WO2000046184A1 - N2-phenylamidine derivatives - Google Patents

N2-phenylamidine derivatives Download PDF

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Publication number
WO2000046184A1
WO2000046184A1 PCT/GB2000/000345 GB0000345W WO0046184A1 WO 2000046184 A1 WO2000046184 A1 WO 2000046184A1 GB 0000345 W GB0000345 W GB 0000345W WO 0046184 A1 WO0046184 A1 WO 0046184A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
substituted
alkoxy
alkylthio
haloalkoxy
Prior art date
Application number
PCT/GB2000/000345
Other languages
French (fr)
Inventor
Mark David Charles
Wilfried Franke
David Eric Green
Thomas Lawley Hough
Dale Robert Mitchell
Donald James Simpson
John Frederick Atherall
Original Assignee
Aventis Cropscience Gmbh
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 IL14446400A priority Critical patent/IL144464A0/en
Priority to US09/890,775 priority patent/US6893650B1/en
Priority to HU0105098A priority patent/HU229457B1/en
Priority to EP00901791A priority patent/EP1150944B1/en
Application filed by Aventis Cropscience Gmbh filed Critical Aventis Cropscience Gmbh
Priority to CA002360943A priority patent/CA2360943C/en
Priority to UA2001096140A priority patent/UA70991C2/en
Priority to DE60004637T priority patent/DE60004637T2/en
Priority to DK00901791T priority patent/DK1150944T3/en
Priority to AT00901791T priority patent/ATE247629T1/en
Priority to BRPI0009314-9A priority patent/BR0009314B1/en
Priority to JP2000597256A priority patent/JP2002536354A/en
Priority to AU23088/00A priority patent/AU768156B2/en
Publication of WO2000046184A1 publication Critical patent/WO2000046184A1/en
Priority to IL144464A priority patent/IL144464A/en
Priority to HK02105179A priority patent/HK1043358A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—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
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • 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
    • 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
    • A01N43/82—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 three ring hetero atoms
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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    • 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
    • A01N47/42—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 containing —N=CX2 groups, e.g. isothiourea
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/12—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to hydrogen atoms
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/14—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to acyclic carbon atoms
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    • C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
    • C07D207/50—Nitrogen atoms
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    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
    • C07D239/72—Quinazolines; Hydrogenated quinazolines
    • C07D239/86—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in position 4
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    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
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    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
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    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
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    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
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    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
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    • C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
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    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring

Definitions

  • This invention relates to the use of compounds as fungicides.
  • WO 95/22532 relates to substituted phenyltriazolinones claimed as herbicides and discloses inter alia a compound of formula A for which there is no characterising data therein.
  • the invention provides the use of a compound of general formula I and salts thereof as fungicides
  • R1 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted, or hydrogen;
  • R 2 and R 3 which may be the same or different, are any group defined for R ⁇ ; cyano; acyl; -OR a or -SR a , where R a is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; or R 2 and R 3 , or R 2 and
  • R ⁇ together with their interconnecting atoms may form a ring, which may be substituted;
  • R 4 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; hydroxy; mercapto; azido; nitro; halogen; cyano; acyl; optionally substituted amino; cyanato; thiocyanato; -SF5; -OR a ; -SR a or
  • R ⁇ which may be the same or different to any other R ⁇ , is any group defined for R 4 ;
  • R ⁇ is optionally substituted carbo- or heterocyclyl
  • X is 0 or S
  • X I is 0, S, NR 9 or a direct bond
  • X 2 is 0, NR 9 or a direct bond
  • R 8 which may be the same or different to any other R 8 , is alkyl, alkenyl, alkynyl, alkoxy, alkylthio, carbo- or heterocyclyl, each of which may be substituted; or is hydrogen;
  • R 9 which may be the same or different to any other R 9 , is optionally substituted alkyl, optionally substituted carbo- or heterocyclyl, hydrogen or acyl; or two R 9 groups on A, together with the connecting atoms, form a 5 to 7 membered ring; where the moiety depicted on the right side of linkage A is attached to R ⁇ ; or -A-R6 and R ⁇ together with benzene ring M form an optionally substituted fused ring system.
  • R ⁇ is alkyl, alkenyl or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl (preferably phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms, or halogen), or is hydrogen.
  • R ⁇ is especially C -
  • R 2 and R 3 which may be the same or different, are alkyl, alkenyl or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl (preferably phenyl, optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms, or by halogen), or is hydrogen, alkoxy, alkoxyalkoxy, benzyloxy, cyano or alkylcarbonyl.
  • R 2 and R 3 which may be the same or different, are especially C- ] -
  • Q alkyl e.g. methyl or ethyl
  • hydrogen
  • m is 0 or 1 , especially 1 .
  • R ⁇ is preferably a group defined for preferred R 4 above.
  • R5 is especially C -
  • the group R ⁇ is preferably attached at the 5 position of ring M.
  • A is a direct bond, -0-, -S(0) n A 1 -, -0(A 1 ) k -, -S(0) n -, -NR 9 A 2 -, -A 2 -, -OA 2 -, -OA 2 -A 1 -, -NR 9 - or -0(A 1 ) k O-.
  • A is a direct bond, -0-, -S-, -NR 9 -, -CHR 7 - or -O-CHR 7 -.
  • A is a direct bond or -0-.
  • R 9 is alkyl, alkenyl, or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl (preferably phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms, or halogen); or is hydrogen (R 9 is especially C ⁇ - C-
  • R 7 is alkyl, alkenyl, or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl (preferably phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms, or by halogen); or is hydroxy; halogen; cyano; acyl; alkoxy; haloalkoxy; alkylthio; or hydrogen (R 7 is especially C - ⁇ -C - ⁇ Q alkyl or hydrogen).
  • A is attached to the 4 position of benzene ring M.
  • R ⁇ is optionally substituted phenyl or optionally substituted aromatic heterocyclyl [preferably thiazolyl, isothiazolyl, thiadiazolyl (particularly 1 ,2,4- thiadiazolyl), pyridyl or pyrimidinyl].
  • R ⁇ may be substituted by one or more substituents, which may be the same or different, and may be selected from the preferred list: alkyl, alkenyl, alkynyl, carbo- or heterocyclyl, each of which may be substituted; hydroxy; mercapto; azido; nitro; halogen; cyano; acyl; optionally substituted amino; cyanato; thiocyanato; -SF5; -OR a ; -SR a and -Si(R a >3, where R a is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted.
  • substituents which may be the same or different, and may be selected from the preferred list: alkyl, alkenyl, alkynyl, carbo- or heterocyclyl, each of which may be substituted; hydroxy; mercapto; azido; nitro; halogen; cyano; acy
  • R ⁇ is hydroxy; halogen; cyano; acyl (preferably
  • R c is alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monalkylamino, dialkylamino or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio); amino; alkylamino; dialkylamino; alkyl; haloalkyl; R a O-alkyl; acyloxyalkyl; cyano-oxyalkyl; alkoxy; haloalkoxy; alkylthio; carbocyclyl (preferably cyclohexyi or cyclopentyl) A optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio; and benzyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio; and benzyl optionally substitute
  • R ⁇ is: cyclopentyl, cyclohexyi or benzyl, optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy, or alkylthio; or is halogen; alkyl; haloalkyl; alkoxyalkyl; hydroxyalkyl; alkoxy; or alkylthio.
  • the invention provides the use of a compound of general formula I and salts thereof as fungicides wherein: R 1 is alkyl, alkenyl or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio or halogen; or is hydrogen;
  • R 2 and R 3 which may be the same or different, are as defined for R 1 in this embodiment, or are alkoxy, alkoxyalkoxy, benzyloxy, cyano or alkylcarbonyl;
  • A is a direct bond, -0-, -S-, -NR 9 -, -CHR 7 - or -O-CHR 7 -, wherein when present, R 9 is alkyl, alkenyl, or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, or halogen; or is hydrogen; and R 7 is a group defined for R 9 in this embodiment, or is hydroxy; halogen; cyano; acyl; alkoxy; haloalkoxy or alkylthio; A is attached to the 4 position of benzene ring M; and
  • R c is alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino, dialkylamino or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio); amino; alkylamino; dialkylamino; alkyl; haloalkyl; R a O-alkyl; acyloxyalkyl; cyano- oxyalkyl; alkoxy; haloalkoxy; alkylthio; carbocyclyl (preferably cyclohexyi or cyclopentyl) optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio; and benzyl optionally substituted by alkyl, haloalkyl, alkoxy, hal
  • R ⁇ is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted, or is hydrogen;
  • R 2 and R 3 which may be the same or different, are any group defined for R 1 , or together with the nitrogen to which they are attached may form a ring, which may be substituted;
  • R 4 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; m is 1 ;
  • R5 is any group defined for R 4 attached to the 5-position of the benzene ring M;
  • R6 is optionally substituted carbo- or heterocyclyl
  • A is a direct bond; -0-; -S-; -NR 9 -, where R 9 is alkyl, alkenyl, or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl; -CHR 7 - or -O-CHR 7 -, where R 7 is alkyl, alkenyl, or alkynyl, which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio; or is hydroxy; halogen; cyano; acyl; alkoxy; haloalkoxy; or alkylthio; where -A-R ⁇ is in the 4-position of the benzene ring M and the moiety depicted on the right side of linkage A
  • Any alkyl group may be straight or branched and is preferably of 1 to 10 carbon atoms, especially 1 to 7 and particularly 1 to 5 carbon atoms.
  • Any alkenyl or alkynyl group may be straight or branched and is preferably of 2 to 7 carbon atoms and may contain up to 3 double or triple bonds which may be conjugated, for example vinyl, allyl, butadienyl or propargyl.
  • Any carbocyclyl group may be saturated, unsaturated or aromatic, and contain 3 to 8 ring-atoms.
  • Preferred saturated carbocyclyl groups are cyclopropyl, cyclopentyl or cyclohexyi.
  • Preferred unsaturated carbocyclyl groups contain up to 3 double bonds.
  • a preferred aromatic carbocyclyl group is phenyl.
  • the term carbocylic should be similarly construed.
  • carbocyclyl includes any fused combination of carbocyclyl groups, for example naphthyl, phenanthryl, indanyl and indenyl.
  • Any heterocyclyl group may be saturated, unsaturated or aromatic, and contain 5 to 7 ring-atoms up to 4 of which may be hetero-atoms such as nitrogen, oxygen and sulfur.
  • heterocyclyl groups are furyl, thienyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, imidazolyl, dioxolanyl, oxazolyl, thiazolyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyranyl, pyridyl, piperidinyl, dioxanyl, morpholino, dithianyl, thiomorpholino, pyridazinyl, pyrimidinyl, pyrazinyl, piperaz
  • heterocyclyl includes fused heterocyclyl groups, for example benzimidazolyl, benzoxazolyl, imidazopyridinyl, benzoxazinyl, benzothiazinyl, oxazolopyridinyl, benzofuranyl, quinolinyl, quinazolinyl, quinoxalinyl, dihydroquinazolinyl, benzothiazolyl, phthalimido, benzofuranyl, benzodiazepinyl, indolyl and isoindolyl.
  • heterocyclic should be similarly construed.
  • Any alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl group, when substituted, may be substituted by one or more substituents, which may be the same or different, and may be selected from the list: hydroxy; mercapto; azido; nitro; halogen; cyano; acyl; optionally substituted amino; optionafly substituted carbocyclyl; optionally substituted heterocyclyl; cyanato; thiocyanato; -SF5; -OR a ;
  • R a is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted.
  • R a is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted.
  • the list includes additionally: alkyl, alkenyl and alkynyl, each of which may be substituted.
  • Preferred substituents on any alkyl, alkenyl or alkynyl group are alkoxy, haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms; halogen; or optionally substituted phenyl.
  • Preferred substituents on any carbocyclyl or heterocyclyl group are alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms; halogen; or optionally substituted phenyl.
  • any alkyl group or any unsaturated ring-carbon in any carbocyclyl or heterocyclyl group the list includes a divalent group such as oxo or imino, which may be substituted by optionally substituted amino, R a or -OR a (where R a is as defined above).
  • Preferred groups are oxo, imino, alkylimino, oximino, alkyloximino or hydrazono.
  • Any amino group when substituted and where appropriate, may be substituted by one or two substituents which may be the same or different, selected from the list: optionally substituted alkyl, optionally substituted amino, -OR a (where R a is as defined above) and acyl groups.
  • substituents which may be the same or different, selected from the list: optionally substituted alkyl, optionally substituted amino, -OR a (where R a is as defined above) and acyl groups.
  • two substituents together with the nitrogen to which they are attached may form a heterocyclyl group, preferably a 5 to 7-membered heterocyclyl group, which may be substituted and may contain other hetero atoms, for example morpholino, thiomorpholino or piperidinyl.
  • R D is as defined for R a , -OR a , -SR a , optionally substituted amino or acyl; and p is 1 or 2.
  • Complexes of compounds of the invention are usually formed from a salt of formula MAn 2 , in which M is a divalent metal cation, e.g. copper, manganese, cobalt, nickel, iron or zinc and An is an anion, e.g. chloride, nitrate or sulfate.
  • M is a divalent metal cation, e.g. copper, manganese, cobalt, nickel, iron or zinc
  • An is an anion, e.g. chloride, nitrate or sulfate.
  • the invention includes individual isomers as well as mixtures thereof.
  • the invention includes individual tautomers as well as mixtures thereof.
  • the invention includes individual isomers as well as mixtures thereof.
  • the compounds of the invention have activity as fungicides, especially against fungal diseases of plants, e.g. mildews and particularly cereal powdery mildew (Erysiphe graminis) and vine downy mildew (Plasmopara viticola), rice blast (Pyricutaria oryzae), cereal eyespot (Pseudocercospore/la herpotrichoides), rice sheath blight ⁇ Pellicularia sasaki ⁇ ), grey mould (Botrytis cinerea), damping off ⁇ Rhizoctonia solani), wheat brown rust (Puccinia recondita), late tomato or potato blight (Phytophthora infestans), apple scab ⁇ Venturia inaequalis), and glume blotch ⁇ Leptosphaeria nodorum).
  • Other fungi against which the compounds may
  • the invention thus also provides a method of combating fungi at a locus infested or liable to be infested therewith, which comprises applying to the locus a compound of formula I.
  • the invention also provides an agricultural composition
  • an agricultural composition comprising a compound of formula I in admixture with an agriculturally acceptable diluent or carrier.
  • composition of the invention may of course include more than one compound of the invention.
  • composition can comprise one or more additional active ingredients, for example compounds known to possess plant-growth regulant, herbicidal, fungicidal, insecticidal, acaricidal, antimicrobial or antibacterial properties.
  • additional active ingredients for example compounds known to possess plant-growth regulant, herbicidal, fungicidal, insecticidal, acaricidal, antimicrobial or antibacterial properties.
  • the compound of the invention can be used in sequence with the other active ingredient.
  • the diluent or carrier in the composition of the invention can be a solid or a liquid optionally in association with a surface-active agent, for example a dispersing agent, emulsifying agent or wetting agent.
  • Suitable surface-active agents include anionic compounds such as a carboxylate, for example a metal carboxylate of a long chain fatty acid; an N-acylsarcosinate; mono- or di-esters of phosphoric acid with fatty alcohol ethoxylates or alkyl phenol ethoxylates or salts of such esters; fatty alcohol sulfates such as sodium dodecyl sulfate, sodium octadecyl sulfate or sodium cetyl sulfate; ethoxylated fatty alcohol sulfates; ethoxyiated alkylphenol sulfates; lignin sulfonates; petroleum sulfonates; alkyl-aryl sulfon
  • butyl-naphthalene sulfonate salts of sulfonated naphthalene-formaldehyde condensates; salts of sulfonated phenol-formaldehyde condensates; or more complex sulfonates such as the amide sulfonates, e.g. the sulfonated condensation product of oleic acid and N-methyl taurine; the dialkyl sulfosuccinates, e.g. the sodium sulfonate of dioctyl succinate; acid derivatives of alkyl glycosides and alkylpolyglycosides materials and their metal salts, e.g. alkyl polyglycoside citrate or tartrate materials; or mono-, di- and tri-alkyl esters of citric acid and their metal salts.
  • the amide sulfonates e.g. the sulfonated condensation product of oleic acid and
  • Nonionic agents include condensation products of fatty acid esters, fatty alcohols, fatty acid amides or fatty-alkyl- or alkenyl-substituted phenols with ethylene and/or propylene oxide; fatty esters of polyhydric alcohol ethers, e.g. sorbitan fatty acid esters; condensation products of such esters with ethylene oxide, e.g.
  • polyoxyethylene sorbitan fatty acid esters alkyl glycosides, alkyl polyglycoside materials; block copolymers of ethylene oxide and propylene oxide; acetylenic glycols such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, ethoxylated acetylenic glycols; acrylic based graft copolymers; alkoxylated siloxane surfactants; or imidazoline type surfactants, e.g. 1 -hydroxyethyl-2-alkylimidazoline.
  • a cationic surface-active agent examples include, for instance, an aliphatic mono-, di-, or polyamine as an acetate, naphthenate or oleate; an oxygen-containing amine such as an amine oxide, polyoxyethylene alkylamine or polyoxypropylene alkylamine; an amide-linked amine prepared by the condensation of a carboxylic acid with a di- or polyamine; or a quaternary ammonium salt.
  • compositions of the invention can take any form known in the art for the formulation of agrochemicals, for example, a solution, an aerosol, a dispersion, an aqueous emulsion, a microemulsion, a dispersible concentrate, a dusting powder, a seed dressing, a fumigant, a smoke, a dispersible powder, an emulsifiable concentrate, granules or an impregnated strip.
  • a dispersible concentrate comprises a compound of the invention dissolved in one or more water miscible or semi-water miscible solvents together with one or more surface activeand/or polymeric material. Addition of the formulation to water results in the crystalisation of the active ingredient, the process being controlled by the surfactants and/or polymers resulting in a fine dispersion.
  • a dusting powder comprises a compound of the invention intimately mixed and ground with a solid pulverulent diluent, for example, kaolin.
  • An emulsifiable concentrate comprises a compound of the invention dissolved in a water-immiscible solvent which forms an emulsion or microemulsion on addition to water in the presence of an emulsifying agent.
  • a granular solid comprises a compound of the invention associated with similar diluents to those that may be employed in dusting powders, but the mixture is granulated by known methods. Alternatively it comprises the active ingredient absorbed or coated on a pre-formed granular carrier, for example, Fuller's earth, attapulgite, silica or limestone grit.
  • Wettable powders, granules or grains usually comprise the active ingredient in admixture with suitable surfactants and an inert powder diluent such as clay or diatomaceous earth.
  • Another suitable concentrate is a flowable suspension concentrate which is formed by grinding the compound with water or other liquid, surfactants and a suspending agent.
  • the concentration of the active ingredient in the composition of the present invention, as applied to plants is preferably within the range of 0.0001 to 1 .0 per cent by weight, especially 0.0001 to 0.01 per cent by weight, in a primary composition, the amount of active ingredient can vary widely and can be, for example, from 5 to 95 per cent by weight of the composition.
  • a compound of the invention is generally applied to seeds, plants or their habitat.
  • the compound can be applied directly to the soil before, at or after drilling so that the presence of active compound in the soil can control the growth of fungi which may attack seeds.
  • the active compound can be applied in any manner which allows it to be intimately mixed with the soil such as by spraying, by broadcasting a solid form of granules, or by applying the active ingredient at the same time as drilling by inserting it in the same drill as the seeds.
  • a suitable application rate is within the range of from 5 to 1 000 g per hectare, more preferably from 1 0 to 500 g per hectare.
  • the active compound can be applied directly to the plant by, for example, spraying or dusting either at the time when the fungus has begun to appear on the plant or before the appearance of fungus as a protective measure.
  • the preferred mode of application is by foliar spraying. It is generally important to obtain good control of fungi in the early stages of plant growth, as this is the time when the plant can be most severely damaged.
  • the spray or dust can conveniently contain a pre- or post-emergence herbicide if this is thought necessary.
  • a suitable rate of application is from 0.025 to 5 kg per hectare, preferably from 0.05 to 1 kg per hectare.
  • the compounds of the invention can be applied to harvested fruits, vegetables or seeds to prevent infection during storage.
  • the compounds of the invention can be applied to plants or parts thereof which have been genetically modified to exhibit a trait such as fungal and/or herbicidal resistance.
  • the compounds of the invention can be used to treat fungal infestations in timber and in public health applications. Also the compounds of the invention can be used to treat fungal infestations in domestic and farm animals. Compounds of the invention may be prepared, in known manner, in a variety of ways.
  • groups R 2 and R 3 in compounds of general formula I can be converted to other groups defined for R 2 and R 3 , by treatment with an appropriate amine or by acylation or alkylation when R 2 or R 3 is hydrogen.
  • reaction conditions comprise stirring with bromine in a suitable solvent.
  • V forms an anion under basic conditions.
  • a z is alternatively a basic primary or secondary nitrogen atom.
  • X z is a leaving group, preferably halogen.
  • preferred reaction conditions comprise treating V with sodium hydride followed by addition of VI.
  • preferred reaction conditions comprise reacting V with VI in the presence of a tertiary amine base such as ethyldiisopropylamine.
  • a z is -CHR 7 -, preferred reaction conditions comprise treating V with potassium terf-butoxide in dimethylformamide at low temperature.
  • Compounds of formula 1Mb i.e. compounds of general formula III where A is a group A w , may be prepared by reacting compounds of formula VII with compounds of formula VIII according to reaction scheme 7.
  • a w is a group which, in compound VII, forms an anion under basic conditions.
  • X w is a leaving group, preferably halogen.
  • Preferred basic conditions comprise reaction of VII with potassium carbonate or sodium hydride followed by addition of VIII.
  • compounds of formula I can be prepared by introducing R° after formation of the amidine moiety.
  • R 1 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted, or is hydrogen;
  • R 2 and R 3 which may be the same or different, are any group defined for R1 ; cyano; acyl; -0R a or -SR a , where R a is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; or R 2 and R 3 , or R 2 and
  • R1 together with their interconnecting atoms may form a ring, which may be substituted;
  • R 4 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted;
  • R5 is any group defined for R 4 ; with the proviso that R ⁇ is not terf-butyl.
  • Other methods will be apparent to the chemist skilled in the art, as will be methods for preparing starting materials and intermediates.
  • compounds of the invention may be prepared using combinatorial chemistry methodology.
  • N.M.R. spectra ( ⁇ H N.M.R.) were determined in deuterochloroform and chemical shifts ( ⁇ ) are quoted in parts per million downfield of tetramethylsilane.
  • phosphorous oxychloride (2.1 8 g) in dry diethyl ether (3 ml) was added dropwise to a stirred solution of NN-diethylformamide ( 1 .43 g) in dry diethyl ether (3 ml) and stirring continued for 20 minutes. Stirring was stopped and the mixture allowed to form two layers. The upper ether layer was removed by decanting, and the lower layer was washed with diethyl ether (x3). The product from stage b) (2 g) in dry diethyl ether (4 ml) was then added dropwise. After addition the mixture was stirred vigorously for 1 hour at room temperature.
  • Example 1 stage b) .
  • This compound was prepared from 4-amino-2,5-dimethylphenol in similar fashion to Examples 1 , 2 or 3, m.p. 212 °C.
  • Example 6 N,N-Dimethyl-N'-[4-(3-trifluoromethylphenoxy)-2,6-xylyl]formamidine (Compound 20) This compound was prepared from the product of stage b) below and dimethylformamide dimethylacetal according to the method of Example 1 , " ⁇ N.M.R. ⁇ (ppm) 2.1 5 (s, 6H, ArCH 3 ), 3.00 (s, 6H, N(CH 3 ) 2 ).
  • Example 1 The title compound was prepared from the product of stage c) according to Example 1 stage b).
  • Example 1 0 The title compound was prepared from the product of stage c) according to Example 1 stage b).
  • Example 1 0 The title compound was prepared from the product of stage c) according to Example 1 stage b).
  • Example 1 0 The title compound was prepared from the product of stage c) according to Example 1 stage b).
  • Example 1 0 The title compound was prepared from the product of stage c) according to Example 1 stage b).
  • stage a The product prepared in stage a) (5.0 g) was stirred in toluene (200 ml) and treated with phosphorous pentoxide (1 0 g). The mixture was heated under reflux for 2 hours and then poured onto ice-water. The mixture was extracted with diethyl ether, the extract dried (MgS ⁇ 4) and concentrated.
  • Pyricularia oryzae rice blast Leptosphaeria nodorum: glume blotch
  • Aqueous solutions or dispersions of the compounds at the desired concentration, including a wetting agent, were applied by spray or by drenching the stem base of the test plants, as appropriate. After a given time, plants or plant parts were inoculated with appropriate test pathogens before or after application of the compounds as appropriate, and kept under controlled environmental conditions suitable for maintaining plant growth and development of the disease. After an appropriate time, the degree of infection of the affected part of the plant was visually estimated. Compounds are assessed on a score of 1 to 3 where 1 is little or no control, 2 is moderate control and 3 is good to total control. At a concentration of 500 ppm (w/v) or less, the following compounds scored 2 or more against the fungi specified.

Abstract

The invention provides fungicidal compounds of formula (I) and salts thereof wherein: R1 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted, or hydrogen; R?2 and R3¿, which may be the same or different, are any group defined for R1; cyano; acyl; -OR?a or -SRa¿, where Ra is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; or R?2 and R3, or R2 and R1¿, together with their interconnecting atoms may form a ring, which may be substituted; R4 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; hydroxy; mercapto; azido; nitro; halogen; cyano; acyl; optionally substituted amino; cyanato; thiocyanato; -SF¿5?; -OR?a; -SRa¿ or -Si(Ra)3; m is 0 to 3; when present R5, which may be the same or different to any other R5, is any group defined for R4; R6 is optionally substituted carbo- or heterocylclyl; and A is a defined linking group, or -A-R?6 and R5¿ together with benzene ring M form an optionally substituted fused ring system.

Description

N^-Phenylamidine Derivatives
This invention relates to the use of compounds as fungicides.
WO 95/22532 relates to substituted phenyltriazolinones claimed as herbicides and discloses inter alia a compound of formula A for which there is no characterising data therein.
Figure imgf000003_0001
The abstract, composition claim and use claim refer only to the use of such compounds as herbicides and indeed the description supports the invention only with herbicidal activity data. There is a sentence in the specification that states that certain compounds show fungicidal activity, although no fungicidal activity data are provided. No indication is given as to which compounds are fungicidal and there is no suggestion that compound A could be fungicidal.
We have now found that certain amidines have fungicidal activity. Therefore, the invention provides the use of a compound of general formula I and salts thereof as fungicides
Figure imgf000003_0002
wherein
R1 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted, or hydrogen;
R2 and R3, which may be the same or different, are any group defined for R^; cyano; acyl; -ORa or -SRa, where Ra is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; or R2 and R3, or R2 and
R^ , together with their interconnecting atoms may form a ring, which may be substituted;
R4 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; hydroxy; mercapto; azido; nitro; halogen; cyano; acyl; optionally substituted amino; cyanato; thiocyanato; -SF5; -ORa; -SRa or
-Si(Ra)3; m is 0 to 3; when present R^, which may be the same or different to any other R^, is any group defined for R4;
R^ is optionally substituted carbo- or heterocyclyl; and
A is a direct bond, -0-, -S(0)n-, -NR9-, -CR7 = CR7-, -C≡C-, -A1-, -A1 -A1-,
-0-(A1)k-0-, -0-(A1)k-, -A3-, -A4-, -A10-, -A1S(0)n-, -A2-, OA2-,
-NR9A2-, -OA2-A1-, -OA2-C(R7) = C(R8)-, -S(0)nA1-, -A1 -A4-, ~A1-A4-C(R8) = N-N = CR8-, -A1-A4-C(R8) = N-X2-X3-, -A1-A -A3-,
-A1-A4-N(R9)-, -A1-A4-X-CH2-, -A1-A -A1-, -A1-A4-CH2X-, -A1-A -C(R8) = N-X2-X3-X1-, -A1-X-C(R8) = N-, -A1-X-C(R8) = N-N = CR8-, -A1-X-C(R8) = N-N(R9)-, -A1-X-A2-X1-, -A1-0-A3-, -A1-0-C(R7) = C(R8)-, -A1-0-N(R9)-A2-N(R9)-, -A1-0-N(R9)-A2-, -A1-N(R9)-A2-N(R9)-, -A1 -N(R9)-A2-, -A1 -N(R9)-N = C(R8)-, -A3-A1 -, -A -A3-, -A2-NR9-,
-A1-A2-X1-, -A1-A1-A2-X1-, -0-A2-N(R9)-A2-, -CR7 = CR7-A2-X1-, -C≡C-A2-X1-, -N = C(R8)-A2-X1-, -C(R8) = N-N = C(R8)-, -C(R8) = N-N(R9)-, -(CH2)2-0-N = C(R8>- or -X-A2-N(R9)- where n is 0, 1 or 2, k is 1 to 9, A1 is -CHR7-, A2 is -C( = X)-, A3 is -C(R8) = N-0-, A4 is -0-N = C(R8)-,
X is 0 or S,
XI is 0, S, NR9 or a direct bond, X2 is 0, NR9 or a direct bond,
X3 is hydrogen, -C( = 0)-, -S02- or a direct bond, R7, which may be the same or different to any other R7, is alkyl, cycloalkyl or phenyl, each of which may be substituted; or is hydrogen, halogen, cyano or acyl;
R8, which may be the same or different to any other R8, is alkyl, alkenyl, alkynyl, alkoxy, alkylthio, carbo- or heterocyclyl, each of which may be substituted; or is hydrogen;
R9, which may be the same or different to any other R9, is optionally substituted alkyl, optionally substituted carbo- or heterocyclyl, hydrogen or acyl; or two R9 groups on A, together with the connecting atoms, form a 5 to 7 membered ring; where the moiety depicted on the right side of linkage A is attached to R^; or -A-R6 and R^ together with benzene ring M form an optionally substituted fused ring system.
Preferably R^ is alkyl, alkenyl or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl (preferably phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms, or halogen), or is hydrogen. R^ is especially C -| -C -| Q alkyl (e.g. methyl) or hydrogen.
Preferably R2 and R3, which may be the same or different, are alkyl, alkenyl or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl (preferably phenyl, optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms, or by halogen), or is hydrogen, alkoxy, alkoxyalkoxy, benzyloxy, cyano or alkylcarbonyl. R2 and R3, which may be the same or different, are especially C-] -
C-| Q alkyl (e.g. methyl or ethyl) or hydrogen.
Preferably R4 is alkyl, alkenyl, or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl (preferably phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms, or halogen); or is hydroxy; halogen; cyano; acyl (preferably -C( = 0)Rc, -C( = S)RC or -S(0)pRc, where Rc is alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino, dialkylamino or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio); alkoxy; haloalkoxy; or alkylthio. R4 is especially C I -C -| Q al yl (e-9- methyl or ethyl) or halogen.
Preferably m is 0 or 1 , especially 1 .
When present, R^ is preferably a group defined for preferred R4 above. R5 is especially C -| -C -] Q alkyl or halogen.
When present, the group R^ is preferably attached at the 5 position of ring M.
Preferably A is a direct bond, -0-, -S(0)nA1 -, -0(A1 )k-, -S(0)n-, -NR9A2-, -A2-, -OA2-, -OA2-A1 -, -NR9- or -0(A1 )kO-. Particularly A is a direct bond, -0-, -S-, -NR9-, -CHR7- or -O-CHR7-. Especially A is a direct bond or -0-. When present,
R9 is alkyl, alkenyl, or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl (preferably phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms, or halogen); or is hydrogen (R9 is especially C^ - C-| o alkyl or hydrogen). When present, R7 is alkyl, alkenyl, or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl (preferably phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms, or by halogen); or is hydroxy; halogen; cyano; acyl; alkoxy; haloalkoxy; alkylthio; or hydrogen (R7 is especially C -\ -C -\ Q alkyl or hydrogen).
Preferably A is attached to the 4 position of benzene ring M.
Preferably R^ is optionally substituted phenyl or optionally substituted aromatic heterocyclyl [preferably thiazolyl, isothiazolyl, thiadiazolyl (particularly 1 ,2,4- thiadiazolyl), pyridyl or pyrimidinyl].
When substituted, R^ may be substituted by one or more substituents, which may be the same or different, and may be selected from the preferred list: alkyl, alkenyl, alkynyl, carbo- or heterocyclyl, each of which may be substituted; hydroxy; mercapto; azido; nitro; halogen; cyano; acyl; optionally substituted amino; cyanato; thiocyanato; -SF5; -ORa; -SRa and -Si(Ra>3, where Ra is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted.
A preferred list of substituents on R^ is: hydroxy; halogen; cyano; acyl (preferably
-C( = 0)Rc, -C( = S)RC or -S(0)pRc, where Rc is alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monalkylamino, dialkylamino or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio); amino; alkylamino; dialkylamino; alkyl; haloalkyl; RaO-alkyl; acyloxyalkyl; cyano-oxyalkyl; alkoxy; haloalkoxy; alkylthio; carbocyclyl (preferably cyclohexyi or cyclopentyl)A optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio; and benzyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio.
A particularly preferred list of substituents on R^ is: cyclopentyl, cyclohexyi or benzyl, optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy, or alkylthio; or is halogen; alkyl; haloalkyl; alkoxyalkyl; hydroxyalkyl; alkoxy; or alkylthio.
In a preferred embodiment, the invention provides the use of a compound of general formula I and salts thereof as fungicides wherein: R1 is alkyl, alkenyl or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio or halogen; or is hydrogen;
R2 and R3, which may be the same or different, are as defined for R1 in this embodiment, or are alkoxy, alkoxyalkoxy, benzyloxy, cyano or alkylcarbonyl;
R4 is alkyl, alkenyl or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio or halogen; or is hydroxy; halogen; cyano; acyl (preferably -C( = 0)RC, -C( = S)RC or -S(0)pRc, where Rc is alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino, dialkylamino or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio); m is 0 or 1 ; when present, R^ is a group defined for R4 in this embodiment;
A is a direct bond, -0-, -S-, -NR9-, -CHR7- or -O-CHR7-, wherein when present, R9 is alkyl, alkenyl, or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, or halogen; or is hydrogen; and R7 is a group defined for R9 in this embodiment, or is hydroxy; halogen; cyano; acyl; alkoxy; haloalkoxy or alkylthio; A is attached to the 4 position of benzene ring M; and
R^ is phenyl or aromatic heterocyclyl, optionally substituted by one or more substituents, which may be the same or different, and may be selected from the list: hydroxy; halogen; cyano; acyl (preferably -C( = 0)Rc, -
C( = S)RC or -S(0)pRc, where Rc is alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, amino, monoalkylamino, dialkylamino or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio); amino; alkylamino; dialkylamino; alkyl; haloalkyl; RaO-alkyl; acyloxyalkyl; cyano- oxyalkyl; alkoxy; haloalkoxy; alkylthio; carbocyclyl (preferably cyclohexyi or cyclopentyl) optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio; and benzyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio. Most compounds of general formula I are novel. Therefore according to a second aspect, the invention provides compounds of formula I wherein
R^ is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted, or is hydrogen;
R2 and R3, which may be the same or different, are any group defined for R 1 , or together with the nitrogen to which they are attached may form a ring, which may be substituted;
R4 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; m is 1 ;
R5 is any group defined for R4 attached to the 5-position of the benzene ring M;
R6 is optionally substituted carbo- or heterocyclyl; and
A is a direct bond; -0-; -S-; -NR9-, where R9 is alkyl, alkenyl, or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl; -CHR7- or -O-CHR7-, where R7 is alkyl, alkenyl, or alkynyl, which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio; or is hydroxy; halogen; cyano; acyl; alkoxy; haloalkoxy; or alkylthio; where -A-R^ is in the 4-position of the benzene ring M and the moiety depicted on the right side of linkage A is attached to R^; or -A-R6 and R^ together with benzene ring M form an optionally substituted fused ring system.
Any alkyl group may be straight or branched and is preferably of 1 to 10 carbon atoms, especially 1 to 7 and particularly 1 to 5 carbon atoms.
Any alkenyl or alkynyl group may be straight or branched and is preferably of 2 to 7 carbon atoms and may contain up to 3 double or triple bonds which may be conjugated, for example vinyl, allyl, butadienyl or propargyl.
Any carbocyclyl group may be saturated, unsaturated or aromatic, and contain 3 to 8 ring-atoms. Preferred saturated carbocyclyl groups are cyclopropyl, cyclopentyl or cyclohexyi. Preferred unsaturated carbocyclyl groups contain up to 3 double bonds. A preferred aromatic carbocyclyl group is phenyl. The term carbocylic should be similarly construed. In addition, the term carbocyclyl includes any fused combination of carbocyclyl groups, for example naphthyl, phenanthryl, indanyl and indenyl.
Any heterocyclyl group may be saturated, unsaturated or aromatic, and contain 5 to 7 ring-atoms up to 4 of which may be hetero-atoms such as nitrogen, oxygen and sulfur. Examples of heterocyclyl groups are furyl, thienyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, imidazolyl, dioxolanyl, oxazolyl, thiazolyl, imidazolyl, imidazolinyl, imidazolidinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyranyl, pyridyl, piperidinyl, dioxanyl, morpholino, dithianyl, thiomorpholino, pyridazinyl, pyrimidinyl, pyrazinyl, piperazinyi, sulfolanyl, tetrazolyl, triazinyl, azepinyl, oxazepinyl, thiazepinyl, diazepinyl and thiazoiinyl. In addition, the term heterocyclyl includes fused heterocyclyl groups, for example benzimidazolyl, benzoxazolyl, imidazopyridinyl, benzoxazinyl, benzothiazinyl, oxazolopyridinyl, benzofuranyl, quinolinyl, quinazolinyl, quinoxalinyl, dihydroquinazolinyl, benzothiazolyl, phthalimido, benzofuranyl, benzodiazepinyl, indolyl and isoindolyl. The term heterocyclic should be similarly construed.
Any alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl group, when substituted, may be substituted by one or more substituents, which may be the same or different, and may be selected from the list: hydroxy; mercapto; azido; nitro; halogen; cyano; acyl; optionally substituted amino; optionafly substituted carbocyclyl; optionally substituted heterocyclyl; cyanato; thiocyanato; -SF5; -ORa;
-SRa and -Si(Ra>3, where Ra is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted. In the case of any carbocyclyl or heterocyclyl group the list includes additionally: alkyl, alkenyl and alkynyl, each of which may be substituted. Preferred substituents on any alkyl, alkenyl or alkynyl group are alkoxy, haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms; halogen; or optionally substituted phenyl. Preferred substituents on any carbocyclyl or heterocyclyl group are alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio, each containing 1 to 5 carbon atoms; halogen; or optionally substituted phenyl. In the case of any alkyl group or any unsaturated ring-carbon in any carbocyclyl or heterocyclyl group the list includes a divalent group such as oxo or imino, which may be substituted by optionally substituted amino, Ra or -ORa (where Ra is as defined above). Preferred groups are oxo, imino, alkylimino, oximino, alkyloximino or hydrazono.
Any amino group, when substituted and where appropriate, may be substituted by one or two substituents which may be the same or different, selected from the list: optionally substituted alkyl, optionally substituted amino, -ORa (where Ra is as defined above) and acyl groups. Alternatively two substituents together with the nitrogen to which they are attached may form a heterocyclyl group, preferably a 5 to 7-membered heterocyclyl group, which may be substituted and may contain other hetero atoms, for example morpholino, thiomorpholino or piperidinyl.
The term acyl includes the residues of sulfur and phosphorus-containing acids as well as carboxylic acids. Typically the residues are covered by the general formulae -C( = Xa)Rb, -S(0)pRb and -P( = Xa)(ORa)(ORa), where appropriate Xa is
0 or S, RD is as defined for Ra, -ORa, -SRa, optionally substituted amino or acyl; and p is 1 or 2. Preferred groups are -C( = 0)Rc, -C( = S)Rc,and -S(0)pRc where Rc is alkyl, C-| to C5 alkoxy, C-] to C5 alkylthio, phenyl, heterocyclyl or amino, each of which may be substituted.
Complexes of compounds of the invention are usually formed from a salt of formula MAn2, in which M is a divalent metal cation, e.g. copper, manganese, cobalt, nickel, iron or zinc and An is an anion, e.g. chloride, nitrate or sulfate.
In cases where the compounds of the invention exist as the E and Z isomers, the invention includes individual isomers as well as mixtures thereof.
In cases where compounds of the invention exist as tautomeric isomers, the invention includes individual tautomers as well as mixtures thereof.
In cases where the compounds of the invention exist as optical isomers, the invention includes individual isomers as well as mixtures thereof. The compounds of the invention have activity as fungicides, especially against fungal diseases of plants, e.g. mildews and particularly cereal powdery mildew (Erysiphe graminis) and vine downy mildew (Plasmopara viticola), rice blast (Pyricutaria oryzae), cereal eyespot (Pseudocercospore/la herpotrichoides), rice sheath blight {Pellicularia sasakiϊ), grey mould (Botrytis cinerea), damping off {Rhizoctonia solani), wheat brown rust (Puccinia recondita), late tomato or potato blight (Phytophthora infestans), apple scab { Venturia inaequalis), and glume blotch {Leptosphaeria nodorum). Other fungi against which the compounds may be active include other powdery mildews, other rusts, and other general pathogens of Deuteromycete, Ascomycete, Phycomycete and Basidomycete origin.
The invention thus also provides a method of combating fungi at a locus infested or liable to be infested therewith, which comprises applying to the locus a compound of formula I.
The invention also provides an agricultural composition comprising a compound of formula I in admixture with an agriculturally acceptable diluent or carrier.
The composition of the invention may of course include more than one compound of the invention.
In addition, the composition can comprise one or more additional active ingredients, for example compounds known to possess plant-growth regulant, herbicidal, fungicidal, insecticidal, acaricidal, antimicrobial or antibacterial properties. Alternatively the compound of the invention can be used in sequence with the other active ingredient.
The diluent or carrier in the composition of the invention can be a solid or a liquid optionally in association with a surface-active agent, for example a dispersing agent, emulsifying agent or wetting agent. Suitable surface-active agents include anionic compounds such as a carboxylate, for example a metal carboxylate of a long chain fatty acid; an N-acylsarcosinate; mono- or di-esters of phosphoric acid with fatty alcohol ethoxylates or alkyl phenol ethoxylates or salts of such esters; fatty alcohol sulfates such as sodium dodecyl sulfate, sodium octadecyl sulfate or sodium cetyl sulfate; ethoxylated fatty alcohol sulfates; ethoxyiated alkylphenol sulfates; lignin sulfonates; petroleum sulfonates; alkyl-aryl sulfonates such as alkyl-benzene sulfonates or lower alkylnaphthalene sulfonates, e.g. butyl-naphthalene sulfonate; salts of sulfonated naphthalene-formaldehyde condensates; salts of sulfonated phenol-formaldehyde condensates; or more complex sulfonates such as the amide sulfonates, e.g. the sulfonated condensation product of oleic acid and N-methyl taurine; the dialkyl sulfosuccinates, e.g. the sodium sulfonate of dioctyl succinate; acid derivatives of alkyl glycosides and alkylpolyglycosides materials and their metal salts, e.g. alkyl polyglycoside citrate or tartrate materials; or mono-, di- and tri-alkyl esters of citric acid and their metal salts.
Nonionic agents include condensation products of fatty acid esters, fatty alcohols, fatty acid amides or fatty-alkyl- or alkenyl-substituted phenols with ethylene and/or propylene oxide; fatty esters of polyhydric alcohol ethers, e.g. sorbitan fatty acid esters; condensation products of such esters with ethylene oxide, e.g. polyoxyethylene sorbitan fatty acid esters; alkyl glycosides, alkyl polyglycoside materials; block copolymers of ethylene oxide and propylene oxide; acetylenic glycols such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, ethoxylated acetylenic glycols; acrylic based graft copolymers; alkoxylated siloxane surfactants; or imidazoline type surfactants, e.g. 1 -hydroxyethyl-2-alkylimidazoline.
Examples of a cationic surface-active agent include, for instance, an aliphatic mono-, di-, or polyamine as an acetate, naphthenate or oleate; an oxygen-containing amine such as an amine oxide, polyoxyethylene alkylamine or polyoxypropylene alkylamine; an amide-linked amine prepared by the condensation of a carboxylic acid with a di- or polyamine; or a quaternary ammonium salt.
The compositions of the invention can take any form known in the art for the formulation of agrochemicals, for example, a solution, an aerosol, a dispersion, an aqueous emulsion, a microemulsion, a dispersible concentrate, a dusting powder, a seed dressing, a fumigant, a smoke, a dispersible powder, an emulsifiable concentrate, granules or an impregnated strip. Moreover it can be in a suitable form for direct application or as a concentrate or primary composition which requires dilution with a suitable quantity of water or other diluent before application.
A dispersible concentrate comprises a compound of the invention dissolved in one or more water miscible or semi-water miscible solvents together with one or more surface activeand/or polymeric material. Addition of the formulation to water results in the crystalisation of the active ingredient, the process being controlled by the surfactants and/or polymers resulting in a fine dispersion.
A dusting powder comprises a compound of the invention intimately mixed and ground with a solid pulverulent diluent, for example, kaolin.
An emulsifiable concentrate comprises a compound of the invention dissolved in a water-immiscible solvent which forms an emulsion or microemulsion on addition to water in the presence of an emulsifying agent.
A granular solid comprises a compound of the invention associated with similar diluents to those that may be employed in dusting powders, but the mixture is granulated by known methods. Alternatively it comprises the active ingredient absorbed or coated on a pre-formed granular carrier, for example, Fuller's earth, attapulgite, silica or limestone grit.
Wettable powders, granules or grains usually comprise the active ingredient in admixture with suitable surfactants and an inert powder diluent such as clay or diatomaceous earth.
Another suitable concentrate is a flowable suspension concentrate which is formed by grinding the compound with water or other liquid, surfactants and a suspending agent.
The concentration of the active ingredient in the composition of the present invention, as applied to plants is preferably within the range of 0.0001 to 1 .0 per cent by weight, especially 0.0001 to 0.01 per cent by weight, in a primary composition, the amount of active ingredient can vary widely and can be, for example, from 5 to 95 per cent by weight of the composition. In use a compound of the invention is generally applied to seeds, plants or their habitat. Thus, the compound can be applied directly to the soil before, at or after drilling so that the presence of active compound in the soil can control the growth of fungi which may attack seeds. When the soil is treated directly the active compound can be applied in any manner which allows it to be intimately mixed with the soil such as by spraying, by broadcasting a solid form of granules, or by applying the active ingredient at the same time as drilling by inserting it in the same drill as the seeds. A suitable application rate is within the range of from 5 to 1 000 g per hectare, more preferably from 1 0 to 500 g per hectare.
Alternatively the active compound can be applied directly to the plant by, for example, spraying or dusting either at the time when the fungus has begun to appear on the plant or before the appearance of fungus as a protective measure. In both such cases the preferred mode of application is by foliar spraying. It is generally important to obtain good control of fungi in the early stages of plant growth, as this is the time when the plant can be most severely damaged. The spray or dust can conveniently contain a pre- or post-emergence herbicide if this is thought necessary. Sometimes, it is practicable to treat the roots, bulbs, tubers or other vegetative propagule of a plant before or during planting, for example, by dipping the roots in a suitable liquid or solid composition. When the active compound is applied directly to the plant a suitable rate of application is from 0.025 to 5 kg per hectare, preferably from 0.05 to 1 kg per hectare.
In addition, the compounds of the invention can be applied to harvested fruits, vegetables or seeds to prevent infection during storage.
In addition, the compounds of the invention can be applied to plants or parts thereof which have been genetically modified to exhibit a trait such as fungal and/or herbicidal resistance.
In addition the compounds of the invention can be used to treat fungal infestations in timber and in public health applications. Also the compounds of the invention can be used to treat fungal infestations in domestic and farm animals. Compounds of the invention may be prepared, in known manner, in a variety of ways.
Compounds of general formula I may be prepared from compounds of general formula II according to Scheme 1 . The following reaction conditions may be used to effect conversion: a) reaction with R2R3NC(R 1 )(OR)2, where R is a group such as alkyl; b) reaction with ROC(R 1 ) = NCN; c) when R^ is hydrogen, by reaction with H(C = 0)NR2R3 in the presence of
POCI3 or SOCI2; or d) in two steps by reaction with phosgene to form the isocyanate and then treatment with R2R3N(C = 0)R 1 . Scheme 1
Figure imgf000016_0001
In addition, groups R2 and R3 in compounds of general formula I can be converted to other groups defined for R2 and R3, by treatment with an appropriate amine or by acylation or alkylation when R2 or R3 is hydrogen.
Compounds of general formula II may be prepared by reduction of the nitro group in compounds of formula III according to reaction scheme 2. Preferred reaction conditions comprise reaction with stannous chloride in concentrated hydrochloric acid. Scheme 2
Figure imgf000017_0001
(III) (II)
Compounds of formula lla, i.e. compounds of general formula II where A is a direct bond, may be prepared according to reaction scheme 3, where Xv is a leaving group.
Scheme 3
Figure imgf000017_0002
(lia)
Compounds of formula Mb, i.e. compounds of general formula II where R4 is halogen, may be prepared according to scheme 4 where X^ represents halogen.
When R4 is bromine preferred reaction conditions comprise stirring with bromine in a suitable solvent. Scheme 4
Halogenation
Figure imgf000018_0001
Figure imgf000018_0002
(lib) Compounds of formula lie, i.e. compounds of general formula II where A is NHC( = 0)-; compounds of formula lid, i.e. compounds of formula II where A is a direct bond and R^ is optionally substituted phthalimido, where the curved line connecting the 3 and 4 positions of the phthalimido group represents the optionally substituted carbocyclic ring; and compounds of formula lie, i.e. compounds of general formula II where A is a direct bond and R^ is pyrrolyl, optionally substituted at the 2 and 5 positions by one or more groups R which may be the same or different; may be prepared from compounds of formula IV according to methodology shown in reaction scheme 5. For certain compounds of formula IV, protection/deprotection of the amino group ortho to R4 may be required to improve yields.
Scheme 5
Figure imgf000019_0001
Compounds of formula Ilia, i.e. compounds of general formula III where A is a group Az, may be prepared by reacting compounds of formula V with compounds of formula VI according to reaction scheme 6. Az is a group which, in compound
V, forms an anion under basic conditions. Az is alternatively a basic primary or secondary nitrogen atom. Xz is a leaving group, preferably halogen. When Az is oxygen, preferred reaction conditions comprise treating V with sodium hydride followed by addition of VI. When Az is sulfur preferred reaction conditions comprise reacting V with VI in the presence of a tertiary amine base such as ethyldiisopropylamine. When Az is -CHR7-, preferred reaction conditions comprise treating V with potassium terf-butoxide in dimethylformamide at low temperature.
When Az is a basic nitrogen atom, no base is required. Scheme 6
Figure imgf000020_0001
Compounds of formula 1Mb, i.e. compounds of general formula III where A is a group Aw, may be prepared by reacting compounds of formula VII with compounds of formula VIII according to reaction scheme 7. Aw is a group which, in compound VII, forms an anion under basic conditions. Xw is a leaving group, preferably halogen. Preferred basic conditions comprise reaction of VII with potassium carbonate or sodium hydride followed by addition of VIII. Scheme 7
Figure imgf000020_0002
(VII) (lllb)
Compounds of formula lllc, i.e. compounds of general formula III where A is 0, may be prepared by reacting compounds of formula IX with boronic acids of formula X according to Scheme 8. Preferred reaction conditions comprise reaction with copper acetate and triethylamine. Scheme 8
R6-B(OH)2(X)/Cu(OAc)2/Et3N
Figure imgf000021_0001
Figure imgf000021_0002
(IX) (Nlc)
Compounds of formula Hid, i.e. compounds of formula III where A is a direct bond may be prepared according to reaction scheme 9 from compounds of formula XI where Xz is a leaving group, preferably halogen. Scheme 9
Figure imgf000021_0003
(XI) (Hid)
Compounds of formula III where A is a direct bond and R° is a heterocyclyl can be prepared using a variety of methods known to a skilled chemist (for example see "Comprehensive Heterocyclic Chemistry", Vols 1 -7, A. R. Katritzky and C. W. Rees) . By way of example, routes to compounds of formula III containing a 1 ,2,4- oxadiazol-3-yl group (compound llle) and a 1 ,3,4-oxadiazol-2-yl group (compound lllf) are shown in schemes 1 0 and 1 1 . Scheme 1 0
Figure imgf000022_0001
(llle)
Scheme 1 1
Figure imgf000022_0002
(lllf)
Alternatively, using similar chemistry to that described above, compounds of formula I can be prepared by introducing R° after formation of the amidine moiety.
In particular, we have found that treating compounds of formula XII to the reaction conditions of Scheme 7 gives compounds of formula la, i.e. compounds of general formula I where A is oxygen, in particularly high yield (see Scheme 1 2). Compounds of formula XII may be prepared by methods similar to those described in Tetrahedron Letters, 38 (31 ) 5403-5406. Scheme 1 2
Figure imgf000023_0001
(XII) (la)
Some compounds of general formula XII are novel, therefore according to a third aspect the invention provides compounds of general formula Xlla,
Figure imgf000023_0002
(Xlla) where
R 1 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted, or is hydrogen; R2 and R3, which may be the same or different, are any group defined for R1 ; cyano; acyl; -0Ra or -SRa, where Ra is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; or R2 and R3, or R2 and
R1 , together with their interconnecting atoms may form a ring, which may be substituted; R4 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; and
R5 is any group defined for R4; with the proviso that R^ is not terf-butyl. Other methods will be apparent to the chemist skilled in the art, as will be methods for preparing starting materials and intermediates.
In addition, compounds of the invention may be prepared using combinatorial chemistry methodology.
The invention is illustrated in the following Examples. Structures of isolated, novel compounds were confirmed by N.M.R. and/or other appropriate analyses. Proton
N.M.R. spectra (^ H N.M.R.) were determined in deuterochloroform and chemical shifts (δ) are quoted in parts per million downfield of tetramethylsilane.
Example 1
N,N-Dimethyl-N,-[4-(3-trifluoromethylbenzylthio)-2,5-xylyl]formamidine (Compound 3) The product from stage b) (1 .0 g) and N,N-dimethyiformamide dimethylacetal (1 .0 ml) were heated at 100 °C for 4 hours. On cooling the mixture was purified by silica gel chromatography eluting with diethyl ether to give the title compound, ^ H N.M.R. δ(ppm) 2.15 (s, 3H, ArCH3), 2.20 (s, 3H, ArCH3), 3.00 (s, 6H, N(CH3)2),
3.95 (s, 2H, SCH2).
Preparation of Starting Materials a) 2-Nitro-5-(3-thfluoromethylbenzylthio)-p-xylene
A mixture of 3-trifluoromethylbenzyl mercaptan (3.42 g), diisopropylethylamine (2.3 g) and 3-chloro-6-nitro-p-xylene (3.0 g) in dry N- methylpyrrolidinone (20 ml) was heated at 1 30°C for 6 hours. On cooling, the mixture was poured into ice-water and the resulting mixture was filtered to give a solid which was washed with ice-water and then air dried. The solid was purified by silica gel chromatography eluting with light petroleum (60-80°C)/ethyl acetate (9:1 ) to give the title product as a solid, m.p. 85-7°C.
b) 4-(3-Trifluoromethylbenzylthio)-2,5-xylidine
To a stirred mixture of stannous chloride (10.8 g) in concentrated hydrochloric acid (24 ml) and ethanol (50 ml) was added the product from stage a) above (2.46 g) and the mixture was heated at 75 °C for 2 hours. On cooling potassium hydroxide solution was added slowly with cooling. The mixture was extracted with diethyl ether (x3) and the combined extracts were washed with brine, dried (MgSO. ), filtered and evaporated to dryness to give a crude residue which was purified by silica gel chromatography eluting with light petroleum (b. p.60-80 °C)/ethyl acetate (3: 1 ) to give the title product, m.p. 58-60 °C.
Example 2 N/N-Diethyl-N/-[4-(3-trifluoromethylphenoxy)-2,5-xylyl]formamidine (Compound 37)
Under an atmosphere of nitrogen, phosphorous oxychloride (2.1 8 g) in dry diethyl ether (3 ml) was added dropwise to a stirred solution of NN-diethylformamide ( 1 .43 g) in dry diethyl ether (3 ml) and stirring continued for 20 minutes. Stirring was stopped and the mixture allowed to form two layers. The upper ether layer was removed by decanting, and the lower layer was washed with diethyl ether (x3). The product from stage b) (2 g) in dry diethyl ether (4 ml) was then added dropwise. After addition the mixture was stirred vigorously for 1 hour at room temperature. The upper ether layer was removed by decanting and the lower layer was washed with ether (x2) . The lower layer was poured into water and the mixture adjusted to pH 9 with sodium carbonate solution. The mixture was extracted with diethyl ether (x3) and the combined extracts were dried (MgSO^, filtered and evaporated to dryness to give a crude oil which was purified by silica gel chromatography eluting with diethyl ether to give the title compound, ^ H N.M.R. δ(ppm) 1 .20 (t, 6H, CH2CH3), 2.1 0 (s, 3H, ArCH3), 2.20 (s, 3H, ArCH3), 3.30-3.50 (br, 4H, CH2CH3) .
Preparation of Starting materials a) 2-Nitro-5-(3-trifluoromethylphenoxy)-jθ-xylene To a suspension of sodium hydride (0.4 g of 60% in oil) in dry N- methylpyrrolidinone ( 1 0 ml) was slowly added 3-trifluoromethylphenol ( 1 .62 g). When effervescence had ceased, 3-chloro-6-nitro-p-xylene ( 1 .85 g) was added and the mixture stirred at 1 20-40 °C for 5 hours. On cooling, the mixture was poured into water and the mixture extracted with diethyl ether (x3). The combined ether extracts were dried (MgS04), filtered and evaporated to give the title compound as a solid, m.p. 68-71 °C.
b) 4-(3-Trifluoromethylphenoxy)-2,5-xylidine This compound was prepared in similar fashion to the product from
Example 1 , stage b) .
Example 3
N-Ethyl-N-methyl-N 4-(3-trifluoromethylphenoxy)-2,5-xylyl]formamidine (Compound 45)
A mixture of the product from Example 4 ( 1 g) and methylethylamine (0.885 g) in acetonitrile (20 ml) was stirred at room temperature for 1 .5 hours. The solvent was removed in vacua and water added. The mixture was extracted with diethyl ether (x3) and the combined ether extracts dried (MgS04), filtered and evaporated to dryness. The crude residue was purified by silica gel chromatography eluting with ethyl acetate/light petroleum (b.p. 40-60 °C) (4:6) to give the title compound,
1 H N.M.R. δ(ppm) 1 .20 (t, 3H, CH2CH3), 2.1 0 (s, 3H, ArCH3), 2.20 (s, 3H,
ArCH3), 3.00 (s, 3H, NCH3), 3.40 (br, 2H, NCH2) .
Example 4
N-Cyano-N,-[4-(3-trifluoromethylphenoxy)-2,5-xylyl]formamidine
(Compound 44)
To a solution of the product from Example 2 stage b) (2 g) in ethanol (5 ml) was added dropwise ethyl cyanoimidate (0.7 g) at room temperature and stirring continued for 2 hours at room temperature. The ethanol was removed in vacua to give a crude residue which was purified by trituration with light petroleum (b.p.
40-60 °C) followed by silica gel chromatography eluting with ethyl acetate/light petroleum (b.p. 40-60 °C) (4:6) to give the title product, m.p. 1 38-40 °C.
Example 5
NN-Dimethyl-N,-[4-(3-phenyl-1 ,2,4-thiadiazol-5-yloxy)-2,5-xylyl]formamidine (Compound 48)
To a suspension of the starting material (see below) (0.57 g) in dimethylformamide ( 1 0 ml) was added potassium carbonate (0.62 g) and the solution stirred at room temperature for 40 minutes. 5-Bromo-3-phenyl-1 ,2,4-thiadiazole (0.72 g) was added and the mixture stirred at 60 °C for 3 hours. On cooling the mixture was poured into water (1 50 ml) and extracted with diethyl ether (3x70 ml). The combined ether extracts were washed with water (20 ml), dried (MgSO. ), filtered and evaporated to dryness to give a crude solid which was purified by silica gel chromatography eluting with diethyl ether to give the title compound as a solid, m.p. 100-5 °C.
Preparation of Starting Materials NN-Dimethyl-N'-(4-hydroxy-2,5-xylyl)formamidine
This compound was prepared from 4-amino-2,5-dimethylphenol in similar fashion to Examples 1 , 2 or 3, m.p. 212 °C.
Example 6 N,N-Dimethyl-N'-[4-(3-trifluoromethylphenoxy)-2,6-xylyl]formamidine (Compound 20) This compound was prepared from the product of stage b) below and dimethylformamide dimethylacetal according to the method of Example 1 , "Η N.M.R. δ(ppm) 2.1 5 (s, 6H, ArCH3), 3.00 (s, 6H, N(CH3)2).
Preparation of starting materials a) 2-Nitro-5-(3-thfluoromethylphenoxy)-m-xytene
A mixture of 3,5-dimethyl-4-nitrophenol ( 1 .67 g), 3-trifluoromethylbenzene boronic acid (3.8 g), copper (II) acetate (1 .82 g) and triethyiamine (2.02 g) in dichloromethane (50 ml) was stirred at room temperature for 48 hours.
The mixture was evaporated to dryness and purified by silica gel chromatography eluting with light petroleum (b.p. 60-80 °C)/ethyl acetate (1 9: 1 ) to give the title product as an oil.
b) 4-(3-Trifluoromethylphenoxy)-2,6-xylidine
This compound was prepared from the product of stage a) above according to the method of Example 1 , stage b). Example 7
N/Λ/-Dimethyl-N/-[6-bromo-4-(3-trifluoromethylphenoxy)-2,5-xylyl]formamidine
(Compound 12)
The title product was prepared from the product of stage c) below and dimethylformamide dimethylacetal according to Example 1 , ^ H N.M.R. δ(ppm) 2.17 (s, 3H, ArCH3), 2.22 (s, 3H, ArCH3), 3.05 (s, 6H, N(CH3)2).
Preparation of Starting Materials a) 2-Nitro-5-(3-trifluoromethylphenoxy)-p-xylene The title product was prepared from 2,5-dimethyl-4-nitrophenol and 3- trifluoromethylbenzene boronic acid according to Example 6, stage a).
b) 4-(3-Trifluoromethylphenoxy)-2,5-xylidine
The title product was prepared from the product of stage a) according to Example 1 , stage b).
c) 6-Bromo-4-(3-trifluoromethylphenoxy)-2,5-xylidine
To a stirred solution of the product from stage b) above (1 .1 2 g) in dichloromethane (20 ml) was added dropwise bromine (0.64 g) in dichloromethane (5 ml) at 0 °C. The mixture was washed with sodium bicarbonate solution, dried (MgSθ4), filtered and evaporated to give a crude oil which was purified by silica gel chromatography eluting with ethyl acetate/ light petroleum (b.p. 60-80 °C) (1 :4) to give the title product.
Example 8
N,N-Dimethyl-N'-[4-(3-trifluoromethylphenyl)-2,5-xylyl]formamidine
(Compound 53)
The title product was prepared from the product of stage c) below and dimethylformamide dimethylacetal according to Example 1 , "Η N.M.R. δ(ppm) 2.00 (s, 3H, ArCH3), 2.20 (s, 3H, ArCH3), 3.00 (s, 6H, (NCH3)2). Preparation of Starting Materials a) N-(4-Bromo-2,5-xylyl)pivalamide
To a solution of 4-bromo-2,5-xylidine (8 g) in pyridine (60 ml) was added pivaloyl chloride (4.7 mi) at room temperature. After 30 minutes, the mixture was poured into dilute hydrochloric acid/ice solution. The precipitate was filtered and washed with water to give the title product.
b) N-(4-(3-Trifluoromethylphenyl)-2,5-xylyl)pivalamide To a solution of the product of stage a) (9.1 g) in dimethoxyethane (14 ml) was added triphenylphosphinepalladium (II) chloride (catalytic amount) and stirred for 10 minutes. 3-Trifluoromethyphenylboronic acid (6.03 g), sodium bicarbonate (8.1 g) and water (102 ml) were added and the mixture heated under reflux for 4 hours. On cooling 1 N sodium hydroxide solution (94 ml) was added the mixture extracted with ethyl acetate. The organic extracts were washed with saturated sodium chloride solution, dried (MgSθ4> and concentrated to give the title product.
c) 4-(3-Trifluoromethylphenyl)-2,5-xylidine The product from stage b) (10.4 g) in glacial acetic acid (36 ml) was treated with hydrochloric acid (24.5 ml of 1 5 % solution) at 70 °C. The mixture was stirred for 3 days at 100 °C. On cooling, water was added and the mixture extracted with ethyl acetate. The organic phase was washed with sodium bicarbonate solution, dried (MgS04) and concentrated to give the title product.
Example 9
N,N-Dimethyl-N 4-(3-trifluoromethylbenzyl)-2,5-xylyl]formamidine (Compound 264) The title compound was prepared from the product of stage d) below in similar fashion to Example 1 , m.p. 75-7 °C. Preparation of Starting Materials a) 2-Nitro-5-(α-cyano-3-trifluoromethylbenzyl)-p-xylene
The title product was prepared from 2-chloro-5-nitro-p-xylene and 3-trifuoromethylbenzyi cyanide according to the methodology in J. Med. Chem., 40, 3942 (1 997).
b) 2-Nitro-5-(3-trifluoromethylbenzoyl)-p-xylene
Potassium ten— butoxide ( 1 .1 2 g) was added to a solution of the product from stage a) (3.3 g) in dry dimethylformamide (30 ml) at 0 °C and stirred at 0 °C for 5 minutes. Hydrogen peroxide (3.5 ml, 30%) was added dropwise and stirring continued for 6 hours at approximately 3 °C. The reaction mixture was allowed to stand at room temperature for 2 days. The reaction mixture was poured into dilute hydrochloric acid (500 ml), and sodium metabisulfite was added. The mixture was extracted with diethyl ether (2x200 ml), washed with water (2x20 ml), dried (MgS04) and concentrated to give a crude product. Trituration from light petroleum (b.p. 40-60 °C) gave a solid which was recrystallised from diisopropyl ether to give the title product.
c) 2-Nitro-5-(3-trifluoromethylbenzyl)-p-xylene
To a solution of the product of stage b) ( 1 g) in dichloromethane (20 ml) at 0 °C was added a solution of trifluoromethane sulfonic acid (0.6 ml) in dichloromethane (10 ml). Triethylsilane (0.8 ml) in dichloromethane (10 ml) was added and stirred at 0 °C for 10 minutes. A further portion of trifluoromethane sulfonic acid (0.6 ml) was added followed by a further portion of triethylsilane (0.8 ml). The mixture was allowed to warm to room temperature and stirred for 1 hour. The mixture was poured into saturated sodium bicarbonate solution (100 ml) and the inorganic solid filtered. The layers were separated and the aqueous layer extracted with dichloromethane (2x50 ml). The combined organic layers were evaporated and recrystallised to give a solid, m.p. 75-7 °C.
d) 4-(3-Trifluoromethylbenzyl)-2,5-xylidine
The title compound was prepared from the product of stage c) according to Example 1 stage b). Example 1 0
N,N-Dimethyl-NH4-(4-fluorobenzamido)-2,5-xylyl]formamidine (Compound 98) The title compound was prepared from the starting material in similar fashion to Example 1 , m.p. 1 66-8 °C.
Preparation of Starting Materials N-(4-Amino-2,5-xylyl)-4-fluorobenzamide To a solution of p-xylylenediamine (3.0 g) and ethyldiisopropylamine (3.8 ml) in dichloromethane (300 ml) at 0 °C, was added dropwise 4-fluorobeπzoyl chloride (3.5 g) . The mixture was warmed to room temperature and stirring continued for 4 hours. Water (200 ml) was added and the mixture was stirred for 30 minutes. The mixture was filtered, washing through with water and dichloromethane. The organic phase was washed with water, dried (MgS04) and evaporated to give a solid, m.p. 1 74-6 °C.
Example 1 1
N/N-Dimethyl-N,-(4-phthalimido-2,5-xylyl)formamidine (Compound 80)
The title compound was prepared from the starting material in similar fashion to Example 1 , m.p. 1 70-3 °C.
Preparation of Starting Materials N-(4-Amino-2,5-xylyl)phthalimide
To a solution of p-xylylenediamine ( 1 .0 g) in N-methylpyrroiidinone was added phthalic anhydride ( 1 .1 g) in N-methylpyrrolidinone ( 1 0 ml) . The mixture was heated at 1 50 °C for 4 hours. On cooling, the mixture was poured into water and then filtered. The cake was washed with water and dried, m.p. 1 67-9 °C.
Example 1 2
NN-Dimethyl-N/-[4-(2,5-dimethyl-1 -pyrrolyl)-2,5-xylyl1formamidine
(Compound 79)
The title compound was prepared from stage c) below in similar fashion to Example 1 , m.p. 90-1 °C. Preparation of Starting Materials a) N-(4-Amino-2,5-xylyl)acetamide
To a solution of p-xylenediamine (2.0 g) in dichloromethane (200 ml) maintained below 10 °C was added Λ/,N-diisopropylamine (2.52 ml) followed by the dropwise addition of acetylchloride (1 .1 5 g). The mixture was allowed to attain room temperature and stirred overnight. Water (120 ml) was added and the suspension filtered. The filtered solid was washed with dichloromethane (2 x100 ml) and water (100 ml). All filtrates were combined and the organic layer separated. The organic layer was washed with water, dried (MgSθ4> and evaporated to give the title product as a solid, m.p. 1 33-5 °C.
b) N-[4-(2,5-Dimethyl-1 -pyrrolyl)-2,5-xylyl]acetamide The product from stage a) 1 .0 g) was added to acetonylacetone (0.7 ml) and the mixture heated at 140 °C for 4 hours. On cooling, the mixture was dissolved in dichloromethane and the solution filtered through (MgSθ4).
Concentration gave a crude product which was purified by silica gel chromatography eluting with diethyl ether, to give the title product.
c) 2,5-Dimethyl-4-(2,5-dimethyl-1 -pyrrolyl)aniline
A mixture of the product from stage b) (0.6 g), aqueous sodium hydroxide solution (10 ml, 10%) and ethanol (30 ml) was heated under reflux for 24 hours. On cooling, the mixture was extracted with diethyl ether (x2). The combined diethyl ether extracts were water washed, dried (MgSθ4> and concentrated to give a crude product. Filtration through silica gave the title product.
Example 1 3 NN-Dimethyl-N,-[4-(2-benzo[b]thiophenyl)-2,5-xylyl)formamidine (Compound 187)
The title compound was prepared from stage b) below in similar fashion to Example 1 , m.p. 67-8 °C. Preparation of Starting Materials a) 2-(4-Nitro-2,5-xylyl)benzo[b]thiophene
A mixture of 2-bromo-5-nitro-p-xylene (200 g), 2-benzo[b]thiopheneboronic acid (200 g), (Ph3P)4Pd (0.36 g) in toluene (60 ml) and ethanol (22 ml) was heated to reflux overnight. Ethyl acetate and water were added and the organic phase was separated. The organic phase was washed with water, dried (MgSθ4) and filtered through a pad of silica to give the title product.
b) 2,5-Dimethyl-4-(2-benzo[b]thiophenyl)aniline
The title compound was prepared from the product of stage a) above according to Example 1 stage b).
Example 14 N,N-Dimethyl-N'-(4-[5-(4-chlorophenyl)-1 ,2,4-oxadiazol-3-yl]-2-tolyl)formamidine (Compound 179)
The title compound was prepared from the product of stage c) below according to Example 1 , m.p. 136-7 °C.
Preparation of Starting Materials a) 3-Methyl-4-nitrobenzamide oxime
To a solution of 3-methyl-4-nitrobenzonitrile (5 g) in ethanol (100 ml) at room temperature was added hydroxylamine hydrochloride (2.25 g) followed by triethylamine (4.5 ml). The mixture was heated under reflux for 2.5 hours. On cooling the mixture was evaporated to a third of its original volume and poured on to water (200 ml). The mixture was filtered to give the title product as a solid, m.p. 1 27-9 °C.
b) 5-(4-Chlorophenyl)-3-(3-methyl-4-nitrophenyl)-1 ,2,4-oxadiazole To a solution of the product from stage a) (1 .9 g) and triethylamine (1 .62 ml) in dichloromethane (50 ml) at room temperature was added 4- chlorobenzoyl chloride (2.05 g). The mixture was stirred at room temperature for 2 hours and then washed with water. Toluene (100 ml) was added and the mixture was heated under Dean and Stark conditions for 5 hours. On cooling the mixture was filtered and concentrated. Trituration with diisopropylamine and light petroleum (b.p. 40-60 °C) gave the title product, m.p. 145-7 °C.
c) 4-[5-(4-Chlorophenyl)-1 ,2,4-oxadiazol-3-yl]-2-methylaniline The title compound was prepared from the product of stage b) according to
Example 1 stage b).
Example 1 5
NN-Dimethyl-N,-[4-(5-tert-butyl-1 ,3,4-oxadiazol-2-yl)-2-methylphenyl]formamidine (Compound 21 1 )
The title compound was prepared from the product of stage c) below according to Example 1 , m.p. 79-80 °C.
Preparation of Starting Materials a) N-(3-Methyl-4-nitrobenzoyl)-N'-pivalolyhydrazine
To a solution of 3-methyl-4-nitrobenzoylhydrazine (3.9 g) in dichloromethane ( 100 ml) was added triethylamine (3.06 ml) followed by pivaloyl chloride (2.6 ml). The mixture was stirred at room temperature for 2 hours. The mixture was washed with water, dried (MgSθ4) and concentrated. Trituration with light petroleum (b.p. 60-80 °C) gave the title product, m.p. 1 25-7 °C.
b) 5-tert-Butyl-2-(3-methyl-4-nitrophenyl)-1 ,3,4-oxadiazole
The product prepared in stage a) (5.0 g) was stirred in toluene (200 ml) and treated with phosphorous pentoxide (1 0 g). The mixture was heated under reflux for 2 hours and then poured onto ice-water. The mixture was extracted with diethyl ether, the extract dried (MgSθ4) and concentrated.
The residue was purified by silica gel chromatography eluting with diethyl ether/light petroleum (b.p. 60-80 °C) to give the title product, m.p. 1 23-5 °C.
c) 2-(4-Amino-3-methyl)-5-tert-butyl-1 ,3,4-oxadiazole
The title compound was prepared from the product of stage b) according to Example 1 stage b). Example 1 6
N-Cyano-N-methyl-N,-[4-(4-chloro-3-trifluoromethylphenoxy)-2-xylyl]formamidine (Compound 373) The product from stage c) (0.4 g) in tetrahydrofuran (10 ml) was treated with sodium hydride (0.05 g). iodomethane (0.075 ml) was added and the mixture was stirred. The mixture was quenched with water and extracted with dichloromethane . The extracts were dried (MgSθ4) and evaporated. The residue product was purified by silica gel chromatography to give the title product, ^ H N.M.R. δ (ppm) 2.10 (s, 3H, ArCH3), 2.20 (s, 3H, ArCH3) and 3.35 (s, 3H,
NCH3).
Example 1 7
N-Cyano-N -[4-(4-chloro-3-trifluoromethylphenoxy)-2,5-xylyl]formamidine (Compound 397)
The title compound was prepared according to Example 4 from the product of stage b) above, m.p. 1 1 1 -4 °C.
Preparation of Starting Materials a) 2-Nitro-5-(4-chloro-3-trifluoromethylphenoxy)-p-xylene
The title compound was prepared according to Example 2 stage a).
b) 4-(4-Chloro-3-trifluoromethylphenoxy)-2,5-xylidine
The title compound was prepared according to Example 1 stage b) from the product of stage a) above.
The following compounds of formula la (see Table 1 ), i.e. compounds of general formula I where -A-R^ is para to the amidine moiety, may be prepared by methods analogous to those of Examples 1 to 1 7. Where the moiety depicted on the right side of linkage A is attached to R^;
Figure imgf000036_0001
(la)
Table 1
Figure imgf000036_0002
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
Those compounds in Table 1 which do not have discrete melting points have the characteristic ^ H N.M.R. shown in Table 2 below. Table 2
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
The following compounds of formula lb (see Table 3), i.e. compounds of general formula I where R^ is hydrogen, R^ is methyl, R^ is methyl, R^ is methyl substituted at the 5-position of the phenyl ring, -A-R^ is para to the amidine moiety and is S-But-phenoxy, may be prepared by methods analogous to those of Examples 1 to 1 7 Where the moiety depicted on the right side of linkage A is attached to R6-
Figure imgf000061_0001
(lb)
Table 3
Figure imgf000061_0002
Those compounds in Table 3 which do not have discrete melting points have the characteristic ^ H N.M.R. shown in Table 4 below. Table 4
Figure imgf000062_0001
Example 18
Λ/.Λ/-Dimethyl-Λ/'-f4-(3-trifluoromethylphenoxy)-2,5-xylyllformamidine sulfate salt
(Compound 602
To a solution of the compound 1 (see Table 1 ) (0.3g) in ethanol (0.3 ml) was added dropwise concentrated sulfuric acid (0.098 g) . The mixture was filtered and the resulting solid was washed with diethyl ether to give the title compound as a solid, m.p. 1 78-80 °C.
The following compounds of formula X (see Table 4), i.e. salts of general formula I where -A-R^ is para to the amidine moiety, R^ is hydrogen, R^ is methyl, An is an anion and u is 1 or 2 depending on the valency of the anion, may be prepared by methods analogous to Example 1 8
Figure imgf000063_0001
(X) Table 4
Figure imgf000063_0002
Those compounds in Table 4 which do not have discrete melting points have the following characteristic ^ H N.M.R. data in CDCI3. Compound 605
1 H N.M.R. δ(ppm) 2.1 5 (s, 3H, ArCH3), 2.25 (s, 3H, ArCH3), 3.20 (s, 3H,
N(CH3)), 3.25 (s, 3H, N(CH3)), 10.20-10.80 (br, 1 H, NH)
Compound 609
1 H N.M.R. δ(ppm) 0.75 (s, 3H, CCH3), 1 .05 (s, 3H, CCH3), 1 .25 (d, 2H, CH2), 1 .75-1 .95 (m, 3H), 2.1 5 (s, 3H, ArCH3), 2.20 (m, 1 H, CH), 2.25 (s, 3H, ArCH3), 2.35 (d, 1 H, CH), 2.60 (t, 1 H, CH), 2.85 (d, 1 H, CH), 3.20 (s, 3H, N(CH3), 3.30 (s, 3H, N(CH3).
The following compounds of formula Ic (see Table 5), i.e. compounds of general formula I where R1 and R^ are hydrogen, R^, R3 ancj R4 are methyl, may be prepared by methods analogous to those of Examples 1 to 1 7. Where the moiety depicted on the right side of linkage A is attached to R^-
Figure imgf000064_0001
(Ic)
Table 5
Figure imgf000064_0002
Test Examples
Compounds were assessed for activity against one or more of the following: Phytophthora infestans: late tomato blight Plasmopara viticola: vine downy mildew Erysiphe graminis f. sp. tritici: wheat powdery mildew
Pyricularia oryzae: rice blast Leptosphaeria nodorum: glume blotch
Aqueous solutions or dispersions of the compounds at the desired concentration, including a wetting agent, were applied by spray or by drenching the stem base of the test plants, as appropriate. After a given time, plants or plant parts were inoculated with appropriate test pathogens before or after application of the compounds as appropriate, and kept under controlled environmental conditions suitable for maintaining plant growth and development of the disease. After an appropriate time, the degree of infection of the affected part of the plant was visually estimated. Compounds are assessed on a score of 1 to 3 where 1 is little or no control, 2 is moderate control and 3 is good to total control. At a concentration of 500 ppm (w/v) or less, the following compounds scored 2 or more against the fungi specified.
Phytophthora infestans
7, 8, 28, 30, 36, 46, and 271.
Plasmopara viticola 149, 331, 373 and 364.
Erysiphe graminis f. sp. Tritici
1-5, 7-9, 11-13, 15-24, 26, 28-41, 43, 45, 46, 48, 51, 52, 55, 56, 58, 59, 61, 62, 65, 68, 76, 84, 86, 90, 100, 101, 104-106, 109, 112, 113, 120, 123, 124, 130, 135, 138, 139, 140, 141, 143, 146, 149, 160,166, 171, 173-175, 183, 187-190, 193-196, 200, 203-205, 207-209, 213, 215-217, 223, 225, 228, 231, 232, 234, 237, 246, 250, 252, 253, 256, 258, 259, 261, 262, 264, 266- 272, 277, 279, 281, 282, 284, 286-288, 290, 291, 295, 298, 299, 301, 303, 310-312, 318, 325, 326, 330, 331, 335, 346, 347, 349, 351, 353, 355-357, 359, 361, 364, 365-368, 370-372, 374, 376-379, 392, 396, 398, 502, 504, 600, 601, 610 and 611.
Pyricularia oryzae 7, 17, 20, 21, 23, 26-28, 30, 32, 34, 36, 38, 41, 43, 45, 51, 54, 55, 59, 63, 94, o, 143, 146, 163, 225, 325, 352, 353, 360, 368, 600 and 611.
Leptosphaeria nodorum
1, 2, 5, 7, 8, 15, 27, 29, 35, 37, 41, 43, 45, 48, 56, 59, 61, 72, 100, 130, 160, 170, 181, 194, 208, 214, 235, 246, 283, 284, 290, 303, 310, 311, 312, 325, 326, 351, 364, 369, 378 and 392

Claims

Claims
The use of a compound of general formula I and salts thereof as fungicides
Figure imgf000067_0001
wherein
R1 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted, or hydrogen;
R2 and R3, which may be the same or different, are any group defined for
R 1 ; cyano; acyl; -ORa or -SRa, where Ra is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; or R2 and R3, or R2 and R^ , together with their interconnecting atoms may form a ring, which may be substituted;
R4 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; hydroxy; mercapto; azido; nitro; halogen; cyano; acyl; optionally substituted amino; cyanato; thiocyanato; -SF5; -ORa;
-SRa or -Si(Ra)3; m is 0 to 3; when present R^, which may be the same or different to any other R°, is any group defined for R4; R6 is optionally substituted carbo- or heterocyclyl; and A is a direct bond, -0-, -S(0)n-, -NR9-, -CR7 = CR7-, -C≡C-, -A-! -, -A1 -A1 -,
-0-(A1 )k-0-, -0-(Al )k-, -A3-, -A4-, -A1 0-, -A1 S(0)n-, -A2-, OA2-,
-NR9A2-, -0A2-A1 -, -OA2-C(R7) = C(R8)-, -S(0)nA1 -, -A1 -A4-,
-A1 -A4-C(R8) = N-N = CR8-, -A1 'A4-C(R8) = N-X2-X3-, -A1 -A4-A3-, -A1-A4-N(R9)-, -A1-A -X-CH2A -A1-A4-A1-, -A1-A4-CH2X-, -Al-A4-C(R8) = N-X2-X3-χ1-, -A1-X-C(R8) = N-, -A1-X-C(R8) = N-N = CR8-, -A1-X-C(R8) = N-N(R9)-, -A1-X-A"-X1-, -A1-0-A3-, -A1-0-C(R7) = C(R8)-, -Al-0-N(R9)-A2-N(R9)-, -Al-0-N(R9)-A2-, -A1-N(R9)-A2-N(R9)-, -A1-N(R9)-A2-, -A1-N(R9HM = C(R8)-, -A3-A1-, -A4-A3-, -A2-NR9-,
-A1-A2-χ1-, -A1-A1-A2-X1-, -0-A2-N(R9)-A2-, -CR7 = CR7-A2-X1-, -C≡C-A2-χ1-, -N = C(R8)-A2-X1-, -C(R8) = N-N = C(R8)-, -C(R8) = N-N(R9)-, -(CH2)2-0-N = C(R8)- or -X-A2-N(R9)- where n is 0, 1 or 2, k is 1 to 9,
A1 is -CHR7-,
A2 is -C( = X)-,
A3 is-C(R8) = N-0-, A4 is -0-N = C(R8)-,
X is O or S, χ1 is O, S, NR9 or a direct bond,
X2 is O, NR9 or a direct bond,
X3 is hydrogen, -C( = 0)-, -S02- or a direct bond, R7, which may be the same or different to any other R7, is alkyl, cycloalkyl or phenyl, each of which may be substituted; or is hydrogen, halogen, cyano or acyl;
R8, which may be the same or different to any other R8, is alkyl, alkenyl, alkynyl, alkoxy, alkylthio, carbo- or heterocyclyl, each of which may be substituted; or is hydrogen;
R9, which may be the same or different to any other R9, is optionally substituted alkyl, optionally substituted carbo- or heterocyclyl, hydrogen or acyl; or two R9 groups on A, together with the connecting atoms, form a 5 to 7 membered ring; where the moiety depicted on the right side of linkage A is attached to R^; or -A-R and R^ together with benzene ring M form an optionally substituted fused ring system.
The use according to claim 2 wherein R 1 is alkyl, alkenyl or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl; or is hydrogen.
The use according to claim 1 wherein R 1 is C-j -C-] Q a"<Y' or hydrogen.
The use according to any preceding claim wherein R2 and R3, which may be the same or different, are alkyl, alkenyl or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen, optionally substituted phenyl; or is hydrogen; alkoxy; alkoxyalkoxy; benzyloxy; cyano; or alkylcarbonyl.
The use according to claim 4 wherein R2 and R3, which may be the same or different, are C I -C -| Q alkyl or hydrogen.
The use according to any preceding claim wherein R4 is alkyl, alkenyl, or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl; or is hydroxy; halogen; cyano; acyl; alkoxy; haloalkoxy; or alkylthio.
The use according to claim 6 wherein R4 is C -J -C -I O alk-yi or halogen.
The use according to any preceding claim wherein m is 0 or 1 .
The use according to any preceding claim wherein, when present, R° is a group defined for R4 in claim 6.
The use according to any preceding claim wherein when present, the group R5 is attached at the 5 position of ring M. The use according to any preceding claim wherein A is a direct bond, -0-, -S(0)nA1 -, -0(A1 )k-, -S(0)n-, -NR9A2-, -A2-, -OA2-, -OA2-A1 -, -NR9- or
-0(A1 )kO-.
The use according to claim 1 1 wherein A is a direct bond, -0-, -S-, -NR9-, -CHR7- or -O-CHR7-.
The use according to any preceding claim wherein, when present, R9 is alkyl, alkenyl, or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl; or is hydrogen
The use according to any preceding claim wherein, when present, R7 is alkyl, alkenyl, or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl; or is hydroxy; halogen; cyano; acyl; alkoxy; haloalkoxy; alkylthio; or hydrogen.
The use according to any preceding claim wherein A is attached to the 4 position of benzene ring M.
The use according to any preceding claim wherein R^ is optionally substituted phenyl or optionally substituted aromatic heterocyclyl.
The use according to any preceding claim wherein when substituted, R^ may be substituted by one or more substituents, which may be the same or different, and may be selected from the list: alkyl, alkenyl, alkynyl, carbo- or heterocyclyl, each of which may be substituted; hydroxy; mercapto; azido; nitro; halogen; cyano; acyl; optionally substituted amino; cyanato; thiocyanato; -SF5; -ORa; -SRa and -Si(Ra)3, where Ra is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted.
The use according to claim 17 wherein when substituted, R^ may be substituted by one or more substituents, which may be the same or different, and may be selected from the list: hydroxy; halogen; cyano; acyl; amino; alkylamino; dialkylamino; alkyl; haloalkyl; RaO-alkyl; acyloxyalkyl; cyano-oxyalkyl; alkoxy; haloalkoxy; alkylthio; carbocyclyl, optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio; and benzyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio.
The use of a compound of general formula I and salts thereof as fungicides
Figure imgf000071_0001
wherein:
R ' is alkyl, alkenyl or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio or halogen; or is hydrogen;
R2 and R3, which may be the same or different, are as defined for R^ , or are alkoxy, alkoxyalkoxy, benzyloxy, cyano or alkylcarbonyl;
R4 is alkyl, alkenyl or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio or halogen; or is hydroxy; halogen; cyano; or acyl; m is 0 or 1 ; when present, R^ is a group defined for R4;
A is a direct bond, -0-, -S-, -NR9-, -CHR7- or -O-CHR7-, wherein, when present, R9 is alkyl, alkenyl, or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, or halogen; or is hydrogen; and R7 is a group defined for R9, or is hydroxy; halogen; cyano; acyl; alkoxy; haloalkoxy or alkylthio; A is attached to the 4 position of benzene ring M; and
R6 is phenyl or aromatic heterocyclyl, optionally substituted by one or more substituents, which may be the same or different, and may be selected from the list: hydroxy; halogen; cyano; acyl; amino; alkylamino; dialkylamino; alkyl; haloalkyl; RaO-alkyl; acyloxyalkyi; cyano-oxyalkyl; alkoxy; haloalkoxy; alkylthio; carbocyclyl, optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio; and benzyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio.
A compound of general formula I and salts thereof
Figure imgf000072_0001
wherein
R1 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted, or is hydrogen;
R2 and R3, which may be the same or different, are any group defined for
Rl , or together with the nitrogen to which they are attached may form a ring, which may be substituted;
R4 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; m is 1 ;
R5 is any group defined for R4 attached to the 5-position of the benzene ring M; R6 is optionally substituted carbo- or heterocyclyl; and A is a direct bond; -0-; -S-; -NR9-, where R9 is alkyl, alkenyl, or alkynyl, each of which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or optionally substituted phenyl; -CHR7- or -O-CHR7-, where
R7 is alkyl, alkenyl, or alkynyl, which may be substituted by alkoxy, haloalkoxy, alkylthio, halogen or phenyl optionally substituted by alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio; or is hydroxy; halogen; cyano; acyl; alkoxy; haloalkoxy; or alkylthio; where -A-R^ is in the 4-position of the benzene ring M and the moiety depicted on the right side of linkage A is attached to R^; or -A-R6 and R^ together with benzene ring M form an optionally substituted fused ring system.
A fungicidal composition comprising at least one compound as claimed in claim 20 in admixture with an agriculturally acceptable diluent or carrier.
A method of combating fungi at a locus infested or liable to be infested therewith, which comprises applying to the locus a compound as defined in any preceding claim.
A compound of general formula Xlla,
Figure imgf000073_0001
(Xlla) where
R^ is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted, or is hydrogen; R2 and R3, which may be the same or different, are any group defined for
Rl ; cyano; acyl; -ORa or -SRa, where Ra is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; or R2 and R3, or R2 and R^ , together with their interconnecting atoms may form a ring, which may be substituted;
R4 is alkyl, alkenyl, alkynyl, carbocyclyl or heterocyclyl, each of which may be substituted; and
R5 is any group defined for R4; with the proviso that R^ is not tert-butyl.
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US09/890,775 US6893650B1 (en) 1999-02-06 2000-02-04 N2-phenylamidine derivatives
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IL14446400A IL144464A0 (en) 1999-02-06 2000-02-04 N<2>-phenylamidine derivatives
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BRPI0009314-9A BR0009314B1 (en) 1999-02-06 2000-02-04 compounds, fungicidal composition, fungal control method and use of a compound.
JP2000597256A JP2002536354A (en) 1999-02-06 2000-02-04 N2-phenylamidine derivative
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IL144464A IL144464A (en) 1999-02-06 2001-07-19 N2ôçä-phenylamidine derivatives and their use in the preparation of fungicides
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GB9902592D0 (en) 1999-03-24
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RU2234504C2 (en) 2004-08-20
AU2308800A (en) 2000-08-25
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KR20010101999A (en) 2001-11-15
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HUP0105098A3 (en) 2002-05-28
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