WO1988000794A1 - Amino ethers and their use as fungicides - Google Patents

Amino ethers and their use as fungicides Download PDF

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Publication number
WO1988000794A1
WO1988000794A1 PCT/DK1987/000090 DK8700090W WO8800794A1 WO 1988000794 A1 WO1988000794 A1 WO 1988000794A1 DK 8700090 W DK8700090 W DK 8700090W WO 8800794 A1 WO8800794 A1 WO 8800794A1
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Prior art keywords
quaternary ammonium
formula
substituted
alkyl
carbon atoms
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PCT/DK1987/000090
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French (fr)
Inventor
Anita Wengel
Axel Svendsen
Per Dausell Klemmensen
Hans Kolind-Andersen
Niels Jacobsen
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A/S Cheminova
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Priority claimed from DK354486A external-priority patent/DK354486D0/en
Application filed by A/S Cheminova filed Critical A/S Cheminova
Publication of WO1988000794A1 publication Critical patent/WO1988000794A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • 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
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic 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
    • 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
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D211/70—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • 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
    • C07D215/04—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/06—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
    • C07D217/04—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines with hydrocarbon or substituted hydrocarbon radicals attached to the ring nitrogen atom
    • 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

Definitions

  • the present invention relates to novel amino ethers and quaternary ammonium salts and N-oxides thereof, and the invention also relates to the use of said compounds as fungicides.
  • (R 1 ) n represents up to three substituents which are the same or different and selected from straight or branched chain, substituted or unsubstituted alkyl having up to 12 carbon atoms, aryl, aryloxy, alkoxy, arylalkyl, haloalkyl, cyano, dialkylamino, alkylthio, halogen and nitro, and n is 0, 1, 2 or 3, or (R 1 ) n together with the benzene ring forms a naphthyl group, X represents 0 or S,
  • R 2 and R 3 each independently represents hydrogen or straight or branched chain alkyl having up to 6 carbon atoms, both of R 2 and R 3 not being hydrogen, however, when X is 0, or R 2 and R 3 when taken together with the corbon atom to which they are attached form a ring of up to 7 carbon atoms,
  • R 4 and R 5 each independently represents straight or branched chain, substituted or unsubstituted alkyl having up to 12 carbon atoms, cycloalkyl, alkenyl, alkynyl, substituted or unsubstituted aryl, or substituted or unsubstituted arylalkyl, or R 4 and R 5 when taken together with the nitrogen atom to Which they are attached form a saturated or unsaturated, substituted or unsubstituted heterocyclic ring which may optionally contain one or more edditional hetero atoms selected from O, N and S, and m is 2 or 3.
  • R 1 -R 5 in the above formula I have preferably, or by way of example, the following meanings:
  • R 1 alkyl is preferably alkyl having 4-10 carbon atoms, more preferably branched chain alkyl having 4-8 carbon atoms, aryl is preferably phenyl, aryloxy is preferably phenoxy, alkoxy is, e.g., methoxy or propoxy, arylalkyl is preferably benzyl, alkyl in haloalkyl, dialkylamino and alkylthio is each preferably alkyl having up to 12 carbon atoms, and halogen is preferably fluoro, chloro or bromo, R 2 and R 3 : alkyl is, e.g., methyl, and the carboxylic ring is, e.g., cyclopropyl, cyclobutyl or cyclohexyl, R 4 and R 5 : alkyl is preferably alkyl having up to
  • cycloalkyl is preferably cyclohexyl
  • alkenyl is preferably allyl
  • alkynyl is preferably propargyl
  • aryl is preferably phenyl
  • arylalkyl is preferably benzyl
  • the optionally substituted heterocyclic ring is preferably piperidino, dimethylpiperidino, ethylpiperidino, morpholino, 2,6-dimethylmorpholino
  • the corresponding quaternary ammonium salts are preferably prepared by reaction with alkyl, alkenyl, suitable aryl or arylalkyl halides, e.g. benzyl chloride, methyl iodide or allyl iodide.
  • suitable aryl or arylalkyl halides e.g. benzyl chloride, methyl iodide or allyl iodide.
  • the corresponding N-oxides are prepared by generally known methods. It has been found that the novel amino ethers of formula I and the corresponding quaternary ammonium salts and N-oxides have fungicidal properties.
  • amino ethers of formula I according to the invention and the said derivatives thereof surprisingly show a considerably superior fungicidal activity to that of the known benzethonium chloride and the corresponding base, which from a chemical point of view are compounds closely related to the compounds of the invention.
  • the active compounds of the invention can be used in practice for combating phytopathogenic fungi as for example Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
  • the active substances of the invention can be used, e.g., for combating the plant diseases Puccinia recondita, Puccinia striiformis and other rust diseases on wheat, Puccinia hordei, Puccinia striiformis and other rust diseases on barley and rust on other host plants as for example coffee, apples, vegetables and ornamental plants.
  • Erysiphe graminis on barley and wheat and other true mildew species on various host plants such as Sphaerotheca fuliginea on cucumber, Podosphaera leucotricha on apples and Uncinula necator on vines.
  • Helminthosporium spp. e.g. Pyrenophora teres (net blotch) on barley.
  • Botrytis cinerea grey mold
  • the active substances are active in vitro against a broad spectrum of fungi.
  • the active substances are active as seed dressing agents against Fusarium spp., Septoria spp., Tilletia spp., Ustilago spp., Helminthosporium spp. and Pseudocer-cosporella herpotrichoides on cereals, Khizoctonia solani on cotton and Corticium sasakii on rice.
  • the active substances of the invention also show extremely good protective properties as well as systemic activity.
  • some of the compounds are sufficiently volatile to be active in the gaseous phase against fungi on plants.
  • the invention also relates to a fungicidal composition, particularly a plant-fungicidal composition, which composition is characterised by containing as an active component at least one compound selected from the amino ethers of the above formula I and quaternary ammonium salts and N-oxides thereof.
  • the invention relates to the use of an amino ether of the above formula I and/or a quater- nary ammonium salt thereof and/or an N-oxide thereof for combating fungi, particularly phytopathogenic fungi.
  • the invention relates to a method of combating fungi, particularly phytopathogenic fungi, which method is characterised by allowing an amino ether of the above formula I and/or a quaternary ammonium salt thereof and/or an N-oxide thereof to affect the fungi concerned and/or their biotope.
  • the invention relates to a process of preparing a fungicidal composition, particulary a plant-fungicidal composition, which process is characterised by mixing an amino ether of the above formula I and/or a quaternary ammonium salt thereof and/or an N- oxide thereof with one or more agents selected from extending agents, surface active agents and other conventional auxiliary agents.
  • amino ethers of formula I according to the invention can be prepared by any known process for preparing similar compounds, e.g. as illustrated in the following Preparation Example.
  • the compounds of the invention may be formulated as compositions such as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates or aerosols.
  • Wettable powders are usually formulated to contain 25, 50 or 75% of toxicant and usually contain, in addition to solid carrier, 3-10% by weight of a dispersing agent and, where necessary 0-10% by weight of stabilisers and/or additives such as penetrants or stickers.
  • Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant and are diluted in the field with further solid carrier to give a composition usually containing 1/2-10% by weight of toxicant.
  • Granules are usually prepared to have a size between 10 and 100 BS mesh, (1.676-0.152 mm) and may be manufactured by agglomeration or impregnation techniques.
  • granules will contain 1/2-25% by weight toxicant and 0-10% by weight of additives such as stabilisers, slow release modifiers and binding agents.
  • Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10-50% w/v toxicant, 2-20% w/v emulsifiers and 0-20% w/v of appropriate additives such as stabilisers, penetrants and corrosion inhibitors.
  • Suspension concentrates are compounded so as to obtain a stable, non-sedimenting, flowable product and usually contain 10-75% by weight of toxicant, 1/2-15% by weight of dispersing agents, 0-10% by weight of suspending agents such as protective colloids and thixotropic agents, 0-10% by weight of appropriate additives such as defoamers, corrosion inhibitors, stabilisers, penetrants and stickers, and as carrier, water or an organic liquid in which the toxicant is substantially- insoluble. Certain organic solids or inorganic salts may be dissolved in the carrier to assist in preventing sedimentation or an antifreeze agents for water.
  • Aqueous dispersions and emulsions for example, compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also lie within the scope of the present invention.
  • the said emulsions may be of the water-in-oil or of the olie-in-water type, and may have a thick "mayonnaise"- like consistency.
  • compositions may also contain other ingredients, for example, other compounds having pesticidal, particularly acaricidal, herbicidal or fungicidal properties.
  • Benzethonium chloride Eksv 1 Erysiphe graminis test (barley/protective spray).
  • Solvent 10% acetone in water.
  • Emulsifier Triton X-155, 100 ppm.
  • the active substance is dissolved in the specified solvent with emulsifier to the concentration desired . Further dilution is carried out by a solution containing 10% acetone in water and 100 ppm Triton X-155.
  • To test for protective activity young barley plants are sprayed to leaf wetness with the composition of active substance. After drying the plants are inoculated with mildew conidia by the brush method. The plants are left 48 hours af 18°C and 100% RH, whereafter they are transferred to a growth chamber at the same temperature and 70-80% RH.
  • Eksempel 2 Erysiphe graminis test (barley/curative spray).
  • Solvent 10% acetone in water.
  • Emulsifier Triton X-155, 100 ppm.
  • the active substance is dissolved in the specified solvent with emulsifier to the concentration desired. Further dilution is carried out by a solution containing 10% acetone in water and 100 ppm Triton X-155.
  • Example 3 Puccinia recondita test (wheat, protective spray).
  • Solvent 10% acetone in water.
  • Emulsifier Triton X-155, 100 ppm.
  • the active substance is dissolved in the specified solvent with emulsifier to the concentration desired. Further dilution is carried out by a solution containing 10% acetone in water and 100 ppm Triton X-155.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Amino ethers of formula (I), wherein (R1)n represents up to three substituents selected from optionally substituted alkyl and aryl, aryloxy, alkoxy, arylalkyl, haloalkyl, cyano, dialkylamino, alkylthio, halogen and nitro, and n is 0, 1, or 3, or (R1)n together with the benzene ring forms a naphthyl group, X is O or S, R2 and R3 is each hydrogen or alkyl, both of R2 and R3 not being hydrogen, however, when X is O, or R2 and R3 when taken together with the carbon atom to which they are attached form a ring of up to 7 carbon atoms, R4 and R5 each is optionally substituted alkyl, cycloalkyl, alkenyl, alkynyl or optionally substituted aryl or arylalkyl, or NR4R5 forms a saturated or unsaturated, optionally substituted heterocyclic ring optionally containing one or more additional hetero atoms selected from O, N and S, and m is 2 or 3, and quaternary ammonium salts and N-oxides thereof, are prepared in a manner known per se. The compounds have fungicidal, particularly plant-fungicidal activity and are therefore applicable in fungicidal compositions and in methods for combating fungi, particularly phytopathogenic fungi.

Description

Amino ethers and their use as fungicides.
The present invention relates to novel amino ethers and quaternary ammonium salts and N-oxides thereof, and the invention also relates to the use of said compounds as fungicides.
It is already known that quaternary ammonium compounds such as benzethonium chloride have fungicidal activity, confer, e.g., Japaness unexamined patent application Jpn Kokai Tokkyo Koho JP/l12902 A2 (84/112902), 29th June, 1984. However, the plant- fungicidal activity of benzethonium chloride and of the corresponding base is considerably lower than that of the amino ethers of the invention.
The novel amino ethers now provided have the general formula I
Figure imgf000003_0001
wherein (R1)n represents up to three substituents which are the same or different and selected from straight or branched chain, substituted or unsubstituted alkyl having up to 12 carbon atoms, aryl, aryloxy, alkoxy, arylalkyl, haloalkyl, cyano, dialkylamino, alkylthio, halogen and nitro, and n is 0, 1, 2 or 3, or (R1)n together with the benzene ring forms a naphthyl group, X represents 0 or S,
R2 and R3 each independently represents hydrogen or straight or branched chain alkyl having up to 6 carbon atoms, both of R2 and R3 not being hydrogen, however, when X is 0, or R2 and R3 when taken together with the corbon atom to which they are attached form a ring of up to 7 carbon atoms,
R4 and R5 each independently represents straight or branched chain, substituted or unsubstituted alkyl having up to 12 carbon atoms, cycloalkyl, alkenyl, alkynyl, substituted or unsubstituted aryl, or substituted or unsubstituted arylalkyl, or R4 and R5 when taken together with the nitrogen atom to Which they are attached form a saturated or unsaturated, substituted or unsubstituted heterocyclic ring which may optionally contain one or more edditional hetero atoms selected from O, N and S, and m is 2 or 3.
The symbols R1-R5 in the above formula I have preferably, or by way of example, the following meanings:
R1 : alkyl is preferably alkyl having 4-10 carbon atoms, more preferably branched chain alkyl having 4-8 carbon atoms, aryl is preferably phenyl, aryloxy is preferably phenoxy, alkoxy is, e.g., methoxy or propoxy, arylalkyl is preferably benzyl, alkyl in haloalkyl, dialkylamino and alkylthio is each preferably alkyl having up to 12 carbon atoms, and halogen is preferably fluoro, chloro or bromo, R2 and R3 : alkyl is, e.g., methyl, and the carboxylic ring is, e.g., cyclopropyl, cyclobutyl or cyclohexyl, R4 and R5 : alkyl is preferably alkyl having up to
5 carbon atoms and more preferably up to 3 carbon atoms, cycloalkyl is preferably cyclohexyl, alkenyl is preferably allyl, alkynyl is preferably propargyl aryl is preferably phenyl, arylalkyl is preferably benzyl, and the optionally substituted heterocyclic ring is preferably piperidino, dimethylpiperidino, ethylpiperidino, morpholino, 2,6-dimethylmorpholino
(cis/trans or cis or trans) or hexa- methyleneimino. The corresponding quaternary ammonium salts are preferably prepared by reaction with alkyl, alkenyl, suitable aryl or arylalkyl halides, e.g. benzyl chloride, methyl iodide or allyl iodide. The corresponding N-oxides are prepared by generally known methods. It has been found that the novel amino ethers of formula I and the corresponding quaternary ammonium salts and N-oxides have fungicidal properties. Thereby, the amino ethers of formula I according to the invention and the said derivatives thereof surprisingly show a considerably superior fungicidal activity to that of the known benzethonium chloride and the corresponding base, which from a chemical point of view are compounds closely related to the compounds of the invention.
The active compounds of the invention can be used in practice for combating phytopathogenic fungi as for example Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
The active substances of the invention can be used, e.g., for combating the plant diseases Puccinia recondita, Puccinia striiformis and other rust diseases on wheat, Puccinia hordei, Puccinia striiformis and other rust diseases on barley and rust on other host plants as for example coffee, apples, vegetables and ornamental plants.
Erysiphe graminis (mildew) on barley and wheat and other true mildew species on various host plants such as Sphaerotheca fuliginea on cucumber, Podosphaera leucotricha on apples and Uncinula necator on vines. Helminthosporium spp., e.g. Pyrenophora teres (net blotch) on barley.
Rhynchosporium spp. and Pseudocercosporella herpotrichoides on cereals.
Cercospora arachidicola on peanuts and other Cercospo- ra species on for example sugar beet, banana and soya bean.
Botrytis cinerea (grey mold) on tomato, strawberry, vine and other host plants.
Venturia inaequalis (scab) on apples.
Pyricularia oryzae on rice. The active substances are active in vitro against a broad spectrum of fungi.
The active substances are active as seed dressing agents against Fusarium spp., Septoria spp., Tilletia spp., Ustilago spp., Helminthosporium spp. and Pseudocer-cosporella herpotrichoides on cereals, Khizoctonia solani on cotton and Corticium sasakii on rice.
Besides an excellent curative activity the active substances of the invention also show extremely good protective properties as well as systemic activity. In addition to this some of the compounds are sufficiently volatile to be active in the gaseous phase against fungi on plants.
In accordance with the above the invention also relates to a fungicidal composition, particularly a plant-fungicidal composition, which composition is characterised by containing as an active component at least one compound selected from the amino ethers of the above formula I and quaternary ammonium salts and N-oxides thereof. Moreover, the invention relates to the use of an amino ether of the above formula I and/or a quater- nary ammonium salt thereof and/or an N-oxide thereof for combating fungi, particularly phytopathogenic fungi.
Furthermore, the invention relates to a method of combating fungi, particularly phytopathogenic fungi, which method is characterised by allowing an amino ether of the above formula I and/or a quaternary ammonium salt thereof and/or an N-oxide thereof to affect the fungi concerned and/or their biotope.
Furthermore, the invention relates to a process of preparing a fungicidal composition, particulary a plant-fungicidal composition, which process is characterised by mixing an amino ether of the above formula I and/or a quaternary ammonium salt thereof and/or an N- oxide thereof with one or more agents selected from extending agents, surface active agents and other conventional auxiliary agents.
The amino ethers of formula I according to the invention can be prepared by any known process for preparing similar compounds, e.g. as illustrated in the following Preparation Example.
Preparation Example Preparation of 2-(2,4-dichlorophenoxy)-2-methyl-propyl N-benzyl-N-ethyl-2-aminoethyl ether, compound No. 1.
Figure imgf000007_0001
A mixture of 2-(2,4-dichlorophenoxy)-2-methyl- 1-propanol (3.00 g, 0.013 mole) benzyltriethylammonium chloride (0.30 g) and 50% aqueous NaOH (15 g) is heated on an oil bath at 70°C with vigorous stirring. To this N-benzyl-N-ethyl-2-amino-1-chloroethane hydrochloride (4.46 g, 0.019 mole) is added in one portion. After 15 minutes additional benzyltriethylammonium chloride (0.30 g) is added and the mixture is stirred for 1 hour. Water (50 ml) is added to the reaction mixture and the mixture is extracted with ether (50 ml). The ether phase is separated and extracted with 4 N hydrochloric acid (50 ml). The acidic phase is separated and basified by adding 20% aqueous sodium hydroxide. Extraction with ether (2 x 50 ml), drying of the combined ether phases over sodium sulphate and removal of the solvent in vacuo leave an oil from which the desired product is isolated by kugelrohr distillation.
Yield 3.45 g (68%); b.p. 190-195°C/0,08 mm Hg; : 1.5385.
Figure imgf000008_0001
In addition to the compound mentioned in the Preparation Example there are emphasized the following amino ethers of formula I which have been prepared by the process described above, and the corresponding quaternary ammonium salts, prepared by generally known processes by reaction with alkyl, alkenyl, suitable aryl or arylalkyl halides, as well as the corresponding N- oxides, prepared by generally known processes.
Figure imgf000009_0001
Figure imgf000010_0001
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
The compounds of the invention may be formulated as compositions such as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates or aerosols. Wettable powders are usually formulated to contain 25, 50 or 75% of toxicant and usually contain, in addition to solid carrier, 3-10% by weight of a dispersing agent and, where necessary 0-10% by weight of stabilisers and/or additives such as penetrants or stickers.
Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant and are diluted in the field with further solid carrier to give a composition usually containing 1/2-10% by weight of toxicant. Granules are usually prepared to have a size between 10 and 100 BS mesh, (1.676-0.152 mm) and may be manufactured by agglomeration or impregnation techniques.
Generally, granules will contain 1/2-25% by weight toxicant and 0-10% by weight of additives such as stabilisers, slow release modifiers and binding agents. Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10-50% w/v toxicant, 2-20% w/v emulsifiers and 0-20% w/v of appropriate additives such as stabilisers, penetrants and corrosion inhibitors. Suspension concentrates are compounded so as to obtain a stable, non-sedimenting, flowable product and usually contain 10-75% by weight of toxicant, 1/2-15% by weight of dispersing agents, 0-10% by weight of suspending agents such as protective colloids and thixotropic agents, 0-10% by weight of appropriate additives such as defoamers, corrosion inhibitors, stabilisers, penetrants and stickers, and as carrier, water or an organic liquid in which the toxicant is substantially- insoluble. Certain organic solids or inorganic salts may be dissolved in the carrier to assist in preventing sedimentation or an antifreeze agents for water.
Aqueous dispersions and emulsions, for example, compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also lie within the scope of the present invention. The said emulsions may be of the water-in-oil or of the olie-in-water type, and may have a thick "mayonnaise"- like consistency.
The compositions may also contain other ingredients, for example, other compounds having pesticidal, particularly acaricidal, herbicidal or fungicidal properties.
The activity of the compounds of the invention is illustrated in detail by the following Application Examples.
Application Examples In the following Application Examples the following compounds are used as reference substances
A
B
Figure imgf000053_0001
Benzethonium chloride Eksempel 1 Erysiphe graminis test (barley/protective spray). Solvent : 10% acetone in water. Emulsifier: Triton X-155, 100 ppm. For preparing an appropriate composition of active substance the active substance is dissolved in the specified solvent with emulsifier to the concentration desired . Further dilution is carried out by a solution containing 10% acetone in water and 100 ppm Triton X-155. To test for protective activity young barley plants are sprayed to leaf wetness with the composition of active substance. After drying the plants are inoculated with mildew conidia by the brush method. The plants are left 48 hours af 18°C and 100% RH, whereafter they are transferred to a growth chamber at the same temperature and 70-80% RH.
7 Days after inoculation the activity of the substance is evaluated.
In this test a clear superiority in activity is shown by, e.g., the compound of Preparation Example I and, e.g., the compounds 5, 7, 8, 9, 17, 36, 38, 41, 43, 45, 54, 58, 65, 67, 68, 69, 70, 71, 76, 78, 85, 86, 87, 91, 94, 95, 96, 99, 106, 110, 128, 138, 139, 141, 142, 144, 145, 146, 148, 151, 152, 154, 159 and 169.
Eksempel 2 Erysiphe graminis test (barley/curative spray). Solvent : 10% acetone in water. Emulsifier: Triton X-155, 100 ppm. For preparing an appropriate composition of active substance the active substance is dissolved in the specified solvent with emulsifier to the concentration desired. Further dilution is carried out by a solution containing 10% acetone in water and 100 ppm Triton X-155.
To test for curative activity young barley plants are sprayed to leaf wetness with the composition af act- ive substance 2 days after the plants have been inoculated with mildew conidia by the brush method. After inoculation and until spraying the plants are left at 18°C and 100% RH, and after spraying they are left in a growth chamber at 18°C and 70-80% RH.
7 Days after inoculation the activity of the substance is evaluated. In this test a clear superiority in activity is shown by, e.g., the compounds listed in Tabel 1. The activity of the compounds is indicated as given below:
3 90-100% disease control 2 50- 89% disease control 1 11- 49% disease control 0 0- 10% disease control
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Example 3 Puccinia recondita test (wheat, protective spray). Solvent : 10% acetone in water. Emulsifier: Triton X-155, 100 ppm. For preparing an appropriate composition of active substance the active substance is dissolved in the specified solvent with emulsifier to the concentration desired. Further dilution is carried out by a solution containing 10% acetone in water and 100 ppm Triton X-155.
To test for protective activity young wheat plants are sprayed to leaf wetness with the composition of active substance. After drying the plants are inoculated with brown rust spores in an aqueous slurry which is sprayed on. The plants are left for 48 hours at 18°C and 100% RH, whereafter they are transferred to a growth chamber at the same temperature and 70-80% RH.
10 Days after inoculation the activity of the substances is evaluated. In this test a clear superiority in activity is shown by, e.g., the compounds listed in Tabel 2.
The activity of the compounds is indicated as given below:
3 90-100% disease control 2 50- 89% disease control
1 11- 49% disease control
0 0- 10% disease control
Figure imgf000059_0001

Claims

Patent Claims 1. Amino ethers, characterised by having the following general formula I
Figure imgf000060_0001
wherein (R1)n represents up to three substituents which are the same or different and selected from straight or branched chain substituted or unsubstituted alkyl having up to 12 carbon atoms, aryl, aryloxy, alkoxy, arylalkyl, haloalkyl, cyano, dialkylamino, alkylthio, halogen and nitro, and n is 0, 1, 2 or 3, or (R1)n together with the benzene ring forms a naphthyl group, X represents O or S,
R2 and R3 each independently represents hydrogen or straight or branched chain alkyl having up to 6 carbon atoms, both of R2 and R3 not being hydrogen, however, when X is 0, or R2 and R3 when taken together with the carbon atom to which they are attached form a ring of up to 7 carbon atoms,
R4 and R5 each independently represents straight or branched chain, substituted or unsubstituted alkyl having up to 12 carbon atoms, cycloalkyl, alkenyl, alkynyl, substituted or ubsubstituted aryl, or substituted or unsubstituted arylalkyl, or R4 and R5 when taken together with the nitrogen atom to which they are attached form a saturated or unsaturated, substituted or unsubstituted heterocyclic ring which may optionally contain one or more additional hetero atoms selected from O, N and S, and m is 2 or 3, and quaternary ammonium salts thereof, preferably prepared by reaction with alkyl, alkenyl, suitable aryl or arylalkyl halides, and N-oxides thereof.
2. A fungicidal composition, particularly a plant-fungicidal composition, characterised by containing as an active component at least one compound selected from amino ethers of formula I as defined in claim 1 and quaternary ammonium salts and N-oxides thereof.
3. Use of an amino ether of formula I as defined in claim 1 and/or a quaternary ammonium salt thereof and/or an N-oxide thereof for combating fungi, particularly phytopathogenic fungi.
4. A method of combating fungi, particularly phytopathogenic fungi, characterised by allowing an amino ether of formula I as defined in claim 1 and/or a quaternary ammonium salt thereof and/or an N-oxide thereof to affect the fungi concerned and/or their biotope.
5. A process of preparing a fungicidal composition, particularly a plant-fungicidal composition, characterised by mixing an amino ether of formula I as defined in claim 1 and/or a quaternary ammonium salt thereof and/or an N-oxide thereof with one or more agents selected from extending agents, surface active agents and other conventional auxiliary agents.
PCT/DK1987/000090 1986-07-25 1987-07-15 Amino ethers and their use as fungicides WO1988000794A1 (en)

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DK354486A DK354486D0 (en) 1986-07-25 1986-07-25 AMINOETHERS AND THEIR USE AS FUNGICIDES
DK625886A DK625886A (en) 1986-07-25 1986-12-23 AMINOETHERS AND THEIR USE AS FUNGICIDES
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WO1995011240A1 (en) * 1993-10-22 1995-04-27 Smithkline Beecham Plc Amine derivatives as calcium channel antagonists

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WO1995011240A1 (en) * 1993-10-22 1995-04-27 Smithkline Beecham Plc Amine derivatives as calcium channel antagonists

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