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WO1998005647A1 - Quinolinium derivatives having fungicidal activity - Google Patents

Quinolinium derivatives having fungicidal activity Download PDF

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Publication number
WO1998005647A1
WO1998005647A1 PCT/US1997/013604 US9713604W WO9805647A1 WO 1998005647 A1 WO1998005647 A1 WO 1998005647A1 US 9713604 W US9713604 W US 9713604W WO 9805647 A1 WO9805647 A1 WO 9805647A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
halo
substituted
phenyl
formula
Prior art date
Application number
PCT/US1997/013604
Other languages
French (fr)
Inventor
Mark E. Cracknell
Patrick J. Mulqueen
Original Assignee
Dow Agrosciences Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Agrosciences Llc filed Critical Dow Agrosciences Llc
Priority to AU39696/97A priority Critical patent/AU3969697A/en
Publication of WO1998005647A1 publication Critical patent/WO1998005647A1/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

Definitions

  • This invention provides novel compounds which are quinolinium salts 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 0, S, SO, S02, NR 6 , 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, 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-2 or R ⁇ and R ⁇ together combine to form a carbocyclic ring containing four to six carbon atoms
  • B is C1-C4 alkyl, C1-C4 alkenyl, C2-C4 alkynyl, perhalo C1-C4 alkyl, halo C1-C4 alkyl, benzyl, substituted benzyl, or polyether;
  • C is halo, C1-C4 alkyl sulphonate, aryl sulphonate, C1-C6 alkyl aryl sulphonate, C1-C4 alkyl sulphate, aryl sulphate, C1-C4 alkyl phosphate, or aryl phosphate;
  • R 9 -R 13 are independently H, CN, NO 2 , OH, halo, C 1 -C 4 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 -C 7 alkoxy, halo C 1 -C 7 alkoxy, C 1 -C7 alkylthio, halo C1-C7 alkylthio, phenyl, substituted phenyl, phenoxy, substituted phenoxy, phenylthio, substituted phenylthio, phenyl C 1 -C4 alkyl, substituted phenyl C 1 -C 4 alkyl, benzoyl, SiR 20 R 21 R 22 or OSiR 20 R 21 R 22 , where R 20 ,R 21 , and R 22 are H, a Ci-C ⁇ straight chain or branched alkyl
  • R 21 , and R 22 is other than H, or R 11 and R 12 or R 12 and R 13 combine to form a carbocyclic ring, provided that unless all of R 9 -R 13 are H or F, then at least two of R 9 -R 13 are H;
  • 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, NO2 , 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 C3 . -C4 alkoxy, and J is N or CH and G is 0, NR 19 or CH, provided that either J is N or G is NR 19 , where R 19 is H, C1-C4 alkyl, C1-C4 acyl, phenylsulfonyl, or substituted phenylsulfonyl ;
  • 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 .
  • polyether refers to an ether group containing 2 to 6 oxygen atoms .
  • aryl refers to an aromatic group containing one or more rings .
  • substituted phenyl refers to phenyl substituted with up to three groups selected from halo, Ci-Cio alkyl, branched C 3 -C6 alkyl, halo C1-C7 alkyl, hydroxy C 1 -C 7 alkyl, C 1 -C7 alkoxy, halo C1-C7 alkoxy, phenoxy, phenyl, O 2 , OH, CN, C 1 -C4 alkanoyloxy, or benzyloxy .
  • substituted phenoxy refers to a phenoxy group substituted with up to three groups selected from halo, C1-C 10 alkyl, branched C3-C6 alkyl, halo C 2 .-C7 alkyl, hydroxy C 3. -C7 alkyl, C1-C7 alkoxy, halo C 1 -C7 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, C 1 -C 1 0 alkyl, branched C 3 -C 6 alkyl, halo C 1 -C 7 alkyl, hydroxy C 1 -C7 alkyl, C1 . -C 7 alkoxy, halo C- ⁇ - - 7 alkoxy, phenoxy, phenyl, N0 2 , OH, CN, C 1 -C 4 alkanoyloxy, or benzyloxy.
  • substituted phenylsulfonyl refers to a phenylsulfonyl group substituted with up to three groups selected from halo, I, C ⁇ -C ⁇ o alkyl, C3-C6 branched alkyl, halo C1-C7 alkyl, hydroxy C1-C7 alkyl, C1-C 7 alkoxy, halo-C ⁇ -C7 alkoxy, phenoxy, phenyl, O2 , OH, CN, C1-C 4 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 5 is H
  • Y is CR 5 wherein R 5 is H
  • R 1 -R 4 are independently H, halo, or C.-C. alkyl, or more preferably halo;
  • B is C 1 -C 4 alkyl
  • C is halo
  • A is a phenyl group of formula (2), above, wherein R'R' 3 are independently halo or C i -C 1 alkyl, or more preferably halo.
  • 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 from the corresponding quinolines by treatment with the appropriate alkyl or aryl halide, sulphonate, sulphate, or phosphate.
  • 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.
  • 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 m test solutions with 10% acetone and 0.01% Triton X-100. Test rates were 400, 100, 25, and 6.25ppm.
  • test inoculum for wheat powdery mildew (E. graminis f . sp . tri ti ci ) 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
  • 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.
  • 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 m 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 emulsiflable formulations are either solids usually known as wettable powders, or liquids usually known as emulsiflable 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 montmo ⁇ llonite 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 emulsif ⁇ ers .
  • 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 cyclohexanone, and complex alcohols, such as 2-ethoxyethanol .
  • Suitable emulsiflers for emulsifiable concentrates are chosen from conventional nomonic surfactants, such as those mentioned above.
  • Aqueous suspensions comprise suspensions of water- msoluble 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 homogemzer .
  • 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 m 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)
  • 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, NR?6, where R6 is H, C¿1?-C4 alkyl, B is C1-C4 alkyl, C1-C4 alkenyl, C2-C4 alkynyl, perhalo C1-C4 alkyl, halo C1-C4 alkyl, benzyl, substituted benzyl, or polyether; C is halo, C1-C4 alkyl sulphonate, aryl sulphonate, C1-C6 alkyl aryl sulphonate, C1-C4 alkyl sulphate, aryl sulphate, C1-C4 alkyl phosphate, or aryl phosphate; 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; (d) a furyl group of formula (3); (e) a thienyl group (4); (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

QUINOLINIUM DERIVATIVES HAVING FUNGICIDAL ACTIVITY
Background of the Invention
This invention provides novel compounds which are quinolinium salts 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
(1) wherein
X is CR5, where R5 is H, Cl or CH3 ;
Y is CR5' where R5 ' is H, Cl, or Br ;
Z is 0, S, SO, S02, NR6, 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, 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 R-2 or R^ and R^ together combine to form a carbocyclic ring containing four to six carbon atoms;
B is C1-C4 alkyl, C1-C4 alkenyl, C2-C4 alkynyl, perhalo C1-C4 alkyl, halo C1-C4 alkyl, benzyl, substituted benzyl, or polyether;
C is halo, C1-C4 alkyl sulphonate, aryl sulphonate, C1-C6 alkyl aryl sulphonate, C1-C4 alkyl sulphate, aryl sulphate, C1-C4 alkyl phosphate, or aryl phosphate;
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_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, SiR20R21R22 or OSiR20R21R22, where R20 ,R21, and R22 are H, a Ci-Cδ straight chain or branched alkyl group, phenyl, or substituted phenyl, provided that at least one of R20,
R21, and R22 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;
I d) a furyl group of formula (3)
ς. > ( 3 )
0 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)
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 imgf000005_0001
wherein
R16 is H, halo, halomethyl, CN, N02 C1-C4 alkyl, C3-C4 branched alkyl, phenyl, substituted phenyl, or C3.-C4 alkoxy, and J is N or CH and G is 0, NR19 or CH, provided that either J is N or G is NR19, where R19 is H, C1-C4 alkyl, C1-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.
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 "polyether" refers to an ether group containing 2 to 6 oxygen atoms .
The term "aryl" refers to an aromatic group containing one or more rings .
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 C2.-C7 alkyl, hydroxy C3.-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 C-χ- -7 alkoxy, phenoxy, phenyl, N02, 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, Cχ-Cιo alkyl, C3-C6 branched alkyl, halo C1-C7 alkyl, hydroxy C1-C7 alkyl, C1-C7 alkoxy, halo-Cι-C7 alkoxy, phenoxy, phenyl, O2 , 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 R5 is H;
Y is CR5 wherein R5 is H;
Z is 0
R1-R4 are independently H, halo, or C.-C. alkyl, or more preferably halo;
B is C1-C4 alkyl;
C is halo; A is a phenyl group of formula (2), above, wherein R'R'3 are independently halo or Ci -C1 alkyl, or more preferably halo.
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 from the corresponding quinolines by treatment with the appropriate alkyl or aryl halide, sulphonate, sulphate, or phosphate.
The following nonlimiting example further illustrates this invention.
Example 1 l-Methyl-5,7-dichloro-4- ( 4-fluorophenoxy) σuinolinium iodide
To a stirred solution of 5 , 7-dichloro-4- (4- fluorophenoxy) -quinoline (0.62 gm, 2 mmol) in acetone (50 ml) was added iodomethane (5 gm) and the mixture heated under reflux for ten hours. The solvent was removed by evaporation and the resultant residue washed with ether giving the product as a yellow solid (0.40 gm) .
Example 2 l-Benzyl-5 , 7-dichloro-4- (4-phenoxy) σuinolinium bromide
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.
Fungicide Utility
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 trrysiptte gramims tzri cici PHR wnea
(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 m 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 . tri ti ci ) 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 imgf000011_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 m 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 emulsiflable formulations are either solids usually known as wettable powders, or liquids usually known as emulsiflable 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 montmoπllonite 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 emulsifιers . 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 cyclohexanone, and complex alcohols, such as 2-ethoxyethanol . Suitable emulsiflers for emulsifiable concentrates are chosen from conventional nomonic surfactants, such as those mentioned above.
Aqueous suspensions comprise suspensions of water- msoluble 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 homogemzer .
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 m 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 imgf000015_0001
wherein
X is CR5, where R5 is H, Cl or CH3 ;
Y is CR5' where R5 ' is H, Cl, or Br;
Z is 0, S, SO, S02, NR6, 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;
Ri-R 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 R^ together combine to form a carbocyclic ring containing four to six carbon a oms;
B is C1-C4 alkyl, C1-C4 alkenyl, C2-C4 alkynyl, perhalo C1-C4 alkyl, halo C1-C4 alkyl, benzyl, substituted benzyl, or polyether ;
C is halo, C1-C4 alkyl sulphonate, aryl sulphonate, C1-C6 alkyl aryl sulphonate, C1-C4 alkyl sulphate, aryl sulphate, C1-C4 alkyl phosphate, or aryl phosphate ;
Figure imgf000015_0002
(a) a Ci-C β saturated or unsaturated straight or branched hydrocarbon chain, optionally including a hetero atom selected from O, S, SO, or Sθ2/ 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 imgf000016_0001
wherein
R9-R13 are independently H, CN, NO2, OH, halo, C1-C4 alkyl, C-3-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, SiR20R21R22 or OSiR20R21R22, where R20 ,R21, and R22 are H, a Ci-Ce straight chain or branched alkyl group, phenyl, or substituted phenyl, provided that at least one of R20, R21, and R22 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!
> (3) 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 imgf000017_0001
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)
(5) J (5a) wherein
Rlβ 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, C1-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 R5 is H;
Z is 0
R'-R4 are independently H, halo, or C,-C4 alkyl;
B is C,-C4 alkyl;
C is halo;
A is a phenyl group of formula (2), above, wherein R9R1J are independently halo or C,-C4 alkyl
3. A compound of Claim 2 wherein R'-R4 are independently H or halo and A is a phenyl group of formula (2) above, wherein R9RIJ are independently halo.
4. The compound 1-methyl -5 , 7-dichloro-4- ( fluorophenoxy) -quinolinium iodide.
5. The compound l-benzyl-5, 7-dichloro-4- (4- phenoxy) quinolinium bromide.
6. 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 imgf000018_0001
(1) 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, NR6, 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;
Figure imgf000019_0001
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 R-2 or R^ and R^ together combine to form a carbocyclic ring containing four to six carbon atoms;
B is C1-C4 alkyl, C1-C4 alkenyl, C2-C4 alkynyl, perhalo C1-C4 alkyl, halo C1-C4 alkyl, benzyl, substituted benzyl, or polyether;
C is halo, C1-C4 alkyl sulphonate, aryl sulphonate, l-Cg alkyl aryl sulphonate, C1-C4 alkyl sulphate, aryl sulphate, C1-C4 alkyl phosphate, or aryl phosphate;
A is
(a) a Cχ-Ci8 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 imgf000020_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, SiR20R21R22 or OSiR20R21R22, where R20 ,R21, and R22 are H, a Cι-C6 straight chain or branched alkyl group, phenyl, or substituted phenyl, provided that at least one of R20, R21, and R22 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
^o J> (3) 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)
j> (4) s wherein R15 is H, halo, halomethyl, CN, θ2 , C1-C4 alkyl, C3-C4 branched alkyl, phenyl, or C1-C4 alkoxy;
(f) a group of formula (5) or (5a)
Figure imgf000021_0001
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 0, NR19 or CH, provided that either J is N or G is NR19, where R19 is H, C1-C4 alkyl, C1-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 [ .3.1.1 (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/US1997/013604 1996-08-01 1997-07-31 Quinolinium derivatives having fungicidal activity WO1998005647A1 (en)

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WO2009125222A3 (en) * 2008-04-11 2010-12-16 The Queen's University Of Belfast Antimicrobial system
US20140256949A1 (en) * 2010-08-10 2014-09-11 Glaxosmithkline Intellectual Property Development Limited Quinolyl amines as kinase inhibitors
US9216965B2 (en) 2012-09-13 2015-12-22 Glaxosmithkline Intellectual Property Development Limited Amino-quinolines as kinase inhibitors
US9586953B2 (en) 2012-09-13 2017-03-07 Glaxosmithkline Intellectual Property Development Limited Prodrugs of amino quinazoline kinase inhibitor
US9604938B2 (en) 2011-08-18 2017-03-28 Glaxosmithkline Intellectual Property Development Limited Amino quinazolines as kinase inhibitors
US9604963B2 (en) 2011-03-04 2017-03-28 Glaxosmithkline Intellectual Property Development Limited Amino-quinolines as kinase inhibitors
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CN113549053A (en) * 2020-04-23 2021-10-26 沈阳中化农药化工研发有限公司 Pyrazoloquine (azolyl) ether compound and application thereof

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EP0326328A2 (en) * 1988-01-29 1989-08-02 DowElanco Quinoline, quinazoline, and cinnoline derivatives
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009125222A3 (en) * 2008-04-11 2010-12-16 The Queen's University Of Belfast Antimicrobial system
US20140256949A1 (en) * 2010-08-10 2014-09-11 Glaxosmithkline Intellectual Property Development Limited Quinolyl amines as kinase inhibitors
US9604963B2 (en) 2011-03-04 2017-03-28 Glaxosmithkline Intellectual Property Development Limited Amino-quinolines as kinase inhibitors
US10220030B2 (en) 2011-03-04 2019-03-05 Glaxosmithkline Intellectual Property Development Limited Amino-quinolines as kinase inhibitors
US9994529B2 (en) 2011-08-18 2018-06-12 Glaxosmithkline Intellectual Property Development Limited Amino quinazolines as kinase inhibitors
US10717711B2 (en) 2011-08-18 2020-07-21 Glaxosmithkline Intellectual Property Development Limited Amino quinazolines as kinase inhibitors
US9604938B2 (en) 2011-08-18 2017-03-28 Glaxosmithkline Intellectual Property Development Limited Amino quinazolines as kinase inhibitors
US9586953B2 (en) 2012-09-13 2017-03-07 Glaxosmithkline Intellectual Property Development Limited Prodrugs of amino quinazoline kinase inhibitor
US9695161B2 (en) 2012-09-13 2017-07-04 Glaxosmithkline Intellectual Property Development Limited Prodrugs of amino quinazoline kinase inhibitor
US9216965B2 (en) 2012-09-13 2015-12-22 Glaxosmithkline Intellectual Property Development Limited Amino-quinolines as kinase inhibitors
US9650364B2 (en) 2013-02-21 2017-05-16 GlaxoSmithKline Intellectual Property Development Limted Quinazolines as kinase inhibitors
CN113549053A (en) * 2020-04-23 2021-10-26 沈阳中化农药化工研发有限公司 Pyrazoloquine (azolyl) ether compound and application thereof
CN113549053B (en) * 2020-04-23 2022-09-13 沈阳中化农药化工研发有限公司 Pyrazoloquine (azolyl) ether compound and application thereof

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