WO2001055137A1 - Azine derivatives as pesticides - Google Patents

Azine derivatives as pesticides Download PDF

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Publication number
WO2001055137A1
WO2001055137A1 PCT/GB2001/000318 GB0100318W WO0155137A1 WO 2001055137 A1 WO2001055137 A1 WO 2001055137A1 GB 0100318 W GB0100318 W GB 0100318W WO 0155137 A1 WO0155137 A1 WO 0155137A1
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Prior art keywords
optionally substituted
alkyl
formula
alkoxy
compounds
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PCT/GB2001/000318
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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
Roger 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 AU28671/01A priority Critical patent/AU2867101A/en
Publication of WO2001055137A1 publication Critical patent/WO2001055137A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—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
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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 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, WO96/08475, WO97/18198, WO98/02424 and WO98/05670.
  • the present invention provides a compound of formula (I):
  • A is optionally substituted Ci- 6 alkylene, optionally substituted C 2 - 6 alkenylene, optionally substituted C 2 - 6 alkynylene, optionally substituted cycloalkylene, optionally substituted - 6 alkyleneoxy, optionally substituted oxy(C 1-6 )alkylene, optionally substituted d- 6 alkylenethio, optionally substituted thio(Ci_ 6 )alkylene, optionally substituted d- 6 alkyleneamino, optionally substituted amino(C 1-6 )alkylene, optionally substituted [C 1-6 alkyleneoxy(C 1-6 )alkylene], optionally substituted [ - 6 alkylenethio(C 1 - 6 )alkylene], optionally substituted [Q- 6 alkylenesulf ⁇ nyl(C 1 - 6 )alkylene], optionally substituted [Q- 6 alkylenesulfonyl(C 1 - 6 )
  • E is N, N-oxide or CR 12 ;
  • Z is O, S or NR 14 ;
  • R 1 is hydrogen, halogen, optionally substituted Q- 6 alkyl, optionally substituted C 2 - 6 alkenyl, optionally substituted C 2 - 6 alkynyl, optionally substituted Q- 6 alkoxy, optionally substituted Q- 6 alkylthio, optionally substituted C - 7 cycloalkyl, cyano, nitro or SF 5 ;
  • R 51 is hydrogen, optionally substituted Q- 10 alkyl, optionally substituted [C -6 alkenyl(Q- 6 )alkyl], optionally substituted [C 2 - 6 alkynyl (Q- 6 )alkyl], optionally substituted C 3 - 7 cycloalkyl, optionally substituted Q-io alkylcarbonyl, optionally substituted Q-io alkoxycarbonyl, formyl, optionally substituted Q -10 alkylaminocarbonyl, optionally substituted di(C 1 -
  • R 53 is optionally substituted Q-io alkyl, optionally substituted [C 2 _ 6 alkenyl(Q- 6 )- alkyl], optionally substituted [C 2-6 alkynyl(C 1 . 6 )alkyl], optionally substituted C 3 . 7 cycloalkyl, optionally substituted Q-10 alkylcarbonyl, optionally substituted Q-io alkoxycarbonyl, optionally substituted Q-10 alkylaminocarbonyl, optionally substituted di(Q- ⁇ alkylaminocarbonyl or optionally substituted phenoxycarbonyl);
  • R 54 and R 55 are, independently optionally substituted Q-io alkyl, optionally substituted Q- 6 alkoxy, optionally substituted [C 2 - 6 alkenyl(Q- 6 )alkyl], optionally substituted [C 2 - 6 alkynyl(Q- 6 )alkyl], optionally substituted C 3 - 7 cycloalkyl, optionally substituted Q.io alkylcarbonyl, optionally substituted C ⁇ o alkoxycarbonyl, formyl, optionally substituted -1 0 alkylaminocarbonyl, optionally substituted di(Q- ⁇ o)alkylaminocarbonyl, hydroxy, amino, optionally substituted Q_6 alkylamino, optionally substituted di(Q- 6 )alkylamino, or optionally substituted phenoxycarbonyl;
  • R 3 , R 4 and R 5 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 C ⁇ - 6 alkylcarbonyl, optionally substituted Q- 6 alkoxycarbonyl or SF 5 ;
  • R 6 is hydrogen, halogen, cyano, optionally substituted Q_ 2 o alkyl, optionally substituted C 2 - 2 o alkenyl, optionally substituted C 2 - 20 alkynyl, optionally substituted C 3 _ 7 cycloalkyl, optionally substituted C 5 -6 cycloalkenyl, formyl, optionally substituted Q- 20 alkoxycarbonyl, optionally substituted C 1-2 o alkylcarbonyl, aminocarbonyl, optionally substituted Q.
  • alkylaminocarbonyl optionally substituted di(Q- 2 o)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- 2 o alkylthio, optionally substituted Q- 2 o alkylsulfinyl, optionally substituted Q- 2 o alkylsulfony
  • R 8 and R 9 are, independently, hydrogen, halogen, cyano, nitro, optionally substituted Q- 6 alkyl, optionally substituted C 2 - 6 alkenyl, optionally substituted C 2 - 6 alkynyl or optionally substituted Q- 6 alkoxy;
  • R 12 is hydrogen, halogen, optionally substituted Q- 6 alkyl, optionally substituted C 2 - 6 alkenyl, optionally substituted C 2 - 6 alkynyl, optionally substituted Q_ 6 alkoxy, optionally substituted Q- 6 alkylthio, optionally substituted Q.
  • R 1 and R 12 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- alkyl, Q- 6 haloalkyl or halogen;
  • R 13 is hydrogen, cyano, nitro, optionally substituted Q- 6 alkyl, optionally substituted
  • C 3 - 7 cycloalkyl optionally substituted (C 2 - 6 )alkenyl(C 1 - 6 )alkyl, optionally substituted (C 2 - 6 )alkynyl(C ⁇ - 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 Q- 6 alkylcarbonylamino, optionally substituted Q- 6 alkoxycarbonylamino, optionally substituted Ci- alkoxy, optionally substituted Q- 6 alkylthio, optionally substituted Q- 6 alkylsulfinyl, optionally substituted Q-6 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl,
  • R 14 is hydrogen, cyano, optionally substituted Q- 8 alkyl, optionally substituted [C 2 - 6 alkenyl(Q_ 6 )alkyl], optionally substituted [C 2 - 6 alkynyl(Q- 6 )alkyl], optionally substituted C 3 - 7 cycloalkyl, optionally substituted [C 3 - 7 cycloalkyl(Q- 6 )alkyl], Q- 6 alkoxy(Q- 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 18 is hydrogen, halogen, nitro, cyano, optionally substitute
  • R 20 and R 21 are, independently, optionally substituted Q- 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 Q- 6 alkyl groups;
  • R and R are, independently, hydrogen, optionally substituted Q- 2 o alkyl, optionally substituted C 3 - 7 cycloalkyl, optionally substituted [C 2 - 2 o alkenyl(Q- 6 )alkyl], optionally substituted [C 2 _ o alkynyl(Q- 6 )alkyl], optionally substituted Q- o alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted Q- o alkylcarbonyl, optionally substituted Q- o alkylsulfonyl or optionally substituted phenylsulfonyl;
  • 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 33 is Q- 6 alkyl, Q- 6 haloalkyl, OR 36 or R 37 R 38 N; where R 34 and R 35 are, independently, hydrogen, Q- 6 alkyl, Q- 6 alkoxy, Q-6 haloalkyl, cyano, Q-6 alkoxycarbonyl, Q- 6 alkylcarbonyl or R 39 R 40 N; R 36 is Q- 6 alkyl, Q- 6 haloalkyl or phenyl(Q- )alkyl; R 37 and R 38 are, independently, hydrogen, Q- 8 alkyl, C 3 _ 7 cycloalkyl, C 2 - 6 alkenyl(Ci- 6 )alkyl, C 2 - 6 alkynyl(Ci- 6 )alkyl, C 2 - 6 haloalkyl, Ci- 6 alkoxy(Ci- 6 )alkyl, Q- 6 alkoxycarbonyl(C ⁇ - 6 )alkyl,
  • Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, wo-propyl, n-butyl, sec-butyl, iso-buty ⁇ , 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 Q- 6 alkyl or halogen), C 5-7 cycloalkenyl (which itself may be optionally substituted with Q -6 alkyl or halogen), hydroxy, Q-io alkoxy, Q- 10 alkoxy(Q- 10 )alkoxy, tri(Q- 4 )alkylsilyl(Q -6 )alkoxy, Ci.
  • One group of optional preferred substituents for alkyl include one or more of halogen, nitro, cyano, HO 2 C, Q-io alkoxy (itself optionally substituted by Q-io alkoxy), aryl(Q- 4 )- alkoxy, Q-io alkylthio, Q-io alkylcarbonyl, Q_ ⁇ o alkoxycarbonyl, Q- alkylaminocarbonyl, di(Q- 6 alkylaminocarbonyl, (Q-6)alkylcarbonyloxy, optionally substituted phenyl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl, heterocyclyloxy, C 3 - 7 cycloalkyl (itself optionally substituted with (Q- 6 )alkyl or halogen), C 3 - 7 cycloalkyloxy, C 5 - 7 cycloalkenyl, Q-6 alkylsulfonyl, Q-
  • 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 Q- 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.
  • 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.
  • heterocyclyl is optionally substituted by Ci- 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 Q- 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 Q- 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-, Ci- 6 alkyl, Q- 6 haloalkyl, Ci- 6 alkoxy(Q-6)alkyl, C 2- 6 alkenyl, C 2 _6 haloalkenyl, C 2 - 6 alkynyl, C 3 - 7 cycloalkyl (which itself may be optionally substituted with Q-e alkyl or halogen), C 5 - 7 cycloalkenyl
  • the substituents include one or more of the substituents listed above for alkyl.
  • substituents include one or more of the substituents listed above for alkyl.
  • one set of preferred substituents are independently selected from one or more of halogen, Q- 6 alkyl, Q-6 haloalkyl, Q- 6 alkoxy(Q- 6 )alkyl, Q- 6 alkoxy, Q- 6 haloalkoxy, Q- 6 alkylthio, Ci-6 haloalkylthio, Q- 6 alkylsulfinyl, Q- 6 haloalkylsulfinyl, Q- 6 alkylsulfonyl, Ci- 6 haloalkylsulfonyl, - 6 alkenyl, C 2 - 6 haloalkenyl, - 6 alkynyl, Q- 7 cycloalkyl, nitro, cyano, CO 2 H, Ci- 6 alkylcarbonyl,
  • 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 Q- 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 (Q- 6 )alkyl groups.
  • the present invention provides a compound of formula (LA) which are compounds of formula (I) where B, D, E, M, Z and n have the values as defined for formula (I) above and R 1 is hydrogen, halogen, optionally substituted Q- 6 alkyl, optionally substituted C 2 - 6 alkenyl, optionally substituted -6 alkynyl, optionally substituted Ci- 6 alkoxy, optionally substituted Ci- 6 alkylthio, optionally substituted C 3 - 7 cycloalkyl, cyano, nitro or SF 5 ; R 12 is hydrogen, halogen, optionally substituted Q-6 alkyl, optionally substituted Q- 6 alkenyl, optionally substituted C -6 alkynyl, optionally substituted Q- 6 alkoxy, optionally substituted Q- 6 alkylthio, optionally substituted Q- 6 alkylsulfinyl, optionally substituted Q_ 6 alkylsulfonyl, cyano, nitro
  • R 6 is hydrogen, halogen, cyano, optionally substituted Q- 2 o alkyl, optionally substituted C 2 - 2 o alkenyl, optionally substituted C 2 - 2 o alkynyl, optionally substituted C 3 - 7 cycloalkyl, optionally substituted C 5 - 6 cycloalkenyl, formyl, optionally substituted Q- 2 o alkoxycarbonyl, optionally substituted Q- 2 o alkylcarbonyl, aminocarbonyl, optionally substituted Q_ 2 o alkylaminocarbonyl, optionally substituted di(Q.
  • the present invention provides a compound of formula (!') where A, B, D, E, M, Z, R 1 , R 3 , R 4 , R 5 , and R 6 have the values as defined for formula (I) above.
  • the invention also provides a compound of formula (LA') which is a compound of formula I' wherein A, B, D, E, M, Z, R 1 , R 3 , R 4 , R 5 , and R 6 have the values as defined for formula (LA) above.
  • LB' is a compound of formula V wherein A, B, D, E, M, Z, R 1 , R 3 , R 4 , R 5 , and R 6 have the values as defined for formula (LB) above.
  • 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: More preferably A is Q- 4 alkylene -C(O)- or Q- 4 alkyleneoxy; or alternatively is C 1- alkylene (optionally substituted by C ⁇ - 3 alkyl).
  • A is CH 2 , CH(CH 3 ) or CH 2 O.
  • A is CH 2 or is CH(CH 3 ).
  • Z is O or S, more preferably O.
  • B is N.
  • E is N or CR 12 where R 12 is hydrogen, halogen, Ci- 6 alkyl, Q- 6 haloalkyl, Ci- 6 alkoxy, Q- 6 haloalkoxy, Ci-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 Ci- 6 alkyl Q- 6 haloalkyl or halogen.
  • E is N or CR 12 where R 12 is hydrogen, halogen, Q-e alkyl, Q- 6 haloalkyl, Q- 6 alkoxy, Q- 6 haloalkoxy, Q- 6 alkoxy (Q- 6 )alkyl, Q- 6 alkylthio or SF 5 .
  • R 8 and R 9 are independently selected from hydrogen, halogen, cyano, nitro, Ci- alkyl, Q-6 haloalkyl, Q- 6 alkoxy(Q_ 6 )alkyl, - 6 alkenyl, - 6 haloalkenyl, - 6 alkynyl, Q- 6 alkoxy or Q- 6 haloalkoxy.
  • R and R are independently selected from hydrogen, halogen, cyano, nitro, Q- 6 alkyl, Q-6 haloalkyl, -6 alkenyl, - 6 haloalkenyl, - 6 alkynyl, Q- 6 alkoxy, Q- 6 haloalkoxy.
  • R and R are independently selected from hydrogen, halogen, Q- 6 alkyl, Q-6 haloalkyl, Q- 6 alkenyl, -6 alkynyl, Ci- 6 alkoxy or Q-6 haloalkoxy.
  • R and R are independently selected from hydrogen or Q- 3 alkyl.
  • R 51 is hydrogen, Q-io 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 Q- 4 alkoxycarbonyl), - 6 alkenyloxy(C 1-4 )alkyl, - 6 alkynyloxy(Q- 4 )alkyl, benzyloxy(Q--- t )alkyl (where the phenyl ring may be optionally substituted with halogen or Q ⁇ alkyl), C 3 - 7 cycloalkyl (Q- 4 )alkyl, heteroaryl(Q -3 )alkyl (where the heteroaryl group may be optionally substituted with halogen), tri(Q- )alkylsilyl(
  • R 51 is hydrogen, Ci- 6 alkyl, Ci- 6 alkylcarbonyloxymethyl, benzoyloxymethyl (where the phenyl ring may be optionally substituted with halogen or Q ⁇ alkyl), Q- 6 alkoxymethyl, -6 alkenyloxymethyl, Q- 6 alkynyloxymethyl, benzyloxymethyl (where the phenyl ring may be optionally substituted with halogen or Q- 4 alkyl), - 6 alkynyl(Q- 6 )alkyl (especially propargyl) or Q-io alkylcarbonyl.
  • R 51 is hydrogen, Ci- 6 alkyl, Q- 6 alkylcarbonyloxymethyl, Q- 6 alkoxymethyl, benzyloxymethyl or benzoyloxymethyl.
  • R 51 is hydrogen, Q- alkyl, Ci- 6 alkylcarbonyloxymethyl or Q- 4 alkoxymethyl.
  • R 52 and R 53 are independently Q-io alkyl, Q-io haloalkyl, - 6 alkenyl- (C ⁇ - 6 )alkyl, C 2 - 6 alkynyl (Q- 6 )alkyl, C 3 - 7 cycloalkyl, Ci- 6 alkylamino, di(Q- 6 )alkylamino, phenyl(C ⁇ - 4 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci- 6 alkyl, Q- 6 haloalkyl, Q- 6 alkoxy or Q- 6 haloalkoxy),
  • R 52 and R 53 are independently Q- 6 alkyl, Q_ haloalkyl, Q- 6 alkenyl(Q- 6 )alkyl, C 2 - 6 alkynyl(Ci- 6 )alkyl, benzyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Q-6 haloalkyl, Q- 6 alkoxy or Q- 6 haloalkoxy).
  • R 1 is preferably hydrogen, halogen, Q-6 alkyl, Q- 6 alkenyl, - 6 alkynyl, Q- 6 haloalkyl, Q- 6 alkoxy(Q- 6 )alkyl, C 3 - 7 cycloalkyl(Q- 4 )alkyl, Q- 6 cyanoalkyl, Q- 6 alkoxy, Q_ 6 haloalkoxy, Q- 6 alkylthio, Q- 6 haloalkylthio, - cycloalkyl, cyano, nitro or SF 5 .
  • R 1 is hydrogen, halogen, Q-6 alkyl, - 6 alkenyl, Q- 6 haloalkyl, Q- 6 alkoxy, Q- 6 haloalkoxy, Q- 6 alkylthio, Q-6 haloalkylthio, - 6 cycloalkyl, cyano, nitro or SF 5 .
  • R 1 is hydrogen, halogen, Q- 6 alkyl, - 6 alkenyl, Q- 6 haloalkyl, Ci- 6 alkoxy, Q- 6 haloalkoxy, Ci-6 alkylthio, Ci-6 haloalkylthio, Q- 6 cycloalkyl, Q- 6 alkoxy(Q- 6 )alkyl, cyano or nitro.
  • R 1 is halogen, Q-6 alkyl, Q.6 haloalkyl, Q- 6 alkoxy or Ci- 6 haloalkoxy.
  • R 3 , R 4 and R 5 are, independently, hydrogen, halogen, Ci- 6 alkyl, Q- 6 haloalkyl, Ci- 6 alkylthio, Q-6 haloalkylthio, Ci-6 alkoxy, Ci- 6 haloalkoxy, Q- 6 alkylsulfinyl, Ci- 6 haloalkylsulfinyl, Q- 6 alkylsulfonyl, Q- 6 haloalkylsulfonyl, cyano, nitro, Q- 6 alkylcarbonyl, Ci- 6 alkoxycarbonyl or SF 5 . More preferably R 3 , R 4 and R 5 are independently hydrogen, Q- 3 alkyl or halogen.
  • 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- 8 haloalkyl, Q- 8 cyanoalkyl, - 6 alkenyl, Q- 6 alkynyl, Q- 7 cycloalkyl, Q- 7 halocycloalkyl, Q- 7 cyanocycloalkyl, Q- 3 alkyl(Q- 7 )cycloalkyl, Q- 3 alkyl(Q- 7 )halocycloalkyl, - 6 cycloalkenyl, Q- 7 cycloalkyl(Q- 6 )alkyl, - 6 cycloalkenyl(Q- 6 )alkyl, Q- 6 haloalkenyl, Q- 6 cyanoalkenyl, Q- 6 alkoxy(Q- 6 )alkyl, C 3 - 6 alkenyloxy(C ⁇ - 6 )alkyl, C 3 - 6 alkynyloxy(C ⁇ - 6 )alkyl, ary
  • R 28 and R 29 are, independently, hydrogen, Q_ 8 alkyl, Q- 7 cycloalkyl, - 6 alkenyl, - 6 alkynyl, Q- 7 cycloalkyl(Q- )alkyl, Q-6 haloalkyl, Q- 6 alkoxy(Q- 6 )alkyl, Q- 6 alkoxycarbonyl, or 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; and R 31 is Q- 6 alkyl or phenyl(Q- 2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q-6 alkyl, Ci- 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- (Ci- 6 )alkyl, C 5 - 6 cycloalkenyl(C ⁇ - 6 )alkyl, Q- 6 alkoxy(Q- 6 )alkyl, C 3 - 6 alkenyloxy(Ci- 6 )alkyl, C 3 - 6 alkynyloxy(Ci-6)alkyl, aryloxy(Q-6)alkyl, Q- 6 carboxyalkyl, Q- 6 alkylcarbonyl- (Q.
  • R 6 is C 1-8 alkyl, Q- 8 haloalkyl, Ci- 8 cyanoalkyl, Q- 7 cycloalkyl, C ⁇ - 3 alkyl (C 3 - 7 ) cycloalkyl, Q- 6 alkoxy (Q- 6 ) alkyl, heterocyclic (optionally substituted by halo, nitro, cyano, Q- 6 alkyl, Ci-6 haloalkyl, Q- 6 alkoxy or Q- 6 haloalkoxy) or R 28 R 29 N where R 28 and R 29 are independently Q- 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-e alkyl groups.
  • R 6 is Q- 8 alkyl, Q- 8 haloalkyl, Q- 8 cyanoalkyl, Ci- 6 alkoxy (Ci- 6 ) alkyl, Q- 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, Ci- 6 alkoxy or Q- 6 haloalkoxy) or di(C i - 8 )alkylamino .
  • R 12 is hydrogen, halogen, Q- 6 alkyl, Ci- 6 haloalkyl, Q- 6 alkoxy (Q- 6 )alkyl, Ci- 6 alkoxy, Ci- 6 haloalkoxy, Ci- 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 Ci- 6 alkyl, Q- 6 haloalkyl or halogen.
  • R 12 is hydrogen, halogen, Ci- 6 alkyl, Ci- 6 haloalkyl, Ci- 6 alkoxy(Q- 6 )alkyl, Ci- 6 alkoxy, Ci-6 haloalkoxy, 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 13 is preferably cyano, nitro, Q-6 alkyl, Ci-6 haloalkyl, Q- cycloalkyl(Q- 6 )alkyl,
  • Q- 7 cycloalkyl, CH (Q- 6 )alkenyl, CH 2 (Q- 6 )alkynyl, 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), Ci-6 alkylcarbonyl, Q-6 alkoxycarbonyl, Q- 6 alkylamino, di(Q-6)alkylamino, Ci-6 alkylcarbonylamino, Q- 6 alkoxycarbonylamino, Ci- 6 alkoxy, Q- 6 alkoxycarbonylamino, Ci- 6 alkoxy, Q- 6 alkoxycarbonylamino, Ci- 6 al
  • R 14 is hydrogen, Q- 8 alkyl, Q- 6 haloalkyl, Q- 6 cyanoalkyl, Q- 6 alkenyl, - 6 haloalkenyl, Q-6 alkynyl, Q- 7 cycloalkyl, Q- 7 cycloalkyl(Q- 6 )alkyl, Q- 6 alkoxy(Ci- 6 )alkyl, Ci-6 alkoxycarbonyl, Q- 6 alkylcarbonyl, Q- 6 alkylaminocarbonyl, di(Ci- 6 )alkylaminocarbonyl, phenyl (which may be optionally substituted by halo, nitro, cyano, Ci- 6 alkyl, Q-6 haloalkyl, Ci-6 alkoxy or Q-6 haloalkoxy) or heteroaryl (which may be optionally substituted by halo, nitro, cyano, Q- 6 alkyl, Q- 6 haloalkyl, Ci- 6
  • R 14 is hydrogen, Q- 8 alkyl or Q- 6 haloalkyl.
  • R 18 is hydrogen, halogen, nitro, cyano, Q- 8 alkyl, Ci- 6 haloalkyl, Ci- 6 cyanoalkyl, Q- 7 cycloalkyl(Q- 6 )alkyl, Q- 6 alkoxy(Q -6 )alkyl, Q- 6 alkoxycarbonyl(Q- 6 )alkyl, Q- 6 alkylcarbonyl(Q-6)alkyl, Q- 6 alkylaminocarbonyl(Q- 6 )alkyl, di(Q- 6 )alkylamino- carbonyl(Q- 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 Q-
  • R 18 is hydrogen, halogen, Q- 8 alkyl or Q. 6 haloalkyl.
  • n 0.
  • Table 1 provides 10 compounds of formula:
  • Table 2 provides 10 compounds of formula:
  • Table 4 provides 10 compounds of formula:
  • Table 9 provides 10 compounds of formula:
  • Table 13 provides 10 compounds of formula:
  • Table 14 provides 10 compounds of formula:
  • Table 18 provides 10 compounds of formula:
  • Table 19 provides 10 compounds of formula:
  • Table 23 provides 10 compounds of formula:
  • Table 27 provides 10 compounds of formula:
  • Table 31 provides 10 compounds of formula:
  • Table 32 provides 10 compounds of formula:
  • Table 40 provides 10 compounds of formula:
  • Table 41 provides 10 compounds of formula:
  • Table 43 provides 10 compounds of formula:
  • Table 46 provides 10 compounds of formula:
  • Table 50 provides 10 compounds of formula:
  • Table 55 provides 10 compounds of formula:
  • Table 56 provides 10 compounds of formula:
  • Table 59 provides 10 compounds of formula:
  • Table 60 provides 10 compounds of formula:
  • Table 65 provides 10 compounds of formula:
  • Table 67 provides 10 compounds of formula:
  • Table 68 provides 10 compounds of formula:
  • Table 69 provides 10 compounds of formula:
  • Table 70 provides 10 compounds of formula:
  • Table 73 provides 10 compounds of formula:
  • Table 77 provides 10 compounds of formula:
  • Table 78 provides 10 compounds of formula:
  • Table 82 provides 10 compounds of formula:
  • Table 83 provides 10 compounds of formula:
  • Table 86 provides 10 compounds of formula:
  • Table 87 provides 10 compounds of formula:
  • Table 91 provides 10 compounds of formula:
  • Table 95 provides 10 compounds of formula:
  • Table 96 provides 10 compounds of formula:
  • Table 100 provides 10 compounds of formula:
  • Table 105 provides 10 compounds of formula:
  • Table 109 provides 10 compounds of formula: wherein D, E, Rl and R6 are as defined in Table 1.
  • Table 110 provides 10 compounds of formula:
  • Table 113 provides 10 compounds of formula:
  • Table 114 provides 10 compounds of formula:
  • Table 122 provides 10 compounds of formula:
  • Table 123 provides 10 compounds of formula:
  • Table 132 provides 10 compounds of formula:
  • Table 133 provides 10 compounds of formula:
  • Table 136 provides 10 compounds of formula:
  • Table 140 provides 10 compounds of formula:
  • Table 141 provides 10 compounds of formula:
  • Table 146 provides 10 compounds of formula:
  • Table 147 provides 10 compounds of formula:
  • Table 149 provides 10 compounds of formula:
  • Table 150 provides 10 compounds of formula:
  • Table 154 provides 10 compounds of formula:
  • Table 156 provides 10 compounds of formula:
  • the compounds of the invention may be made in a variety of ways.
  • a base such as triethylamine or
  • thiophenols are known compounds or may be prepared by known methods.
  • Benzofurans may be made from ortho-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
  • Indoles may be made from ortho-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 N (where B, D, E, Z, R 1 R 3 , R 4 , R 5 , R 6 and R 51 are as defined above in relation to formula I) may be prepared by reacting a compound of formula ⁇ (where B, D, E, Z, R 1 R 3 , R 4 , R 5 , R 6 and R 51 are as defined above in relation to formula I) 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(para-tolyl)-l,3-dithia-2,4-diphosphetane-2,4- disulfide (Davy reagent p
  • Compounds of formula VI may be made from compounds of formula N ⁇ (where B, D, E, Z, R 1 R 3 , R 4 , R 5 , R 6 and R 51 are as defined above in relation to formula I) by treatment with ⁇ , ⁇ -dimethylformamide dialkyl acetal in a suitable solvent such as toluene or N,N-dimethylformamide. Frequently this reaction produces a mixture of E and Z isomers which are sometimes separable by standard techniques such as flash column chromatography and recrystallisation.
  • Compounds LI or N may be treated with an electrophile (such as an alkyl halide, dialkyl sulfate, chloromethylether, trialkyloxonium salt or alkyl chloroformate) optionally in the presence of a base.
  • an electrophile such as an alkyl halide, dialkyl sulfate, chloromethylether, trialkyloxonium salt or alkyl chloroformate
  • An alternative method for making compounds LI involves the acylation of a compound of formula XI (where A, D, E, R 1 , R 3 , R 4 , R 5 and R 51 are as defined above in relation to formula I) followed by cyclisation, optionally in the presence of an acidic catalyst such as para- toluene sulfonic acid in a suitable solvent such as xylene or 1,1,2,2- tetrachloroethane.
  • an acidic catalyst such as para- toluene sulfonic acid in a suitable solvent such as xylene or 1,1,2,2- tetrachloroethane.
  • Compounds XI (where A, D, E, R 1 , R 3 , R 4 , R 5 and R 51 are as defined above in relation to formula I) may be prepared from compounds XLI (where A, D, E, R 1 , R 3 , R 4 , R 5 and R 51 are as defined above in relation to formula I) by a sequential procedure of nitration followed by reduction, using known procedures.
  • compounds XLI may be prepared by the dealkylation of compounds XLLl (where A, D, E, R 1 , R 3 , R 4 , R 5 and R 51 are as defined above in relation to formula I) where R is an alkyl group (especially methyl) or substituted alkyl group (especially benzyl) under standard conditions.
  • Compounds XLH (where A, D, E, R 1 , R 3 , R 4 , R 5 and R 51 are as defined above in relation to formula I) may be prepared from compounds m (where D, E, R 1 , and R 51 are as defined above in relation to formula I) by processes analogous to those already described for compounds LI.
  • Heteroaryl ⁇ -oxides can be prepared using 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. Lnsects, 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. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects), Trialeurodes 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
  • Alternaria spp. on vegetables for example carrots), oil-seed rape, apples, tomatoes, potatoes, cereals (for example wheat) and other hosts
  • Nenturia spp. including Nenturia 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.
  • viruses for example Polymyxa graminis on cereals as the
  • 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 0. lg tolOkg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to lkg per hectare.
  • a compound of formula (I) When used in a seed dressing, a compound of formula (I) is used at a rate of 0.000 lg to lOg (for example 0.001 g 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).
  • Dispersible Concentrates 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 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 SOLNESSO 100, SOLNESSO 150 and SOLNESSO 200; SOLNESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), ⁇ -alkylpyrrolidones (such as ⁇ -methylpyrrolidone or ⁇ -octylpyrrolidone), dimethyl amides of fatty acids (such as Q-Qo fatty acid dimethylamide) and chlorinated hydrocarbons.
  • aromatic hydrocarbons such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLNESSO 100, SOLNESSO 150 and SOLNESSO 200; SOLNESSO is a Registered Trade Mark
  • ketones such as
  • 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.
  • 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 n-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 (L) 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- isopropyl- and tri-isopropyl-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
  • 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).
  • Suitable formulation types include granules of fertiliser.
  • the mixtures suitably contain up to 25% by weight of the compound of formula (L).
  • 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
  • Chloronicotinyl compounds such as imidacloprid, thiacloprid, acetamiprid, nitenpyram or thiamethoxam;
  • Diacylhydrazines such as tebufenozide, chromafenozide or methoxyfenozide;
  • Diphenyl ethers such as diofenolan or pyriproxifen; o) Indoxacarb; p) Chlorfenapyr; or q) Pymetrozine.
  • 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 (S SF- 129), 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethyl- benzimidazole-1-sulphonamide, ⁇ -[N-(3-chloro-2,6-xylyl)-2-methoxy- acetamido]- ⁇ -butyrolactone, 4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-l- sulfonamide (IKF-916, cyamidazosulfamid), 3-5-dichloro-N-(3-chloro-l-ethyl-l-methyl-2- oxopropyl)-4-methylbenzamide (RH-7281, zoxamide),
  • 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 PLXTM.
  • 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
  • EXAMPLE 2 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.
  • 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
  • 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.
  • PCRO data are set out in the table below.

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; 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 ring containing E and D; Y is O, S or NR13; Z is O, S or NR14; n is 0 or 1; and A and the various R groups are defined organic radicals; their preparation and use and compositions containing them.

Description

AZINE DERIVATIVES AS PESTICIDES
The present invention relates to 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, WO96/08475, WO97/18198, WO98/02424 and WO98/05670. The present invention provides a compound of formula (I):
Figure imgf000003_0001
wherein n is 0 or 1; A is optionally substituted Ci-6 alkylene, optionally substituted C2-6 alkenylene, optionally substituted C2-6 alkynylene, optionally substituted cycloalkylene, optionally substituted -6 alkyleneoxy, optionally substituted oxy(C1-6)alkylene, optionally substituted d-6 alkylenethio, optionally substituted thio(Ci_6)alkylene, optionally substituted d-6 alkyleneamino, optionally substituted amino(C1-6)alkylene, optionally substituted [C1-6 alkyleneoxy(C1-6)alkylene], optionally substituted [ -6 alkylenethio(C1-6)alkylene], optionally substituted [Q-6 alkylenesulfιnyl(C1-6)alkylene], optionally substituted [Q-6 alkylenesulfonyl(C1-6)alkylene] or optionally substituted [Q-6 alkyleneamino(C1-6)alkylene]; B is N, N-oxide or CR18;
D is CR8=CR9, CR8=N, N=CR9, CR8=N(O) or N(O)=CR9;
E is N, N-oxide or CR12;
M is OC(=Y), N(R51)C(=Y), N=C(OR52), N=C(SR53) or N=C(NR54R55) where O or N is the atom of attachment to the ring containing E and D; 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 C2-6 alkynyl, optionally substituted Q-6 alkoxy, optionally substituted Q-6 alkylthio, optionally substituted C -7 cycloalkyl, cyano, nitro or SF5; R51 is hydrogen, optionally substituted Q-10 alkyl, optionally substituted [C -6 alkenyl(Q-6)alkyl], optionally substituted [C2-6 alkynyl (Q-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted Q-io alkylcarbonyl, optionally substituted Q-io alkoxycarbonyl, formyl, optionally substituted Q-10 alkylaminocarbonyl, optionally substituted di(C1-1o)alkylaminocarbonyl, 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; R52 is optionally substituted Q-10 alkyl, optionally substituted [C2- alkenyl(Q-6)- alkyl], optionally substituted [C2-6 alkynyl(Cj-6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted Q-to alkylcarbonyl, optionally substituted Q-ι0 alkoxycarbonyl, formyl, optionally substituted C^o alkylaminocarbonyl, optionally substituted di(Q-ιo)- alkylaminocarbonyl, amino, optionally substituted Q-6 alkylamino, optionally substituted di(Cι.6)alkylamino, optionally substituted phenoxycarbonyl, tri(Q-4)alkylsilyl, aryldi- (Q- )alkylsilyl, (Q-^alkyldiarylsilyl or triarylsilyl;
R53 is optionally substituted Q-io alkyl, optionally substituted [C2_6 alkenyl(Q-6)- alkyl], optionally substituted [C2-6 alkynyl(C1.6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted Q-10 alkylcarbonyl, optionally substituted Q-io alkoxycarbonyl, optionally substituted Q-10 alkylaminocarbonyl, optionally substituted di(Q- ^alkylaminocarbonyl or optionally substituted phenoxycarbonyl);
R54 and R55 are, independently optionally substituted Q-io alkyl, optionally substituted Q-6 alkoxy, optionally substituted [C2-6 alkenyl(Q-6)alkyl], optionally substituted [C2-6 alkynyl(Q-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted Q.io alkylcarbonyl, optionally substituted C^o alkoxycarbonyl, formyl, optionally substituted -10 alkylaminocarbonyl, optionally substituted di(Q-ιo)alkylaminocarbonyl, hydroxy, amino, optionally substituted Q_6 alkylamino, optionally substituted di(Q-6)alkylamino, 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 Cι-6 alkylcarbonyl, optionally substituted Q-6 alkoxycarbonyl or SF5;
R6 is hydrogen, halogen, cyano, optionally substituted Q_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 Q-20 alkoxycarbonyl, optionally substituted C1-2o alkylcarbonyl, aminocarbonyl, optionally substituted Q. o 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-2o alkylsulfinyl, optionally substituted Q-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 Q-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl or optionally substituted Q-6 alkoxy;
R12 is hydrogen, halogen, optionally substituted Q-6 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 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 Q- 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(C1-6)alkyl, optionally substituted (C2-6)alkynyl(Cι-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 Q-6 alkylcarbonylamino, optionally substituted Q-6 alkoxycarbonylamino, optionally substituted Ci- 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(Q_6)alkyl], optionally substituted [C2-6 alkynyl(Q-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted [C3-7 cycloalkyl(Q-6)alkyl], Q-6 alkoxy(Q-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; R18 is hydrogen, halogen, nitro, cyano, optionally substituted Q-8 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted C3-7 cycloalkyl, optionally substituted Ci- 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-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 Q-6 alkyl groups; R26 is hydrogen, optionally substituted Q_20 alkyl, optionally substituted [C2-20 alkenyl(Q-6)alkyl], optionally substituted [C -20 alkynyl(Q-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted [heterocyclyl(Q-6)alkylCH=N] or di(Q-6)alkylC=N; n
R and R are, independently, hydrogen, optionally substituted Q-2o alkyl, optionally substituted C3-7 cycloalkyl, optionally substituted [C2-2o alkenyl(Q-6)alkyl], optionally substituted [C2_ o alkynyl(Q-6)alkyl], optionally substituted Q- o alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted Q- o alkylcarbonyl, optionally substituted Q- o alkylsulfonyl or optionally substituted phenylsulfonyl;
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-2)alkyl or optionally substituted Q-20 alkyl provided that when E is CR12, Z is O and M is N(R51)C(=O) or N(R51)C(=S), then D is not CR8=CR9 and when E is CR12, Z is S, B is CR18 and M is N(R51)C(=O) or N(R51)C(=S), then D is not CR8=CR9.
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, Q-6 alkyl, Ci-6 haloalkyl, Q-6 cyanoalkyl, Q-6 alkoxy(Q-6)alkyl, Q-6 alkoxy, cyano, =O, =NR33, =CR34R35; wherein R33 is Q-6 alkyl, Q-6 haloalkyl, OR36 or R37R38N; R36 is C e alkyl, Q-6 haloalkyl or phenyl(Q-2)alkyl; R37 and R38 are, independently, hydrogen, Q-8 alkyl, C3- cycloalkyl, C2-6 alkenyl(Cι-6)alkyl, C2-6 alkynyl(Cι-6)alkyl, C2-6 haloalkyl, Q-6 alkoxy(Q-6)alkyl, Q-6 alkoxycarbonyl(C1_6)alkyl, carboxy(Q-6)alkyl, phenyl(Q-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 Q-6 alkyl groups; R34 and R35 are, independently, hydrogen, Q-6 alkyl, Q-6 alkoxy, Q- haloalkyl, cyano, Q-6 alkoxycarbonyl, Q-6 alkylcarbonyl or R39R40N; R39 and R40 are, independently, hydrogen, Q-8 alkyl, C3-7 cycloalkyl, C2-6 alkenyl(Q.6)alkyl, C2-6 alkynyl(Q-6)alkyl, C2-6 haloalkyl, Ci-6 alkoxy(Q-6)alkyl, Q-6 alkoxycarbonyl(Q-6)alkyl, carboxy(Q-6)alkyl, phenyl(Ci-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 Ci-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, Q-6 alkyl, Q.6 haloalkyl, Q-6 cyanoalkyl, Q-6 alkoxy(Q-6) alkyl, Q-6 alkoxy, cyano, =O, =NR33 and
=CR34R35, wherein R33 is Q-6 alkyl, Q-6 haloalkyl, OR36 or R37R38N; where R34 and R35 are, independently, hydrogen, Q-6 alkyl, Q-6 alkoxy, Q-6 haloalkyl, cyano, Q-6 alkoxycarbonyl, Q-6 alkylcarbonyl or R39R40N; R36 is Q-6 alkyl, Q-6 haloalkyl or phenyl(Q- )alkyl; R37 and R38 are, independently, hydrogen, Q-8 alkyl, C3_7 cycloalkyl, C2-6 alkenyl(Ci-6)alkyl, C2-6 alkynyl(Ci-6)alkyl, C2-6 haloalkyl, Ci-6 alkoxy(Ci-6)alkyl, Q-6 alkoxycarbonyl(Cι-6)alkyl, carboxy(Ci-6)alkyl or phenyl(Ci-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 Ci-6 alkyl groups; R39 and R40 are, independently, hydrogen, Q-8 alkyl, C3-7 cycloalkyl, C2-6 alkenyl(Q-6)alkyl, C2-6 alkynyl(Q_6)alkyl, C2-6 haloalkyl, Q-6 alkoxy(Q-6)alkyl, Q-6 alkoxycarbonyl(Q-6)alkyl, carboxy(Q-6) alkyl or phenyl(Q-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 Q-6 alkyl groups.
Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, wo-propyl, n-butyl, sec-butyl, iso-buty\, tert-butyl or neσ-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 Q-6 alkyl or halogen), C5-7 cycloalkenyl (which itself may be optionally substituted with Q-6 alkyl or halogen), hydroxy, Q-io alkoxy, Q-10 alkoxy(Q-10)alkoxy, tri(Q-4)alkylsilyl(Q-6)alkoxy, Ci.6 alkoxycarbonyl(Q-io)alkoxy, .in haloalkoxy, Q-io deuteroalkoxy, aryl(Q-4)alkoxy (where the aryl group may be further optionally substituted), C3-7 cycloalkyloxy (where the cycloalkyl group may be optionally substituted with Ci-6 alkyl or halogen), Q-io alkenyloxy, Q-io alkynyloxy, SH, Q-10 alkylthio, Ci.10 haloalkylthio, aryl(C1-4)alkylthio (where the aryl group may be further optionally substituted), C3-7 cycloalkylthio (where the cycloalkyl group may be optionally substituted with Q-6 alkyl or halogen), tri(Q-4)alkylsilyl(C1-6)alkylthio, arylthio (where the aryl group may be further optionally substituted), Ci-6 alkylsulfonyl, Q-6 haloalkylsulfonyl, Q-6 alkylsulfinyl, Q-6 haloalkylsulfinyl, arylsulfonyl (where the aryl group may be further optionally substituted), tri(Q-4)alkylsilyl, aryldi(Q-4)alkylsilyl, (Q-4)alkyldiarylsilyl, triarylsilyl, Q-io alkylcarbonyl, HO C, Q-io alkoxycarbonyl, aminocarbonyl, Q-6 alkylaminocarbonyl, di(Q-6 alkyl)aminocarbonyl, N-(Q-3 alkyl)-N-(Q.3 alkoxy)aminocarbonyl, Cι-6 alkylcarbonyloxy, arylcarbonyloxy (where the aryl group may be further optionally substituted), di(Cι_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 Q-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 Q-6 alkyl or halogen), amino, Q-6 alkylamino, di(Q-6)alkylamino, alkylcarbonylamino, N-alkylcarbonyl-N-alkylamino.
One group of optional preferred substituents for alkyl include one or more of halogen, nitro, cyano, HO2C, Q-io alkoxy (itself optionally substituted by Q-io alkoxy), aryl(Q-4)- alkoxy, Q-io alkylthio, Q-io alkylcarbonyl, Q_ιo alkoxycarbonyl, Q- alkylaminocarbonyl, di(Q-6 alkylaminocarbonyl, (Q-6)alkylcarbonyloxy, optionally substituted phenyl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl, heterocyclyloxy, C3-7 cycloalkyl (itself optionally substituted with (Q-6)alkyl or halogen), C3-7 cycloalkyloxy, C5-7 cycloalkenyl, Q-6 alkylsulfonyl, Q- alkylsulfinyl, tri(Q-4)alkylsilyl, tri(Q- )alkylsilyl(Q-6)- alkoxy, aryldi(Q- )alkylsilyl, (Q-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 Q-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 Ci-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 Q-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 Q-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-, Ci-6 alkyl, Q-6 haloalkyl, Ci-6 alkoxy(Q-6)alkyl, C2-6 alkenyl, C2_6 haloalkenyl, C2-6 alkynyl, C3-7 cycloalkyl (which itself may be optionally substituted with Q-e alkyl or halogen), C5-7 cycloalkenyl
(which itself may be optionally substituted with Q_6 alkyl or halogen), hydroxy, Q-ι0 alkoxy, Q-io alkoxy(Q-io)alkoxy, tri(Q- )alkylsilyl(Q-6)alkoxy, Q-6 alkoxycarbonyl(Q-i0)alkoxy, Q-io haloalkoxy, Q-io deuteroalkoxy, aryl(Q-4)alkoxy (where the aryl group may be further optionally substituted), C3-7 cycloalkyloxy (where the cycloalkyl group may be optionally substituted with Q-6 alkyl or halogen), Q-io alkenyloxy, Q-10 alkynyloxy, SH, .io alkylthio, Q-io haloalkylthio, aryl(Q-4)alkylthio (where the aryl group may be further optionally substituted), C3.7 cycloalkylthio (where the cycloalkyl group may be optionally substituted with Q-6 alkyl or halogen), tri(Q- )alkylsilyl(Q-6)alkylthio, arylthio (where the aryl group may be further optionally substituted), Q-6 alkylsulfonyl, Q-6 haloalkylsulfonyl, Q-6 alkylsulfinyl, Q-6 haloalkylsulfinyl, arylsulfonyl (where the aryl group may be further optionally substituted), tri(Q- )alkylsilyl, aryldi(Q-4)alkylsilyl, (Q-4)alkyldiarylsilyl, triarylsilyl, Q-io alkylcarbonyl, HO2C, Q-io alkoxycarbonyl, aminocarbonyl, Q_6 alkylaminocarbonyl, di(Q-6 alkylaminocarbonyl, N-(Q_3 alkyl)-N-(Q_3 alkoxy)amino- carbonyl, Q-6 alkylcarbonyloxy, arylcarbonyloxy (where the aryl group may be further optionally substituted), di(Q-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 Q-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 Q-6 alkyl or halogen), amino, Q-6 alkylamino, di(Q-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, Q-6 alkyl, Q-6 haloalkyl, Q-6 alkoxy(Q-6)alkyl, Q-6 alkoxy, Q-6 haloalkoxy, Q-6 alkylthio, Ci-6 haloalkylthio, Q-6 alkylsulfinyl, Q-6 haloalkylsulfinyl, Q-6 alkylsulfonyl, Ci-6 haloalkylsulfonyl, -6 alkenyl, C2-6 haloalkenyl, -6 alkynyl, Q-7 cycloalkyl, nitro, cyano, CO2H, Ci-6 alkylcarbonyl, Q-6 alkoxycarbonyl, R41R42N or R43R 4NC(O) wherein R41, R42, R43 and R44 are, independently, hydrogen or Q-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 Q-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 (Q-6)alkyl groups. In one particular aspect the present invention provides a compound of formula (LA) which are compounds of formula (I) where B, D, E, M, Z and n have the values as defined for formula (I) above and R1 is hydrogen, halogen, optionally substituted Q-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted -6 alkynyl, optionally substituted Ci-6 alkoxy, optionally substituted Ci-6 alkylthio, optionally substituted C3-7 cycloalkyl, cyano, nitro or SF5; R12 is hydrogen, halogen, optionally substituted Q-6 alkyl, optionally substituted Q-6 alkenyl, optionally substituted C -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, R32ON=C(R30), optionally substituted Q-6 alkylcarbonyl, optionally substituted Ci-6 alkoxycarbonyl or SF5; 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 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, Ci-6 haloalkyl or halogen; R3, R4 and R5 are, independently, hydrogen, halogen, optionally substituted Ci-6 alkyl, optionally substituted Ci-6 alkoxy, optionally substituted Q-6 alkylthio, optionally substituted Ci-6 alkylsulfinyl, optionally substituted Q_6 alkylsulfonyl, cyano, nitro, optionally substituted Q-6 alkylcarbonyl, optionally substituted Q-6 alkoxycarbonyl or SF5;
R6 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 Q-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 alkylheteroarylaminocarbonyl, optionally substituted diheteroarylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, R O, HS, optionally substituted Q-2o alkylthio, optionally substituted Q-2o alkylsulfinyl, optionally substituted Q-2o alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl, R28R29N or R31ON=C(R27); A is optionally substituted Q-6 alkylene, optionally substituted -6 alkenylene, optionally substituted -6 alkynylene, optionally substituted Ci-6 alkylenoxy, optionally substituted oxy(Q-6)alkylene, optionally substituted Q-6 alkylenethio, optionally substituted thio(Q-6)alkylene, optionally substituted Ci-6 alkylenamino, optionally substituted amino(Q-6)alkylene, optionally substituted [Q-6 alkyleneoxy(Q-6)alkylene], optionally substituted [Q-6 alkylenethio(Q-6)alkylene], optionally substituted [Ci-6 alkylenesulfinyl(Q-6)alkylene], optionally substituted [Q-6 alkylenesulfonyl(Ci-6)alkylene] or optionally substituted [Q-6 alkyleneamino(Q-6)alkylene]; R13 is hydrogen, cyano, nitro, optionally substituted Q-6 alkyl, optionally substituted C3-7 cycloalkyl, optionally substituted (Q-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 Ci- alkylamino, optionally substituted di(Q-6)alkylamino, optionally substituted Ci-6 alkylcarbonylamino, optionally substituted Ci-6 alkoxycarbonylamino, optionally substituted Ci-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 Ci-6 acyloxy; R14 is hydrogen, cyano, optionally substituted Q-8 alkyl, optionally substituted [Q-6 alkenyl(Q-6)alkyl], optionally substituted [Q-6 alkynyl(Q-6)- alkyl], optionally substituted Q-7 cycloalkyl, optionally substituted [C3-7 cycloalkyl(Q-6)- alkyl], Q-6 alkoxy(Ci-6)alkyl, optionally substituted Q-6 alkoxycarbonyl, optionally substituted Q-6 alkylcarbonyl, optionally substituted Ci-6 alkylaminocarbonyl, optionally substituted di(Q-6)alkylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl; R18 is hydrogen, halogen, nitro, cyano, optionally substituted Q-8 alkyl, optionally substituted Q-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted Q-7 cycloalkyl, optionally substituted Q- alkoxycarbonyl, optionally substituted Ci-6 alkylcarbonyl, optionally substituted Q-6 alkylaminocarbonyl, optionally substituted di(Q-6)alkylaminocarbonyl, optionally substituted phenyl or optionally substituted heteroaryl; and R51 is hydrogen, optionally substituted Q-10 alkyl, optionally substituted [Q-6 alkenyl- (Q-6)alkyl], optionally substituted [Q-6 alkynyl(Q-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted Q-io alkylcarbonyl, optionally substituted Q-10 alkoxycarbonyl, formyl, optionally substituted Q-io alkylaminocarbonyl, optionally substituted di(Q-ιo)alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted Q-6 alkylthio, optionally substituted Ci-6 alkylsulfinyl, optionally substituted Ci-6 alkylsulfonyl, optionally substituted Ci-6 arylthio, optionally substituted Ci-6 arylsulfinyl, optionally substituted Q-6 arylsulfonyl or R20R21NS provided that when E is CR12 and M is N(R51)C(=O) or N(R51)C(=S), then D is not CR8=CR9.
In a further aspect the present invention also provides a compound of formula (LB) which are compounds of formula (I) where A, B, M, Z, n, R1, R3, R4, R5, and R6 have the values as defined for formula (I) above and D is CR8=CR9, CR8=N or N=CR9, where R8 and R9 are as defined in relation to formula (I) above and E is N or CR12 where R12 is as defined in relation to formula (I) above.
In yet another aspect the present invention provides a compound of formula (!')
Figure imgf000014_0001
where A, B, D, E, M, Z, R1, R3, R4, R5, and R6 have the values as defined for formula (I) above. The invention also provides a compound of formula (LA') which is a compound of formula I' wherein A, B, D, E, M, Z, R1, R3, R4, R5, and R6 have the values as defined for formula (LA) above. There is further provided a compound of formula (LB') which is a compound of formula V wherein A, B, D, E, M, Z, R1, R3, R4, R5, and R6 have the values as defined for formula (LB) above.
Preferably 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: More preferably A is Q-4 alkylene -C(O)- or Q-4 alkyleneoxy; or alternatively is C1- alkylene (optionally substituted by Cι-3 alkyl).
Even more preferably A is CH2, CH(CH3) or CH2O.
Most preferably A is CH2 or is CH(CH3).
M is preferably N(R51)C(=Y) or N=C(SR53) where N is the atom of attachment to the ring containing E and D; alternatively it may be N=C(OR52) where N is the atom of attachment to the ring containing E and D.
More preferably M is N(R 1)C(=O) where N is the atom of attachment to the ring containing E and D; and R51 is hydrogen, Q-6 alkyl, Ci-6 alkoxy (Ci-6 )alkyl, benzyloxymethyl or benzoyloxymethyl. M is even more preferably NR51C(=O), where where N is the atom of attachment to the ring containing E and D and R51 is hydrogen, Q-4 alkyl, Q- alkoxy (Q-- alkyl, benzyloxymethyl or benzoyloxymethyl.
Preferably Z is O or S, more preferably O.
Preferably B is N. A preferred value for D is CR8=CR9.
Preferably E is N or CR12 where R12 is hydrogen, halogen, Ci-6 alkyl, Q-6 haloalkyl, Ci-6 alkoxy, Q-6 haloalkoxy, Ci-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 Ci-6 alkyl Q-6 haloalkyl or halogen.
More preferably E is N or CR12 where R12 is hydrogen, halogen, Q-e alkyl, Q-6 haloalkyl, Q-6 alkoxy, Q-6 haloalkoxy, Q-6 alkoxy (Q-6)alkyl, Q-6 alkylthio or SF5. Preferably R8 and R9 are independently selected from hydrogen, halogen, cyano, nitro, Ci- alkyl, Q-6 haloalkyl, Q-6 alkoxy(Q_6)alkyl, -6 alkenyl, -6 haloalkenyl, -6 alkynyl, Q-6 alkoxy or Q-6 haloalkoxy.
More preferably R and R are independently selected from hydrogen, halogen, cyano, nitro, Q-6 alkyl, Q-6 haloalkyl, -6 alkenyl, -6 haloalkenyl, -6 alkynyl, Q-6 alkoxy, Q-6 haloalkoxy.
Yet more preferably R and R are independently selected from hydrogen, halogen, Q-6 alkyl, Q-6 haloalkyl, Q-6 alkenyl, -6 alkynyl, Ci-6 alkoxy or Q-6 haloalkoxy.
Most preferably R and R are independently selected from hydrogen or Q-3 alkyl.
It is preferred that R51 is hydrogen, Q-io 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 Q-4 alkoxycarbonyl), -6 alkenyloxy(C1-4)alkyl, -6 alkynyloxy(Q-4)alkyl, benzyloxy(Q--t)alkyl (where the phenyl ring may be optionally substituted with halogen or Q^ alkyl), C3-7 cycloalkyl (Q-4)alkyl, heteroaryl(Q-3)alkyl (where the heteroaryl group may be optionally substituted with halogen), tri(Q- )alkylsilyl(Q-6)alkyl, -6 alkenyl(Q-6)alkyl (especially allyl), Q-6 haloalkenyl(Q-6)alkyl, Q^ alkoxycarbonyl(C2-6)alkenyl(Q-6)alkyl, Q-6 alkynyl(Q-6)alkyl, tri(Q-4)alkylsilyl(C2-6)alkynyl(Q-6)alkyl or Q-io alkylcarbonyl.
It is more preferred that R51 is hydrogen, Ci-6 alkyl, Ci-6 alkylcarbonyloxymethyl, benzoyloxymethyl (where the phenyl ring may be optionally substituted with halogen or Q^ alkyl), Q-6 alkoxymethyl, -6 alkenyloxymethyl, Q-6 alkynyloxymethyl, benzyloxymethyl (where the phenyl ring may be optionally substituted with halogen or Q-4 alkyl), -6 alkynyl(Q-6)alkyl (especially propargyl) or Q-io alkylcarbonyl.
Even more preferably R51 is hydrogen, Ci-6 alkyl, Q-6 alkylcarbonyloxymethyl, Q-6 alkoxymethyl, benzyloxymethyl or benzoyloxymethyl. YYeett mmoorree pprreeffeerraabbllyy RR5511 iiss hhyyddrrooggeenn,, QQ--66 aallkkyyll, Ci-6 alkoxy (Q^alkyl, benzyloxymethyl or benzoyloxymethyl; or is Q-6 alkylcarbonyloxymethyl Most preferably R51 is hydrogen, Q- alkyl, Ci-6 alkylcarbonyloxymethyl or Q-4 alkoxymethyl.
Preferably R52 and R53 are independently Q-io alkyl, Q-io haloalkyl, -6 alkenyl- (Cι-6)alkyl, C2-6 alkynyl (Q-6)alkyl, C3-7 cycloalkyl, Ci-6 alkylamino, di(Q-6)alkylamino, phenyl(Cι-4)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Q-6 haloalkyl, Q-6 alkoxy or Q-6 haloalkoxy),
Even more preferably R52 and R53 are independently Q-6 alkyl, Q_ haloalkyl, Q-6 alkenyl(Q-6)alkyl, C2-6 alkynyl(Ci-6)alkyl, benzyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Q-6 haloalkyl, Q-6 alkoxy or Q-6 haloalkoxy). R1 is preferably hydrogen, halogen, Q-6 alkyl, Q-6 alkenyl, -6 alkynyl, Q-6 haloalkyl, Q-6 alkoxy(Q-6)alkyl, C3-7 cycloalkyl(Q-4)alkyl, Q-6 cyanoalkyl, Q-6 alkoxy, Q_6 haloalkoxy, Q-6 alkylthio, Q-6 haloalkylthio, - cycloalkyl, cyano, nitro or SF5.
More preferably R1 is hydrogen, halogen, Q-6 alkyl, -6 alkenyl, Q-6 haloalkyl, Q-6 alkoxy, Q-6 haloalkoxy, Q-6 alkylthio, Q-6 haloalkylthio, -6 cycloalkyl, cyano, nitro or SF5.
Even more preferably R1 is hydrogen, halogen, Q-6 alkyl, -6 alkenyl, Q-6 haloalkyl, Ci-6 alkoxy, Q-6 haloalkoxy, Ci-6 alkylthio, Ci-6 haloalkylthio, Q-6 cycloalkyl, Q-6 alkoxy(Q-6)alkyl, cyano or nitro.
Most preferably R1 is halogen, Q-6 alkyl, Q.6 haloalkyl, Q-6 alkoxy or Ci-6 haloalkoxy.
Preferably R3, R4 and R5 are, independently, hydrogen, halogen, Ci-6 alkyl, Q-6 haloalkyl, Ci-6 alkylthio, Q-6 haloalkylthio, Ci-6 alkoxy, Ci-6 haloalkoxy, Q-6 alkylsulfinyl, Ci-6 haloalkylsulfinyl, Q-6 alkylsulfonyl, Q-6 haloalkylsulfonyl, cyano, nitro, Q-6 alkylcarbonyl, Ci-6 alkoxycarbonyl or SF5. More preferably R3, R4 and R5 are independently hydrogen, Q-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-8 haloalkyl, Q-8 cyanoalkyl, -6 alkenyl, Q-6 alkynyl, Q-7 cycloalkyl, Q-7 halocycloalkyl, Q-7 cyanocycloalkyl, Q-3 alkyl(Q-7)cycloalkyl, Q-3 alkyl(Q-7)halocycloalkyl, -6 cycloalkenyl, Q-7 cycloalkyl(Q-6)alkyl, -6 cycloalkenyl(Q-6)alkyl, Q-6 haloalkenyl, Q-6 cyanoalkenyl, Q-6 alkoxy(Q-6)alkyl, C3-6 alkenyloxy(Cι-6)alkyl, C3-6 alkynyloxy(Cι-6)alkyl, aryloxy(Q-6)alkyl, Cι-6 carboxyalkyl, Q-6 alkylcarbonyl(Ci-6)alkyl, C2-6 alkenylcarbonyl(Cι-6)alkyl, C2_6 alkynylcarbonyl(Q-6)alkyl, Q-6 alkoxycarbonyl(Q-6)alkyl, C3-6 alkenyloxycarbonyl(Q_6)alkyl, -6 alkynyloxycarbonyl(Cι-6)alkyl, aryloxycarbonyl(Q_6)alkyl, Q-e alkylthio(Q-6)alkyl, Ci-6 alkylsulfinyl(Cι-6)alkyl, Ci-6 alkylsulfonyl(Q-6)alkyl, aminocarbonyl(Q-6)alkyl, aminocarbonyl(C2-6)alkenyl, aminocarbonyl(Q-6)alkynyl, Cι-6 alkylaminocarbonyl(Ci-6)alkyl, di(Q-6)alkylaminocarbonyl(Cι-6)alkyl, Q-6 alkylaminocarbonyl(Q-6)alkenyl, di(Q-6)- alkylaminocarbonyl(Cι-6)alkenyl, alkylaminocarbonyl(Q_6)alkynyl, di(Q-6)alkylamino- carbonyl(Ci-e)alkynyl, phenyl (optionally substituted by halo, nitro, cyano, Q-6 alkyl, Q-6 haloalkyl, Q-6 alkoxy or Ci-6 haloalkoxy) ,_phenyl(Q-4)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q-e alkyl, Q-6 haloalkyl, Q-6 alkoxy or Q-6 haloalkoxy), phenyl(Q-4)alkenyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Q-6 haloalkyl, Q-6 alkoxy or Q-6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Q-6 alkyl, Ci-6 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), 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(Q- )alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q-6 alkyl, Q-6 haloalkyl, Q-6 alkoxy or Q-e haloalkoxy), R26O, Q-8 alkylthio, R28R29N or R31ON=C(R27); where R26 is Q-8 alkyl, Ci-6 haloalkyl; R27 is Q-6 alkyl, Q-6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Ci-6 haloalkyl, Q-6 alkoxy or Q-6 haloalkoxy); R27 is Ci-6 alkyl, Q-6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, Q-6 alkyl, Q-6 haloalkyl, Q.6 alkoxy or Ci-6 haloalkoxy);
R28 and R29 are, independently, hydrogen, Q_8 alkyl, Q-7 cycloalkyl, -6 alkenyl, -6 alkynyl, Q-7 cycloalkyl(Q- )alkyl, Q-6 haloalkyl, Q-6 alkoxy(Q-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; 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, Ci-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- (Ci-6)alkyl, C5-6 cycloalkenyl(Cι-6)alkyl, Q-6 alkoxy(Q-6)alkyl, C3-6 alkenyloxy(Ci-6)alkyl, C3-6 alkynyloxy(Ci-6)alkyl, aryloxy(Q-6)alkyl, Q-6 carboxyalkyl, Q-6 alkylcarbonyl- (Q.6)alkyl, C2-6 alkenylcarbonyl(Ci-6)alkyl, C2-6 alkynylcarbonyl(Q-6)alkyl, Q-6 alkoxycarbonyl(Ci-6)alkyl, C3-6 alkenyloxycarbonyl(Q-6)alkyl, -6 alkynyloxycarbonyl-
(Cι-6)alkyl, aryloxycarbonyl(Q-6)alkyl, Ci-6 alkylthio(Q-6)alkyl, Ci-6 alkylsulfinyl(Q-6)alkyl, Q-6 alkylsulfonyl(Ci-6)alkyl, aminocarbonyl(Q-6)alkyl, Ci-6 alkylaminocarbonyl(Ci-6)alkyl, di(Cι-6)alkylaminocarbonyl(Q-6)alkyl, phenyl(Cι-4)alkyl (wherein the phenyl group may be optionally substituted by halo, nitro, cyano, Q-6 alkyl, Q-6 haloalkyl, Ci-6 alkoxy or Q-6 haloalkoxy), heteroaryl (Q-4)alkyl (wherein the heteroaryl group may be optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Q-6 haloalkyl, Q-6 alkoxy or Ci-6 haloalkoxy), heterocyclyl (Q-4)alkyl (wherein the heterocyclyl group may be optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q-6 haloalkyl, Ci-6 alkoxy or Q-6 haloalkoxy), Q-6 alkenyl, Q-6 haloalkenyl, Q-6 cyanoalkenyl, -6 cycloalkenyl, aminocarbonyl(Q-6)alkenyl, Q-6 alkylaminocarbonyl(Q-6)alkenyl, di(Q-6)alkylaminocarbonyl(Q-6)alkenyl, phenyl(Q-4)alkenyl, (wherein the phenyl group may be optionally substituted by halo, nitro, cyano, Q-6 alkyl, Ci-6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy), Q-6 alkynyl, aminocarbonyl(Q-6)alkynyl, alkylaminocarbonyl(Q-6)alkynyl, di(Q-6)alkylamino- carbonyl(Q-6)alkynyl, Q-7 cycloalkyl, Q-7 halocycloalkyl, Q-7 cyanocycloalkyl, Q-3 alkyl(Q-7)cycloalkyl, Q-3 alkyl(Q-7)halocycloalkyl, phenyl (which may be optionally substituted by halo, nitro, cyano, Q-6 alkyl, Ci-6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy), heteroaryl (which may be optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Ci-6 haloalkyl, Q-6 alkoxy or Q-6 haloalkoxy), heterocyclyl (which may be optionally substituted by halo, nitro, cyano, Q-6 alkyl, Ci-6 haloalkyl, Q-6 alkoxy or Ci-6 haloalkoxy), Q-8 alkylthio, R26O, R28R29N or R31ON=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, Ci-6 alkoxy or Ci-6 haloalkoxy), Q-6 alkyl or Ci-6 haloalkyl; R28 and R29 are, independently, hydrogen, Q-8 alkyl, Q-7 cycloalkyl(Q-4)alkyl, Q-6 haloalkyl, Q-6 alkoxy(Ci-6)alkyl, Q-7 cycloalkyl, -6 alkenyl, Q-6 alkynyl or Q-6 alkoxycarbonyl; and R31 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 C1-8 alkyl, Q-8 haloalkyl, Ci-8 cyanoalkyl, Q-7 cycloalkyl, Cι-3 alkyl (C3-7) cycloalkyl, Q-6 alkoxy (Q-6) alkyl, heterocyclic (optionally substituted by halo, nitro, cyano, Q-6 alkyl, Ci-6 haloalkyl, Q-6 alkoxy or Q-6 haloalkoxy) or R28R29N where R28 and R29 are independently Q-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-e alkyl groups.
Most preferably R6 is Q-8 alkyl, Q-8 haloalkyl, Q-8 cyanoalkyl, Ci-6 alkoxy (Ci-6) alkyl, Q-7 cycloalkyl, Q-3 alkyl (C3-7) cycloalkyl, heterocyclyl (which may be optionally substituted by halo, nitro, cyano, Q-6 alkyl, Q-6 haloalkyl, Ci-6 alkoxy or Q-6 haloalkoxy) or di(C i -8)alkylamino .
Preferably R12 is hydrogen, halogen, Ci-6 alkyl, Q-6 haloalkyl, Ci-6 alkoxy (Q-e)alkyl, Q-e alkenyl, Q-6 alkynyl, Q-6 alkoxy, Q-6 haloalkoxy, Q-6 alkylthio, Ci-6 haloalkylthio, Q-6 alkylsulfinyl, Q-6 haloalkylsulfinyl, Q-6 alkylsulfonyl, Ci-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, Ci-6 alkyl, Q-6 haloalkyl, Q-6 alkoxy or Ci-6 haloalkoxy) or Ci-6 alkyl.
More preferably R12 is hydrogen, halogen, Q-6 alkyl, Ci-6 haloalkyl, Q-6 alkoxy (Q-6)alkyl, Ci-6 alkoxy, Ci-6 haloalkoxy, Ci-6 alkylthio, or R1 and R12 together with the atoms to which they are attached form a cyclopentane or benzene ring optionally substituted by Ci-6 alkyl, Q-6 haloalkyl or halogen.
Most preferably R12 is hydrogen, halogen, Ci-6 alkyl, Ci-6 haloalkyl, Ci-6 alkoxy(Q-6)alkyl, Ci-6 alkoxy, Ci-6 haloalkoxy, 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. R13 is preferably cyano, nitro, Q-6 alkyl, Ci-6 haloalkyl, Q- cycloalkyl(Q-6)alkyl,
Q-7 cycloalkyl, CH (Q-6)alkenyl, CH2(Q-6)alkynyl, 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), Ci-6 alkylcarbonyl, Q-6 alkoxycarbonyl, Q-6 alkylamino, di(Q-6)alkylamino, Ci-6 alkylcarbonylamino, Q-6 alkoxycarbonylamino, Ci-6 alkoxy, Q-6 alkylthio, Ci-6 haloalkylthio, Q-6 alkylsulfinyl, Q-6 haloalkylsulfinyl, Q-6 alkylsulfonyl, Ci-6 haloalkylsulfonyl, arylthio, arylsulfinyl, arylsulfonyl or (C i -6)alkylcarbonyloxy.
Preferably R14 is hydrogen, Q-8 alkyl, Q-6 haloalkyl, Q-6 cyanoalkyl, Q-6 alkenyl, -6 haloalkenyl, Q-6 alkynyl, Q-7 cycloalkyl, Q-7 cycloalkyl(Q-6)alkyl, Q-6 alkoxy(Ci-6)alkyl, Ci-6 alkoxycarbonyl, Q-6 alkylcarbonyl, Q-6 alkylaminocarbonyl, di(Ci-6)alkylaminocarbonyl, phenyl (which may be optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Q-6 haloalkyl, Ci-6 alkoxy or Q-6 haloalkoxy) or heteroaryl (which may be optionally substituted by halo, nitro, cyano, Q-6 alkyl, Q-6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy).
More preferably R14 is hydrogen, Q-8 alkyl or Q-6 haloalkyl. Preferably R18 is hydrogen, halogen, nitro, cyano, Q-8 alkyl, Ci-6 haloalkyl, Ci-6 cyanoalkyl, Q-7 cycloalkyl(Q-6)alkyl, Q-6 alkoxy(Q-6)alkyl, Q-6 alkoxycarbonyl(Q-6)alkyl, Q-6 alkylcarbonyl(Q-6)alkyl, Q-6alkylaminocarbonyl(Q-6)alkyl, di(Q-6)alkylamino- carbonyl(Q-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 Q-6 haloalkoxy), heteroaryl(Q-6)alkyl (wherein the heteroaryl group may be optionally substituted by halo, nitro, cyano, Q-6 alkyl, Ci-6 haloalkyl, Ci-6 alkoxy or Q-6 haloalkoxy), Q-6 alkenyl, -6 haloalkenyl, Q-6 alkynyl, Q-7 cycloalkyl, Q-6 alkoxycarbonyl, Q-6 alkylcarbonyl, Q-e alkylaminocarbonyl, di(Q ^alkylaminocarbonyl, phenyl (which may be optionally substituted by halo, nitro, cyano, Q-e 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.
Preferably n is 0.
The compounds in the following Tables illustrate compounds of the invention. Table 1 provides 10 compounds of formula:
Figure imgf000021_0001
wherein D, E, Rl and R6 are as defined in Table 1
TABLE 1
Figure imgf000021_0004
Table 2 provides 10 compounds of formula:
Figure imgf000021_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 3 provides 10 compounds of formula:
Figure imgf000021_0003
wherein D, E, Rl and R6 are as defined in Table 1.
Table 4 provides 10 compounds of formula:
Figure imgf000022_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 5 provides 10 compounds of formula:
Figure imgf000022_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 6 provides 10 compounds of formula:
Figure imgf000022_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 7 provides 10 compounds of formula:
Figure imgf000022_0004
wherein D, E, Rl and R6 are as defined in Table 1. Table 8 provides 10 compounds of formula:
Figure imgf000022_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 9 provides 10 compounds of formula:
Figure imgf000023_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 10 provides 10 compounds of formula:
R
Figure imgf000023_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 11 provides 10 compounds of formula:
Figure imgf000023_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 12 provides 10 compounds of formula:
Figure imgf000023_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 13 provides 10 compounds of formula:
Figure imgf000024_0001
wherein D, E, Rl and R6 are as defined in Table 1.
Table 14 provides 10 compounds of formula:
Figure imgf000024_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 15 provides 10 compounds of formula:
Figure imgf000024_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 16 provides 10 compounds of formula:
Figure imgf000024_0004
wherein D, E, Rl and R6 are as defined in Table 1. Table 17 provides 10 compounds of formula:
Figure imgf000024_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 18 provides 10 compounds of formula:
Figure imgf000025_0001
wherein D, E, Rl and R6 are as defined in Table 1.
Table 19 provides 10 compounds of formula:
Figure imgf000025_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 20 provides 10 compounds of formula:
Figure imgf000025_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 21 provides 10 compounds of formula:
Figure imgf000025_0004
wherein D, E, Rl and R6 are as defined in Table 1. Table 22 provides 10 compounds of formula:
Figure imgf000025_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 23 provides 10 compounds of formula:
Figure imgf000026_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 24 provides 10 compounds of formula:
Figure imgf000026_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 25 provides 10 compounds of formula:
Figure imgf000026_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 26 provides 10 compounds of formula:
Figure imgf000026_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 27 provides 10 compounds of formula:
Figure imgf000027_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 28 provides 10 compounds of formula:
Figure imgf000027_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 29 provides 10 compounds of formula:
Figure imgf000027_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 30 provides 10 compounds of formula:
Figure imgf000027_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 31 provides 10 compounds of formula:
Figure imgf000027_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 32 provides 10 compounds of formula:
Figure imgf000028_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 33 provides 10 compounds of formula:
Figure imgf000028_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 34 provides 10 compounds of formula:
Figure imgf000028_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 35 provides 10 compounds of formula:
Figure imgf000028_0004
wherein D, E, Rl and R6 are as defined in Table 1. Table 36 provides 10 compounds of formula:
Figure imgf000029_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 37 provides 10 compounds of formula:
Figure imgf000029_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 38 provides 10 compounds of formula:
Figure imgf000029_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 39 provides 10 compounds of formula:
Figure imgf000029_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 40 provides 10 compounds of formula:
wherein D, E, Rl and R6 are as defined in Table 1.
Table 41 provides 10 compounds of formula:
Figure imgf000030_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 42 provides 10 compounds of formula:
Figure imgf000030_0002
wherein D, E, Rl and R6 are as defined in Table 1.
Table 43 provides 10 compounds of formula:
Figure imgf000030_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 44 provides 10 compounds of formula:
Figure imgf000030_0004
wherein D, E, Rl and R6 are as defined in Table 1. Table 45 provides 10 compounds of formula:
Figure imgf000031_0001
wherein D, E, Rl and R6 are as defined in Table 1.
Table 46 provides 10 compounds of formula:
Figure imgf000031_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 47 provides 10 compounds of formula:
Figure imgf000031_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 48 provides 10 compounds of formula:
Figure imgf000031_0004
wherein D, E, Rl and R6 are as defined in Table 1. Table 49 provides 10 compounds of formula:
Figure imgf000031_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 50 provides 10 compounds of formula:
Figure imgf000032_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 51 provides 10 compounds of formula:
Figure imgf000032_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 52 provides 10 compounds of formula:
Figure imgf000032_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 53 provides 10 compounds of formula:
Figure imgf000032_0004
wherein D, E, Rl and R6 are as defined in Table 1. Table 54 provides 10 compounds of formula:
Figure imgf000032_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 55 provides 10 compounds of formula:
Figure imgf000033_0001
wherein D, E, Rl and R6 are as defined in Table 1.
Table 56 provides 10 compounds of formula:
Figure imgf000033_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 57 provides 10 compounds of formula:
Figure imgf000033_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 58 provides 10 compounds of formula:
Figure imgf000033_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 59 provides 10 compounds of formula:
Figure imgf000033_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 60 provides 10 compounds of formula:
Figure imgf000034_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 61 provides 10 compounds of formula:
Figure imgf000034_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 62 provides 10 compounds of formula:
Figure imgf000034_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 63 provides 10 compounds of formula:
Figure imgf000034_0004
wherein D, E, Rl and R6 are as defined in Table 1. Table 64 provides 10 compounds of formula:
Figure imgf000035_0001
wherein D, E, Rl and R6 are as defined in Table 1.
Table 65 provides 10 compounds of formula:
Figure imgf000035_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 66 provides 10 compounds of formula:
Figure imgf000035_0003
wherein D, E, Rl and R6 are as defined in Table 1.
Table 67 provides 10 compounds of formula:
Figure imgf000035_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 68 provides 10 compounds of formula:
Figure imgf000035_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 69 provides 10 compounds of formula:
Figure imgf000036_0001
wherein D, E, Rl and R6 are as defined in Table 1.
Table 70 provides 10 compounds of formula:
Figure imgf000036_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 71 provides 10 compounds of formula:
Figure imgf000036_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 72 provides 10 compounds of formula:
Figure imgf000036_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 73 provides 10 compounds of formula:
Figure imgf000037_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 74 provides 10 compounds of formula:
Figure imgf000037_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 75 provides 10 compounds of formula:
Figure imgf000037_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 76 provides 10 compounds of formula:
Figure imgf000037_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 77 provides 10 compounds of formula:
Figure imgf000037_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 78 provides 10 compounds of formula:
Figure imgf000038_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 79 provides 10 compounds of formula:
Figure imgf000038_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 80 provides 10 compounds of formula:
Figure imgf000038_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 81 provides 10 compounds of formula:
Figure imgf000038_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 82 provides 10 compounds of formula:
Figure imgf000039_0001
wherein D, E, Rl and R6 are as defined in Table 1.
Table 83 provides 10 compounds of formula:
Figure imgf000039_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 84 provides 10 compounds of formula:
Figure imgf000039_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 85 provides 10 compounds of formula:
Figure imgf000039_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 86 provides 10 compounds of formula:
Figure imgf000039_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 87 provides 10 compounds of formula:
Figure imgf000040_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 88 provides 10 compounds of formula:
Figure imgf000040_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 89 provides 10 compounds of formula:
Figure imgf000040_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 90 provides 10 compounds of formula:
Figure imgf000040_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 91 provides 10 compounds of formula:
Figure imgf000041_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 92 provides 10 compounds of formula:
Figure imgf000041_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 93 provides 10 compounds of formula:
Figure imgf000041_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 94 provides 10 compounds of formula:
Figure imgf000041_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 95 provides 10 compounds of formula:
Figure imgf000041_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 96 provides 10 compounds of formula:
Figure imgf000042_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 97 provides 10 compounds of formula:
Figure imgf000042_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 98 provides 10 compounds of formula:
Figure imgf000042_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 99 provides 10 compounds of formula:
Figure imgf000042_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 100 provides 10 compounds of formula:
Figure imgf000043_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 101 provides 10 compounds of formula:
Figure imgf000043_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 102 provides 10 compounds of formula:
Figure imgf000043_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 103 provides 10 compounds of formula:
Figure imgf000043_0004
wherein D, E, Rl and R6 are as defined in Table 1. Table 104 provides 10 compounds of formula:
Figure imgf000043_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 105 provides 10 compounds of formula:
Figure imgf000044_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 106 provides 10 compounds of formula:
Figure imgf000044_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 107 provides 10 compounds of formula:
Figure imgf000044_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 108 provides 10 compounds of formula:
Figure imgf000044_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 109 provides 10 compounds of formula:
Figure imgf000045_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 110 provides 10 compounds of formula:
Figure imgf000045_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 111 provides 10 compounds of formula:
Figure imgf000045_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 112 provides 10 compounds of formula:
Figure imgf000045_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 113 provides 10 compounds of formula:
Figure imgf000045_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 114 provides 10 compounds of formula:
Figure imgf000046_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 115 provides 10 compounds of formula:
Figure imgf000046_0002
wherein D, E, Rl and R6 are as defined in Table 1 Table 116 provides 10 compounds of formula:
Figure imgf000046_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 117 provides 10 compounds of formula:
Figure imgf000046_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 118 provides 10 compounds of formula: R
Figure imgf000047_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 119 provides 10 compounds of formula:
Figure imgf000047_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 120 provides 10 compounds of formula:
Figure imgf000047_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 121 provides 10 compounds of formula:
Figure imgf000047_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 122 provides 10 compounds of formula:
Figure imgf000047_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 123 provides 10 compounds of formula:
Figure imgf000048_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 124 provides 10 compounds of formula:
Figure imgf000048_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 125 provides 10 compounds of formula:
Figure imgf000048_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 126 provides 10 compounds of formula:
Figure imgf000048_0004
wherein D, E, Rl and R6 are as defined in Table 1. Table 127 provides 10 compounds of formula:
Figure imgf000049_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 128 provides 10 compounds of formula:
Figure imgf000049_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 129 provides 10 compounds of formula:
Figure imgf000049_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 130 provides 10 compounds of formula:
Figure imgf000049_0004
wherein D, E, Rl and R6 are as defined in Table 1. Table 131 provides 10 compounds of formula:
Figure imgf000049_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 132 provides 10 compounds of formula:
Figure imgf000050_0001
wherein D, E, Rl and R6 are as defined in Table 1.
Table 133 provides 10 compounds of formula:
Figure imgf000050_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 134 provides 10 compounds of formula:
Figure imgf000050_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 135 provides 10 compounds of formula:
Figure imgf000050_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 136 provides 10 compounds of formula:
Figure imgf000051_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 137 provides 10 compounds of formula:
Figure imgf000051_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 138 provides 10 compounds of formula:
Figure imgf000051_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 139 provides 10 compounds of formula:
Figure imgf000051_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 140 provides 10 compounds of formula:
Figure imgf000051_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 141 provides 10 compounds of formula:
Figure imgf000052_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 142 provides 10 compounds of formula:
Figure imgf000052_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 143 provides 10 compounds of formula:
Figure imgf000052_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 144 provides 10 compounds of formula:
Figure imgf000052_0004
wherein D, E, Rl and R6 are as defined in Table 1. Table 145 provides 10 compounds of formula:
Figure imgf000053_0001
wherein D, E, Rl and R6 are as defined in Table 1.
Table 146 provides 10 compounds of formula:
Figure imgf000053_0002
wherein D, E, Rl and R6 are as defined in Table 1.
Table 147 provides 10 compounds of formula:
Figure imgf000053_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 148 provides 10 compounds of formula:
Figure imgf000053_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 149 provides 10 compounds of formula:
Figure imgf000053_0005
wherein D, E, Rl and R6 are as defined in Table 1.
Table 150 provides 10 compounds of formula:
Figure imgf000054_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 151 provides 10 compounds of formula:
Figure imgf000054_0002
wherein D, E, Rl and R6 are as defined in Table 1. Table 152 provides 10 compounds of formula:
Figure imgf000054_0003
wherein D, E, Rl and R6 are as defined in Table 1. Table 153 provides 10 compounds of formula:
Figure imgf000054_0004
wherein D, E, Rl and R6 are as defined in Table 1.
Table 154 provides 10 compounds of formula:
Figure imgf000055_0001
wherein D, E, Rl and R6 are as defined in Table 1. Table 155 provides 10 compounds of formula:
Figure imgf000055_0002
wherein D, E, Rl and R6 are as defined in Table 1.
Table 156 provides 10 compounds of formula:
Figure imgf000055_0003
wherein D, E, Rl and R6 are as defined in Table 1.
The compounds of the invention may be made in a variety of ways. For example compounds of formula LI (where B, D, E, Z, R1, R3, R4, R5, R6 and R51 are as defined above in relation to formula I and A is optionally substituted alkylene, alkenylene, alkynylene, alkylenoxy, alkylenamino or alkylenethio) may be prepared by reacting an amine of formula LLI (where D, E, R1 and R51 are as defined above in relation to formula I) with an appropriate acid of formula IN (where B, Z, R3, R4, R5 and R6 are as defined above in relation to formula I and X = OH), 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. Alternatively the amine HI (where D, E, R and R are as defined above in relation to formula I) may be reacted with a suitable acid halide IN (X = halogen, and B, Z, R3, R4, R5 and R6 are as defined above in relation to formula I), acid anhydride IN (X = OCOalkyl, and B, Z, R3, R4, R5 and R are as defined above in relation to formula I) or ester IN (X = alkoxy, substituted alkoxy or aryloxy, especially methoxy, and B, Z, R3, R4, R5 and R6 are as defined above in relation to formula I) 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, Ν,Ν-dimethylacetamide or mesitylene).
Compounds LT, wherein A is optionally substituted oxyalkylene may be prepared in an analogous manner starting from amine LLI (where D, E, R1 and R51 are as defined above in relation to formula I) and a suitable chloroformate IN (X = Cl, and B, Z, R3, R4, R5 and R6 are as defined above in relation to formula I).
Compounds of formula LU are known compounds or may be made from known compounds by known methods. The syntheses of substituted benzimidazoles, benzoxazoles and benthiazoles are well known (see for example, Alan R. Katritzky and Charles W. Rees, Comprehensive Heterocyclic Chemistry, Nol. 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. Dunwell, 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) and similar processes may be utilised in the synthesis of compounds IN from appropriate starting materials. 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 ortho-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 ortho-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 N (where B, D, E, Z, R1 R3, R4, R5, R6 and R51 are as defined above in relation to formula I) may be prepared by reacting a compound of formula π (where B, D, E, Z, R1 R3, R4, R5, R6 and R51 are as defined above in relation to formula I) 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(para-tolyl)-l,3-dithia-2,4-diphosphetane-2,4- disulfide (Davy reagent p-tolyl) or phophorus pentasulfide in a suitable solvent such as toluene or fluorobenzene.
Compounds of formula VI (where B, D, E, Z, R1 R3, R4, R5, R6 and R51 are as defined above in relation to formula I and R34 = ΝMe2, R35 = H) may be made from compounds of formula Nπ (where B, D, E, Z, R1 R3, R4, R5, R6 and R51 are as defined above in relation to formula I) by treatment with Ν,Ν-dimethylformamide dialkyl acetal in a suitable solvent such as toluene or N,N-dimethylformamide. Frequently this reaction produces a mixture of E and Z isomers which are sometimes separable by standard techniques such as flash column chromatography and recrystallisation.
Compounds VI (where B, D, E, Z, R1 R3, R4, R5, R6 and R51 are as defined above in relation to formula I and R34 = NMe2, R35 = H) may be treated subsequently with amines (HNR39R40) to give Compounds VI (where B, D, E, Z, R1 R3, R4, R5, R6 and R51 are as defined above in relation to formula I and R34 = NR39R40, R35 = H). Compounds Nπ (where B, D, E, Z, R1 R3, R4, R5, R6 and R51 are as defined above in relation to formula I) may be treated in an analogous manner with trialkylorthoformates to afford Compounds VI (where B, D, E, Z, R1 R3, R4, R5, R6 and R51 are as defined above in relation to formula I and R34 = alkoxy, R35 = H).
Compounds LI or N (where R51 = H, and B, D, E, Z, R1 R3, R4, R5 and R6 are as defined above in relation to formula I) may be treated with an electrophile (such as an alkyl halide, dialkyl sulfate, chloromethylether, trialkyloxonium salt or alkyl chloroformate) optionally in the presence of a base. For compounds L (where R51 = H and B, D, E, Z, R1 R3, R4, R5 and R6 are as defined above in relation to formula I), such treatment usually produces compounds El (where R51 = alkyl, alkenylalkyl, alkynylalkyl, cycloalkyl, alkoxyalkyl, alkoxycarbonyl, and B, D, E, Z, R1 R3, R4, R5 and R6 are as defined above in relation to formula I). In contrast, for compounds N (where R51 = H, and B, D, E, Z, R1 R3, R4, R5 and R6 are as defined above in relation to formula I), the predominant products are compounds NLLI (where R53 = alkyl, alkenylalkyl, alkynylalkyl, cycloalkyl, alkoxyalkyl and B, D, E, Z, R1 R3, R4, R5 and R6 are as defined above in relation to formula I).
Those skilled in the art will recognise that analogous reactions involving sulfenylation, sulfonylation and acylation are possible for compounds LI (where A, B, D, E, Z, R1 R3, R4, R5, R6 and R51 are as defined above in relation to formula I).
Compounds NTH (where B, D, E, Z, R1 R3, R4, R5, R6 and R53 are as defined above in relation to formula I) 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 LX (where B, D, E, Z, R1 R3, R4, R5, R6 and R52 are as defined above in relation to formula I) and X (where B, D, E, Z, R1 R3, R4, R5, R6, R54 and R55 are as defined above in relation to formula I) respectively. An alternative method for making compounds LI (where A, D, E, R1, R3, R4, R5, R6 and R51 are as defined above in relation to formula I, and Z = O, B = Ν) involves the acylation of a compound of formula XI (where A, D, E, R1, R3, R4, R5 and R51 are as defined above in relation to formula I) followed by cyclisation, optionally in the presence of an acidic catalyst such as para- toluene sulfonic acid in a suitable solvent such as xylene or 1,1,2,2- tetrachloroethane.
Compounds XI (where A, D, E, R1, R3, R4, R5 and R51 are as defined above in relation to formula I) may be prepared from compounds XLI (where A, D, E, R1, R3, R4, R5 and R51 are as defined above in relation to formula I) by a sequential procedure of nitration followed by reduction, using known procedures. In turn, compounds XLI may be prepared by the dealkylation of compounds XLLl (where A, D, E, R1, R3, R4, R5 and R51 are as defined above in relation to formula I) where R is an alkyl group (especially methyl) or substituted alkyl group (especially benzyl) under standard conditions. Compounds XLH (where A, D, E, R1, R3, R4, R5 and R51 are as defined above in relation to formula I) may be prepared from compounds m (where D, E, R1, and R51 are as defined above in relation to formula I) by processes analogous to those already described for compounds LI. Heteroaryl Ν-oxides can be prepared using known methods.
Figure imgf000059_0001
XIII
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. Lnsects, 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), Be isia 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. (leaf iner), 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; Nenturia spp. (including Nenturia 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 pomi), Cedar apple rust (Gymnosporangium juniperi- virginianae), sooty blotch (Gloeodes pomigena), flyspeck (Schizothyrium pomi) 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 cucumeris 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 (B YMN) 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.
Ln 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 0. lg tolOkg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to lkg per hectare.
When used in a seed dressing, a compound of formula (I) is used at a rate of 0.000 lg to lOg (for example 0.001 g 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 SOLNESSO 100, SOLNESSO 150 and SOLNESSO 200; SOLNESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), Ν-alkylpyrrolidones (such as Ν-methylpyrrolidone or Ν-octylpyrrolidone), dimethyl amides of fatty acids (such as Q-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 n-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 (L) 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- isopropyl- and tri-isopropyl-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 (L). 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, chloφyrifos, 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 (S SF- 129), 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethyl- benzimidazole-1-sulphonamide, α-[N-(3-chloro-2,6-xylyl)-2-methoxy- acetamido]-γ-butyrolactone, 4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-l- sulfonamide (IKF-916, cyamidazosulfamid), 3-5-dichloro-N-(3-chloro-l-ethyl-l-methyl-2- oxopropyl)-4-methylbenzamide (RH-7281, zoxamide), N-allyl-4,5,-dimethyl-2- trimethylsilylthiophene-3-carboxamide (MON65500), N-( 1 -cyano- 1 ,2-dimethylpropyl)-2- (2,4-dichlorophenoxy)propionamide (AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide, acibenzolar (CGA245704), alanycarb, aldimoφh, anilazine, azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S, bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, caφropamid, 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 1,1 '-dioxide, dichlofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O,O-di-iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethomoφh, dimethirimol, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemoφh, 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, fenpropimoφh, 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 dimethyldithio- carbamate, nitrothal-isopropyl, 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, prop- iconazole, propineb, propionic acid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyr- oxyfur, 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, tridemoφh, 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 PLX™. 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 1.07 in Table I
Figure imgf000073_0001
The benzoxazoleacetic acid (200 mg, 0.81 mmol) was suspended in dichloromethane
(5 ml) and DMF (catalytic amount) was added. Oxalyl chloride (0.08 ml, 0.92 mmol) was added drop wise and the mixture was allowed to stir at room temperature for 3 hours. The solvent was removed under reduced pressure and the residue was dissolved in dichloromethane (5 ml) and the solution was heated to reflux. The aminopyrimidine (109 mg, 0.89 mmol) was added to the refluxing solution and the solution was stirred at reflux for 8 hours. The reaction mixture was allowed to cool and the solution was partitioned between ethyl acetate and saturated aqueous sodium hydrogen carbonate solution. The organic layer was dried (MgSO4), filtered and evaporated. The residue was purified by filtration through a silica plug with ethyl acetate to give the desired product (141 mg, 50%). Proton NMR data (CDC13) :
1.11 (s,9H); 1.30 (t,3H) t; 2.80 (q,2H) ; 2.85 (s,2H) ; 3.89 (d,2H) ; 7.27 (dd,lH); 7.52 (d,lH) ; 7.62 (d,lH); 7.94 (br s, 1H); 7.97 (d,lH); 8.54 (d,lH)
Compounds 1.01 and 1.03 in Table I were prepared in an analogous manner. Proton NMR data (CDC13) for compound No 1.01 in Table 1: 1.30 (t,3H); 2.67 (s,3H); 3.82 (q,2H); 3.89 (s,2H); 7.25 (dd,lH); 7.50 (d,lH); 7.60 (d,lH); 7.82 (br s,lH); 7.96 (d,lH); 8.54 (d,lH) Proton NMR data (CDC13) for compound No 1.03 in Table 1:
1.00 (t,3H); 1.30 (t,3H); 1.95 (m,2H); 2.80 (q,2H); 2.94 (t,2H); 3.88 (s,2H); 7.26 (dd,lH); 7.52 (d,lH); 7.63 (d,lH); 7.90 (br s,lH); 7.98 (d,lH); 8.54 (d,lH)
EXAMPLE 2 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 Nos. 1.07 and 1.03 each gave a mortality score of 9 whilst compound No. 1.01 gave a score of 5.
In addition, in a similar test against two-spotted spider mites (Tetranychus urticae) Compound Nos. 1.01, 1.03 and 1.07 each gave a mortality score of 9. EXAMPLE 3
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 (UNCLNE), on vines; Phytophthora infestans lycopersici (PHYTLN) 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:
Mean 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. PCRO data are set out in the table below.
TABLE 157
Figure imgf000076_0001

Claims

Claims
1. A compound of formula (I):
Figure imgf000077_0001
wherein n is 0 or 1; A is optionally substituted Q-6 alkylene, optionally substituted -6 alkenylene, optionally substituted -6 alkynylene, optionally substituted cycloalkylene, optionally substituted Ci-6 alkyleneoxy, optionally substituted oxy(Q-6)alkylene, optionally substituted Q-6 alkylenethio, optionally substituted thio(Q-6)alkylene, optionally substituted Ci-6 alkyleneamino, optionally substituted amino(Q-6)alkylene, optionally substituted [Q-6 alkyleneoxy(Q-6)alkylene], optionally substituted [Ci-6 alkylenethio(Q-6)alkylene], optionally substituted [Q-6 alkylenesulfmyl(Q-6)alkylene], optionally substituted [Q-6 alkylenesulfonyl- (Q-6)alkylene] or optionally substituted [Q-6 alkyleneamino(Q-6)alkylene]; B is N, N-oxide or CR18; D is CR8=CR9, CR8=N, N=CR9, CR8=N(O) or N(O)=CR9;
E is N, N-oxide or CR12;
M is OC(=Y), N(R51)C(=Y), N=C(OR52), N=C(SR53) or N=C(NR54R55) where O or N is the atom of attachment to the ring containing E and D; Y is O, S or NR13; Z is O, S or NR14;
R1 is hydrogen, halogen, optionally substituted Q-e alkyl, optionally substituted -6 alkenyl, optionally substituted -6 alkynyl, optionally substituted Q-6 alkoxy, optionally substituted Ci-6 alkylthio, optionally substituted Q-7 cycloalkyl, cyano, nitro or SF5; R51 is hydrogen, optionally substituted Q-io alkyl, optionally substituted [Q-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-io alkoxycarbonyl, formyl, optionally substituted Q-io alkylaminocarbonyl, optionally substituted di(Q-ιo)alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted Q-6 alkylthio, optionally substituted Q-6 alkylsulfinyl, optionally substituted Q-6 alkylsulfonyl, optionally substituted Ci-6 arylthio, optionally substituted Q-6 arylsulfinyl, optionally substituted Q-e arylsulfonyl or R20R21NS(O)P where p is 0, 1 or 2, especially 0; R52 is optionally substituted Q-io alkyl, optionally substituted [Q-6 alkenyl(Q-6)alkyl], optionally substituted [Q-6 alkynyl(Q-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted Q-io alkylcarbonyl, optionally substituted Q-io alkoxycarbonyl, formyl, optionally substituted Q-10 alkylaminocarbonyl, optionally substituted di(Q-ιo)alkylaminocarbonyl, , amino, optionally substituted Q-6 alkylamino, optionally substituted di(Q-6)alkylamino, optionally substituted phenoxycarbonyl, tri(Q- )alkylsilyl, aryldi(Q-4)alkylsilyl, (Q- )alkyldiarylsilyl or triarylsilyl;
R53 is optionally substituted Q-io alkyl, optionally substituted [Q-6 alkenyl- (Q-6)alkyl], optionally substituted [C2-6 alkynyl(Ci-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted Q-10 alkylcarbonyl, optionally substituted Q-io alkoxycarbonyl, optionally substituted Q-io alkylaminocarbonyl, optionally substituted di(Cι-1o)alkylaminocarbonyl 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(Q-6)alkyl], optionally substituted Q-7 cycloalkyl, optionally substituted Q-io alkylcarbonyl, optionally substituted Q-io alkoxycarbonyl, formyl, optionally substituted Q-io alkylaminocarbonyl, optionally substituted di(Q-io)alkylaminocarbonyl, hydroxy, amino, optionally substituted Q-6 alkylamino, optionally substituted di(Q-6)alkylamino, 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-6 alkylcarbonyl, optionally substituted Ci-6 alkoxycarbonyl or SF5; R6 is hydrogen, halogen, cyano, optionally substituted Q-2o alkyl, optionally substituted Q-2o alkenyl, optionally substituted Q-?o alkynyl, optionally substituted Q-7 cycloalkyl, optionally substituted -6 cycloalkenyl, formyl, optionally substituted Q. o alkoxycarbonyl, optionally substituted C1-2o 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-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 Ci-6 alkyl, optionally substituted -6 alkenyl, optionally substituted -6 alkynyl or optionally substituted Q-6 alkoxy;
R12 is hydrogen, halogen, optionally substituted Ci-6 alkyl, optionally substituted Q-e alkenyl, optionally substituted Q-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 Ci-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 Ci-6 alkyl, Ci-6 haloalkyl or halogen;
R13 is hydrogen, cyano, nitro, optionally substituted Q-6 alkyl, optionally substituted Q-7 cycloalkyl, optionally substituted (Q-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 Q-6 alkylcarbonylamino, optionally substituted Q-6 alkoxycarbonylamino, optionally substituted Ci-6 alkoxy, optionally substituted Ci-6 alkylthio, optionally substituted Ci-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 [Q-6 alkenyl(Q-6)alkyl], optionally substituted [Q-6 alkynyl(Q-6)alkyl], optionally substituted Q-7 cycloalkyl, optionally substituted [Q-7 cycloalkyl(Q-6)alkyl], C]-6 alkoxy(Cι-6)alkyl, optionally substituted Ci-6 alkoxycarbonyl, optionally substituted Q-6 alkylcarbonyl, optionally substituted Ci-6 alkylaminocarbonyl, optionally substituted di(Q-6)alkylaπιinocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl;
R18 is hydrogen, halogen, nitro, cyano, optionally substituted Q-8 alkyl, optionally substituted -6 alkenyl, optionally substituted Q-6 alkynyl, optionally substituted Q-7 cycloalkyl, optionally substituted Ci-6 alkoxycarbonyl, optionally substituted Q-6 alkylcarbonyl, optionally substituted Ci-6 alkylaminocarbonyl, optionally substituted di(Q-6)alkylarninocarbonyl, optionally substituted phenyl or optionally substituted heteroaryl;
R20 and R21 are, independently, optionally substituted Q-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 Ci-6 alkyl groups;
R26 is hydrogen, optionally substituted Q-2o alkyl, optionally substituted [Q-2o alkenyl(Q-6)alkyl], optionally substituted [Q-20 alkynyl(Q-6)alkyl], optionally substituted Q-7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted [heterocyclyl(Q-6)alkylCH=N] or di(Q-6)alkylC=N;
R28 and R29 are, independently, hydrogen, optionally substituted Q- o alkyl, optionally substituted Q-7 cycloalkyl, optionally substituted [Q-2o alkenyl(Q-6)alkyl], optionally substituted [Q-20 alkynyl(Q-6)alkyl], optionally substituted Q-20 alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted Cι-2o alkylcarbonyl, optionally substituted Q-2o alkylsulfonyl or optionally substituted phenylsulfonyl;
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.2)alkyl or optionally substituted C1-20 alkyl provided that when
E is CR12, Z is O and M is N(R51)C(=O) or N(R51)C(=S), then D is not CR8=CR9 and when E is CR12, Z is S, B is CR18 and M is N(R51)C(=O) or N(R51)C(=S), then D is not CR8=CR9.
2. A compound according to claim 1 of formula I'
Figure imgf000081_0001
where A, B, D, E, M, Z, R1, 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 ring containing E and D and R51 is as defined in claim 1.
4. A compound according to any preceding claim wherein A is Q-6 alkylene (optionally substituted by halogen, C1-3 alkyl, Q-3 haloalkyl, C1-3 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 D is CR8=CR9 and E is N or CR wherein R , R and R are as defined in claim 1. A compound according to any preceding claim wherein R6 is Q-8 alkyl, Ci-6 haloalkyl, Ci-6 cyanoalkyl, Q-6 alkenyl, C2-6 alkynyl, Q- cycloalkyl, C3-7 halocycloalkyl, C3-7 cyanocycloalkyl, Q-3 alkyl(C3-7)cycloalkyl, Cι-3 alkyl(C3-7)halocycloalkyl, -6 cycloalkenyl, Q-7 cycloalkyl(Cι-6)alkyl, C5-6 cycloalkenyl(Q-6)alkyl, C2-6 haloalkenyl, Cι-6cyanoalkenyl, Q-6 alkoxy(Q-6)alkyl,
C3-6 alkenyloxy(Cι-6)alkyl, C3-6 alkynyl oxy(Q-6)alkyl, aryloxy(Cι-6)alkyl, Ci-6 carboxyalkyl, Ci-6 alkylcarbonyl(Q-6)alkyl, C2-6 alkenylcarbonyl(Q-6)alkyl, C2-6 alkynylcarbonyl(Ci-6)alkyl, Q-6 alkoxycarbonyl(Q-6)alkyl, C3-6 alkenyloxycarbonyl(Cι-6)alkyl, C3-6 alkynyloxycarbonyl(Q-6)alkyl, aryloxycarbonyl(Ci-6)alkyl, Ci-6 alkylthio(Cι-e)alkyl, Q-6 alkylsulfinyl(Q-6)alkyl, Ci-6 alkylsulfonyl(Cι-6)alkyl, aminocarbonyl(Q-6)alkyl, aminocarbonyl(Q-6)alkenyl, aminocarbonyl(C2-6)alkynyl, Ci-6 alkylaminocarbonyl(Cι-6)alkyl, di(Q-6)alkylamino- carbonyl(Q-6)alkyl, Ci-6 alkylaminocarbonyl(Q-6)alkenyl, di(Q-6)alkylamino- carbonyl(Ci-6)alkenyl, alkylaminocarbonyl(Q-6)alkynyl, di(Q.6)alkylaminocarbonyl- (Ci-6)alkynyl, phenyl (optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Q-6 haloalkyl, Q-6 alkoxy or Ci-6 haloalkoxy), phenyl(Q-4)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Q-6 haloalkyl, Q-6 alkoxy or Ci-6 haloalkoxy), phenyl(Q-4)alkenyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Q-6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Q-6 alkyl,
Ci-6 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 Ci-6 haloalkoxy), heteroaryl(Q- )alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Q-6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy), heterocyclyl(Q- )alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q-6 alkyl, Ci-6 haloalkyl, Q-6 alkoxy or Q-6 haloalkoxy), R26O, Q-8 alkylthio, R28R29N or R31ON=C(R27); where R26 is Q-8 alkyl, Q-6 haloalkyl; 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 Ci-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); R and R are, independently, hydrogen, Q-8 alkyl, Q-7 cycloalkyl, C3-6 alkenyl, Q-6 alkynyl, Q-7 cycloalkyl(Q- )alkyl, Q-6 haloalkyl, Q-6 alkoxy(Q-6)alkyl, Cι-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; 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 Ci-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/GB2001/000318 2000-01-28 2001-01-26 Azine derivatives as pesticides WO2001055137A1 (en)

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