WO2014105845A1 - 3-alkyl-5-fluoro-4-substituted-imino-3,4-dihydropyrimidin-2(1h)-one derivatives as fungicides - Google Patents

3-alkyl-5-fluoro-4-substituted-imino-3,4-dihydropyrimidin-2(1h)-one derivatives as fungicides Download PDF

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Publication number
WO2014105845A1
WO2014105845A1 PCT/US2013/077542 US2013077542W WO2014105845A1 WO 2014105845 A1 WO2014105845 A1 WO 2014105845A1 US 2013077542 W US2013077542 W US 2013077542W WO 2014105845 A1 WO2014105845 A1 WO 2014105845A1
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Prior art keywords
alkyl
optionally substituted
phenyl
compound according
haloalkyl
Prior art date
Application number
PCT/US2013/077542
Other languages
French (fr)
Inventor
Beth Lorsbach
Ronald Ross
W. John OWEN
Jeffery D. Webster
Lindsay Stelzer
Chenglin Yao
Paul LEPLAE
Christopher GALLIFORD
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
Priority to ES13869177T priority Critical patent/ES2874475T3/en
Priority to NZ708981A priority patent/NZ708981A/en
Priority to MX2015008565A priority patent/MX2015008565A/en
Priority to RU2015131832A priority patent/RU2644014C2/en
Priority to CA2894553A priority patent/CA2894553C/en
Priority to JP2015550744A priority patent/JP2016503816A/en
Priority to US14/655,570 priority patent/US9642368B2/en
Priority to KR1020157020513A priority patent/KR102309245B1/en
Application filed by Dow Agrosciences Llc filed Critical Dow Agrosciences Llc
Priority to CN201380073784.4A priority patent/CN105007737A/en
Priority to PL13869177T priority patent/PL2953463T3/en
Priority to EP13869177.9A priority patent/EP2953463B1/en
Priority to AU2013370494A priority patent/AU2013370494B2/en
Publication of WO2014105845A1 publication Critical patent/WO2014105845A1/en
Priority to IL239597A priority patent/IL239597B/en
Priority to HK16103307.4A priority patent/HK1215357A1/en
Priority to US15/589,733 priority patent/US10059703B2/en
Priority to IL257964A priority patent/IL257964B/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N47/02—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 no bond to a nitrogen atom
    • 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
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters thereof
    • 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
    • A01N47/40—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 a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
    • C07B59/002—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/495—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with two or more nitrogen atoms as the only ring heteroatoms, e.g. piperazine or tetrazines
    • A61K31/505—Pyrimidines; Hydrogenated pyrimidines, e.g. trimethoprim
    • A61K31/513—Pyrimidines; Hydrogenated pyrimidines, e.g. trimethoprim having oxo groups directly attached to the heterocyclic ring, e.g. cytosine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/05—Isotopically modified compounds, e.g. labelled

Definitions

  • Fungicides are compounds, of natural or synthetic origin, which act to protect and/or cure plants against damage caused by agriculturally relevant fungi. Generally, no single fungicide is useful in all situations. Consequently, research is ongoing to produce fungicides that may have better performance, are easier to use, and cost less.
  • the present disclosure relates to 3-alkyl-5-fluoro-4-imino-3,4-dihydropyrimidin-
  • 2(lH)one compounds and their use as fungicides.
  • the compounds of the present disclosure may offer protection against ascomycetes, basidiomycetes, deuteromycetes and oomycetes.
  • One embodiment of the present disclosure may include compounds of Formula I:
  • R 2 is:
  • n is an integer from 1-3.
  • R 3 is -S(0) 2 R 9 ;
  • R 4 is independently C1-C6 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 haloalkylthio, amino, C1-C 3 alkylamino, C2-C6 alkoxycarbonyl, C 2 -C6 alkylcarbonyl, C 2 -C6 alkylaminocarbonyl, hydroxyl, deuterium, or C 3 -C6 trialkylsilyl;
  • R 5 is H, C1-C6 alkyl, C 2 -C6 alkenyl, C 3 -C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxyalkyl, phenyl or benzyl wherein each of the phenyl or the benzyl may be optionally substituted with 1-3 R 10 , or with a 5- or 6-membered saturated or unsaturated ring system, or with a 5-6 fused ring system, or with a 6-6 fused ring system each containing 1-3 heteroatoms wherein each ring may be optionally substituted with 1-3 R 10 , biphenyl or naphthyl optionally substituted with 1-3 R 10 ;
  • R 6 is independently halogen, C1-C6 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, d- C4 alkylthio, C1-C4 haloalkylthio, amino, C1-C3 alkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C 2 -C6 alkylaminocarbonyl, hydroxyl, deuterium, or C3-C6 trialkylsilyl;
  • R 7 is H, C1-C6 alkyl, C 2 -C6 alkenyl, C 3 -C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxyalkyl, phenyl or benzyl wherein each of the phenyl or the benzyl may be optionally substituted with 1-3 R 10 , or with a 5- or 6-membered saturated or unsaturated ring system, or with a 5-6 fused ring system, or with a 6-6 fused ring system each containing 1-3 heteroatoms wherein each ring may be optionally substituted with 1-3 R 10 , biphenyl or naphthyl optionally substituted with 1-3 R 10 ;
  • R 8 is H, Ci-C 6 alkyl, or Ci-C 6 haloalkyl
  • R 9 is C1-C6 alkyl, C1-C6 haloalkyl, amino, C1-C6 alkylamino, C2-C6 dialkylamino, a phenyl or benzyl wherein each of the phenyl or the benzyl may be optionally substituted with 1- 3 R 10 , or a 5- or 6-membered saturated or unsaturated ring containing 1-3 heteroatoms wherein each ring may be optionally substituted with 1-3 R , or with a 5-6 fused ring system, or with a 6-6 fused ring system each containing 1-3 heteroatoms wherein each ring may be optionally substituted with 1-3 R 10 , biphenyl or naphthyl optionally substituted with 1-3 R 10 ; and R 10 is independently halogen, C1-C6 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, Ci- C4 alkyl
  • R 4 is independently C1-C6 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, hydroxyl, or deuterium.
  • R 5 is C1-C6 alkyl, C1-C6 haloalkyl, phenyl or benzyl wherein each of the phenyl or the benzyl may be optionally substituted with 1-3 R 10 .
  • R 6 is independently halogen, Ci-C 6 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 alkylthio, or deuterium.
  • R 7 is C1-C6 alkyl, C1-C6 haloalkyl, phenyl or benzyl wherein each of the phenyl or the benzyl may be optionally substituted with 1-3 R 10 .
  • R 10 is independently halogen, C1-C6 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, cyano, or nitro.
  • R 9 is phenyl optionally substituted with 1- 3 R 10 , or a 5- or 6-membered saturated or unsaturated ring containing 1-3 heteroatoms optionally substituted with 1-3 R 10 .
  • R 10 is independently halogen, C1-C6 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy.
  • R 1 is C1-C3 alkyl.
  • R 2 is C1-C 3 alkyl
  • R 5 is C1-C 3 alkyl or phenyl.
  • R 1 is C1-C 3 alkyl.
  • R 9 is selected from the group consisting of:
  • R 5 is C1-C3 alkyl or phenyl.
  • R 1 is Ci- C 3 alkyl.
  • R 1 is: Ci-C 6 alkyl optionally substituted with 1-3 R 4 ;
  • R 3 is -S(0) 2 R 9 ;
  • R 4 is hydroxyl, or deuterium
  • R 5 is C1-C6 alkyl, or phenyl
  • R 6 is deuterium
  • R 7 is C1-C6 alkyl, or phenyl optionally substituted with 1-3 R 10 ;
  • R 8 is H; n is 1
  • R 9 is Ci-C 6 alkyl, or a phenyl optionally substituted with 1- 3 R 10 , or a 5- or 6-membered saturated or unsaturated ring containing 1 -3 heteroatoms wherein each ring may be optionally substituted with 1-3 R 10 ;
  • R 10 is independently halogen, C1-C6 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, or cyano.
  • compositions for the control of a fungal pathogen including; at least one compound of Formula I; and a phytologically acceptable carrier material, wherein said compositon is effective for the control of at least one pathogenic fungus or pathogenic fungus like organism.
  • the pathogenic fungus or fungus like pathogen is
  • Also proposed is a method for treating a plant comprising the steps of: applying a fungicidally effective amount of at least one of the compounds of Formula 1 to at least one surface, selected from the group of surfaces consiting of: at least one portion of a plant, an area adjacent to a plant, soil in contact with a plant, soild adjacent to a plant, a seed, and agricultural equipment.
  • the fungicidally effective amount Formula I is applied to a surface in the range of about 0.01g/m 2 to about 0.45 g/m 2 of Formula I.
  • Another embodiment of the present disclosure may include a fungicidal composition for the control or prevention of fungal attack comprising the compounds described below and a phytologically acceptable carrier material.
  • Yet another embodiment of the present disclosure may include a method for the control or prevention of fungal attack on a plant, the method including the steps of applying a fungicidally effective amount of one or more of the compounds described below to at least one of the fungus, the plant, an area adjacent to the plant, and the seed adapted to produce the plant.
  • alkyl refers to a branched, unbranched, or cyclic carbon chain, including methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
  • alkenyl refers to a branched, unbranched or cyclic carbon chain containing one or more double bonds including ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclohexenyl, and the like.
  • alkynyl refers to a branched or unbranched carbon chain containing one or more triple bonds including propynyl, butynyl and the like.
  • 'R' refers to the group consisting of Ci-8 alkyl, C -8 alkenyl or C -8 alkynyl, unless stated otherwise.
  • alkoxy refers to an -OR substituent.
  • alkoxycarbonyl refers to a -C(0)-OR substituent.
  • alkylcarbonyl refers to a -C(0)-R substituent.
  • alkylsulfonyl refers to an -S0 2 -R substituent.
  • alkylthio refers to an -S-R substituent.
  • halothio refers to a sulfur substituted with three or five F substituents.
  • halo alkylthio refers to an alkylthio, which is substituted with CI, F, I, or Br or any combination thereof.
  • alkylaminocarbonyl refers to a -C(0)-N(H)-R substituent.
  • hydroxyl refers to an -OH substituent.
  • amino refers to a -NH 2 substituent.
  • alkylamino refers to a -N(H)-R substituent.
  • dialkylamino refers to a -NR 2 substituent.
  • alkoxyalkyl refers to an alkoxy substitution on an alkyl.
  • halogen refers to one or more halogen atoms, defined as F,
  • nitro refers to a -N0 2 substituent.
  • Fungicidally effective amount of the compounds include amounts sufficient to kill or control true fungi, pseudo-fungi, and related organisms including water moulds.
  • Another embodiment of the present disclosure is a use of a compound of Formula
  • a compound of Formula I for protection of a plant against attack by a phytopathogenic organism or the treatment of a plant infested by a phytopathogenic organism, comprising the application of a compound of Formula I, or a composition comprising the compound to soil, a plant, a part of a plant, foliage, and/or seeds.
  • composition useful for protecting a plant against attack by a phytopathogenic organism and/or treatment of a plant infested by a phytopathogenic organism comprising a compound of Formula I and a phytologically acceptable carrier material.
  • the compounds of the present disclosure may be applied by any of a variety of known techniques, either as the compounds or as formulations comprising the compounds.
  • the compounds may be applied to the roots, seeds or foliage of plants for the control of various fungi, without damaging the commercial value of the plants.
  • the materials may be applied in the form of any of the generally used formulation types, for example, as solutions, dusts, wettable powders, flowable concentrates, or emulsifiable concentrates.
  • the compounds of the present disclosure are applied in the form of a formulation, comprising one or more of the compounds of Formula I with a phytologically acceptable carrier.
  • Concentrated formulations may be dispersed in water, or other liquids, for application, or formulations may be dust-like or granular, which may then be applied without further treatment.
  • the formulations can be prepared according to procedures that are
  • the present disclosure contemplates all vehicles by which one or more of the compounds may be formulated for delivery and use as a fungicide.
  • formulations are applied as aqueous suspensions or emulsions.
  • Such suspensions or emulsions may be produced from water-soluble, water suspendible, or emulsifiable formulations which are solids, usually known as wettable powders; or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or suspension concentrates.
  • any material to which these compounds may be added may be used, provided it yields the desired utility without significant interference with the activity of these compounds as antifungal agents.
  • Wettable powders which may be compacted to form water dispersible granules, comprise an intimate mixture of one or more of the compounds of Formula I, an inert carrier and surfactants.
  • concentration of the compound in the wettable powder may be from about 10 percent to about 90 percent by weight based on the total weight of the wettable powder, more preferably about 25 weight percent to about 75 weight percent.
  • the compounds may be compounded with any finely divided solid, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like.
  • the finely divided carrier and surfactants are typically blended with the compound(s) and milled.
  • Emulsifiable concentrates of the compounds of Formula I may comprise a convenient concentration, such as from about 10 weight percent to about 50 weight percent of the compound, in a suitable liquid, based on the total weight of the concentrate.
  • the compounds may be dissolved in an inert carrier, which is either a water-miscible solvent or a mixture of water-immiscible organic solvents, and emulsifiers.
  • the concentrates may be diluted with water and oil to form spray mixtures in the form of oil-in- water emulsions.
  • Useful organic solvents include aromatics, especially the high-boiling naphthalenic and olefmic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as 2-ethoxyethanol.
  • Emulsifiers which may be advantageously employed herein may be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers.
  • nonionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene.
  • Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts.
  • Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulfonic acids, oil-soluble salts or sulfated polyglycol ethers and appropriate salts of phosphated polyglycol ether.
  • Representative organic liquids which may be employed in preparing the emulsiftable concentrates of the compounds of the present invention are the aromatic liquids such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives such as the «-butyl ether, ethyl ether or methyl ether of diethylene glycol, the methyl ether of triethylene glycol, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters, cast
  • Organic liquids include xylene, and propyl benzene fractions, with xylene being most preferred in some cases.
  • Surface-active dispersing agents are typically employed in liquid formulations and in an amount of from 0.1 to 20 percent by weight based on the combined weight of the dispersing agent with one or more of the compounds.
  • the formulations can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.
  • Aqueous suspensions comprise suspensions of one or more water-insoluble compounds of Formula I, dispersed in an aqueous vehicle at a concentration in the range from about 5 to about 0 weight percent, based on the total weight of the aqueous suspension.
  • Suspensions are prepared by finely grinding one or more of the compounds, and vigorously mixing the ground material into a vehicle comprised of water and surfactants chosen from the same types discussed above.
  • a vehicle comprised of water and surfactants chosen from the same types discussed above.
  • Other components 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 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.
  • Aqueous emulsions comprise emulsions of one or more water-insoluble pesticidally active ingredients emulsified in an aqueous vehicle at a concentration typically in the range from about 5 to about 50 weight percent, based on the total weight of the aqueous emulsion. If the pesticidally active ingredient is a solid it must be dissolved in a suitable water- immiscible solvent prior to the preparation of the aqueous emulsion.
  • Emulsions are prepared by emulsifying the liquid pesticidally active ingredient or water-immiscible solution thereof into an aqueous medium typically with inclusion of surfactants that aid in the formation and stabilization of the emulsion as described above. This is often accomplished with the aid of vigorous mixing provided by high shear mixers or homogenizers.
  • the compounds of Formula I can also be applied as granular formulations, which are particularly useful for applications to the soil.
  • Granular formulations generally contain from about 0.5 to about 10 weight percent, based on the total weight of the granular formulation of the compound(s), dispersed in an inert carrier which consists entirely or in large part of coarsely divided inert material such as attapulgite, bentonite, diatomite, clay or a similar inexpensive substance.
  • Such formulations are usually prepared by dissolving the compounds in a suitable solvent and applying it to a granular carrier which has been preformed to the appropriate particle size, in the range of from about 0.5 to about 3 mm.
  • a suitable solvent is a solvent in which the compound is substantially or completely soluble.
  • Such formulations may also be prepared by making a dough or paste of the carrier and the compound and solvent, and crushing and drying to obtain the desired granular particle.
  • Dusts containing the compounds of Formula I may be prepared by intimately mixing one or more of the compounds 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 weight percent of the compounds, based on the total weight of the dust.
  • 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 weight percent of the compounds, based on the total weight of the dust.
  • the formulations may additionally contain adjuvant surfactants to enhance deposition, wetting and penetration of the compounds onto the target crop and organism.
  • adjuvant surfactants may optionally be employed as a component of the formulation or as a tank mix.
  • the amount of adjuvant surfactant will typically vary from 0.01 to 1.0 percent by volume, based on a spray-volume of water, preferably 0.05 to 0.5 volume percent.
  • Suitable adjuvant surfactants include, but are not limited to ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulfosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines, blends of surfactants with mineral or vegetable oils, crop oil concentrate (mineral oil (85%) + emulsifiers (15%)); nonylphenol ethoxylate;
  • benzylcocoalkyldimethyl quaternary ammonium salt blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; Cg-Cn alkylpolyglycoside; phosphated alcohol ethoxylate; natural primary alcohol( Ci 2 -Ci 6 ) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate + urea ammonium nitrrate;
  • the formulations may also include oil-in-water emulsions such as those disclosed in U.S. Patent Application Serial No. 11/495,228, the disclosure of which is expressly incorporated by reference herein.
  • the formulations may optionally include combinations that contain other pesticidal compounds.
  • additional pesticidal compounds may be fungicides, insecticides, herbicides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present invention in the medium selected for application, and not antagonistic to the activity of the present compounds. Accordingly, in such
  • the other pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use.
  • the compounds of Formula I and the pesticidal compound in the combination can generally be present in a weight ratio of from 1 : 100 to 100 : 1.
  • the compounds of the present disclosure may also be combined with other fungicides to form fungicidal mixtures and synergistic mixtures thereof.
  • the fungicidal compounds of the present disclosure are often applied in conjunction with one or more other fungicides to control a wider variety of undesirable diseases.
  • the presently claimed compounds may be formulated with the other fungicide(s), tank mixed with the other fungicide(s) or applied sequentially with the other fungicide(s).
  • Such other fungicides may include (RS)-N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide, 1 ,2-dichloropropane, 1 ,3- dichloro-l , l ,3,3-tetrafluoroacetone hydrate, l-chloro-2,4-dinitronaphthalene, l-chloro-2- nitropropane, 2-(2-heptadecyl-2-imidazolin- 1 -yl)ethanol, 2,3-dihydro-5-phenyl-l ,4-dithi-ine 1 ,1 ,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride, 2- methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop- 1 - eny
  • carbendazim benzenesulfonate carbendazim sulfite, carboxin, carpropamid, carvacrol, carvone, CECA, Cheshunt mixture, chinomethionat, chitosan, chlazafenone, chlobenthiazone, chloraniformethan, chloranil, chlorfenazole, chlorodimtronaphthalenes, chlorquinox, chloroneb, chloropicrin, chlorothalonil, chlozolinate, climbazole, clotrimazole, Coniothyrium minitans, copper acetate, copper bis(3-phenylsalicylate), copper carbonate, basic, copper hydroxide, copper naphthenate, copper octanoate, copper oleate, copper oxychloride, copper silicate, copper sulfate, copper sulfate (tribasic), copper zinc chromate, coumoxystrobin, cresol, cufraneb, cupric
  • the compounds of the present invention may be combined with other pesticides, including insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present invention in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof.
  • the fungicidal compounds of the present disclosure may be applied in conjunction with one or more other pesticides to control a wider variety of undesirable pests.
  • the presently claimed compounds may be formulated with the other pesticide(s), tank mixed with the other pesticide(s) or applied sequentially with the other pesticide(s).
  • Typical insecticides include, but are not limited to: 1 ,2-dichloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos- ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cy
  • the compounds of the present invention may be combined with herbicides that are compatible with the compounds of the present invention in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof.
  • the fungicidal compounds of the present disclosure may be applied in conjunction with one or more herbicides to control a wide variety of undesirable plants.
  • the presently claimed compounds may be formulated with the herbicide(s), tank mixed with the herbicide(s) or applied sequentially with the herbicide(s).
  • Typical herbicides include, but are not limited to: 4-CPA, 4-CPA- potassium, 4-CPA-sodium; 4-CPB; 4-CPP; 2,4-D, 2,4-D-ethyl, 2,4-D-heptylammonium, 2,4-D- isobutyl, 2,4-D-isoctyl, 2,4-D-isopropyl, 2,4-D-isopropylammonium, 2,4-D-lithium, 2,4-D- meptyl, 2,4-D-methyl, 2,4-D-octyl, 2,4-D-pentyl, 2,4-D-potassium, 2,4-D-propyl, 2,4-D-sodium, 2,4-D-tefuryl, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium, 2,4-D-tris(2- hydroxypropyl)ammonium, 2,4-D-t
  • aminocyclopyrachlor aminocyclopyrachlor, aminocyclopyrachlor-methyl, aminocyclopyrachlor- potassium,aminopyralid, aminopyralid-potassium, aminopyralid-tris(2- hydroxypropyl)ammonium, amiprofos-methyl, amiprophos, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, asulam-potassium, asulam-sodium, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, benazolin- dimethylammonium, benazolin-ethyl, benazolin-potassium, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulfuron-methyl, bensulide, benthiocarb, bentazone
  • chlorflurenol chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlornidine, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorprocarb, chlorpropham, chlorsulfuron, chlorthal, chlorthal-dimethyl, chlorthal-monomethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clacyfos, clethodim, cliodinate, clodinafop, clodinafop- propargyl, clofop, clofop-isobutyl,clomazone, clomeprop, cloprop, cloproxydim, clopyralid, clopyralid-methyl, clopyralid-olamine, clopyralid-potassium, clopyralid-tris(
  • sulfentrazone sulfometuron, sulfometuron-methyl, sulfosate, sulfosulfuron, sulfuric acid, sulglycapin, swep, tavron, TCA, TCA-ammonium, TCA-calcium, TCA-ethadyl, TCA- magnesium, TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl,
  • Another embodiment of the present disclosure is a method for the control or prevention of fungal attack.
  • This method comprises applying to the soil, plant, roots, foliage, seed or locus of the fungus, or to a locus in which the infestation is to be prevented (for example applying to cereal plants), a fungicidally effective amount of one or more of the compounds of Formula I.
  • the compounds are suitable for treatment of various plants at fungicidal levels, while exhibiting low phytotoxicity.
  • the compounds may be useful both in a protectant and/or an eradicant fashion.
  • the compounds have been found to have significant fungicidal effect particularly for agricultural use. Many of the compounds are particularly effective for use with agricultural crops and horticultural plants. Additional benefits may include, but are not limited to, improving the health of a plant; improving the yield of a plant (e.g. increased biomass and/or increased content of valuable ingredients); improving the vigor of a plant (e.g. improved plant growth and/or greener leaves); improving the quality of a plant (e.g. improved content or composition of certain ingredients); and improving the tolerance to abiotic and/or biotic stress of the plant.
  • the compounds have broad ranges of activity against fungal pathogens.
  • Exemplary pathogens may include, but are not limited to, wheat leaf blotch (Septoria tritici, also known as Mycosphaerella graminicola), apple scab (Venturia inaequalis), and Cercospora leaf spots of sugar beets (Cercospora beticola), leaf spots of peanut (Cercospora arachidicola and Cercosporidium personation) and other crops, and black sigatoka of bananas (Mycosphaerella fujiensis).
  • the exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage of growth thereof, as well as the part of the plant or other product to be contacted with the compound. Thus, all the compounds, and formulations containing the same, may not be equally effective at similar concentrations or against the same fungal species.
  • the compounds are effective in use with plants in a disease-inhibiting and phytologically acceptable amount.
  • the term "disease-inhibiting and phytologically acceptable amount” refers to an amount of a compound that 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 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm being preferred.
  • the exact amount of a 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.
  • a suitable application rate is typically in the range from about 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per square meter, g/m 2 ).
  • the compounds of Formula I may be made using well-known chemical procedures. Intermediates not specifically mentioned in this disclosure are either commercially available, may be made by routes disclosed in the chemical literature, or may be readily synthesized from commercial starting materials utilizing standard procedures.
  • Example 1 Preparation of (£ ' )-5-fluoro-l-((4-methoxypheny])sulfonyl)-3- methyl-4-(niethylimino)-3,4-dihydropyrimidin-2(l/ )-one (Fl)
  • Example 5 Preparation of methyl (5-fluoro-l-((4-methoxyphenyl)sulfonyl)-
  • Example 7 Preparation of 5-fluoro-4-((2-fluorobenzyl)imino)-l-((4- methoxyphenyl)sulfony -3-methy]-3,4-dihydropyrimidin-2(lH)-one (F53)
  • Example 10 Preparation of 5-fluoro-l-((4-methoxyphenyl)sulfonyl)-3- trideuteriomethyl-4-(trideuteriomethylimino)-3,4-dihydropyrimidin-2(lH)-one (F63)
  • Example 16 Evaluation of Fungicidal Activity: Leaf Blotch of Wheat
  • the following table presents the activity of typical compounds of the present disclosure when evaluated in these experiments.
  • the effectiveness of the test compounds in controlling disease was determined by assessing the severity of disease on treated plants, then converting the severity to percent control based on the level of disease on untreated, inoculated plants.

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Abstract

This present disclosure is related to the field of 3-alkyl-5-fluoro-4-substituted-imino-3,4-5 dihydropyrimidin-2(1 H)-ones and their derivatives and to the use of these compounds as fungicides. Also provided are methods of controlling a fungal disease such as Septoria tritici, comprising administering an effective amount of the fungicide compound to at lease one surface associated with the plant, seed or soil.

Description

3-ALKYL-5-FLUORO-4-SUBSTITUTED-IMINO-3,4-DIHYDROPYRIMIDIN-2(lH)-
ONE DERIVATIVES AS FUNGICIDES
Cross Reference To Related Applications
[0001 ] This application claims the benefit of U.S. Provisional Patent Application Serial
No. 61/747683 filed December 31 , 2012, which is expressly incorporated by reference herein.
Background and Summary of the Invention
[0002] Fungicides are compounds, of natural or synthetic origin, which act to protect and/or cure plants against damage caused by agriculturally relevant fungi. Generally, no single fungicide is useful in all situations. Consequently, research is ongoing to produce fungicides that may have better performance, are easier to use, and cost less.
[0003] The present disclosure relates to 3-alkyl-5-fluoro-4-imino-3,4-dihydropyrimidin-
2(lH)one compounds and their use as fungicides. The compounds of the present disclosure may offer protection against ascomycetes, basidiomycetes, deuteromycetes and oomycetes.
[0004] One embodiment of the present disclosure may include compounds of Formula I:
Figure imgf000002_0001
Formula I wherein R1 is:
C1-C6 alkyl optionally substituted with 1-3 R4
-C(=0)R5;
-C(=0)OR5;
-CH2OC(=0)R5; or
-(CHR8)nR7;
R2 is:
C1-C6 alkyl optionally substituted with 1-3 R6
-C(=0)R7; -C(=0)OR7; or
-(CHR8)nR7;
wherein n is an integer from 1-3.; R3 is -S(0)2R9;
R4 is independently C1-C6 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 haloalkylthio, amino, C1-C3 alkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C2-C6 alkylaminocarbonyl, hydroxyl, deuterium, or C3-C6 trialkylsilyl;
R5 is H, C1-C6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxyalkyl, phenyl or benzyl wherein each of the phenyl or the benzyl may be optionally substituted with 1-3 R10, or with a 5- or 6-membered saturated or unsaturated ring system, or with a 5-6 fused ring system, or with a 6-6 fused ring system each containing 1-3 heteroatoms wherein each ring may be optionally substituted with 1-3 R10, biphenyl or naphthyl optionally substituted with 1-3 R10;
R6 is independently halogen, C1-C6 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, d- C4 alkylthio, C1-C4 haloalkylthio, amino, C1-C3 alkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C2-C6 alkylaminocarbonyl, hydroxyl, deuterium, or C3-C6 trialkylsilyl;
R7 is H, C1-C6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxyalkyl, phenyl or benzyl wherein each of the phenyl or the benzyl may be optionally substituted with 1-3 R10, or with a 5- or 6-membered saturated or unsaturated ring system, or with a 5-6 fused ring system, or with a 6-6 fused ring system each containing 1-3 heteroatoms wherein each ring may be optionally substituted with 1-3 R10, biphenyl or naphthyl optionally substituted with 1-3 R10;
R8 is H, Ci-C6 alkyl, or Ci-C6 haloalkyl;
R9 is C1-C6 alkyl, C1-C6 haloalkyl, amino, C1-C6 alkylamino, C2-C6 dialkylamino, a phenyl or benzyl wherein each of the phenyl or the benzyl may be optionally substituted with 1- 3 R10, or a 5- or 6-membered saturated or unsaturated ring containing 1-3 heteroatoms wherein each ring may be optionally substituted with 1-3 R , or with a 5-6 fused ring system, or with a 6-6 fused ring system each containing 1-3 heteroatoms wherein each ring may be optionally substituted with 1-3 R10, biphenyl or naphthyl optionally substituted with 1-3 R10; and R10 is independently halogen, C1-C6 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, Ci- C4 alkylthio, C1-C4 haloalkylthio, amino, Ci-C6 alkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C2-C6 alkylaminocarbonyl, C2-C6 dialkylamino, hydroxy, cyano, or nitro.
[0005] In a further embodiment, R4 is independently C1-C6 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, hydroxyl, or deuterium.
[0006] In still another embodiment, R5 is C1-C6 alkyl, C1-C6 haloalkyl, phenyl or benzyl wherein each of the phenyl or the benzyl may be optionally substituted with 1-3 R10.
[0007] In yet another embodiment, R6 is independently halogen, Ci-C6 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 alkylthio, or deuterium.
[0008] In another embodiment, R7 is C1-C6 alkyl, C1-C6 haloalkyl, phenyl or benzyl wherein each of the phenyl or the benzyl may be optionally substituted with 1-3 R10.
[0009] Still, in another embodiment, R10 is independently halogen, C1-C6 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, cyano, or nitro.
[0010] In yet another embodiment, R9 is phenyl optionally substituted with 1- 3 R10 , or a 5- or 6-membered saturated or unsaturated ring containing 1-3 heteroatoms optionally substituted with 1-3 R10. In a further embodiment, R10 is independently halogen, C1-C6 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy.
[0011] In one embodiment, R1 is C1-C3 alkyl. In another embodiment, R2 is C1-C3 alkyl,
-C(=0)R5, or -C(=0)OR5. In a further embodiment, R5 is C1-C3 alkyl or phenyl. In another embodiment R1 is C1-C3 alkyl.
[0012] In another embodiment, R9 is selected from the group consisting of:
Figure imgf000005_0001
[0013] In a further embodiment, R2 is C1-C3 alkyl, -C(=0)R5, or -C(=0)OR5. In another further embodiment, R5 is C1-C3 alkyl or phenyl. In still another further embodiment, R1 is Ci- C3 alkyl.
[001 ] Also proposed is a compound according to Formula I, wherein R1 is: Ci-C6 alkyl optionally substituted with 1-3 R4;
-C(=0)R5; or
-CH2OC(=0)R5;
R2 is: Ci-C6 alkyl optionally substituted with 1-3 R5; -C(=0)R7; -C(=0)OR7; or - (CHR8)nR7;
R3 is -S(0)2R9;
R4 is hydroxyl, or deuterium;
R5 is C1-C6 alkyl, or phenyl;
R6 is deuterium;
R7 is C1-C6 alkyl, or phenyl optionally substituted with 1-3 R10;
R8 is H; n is 1
R9 is Ci-C6 alkyl, or a phenyl optionally substituted with 1- 3 R10, or a 5- or 6-membered saturated or unsaturated ring containing 1 -3 heteroatoms wherein each ring may be optionally substituted with 1-3 R10; and
R10 is independently halogen, C1-C6 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, or cyano.
[0015] Also proposed is a composition for the control of a fungal pathogen, including; at least one compound of Formula I; and a phytologically acceptable carrier material, wherein said compositon is effective for the control of at least one pathogenic fungus or pathogenic fungus like organism. [0016] In a further embodiment, the pathogenic fungus or fungus like pathogen is
Septoria tritici.
[0017] Also proposed is a method for treating a plant, comprising the steps of: applying a fungicidally effective amount of at least one of the compounds of Formula 1 to at least one surface, selected from the group of surfaces consiting of: at least one portion of a plant, an area adjacent to a plant, soil in contact with a plant, soild adjacent to a plant, a seed, and agricultural equipment.
[0018] In a further embodiment, the fungicidally effective amount Formula I is applied to a surface in the range of about 0.01g/m2 to about 0.45 g/m2 of Formula I.
[0019] Another embodiment of the present disclosure may include a fungicidal composition for the control or prevention of fungal attack comprising the compounds described below and a phytologically acceptable carrier material.
[0020] Yet another embodiment of the present disclosure may include a method for the control or prevention of fungal attack on a plant, the method including the steps of applying a fungicidally effective amount of one or more of the compounds described below to at least one of the fungus, the plant, an area adjacent to the plant, and the seed adapted to produce the plant.
[0021 ] The term "alkyl" refers to a branched, unbranched, or cyclic carbon chain, including methyl, ethyl, propyl, butyl, isopropyl, isobutyl, tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
[0022] The term "alkenyl" refers to a branched, unbranched or cyclic carbon chain containing one or more double bonds including ethenyl, propenyl, butenyl, isopropenyl, isobutenyl, cyclohexenyl, and the like.
[0023] The term "alkynyl" refers to a branched or unbranched carbon chain containing one or more triple bonds including propynyl, butynyl and the like.
[0024] As used throughout this specification, the term 'R' refers to the group consisting of Ci-8 alkyl, C -8 alkenyl or C -8 alkynyl, unless stated otherwise.
[0025] The term "alkoxy" refers to an -OR substituent.
[0026] The term "alkoxycarbonyl" refers to a -C(0)-OR substituent. [0027] The term "alkylcarbonyl" refers to a -C(0)-R substituent.
[0028] The term "alkylsulfonyl" refers to an -S02-R substituent.
[0029] The term "alkylthio" refers to an -S-R substituent.
[0030] The term "halothio" refers to a sulfur substituted with three or five F substituents.
[0031 ] The term "halo alkylthio" refers to an alkylthio, which is substituted with CI, F, I, or Br or any combination thereof.
[0032] The term "alkylaminocarbonyl" refers to a -C(0)-N(H)-R substituent.
[0033] The term "trialkylsilyl" refers to -SiR3.
[0034] The term "cyano" refers to a -C=N substituent.
[0035] The term "hydroxyl" refers to an -OH substituent.
[0036] The term "amino" refers to a -NH2 substituent.
[0037] The term "alkylamino" refers to a -N(H)-R substituent.
[0038] The term "dialkylamino" refers to a -NR2 substituent.
[0039] The term "alkoxyalkyl" refers to an alkoxy substitution on an alkyl.
[0040] The term "halogen" or "halo" refers to one or more halogen atoms, defined as F,
CI, Br, and I.
[0041 ] The term "nitro" refers to a -N02 substituent.
[0042] Unless specifically noted or clearly implied otherwise the term "about" refers to a range of values of plus or minus 10 percent, e.g. about 1 refers to the range 0.9 to 1.1.
[0043] Throughout the disclosure, reference to the compounds of Formula I is read as also including optical isomers and salts of Formula I, and hydrates thereof. Specifically, when Formula I contains a branched chain alkyl group, it is understood that such compounds include optical isomers and racemates thereof. Exemplary salts include: hydrochloride, hydrobromide, hydroiodide, and the like. Additionally, the compounds of Formula I may include tautomeric forms.
[0044] Certain compounds disclosed in this document can exist as one or more isomers.
It will be appreciated by those skilled in the art that one isomer may be more active than the others. The structures disclosed in the present disclosure are drawn in only one geometric form for clarity, but are intended to represent all geometric and tautomeric forms of the molecule. [0045] It is also understood by those skilled in the art that additional substitution is allowable, unless otherwise noted, as long as the rules of chemical bonding and strain energy are satisfied and the product still exhibits fungicidal activity.
[0046] Fungicidally effective amount of the compounds include amounts sufficient to kill or control true fungi, pseudo-fungi, and related organisms including water moulds.
[0047] Another embodiment of the present disclosure is a use of a compound of Formula
I, for protection of a plant against attack by a phytopathogenic organism or the treatment of a plant infested by a phytopathogenic organism, comprising the application of a compound of Formula I, or a composition comprising the compound to soil, a plant, a part of a plant, foliage, and/or seeds.
[0048] Additionally, another embodiment of the present disclosure is a composition useful for protecting a plant against attack by a phytopathogenic organism and/or treatment of a plant infested by a phytopathogenic organism comprising a compound of Formula I and a phytologically acceptable carrier material.
[0049] Additional features and advantages of the present invention will become apparent to those skilled in the art upon consideration of the following detailed description of the illustrative embodiments exemplifying the best mode of carrying out the invention as presently perceived.
Detailed Description of the Disclosure
[0050] The compounds of the present disclosure may be applied by any of a variety of known techniques, either as the compounds or as formulations comprising the compounds. For example, the compounds may be applied to the roots, seeds or foliage of plants for the control of various fungi, without damaging the commercial value of the plants. The materials may be applied in the form of any of the generally used formulation types, for example, as solutions, dusts, wettable powders, flowable concentrates, or emulsifiable concentrates.
[0051] Preferably, the compounds of the present disclosure are applied in the form of a formulation, comprising one or more of the compounds of Formula I with a phytologically acceptable carrier. Concentrated formulations may be dispersed in water, or other liquids, for application, or formulations may be dust-like or granular, which may then be applied without further treatment. The formulations can be prepared according to procedures that are
conventional in the agricultural chemical art. [0052] The present disclosure contemplates all vehicles by which one or more of the compounds may be formulated for delivery and use as a fungicide. Typically, formulations are applied as aqueous suspensions or emulsions. Such suspensions or emulsions may be produced from water-soluble, water suspendible, or emulsifiable formulations which are solids, usually known as wettable powders; or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or suspension concentrates. As will be readily appreciated, any material to which these compounds may be added may be used, provided it yields the desired utility without significant interference with the activity of these compounds as antifungal agents.
[0053] Wettable powders, which may be compacted to form water dispersible granules, comprise an intimate mixture of one or more of the compounds of Formula I, an inert carrier and surfactants. The concentration of the compound in the wettable powder may be from about 10 percent to about 90 percent by weight based on the total weight of the wettable powder, more preferably about 25 weight percent to about 75 weight percent. In the preparation of wettable powder formulations, the compounds may be compounded with any finely divided solid, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten, montmorillonite clays, diatomaceous earths, purified silicates or the like. In such operations, the finely divided carrier and surfactants are typically blended with the compound(s) and milled.
[0054] Emulsifiable concentrates of the compounds of Formula I may comprise a convenient concentration, such as from about 10 weight percent to about 50 weight percent of the compound, in a suitable liquid, based on the total weight of the concentrate. The compounds may be dissolved in an inert carrier, which is either a water-miscible solvent or a mixture of water-immiscible organic solvents, and emulsifiers. The concentrates may be diluted with water and oil to form spray mixtures in the form of oil-in- water emulsions. Useful organic solvents include aromatics, especially the high-boiling naphthalenic and olefmic portions of petroleum such as heavy aromatic naphtha. Other organic solvents may also be used, for example, terpenic solvents, including rosin derivatives, aliphatic ketones, such as cyclohexanone, and complex alcohols, such as 2-ethoxyethanol.
[0055] Emulsifiers which may be advantageously employed herein may be readily determined by those skilled in the art and include various nonionic, anionic, cationic and amphoteric emulsifiers, or a blend of two or more emulsifiers. Examples of nonionic emulsifiers useful in preparing the emulsifiable concentrates include the polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines or fatty acids with ethylene oxide, propylene oxides such as the ethoxylated alkyl phenols and carboxylic esters solubilized with the polyol or polyoxyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include the oil-soluble salts (e.g., calcium) of alkylaryl sulfonic acids, oil-soluble salts or sulfated polyglycol ethers and appropriate salts of phosphated polyglycol ether.
[0056] Representative organic liquids which may be employed in preparing the emulsiftable concentrates of the compounds of the present invention are the aromatic liquids such as xylene, propyl benzene fractions; or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate; kerosene; dialkyl amides of various fatty acids, particularly the dimethyl amides of fatty glycols and glycol derivatives such as the «-butyl ether, ethyl ether or methyl ether of diethylene glycol, the methyl ether of triethylene glycol, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; and the like. Mixtures of two or more organic liquids may also be employed in the preparation of the emulsiftable concentrate. Organic liquids include xylene, and propyl benzene fractions, with xylene being most preferred in some cases. Surface-active dispersing agents are typically employed in liquid formulations and in an amount of from 0.1 to 20 percent by weight based on the combined weight of the dispersing agent with one or more of the compounds. The formulations can also contain other compatible additives, for example, plant growth regulators and other biologically active compounds used in agriculture.
[0057] Aqueous suspensions comprise suspensions of one or more water-insoluble compounds of Formula I, dispersed in an aqueous vehicle at a concentration in the range from about 5 to about 0 weight percent, based on the total weight of the aqueous suspension.
Suspensions are prepared by finely grinding one or more of the compounds, and vigorously mixing the ground material into a vehicle comprised of water and surfactants chosen from the same types discussed above. Other components, 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 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.
[0058] Aqueous emulsions comprise emulsions of one or more water-insoluble pesticidally active ingredients emulsified in an aqueous vehicle at a concentration typically in the range from about 5 to about 50 weight percent, based on the total weight of the aqueous emulsion. If the pesticidally active ingredient is a solid it must be dissolved in a suitable water- immiscible solvent prior to the preparation of the aqueous emulsion. Emulsions are prepared by emulsifying the liquid pesticidally active ingredient or water-immiscible solution thereof into an aqueous medium typically with inclusion of surfactants that aid in the formation and stabilization of the emulsion as described above. This is often accomplished with the aid of vigorous mixing provided by high shear mixers or homogenizers.
[0059] The compounds of Formula I can also be applied as granular formulations, which are particularly useful for applications to the soil. Granular formulations generally contain from about 0.5 to about 10 weight percent, based on the total weight of the granular formulation of the compound(s), dispersed in an inert carrier which consists entirely or in large part of coarsely divided inert material such as attapulgite, bentonite, diatomite, clay or a similar inexpensive substance. Such formulations are usually prepared by dissolving the compounds in a suitable solvent and applying it to a granular carrier which has been preformed to the appropriate particle size, in the range of from about 0.5 to about 3 mm. A suitable solvent is a solvent in which the compound is substantially or completely soluble. Such formulations may also be prepared by making a dough or paste of the carrier and the compound and solvent, and crushing and drying to obtain the desired granular particle.
[0060] Dusts containing the compounds of Formula I may be prepared by intimately mixing one or more of the compounds 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 weight percent of the compounds, based on the total weight of the dust.
[0061] The formulations may additionally contain adjuvant surfactants to enhance deposition, wetting and penetration of the compounds onto the target crop and organism. These adjuvant surfactants may optionally be employed as a component of the formulation or as a tank mix. The amount of adjuvant surfactant will typically vary from 0.01 to 1.0 percent by volume, based on a spray-volume of water, preferably 0.05 to 0.5 volume percent. Suitable adjuvant surfactants include, but are not limited to ethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols, salts of the esters or sulfosuccinic acids, ethoxylated organosilicones, ethoxylated fatty amines, blends of surfactants with mineral or vegetable oils, crop oil concentrate (mineral oil (85%) + emulsifiers (15%)); nonylphenol ethoxylate;
benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; Cg-Cn alkylpolyglycoside; phosphated alcohol ethoxylate; natural primary alcohol( Ci2-Ci6) ethoxylate; di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap; nonylphenol ethoxylate + urea ammonium nitrrate;
emulsified methylated seed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amine ethoxylate (15 EO); PEG(400) dioleate-99. The formulations may also include oil-in-water emulsions such as those disclosed in U.S. Patent Application Serial No. 11/495,228, the disclosure of which is expressly incorporated by reference herein.
[0062] The formulations may optionally include combinations that contain other pesticidal compounds. Such additional pesticidal compounds may be fungicides, insecticides, herbicides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present invention in the medium selected for application, and not antagonistic to the activity of the present compounds. Accordingly, in such
embodiments, the other pesticidal compound is employed as a supplemental toxicant for the same or for a different pesticidal use. The compounds of Formula I and the pesticidal compound in the combination can generally be present in a weight ratio of from 1 : 100 to 100 : 1.
The compounds of the present disclosure may also be combined with other fungicides to form fungicidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure are often applied in conjunction with one or more other fungicides to control a wider variety of undesirable diseases. When used in conjunction with other fungicide(s), the presently claimed compounds may be formulated with the other fungicide(s), tank mixed with the other fungicide(s) or applied sequentially with the other fungicide(s). Such other fungicides may include (RS)-N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide, 1 ,2-dichloropropane, 1 ,3- dichloro-l , l ,3,3-tetrafluoroacetone hydrate, l-chloro-2,4-dinitronaphthalene, l-chloro-2- nitropropane, 2-(2-heptadecyl-2-imidazolin- 1 -yl)ethanol, 2,3-dihydro-5-phenyl-l ,4-dithi-ine 1 ,1 ,4,4-tetraoxide, 2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride, 2- methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine, 4-(2-nitroprop- 1 - enyl)phenyl thiocyanateme, N-3, 5-dichlorophenyl-succinimide, N-3-nitrophenylitaconimide, 2- (thiocyanatomethylthio)-benzothiazole, (3-ethoxypropyl)mercury bromide, 2- methoxyethylmercury chloride, 2-phenylphenol, 8-hydroxyquinoline sulfate, 8- phenylmercurioxyquinoline, acibenzolar, acibenzolar-S-methyl, acypetacs, acypetacs-copper, acypetacs-zinc, albendazole, aldimorph, allicin, allyl alcohol, ametoctradin, amisulbrom, amobam, Ampelomyces quisqualis, ampropylfos, anilazine, antimycin, asomate, aureofungin, azaconazole, azithiram, azoxystrobin, Bacillus subtilis, Bacillus subtilis strain QST713, barium polysulfide, Bayer 32394, benalaxyl, benalaxyl-M, benquinox, benodanil, benomyl, bentaluron, benthiavalicarb, benthiavalicarb-isopropyl, benthiazole, benzamacril, benzamacril-isobutyl, benzamorf, benzohydroxamic acid, benzovindiflupyr, benzylaminobenzene-sulfonate (BABS) salt, berberine, berberine chloride, bethoxazin, bicarbonates, bifujunzhi, binapacryl, biphenyl, bismerthiazol, bis(methylmercury) sulfate, bis(tributyltin) oxide, bitertanol, bithionol, bixafen, blasticidin-S, borax, Bordeaux mixture, boscalid, bromothalonil, bromuconazole, bupirimate, Burgundy mixture, buthiobate, butylamine, cadmium calcium copper zinc chromate sulfate, calcium polysulfide, Candida oleophila, captafol, captan, carbamorph, carbendazim,
carbendazim benzenesulfonate, carbendazim sulfite, carboxin, carpropamid, carvacrol, carvone, CECA, Cheshunt mixture, chinomethionat, chitosan, chlazafenone, chlobenthiazone, chloraniformethan, chloranil, chlorfenazole, chlorodimtronaphthalenes, chlorquinox, chloroneb, chloropicrin, chlorothalonil, chlozolinate, climbazole, clotrimazole, Coniothyrium minitans, copper acetate, copper bis(3-phenylsalicylate), copper carbonate, basic, copper hydroxide, copper naphthenate, copper octanoate, copper oleate, copper oxychloride, copper silicate, copper sulfate, copper sulfate (tribasic), copper zinc chromate, coumoxystrobin, cresol, cufraneb, cupric hydrazinium sulfate, cuprobam, cuprous oxide, cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil, cyprofuram, dazomet, dazomet-sodium, DBCP, debacarb, decafentin, dehydroacetic acid, diammonium ethylenebis- (dithiocarbamate), dichlofluanid, dichlone, dichloran, dichlorophen, dichlozoline, diclobutrazol, diclocymet, diclomezine, diclomezine-sodium, diethofencarb, diethyl pyrocarbonate, difenoconazole, difenzoquat ion, diflumetorim, dimetachlone, dimethirimol, dimethomorph, dimoxystrobin, dingjunezuo, diniconazole, diniconazole-M, dinobuton, dinocap, dinocap-4, dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon, diphenylamine, dipyrithione, disulflram, ditalimfos, dithianon, dithioether, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, dodemorph, dodemorph acetate, dodicin, dodicin hydrochloride, dodicin- sodium, dodine, dodine free base, drazoxolon, EBP, edifenphos, enestrobin, enestroburin, enoxastrobin, epoxiconazole, ESBP, etaconazole, etem, ethaboxam, ethirim, ethirimol, ethoxyquin, ethirimol, ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate, etridiazole, famoxadone, fenamidone, fenaminosulf, fenaminstrobin, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenjuntong, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin, fentin acetate, fentin chloride, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flufenoxystrobin, flumetover, flumorph, fluopicolide, fluopyram, fiuoroimide, fiuotrimazole, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, fluthiacet- methyl, fiutianil, flutolanil, flutriafol, fiuxapyroxad, folpet, formaldehyde, fosetyl, fosetyl- aluminium, fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole, furconazole-cis, furfural, furmecyclox, furophanate, Fusarium oxysporum, Gliocladium spp., glyodine, griseofulvin, guazatine, guazatine acetates, GY-81, halacrinate, Hercules 3944,
hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiofos, huanjunzuo, hydrargaphen, hymexazol, ICIA0858, imazalil, imazalil nitrate, imazalil sulfate, imibenconazole, iminoctadine, iminoctadine triacetate, iminoctadine tris(albesilate), inezin, iodocarb, iodomethane, ipconazole, ipfenpyrazolone, iprobenfos, iprodione, iprovalicarb, isopamphos, isoprothiolane, isopyrazam, isotianil, isovaledione, jiaxiangjunzhi, kasugamycin, kasugamycin hydrochloride hydrate, kejunlin, kresoxim-methyl, laminarin, lvdingjunzhi, mancopper, mancozeb, mandipropamid, maneb, mebenil, mecarbinzid, mefenoxam,
mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuric oxide, mercurous chloride, metalaxyl, metalaxyl-M, metam, metam-ammonium, metam-potassium, metam-sodium, metazoxolon, metconazole, methasulfocarb, methfuroxam, methyl bromide, methyl iodide, methyl isothiocyanate, methylmercury benzoate, methylmercury dicyandiamide, methylmercury pentachlorophenoxide, metiram, metominostrobin, metrafenone, metsulfovax, mildiomycin, milneb, moroxydine, moroxydine hydrochloride, mucochloric anhydride, myclobutanil, myclozolin, N-ethylmercurio-4-toluenesulfonanilide, N-(ethylmercury)-p-toluenesulphonanilide, nabam, natamycin, nickel bis(dimethyldithiocarbamate), nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone, ofurace, oleic acid (fatty acids), orysastrobin, osthol, oxadixyl, oxathiapiprolin, oxine-copper, oxpoconazole fumarate, oxycarboxin, parinol, pefurazoate, penconazole, pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate,
penthiopyrad, phenamacril, phenylmercuriurea, phenylmercury acetate, phenylmercury chloride, phenylmercury derivative of pyrocatechol, phenylmercury dimethyldithiocarbamate, phenylmercury nitrate, phenylmercury salicylate, Phlebiopsis gigantea, phosdiphen, phosphonic acid, phthalide, picoxystrobin, piperalin, polycarbamate, polyoxin B, polyoxins, polyoxorim, polyoxorim-zinc, potassium azide, potassium bicarbonate, potassium hydroxyquinoline sulfate, potassium polysulfide, potassium thiocyanate, probenazole, prochloraz, prochloraz-manganese, procymidone, propamidine, propamidine dihydrochloride, propamocarb, propamocarb hydrochloride, propiconazole, propineb, proquinazid, prothiocarb, prothiocarb hydrochloride, prothioconazole, pyracarbolid, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyridinitril, pyrifenox, pyrimethanil, pyriofenone, pyrisoxazole, pyroquilon, pyroxychlor, pyroxyfur, quinacetol, quinacetol sulfate, quinazamid, quinoclamine, quinconazole, quinoxyfen, quintozene, rabenzazole, Reynoutria sachalinensis extract, saisentong, salicylanilide, santonin, sedaxane, silthiofam, simeconazole, sodium 2- phenylphenoxide, sodium azide, sodium bicarbonate, sodium orthophenylphenoxide, sodium pentachlorophenoxide, sodium polysulfide, spiroxamine, Streptomyces griseoviridis, streptomycin, streptomycin sesquisulfate, SSF-109, sulfur, sultropen, SYP-Z048, tar oils, tebuconazole, tebufloquin, tecloftalam, tecnazene, tecoram, tetraconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, thiochlorfenphim, thiodiazole-copper, thiomersal, thiophanate, thiophanate-methyl, thioquinox, thiram, tiadinil, tioxymid, tolclofos-methyl, tolylfluanid, tolylmercury acetate, triadimefon, triadimenol, triamiphos, triarimol, triazbutil, triazoxide, tributyltin oxide, trichlamide, triclopyricarb, Trichoderma spp., tricyclazole, tridemorph, trifioxystrobin, triflumizole, triforine, triticonazole, uniconazole, uniconazole-P, urbacid, validamycin, valifenalate, valiphenal, vangard, vinclozolin, xiwojunan, zarilamid, zineb, zinc naphthenate, zinc thiazole, ziram, and zoxamide, and any combinations thereof.
[0063] Additionally, the compounds of the present invention may be combined with other pesticides, including insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof that are compatible with the compounds of the present invention in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more other pesticides to control a wider variety of undesirable pests. When used in conjunction with other pesticides, the presently claimed compounds may be formulated with the other pesticide(s), tank mixed with the other pesticide(s) or applied sequentially with the other pesticide(s). Typical insecticides include, but are not limited to: 1 ,2-dichloropropane, abamectin, acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin, allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan, amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos- ethyl, azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluron, borax, boric acid, bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, cinerin I, cinerin II, cinerins, cismethrin, cloethocarb, closantel, clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate, copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl, demeton-S, demeton-S-methyl, demeton- S-methylsulphon, diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, d- limonene, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate, EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane, eprinomectin, esdepallethrine, esfenvalerate, etaphos, ethiofencarb, ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazafior, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid, flubendiamide, flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, flufiprole, fluvalinate, fonofos, formetanate, formetanate
hydrochloride, formothion, formparanate, formparanate hydrochloride, fosmethilan, fospirate, fosthietan, furathiocarb, furethrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD, heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb, isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolin II, jodfenphos, juvenile hormone I, juvenile hormone II, juvenile hormone III, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane, lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox, mecarbam, mecarphon, menazon, meperfluthrin, mephosfolan, mercurous chloride, mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, methylchloroform, methylene chloride, metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, molosultap, monocrotophos, monomehypo, monosultap, morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, para- dichlorobenzene, parathion, parathion-metbyl, penfluron, pentachlorophenol, permethrin, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-metbyl, potassium arsenite, potassium thiocyanate, pp'-DDT, prallethrin, precocene I, precocene II, precocene III, primidophos, profenofos, profluralin, promacyl, promecarb, propaphos, propetamphos, propoxur, prothidathion, prothiofos, prothoate, protrifenbute, pyraclofos, pyrafluprole, pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins, pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos, quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan, selamectin, silaf uofen, silica gel, sodium arsenite, sodium fluoride, sodium hexafiuorosilicate, sodium thiocyanate, sophamide, spinetoram, spinosad, spiromesifen, spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep, sulfoxaflor, sulfuryl fluoride, sulprofos, tau-f uvalinate, tazimcarb, TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane, tetrachlorvinphos, tetramethrin, tetramethylfluthrin, theta-cypermethrin, thiacloprid,
thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon, thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene, triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, vaniliprole, XMC, xylylcarb, zeta-cypermethrin, zolaprofos, and any combinations thereof.
[0064] Additionally, the compounds of the present invention may be combined with herbicides that are compatible with the compounds of the present invention in the medium selected for application, and not antagonistic to the activity of the present compounds to form pesticidal mixtures and synergistic mixtures thereof. The fungicidal compounds of the present disclosure may be applied in conjunction with one or more herbicides to control a wide variety of undesirable plants. When used in conjunction with herbicides, the presently claimed compounds may be formulated with the herbicide(s), tank mixed with the herbicide(s) or applied sequentially with the herbicide(s). Typical herbicides include, but are not limited to: 4-CPA, 4-CPA- potassium, 4-CPA-sodium; 4-CPB; 4-CPP; 2,4-D, 2,4-D-ethyl, 2,4-D-heptylammonium, 2,4-D- isobutyl, 2,4-D-isoctyl, 2,4-D-isopropyl, 2,4-D-isopropylammonium, 2,4-D-lithium, 2,4-D- meptyl, 2,4-D-methyl, 2,4-D-octyl, 2,4-D-pentyl, 2,4-D-potassium, 2,4-D-propyl, 2,4-D-sodium, 2,4-D-tefuryl, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium, 2,4-D-tris(2- hydroxypropyl)ammonium, 2,4-D-trolamine; 2,4-D-2-butoxypropyl, 2,4-D choline salt, 2,4-D esters and amines; 2,4-D-2-ethylhexyl, 2,4-D-3-butoxypropyl, 2,4-D-ammonium; 2,4-DB, 2,4- DB-butyl, 2,4-DB-dimethylammonium, 2,4-DB-isoctyl, 2,4-DB-potassium, 2,4-DB-sodium, 2,4- D-butotyl, 2,4-D-butyl, 2,4-D-diethylammonium, 2,4-D-dimethylammonium, 2,4-D-diolamine, 2,4-D-dodecylammonium; 3,4-DA; 3,4-DB; 2,4-DEB; 2,4-DEP; 3,4-DP; 2,3,6-TBA; 2,3,6-TBA- dimethylammonium, 2,3,6-TBA-lithium, 2,3,6-TBA-potassium, 2,3,6-TBA-sodium, 2,4,5-T; 2,4,5-T-2-butoxypropyl, 2,4,5-T-2-ethylhexyl, 2,4,5-T-3-butoxypropyl; 2,4,5-TB, 2,4,5-T- butometyl, 2,4,5-T-butotyl, 2,4,5-T -butyl, 2,4,5 -T-isobutyl, 2,4,5-T-isoctyl, 2,4,5-T-isopropyl, 2,4,5-T-methyl, 2,4,5-T-pentyl, 2,4,5-T-sodium, 2,4,5-T-triethylammonium, 2,4,5-T-trolamine; acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, alloxydim-sodium, allyl alcohol, alorac, ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron,
aminocyclopyrachlor, aminocyclopyrachlor-methyl, aminocyclopyrachlor- potassium,aminopyralid, aminopyralid-potassium, aminopyralid-tris(2- hydroxypropyl)ammonium, amiprofos-methyl, amiprophos, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, asulam-potassium, asulam-sodium, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, benazolin- dimethylammonium, benazolin-ethyl, benazolin-potassium, bencarbazone, benfluralin, benfuresate, bensulfuron, bensulfuron-methyl, bensulide, benthiocarb, bentazone, bentazone- sodium, bentranil, benzadox, benzadox-ammonium, benzfendizone, benzipram, benzobicyclon, benzofenap, benzofluor, benzoylprop, benzoylprop-ethyl, benzthiazuron, bicyclopyrone, bifenox, bilanafos, bispyribac, bispyribac-sodium, borax, bromacil, bromacil-lithium, bromacil-sodium, bromobonil, bromobutide, bromofenoxim, bromoxynil, bromoxynil butyrate, bromoxynil heptanoate, bromoxynil octanoate, bromoxynil-potassium, brompyrazon, butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole chlorprocarb, carboxazole, carfentrazone, carfentrazone-ethyl, CDEA, CEPC, chlomethoxyfen, chloramben, chloramb en-ammonium, chloramben-diolamine, chloramb en-methyl, chloramben-methylammonium, chloramben-sodium, chloranocryl, chlorazifop, chlorazifop-propargyl, chlorazine, chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenac-ammonium, chlorfenac-sodium, chlorfenprop, chlorflurazole,
chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlornidine, chlornitrofen, chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorprocarb, chlorpropham, chlorsulfuron, chlorthal, chlorthal-dimethyl, chlorthal-monomethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, cisanilide, clacyfos, clethodim, cliodinate, clodinafop, clodinafop- propargyl, clofop, clofop-isobutyl,clomazone, clomeprop, cloprop, cloproxydim, clopyralid, clopyralid-methyl, clopyralid-olamine, clopyralid-potassium, clopyralid-tris(2- hydroxypropyl)ammonium, cloransulam, cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumyluron, cyanamide, cyanatryn, cyanazine, cycloate,
cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyhalofop-butyl, cyperquat, cyperquat chloride, cyprazine, cyprazole, cypromid, daimuron, dalapon, dalapon-calcium, dalapon- magnesium, dalapon-sodium, dazomet, dazomet-sodium, delachlor, desmedipham, desmetryn, di-allate, dicamba, dicamba-diglycolamine, dicamba-dimethylammonium, dicamba-diolamine, dicamba-isopropylammonium, dicamba-methyl, dicamba-olamine, dicamba-potassium, dicamba- sodium, dicamba-trolamine, dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-2- ethylhexyl, dichlorprop-butotyl, dichlorprop-dimethylammonium, dichlorprop-ethylammonium, dichlorprop-isoctyl, dichlorprop-methyl, dichlorprop-P, dichlorprop-P-2-ethylhexyl, dichlorprop- P-dimethylammonium, dichlorprop-potassium, dichlorprop-sodium, diclofop, diclofop-methyl, diclosulam, diethamquat, diethamquat dichloride, diethatyl, difenopenten, difenopenten-ethyl, difenoxuron, difenzoquat, difenzoquat metilsulfate, diflufenican, diflufenzopyr, diflufenzopyr- sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid- P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoseb acetate, dinoseb-ammonium, dinoseb-diolamine, dinoseb-sodium, dinoseb-trolamine, dinoterb, dinoterb acetate, diphenamid, dipropetryn, diquat, diquat dibromide, disul, disul-sodium, dithioether, dithiopyr, diuron, DMPA, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium, DSMA, EBEP, eglinazine, eglinazine-ethyl, endothal, endothal-diammonium, endothal- dipotassium, endothal-disodium, epronaz, EPTC, erbon, erlujixiancaoan, esprocarb, ethachlor, ethalfluralin, ethbenzamide, ethametsulfuron, ethametsulfuron-methyl, ethaprochlor,
ethidimuron, ethiolate, ethion, ethiozin, ethobenzamid, etobenzamid, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoprop-3- butoxypropyl, fenoprop-butometyl, fenoprop-butotyl, fenoprop-butyl, fenoprop-isoctyl, fenoprop-methyl, fenoprop-potassium, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop- P-ethyl, fenoxaprop-P-ethyl + isoxadifen-ethyl, fenoxasulfone, fenteracol, fenthiaprop, fentrazamide, fenuron, fenuron TCA, ferrous sulfate, flamprop, flamprop-isopropyl, fenthiaprop- ethyl, flamprop-M, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-butyl, fluazifop-methyl, fluazifop-P, fluazifop-P-butyl, fluazolate, flucarbazone, flucarbazone-sodium, fiucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr, flufenpyr-ethyl, flumetsulam, flumezin, flumiclorac, flumiclorac-pentyl, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoroglycofen- ethyl,fluoromidine, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate,
flupropanate-sodium, flupyrsulfuron, flupyrsulfuron-methyl, flupyrsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, flurtamone, fluthiacet, fomesafen, fomesafen-sodium,foramsulfuron, fosamine, fosamine-ammonium, fucaojing, fucaomi, funaihecaoling, furyloxyfen, glufosinate, glufosinate-ammonium, glufosinate-P, glufosinate-ammonium, glufosinate-P-sodium, glyphosate, glyphosate- diammonium, glyphosate-dimethylammonium, glyphosate-isopropylammonium, glyphosate- monoammonium, glyphosate-potassium, glyphosate-sesquisodium, glyphosate-trimesium, halosafen, halosulfuron, halosulfuron-methyl, haloxydine, haloxyfop, haloxyfop-etotyl, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-etotyl, haloxyfop-P-methyl, haloxyfop-sodium, herbimycin, hexachloroacetone, hexaflurate, hexazinone, huancaiwo, huangcaoling,
imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium,imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin- ammonium, imazaquin-methyl, imazaquin-sodium, imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan, indaziflam, iodobonil, iodomethane, iodosulfuron, iodosulfuron- methyl, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, ioxynil, ioxynil octanoate, ioxynil-lithium, ioxynil-sodium, ipazine, ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin, isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox, ketospiradox-potassium, kuicaoxi, lactofen, lenacil, linuron, lvxiancaolin, MAA, MAMA, MCPA, esters and amines, MCPA-2-ethylhexyl, MCPA-butotyl, MCPA-butyl, MCPA-dimethylammonium, MCPA- diolamine, MCPA-ethyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-methyl,
MCPA-olamine, MCPA-potassium, MCPA-sodium, MCPA-thioethyl, MCPA-trolamine, MCPB, MCPB-ethyl, MCPB-methyl, MCPB-sodium, mecoprop, mecoprop-2-ethylhexyl, mecoprop- dimethylammonium, mecoprop-diolamine, mecoprop-ethadyl, mecoprop-isoctyl, mecoprop- methyl, mecoprop-P, mecoprop-P-2-ethylhexyl, mecoprop-P-dimethylammonium, mecoprop-P- isobutyl, mecoprop-potassium, mecoprop-P-potassium, mecoprop-sodium, mecoprop-trolamine, medinoterb, medinoterb acetate, mefenacet, mefluidide, mefluidide-diolamine, mefluidide- potassium, mesoprazine, mesosulfuron, mesosulfuron-methyl, mesotrione, metam, metam- ammonium, metam-potassium, metam-sodium, metamifop, metamitron, metazachlor, metazosulfuron, metsulfuron-methyl, metflurazon, methabenzthiazuron, methalpropalin, methazole, methiobencarb, methiopyrisulfuron,methiozolin, methiuron, methometon, methoprotryne, methoxyphenone, methyl bromide, methyl iodide, methyl isothiocyanate, methyldymron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monosulfuron, monosulfuron-ester, monuron, monuron TCA, morfamquat, morfamquat dichloride, MSMA, naproanilide, napropamide, naptalam, naptalam-sodium, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen, norflurazon, noruron, OCH, orbencarb, ori/zo-dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon, oxapyrazon-dimolamine, oxapyrazon-sodium, oxasulfuron, oxaziclomefone, oxyfluorfen, paraflufen-ethyl, parafluron, paraquat, paraquat dichloride, paraquat dimetilsulfate, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron, phenylmercury acetate, picloram, picloram-2-ethylhexyl, picloram-isoctyl, picloram-methyl, picloram-olamine, picloram-potassium, picloram-triethylammonium, picloram- tris(2-hydroxypropyl)ammonium, picolinafen, pinoxaden, piperophos, potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron, primisulfuron-methyl, procyazine, prodiamine, profluazol, profluralin, profoxydim, proglinazine, proglinazine-ethyl, prohexadione-calcium, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, proxan, proxan-sodium, prynachlor, pydanon, pyraclonil, pyraflufen, pyrasulfotole, pyrazogyl, pyrazolynate, pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz-isopropyl, pyribambenz -propyl, pyribenzoxim, pyributicarb, pyriclor, pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyrithiobac-methyl, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quinonamid, quizalofop-ethyl, quizalofop, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, rhodethanil, rimsulfuron, saflufenacil, S-metolachlor, sebuthylazine, secbumeton, sethoxydim, shuangjiaancaolin, siduron, simazine, simeton, simetryn, SMA, S- metolachlor, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate,
sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosate, sulfosulfuron, sulfuric acid, sulglycapin, swep, tavron, TCA, TCA-ammonium, TCA-calcium, TCA-ethadyl, TCA- magnesium, TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiocarbazil, tioclorim, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, tricamba, triclopyr esters and amines, triclopyr-butotyl, triclopyr-ethyl, triclopyr- triethylammonium, tridiphane, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifluralin, trifiusulfuron, triflusulfuron-methyl, trifop, trifop-methyl, trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac, tritosulfuron, vernolate, xylachlor and zuomihuanglong.
[0065] Another embodiment of the present disclosure is a method for the control or prevention of fungal attack. This method comprises applying to the soil, plant, roots, foliage, seed or locus of the fungus, or to a locus in which the infestation is to be prevented (for example applying to cereal plants), a fungicidally effective amount of one or more of the compounds of Formula I. The compounds are suitable for treatment of various plants at fungicidal levels, while exhibiting low phytotoxicity. The compounds may be useful both in a protectant and/or an eradicant fashion.
[0066] The compounds have been found to have significant fungicidal effect particularly for agricultural use. Many of the compounds are particularly effective for use with agricultural crops and horticultural plants. Additional benefits may include, but are not limited to, improving the health of a plant; improving the yield of a plant (e.g. increased biomass and/or increased content of valuable ingredients); improving the vigor of a plant (e.g. improved plant growth and/or greener leaves); improving the quality of a plant (e.g. improved content or composition of certain ingredients); and improving the tolerance to abiotic and/or biotic stress of the plant.
[0067] It will be understood by those in the art that the efficacy of the compound for the foregoing fungi establishes the general utility of the compounds as fungicides.
[0068] The compounds have broad ranges of activity against fungal pathogens.
Exemplary pathogens may include, but are not limited to, wheat leaf blotch (Septoria tritici, also known as Mycosphaerella graminicola), apple scab (Venturia inaequalis), and Cercospora leaf spots of sugar beets (Cercospora beticola), leaf spots of peanut (Cercospora arachidicola and Cercosporidium personation) and other crops, and black sigatoka of bananas (Mycosphaerella fujiensis). The exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage of growth thereof, as well as the part of the plant or other product to be contacted with the compound. Thus, all the compounds, and formulations containing the same, may not be equally effective at similar concentrations or against the same fungal species.
[0069] The compounds are effective in use with plants in a disease-inhibiting and phytologically acceptable amount. The term "disease-inhibiting and phytologically acceptable amount" refers to an amount of a compound that 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 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm being preferred. The exact amount of a 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. A suitable application rate is typically in the range from about 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per square meter, g/m2).
[0070] Any range or desired value given herein may be extended or altered without losing the effects sought, as is apparent to the skilled person for an understanding of the teachings herein.
[0071 ] The compounds of Formula I may be made using well-known chemical procedures. Intermediates not specifically mentioned in this disclosure are either commercially available, may be made by routes disclosed in the chemical literature, or may be readily synthesized from commercial starting materials utilizing standard procedures.
[0072] The following examples are presented to illustrate the various aspects of the compounds of the present disclosure and should not be construed as limitations to the claims.
[0073] Example 1: Preparation of (£')-5-fluoro-l-((4-methoxypheny])sulfonyl)-3- methyl-4-(niethylimino)-3,4-dihydropyrimidin-2(l/ )-one (Fl)
Figure imgf000024_0001
5-fluoro-4-imino-l-((4-methoxyphenyl)sulfonyl)-3,4-dihydropyrimidin-2(lH)-one (1.8 g, 6.01 mmol, prepared as described in WO 2011/017547) was stirred at room temperature in dimethylformamide (DMF, 10 mL) under a blanket of nitrogen. Anhydrous potassium carbonate (K2CO3, 1.662 g, 12.03 mmol), and iodomethane (0.562 mL, 9.02 mmol) were added. The reaction mixture was stirred at ambient temperature for 3 days (d), poured onto ice water, and extracted with ethyl acetate (EtOAc, 4 x 50 mL). The combined organic fractions were washed with saturated NaCl solution (100 mL), dried over anhydrous magnesium sulfate (MgS04), filtered and evaporated to yield the crude product mixture as a yellow solid (2 g). The crude mixture was purified by silica gel chromatography using a 0- 100% EtOAc/hexanes gradient to provide the title compound as a white solid (0.16 g, 8.1%). Characterization data for this compound is listed in Table 2.
[0074] Example 2: Preparation of V-(5-fluoro-l-((4-methoxyphenyl)sulfonyl)-2-oxo- 2,3-dihydropyrimidin-4(lH)-ylidene)acetamide
Figure imgf000025_0001
A dry 100 mL round bottom flask equipped with magnetic stirrer and nitrogen inlet was charged with 4-amino-5-fluoro-l-((4-methoxyphenyl)sulfonyl)pyrimidin-2(lH)-one (1.0 g, 3.34 mmol) and 50 mL of anhydrous acetonitrile (CH3CN). To this solution was added anhydrous pyridine (0.27 mL, 3.34 mmol) followed by acetic anhydride (0.35 mL, 3.68 mmol). The reaction was stirred at ambient temperature for 17 hours (h). The reaction mixture was concentrated and the residue was chromatographed by silica gel flash chromatography eluting with a gradient of 100%> hexane to 100% ethyl acetate (EtOAc). The pure fractions were combined and concentrated under vacuum on a rotary evaporator to afford N-(5-fluoro-l-((4-methoxyphenyl)sulfonyl)-2- oxo-2,3-dihydropyrimidin-4(lH)-ylidene)acetamide as a white solid (770 mg, 67.5%): !H NMR
(400 MHz, DMSO- e) δ 10.82 (s, 1H), 8.61 (d, J= 6.1 Hz, 1H), 8.09 - 7.98 (m, 2H), 7.31 - 7.17 (m, 2H), 3.88 (s, 3H), 2.27 (s, 3H).
[0075] Example 3: Preparation of V-(5-fluoro-l-((4-methoxyphenyl)sulfonyl)-3- methyl-2-oxo-2,3-dihydropyrimidin-4(lH)-ylidene)acetamide (F31)
Figure imgf000026_0001
A dry 50 mL round bottom flask equipped with magnetic stirrer and nitrogen inlet was charged with N-(5-fluoro-l-((4-methoxyphenyl)sulfonyl)-2-oxo-2,3-dihydropyrimidin-4(lH)- ylidene)acetamide (0.5 g, 1.465 mmol) and 10 mL of anhydrous N,N-dimethyl formamide (DMF). To this solution was added powdered lithium carbonate (216 mg, 2.93 mmol) followed by iodomethane (182 μΐ^, 2.93 mmol). The reaction was stirred at ambient temperature for 12 hours. Additional lithium carbonate (108 mg, 1.465 mmoles) and iodomethane (91 \L, 1.465 mmoles) were added, and the reaction was stirred at ambient temperature for another two hours. The reaction mixture was poured into 50 mL of dichloromethane (CH2CI2 DCM), and washed with 20 mL of water and 20 mL of saturated aqueous sodium chloride solution. The organic extract was dried over anhydrous magnesium sulfate (MgS04), filtered, and concentrated under vacuum on a rotary evaporator. The resulting crude product was purified by silica gel flash chromatography eluting with a gradient of 100% hexane to 100% ethyl acetate. The pure fractions were combined and concentrated under vacuum on a rotary evaporator to afford the title compound as a white solid (298 mg, 57.2%). Characterization data for this compound is listed in Table 2.
[0076] The following compounds were prepared as described in US 2011/0263627 Al , and were used to make the compounds prepared as in Examples 4, 5 and 6:
Figure imgf000026_0002
[0077] 5-fluoro-4-imino-3-methyl-l-tosy]-3,4-dihydropyrimidin-2(lH)-one (1 19 mg,
56%): mp 148.9-150.2 °C; 1H NMR (300 MHz, DMSO- ) δ 8.54 (br s, 1H), 7.99 (d, J= 6.0 Hz, 1H), 7.93 (d, J= 8.2 Hz, 2H), 7.49 (d, J= 8.6 Hz, 2H), 3.12 (s, 3H), 2.43 (s, 3H); ESIMS m/z 297.1 ([M]+).
Figure imgf000027_0001
[0078] 5-fluoro-4-imino-3-niethyl-l-(m-tolylsulfony])-3,4-dihydropyrimidin-2(l/ )- one (60 mg, 30%): mp 198.6-199.9 °C; XH NMR (300 MHz, DMSO-Js) δ 2.42 (s, 3H), 3.13 (s, 3H), 7.54-7.61 (m, 2H), 7.83-7.86 (m, 2H), 7.99 (d, J= 5.9 Hz, 1H), 8.56 (br s, 1H); ESIMS m/z 297.1 ([M]+).
Figure imgf000027_0002
[0079] l-(4-chloro-2,5-dimethylphenylsulfonyl)-5-fluoro-4-imino-3-methyl-3,4- dihydropyrimidin-2(lH)-one (53 mg, 26%): mp 145.0-147.0 °C; 1H MR (300 MHz, DMSO d6) δ 8.60 (br s, 1H), 8.04 (d, J= 6.2 Hz, 1H), 8.03 (s, 1H), 7.61 (s, 1H), 3.12 (s, 3H), 2.45 (s, 3H), 2.40 (s, 3H); ESIMS m/z 345.0 ([M]+).
Figure imgf000027_0003
[0080] l-(2,5-dichlorothiophen-3-ylsulfonyl)-5-fluoro-4-imino-3-methyl-3,4- dihydropyrimidin-2(lH)-one (22 mg, 11%): mp 261.1-263.4 °C; 'H NMR (300 MHz, DMSO- d6) δ 8.70 (br s, 1H), 7.94 (d, J= 5.8 Hz, 1H), 7.63 (s, 1H), 3.18 (s, 3H); ESIMS m/z 356.9 ([M]+).
[0081 ] Example 4: Preparation of V-(5-fluoro-l-((4-methoxyphenyl)sulfonyl)-3- methyl-2-oxo-2,3-dihydropyrimidin-4(lH)-ylidene)acetamide (F31)
Figure imgf000028_0001
To a solution of 5-fluoro-4-imino-l-((4-methoxyphenyl)sulfonyl)-3-methyl-3,4- dihydropyrimidin-2(lH)-one (0.100 g, 0.319 mmol, prepared as described in US 2011/0263627 Al) in CH2C12 (5 ml) at 0 °C was added pyridine (0.03 mL, 0.383 mmol) followed by acetyl chloride (0.025 mL, 0.351 mmol). The reaction mixture was warmed to room temperature and stirred for 16 h. The solvent was evaporated under reduced pressure and the residue was purified by means of column chromatography on silica gel (hexanes/EtOAc, 7/3) in order to obtain the title compound as a white solid (0.077 g, 68%). Characterization data for this compound is listed in Table 2.
[0082] Example 5: Preparation of methyl (5-fluoro-l-((4-methoxyphenyl)sulfonyl)-
3-methyl-2-oxo-2,3-dihydropyrimidin-4(lH)-ylidene)carbamate (F27)
Figure imgf000028_0002
To a solution of 5-fluoro-4-imino-l-((4-methoxyphenyl)sulfonyl)-3-methyl-3,4- dihydropyrimidin-2(lH)-one (0.170 g, 0.530 mmol) in DCM (12 mL) at -10 °C was added pyridine (0.340 mL, 4.240 mmol) followed by methyl chloroformate (0.330 mL, 4.240 mmol). The reaction mixture was stirred at -10 °C for 48 h. The solvent was evaporated under reduced pressure and the residue was purified by means of column chromatography on silica gel
(hexanes/EtOAc, 7/3) in order to obtain the title compound as white solid (0.080 g, 40%).
Characterization data for this compound is listed in Table 2.
[0083] Example 6: Preparation of phenyl (5-fluoro-l-((4-methoxyphenyl)sulfonyl)-3- methyl-2-oxo-2,3-dihydropyrimidin-4(lH)-ylidene)carbamate (F24)
Figure imgf000029_0001
To a solution of 5-fluoro-4-imino-l-((4-methoxyphenyl)sulfonyl)-3-methyl-3,4- dihydropyrimidin-2(lH)-one (0.110 g, 0.350 mmol) in DCM (8 mL) at 0 °C was added pyridine (0.034 mL, 0.420 mmol) followed by phenyl chloroformate (0.05 mL, 0.385 mmol). The reaction mixture was warmed to room temperature and stirred for 16 h. The solvent was evaporated under reduced pressure and the residue was purified by means of column chromatography on silica gel (hexanes/EtOAc, 7/3) in order to obtain the title compound as a white solid (0.110 g, 72%). Characterization data for this compound is listed in Table 2.
[0084] Example 7: Preparation of 5-fluoro-4-((2-fluorobenzyl)imino)-l-((4- methoxyphenyl)sulfony -3-methy]-3,4-dihydropyrimidin-2(lH)-one (F53)
Figure imgf000029_0002
A solution of 5-fluoro-4-imino-l-((4-methoxyphenyl)sulfonyl)-3-methyl-3,4-dihydropyrimidin- 2(lH)-one (0.219 g, 0.700 mmol) and potassium carbonate (0.290 g, 2.100 mmol) in 2- fluorobenzylbromide (2.5 mL, 21.0 mmol) in a sealed vial was placed in a Biotage Initiator microwave reactor for 16 h at 100 °C, with external IR-sensor temperature monitoring from the side of the vessel. The reaction mixture was concentrated under vacuum and the residue was purified by means of column chromatography on silica gel (hexanes/EtOAc, 6/4) in order to obtain the title compound as an off-white solid (0.058 g, 22%). Characterization data for this compound is listed in Table 2.
[0085] Example 9: Preparation of 5-fluoro-l-(phenylsulfonyl)-3-trideuteriomethyl-
4-(trideuteriomethy]imino)-3,4-dihydropyrimidin-2(lH)-one (F61)
Figure imgf000030_0001
To a dry suspension of 4-amino-5-fluoro-l-(phenylsulfonyl)pyrimidin-2(lH)-one (600 mg, 2.29 mmol) and lithium carbonate (333 mg, 4.51 mmol) in DMF (7 mL), was added trideuteriomethyl iodide (807 mg, 5.64 mmol). The reaction mixture was heated at 45 °C for 3.5 h. The reaction mixture was cooled to room temperature and partitioned between EtOAc (10 mL) and saturated aqueous sodium chloride solution (10 mL). The layers were separated and the aqueous fraction re-extracted with EtOAc (10 mL). The organic layers were combined, washed with brine (4 x 10 mL), dried ( a2SO/i), concentrated, and the residue was purified by silica gel flash
chromatography eluting with a gradient of 100% hexane to 80% ethyl acetate. The pure fractions were combined and concentrated under vacuum on a rotary evaporator to afford the title compound as a white solid (23 mg, 3.6%). Characterization data for this compound is listed in Table 2.
[0086] Example 10: Preparation of 5-fluoro-l-((4-methoxyphenyl)sulfonyl)-3- trideuteriomethyl-4-(trideuteriomethylimino)-3,4-dihydropyrimidin-2(lH)-one (F63)
Figure imgf000030_0002
To a dry suspension of 4-amino-5-fluoro-l-((4-methoxyphenyl)sulfonyl)pyrimidin-2(lH)-one (1.11 g, 3.70 mmol) and lithium carbonate (410 mg, 5.55 mmol) in DMF (7 mL), was added trideuteriomethyl iodide (1.36 g, 9.40 mmol). The reaction mixture was heated at 50 °C for 2 h. The reaction mixture was cooled to room temperature and partitioned between EtOAc (10 mL) and saturated aqueous sodium chloride solution (10 mL). The layers were separated and the aqueous fraction re-extracted with EtOAc (10 mL). The organic layers were combined, washed with brine (4 x 10 mL), dried (Na2S04), concentrated, and the residue was purified by silica gel flash chromatography eluting with a gradient of 100% hexane to 80% ethyl acetate. The pure fractions were combined and concentrated under vacuum on a rotary evaporator to afford the title comopund as a white solid (15 mg, 2.5%). Characterization data for this compound is listed in Table 2.
[0087] Example 11: Preparation of 5-fluoro-l-((4-methylphenyl)sulfonyl)-3- trideuteriomethyl-4-(trideuteriomethylimino)-3,4-dihydropyrimidin-2(l )-one (F62)
Figure imgf000031_0001
To a dry suspension of 4-amino-5-fluoro-l-((4-methylphenyl)sulfonyl)pyrimidin-2(lH)-one (322 mg, 2.22 mmol) and lithium carbonate (333 mg, 4.51 mmol) in DMF (7 mL), was added trideuteriomethyl iodide (5.64 mmol, 807 mg). The reaction mixture was heated at 50 °C for 4 h. The reaction mixture was cooled to room temperature and partitioned between EtOAc (10 mL) and saturated aqueous sodium chloride solution (10 mL). The layers were separated and the aqueous fraction re-extracted with EtOAc (10 mL). The organic layers were combined, washed with brine (4 x 10 mL), dried (Na2SC>4), concentrated, and the residue was purified by silica gel flash chromatography eluting with a gradient of 100% hexane to 80% ethyl acetate. The pure fractions were combined and concentrated under vacuum on a rotary evaporator to afford the title compound as a white solid (10 mg, 1.5% yield). Characterization data for this compound is listed in Table 2.
[0088] Example 12: Preparation of (E)-7V-(3-benzoyl-5-fluoro-2-oxo-l-tosyl-2,3- dihydropyrimidin-4(lH)-ylidene)benzamide (F37)
Figure imgf000032_0001
A suspension of 4-amino-5-fluoro-l-tosylpyrimidin-2(lH)-one (500 mg, 1.77 mrnol), triethylamine (714 mg, 7.06 mmol) and dioxane (2.5 ml) was stirred at room temperature.
Benzoyl chloride (0.40 ml, 3.4 mmol) was added dropwise, giving the mixture a light reddish cast. The reaction was stirred overnight at room temperature. The dark brown mixture was diluted with water and extracted with dichloromethane. The combined organic layers were dried over sodium sulfate, and concentrated. The residue was purified by normal phase
chromatography (gradient, 10 to 60% EtOAC/hexane) and triturated in ethyl acetate to provide the title compound as an off white solid (278 mg, 32%). Characterization data for this compound is listed in Table 2.
[0089] Example 13: Preparation of (5-fluoro-3-(hydroxymethyl)-4-imino-l-tosyl-3,4- dihydropyrimidin-2(lH)-one
Figure imgf000032_0002
A 500 mL round-bottomed flask equipped with a magnetic stir bar was charged with 33% aqueous formaldehyde (20 g, 246 mmol), 4-amino-5-fluoro-l-tosylpyrimidin-2(lH)-one (10 g, 35.3 mmol) and distilled water (200 mL) to give a white suspension. The mixture was stirred under nitrogen at reflux for 3 hours. The mixture was cooled and filtered. The filter cake was washed with 25 mL of water and air dried for five minutes to yield the title compound as a white solid (2.2 g, 22%): 1H NMR (400 MHz, DMSO- ) δ 9.28 (t, J= 6.1 Hz, 1H), 8.35 (d, J= 6.6 Hz, 1H), 7.95 - 7.84 (m, 2H), 7.50 - 7.41 (m, 2H), 5.95 (t, J= 6.9 Hz, 1H), 4.72 (t, J= 6.4 Hz, 2H), 2.41 (s, 3H); 1JC MR (101 MHz, DMSO-A) δ 156.16 (d, J = 15.1 Hz), 149.21 , 145.64, 137.99, 135.51, 133.56, 129.24 (d, J= 63.5 Hz), 123.83 (d, J = 35.3 Hz), 63.32, 21.13; 19F NMR (376 MHz, OMSO-d6) δ -164.79.
[0090] Example 14: Preparation of 5-fluoro-4-imino-3-(methoxymethyl)-l-tosyl-3,4- dihydropyrimidin-2(lH)-one
Figure imgf000033_0001
In a 4 mL vial equipped with a magnetic stir bar charged with Deoxyfluor ® (50% in THF, 900 mg, 2.0 mmol) was added 5-fluoro-3-(hydroxymethyl)-4-imino-l-tosyl-3,4-dihydropyrimidin- 2(lH)-one (140 mg, 0.45 mmol). After stirring for two minutes the suspension transformed into an orange solution, which was stirred for an additional 30 minutes. The solution was cooled to 0 °C and was quenched by careful addition of methanol (1 mL). The solution was concentrated under a stream of nitrogen gas and the resulting residue was purified by silica gel
chromatography, eluting with a solvent gradient of 0 to 100% EtOAc in hexanes to furnish the title compound as a colorless oil (14 mg, 9%): XH NMR (400 MHz, acetone-i¾) δ 8.37 (s, 1H), 8.26 (d, J= 6.5 Hz, 1H), 8.02 - 7.95 (m, 2H), 7.50 - 7.41 (m, 2H), 4.90 - 4.82 (m, 2H), 3.29 (s, 3H), 2.45 (s, 3H); 13C MR (101 MHz, acetone-< 6) δ 158.52 (d, J = 14.7 Hz), 150.26, 146.86, 139.16 (d, J= 3.7 Hz), 136.71 , 134.98, 130.38 (d, J= 17.5 Hz), 124.79 (d, J= 35.6 Hz), 72.49 (d, J= 12.2 Hz), 56.45, 21.60; ESIMS m/z 328 ([M+H]+), 326 ([M-H]").
[0091 ] Example 15: Preparation of Z)-(5-fluoro-6-(isobutyrylimino)-2-oxo-3-tosyl- 2,3-dihydropyrimidin-l(6H)-yl)methyl isobutyrate (F25)
Figure imgf000034_0001
A solution of the mixture containing 5-fluoro-3-(hydroxymethyl)-4-imino-l-tosyl-3,4- dihydropyrimidin-2(lH)-one (250 mg of mixture, 0.23 mmol), N,N-diisopropylethylamine (307 mg, 2.37 mmol) and 4-dimethylaminopyridine (48 mg, 0.40 mmol) in dichloromethane (6 ml) was stirred at room temperature. Isobutyryl chloride (91 μί, 0.87 mmol) was added and the solution was stirred overnight at room temperature. The reaction mixture was concentrated and purification of the residue by normal phase chromatography (gradient, 0 to 60% EtOAc/hexane) provided the title compound as an off-white foam (74 mg, 70%). Characterization data for this compound is listed in Table 2.
[0092] Example 16: Evaluation of Fungicidal Activity: Leaf Blotch of Wheat
{Mycosphaerella graminicola; anamorph: Septoria tritici; Bayer code SEPTTR)
Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50% mineral soil/50% soil-less Metro mix until the first leaf was fully emerged, with 7-10 seedlings per pot. These plants were inoculated with an aqueous spore suspension of Septoria tritici either prior to or after fungicide treatments. After inoculation the plants were kept in 100% relative humidity (one day in a dark dew chamber followed by two to three days in a lighted dew chamber) to permit spores to germinate and infect the leaf. The plants were then transferred to a greenhouse for disease to develop. [0093] The following tables present the activity of typical compounds of the present disclosure when evaluated in these experiments. The effectiveness of the test compounds in controlling disease was determined by assessing the severity of disease on treated plants, then converting the severity to percent control based on the level of disease on untreated, inoculated plants. Table 1. Compound Structures and Preparation
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
Table 2. Analytical Data for Compounds in Table 1
Figure imgf000049_0002
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Mp ESIMS 13C NMR or 19F NMR
No. 1H NMR (5)a
(°C) m/z (δ)
8.04 (d, J = 8.2 Hz, 2H),
7.89 (d,J=6.7Hz, 1H),
185- 364
F45 7.73 (t,J=7.5 Hz, 1H), —
186 ([M+Na]+)
7.59 (t,J= 7.9 Hz, 2H),
3.78 (s, 3H), 3.24 (s, 3H)
7.92 (t,J= 7.8 Hz, 3H),
145- 378 7.40 (d,J=8.1 Hz, 2H),
F46 —
146 ([M+Na]+) 3.80 (s, 3H), 3.26 (s, 3H),
2.48 (s, 3H)
7.94 (dd,J= 17.7, 7.6 Hz,
3H), 7.42 (d,J=8.3Hz,
125- 392
F47 2H), 3.80 (s, 3H), 3.27 (s, —
126 ([M+Na]+)
3H), 2.83 - 2.66 (m, 2H),
1.28(t,J=7.6Hz, 3H)
7.94 (dd,J=21.7, 7.6 Hz,
3H), 7.44 (d,J=8.5Hz,
116- 406 2H), 3.80 (s, 3H), 3.27 (s,
F48 —
117 ([M+Na]+) 3H),3.02 (dt,J= 13.8,6.9
Hz, 1H), 1.29 (d,J=6.9
Hz, 6H)
7.97- 7.77 (m, 3H), 7.51
200- 378 (dt,J= 15.3,7.7 Hz, 2H),
F49 —
201 ([M+Na]+) 3.80 (s, 3H), 3.27 (s, 3H),
2.48 (s, 3H)
8.04 (s, 1H), 7.92 (d,J=6.6
178- 426 Hz, 1H), 7.34 (s, 1H), 3.82
F50 —
179 ([M+Na]+) (s, 3H), 3.27 (s, 3H), 2.46
(d,J= 10.6 Hz, 6H)
Figure imgf000064_0001
Figure imgf000065_0001
Mp ESIMS 13C NMR or 19F NMR
No. 1H NMR (5)a
(°C) m/z (δ)
8.03 (s, 1H), 7.71 (d,J=8.9
Hz, 1H), 7.46 (t,J=7.6Hz,
1H), 7.29 (s, 1H), 7.23 -
208- 476 7.18 (m, 1H), 7.11 (t,J =
F58 —
210 ([M+Na ) 7.2 Hz, 1H), 7.06 -6.96 (m,
1H), 4.98 (s, 2H), 3.25 (s,
3H), 2.47 (s, 3H), 2.42 (s,
3H)
7.69 (d,J=8.8Hz, 1H),
7.49 (t,J= 7.5 Hz, 1H),
108- 7.37 (s, 1H), 7.25 - 7.20 (m,
F59 — —
111 1H), 7.14 (t,J=7.4 Hz,
1H), 7.09 - 6.98 (m, 1H),
5.01 (s, 2H), 3.33 (s, 3H)
8.07-8.04 (d,J=8.8Hz,
304.1 19F NMR (376 MHz,
F61 — 2H), 7.73-7.64 (m, 3H),
([M+H]+) CDC13)8 -154.6
7.60 - 7.54 (m, 2H)
7.99 (d,J=9.2Hz, 2H),
333.8 7.72 (m, 1H), 7.65 (d,J= 19F NMR (376 MHz,
F62 —
([M+Hf) 9.2 Hz, 2H), 7.05-6.97 (m, CDC13)5 -155.2
2H), 3.89 (s, 3H)
7.93 (d,J=8.8Hz, 2H),
318.0 7.65 (d,J=8.8Hz, 2H), 19F NMR (376 MHz,
F63 —
([M+H]+) 7.38 - 7.35 (m, 1H), 2.46 (s, CDC13)6 -154.9
3H)
All !H NMR data measured in CDC13 at 400 MHz unless otherwise noted.
[0094] The following table presents the activity of typical compounds of the present disclosure when evaluated in these experiments. The effectiveness of the test compounds in controlling disease was determined by assessing the severity of disease on treated plants, then converting the severity to percent control based on the level of disease on untreated, inoculated plants.
In each case of Table I the rating scale is as follows:
Figure imgf000067_0001
Table 3. One-Day Protectant (IDP) and Three-Day Curative (3DC) Activity of Compounds on SEPTTR at 100 ppm
Figure imgf000067_0002
SEPTTR SEPTTR 100 100
Cmpd
PPM PPM
1DP 3DC
F25 D A
F26 A A
F27 D D
F28 D B
F29 A A
F30 A A
F31 A A
F32 A A
F33 A C
F34 A D
F35 A C
F36 A B
F37 D D
F38 A A
F39 C C
F40 D D
F41 D D
F42 A D
F43 D D
F44 A A
F45 D D
F46 D D
F47 D D
F48 D D
F49 D D
F50 D D
F51 D D
F52 D D
F53 D D
F54 D D
F55 D D
F56 D D
F57 D D
F58 D D
F59 D D
F61 D D
F62 D D
F63 D D

Claims

WHAT IS CLAIMED IS:
1. A compound of Formula I
Figure imgf000069_0001
Formula I wherein R is:
C1-C6 alkyl optionally substituted with 1-3 R4;
-C(=0)R5;
-C(=0)OR5;
-CH2OC(=0)R5; or
-(CHR8)nR7;
R2 is:
C1-C6 alkyl optionally substituted with 1-3 R6;
-C(=0)R7;
-C(=0)OR7; or
-(CHR8)nR7;
wherein n is an integer from 1-3;
R3 is -S(0)2R9;
R4 is independently C1-C6 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 haloalkylthio, amino, C1-C3 alkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C2-C6 alkylaminocarbonyl, hydroxyl, deuterium, or C3-C6 trialkylsilyl; R5 is H, C1-C6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxyalkyl, phenyl or benzyl wherein each of the phenyl or the benzyl may be optionally substituted with 1-3 R10, or with a 5- or 6-membered saturated or unsaturated ring system, or with a 5-6 fused ring system, or with a 6-6 fused ring system each containing 1-3 heteroatoms wherein each ring may be optionally substituted with 1 -3 R , biphenyl or naphthyl optionally substituted with 1-3 R ;
R6 is independently halogen, Ci-C6 alkyl, Ci-C4 haloalkyl, Ci-C4 alkoxy, Ci-C4 haloalkoxy, Cj- C4 alkylthio, C1-C4 haloalkylthio, amino, C1-C3 alkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C2-C6 alkylaminocarbonyl, hydroxyl, deuterium, or C3-C6 trialkylsilyl;
R7 is H, C1-C6 alkyl, C2-C6 alkenyl, C3-C6 alkynyl, C1-C6 haloalkyl, C1-C6 alkoxyalkyl, phenyl or benzyl wherein each of the phenyl or the benzyl may be optionally substituted with 1 -3 R10, or with a 5- or 6-membered saturated or unsaturated ring system, or with a 5-6 fused ring system, or with a 6-6 fused ring system each containing 1-3 heteroatoms wherein each ring may be optionally substituted with 1 -3 R10, biphenyl or naphthyl optionally substituted with 1-3 R10;
R8 is H, Ci-C6 alkyl, or Ci-C6 haloalkyl; R9 is C1-C6 alkyl, C1-C6 haloalkyl, amino, Ci-C6 alkylamino, C2-C6 dialkylamino, a phenyl or benzyl wherein each of the phenyl or the benzyl may be optionally substituted with 1 - 3 R10, or a 5- or 6-membered saturated or unsaturated ring containing 1 -3 heteroatoms wherein each ring may be optionally substituted with 1 -3 R10, or with a 5-6 fused ring system, or with a 6-6 fused ring system each containing 1-3 heteroatoms wherein each ring may be optionally substituted with 1 -3 R10, biphenyl or naphthyl optionally substituted with 1-3 R10; and
R10 is independently halogen, C1-C6 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, Ci- C4 alkylthio, C1-C4 haloalkylthio, amino, C1-C6 alkylamino, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, C2-C6 alkylaminocarbonyl, C2-C6 dialkylamino, hydroxy, cyano, or nitro.
2. A compound according to claim 1 , wherein R4 is independently Ci-Ce alkyl, C1-C4 alkoxy, C1-C4 alkylthio, hydroxyl, or deuterium.
3. A compound according to claim 1 , wherein R5 is C1-C6 alkyl, Ci-C6 haloalkyl, phenyl or benzyl wherein each of the phenyl or the benzyl may be optionally substituted with 1 -3 R10.
4. A compound according to claim 1 , wherein R6 is independently halogen, C1-C6 alkyl, Ci- C4 haloalkyl, C1-C4 alkoxy, C1-C4 alkylthio, or deuterium.
5. A compound according to claim 1 , wherein R7 is C1-C6 alkyl, C1-C6 haloalkyl, phenyl or benzyl wherein each of the phenyl or the benzyl may be optionally substituted with 1 -3 R10.
6. A compound according to claim 1 , wherein R10 is independently halogen, Ci-Ce alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, cyano, or nitro.
7. A compound according to claim 1 , wherein R9 is phenyl optionally substituted with 1 - 3 R10 or a 5- or 6-membered saturated or unsaturated ring containing 1-3 heteroatoms optionally substituted with 1-3 R10.
8. A compound according to claim 7, wherein R10 is independently halogen, C1-C6 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy.
9. A compound according to claim 1 , wherein R1 is C1-C3 alkyl.
10. A compound according to claim 1 , wherein R2 is C1-C3 alkyl, -C(=0)R5, or -C(=0)OR5.
1 1. A compound according to claim 10, wherein R5 is C1-C3 alkyl or phenyl.
12. A compound according to claim 1 1 , wherein R1 is C1-C3 alkyl.
13. A compound according to claim 1 wherein R9 is selected from the group consisting of:
14. A compound according to claim 13, wherein R2 is C1-C3 alkyl, -C(=0)R5, or -C(=0)OR5.
15. A compound according to claim 14, wherein R5 is C1-C3 alkyl or phenyl.
16. A compound according to claim 15, wherein R1 is C1-C3 alkyl.
17. A compound according to claim 1, wherein R1 is: C1-C6 alkyl optionally substituted with 1-3 R4;
-C(=0)R5; or
-CH2OC(=0)R5;
R2 is: Ci-C5 alkyl optionally substituted with 1-3 R6; -C(=0)R7; -C(=0)OR7; or - (CHR8)nR7;
R3 is -S(0)2R9;
R4 is hydroxyl, or deuterium;
R5 is C1-C6 alkyl, or phenyl;
R6 is deuterium;
R7 is C1-C6 alkyl, or phenyl optionally substituted with 1-3 R10;
R8 is H; n is 1
R9 is Ci-C6 alkyl, or a phenyl optionally substituted with 1- 3 R , or a 5- or 6-membered saturated or unsaturated ring containing 1-3 heteroatoms wherein each ring may be optionally substituted with 1-3 R10; and
R10 is independently halogen, C1-C6 alkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, or cyano.
18. A composition for the control of a fungal pathogen, including; at least one compound of Formula I; and a phytologically acceptable carrier material, wherein said compositon is effective for the control of at least one pathogenic fungus or pathogenic fungus like organism.
19. The composition of claim 18, wherein the pathogenic fungus or fungus like pathogen is Septoria tritici.
20. A method for treating a plant, comprising the steps of:
applying a fungicidally effective amount of at least one of the compounds of Formula 1 to at least one surface, selected from the group of surfaces consiting of: at least one portion of a plant, an area adjacent to a plant, soil in contact with a plant, soild adjacent to a plant, a seed, and agricultural equipment.
21. The method of claim 20, wherein the fungicidally effective amount Formula I is applied to a surface in the range of about 0.01g/m2 to about 0.45 g/m2 of Formula I.
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US10059703B2 (en) 2018-08-28
AU2013370494B2 (en) 2017-08-17
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