H, C1-C4 alkyl, C1-C4 alkenyl, C2-C4 alkynyl, C1-C4 acyl, CN, or OH, or R7 and R8 together combine to form a carbocyclic ring containing four to six carbon atoms; R1-R4 are independently H, OH, Nθ2 , halo, I, C1-C4 alkyl, C3-C4 branched alkyl, C3.-C4 alkoxy, halo C1-C4 alkyl, halo C1-C4 alkoxy, or halo C1-C4 alkylthio, or R1 and R^ or R2 and R^ together combine to form a carbocyclic ring containing four to six carbon atoms;
B is
Figure imgf000004_0001
wherein ? is 1 or 2, R17 is H, C1-C4 alkyl, C1-C4 acyl, CR7R8, where R7 and R8 are independently H, C1-C4 alkyl, Cι~ C4 alkenyl, C2-C4 alkynyl, or R7 and R8 together combine to form one or more optionally substituted carbocyclic rings containing four to six carbon atoms on each ring, and R*° and R21 are independently H, lower alkyl, cycloalkyl, optionally substituted phenyl, or NR"°R21 together combine to form part of a saturated or unsaturated heterocyclic ring containing 1 to 3 nitrogen atoms; and
A is
(a) a C1-C18 saturated or unsaturated straight or branched hydrocarbon chain, optionally including a hetero atom selected from O, S, SO, or SO2 , and optionally substituted with halo, halo C1-C4 alkoxy, OH, or C1-C4 acyl;
(b) C3-C8 cycloalkyl or cycloalkenyl;
(c) a phenyl group of formula (2)
Figure imgf000004_0002
wherein R9-R13 are independently H, CN, NO2 , OH, halo, C1-C4 alkyl, C3-C4 branched alkyl, C2-C4 alkanoyl, halo C1-C7 alkyl, hydroxy C1-C7 alkyl, C1-C7 alkoxy, halo C1-C7 alkoxy, C1-C7 alkylthio, halo C1-C7 alkylthio, phenyl, substituted phenyl, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, phenyl C1-C4 alkyl, substituted phenyl C1-C4 alkyl, benzoyl, SiR30R31R32 or OSiR30R31R32, where R30 ,R31, and R32 are H, a C-.-C6 straight chain or branched alkyl group, phenyl, or substituted phenyl, provided that at least one of R30, R31, and R32 is other than H, or R11 and R12 or R12 and R13 combine to form a carbocyclic ring, provided that unless all of R9-R13 are H or F, then at least two of R9-R13 are H;
a furyl group of formula (3)
^~.R^ fi. > (3 o wherein
R14 is H, halo, halomethyl, CN, NO2 , C1-C4 alkyl, C3-C4 branched alkyl, phenyl, or C1-C4 alkoxy;
(e) a thienyl group of formula (4)
Figure imgf000005_0001
wherein
R15 is H, halo, halomethyl, CN, N02 , C1-C4 alkyl, C3-C4 branched alkyl, phenyl, or C1-C4 alkoxy;
(f) a group of formula (5) or (5a)
Figure imgf000005_0002
wherein R16 is H, halo, halomethyl, CN, N02 , C1-C4 alkyl, C3-C4 branched alkyl, phenyl, substituted phenyl, or C1-C4 alkoxy, and J is N or CH and G is O, NR19 or CH, provided that either J is N or G is NR19, where R19 is H, C1-C4 alkyl, Cι~ C4 acyl, phenylsulfonyl , or substituted phenylsulfonyl ;
(g) a group selected from pyridyl or substituted pyridyl;
(h) a group selected from pyrimidinyl or substituted pyrimidinyl; or
(1) a group selected from 1-naphthyl, substituted 1- naphthyl, 4-pyrazolyl, 3-methyl-4-pyrazolyl , 1,3- benzodioxolyl, tricyclo [3.3.1.1 (3 , 7 ) ] dec-2-yl , l-(3- chlorophenyl) -lH-tetrazol-5-yl, pyridyl, substituted pyridyl, or an ac d addition salt of a compound of formula (1), or an N-oxide of a compound of formula (1) where Y is CH.
Detailed Description of the Invention
Throughout this document, all temperatures are given in degrees Celsius and all percentages are weight percentages, unless otherwise stated.
The term halo, used alone or in combination with other terms, refers to F, Cl, or Br .
The term "alkyl" refers to a straight chain alkyl radical .
The term "branched alkyl" refers to all alkyl isomers containing the designated number of carbon atoms, except the straight chain isomers. The term "alkoxy" refers to a straight or branched chain alkoxy group .
The term "halo alkyl" refers to a straight or branched alkyl group, substituted with one or more halo atoms.
The term "halo alkoxy" refers to an alkoxy group, substituted with one or more halo atoms.
The term "halo alkylthio" refers to a straight or branched alkylthio group, substituted with one or more halo atoms .
The term "acyl" refers to straight or branched chain alkanol .
The term "substituted phenyl" refers to phenyl substituted with up to three groups selected from halo, Ci- Cio alkyl, branched C3-C6 alkyl, halo C1-C7 alkyl, hydroxy C1-C7 alkyl, C1-C7 alkoxy, halo C1-C7 alkoxy, phenoxy, phenyl, O2 , OH, CN, C1-C4 alkanoyloxy, or benzyloxy.
The term "substituted phenoxy" refers to a phenoxy group substituted with up to three groups selected from halo, C1-C10 alkyl, branched C3-C6 alkyl, halo C1-C7 alkyl, hydroxy C1-C7 alkyl, C1-C7 alkoxy, halo C1-C7 alkoxy, phenoxy, phenyl, NO2, OH, CN, C1-C4 alkanoyloxy, or benzyloxy.
The term "substituted phenylthio" refers to a phenylthio group substituted with up to three groups selected from halo, C1-C10 alkyl, branched C3-C6 alkyl, halo C1-C7 alkyl, hydroxy C1-C7 alkyl, C1-C7 alkoxy, halo C1-C7 alkoxy, phenoxy, phenyl, NO2, OH, CN, C1-C4 alkanoyloxy, or benzyloxy.
The term "substituted phenylsulfonyl" refers to a phenylsulfonyl group substituted with up to three groups selected from halo, I, C1-C10 alkyl, C3-C6 branched alkyl, halo C1-C7 alkyl, hydroxy C1-C7 alkyl, C1-C7 alkoxy, halo- C1-C7 alkoxy, phenoxy, phenyl, NO2 , OH, CN, C1-C4 alkanoyloxy, or benzyloxy.
The term "unsaturated hydrocarbon chain" refers to a hydrocarbon chain containing one to three multiple bond sites .
The term "carbocyclic ring" refers to a saturated or unsaturated ring of four to seven carbon atoms .
While all the compounds of this invention have fungicidal activity, certain classes of compounds may be preferred for reasons such as greater efficacy or ease of synthesis . These preferred classes include those compounds of formula (1), above, wherein:
X is CR5 wherein R is H;
Y is CR5 wherein R5 is H;
Z is 0
R'-R4 are independently H, halo, or C,-C4 alkyl, or more preferably halo;
B is Cr ^R17 or 0 OR17 wherein R17 is H, C1-C4 alkyl, CR7R8, where R7 and R8 are independently H, C1-C4 alkyl, Cι~ C4 alkenyl, C2-C4 alkynyl, or R7 and R8 together combine to form one or more optionally substituted carbocyclic rings containing four to six carbon atoms in each ring; and
A is a phenyl group of formula (2), above, wherein R9Rn are independently halo or C,-C4 alkyl, or more preferably halo. The compounds of formula (1) have been found to control fungi, particularly plant pathogens. When employed in the treatment or prevention of plant fungal diseases, the compounds are applied to seeds or plants in a disease- inhibiting and phytologically-acceptable amount. The term "disease-inhibiting and phytologically-acceptable amount", as used herein, refers to an amount of a compound of the invention which kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 1 to 1000 ppm, with 10 to 500 ppm being preferred. The exact concentration o£ compound required varies with the fungal disease to be controlled, the type of formulation employed, the method of application, the particular plant species, climate conditions, and the like. The compounds of this invention may also be used to protect stored grain and other non-plant loci from fungal infestation.
The following tests were performed to determine the fungicidal efficacy of the compounds of this invention.
Fungicide Utility
The compounds of the present invention have been found to control fungi, particularly plant pathogens. When employed in the treatment of plant fungal diseases, the compounds are applied to the plants in a disease inhibiting and phytologically acceptable amount. As used herein, the term "disease inhibiting and phytologically acceptable amount", refers to an amount of a compound of the present invention which kills or inhibits the plant disease for which control is desired, but is not significantly toxic to the plant. This amount will generally be from about 1 to 1000 ppm, with 10 to 500 ppm being preferred. The exact concentration of compound required varies with the fungal disease to be controlled, the type formulation employed, the method of application, the particular plant species, climate conditions and the like. A suitable application rate is typically in the range from about 0.10 to about 4 lb/A. The compounds of the invention may also be used to protect stored grain and other non-plant loci from fungal infestation.
The following experiments were performed in the laboratory to determine the fungicidal efficacy of the compounds of the invention.
The test compounds were formulated for application by foliar spray. The following plant pathogens and their corresponding plants were employed.
Pathogen Designation in Host following Table
Erysiphe qraminiε tri tici PMW wheat
(powdery mildew)
Screening Method for PMW:
Wheat c.v. Monon was grown in the greenhouse from seed in a soil-less peat-based potting mixture ("Metromix") . The seedlings were used for testing at the 1.5 leaf stage. Compound formulation was accomplished by dissolving technical materials in acetone, with serial dilutions then made in acetone to obtain desired rates . Final treatment volumes were obtained by adding nine volumes 0.011% aqueous Triton X-100, resulting in test solutions with 10% acetone and 0.01% Triton X-100. Test rates were 400, 100, 25, and 6.25ppm.
In a high volume foliar application, plants were sprayed to runoff (using two opposing Spraying Systems 1/4JAUPM air atomization nozzles operated at approximately 138 kPa. Test inoculum for wheat powdery mildew ( E. graminis f. sp . tritici ) was produced in vivo on stock plants in the greenhouse. The test plants were inoculated by dusting spores from stock plants on test plants 24 hours after spray application After inoculation the test plants were kept in the greenhouse for seven days, until disease on the untreated control plants was fully developed. Seven days after inoculation, the disease incidence on the leaves was assessed visually.
The following table presents the activity of typical compounds of the present invention when evaluated in these experiments. The effectiveness of test compounds in controlling disease was rated using the following scale.
NT = not tested against specific organism 0 = 0% control
1-49% control + **■* 50-100% control
Figure imgf000012_0001
Figure imgf000013_0001
The compounds of this invention are made using well known chemical procedures. The required starting materials are commercially available, or readily synthesized utilizing standard procedures, several of which are disclosed in U.S. Patent 5,145,843. The compounds of formula (1) are then prepared by reduction of the corresponding quinolines with suitable reducing agents, such as, for example, diisobutylaluminium hydride, in a suitable solvent, such as, for example, ether, and subsequent acylation.
The following nonlimiting example further illustrates this invention.
Example 1 l-Methoxycarbonyl-5 , 7-dichloro-4-
(4-fluorophenoxy) -1.2-dihvdroguinoline
To a stirred suspension of 5, 7-dichloro-4- (4- fluorophenoxy) -quinoline (0.62 gm, .2 mmol) in dry ether (10 ml) at room temperature was added a solution of diisobutylaluminium hydride (2.5 ml; 1M in THF) . After 30 minutes, methyl chloroformate (0.5 ml) was added while cooling in ice, and the mixture was allowed to stand at room temperature 16 hours. Water was added followed by 1M HC1 (4 ml) and the mixture was extracted with ether. Extracts were washed with saturated brine, dried with magnesium sulphate and evaporated to a viscous oil which crystallized (0.75 gm, 100%). Recrystallisation from ether/hexane gave a colorless solid (mp 110°). Found: C: 55.66, H: 3.31, N: 3.55; Cι7HιιNCl2F03 requires: C: 55.61, H: 3.02, N: 3.81%. δ(CDCl3) 3.84 (3H s, MeO) , 4.29 (2H d J--5Hz, H-2), 5.35 (1H t J=5Hz, H-3), 6.94-7.05 (4H m , 4-fluorophenyl ) , 7.18 (1H d J=2Hz, H-6) , 7.57 (1H br, H-8) .
Example 2 5 , 7 -Dichloro-4- ( 4-fluorophenoxy) -
1 , 2-dihvdroσuinoline
To a stirred suspension of lithium aluminium hydride (Aldrich, 3.7 gm, 0.1 mole) in THF (250 ml) was added 5,7- dichloro-4- (4-fluorophenoxy ) -quinoline (15. gm, 0.05 mole) in THF (100ml) giving a green color. The mixture was stirred for 1 hour then quenched with water (3.5 ml) in THF (10ml), then with 10M NaOH ( 3.5 ml ) , and finally with water (3.5 ml) with cooling. The mixture was filtered and the filtrate evaporated to a viscous oil (15.05 gm, 97.1%) and stored at -20°. δ(CDCl3) 4.05 (2H d, J--5Hz, H-2), 5.20 ( 1H t, J=5Hz, H-3), 6.44 (1H d, J=2Hz, H-6), 6.68 (1H d, J=2Hz, H-8), 6.90-7.05 (4H m , 4-fluorophenyl ) .
Example3 l-Acetyl-5 , 7-dichloro-4- (4-fluorophenoxy) - 1 , 2-dihvdroαuinoline
To 5, 7-dichloro-4- (4-fluorophenoxy ) -1,2- dihydroquinoline (0.93 gm, 3.00 mmol) and triethylamine (2 ml) in dry dichloromethane (10 ml), cooled to -70°' was added acetyl chloride (0.3 ml , 4.2 mmol ) . The mixture was allowed to warm to ambient temperature over 2 hours then stood for 20 hours. Water was added, the organic phase separated, washed with brine and evaporated to an oil.
Chroma ography on flash silica, eluting with dichloromethane gave an oil (0.82 gm, 77.6%) . δ(CDCl3) 2.28{3H s, CH3CO) , 4.33 (2H br, H-2), 5.39 (1H t, J=5Hz, H-3), 6.95-7.07 (4H m , 4-fluorophenyl) , 7.27 (2H s, H-6, 8).
Example 4 1-Trifluoroacetyl-5 , 7-dichloro-4- (4-fluorophenoxy) -
1 , 2-dihvdroσuinoline
To 5, 7 -dichloro-4- (4-fluorophenoxy) -1,2- dihydroquinoline (1.55 gm, 5 mmol) and triethylamine (2.5 ml) in dry dichloromethane (25 ml), cooled to -70°' was added trifluoroacetic anhydride (1.3 ml, 10 mmol) over one minute. The mixture was allowed to warm to ambient temperature over 2 hours then stood for 20 hours. Water was added, the organic phase separated, washed with brine and evaporated to an oil which solidified (2.02 gm, 99.5%) and recrystallized from hexane (m.p. 106.5°). δ(CDCl3) 4.25 (2H br, H-2), 5.39 (1H t, J=5Hz, H-3), 6.98-7.10 (4H m, 4- fluorophenyl) , 7.37 (1H d, J=2Hz, H-6), 7.64 (1H br, H-6).
Example 5
4- (3- (4-t-butylphenyl) ) propyl-8-fluoro-1.2- dihydroσuinoline 4- (3- (4-t-butylphenyl) )propyl-8-fluoroquinoline (1.6g, 5mmol) was dissolved with stirring in dry THF (25mls) and a 1M solution of di-isobutylaluminium hydride (lOmls, 10mmol) added dropwise. The mixture was heated under reflux conditions for sixteen hours and allowed to cool to room temperature. The mixture was quenched with saturated ammonium chloride and extracted with diethyl ether (2xl00mls) . The organic phase was washed with water and saturated brine and dried over anhydrous sodium sulphate. Evaporation of the solvent under reduced pressure and purification of the residue by chromatography gave the product (0.45g, 28%) as a cream solid, m.p. 90°C. (Found: C, 81.48; H, 8.37; N, 4.29%. C22H26F calculated: C, 81.69; H, 8.10; N, 4.33%) Example 6
1- (Pyrazoylcarbonyl) -4- (3- (4-t-Butylphenyl) )propyl-8- fluoro-1.2-dihvdroαuinoline
4- (3- (4-t-Butylphenyl) ) propyl-8-fluoro-1, 2- dihydroquinoline (0.44g, 1.37mmol) was slurried in dichloromethane (20mls) and triethylamine (0.42g, 4.11mmol) added dropwise. The mixture was cooled in ice and triphosgene (0.41g, 1.37mmol) was added in portions, solids dissolving to give a yellow solution. This was then stirred overnight, diluted with 1:2 ethyl acetate :hexane and filtered through silica, the product being eluted with 1:2 ethyl acetate :hexane . Evaporation of the solvent under reduced pressure gave the intermediate carbamoyl chloride (0.45g) as a cream, oily solid. The intermediate was dissolved in dichloromethane (25mls) and 4-dimethylaminopyridine (0.05g) and triethylamine (0.5g, 5mmol) added. Pyrazole (0.47g. 6.84mmol) was added and the mixture stirred overnigh . The reaction mixture was adsorbed onto silica and the product eluted with 25-50% ethyl acetate : hexane . The desired product (0.32g, 56%) was isolated as a clear glass. (Found: C, 74.41; H, 7.27; N, 9.93%. C26H29 N3O calculated: C, 74.61; H, 6.98; N, 10.04%.)
The following Table identifies compounds of formula (1! prepared by the processes illustrated in the foregoing exam les .
Figure imgf000016_0001
Figure imgf000017_0001
The compounds of this invention are applied in the form of compositions, which are important embodiments of the invention, and which comprise one or more compounds of formula (1) with a phytologically-acceptable inert carrier. The composition may optionally include fungicidal combinations which comprise at least 1% of one or more compounds of formula (1) with another fungicide.
The compositions are either concentrated formulations which are dispersed in water for application, or are dust or granular formulations which are applied without further treatment. The compositions are prepared according to procedures which are conventional in the agricultural chemical art, but which are novel and important because of the presence therein of the compounds of this invention. Some description of the formulation of the compositions will, however, be given to assure that agricultural chemists can readily prepare any desired composition.
The dispersions in which the compounds are applied are most often aqueous suspensions or emulsions prepared from concentrated formulations of the compounds. Such water- soluble, water suspendable, or emulsifiable formulations are either solids usually known as wettable powders, or liquids usually known as emulsifiable concentrates or aqueous suspensions. Wettable powders, which may be compacted to form water dispersible granules, comprise an intimate mixture of the active compound, an inert carrier and surfactants. The concentration of the active compound is usually from about 10% to 90%. The inert carrier is usually chosen from among the attapulgite clays, the montmorillonite clays, the diatomaceous earths, or the purified silicates. Effective surfactants, comprising from about 0.5% to about 10% of the wettable powder, are found among the sulfonated lignins, the naphthalenesulfonates, alkylbenzenesulfonates , the alkyl sulfates, and non-ionic surfactants, such as, for example, ethylene oxide adducts of alkyl phenols.
Emulsifiable concentrates of the compounds comprise a convenient concentration of a compound, such as from about 10% to about 50% of liquid, dissolved in an inert carrier, which is either a water miscible solvent or a mixture of water-immiscible organic solvents, and emulsifiers. Useful organic solvents include aromatics, especially the high- boiling naphthalenic and olefinic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, such as, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclkohexanone, and complex alcohols, such as 2- ethoxyethanol . Suitable emulsifiers for emulsifiable concentrates are chosen from conventional nonionic surfactants, such as those mentioned above.
Aqueous suspensions comprise suspensions of water- insoluble compounds of this invention, dispersed in an aqueous vehicle at a concentration in the range from about 5% to about 50%. Suspensions are prepared by finely grinding the compound, and vigorously mixing it into a vehicle comprised of water and surfactants chosen from the same types discussed above. Inert ingredients, such as inorganic salts and synthetic or natural gums, may also be added, to increase the density and viscosity of the aqueous vehicle. It is often most effective to grind and mix the compound at the same time by preparing the aqueous mixture, and homogenizing it in an implement such as a sand mill, ball mill, or piston-type homogenizer.
The compounds may also be applied as granular compositions, which are particularly useful for applications to the soil. Granular compositions usually contain from about 0.5% to about 10% of the compound, dispersed in an inert carrier which consists entirely of in large part of clay or a similar inexpensive substance. Such compositions are usually prepared by dissolving the compound in a suitable solvent, and applying it to a granular carrier which a] has been pre-formed to the appropriate particle size, in the range of from about 0.5 to 3 mm. Such compositions may also be formulated by making a dough or past of the carrier and compound, and crushing and drying to obtain the desired granular particle.
Dusts containing the compounds are prepared simply by intimately mixing the compound in powdered form with a suitable dusty agricultural carrier, such as, for example, kaolin clay, ground volcanic rock, and the like. Dusts can suitably contain from about 1% to about 10% of the compound.

Claims

What is claimed is
1. A compound of formula (1)
Figure imgf000020_0001
wherein
X is CR5, where R5 is H, Cl or CH3 ;
Y is CR5' where R5 ' is H, Cl, or Br;
Z is O, S, SO, S02,CH2, CH2CH2, NR6 , where R6 is H, Cj.- C4 alkyl, C1-C4 acyl, CR7R8 , where R7 and R8 are independently H, C1-C4 alkyl, C1-C4 alkenyl, C2-C4 alkynyl, C1-C4 acyl, CN, or OH, or R7 and R8 together combine to form a carbocyclic ring containing four to six carbon atoms;
R-L-R4 are independently H, OH, NO2 , halo, I, C1-C4 alkyl, C3-C4 branched alkyl, C1-C4 alkoxy, halo C1-C4 alkyl, halo C1-C4 alkoxy, or halo C1-C4 alkylthio, or R*1- and R^ or R* and R*--* together combine to form a carbocyclic ring containing four to six carbon atoms;
B is
Figure imgf000020_0002
7 wherein s is 1 or 2 , R17 is H, C1-C4 alkyl, C1-C4 acyl, CR7R8, where R7 and R8 are independently H, C1-C4 alkyl, Ci- C4 alkenyl, C2-C4 alkynyl, or R7 and R8 together combine to form one or more optionally substituted carbocyclic rings containing four to six carbon atoms on each ring, and R20 and R21 are independently H, lower alkyl, cycloalkyl, optionally substituted phenyl, or NR20R21 together combine to form part of a saturated or unsaturated heterocyclic ring containing 1 to 3 nitrogen atoms; and
A is
(a) a C1-C18 saturated or unsaturated straight or branched hydrocarbon chain, optionally including a hetero atom selected from 0, S, SO, or SO2 , and optionally substituted with halo, halo C1-C4 alkoxy, OH, or C1-C4 acyl;
(b) C3-C8 cycloalkyl or cycloalkenyl ,-
(c) a phenyl group of formula (2)
Figure imgf000021_0001
wherein
R9-R13 are independently H, CN, NO2, OH, halo, C1-C4 alkyl, C3-C4 branched alkyl, C2-C4 alkanoyl, halo C1-C7 alkyl, hydroxy C1-C7 alkyl, C1-C7 alkoxy, halo C1-C7 alkoxy, C1-C7 alkylthio, halo C1-C7 alkylthio, phenyl, substituted phenyl, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, phenyl C1-C4 alkyl, substituted phenyl C1-C4 alkyl, benzoyl, SiR30R31R32 or OSiR30R31R32, where R30 ,R31, and R32 are H, a Ci-Cβ straight chain or branched alkyl group, phenyl, or substituted phenyl, provided that at least one of R30, R31, and R32 is other than H, or R11 and R12 or R12 and R13 combine to form a carbocyclic ring, provided that unless all of R9-R13 are H or F, then at least two of R9-R13 are H;
(d) a furyl group of formula (3)
Figure imgf000022_0001
wherein
R14 is H, halo, halomethyl, CN, Nθ2 , C1-C4 alkyl, C3-C4 branched alkyl, phenyl, or C1-C4 alkoxy;
(e) a thienyl group of formula (4)
Figure imgf000022_0002
wherein
R15 is H, halo, halomethyl, CN, NO2 , C1-C4 alkyl, C3-C4 branched alkyl, phenyl, or C1-C4 alkoxy;
(f) a group of formula (5) or (5a)
Figure imgf000022_0003
wherein
R16 is H, halo, halomethyl, CN, NO2 , C1-C4 alkyl, C3-C4 branched alkyl, phenyl, substituted phenyl, or C1-C4 alkoxy, and J is N or CH and G is O, NR19 or CH, provided that either J is N or G is NR19, where R19 is H, C1-C4 alkyl, Cι~ C4 acyl, phenylsulfonyl, or substituted phenylsulfonyl;
(g) a group selected from pyridyl or substituted pyridyl ;
(h) a group selected from pyrimidinyl or substituted pyrimidinyl; or
(i) a group selected from 1-naphthyl, substituted 1- naphthyl, 4-pyrazolyl, 3-methyl-4-pyrazolyl, 1,3- benzodioxolyl , tricyclo[3.3.1.1 (3,7) ]dec-2-yl, l-(3- chlorophenyl) -lH-tetrazol-5-yl, pyridyl, substituted pyridyl, or an acid addition salt of a compound of formula (1) , or an N-oxide of a compound of formula (1) where Y is CH.
2. A compound of Claim 1 wherein
X is CR5 wherein R5 is H;
Y is CR5 wherein Rs is H;
Z is 0
R'-R4 are independently H, halo, or C,-C4 alkyl;
B isC ^R17 or O OR17 wherein R17 is H, C1-C4 alkyl, CR7R8, where R7 and R8 are independently H, C1-C4 alkyl, Ci- C4 alkenyl, C2-C4 alkynyl, or R7 and R8 together combine to form one or more optionally substituted carbocyclic rings containing four to six carbon atoms in each ring; and
A is a phenyl group of formula (2), above, wherein R5R1J are independently halo or C,-C..
3. A compound of Claim 2 wherein
RJ-R4 are independently halo;
B is O OR17 wherein R17 is H, C1-C4 alkyl, CR7R8, where R7 and R8 are independently H, C1-C4 alkyl, C1-C4 alkenyl, C2-C4 alkynyl, or R7 and R8 together combine to form one or more optionally substituted carbocyclic rings containing four to six carbon atoms in each ring; and
A is a phenyl group of formula (2). above, wherein R9R13 is independently halo.
4. The compound l-benzoyl-4- (4-fluorophenoxy) -5, 7- dichloro-1 , 2-dihydroquinoline .
5. The compound l-acetyl-4- (4-fluorophenoxy) -5, 7- dichloro-1 , 2 -dihydroquinloine .
6. The compound 1- (methanesulphonyl )methylsulphonyl- 4- (4-fluorophenoxy) -5, 7-dichloro-l , 2-dihydroquinoline .
7. The compound 1-trifluoroacetyl-4- (4- fluorophenoxy) -5 , 7-dichloro-l , 2-dihydroquinoline .
8. The compound l-formyl-4- (4-fluorophenoxy ) -5 , 7- dichloro-1 , 2-dihydroquinoline .
9. The compound 1- (2 , 3 : 4 , 6-di-0-isopropylidene-2- keto-L-gulonyl) -4- (4-fluorophenoxy) -5, 7-dichloro-l, 2- dihydroquinoline .
10. A fungicidal method which comprises applying to the locus to be protected from fungus a fungicidally- effective amount of a compound of formula (1)
Figure imgf000024_0001
wherein
X is CR5, where R5 is H, Cl or CH3 ;
Y is CR5' where R5' is H, Cl, or Br;
Z is O, S, SO, S02, CH2, CH2CH2, NR6, where R6 is H, Ci- C4 alkyl, C1-C4 acyl, CR7R8 , where R7 and R8 are independently H, C1-C4 alkyl, C1-C4 alkenyl, C2-C4 alkynyl, C1-C4 acyl, CN, or OH, or R7 and R8 together combine to form a carbocyclic ring containing four to six carbon atoms;
R-L-R4 are independently H, OH, NO2 , halo, I, C1-C4 alkyl, C3-C4 branched alkyl, C1-C4 alkoxy, halo C1-C4 alkyl, halo C1-C4 alkoxy, or halo C1-C4 alkylthio, or R1 and R2 or R2 and R3 together combine to form a carbocyclic ring containing four to six carbon atoms;
Figure imgf000025_0001
wherein o is 1 or 2, and R17 is H, C1-C4 alkyl, C1-C4 acyl, CR7R8, where R7 and R8 are independently H, C1-C4 alkyl, C3.- C4 alkenyl, C2-C4 alkynyl, or R7 and R8 together combine to form one or more optionally substituted carbocyclic rings containing four to six carbon atoms on each ring; and
A is
(a) a C1-C3.8 saturated or unsaturated straight or branched hydrocarbon chain, optionally including a hetero atom selected from O, S, SO, or SO2 , and optionally substituted with halo, halo C1-C4 alkoxy, OH, or C1-C4 acyl ;
(b) C3-C8 cycloalkyl or cycloalkenyl;
(c) a phenyl group of formula (2)
Figure imgf000025_0002
wherein
R9-R13 are independently H, CN, NO2, OH, halo, C1-C4 alkyl, C3-C4 branched alkyl, C2-C4 alkanoyl, halo C1-C7 alkyl, hydroxy C1-C7 alkyl, C1-C7 alkoxy, halo C1-C7 alkoxy, C1-C7 alkylthio, halo C1-C7 alkylthio, phenyl, substituted phenyl, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, phenyl C1-C4 alkyl, substituted phenyl C1-C4 alkyl, benzoyl , SiR30R31R32 or OSiR30R31R32, where R30 . R31. and R32 are H, a C1-C6 straight chain or branched alkyl group, phenyl, or substituted phenyl, provided that at least one of R30, R31, and R32 is other than H, or R11 and R12 or R12 and R13 combine to form a carbocyclic ring, provided that unless all of R9-R13 are H or F, then at least two of R9-R13 are H;
(d) a furyl group of formula (3)
Figure imgf000026_0001
wherein
R14 is H, halo, halomethyl, CN, NO2 , C1-C4 alkyl, C3-C4 branched alkyl, phenyl, or C1-C4 alkoxy;
(e) a thienyl group of formula (4)
tRl5
^ J (4) s wherein
R15 is H, halo, halomethyl, CN, NO2 , C1-C4 alkyl, C3-C4 branched alkyl, phenyl, or C1-C4 alkoxy;
(f) a group of formula (5) or (5a)
Figure imgf000026_0002
wherein
R16 is H, halo, halomethyl, CN, NO2, C1-C4 alkyl, C3-C4 branched alkyl, phenyl, substituted phenyl, or C1-C4 alkoxy, and J is N or CH and G is O, NR19 or CH, provided that either J is N or G is NR19, where R19 is H, C1-C4 alkyl, Ci- C4 acyl, phenylsulfonyl, or substituted phenylsulfonyl;
(g) a group selected from pyridyl or substituted pyridyl ;
(h) a group selected from pyrimidinyl or substituted pyrimidinyl; or
(i) a group selected from 1-naphthyl, substituted 1- naphthyl, 4-pyrazolyl, 3-methyl-4-pyrazolyl , 1,3- benzodioxolyl, tricyclo [3.3.1.1 (3 , 7 ) ] dec-2-yl, l-(3- chlorophenyl) -lH-tetrazol-5-yl, pyridyl, substituted pyridyl, or an acid addition salt of a compound of formula (1), or an N-oxide of a compound of formula (1) where Y is CH.
PCT/US1997/013089 1996-08-01 1997-07-31 1,2-dihydroquinoline derivatives having fungicidal activity WO1998005646A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2183194A1 (en) * 1971-04-26 1973-12-14 Monroy Heliodoro
EP0173208A1 (en) * 1984-08-30 1986-03-05 Nihon Tokushu Noyaku Seizo K.K. Tetrahydroquinolin-1-yl-carbonyl-imidazole derivatives
EP0326330A2 (en) * 1988-01-29 1989-08-02 DowElanco Quinoline, quinazoline, and cinnoline fungicides
EP0326328A2 (en) * 1988-01-29 1989-08-02 DowElanco Quinoline, quinazoline, and cinnoline derivatives

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2183194A1 (en) * 1971-04-26 1973-12-14 Monroy Heliodoro
EP0173208A1 (en) * 1984-08-30 1986-03-05 Nihon Tokushu Noyaku Seizo K.K. Tetrahydroquinolin-1-yl-carbonyl-imidazole derivatives
EP0326330A2 (en) * 1988-01-29 1989-08-02 DowElanco Quinoline, quinazoline, and cinnoline fungicides
EP0326328A2 (en) * 1988-01-29 1989-08-02 DowElanco Quinoline, quinazoline, and cinnoline derivatives

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 75, no. 25, 20 December 1971, Columbus, Ohio, US; abstract no. 151656t, CROMARTY,A. ET AL: "Azabenzocycloheptenones. XIII. Ring ..." XP002048117 *
J. CHEM. S9OC. C, vol. 21, - 1071, pages 3536 - 3540 *

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