WO2001055136A1 - Benzoxazole derivatives and their use as pesticides - Google Patents

Benzoxazole derivatives and their use as pesticides Download PDF

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Publication number
WO2001055136A1
WO2001055136A1 PCT/GB2001/000314 GB0100314W WO0155136A1 WO 2001055136 A1 WO2001055136 A1 WO 2001055136A1 GB 0100314 W GB0100314 W GB 0100314W WO 0155136 A1 WO0155136 A1 WO 0155136A1
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Prior art keywords
optionally substituted
alkyl
alkoxy
formula
haloalkyl
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PCT/GB2001/000314
Other languages
French (fr)
Inventor
Sarah Armstrong
Nigel John Barnes
Susan Patricia Barnett
Eric Daniel Clarke
Patrick Jelf Crowley
Torquil Eoghan Macleod Fraser
David John Hughes
Christopher John Mathews
Rogers Salmon
Stephen Christopher Smith
Russell Viner
William Guy Whittingham
John Williams
Alan John Whittle
William Roderick Mound
Christopher John Urch
Brian Leslie Pilkington
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Syngenta Limited
PILKINGTON, Joan
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Application filed by Syngenta Limited, PILKINGTON, Joan filed Critical Syngenta Limited
Priority to AU28670/01A priority Critical patent/AU2867001A/en
Publication of WO2001055136A1 publication Critical patent/WO2001055136A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to azole and azine derivatives, to processes for preparing them, to fungicidal, insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them, to methods of using them to combat fungal diseases
  • Azole and azine derivatives are disclosed in WO95/31448, WO97/18198, WO98/02424, WO98/05670 and WOOO/015622.
  • the present invention provides a compound of formula (I):
  • A is optionally substituted C ⁇ . 6 alkylene, optionally substituted C 2 _ 6 alkenylene, optionally substituted C 2 _ 6 alkynylene, optionally substituted cycloalkylene, optionally substituted C ⁇ _ 6 alkyleneoxy, optionally substituted oxy(C ⁇ _ 6 )alkylene, optionally substituted C*_ 6 alkylenethio, optionally substituted thio(C ⁇ _ 6 )alkylene, optionally substituted C 1-6 alkyleneamino, optionally substituted amino(C ⁇ _ 6 )alkylene, optionally substituted [C ⁇ _ 6 alkyleneoxy(C ⁇ _ 6 )alkylene], optionally substituted [C ⁇ _ 6 alkylenethio(C ⁇ _ 6 )alkylene], optionally substituted [C ⁇ _ 6 alkylenesulf ⁇ nyl(C ⁇ _ 6 )alkylene], optionally substituted [C ⁇ _ 6 alkylenesulfonyl(C ⁇ _ )alkylene] or
  • E is N, N-oxide or CR 12 ;
  • W is CR 1 or N;
  • X is N, N-oxide or CR 11 and R 11 is hydrogen, optionally substituted C 1-6 alkyl or optionally substituted phenyl, with the proviso that the ring containing D, E, X and W contains at least one atom that is other than a carbon atom;
  • R 1 is hydrogen, halogen, optionally substituted C ⁇ _ 6 alkyl, optionally substituted C 2 . 6 alkenyl, optionally substituted C 2 . 6 alkynyl, optionally substituted C 1-6 alkoxy, optionally substituted C ⁇ _ 6 alkylthio, optionally substituted C 3 . 7 cycloalkyl, cyano, nitro or SF 5 ;
  • R 7 is hydrogen or optionally substituted C ⁇ _ 6 alkyl;
  • R 51 is hydrogen, optionally substituted Ci-io alkyl, optionally substituted [C 2-6 alkenyl(C ⁇ _ 6 )alkyl], optionally substituted [C . 6 alkynyl(C ⁇ _ 6 )alkyl], optionally substituted C 3 .
  • R 53 is optionally substituted C ⁇ _ ⁇ o alkyl, optionally substituted [C 2 _ 6 alkenyl(C ⁇ _ 6 )- alkyl], optionally substituted fC 2 . 6 alkynyl(C ⁇ _ 6 )alkyl], optionally substituted C 3 _ 7 cycloalkyl, optionally substituted CM O alkylcarbonyl, optionally substituted CM O alkoxycarbonyl, optionally substituted C MO alkylaminocarbonyl, optionally substituted di(C ⁇ - ⁇ o)alkyl- aminocarbonyl or optionally substituted phenoxycarbonyl);
  • R 54 and R 55 are, independently optionally substituted C MO alkyl, optionally substituted C ⁇ _ 6 alkoxy, optionally substituted [C 2 . 6 alkenyl(C ⁇ _ 6 )alkyl], optionally substituted [C 2-6 alkynyl(C ⁇ _ 6 )alkyl], optionally substituted C 3 .
  • R , R and R " are, independently, hydrogen, halogen, optionally substituted C ⁇ -6 alkyl, optionally substituted C ⁇ _ 6 alkoxy, optionally substituted C ⁇ _ alkylthio, optionally substituted C ⁇ _ 6 alkylsulfinyl, optionally substituted C ⁇ _ 6 alkylsulfonyl, cyano, nitro, optionally substituted C 1-6 alkylcarbonyl, optionally substituted C ⁇ _ 6 alkoxycarbonyl or SF 5
  • R 8 and R 9 are, independently, hydrogen, halogen, cyano, nitro, optionally substituted
  • R 13 is hydrogen, cyano, nitro, optionally substituted C ⁇ -6 alkyl, optionally substituted C 3-7 cycloalkyl, optionally substituted (C 2-6 )alkenyl(C ⁇ _ )alkyl, optionally substituted (C 2 _ 6 )alkynyl(C ⁇ _ )alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted C ⁇ _ 6 alkylcarbonyl, optionally substituted C-.
  • R 14 is hydrogen, cyano, optionally substituted C]_ 8 alkyl, optionally substituted [C 2 _ 6 alkenyl(C ⁇ _ 6 )alkyl], optionally substituted [C 2 _ alkynyl(C ⁇ _ 6 )alkyl], optionally substituted C 3 .
  • cycloalkyl optionally substituted [C 3 _ 7 cycloalkyl(C ⁇ _ 6 )alkyl], C*_ 6 alkoxy(C ⁇ _ 6 )alkyl, optionally substituted C ⁇ _ 6 alkoxycarbonyl, optionally substituted C ⁇ _ 6 alkylcarbonyl, optionally substituted C ⁇ _ 6 alkylaminocarbonyl, optionally substituted di( . ⁇ alkylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl;
  • R is hydrogen, halogen, nitro, cyano, optionally substituted C ⁇ _ 8 alkyl, optionally substituted C 2 . alkenyl, optionally substituted C 2 _ alkynyl, optionally substituted C 3 _ cycloalkyl, optionally substituted C ⁇ _ 6 alkoxycarbonyl, optionally substituted C ⁇ _ 6 alkylcarbonyl, optionally substituted C ⁇ _ 6 alkylaminocarbonyl, optionally substituted di(C ⁇ - 6 )alkylaminocarbonyl, optionally substituted phenyl or optionally substituted heteroaryl;
  • R 20 and R 21 are, independently, optionally substituted C ⁇ _ 6 alkyl or R 20 and R 21 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two C ⁇ _ 6 alkyl groups;
  • R 26 is hydrogen, optionally substituted C ⁇ _ 2 o alkyl, optionally substituted [C 2 _ 0 alkenyl (C ⁇ . 6 )alkyl], optionally substituted [C 2 _ 2 o alkynyl(C 1 .
  • R 28 and R 29 are, independently, hydrogen, optionally substituted C ⁇ _ 2 o alkyl, optionally substituted C 3-7 cycloalkyl, optionally substituted [C 2 . 2 o alkenyl(C ⁇ _ 6 )alkyl], optionally substituted [C 2 .
  • R 28 and R 29 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two C ⁇ -6 alkyl groups;
  • R 27 and R 30 are independently hydrogen, optionally substituted phenyl or optionally substituted C ⁇ _ 6 alkyl;
  • R and R are, independently, hydrogen, optionally substituted phenyl (C ⁇ _ 2 )alkyl or optionally substituted C ⁇ _ o alkyl provided that when A is CH 2 , M is CONH, D is S, and X is N then E and W cannot both be C-Cl.
  • the ring containing D, E W and X may contain no more than 3 heteroatoms.
  • the compounds of formula (I) may exist in different geometric or optical isomers or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
  • R 37 and R 38 are, independently, hydrogen, C t _ 8 alkyl, C 3 . 7 cycloalkyl, C 2 _ 6 alkenyl(C ⁇ _ )alkyl, C 2 .
  • R 34 and R 35 are, independently, hydrogen, C ⁇ - alkyl, C ⁇ _ 6 alkoxy, C ⁇ _ 6 haloalkyl, cyano, C ⁇ _ 6 alkoxycarbonyl, C ⁇ -6 alkylcarbonyl or R 39 R 40 N; R 39 and R 40 are, independently, hydrogen, Cu 8 alkyl, C
  • R 34 and R 35 are, independently, hydrogen, C ⁇ _ 6 alkyl, C ⁇ _ 6 alkoxy, C-_ 6 haloalkyl, cyano, C ⁇ _ 6 alkoxycarbonyl, C ⁇ _6 alkylcarbonyl or R 39 R 40 N;
  • R 36 is C ⁇ _ 6 alkyl, C ⁇ _ 6 haloalkyl or phenyl(C ⁇ _ 2 )alkyl;
  • R 37 and R 38 are, independently, hydrogen, C ⁇ -8 alkyl, C 3 . 7 cycloalkyl, C 2 .
  • R 37 and R 38 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two C ⁇ _ 6 alkyl groups;
  • R 39 and R 40 are, independently, hydrogen, C 1-8 alkyl, C 3 _ 7 cycloalkyl, C 2 .
  • Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, rc-butyl, «-pentyl, n-hexyl, ts ⁇ -propyl, n-butyl, sec-butyl, w ⁇ -butyl, tert-butyl or ne ⁇ -pentyl.
  • the optional substituents on alkyl include one or more of halogen, nitro, cyano, NCS-, C 3 . 7 cycloalkyl (which itself may be optionally substituted with C ⁇ _ 6 alkyl or halogen), C 5 . 7 cycloalkenyl (which itself may be optionally substituted with C ⁇ _ 6 alkyl or halogen), hydroxy, C M0 alkoxy, C M0 alkoxy(C 0 )alkoxy, tri(C ⁇ - )alkylsilyl(C ⁇ _ 6 )alkoxy, C ⁇ .
  • One group of optional preferred substituents for alkyl include one or more of halogen, nitro, cyano, HO 2 C, C MO alkoxy (itself optionally substituted by C MO alkoxy), ary Ci.-t)- alkoxy, C MO alkylthio, C MO alkylcarbonyl, C MO alkoxycarbonyl, _ 6 alkylaminocarbonyl, di(Ci_ 6 alkylaminocarbonyl, (C ⁇ _6)alkylcarbonyloxy, optionally substituted phenyl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl, heterocyclyloxy, C 3 .
  • Alkenyl and alkynyl moieties can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)- or ⁇ -configuration. Examples are vinyl, allyl and propargyl.
  • the optional substituents on alkenyl or alkynyl include one or more of the substituents listed above for alkyl but especially preferred substituents are one or more of halogen, aryl and C 3 _ 7 cycloalkyl.
  • acyl is optionally substituted C ⁇ _ 6 alkylcarbonyl (for example acetyl), optionally substituted C 2 _ 6 alkenylcarbonyl, optionally substituted C 2 . 6 alkynylcarbonyl, optionally substituted arylcarbonyl (for example benzoyl) or optionally substituted heteroarylcarbonyl.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF 3 , CF 2 C1, CF 3 CH 2 or CHF 2 CH 2 .
  • Aryl includes naphthyl, anthracyl, fluorenyl and indenyl but is preferably phenyl.
  • heteroaryl refers to an aromatic ring containing up to 10 atoms including one or more heteroatoms (preferably one or two heteroatoms) selected from O, S and N. Examples of such rings include pyridine, pyrimidine, furan, quinoline, quinazoline, pyrazole, thiophene, thiazole, oxazole and isoxazole.
  • heterocycle and heterocyclyl refer to a non-aromatic ring containing up to 10 atoms including one or more (preferably one or two) heteroatoms selected from O, S and N.
  • rings examples include 1 ,3-dioxolane, tetrahydrofuran and morpholine. It is preferred that heterocyclyl is optionally substituted by C ⁇ _ 6 alkyl.
  • Cycloalkyl includes cyclopropyl, cyclopentyl and cyclohexyl.
  • the optional substituents for cycloalkyl include one or more of the substituents listed above for alkyl but especially preferred substituents are one or more of halogen, cyano and C ⁇ _ 3 alkyl.
  • Cycloalkenyl includes cyclopentenyl and cyclohexenyl.
  • the optional substituents for cycloalkenyl include one or more of the substituents listed above for alkyl but especially preferred substituents include one or more of C ⁇ _ 3 alkyl, halogen and cyano.
  • Carbocyclic rings include aryl, cycloalkyl and cycloalkenyl groups.
  • aryl such as phenyl and heteroaryl groups
  • substituents are independently selected from one or more of halogen, nitro, cyano, NCS-, C ⁇ _ alkyl, C ⁇ _ 6 haloalkyl, C ⁇ _ 6 alkoxy(C ⁇ _ 6 )alkyl, C 2 _ 6 alkenyl, C 2 _ 6 haloalkenyl, C 2 _ 6 alkynyl, C 3 .
  • cycloalkyl (which itself may be optionally substituted with C ⁇ _6 alkyl or halogen), C 5 - 7 cycloalkenyl
  • substituted heterocyclyl groups include one or more of the substituents listed above for alkyl.
  • substituents listed above for alkyl include one or more of the substituents listed above for alkyl.
  • substituents listed above for alkyl include one or more of the substituents listed above for alkyl.
  • substituents listed above for alkyl include one or more of the substituents listed above for alkyl.
  • substituents listed above for alkyl substituents listed above for alkyl.
  • substituted phenyl moieties heterocyclyl and heteroaryl groups one set of preferred substituents are independently selected from one or more of halogen, .
  • dialkylamino substituents include those where the dialkyl groups together with the N atom to which they are attached form a five, six or seven- membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two C)_ 6 alkyl groups.
  • heterocyclic rings are formed by joining two groups on an N atom, the resulting rings are suitably pyrrolidine, piperidine, thiomorpholine and morpholine each of which may be substituted by one or two (C ⁇ _ 6 )alkyl groups.
  • R 1 is hydrogen, halogen, optionally substituted C ⁇ _ 6 alkyl, optionally substituted C 2 .
  • R 32 ON C(R 30 ), optionally substituted C ⁇ _ 6 alkylcarbonyl, optionally substituted C ⁇ _ 6 alkoxycarbonyl or SF 5 ; or R 1 and R 19 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated ring carbocylic or heterocyclic ring which may contain one or two hetero atoms selected from O, N or S and which may be optionally substituted by C ⁇ _ 6 alkyl, C ⁇ -6 haloalkyl or halogen; R 3 , R 4 and R 5 are, independently, hydrogen, halogen, optionally
  • A is optionally substituted C ⁇ _6 alkylene, optionally substituted C 2 .
  • R 13 is hydrogen, cyano, nitro, optionally substituted C ⁇ .
  • R 14 is hydrogen, cyano, optionally substituted C ⁇ _ 8 alkyl, optionally substituted [C 2 _ 6 alkenyl(C 1 .
  • R 18 is hydrogen, halogen, nitro, cyano, optionally substituted C ⁇ _ 8 alkyl, optionally substituted C 2 _ 6 alkenyl, optionally substituted
  • cycloalkyl optionally substituted C MO alkylcarbonyl, optionally substituted CM O alkoxycarbonyl, formyl, optionally substituted CM O alkylaminocarbonyl, optionally substituted di(C ⁇ _ ⁇ o)alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted C ⁇ _ 6 alkylthio, optionally substituted C MS alkylsulfinyl, optionally substituted alkylsulfonyl, optionally substituted C ⁇ _ 6 arylthio, optionally substituted C 1-6 arylsulfinyl, optionally substituted C 1-6 arylsulfonyl or R 20 R 21 NS.
  • the invention also provides a compound of formula (IA') which is a compound of formula F wherein A, B, D, E, M, W, X, Z, R 3 , R 4 , R 5 , and R 6 have the values as defined for formula (IA) above.
  • a compound of formula (IB') which is a compound of formula F wherein A, B, D, E, M, W, X, Z, R 3 , R 4 , R 5 , and R 6 have the values as defined for formula (IB) above.
  • the present invention provides a compound of formula (IC) which is a compound of formula (F) wherein,
  • E is N or CR 12 ;
  • W is CR 1 or N:
  • X is N or CR U ;
  • R 11 is hydrogen, C ⁇ _ 6 alkyl or phenyl with the proviso that at least one ofW and X is N;
  • R 1 is hydrogen, halogen, C ⁇ _ 6 alkyl, C 2 _ 6 alkenyl, C 2 _ 6 alkynyl, C ⁇ _ 6 cyanoalkyl, C ⁇ ⁇ haloalkyl, - ⁇ alkoxy, - ⁇ haloalkoxy, C ⁇ _ alkylthio, . 6 haloalkylthio, C 3 . 6 cycloalkyl, C 3 _ cycloalkyl(C ⁇ _ )alkyl, C ⁇ _ 6 alkoxy(C ⁇ _ )alkyl, cyano, nitro or SF 5 ;
  • B is N or CR 18.
  • Z is O, S or NR 14 ;
  • R 51 is hydrogen, C MO alkyl, benzyloxymethyl, benzoyloxymethyl, C ⁇ _ 6 alkoxy- (C ⁇ _ 6 )alkyl, C 2 . 6 alkenyl (C ⁇ _ 6 )alkyl (especially allyl), C 2 . 6 alkynyl(C ⁇ _ 6 )alkyl (especially propargyl), C MO alkylcarbonyl or C MO alkoxycarbonyl (especially w ⁇ butoxycarbonyl);
  • R 52 is CM O alkyl, CM O haloalkyl, C 2 . 6 alkenyl(C[.
  • R 53 is C MO alkyl, benzyloxymethyl, benzoyloxymethyl, C ⁇ _ 6 alkoxy(C ⁇ -6 )alkyl, C .
  • R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, C*_ 6 alkyl, C ⁇ _ 6 alkoxy, C ⁇ _ 6 haloalkoxy, C ⁇ _ 6 alkylthio, C ⁇ _ 6 haloalkyl thio, _ 6 alkylsulfinyl, C ⁇ _ 6 haloalkylsulfinyl, C ⁇ _ 6 alkylsulfonyl, C ⁇ _ 6 haloalkylsulfonyl, C ⁇ _ 6 haloalkyl, cyano, nitro, C ⁇ -6 alkylcarbonyl, C ⁇ _ 6 alkoxycarbonyl or SF 5 ;
  • R 6 is cyano, _ 8 alkyl, C ⁇ _ 6 haloalkyl, C ⁇ -6 cyanoalkyl, C 2 . 6 alkenyl, C 2 _ 6 alkynyl, C 3 _ cycloalkyl, C 3 _ 7 halocycloalkyl, C 3 . 7 cyanocycloalkyl, C ⁇ _ 3 alkyl(C 3 .
  • alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C ⁇ _ 6 alkyl, C ⁇ _ 6 haloalkyl, C ⁇ _ 6 alkoxy or d_ 6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, C ⁇ _ 6 haloalkyl, C ⁇ _ 6 alkoxy or C ⁇ _ 6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, C*_ 6 alkyl, C ⁇ _ 6 haloalkyl, C ⁇ _ 6 alkoxy or Cj_ 6 haloalkoxy), , heteroaryl(C ⁇ _ )alkyl (where the heteroaryl may be substituted by halo, nitro, cyano, C ⁇ _ 6 alkyl, C ⁇ _ 6 haloalkyl, C ⁇ _ 6 alkoxy or C ⁇ _ 6 halo
  • Ci_ 6 alkoxy or C ⁇ _ 6 haloalkoxy), R 26 O, C,_ 8 alkylthio, R 28 R 29 N or R 31 ON C(R 27 );
  • R 8 and R 9 are, independently, hydrogen, halogen, C ⁇ _ 6 alkyl, C ⁇ _ 6 haloalkyl C 2 . 6 alkenyl, C ⁇ _ 6 alkynyl, C ⁇ _ 6 alkoxy or C ⁇ _ 6 haloalkoxy; R 12 is hydrogen, halogen, C ⁇ _ 6 alkyl, C 2 .
  • R 13 is cyano, nitro, C ⁇ _ 6 alkyl, C ⁇ -6 haloalkyl, C 3 . 7 cycloalkyl, C 3 _ 7 cycloalkyl- (C ⁇ _ 6 )alkyl, CH 2 (C 2 _ 6 )alkenyl, CH 2 (C 2 _ 6 )alkynyl, phenyl (optionally substituted by halo, nitro, cyano, C ⁇ _ 6 alkyl, C ⁇ _6 haloalkyl, C ⁇ _ 6 alkoxy or C ⁇ _6 haloalkoxy) heteroaryl (optionally substituted by halo, nitro, cyano, C ⁇ _ 6 alkyl, C ⁇ _ 6 haloalkyl, C ⁇ _ 6 alkoxy or C ⁇ _ 6 haloalkoxy), Ci_ 6 alkylcarbonyl, C ⁇ _ 6 alkoxycarbonyl, C ⁇ _ 6 alkylamino, di(C ⁇ _ 6 )alkyla
  • R 14 is hydrogen, C ⁇ _ 8 alkyl, C ⁇ _ 6 haloalkyl, C ⁇ _ 6 cyanoalkyl, C 2 _ 6 alkenyl, C 2 . 6 alkynyl, C 3 . 7 cycloalkyl, C 2 .
  • R 15 is Ci. 6 alkyl, OR 22 or NR 23 R 24 ;
  • R 16 is hydrogen, C ⁇ _ 6 alkyl or C ⁇ -6 haloalkyl;
  • R 17 is hydrogen, C ⁇ _ 6 alkyl, C ⁇ _ 6 haloalkyl, C ⁇ _ 6 alkoxy, cyano, C ⁇ _6 alkoxycarbonyl,
  • R 18 is hydrogen, halogen, nitro, cyano, C ⁇ _ 8 alkyl, C ⁇ _ 6 haloalkyl, C ⁇ _ 6 cyanoalkyl, C 2-6 alkenyl, C 2 _ 6 alkynyl, C 3 _ 7 cycloalkyl, C 2 .
  • R 20 and R 21 are, independently, hydrogen, Q- 6 alkyl, CH 2 (C ⁇ _ 4 haloalkyl), Q_ 6 cyanoalkyl, C ⁇ _ 6 alkoxy(C 1 _ 6 )alkyl, Q_ 6 alkylthio(Q.
  • R 20 and R 21 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q- 6 alkyl groups;
  • R 22 is C ⁇ -6 alkyl or optionally substituted phenyl(Q -2 )alkyl
  • R 23 and R 24 are, independently, hydrogen, Q_ 8 alkyl or phenyl (optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q.6 haloalkyl, Q_ alkoxy or Q_ 6 haloalkoxy);
  • R 26 is hydrogen, Q_ 8 alkyl, Q_6 haloalkyl, Q_ 6 cyanoalkyl, C 2 _ 6 alkenyl, C 2-6 alkynyl, Q. 6 alkoxy(Q_6)alkyl, phenyl(Q_ 4 )alkyl , (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q. 6 alkoxy or Q. 6 haloalkoxy), heteroaryl(Q -4 )alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Q. 6 alkyl, Q.
  • R 27 is Q- 6 alkyl, Q- 6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano,
  • R 28 and R 29 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q- 6 alkyl groups;
  • R 30 is hydrogen or Q_ 3 alkyl
  • R 31 and R 32 are, independently, Q. 6 alkyl or phenyl(Q. 2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q_ 6 haloalkyl, Q_ 6 alkoxy or Q- 6 haloalkoxy); and
  • R 46 and R 47 are, independently, hydrogen, Q_ 8 alkyl, C 3 . 7 cycloalkyl, C 3 . 6 alkenyl, C 3 _ 6 alkynyl, C 2 . 6 haloalkyl, C ⁇ _6 alkoxy(Q_ 6 )alkyl, C ⁇ _6 alkoxycarbonyl(Q_ 6 )alkyl, carboxy(C ⁇ _ 6 )alkyl or phenyl(Q.
  • R 46 and R 47 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q_ 6 alkyl groups.
  • A is Q_ 6 alkylene (optionally substituted by Q. 3 alkyl, Q_ 3 haloalkyl, Q. 3 cyanoalkyl, Q_ 6 alkoxycarbonyl), -C(O)- or Q. 6 alkyleneoxy: More preferably A is Q ⁇ alkylene -C(O)- or Q ⁇ alkyleneoxy; or alternatively is C 1- alkylene (optionally substituted by Q -3 alkyl).
  • A is CH 2 , CH(CH 3 ) or CH 2 O. Most preferably A is CH 2 or CH(CH 3 ).
  • M is C(O)NR 51 where the N atom is attached to the group "A"
  • Z is O or S, more preferably O.
  • B is N.
  • E is N or CR 12
  • R 12 is hydrogen, halogen, Q_ 6 alkyl, Q_ 6 haloalkyl, Q_ 6 alkoxy, Q_ haloalkoxy, Q_ 6 alkoxy (Q_ 6 )alkyl, Q_6 alkylthio or SF 5 ; or R 1 and R 12 together with the atoms to which they are attached form a benzene ring optionally substituted by C ⁇ . 6 alkyl Q_ 6 haloalkyl or halogen.
  • W is preferably N or CR 1 .
  • X is N or CR 11 where R 1 ' is hydrogen, Q ⁇ alkyl or phenyl. It is preferred that R 51 is hydrogen, C MO alkyl, Q_ 6 alkylcarbonyloxy(Q_ 6 )alkyl, benzoyloxymethyl (where the phenyl ring may be optionally substituted with halogen or Q.
  • R 51 is hydrogen, Q.
  • R 51 is hydrogen, Q. 6 alkyl, Q_ 6 alkylcarbonyloxymethyl, Q_ 6 alkoxymethyl, benzyloxymethyl or benzoyloxymethyl.
  • R 51 is hydrogen, Q. alkyl, Q-_. alkoxy (Q_ )alkyl, benzyloxymethyl or benzoyloxymethyl; or is Q_ 6 alkylcarbonyloxymethyl Most preferably R 51 is hydrogen, C alkyl, Q_ 6 alkylcarbonyloxymethyl or C ⁇ _ 4 alkoxymethyl.
  • R 52 and R 53 are independently Q_ ⁇ o alkyl, CM 0 haloalkyl, C 2 . 6 alkenyl- (C ⁇ -6)alkyl, C 2 _ 6 alkynyl (Q_6)alkyl, C 3 _ 7 cycloalkyl, C ⁇ _ 6 alkylamino, di(Q. 6 )alkylamino, phenyl(C )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q_ 6 haloalkoxy),
  • R 52 and R 53 are independently Q_ alkyl, C ⁇ _ 6 haloalkyl, C 2 . 6 alkenyl(C ⁇ _6)alkyl, C 2 _ 6 alkynyl (Q_ 6 )alkyl, benzyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q. 6 alkyl, Q_ 6 haloalkyl, Q_ 6 alkoxy or Q_ 6 haloalkoxy).
  • R 1 is preferably hydrogen, halogen, Q.6 alkyl, C 2 . 6 alkenyl, C 2 _ 6 alkynyl, Q_ 6 haloalkyl, C ⁇ _ 6 alkoxy(Q.
  • R 1 is hydrogen, halogen, Q_ 6 alkyl, C 2 . 6 alkenyl, C ⁇ _6 haloalkyl, Q. 6 alkoxy, C ⁇ _ 6 haloalkoxy, Q_ 6 alkylthio, C ⁇ _ 6 haloalkylthio, C 3 . 6 cycloalkyl, cyano, nitro or SF 5 .
  • R 1 is hydrogen, halogen, Q_ 6 alkyl, C 2 . 6 alkenyl, C ⁇ _ 6 haloalkyl,
  • R 1 is halogen, Q_ 6 alkyl, Q- 6 haloalkyl, Q_ 6 alkoxy or Q- 6 haloalkoxy.
  • R 3 , R 4 and R 5 are, independently, hydrogen, halogen, Q_ 6 alkyl, C ⁇ _ 6 haloalkyl, Q_6 alkylthio, C ⁇ _ haloalkylthio, Q. 6 alkoxy, C ⁇ _ 6 haloalkoxy, C ⁇ . 6 alkylsulfinyl, Q- 6 haloalkylsulfinyl, Q- 6 alkylsulfonyl, Q. 6 haloalkylsulfonyl, cyano, nitro, Q_ 6 alkylcarbonyl, or Q_6 alkoxycarbonyl..
  • R 3 , R 4 and R 5 are independently hydrogen, C ⁇ . 3 alkyl or halogen. Most preferably R 3 , R 4 and R 5 are independently, hydrogen, or halogen (especially fluorine) but most preferably each is hydrogen.
  • R 6 is preferably Q. 8 alkyl, Q_ haloalkyl, Q_6 cyanoalkyl, C 2 _ 6 alkenyl, C 2 . 6 alkynyl,
  • phenyl(C ⁇ )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q. 6 haloalkyl, Q. 6 alkoxy or C ⁇ _ 6 haloalkoxy), phenyl- (C 2- )alkenyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q. haloalkyl, Q. 6 alkoxy or Q.
  • heteroaryl optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q_ haloalkyl, Q_6 alkoxy or Q_ 6 haloalkoxy
  • heterocyclyl wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q_ 6 haloalkyl, Q_ 6 alkoxy or Q_ 6 haloalkoxy
  • heteroary Q ⁇ alkyl wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Q. 6 alkyl, Q. 6 haloalkyl, Q.
  • R 27 is Q.6 alkyl, Q.6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, Q. 6 alkyl, Q. 6 haloalkyl, Q_ 6 alkoxy or Q_ 6
  • R and R are, independently, hydrogen, Q. 8 alkyl, C 3 . 7 cycloalkyl, C 3 _ 6 alkenyl, C 3 . 6 alkynyl, C 3 _ 7 cycloalkyl(Q ⁇ )alkyl, C 2 . 6 haloalkyl, Q.6 alkoxy(Q_ 6 )alkyl, Q ⁇ alkoxycarbonyl, or R and R together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q.
  • R is Q_6 alkyl or phenyl(Q_ 2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q_ 6 haloalkyl, Q_ 6 alkoxy or Q_ 6 haloalkoxy).
  • R 6 is Q_ 8 alkyl, Q. 8 haloalkyl, Q. 8 cyanoalkyl, C 3 . 7 cycloalkyl- (Q_ 6 )alkyl, C 5 . 6 cycloalkenyl(Q- 6 )alkyl, Q_ 6 alkoxy(Q_ 6 )alkyl, C 3 . 6 alkenyloxy(Q. 6 )alkyl, C 3 _ 6 alkynyloxy(C ⁇ _ 6 )alkyl, aryloxy(Q_ 6 )alkyl, C ⁇ _ 6 carboxyalkyl, Q ⁇ alkylcarbonyl- (C ⁇ .
  • heterocycly Q- ⁇ alkyl (wherein the heterocyclyl group may be optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q. haloalkyl, Q.6 alkoxy or Q_ 6 haloalkoxy), C 2 _ 6 alkenyl, C 2 - 6 haloalkenyl, Q. 6 cyanoalkenyl, C 5 . 6 cycloalkenyl, aminocarbonyl(C 2 _ 6 )alkenyl, Ci.
  • R 26 is Q_ 8 alkyl or Q_ 6 haloalkyl
  • R 27 is phenyl (which may be optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q_ 6 haloalkyl, Q_ 6 alkoxy or Q_ 6 haloalkoxy), C ⁇ _ 6 alkyl or C ⁇ _ 6 haloalkyl
  • R 8 and R 9Q are, independently, hydrogen, Q -8 alkyl, C 3 . 7 cycloalkyl(C ⁇ . )alkyl, C 2 .
  • R 6 haloalkyl, .6 alkoxy(Q_ 6 )alkyl, C 3 . 7 cycloalkyl, _ 6 alkenyl, C 3 _ 6 alkynyl or Q_ 6 alkoxycarbonyl; and R is phenyl (Q_ 2 )alkyl (wherein the phenyl group may be optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q_ 6 haloalkyl, Q_ 6 alkoxy or Q_ 6 haloalkoxy) or Q_6 alkyl. Even more preferably R 6 is C ⁇ _ 8 alkyl, Q_ 8 haloalkyl, C)_ 8 cyanoalkyl, C 3 _ 7 cycloalkyl,
  • R 6 is Q. 8 alkyl, Q_ 8 haloalkyl, Q_ 8 cyanoalkyl, Q. 6 alkoxy (Q_ 6 ) alkyl, C 3 _ 7 cycloalkyl, Q. 3 alkyl (C 3 . 7 ) cycloalkyl, heterocyclyl (which may be optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q. 6 haloalkyl, Q_ 6 alkoxy or Q_ 6 haloalkoxy) or di(Q. 8 )alkylamino.
  • R 12 is hydrogen, halogen, Q_ 6 alkyl, Q. 6 haloalkyl, Q_ 6 alkoxy (Q. 6 )alkyl, Q_ 6 alkoxy, Q- 6 haloalkoxy, Q. 6 alkylthio, or R 1 and R 12 together with the atoms to which they are attached form a cyclopentane or benzene ring optionally substituted by Q. 6 alkyl, Q_ 6 haloalkyl or halogen.
  • R 12 is hydrogen, halogen, Q_ 6 alkyl, Q_ 6 haloalkyl, Q. 6 alkoxy- (C ⁇ _ 6 )alkyl, Q_ 6 alkoxy, C ⁇ _ 6 haloalkoxy, or R 1 and R 12 together with the atoms to which they are attached form a cyclopentane ring optionally substituted by Q_ 6 alkyl, Q. 6 haloalkyl or halogen;
  • R 13 is preferably cyano, nitro, Q_ 6 alkyl, Q_ 6 haloalkyl, C 3 . cycloalkyl(Q_ 6 )alkyl, C 3 . 7 cycloalkyl, CH 2 (C 2 . 6 )alkenyl, CH 2 (C 2 _ 6 )alkynyl, phenyl (which may be optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q_ 6 haloalkyl, Q_ 6 alkoxy or C ⁇ .
  • heteroaryl which may be optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q_ 6 haloalkyl, Q_ 6 alkoxy or Q. 6 haloalkoxy
  • Q. 6 alkylcarbonyl C ⁇ _ 6 alkoxycarbonyl, Q_ 6 alkylamino, di(Q_6)alkylamino, C ⁇ _ 6 alkylcarbonylamino, C ⁇ _ 6 alkoxycarbonylamino, Q. 6 alkoxy, C ⁇ _ 6 alkylthio, Q.6 haloalkylthio, Q_ 6 alkylsulfinyl, C ⁇ .
  • R 14 is hydrogen, Q. 8 alkyl, Q. 6 haloalkyl, Q_ 6 cyanoalkyl, C . 6 alkenyl, C 2 . 6 haloalkenyl, C 2 .6 alkynyl, C 3 . 7 cycloalkyl, C 3 . 7 cycloalkyl(Q_ 6 )alkyl, C ⁇ _6 alkoxy- (C ⁇ _ 6 )alkyl, C ⁇ _ 6 alkoxycarbonyl, Q. 6 alkylcarbonyl, Q.
  • R 14 is hydrogen, Q_ 8 alkyl or Q_ 6 haloalkyl.
  • R 18 is hydrogen, halogen, nitro, cyano, Q. 8 alkyl, C ⁇ _ 6 haloalkyl, Q. 6 cyanoalkyl, C 3-7 cycloalkyl(Q. 6 )alkyl, C ⁇ _ 6 alkoxy(C ⁇ _ 6 )alkyl, C ⁇ . 6 alkoxycarbonyl(Q- 6 )alkyl, Q. 6 alkylcarbonyl(C ⁇ _ 6 )alkyl, C ⁇ -6 alkylaminocarbonyl(C ⁇ .
  • R 18 is hydrogen, halogen, Q_ 8 alkyl or Q_ 6 haloalkyl.
  • pyrazoles 2,4,5,6-tetrahydro-cyclopentapyrazoles, 4,5,6,7-tetrahydro-[2H]- indazoles and indazoles which may be optionally substituted by substituents chosen from halo, Q. 6 alkyl, Q. 6 haloalkyl, Q_ 6 alkoxy, Q_6 alkoxy(Q_ 6 )alkyl or Q_ 6 haloalkoxy.
  • the rings include 5-linked l-methyl-[lH]-pyrazoles optionally substituted at the 3-position with Q_ 6 alkyl, haloalkyl or alkoxyalkyl and at the 4-position with halo or alkoxy; 3-linked 2,4,5,6-tetrahydro-2-methylcyclopentapyrazoles optionally substituted at the 6-position with alkyl (especially methyl), haloalkyl or halo; 3-linked 4,5,6,7-tetrahydro- 2-methyl-[2H] -indazoles optionally substituted at the 7-position with alkyl (especially methyl), haloalkyl or halo and 3-linked 2-methyl-[2H]-indazoles optionally substituted at the 7-position with alkyl, haloalkyl or halo (especially fluoro).
  • Table 1 provides compounds of formula (F) wherein A is CH 2 , M is CONH, Z is O, B is N, R 3 , R 4 and R 5 are each hydrogen; and, D, E, W, X and R 6 are as defined in the Table.
  • Table 2 provides 70 compounds of formula
  • Table 3 provides 80 compounds of formula
  • Table 4 provides 60 compounds of formula
  • Table 5 provides 80 compounds of formula
  • Table 10 provides 60 compounds of formula
  • Table 13 provides 80 compounds of formula
  • Table 14 provides 60 compounds of formula
  • Table 29 provides 80 compounds of formula
  • Table 30 provides 60 compounds of formula
  • Table 32 provides 60 compounds of formula
  • Table 38 provides 60 compounds of formula
  • Table 41 provides 80 compounds of formula
  • Table 42 provides 60 compounds of formula
  • Table 44 provides 60 compounds of formula
  • Table 50 provides 60 compounds of formula
  • Table 62 provides 60 compounds of formula
  • Table 64 provides 60 compounds of formula
  • Table 71 provides 80 compounds of formula
  • Table 72 provides 60 compounds of formula
  • Table 74 provides 60 compounds of formula
  • Table 75 provides 80 compounds of formula
  • Table 76 provides 60 compounds of formula
  • Table 78 provides 60 compounds of formula
  • Table 79 provides 80 compounds of formula
  • Table 80 provides 60 compounds of formula
  • Table 96 provides 60 compounds of formula
  • Table 100 provides 60 compounds of formula
  • Table 102 provides 60 compounds of formula
  • Table 104 provides 60 compounds of formula
  • Table 109 provides 80 compounds of formula
  • Table 113 provides 80 compounds of formula
  • Table 114 provides 60 compounds of formula
  • the compounds of the invention may be made in a variety of ways.
  • the compounds of formula TV i.e. compounds of formula (I) where R 51 is hydrogen and R 3 , R 4 , R 5 , R 6 , A, B, Z, D, E, W and X are as defined above in relation to formula I
  • R 51 is hydrogen and R 3 , R 4 , R 5 , R 6 , A, B, Z, D, E, W and X are as defined above in relation to formula I
  • R a is OH, halogen or OCOalkyl
  • R 51 is hydrogen and R 3 , R 4 , R 5 , R 6 , A, B and Z are as defined in relation to formula (I)
  • R a OH
  • the reaction is conducted preferably in the presence of a suitable coupling reagent such as 1 ,3-dicyclohexylcarbodiimide, 1,3-diisopropylcarbodiimide, l-(3- dimethylaminopropyl)-3-ethylcarbodiimide or l,l'-carbonyldiimidazole optionally in the presence of a catalyst such as 4-(dimethylamino)pyridine.
  • a suitable coupling reagent such as 1 ,3-dicyclohexylcarbodiimide, 1,3-diisopropylcarbodiimide, l-(3- dimethylaminopropyl)-3-ethylcarbodiimide or l,l'-carbonyldiimidazole
  • a catalyst such as 4-(dimethylamino)pyridine.
  • a base such as triethylamine or sodium methoxide
  • a suitable solvent such as 1,1,2,2-tetrachloroethane, tetrahydrofuran, N
  • a particularly suitable method for making the amines of formula HI is by treating an acid of formula V (where R 3 , R 4 , R 5 , R 6 , A, B and Z are as defined in relation to formula (I)) with a reagent such as diphenylphosphoryl azide in the presence of a base such as triethylamine in a solvent such as toluene at reflux.
  • a reagent such as diphenylphosphoryl azide in the presence of a base such as triethylamine in a solvent such as toluene at reflux.
  • R t-butyl
  • diazotising conditions such as t-butyl nitrite in THF or sodium nitrite in sulfuric acid
  • Benzothiophenes may be made from appropriate thiophenols by processes similar to those described by Robert D Schuetz and Richard L Titus (J. Heterocycl. Chem., 4, No 4, 465 (1967); suitable thiophenols are known compounds or may be prepared by known methods.
  • Benzofurans may be made from ort/i ⁇ -halophenols as described by Henning Lutjens and Peter J Scammells, Tetrahedron Letters 39 (1998), 6581-6584, Terence C Owen et al., Tetrahedron Letters 30, No 13, 1597 (1989) and Fred G Schreiber and Robert Stevenson J.C.S. Perkin 1, 90, 1977.
  • Indoles may be made from ort/ ⁇ o-haloanilines according to the methods of Cheng-yi Chen et al., J. Org. Chem. 1997, 62, 2676, Takao Sakamoto et al., J. Org. Chem. 1997, 62, 6507 and Alan D. Adams et al., WO9827974.
  • Appropriate ortho- substituted phenols and anilines may be prepared by known methods from commercially available 4-hydroxyphenylacetic acid and 4-aminophenylacetic acid.
  • a compound of formula C (i.e. a compound of formula I where A, E, W, X, D, B, Z, R 51 , R 3 , R 4 , R 5 and R 6 are as defined above in relation to formula I) may be prepared by reacting a compound of formula IV with a suitable thionating agent such as 2,4-bis(4- methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson's reagent), 2,4- bis(methylthio)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Davy reagent methyl), 2,4- bis(p ⁇ r -tolyl)-l,3-dithia-2,4-diphosphetane-2,4-disulf ⁇ de (Davy reagent -tolyl) or phophorus pentasulfide in a
  • Compounds of formula IV (where R 51 is hydrogen) or DC (where R 51 is hydrogen) may be treated with an alkylating agent (such as an alkyl halide, dialkyl sulfate, chloromethylether or trialkyloxonium salt) optionally in the presence of a base to give additional compounds of formula (IV) or (DC).
  • an alkylating agent such as an alkyl halide, dialkyl sulfate, chloromethylether or trialkyloxonium salt
  • An alternative method for making compounds of formula XDI involves the acylation of compounds of formula XIV (where A, E, W, X, D, M, R 3 , R 4 , R 5 and R 6 are as defined above in relation to formula I) followed by cyclisation, optionally in the presence of an acidic catalyst such as /. ra-toluene sulfonic acid in a suitable solvent such as xylene or 1,1,2,2-tetrachloroethane.
  • Compounds of formula XIV may be prepared from compounds of formula XV (where A, E, W, X, D, M, R 3 , R 4 and R 5 are as defined above in relation to formula I) by a sequential procedure of nitration followed by reduction, using known procedures.
  • compounds of formula XV may be prepared by the dealkylation of compounds of formula XVI (where A, E, W, X, D, M, R 3 , R 4 and R 5 are as defined above in relation to formula I and R is an alkyl group (especially methyl) or substituted alkyl group (especially benzyl)) under standard conditions.
  • Compounds XVI may be prepared from compound II by processes analogous to those already described for compounds IV.
  • Heteroaryl N-oxides can be produced by known methods.
  • the compounds of formula (I) can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests.
  • the pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies).
  • pest species which may be controlled by the compounds of formula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp.
  • the compounds of formula (I) are also active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae (Magnaporthe grisea) on rice and wheat and other Pyricularia spp. on other hosts; Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts (for example turf, rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental plants); Erysiphe cichoracearum on cucurbits (for example melon); Erysiphe graminis (powdery mildew) on barley, wheat, rye and turf and other powdery mildews on various hosts, such as Sphaerotheca macularis on hops, Sphaerotheca fusca (Sphaerothe
  • Botrytis cinerea grey mould
  • Botrytis cinerea grey mould
  • Alternaria spp. on vegetables (for example carrots), oil-seed rape, apples, tomatoes, potatoes, cereals (for example wheat) and other hosts
  • Venturia spp. including Venturia inaequalis (scab)) on apples, pears, stone fruit, tree nuts and other hosts
  • Cladosporium spp. on a range of hosts including cereals (for example wheat) and tomatoes
  • Plasmopara viticola on vines other downy mildews, such as Bremia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts, Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on cucurbits; Pythium spp. (including Pythium ultimum) on turf and other hosts; Phytophthora infestans on potatoes and tomatoes and other Phytophthora spp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco, cocoa and other hosts; Thanatephorus cucume ⁇ s on rice and turf and other Rhizoctonia spp.
  • downy mildews such as Bremia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts, Pseudoperonospora humuli on hops and Pseudoperonospora cu
  • mice such as wheat and barley, peanuts, vegetables, cotton and turf; Sclerotinia spp. on turf, peanuts, potatoes, oil-seed rape and other hosts; Sclerotium spp. on turf, peanuts and other hosts; Gibberella fujikuroi on rice; Colletotrichum spp. on a range of hosts including turf, coffee and vegetables; Laetisaria fuciformis on turf; Mycosphaerella spp. on bananas, peanuts, citrus, pecans, papaya and other hosts; Diaporthe spp. on citrus, soybean, melon, pears, lupin and other hosts; Elsinoe spp.
  • Verticillium spp. on a range of hosts including hops, potatoes and tomatoes; Pyrenopeziza spp. on oil-seed rape and other hosts; Oncobasidium theobromae on cocoa causing vascular streak dieback; Fusarium spp., Typhula spp., Microdochium nivale,
  • a compound of formula (I) may move acropetally, basipetally or locally in plant tissue to be active against one or more fungi. Moreover, a compound of formula (I) may be volatile enough to be active in the vapour phase against one or more fungi on the plant.
  • the invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a pest, a locus of pest, or to a plant susceptible to attack by a pest, and a method of combating and controlling fungi which comprises applying a fungicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a plant, to a seed of a plant, to the locus of the plant or seed, to soil or to any other growth medium (for example a nutrient solution).
  • the compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
  • plant as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes protectant, curative, systemic, eradicant and antisporulant treatments.
  • the compounds of formula (I) are preferably used for agricultural, horticultural and turfgrass purposes in the form of a composition.
  • a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA).
  • SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula (I).
  • the composition is generally used for the control of pests or fungi such that a compound of formula (I) is applied at a rate of from O.lg to 10kg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 1kg per hectare.
  • a compound of formula (I) When used in a seed dressing, a compound of formula (I) is used at a rate of O.OOOlg to lOg (for example O.OOlg or 0.05g), preferably 0.005g to lOg, more preferably 0.005g to 4g, per kilogram of seed.
  • the present invention provides an insecticidal, acaricidal, nematicidal, molluscicidal or fungicidal composition
  • an insecticidal, acaricidal, nematicidal, molluscicidal or fungicidal composition comprising an insecticidally, acaricidally, nematicidally, molluscicidally or fungicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor.
  • the composition is preferably an insecticidal, acaricidal, nematicidal or fungicidal composition.
  • the invention provides a method of combating and controlling pests or fungi at a locus which comprises treating the pests or fungi or the locus of the pests or fungi with an insecticidally, acaricidally, nematicidally, molluscicidally or fungicidally effective amount of a composition comprising a compound of formula (I).
  • the compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
  • compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations.
  • the formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).
  • Dustable powders may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
  • solid diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers
  • Soluble powders may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • water-soluble organic solids such as a polysaccharide
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary.
  • a hard core material such as sands, silicates, mineral carbonates, sulphates or phosphates
  • Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils.
  • One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • DC Dispersible Concentrates
  • a compound of formula (I) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether.
  • organic solvent such as a ketone, alcohol or glycol ether.
  • surface active agent for example to improve water dilution or prevent crystallisation in a spray tank.
  • Emulsifiable concentrates or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents).
  • Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C 8 -Qo fatty acid dimethylamide) and chlorinated hydrocarbons.
  • aromatic hydrocarbons such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark
  • ketones such as cycl
  • An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.
  • Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion.
  • Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of formula (I) is present initially in either the water or the solvent/SFA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs.
  • An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation.
  • An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
  • SC Suspension concentrates
  • SCs may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I).
  • SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound.
  • One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle.
  • a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
  • Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example n-butane).
  • a compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as «-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
  • a compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
  • Capsule suspensions may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor.
  • the polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure.
  • the compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment.
  • a compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
  • a composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)).
  • additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).
  • a compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS).
  • DS powder for dry seed treatment
  • SS water soluble powder
  • WS water dispersible powder for slurry treatment
  • CS capsule suspension
  • the preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above.
  • Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
  • Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di- /s ⁇ propyl- and tr s ⁇ propyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphospho
  • Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.
  • Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
  • Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
  • hydrophilic colloids such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose
  • swelling clays such as bentonite or attapulgite
  • a compound of formula (I) may be applied by any of the known means of applying pesticidal or fungicidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.
  • a locus of the pests such as a habitat of the pests, or a growing plant liable to infestation by the pest
  • a compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
  • compositions for use as aqueous preparations are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use.
  • These concentrates which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
  • a compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers).
  • fertilisers for example nitrogen-, potassium- or phosphorus-containing fertilisers.
  • Suitable formulation types include granules of fertiliser.
  • the mixtures suitably contain up to 25% by weight of the compound of formula (I).
  • the invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula (I).
  • compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.
  • the resulting composition may have a broader spectrum of activity or a greater level of intrinsic activity than the compound of formula (I) alone. Further the other fungicide may have a synergistic effect on the fungicidal activity of the compound of formula (I).
  • the compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components.
  • the particular additional active ingredient will depend upon the intended utility of the composition.
  • Suitable pesticides include the following: a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate; b) Organophosphates, such as, profenofos, sulprofos, acephat
  • pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the composition.
  • selective insecticides for particular crops for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed.
  • insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).
  • acaricidal ovo-larvicides such as clofentezine, flubenzimine, hexythiazox or tetradifon
  • acaricidal motilicides such as dicofol or propargite
  • acaricides such as bromopropylate or chlorobenzilate
  • growth regulators such
  • fungicidal compounds which may be included in the composition of the invention are (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy- iminoacetamide (SSF- 129), 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole- 1 -sulphonamide, ⁇ -[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]- ⁇ -butyrolactone, 4-chloro- 2-cyano-N,N-dimethyl-5-p-tolylimidazole-l-sulfonamide (IKF-916, cyamidazosulfamid), 3- 5-dichloro-N-(3-chloro- 1 -ethyl- 1 -methyl-2-oxopropyl)-4-methylbenzamide (RH-7281 , zoxamide), N-ally
  • the compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
  • synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.
  • Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
  • a rice selective herbicide which may be included is propanil.
  • An example of a plant growth regulator for use in cotton is PDCTM.
  • Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW).
  • SE suspoemulsion
  • Methyl 3-methyl-l,2,4-thiadiazole-5-carboxylate (10% solution in mesitylene, 2 ml, approximately 200 mg, 1.2 mmol), toluene (1 ml) and (2-(2,2-dimethylpropyl)benzoxazol-5- yl)methylamine (0.30 g, 1.38 mmol) were added to a Wheaton vial and heated at 150°C for 1 hour. The solvents were evaporated under reduced pressure and the residue was purified by preparative thin layer chromatography eluting with 30% ethyl acetate in hexane to Compound 87 of Table 1 (0.21 g, 51%).
  • EXAMPLE 4 This Example describes the preparation of compound No 7 in Table I 4-Chloro-3-ethyl-l-methyl-[lH]-pyrazole-5-carboxylic acid (93 mg, 0.50 mmol) was dissolved in dichloromethane (2 ml) and dicyclohexylcarbodiimide (0.08 ml, 0.50 mmol) in dichloromethane (1 ml) was added. (2-(2,2-Dimethylpropyl)benzoxazol-5-yl)methylamine (108 mg, 0.50 mmol) in dichloromethane (1 ml) was added dropwise, followed by 4- dimethylaminopyridine (catalytic quantity). The mixture was stirred at room temperature for 90 minutes.
  • a useful branched chain amine intermediate may be prepared by the following method.
  • Methyl (2-(2,2-dimethylpropyl)benzoxazol-5-yl)acetate 14.85 g, 57.0 mmol was dissolved in THF (200 ml) and the solution was cooled to -75°C.
  • Lithium bis- trimethylsilylamide 1.0 M in THF, 62.7 ml, 62.7 mmol was added dropwise over 90 minutes so that the temperature never exceeded -70oC.
  • the mixture was then allowed to stir for 1 hour at -75oC and methyl iodide (63 ml, 570 mmol) was added dropwise. The mixture was allowed to warm to room temperature overnight.
  • This Example illustrates the pesticidal/insecticidal properties of compounds of formula (I).
  • the activities of individual compounds of formula (I) were determined using a variety of pests.
  • the pests were treated with a liquid composition containing 500 parts per million (ppm) by weight of a compound.
  • Each composition was made by dissolving the compound in an acetone and ethanol (50:50 by volume) mixture and diluting the solution with water containing 0.05% by volume of a wetting agent, SYNPERONIC NP8, until the liquid composition contained the required concentration of the compound.
  • test procedure adopted with regard to each pest was essentially the same and comprised supporting a number of the pests on a medium which was usually a substrate, a host plant or a foodstuff on which the pests feed, and treating either or both the medium and the pests with a composition. Pest mortality was assessed usually between two and five days after treatment.
  • results of the tests against peach aphid are presented below.
  • Chinese cabbage leaves were infested with aphids, the infested leaves were sprayed with the test composition, and the mortality assessed after three days.
  • the results indicate a grading of mortality (score) designated as 9, 5 or 0 wherein 9 indicates 80-100% mortality, 5 indicates 40-79% mortality and 0 indicates less than 40% mortality.
  • EXAMPLE 6 This Example illustrates the fungicidal properties of compounds of formula (I). The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.
  • Test compounds were individually formulated as a solution either in acetone or acetone/ethanol (1:1 by volume) which was diluted in deionised water to a concentration of lOOppm (that is, lmg of compound in a final volume of 10ml) immediately before use.
  • lOOppm concentration of lmg of compound in a final volume of 10ml
  • Uncinula necator (UNCINE), on vines; Phytophthora infestans lycopersici (PHYTIN) on tomatoes; Puccinia recondita (PUCCRT), on wheat; and Pyricularia oryzae (PYRIOR) on rice.
  • Each treatment was applied to two or more replicate plants for Phytophthora infestans lycopersici and Uncinula necator.
  • Puccinia recondita and Pyricularia oryzae two replicate pots each containing 6 to 10 plants were used for each treatment. The plants were inoculated one day before (Erad) or one day after (Prot) chemical application.
  • the Phytophthora infestans lycopersici, Puccinia recondita and Pyricularia oryzae plants were inoculated with a calibrated fungal spore suspension.
  • the Uncinula necator plants were inoculated using a 'blowing' inoculation technique.
  • Phytophthora infestans lycopersici Assessments were performed on a single leaf of each of the replicate plants for Uncinula necator. For Puccinia recondita and Pyricularia recondita assessments were carried out collectively on the plants in each replicate pot.
  • the disease level present (that is, the percentage leaf area covered by actively sporulating disease) was assessed visually. For each treatment, the assessed values for all its replicates were meaned to provide mean disease values. Untreated control plants were assessed in the same manner. The data were then processed by the method, described hereinafter, to provide PRCO (Percentage Reduction from Control) values.
  • PRCO Percentage Reduction from Control
  • PRCO 100 - ⁇ Mean disease level for treatment A ⁇ x 100
  • the PRCO is then rounded to the nearest whole number; therefore, in this particular example, the PRCO result is 71.

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Abstract

A compound of formula (I) wherein B is N, N-oxide or CR18; D is O, S, NR?7, CR8=CR9, CR8¿=N, N=CR9, CR8=N(O) or N(O)=CR9; E is N, N-oxide or CR12; W is CR1 or N; X is N, N-oxide or CR?11 and R11¿ is hydrogen, optionally substituted C¿1-6? alkyl or optionally substituted phenyl, with the proviso that the ring containing D, E, X and W contains at least one atom that is other than a carbon atom and the ring containing D, E, W and X may contain no more than 3 heteroatoms; M is N(R?51¿)C(=Y), N=C(OR52), N=C(SR53) or N=C(NR54R55) where N is the atom of attachment to the group 'A'; Y is O, S or NR13; Z is O, S or NR14; and A and the various R groups are defined organic radicals; their preparation and use and compositions containing them.

Description

BENZOXAZOLE DERIVATIVES AND THEIR USE AS PESTICIDES
The present invention relates to azole and azine derivatives, to processes for preparing them, to fungicidal, insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them, to methods of using them to combat fungal diseases
(especially fungal diseases of plants) and to methods of using them to combat and control insect, acarine, mollusc and nematode pests.
Azole and azine derivatives are disclosed in WO95/31448, WO97/18198, WO98/02424, WO98/05670 and WOOO/015622. The present invention provides a compound of formula (I):
Figure imgf000003_0001
wherein
A is optionally substituted Cι.6 alkylene, optionally substituted C2_6 alkenylene, optionally substituted C2_6 alkynylene, optionally substituted cycloalkylene, optionally substituted Cι_6 alkyleneoxy, optionally substituted oxy(Cι_6)alkylene, optionally substituted C*_6 alkylenethio, optionally substituted thio(Cι_6)alkylene, optionally substituted C1-6 alkyleneamino, optionally substituted amino(Cι_6)alkylene, optionally substituted [Cι_6 alkyleneoxy(Cι_6)alkylene], optionally substituted [Cι_6 alkylenethio(Cι_6)alkylene], optionally substituted [Cι_6 alkylenesulfιnyl(Cι_6)alkylene], optionally substituted [Cι_6 alkylenesulfonyl(Cι_ )alkylene] or optionally substituted [Cι_6 alkyleneamino(Cι_6)alkyIene]; B is N, N-oxide or CR18;
D is O, S, NR7, CR8=CR9, CR8=N, N=CR9, CR8=N(O) or N(O)=CR9; E is N, N-oxide or CR12; W is CR1 or N; X is N, N-oxide or CR11 and R11 is hydrogen, optionally substituted C1-6 alkyl or optionally substituted phenyl, with the proviso that the ring containing D, E, X and W contains at least one atom that is other than a carbon atom;
M is N(R51)C(=Y), N=C(OR52), N=C(SR53) or N=C(NR54R55) where N is the atom of attachment to the group "A"; Y is O, S or NR13; Z is O, S or NR14;
R1 is hydrogen, halogen, optionally substituted Cι_6 alkyl, optionally substituted C2.6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted C1-6 alkoxy, optionally substituted Cι_6 alkylthio, optionally substituted C3.7 cycloalkyl, cyano, nitro or SF5; R7 is hydrogen or optionally substituted Cι_6 alkyl;
R51 is hydrogen, optionally substituted Ci-io alkyl, optionally substituted [C2-6 alkenyl(Cι_6)alkyl], optionally substituted [C .6 alkynyl(Cι_6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted CMO alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, formyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(Cι_ιo)alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted Cι-6 alkylthio, optionally substituted Cι_6 alkylsulfinyl, optionally substituted C1-6 alkylsulfonyl, optionally substituted Cι_6 arylthio, optionally substituted Cι_ arylsulfinyl, optionally substituted Cι_6 arylsulfonyl or R20R21NS(O)p where p is 0, 1 or 2, especially 0; R52 is optionally substituted CMO alkyl, optionally substituted [C2. alkenyl(Cι_6)- alkyl], optionally substituted [C2_6 alkynyl(Cι_6)alkyl], optionally substituted C3_7 cycloalkyl, optionally substituted Cι_10 alkylcarbonyl, optionally substituted Cι_ιo alkoxycarbonyl, formyl, optionally substituted Cι_ιo alkylaminocarbonyl, optionally substituted di(Cι_ιo)- alkylaminocarbonyl, amino, optionally substituted Cι_6 alkylamino, optionally substituted di(Cι_ )alkylamino, optionally substituted phenoxycarbonyl, tri(Cι_ )alkylsilyl, aryldi(Cι_ )alkylsilyl, (C1-4)alkyldiarylsilyl or triarylsilyl;
R53 is optionally substituted Cι_ιo alkyl, optionally substituted [C2_6 alkenyl(Cι_6)- alkyl], optionally substituted fC2.6 alkynyl(Cι_6)alkyl], optionally substituted C3_7 cycloalkyl, optionally substituted CMO alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(Cι-ιo)alkyl- aminocarbonyl or optionally substituted phenoxycarbonyl);
R54 and R55 are, independently optionally substituted CMO alkyl, optionally substituted Cι_6 alkoxy, optionally substituted [C2.6 alkenyl(Cι_6)alkyl], optionally substituted [C2-6 alkynyl(Cι_6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted CMO alkylcarbonyl, optionally substituted C MO alkoxycarbonyl, formyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(Cι_ιo)alkylaminocarbonyl, hydroxy, amino, optionally substituted Cι_6 alkylamino, optionally substituted di(Cι_6)alkylamino, or optionally substituted phenoxycarbonyl; R , R and R" are, independently, hydrogen, halogen, optionally substituted Cι-6 alkyl, optionally substituted Cι_6 alkoxy, optionally substituted Cι_ alkylthio, optionally substituted Cι_6 alkylsulfinyl, optionally substituted Cι_6 alkylsulfonyl, cyano, nitro, optionally substituted C1-6 alkylcarbonyl, optionally substituted Cι_6 alkoxycarbonyl or SF5; R6 is hydrogen, halogen, cyano, optionally substituted Cι-2o alkyl, optionally substituted C2.2o alkenyl, optionally substituted C2_20 alkynyl, optionally substituted C3.7 cycloalkyl, optionally substituted C5.6 cycloalkenyl, formyl, optionally substituted C].2o alkoxycarbonyl, optionally substituted Cι_ o alkylcarbonyl, aminocarbonyl, optionally substituted C^o alkylaminocarbonyl, optionally substituted di(Cι_2o)alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-alkyl-N-arylaminocarbonyl, optionally substituted diarylaminocarbonyl, optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted N-alkyl-N-heteroarylaminocarbonyl, optionally substituted diheteroarylarmnocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, HS, optionally substituted Cι_2o alkylthio, optionally substituted Cι.2o alkylsulfinyl, optionally substituted Cι_2o alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl, R26O, R28R29N or R31ON=C(R27); R8 and R9 are, independently, hydrogen, halogen, cyano, nitro, optionally substituted
Cι-6 alkyl, optionally substituted C2_6 alkenyl, optionally substituted C2_6 alkynyl or optionally substituted C1-6 alkoxy;
R is hydrogen, halogen, optionally substituted Cι-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted Cι-6 alkoxy, optionally substituted Cι_6 alkylthio, optionally substituted Cι_6 alkylsulfinyl, optionally substituted Cι_6 alkylsulfonyl, cyano, nitro, formyl, optionally substituted C1- alkylcarbonyl, optionally substituted Cι_6 alkoxycarbonyl, SF5, R32ON=C(R30), or R1 and R12 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated, carbocyclic or heterocyclic ring which may contain one or two heteroatoms selected from O, N or S and which may be optionally substituted by C1-6 alkyl,
Figure imgf000005_0001
haloalkyl or halogen;
R13 is hydrogen, cyano, nitro, optionally substituted Cι-6 alkyl, optionally substituted C3-7 cycloalkyl, optionally substituted (C2-6)alkenyl(Cι_ )alkyl, optionally substituted (C2_6)alkynyl(Cι_ )alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted Cι_6 alkylcarbonyl, optionally substituted C-.6 alkoxycarbonyl, optionally substituted Cι_6 alkylamino, optionally substituted di(Cι_6)alkylamino, optionally substituted Cι_ alkylcarbonylamino, optionally substituted Cι_6 alkoxycarbonylamino, optionally substituted Cι_6 alkoxy, optionally substituted CMS alkylthio, optionally substituted Cι-6 alkylsulfinyl, optionally substituted Cι_6 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or Cι-6 alkylcarbonyloxy;
R14 is hydrogen, cyano, optionally substituted C]_8 alkyl, optionally substituted [C2_6 alkenyl(Cι_6)alkyl], optionally substituted [C2_ alkynyl(Cι_6)alkyl], optionally substituted C3. cycloalkyl, optionally substituted [C3_7 cycloalkyl(Cι_6)alkyl], C*_6 alkoxy(Cι_6)alkyl, optionally substituted Cι_6 alkoxycarbonyl, optionally substituted Cι_6 alkylcarbonyl, optionally substituted Cι_6 alkylaminocarbonyl, optionally substituted di( . ^alkylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl;
R is hydrogen, halogen, nitro, cyano, optionally substituted Cι_8 alkyl, optionally substituted C2. alkenyl, optionally substituted C2_ alkynyl, optionally substituted C3_ cycloalkyl, optionally substituted Cι_6 alkoxycarbonyl, optionally substituted Cι_6 alkylcarbonyl, optionally substituted Cι_6 alkylaminocarbonyl, optionally substituted di(Cι-6)alkylaminocarbonyl, optionally substituted phenyl or optionally substituted heteroaryl;
R20 and R21 are, independently, optionally substituted Cι_6 alkyl or R20 and R21 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Cι_6 alkyl groups;
R26 is hydrogen, optionally substituted Cι_2o alkyl, optionally substituted [C2_ 0 alkenyl (Cι.6)alkyl], optionally substituted [C2_2o alkynyl(C1. )alkyl], optionally substituted C3_7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted [heterocyclyl(Cι_6)alkylCH=N] or di(Cι_6)alkylC=N; R28 and R29 are, independently, hydrogen, optionally substituted Cι_2o alkyl, optionally substituted C3-7 cycloalkyl, optionally substituted [C2.2o alkenyl(Cι_6)alkyl], optionally substituted [C2.2o alkynyl(Cι_6)alkyl], optionally substituted Cι_20 alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted Cι_2o alkylcarbonyl, optionally substituted C-_2o alkylsulfonyl or optionally substituted phenylsulfonyl; or R28 and R29 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Cι-6 alkyl groups; R27 and R30 are independently hydrogen, optionally substituted phenyl or optionally substituted Cι_6 alkyl; and
R and R are, independently, hydrogen, optionally substituted phenyl (Cι_2)alkyl or optionally substituted Cι_ o alkyl provided that when A is CH2, M is CONH, D is S, and X is N then E and W cannot both be C-Cl. The ring containing D, E W and X may contain no more than 3 heteroatoms.
The compounds of formula (I) may exist in different geometric or optical isomers or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
When present, optional substituents on alkylene, alkenylene or alkynylene moieties include, subject to valency constraints, one or more of hydroxy, halogen, Cι.6 alkyl, Cι_6 haloalkyl, Cι_6 cyanoalkyl, Cι_6 alkoxy(Cι_6)alkyl, C-_6 alkoxy, cyano, =O, =NR33, =CR34R35; wherein R33 is Cι_6 alkyl, Cι_6 haloalkyl, OR36 or R37R38N; R36 is Cι.6 alkyl, Cι.6 haloalkyl or phenyl(Cι-2)alkyl; R37 and R38 are, independently, hydrogen, Ct_8 alkyl, C3.7 cycloalkyl, C2_6 alkenyl(Cι_ )alkyl, C2.6 alkynyl (Cι_6)alkyl, C2_6 haloalkyl, C1-6 alkoxy(Cι_6)alkyl, C*_6 alkoxycarbonyl(Cι_6)alkyl, carboxy(Cι_6)alkyl, phenyl(C*_2)alkyl, or R37 and R38 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Cι_6 alkyl groups; R34 and R35 are, independently, hydrogen, Cι- alkyl, Cι_6 alkoxy, Cι_6 haloalkyl, cyano, Cι_6 alkoxycarbonyl, Cι-6 alkylcarbonyl or R39R40N; R39 and R40 are, independently, hydrogen, Cu8 alkyl, C3.7 cycloalkyl, C2_6 alkenyl(Cι_6)alkyl, C2_6 alkynyl(Cι_ )alkyl, C2.6 haloalkyl, Cι_6 alkoxy(Cι_6)alkyl, Cι_ alkoxycarbonyl(Cι_6)alkyl, carboxy(Cι_6)alkyl, phenyl (Cι_2)alkyl, or R39 and R40 together with the N atom to which they are attached form a five, six or seven- membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Cι_6 alkyl groups. One group of preferred optional substituents on alkylene, alkenylene or alkynylene moieties include, subject to valency constraints, one or more of halogen, C*_6 alkyl, Cι_ haloalkyl, Cι_6 cyanoalkyl, _ alkoxy(Cι_6) alkyl, Cι_6 alkoxy, cyano, =O, =NR33 and =CR3 R35, wherein R33 is C1-6 alkyl, Cι_6 haloalkyl. OR36 or R37R38N; where R34 and R35 are, independently, hydrogen, Cι_6 alkyl, Cι_6 alkoxy, C-_6 haloalkyl, cyano, Cι_6 alkoxycarbonyl, Cι_6 alkylcarbonyl or R39R40N; R36 is Cι_6 alkyl, Cι_6 haloalkyl or phenyl(Cι_2)alkyl; R37 and R38 are, independently, hydrogen, Cι-8 alkyl, C3.7 cycloalkyl, C2.6 alkenyl(Cι_6)alkyl, C2_6 alkynyl(Cι_6)alkyl, C2.6 haloalkyl, Cι_6 alkoxy(Cι.6)alkyl, Cι_6 alkoxycarbonyl (Cι_6)alkyl, carboxy(Cι_6)alkyl or phenyl(Cι_2)alkyl or R37 and R38 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Cι_6 alkyl groups; R39 and R40 are, independently, hydrogen, C1-8 alkyl, C3_7 cycloalkyl, C2.6 alkenyl(Cι_6)alkyl, C2_6 alkynyl(Cι_6)alkyl, C2_6 haloalkyl, C1-6 alkoxy(Cι_6)alkyl, Cι_6 alkoxycarbonyl(Cι_6)alkyl, carboxy(Cι_6)alkyl or phenyl(Cι_ )alkyl; or R39 and R40 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Cι_6 alkyl groups.
Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, rc-butyl, «-pentyl, n-hexyl, tsø-propyl, n-butyl, sec-butyl, wσ-butyl, tert-butyl or neø-pentyl.
When present, the optional substituents on alkyl include one or more of halogen, nitro, cyano, NCS-, C3.7 cycloalkyl (which itself may be optionally substituted with Cι_6 alkyl or halogen), C5.7 cycloalkenyl (which itself may be optionally substituted with Cι_6 alkyl or halogen), hydroxy, CM0 alkoxy, CM0 alkoxy(C 0)alkoxy, tri(Cι- )alkylsilyl(Cι_6)alkoxy, Cι.6 alkoxycarbonyl(Cι_10)alkoxy, CMO haloalkoxy, CMO deuteroalkoxy, aryl(Cι ^alkoxy (where the aryl group may be further optionally substituted), C3_7 cycloalkyloxy (where the cycloalkyl group may be optionally substituted with Cι_6 alkyl or halogen), CMO alkenyloxy, CMO alkynyloxy, SH, CMO alkylthio, CMO haloalkylthio, aryl(Cι-4)alkylthio (where the aryl group may be further optionally substituted), C3_ cycloalkylthio (where the cycloalkyl group may be optionally substituted with Cι_6 alkyl or halogen), tri(Cι-4)alkylsilyl(Cι_6)alkylthio, arylthio (where the aryl group may be further optionally substituted), Cι_6 alkylsulfonyl, Cι_6 haloalkylsulfonyl, Cι_6 alkylsulfinyl, Cι-6 haloalkylsulfinyl, arylsulfonyl (where the aryl group may be further optionally substituted), tri(Cι^)alkylsilyl, aryldi(Cι- )alkylsilyl,
Figure imgf000008_0001
triarylsilyl, CMO alkylcarbonyl, HO C, Cι_10 alkoxycarbonyl, aminocarbonyl, Cι_6 alkylaminocarbonyl, di(Cι-6 alkylaminocarbonyl, N-(Cι_3 alkyl)-N-(Cι_3 alkoxy)aminocarbonyl, Cι_6 alkylcarbonyloxy, arylcarbonyloxy (where the aryl group may be further optionally substituted), di(C1_6)alkylaminocarbonyloxy, aryl (which itself may be further optionally substituted), heteroaryl (which itself may be further optionally substituted), heterocyclyl (which itself may be optionally substituted with Cι_6 alkyl or halogen), aryloxy, (which itself may be further optionally substituted), heteroaryloxy, (which itself may be further optionally substituted), heterocyclyloxy, (which itself may be optionally substituted with Cι-6 alkyl or halogen), amino, Cι_6 alkylamino, di(C1.6)alkylamino, alkylcarbonylamino, N-alkylcarbonyl-N-alkylamino.
One group of optional preferred substituents for alkyl include one or more of halogen, nitro, cyano, HO2C, CMO alkoxy (itself optionally substituted by CMO alkoxy), ary Ci.-t)- alkoxy, CMO alkylthio, CMO alkylcarbonyl, CMO alkoxycarbonyl, _6 alkylaminocarbonyl, di(Ci_6 alkylaminocarbonyl, (Cι_6)alkylcarbonyloxy, optionally substituted phenyl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl, heterocyclyloxy, C3.7 cycloalkyl (itself optionally substituted with (Cι_6)alkyl or halogen), C3_7 cycloalkyloxy, C5.7 cycloalkenyl, Cι-6 alkylsulfonyl, Cι_6 alkylsulfinyl, tri(C1-4)alkylsilyl, tri(Cι_ )alkylsilyl- (C1-6)alkoxy, aryldi(Cι- )alkylsilyl, (C1-4)alkyldiarylsilyl and triarylsilyl.
Alkenyl and alkynyl moieties can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)- or ©-configuration. Examples are vinyl, allyl and propargyl. When present, the optional substituents on alkenyl or alkynyl include one or more of the substituents listed above for alkyl but especially preferred substituents are one or more of halogen, aryl and C3_7 cycloalkyl.
In the context of this specification acyl is optionally substituted Cι_6 alkylcarbonyl (for example acetyl), optionally substituted C2_6 alkenylcarbonyl, optionally substituted C2.6 alkynylcarbonyl, optionally substituted arylcarbonyl (for example benzoyl) or optionally substituted heteroarylcarbonyl.
Halogen is fluorine, chlorine, bromine or iodine.
Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF3, CF2C1, CF3CH2 or CHF2CH2.
Aryl includes naphthyl, anthracyl, fluorenyl and indenyl but is preferably phenyl. The term heteroaryl refers to an aromatic ring containing up to 10 atoms including one or more heteroatoms (preferably one or two heteroatoms) selected from O, S and N. Examples of such rings include pyridine, pyrimidine, furan, quinoline, quinazoline, pyrazole, thiophene, thiazole, oxazole and isoxazole. The terms heterocycle and heterocyclyl refer to a non-aromatic ring containing up to 10 atoms including one or more (preferably one or two) heteroatoms selected from O, S and N. Examples of such rings include 1 ,3-dioxolane, tetrahydrofuran and morpholine. It is preferred that heterocyclyl is optionally substituted by Cι_6 alkyl. Cycloalkyl includes cyclopropyl, cyclopentyl and cyclohexyl. The optional substituents for cycloalkyl include one or more of the substituents listed above for alkyl but especially preferred substituents are one or more of halogen, cyano and Cι_3 alkyl.
Cycloalkenyl includes cyclopentenyl and cyclohexenyl. The optional substituents for cycloalkenyl include one or more of the substituents listed above for alkyl but especially preferred substituents include one or more of Cι_3 alkyl, halogen and cyano. Carbocyclic rings include aryl, cycloalkyl and cycloalkenyl groups. For substituted aryl such as phenyl and heteroaryl groups the substituents are independently selected from one or more of halogen, nitro, cyano, NCS-, Cι_ alkyl, Cι_6 haloalkyl, Cι_6 alkoxy(Cι_6)alkyl, C2_6 alkenyl, C2_6 haloalkenyl, C2_6 alkynyl, C3. cycloalkyl (which itself may be optionally substituted with Cι_6 alkyl or halogen), C5-7 cycloalkenyl
(which itself may be optionally substituted with Cι_ alkyl or halogen), hydroxy, C O alkoxy, CMO alkoxy(Cι_ιo)alkoxy, tri(Cι_ )alkylsilyl(Cι_6)alkoxy, C^ alkoxycarbonyl(Cι_ιo)alkoxy, CMO haloalkoxy, CMO deuteroalkoxy, aryl(Cι._ )alkoxy (where the aryl group may be further optionally substituted), C3_7 cycloalkyloxy (where the cycloalkyl group may be optionally substituted with Cι_6 alkyl or halogen), CMO alkenyloxy, CMO alkynyloxy, SH, CMO alkylthio, CMO haloalkylthio, aryl(Cι_4)alkylthio (where the aryl group may be further optionally substituted), C3_7 cycloalkylthio (where the cycloalkyl group may be optionally substituted with Cι-6 alkyl or halogen), tri(Cι^)alkylsilyl(C1_6)alkylthio, arylthio (where the aryl group may be further optionally substituted), Cι_6 alkylsulfonyl, Cι_6 haloalkylsulfonyl, Cι_6 alkylsulfinyl, Cι_6 haloalkylsulfinyl, arylsulfonyl (where the aryl group may be further optionally substituted), tri(Cι_ )alkylsilyl, aryldi(Cι_4)alkylsilyl, (Cι- )alkyldiarylsilyl, triarylsilyl, CMO alkylcarbonyl, HO2C, Cι-10 alkoxycarbonyl, aminocarbonyl, Cι_6 alkylaminocarbonyl, di(Cι-6 alkylaminocarbonyl, N-( -3 alkyl)-N-(C1-3 alkoxy)aminocarbonyl, Cι_6 alkylcarbonyloxy, arylcarbonyloxy (where the aryl group may be further optionally substituted), di(Ci_6)alkylaminocarbonyloxy, aryl (which itself may be further optionally substituted), heteroaryl (which itself may be further optionally substituted), heterocyclyl (which itself may be optionally substituted with Cι_6 alkyl or halogen), aryloxy, (which itself may be further optionally substituted), heteroaryloxy, (which itself may be further optionally substituted), heterocyclyloxy, (which itself may be optionally substituted with Cι-6 alkyl or halogen), amino, C*_6 alkylamino, di(Cι_6)alkylamino, alkylcarbonylamino, N-alkylcarbonyl-N-alkylamino .
For substituted heterocyclyl groups the substituents include one or more of the substituents listed above for alkyl. For substituted phenyl moieties, heterocyclyl and heteroaryl groups one set of preferred substituents are independently selected from one or more of halogen, .6 alkyl, Cι_6 haloalkyl, C1-6 alkoxy(Cι_6)alkyl, Cι_6 alkoxy, Cι_6 haloalkoxy, Cι_6 alkylthio, C1-6 haloalkylthio, Cι_6 alkylsulfinyl, C1-6 haloalkylsulfinyl, C]_6 alkylsulfonyl, Cι_6 haloalkylsulfonyl, C2.6 alkenyl, C2.6 haloalkenyl, C2_6 alkynyl, C3.7 cycloalkyl, nitro, cyano, C02H, Cι_6 alkylcarbonyl, Cι-6 alkoxycarbonyl, R41R42N or R43R44NC(O) wherein R41, R42, R43 and R44 are, independently, hydrogen or Cι_6 alkyl.
It is to be understood that dialkylamino substituents include those where the dialkyl groups together with the N atom to which they are attached form a five, six or seven- membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two C)_6 alkyl groups. When heterocyclic rings are formed by joining two groups on an N atom, the resulting rings are suitably pyrrolidine, piperidine, thiomorpholine and morpholine each of which may be substituted by one or two (Cι_6)alkyl groups.
In one particular aspect the present invention provides a compound of formula (IA) which are compounds of formula (I) where B, E, M, W and Z have the values as defined for formula (I) above and X is N or CR11 where R11 is hydrogen, Cι_6 alkyl or phenyl, and D is O, S, NR7, CR8=CR9, CR8=N, N=CR9, CR8=N(0) or N(O)=CR9 where R8 and R9 are as defined in relation to formula (I) above, R is hydrogen or Cι_6 alkyl, R is hydrogen, halogen, optionally substituted Cι_6 alkyl, optionally substituted C2_6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted Cι_6 alkoxy, optionally substituted Cι_6 alkylthio, optionally substituted C3_ cycloalkyl, cyano, nitro or SF5; R 1 is hydrogen, halogen, optionally substituted Cι_6 alkyl, optionally substituted C2.6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted C1-6 alkoxy, optionally substituted C-_ alkylthio, optionally substituted Cι_6 alkylsulfinyl, optionally substituted Cι_6 alkylsulfonyl, cyano, nitro, formyl, R32ON=C(R30), optionally substituted Cι_6 alkylcarbonyl, optionally substituted Cι_6 alkoxycarbonyl or SF5; or R 1 and R 19 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated ring carbocylic or heterocyclic ring which may contain one or two hetero atoms selected from O, N or S and which may be optionally substituted by Cι_6 alkyl, Cι-6 haloalkyl or halogen; R3, R4 and R5 are, independently, hydrogen, halogen, optionally substituted C1-6 alkyl, optionally substituted Cι-6 alkoxy, optionally substituted C1-6 alkylthio, optionally substituted Cι-6 alkylsulfinyl, optionally substituted Cι_6 alkylsulfonyl, cyano, nitro, optionally substituted Cι_6 alkylcarbonyl, optionally substituted Cι_ alkoxycarbonyl or SF5; R6 is hydrogen, halogen, cyano, optionally substituted C1-2o alkyl, optionally substituted C2_2o alkenyl, optionally substituted C .2o alkynyl, optionally substituted C3.7 cycloalkyl, optionally substituted C5.6 cycloalkenyl, formyl, optionally substituted C1-2o alkoxycarbonyl, optionally substituted Cι_20 alkylcarbonyl, aminocarbonyl, optionally substituted Cι_20 alkylaminocarbonyl, optionally substituted di(Cι_20)alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-alkyl-N-arylaminocarbonyl, optionally substituted diarylaminocarbonyl, optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted alkylheteroarylaminocarbonyl, optionally substituted diheteroarylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, R26O, HS, optionally substituted Cι_2o alkylthio, optionally substituted Cι_2o alkylsulfinyl, optionally substituted C-..20 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl , R28R29N or R31ON=C(R27); A is optionally substituted Cι_6 alkylene, optionally substituted C2.6 alkenylene, optionally substituted C2_6 alkynylene, optionally substituted Cι-6 alkyleneoxy, optionally substituted oxy(C1_6)alkylene, optionally substituted Cι_6 alkylenethio, optionally substituted thio(Cι_6)alkylene, optionally substituted Cι_6 alkyleneamino, optionally substituted amino(C1- )alkylene, optionally substituted [ .6 alkyleneoxy(Cι_ )alkylene], optionally substituted [ -ό alkylenethio(Cι_6)alkylene], optionally substituted [Cι_6 alkylenesulfinyl(C|_6)alkylene], optionally substituted [Cι_6 alkylenesulfonyl(Cι_6)alkylene] or optionally substituted [Cι_6 alkyleneamino(Cι_ )alkylene]; R13 is hydrogen, cyano, nitro, optionally substituted Cι.6 alkyl, optionally substituted C3_7 cycloalkyl, optionally substituted (C2_6)alkenyl(Cι_ )alkyl, optionally substituted (C2-6)alkynyl(Cι_6)alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted Cι_6 alkylcarbonyl, optionally substituted Cj._6 alkoxycarbonyl, optionally substituted Cι_6 alkylamino, optionally substituted di(Cι_ )alkylamino, optionally substituted Cι_6 alkylcarbonylamino, optionally substituted C\.(, alkoxycarbonylamino, optionally substituted Cι_6 alkoxy, optionally substituted C-^ alkylthio, optionally substituted C1-6 alkylsulfinyl, optionally substituted _6 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or Cι_6 acyloxy; R14 is hydrogen, cyano, optionally substituted Cι_8 alkyl, optionally substituted [C2_6 alkenyl(C1.6)alkyl], optionally substituted [C2.6 alkynyl - (C1_6)alkyl], optionally substituted C3_7 cycloalkyl, optionally substituted [C3_7 cycloalkyl(C]_6)alkyl], d_6 alkoxy(Cι-6)alkyl, optionally substituted C alkoxycarbonyl, optionally substituted Cι_6 alkylcarbonyl, optionally substituted Cι_6 alkylaminocarbonyl, optionally substituted di(Cι_6)alkyl-aminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl; and R18 is hydrogen, halogen, nitro, cyano, optionally substituted Cι_8 alkyl, optionally substituted C2_6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted C3- cycloalkyl, optionally substituted Cι_6 alkoxycarbonyl, optionally substituted C1-6 alkylcarbonyl, optionally substituted .6 alkylaminocarbonyl, optionally substituted di(Cι_6)alkylaminocarbonyl, optionally substituted phenyl or optionally substituted heteroaryl; and R51 is hydrogen, optionally substituted Cι_ι0 alkyl, optionally substituted [C2-6 alkenyl(Cι_6)alkyl], optionally substituted [C2-6 alkynyl(Cι_6)alkyl], optionally substituted C3. η cycloalkyl, optionally substituted CMO alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, formyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(Cι_ιo)alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted Cι_6 alkylthio, optionally substituted CMS alkylsulfinyl, optionally substituted
Figure imgf000013_0001
alkylsulfonyl, optionally substituted Cι_6 arylthio, optionally substituted C1-6 arylsulfinyl, optionally substituted C1-6 arylsulfonyl or R20R21NS.
In a further aspect the present invention also provides a compound of formula (IB) which are compounds of formula (I) where A, B, E, M, W, Z, R3, R4, R5, and R6 have the values as defined for formula (I) above and D is O, S, NR7, CR8=CR9, CR8=N, N=CR9, where R and R are as defined in relation to formula (I) above.
In yet another aspect the present invention provides a compound of formula (V)
Figure imgf000013_0002
where A, B, D, E, M, W, X, Z, R3, R4, R5, and R6 have the values as defined for formula (I) above. The invention also provides a compound of formula (IA') which is a compound of formula F wherein A, B, D, E, M, W, X, Z, R3, R4, R5, and R6 have the values as defined for formula (IA) above. There is further provided a compound of formula (IB') which is a compound of formula F wherein A, B, D, E, M, W, X, Z, R3, R4, R5, and R6 have the values as defined for formula (IB) above.
In another aspect the present invention provides a compound of formula (IC) which is a compound of formula (F) wherein,
D is O, S, NR7, CR8=CR9, where R7 is Cι_6 alkyl, especially, O, S or NR7 where R7 is Cι_6 alkyl
E is N or CR12;
W is CR1 or N:
X is N or CRU; R11 is hydrogen, Cι_6 alkyl or phenyl with the proviso that at least one ofW and X is N; R1 is hydrogen, halogen, Cι_6 alkyl, C2_6 alkenyl, C2_6 alkynyl, Cι_6 cyanoalkyl, C\^ haloalkyl, -β alkoxy, -β haloalkoxy, Cι_ alkylthio, .6 haloalkylthio, C3.6 cycloalkyl, C3_ cycloalkyl(Cι_ )alkyl, Cι_6 alkoxy(Cι_ )alkyl, cyano, nitro or SF5;
A is C ι-6 alkylene, Cι-6 alkenylene, Cι_6 alkyleneoxy, oxy(Cι_6)alkylene, Cι_6 alkyleneamino or Cι_6 alkylenethio, each of which is optionally substituted by Cι_3 alkyl, Cι-3 haloalkyl, Cι_3 cyanoalkyl, halogen, C-_3 alkoxy, C*.6 alkoxycarbonyl, cyano, =0, =NR15 or
=CRI6R17;
B is N or CR 18.
M is N(R51)C(=Y), N=C(SR53) or N=C(OR52), especially N(R51)C(=Y) or N=C(SR53) where O or N is the atom of attachment to the group "A"; Y is O, S or NR13;
Z is O, S or NR14;
R51 is hydrogen, CMO alkyl, benzyloxymethyl, benzoyloxymethyl, Cι_6alkoxy- (Cι_6)alkyl, C2.6 alkenyl (Cι_6)alkyl (especially allyl), C2.6 alkynyl(Cι_6)alkyl (especially propargyl), CMO alkylcarbonyl or CMO alkoxycarbonyl (especially wσbutoxycarbonyl); R52 is CMO alkyl, CMO haloalkyl, C2.6 alkenyl(C[.6)alkyl, C2-6 alkynyl (Cι_6)alkyl, C3_7 cycloalkyl, Cι_6 alkylamino, di(Cι-6)alkylamino, phenyl (Cι^)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Cι_6 alkyl, Cι-6 haloalkyl, Cι_6 alkoxy or Cι_6 haloalkoxy); R53 is CMO alkyl, benzyloxymethyl, benzoyloxymethyl, Cι_6alkoxy(Cι-6)alkyl, C .6 alkenyl(Cι_6)alkyl (especially allyl), C2.6 alkynyl(Cι_6)alkyl (especially propargyl), C MO alkylcarbonyl or CMO alkoxycarbonyl (especially /.søbutoxycarbonyl);
R3, R4 and R5 are independently selected from hydrogen, halogen, C*_6 alkyl, Cι_6 alkoxy, Cι_6 haloalkoxy, Cι_6 alkylthio, Cι_6 haloalkyl thio, _6 alkylsulfinyl, Cι_6 haloalkylsulfinyl, Cι_6 alkylsulfonyl, Cι_6 haloalkylsulfonyl, Cι_6 haloalkyl, cyano, nitro, Cι-6 alkylcarbonyl, Cι_6 alkoxycarbonyl or SF5;
R6 is cyano, _8 alkyl, Cι_6 haloalkyl, Cι-6 cyanoalkyl, C2.6 alkenyl, C2_6 alkynyl, C3_ cycloalkyl, C3_7 halocycloalkyl, C3.7 cyanocycloalkyl, Cι_3 alkyl(C3.7)cycloalkyl, Cι_3 alkyl- (C _7)halocycloalkyl, C5_6 cycloalkenyl, C3_7 cycloalkyl(Cι_6)alkyl, C5_6 cycloalkenyl- (Cι_6)alkyl, C2.6 haloalkenyl, Ci-β cyanoalkenyl, Cι_6 alkoxy(Cι_6)alkyl, C3.6 alkenyloxy- (Cι_6)alkyl, C3.6 alkynyloxy(Cι_6)alkyl, aryloxy(Cι_6)alkyl, formyl, Cι_6 carboxyalkyl, Cι_6 alkylcarbonyl(Cι_6)alkyl, C2_6 alkenylcarbonyl(Cι_6)alkyl, C2.6 alkynylcarbonyl(Cι_6)alkyl, Cj-6 alkoxycarbonyl(Cι_6)alkyl, C3.6 alkenyloxycarbonyl(Cι_6)alkyl, C3_6 alkynyloxycarbonyl- (Cι_6)alkyl, aryloxycarbonyl(Ci.6)alkyl, Cι_6 alkylthio(Cι_6)alkyl, Cι_6 alkylsulfinyl(Cι_6)alkyl, Cι-6 alkylsulfonyl(Cι_6)alkyl, aminocarbonyl(Cι_6)alkyl, aminocarbonyl(C2.6)alkenyl, aminocarbonyl(C2.6)alkynyl, Cι_6 alkylaminocarbonyl(Cι_6)alkyl, di(Cι_6)alkylamino- carbonyl(Cι_6)alkyl, Cι_6 alkylaminocarbonyl(Cι_6)alkenyl, di(Cι_6)alkylamino- carbonyl(C i .6)alkenyl, alkylaminocarbonyl (C i _6)alkynyl, di(C i _6)alkylaminocarbonyl(Cι . 6)alkynyl, Cι_6 alkoxycarbonyl, Cι_6 alkylcarbonyl, aminocarbonyl, Cι_6 alkylaminocarbonyl, di(Cι.6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, C-_6 alkyl, Cι_6 haloalkyl, Q_6 alkoxy or Cι_6 haloalkoxy), phenyl(Cι_4)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Cι_6 alkyl, Cι_6 haloalkyl, Cι_6 alkoxy or Cι_6 haloalkoxy), phenyl(C2. )alkenyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Cι_6 alkyl, Cι_6 haloalkyl, Cι_6 alkoxy or d_6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Cι_6 haloalkyl, Cι_6 alkoxy or Cι_6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, C*_6 alkyl, Cι_6 haloalkyl, Cι_6 alkoxy or Cj_6 haloalkoxy),, heteroaryl(Cι_ )alkyl (where the heteroaryl may be substituted by halo, nitro, cyano, Cι_6 alkyl, Cι_6 haloalkyl, Cι_6 alkoxy or Cι_6 haloalkoxy), heterocyclyKQ. )alkyl (where the heterocyclyl may be substituted by halo, cyano, Cι_6 alkyl, Cι_6 haloalkyl,
Ci_6 alkoxy or Cι_6 haloalkoxy), R26O, C,_8 alkylthio, R28R29N or R31ON=C(R27);
R8 and R9 are, independently, hydrogen, halogen, Cι_6 alkyl, Cι_6 haloalkyl C2.6 alkenyl, Cι_6 alkynyl, Cι_6 alkoxy or Cι_6 haloalkoxy; R12 is hydrogen, halogen, Cι_6 alkyl, C2.6 alkenyl, Cι_6 alkynyl, Cι_6 haloalkyl, Q-6 alkoxy, Cι_6 alkoxy (Cι-6)alkyl, Cι_6 haloalkoxy, C1-6 alkylthio, Cι_6 haloalkylthio, Cι_6 alkylsulfinyl, Cι_6 haloalkylsulfinyl, Cι_6 alkylsulfonyl, Cι_6 haloalkylsulfonyl, Cι_6 haloalkyl, cyano, nitro, formyl, CH=NOR32, Cι_6 alkylcarbonyl, Cι_6 alkoxycarbonyl or SF5; or together R1 and R12 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated ring carbocylic or heterocyclic ring which may contain one or two hetero atoms selected from O, N or S and which may be optionally substituted by Cι_6 alkyl, C-._6 haloalkyl or halogen;
R13 is cyano, nitro, Cι_6 alkyl, Cι-6 haloalkyl, C3.7 cycloalkyl, C3_7 cycloalkyl- (Cι_6)alkyl, CH2(C2_6)alkenyl, CH2(C2_6)alkynyl, phenyl (optionally substituted by halo, nitro, cyano, Cι_6 alkyl, Cι_6 haloalkyl, Cι_6 alkoxy or Cι_6 haloalkoxy) heteroaryl (optionally substituted by halo, nitro, cyano, Cι_6 alkyl, Cι_6 haloalkyl, Cι_6 alkoxy or Cι_6 haloalkoxy), Ci_6 alkylcarbonyl, Cι_6 alkoxycarbonyl, Cι_6 alkylamino, di(Cι_6)alkylamino, Cι_6 alkylcarbonylamino, Cι.6 alkoxycarbonylamino, Cι_6 alkoxy, Q-6 alkylthio, Q-6 alkylsulfinyl, C!_6 alkylsulfonyl, Cι_6 haloalkylthio, Cι_6 haloalkylsulfinyl, Cι.6 haloalkylsulfonyl, arylthio, arylsulfinyl, arylsulfonyl or OCO(Cι_6)alkyl;
R14 is hydrogen, Cι_8 alkyl, Cι_6 haloalkyl, Cι_6 cyanoalkyl, C2_6 alkenyl, C2.6 alkynyl, C3.7 cycloalkyl, C2.6 haloalkenyl, C3_7 cycloalkyl(Cι-6)alkyl, Cι_6 alkoxy(Cι_6)alkyl, Cι-6 alkoxycarbonyl, Cι_6 alkylcarbonyl, Q_6 alkylaminocarbonyl, di(Cι_6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, Cι-6 alkyl, Cι_6 haloalkyl, Cι_6 alkoxy or Cι_6 haloalkoxy) or heteroaryl (optionally substituted by halo, nitro, cyano, Cι_6 alkyl, Cι_6 haloalkyl, Cι.6 alkoxy or Cι_6 haloalkoxy); R15 is Ci.6 alkyl, OR22 or NR23R24; R16 is hydrogen, Cι_6 alkyl or Cι-6 haloalkyl; R17 is hydrogen, Cι_6 alkyl, Cι_6 haloalkyl, Cι_6 alkoxy, cyano, Cι_6 alkoxycarbonyl,
C1-6 alkylcarbonyl or NR46R47;
R18 is hydrogen, halogen, nitro, cyano, Cι_8 alkyl, Cι_6 haloalkyl, Cι_6 cyanoalkyl, C2-6 alkenyl, C2_6 alkynyl, C3_7 cycloalkyl, C2.6 haloalkenyl, C3-7 cycloalkyl (Q_6)alkyl, Cι_6 alkoxy(Cι_6)alkyl, Cι_6 alkoxycarbonyl, Cι_6 alkylcarbonyl, Cι_6 alkylaminocarbonyl, di(Cι_6)alkylaminocarbonyl, Cι_6 alkoxycarbonyl(Cι-6)alkyl, Cι_6 alkylcarbonyl(Cι_6)alkyl,
Cι_6 alkylaminocarbonyl(Cι.6)alkyl, di(Cι_6)alkylaminocarbonyl(Cι_ )alkyl, phenyl (optionally substituted by halo, nitro, cyano, Cι_ alkyl, Cι_6 haloalkyl, Cι_ alkoxy or Q-6 haloalkoxy), phenyl(Cι_6)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci_6 alkyl, Q_6 haloalkyl, Cι_6 alkoxy or Q_6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Cι-6 alkoxy or Q.6 haloalkoxy) or heteroaryl(Cι_6)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q-6 haloalkoxy); R20 and R21 are, independently, hydrogen, Q-6 alkyl, CH2(Cι_4 haloalkyl), Q_6 cyanoalkyl, Cι_6 alkoxy(C1_6)alkyl, Q_6 alkylthio(Q.6)alkyl, Q_6 alkoxy(Q_6)alkoxy- (Cι-6)alkyl, phenyl(Q.4)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q-6 alkyl, Q_6 haloalkyl, Q-6 alkoxy or Q_6 haloalkoxy), heteroaryl(Q_ )alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy), heterocyclyl (Q_4)alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q.6 haloalkoxy), or R20 and R21 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q-6 alkyl groups;
R22 is C ι-6 alkyl or optionally substituted phenyl(Q-2)alkyl;
R23 and R24 are, independently, hydrogen, Q_8 alkyl or phenyl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q_ alkoxy or Q_6 haloalkoxy);
R26 is hydrogen, Q_8 alkyl, Q_6 haloalkyl, Q_6 cyanoalkyl, C2_6 alkenyl, C2-6 alkynyl, Q.6 alkoxy(Q_6)alkyl, phenyl(Q_4)alkyl , (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), heteroaryl(Q-4)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q_6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q.^ haloalkoxy), heterocycly Q-^alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy), Q.6 alkoxycarbonyl(Q.6)alkyl or N=C(CH3)2;
R27 is Q-6 alkyl, Q-6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano,
Q.6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Q.6 haloalkoxy), RR2288 aanndd RR2299 aarree,, iinnddeeppeennddeennttllyy,, hhyyddrrooggeenn,, QQ__88 aallkkjyl, C3-7 cycloalkyl, C3-6 alkenyl, C3_6 alkynyl, C3. cycloalkyl(Q-4)alkyl, C2-6 haloalkyl, Cι_6 alkoxy(Cι-6)alkyl, Q.6 alkoxycarbonyl, or R28 and R29 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q-6 alkyl groups;
R30 is hydrogen or Q_3 alkyl;
R31 and R32 are, independently, Q.6 alkyl or phenyl(Q.2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q-6 haloalkoxy); and
R46 and R47 are, independently, hydrogen, Q_8 alkyl, C3.7 cycloalkyl, C3.6 alkenyl, C3_6 alkynyl, C2.6 haloalkyl, Cι_6 alkoxy(Q_6)alkyl, Cι_6 alkoxycarbonyl(Q_6)alkyl, carboxy(Cι_6)alkyl or phenyl(Q.2)alkyl; or R46 and R47 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q_6 alkyl groups.
Preferably A is Q_6 alkylene (optionally substituted by Q.3 alkyl, Q_3 haloalkyl, Q.3 cyanoalkyl, Q_6 alkoxycarbonyl), -C(O)- or Q.6 alkyleneoxy: More preferably A is Q^ alkylene -C(O)- or Q^ alkyleneoxy; or alternatively is C1- alkylene (optionally substituted by Q-3 alkyl).
Even more preferably A is CH2, CH(CH3) or CH2O. Most preferably A is CH2 or CH(CH3).
A preferred value of M is C(O)NR51 where the N atom is attached to the group "A" Preferably Z is O or S, more preferably O.
Preferably B is N.
Preferred values for D are CH=CH, S or NR7 where R7 is Q_6 alkyl, more preferably D is S or N-Q.6 alkyl, most preferably N-Q_6 alkyl.
Preferably E is N or CR12 where R12 is hydrogen, halogen, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy, Q_ haloalkoxy, Q_6 alkoxy (Q_6)alkyl, Q_6 alkylthio or SF5; or R1 and R12 together with the atoms to which they are attached form a benzene ring optionally substituted by C ι.6 alkyl Q_6 haloalkyl or halogen. W is preferably N or CR1.
X is N or CR11 where R1 ' is hydrogen, Q^ alkyl or phenyl. It is preferred that R51 is hydrogen, CMO alkyl, Q_6 alkylcarbonyloxy(Q_6)alkyl, benzoyloxymethyl (where the phenyl ring may be optionally substituted with halogen or Q. alkyl), Q_6 alkoxy(Q_6)alkyl (where the alkyl group may be optionally substituted by aryl or C alkoxycarbonyl), C2_6 alkenyloxy(Q_4)alkyl, C2_6 alkynyloxy(Q__ alkyl, benzyloxy- (Cι_4)alkyl (where the phenyl ring may be optionally substituted with halogen or Q.4 alkyl), C3_7 cycloalkyl(Q_ )alkyl, heteroaryl(Cι_ )alkyl (where the heteroaryl group may be optionally substituted with halogen), tri(Q_ )alkylsilyl(Q_6)alkyl, C2_6 alkenyl (Cι_6)alkyl (especially allyl), C2.6 haloalkenyl(Cι_6)alkyl, C)_ alkoxycarbonyl(C .6)alkenyl(Cι_6)alkyl, C2_6 alkynyl(Cι_6)alkyl, tri(C1_4)alkylsilyl(C2_6)alkynyl(Cι_6)alkyl or CMO alkylcarbonyl. It is more preferred that R51 is hydrogen, Q.6 alkyl, Q_6 alkylcarbonyloxymethyl, benzoyloxymethyl (where the phenyl ring may be optionally substituted with halogen or Q^ alkyl), Q_6 alkoxymethyl, C2_6 alkenyloxymethyl, C2_6 alkynyloxymethyl, benzyloxymethyl (where the phenyl ring may be optionally substituted with halogen or Q_4 alkyl), C2_6 alkynyl (Q_6)alkyl (especially propargyl) or CM0 alkylcarbonyl.
Even more preferably R51 is hydrogen, Q.6 alkyl, Q_6 alkylcarbonyloxymethyl, Q_6 alkoxymethyl, benzyloxymethyl or benzoyloxymethyl.
Yet more preferably R51 is hydrogen, Q. alkyl, Q-_. alkoxy (Q_ )alkyl, benzyloxymethyl or benzoyloxymethyl; or is Q_6 alkylcarbonyloxymethyl Most preferably R51 is hydrogen, C alkyl, Q_6 alkylcarbonyloxymethyl or Cι_4 alkoxymethyl.
Preferably R52 and R53 are independently Q_ιo alkyl, CM0 haloalkyl, C2.6 alkenyl- (Cι-6)alkyl, C2_6 alkynyl (Q_6)alkyl, C3_7 cycloalkyl, Cι_6 alkylamino, di(Q.6)alkylamino, phenyl(C )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy),
Even more preferably R52 and R53 are independently Q_ alkyl, Cι_6 haloalkyl, C2.6 alkenyl(Cι_6)alkyl, C2_6 alkynyl (Q_6)alkyl, benzyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy). R1 is preferably hydrogen, halogen, Q.6 alkyl, C2.6 alkenyl, C2_6 alkynyl, Q_6 haloalkyl, Cι_6 alkoxy(Q.6)alkyl, C3_7 cycloalkyl (Q^alkyl, Q_6 cyanoalkyl, Q_6 alkoxy, Q.6 haloalkoxy, Q_ alkylthio, Q_6 haloalkylthio, C3_6 cycloalkyl, cyano, nitro or SF5.
More preferably R1 is hydrogen, halogen, Q_6 alkyl, C2.6 alkenyl, Cι_6 haloalkyl, Q.6 alkoxy, Cι_6 haloalkoxy, Q_6 alkylthio, Cι_6 haloalkylthio, C3.6 cycloalkyl, cyano, nitro or SF5. Even more preferably R1 is hydrogen, halogen, Q_6 alkyl, C2.6 alkenyl, Cι_6 haloalkyl,
Cι_6 alkoxy, Q_6 haloalkoxy, Q_6 alkylthio, Q_6 haloalkylthio, C3_6 cycloalkyl, Cι_6 alkoxy(Q.6)alkyl, cyano or nitro. Most preferably R1 is halogen, Q_6 alkyl, Q-6 haloalkyl, Q_6 alkoxy or Q-6 haloalkoxy.
Preferably R3, R4 and R5 are, independently, hydrogen, halogen, Q_6 alkyl, Cι_6 haloalkyl, Q_6 alkylthio, Cι_ haloalkylthio, Q.6 alkoxy, Cι_6 haloalkoxy, Cι.6 alkylsulfinyl, Q-6 haloalkylsulfinyl, Q-6 alkylsulfonyl, Q.6 haloalkylsulfonyl, cyano, nitro, Q_6 alkylcarbonyl, or Q_6 alkoxycarbonyl..
More preferably R3, R4 and R5 are independently hydrogen, Cι.3 alkyl or halogen. Most preferably R3, R4 and R5 are independently, hydrogen, or halogen (especially fluorine) but most preferably each is hydrogen. R6 is preferably Q.8 alkyl, Q_ haloalkyl, Q_6 cyanoalkyl, C2_6 alkenyl, C2.6 alkynyl,
C3.7 cycloalkyl, C3_7 halocycloalkyl, C3_7 cyanocycloalkyl, Cι_3 alkyl(C3_7)cycloalkyl, Cj-3 alkyl(C3_7)halocycloalkyl, C5_6 cycloalkenyl, C3.7 cycloalkyl (Q_6)alkyl, C5.6 cycloalkenyl(Cι_6)alkyl, C2_6 haloalkenyl, Q_6cyanoalkenyl, Q_6 alkoxy(Cι_6)alkyl, C3-6 alkenyloxy (Cι.6)alkyl, C3_6 alkynyloxy(Q_6)alkyl, aryloxy(Cι_6)alkyl, Q_6 carboxyalkyl, Cι_6 alkylcarbonyl(Q.6)alkyl, C2_6 alkenylcarbonyl(Cι.6)alkyl, C2_6 alkynylcarbonyl(Q_6)alkyl, Cι_6 alkoxycarbonyl(Q_6)alkyl, C3_6 alkenyloxycarbonyl(Cι_6)alkyl, .6 alkynyloxycarbonyl- (Q_6)alkyl, aryloxycarbonyl(Cι_6) alkyl, Q.6 alkylthio(Q_6)alkyl, Ci.6 alkylsulfιnyl(Cι^)alkyl, Cι_6 alkylsulfonyl(Cι_6)alkyl, aminocarbonyl(Q-6)alkyl, aminocarbonyl(C2_6)alkenyl, aminocarbonyl(C2_6)alkynyl, Q.6 alkylaminocarbonyl (Q_6)alkyl, di(Q_6)alkylamino- carbonyl(Ci_6)alkyl, Q.6 alkylaminocarbonyl(Cι_6)alkenyl, di(Q_6)alkylaminocarbonyl- (Cι_6)alkenyl, alkylaminocarbonyl(Q_6)alkynyl, di(Cι_6)alkylaminocarbonyl(Cι.6)alkynyl, phenyl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q.6 alkoxy or Cι-6 haloalkoxy), phenyl(Cι^)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Cι_6 haloalkoxy), phenyl- (C2- )alkenyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q. haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_ haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy), heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy), heteroary Q^alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q_6 haloalkoxy), heterocyclyl(Q_ )alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy), R26O, Cue alkylthio, R28R29N or R31ON=C(R27); where R26 is Q.8 alkyl, Q_6 haloalkyl; R27 is Cι-6 alkyl, Cι_6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Q.6 haloalkoxy); R27 is Q.6 alkyl, Q.6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Q_6
98 9 haloalkoxy); R and R are, independently, hydrogen, Q.8 alkyl, C3.7 cycloalkyl, C3_6 alkenyl, C3.6 alkynyl, C3_7 cycloalkyl(Q^)alkyl, C2.6 haloalkyl, Q.6 alkoxy(Q_6)alkyl, Q^ alkoxycarbonyl, or R and R together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q.6 alkyl groups; and R is Q_6 alkyl or phenyl(Q_2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy).
More preferably R6 is Q_8 alkyl, Q.8 haloalkyl, Q.8 cyanoalkyl, C3.7 cycloalkyl- (Q_6)alkyl, C5.6 cycloalkenyl(Q-6)alkyl, Q_6 alkoxy(Q_6)alkyl, C3.6 alkenyloxy(Q.6)alkyl, C3_6 alkynyloxy(Cι_6)alkyl, aryloxy(Q_6)alkyl, Cι_6 carboxyalkyl, Q^ alkylcarbonyl- (Cι.ό)alkyl, C2_6 alkenylcarbonyl(Cι.6)alkyl, C2.6 alkynylcarbonyl(Q.6)alkyl, Cι.6 alkoxycarbonyl(Q-6)alkyl, C3_6 alkenyloxycarbonyl(Cι.6)alkyl, C3_6 alkynyloxycarbonyl- (Q.6)alkyl, aryloxycarbonyl(Q_6)alkyl, Q_6 alkylthio(Q_6)alkyl, Q_6 alkylsulfinyl(Q_6)alkyl, Cι_6 alkylsulfonyl(Cι_6)alkyl, aminocarbonyl(Ci_6)alkyl, Q.6 alkylaminocarbonyl(Q_6)alkyl, di(Q.6)alkylaminocarbonyl(Q_6)alkyl, phenyl(Q^)alkyl (wherein the phenyl group may be optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy), heteroaryl(Q. )alkyl (wherein the heteroaryl group may be optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), heterocycly Q-^alkyl (wherein the heterocyclyl group may be optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q. haloalkyl, Q.6 alkoxy or Q_6 haloalkoxy), C2_6 alkenyl, C2-6 haloalkenyl, Q.6 cyanoalkenyl, C5.6 cycloalkenyl, aminocarbonyl(C2_6)alkenyl, Ci.6 alkylaminocarbonyl (C i _6)alkenyl, di(C i _6)alkylaminocarbonyl(C i _6)alkenyl, phenyl- (C2.4)alkenyl, (wherein the phenyl group may be optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Q.6 haloalkoxy), C2_6 alkynyl, aminocarbonyl- (C2_6)alkynyl, alkylaminocarbonyl(Cι_6)alkynyl, di(Q.6)alkylaminocarbonyl(Q_6)alkynyl, C3.7 cycloalkyl, C3.7 halocycloalkyl, C3_7 cyanocycloalkyl, Cι_3 alkyl(C3_7)cycloalkyl, Q_3 alkyl(C3_ )halocycloalkyl, phenyl (which may be optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy), heteroaryl (which may be optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy), heterocyclyl (which may be optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q.6 alkoxy or Q_6 haloalkoxy), Q_8 alkylthio, R26O, R28R29N or R3ION=C(R27); where R26 is Q_8 alkyl or Q_6 haloalkyl; R27 is phenyl (which may be optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy), Cι_6 alkyl or Cι_6 haloalkyl; R 8 and R 9Q are, independently, hydrogen, Q-8 alkyl, C3.7 cycloalkyl(Cι. )alkyl, C2.6 haloalkyl, .6 alkoxy(Q_6)alkyl, C3.7 cycloalkyl, _6 alkenyl, C3_6 alkynyl or Q_6 alkoxycarbonyl; and R is phenyl (Q_2)alkyl (wherein the phenyl group may be optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy) or Q_6 alkyl. Even more preferably R6 is Cι_8 alkyl, Q_8 haloalkyl, C)_8 cyanoalkyl, C3_7 cycloalkyl,
Q.3 alkyl (C3_7) cycloalkyl, Q.6 alkoxy (Q-β) alkyl, heterocyclic (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q_6 haloalkoxy) or R28R29N where R28 and R29 are independently Cι_8 alkyl or together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q_6 alkyl groups.
Most preferably R6 is Q.8 alkyl, Q_8 haloalkyl, Q_8 cyanoalkyl, Q.6 alkoxy (Q_6) alkyl, C3_7 cycloalkyl, Q.3 alkyl (C3.7) cycloalkyl, heterocyclyl (which may be optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy) or di(Q.8)alkylamino.
Preferably R12 is hydrogen, halogen, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy (Q_6)alkyl, C2-6 alkenyl, Q.6 alkynyl, Q_6 alkoxy, Q_6 haloalkoxy, Q_6 alkylthio, Cι_6 haloalkylthio,
Figure imgf000022_0001
alkylsulfinyl, Q_6 haloalkylsulfinyl, Q_6 alkylsulfonyl, Q_6 haloalkylsulfonyl, cyano, nitro, formyl, Q_6 alkylcarbonyl, Q_6 alkoxycarbonyl, CH=NOR32, or R1 and R12 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated, carbocylic or heterocyclic ring which may contain one or two heteroatoms selected from O, N or S and which may be optionally substituted by Q-6 alkyl, Q_6 haloalkyl or halogen; and R is phenyl(Q.2)alkyl (wherein the phenyl group may be optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy) or Q-6 alkyl.
More preferably R12 is hydrogen, halogen, Q_6 alkyl, Q.6 haloalkyl, Q_6 alkoxy (Q.6)alkyl, Q_6 alkoxy, Q-6 haloalkoxy, Q.6 alkylthio, or R1 and R12 together with the atoms to which they are attached form a cyclopentane or benzene ring optionally substituted by Q.6 alkyl, Q_6 haloalkyl or halogen.
Most preferably R12 is hydrogen, halogen, Q_6 alkyl, Q_6 haloalkyl, Q.6 alkoxy- (Cι_6)alkyl, Q_6 alkoxy, Cι_6 haloalkoxy, or R1 and R12 together with the atoms to which they are attached form a cyclopentane ring optionally substituted by Q_6 alkyl, Q.6 haloalkyl or halogen;
R13 is preferably cyano, nitro, Q_6 alkyl, Q_6 haloalkyl, C3. cycloalkyl(Q_6)alkyl, C3.7 cycloalkyl, CH2(C2.6)alkenyl, CH2(C2_6)alkynyl, phenyl (which may be optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Cι.6 haloalkoxy), heteroaryl (which may be optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q.6 haloalkoxy), Q.6 alkylcarbonyl, Cι_6 alkoxycarbonyl, Q_6 alkylamino, di(Q_6)alkylamino, Cι_6 alkylcarbonylamino, Cι_6 alkoxycarbonylamino, Q.6 alkoxy, Cι_6 alkylthio, Q.6 haloalkylthio, Q_6 alkylsulfinyl, Cι.6 haloalkylsulfinyl, Q.6 alkylsulfonyl, Q.6 haloalkylsulfonyl, arylthio, arylsulfinyl, arylsulfonyl or (Q ^alkylcarbonyloxy.
Preferably R14 is hydrogen, Q.8 alkyl, Q.6 haloalkyl, Q_6 cyanoalkyl, C .6 alkenyl, C2.6 haloalkenyl, C2.6 alkynyl, C3.7 cycloalkyl, C3.7 cycloalkyl(Q_6)alkyl, Cι_6 alkoxy- (Cι_6)alkyl, Cι_6 alkoxycarbonyl, Q.6 alkylcarbonyl, Q.6 alkylaminocarbonyl, di(Cι_6)alkylaminocarbonyl, phenyl (which may be optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q-6 haloalkoxy) or heteroaryl (which may be optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q.6 alkoxy or Q_6 haloalkoxy).
More preferably R14 is hydrogen, Q_8 alkyl or Q_6 haloalkyl. Preferably R18 is hydrogen, halogen, nitro, cyano, Q.8 alkyl, Cι_6 haloalkyl, Q.6 cyanoalkyl, C3-7 cycloalkyl(Q.6)alkyl, Cι_6 alkoxy(Cι_6)alkyl, Cι.6 alkoxycarbonyl(Q-6)alkyl, Q.6 alkylcarbonyl(Cι_6)alkyl, Cι-6 alkylaminocarbonyl(Cι.6)alkyl, di(Q-6)alkylamino- carbonyl(Cι_6)alkyl, phenyl(Q_6)alkyl (wherein the phenyl group may be optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Cι_6 haloalkoxy), heteroaryl(Q.6)alkyl (wherein the heteroaryl group may be optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy), C2_6 alkenyl, .6 haloalkenyl, C2_6 alkynyl, Q.7 cycloalkyl, Q_6 alkoxycarbonyl, Cι_6 alkylcarbonyl, Q.6 alkylaminocarbonyl, di(Q.6)alkylaminocarbonyl, phenyl (which may be optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q_6 haloalkyl, Q.6 alkoxy or Q_6 haloalkoxy) or heteroaryl (which may be optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q.6 alkoxy or Q_6 haloalkoxy).
More preferably R18 is hydrogen, halogen, Q_8 alkyl or Q_6 haloalkyl.
More preferred optionally substituted rings of formula
Figure imgf000024_0001
include pyrazoles, 2,4,5,6-tetrahydro-cyclopentapyrazoles, 4,5,6,7-tetrahydro-[2H]- indazoles and indazoles which may be optionally substituted by substituents chosen from halo, Q.6 alkyl, Q.6 haloalkyl, Q_6 alkoxy, Q_6 alkoxy(Q_6)alkyl or Q_6 haloalkoxy. Even more preferably the rings include 5-linked l-methyl-[lH]-pyrazoles optionally substituted at the 3-position with Q_6 alkyl, haloalkyl or alkoxyalkyl and at the 4-position with halo or alkoxy; 3-linked 2,4,5,6-tetrahydro-2-methylcyclopentapyrazoles optionally substituted at the 6-position with alkyl (especially methyl), haloalkyl or halo; 3-linked 4,5,6,7-tetrahydro- 2-methyl-[2H] -indazoles optionally substituted at the 7-position with alkyl (especially methyl), haloalkyl or halo and 3-linked 2-methyl-[2H]-indazoles optionally substituted at the 7-position with alkyl, haloalkyl or halo (especially fluoro).
The compounds in the following Tables illustrate compounds of the invention. Table 1 provides compounds of formula (F) wherein A is CH2, M is CONH, Z is O, B is N, R3, R4 and R5 are each hydrogen; and, D, E, W, X and R6 are as defined in the Table.
Figure imgf000024_0002
wherein D, E, W, X and R6 are as defined in Table 1.
TABLE 1
Figure imgf000024_0003
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Table 2 provides 70 compounds of formula
Figure imgf000028_0001
wherein X, D, R6 and "Ring" are as defined in Table 2
Figure imgf000028_0002
Figure imgf000029_0002
Table 3 provides 80 compounds of formula
Figure imgf000029_0001
wherein D, E, W, X and R6 are as defined in Table 3
Figure imgf000029_0003
Figure imgf000031_0002
Table 4 provides 60 compounds of formula
Figure imgf000031_0001
wherein X, D, R6 and "Ring" are as defined in Table 4
Figure imgf000031_0003
Figure imgf000032_0001
Figure imgf000033_0004
Table 5 provides 80 compounds of formula
Figure imgf000033_0001
wherein D, E, W, X and R6 are as defined in Table 3 Table 6 provides 60 compounds of formula
Figure imgf000033_0002
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 7 provides 80 compounds of formula
Figure imgf000033_0003
wherein D, E, W, X and R6 are as defined in Table 3 Table 8 provides 60 compounds of formula
Figure imgf000034_0001
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 9 provides 80 compounds of formula
Figure imgf000034_0002
wherein D, E, W, X and R6 are as defined in Table 3
Table 10 provides 60 compounds of formula
Figure imgf000034_0003
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 11 provides 80 compounds of formula
Figure imgf000034_0004
wherein D, E, W, X and R6 are as defined in Table 3 Table 12 provides 60 compounds of formula
/Rings
Figure imgf000034_0005
wherein X, D, R6 and "Ring" are as defined in Table 4
Table 13 provides 80 compounds of formula
Figure imgf000035_0001
wherein D, E, W, X and R6 are as defined in Table 3
Table 14 provides 60 compounds of formula
Figure imgf000035_0002
wherein X. D, R6 and "Ring" are as defined in Table 4 Table 15 provides 80 compounds of formula
Figure imgf000035_0003
wherein D, E, W, X and R6 are as defined in Table 3 Table 16 provides 60 compounds of formula
Figure imgf000035_0004
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 17 provides 80 compounds of formula
Figure imgf000036_0001
wherein D, E, W, X and R6 are as defined in Table 3 Table 18 provides 60 compounds of formula
Figure imgf000036_0002
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 19 provides 80 compounds of formula
Figure imgf000036_0003
wherein D, E, W, X and R6 are as defined in Table 3 Table 20 provides 60 compounds of formula
Figure imgf000036_0004
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 21 provides 80 compounds of formula
Figure imgf000036_0005
wherein D, E, W, X and R6 are as defined in Table 3 Table 22 provides 60 compounds of formula
Figure imgf000037_0001
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 23 provides 80 compounds of formula
Figure imgf000037_0002
wherein D, E, W, X and R6 are as defined in Table 3 Table 24 provides 60 compounds of formula
Figure imgf000037_0003
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 25 provides 80 compounds of formula
Figure imgf000037_0004
wherein D, E, W, X and R6 are as defined in Table 3 Table 26 provides 60 compounds of formula
Figure imgf000037_0005
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 27 provides 80 compounds of formula
Figure imgf000038_0001
wherein D, E, W, X and R6 are as defined in Table 3 Table 28 provides 60 compounds of formula
Figure imgf000038_0002
wherein X, D, R6 and "Ring" are as defined in Table 4
Table 29 provides 80 compounds of formula
Figure imgf000038_0003
wherein D, E, W, X and R6 are as defined in Table 3
Table 30 provides 60 compounds of formula
Figure imgf000038_0004
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 31 provides 80 compounds of formula
Figure imgf000038_0005
wherein D, E, W, X and R6 are as defined in Table 3
Table 32 provides 60 compounds of formula
Figure imgf000039_0001
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 33 provides 80 compounds of formula
Figure imgf000039_0002
wherein D, E, W, X and R6 are as defined in Table 3 Table 34 provides 60 compounds of formula
Figure imgf000039_0003
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 35 provides 80 compounds of formula
Figure imgf000039_0004
wherein D, E, W, X and R6 are as defined in Table 3 Table 36 provides 60 compounds of formula
Figure imgf000040_0001
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 37 provides 80 compounds of formula
Figure imgf000040_0002
wherein D, E, W, X and R6 are as defined in Table 3
Table 38 provides 60 compounds of formula
Figure imgf000040_0003
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 39 provides 80 compounds of formula
Figure imgf000040_0004
wherein D, E, W, X and R6 are as defined in Table 3 Table 40 provides 60 compounds of formula
Figure imgf000040_0005
wherein X, D, R6 and "Ring" are as defined in Table 4
Table 41 provides 80 compounds of formula
Figure imgf000041_0001
wherein D, E, W, X and R6 are as defined in Table 3
Table 42 provides 60 compounds of formula
Figure imgf000041_0002
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 43 provides 80 compounds of formula
Figure imgf000041_0003
wherein D, E, W, X and R6 are as defined in Table 3
Table 44 provides 60 compounds of formula
Figure imgf000041_0004
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 45 provides 80 compounds of formula
Figure imgf000041_0005
wherein D, E, W, X and R6 are as defined in Table 3 Table 46 provides 60 compounds of formula
Figure imgf000042_0001
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 47 provides 80 compounds of formula
Figure imgf000042_0002
wherein D, E, W, X and R6 are as defined in Table 3 Table 48 provides 60 compounds of formula
Figure imgf000042_0003
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 49 provides 80 compounds of formula
Figure imgf000042_0004
wherein D, E, W, X and R6 are as defined in Table 3
Table 50 provides 60 compounds of formula
Figure imgf000042_0005
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 51 provides 80 compounds of formula
Figure imgf000043_0001
wherein D, E, W, X and R6 are as defined in Table 3 Table 52 provides 60 compounds of formula
Figure imgf000043_0002
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 53 provides 80 compounds of formula
Figure imgf000043_0003
wherein D, E, W, X and R6 are as defined in Table 3 Table 54 provides 60 compounds of formula
Figure imgf000043_0004
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 55 provides 80 compounds of formula
Figure imgf000044_0001
wherein D, E, W, X and R6 are as defined in Table 3 Table 56 provides 60 compounds of formula
Figure imgf000044_0002
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 57 provides 80 compounds of formula
Figure imgf000044_0003
wherein D, E, W, X and R6 are as defined in Table 3 Table 58 provides 60 compounds of formula
Figure imgf000044_0004
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 59 provides 80 compounds of formula
Figure imgf000044_0005
wherein D, E, W, X and R6 are as defined in Table 3 Table 60 provides 60 compounds of formula
Figure imgf000045_0001
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 61 provides 80 compounds of formula
Figure imgf000045_0002
wherein D, E, W, X and R6 are as defined in Table 3
Table 62 provides 60 compounds of formula
Figure imgf000045_0003
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 63 provides 80 compounds of formula
Figure imgf000045_0004
wherein D, E, W, X and R6 are as defined in Table 3
Table 64 provides 60 compounds of formula
Figure imgf000045_0005
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 65 provides 80 compounds of formula
Figure imgf000046_0001
wherein D, E, W, X and R6 are as defined in Table 3 Table 66 provides 60 compounds of formula
Figure imgf000046_0002
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 67 provides 80 compounds of formula
Figure imgf000046_0003
wherein D, E, W, X and R6 are as defined in Table 3 Table 68 provides 60 compounds of formula
Figure imgf000046_0004
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 69 provides 80 compounds of formula
Figure imgf000046_0005
wherein D, E, W, X and R6 are as defined in Table 3 Table 70 provides 60 compounds of formula
Figure imgf000047_0001
wherein X, D, R6 and "Ring" are as defined in Table 4
Table 71 provides 80 compounds of formula
Figure imgf000047_0002
wherein D, E, W, X and R6 are as defined in Table 3
Table 72 provides 60 compounds of formula
Figure imgf000047_0003
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 73 provides 80 compounds of formula
Figure imgf000047_0004
wherein D, E, W, X and R6 are as defined in Table 3
Table 74 provides 60 compounds of formula
Figure imgf000047_0005
wherein X, D, R6 and "Ring" are as defined in Table 4
Table 75 provides 80 compounds of formula
Figure imgf000048_0001
wherein D, E, W, X and R6 are as defined in Table 3
Table 76 provides 60 compounds of formula
Figure imgf000048_0002
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 77 provides 80 compounds of formula
Figure imgf000048_0003
wherein D, E, W, X and R6 are as defined in Table 3
Table 78 provides 60 compounds of formula
Figure imgf000048_0004
wherein X, D, R6 and "Ring" are as defined in Table 4
Table 79 provides 80 compounds of formula
Figure imgf000049_0001
wherein D, E, W, X and R6 are as defined in Table 3
Table 80 provides 60 compounds of formula
Figure imgf000049_0002
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 81 provides 80 compounds of formula
Figure imgf000049_0003
wherein D, E, W, X and R6 are as defined in Table 3 Table 82 provides 60 compounds of formula
Figure imgf000049_0004
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 83 provides 80 compounds of formula
Figure imgf000049_0005
wherein D, E, W, X and R6 are as defined in Table 3 Table 84 provides 60 compounds of formula
Figure imgf000050_0001
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 85 provides 80 compounds of formula
Figure imgf000050_0002
wherein D, E, W, X and R6 are as defined in Table 3 Table 86 provides 60 compounds of formula
Figure imgf000050_0003
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 87 provides 80 compounds of formula
Figure imgf000050_0004
wherein D, E, W, X and R6 are as defined in Table 3 Table 88 provides 60 compounds of formula
Figure imgf000050_0005
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 89 provides 80 compounds of formula
Figure imgf000051_0001
wherein D, E, W, X and R6 are as defined in Table 3 Table 90 provides 60 compounds of formula
Figure imgf000051_0002
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 91 provides 80 compounds of formula
Figure imgf000051_0003
wherein D, E, W, X and R6 are as defined in Table 3 Table 92 provides 60 compounds of formula
Figure imgf000051_0004
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 93 provides 80 compounds of formula
Figure imgf000051_0005
wherein D, E, W, X and R6 are as defined in Table 3 Table 94 provides 60 compounds of formula
Figure imgf000052_0001
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 95 provides 80 compounds of formula
Figure imgf000052_0002
wherein D, E, W, X and R6 are as defined in Table 3
Table 96 provides 60 compounds of formula
Figure imgf000052_0003
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 97 provides 80 compounds of formula
Figure imgf000052_0004
wherein D, E, W, X and R6 are as defined in Table 3 Table 98 provides 60 compounds of formula
Figure imgf000053_0001
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 99 provides 80 compounds of formula
Figure imgf000053_0002
wherein D, E, W, X and R6 are as defined in Table 3
Table 100 provides 60 compounds of formula
Figure imgf000053_0003
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 101 provides 80 compounds of formula
Figure imgf000053_0004
wherein D, E, W, X and R6 are as defined in Table 3
Table 102 provides 60 compounds of formula
Figure imgf000053_0005
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 103 provides 80 compounds of formula
Figure imgf000054_0001
wherein D, E, W, X and R6 are as defined in Table 3
Table 104 provides 60 compounds of formula
Figure imgf000054_0002
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 105 provides 80 compounds of formula
Figure imgf000054_0003
wherein D, E, W, X and R6 are as defined in Table 3 Table 106 provides 60 compounds of formula
Figure imgf000054_0004
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 107 provides 80 compounds of formula
Figure imgf000054_0005
wherein D, E, W, X and R6 are as defined in Table 3 Table 108 provides 60 compounds of formula
Figure imgf000055_0001
wherein X, D, R6 and "Ring" are as defined in Table 4
Table 109 provides 80 compounds of formula
Figure imgf000055_0002
wherein D, E, W, X and R6 are as defined in Table 3 Table 110 provides 60 compounds of formula
Figure imgf000055_0003
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 111 provides 80 compounds of formula
Figure imgf000055_0004
wherein D, E, W, X and R6 are as defined in Table 3 Table 112 provides 60 compounds of formula
Figure imgf000055_0005
wherein X, D, R6 and "Ring" are as defined in Table 4
Table 113 provides 80 compounds of formula
Figure imgf000056_0001
wherein D, E, W, X and R6 are as defined in Table 3
Table 114 provides 60 compounds of formula
Figure imgf000056_0002
wherein X, D, R6 and "Ring" are as defined in Table 4 Table 115 provides 80 compounds of formula
Figure imgf000056_0003
wherein D, E, W, X and R6 are as defined in Table 3 Table 116 provides 60 compounds of formula
Figure imgf000056_0004
wherein X, D, R6 and "Ring" are as defined in Table 4
The compounds of the invention may be made in a variety of ways. For example the compounds of formula TV i.e. compounds of formula (I) where R51 is hydrogen and R3, R4, R5, R6, A, B, Z, D, E, W and X are as defined above in relation to formula I may be made by reacting a compound of formula II (where D, E, W and X are as defined in relation to formula (I) and Ra is OH, halogen or OCOalkyl) with a compound of formula HI (where R51 is hydrogen and R3, R4, R5, R6, A, B and Z are as defined in relation to formula (I)). For Ra = OH the reaction is conducted preferably in the presence of a suitable coupling reagent such as 1 ,3-dicyclohexylcarbodiimide, 1,3-diisopropylcarbodiimide, l-(3- dimethylaminopropyl)-3-ethylcarbodiimide or l,l'-carbonyldiimidazole optionally in the presence of a catalyst such as 4-(dimethylamino)pyridine. This coupling reaction may also be conducted with a suitable acid halide (Ra = halogen, especially chlorine), acid anhydride (Ra = OCOalkyl) or ester (Ra = alkoxy, substituted alkoxy or aryloxy, especially methoxy) optionally in the presence of a base such as triethylamine or sodium methoxide and in a suitable solvent (such as 1,1,2,2-tetrachloroethane, tetrahydrofuran, N,N-dimethylacetamide or mesitylene) The acids and esters of formula II and the amines of formula in are known compounds or can be made by known methods. A particularly suitable method for making the amines of formula HI (where R51 is hydrogen) is by treating an acid of formula V (where R3, R4, R5, R6, A, B and Z are as defined in relation to formula (I)) with a reagent such as diphenylphosphoryl azide in the presence of a base such as triethylamine in a solvent such as toluene at reflux. Treatment of the isocyanate VI (where R3, R4, R5, R6, A, B and Z are as defined in relation to formula (I)) (which may or may not be isolated) with an alcohol (such as t-butanol or 2-trimethylsilylethanol) may give the carbamate VII (where R3, R4, R5, R6, A, B and Z are as defined in relation to formula (I) and Rb is the residue from the alcohol). Conditions for the removal of the carbamate group from intermediate VII depend on the nature of Rb. For example if R = t-butyl then treatment with an acid such as trifluoroacetic acid in a solvent such as tetrahydrofuran may produce amine HI (R51 = H). If however Rb = 2- trimethylsilylethyl then treatment with tetrabutylammonium fluoride in a solvent such as tetrahydrofuran may produce amine HI (R51 = H).
A particularly suitable method for producing acids of formula II (Ra = OH) is to treat an aminoheterocycle of formula VEH (where D, E, W and X are as defined in relation to formula (I) and Rb = NH2) under diazotising conditions (such as t-butyl nitrite in THF or sodium nitrite in sulfuric acid) followed by treatment with copper (I) cyanide which may give the nitrile VIH (Rb = CN) which may then be hydrolysed (for example by heating in aqueous sodium hydroxide solution) to give the acid II (Ra = OH) upon work-up. Alternatively, acids of formula II (Ra = OH) may be formed by treating heterocycles of formula VET (Rb = hydrogen or halogen, especially bromine or iodine) in a solvent (such as tetrahydrofuran or diethyl ether) with an organometallic species (such as a Grignard reagent or alkyl lithium especially n-butyl lithium) followed by treatment with carbon dioxide. Acids of formula π (Ra = OH) may be converted into acid halides (Ra = halogen), anhydrides (Ra = C(O)alkyl) and esters (Ra = alkoxy, substituted alkoxy or aryloxy, especially methoxy) using known transformations.
The syntheses of substituted benzimidazoles, benzoxazoles and benzothiazoles are well known (see for example, Alan R. Katritzky and Charles W. Rees, Comprehensive
Heterocyclic Chemistry, Vol. 6, Pergamon Press, 1984, Helmut M Hugel, Synth. Commun., 15 (12), 1075-1080, (1985), J. Scheigetz, R. Zamboni and B. Roy, Synth. Commun., 25 (18), 2791-2806, (1995), David W. Du vell, Delme Evans, Terence A. Hicks, J. Med. Chem., 1975, 18, No. 1, 53; Abdou O. Abdelhamid, Cyril Parkanyi, S.M. Khaledur Rashid and Winston D. Lloyd, J. Heterocyclic Chem., 25, 403, (1988); Teruyuki Kondo. Sungbong Yang, Keun-Tae Huh, Masanobu Kobayashi. Shinju Kotachi and Yoshihisa Watanabe, Chemistry Letters, 1275, 1991; Dale L. Boger, J. Org. Chem., 43, No 11, 2296, 1978). Benzothiophenes may be made from appropriate thiophenols by processes similar to those described by Robert D Schuetz and Richard L Titus (J. Heterocycl. Chem., 4, No 4, 465 (1967); suitable thiophenols are known compounds or may be prepared by known methods. Benzofurans may be made from ort/iσ-halophenols as described by Henning Lutjens and Peter J Scammells, Tetrahedron Letters 39 (1998), 6581-6584, Terence C Owen et al., Tetrahedron Letters 30, No 13, 1597 (1989) and Fred G Schreiber and Robert Stevenson J.C.S. Perkin 1, 90, 1977. Indoles may be made from ort/ϊo-haloanilines according to the methods of Cheng-yi Chen et al., J. Org. Chem. 1997, 62, 2676, Takao Sakamoto et al., J. Org. Chem. 1997, 62, 6507 and Alan D. Adams et al., WO9827974. Appropriate ortho- substituted phenols and anilines may be prepared by known methods from commercially available 4-hydroxyphenylacetic acid and 4-aminophenylacetic acid.
A compound of formula C (i.e. a compound of formula I where A, E, W, X, D, B, Z, R51, R3, R4, R5 and R6 are as defined above in relation to formula I) may be prepared by reacting a compound of formula IV with a suitable thionating agent such as 2,4-bis(4- methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson's reagent), 2,4- bis(methylthio)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Davy reagent methyl), 2,4- bis(pαr -tolyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfιde (Davy reagent -tolyl) or phophorus pentasulfide in a suitable solvent such as toluene or fluorobenzene.
Compounds of formula IV (where R51 is hydrogen) or DC (where R51 is hydrogen) may be treated with an alkylating agent (such as an alkyl halide, dialkyl sulfate, chloromethylether or trialkyloxonium salt) optionally in the presence of a base to give additional compounds of formula (IV) or (DC). For compounds of formula IV (where R51 is hydrogen), this reaction usually produces compounds IV (where R ! = alkyl, alkenylalkyl, alkynylalkyl, cycloalkylalkyl, alkoxyalkyl, alkylcarbonyloxyalkyl). In contrast, for compounds DC, the predominant products are compounds X (where A, E, W, X, D, B, Z, R51, R3, R4, R5 and R6 are as defined above in relation to formula I and R53 = alkyl, alkenylalkyl, alkynylalkyl, cycloalkyl, alkoxyalkyl).
Those skilled in the art will recognise that analogous reactions involving sulfenylation, sulfonylation and acylation are possible for compounds IV (R51 = H).
Compounds of formula IV (R51 = alkoxyalkyl or acyloxyalkyl) may also be prepared from compounds of formula IV (R51 = H) by sequential reaction with formaldehyde and an alkylating or acylating agent.
Compounds of formula X (especially when R53 = CH3) may be reacted with alcohols, hydroxylamines, amines and hydrazines, optionally in the presence of a mercuric salt (such as mercuric chloride), according to known procedures to give compounds of formulae XI and Xπ respectively (where E, W, X, D, B, Z, R51, R3, R4, R5, R6' R52 R54 and R55 are as defined in relation to formula (I)).
An alternative method for making compounds of formula XDI (i.e. compounds of formula (I) where A, E, W, X, D, M, R3, R4, R5 and R6 are as defined above in relation to formula I) involves the acylation of compounds of formula XIV (where A, E, W, X, D, M, R3, R4 and R5 are as defined above in relation to formula I) followed by cyclisation, optionally in the presence of an acidic catalyst such as /. ra-toluene sulfonic acid in a suitable solvent such as xylene or 1,1,2,2-tetrachloroethane. Compounds of formula XIV may be prepared from compounds of formula XV (where A, E, W, X, D, M, R3, R4 and R5 are as defined above in relation to formula I) by a sequential procedure of nitration followed by reduction, using known procedures. In turn, compounds of formula XV may be prepared by the dealkylation of compounds of formula XVI (where A, E, W, X, D, M, R3, R4 and R5 are as defined above in relation to formula I and R is an alkyl group (especially methyl) or substituted alkyl group (especially benzyl)) under standard conditions. Compounds XVI may be prepared from compound II by processes analogous to those already described for compounds IV.
Heteroaryl N-oxides can be produced by known methods.
The compounds of formula V, VIH and XVI are known compounds or can be made by known methods. O 01/55136
58
Figure imgf000060_0001
V VI
Figure imgf000060_0002
VII VIII
Figure imgf000060_0003
IX
Figure imgf000060_0004
XI XII
Figure imgf000060_0005
XIII XIV
Figure imgf000060_0006
XV XVI The compounds of formula (I) can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests. The pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies).
Examples of pest species which may be controlled by the compounds of formula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (white flies), Bemisia tabaci (white fly), Ostrinia nubilalis (European corn borer), Spodoptera littoralis (cotton leafworm), Heliothis virescens (tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpa zea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae (white butterfly), Plutella xylostella (diamond back moth), Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locusta migratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp. (rootworms), Panonychus ulmi (European red mite), Panonychus citri (citrus red mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpus spp. (flat mites), Boophilus microplus (cattle tick), Dermacentor variabilis (American dog tick), Ctenocephalides felis (cat flea), Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), termites of the Mastotermitidae (for example Mastotermes spp.), the Kalotermitidae (for example Neotermes spp.), the Rhinotermitidae (for example Coptotermes formosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R. hesperus, and R. santonensis) and the Termitidae (for example Globitermes sulphureus), Solenopsis geminata (fire ant), Monomorium pharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. (biting and sucking lice), Meloidogyne spp. (root knot nematodes), Globodera spp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulus spp. (citrus nematodes), Haemonchus contortus (barber pole worm), Caenorhabditis elegans_ (vinegar eelworm), Trichostrongylus spp. (gastro intestinal nematodes) and Deroceras reticulatum (slug).
The compounds of formula (I) are also active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae (Magnaporthe grisea) on rice and wheat and other Pyricularia spp. on other hosts; Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts (for example turf, rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental plants); Erysiphe cichoracearum on cucurbits (for example melon); Erysiphe graminis (powdery mildew) on barley, wheat, rye and turf and other powdery mildews on various hosts, such as Sphaerotheca macularis on hops, Sphaerotheca fusca (Sphaerotheca fuliginea) on cucurbits (for example cucumber), Leveillula taurica on tomatoes, aubergine and green pepper, Podosphaera leucotricha on apples and Uncinula necator on vines; Cochliobolus spp., Helminthosporium spp., Drechslera spp. (Pyrenophora spp.), Rhynchosporium spp., Mycosphaerella graminicola (Septoria tritici) and Phaeosphaeria nodorum (Stagonospora nodorum or Septoria nodorum), Pseudocercosporella herpotrichoides and Gaeumannomyces graminis on cereals (for example wheat, barley, rye), turf and other hosts; Cercospora arachidicola and Cercosporidium personatum on peanuts and other Cercospora spp. on other hosts, for example sugar beet, bananas, soya beans and rice; Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables, vines and other hosts and other Botrytis spp. on other hosts; Alternaria spp. on vegetables (for example carrots), oil-seed rape, apples, tomatoes, potatoes, cereals (for example wheat) and other hosts; Venturia spp. (including Venturia inaequalis (scab)) on apples, pears, stone fruit, tree nuts and other hosts; Cladosporium spp. on a range of hosts including cereals (for example wheat) and tomatoes; Monilinia spp. on stone fruit, tree nuts and other hosts; Didymella spp. on tomatoes, turf, wheat, cucurbits and other hosts; Phoma spp. on oil-seed rape, turf, rice, potatoes, wheat and other hosts; Aspergillus spp. and Aureobasidium spp. on wheat, lumber and other hosts; Ascochyta spp. on peas, wheat, barley and other hosts; Stemphylium spp. (Pleospora spp.) on apples, pears, onions and other hosts; summer diseases (for example bitter rot (Glomerella cingulata), black rot or frogeye leaf spot (Botryosphaeria obtusa), Brooks fruit spot (Mycosphaerella pomϊ), Cedar apple rust (Gymnosporangiumjuniperi-virginianae), sooty blotch (Gloeodes pomigena), flyspeck (Schizothyrium pomϊ) and white rot (Botryosphaeria dothidea)) on apples and pears;
Plasmopara viticola on vines; other downy mildews, such as Bremia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts, Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on cucurbits; Pythium spp. (including Pythium ultimum) on turf and other hosts; Phytophthora infestans on potatoes and tomatoes and other Phytophthora spp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco, cocoa and other hosts; Thanatephorus cucumeήs on rice and turf and other Rhizoctonia spp. on various hosts such as wheat and barley, peanuts, vegetables, cotton and turf; Sclerotinia spp. on turf, peanuts, potatoes, oil-seed rape and other hosts; Sclerotium spp. on turf, peanuts and other hosts; Gibberella fujikuroi on rice; Colletotrichum spp. on a range of hosts including turf, coffee and vegetables; Laetisaria fuciformis on turf; Mycosphaerella spp. on bananas, peanuts, citrus, pecans, papaya and other hosts; Diaporthe spp. on citrus, soybean, melon, pears, lupin and other hosts; Elsinoe spp. on citrus, vines, olives, pecans, roses and other hosts; Verticillium spp. on a range of hosts including hops, potatoes and tomatoes; Pyrenopeziza spp. on oil-seed rape and other hosts; Oncobasidium theobromae on cocoa causing vascular streak dieback; Fusarium spp., Typhula spp., Microdochium nivale,
Ustilago spp., Urocystis spp., Tilletia spp. and Claviceps purpurea on a variety of hosts but particularly wheat, barley, turf and maize; Ramularia spp. on sugar beet, barley and other hosts; post-harvest diseases particularly of fruit (for example Penicillium digitatum, Penicillium italicum and Trichoderma viride on oranges, Colletotrichum musae and Gloeosporium musarum on bananas and Botrytis cinerea on grapes); other pathogens on vines, notably Eutypa lata, Guignardia bidwellii, Phellinus igniarus, Phomopsis viticola, Pseudopeziza tracheiphila and Stereum hirsutum; other pathogens on trees (for example Lophodermium seditiosum) or lumber, notably Cephaloascus fragrans, Ceratocystis spp., Ophiostoma piceae, Penicillium spp., Trichoderma pseudokoningii, Trichoderma viride, Trichoderma harzianum, Aspergillus niger, Leptographium lindbergi and Aureobasidium pullulans; and fungal vectors of viral diseases (for example Polymyxa graminis on cereals as the vector of barley yellow mosaic virus (BYMV) and Polymyxa betae on sugar beet as the vector of rhizomania). A compound of formula (I) may move acropetally, basipetally or locally in plant tissue to be active against one or more fungi. Moreover, a compound of formula (I) may be volatile enough to be active in the vapour phase against one or more fungi on the plant. The invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a pest, a locus of pest, or to a plant susceptible to attack by a pest, and a method of combating and controlling fungi which comprises applying a fungicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a plant, to a seed of a plant, to the locus of the plant or seed, to soil or to any other growth medium (for example a nutrient solution). The compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
The term "plant" as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes protectant, curative, systemic, eradicant and antisporulant treatments.
As fungicides, the compounds of formula (I) are preferably used for agricultural, horticultural and turfgrass purposes in the form of a composition.
In order to apply a compound of formula (I) as an insecticide, acaricide, nematicide or molluscicide to a pest, a locus of pest, or to a plant susceptible to attack by a pest, or, as a fungicide to a plant, to a seed of a plant, to the locus of the plant or seed, to soil or to any other growth medium, a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA). SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula (I). The composition is generally used for the control of pests or fungi such that a compound of formula (I) is applied at a rate of from O.lg to 10kg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 1kg per hectare. When used in a seed dressing, a compound of formula (I) is used at a rate of O.OOOlg to lOg (for example O.OOlg or 0.05g), preferably 0.005g to lOg, more preferably 0.005g to 4g, per kilogram of seed.
In another aspect the present invention provides an insecticidal, acaricidal, nematicidal, molluscicidal or fungicidal composition comprising an insecticidally, acaricidally, nematicidally, molluscicidally or fungicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor. The composition is preferably an insecticidal, acaricidal, nematicidal or fungicidal composition.
In a still further aspect the invention provides a method of combating and controlling pests or fungi at a locus which comprises treating the pests or fungi or the locus of the pests or fungi with an insecticidally, acaricidally, nematicidally, molluscicidally or fungicidally effective amount of a composition comprising a compound of formula (I). The compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
The compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).
Dustable powders (DP) may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
Soluble powders (SP) may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG). Wettable powders (WP) may be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).
Granules (GR) may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).
Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C8-Qo fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of formula (I) is present initially in either the water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example n-butane). A compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as «-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
A compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment. A compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)). Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).
A compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS). The preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.
Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di- /søpropyl- and tr søpropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulphosuccinamates, paraffin or olefine sulphonates, taurates and lignosulphonates.
Suitable SFAs of the amphoteric type include betaines, propionates and glycinates. Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
A compound of formula (I) may be applied by any of the known means of applying pesticidal or fungicidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.
A compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used. A compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers). Suitable formulation types include granules of fertiliser. The mixtures suitably contain up to 25% by weight of the compound of formula (I).
The invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula (I).
The compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity. By including another fungicide, the resulting composition may have a broader spectrum of activity or a greater level of intrinsic activity than the compound of formula (I) alone. Further the other fungicide may have a synergistic effect on the fungicidal activity of the compound of formula (I).
The compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition. Examples of suitable pesticides include the following: a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate; b) Organophosphates, such as, profenofos, sulprofos, acephate, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon; c) Carbamates (including aryl carbamates), such as pirimicarb, triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl or oxamyl; d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron, flufenoxuron or chlorfluazuron; e) Organic tin compounds, such as cyhexatin, fenbutatin oxide or azocyclotin; f) Pyrazoles, such as tebufenpyrad and fenpyroximate; g) Macrolides, such as avermectins or milbemycins, for example abamectin, emamectin benzoate, ivermectin, milbemycin, spinosad or azadirachtin; h) Hormones or pheromones; i) Organochlorine compounds such as endosulfan, benzene hexachloride, DDT, chlordane or dieldrin; j) Amidines, such as chlordimeform or amitraz; k) Fumigant agents, such as chloropicrin, dichloropropane, methyl bromide or metam; 1) Chloronicotinyl compounds such as imidacloprid, thiacloprid, acetamiprid, nitenpyram or thiamethoxam; m) Diacylhydrazines, such as tebufenozide, chromafenozide or methoxyfenozide; n) Diphenyl ethers, such as diofenolan or pyriproxifen; o) Indoxacarb; p) Chlorfenapyr; or q) Pymetrozine.
In addition to the major chemical classes of pesticide listed above, other pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the composition. For instance, selective insecticides for particular crops, for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed. Alternatively insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).
Examples of fungicidal compounds which may be included in the composition of the invention are (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy- iminoacetamide (SSF- 129), 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole- 1 -sulphonamide, α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone, 4-chloro- 2-cyano-N,N-dimethyl-5-p-tolylimidazole-l-sulfonamide (IKF-916, cyamidazosulfamid), 3- 5-dichloro-N-(3-chloro- 1 -ethyl- 1 -methyl-2-oxopropyl)-4-methylbenzamide (RH-7281 , zoxamide), N-allyl-4,5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide (MOΝ65500), N- (1 -cyano- l,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide (AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide, acibenzolar (CGA245704), alanycarb, aldimo h, anilazine, azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S, bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulphate, copper tallate and Bordeaux mixture, cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulphide l,l'-dioxide, dichlofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, 0,0-di-z.sO-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethirimol, ethyl(Z)-N-benzyl-N([methyl(methyl-thioethylideneaminooxycarbonyl)amino]thio)- -β-alaninate, etridiazole, famoxadone, fenamidone (RPA407213), fenarimol, fenbuconazole, fenfuram, fenhexamid (KBR2738), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos, iprodione, iprovalicarb (SZX0722), isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054, LY211795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metconazole, metiram, metiram-zinc, metominostrobin, myclobutanil, neoasozin, nickel dimethyldithiocarbamate, nitrothal-i^opropyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-Al, phosphorus acids, phthalide, picoxystrobin (ZA1963), polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, propionic acid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, sipconazole (F-155), sodium pentachlorophenate, spiroxamine, streptomycin, sulphur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamid, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl, thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin (CGA279202), triforine, triflumizole, triticonazole, validamycin A, vapam, vinclozolin, zineb and ziram.
The compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
Examples of suitable synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.
Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
An example of a rice selective herbicide which may be included is propanil. An example of a plant growth regulator for use in cotton is PDC™. Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.
The invention is illustrated by the following Examples, EXAMPLE 1
This Example describes the preparation of compound No 97 in Table I Step l
(2-(2,2-Dimethylpropyl)benzoxazol-5-yl)acetic acid (5.0 g, 20.24 mmol) was suspended in toluene (100 ml) and triethylamine (3.1 ml, 22.24 mmol) was added. The mixture was heated to reflux and a solution of diphenylphosphoryl azide (4.58 ml, 21.25 mmol) in toluene (40 ml) was added dropwise. The mixture was heated at reflux for 2 hours after which it was allowed to cool and 2-trimethylsilylethanol (6.8 ml, 47.44 mmol) was added. The resulting mixture was then heated at reflux for 3 hours. The mixture was allowed to cool and the solvent was evaporated under reduced pressure. The residue was purified by flash chromatography on silica gel eluting with ethyl acetate to give N-(2- trimethylsilylethoxycarbonyl)-l-(2-(2,2-dimethylpropyl)benzoxazol-5-yl)methylamine (5.86 g, 80%).
1H NMR (CDC13) δ ppm: 0.03 (s,9H); 1.00 (br t,2H); 1.09 (s,9H); 2.81 (s,2H); 4.19 (br t,2H); 4.44 (d,2H); 5.11 (br s,lH); 7.24 (dd,lH); 7.44 (d,lH); 7.59 (d,lH) Step 2 N-(2-Trimethylsilylethoxycarbonyl)- 1 -(2-(2,2-dimethylpropyl)benzoxazol-5- yl)methylamine (5.85 g, 16.2 mmol) was suspended in THF (50 ml) and tetrabutylammonium fluoride (1.0 M in THF, 25 ml, 25 mmol) was added. The mixture was heated to reflux for 30 min. after which it was allowed to cool. The mixture was evaporated and the residue was purified by flash chromatography on silica gel using 0.1% triethylamine, 5% methanol in dichloromethane to give (2-(2,2-dimethylpropyl)benzoxazol-5- yl)methylamine (2.85 g, 81%).
1H NMR (CDC13) δ ppm: 1.09 (s,9H); 1.62 (br s,2H); 2.82 (s,2H); 3.98 (s,2H); 7.27 (dd,lH); 7.45 (d,lH); 7.63 (d,lH) Step 3 l,2-Dimethyl-[lH]-imidazole-5-carboxylic acid (77 mg, 0.55 mmol) was dissolved in
THF (5 ml) and (2-(2,2-dimethylpropyl)benzoxazol-5-yl)methylamine (109 mg, 0.5 mmol) was added, followed by l-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (106 mg, 0.55 mmol) and 4-dimethylaminopyridine (catalytic amount). The suspension was warmed to 60°C for 2 hours. The mixture was allowed to cool and was partitioned between water and ethyl acetate. The aqueous layer was extracted with ethyl acetate (2 x 30 ml) and the combined organic layers were dried (MgSO ), filtered and evaporated. The residue was purified by chromatography on silica gel eluting with 10% methanol is dichloromethane to give Compound 97 of Table 1 (96 mg, 56%). 1H NMR (CDCI3) δ ppm: 1.06 (s,9H); 2.36 (s,3H); 2.79 (s,2H); 3.82 (s,3H); 4.62 (d,2H); 7.16 (t,lH); 7.27 (dd,lH); 7.37 (s,lH); 7.42 (d,lH); 7.60 (d,lH)
EXAMPLE 2 This Example describes the preparation of compound No 17 in Table 2 2,4,5,6-Tetrahydro-2.6-dimethyl-3-cyclopentapyrazolecarboxylic acid (0.18 g, 1.0 mmol) was suspended in THF (5 ml) and cooled to 0°C. 4-Methylmorpholine (0.13 ml, 1.2 mmol) and isobutylchloroformate (0.14 ml, 1.05 mmol) were added and the mixture was allowed to stir for 45 minutes. (2-(2,2-Dimethylpropyl)benzoxazol-5-yl)methylamine (0.22 g, 1.0 mmol) and more 4-methylmorpholine (0.13 ml, 1.2 mmol) were dissolved in THF (5 ml) and added to the reaction mixture. The mixture was left to stir for 30 minutes. The mixture was partitioned between water and ethyl acetate. The organic layer was washed with brine, dried (MgSO ), filtered and evaporated. The residue was purified by flash chromatography on silica gel eluting with ethyl acetate to give the Compound 17 of Table 2 as an oil (0.14 g, 37%). IH NMR (CDC13) δ ppm: 1.10 (s,9H); 1.29 (d,3H); 2.01 (m,lH); 2.65 (m,3H); 2.82 (s,2H); 3.14 (m,lH); 4.18 (s,3H); 4.69 (m,2H); 6.10 (br t,lH); 7.30 (dd,lH); 7.46 (d,lH); 7.63 (d,lH)
EXAMPLE 3 This Example describes the preparation of compound No 87 in Table I Step 1
5-Methyl-l,3,4-oxathiazol-2-one (5.3 g, 61 mmol) was dissolved in mesitylene (100 ml). Methyl cyanoformate (12.5 g, 150 mmol) was added and the mixture was heated to reflux for 7 hours. The reaction mixture was concentrated under reduced pressue to give an approximately 10% solution of methyl 3-methyl-l,2,4-thiadiazole-5-carboxylate in mesitylene which was used without further purification. IH NMR (CDC13) δ ppm: 2.80 (s,3H); 4.05 (s,3H) Step 2
Methyl 3-methyl-l,2,4-thiadiazole-5-carboxylate (10% solution in mesitylene, 2 ml, approximately 200 mg, 1.2 mmol), toluene (1 ml) and (2-(2,2-dimethylpropyl)benzoxazol-5- yl)methylamine (0.30 g, 1.38 mmol) were added to a Wheaton vial and heated at 150°C for 1 hour. The solvents were evaporated under reduced pressure and the residue was purified by preparative thin layer chromatography eluting with 30% ethyl acetate in hexane to Compound 87 of Table 1 (0.21 g, 51%). 1H NMR (CDCI3) δ ppm: 1.10 (s,9H); 2.65 (s,3H); 2.85 (s,2H); 4.75 (d,2H); 7.30 (dd,lH); 7.50 (d,lH); 7.55 (br s,lH); 7.65 (d,lH)
EXAMPLE 4 This Example describes the preparation of compound No 7 in Table I 4-Chloro-3-ethyl-l-methyl-[lH]-pyrazole-5-carboxylic acid (93 mg, 0.50 mmol) was dissolved in dichloromethane (2 ml) and dicyclohexylcarbodiimide (0.08 ml, 0.50 mmol) in dichloromethane (1 ml) was added. (2-(2,2-Dimethylpropyl)benzoxazol-5-yl)methylamine (108 mg, 0.50 mmol) in dichloromethane (1 ml) was added dropwise, followed by 4- dimethylaminopyridine (catalytic quantity). The mixture was stirred at room temperature for 90 minutes. The reaction mixture was partitioned between water and dichloromethane, and the aqueous layer was extracted with dichloromethane (3 x 20 ml). The combined organic layers were washed with brine, dried (MgS0 ), filtered and evaporated. The residue was purified by chromatography on silica gel eluting with ethyl acetate (10-25% gradient elution) in hexane to give Compound 7 in Table 1 (109 mg, 57%). IH NMR (CDC13) δ ppm: 1.10 (s,9H); 1.25 (t,3H); 2.55 (q,2H); 2.80 (s,2H); 4.15 (s,3H); 4.70 (d,2H); 7.10 (br s,lH); 7.30 (dd,lH); 7.50 (d,lH); 7.70 (d,lH)
A useful branched chain amine intermediate may be prepared by the following method.
Preparative Example A Preparation of l-(2-(2,2-dimethylpropyl)benzoxazol-5-yl)ethylamine. Step l
Methyl (2-(2,2-dimethylpropyl)benzoxazol-5-yl)acetate (14.85 g, 57.0 mmol) was dissolved in THF (200 ml) and the solution was cooled to -75°C. Lithium bis- trimethylsilylamide (1.0 M in THF, 62.7 ml, 62.7 mmol) was added dropwise over 90 minutes so that the temperature never exceeded -70oC. The mixture was then allowed to stir for 1 hour at -75oC and methyl iodide (63 ml, 570 mmol) was added dropwise. The mixture was allowed to warm to room temperature overnight. The mixture was partitioned between water and ethyl acetate and the organic solution was washed with brine, dried (MgSO ), filtered and evaporated to give methyl 2-(2-(2,2-dimethylpropyl)benzoxazol-5-yl)propionate which was used without further purification.
IH NMR (CDC13) δ ppm: 1.10 (s,9H); 1.55 (d,3H); 2.82 (s,2H); 4.68 (s,3H); 4.85 (q,lH); 7.23 (dd,lH); 7.43 (d,lH); 7.62 (d,lH) Step 2 Methyl 2-(2-(2,2-dimethylpropyl)benzoxazol-5-yl)propionate (2.92 g, 10.6 mmol) was dissolved in methanol (25 ml) and aqueous sodium hydroxide (1.0 M, 11 ml, 11 mmol) was added dropwise and the mixture was stirred at room temperature for 45 minutes. Brine (100 ml) and aqueous hydrochloric acid (2.0 M, 10 ml) were added and the mixture was extracted with ethyl acetate which was dried (MgSO ), filtered and evaporated to give 2-(2- (2,2-dimethylpropyl)benzoxazol-5-yl)propionic acid as a yellow oil which crystallised on standing (2.63 g, 95%).
IH NMR (CDC13) δ ppm: 1.11 (s,9H); 1.58 (d,3H); 2.82 (s,2H); 3.88 (q,lH); 7.26 (dd,lH); 7.43 (d,lH); 7.69 (d,lH) Step 3
2-(2-(2,2-Dimethylpropyl)benzoxazol-5-yl)propionic acid (2.63 g, 10 mmol) was suspended in toluene (20 ml) and triethylamine (1.70 ml, 12 mmol) was added. The mixture was heated to reflux and a solution of diphenylphosphoryl azide (2.4 ml, 11 mmol) in toluene (5 ml) was added dropwise. The mixture was heated at reflux for 90 min after which it was allowed to cool and 2-trimethylsilylethanol (1.75 ml, 12 mmol) was added. The resulting mixture was then heated at reflux for 3 hours. The mixture was allowed to cool and then dilueted with toluene (100 ml) and washed with water (5 x 100 ml) and brine (100 ml). The organic layer was dried (MgSO4), filtered and under reduced pressure. The residue was purified by flash chromatography on silica gel eluting with 15% ethyl acetate in hexane to give N-(2-trimethylsilylethoxycarbonyl)- 1 -(2-(2,2-dimethylpropyl)benzoxazol-5- yl)ethylamine (2.65 g, 72%).
IH NMR (CDC13) δ ppm: 0.01 (s,9H); 0.95 (t,2H); 1.08 (s,9H); 1.50 (d,3H); 2.81 (s,2H); 4.13 (t,2H); 4.35 (m,lH); 4.95 (m,lH); 7.25 (dd,lH); 7.44 (d,lH); 7.63 (d,lH) Step 4 N-(2-Trimethylsilylethoxycarbonyl)- 1 -(2-(2,2-dimethylpropyl)benzoxazol-5- yl)ethylamine (2.65 g, 7.1 mmol) was suspended in THF (25 ml) and tetrabutylammonium fluoride (1.0 M in THF, 10.0 ml, 10.0 mmol) was added. The mixture was heated to reflux for 30 minutes after which it was allowed to cool. The solvent was evaporated under reduced pressure and the residue was partitioned between water and ether. The organic layer was washed with brine, dried (MgSO4) filtered and evaporated under reduced pressure to give 1- (2-(2,2-dimethylpropyl)benzoxazol-5-yl)ethylamine which was used with no further purification (1.36 g, 83%). 1H NMR (CDCI3) δ ppm: 1.09 (s,9H); 1.44 (d,3H); 1.80 (br s,2H); 2.82 (s,2H); 4.25 (q,lH);
7.31 (dd,lH); 7.44 (d,lH); 7.67 (d,lH)
The following compounds were synthesised by routes analogous to those described in
Example 4 above. Compound 1 in Table 1
IH NMR (CDCI3) δ ppm: 1.25 (t,3H); 2.65 (s,3H); 2.65 (q,2H); 4.15 (s,3H); 4.75 (d,2H);
7.10 (br s,lH); 7.33 (dd,lH); 7.45 (d,lH); 7.65 (d,lH)
Compound 3 in Table 1
IH NMR (CDCI3) δ ppm: 1.10 (t,3H); 1.25 (t,3H); 1.95 (m,2H); 2.65 (q,2H); 2.90 (t,2H); 4.15 (s,3H); 4.75 (d,2H); 7.10 (br s,lH); 7.30 (d,lH); 7.45 (d,lH); 7.65 (s,lH)
The following compounds were synthesised by routes analogous to those described in
Example 1 above.
Compound 11 in Table 4
IH NMR (CDC13) δ ppm: 1.29 (dd,3H); 1.62 (d,3H); 2.04 (m,lH); 2.64 (s,3H); 3.15 (m,lH) 4.13 (s,3H); 5.33 (p,lH); 5.98 (d,lH); 7.30 (dt,lH); 7.44 (d,lH); 7.61 (s,lH)
Compound 11 in Table 2
IH NMR (CDC13) δ ppm: 1.28 (d,3H); 1.99 (m, 2H); 2.64 (s,3H); 2.66 (m, 3H); 3.12
(m,lH); 4.18 (s,3H); 4.70 (m,2H); 6.10 (t,lH); 7.28 (dd,lH); 7.44 (d,lH); 7.60 (d,lH)
Compound 17 in Table 4 IH NMR (CDC13) δ ppm: 1.09 (s,9H); 1.62 (d,3H); 2.05 (m,lH); 2.74 (m,3H); 2.83 (s,2H);
3.16 (m,lH); 4.14 (s,3H); 5.34 (ρ,lH); 6.00 (d,lH); 7.32 (dt,lH); 7.48 (d,lH); 7.67 (s,lH)
Compound 17 in Table 1
IH NMR (CDC13) δ ppm: 1.08 (s,9H); 1.24 (t,3H); 2.63 (q,2H); 2.82 (s,2H); 3.79 (s,3H);
4.12 (s,3H); 4.69 (d,2H); 7.29 (dd,lH); 7.44 (d,lH); 7.59 (br t,lH); 7.63 (d,lH). EXAMPLE 5
This Example illustrates the pesticidal/insecticidal properties of compounds of formula (I). The activities of individual compounds of formula (I) were determined using a variety of pests. The pests were treated with a liquid composition containing 500 parts per million (ppm) by weight of a compound. Each composition was made by dissolving the compound in an acetone and ethanol (50:50 by volume) mixture and diluting the solution with water containing 0.05% by volume of a wetting agent, SYNPERONIC NP8, until the liquid composition contained the required concentration of the compound. The test procedure adopted with regard to each pest was essentially the same and comprised supporting a number of the pests on a medium which was usually a substrate, a host plant or a foodstuff on which the pests feed, and treating either or both the medium and the pests with a composition. Pest mortality was assessed usually between two and five days after treatment.
The results of the tests against peach aphid (Myzus persicae) are presented below. In this test Chinese cabbage leaves were infested with aphids, the infested leaves were sprayed with the test composition, and the mortality assessed after three days. The results indicate a grading of mortality (score) designated as 9, 5 or 0 wherein 9 indicates 80-100% mortality, 5 indicates 40-79% mortality and 0 indicates less than 40% mortality.
Compound No. 7 of Table 1, compound No. 11 of Table 2, compound No. 17 of Table 4 and compound Nos. 17 of Table 2, each gave a mortality score of 9 whilst compound No. 1 of Table 1, compound No.87 of Table 1, compound No.67 of Table 2, compound No. 117 of Table 1 and compound No.137 of Table 1 , gave a score of 5. In addition, in a similar test against two-spotted spider mites (Tetranychus urticae)
Compound Nos.7 of Table 1, compound No. 17 of Table 2, compound No. 117 of Table 1 and compound No.137 of Table 1, gave a score of 9 whilst compound No. 87 of Table 1 gave a score of 5.
EXAMPLE 6 This Example illustrates the fungicidal properties of compounds of formula (I). The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.
Plants were grown in John Innes Potting Compost (No.l or 2) in 4cm diameter, 3.5cm depth minipots. The test compounds were individually formulated as a solution either in acetone or acetone/ethanol (1:1 by volume) which was diluted in deionised water to a concentration of lOOppm (that is, lmg of compound in a final volume of 10ml) immediately before use. When foliar sprays were applied to monocotyledonous crops, TWEEN 20 (0.1% by volume) was added. TWEEN is a registered trade mark.
Individual compounds of formula (I) were applied as a foliar (Folr) application (where the chemical solution was applied to the foliage of the test plants by spraying the plant to maximum droplet retention.)
These tests were carried out against Uncinula necator (UNCINE), on vines; Phytophthora infestans lycopersici (PHYTIN) on tomatoes; Puccinia recondita (PUCCRT), on wheat; and Pyricularia oryzae (PYRIOR) on rice. Each treatment was applied to two or more replicate plants for Phytophthora infestans lycopersici and Uncinula necator. For tests on Puccinia recondita and Pyricularia oryzae two replicate pots each containing 6 to 10 plants were used for each treatment. The plants were inoculated one day before (Erad) or one day after (Prot) chemical application. The Phytophthora infestans lycopersici, Puccinia recondita and Pyricularia oryzae plants were inoculated with a calibrated fungal spore suspension. The Uncinula necator plants were inoculated using a 'blowing' inoculation technique.
After chemical application and inoculation, the plants were incubated under high humidity conditions and then put into an appropriate environment to allow infection to proceed, until the disease was ready for assessment. The time period between chemical application and assessment varied from five to fourteen days according to the disease and environment. However, each individual disease was assessed after the same time period for all compounds. Assessments were performed on each of two leaves on each of the replicate plants for
Phytophthora infestans lycopersici. Assessments were performed on a single leaf of each of the replicate plants for Uncinula necator. For Puccinia recondita and Pyricularia recondita assessments were carried out collectively on the plants in each replicate pot.
The disease level present (that is, the percentage leaf area covered by actively sporulating disease) was assessed visually. For each treatment, the assessed values for all its replicates were meaned to provide mean disease values. Untreated control plants were assessed in the same manner. The data were then processed by the method, described hereinafter, to provide PRCO (Percentage Reduction from Control) values. An example of a typical calculation is as follows:
an disease level for treatment A = 25% Mean disease level on untreated controls = 85%
PRCO = 100 - { Mean disease level for treatment A } x 100
{Mean disease level on untreated controls}
= 100 - (25 x 100) = 70.6 85 The PRCO is then rounded to the nearest whole number; therefore, in this particular example, the PRCO result is 71.
It is possible for negative PRCO values to be obtained. If no test data were available this is indicated in the Table below by a "-".
PRCO results are shown below.
TABLE 11
Figure imgf000081_0001

Claims

CLA S
A compound of formula (I):
Figure imgf000082_0001
wherein A is optionally substituted Q.6 alkylene, optionally substituted C2_6 alkenylene, optionally substituted C2_6 alkynylene, optionally substituted cycloalkylene, optionally substituted Q.6 alkyleneoxy, optionally substituted oxy(Cι_6)alkylene, optionally substituted Q_6 alkylenethio, optionally substituted thio(Q_6)alkylene, optionally substituted Q.6 alkyleneamino, optionally substituted amino(Q_6)alkylene, optionally substituted [Q_6 alkyleneoxy(Q_6)alkylene], optionally substituted [Cι_ alkylenethio(Cι_6)alkylene], optionally substituted [Q_6 alkylenesulfinyl(Q_ 6)alkylene], optionally substituted [Q_6 alkylenesulfonyl(Cι_6)alkylene] or optionally substituted [Q_6 alkyleneamino(Cι_6)alkylene]; B is N, N-oxide or CR18; D is O, S, NR7, CR8=CR9, CR8=N, N=CR9, CR8=N(O) or N(0)=CR9;
E is N, N-oxide or CR12; W is CR1 or N;
X is N, N-oxide or CR11 and R11 is hydrogen, optionally substituted Q_6 alkyl or optionally substituted phenyl, with the proviso that the ring containing D, E, X and W contains at least one atom that is other than a carbon atom and the ring containing
D, E W and X may contain no more than 3 heteroatoms;
M is N(R51)C(=Y), N=C(OR52), N=C(SR53) or N=C(NR54R55) where N is the atom of attachment to the group "A"; Y is O, S or NR13; Z is O, S or NR14;
R1 is hydrogen, halogen, optionally substituted Q_6 alkyl, optionally substituted C2.6 alkenyl, optionally substituted Q_6 alkynyl, optionally substituted Q.6 alkoxy, optionally substituted Q_ alkylthio, optionally substituted C3_7 cycloalkyl, cyano, nitro or SF5; R7 is hydrogen or optionally substituted Q 6 alkyl,
R51 is hydrogen, optionally substituted Q 10 alkyl, optionally substituted [C 6 alkenyl(Q 6)alkyl], optionally substituted [Q 6 alkynyl(Q 6)alkyl], optionally substituted Q 7 cycloalkyl, optionally substituted Q io alkylcarbonyl, optionally substituted Q ι0 alkoxycarbonyl, formyl, optionally substituted Q io alkylaminocarbonyl, optionally substituted dι(Q ιo)alkylamιnocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted Q 6 alkylthio, optionally substituted Q 6 alkylsulfinyl, optionally substituted Q 6 alkylsulfonyl, optionally substituted Q 6 arylthio, optionally substituted Q 6 arylsulfinyl, optionally substituted Q 6 arylsulfonyl or R20R 1NS(O)p where p is 0, 1 or 2, especially 0,
R S9 is optionally substituted Q io alkyl, optionally substituted [Q 6 alkenyl- (Q 6)alkyl], optionally substituted [C2 6 alkynyl(Q 6)alkyl], optionally substituted C3 η cycloalkyl, optionally substituted Q io alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, formyl, optionally substituted Q io alkylaminocarbonyl, optionally substituted di(Q ιo)alkylamιnocarbonyl, amino, optionally substituted Q 6 alkylamino, optionally substituted dι(Q 6)alkylamιno, optionally substituted phenoxycarbonyl, tπ(Q_ )alkylsιlyl,
Figure imgf000083_0001
or tπarylsilyl; R53 is optionally substituted Ct io alkyl, optionally substituted [C2 6 alkenyl(Cι ό)alkyl], optionally substituted [C2 6 alkynyl(Q 6)alkyl], optionally substituted C3 cycloalkyl, optionally substituted Q ι0 alkylcarbonyl, optionally substituted Q io alkoxycarbonyl, optionally substituted Q io alkylaminocarbonyl, optionally substituted dι(Q ιo)alkylamιnocarbonyl or optionally substituted phenoxycarbonyl), R54 and R55 are, independently optionally substituted Q io alkyl, optionally substituted Q 6 alkoxy, optionally substituted [Q 6 alkenyl(Q 6)alkyl], optionally substituted [Q 6 alkynyl(Cι 6)alkyl], optionally substituted C3 7 cycloalkyl, optionally substituted Q ι0 alkylcarbonyl, optionally substituted Q ι0 alkoxycarbonyl, formyl, optionally substituted Q io alkylaminocarbonyl, optionally substituted dι(Q ιo)alkylamιnocarbonyl, hydroxy, amino, optionally substituted Q 6 alkylamino, optionally substituted dι(Q 6)alkylammo, or optionally substituted phenoxycarbonyl, R3, R4 and R5 are, independently, hydrogen, halogen, optionally substituted Q 6 alkyl, optionally substituted Q 6 alkoxy, optionally substituted Q 6 alkylthio, optionally substituted Q 6 alkylsulfinyl, optionally substituted Q 6 alkylsulfonyl, cyano, nitro, optionally substituted Q alkylcarbonyl, optionally substituted Q_6 alkoxycarbonyl or SF5; R is hydrogen, halogen, cyano, optionally substituted Q_2o alkyl, optionally substituted C2.2o alkenyl, optionally substituted C2_2o alkynyl, optionally substituted C3.7 cycloalkyl, optionally substituted C5_6 cycloalkenyl, formyl, optionally substituted Q.2o alkoxycarbonyl, optionally substituted Cι_2o alkylcarbonyl, aminocarbonyl, optionally substituted Q.2o alkylaminocarbonyl, optionally substituted di(Q_2o)alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-alkyl-N-arylaminocarbonyl, optionally substituted diarylaminocarbonyl, optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted N-alkyl-N- heteroarylaminocarbonyl, optionally substituted diheteroarylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, HS, optionally substituted Q_2o alkylthio, optionally substituted Q.20 alkylsulfinyl, optionally substituted Q_20 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl, R26O, R28R29N or R31ON=C(R27); R8 and R9 are, independently, hydrogen, halogen, cyano, nitro, optionally substituted Q.6 alkyl, optionally substituted C2_ alkenyl, optionally substituted C2.6 alkynyl or optionally substituted Q.6 alkoxy; R12 is hydrogen, halogen, optionally substituted Q_ alkyl, optionally substituted C2.6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted Q_6 alkoxy, optionally substituted Q.6 alkylthio, optionally substituted Q_6 alkylsulfinyl, optionally substituted Q.6 alkylsulfonyl, cyano, nitro, formyl, optionally substituted Q_6 alkylcarbonyl, optionally substituted Q.6 alkoxycarbonyl, SF5, R32ON=C(R30), or R1
19 and R together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated, carbocyclic or heterocyclic ring which may contain one or two heteroatoms selected from O, N or S and which may be optionally substituted by Q.6 alkyl, Q.6 haloalkyl or halogen; R13 is hydrogen, cyano, nitro, optionally substituted Q_6 alkyl, optionally substituted C3-7 cycloalkyl, optionally substituted (C2.6)alkenyl(Q.6)alkyl, optionally substituted (Q_6)alkynyl-
(Q.6)alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted Q.6 alkylcarbonyl, optionally substituted Q_6 alkoxycarbonyl, optionally substituted Q_6 alkylamino, optionally substituted di(Q_6)alkylamino, optionally substituted Cι_6 alkylcarbonylamino, optionally substituted Q.6 alkoxycarbonylamino, optionally substituted Q_6 alkoxy, optionally substituted Q_6 alkylthio, optionally substituted Q_6 alkylsulfinyl, optionally substituted Q_6 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or Q_6 alkylcarbonyloxy; R14 is hydrogen, cyano, optionally substituted Q.8 alkyl, optionally substituted [C2_6 alkenyl(Cι^)alkyl], optionally substituted [C2.6 alkynyl(Q.6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted [C3.7 cycloalkyl(Cι.6)alkyl], Cι_ alkoxy(Cι.6)alkyl, optionally substituted Q.6 alkoxycarbonyl, optionally substituted Q.6 alkylcarbonyl, optionally substituted Q.6 alkylaminocarbonyl, optionally substituted di(Q_6)alkylamino- carbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl; R is hydrogen, halogen, nitro, cyano, optionally substituted Q.8 alkyl, optionally substituted _6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted C3.7 cycloalkyl, optionally substituted Q.6 alkoxycarbonyl, optionally substituted Q_6 alkylcarbonyl, optionally substituted Q-6 alkylaminocarbonyl, optionally substituted di(Q_ 6)alkylaminocarbonyl, optionally substituted phenyl or optionally substituted heteroaryl; R20 and R21 are, independently, optionally substituted Q_ alkyl or R20and R21 together with the N atom to which they are attached form a five, six or seven- membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q_6 alkyl groups; R26 is hydrogen, optionally substituted Q_2o alkyl, optionally substituted [C2.2o alkenyl(Cι^)alkyl], optionally substituted [C2.2o alkynyl(Q.6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted [heterocyclyl(Cι^)alkylCH=N] or di(Cι^)alkylC=N;
R28 and R29 are, independently, hydrogen, optionally substituted Q.2o alkyl, optionally substituted C3.7 cycloalkyl, optionally substituted [C2.2o alkenyl(Cι^)alkyl], optionally substituted [C2.20 alkynyl(Q_6)alkyl], optionally substituted Q_2o alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted Q.2o alkylcarbonyl, optionally substituted Q.20 alkylsulfonyl or optionally substituted phenylsulfonyl; or R28 and R29 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q.6 alkyl groups; R27 and R30 are independently hydrogen, optionally substituted phenyl or optionally substituted Q-6 alkyl; and R31 and R32 are, independently, hydrogen, optionally substituted phenyl (Q- )alkyl or optionally substituted Q.2o alkyl provided that when A is CH2, M is CONH, D is S, and X is N then E and W cannot both be C-Cl.
A compound according to claim 1 which is a compound of formula I'
Figure imgf000086_0001
where A, B, D, E, M, W, X, Z, R3, R4, R5, and R6 have the values as defined for formula (I) in claim 1.
3. A compound according to claim 1 or claim 2 wherein M is C(O)NR51 where the N atom is attached to the group "A".
4. A compound according to any preceding claim wherein A is Q.6 alkylene (optionally substituted by halogen, Q.3 alkyl, Q.3 haloalkyl, Q.3 cyanoalkyl, Q.6 alkoxycarbonyl), -C(O)- or Q.6 alkyleneoxy.
5. A compound according to any preceding claim wherein Z is O or S and B is N.
6. A compound according to any preceding claim wherein the optionally substituted ring of formula
Figure imgf000086_0002
is a pyrazoles, a 2,4,5,6-tetrahydro-cyclopentapyrazole, a 4,5,6,7-tetrahydro-[2H]- indazole or an indazole which may be optionally substituted by substituents chosen from halo, Q.6 alkyl, Q-6 haloalkyl, Q^ alkoxy, Q.6 alkoxy (Q.6)alkyl or Q.6 haloalkoxy. A compound according to any preceding claim wherein R is Q_8 alkyl, Q_6 haloalkyl, Q_6 cyanoalkyl, C2.6 alkenyl, C2_6 alkynyl, C3.7 cycloalkyl, C3_7 halocycloalkyl, C3.7 cyanocycloalkyl, Q.3 alkyl(C3.7)cycloalkyl, Q.3 alkyl(C3_ )halocycloalkyl, C5_6 cycloalkenyl, C3.7 cycloalkyl(Cι.6)alkyl, C5.6 cycloalkenyl(Q_6)alkyl, C2_6 haloalkenyl, Cι_6cyanoalkenyl, Cι_6 alkoxy(Q.6)alkyl, C3_6 alkenyloxy(Cι_6)alkyl, C3.6 alkynyloxy(Cι_6)alkyl, aryloxy(C1_6)alkyl, Cι_6 carboxyalkyl, Cι_6 alkylcarbonyl(Cι_6)alkyl, C2_6 alkenylcarbonyl(Cι_6)alkyl, C2_6 alkynylcarbonyl(Cι_6)alkyl, Cι.6 alkoxycarbonyl(Q_6)alkyl, C3_6 alkenyloxycarbonyl(Q.6)alkyl, C3_6 alkynyloxycarbonyl(Q-6)alkyl, aryloxycarbonyl(Ci.6)alkyl, Cι_6 alkylthio(Cι_6)alkyl, Cι_6 alkylsulfinyl(Q_6)alkyl, Ci.6 alkylsulfonyl(Cι.6)alkyl, aminocarbonyl(Cι_6)alkyl, aminocarbonyl(C2_6)alkenyl, aminocarbonyl(C2_6)alkynyl, Cι_6 alkylaminocarbonyl(Cι.6)alkyl, di(Q.6)alkylamino- carbonyl(Q_6)alkyl, Q.6 alkylaminocarbonyl (Q_6)alkenyl, di(Q_6)alkylamino- carbonyl(Q-6)alkenyl, alkylaminocarbonyl(Q_6)alkynyl, di(Q_6)alkylamino- carbonyl(Cι_6)alkynyl, phenyl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), pheny Q^alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy), phenyl(C2.4)alkenyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or
Q_6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.<5 haloalkyl, Cι.6 alkoxy or Q_6 haloalkoxy), heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q.6 haloalkoxy), heteroaryl(Q^)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or
Q-6 haloalkoxy), heterocyclyl(Cι_ )alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q. alkyl, Q. haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy), R26O, Q_8 alkylthio, R28R29N or R31ON=C(R27); where R26 is Q.8 alkyl, Cι_6 haloalkyl; R27 is Cι_6 alkyl, Cι_6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy); R27 is
Q.6 alkyl, Q_6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy); R28 and R29 are, independently, hydrogen, Q_8 alkyl, C3_7 cycloalkyl, C3_6 alkenyl, C3_6 alkynyl, Q_ cycloalkyl- (Cι^)alkyl, C2.6 haloalkyl, Cι_6 alkoxy(Cι_6)alkyl, Cι_6 alkoxycarbonyl, or R and R together with the N atom to which they are attached form a five, six or seven- membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q.6 alkyl groups; and R31 is Q.6 alkyl or phenyl(Q.2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q_6 haloalkyl, Q-6 alkoxy or Q_6 haloalkoxy).
8. A fungicidal, insecticidal, acaricidal, molluscicidal or nematicidal composition comprising a fungicidally, insecticidally, acaricidally, molluscicidally or nematicidally effective amount of a compound of formula (I) as claimed in claim 1 and a carrier or diluent therefor.
9. A method of combating and controlling fungi comprising applying to a plant, to a seed of a plant, to the locus of the plant or seed or to the soil a fungicidally effective amount of a compound of formula (I) as claimed in claim 1.
10. A method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as claimed in claim 1.
PCT/GB2001/000314 2000-01-28 2001-01-26 Benzoxazole derivatives and their use as pesticides WO2001055136A1 (en)

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