WO2001055139A1 - Derive d'isothiazole et utilisations de ceux-ci sous forme de pesticides - Google Patents

Derive d'isothiazole et utilisations de ceux-ci sous forme de pesticides Download PDF

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Publication number
WO2001055139A1
WO2001055139A1 PCT/GB2001/000301 GB0100301W WO0155139A1 WO 2001055139 A1 WO2001055139 A1 WO 2001055139A1 GB 0100301 W GB0100301 W GB 0100301W WO 0155139 A1 WO0155139 A1 WO 0155139A1
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optionally substituted
alkyl
alkoxy
haloalkyl
cyano
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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 Ltd
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Syngenta Ltd
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Priority to AU2001228667A priority Critical patent/AU2001228667A1/en
Publication of WO2001055139A1 publication Critical patent/WO2001055139A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

  • the present invention relates to azole derivatives, to processes for preparing them, to fungicidal, insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them, to methods of using them to combat fungal diseases (especially fungal diseases of plants) and to methods of using them to combat and control insect, acarine, mollusc and nematode pests.
  • Azole and azine derivatives are disclosed in WO95/31448, WO97/18198, WO98/02424, WO98/05670 and WO98/17630.
  • the present invention provides a compound of formula (I):
  • A is optionally substituted C ⁇ - 6 alkylene, optionally substituted C 2 . 6 alkenylene, optionally substituted C 2 . 6 alkynylene, optionally substituted cycloalkylene, optionally substituted C ⁇ . 6 alkylenoxy, optionally substituted oxy(C ⁇ . 6 )alkylene, optionally substituted C ⁇ - 6 alkylenethio, optionally substituted thio(C ⁇ - 6 )alkylene, optionally substituted C ⁇ _ 6 alkylenamino, optionally substituted amino(C ⁇ .6)alkylene, optionally substituted [C ⁇ .
  • D is S or NR 7 ;
  • E is N or CR 12 ;
  • R 1 is hydrogen, halogen, optionally substituted d. 6 alkyl, optionally substituted C 2 . 6 alkenyl, optionally substituted C 2 . 6 alkynyl, optionally substituted d_ 6 alkoxy, optionally substituted C ⁇ . 6 alkylthio, optionally substituted C 3 . 7 cycloalkyl, cyano, nitro or SF 5 ;
  • R 2 is optionally substituted C ⁇ o alkyl, optionally substituted [C 2 . 6 alkenyl(d- 6 )- alkyl], optionally substituted [C 2 . 6 alkynyl (C 1 . 6 )alkyl], optionally substituted C 3 .
  • R 3 , R 4 and R 5 are, independently, hydrogen, halogen, optionally substituted d. 6 alkyl, optionally substituted d. 6 alkoxy, optionally substituted . 6 alkylthio, optionally substituted Ci. 6 alkylsulfinyl, optionally substituted - 6 alkylsulfonyl, cyano, nitro, optionally substituted d. 6 alkylcarbonyl, optionally substituted d- 6 alkoxycarbonyl or SF 5 ;
  • R 6 is hydrogen, halogen, cyano, optionally substituted d- 20 alkyl, optionally substituted C 2 . 2 o alkenyl, optionally substituted C 2 . 20 alkynyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted C5.. 3 cycloalkenyl, formyl, optionally substituted d- 20 alkoxycarbonyl, optionally substituted C 1 -2 0 alkylcarbonyl, aminocarbonyl, optionally substituted d. 2 oalkylaminocarbonyl, optionally substituted di(C ⁇ .
  • alkylaminocarbonyl optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-(C 1 . 6 )alkyl-N-arylaminocarbonyl, optionally substituted diarylaminocarbonyl, optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted N-(C 1 - 6 )alkyl-N-heteroarylaminocarbonyl, optionally substituted diheteroarylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, SH, optionally substituted d- 2 o alkylthio, optionally substituted _ 2 o alkylsulfinyl, optionally substituted d.
  • R 7 is hydrogen or . alkyl
  • R is hydrogen, halogen, optionally substituted Cj. 6 alkyl, optionally substituted C 2 . 6 alkenyl, optionally substituted C . 6 alkynyl, optionally substituted d- 6 alkoxy, optionally substituted - 6 alkylthio, optionally substituted d. 6 alkylsulfinyl, optionally substituted d_ 6 alkylsulfonyl, cyano, nitro, formyl, optionally substituted Cj.
  • 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, carbocylic or heterocyclic ring which may contain one or two heteroatoms selected from O, N or S and which is optionally substituted by d disrupt 6 alkyl, d_ 6 haloalkyl or halogen;
  • R 13 is hydrogen, cyano, nitro, optionally substituted d_ 6 alkyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted (C 2 . 6 )alkenyl(d_ 6 )alkyl, optionally substituted (C 2 - 6 )alkynyl(C ⁇ - 6 )alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted d_ 6 alkylcarbonyl, optionally substituted d- 6 alkoxycarbonyl, optionally substituted d.
  • R 14 is hydrogen, cyano, optionally substituted d. 8 alkyl, optionally substituted [C 2 _ 6 alkenyl (d_ 6 )alkyl], optionally substituted [C 2 . 6 alkynyl(d- 6 )alkyl], optionally substituted C 3 - 7 cycloalkyl, optionally substituted [C 3 . 7 cycloalkyl (C 1 . 6 )alkyl], d- 6 alkoxy(d. 6 )alkyl, optionally substituted d. 6 alkoxycarbonyl, optionally substituted d- 6 alkylcarbonyl, optionally substituted d- 6 alkylaminocarbonyl, optionally substituted di(d. ⁇ alkylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl;
  • R 18 is hydrogen, halogen, nitro, cyano, optionally substituted d_ 8 alkyl, optionally substituted C 2 . 6 alkenyl, optionally substituted C 2 .6 alkynyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted d. 6 alkoxycarbonyl, optionally substituted d_ 6 alkylcarbonyl, optionally substituted C ⁇ _6 alkylaminocarbonyl, optionally substituted di(C 1 . 6 )alkylaminocarbonyl, optionally substituted phenyl or optionally substituted heteroaryl;
  • R 20 and R 21 are, independently, optionally substituted d_ 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 d. alkyl groups; R 32 and R 31 are, independently, hydrogen, optionally substituted phenyl (C ⁇ _ 2 )alkyl or optionally substituted d. 20 alkyl;
  • R and R are independently hydrogen, optionally substituted phenyl or optionally substituted d. 6 alkyl;
  • R 26 is hydrogen, optionally substituted d_ 2 o alkyl, optionally substituted [C 2 . 20 alkenyl(C ⁇ _ 6 )alkyl], optionally substituted [C 2 . 20 alkynyl(d- 6 ) alkyl], optionally substituted C 3 .
  • R 28 and R 29 are, independently, hydrogen, optionally substituted d- 20 alkyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted [C 2 . 2 o alkenyl(d- 6 )alkyl], optionally substituted [C 2 . 20 alkynyl(Ci.
  • alkoxycarbonyl optionally substituted phenoxycarbonyl, formyl, optionally substituted C 1 - 20 alkylcarbonyl, optionally substituted d_ 2 o alkylsulfonyl or optionally substituted phenylsulfonyl.
  • One group of preferred compounds of formula (I) is a group wherein A is optionally substituted d-6 alkylene, optionally substituted C 2 . 6 alkenylene, optionally substituted C 2 _ alkynylene, optionally substituted d-6 alkylenoxy, optionally substituted oxy(C ⁇ _ 6 )alkylene, optionally substituted d-6 alkylenethio, optionally substituted thio(C ⁇ _ 6 )alkylene, optionally substituted d_ 6 alkylenamino, optionally substituted amino(C ⁇ -6)alkylene, optionally substituted [d-6 alkyleneoxy(d-6)alkylene], optionally substituted [C ⁇ _ 6 alkylenethio(C ⁇ .6)alkylene], optionally substituted [d.
  • B is N, N-oxide or CR 18 ;
  • D is S or NR 7 ;
  • E is N or CR 12 ;
  • Z is O, S or NR 14 ;
  • R 1 is hydrogen, halogen, optionally substituted d_ 6 alkyl, optionally substituted C 2 . 6 alkenyl, optionally substituted C 2 _6 alkynyl, optionally substituted d_ 6 alkoxy, optionally substituted d- 6 alkylthio, optionally substituted C 3 . 7 cycloalkyl, cyano, nitro or SF 5 ;
  • R 3 , R 4 and R 5 are, independently, hydrogen, halogen, optionally substituted C ⁇ _ 6 alkyl, optionally substituted d. 6 alkoxy, optionally substituted C ⁇ - 6 alkylthio, optionally substituted d- 6 alkylsulfinyl, optionally substituted d_ 6 alkylsulfonyl, cyano, nitro, optionally substituted d- 6 alkylcarbonyl, optionally substituted C ⁇ - 6 alkoxycarbonyl or SF 5 ;
  • R 6 is hydrogen, halogen, cyano, optionally substituted d_ 2 o alkyl, optionally substituted C 2 . 20 alkenyl, optionally substituted C 2 . 2 o alkynyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted C 5 - 6 cycloalkenyl, formyl, optionally substituted d- 2 o alkoxycarbonyl, optionally substituted C1-20 alkylcarbonyl, aminocarbonyl, optionally substituted Cj. 2 o alkylaminocarbonyl, optionally substituted di(C 1 .
  • R 7 is hydrogen or C ⁇ . ⁇ alkyl
  • R 2 is optionally substituted CM O alkyl, optionally substituted [C 2 _ 6 alkenyl(d_ 6 )- alkyl], optionally substituted [C 2 -6 alkynyl(C ⁇ _6)alkyl], optionally substituted C 3 . 7 cycloalkyl, optionally substituted C MO alkylcarbonyl, optionally substituted C ⁇ o alkoxycarbonyl, formyl, optionally substituted C O alkylaminocarbonyl, optionally substituted di(C 1 . 1 o)alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted d.
  • 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 ring carbocylic or heterocyclic ring which may contain one or two heteroatoms selected from O, N or S and which may be optionally substituted by C ⁇ _ 6 alkyl, d. 6 haloalkyl or halogen;
  • R 13 is hydrogen, cyano, nitro, optionally substituted C ⁇ - 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 1 . 6 )alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted d- 6 alkylcarbonyl, optionally substituted C ⁇ _ 6 alkoxycarbonyl, optionally substituted d-6 alkylamino, optionally substituted di(C).
  • R 14 is hydrogen, cyano, optionally substituted d. 8 alkyl, optionally substituted [C 2 . 6 alkenyl(C 1 . 6 )alkyl], optionally substituted [C 2 . 6 alkynyl(C ⁇ _ 6 )alkyl], optionally substituted C 3 . 7 cycloalkyl, optionally substituted [C 3 . 7 cycloalkyl(C 1 . 6 )alkyl], Cj. 6 alkoxy(d- 6 )alkyl, optionally substituted C ⁇ _6 alkoxycarbonyl, optionally substituted C ⁇ - 6 alkylcarbonyl, optionally substituted d-6 alkylaminocarbonyl, optionally substituted di(d. 6 )alkylamino- carbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl;
  • R 18 is hydrogen, halogen, nitro, cyano, optionally substituted d- 8 alkyl, optionally substituted C 2 _ 6 alkenyl, optionally substituted C 2 . 6 alkynyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted d-6 alkoxycarbonyl, optionally substituted C ⁇ - 6 alkylcarbonyl, optionally substituted C ⁇ -6 alkylaminocarbonyl, optionally substituted di(C 1 .
  • R 20 and R 21 are, independently, optionally substituted d_ 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 d_ 6 alkyl groups;
  • R 26 is hydrogen, optionally substituted d. 2 o alkyl, optionally substituted [C 2 . 2 o alkenyl(C 1 . 6 )alkyl], optionally substituted [C 2 .
  • R 28 and R 29 are, independently, hydrogen, optionally substituted d- 20 alkyl, optionally substituted C 3 - 7 cycloalkyl, optionally substituted [C 2 . 0 alkenyl (d_ 6 )alkyl], optionally substituted [C 2 . 2 o alkynyl(d- ⁇ )alkyl], optionally substituted d_ o alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted d.
  • alkylcarbonyl optionally substituted C ⁇ - 0 alkylsulfonyl or optionally substituted phenylsulfonyl; 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 d- 6 alkyl groups;
  • R 27 and R 30 are independently hydrogen, optionally substituted phenyl or optionally substituted d- 6 alkyl
  • R 31 and R 32 are, independently, hydrogen, optionally substituted phenyl (C 1 . 2 )alkyl or optionally substituted d-20 alkyl.
  • 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, C 1 - 6 haloalkyl, OR 36 or NR 37 R 38 ; where R 34 and R 35 are, independently, hydrogen, C,- 6 alkyl, d. 6 alkoxy, d. 6 haloalkyl, cyano, d- 6 alkoxycarbonyl, C]_ 6 alkylcarbonyl or NR 39 R 40 ; R 36 is d- 6 alkyl, C ⁇ _ 6 haloalkyl or phenyl(d.
  • R 37 and R 38 are, independently, hydrogen, C ⁇ _ 8 alkyl, C 3 . 7 cycloalkyl, C 2 . 6 alkenyl(C ⁇ _ 6 )alkyl, C 2 . 6 alkynyl(d_ 6 )alkyl, C 2 _ 6 haloalkyl, d_ 6 alkoxy(C 1 _ 6 )alkyl, d-6 alkoxycarbonyl (d. 6 )alkyl, carboxy(d- 6 )alkyl or phenyl(C ⁇ .
  • R 39 and R 40 are, independently, hydrogen, d. 8 alkyl, C 3 . 7 cycloalkyl, C 2 _ 6 alkenyl(d_ 6 )alkyl, C 2 . 6 alkynyl(C ⁇ - 6 )alkyl, C 2 . 6 haloalkyl, C ⁇ _ 6 alkoxy(d. 6 )alkyl, C ⁇ _ 6 alkoxycarbonyl(C 1 .
  • R 39 and R 40 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 heteroatoms selected from O, N or S and which is optionally substituted by one or two d_6 alkyl groups.
  • Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, rc-butyl, rc-pentyl, n-hexyl, wo-propyl, «-butyl, sec-butyl, wobutyl, tert-butyl or ne ⁇ -pentyl.
  • the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, NCS-, C 3 . 7 cycloalkyl (itself optionally substituted with d- 6 alkyl or halogen), C 5 . 7 cycloalkenyl (itself optionally substituted with C ⁇ - 6 alkyl or halogen), hydroxy, d-io alkoxy, d-io alkoxy(d- ⁇ alkoxy, tri(C 1 ⁇ )alkylsilyl(C 1 .6)alkoxy, d- 6 alkoxycarbonyl(C 1 .
  • alkylsilyl aryldi(C ⁇ )alkylsilyl, (C 1 . )alkyldiarylsilyl, triarylsilyl, d_ ⁇ o alkylcarbonyl, HO 2 C, Cj-io alkoxycarbonyl, aminocarbonyl, C e alkylaminocarbonyl, di(C ⁇ - 6 alkylaminocarbonyl, N-(C ⁇ _ 3 alkyl)-N-(d. 3 alkoxy)aminocarbonyl, C ⁇ .
  • 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 those optional substituents given above for an alkyl moiety.
  • acyl is optionally substituted d. 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.
  • alkylcarbonyl for example acetyl
  • C 2 _6 alkenylcarbonyl optionally substituted C 2 - 6 alkynylcarbonyl
  • arylcarbonyl for example benzoyl
  • heteroarylcarbonyl for example benzoyl
  • 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.
  • heteroatoms preferably one or two heteroatoms
  • examples of such rings include pyridine, pyrimidine, furan, quinoline, quinazoline, pyrazole, thiophene, thiazole, oxazole and isoxazole.
  • heterocycle and heterocyclyl refer to a non-aromatic ring containing up to 10 atoms including one or more (preferably one or two) heteroatoms selected from O, S and N.
  • examples of such rings include 1,3-dioxolane, tetrahydrofuran and morpholine.
  • the optional substituents on heterocyclyl include C ⁇ .(, alkyl as well as those optional substituents given above for an alkyl moiety.
  • Cycloalkyl includes cyclopropyl, cyclopentyl and cyclohexyl.
  • Cycloalkenyl includes cyclopentenyl and cyclohexenyl.
  • cycloalkyl or cycloalkenyl include d_ 3 alkyl as well as those optional substituents given above for an alkyl moiety.
  • Carbocyclic rings include aryl, cycloalkyl and cycloalkenyl groups.
  • the optional substituents on aryl or heteroaryl are selected, independently, from halogen, nitro, cyano, NCS-, d_ 6 alkyl, d_ 6 haloalkyl, C ⁇ - 6 alkoxy(C ! . 6 )alkyl, C 2 . 6 alkenyl, C 2 _6 haloalkenyl, C 2 . 6 alkynyl, C 3 . 7 cycloalkyl (itself optionally substituted with C ⁇ - 6 alkyl or halogen), C 5 . 7 cycloalkenyl (itself optionally substituted with d- 6 alkyl or halogen), hydroxy, C MO alkoxy, C MO alkoxy(C 1 .
  • substituents are independently selected from halogen, d_ 6 alkyl, d_ haloalkyl, d. 6 alkoxy(d. 6 )alkyl, d- 6 alkoxy, d-6 haloalkoxy, d_ 6 alkylthio, d. 6 haloalkylthio, d_ 6 alkylsulfinyl, d_ 6 haloalkylsulfinyl, d.
  • 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 heteroatoms selected from O, N or S and which is optionally substituted by one or two independently selected (d- ⁇ 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 independently selected (d_ 6 ) alkyl groups.
  • the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, HO 2 C, C M O alkoxy (itself optionally substituted by C O alkoxy), aryl(C ⁇ _ 4 )alkoxy, C MO alkylthio, C MO alkylcarbonyl, C O alkoxycarbonyl, Ci- 6 alkylaminocarbonyl, di(C ⁇ -6 alkyl)aminocarbonyl, (C 1 . 6 )alkylcarbonyloxy, optionally substituted phenyl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl, heterocyclyloxy, C 3 .
  • the optional substituents on alkenyl or alkynyl include one or more of halogen, aryl and C . cycloalkyl.
  • heterocyclyl is optionally substituted by Cue alkyl.
  • the optional substituents for cycloalkyl include halogen, cyano and d- 3 alkyl.
  • the optional substituents for cycloalkenyl include d. 3 alkyl, halogen and cyano.
  • the present invention provides a compound of formula (IA):
  • R 1 is hydrogen, halogen, Ci- 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, d_ 6 cyanoalkyl, d. 6 haloalkyl, Ci- 6 alkoxy, d_ 6 haloalkoxy, d. 6 alkylthio, d-6 haloalkylthio, C 3 . 6 cycloalkyl, C 3 .
  • A is Cue alkylene, Cue alkenylene, d- 6 alkylenoxy, oxy(d-6)alkylene, d- 6 alkylenamino or d_ 6 alkylenethio, each of which is optionally substituted by d_ 3 alkyl, d_ 3 haloalkyl, d_ 3 cyanoalkyl, halogen, d_ 3 alkoxy, C].
  • B is N or CR 18 ;
  • D is S or NR 7 where R 7 is hydrogen or d_ 6 alkyl;
  • E is N or CR 12 ;
  • Y is O, S or NR 13 ;
  • Z is O, S or NR 14 ;
  • R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, d- 6 alkyl, d_ 6 alkoxy, d. 6 haloalkoxy, d- 6 alkylthio, C ⁇ . 6 haloalkylthio, d-6 alkylsulfinyl, C ⁇ . 6 haloalkylsulfinyl, Cu 6 alkylsulfonyl, d. 6 haloalkylsulfonyl, d-6 haloalkyl, cyano, nitro, d. 6 alkylcarbonyl, d- 6 alkoxycarbonyl or SF 5 ;
  • R 6 is cyano, C1- 8 alkyl, d- 6 haloalkyl, d. 6 cyanoalkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, C 3 . 7 cycloalkyl, C 3 . 7 halocycloalkyl, C 3 . 7 cyanocycloalkyl, d. 3 alkyl(C 3 . 7 )cycloalkyl, d_ 3 alkyl(C 3 . 7 )halocycloalkyl, C 5 . 6 cycloalkenyl, C 3 . 7 cycloalkyl(C 1 . 6 )alkyl, C 5 .
  • phenyl(C 2 . 4 )alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d_6 alkyl, Ci-6 haloalkyl, d_6 alkoxy or d.
  • heteroaryl optionally substituted by halo, nitro, cyano, Cue alkyl, d_6 haloalkyl, d_6 alkoxy or d_ haloalkoxy
  • heterocyclyl optionalall substituted by halo, nitro, cyano, d- 6 alkyl, d- 6 haloalkyl, Cu alkoxy or d- 6 haloalkoxy
  • heteroaryl may be substituted by halo, nitro, cyano, C ⁇ _6 alkyl, Ci-6 haloalkyl, d-6 alkoxy or d-6 haloalkoxy
  • heterocyclyl C 1 . 4 )alkyl (where the heterocyclyl may be substituted by halo, cyano, d_ 6 alkyl, Ci- 6 haloalkyl, d. 6 alkoxy or d-6 haloalkoxy)
  • R 26 O, d. 8 alkylthio, R 28 R 29 N or R 31 ON C(R 27 );
  • R 2 is C MO alkyl, benzyloxymethyl, benzoyloxymethyl, C 1 _ 6 alkoxy(C 1 . 6 )alkyl, C 2 . 6 alkenyl (C 1 . 6 )alkyl (especially allyl), C 2 . 6 alkynyl(C ⁇ - 6 )alkyl (especially propargyl), C MO alkylcarbonyl or C MO alkoxycarbonyl;
  • R 13 is cyano, nitro, d- 6 alkyl, C ⁇ . 6 haloalkyl, C 3 . 7 cycloalkyl, C 3 . 7 cycloalkyl(C 1 - 6 )alkyl, CH 2 (C 2 .
  • R 14 is hydrogen, d_ 8 alkyl, d_ 6 haloalkyl, d. 6 cyanoalkyl, C 2 .
  • R 33 is d. 6 alkyl, OR 36 or NR 37 R 38 ;
  • R 34 is hydrogen, d- 6 alkyl or d_ 6 haloalkyl;
  • R 35 is hydrogen, Cue alkyl, d-6 haloalkyl, Ci- ⁇ alkoxy, cyano, d- 6 alkoxycarbonyl, d. 6 alkylcarbonyl or NR 39 R 40 ;
  • R 18 is hydrogen, halogen, nitro, cyano, C ⁇ -8 alkyl, d- 6 haloalkyl, d- 6 cyanoalkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, C 3 - 7 cycloalkyl, C 2 _ 6 haloalkenyl, C 3 . 7 cycloalkyl(d- 6 )alkyl, d. 6 alkoxy(C ⁇ .
  • R 37 and R 38 are, independently, hydrogen, d_ 8 alkyl or phenyl (optionally substituted by halo, nitro, cyano, d. 6 alkyl, Ci- 6 haloalkyl, d_ 6 alkoxy or d_ haloalkoxy); R 26 is hydrogen, d_ 8 alkyl, d. 6 haloalkyl, d_ 6 cyanoalkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl,
  • R 27 is d-6 alkyl, d-e haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, d- 6 alkyl, Ci-6 haloalkyl, d_6 alkoxy or C ⁇ _6 haloalkoxy);
  • R 28 and R 29 are, independently, hydrogen, d. 8 alkyl, C 3 . 7 cycloalkyl, C 3 . 6 alkenyl,
  • R 30 is hydrogen or d_ 3 alkyl
  • R 31 and R 32 are, independently, C ⁇ _ 6 alkyl or phenyl(d_ 2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d_ 6 alkyl, C ⁇ _ 6 haloalkyl, d. 6 alkoxy or d- 6 haloalkoxy); and R 39 and R 40 are, independently, hydrogen, d. 8 alkyl, C 3 . 7 cycloalkyl, C 3 . 6 alkenyl,
  • R 37 and R 38 are, independently, hydrogen, d. 8 alkyl or phenyl (which may be optionally substituted by halo, nitro, cyano, d_ 6 alkyl, C ⁇ _ 6 haloalkyl, C ⁇ _ 6 alkoxy or d.
  • R 34 is hydrogen, C ⁇ _ 6 alkyl or C ⁇ 6 haloalkyl
  • R 35 is hydrogen, C ⁇ - 6 alkyl, C ⁇ - 6 haloalkyl, C ⁇ _ 6 alkoxy, cyano, C ⁇ _ 6 alkoxycarbonyl, C ⁇ _ 6 alkylcarbonyl or NR 39 R 40
  • R 39 and R 40 are, independently, hydrogen, C ⁇ - 8 alkyl, C 3 . 7 cycloalkyl, C 3 . 6 alkenyl, C 3 - 6 alkynyl, C 2 .
  • R 39 and R 40 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 heteroatoms selected from O, N or S and which may be optionally substituted by one or two d_ 6 alkyl groups.
  • A is more preferably d_ 4 alkylene (optionally substituted by halogen, d. 3 alkyl or C ⁇ -3 alkoxy, -C(O)- or d-4 alkyleneoxy (which may be optionally substituted by d. 3 alkyl).
  • A is d- alkyl-substituted d_ 4 alkylene, fluoro- substituted d-4 alkylene, methoxy-substituted d-4 alkylene, -C(O)- or C 2 . alkyleneoxy; still more preferably A is d_ 2 alkyl-substituted C alkylene, fluoro-substituted Cj. 4 alkylene or methoxy-substituted Cj. 4 alkylene. It is further preferred that A is CH(CH 3 )CH 2 , CH 2 CH(CH 3 ), CH(CH 3 ), CHF,
  • A is CH(CH 3 )CH 2 , CH 2 CH(CH 3 ), CH(CH 3 ), CHF or CH(CH 3 )O; especially preferred that A is CHF, CH(OCH 3 ) or CH(CH 3 ); and most preferably A is CHF or CH(CH 3 ).
  • B is preferably N, C-H, C-halogen or C-C 1 . 3 alkyl. B is more preferably N.
  • D is preferably S.
  • E is preferably CR 12 .
  • Y is preferably O or S.
  • Y is more preferably O.
  • Z is O or S.
  • Z is more preferably O.
  • R 1 is hydrogen, halogen, d. 6 alkyl, d. 6 cyanoalkyl, Cue haloalkyl, C3- 7 cycloalkyl(d_ 4 )alkyl, d. 6 alkoxy(d. 6 )alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, C ⁇ _ 6 alkoxy, d_ 6 haloalkoxy, Cue alkylthio, C ⁇ - 6 haloalkylthio, d- 6 cycloalkyl, cyano, nitro or SF 5 .
  • R 1 is more preferably hydrogen, halogen, C ⁇ _ 6 alkyl, C 2 . 6 alkenyl, Ci- 6 haloalkyl, C ⁇ _ 6 alkoxy, d- 6 haloalkoxy, C ⁇ . 6 alkylthio, Ci-6 haloalkylthio, C 3 _ 6 cycloalkyl, cyano, nitro or SF 5 . It is even more preferred that R 1 is hydrogen, halogen, Ci- 6 alkyl, C ⁇ . 6 haloalkyl, C ⁇ . 6 alkoxy(C ⁇ _ 6 )alkyl, C .
  • R 1 is halogen, d. 6 alkyl, d. 6 haloalkyl, d. 6 alkoxy or d- 6 haloalkoxy.
  • R 2 is preferably C MO alkyl, benzyloxymethyl, benzoyloxymethyl, C 1 . 6 alkoxy(C 1 .6)alkyl, C 2 . 6 alkenyl(d. 6 )alkyl (especially allyl), C 2 . 6 alkynyl(C 1 . 6 )alkyl (especially propargyl), C O alkylcarbonyl or C MO alkoxycarbonyl.
  • R 3 , R 4 and R 5 are, independently, hydrogen, halogen, C
  • R 3 , R 4 and R 5 are, independently, hydrogen or halogen (especially fluorine).
  • R 6 is cyano, C ⁇ . 8 alkyl, C ⁇ . 8 haloalkyl, d. 8 cyanoalkyl, C 3 . 7 cycloalkyl(d.6)alkyl, C5-6 cycloalkenyl(d-6)alkyl, d- 6 alkoxy(d- 6 )alkyl, C 3 . 6 alkenyloxy(C 1 . 6 )alkyl, C 3 . 6 alkynyloxy(C 1 . 6 )alkyl, aryloxy(C 1 . 6 )alkyl, Cue carboxyalkyl, d. 6 alkylcarbonyl(d- 6 )alkyl, C 2 .
  • alkyl (where the heterocyclyl group is optionally substituted by halo, cyano, d_ 6 alkyl, d-6 haloalkyl, d_ 6 alkoxy or d_ 6 haloalkoxy), C 2 _ 6 alkenyl, C 2 _ 6 haloalkenyl, d_ 6 cyanoalkenyl, C 5 -6 cycloalkenyl, aminocarbonyl(C 2 _ 6 )alkenyl, d- 6 alkylaminocarbonyl(d- 6 )alkenyl, di(C 1 - 6 )alkylaminocarbonyl(C 1 - 6 )alkenyl, phenyl(C 2 .
  • alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d- 6 alkyl, d_ 6 haloalkyl, d-6 alkoxy or C ⁇ _ 6 haloalkoxy), C 2 - 6 alkynyl, aminocarbonyl(C . 6 )alkynyl, alkylaminocarbonyl (C 1 _ 6 )alkynyl, di(C 1 . 6 )alkylaminocarbonyl(C 1 - 6 )alkynyl, C 3 . 7 cycloalkyl, C 3 - 7 halocycloalkyl, C 3 . 7 O 01/55139
  • cyanocycloalkyl d. 3 alkyl(C 3 - 7 )cycloalkyl, C1.3 alkyl (C 3 . 7 )halocycloalkyl, C 5 - 6 cycloalkenyl, formyl, d_6 alkoxycarbonyl, Cue alkylcarbonyl, aminocarbonyl, Ci- 6 alkylaminocarbonyl, di(C 1 .
  • R 27 is phenyl (optionally substituted by halo, nitro, cyano, C ⁇ - 6 alkyl, Ci-6 haloalkyl, Cue alkoxy or Cue haloalkoxy), Ci- 6 alkyl or C ⁇ _ 6 haloalkyl;
  • R 28 and R 29 are, independently, hydrogen, C ⁇ _ 8 alkyl, C 3 . 7 cycloalkyl(C 1 - 4 )alkyl, C 2 . 6 haloalkyl, d. 6 alkoxy(C ⁇ . 6 )alkyl, C 3 . 7 cycloalkyl, C 3 . 6 alkenyl, C 3 .
  • R 31 is phenyl(C ⁇ . 2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d_ 6 haloalkyl, Ci- 6 alkoxy or d_ 6 haloalkoxy) or d- 6 alkyl.
  • R 6 is d_ 8 alkyl, C ⁇ - 8 haloalkyl, d_ 8 cyanoalkyl, C 3 . 7 cycloalkyl(C 1 . 6 )alkyl, C 5 . 6 cycloalkenyl(Ci- 6 )alkyl, Ci-6 alkoxy(C 1 . 6 )alkyl, C 3 _ 6 alkenyloxy(d- 6 )alkyl, C 3 - 6 alkynyloxy(C 1 - 6 )alkyl, aryloxy(C 1 .
  • heteroaryl(C ⁇ - 4 )alkyl wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Cj_ 6 alkyl, C ⁇ - 6 haloalkyl, C ⁇ _ 6 alkoxy or C ⁇ - 6 haloalkoxy
  • heterocyclyl(C ⁇ _ )alkyl wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, d. 6 alkyl, d- 6 haloalkyl, C ⁇ .6 alkoxy or d. 6 haloalkoxy
  • alkynyl aminocarbonyl(C 2 - 6 )alkynyl, alkylaminocarbonyl (C ⁇ alkynyl, di(C 1 . 6 )alkylaminocarbonyl(C ] . 6 )alkynyl, C 3 . 7 cycloalkyl, C 3 . 7 halocycloalkyl, C 3 . 7 cyanocycloalkyl, C 1 -3 alkyl(C 3 . 7 )cycloalkyl, C1.3 alkyl(C 3 .
  • R 26 is Cj.g alkyl or d-6 haloalkyl
  • R 27 is phenyl (optionally substituted by halo, nitro, cyano, d_ alkyl, Cj- ⁇ haloalkyl, d.6 alkoxy or d. 6 haloalkoxy), Ci- 6 alkyl or d_ 6 haloalkyl
  • R 28 and R 29 are, independently, hydrogen, d_ 8 alkyl, C 3 . 7 cycloalkyl(C ⁇ )alkyl, C 2 . 6 haloalkyl, C 1 . 6 alkoxy(C 1 .
  • R 6 is phenyl(C 1 . 2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d_6 alkyl, d- 6 haloalkyl, Cue alkoxy or d. 6 haloalkoxy) or d. 6 alkyl.
  • R 6 is more preferably d-8 alkyl, d_ 8 haloalkyl, d_ 8 cyanoalkyl, C 2 . 6 alkenyl, C 2 .
  • heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C ⁇ - 6 alkyl, d_6 haloalkyl, d_6 alkoxy or d_ 6 haloalkoxy), heteroaryl (Ci_ 4 )alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Cue alkyl, d_6 haloalkyl, Cue alkoxy or d_ haloalkoxy), heterocyclyl (C 1 .
  • R 28 and R 29 are, independently, hydrogen, d_ 8 alkyl, C 3 . 7 cycloalkyl, C . 6 alkenyl, C 3 _ 6 alkynyl, C 3 _ 7 cycloalkyl(C 1 . 4 )alkyl, C 2 _6 haloalkyl, d_6 alkoxy(C ⁇ .
  • R 6 alkyl, Ci- 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 heteroatoms selected from O, N or S and which may be optionally substituted by one or two d- 6 alkyl groups; and R 31 is d_ 6 alkyl or phenyl(C ⁇ - 2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d_ 6 alkyl, d- 6 haloalkyl, d_ 6 alkoxy or d. 6 haloalkoxy); and R 6 is still more preferably d.
  • R 6 is C ⁇ _ 8 alkyl, d-8 haloalkyl, d_ 8 cyanoalkyl, C ⁇ _ 6 alkoxy (d_ 6 ) alkyl, C 3 . 7 cycloalkyl, d_ 3 alkyl (C 3 _ 7 ) cycloalkyl, heterocyclyl (optionally substituted by halo, nitro, cyano, Cu alkyl, C ⁇ . 6 haloalkyl, d-6 alkoxy or d. 6 haloalkoxy) or di(C ⁇ _g)alkylamino. It is yet more preferred that R 6 is d. 8 alkyl, d_ 8 haloalkyl, d.
  • R 6 is most preferably C ⁇ . 8 alkyl, d-g haloalkyl, C ⁇ . 8 cyanoalkyl, C 3 . 7 cycloalkyl, d- 3 alkyl(C 3 - 7 )cycloalkyl, d. 6 alkoxy(C 1 . 6 )alkyl or R 28 R 29 N; where R 28 and R 29 are, independently, d. 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 further heteroatom selected from O, N or S and which may be optionally substituted by one or two d- 6 alkyl groups.
  • R 12 is hydrogen, halogen, C ⁇ - 6 alkyl, Ci- 6 haloalkyl, d_ 6 alkoxy(C 1 . 6 )alkyl, C 2 . 6 alkenyl, d.6 alkynyl, d_6 alkoxy, d. 6 haloalkoxy, d. 6 alkylthio, C ⁇ .
  • R 12 is hydrogen, halogen, d- 6 alkyl, d_ 6 haloalkyl, d_ 6 alkoxy(C 1 - 6 )alkyl, Cue alkoxy, Cue haloalkoxy, d. 6 alkylthio or SF 5 ; or R 1 and R 12 together with the atoms to which they are attached form a cyclopentane or benzene ring optionally substituted by d. 6 alkyl, d- haloalkyl or halogen.
  • R 12 is even more preferably hydrogen, halogen, d. 6 alkyl, d- 6 haloalkyl, d_ 6 alkoxy, d- 6 haloalkoxy, d_ 6 alkoxy(C ⁇ _6)alkyl, d_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 d. 6 alkyl, Cue haloalkyl or halogen; or alternatively the ring may be a cyclopentane ring.
  • R 12 is hydrogen, halogen, d. 6 alkyl, C ⁇ . 6 haloalkyl, d- 6 alkoxy(C 1 . 6 )alkyl, d- 6 alkoxy, d_ 6 haloalkoxy, or R 1 and R 12 together with the atoms to which they are attached form a cyclopentane ring optionally substituted by d_ 6 alkyl, C ⁇ _ 6 haloalkyl or halogen.
  • R 12 is most preferably halogen, C ⁇ . 6 alkyl, C ⁇ _ 6 haloalkyl, Ci- 6 alkoxy, C ⁇ - 6 alkoxy(d- 6 )alkyl or d-6 haloalkoxy. It is preferred that R 13 is cyano, nitro, Cue alkyl, d_ 6 haloalkyl, C 3 . 7 cycloalkyl(d- 6 )alkyl, C 3 . 7 cycloalkyl, (C 2 . 6 )alkenylCH 2 , (C 2 .
  • alkoxycarbonylamino Cue alkoxy, C ⁇ _ 6 alkylthio, d-6 haloalkylthio, d. 6 alkylsulfinyl, Ci-6 haloalkylsulfinyl, Ci- 6 alkylsulfonyl, d_ 6 haloalkylsulfonyl, arylthio, arylsulfinyl, arylsulfonyl or (C ⁇ _ 6 )alkylcarbonyloxy.
  • R 14 is hydrogen, d_ 8 alkyl, d- 6 haloalkyl, d. 6 cyanoalkyl, C 2 - 6 alkenylCH 2 , C 2 . 6 haloalkenylCH 2 , C 2 . 6 alkynylCH 2 , C 3 . 7 cycloalkyl, C 3 . 7 cycloalkyl(C 1 . 6 )alkyl, Cue alkoxy(C I . 6 )alkyl, C ⁇ . 6 alkoxycarbonyl, Ci- 6 alkylcarbonyl, C ⁇ . 6 alkylaminocarbonyl, di(Ci.
  • R 14 is hydrogen, d- 8 alkyl or d_ 6 haloalkyl. It is preferred that R 18 is hydrogen, halogen, nitro, cyano, d_ 8 alkyl, d- 6 haloalkyl, Ci- 6 cyanoalkyl, C 3 . 7 cycloalkyl(d- 6 )alkyl, Ci_ 6 alkoxy(C ⁇ - 6 )alkyl, d- 6 alkoxycarbonyl(Ci- 6 )alkyl, C ⁇ . 6 alkylcarbonyl(d.
  • R 18 is hydrogen, halogen, C ⁇ _ 8 alkyl or d_ 6 haloalkyl.
  • Tables 1 to 74 below illustrate compounds of the invention.
  • Table 1 provides 129 compounds of formula (1):
  • R and R are as defined in Table 1.
  • Table 2 provides 70 compounds of formula (2):
  • R 6 and R 2 are as defined in Table 2.
  • Table 3 provides 140 compounds of formula (3):
  • R , 1 , r R>6 and R are as defined in Table 3.
  • Table 4 provides 140 compounds of formula (4):
  • R and R are as defined in Table 3.
  • Table 5 provides 140 compounds of formula (5):
  • R 1 , R 6 and R 2 are as defined in Table 3.
  • Table 6 provides 140 compounds of formula (6):
  • R 1 , R 6 and R 2 are as defined in Table 3.
  • Table 7 provides 140 compounds of formula (7):
  • R 1 , R 6 and R 2 are as defined in Table 3.
  • Table 8 provides 140 compounds of formula (8):
  • R , R and R are as defined in Table 3.
  • Table 9 provides 140 compounds of formula (9):
  • R and R are as defined in Table 3.
  • Table 10 provides 140 compounds of formula (10):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 12 provides 140 compounds of formula (12):
  • Table 13 provides 140 compounds of formula (13):
  • Table 14 provides 140 compounds of formula (14):
  • Table 15 provides 140 compounds of formula (15):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 16 provides 140 compounds of formula (16):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 17 provides 140 compounds of formula (17):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 18 provides 140 compounds of formula (18):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 19 provides 140 compounds of formula (19):
  • R 1 , R 6 and R 2 are as defined in Table 3.
  • Table 20 provides 140 compounds of formula (20):
  • Table 23 provides 140 compounds of formula (23):
  • Table 24 provides 140 compounds of formula (24):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 25 provides 140 compounds of formula (25):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 26 provides 140 compounds of formula (26):
  • Table 27 provides 140 compounds of formula (27):
  • Table 28 provides 140 compounds of formula (28):
  • Table 29 provides 140 compounds of formula (29):
  • Table 30 provides 140 compounds of formula (30):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 31 provides 140 compounds of formula (31):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 32 provides 140 compounds of formula (32):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 33 provides 140 compounds of formula (33):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 34 provides 140 compounds of formula (34):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 36 provides 140 compounds of formula (36):
  • Table 37 provides 140 compounds of formula (37):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 38 provides 140 compounds of formula (38):
  • Table 39 provides 140 compounds of formula (39):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 40 provides 140 compounds of formula (40):
  • Table 41 provides 140 compounds of formula (41):
  • Table 42 provides 140 compounds of formula (42):
  • Table 43 provides 140 compounds of formula (43):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 44 provides 140 compounds of formula (44):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 45 provides 140 compounds of formula (45):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 46 provides 140 compounds of formula (46):
  • R 6 and R 2 are as defined in Table 3.
  • Table 47 provides 140 compounds of formula (47):
  • R 1 , R 6 and R 2 are as defined in Table 3.
  • Table 48 provides 140 compounds of formula (48):
  • Table 49 provides 140 compounds of formula (49):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 51 provides 140 compounds of formula (51)
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 53 provides 140 compounds of formula (53):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 54 provides 140 compounds of formula (54):
  • Table 56 provides 140 compounds of formula (56):
  • Table 57 provides 140 compounds of formula (57):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 58 provides 140 compounds of formula (58):
  • Table 60 provides 140 compounds of formula (60):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 61 provides 140 compounds of formula (61):
  • R 6 and R 2 are as defined in Table 3.
  • Table 62 provides 140 compounds of formula (62):
  • Table 63 provides 140 compounds of formula (63):
  • Table 64 provides 140 compounds of formula (64):
  • Table 65 provides 140 compounds of formula (65):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 67 provides 140 compounds of formula (67):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 68 provides 140 compounds of formula (68):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 69 provides 140 compounds of formula (69):
  • R 1 , R 6 and R 2 are as defined in Table 3
  • Table 70 provides 140 compounds of formula (70):
  • Table 72 provides 70 compounds of formula (72):
  • Table 73 provides 70 compounds of formula (73):
  • Table 74 provides 70 compounds of formula (74):
  • R 6 and R 2 are as defined in Table 2.
  • Table 75 shows selected NMR data, all with CDC1 3 , as the solvent (unless otherwise stated; if a mixture of solvents is present, this is indicated as, for example (CDC1 3 / d ⁇ - DMSO)), (no attempt is made to list all characterising data in all cases) for compounds of Tables 1 to 74.
  • Table 75 shows selected NMR data, all with CDC1 3 , as the solvent (unless otherwise stated; if a mixture of solvents is present, this is indicated as, for example (CDC1 3 / d ⁇ - DMSO)), (no attempt is made to list all characterising data in all cases) for compounds of Tables 1 to 74.
  • a compound of formula (I) which is a compound of formula (A) [wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , A, B, D, E and Z are as defined above in relation to a compound of formula (I)] may be made from a compound of formula (B) [wherein R 1 , R , R , R 5 , R , A, B, D, E and Z are as defined above in relation to a compound of formula (I)] by treatment with an alkylating agent (such as an alkyl halide, dialkyl sulfate or trialkyloxonium salt), an acylating agent (such as an acid chloride) or similar reagent (such as a carbamoyl chloride, or sulfenyl chloride), optionally in the presence of a base.
  • an alkylating agent such as an alkyl halide, dialkyl sulfate or trialkyloxonium salt
  • a compound of formula (A) may be separated from a compound of formula (C) and purified by routine techniques such as recrystallisation, chromatography or trituration with a suitable solvent.
  • a compound of formula (B) [wherein B, D, E, Z, R 1 R 3 , R 4 , R 5 , R 6 , 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 (II), [where D, E, and R 1 are as defined above in relation to a compound of formula (I)] with an appropriate acid (ITJ) [where B, Z, R 3 , R 4 , R 5 and R 6 are as defined above in relation to formula (I), A is optionally substituted alkylene, alkenylene, alkynylene, alky
  • Compounds of formula (IT) are known compounds or may be made from known compounds by known methods.
  • a compound of formula (Hie), [where J represents a single bond or suitable group (such as CH 2 )] may be treated with a suitable base, such as lithium diisopropylamide, sodium hydride or lithium hexamethyldisilazide in a suitable solvent such as tetrahydrofuran and then treated with an alkylating agent (such as an alkyl halide), a halogenating agent (such as an N- halosuccinimide, or N-fluorosulfonimide) or another electrophilic agent, Rf-LG, (LG designates a suitable leaving group such as a halide) to introduce a new substituent R f .
  • This procedure may be repeated to introduce a second substituent R g , which may be the same or different to R f :
  • a compound of formula (HI) bearing a fragment which is sufficiently chemically reactive undergoes reactions typical of that fragment.
  • a compound of formula (Hid) [wherein X is alkoxy and J represents a single bond or suitable group (such as CH 2 )] will undergo certain reactions typical of an ⁇ -ketoester.
  • a compound of formula (Hid) may be reduced by metal hydrides such as sodium borohydride in a suitable solvent such as ethanol to give the corresponding alcohol:
  • Benzofurans may be made from ort zo-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.
  • the fused heterocyclic ring may be formed by ring synthesis from a suitably substituted benzene ring (VH) [wherein the atoms or groups Q and G are suitable precursors for the formation of the desired heterocyclic rriinngg,, XX iiss aallkkooxxyy aanndd AA,, RR 33 ,, RR 44 aanndd RR 55 aarree aass ddeefifinneedd i in relation to a compound of formula (I)] by processes analogous to those described above:
  • NH Heteroaryl ⁇ -oxides may be prepared by known methods.
  • the compounds of formula (I) can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests.
  • the pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies).
  • pest species which may be controlled by the compounds of formula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp.
  • Brevipalpus spp. flat mites
  • Boophilus microplus cattle tick
  • Dermacentor variabilis American dog tick
  • Ctenocephalides felis cat flea
  • Liriomyza spp. leafminer
  • Musca domestica housefly
  • Aedes aegypti mosquito
  • Anopheles spp. mosquitoes
  • Culex spp. mosquitoes
  • Termitidae for example Globitermes sulphureus
  • Solenopsis geminata fire ant
  • Monomorium pharaonis pharaoh's ant
  • Damalinia spp. Linognathus spp. (biting and sucking lice)
  • Meloidogyne spp. root knot nematodes
  • Globodera spp. Heterodera spp.
  • cyst nematodes Pratylenchus spp. (lesion nematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulus spp.
  • the compounds of formula (I) are also active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryz e (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 (Sphaero
  • Botrytis cinerea grey mould
  • Botrytis cinerea grey mould
  • Alternaria spp. on vegetables (for example carrots), oil-seed rape, apples, tomatoes, potatoes, cereals (for example wheat) and other hosts
  • Venturia spp. including Venturia inaequalis (scab)) on apples, pears, stone fruit, tree nuts and other hosts
  • Cladosporium spp. on a range of hosts including cereals (for example wheat) and tomatoes
  • 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).
  • a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or mol
  • the compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
  • plant as used herein includes seedlings, bushes and trees.
  • 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).
  • all compositions both solid and liquid formulations
  • the composition is generally used for the control of pests or fungi such that a compound of formula (I) is applied at a rate of from O.lg 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 O.OOlg or 0.05g), preferably 0.005g to lOg, more preferably 0.005g to 4g, per kilogram of seed.
  • the present invention provides an insecticidal, acaricidal, nematicidal, molluscicidal or fungicidal composition
  • 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, moUuscicidally 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. O 01/55139schreibskybeats, 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.
  • DP dustable powders
  • SP soluble powders
  • SG water soluble granules
  • WP water dispersible granules
  • GR granules
  • SL soluble concentrates
  • OL oil miscible liquids
  • UL ultra
  • 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.
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils.
  • One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • DC Dispersible Concentrates
  • a compound of formula (I) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).
  • Emulsifiable concentrates (EC) or oil-in- water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents).
  • Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C 8 -Cio fatty acid dimethylamide) and chlorinated hydrocarbons.
  • aromatic hydrocarbons such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark
  • ketones such as
  • An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.
  • Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion.
  • Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of formula (I) is present initially in either the water or the solvent/SFA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs.
  • An ME may be either an oil-in- water or a water-in-oil O 01/55139 . , PCT/GBOl/00301
  • 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 (CS) may be prepared in a manner similar to the preparation of
  • each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor.
  • the polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure.
  • the compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment.
  • a compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
  • a composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)).
  • additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).
  • a compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS).
  • DS powder for dry seed treatment
  • SS water soluble powder
  • WS water dispersible powder for slurry treatment
  • CS capsule suspension
  • the preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above.
  • Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
  • Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di- is ⁇ propyl- and tri-wopropyl-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
  • 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 WO 01/55139 _ 6 8 .
  • PCT/GBOl/00301 PCT/GBOl/00301
  • 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 (I). WO 01/55139 ,_ PCT/GBOl/00301
  • the invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula (I).
  • compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.
  • the resulting composition may have a broader spectrum of activity or a greater level of intrinsic activity than the compound of formula (I) alone. Further the other fungicide may have a synergistic effect on the fungicidal activity of the compound of formula (I).
  • the compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components.
  • the particular additional active ingredient will depend upon the intended utility of the composition.
  • Suitable pesticides include the following: a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate; b) Organophosphates, such as, profenofos, sulprofos, acephat
  • 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 (SSF-129), 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole- 1-sulphonamide, ⁇ -[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]- ⁇ -butyrolactone, 4-chloro- 2-cyano-N,N-dimethyl-5-p-tolylimidazole-l-sulfonamide (IKF-916, cyamidazosulfamid), 3-5-dichloro-N-(3-chloro- 1 -ethyl- 1 -methyl-2-oxopropyl)-4-methylbenzamide (RH-7281 , zoxamide), N-allyl-
  • 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 PIXTM.
  • 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
  • Step 1 Preparation of N-(4-chloro-3-methylisothiazol-5-yl)-4- methoxyphenylacetamide.
  • 4-Methoxyphenylacetic acid (33.2g, 0.2mol) and N,N-dimethylformamide (1ml) were dissolved in dichloromethane (300ml) and the mixture cooled in an ice-bath.
  • Oxalyl chloride (27.94g, 0.22mol) was added dropwise, and once the addition was complete the cooling bath O 01/55139 73
  • N-(4-Chloro-3-methylisothiazol-5-yl)-4-methoxyphenylacetamide (32.8g, 0.1 lmol) was dissolved in dichloromethane (300ml) and cooled to below -70°C.
  • a solution of boron tribromide in dichloromethane (IM, 332ml, 0.332mol) was added dropwise, maintaining the internal temperature below -65°C.
  • IM boron tribromide in dichloromethane
  • Step 6 Preparation of N-(4-chloro-3-methylisothiazol-5-yl)-[2-(2,2,2-trifluoroethyl)- benzoxazol-5-yl]acetamide.
  • N-(4-chloro-3-methylisothiazol-5-yl)-3-(2,2,2-trifluoropropionamido)-4-hydroxy- phenylacetamide (14.4g) was suspended in 1,1,2,2-tetrachloroethane (140 mL) containing j ⁇ r -toluenesulfonic acid (1.68g) and the mixture was heated to reflux with stirring for 2h.
  • Step 7 Preparation of N-(4-chloro-2-ethoxymethyl-3-methylisothiazolin-5-ylidene)-[2- (2,2,2-trifluoroethyI)benzoxazol-5-yl]acetamide N-(4-chloro-3-methylisothiazol-5-yl)-[2-(2,2,2-trifluoroethyl)benzoxazol-5- yl]acetamide (1.50 g) in dry dichloromethane (15 mL) was stirred at ambient temperature under an atmosphere of nitrogen and N,O-bis(trimethylsilyl)acetamide (0.995 mL) was added.
  • EXAMPLE 4 This Example illustrates the preparation of Compound No. 61 of Table No. 1. N-(4-chloro-3-methylisothiazol-5-yl)-(2-methylbenzoxazol-5-yl)acetamide (0.64 g) in dry tetrahydrofuran (10 mL) was stirred at ambient temperature under an atmosphere of nitrogen and treated with lithium bis(trimethylsilyl)amide (2.2mL of IM solution in tetrahydrofuran ). The mixture was stirred for 30 minutes at 50°C then cooled to ambient temperature. Ethyl chloromethyl ether ( 0.62 g) was added then the reaction stirred for 3 h.
  • a solution of lithium diisopropylamide (2.0M solution in tetrahydrofuran /ethyl benzene / heptane, 34.0ml, 0.0667mol) was added dropwise to a solution of methyl 4- methoxyphenyl-acetate (12.0g, 0.0667 mol) in tetrahydrofuran (150ml) at -70°C under a nitrogen atmosphere and the mixture stirred at -70 °C for lhour.
  • a solution of methyl iodide (9.5 g, 0.0667mol) in tetrahydrofuran (20ml) was added dropwise and the mixture was stirred at -70°C for a further lhour. The cooling bath was removed and the mixture allowed to warm to room temperature overnight.
  • Step 4 Preparation of N-(4-chloro-3-methyIisothiazol-5-yI)-2-(4-hydroxyphenyl)propionamide Boron tribromide (1.0 M solution in dichloromethane, 110 ml, 0.11 mol) was added dropwise to a stirred solution of N-(4-chloro-3-methylisothiazol-5-yl)-2-(4-methoxyphenyl)- propionamide (12.5 g, 0.040 mol) in dichloromethane (200 ml) at -70 °C. Once the addition was complete the cooling bath was removed and the mixture allowed to warm to room temperature overnight. The mixture was cooled to 0 °C and excess methanol added cautiously.
  • N-(4-chloro-3-methylisothiazol-5-yl)-2-(4-hydroxy-3- nitrophenyl)propionamide (11.0 g, 0.0322 mol)and 3% platinum on carbon in N,N- dimethylformamide (100 ml) was hydrogenated at 15 bar for 6 hours at room temperature.
  • the catalyst was removed by filtration and the filtrate evaporated in vacuo to give N-(4- chloro-3-methylisothiazol-5-yl)-2-(3-amino-4-hydroxyphenyl)propionamide (9.0 g) as an off- white solid, m.p. 222-223 °C.
  • Oxalyl chloride (4.46 g, 0.035 mol) was added dropwise to a solution of 2-(2- heptafluoro-propylbenzoxazol-5-yl)propionic acid (6.3 g, 0.0176 mol) in dichloromethane (60 ml) and the mixture stirred at room temperature overnight. The solvent was evaporated in vacuo, and the residue dissolved in 1,2-dichloroethane (70 ml) and warmed to reflux.
  • N,O-bis(trimethylsilyl)acetamide (0.50 g, 0.00245 mol) was added to a solution of N-(4-chloro-3-methylisothiazol-5-yl)-2-[2-heptafluoropropylbenzoxazol-5- yl]propionamide (1.00 g, 0.002 mol) in dichloromethane (10 ml) and the mixture stirred at room temperature for 15 minutes. Chloromethylethyl ether (0.386 g, 0.004 mol) was added and stirring was continued for 48hours. The reaction mixture was diluted with dichloromethane and poured into water.
  • N,O-bis(trimethylsilyl)acetamide (0.219 g, 0.00108 mol) was added to a solution of N-(4-chloro-3-methylisothiazol-5-yl)-[2-(2,2-dimethylpropylbenzoxazol-5-yl]- fluoroacetamide (0.35 g, 0.0009 mol) in dichloromethane (4 ml) and the mixture stirred at room temperature for 20 minutes. Chloromethylethyl ether (0.167 g, 0.0018 mol) was added and stirring was continued for 72hours. The reaction mixture was quenched by addition of saturated aqueous sodium bicarbonate solution and extracted with ethyl acetate.
  • EXAMPLE 8 This Example illustrates the preparation of Compound No. 94 of Table No. 1. Di-tert-amyl dicarbonate (0.184 ml, 0.00075 mol) was added to a solution of N-(4- chloro-3-methylisothiazol-5-yl)-(2-[2,2-dimethylpropyl]benzoxazol-5-yl)acetamide (0.189 g, 0.0005 mol) and 4-dimethylaminopyridine (0.006 g) in acetonitrile and the mixture stirred at room temperature for 3 h.
  • reaction mixture was partitioned between saturated aqueous sodium bicarbonate solution and ethyl acetate.
  • the organic phase was washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo.
  • the residue was purified by flash column chromatography on silica gel, eluting initially with ethyl acetate : O 01/55139 _ 91 _ PCT/GBOl/00301
  • Step 2 Preparation of 2-(2,2-dimethyIpropyl)-5-methoxybenzoxazole
  • N-(2-hydroxy-5-methoxyphenyl)-3,3-dimethylbutyramide (2.85 g, 0.012 mol) and p ⁇ r ⁇ -toluenesulfonic acid (0.05 g) were heated together in refluxing 1,1,2,2- tetrachloroethane (50 ml) for 6 h.
  • Step 4 Preparation of methyl [2-(2,2-dimethylpropyI)benzoxazol-5-yl]oxyacetate and [2-(2,2-dimethylpropyl)benzoxazol-5-yl]oxyacetic acid
  • 2-(2,2-dimethylpropyl)-5-hydroxybenzoxazole (1.94 g, 0.00946 mol)
  • potassium carbonate (1.31 g, 0.00946 mol
  • methyl bromoacetate (1.45 g, 0.00946 mol) in N,N-dimethylformamide (20 ml) were heated together at 110 °C overnight.
  • Step 6 Preparation of N-(4-chloro-2-ethoxymethyl-3-methylisothiazolin-5-ylidene)-3- [2-(2,2-dimethylpropyl)benzoxazol-5-yl]oxyacetamide
  • N,O-bis(trimethylsilyl)acetamide (0.155 g, 0.00135 mol) in dichloromethane (1 ml) was added to a solution of N-(4-chloro-3-methylisothiazol-5-yl)-[2- (2,2-dimethylpropyl)-benzoxazol-5-yl]oxyacetamide (0.250 g, 0.000635 mol) in dichloromethane (4 ml) and the mixture stirred at room temperature for 20 minutes.
  • EXAMPLE 11 This Example illustrates the preparation of Compound No. 66 of Table No. 51.
  • Step 1 Preparation of methyl 4-hydroxy-3-iodophenylacetate Potassium iodate (3.9 g, 0.018 mol) and iodine (9.2 g, 0.036 mol) were added to a solution of methyl 4-hydroxyphenylacetate (15.0 g, 0.090 mol) in glacial acetic acid (340 ml) and water (90 ml) at 5 °C and the mixture stirred at 5 °C for 1 h. The cooling bath was removed and the mixture allowed to warm to room temperature and stirred for a further 20 h.
  • 5-Amino-4-chloro-3-methylisothiazole (0.246 g, 0.00165 mol) was added to a suspension of sodium methoxide (0.210 g, 0.0039 mol) in tetrahydrofuran (6 ml) and the mixture stirred at room temperature for 20 minutes.
  • a solution of methyl [2-(2- methylpropyl)benzofuran-5-yl]acetate (0.370 g, 0.0015 mol) in tetrahydrofuran (4 ml) was added dropwise and the mixture stirred at room temperature for 20 h.
  • the mixture was diluted with water, acidifed with saturated aqueous ammonium chloride solution and extracted with ethyl acetate.
  • Step 4 Preparation of N-(4-chloro-2-ethoxymethyl-3-methylisothiazolin-5-yIidene)-3- [2-(2-methylpropyI)benzofuran-5-yl]acetamide
  • N,O-bis(trimethylsilyl)acetamide 0.325 g, 0.00160 mol
  • dichloromethane 1 ml
  • N-(4-chloro-3-methylisothiazol-5-yl)-[2- (2,2-dimethylpropyl)-benzoxazol-5-yl]oxyacetamide 0.475 g, 0.00132 mol
  • dichloromethane 4 ml
  • Iron powder (8.1 g) was added to a solution of methyl 4-fluoro-3-nitrophenylacetate (27. 24 g, 0.128 mol) in a mixture of concentrated hydrochloric acid (1.5 ml), isopropanol (265 ml) and water (26.5 ml) and the mixture stirred at room temperature for 1 hour. A second portion of iron powder (8.1 g) was added, and the mixture heated to reflux for 1 hour. A further quantity of concentrated hydrochloric acid was added and the mixture refluxed for a further 1 hour. The mixture was cooled to room temperature, filtered through a plug of 01/55139
  • the cooling bath was removed and the mixture allowed to warm to room temperature over a period of 1 h.
  • the mixture was diluted with water, acidified with 2M aqueous hydrochloric acid and extracted with ethyl acetate.
  • the organic extract was dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo to give methyl 2-[2-(2-methylpropyl)benzothiazol-5-yl]propionate (1.15 g) used without further purification in the next step.
  • 5-Amino-4-chloro-3-ethylisothiazole (0.81 g, 0.005 mol) was added to a suspension of sodium methoxide (0.56 g, 0.010 mol) in tetrahydrofuran (5 ml) and the mixture stirred at room temperature for 25 minutes.
  • a solution of give methyl 2-[2-(2-methylpropyl)benzo- thiazol-5-yl]pro ⁇ ionate (1.15 g, 0.004 mol) in tetrahydrofuran (4 ml) was added dropwise and the mixture stirred at room temperature for 1 ⁇ 2 h.
  • the mixture was diluted with saturated aqueous ammonium chloride solution and extracted with dichloromethane.
  • 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 of formula (I).
  • 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, S YNPERONIC NP8, until the liquid composition contained the required concentration of the compound.
  • SYNPERONIC is a registered trade mark.
  • 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.
  • Tests were also conducted against root knot nematodes (Meloidogyne incognita) using an in vitro test in which nematodes were suspended in a liquid composition which had been prepared as described above except that it contained a concentration of 12.5ppm by weight of a compound of formula (I) and it contained no SYNPERONIC NP8.
  • results from these tests are displayed in Table 76, in which each mortality (score) is designated as 9, 5 or 0 wherein 9 indicates 80-100%) mortality, 5 indicates 40-79% mortality and 0 indicates less than 40% mortality; and Dm represents Drosophila melanogaster; Mp represents Myzus persicae; Hv represents Heliothis virescens; Px represents Plutella xylostella; Tu represents Tetranychus urticae; Db represents Diabrotica balteata; and Mi represents Meloidogyne incognita.
  • EXAMPLE 14 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.
  • Uncinula necator (UNCINE), on vines; Phytophthora infestans lycopersici (PHYTIN) on tomatoes; Puccinia recondita (PUCCRT), on wheat; and Pyricularia oryzae (PYRIOR) on rice.
  • Each treatment was applied to two or more replicate plants for Phytophthora infestans lycopersici and Uncinula necator.
  • Puccinia recondita and Pyricularia oryzae two replicate pots each containing 6 to 10 plants were used for each treatment. The plants were inoculated one day before (Erad) or one day after (Prot) chemical application.
  • the Phytophthora infestans lycopersici, Puccinia recondita and Pyricularia oryzae plants were inoculated with a calibrated fungal spore suspension.
  • the Uncinula necator plants were inoculated using a 'blowing' inoculation technique.
  • Phytophthora infestans lycopersici Assessments were performed on a single leaf of each of the replicate plants for Uncinula necator. For Puccinia recondita and Pyricularia recondita assessments were carried out collectively on the plants in each replicate pot.
  • the disease level present (that is, the percentage leaf area covered by actively sporulating disease) was assessed visually. For each treatment, the assessed values for all its replicates were meaned to provide mean disease values. Untreated control plants were assessed in the same manner. The data were then processed by the method, described hereinafter, to provide PRCO (Percentage Reduction from Control) values.
  • PRCO Percentage Reduction from Control
  • PRCO 100 - ⁇ Mean disease level for treatment A ⁇ x 100 ⁇ Mean disease level on untreated controls ⁇
  • the PRCO is then rounded to the nearest whole number; therefore, in this particular example, the PRCO result is 71. If no test data were available this is indicated in the table by
  • PHYTIN Phytophthora infestans lycopersici
  • PYRIOR Pyricularia oryzae
  • PUCCRT Puccinia triticina

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne des composés représentés par la formule (I). Dans cette formule B est N, N-oxyde ou CR18, D est S ou NR7; E est N ou CR12; M est N-C(=Y), N étant l'atome de liaison au cycle qui contient D et E; Y est O, S ou NR13, Z est O, S ou NR14; et A et les divers groupes R sont des radicaux organiques définis. Cette invention concerne aussi la préparation et l'utilisation de ces composés.
PCT/GB2001/000301 2000-01-28 2001-01-26 Derive d'isothiazole et utilisations de ceux-ci sous forme de pesticides Ceased WO2001055139A1 (fr)

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GB0002034A GB0002034D0 (en) 2000-01-28 2000-01-28 Chemical compounds
GB0002034.7 2000-01-28

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6703347B2 (en) * 2000-01-28 2004-03-09 Syngenta Limited Isothiazole derivatives and their use as pesticides
WO2007077889A1 (fr) * 2005-12-27 2007-07-12 Nippon Soda Co., Ltd. Compose benzoisothiazoline et agent d’elimination d’organismes nuisibles
JP2009504720A (ja) * 2005-08-19 2009-02-05 シンジェンタ リミテッド 農薬として使用されるベンゾキサゾール誘導体の調製のための化学的方法
US7872033B2 (en) 2007-04-17 2011-01-18 Abbott Laboratories Compounds as cannabinoid receptor ligands
US7973069B2 (en) 2004-07-14 2011-07-05 Ptc Therapeutics, Inc. Methods for treating hepatitis C
KR101068152B1 (ko) * 2009-02-17 2011-09-27 한국화학연구원 항진균 활성을 갖는 플루오로페닐 벤조옥사졸 유도체, 이의제조방법 및 이의 용도
US8501794B2 (en) 2007-04-17 2013-08-06 Abbvie Inc. Compounds as cannabinoid receptor ligands
US8735434B2 (en) 2007-05-18 2014-05-27 Abbvie Inc. Compounds as cannabinoid receptor ligands
US8841334B2 (en) 2006-05-31 2014-09-23 Abbvie Inc. Compounds as cannabinoid receptor ligands and uses thereof
US8846730B2 (en) 2008-09-08 2014-09-30 Abbvie Inc. Compounds as cannabinoid receptor ligands
US8859596B2 (en) 2008-09-16 2014-10-14 Abbvie Inc. Compounds as cannabinoid receptor ligands
US8865753B2 (en) 2007-03-28 2014-10-21 Abbvie Inc. Compounds as cannabinoid receptor ligands
US8895592B2 (en) 2008-12-16 2014-11-25 Abbvie Inc. Compounds as cannabinoid receptor ligands
US9006275B2 (en) 2006-05-31 2015-04-14 Abbvie Inc. Compounds as cannabinoid receptor ligands and uses thereof
US9193713B2 (en) 2007-10-12 2015-11-24 Abbvie Inc. Compounds as cannabinoid receptor ligands

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995031448A1 (fr) * 1994-05-17 1995-11-23 Dowelanco Pesticides de n-(5-isothiazolyle)amide
WO1997018198A1 (fr) * 1995-11-14 1997-05-22 Bayer Aktiengesellschaft 5-aminoisothiazoles acyles avec effet insecticide, produits intermediaires et procede de production correspondant
WO1998002424A1 (fr) * 1996-07-16 1998-01-22 Bayer Aktiengesellschaft N-(5-isothiazolyl)-thioamides substitues

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995031448A1 (fr) * 1994-05-17 1995-11-23 Dowelanco Pesticides de n-(5-isothiazolyle)amide
WO1997018198A1 (fr) * 1995-11-14 1997-05-22 Bayer Aktiengesellschaft 5-aminoisothiazoles acyles avec effet insecticide, produits intermediaires et procede de production correspondant
WO1998002424A1 (fr) * 1996-07-16 1998-01-22 Bayer Aktiengesellschaft N-(5-isothiazolyl)-thioamides substitues

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6703347B2 (en) * 2000-01-28 2004-03-09 Syngenta Limited Isothiazole derivatives and their use as pesticides
US7973069B2 (en) 2004-07-14 2011-07-05 Ptc Therapeutics, Inc. Methods for treating hepatitis C
JP2009504720A (ja) * 2005-08-19 2009-02-05 シンジェンタ リミテッド 農薬として使用されるベンゾキサゾール誘導体の調製のための化学的方法
WO2007077889A1 (fr) * 2005-12-27 2007-07-12 Nippon Soda Co., Ltd. Compose benzoisothiazoline et agent d’elimination d’organismes nuisibles
US8841334B2 (en) 2006-05-31 2014-09-23 Abbvie Inc. Compounds as cannabinoid receptor ligands and uses thereof
US9006275B2 (en) 2006-05-31 2015-04-14 Abbvie Inc. Compounds as cannabinoid receptor ligands and uses thereof
US8865753B2 (en) 2007-03-28 2014-10-21 Abbvie Inc. Compounds as cannabinoid receptor ligands
US8835475B2 (en) 2007-04-17 2014-09-16 Abbvie Inc. Compounds as cannabinoid receptor ligands
US8501794B2 (en) 2007-04-17 2013-08-06 Abbvie Inc. Compounds as cannabinoid receptor ligands
US7872033B2 (en) 2007-04-17 2011-01-18 Abbott Laboratories Compounds as cannabinoid receptor ligands
US8735434B2 (en) 2007-05-18 2014-05-27 Abbvie Inc. Compounds as cannabinoid receptor ligands
US9193713B2 (en) 2007-10-12 2015-11-24 Abbvie Inc. Compounds as cannabinoid receptor ligands
US8846730B2 (en) 2008-09-08 2014-09-30 Abbvie Inc. Compounds as cannabinoid receptor ligands
US8859596B2 (en) 2008-09-16 2014-10-14 Abbvie Inc. Compounds as cannabinoid receptor ligands
US8895592B2 (en) 2008-12-16 2014-11-25 Abbvie Inc. Compounds as cannabinoid receptor ligands
KR101068152B1 (ko) * 2009-02-17 2011-09-27 한국화학연구원 항진균 활성을 갖는 플루오로페닐 벤조옥사졸 유도체, 이의제조방법 및 이의 용도

Also Published As

Publication number Publication date
GB0002034D0 (en) 2000-03-22
AU2001228667A1 (en) 2001-08-07

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