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WO2001055141A1 - Azine derivatives as pesticides - Google Patents

Azine derivatives as pesticides Download PDF

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Publication number
WO2001055141A1
WO2001055141A1 PCT/GB2001/000313 GB0100313W WO0155141A1 WO 2001055141 A1 WO2001055141 A1 WO 2001055141A1 GB 0100313 W GB0100313 W GB 0100313W WO 0155141 A1 WO0155141 A1 WO 0155141A1
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Prior art keywords
optionally substituted
alkyl
alkoxy
haloalkyl
cyano
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PCT/GB2001/000313
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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 Ltd
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Syngenta Ltd
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Priority to AU30343/01A priority Critical patent/AU3034301A/en
Publication of WO2001055141A1 publication Critical patent/WO2001055141A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/48—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —S—C≡N groups
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • 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
    • C07D417/14—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 three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring

Definitions

  • 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, W097/18198, WO98/02424, WO98/05670 and WO98/17630.
  • the present invention provides a compound of formula (I):
  • n is 0 or 1 ;
  • B is N, N-oxide or CR 5 ;
  • Y is O, S or NR 6 ;
  • Z is O, S or NR 7 ;
  • R 1 is hydrogen, halogen, optionally substituted C,. 6 alkyl, optionally substituted C 2.6 alkenyl, optionally substituted C 2 ⁇ alkynyl, optionally substituted C ⁇ alkoxy, optionally substituted C, .6 alkylthio, optionally substituted C 3 . 7 cycloalkyl, cyano, nitro or SF 5 ;
  • R 2 is hydrogen, halogen, optionally substituted C,. 6 alkyl, optionally substituted C 2.6 alkenyl, optionally substituted C 2 . 6 alkynyl, optionally substituted C,_ 6 alkoxy, optionally substituted C, .6 alkylthio, optionally substituted C,. 6 alkylsulfinyl, optionally substituted C, .6 alkyl- sulfonyl, cyano, nitro, formyl, optionally substituted C,.
  • R 1 and R 2 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 C,. 6 alkyl, C,. 6 haloalkyl or halogen;
  • R 3 is optionally substituted aryl, optionally substituted arylcarbonyl, optionally substituted C,. 10 alkyl [but not C,.
  • R 4 is hydrogen, halogen, cyano, optionally substituted C 2Q alkyl, optionally substituted C 2.20 alkenyl, optionally substituted C 2 . 20 alkynyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted C 5 . 6 cycloalkenyl, formyl, optionally substituted C,. 20 alkoxycarbonyl, optionally substituted C,. 20 alkylcarbonyl, aminocarbonyl, optionally substituted C,. 20 alkylaminocarbonyl, optionally substituted di(C,.
  • alkylaminocarbonyl optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-(C,. 6 )alkyl-N-arylaminocarbonyl, optionally substituted diarylaminocarbonyl, optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted N-(C 1 .
  • R 5 is hydrogen, halogen, nitro, cyano, optionally substituted C,_ 8 alkyl, optionally substituted C 2 . 6 alkenyl, optionally substituted C 2 . 6 alkynyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted C,_ 6 alkoxycarbonyl, optionally substituted C,. 6 alkylcarbonyl, optionally substituted C,. 6 alkylaminocarbonyl, optionally substituted di-(C,_ 6 )alkylamino- carbonyl, optionally substituted phenyl or optionally substituted heteroaryl; R 6 is hydrogen, cyano, nitro, optionally substituted C,.
  • R 7 is hydrogen, cyano, optionally substituted C,. g alkyl, optionally substituted [C 2.6 alkenyl(C,. 6 )alkyl], optionally substituted [C 2 . 6 alkynyl(C,. 6 )alkyl], optionally substituted C 3.7 cycloalkyl, optionally substituted [C 3 . 7 cycloalkyl(C,. 6 )alkyl], C,. 6 alkoxy (C, .6 )alkyl, optionally substituted C,_ 6 alkoxycarbonyl, optionally substituted C,.
  • R 8 and R 15 are, independently, hydrogen, optionally substituted phenyl (C ].2 )alkyl or optionally substituted C,. 20 alkyl;
  • R 9 and R 16 are, independently, hydrogen, optionally substituted phenyl or optionally substituted C,. 6 alkyl;
  • R 10 and R 11 are, independently, optionally substituted C,. 6 alkyl; or R 10 and R 11 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 and S and which is optionally substituted by one or two independently selected C,. 6 alkyl groups;
  • R 12 is hydrogen, optionally substituted C,_ 20 alkyl, optionally substituted [C 2.20 alkenyl- (C,. 6 )alkyl], optionally substituted [C 2 . 20 alkynyl(C,.
  • R 13 and R 14 are, independently, hydrogen, optionally substituted C,. 20 alkyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted [C 2 . 20 alkenyl(C,. 6 )alkyl], optionally substituted [C 2 . 20 alkynyl(C,. 6 )alkyl], optionally substituted C,. 20 alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted alkylcarbonyl, optionally substituted C, .20 alkylsulfonyl or optionally substituted phenylsulfonyl.
  • One group of preferred compounds is a group where n is 0 or 1 ; B is N, N-oxide or CR 5 ; Y is O, S or NR 6 ; Z is O, S or NR 7 ; R 3 is optionally substituted C wo alkyl, optionally substituted [C 2 . 6 alkenyl(C,. 6 )alkyl], optionally substituted [C 2 . 6 alkynyl(C,. 6 )alkyl], optionally substituted C 3 . 7 cycloalkyl, optionally substituted C 0 alkylcarbonyl, optionally substituted C, .10 alkoxycarbonyl, formyl, optionally substituted C,.
  • R a is Cj. 6 alkyl, C, ⁇ haloalkyl or optionally substituted phenyl; r is 0, 1 or 2; R 4 is hydrogen, halogen, cyano, optionally substituted C,. 20 alkyl, optionally substituted C 2 . 20 alkenyl, optionally substituted C 2 . 20 alkynyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted C 5 .
  • 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 12 0, HS, optionally substituted C, .20 alkylthio, optionally substituted C,.
  • R 1 is hydrogen, halogen, optionally substituted C,. 6 alkyl, optionally substituted C 2 . 6 alkenyl, optionally substituted C 2.6 alkynyl, optionally substituted C,. 6 alkoxy, optionally substituted C,.
  • R 1 and R 2 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated ring carbocylic or heterocyclic ring which may contain one or two hetero atoms selected from O, N or S and which may be optionally substituted by C,_ 6 alkyl, C w haloalkyl or halogen;
  • R 6 is hydrogen, cyano, nitro, optionally substituted C,. 6 alkyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted - (C 2.6 )alkenyl(C,. 6 )alkyl, optionally substituted (C 2 .
  • R 7 is hydrogen, cyano, optionally substituted C, .8 alkyl, optionally substituted [C 2 .
  • R 5 is hydrogen, halogen, nitro, cyano, optionally substituted C,. 8 alkyl, optionally substituted C 2.6 alkenyl, optionally substituted C 2 . 6 alkynyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted C,. 6 alkoxycarbonyl, optionally substituted C,_ 6 alkylcarbonyl, optionally substituted C,_ 6 alkylaminocarbonyl, optionally substituted di(C,.
  • R 10 and R 11 are, independently, optionally substituted C,_ 6 alkyl or R 10 and R n together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two C,. 6 alkyl groups;
  • R 12 is hydrogen, optionally substituted C, .20 alkyl, optionally substituted [C 2 . 20 alkenyl(C,.
  • R 13 and R 14 are, independently, hydrogen, optionally substituted C,. 20 alkyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted [C 2 . 20 alkenyl(C,. 6 )alkyl], optionally substituted [C 2 . 20 alkynyl(C,.
  • R 13 and R 14 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two C,.
  • R 16 and R 9 are independently hydrogen, optionally substituted phenyl or optionally substituted C, .6 alkyl; and R 15 and R 8 are, independently, hydrogen, optionally substituted phenyl (C, .2 )alkyl or optionally substituted C,. 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 20 is C, .6 alkyl, C j . 6 haloalkyl or phenyl(Cj. 2 )alkyl
  • R 21 and R 22 are, independently, hydrogen, C, .8 alkyl, C 3 . 7 cycloalkyl, C 2 . 6 alkenyl(C,. 6 )alkyl, C 2 . 6 alkynyl(C,. 6 )alkyl, C 2 . 6 haloalkyl, C,_ 6 alkoxy (C,. 6 )alkyl, C ] . 6 alkoxycarbonyl(C,.
  • R 21 and R 22 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 is optionally substituted by one or two C,. 6 alkyl groups;
  • R 23 and R 24 are, independently, hydrogen, C,. 8 alkyl, C 3 . 7 cycloalkyl, C 2 . 6 alkenyl(C,. 6 )alkyl, C 2-6 alkynyl(C, .6 )alkyl, C 2 .
  • Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, H-propyl, n-butyl, n-pentyl, n-hexyl, wo-propyl, n-butyl, sec-butyl, wO-butyl, tert-butyl or Heo-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 C,. 6 alkyl or halogen), C 5 . 7 cycloalkenyl (itself optionally substituted with C,. 6 alkyl or halogen), hydroxy, C M0 alkoxy, C,. 10 alkoxy(C 0 )alkoxy, tri(C M )alkylsilyl(C 1 . 6 )alkoxy, C w alkoxycarbonyl(C,. 10 )alkoxy, 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.
  • alkenyl or alkynyl include those optional substituents given above for an alkyl moiety.
  • acyl is optionally substituted C,_ 6 alkylcarbonyl
  • 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,_ 6 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 C, .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-, C,. 6 alkyl, C, .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 C,.
  • Haloalkenyl groups are alkenyl groups which are substituted with one or more of the same or different halogen atoms
  • 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 (C, .6 )alkyl groups.
  • heterocyclic rings are formed by joining two groups on an N atom, the resulting rings are suitably pyrrolidine, piperidine, thiomorpholine and morpholine each of which may be substituted by one or two independently selected (C,_ 6 ) alkyl groups.
  • the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, HO 2 C, C,. 10 alkoxy (itself optionally substituted by C,. 10 alkoxy), aryl(C M )alkoxy, C,. 10 alkylthio, C,. 10 alkylcarbonyl, C 0 alkoxycarbonyl, C,. 6 alkylaminocarbonyl, di(C,. 6 alkylaminocarbonyl, (C 1 .
  • alkylsulfonyl C ⁇ alkylsulfinyl, tri(C M )alkylsilyl, tri(C )alkylsilyl(C, ⁇ )alkoxy, aryldi(C M )alkylsilyl, (C )alkyldiarylsilyl and triarylsilyl.
  • the optional substituents on alkenyl or alkynyl include one or more of halogen, aryl and C 3 . 7 cycloalkyl. It is more preferred that heterocyclyl is optionally substituted by C,. 6 alkyl.
  • the optional substituents for cycloalkyl include halogen, cyano and C j.3 alkyl.
  • the optional substituents for cycloalkenyl include C ⁇ alkyl, halogen and cyano.
  • the present invention provides a compound of formula (IA):
  • n, B, Y, Z, R 1 , R 2 , R 3 and R 4 are as defined above for a compound of formula (I).
  • One group of preferred compounds of formula (I A) is a group where R 1 is hydrogen, halogen, C,. 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, C w cyanoalkyl, C,. 6 haloalkyl, C ⁇ alkoxy, C j.6 haloalkoxy, C,. 6 alkylthio, C, ⁇ haloalkylthio, C 3 . 6 cycloalkyl, C 3 .
  • R 4 is cyano, C N8 alkyl, C,. 6 haloalkyl, C, .6 cyanoalkyl, C 2.6 alkenyl, C 2 . 6 alkynyl, C 3 .
  • heteroaryl optionally substituted by halo, nitro, cyano, C,_ 6 alkyl, C,_ 6 haloalkyl, C 6 alkoxy or C,. 6 haloalkoxy
  • heterocyclyl optionalall substituted by halo, nitro, cyano, C t . 6 alkyl, C, ⁇ haloalkyl, C 6 alkoxy or C,_ 6 haloalkoxy
  • heteroaryl(C M )alkyl where the heteroaryl may be substituted by halo, nitro, cyano, C,_ 6 alkyl, C, ⁇ haloalkyl, C,. 6 alkoxy or C,.
  • R 2 is hydrogen, halogen, C, .6 alkyl, C 2.6 alkenyl, C,. 6 alkynyl, C,. 6 haloalkyl, C,. 6 alkoxy, C,_ 6 alkoxy (C,.
  • R 1 and R 2 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated ring carbocylic or heterocyclic ring which may contain one or two hetero atoms selected from O, N or S and which may be optionally substituted by C,. 6 alkyl, C,. 6 haloalkyl or halogen; R 6 is cyano, nitro, C 1-6 alkyl, C, ⁇ haloalkyl, C 3 .
  • R 7 is hydrogen, C,. 8 alkyl, C,. 6 haloalkyl, C, .6 cyanoalkyl, C 2.6 alkenyl, C 2 . 6 alkynyl, C 3 . 7 cycloalkyl, C 2 . 6 haloalkenyl, C 3 .
  • R 5 is hydrogen, halogen, nitro, cyano, C M alkyl, C w haloalkyl, C,. 6 cyanoalkyl, C 2 . 6 alkenyl, C 2.6 alkynyl, C 3.7 cycloalkyl, C 2 . 6 haloalkenyl, C 3 . 7 cycloalkyl(C,. 6 )alkyl, C,. 6 alkoxy - (C,.
  • R 12 is hydrogen, C,. g alkyl, C, .6 haloalkyl, C, .6 cyanoalkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, C,.
  • heterocyclyl optionally substituted by halo, nitro, cyano, C j _ 6 alkyl, C,. 6 haloalkyl, C 1-6 alkoxy or C,_ 6 haloalkoxy
  • heterocyclyl(C M )alkyl wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C ⁇ alkyl, C 6 haloalkyl
  • R 16 is C 1-6 alkyl, C, .6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C ⁇ haloalkyl, C j.6 alkoxy or C,. 6 haloalkoxy),
  • R 13 and R 14 are, independently, hydrogen, C, .g alkyl, C 3.7 cycloalkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, C 3 .
  • R 15 and R 8 are, independently, C,. 6 alkyl or phenyl(C,. 2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,. 6 haloalkyl, C, ⁇ alkoxy or C,. 6 haloalkoxy).
  • n is preferably 0.
  • B is preferably N.
  • Y is preferably O or S.
  • Y is more preferably O.
  • Z is preferably O or S.
  • Z is more preferably O.
  • R 1 is hydrogen, halogen, C,. 6 alkyl, C,_ 6 cyanoalkyl, C,_ 6 haloalkyl, C 3.7 cycloalkyl(C, .4 )alkyl, C ⁇ 6 alkoxy (C ⁇ alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, C,_ 6 alkoxy, C, .6 haloalkoxy, C, .6 alkylthio, C,. 6 haloalkylthio, C 3 . 6 cycloalkyl, cyano, nitro or SF 5 .
  • R is more preferably hydrogen, halogen, C,. 6 alkyl, C 2 .
  • R 1 is hydrogen, halogen, C,. 6 alkyl, C,_ 6 haloalkyl, C, .6 alkoxy(C 1 . 6 )alkyl, C 2 . 6 alkenyl, Cj. 6 alkoxy, C 6 haloalkoxy, C,_ 6 alkylthio, C,. 6 haloalkylthio, C 3 . 6 cycloalkyl or cyano.
  • R 1 is halogen, C j . 6 alkyl, C,. 6 haloalkyl, C, .6 alkoxy or C, .6 haloalkoxy.
  • R is hydrogen, halogen, C,. 6 alkyl, C,. 6 haloalkyl, C 1-6 alkoxy(C,. 6 )alkyl, C 2 . 6 alkenyl, C ⁇ alkynyl, C,. 6 alkoxy, C ⁇ haloalkoxy, C, .6 alkylthio, C, .6 haloalkylthio, C,. 6 alkylsulfinyl, C M haloalkylsulfinyl, C,. 6 alkylsulfonyl, C j.6 haloalkylsulfonyl, cyano, nitro, formyl, C 6 alkylcarbonyl, C,.
  • R 1 and R 2 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 C,. 6 alkyl, C,_ 6 haloalkyl or halogen; where R 8 is phenyl(C ] .
  • R 2 is hydrogen, halogen, C,. 6 alkyl, C ⁇ haloalkyl, C 6 alkoxy (C 1 . 6 )alkyl, C, ⁇ alkoxy, C 6 haloalkoxy, C ⁇ 6 alkylthio or SF 5 ; or R 1 and R 2 together with the atoms to which they are attached form a cyclopentane or benzene ring optionally substituted by C ⁇ . 6 alkyl, Cj. 6 haloalkyl or halogen.
  • R 2 is even more preferably hydrogen, halogen, C,_ 6 alkyl, C,_ 6 haloalkyl, C, .6 alkoxy,
  • R 2 is hydrogen, halogen, C,_ 6 alkyl, C,. 6 haloalkyl, C, .6 alkoxy (C,. 6 )alkyl, C M alkoxy, C,_ 6 haloalkoxy; or R 1 and R 2 together with the atoms to which they are attached form a cyclopentane ring optionally substituted by C,_ 6 alkyl, C,_ 6 haloalkyl or halogen.
  • R 2 is most preferably halogen, C,. 6 alkyl, C,. 6 haloalkyl, C,. 6 alkoxy, C, ⁇ alkoxy (C,. 6 )alkyl or C ⁇ haloalkoxy. It is preferred that R 3 is C 7 . 10 alkyl, C,. 6 alkylcarbonyloxy(C,. 6 )alkyl, di(C,. 6 )alkylaminocarbonyloxy(C ] . 6 )alkyl, benzoyloxymethyl (where the phenyl ring is optionally substituted with halogen or C M alkyl), C,.
  • alkoxy ⁇ alkyl (where the alkyl group is substituted by aryl or C M alkoxycarbonyl), tri(C ] . 4 )alkylsilyl(C 1 . 6 )alkoxy(C 1.6 )alkyl, C 3.7 cycloalkyloxy(C 1 . 6 )alkyl (where the cycloalkyl group is optionally substituted with C ⁇ alkyl), C 7-10 alkoxy(C,. 6 )alkyl, C,. 6 haloalkyloxymethyl, C 2 .
  • R 3 may preferably be (C 7 . ]0 )alkyl (optionally substituted by aryl);
  • [(C 2.6 )alkenyl(C M )alkyl] (optionally substituted by halo, (C )alkyl or aryl); - (C )alkyl (substituted with aryl(C M )alkoxy; tri(C M )alkylsilyl(C,. 6 )alkoxy; - (C, .6 )alkylcarbonyloxy; (C 7 . 10 )alkoxy; [(C,. 6 )alkyl substituted (C 3 . 7 )cycloalkyl]oxy; aryl- (C, alkylthio; tri(C M )alkylsilyl(C 1 .
  • R 3 is (C M )alkyl (substituted with aryl(C M )alkoxy; tri(C M )alkylsilyl- (C, .6 )alkoxy; (C ⁇ .6 )alkylcarbonyloxy; (C 7 .
  • R 3 is C,. 6 alkylcarbonyloxymethyl, benzoyloxymethyl (where the phenyl ring is optionally substituted with halogen or C,. 4 alkyl), C,. 6 alkoxy- (C, .6 )alkyl (where the alkyl group is substituted by aryl), tri(C 1 . 4 )alkylsilyl(C,. 6 )alkoxy- methyl, C 3.7 cycloalkyloxymethyl (where the cycloalkyl group is optionally substituted with C, .6 alkyl), C 7.10 alkoxymethyl, C 2 . 6 alkenyloxymethyl, C 2 .
  • R 3 is more preferably C 6 alkylcarbonyloxymethyl, C 2 . 6 alkenyloxymethyl or C 2.6 alkynyloxymethyl .
  • R 4 is cyano, C s alkyl, C,. 8 haloalkyl, C,_ 8 cyanoalkyl, C 3 . 7 cycloalkyl(C w )alkyl, C 5 . 6 cycloalkenylCC ⁇ alkyl, C,. 6 alkoxy(C,. 6 )alkyl, C 3 . 6 alkenyl- oxy(C, .6 )alkyl, C 3.6 alkynyloxy(C,. 6 )alkyl, aryloxy(C, alkyl, C,. 6 carboxyalkyl, C,_ 6 alkylcarbonyl C ⁇ alkyl, C 2.6 alkenylcarbonyl(C,.
  • R 16 is phenyl (optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,.
  • R 13 and R 14 are, independently, hydrogen, C t . 8 alkyl, C 3.7 cycloalkyl(C )alkyl, C 2 . 6 haloalkyl, C,. 6 C 3.7 cycloalkyl, C 3 . 6 alkenyl, C 3.6 alkynyl or C,. 6 alkoxycarbonyl; and R 15 is (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.
  • R 4 may preferably be C,. 8 alkyl, C,. 6 haloalkyl, C,_ 6 cyanoalkyl, C 2.6 alkenyl, C 2 . 6 alkynyl, C 3 . 7 cycloalkyl, C 3 . 7 halocycloalkyl, C 3 . 7 cyanocycloalkyl, C,. 3 alkyl(C 3. 7 )cycloalkyl, C,. 3 alkyl(C 3 . 7 )halocycloalkyl, C 5 .
  • heteroaryl optionally substituted by halo, nitro, cyano, C,_ 6 alkyl, C j . 6 haloalkyl, C,. 6 alkoxy or C,. 6 haloalkoxy
  • heterocyclyl wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,.
  • heteroaryl (C )alkyl wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C, .6 alkyl, C,_ 6 haloalkyl, C ⁇ alkoxy or C _ 6 haloalkoxy
  • heterocyclyl(C )alkyl wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,. 6 haloalkyl, C,. 6 alkoxy or C,. 6 haloalkoxy
  • R 16 is C,. 6 alkyl, C,_ 6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, C ⁇ alkyl, C,. 6 haloalkyl, C,. 6 alkoxy or C,_ 6 haloalkoxy); R 16 is C, .6 alkyl, C ] . 6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, C,.
  • R 13 and R 14 are, independently, hydrogen, C, .g alkyl, C 3.7 cycloalkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, C 3 . 7 cycloalkyl(C M )alkyl, C 2.6 haloalkyl, C, .6 alkoxy(C,.
  • R 6 alkyl, C 6 alkoxycarbonyl, or R 13 and R 14 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two C,_ 6 alkyl groups; and R 15 is C,. 6 alkyl or phenyl(C, .2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C, .6 alkyl, C, ⁇ haloalkyl, C,.
  • R 4 is C, .g alkyl, C, .g haloalkyl, C Ng cyanoalkyl, C 3 . 7 cycloalkyl, C ⁇ alkyl (C 3 . 7 ) cycloalkyl, C L6 alkoxy (C, .6 ) alkyl, heterocyclic (optionally substituted by halo, nitro, cyano, C ⁇ alkyl, C,_ 6 haloalkyl, C,_ 6 alkoxy or C,.
  • R 13 andR 14 are independently C, .g 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 C ⁇ alkyl groups.
  • R 4 is more preferably C,. s alkyl, C,. 6 haloalkyl, C,. 6 cyanoalkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, C 3 . 7 cycloalkyl, C 3 . 7 halocycloalkyl, C 3 .
  • heterocyclyl wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,. 6 haloalkyl, C, .6 alkoxy or C U6 haloalkoxy
  • heteroaryl(C M )alkyl wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C, ⁇ alkyl, C,. 6 haloalkyl, C,. 6 alkoxy or C,.
  • R 13 and R 14 are, independently, hydrogen, C 1-8 alkyl, C 3.7 cycloalkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, C 3 . 7 cycloalkyl(C M )alkyl, C 2 . 6 haloal-kyl, C, ⁇ alkoxy(C ! . 6 )alkyl, C,.
  • R 13 and R 14 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 C,. 6 alkyl groups; and R 15 is C,. 6 alkyl or phenyl(C,. 2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,_ 6 alkyl, C,.
  • R 4 is more preferably C,_ 8 alkyl, C,_ 8 haloalkyl, cyanoalkyl, C 3.7 cycloalkyl, C i alkyl(C 3 . 7 )cycloalkyl, C,_ 6 alkoxy(C j . 6 )alkyl, heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C,_ 6 alkyl, C,.
  • R 13 andR 14 are, independently, C, .g 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 heteroatoms selected from O, N or S and which may be optionally substituted by one or two C ⁇ alkyl groups.
  • R 4 is haloalkyl, C,. g cyanoalkyl, C 3 . 7 cycloalkyl(C !.6 )alkyl, C 5 . 6 cycloalkenyl(C,.
  • heterocyclyl - (C M )alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, - C, ⁇ alkyl, C,_ 6 haloalkyl, C 6 alkoxy or C ⁇ _ 6 haloalkoxy), C 2 . 6 alkenyl, C 2 . 6 haloalkenyl, - C,. 6 cyanoalkenyl, C 5.6 cycloalkenyl, aminocarbonyl(C 2 . 6 )alkenyl, C ⁇ alkylamino-carbony ⁇ C,.
  • R 16 is phenyl (optionally substituted by halo, nitro, cyano, C j.6 alkyl, C ⁇ haloalkyl, C 1-6 alkoxy or C, ⁇ haloalkoxy), C, ⁇ alkyl or C 6 haloalkyl;
  • R 13 and R 14 are, independently, hydrogen, C ⁇ . 8 alkyl, C 3 . 7 cycloalkyl(C M )alkyl, C 2 . 6 haloalkyl, C, .6 alkoxy(C, .6 )alkyl, C 3 . 7 cycloalkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl or C,.
  • R 15 is phenyl(C 1.2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, 6 alkyl, C, .6 haloalkyl, C,. 6 alkoxy or C ⁇ 6 haloalkoxy) or C,_ 6 alkyl.
  • R 4 is C ⁇ alkyl, C,. 8 haloalkyl, C ⁇ cyanoalkyl, C,. 6 alkoxy (C,_ 6 ) alkyl, C 3 . 7 cycloalkyl, Cj. 3 alkyl (C 3 . 7 ) cycloalkyl, heterocyclyl (optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,. 6 haloalkyl, C,. 6 alkoxy or C,_ 6 haloalkoxy) or di(C 1.g )alkylamino. It is yet more preferred that R 4 is Cj. g alkyl, C,.
  • haloalkyl C,. g cyanoalkyl, C,. 6 alkoxy (C, .6 ) alkyl, C 3 . 7 cycloalkyl, C,. 3 alkyl (C 3 . 7 ) cycloalkyl, heterocyclyl (optionally substituted by C ⁇ _ 6 alkyl) or di(C,. 8 )alkylamino.
  • R 4 is most preferably C,. g alkyl, C,. g haloalkyl, C,. 8 cyanoalkyl, C 3 . 7 cycloalkyl, C,_ 3 alkyl(C 3.7 )cycloalkyl, C,. 6 alkoxy (C,. 6 )alkyl or R 13 R 14 N; where R 13 andR 14 are, indepen- dently, C, .g 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 C,_ 6 alkyl groups.
  • R 5 is hydrogen, halogen, nitro, cyano, C ⁇ alkyl, C j.6 haloalkyl, C,_ 6 cyanoalkyl, C 3 . 7 cycloalkyl(C,. 6 )alkyl, C,. 6 alkoxy(C,. 6 )alkyl, C,. 6 alkoxycarbonyl(C,. 6 )alkyl, C,_ 6 alkylcarbonyl(C,. 6 )alkyl, C,. 6 alkylaminocarbonyl(C ⁇ . 6 )alkyl, di(C,. 6 )alkylamino- carbony ⁇ C j . alkyl, phenyl(C,.
  • R 5 is hydrogen, halogen, C,. g alkyl or C,. 6 haloalkyl. It is preferred that R 6 is cyano, nitro, C,_ 6 alkyl, C, ⁇ haloalkyl, C 3 . 7 cycloalkyl(C !.6 )alkyl, C 3 . 7 cycloalkyl, CH 2 (C 2 . 6 )alkenyl, CH 2 (C 2 . 6 )alkynyl, phenyl (optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,_ 6 haloalkyl, C,.
  • R 7 is hydrogen, C 1-g alkyl, C,. 6 haloalkyl, C,_ 6 cyanoalkyl, C 2.6 alkenyl, C 2.6 haloalkenyl, C 2 . 6 alkynyl, C 3 . 7 cycloalkyl, C 3 . 7 cycloalkyl(C,. 6 )alkyl, C, ⁇ alkoxy(C !.6 )alkyl, C 6 alkoxycarbonyl, C,. 6 alkylcarbonyl, C,. 6 alkylaminocarbonyl, di(C,.
  • R 7 is hydrogen, C,. g alkyl or Cj. 6 haloalkyl.
  • the compounds of Tables 1 to 86 illustrate compounds of the invention.
  • Table 1 provides 410 compounds of formula (1): wherein R 3 and R 4 are as defined in Table 1.
  • R 4 and R 3 are as defined in Table 2.
  • Table 3 provides 290 compounds of formula (3):
  • R 3 and R 4 are as defined in Table 2.
  • Table 4 provides 290 compounds of formula (4):
  • R 3 and R 4 are as defined in Table 2.
  • Table 5 provides 290 compounds of formula (5):
  • R 3 and R 4 are as defined in Table 2.
  • Table 6 provides 290 compounds of formula (6):
  • R 3 and R 4 are as defined in Table 2.
  • Table 7 provides 290 compounds of formula (7):
  • R 3 and R 4 are as defined in Table 2.
  • Table 8 provides 290 compounds of formula (8):
  • R 3 and R 4 are as defined in Table 2.
  • Table 9 provides 290 compounds of formula (9): wherein R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • Table 13 provides 290 compounds of formula (13):
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • Table 17 provides 290 compounds of formula (17):
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • Table 20 provides 290 compounds of formula (20): wherein R 3 and R 4 are as defined in Table 2.
  • Table 21 provides 290 compounds of formula (21):
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • Table 27 provides 290 compounds of formula (27):
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • Table 30 provides 290 compounds of formula (30):
  • R 3 and R 4 are as defined in Table 2.
  • Table 31 provides 290 compounds of formula (31): wherein R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • Table 33 provides 290 compounds of formula (33):
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • Table 35 provides 290 compounds of formula (35):
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • Table 37 provides 290 compounds of formula (37):
  • R 3 and R 4 are as defined in Table 2.
  • Table 39 provides 290 compounds of formula (39):
  • R 3 and R 4 are as defined in Table 2.
  • Table 40 provides 290 compounds of formula (40):
  • R 3 and R 4 are as defined in Table 2.
  • Table 42 provides 290 compounds of formula (42): wherein R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • Table 45 provides 290 compounds of formula (45):
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • Table 50 provides 290 compounds of formula (50):
  • R 3 and R 4 are as defined in Table 2.
  • Table 51 provides 290 compounds of formula (51):
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • Table 53 provides 290 compounds of formula (53): wherein R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • R 3 and R 4 are as defined in Table 2.
  • Table 57 provides 290 compounds of formula (57):
  • R 3 and R 4 are as defined in Table 2.
  • Table 58 provides 290 compounds of formula (58):
  • R 3 and R 4 are as defined in Table 2.
  • Table 59 provides 290 compounds of formula (59):
  • R 3 and R 4 are as defined in Table 2.
  • Table 60 provides 290 compounds of formula (60):
  • R 3 and R 4 are as defined in Table 2.
  • Table 61 provides 290 compounds of formula (61):
  • R 3 and R 4 are as defined in Table 2.
  • Table 62 provides 290 compounds of formula (62):
  • R 3 and R 4 are as defined in Table 2.
  • Table 63 provides 290 compounds of formula (63):
  • R 3 and R 4 are as defined in Table 2.
  • Table 64 provides 290 compounds of formula (64): wherein R 3 and R 4 are as defined in Table 2.
  • Table 65 provides 290 compounds of formula (65):
  • R 3 and R 4 are as defined in Table 2.
  • Table 66 provides 290 compounds of formula (66):
  • R 3 and R 4 are as defined in Table 2.
  • Table 68 provides 290 compounds of formula (68):
  • R 3 and R 4 are as defined in Table 2.
  • Table 69 provides 290 compounds of formula (69): wherein R 3 and R 4 are as defined in Table 2.
  • Table 70 provides 290 compounds of formula (70):
  • R 3 and R 4 are as defined in Table 2.
  • Table 71 provides 290 compounds of formula (71):
  • R 3 and R 4 are as defined in Table 2.
  • Table 72 provides 290 compounds of formula (72):
  • R 3 and R 4 are as defined in Table 2.
  • Table 73 provides 290 compounds of formula (73):
  • R 3 and R 4 are as defined in Table 2.
  • Table 74 provides 290 compounds of formula (74):
  • R 3 and R 4 are as defined in Table 2.
  • Table 75 provides 290 compounds of formula (75):
  • R 3 and R 4 are as defined in Table 2.
  • Table 76 provides 290 compounds of formula (76):
  • R 3 and R 4 are as defined in Table 2.
  • Table 77 provides 290 compounds of formula (77):
  • R 3 and R 4 are as defined in Table 2.
  • Table 78 provides 290 compounds of formula (78):
  • R 3 and R 4 are as defined in Table 2.
  • Table 79 provides 290 compounds of formula (79):
  • R 3 and R 4 are as defined in Table 2.
  • Table 80 provides 290 compounds of formula (80): wherein R 3 and R 4 are as defined in Table 2.
  • Table 81 provides 290 compounds of formula (81):
  • R 3 and R 4 are as defined in Table 2.
  • Table 82 provides 290 compounds of formula (82):
  • R 3 and R 4 are as defined in Table 2.
  • Table 83 provides 290 compounds of formula (83):
  • R 3 and R 4 are as defined in Table 2.
  • Table 84 provides 290 compounds of formula (84):
  • R 3 and R 4 are as defined in Table 2.
  • Table 85 provides 290 compounds of formula (85):
  • R 3 and R 4 are as defined in Table 2.
  • Table 86 provides 290 compounds of formula (86):
  • R 3 and R 4 are as defined in Table 2.
  • Table 87 shows selected melting point and 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 6 -DMSO)), (no attempt is made to list all characterising data in all cases) for compounds of Tables 1 to 86.
  • the compounds of the invention may be made in a variety of ways.
  • a compound of formula (I) may be prepared by acylating a compound of formula (II) with a compound of formula (III), preferably in the presence of a known coupling agent such as 1,3-dicyclohexylcarbodiimide, 1,3-ditsopropylcarbodiimide or l-(3-dimethylamino- propyl)-3-ethylcarbodiimide.
  • a compound of formula (III) may first be converted to an acid chloride or anhydride suitable for reaction with an amine to form an amide; such procedures are well known and are described, for example, in J. March, Advanced Organic Chemistry, Third Edition, John Wiley and Sons, New York, 1985, pages 370-376 and references therein.
  • Compounds of formula (II) are either known compounds or may be prepared from commercially available starting materials by methods described in the literature (see, for example, C. Oliver Kappe, Robert Flammang, and Curt Wentrup, Heterocycles, Vol. 37, No. 3, 1615, (1994); A. Adams and R. Slack, J. Chem. Soc, 3061, (1959); and Ronald Ehackler, Kenneth W. Burow, Jr., Sylvester V. Raster and David I. Wickiser, J. Heterocyclic Chem, 26, 1575, (1989)).
  • a compound of formula (III) may be prepared by hydrolysis of the corresponding compound of formula (IV) (wherein R is preferably C,. 6 alkyl) by a method known in the art.
  • a compound of formula (IV) may be hydrolysed under neutral, basic or acidic conditions; the reaction conditions are chosen such that substituent R 4 is unchanged during the hydrolysis reaction.
  • Compounds of formula (IV) capable of ready hydrolysis under different conditions are known in the literature and suitable compounds of formula (IV) may be selected, for example, by reference to Theodora W. Greene, Protective Groups in Organic Synthesis, Chapter 5, John Wiley and Sons, New York, 1981.
  • a compound of formula (IV) may be prepared from a compound of formula (V) under conditions described in the literature (see, for example, David W. Dunwell, Delme Evans, Terence A. Hicks, J. Med. Chem., 1975, Vol. 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, 1275-1278, 1991; Dale L. Boger, J. Org.
  • R 4 may be an atom or group which itself may be converted into other functional groups; procedures are known in the literature for such transformations involving benzoxazoles and benzothiazoles (for example, Lazer, Edward S., Adams, Julian; Miao, Clara K.; Farina, Peter, Eur. Pat. Appl. EP0535521). Alternatively R 4 may contain atoms or groups which may be replaced by other moieties under known conditions.
  • a compound of formula (V) may be prepared by reduction of a compound of formula (VI) and such procedures are known in the art (see, for example, J. March, Advanced Organic Chemistry, Third Edition, John Wiley and Sons, New York, 1985, and references therein).
  • a compound of formula (VI), wherein Z is oxygen may be prepared by the nitration of a compound of formula (VII) under known conditions.
  • (VI) (wherein Z is sulfur) may be prepared from a compound of formula (VI) (wherein Z is oxygen) using conditions similar to those described by J. Scheigetz, R. Zamboni and B. Roy, Synth. Commun., 25 (1995) (18), pages 2791-2806.
  • a compound of formula (VI) (wherein Z is nitrogen) may be prepared from a compound of formula (VII) by a sequence of acylation, nitration and deacylation, using conditions known in the art.
  • Compounds of formula (VII) are either commercially available compounds or may be made from commercially available materials by known methods.
  • a compound of formula (I) may be prepared by treating a compound of formula (VIII) with, for example, an acid in the presence of a coupling reagent, an orthoester, acid chloride, hydroxyimoyl chloride or an alcohol in the presence of a ruthenium catalyst as described previously for the preparation of a compound of formula (IV).
  • a compound of formula (VIII) may be obtained by reduction of a compound of formula (IX), itself obtained from a compound of formula (X) using the procedures described above for the transformation of a compound of formula (VII) to a compound of formula (V).
  • a compound of formula (X) may be prepared by reacting a compound of formula
  • a compound of formula (X), wherein Z is oxygen may be obtained by reacting a compound of formula (XI), wherein Z is oxygen, with a suitable reagent such as boron tribromide, hydriodic acid or another suitable reagent, as described by Theodora W. Greene, Protective Groups in Organic Synthesis, Chapter 1 , John Wiley and Sons, New York, 1981.
  • a suitable reagent such as boron tribromide, hydriodic acid or another suitable reagent
  • a compound of formula (XI) (wherein Z is oxygen) may be prepared by coupling a compound of formula (II) with a compound of formula (XII) (wherein Z is oxygen) in a manner analogous to that described above for the transformation of a compound of formula (III) to a compound of formula (I).
  • Compounds of formula (XII) (wherein Z is oxygen) are known compounds.
  • An alternative method for preparing a compound of formula (IV) (wherein Z is sulfur) involves the cyclisation of a compound of formula (XIII) (wherein LG is a halogen, such as fluorine, chlorine or bromine) as described, for example, in Comprehensive Heterocyclic Chemistry, Volume 6, Ed.
  • a compound of formula (XIII) may be prepared by reacting a compound of formula (XIV) with a suitable thionating agent such as 2,4-bis(4-methoxyphenyl)-l,3-dithia-2,4-diphosphetane- 2,4-disulfide (Lawesson's reagent), 2,4-bis(methylthio)-l,3-dithia-2,4-diphosphetane-2,4- disulfide (Davy reagent methyl), 2,4-bis(p ⁇ r ⁇ -tolyl)-l,3-dithia-2,4-diphosphetane-2,4- disulfide (Davy reagent /?-tolyl) or phosphorus pentasulfide in a suitable solvent such as toluene or fluorobenzene.
  • a suitable thionating agent such as 2,4-bis(4-methoxyphenyl)-l,3-di
  • a compound of formula (XIV) may be derived from a compound of formula (XV) by nitration followed by reduction of the resultant nitrohalobenzene compound and subsequent acylation of the resultant aminohalobenzene compound, using procedures well known to those skilled in the art.
  • Compounds of formula (XV) are commercially available or may be made from commercially available materials using known methods.
  • a compound of formula (III) (wherein n is zero) may also be prepared by halogenation of a compound of formula (XVI) followed by displacement of the resultant compound of formula (XVII) (where Hal is chloro or bromo) with cyanide. Hydrolysis of the resultant compound of formula (XVIII) gives a compound of formula (III).
  • suitable alkylating agents include, but are not restricted to, alkyl halides (such as methyl iodide) and alkyl sulfates (such as dimethylsulfate).
  • Suitable acylating agents include anhydrides (such as acetic anhydride), acid chlorides (such as acetyl chloride or benzoyl chloride) and chloroformates (such as ethyl chloroformate).
  • Suitable sulphonylating agents include, but are not restricted to, sulphonyl chloride.
  • Suitable sulphenylating agents include, but are not restricted to, sulphenyl chloride.
  • Suitable bases include organic bases (such as triethylamine or pyridine), alkali metal alkoxides (such as potassium tert-butoxide) and inorganic bases (such as sodium hydride or sodium hydroxide).
  • Suitable phase transfer catalysts may be selected by reference to the literature (see, for example, J. March, Advanced Organic Chemistry, Third Edition, John Wiley and Sons, New York, 1985, pages 320-322 and references therein).
  • a compound of formula (IV) may be prepared by treating a compound of formula (XIX) with an optionally substituted haloalkyl ester, preferably in the presence of a base such as potassium carbonate. Similarly, a compound of formula (XX) can be reacted with appropriate malonate derivatives in the presence of suitable catalysts, for example palladium (0) derivatives, to give a compound of formula (IV).
  • suitable catalysts for example palladium (0) derivatives
  • a compound of formula (I) (where Y is S) may be prepared by reacting a compound of formula (I) (where Y is O) with a suitable thionating agent such as 2,4-bis(4- methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson's reagent), 2,4- bis(methylthio)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Davy reagent methyl), 2,4- bis(p ⁇ r -tolyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Davy reagent -tolyl) or phosphorus pentasulfide in a suitable solvent such as toluene or fluorobenzene.
  • a suitable thionating agent such as 2,4-bis(4- meth
  • a compound of formula (I) (where Y is S and R 3 is H) may be reacted with an alkylating agent R-X (for example methyl iodide) in the presence of a base (for example sodium bis(trimethylsilyl)amide) to give a compounds of formula (XXI), which is then treated with a compound of formula R 6 -NH 2 to give a compound of formula (I) (where Y is N-R 6 and R 3 is H).
  • R-X for example methyl iodide
  • a base for example sodium bis(trimethylsilyl)amide
  • 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. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp.
  • Rhinotermitidae for example Coptotermes formosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R. hesperus, and R. santonensis
  • Termitidae for example Globitermes sulphur eus
  • Solenopsis geminata fire ant
  • Monomorium pharaonis pharaoh's ant
  • Damalinia spp. and Linognathus spp. biting and sucking lice
  • Meloidogyne spp. root knot nematodes
  • the compounds of formula (I) are also active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae (Magnaporthe grisea) on rice and wheat and other Pyricularia spp. on other hosts; Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts (for example turf, rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental plants); Erysiphe cichoracearum on cucurbits (for example melon); Erysiphe graminis (powdery mildew) on barley, wheat, rye and turf and other powdery mildews on various hosts, such as Sphaerotheca macularis on hops, Sphaerotheca fusca (Sphaerothe
  • Botrytis cinerea grey mould
  • Botrytis cinerea grey mould
  • Alternaria spp. on vegetables (for example carrots), oil-seed rape, apples, tomatoes, potatoes, cereals (for example wheat) and other hosts
  • Venturia spp. including Venturia inaequalis (scab)) on apples, pears, stone fruit, tree nuts and other hosts
  • Cladosporium spp. on a range of hosts including cereals (for example wheat) and tomatoes
  • a compound of formula (I) may move acropetally, basipetally or locally in plant tissue to be active against one or more fungi. Moreover, a compound of formula (I) may be volatile enough to be active in the vapour phase against one or more fungi on the plant.
  • the invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a pest, a locus of pest, or to a plant susceptible to attack by a pest, and a method of combating and controlling fungi which comprises applying a fungicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a plant, to a seed of a plant, to the locus of the plant or seed, to soil or to any other growth medium (for example a nutrient solution).
  • the compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
  • plant as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes protectant, curative, systemic, eradicant and antisporulant treatments.
  • the compounds of formula (I) are preferably used for agricultural, horticultural and turfgrass purposes in the form of a composition.
  • a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA).
  • SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula (I).
  • the composition is generally used for the control of pests or fungi such that a compound of formula (I) is applied at a rate of from O.lg to 10kg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 1kg per hectare.
  • a compound of formula (I) When used in a seed dressing, a compound of formula (I) is used at a rate of 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
  • 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
  • Dustable powders may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
  • solid diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers
  • Soluble powders may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • water-soluble organic solids such as a polysaccharide
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary.
  • a hard core material such as sands, silicates, mineral carbonates, sulphates or phosphates
  • Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils.
  • One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • DC Dispersible Concentrates
  • a compound of formula (I) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. 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 methyl- cyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol),
  • 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 methyl- cyclohexanone
  • 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 -C 10 fatty acid dimethylamide
  • chlorinated hydrocarbons such as C 8 -C 10 fatty acid dimethylamide
  • Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion.
  • Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of formula (I) is present initially in either the water or the solvent/SFA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs.
  • An ME may be either an oil-in- water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation.
  • An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
  • SC Suspension concentrates
  • SCs may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I).
  • SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound.
  • One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle.
  • a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
  • Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example «-butane).
  • a compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as «-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
  • a compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
  • Capsule suspensions (CS) may be prepared in a manner similar to the preparation of
  • 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 coa- cervation 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 dode- cylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di-wopropyl- 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 (pre- dominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric 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 octyl- phenol, 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.
  • 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
  • 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 pests
  • 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,
  • 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).
  • 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.
  • 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 thiamethoxarn; m) Diacylhydrazines, such as tebufenozide, chromafenozide or methoxyfenozide; n) Diphenyl ethers, such as diofenolan or pyriproxifen; o) Indoxacarb; p) Chlorfenapyr; or q) Pymetrozine.
  • other 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).
  • 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- 1 - 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.
  • 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 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.
  • other formulation types may be prepared.
  • one active ingredient is a water insoluble solid and the other a water insoluble liquid
  • the resultant composition is a suspoemulsion (SE) formulation.
  • Nitric acid (69% by weight, 16M, 20ml) was added dropwise to a solution of methyl (4-hydroxyphenyl)acetate [from step 2] (50.0g, 0.3mole) in acetic acid (500ml), maintaining the temperature of the reaction below 15°C by external cooling. (An induction period was observed for this reaction.) Once gas chromatographic analysis had confirmed that the reaction was complete, the mixture was carefully quenched into water (21) with vigorous stirring. An emulsion formed which subsequently crystallised. After filtration, washing with water and drying, the desired product was obtained as a yellow powder.
  • Compound No.297 of Table No.l. was prepared from (-) chloromethyl menthyl ether.
  • step 1 The solution obtained from step 1 (21.16 g) was treated with benzoyl chloride (51.4 ml) and concentrated sulfuric acid (0.62 g), and the mixture was heated to 100°C for 6.5 hours. The mixture was allowed to cool and the reaction mixture was distilled at atmospheric pressure (66-96°C) to give the desired product (1.56 g) as a colourless oil.
  • step 2 The solution obtained from step 1 (21.16 g) was treated with benzoyl chloride (51.4 ml) and concentrated sulfuric acid (0.62 g), and the mixture was heated to 100°C for 6.5 hours. The mixture was allowed to cool and the reaction mixture was distilled at atmospheric pressure (66-96°C) to give the desired product (1.56 g) as a colourless oil.
  • reaction mixture was allowed to cool and was passed through a plug of silica eluting with ethyl acetate/hexane 1 :2.
  • the solvents were evaporated and the residue purified by column chromatography (silica eluting with ethyl acetate hexane 1 :7) to give the desired product (18 mg) as an orange oil.
  • the following compounds were each prepared individually using a similar procedure.
  • Compound No.127 of Table No.l was prepared as an orange oil.
  • Compound No.137 of Table No.l was prepared as a yellow oil.
  • Compound No.147 of Table No.l was prepared as an orange oil.
  • Compound No.157 of Table No.l was prepared as an orange oil.
  • Compound No.167 of Table No.1 was prepared as a yellow oil.
  • Compound No.177 of Table No.1 was prepared as an orange oil.
  • Compound No.197 of Table No.l was prepared as an orange oil.
  • Compound No.317 of Table No.l was prepared as an orange oil.
  • Compound No.327 of Table No.l was prepared as an orange oil.
  • Compound No.337 of Table No.l was prepared as an orange oil.
  • Compound No.207 of Table No.l was prepared as an yellow gum.
  • Compound No.347 of Table No.l was prepared as an orange oil.
  • Compound No.377 of Table No.1 was prepared as a pale yellow oil.
  • Compound No.387 of Table No.l was prepared as an orange oil.
  • Compound No.77 of Table No.l was prepared as an orange oil.
  • EXAMPLE 7 This Example illustrates the preparation of Compound No.97 of Table No.l. N-(4-Chloro-3-methylisothiazol-5-yl)-(2-[2,2-dimethylpropyl]benzoxazol-5-yl)- acetamide [from Example 1] (0.37g) was dissolved in chloromethyl allyl ether (0.8 ml, prepared by an analogous method to that described in example 4) and triethylamine (0.28 ml) was added. The mixture was heated to 70°C for 90 minutes. The mixture was allowed to cool and saturated aqueous sodium bicarbonate solution (10 ml) was added. The mixture was extracted with ethyl acetate (4 x 5 ml).
  • Compound No.107 of Table No.l was prepared as a yellow oil.
  • Compound No.227 of Table No.l was prepared as a pale yellow oil.
  • N-(4-Chloro-3-methylisothiazol-5-yl)-(2-[2,2-dimethylpropyl]benzoxazol-5-yl)- acetamide [from Example 1] (0.57g) was dissolved in dichloromethane (8 ml) and N,0- bis(trimethylsilyl)acetamide (0.34 g) was added, followed by d 2 -chloromethyl ethyl ether [from Example 4] (0.29 g). The mixture was stirred at ambient temperature for 65 hours.
  • Compound No.257 of Table No.l was prepared as a pale yellow oil.
  • Compound No.237 of Table No.l was prepared as a pale yellow oil.
  • EXAMPLE 9 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, SYNPERONIC 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 88, 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 10 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 concen-tration 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 sporula- ting 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 asses-sed 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. It is possible for negative PRCO values to be obtained.
  • PHYTIN Phytophthora infestans lycopersici
  • PUCCRT Puccinia recondita
  • PYRIOR Pyricularia oryzae EXAMPLE 11
  • 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 techniques employed were as follows.
  • Test compounds were individually formulated as a solution either in acetone or acetone/ethanol (1:1 by volume) which was diluted in reverse osmosis 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
  • 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 Blumeria graminis f.sp. tritici plants were inoculated using a 'shake' inoculation technique.
  • the plants were reincubated under high humidity conditions for 24hours prior to assessment.
  • the time period between chemical application and assessment varied from five to nine days according to the disease and environment. However, each individual disease was assessed after the same time period for all the compounds tested against that particular disease.
  • 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 either of two alternative methods, described below, each providing its own PRCO (Percentage Reduction from Control) value. All assessments on plants grown on cellulose media (and some grown in soil) used method 1. METHOD 1 This method uses banded assessment values.
  • the mean disease values are banded in the manner shown below. If the disease level value falls exactly mid- way between two of the points, the result will be the lower of the two points.
  • PRCO 100 - ⁇ Banded mean disease level for treatment A ⁇ x 100 O 01/55141
  • the PRCO is then rounded to the nearest whole number; therefore, in this particular example, the PRCO result is 67.
  • This method uses unhanded assessment values (that is, the mean disease values are used in the PRCO calculation without a banding step).
  • 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.
  • LEPTNO Stagonospora nodorum
  • PLASVI Plasmopara viticola
  • PHYTIN Phytophthora infestans lycopersici

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Abstract

A compound of formula (I), wherein n is 0 or 1; B is N, N-oxide or CR5; Y is O, S or NR6; Z is O, S or NR?7; and R1, R2, R3 and R4¿ are defined organic radicals; their preparation and use and compositions containing them.

Description

AZINE DERIVATIVES AS PESTICIDES
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, W097/18198, WO98/02424, WO98/05670 and WO98/17630. The present invention provides a compound of formula (I):
Figure imgf000002_0001
wherein n is 0 or 1 ; B is N, N-oxide or CR5; Y is O, S or NR6; Z is O, S or NR7;
R1 is hydrogen, halogen, optionally substituted C,.6 alkyl, optionally substituted C2.6 alkenyl, optionally substituted C2^ alkynyl, optionally substituted C^ alkoxy, optionally substituted C,.6 alkylthio, optionally substituted C3.7 cycloalkyl, cyano, nitro or SF5;
R2 is hydrogen, halogen, optionally substituted C,.6 alkyl, optionally substituted C2.6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted C,_6 alkoxy, optionally substituted C,.6 alkylthio, optionally substituted C,.6 alkylsulfinyl, optionally substituted C,.6 alkyl- sulfonyl, cyano, nitro, formyl, optionally substituted C,.6 alkylcarbonyl, optionally substituted C,_6 alkoxycarbonyl, SF5 or R8ON=C(R9); or R1 and R2 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 C,.6 alkyl, C,.6 haloalkyl or halogen; R3 is optionally substituted aryl, optionally substituted arylcarbonyl, optionally substituted C,.10 alkyl [but not C,.6 alkyl, CH2(CM haloalkyl), C,_5 cyanoalkyl, C,.6 alkoxy(C, alkyl, C,.6 alkylthio(C,.6)alkyl, C,.6 alkoxy(C1.6)alkoxy(C,.6)alkyl, C,.6 alkylcarbonyl(C,.6)alkyl, -C,.6 alkoxycarbonyl(C,.6)alkyl or optionally substituted phenyl(C,.4)alkyl], optionally substituted [C2.6 alkenyl(C,.6)alkyl] [but not C3.6 alkenyl], optionally substituted [C2.6 alkynyl(C,.6)alkyl] [but not C3.6 alkynyl], optionally substituted C3.7 cycloalkyl, optionally substituted C,.10 alkylcarbonyl [ but not C,.6 alkylcarbonyl], optionally substituted C,.10 alkoxycarbonyl [but not C,.6 alkoxycarbonyl], optionally substituted C,_10 alkylaminocarbonyl [but not C^ alkylaminocarbonyl], optionally substituted di(CM0)alkylaminocarbonyl [but not di- (C,.6)alkylaminocarbonyl], optionally substituted C,.6 alkyl-thio, optionally substituted C,.6 alkylsulfinyl, optionally substituted C,.6 alkylsulfonyl [but not 8(0)^"; where Ra is C,.6 alkyl or C,.6 haloalkyl and r is 0, 1 or 2]; or R10RπNS(O)p; p is 0, 1 or 2;
R4 is hydrogen, halogen, cyano, optionally substituted C 2Q alkyl, optionally substituted C2.20 alkenyl, optionally substituted C2.20 alkynyl, optionally substituted C3.7 cycloalkyl, optionally substituted C5.6 cycloalkenyl, formyl, optionally substituted C,.20 alkoxycarbonyl, optionally substituted C,.20 alkylcarbonyl, aminocarbonyl, optionally substituted C,.20 alkylaminocarbonyl, optionally substituted di(C,.20)alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-(C,.6)alkyl-N-arylaminocarbonyl, optionally substituted diarylaminocarbonyl, optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted N-(C1.6)alkyl-N-heteroarylaminocarbonyl, optionally substituted diheteroaryl- aminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, SH, optionally substituted C,.20 alkylthio, optionally substituted C,.20 alkylsulfinyl, optionally substituted C .20 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl, R12O, R13R14N or R15ON=C(R16);
R5 is hydrogen, halogen, nitro, cyano, optionally substituted C,_8 alkyl, optionally substituted C2.6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted C3.7 cycloalkyl, optionally substituted C,_6 alkoxycarbonyl, optionally substituted C,.6 alkylcarbonyl, optionally substituted C,.6 alkylaminocarbonyl, optionally substituted di-(C,_6)alkylamino- carbonyl, optionally substituted phenyl or optionally substituted heteroaryl; R6 is hydrogen, cyano, nitro, optionally substituted C,.6 alkyl, optionally substituted C3.7 cycloalkyl, optionally substituted (C2.5)alkenyl(C,.6)alkyl, optionally substituted - (C2.6)alkynyl(C,.6)alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted C,_6 alkylcarbonyl, optionally substituted C,.6 alkoxycarbonyl, optionally substituted C,.6 alkylamino, optionally substituted di(C,.6)alkylamino, optionally substituted C,_6 alkylcarbonylamino, optionally substituted C,.6 alkoxycarbonylamino, optionally substituted C,.6 alkoxy, optionally substituted C,.6 alkylthio, optionally substituted C,_6 alkylsulfinyl, optionally substituted C,^ alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or C,.6 alkylcarbonyloxy;
R7 is hydrogen, cyano, optionally substituted C,.g alkyl, optionally substituted [C2.6 alkenyl(C,.6)alkyl], optionally substituted [C2.6 alkynyl(C,.6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted [C3.7 cycloalkyl(C,.6)alkyl], C,.6 alkoxy (C,.6)alkyl, optionally substituted C,_6 alkoxycarbonyl, optionally substituted C,.6 alkylcarbonyl, optionally substituted C,_6 alkylaminocarbonyl, optionally substituted di(C,.6)alkylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl; R8 and R15 are, independently, hydrogen, optionally substituted phenyl (C].2)alkyl or optionally substituted C,.20 alkyl;
R9 and R16 are, independently, hydrogen, optionally substituted phenyl or optionally substituted C,.6 alkyl;
R10 and R11 are, independently, optionally substituted C,.6 alkyl; or R10and R11 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 and S and which is optionally substituted by one or two independently selected C,.6 alkyl groups; R12 is hydrogen, optionally substituted C,_20 alkyl, optionally substituted [C2.20 alkenyl- (C,.6)alkyl], optionally substituted [C2.20 alkynyl(C,.6) alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, (C,.6)alkylCH=N, optionally substituted arylCH=N, optionally substituted [aryl(C,.6)alkyl]CH=N, optionally substituted heteroarylCH=N, optionally substituted [heterocyclyl(C,.6)alkyl]CH=N, optionally substituted arylC(CH3)=N, optionally substituted heteroarylC(CH3)=N or optionally substituted di(C,.6)aikylC=N; and R13 and R14 are, independently, hydrogen, optionally substituted C,.20 alkyl, optionally substituted C3.7 cycloalkyl, optionally substituted [C2.20 alkenyl(C,.6)alkyl], optionally substituted [C2.20 alkynyl(C,.6)alkyl], optionally substituted C,.20 alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted
Figure imgf000005_0001
alkylcarbonyl, optionally substituted C,.20 alkylsulfonyl or optionally substituted phenylsulfonyl.
One group of preferred compounds is a group where n is 0 or 1 ; B is N, N-oxide or CR5; Y is O, S or NR6; Z is O, S or NR7; R3 is optionally substituted Cwo alkyl, optionally substituted [C2.6 alkenyl(C,.6)alkyl], optionally substituted [C2.6 alkynyl(C,.6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted C 0 alkylcarbonyl, optionally substituted C,.10 alkoxycarbonyl, formyl, optionally substituted C,.10 alkylaminocarbonyl, optionally substituted di(C1.10)alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted C,_6 alkylthio, optionally substituted C,_6 alkylsulfinyl, optionally substituted C,_6 alkylsulfonyl, optionally substituted C,.6 arylthio, optionally substituted C,_6 arylsulfinyl, optionally substituted C,_6 arylsulfonyl or R10RnNS; provided that R3 is not C 6 alkyl, CH2(CM haloalkyl), C,_6 cyanoalkyl, C3.6 alkenyl, C3.6 alkynyl, C,.6 alkoxy (C,.6)alkyl, C,.6 alkylthio(C,.6)alkyl, C,.6 alkoxy(C,.6)alkoxy(C,.6)alkyl, C,.6 alkylcarbonyl, C,.6 alkoxycarbonyl, formyl, C,.6 alkylcarbonyl(C,.6)alkyl, C,.6 alkoxy carbonyl(C,.6)alkyl, C,_6 alkylaminocarbonyl, di(C,^)alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted phenyl(CM)alkyl or S(0).Ra; Ra is Cj.6 alkyl, C,^ haloalkyl or optionally substituted phenyl; r is 0, 1 or 2; R4 is hydrogen, halogen, cyano, optionally substituted C,.20 alkyl, optionally substituted C2.20 alkenyl, optionally substituted C2.20 alkynyl, optionally substituted C3.7 cycloalkyl, optionally substituted C5.6 cycloalkenyl, formyl, optionally substituted C,_2Q alkoxycarbonyl, optionally substituted C,_20 alkylcarbonyl, aminocarbonyl, optionally substituted C,.20 alkylaminocarbonyl, optionally substituted di(C,.20)alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N- alkyl-N-arylaminocarbonyl, optionally substituted diarylaminocarbonyl, optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted alkylheteroarylaminocarbonyl, optionally substituted diheteroarylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, R120, HS, optionally substituted C,.20 alkylthio, optionally substituted C,.20 alkylsulfinyl, optionally substituted C,.20 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl , R13R14N or R15ON=C(R16); R1 is hydrogen, halogen, optionally substituted C,.6 alkyl, optionally substituted C2.6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted C,.6 alkoxy, optionally substituted C,.6 alkylthio, optionally substituted C3.7 cycloalkyl, cyano, nitro or SF5; R2 is hydrogen, halogen, optionally substituted C,_6 alkyl, optionally substituted C2.6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted C,.6 alkoxy, optionally substituted C,.6 alkylthio, optionally substituted C,_6 alkylsulfinyl, optionally substituted Cw alkylsulfonyl, cyano, nitro, formyl, R8ON=C(R9), optionally substituted C,.6 alkylcarbonyl, optionally substituted C,.6 alkoxycarbonyl or SF5; or R1 and R2 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated ring carbocylic or heterocyclic ring which may contain one or two hetero atoms selected from O, N or S and which may be optionally substituted by C,_6 alkyl, Cw haloalkyl or halogen; R6 is hydrogen, cyano, nitro, optionally substituted C,.6 alkyl, optionally substituted C3.7 cycloalkyl, optionally substituted - (C2.6)alkenyl(C,.6)alkyl, optionally substituted (C2.6)alkynyl(C,.6)alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted C,_6 alkylcarbonyl, optionally substituted C,_6 alkoxycarbonyl, optionally substituted C,.6 alkylamino, optionally substituted di(C,.6)alkylamino, optionally substituted C,_6 alkylcarbonylamino, optionally substituted - C,.6 alkoxycarbonylamino, optionally substituted C,_6 alkoxy, optionally substituted C,.6 alkylthio, optionally substituted C,_6 alkylsulfinyl, optionally substituted C,.6 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or Cu6 acyloxy; R7 is hydrogen, cyano, optionally substituted C,.8 alkyl, optionally substituted [C2.6 alkenyl(C,.6)alkyl], optionally substituted [C2.6 alkynyl - (C,.6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted [C3.7 cycloalkyl - (C,.6)alkyl], C,.6 alkoxy(C,^)alkyl, optionally substituted C,.6 alkoxycarbonyl, optionally substituted C,.6 alkylcarbonyl, optionally substituted C,.6 alkylaminocarbonyl, optionally substituted di(C,.6)alkylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl; R5 is hydrogen, halogen, nitro, cyano, optionally substituted C,.8 alkyl, optionally substituted C2.6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted C3.7 cycloalkyl, optionally substituted C,.6 alkoxycarbonyl, optionally substituted C,_6 alkylcarbonyl, optionally substituted C,_6 alkylaminocarbonyl, optionally substituted di(C,.6)alkylaminocarbonyl, optionally substituted phenyl or optionally substituted heteroaryl; R10 and R11 are, independently, optionally substituted C,_6 alkyl or R10and Rn together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two C,.6 alkyl groups; R12 is hydrogen, optionally substituted C,.20 alkyl, optionally substituted [C2.20 alkenyl(C,.6)alkyl], optionally substituted [C2.20 alkynyl(C,.6) alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted [heterocyclyl(C,.6)alkylCH=N] or di(C,_6) alkylC=N; R13 and R14 are, independently, hydrogen, optionally substituted C,.20 alkyl, optionally substituted C3.7 cycloalkyl, optionally substituted [C2.20 alkenyl(C,.6)alkyl], optionally substituted [C2.20 alkynyl(C,.6)alkyl], optionally substituted C,.20 alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted C,.20 alkylcarbonyl, optionally substituted C,_20 alkylsulfonyl or optionally substituted phenylsulfonyl; or R13 and R14 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two C,.6 alkyl groups; R16 and R9 are independently hydrogen, optionally substituted phenyl or optionally substituted C,.6 alkyl; and R15 and R8 are, independently, hydrogen, optionally substituted phenyl (C,.2)alkyl or optionally substituted C,.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.
When present, optional substituents on alkylene, alkenylene or alkynylene moieties include (subject to valency constraints) one or more of hydroxy, halogen, C,.6 alkyl, C,.6 haloalkyl, C,^ cyanoalkyl, C,.6 alkoxy(C,.6) alkyl, C,.6 alkoxy, cyano, =O, =NR17 and
=CR18R19; and, especially, one or more of halogen, C,_6 alkyl, C,.6 haloalkyl, C,_6 cyanoalkyl, C,.6 alkoxy(C,_6) alkyl, C,.6 alkoxy, cyano, =O, =NR17 and =CR18R19; wherein R17 is C,_6 alkyl, C,.6 haloalkyl, OR20 or NR2IR22; where R18 and R19 are, independently, hydrogen, Cw alkyl, C,^ alkoxy, C,.6 haloalkyl, cyano, C,.6 alkoxycarbonyl, C,.6 alkylcarbonyl or NR23R24; R20 is C,.6 alkyl, Cj.6 haloalkyl or phenyl(Cj.2)alkyl; R21 and R22 are, independently, hydrogen, C,.8 alkyl, C3.7 cycloalkyl, C2.6 alkenyl(C,.6)alkyl, C2.6 alkynyl(C,.6)alkyl, C2.6 haloalkyl, C,_6 alkoxy (C,.6)alkyl, C].6 alkoxycarbonyl(C,.6)alkyl, carboxy(C,^)alkyl or phenyl(C,.2)alkyl; or R21 and R22 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 is optionally substituted by one or two C,.6 alkyl groups; R23 and R24 are, independently, hydrogen, C,.8 alkyl, C3.7 cycloalkyl, C2.6 alkenyl(C,.6)alkyl, C 2-6 alkynyl(C,.6)alkyl, C2.6 haloalkyl, C,^ alkoxy(C,.6)alkyl, C,.6 alkoxycarbonyl(C,_6)alkyl, carboxy(C1.6)alkyl or phenyl(C,.2)alkyl; or R23 and R24 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 C,.6 alkyl groups.
Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, H-propyl, n-butyl, n-pentyl, n-hexyl, wo-propyl, n-butyl, sec-butyl, wO-butyl, tert-butyl or Heo-pentyl.
When present, the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, NCS-, C3.7 cycloalkyl (itself optionally substituted with C,.6 alkyl or halogen), C5.7 cycloalkenyl (itself optionally substituted with C,.6 alkyl or halogen), hydroxy, CM0 alkoxy, C,.10 alkoxy(C 0)alkoxy, tri(CM)alkylsilyl(C1.6)alkoxy, Cw alkoxycarbonyl(C,.10)alkoxy, C,.10 haloalkoxy, aryl(CM)alkoxy (where the aryl group is optionally substituted), C3.7 cycloalkyloxy (where the cycloalkyl group is optionally substituted with C,„6 alkyl or halogen), C,.10 alkenyloxy, C,.10 alkynyloxy, SH, C,.10 alkylthio, C,.10 haloalkylthio, aryl(CM)alkylthio (where the aryl group is optionally substituted), C3.7 cycloalkylthio (where the cycloalkyl group is optionally substituted with C,_6 alkyl or halogen), tri(CM)alkylsilyl(C,.6)alkylthio, arylthio (where the aryl group is optionally substituted), C,.6 alkylsulfonyl, C,_6 haloalkylsulfonyl, C,.6 alkylsulfinyl, C,_6 haloalkylsulfinyl, arylsulfonyl (where the aryl group may be further optionally substituted), tri(C,.4)alkylsilyl, aryldi(CM)alkylsilyl, (C )alkyldiaxylsilyl, triarylsilyl, C,.,0 alkylcarbonyl, HO2C, C,.10 alkoxycarbonyl, aminocarbonyl, C,.6 alkylaminocarbonyl, di(C,.6 alkylaminocarbonyl, N-(C,.3 alkyl)-N-(C,.3 alkoxy)aminocarbonyl, C,.6 alkylcarbonyloxy, arylcarbonyloxy (where the aryl group is optionally substituted), di(C,.6)alkylaminocarbonyloxy, aryl (itself optionally substituted), heteroaryl (itself optionally substituted), heterocyclyl (itself optionally substituted with C,_6 alkyl or halogen), aryloxy (where the aryl group is optionally substituted), heteroaryloxy, (where the heteroaryl group is optionally substituted), heterocyclyloxy (where the heterocyclyl group is optionally substituted with C,.6 alkyl or halogen), amino, C,.6 alkylamino, di(C,.6)alkylamino, C,_6 alkylcarbonylamino and N-(Cι.6)alkylcarbonyl-N-(C,.6)alkylamino. 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 those optional substituents given above for an alkyl moiety. In the context of this specification acyl is optionally substituted C,_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. When present, the optional substituents on heterocyclyl include C,_6 alkyl as well as those optional substituents given above for an alkyl moiety.
Cycloalkyl includes cyclopropyl, cyclopentyl and cyclohexyl.
Cycloalkenyl includes cyclopentenyl and cyclohexenyl.
When present, the optional substituents on cycloalkyl or cycloalkenyl include C,.3 alkyl as well as those optional substituents given above for an alkyl moiety.
Carbocyclic rings include aryl, cycloalkyl and cycloalkenyl groups. When present, the optional substituents on aryl or heteroaryl are selected, independently, from halogen, nitro, cyano, NCS-, C,.6 alkyl, C,.6 haloalkyl, C,.6 alkoxy(C,.6)alkyl, C2.6 alkenyl, C2.6 haloalkenyl, C2.6 alkynyl, C3.7 cycloalkyl (itself optionally substituted with C,.6 alkyl or halogen), C5.7 cycloalkenyl (itself optionally substituted with C,.6 alkyl or halogen), hydroxy, C,.10 alkoxy, C 0 alkoxy(C,.10)alkoxy, tri(CM)alkylsilyl(C1.6)alkoxy, C,.6 alkoxycarbonyl(C,.10)alkoxy, C,.10 haloalkoxy, aryl(CM)alkoxy (where the aryl group is optionally substituted), C3.7 cycloalkyloxy (where the cycloalkyl group is optionally substituted with C,.6 alkyl or halogen), C,.10 alkenyloxy, C,.10 alkynyloxy, SH, Cj.,0 alkylthio, C,.10 haloalkylthio, aryl(CM)alkylthio (where the aryl group may be further optionally substituted), C3.7 cycloalkylthio (where the cycloalkyl group is optionally substituted with C,_6 alkyl or halogen), tri(C1.4)alkylsilyl(C,.6)alkylthio, arylthio (where the aryl group is optionally substituted), C,.6 alkylsulfonyl, C,.6 haloalkylsulfonyl, C,.6 alkylsulfinyl, C,.6 haloalkylsulfinyl, arylsulfonyl (where the aryl group is optionally substituted), tri(CM)alkylsilyl, aryldi(C1.4)alkylsilyl, (CM)alkyldiarylsilyl, triarylsilyl, C,.10 alkylcarbonyl, HO2C, C 0 alkoxycarbonyl, aminocarbonyl, C,.6 alkylaminocarbonyl, di(C,.6 alkylaminocarbonyl, N-(C,.3 alky -N- C^ alkoxy)aminocarbonyl, C,.6 alkylcarbonyloxy, arylcarbonyloxy (where the aryl group is optionally substituted), di(C,.6)alkylaminocarbonyloxy, aryl (itself optionally substituted), heteroaryl (which itself may be further optionally substituted), heterocyclyl (itself optionally substituted with C,.6 alkyl or halogen), aryloxy (where the aryl group is optionally substituted), heteroaryloxy (where the heteroaryl group is optionally substituted), heterocyclyloxy (where the heterocyclyl group is optionally substituted with C,.6 alkyl or halogen), amino, C,.6 alkylamino, di(C,.6)alkylamino, Cw alkylcarbonylamino and N-(C,.6)alkylcarbonyl-N-(Cw)alkylamino. For substituted phenyl moieties, heterocyclyl and heteroaryl groups it is preferred that one or more substituents are independently selected from halogen, C,_6 alkyl, C,.6 haloalkyl, C,.6 alkoxy(C,.6)alkyl, C,.6 alkoxy, C,.6 haloalkoxy, C,.6 alkylthio, C 6 haloalkylthio, C,.6 alkylsulfinyl, C,.6 haloalkylsulfinyl, C,.6 alkylsulfonyl, C,_6 haloalkylsulfonyl, C2.6 alkenyl, C2.6 haloalkenyl, C2.6 alkynyl, C3.7 cycloalkyl, nitro, cyano, CO2H, C 6 alkylcarbonyl, C,_6 alkoxycarbonyl, R25R26N or R27R28NC(0); wherein R25, R26, R27 and R28 are, independently, hydrogen or C,.6 alkyl. Haloalkenyl groups are alkenyl groups which are substituted with one or more of the same or different halogen atoms
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 heteroatoms selected from O, N or S and which is optionally substituted by one or two independently selected (C,.6)alkyl groups. When heterocyclic rings are formed by joining two groups on an N atom, the resulting rings are suitably pyrrolidine, piperidine, thiomorpholine and morpholine each of which may be substituted by one or two independently selected (C,_6) alkyl groups. Preferably the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, HO2C, C,.10 alkoxy (itself optionally substituted by C,.10 alkoxy), aryl(CM)alkoxy, C,.10 alkylthio, C,.10 alkylcarbonyl, C 0 alkoxycarbonyl, C,.6 alkylaminocarbonyl, di(C,.6 alkylaminocarbonyl, (C1.6)alkylcarbonyloxy, optionally substituted phenyl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl, heterocyclyloxy, C3.7 cycloalkyl (itself optionally substituted with (C,.6)alkyl or halogen), C3.7 cycloalkyloxy, C5.7 cycloalkenyl, C,.6 alkylsulfonyl, C^ alkylsulfinyl, tri(CM)alkylsilyl, tri(C )alkylsilyl(C,^)alkoxy, aryldi(CM)alkylsilyl, (C )alkyldiarylsilyl and triarylsilyl. Preferably the optional substituents on alkenyl or alkynyl include one or more of halogen, aryl and C3.7 cycloalkyl. It is more preferred that heterocyclyl is optionally substituted by C,.6 alkyl.
Preferably the optional substituents for cycloalkyl include halogen, cyano and Cj.3 alkyl.
Preferably the optional substituents for cycloalkenyl include C^ alkyl, halogen and cyano. In a further aspect, the present invention provides a compound of formula (IA):
Figure imgf000011_0001
wherein n, B, Y, Z, R1, R2, R3 and R4 are as defined above for a compound of formula (I). One group of preferred compounds of formula (I A) is a group where R1 is hydrogen, halogen, C,.6 alkyl, C2.6 alkenyl, C2.6 alkynyl, Cw cyanoalkyl, C,.6 haloalkyl, C^ alkoxy, Cj.6 haloalkoxy, C,.6 alkylthio, C,^ haloalkylthio, C3.6 cycloalkyl, C3.7 cycloalkyl(C )alkyl, C,.6 alkoxy(Cw)alkyl, cyano, nitro or SF5; n is 0; B is N or CR5; Y is O, S or NR6; Z is O, S or NR7; R3 is (C7.10)alkyl (optionally substituted by aryl); [(C2.6)alkenyl(CM)alkyl] (optionally substituted by halo, (CM)alkyl or aryl); (CM)alkyl (substituted with aryl (C )alkoxy; tri(CM)alkylsilyl(C1.6)alkoxy; (C,.6)alkylcarbonyloxy; (C7.10)alkoxy; [(C,.6)alkyl substituted (C3.7)cycloalkyl]oxy; aryl(CM)alkylthio; tri(CM)alkylsilyl(C,.6) alkylthio; (C7.10)alkythio; or [(C,.6)alkyl substituted (C3.7)cycloalkyl]thio) or (C,.4)alkyl (substituted with aryl and (CM)alkoxy); R4 is cyano, CN8 alkyl, C,.6 haloalkyl, C,.6 cyanoalkyl, C2.6 alkenyl, C2.6 alkynyl, C3.7 cycloalkyl, C3.7 halocycloalkyl, C3.7 cyanocycloalkyl, C,.3 alkyl(C3.7)cycloalkyl, C,.3 alkyl(C3.7)halocycloalkyl, C5.6 cycloalkenyl, C3.7 cycloalkyl(C].6)alkyl, C5.6 cycloalkeny^ alkyl, C2.6 haloalkenyl, C,.6 cyanoalkenyl, CM alkoxy(C,.6)alkyl, C3.6 alkenyloxy(C,.6)alkyl, C3.6 alkynyloxy (C,^)alkyl, aryloxy (C,^)alkyl, formyl, C,.6 carboxyalkyl, C,.6 alkylcarbonyl(C1^)alkyl, C2.6 alkenylcarbonyl - (C^)alkyl, C2.6 alkynylcarbonyl(C,.6)alkyl, C,.6 alkoxycarbonyl(C!.6)alkyl, C3.6 alkenyloxycarbonyl(C1.6)alkyl, C3.6 alkynyloxycarbonyl(Cι.6)alkyl, aryloxycarbonyl - (C,.6)alkyl, CM alkylthio(C,.6)alkyl, C,.6 alkylsulfinyl(C,.6)alkyl, C,.6 alkylsulfonyl - (C,.6)alkyl, aminocarbonyl(C,.6)alkyl, aminocarbonyl(C2.6)alkenyl, aminocarbonyl - (C2.6)alkynyl, C,.6alkylaminocarbonyl(C1.6)alkyl, di(C,.6)alkylaminocarbonyl(C1.6)alkyl, C,.6 alkylaminocarbonyl(C,^)alkenyl, di(C1^)alkylaminocarbonyl(C1.6)alkenyl, alkyl-amino- carbonyl(Cw)alkynyl, di(C,^)alkylaminocarbonyl(C1.6)alkynyl, C,.6 alkoxycarbonyl, CU6 alkylcarbonyl, aminocarbonyl, C1-6 alkylaminocarbonyl, di(C1^)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, C^ alkyl, C,.6 haloalkyl, C,^ alkoxy or C,_6 haloalkoxy), phenyl(CM)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,_6 haloalkyl, C,^ alkoxy or C,.6 haloalkoxy), phenyl(C2.4)alkenyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, C,_6 alkyl, C,_6 haloalkyl, C 6 alkoxy or C,.6 haloalkoxy), heterocyclyl (optionall substituted by halo, nitro, cyano, Ct.6 alkyl, C,^ haloalkyl, C 6 alkoxy or C,_6 haloalkoxy), heteroaryl(CM)alkyl (where the heteroaryl may be substituted by halo, nitro, cyano, C,_6 alkyl, C,^ haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), heterocyclyl(CM)alkyl (where the heterocyclyl may be substituted by halo, cyano, C,.6 alkyl, C,_6 haloalkyl, C,_6 alkoxy or C,.6 haloalkoxy), R12O, C,.8 alkylthio, R13R14N or R15ON=C(R16); R2 is hydrogen, halogen, C,.6 alkyl, C2.6 alkenyl, C,.6 alkynyl, C,.6 haloalkyl, C,.6 alkoxy, C,_6 alkoxy (C,.6)alkyl, C,.6 haloalkoxy, C,_6 alkylthio, C,^ haloalkylthio, Cj.6 alkylsulfinyl, C,_6 haloalkylsulfinyl, C,.6 alkylsulfonyl, C,.6 haloalkylsulfonyl, C,.6 haloalkyl, cyano, nitro, formyl, CH=NOR8, C,.6 alkylcarbonyl, Cw alkoxycarbonyl or SF5; or together R1 and R2 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated ring carbocylic or heterocyclic ring which may contain one or two hetero atoms selected from O, N or S and which may be optionally substituted by C,.6 alkyl, C,.6 haloalkyl or halogen; R6 is cyano, nitro, C1-6 alkyl, C,^ haloalkyl, C3.7 cycloalkyl, C3.7 cycloalkyl - (C,.6)alkyl, CH2(C2.6)alkenyl, CH2(C2.6)alkynyl, phenyl (optionally substituted by halo, nitro, cyano, C,_6 alkyl, CL6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy) heteroaryl (optionally substituted by halo, nitro, cyano, CL6 alkyl, C,.6 haloalkyl, C,^ alkoxy or C,.6 haloalkoxy), C,.6 alkylcarbonyl, Cw alkoxycarbonyl, C,^ alkylamino, di(C,.6)alkylamino, CL6 alkylcarbonylamino, C,^ alkoxycarbonylamino, C,_6 alkoxy, C^ alkylthio, C,.6 alkylsulfinyl, CL6 alkylsulfonyl, Cw haloalkylthio, Cw haloalkylsulfinyl, C,^ haloalkylsulfonyl, arylthio, arylsulfinyl, arylsulfonyl or OCO(Cι.6)alkyl; R7 is hydrogen, C,.8 alkyl, C,.6 haloalkyl, C,.6 cyanoalkyl, C2.6 alkenyl, C2.6 alkynyl, C3.7 cycloalkyl, C2.6 haloalkenyl, C3.7 cycloalkyl - (C,.6)alkyl, C,^ alkoxy(C1^)alkyl, C,.6 alkoxycarbonyl, CU6 alkylcarbonyl, C,_6 alkylaminocarbonyl, di(Cι^)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, C,_6 alkyl, C,^ haloalkyl, C 6 alkoxy or C,.6 haloalkoxy) or heteroaryl (optionally substituted by halo, nitro, cyano, C,^ alkyl, C,_6 haloalkyl, C,_6 alkoxy or C,_6 haloalkoxy); R5 is hydrogen, halogen, nitro, cyano, CM alkyl, Cw haloalkyl, C,.6 cyanoalkyl, C2.6 alkenyl, C2.6 alkynyl, C3.7 cycloalkyl, C2.6 haloalkenyl, C3.7 cycloalkyl(C,.6)alkyl, C,.6 alkoxy - (C,.6)alkyl, C,.6 alkoxycarbonyl, C,.6 alkylcarbonyl, C,.6 alkylaminocarbonyl, di - (C1.6)alkylaminocarbonyl, Cj.6 alkoxycarbonyl(Cw)alkyl, C,.6 alkylcarbonyl(C!.6)alkyl, CL6 alkylaminocarbony^C^^alkyl, di(C1.6)alkylaminocarbonyl(C,.6)alkyl, phenyl (optionally substituted by halo, nitro, cyano, C,_6 alkyl, C,.6 haloalkyl, C 6 alkoxy or C 6 haloalkoxy), phenyl(C,.6)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,_6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Cj.6 alkyl, C,_6 haloalkyl, C,^ alkoxy or C 6 haloalkoxy) or heteroaryl-(C,. 6)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C^ alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy); R12 is hydrogen, C,.g alkyl, C,.6 haloalkyl, C,.6 cyanoalkyl, C2.6 alkenyl, C2.6 alkynyl, C,.6 alkoxy^^alkyl, phenyl - (CM)alkyl , (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,_6 haloalkyl, C,_6 alkoxy or C,_6 haloalkoxy), heteroaryl(C1.4)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C,_6 alkyl, C,.6 haloalkyl, C,_6 alkoxy or C 6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, Cj_6 alkyl, C,.6 haloalkyl, C1-6 alkoxy or C,_6 haloalkoxy), heterocyclyl(CM)alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C^ alkyl, C 6 haloalkyl,
C,^ alkoxy or CL6 haloalkoxy), C,.6 alkoxycarbonyl alkyl or N=C(CH3)2; R16 is C 1-6 alkyl, C,.6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, C,.6 alkyl, C^ haloalkyl, Cj.6 alkoxy or C,.6 haloalkoxy), R13 and R14 are, independently, hydrogen, C,.g alkyl, C3.7 cycloalkyl, C3.6 alkenyl, C3.6 alkynyl, C3.7 cycloalkyl(CM)alkyl, C2.6 haloalkyl, -C,.6 alkoxy(C1.6)alkyl, CN6 alkoxycarbonyl, or R13 and R14 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two C^ alkyl groups; R15 and R8 are, independently, C,.6 alkyl or phenyl(C,.2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, C,^ alkoxy or C,.6 haloalkoxy). n is preferably 0. B is preferably N.
Y is preferably O or S.
Y is more preferably O. Z is preferably O or S.
Z is more preferably O.
It is preferred that R1 is hydrogen, halogen, C,.6 alkyl, C,_6 cyanoalkyl, C,_6 haloalkyl, C3.7 cycloalkyl(C,.4)alkyl, Cμ6 alkoxy (C^alkyl, C2.6 alkenyl, C2.6 alkynyl, C,_6 alkoxy, C,.6 haloalkoxy, C,.6 alkylthio, C,.6 haloalkylthio, C3.6 cycloalkyl, cyano, nitro or SF5. R is more preferably hydrogen, halogen, C,.6 alkyl, C2.6 alkenyl, C,.6 haloalkyl, C 1-6 alkoxy, C^ haloalkoxy, C,_6 alkylthio, C,.6 haloalkylthio, C3.6 cycloalkyl, cyano, nitro or SF5 It is even more preferred that R1 is hydrogen, halogen, C,.6 alkyl, C,_6 haloalkyl, C,.6 alkoxy(C1.6)alkyl, C2.6 alkenyl, Cj.6 alkoxy, C 6 haloalkoxy, C,_6 alkylthio, C,.6 haloalkylthio, C3.6 cycloalkyl or cyano.
It is most preferred that R1 is halogen, Cj.6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy.
It is preferred that R is hydrogen, halogen, C,.6 alkyl, C,.6 haloalkyl, C 1-6 alkoxy(C,.6)alkyl, C2.6 alkenyl, C^ alkynyl, C,.6 alkoxy, C^ haloalkoxy, C,.6 alkylthio, C,.6 haloalkylthio, C,.6 alkylsulfinyl, CM haloalkylsulfinyl, C,.6 alkylsulfonyl, Cj.6 haloalkylsulfonyl, cyano, nitro, formyl, C 6 alkylcarbonyl, C,.6 alkoxycarbonyl, SF5 or CH^NOR8; or R1 and R2 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 C,.6 alkyl, C,_6 haloalkyl or halogen; where R8 is phenyl(C].2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Cj_6 alkyl, C,_6 haloalkyl, C,.6 alkoxy or C,_6 haloalkoxy) or C 6 alkyl.
It is more preferred that R2 is hydrogen, halogen, C,.6 alkyl, C^ haloalkyl, C 6 alkoxy (C1.6)alkyl, C,^ alkoxy, C 6 haloalkoxy, Cμ6 alkylthio or SF5; or R1 and R2 together with the atoms to which they are attached form a cyclopentane or benzene ring optionally substituted by Cι.6 alkyl, Cj.6 haloalkyl or halogen. R2 is even more preferably hydrogen, halogen, C,_6 alkyl, C,_6 haloalkyl, C,.6 alkoxy,
C,_6 haloalkoxy, C^ alkoxy(C!.6)alkyl, C,.6 alkylthio or SF5; or R1 and R2 together with the atoms to which they are attached form a benzene ring optionally substituted by C,.6 alkyl, Cμ6 haloalkyl or halogen; or alternatively the ring may be a cyclopentane ring.
It is further preferred that R2 is hydrogen, halogen, C,_6 alkyl, C,.6 haloalkyl, C,.6 alkoxy (C,.6)alkyl, CM alkoxy, C,_6 haloalkoxy; or R1 and R2 together with the atoms to which they are attached form a cyclopentane ring optionally substituted by C,_6 alkyl, C,_6 haloalkyl or halogen.
R2 is most preferably halogen, C,.6 alkyl, C,.6 haloalkyl, C,.6 alkoxy, C,^ alkoxy (C,.6)alkyl or C^ haloalkoxy. It is preferred that R3 is C7.10 alkyl, C,.6 alkylcarbonyloxy(C,.6)alkyl, di(C,.6)alkylaminocarbonyloxy(C].6)alkyl, benzoyloxymethyl (where the phenyl ring is optionally substituted with halogen or CM alkyl), C,.6 alkoxy ^alkyl (where the alkyl group is substituted by aryl or CM alkoxycarbonyl), tri(C].4)alkylsilyl(C1.6)alkoxy(C1.6)alkyl, C3.7 cycloalkyloxy(C1.6)alkyl (where the cycloalkyl group is optionally substituted with C^ alkyl), C7-10 alkoxy(C,.6)alkyl, C,.6 haloalkyloxymethyl, C2.6 alkenyloxy(CM)alkyl, C2.6 alkynyloxy(C )alkyl, benzyloxy(CM)alkyl (where the phenyl ring is optionally substituted with halogen or C alkyl), C3.7 cycloalkyl(C1_4)alkyl, heteroaryl(C1.3)alkyl (where the heteroaryl group is optionally substituted with halogen or C,_3 alkyl), tri(CM)alkylsilyl - (C,.6)alkyl, C2.6 haloalkenyl(C,.6)alkyl, CM alkoxycarbonyl(C2.6)alkenyl(C,.6)alkyl, aryl - (C2 alkenyl(C,.6)alkyl, tri(CM)alkylsilyl(C2.6)alkynyl(C,.6)alkyl or C7.10 alkylcarbonyl. Alternatively R3 may preferably be (C7.]0)alkyl (optionally substituted by aryl);
[(C2.6)alkenyl(CM)alkyl] (optionally substituted by halo, (C )alkyl or aryl); - (C )alkyl (substituted with aryl(CM)alkoxy; tri(CM)alkylsilyl(C,.6)alkoxy; - (C,.6)alkylcarbonyloxy; (C7.10)alkoxy; [(C,.6)alkyl substituted (C3.7)cycloalkyl]oxy; aryl- (C, alkylthio; tri(CM)alkylsilyl(C1.6) alkylthio; (C7.10)alkythio; or [(Chalky, substituted (C3. 7)cycloalkyl]thio) or (CM)alkyl (substituted with aryl and (CM)alkoxy); for such a group, more preferably R3 is (CM)alkyl (substituted with aryl(CM)alkoxy; tri(CM)alkylsilyl- (C,.6)alkoxy; (Cι.6)alkylcarbonyloxy; (C7.10)alkoxy; or [(CM)alkyl substituted - (C3.7)cycloalkyl]oxy) or (CM)alkyl (substituted with aryl and (CM)alkoxy).
It is further preferred that R3 is C,.6 alkylcarbonyloxymethyl, benzoyloxymethyl (where the phenyl ring is optionally substituted with halogen or C,.4 alkyl), C,.6 alkoxy- (C,.6)alkyl (where the alkyl group is substituted by aryl), tri(C1.4)alkylsilyl(C,.6)alkoxy- methyl, C3.7 cycloalkyloxymethyl (where the cycloalkyl group is optionally substituted with C,.6 alkyl), C7.10 alkoxymethyl, C2.6 alkenyloxymethyl, C2.6 alkynyloxymethyl, benzyl- oxymethyl (where the phenyl ring is optionally substituted with halogen or C,_4 alkyl), heteroaryl(C,.3)alkyl (where the heteroaryl group is optionally substituted with halogen) or C7.10 alkylcarbonyl.
R3 is more preferably C 6 alkylcarbonyloxymethyl, C2.6 alkenyloxymethyl or C2.6 alkynyloxymethyl .
It is preferred that R4 is cyano, C s alkyl, C,.8 haloalkyl, C,_8 cyanoalkyl, C3.7 cycloalkyl(Cw)alkyl, C5.6 cycloalkenylCC^alkyl, C,.6 alkoxy(C,.6)alkyl, C3.6 alkenyl- oxy(C,.6)alkyl, C3.6 alkynyloxy(C,.6)alkyl, aryloxy(C, alkyl, C,.6 carboxyalkyl, C,_6 alkylcarbonyl C^alkyl, C2.6 alkenylcarbonyl(C,.6)alkyl, C2.6 alkynylcarbonyl(C!.6)alkyl, Cμ6 alkoxycarbonyl(C,.6)alkyl, C3.6 alkenyloxycarbonyl(C,.6)alkyl, C3.6 alkynyloxy- carbonyl(Cw)alkyl, aryloxycarbonyl(C,.6)alkyl, C,.6 alkylthio(C,.6)alkyl, C,.6 alkylsulfinyl(C,_ 6)alkyl, C1-6 alkylsulfonyl(C!.6)alkyl, aminocarbonyl(C1.6)alkyl, C,.6alkylarninocarbonyl(C,. 6)alkyl, di(C,^)alkylaminocarbonyl(C1.6)alkyl, phenyl(CM)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C^ haloalkyl, C,_6 alkoxy or C,_6 haloalkoxy), heteroaryl(CM)alkyl (where the heteroaryl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,_6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), heterocyclyl- (CM)alkyl (where the heterocyclyl group is optionally substituted by halo, cyano, C,.6 alkyl, Cτ.6 haloalkyl, C,.6 alkoxy or C,_6 haloalkoxy), C2.6 alkenyl, C2.6 haloalkenyl, C,.6 cyanoalkenyl, C5.6 cycloalkenyl, aminocarbonyl(C2.6)alkenyl, C,.6 alkylaminocarbonyl- (C,.6)alkenyl, di(Cι_6)alkylaminocarbonyl(C,.6)alkenyl, phenyl(C2 l)-alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,_6 haloalkoxy), C2.6 alkynyl, aminocarbonyl(C2.6)alkynyl, alkylaminocarbonyl- (Cj.6)alkynyl, di(C,.6)alkylaminocarbonyl(C1.6)alkynyl, C3.7 cycloalkyl, C3.7 halocycloalkyl, C3.7 cyanocycloalkyl, C,_3 alkyl(C3.7)cycloalkyl, C,.3 alkyl(C3.7)-halocycloalkyl, C5.6 cycloalkenyl, formyl, CL6 alkoxycarbonyl, C1-6 alkylcarbonyl, aminocarbonyl, C,_6 alkylaminocarbonyl, di(C,.6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, C,.6 alkyl, C 6 haloalkyl, C,.6 alkoxy or C1-6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,_6 haloalkyl, C,.6 alkoxy or C,_6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, C,_6 alkyl, C^ haloalkyl, C^ alkoxy or C,.6 haloalkoxy), C^ alkylthio, R12O, R,3R14N or R15ON=C(R16); where R12 is hydrogen, Cι.g alkyl, C,^ haloalkyl, C^ cyanoalkyl, C,.6 alkoxy(C,.6)alkyl, phenyl(C,.4)alkyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,_6 haloalkyl, C,.6 alkoxy or C,_6 haloalkoxy), heteroaryl(CM)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C,_6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,_6 haloalkoxy), heterocyclyl(Cμ4)alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C,_6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or C^ haloalkoxy), C^ alkoxycarbonyl(C!.6)alkyl, C2.6 alkenyl, C2.6 alkynyl or N=C(CH3)2; R16 is phenyl (optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, C,^ alkoxy or C,_6 haloalkoxy), C,.6 alkyl or C^ haloalkyl; R13 and R14 are, independently, hydrogen, Ct.8 alkyl, C3.7cycloalkyl(C )alkyl, C2.6 haloalkyl, C,.6
Figure imgf000018_0001
C3.7 cycloalkyl, C3.6 alkenyl, C3.6 alkynyl or C,.6 alkoxycarbonyl; and R15 is
Figure imgf000018_0002
(wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,_6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy) or C,.6 alkyl. Alternatively R4 may preferably be C,.8 alkyl, C,.6 haloalkyl, C,_6 cyanoalkyl, C2.6 alkenyl, C2.6 alkynyl, C3.7 cycloalkyl, C3.7 halocycloalkyl, C3.7 cyanocycloalkyl, C,.3 alkyl(C3. 7)cycloalkyl, C,.3 alkyl(C3.7)halocycloalkyl, C5.6 cycloalkenyl, C3.7 cycloalkyl(C,.6)alkyl, C5.6 cycloalkenyl(C^)alkyl, C2.6 haloalkenyl, C,.6 cyanoalkenyl, C,_6 alkoxy (C,.6)alkyl, C3.6 alkenyloxy(C!.6)alkyl, C3.6 alkynyloxy(C,.6)alkyl, aryloxy - (C,.6)alkyl, C,^ carboxyalkyl, C,.6 alkylcarbonyl(C,.6)alkyl, C2.6 alkenylcarbonyl(C,.6)alkyl, C2.6 alkynylcarbonyl(C1.6)alkyl, C^ alkoxycarbonyl(C1.6)alkyl, C3.6 alkenyloxycarbonyl- (C,.6)alkyl, C3.6 alkynyloxycarbonyl(C1.6)alkyl, aryloxycarbonyl(C1.6)alkyl, C^ alkylthio (C,.6)alkyl, C,.6 alkylsulfiny C^alkyl, C 6 alkylsulfonyl(C,.6)alkyl, aminocarbonyl - (C,^)alkyl, aminocarbonyl(C2.6)alkenyl, aminocarbonyl(C2.6)alkynyl, C,.6alkylamino- carbonyl(C1.6)alkyl, di(Cι.6)alkylaminocarbonyl(C1.6)alkyl, C,.6 alkylaminocarbonyl
(C ^alkenyl, di(C1.6)alkylaminocarbonyl(C,.6)alkenyl, alkylaminocarbonyl(C,.6)alkynyl, di- (C1.6)alkylaminocarbonyl(C1.6)alkynyl, phenyl (optionally substituted by halo, nitro, cyano, C]_6 alkyl, C,.6 haloalkyl, C,_6 alkoxy or C,^ haloalkoxy), phenyl(C )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C^ alkyl, C,.6 haloalkyl, C,_6 alkoxy or C^ haloalkoxy), phenyl(C2j,)alkenyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,_6 alkyl, Cj.6 haloalkyl, C 6 alkoxy or C,.6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, C,_6 alkyl, Cj.6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, C,_6 alkoxy or C,_6 haloalkoxy), heteroaryl (C )alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,_6 haloalkyl, C^ alkoxy or C _6 haloalkoxy), heterocyclyl(C )alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), R12O, C,.8 alkylthio, R13R14N or R15ON=C(R16); where R12 is C s alkyl, C^ haloalkyl; R16 is C,.6 alkyl, C,_6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, C^ alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,_6 haloalkoxy); R16 is C,.6 alkyl, C].6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, C,„6 alkoxy or C,.6 haloalkoxy); R13 and R14 are, independently, hydrogen, C,.g alkyl, C3.7 cycloalkyl, C3.6 alkenyl, C3.6 alkynyl, C3.7 cycloalkyl(CM)alkyl, C2.6 haloalkyl, C,.6 alkoxy(C,.6)alkyl, C 6 alkoxycarbonyl, or R13 and R14 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two C,_6 alkyl groups; and R15 is C,.6 alkyl or phenyl(C,.2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,^ haloalkyl, C,.6 alkoxy or C^ haloalkoxy); for such a group, more preferably R4 is C,.g alkyl, C,.g haloalkyl, CNg cyanoalkyl, C3.7 cycloalkyl, C^ alkyl (C3.7) cycloalkyl, CL6 alkoxy (C,.6) alkyl, heterocyclic (optionally substituted by halo, nitro, cyano, C^ alkyl, C,_6 haloalkyl, C,_6 alkoxy or C,.6 haloalkoxy) or R13R14N where R13 andR14 are independently C,.g 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 C^ alkyl groups. R4 is more preferably C,.s alkyl, C,.6 haloalkyl, C,.6 cyanoalkyl, C2.6 alkenyl, C2.6 alkynyl, C3.7 cycloalkyl, C3.7 halocycloalkyl, C3.7 cyanocycloalkyl, C,.3 alkyl(C3.7)cycloalkyl, C,.3 alkyl(C3.7)halocycloalkyl, C5.6 cycloalkenyl, C3.7 cycloalkyl(C,.6)alkyl, C5.6 cycloalkenyl(C1.6)alkyl, C2.6 haloalkenyl, C,_6 cyanoalkenyl, C,.6 alkoxy (C,.6)alkyl, C3.6 alkenyloxy (Chalky 1, C3.6 alkynyloxy(C,.6)alkyl, aryloxy(C!.6)alkyl, C,.6 carboxyalkyl, Cj.6 alkylcarbony^Cj^alkyl, C2.6 alkenylcarbonyl(C,.6)alkyl, C2.6 alkynylcarbonyl(C,.6)alkyl, C,.6 alkoxycarbonyl(C,.6)alkyl, C3.6 alkenyloxycarbonyl(C!.6)alkyl, C3.6 alkynyloxycarbonyl(C,.6)alkyl, aryloxycarbonyl(C1.6)alkyl, C,.6 alkylthio(C].6)alkyl, C,_6 alkylsulfiny^C^alkyl, Cμ6 alkylsulfonyl(C,.6)alkyl, aminocarbonyl(C,.6)alkyl, aminocarbonyl(C2.6)alkenyl, aminocarbonyl(C2.6)alkynyl, C,.6 alkylaminocarbonyl(C1.6)alkyl, di(C1.6)alkylaminocarbonyl(C,.6)alkyl, C,_6 alkylaminocarbonyl(C,.6)alkenyl, di(C,.6)alkyl- aminocarbonyl(C!.6)alkenyl, alkylaminocarbony^CL^alkynyl, di(C1.6)alkylaminocarbonyl- (C,.6)alkynyl, phenyl (optionally substituted by halo, nitro, cyano, C,_6 alkyl, C,_6 haloalkyl, CL6 alkoxy or C,^ haloalkoxy), phenyl(C )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, C,_6 alkoxy or C,.6 haloalkoxy), phenyl(C2.4)alkenyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,_6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, C^ alkyl, C,.6 haloalkyl, C,_6 alkoxy or C,.6 haloalkoxy), heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or CU6 haloalkoxy), heteroaryl(CM)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C,^ alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), heterocyclyl(CM)alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C,_6 alkyl, C,^ haloalkyl, C,_6 alkoxy or C,_6 haloalkoxy), R12O, C,.g alkylthio, R13R14N or R15ON=C(R16); where R12 is CM alkyl, C,.6 haloalkyl; R16 is C,.6 alkyl, C,.6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,^ haloalkyl, C,.6 alkoxy or C,^ haloalkoxy); R13 and R14 are, independently, hydrogen, C1-8 alkyl, C3.7 cycloalkyl, C3.6 alkenyl, C3.6 alkynyl, C3.7 cycloalkyl(CM)alkyl, C2.6 haloal-kyl, C,^ alkoxy(C!.6)alkyl, C,.6 alkoxycarbonyl, or R13 and R14 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 C,.6 alkyl groups; and R15 is C,.6 alkyl or phenyl(C,.2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,_6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or CL6 haloalkoxy); and R4 is more preferably C,_8 alkyl, C,_8 haloalkyl,
Figure imgf000020_0001
cyanoalkyl, C3.7 cycloalkyl, C i alkyl(C3.7)cycloalkyl, C,_6 alkoxy(Cj.6)alkyl, heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C,_6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,^ haloalkoxy) or R13R14N; where R13 andR14 are, independently, C,.g 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 heteroatoms selected from O, N or S and which may be optionally substituted by one or two C^ alkyl groups. It is further preferred that R4 is
Figure imgf000020_0002
haloalkyl, C,.g cyanoalkyl, C3.7 cycloalkyl(C!.6)alkyl, C5.6 cycloalkenyl(C,.6)alkyl, C,.6 alkoxy (C,.6)alkyl, C3.6 alkenyloxy(C!.6)alkyl, C3.6 alkynyloxy(C[.6)alkyl, aryloxy(C1.6)alkyl, C,.6 carboxyalkyl, C,.6 alkylcarbonyl(C,.6)alkyl, C2.6 alkenylcarbonyl(C,.6)alkyl, C2.6 alkynylcarbonyl(C,.6)alkyl, C,.6 alkoxycarbonyl(Cj.6)alkyl, C3.6 alkenyloxycarbonyl(C,.6)alkyl, C3.6 alkynyloxycarbonyl- (C^alkyl, aryloxycarbonyl(C,.6)alkyl, C,_6 alkylthio C^alkyl, C,.6 alkylsulfinyl(C,.6)alkyl, C 6 alkylsulfonyl(C,.6)alkyl, aminocarbony^CL^alkyl, C,.6alkylaminocarbonyl(C1.6)alkyl, di(C1.6)alkylaminocarbonyl(C,.6)alkyl, phenyl(CM)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,_6 alkyl, C,_6 haloalkyl, C,.6 alkoxy or C,_6 haloalkoxy), heteroaryl(CM)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, Cμ6 haloalkyl, C,.6 alkoxy or Cμ6 haloalkoxy), heterocyclyl - (CM)alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, - C,^ alkyl, C,_6 haloalkyl, C 6 alkoxy or Cλ_6 haloalkoxy), C2.6 alkenyl, C2.6 haloalkenyl, - C,.6 cyanoalkenyl, C5.6 cycloalkenyl, aminocarbonyl(C2.6)alkenyl, C^alkylamino-carbony^C,. 6)alkenyl, di(C16)alkylaminocarbonyl(C1.6)alkenyl, phenyl(C2^,)alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Cι_6 alkyl, C 6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), C2.6 alkynyl, aminocarbonyl(C2.6)alkynyl, alkylamino-carbony^ . 6)alkynyl, di(C1.6)alkylaminocarbonyl(C1.6)alkynyl, C3.7 cycloalkyl, C3.7 halocycloalkyl, C3.7 cyanocycloalkyl, C,.3 alkyl(C3.7)cycloalkyl, C,.3 alkyl(C3.7)halocycloal-kyl, phenyl (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C,.6 haloalkyl, C,_6 alkoxy or C,.6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, C,.6 alkyl, C^ haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), C,.g alkylthio, R12O, R13R14N or R15ON=C(R16); where R12 is C1-g alkyl or C,.6 haloalkyl; R16 is phenyl (optionally substituted by halo, nitro, cyano, Cj.6 alkyl, C^ haloalkyl, C1-6 alkoxy or C,^ haloalkoxy), C,^ alkyl or C 6 haloalkyl; R13 and R14 are, independently, hydrogen, Cι.8 alkyl, C3.7 cycloalkyl(CM)alkyl, C2.6 haloalkyl, C,.6 alkoxy(C,.6)alkyl, C3.7 cycloalkyl, C3.6 alkenyl, C3.6 alkynyl or C,.6 alkoxycarbonyl; and R15 is phenyl(C1.2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, 6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or Cμ6 haloalkoxy) or C,_6 alkyl.
It is even more preferred that R4 is C^ alkyl, C,.8 haloalkyl, C^ cyanoalkyl, C,.6 alkoxy (C,_6) alkyl, C3.7 cycloalkyl, Cj.3 alkyl (C3.7) cycloalkyl, heterocyclyl (optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,_6 haloalkoxy) or di(C1.g)alkylamino. It is yet more preferred that R4 is Cj.g alkyl, C,.g haloalkyl, C,.g cyanoalkyl, C,.6 alkoxy (C,.6) alkyl, C3.7 cycloalkyl, C,.3 alkyl (C3.7) cycloalkyl, heterocyclyl (optionally substituted by Cι_6 alkyl) or di(C,.8)alkylamino.
R4 is most preferably C,.g alkyl, C,.g haloalkyl, C,.8 cyanoalkyl, C3.7 cycloalkyl, C,_3 alkyl(C3.7)cycloalkyl, C,.6 alkoxy (C,.6)alkyl or R13R14N; where R13 andR14 are, indepen- dently, C,.g 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 C,_6 alkyl groups.
It is preferred that R5 is hydrogen, halogen, nitro, cyano, C^ alkyl, Cj.6 haloalkyl, C,_6 cyanoalkyl, C3.7 cycloalkyl(C,.6)alkyl, C,.6 alkoxy(C,.6)alkyl, C,.6 alkoxycarbonyl(C,.6)alkyl, C,_6 alkylcarbonyl(C,.6)alkyl, C,.6alkylaminocarbonyl(Cι.6)alkyl, di(C,.6)alkylamino- carbony^Cj. alkyl, phenyl(C,.6)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C1-6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), heteroaryl- (C,.6)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, CL6 haloalkyl, C,^ alkoxy or C,.6 haloalkoxy), C2.6 alkenyl, C2.6 haloalkenyl, C2.6 alkynyl, C3.7 cycloalkyl, C,_6 alkoxycarbonyl, C,.6 alkylcarbonyl, C,.6 alkylaminocarbonyl, di(C,.6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy) or heteroaryl (optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,_6 haloalkyl, CL6 alkoxy or C,.6 haloalkoxy).
It is more preferred that R5 is hydrogen, halogen, C,.g alkyl or C,.6 haloalkyl. It is preferred that R6 is cyano, nitro, C,_6 alkyl, C,^ haloalkyl, C3.7 cycloalkyl(C!.6)alkyl, C3.7 cycloalkyl, CH2(C2.6)alkenyl, CH2(C2.6)alkynyl, phenyl (optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,_6 haloalkyl, C,.6 alkoxy or C,^ haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), C,.6 alkylcarbonyl, C,.6 alkoxycarbonyl, C,_6 alkylamino, di(C,.6)alkylamino, C,.6 alkylcarbonylamino, C,.6 alkoxycarbonylamino, C,.6 alkoxy, C,.6 alkylthio, C1-6 haloalkylthio, C,-6 alkylsulfinyl, C<_6 haloalkylsulfinyl, C,.6 alkylsulfonyl, C,.6 haloalkylsulfonyl, arylthio, arylsulfinyl, arylsulfonyl or (C,.6)alkylcarbonyloxy.
It is preferred that R7 is hydrogen, C1-g alkyl, C,.6 haloalkyl, C,_6 cyanoalkyl, C2.6 alkenyl, C2.6 haloalkenyl, C2.6 alkynyl, C3.7 cycloalkyl, C3.7 cycloalkyl(C,.6)alkyl, C,^ alkoxy(C!.6)alkyl, C 6 alkoxycarbonyl, C,.6 alkylcarbonyl, C,.6 alkylaminocarbonyl, di(C,.6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, C,_6 alkyl, C,_6 haloalkyl, C^ alkoxy or C,.6 haloalkoxy) or heteroaryl (optionally substituted by halo, nitro, cyano, C,_6 alkyl, C,_6 haloalkyl, C,.6 alkoxy or C,_6 haloalkoxy).
It is more preferred that R7 is hydrogen, C,.g alkyl or Cj.6 haloalkyl. The compounds of Tables 1 to 86 illustrate compounds of the invention.
Table 1 provides 410 compounds of formula (1):
Figure imgf000023_0001
wherein R3 and R4 are as defined in Table 1.
Table 1
Figure imgf000023_0002
Table 1 continued
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0002
Table 2 provides 290 compounds of formula (2):
Figure imgf000033_0001
wherein R4 and R3 are as defined in Table 2.
Table 2
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0002
Table 3 provides 290 compounds of formula (3):
Figure imgf000040_0001
wherein R3 and R4 are as defined in Table 2.
Table 4 provides 290 compounds of formula (4):
Figure imgf000041_0001
wherein R3 and R4 are as defined in Table 2.
Table 5 provides 290 compounds of formula (5):
Figure imgf000041_0002
wherein R3 and R4 are as defined in Table 2.
Table 6 provides 290 compounds of formula (6):
Figure imgf000041_0003
wherein R3 and R4 are as defined in Table 2.
Table 7 provides 290 compounds of formula (7):
Figure imgf000041_0004
wherein R3 and R4 are as defined in Table 2.
Table 8 provides 290 compounds of formula (8):
Figure imgf000041_0005
wherein R3 and R4 are as defined in Table 2.
Table 9 provides 290 compounds of formula (9):
Figure imgf000042_0001
wherein R3 and R4 are as defined in Table 2.
Table 10 provides 290 compounds of formula (10):
Figure imgf000042_0002
wherein R3 and R4 are as defined in Table 2.
Table 11 provides 290 compounds of formula (11):
Figure imgf000042_0003
wherein R3 and R4 are as defined in Table 2.
Table 12 provides 290 compounds of formula (12):
Figure imgf000042_0004
wherein R3 and R4 are as defined in Table 2.
Table 13 provides 290 compounds of formula (13):
Figure imgf000042_0005
wherein R3 and R4 are as defined in Table 2.
Table 14 provides 290 compounds of formula (14):
Figure imgf000042_0006
wherein R3 and R4 are as defined in Table 2.
Table 15 provides 290 compounds of formula (15):
Figure imgf000043_0001
wherein R3 and R4 are as defined in Table 2.
Table 16 provides 290 compounds of formula (16):
Figure imgf000043_0002
wherein R3 and R4 are as defined in Table 2.
Table 17 provides 290 compounds of formula (17):
Figure imgf000043_0003
wherein R3 and R4 are as defined in Table 2.
Table 18 provides 290 compounds of formula (18):
Figure imgf000043_0004
wherein R3 and R4 are as defined in Table 2.
Table 19 provides 290 compounds of formula (19):
Figure imgf000043_0005
wherein R3 and R4 are as defined in Table 2.
Table 20 provides 290 compounds of formula (20):
Figure imgf000044_0001
wherein R3 and R4 are as defined in Table 2.
Table 21 provides 290 compounds of formula (21):
Figure imgf000044_0002
wherein R3 and R4 are as defined in Table 2.
Table 22 provides 290 compounds of formula (22):
Figure imgf000044_0003
wherein R3 and R4 are as defined in Table 2.
Table 23 provides 290 compounds of formula (23):
Figure imgf000044_0004
wherein R3 and R4 are as defined in Table 2.
Table 24 provides 290 compounds of formula (24):
Figure imgf000044_0005
wherein R3 and R4 are as defined in Table 2. Table 25 provides 290 compounds of formula (25):
Figure imgf000044_0006
wherein R3 and R4 are as defined in Table 2.
Table 26 provides 290 compounds of formula (26):
Figure imgf000045_0001
wherein R3 and R4 are as defined in Table 2.
Table 27 provides 290 compounds of formula (27):
Figure imgf000045_0002
wherein R3 and R4 are as defined in Table 2.
Table 28 provides 290 compounds of formula (28):
Figure imgf000045_0003
wherein R3 and R4 are as defined in Table 2.
Table 29 provides 290 compounds of formula (29):
Figure imgf000045_0004
wherein R3 and R4 are as defined in Table 2.
Table 30 provides 290 compounds of formula (30):
Figure imgf000045_0005
wherein R3 and R4 are as defined in Table 2.
Table 31 provides 290 compounds of formula (31):
Figure imgf000046_0001
wherein R3 and R4 are as defined in Table 2.
Table 32 provides 290 compounds of formula (32):
Figure imgf000046_0002
wherein R3 and R4 are as defined in Table 2.
Table 33 provides 290 compounds of formula (33):
Figure imgf000046_0003
wherein R3 and R4 are as defined in Table 2.
Table 34 provides 290 compounds of formula (34):
Figure imgf000046_0004
wherein R3 and R4 are as defined in Table 2.
Table 35 provides 290 compounds of formula (35):
Figure imgf000046_0005
wherein R3 and R4 are as defined in Table 2.
Table 36 provides 290 compounds of formula (36):
Figure imgf000046_0006
wherein R3 and R4 are as defined in Table 2.
Table 37 provides 290 compounds of formula (37):
Figure imgf000047_0001
wherein R3 and R4 are as defined in Table 2. Table 38 provides 290 compounds of formula (38):
Figure imgf000047_0002
wherein R3 and R4 are as defined in Table 2.
Table 39 provides 290 compounds of formula (39):
Figure imgf000047_0003
wherein R3 and R4 are as defined in Table 2.
Table 40 provides 290 compounds of formula (40):
Figure imgf000047_0004
wherein R3 and R4 are as defined in Table 2. Table 41 provides 290 compounds of formula (41):
Figure imgf000047_0005
wherein R3 and R4 are as defined in Table 2.
Table 42 provides 290 compounds of formula (42):
Figure imgf000048_0001
wherein R3 and R4 are as defined in Table 2.
Table 43 provides 290 compounds of formula (43):
Figure imgf000048_0002
wherein R3 and R4 are as defined in Table 2.
Table 44 provides 290 compounds of formula (44):
Figure imgf000048_0003
wherein R3 and R4 are as defined in Table 2.
Table 45 provides 290 compounds of formula (45):
Br
R (45)
' 3 R3 wherein R3 and R4 are as defined in Table 2.
Table 46 provides 290 compounds of formula (46):
Figure imgf000048_0004
wherein R3 and R4 are as defined in Table 2. Table 47 provides 290 compounds of formula (47):
Figure imgf000048_0005
wherein R3 and R4 are as defined in Table 2. Table 48 provides 290 compounds of formula (48):
Figure imgf000049_0001
wherein R3 and R4 are as defined in Table 2.
Table 49 provides 290 compounds of formula (49):
Figure imgf000049_0002
wherein R3 and R4 are as defined in Table 2.
Table 50 provides 290 compounds of formula (50):
Figure imgf000049_0003
wherein R3 and R4 are as defined in Table 2.
Table 51 provides 290 compounds of formula (51):
Figure imgf000049_0004
wherein R3 and R4 are as defined in Table 2.
Table 52 provides 290 compounds of formula (52):
Figure imgf000049_0005
wherein R3 and R4 are as defined in Table 2.
Table 53 provides 290 compounds of formula (53):
Figure imgf000050_0001
wherein R3 and R4 are as defined in Table 2.
Table 54 provides 290 compounds of formula (54):
Figure imgf000050_0002
wherein R3 and R4 are as defined in Table 2.
Table 55 provides 290 compounds of formula (55):
Figure imgf000050_0003
wherein R3 and R4 are as defined in Table 2.
Table 56 provides 290 compounds of formula (56):
Figure imgf000050_0004
wherein R3 and R4 are as defined in Table 2.
Table 57 provides 290 compounds of formula (57):
Figure imgf000050_0005
wherein R3 and R4 are as defined in Table 2.
Table 58 provides 290 compounds of formula (58):
Figure imgf000050_0006
wherein R3 and R4 are as defined in Table 2.
Table 59 provides 290 compounds of formula (59):
Figure imgf000051_0001
wherein R3 and R4 are as defined in Table 2.
Table 60 provides 290 compounds of formula (60):
Figure imgf000051_0002
wherein R3 and R4 are as defined in Table 2.
Table 61 provides 290 compounds of formula (61):
Figure imgf000051_0003
wherein R3 and R4 are as defined in Table 2.
Table 62 provides 290 compounds of formula (62):
Figure imgf000051_0004
wherein R3 and R4 are as defined in Table 2.
Table 63 provides 290 compounds of formula (63):
Figure imgf000051_0005
wherein R3 and R4 are as defined in Table 2.
Table 64 provides 290 compounds of formula (64):
Figure imgf000052_0001
wherein R3 and R4 are as defined in Table 2.
Table 65 provides 290 compounds of formula (65):
Figure imgf000052_0002
wherein R3 and R4 are as defined in Table 2.
Table 66 provides 290 compounds of formula (66):
Figure imgf000052_0003
wherein R3 and R4 are as defined in Table 2. Table 67 provides 290 compounds of formula (67):
Figure imgf000052_0004
wherein R3 and R4 are as defined in Table 2.
Table 68 provides 290 compounds of formula (68):
Figure imgf000052_0005
wherein R3 and R4 are as defined in Table 2.
Table 69 provides 290 compounds of formula (69):
Figure imgf000053_0001
wherein R3 and R4 are as defined in Table 2.
Table 70 provides 290 compounds of formula (70):
Figure imgf000053_0002
wherein R3 and R4 are as defined in Table 2.
Table 71 provides 290 compounds of formula (71):
Figure imgf000053_0003
wherein R3 and R4 are as defined in Table 2.
Table 72 provides 290 compounds of formula (72):
Figure imgf000053_0004
wherein R3 and R4 are as defined in Table 2.
Table 73 provides 290 compounds of formula (73):
Figure imgf000053_0005
wherein R3 and R4 are as defined in Table 2.
Table 74 provides 290 compounds of formula (74):
Figure imgf000053_0006
wherein R3 and R4 are as defined in Table 2.
Table 75 provides 290 compounds of formula (75):
Figure imgf000054_0001
wherein R3 and R4 are as defined in Table 2.
Table 76 provides 290 compounds of formula (76):
Figure imgf000054_0002
wherein R3 and R4 are as defined in Table 2.
Table 77 provides 290 compounds of formula (77):
Figure imgf000054_0003
wherein R3 and R4 are as defined in Table 2.
Table 78 provides 290 compounds of formula (78):
Figure imgf000054_0004
wherein R3 and R4 are as defined in Table 2.
Table 79 provides 290 compounds of formula (79):
Figure imgf000054_0005
wherein R3 and R4 are as defined in Table 2.
Table 80 provides 290 compounds of formula (80):
Figure imgf000055_0001
wherein R3 and R4 are as defined in Table 2.
Table 81 provides 290 compounds of formula (81):
Figure imgf000055_0002
wherein R3 and R4 are as defined in Table 2.
Table 82 provides 290 compounds of formula (82):
Figure imgf000055_0003
wherein R3 and R4 are as defined in Table 2.
Table 83 provides 290 compounds of formula (83):
Figure imgf000055_0004
wherein R3 and R4 are as defined in Table 2.
Table 84 provides 290 compounds of formula (84):
Figure imgf000055_0005
wherein R3 and R4 are as defined in Table 2.
Table 85 provides 290 compounds of formula (85):
Figure imgf000055_0006
wherein R3 and R4 are as defined in Table 2.
Table 86 provides 290 compounds of formula (86):
Figure imgf000056_0001
wherein R3 and R4 are as defined in Table 2.
The following abbreviations are used throughout this description: m.p. = melting point ppm = parts per million s = singlet br = broad d = doublet dd = doublet of doublets t = triplet q = quartet m = multiplet
Table 87 shows selected melting point and selected NMR data, all with CDC13 as the solvent (unless otherwise stated; if a mixture of solvents is present, this is indicated as, for example, (CDC13 / d6-DMSO)), (no attempt is made to list all characterising data in all cases) for compounds of Tables 1 to 86.
TABLE 87
Figure imgf000056_0002
TABLE 87 continued
Figure imgf000057_0001
TABLE 87 continued
Figure imgf000058_0001
The compounds of the invention may be made in a variety of ways.
A compound of formula (I) may be prepared by acylating a compound of formula (II) with a compound of formula (III), preferably in the presence of a known coupling agent such as 1,3-dicyclohexylcarbodiimide, 1,3-ditsopropylcarbodiimide or l-(3-dimethylamino- propyl)-3-ethylcarbodiimide. Alternatively a compound of formula (III) may first be converted to an acid chloride or anhydride suitable for reaction with an amine to form an amide; such procedures are well known and are described, for example, in J. March, Advanced Organic Chemistry, Third Edition, John Wiley and Sons, New York, 1985, pages 370-376 and references therein. Compounds of formula (II) are either known compounds or may be prepared from commercially available starting materials by methods described in the literature (see, for example, C. Oliver Kappe, Robert Flammang, and Curt Wentrup, Heterocycles, Vol. 37, No. 3, 1615, (1994); A. Adams and R. Slack, J. Chem. Soc, 3061, (1959); and Ronald E Hackler, Kenneth W. Burow, Jr., Sylvester V. Raster and David I. Wickiser, J. Heterocyclic Chem, 26, 1575, (1989)).
A compound of formula (III) may be prepared by hydrolysis of the corresponding compound of formula (IV) (wherein R is preferably C,.6 alkyl) by a method known in the art. A compound of formula (IV) may be hydrolysed under neutral, basic or acidic conditions; the reaction conditions are chosen such that substituent R4 is unchanged during the hydrolysis reaction. Compounds of formula (IV) capable of ready hydrolysis under different conditions are known in the literature and suitable compounds of formula (IV) may be selected, for example, by reference to Theodora W. Greene, Protective Groups in Organic Synthesis, Chapter 5, John Wiley and Sons, New York, 1981.
A compound of formula (IV) may be prepared from a compound of formula (V) under conditions described in the literature (see, for example, David W. Dunwell, Delme Evans, Terence A. Hicks, J. Med. Chem., 1975, Vol. 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, 1275-1278, 1991; Dale L. Boger, J. Org. Chem., 43, No 11 , 2296, 1978 ). The substituent R4 may be an atom or group which itself may be converted into other functional groups; procedures are known in the literature for such transformations involving benzoxazoles and benzothiazoles (for example, Lazer, Edward S., Adams, Julian; Miao, Clara K.; Farina, Peter, Eur. Pat. Appl. EP0535521). Alternatively R4 may contain atoms or groups which may be replaced by other moieties under known conditions. A compound of formula (V) may be prepared by reduction of a compound of formula (VI) and such procedures are known in the art (see, for example, J. March, Advanced Organic Chemistry, Third Edition, John Wiley and Sons, New York, 1985, and references therein). A compound of formula (VI), wherein Z is oxygen, may be prepared by the nitration of a compound of formula (VII) under known conditions. A compound of formula
(VI) (wherein Z is sulfur) may be prepared from a compound of formula (VI) (wherein Z is oxygen) using conditions similar to those described by J. Scheigetz, R. Zamboni and B. Roy, Synth. Commun., 25 (1995) (18), pages 2791-2806. A compound of formula (VI) (wherein Z is nitrogen) may be prepared from a compound of formula (VII) by a sequence of acylation, nitration and deacylation, using conditions known in the art.
Compounds of formula (VII) are either commercially available compounds or may be made from commercially available materials by known methods.
Alternatively, a compound of formula (I) may be prepared by treating a compound of formula (VIII) with, for example, an acid in the presence of a coupling reagent, an orthoester, acid chloride, hydroxyimoyl chloride or an alcohol in the presence of a ruthenium catalyst as described previously for the preparation of a compound of formula (IV).
A compound of formula (VIII) may be obtained by reduction of a compound of formula (IX), itself obtained from a compound of formula (X) using the procedures described above for the transformation of a compound of formula (VII) to a compound of formula (V). A compound of formula (X) may be prepared by reacting a compound of formula
(VII) with a compound of formula (II) in a manner analogous to that described above for the transformation of a compound of formula (III) to a compound of formula (I).
Alternatively, a compound of formula (X), wherein Z is oxygen, may be obtained by reacting a compound of formula (XI), wherein Z is oxygen, with a suitable reagent such as boron tribromide, hydriodic acid or another suitable reagent, as described by Theodora W. Greene, Protective Groups in Organic Synthesis, Chapter 1 , John Wiley and Sons, New York, 1981.
A compound of formula (XI) (wherein Z is oxygen) may be prepared by coupling a compound of formula (II) with a compound of formula (XII) (wherein Z is oxygen) in a manner analogous to that described above for the transformation of a compound of formula (III) to a compound of formula (I). Compounds of formula (XII) (wherein Z is oxygen) are known compounds. An alternative method for preparing a compound of formula (IV) (wherein Z is sulfur) involves the cyclisation of a compound of formula (XIII) (wherein LG is a halogen, such as fluorine, chlorine or bromine) as described, for example, in Comprehensive Heterocyclic Chemistry, Volume 6, Ed. Katritzky and Rees, Pergamon Press, 1984. A compound of formula (XIII) may be prepared by reacting a compound of formula (XIV) 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(pαrα-tolyl)-l,3-dithia-2,4-diphosphetane-2,4- disulfide (Davy reagent /?-tolyl) or phosphorus pentasulfide in a suitable solvent such as toluene or fluorobenzene. A compound of formula (XIV) may be derived from a compound of formula (XV) by nitration followed by reduction of the resultant nitrohalobenzene compound and subsequent acylation of the resultant aminohalobenzene compound, using procedures well known to those skilled in the art. Compounds of formula (XV) are commercially available or may be made from commercially available materials using known methods.
A compound of formula (III) (wherein n is zero) may also be prepared by halogenation of a compound of formula (XVI) followed by displacement of the resultant compound of formula (XVII) (where Hal is chloro or bromo) with cyanide. Hydrolysis of the resultant compound of formula (XVIII) gives a compound of formula (III).
Treatment of a compound of formula (I) (wherein R3 is hydrogen and Y is not S) with an alkylating, acylating, sulphonylating, or sulphenylating agent, optionally in the presence of a base and a phase transfer catalyst, provides a compound of formula (I) (wherein R3 is an alkyl, acyl, sulfenyl or sulfonyl group). Examples of suitable alkylating agents include, but are not restricted to, alkyl halides (such as methyl iodide) and alkyl sulfates (such as dimethylsulfate). Suitable acylating agents include anhydrides (such as acetic anhydride), acid chlorides (such as acetyl chloride or benzoyl chloride) and chloroformates (such as ethyl chloroformate). Suitable sulphonylating agents include, but are not restricted to, sulphonyl chloride. Suitable sulphenylating agents include, but are not restricted to, sulphenyl chloride. Suitable bases include organic bases (such as triethylamine or pyridine), alkali metal alkoxides (such as potassium tert-butoxide) and inorganic bases (such as sodium hydride or sodium hydroxide). Suitable phase transfer catalysts may be selected by reference to the literature (see, for example, J. March, Advanced Organic Chemistry, Third Edition, John Wiley and Sons, New York, 1985, pages 320-322 and references therein).
In a further approach, a compound of formula (IV) may be prepared by treating a compound of formula (XIX) with an optionally substituted haloalkyl ester, preferably in the presence of a base such as potassium carbonate. Similarly, a compound of formula (XX) can be reacted with appropriate malonate derivatives in the presence of suitable catalysts, for example palladium (0) derivatives, to give a compound of formula (IV). The synthesis of compounds of formula (XIX) and (XX) where B is carbon and Z is oxygen, nitrogen or sulfur from commercially available materials is well described in the literature (for example see the methods described in Tetrahedron Lett. 1992, 33(49), 7499; Heterocycles 1984, 22(1), 195; J. Heterocyc Chem. 1967, 4(4), 465; Tetrahedron Lett. 1998, 39, 6581; Tetrahedron Lett. 1989, 30(13), 1591 ; J.Chem. Soc. Perkin 1 1977, 90; J. Org. Chem 1997, 62, 2676; J. Org. Chem 1997, 62, 6507 and WΟ9827974). A compound of formula (I) (where Y is S) may be prepared by reacting a compound of formula (I) (where Y is O) with a suitable thionating agent such as 2,4-bis(4- methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson's reagent), 2,4- bis(methylthio)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Davy reagent methyl), 2,4- bis(pαr -tolyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Davy reagent -tolyl) or phosphorus pentasulfide in a suitable solvent such as toluene or fluorobenzene.
A compound of formula (I) (where Y is S and R3 is H) may be reacted with an alkylating agent R-X (for example methyl iodide) in the presence of a base (for example sodium bis(trimethylsilyl)amide) to give a compounds of formula (XXI), which is then treated with a compound of formula R6-NH2 to give a compound of formula (I) (where Y is N-R6 and R3 is H). Chemical Formulae
Figure imgf000063_0001
(la) (lb)
Figure imgf000063_0002
(ll) (III)
Figure imgf000063_0003
(IV) (V)
Figure imgf000063_0004
Figure imgf000064_0001
(VIII)
(IX)
Figure imgf000064_0002
(X) (XI)
Figure imgf000064_0003
(XIII)
(XII)
Figure imgf000064_0004
(XIV) (XV)
Figure imgf000064_0005
(XVI) (XVII) (XVIII)
Figure imgf000064_0006
(XIX) (XXI)
The compounds of formula (I) can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests. The pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies). Examples of pest species which may be controlled by the compounds of formula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (white flies), Bemisia tabaci (white fly), Ostrinia nubilalis (European corn borer), Spodoptera littoralis (cotton leafworm), Heliothis virescens (tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpa zea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae (white butterfly), Plutella xylostella (diamond back moth), Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locusta migratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp. (rootworms), Panonychus ulmi (European red mite), Panonychus citri (citrus red mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpus spp. (flat mites), Boophilus microplus (cattle tick), Dermacentor variabilis (American dog tick), Ctenocephalides felis (cat flea), Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. (blowflies), Blattella germanica (cockroach), Peήplaneta 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 sulphur eus), Solenopsis geminata (fire ant), Monomorium pharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. (biting and sucking lice), Meloidogyne spp. (root knot nematodes), Globodera spp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulus spp.(citrus nematodes), Haemonchus contortus (barber pole worm), Caenorhabditis elegans_ (vinegar eelworm), Trichostrongylus spp. (gastro intestinal nematodes) and Deroceras reticulatum (slug).
The compounds of formula (I) are also active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae (Magnaporthe grisea) on rice and wheat and other Pyricularia spp. on other hosts; Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts (for example turf, rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental plants); Erysiphe cichoracearum on cucurbits (for example melon); Erysiphe graminis (powdery mildew) on barley, wheat, rye and turf and other powdery mildews on various hosts, such as Sphaerotheca macularis on hops, Sphaerotheca fusca (Sphaerotheca fuliginea) on cucurbits (for example cucumber), Leveillula taurica on tomatoes, aubergine and green pepper, Podosphaera leucotricha on apples and Uncinula necator on vines; Cochliobolus spp., Helminthosporium spp., Drechslera spp. (Pyrenophora spp.), Rhynchosporium spp., Mycosphaerella graminicola (Septoria tritici) and Phaeosphaeria nodorum (Stagonospora nodorum or Septoria nodorum), Pseudocercosporella herpotrichoides and Gaeumannomyces graminis on cereals (for example wheat, barley, rye), turf and other hosts; Cercospora arachidicola and Cercosporidium personatum on peanuts and other Cercospora spp. on other hosts, for example sugar beet, bananas, soya beans and rice; Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables, vines and other hosts and other Botrytis spp. on other hosts; Alternaria spp. on vegetables (for example carrots), oil-seed rape, apples, tomatoes, potatoes, cereals (for example wheat) and other hosts; Venturia spp. (including Venturia inaequalis (scab)) on apples, pears, stone fruit, tree nuts and other hosts; Cladosporium spp. on a range of hosts including cereals (for example wheat) and tomatoes; Monilinia spp. on stone fruit, tree nuts and other hosts; Didymella spp. on tomatoes, turf, wheat, cucurbits and other hosts; Phoma spp. on oil-seed rape, turf, rice, potatoes, wheat and other hosts; Aspergillus spp. and Aureobasidium spp. on wheat, lumber and other hosts; Ascochyta spp. on peas, wheat, barley and other hosts; Stemphylium spp. (Pleospora spp.) on apples, pears, onions and other hosts; summer diseases (for example bitter rot (Glomerella cingulata), black rot or frogeye leaf spot (Botryosphaeria obtusά), Brooks fruit spot (Mycosphaerella pomi), Cedar apple rust (Gymnosporangiumjuniperi-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; Gibber ella fujikuroi on rice; Colletotrichum spp. on a range of hosts including turf, coffee and vegetables; Laetisaria fuciformis on turf; Mycosphaerella spp. on bananas, peanuts, citrus, pecans, papaya and other hosts; Diaporthe spp. on citrus, soybean, melon, pears, lupin and other hosts; Elsinoe spp. on citrus, vines, olives, pecans, roses and other hosts; Verticillium spp. on a range of hosts including hops, potatoes and tomatoes; Pyrenopeziza spp. on oil-seed rape and other hosts; Oncobasidium theobromae on cocoa causing vascular streak dieback; Fusarium spp., Typhula spp., Microdochium nivale, Ustilago spp., Urocystis spp., Tilletia spp. and Claviceps purpurea on a variety of hosts but particularly wheat, barley, turf and maize; Ramularia spp. on sugar beet, barley and other hosts; post-harvest diseases particularly of fruit (for example Penicillium digitatum, Penicillium italicum and Trichoderma viride on oranges, Colletotrichum musae and Gloeosporium musarum on bananas and Botrytis cinerea on grapes); other pathogens on vines, notably Eutypa lata, Guignardia bidwellii, Phellinus igniarus, Phomopsis viticola, Pseudopeziza tracheiphila and Stereum hirsutum; other pathogens on trees (for example Lophodermium seditiosum) or lumber, notably Cephaloascus fragrans, Ceratocystis spp., Ophiostoma piceae, Penicillium spp., Trichoderma pseudokoningii, Trichoderma viride, Trichoderma harzianum, Aspergillus niger, Leptographium lindbergi and Aureobasidium pullulans; and fungal vectors of viral diseases (for example Polymyxa graminis on cereals as the vector of barley yellow mosaic virus (BYMV) and Polymyxa betae on sugar beet as the vector of rhizomania). A compound of formula (I) may move acropetally, basipetally or locally in plant tissue to be active against one or more fungi. Moreover, a compound of formula (I) may be volatile enough to be active in the vapour phase against one or more fungi on the plant. The invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a pest, a locus of pest, or to a plant susceptible to attack by a pest, and a method of combating and controlling fungi which comprises applying a fungicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a plant, to a seed of a plant, to the locus of the plant or seed, to soil or to any other growth medium (for example a nutrient solution). The compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
The term "plant" as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes protectant, curative, systemic, eradicant and antisporulant treatments.
As fungicides, the compounds of formula (I) are preferably used for agricultural, horticultural and turfgrass purposes in the form of a composition.
In order to apply a compound of formula (I) as an insecticide, acaricide, nematicide or molluscicide to a pest, a locus of pest, or to a plant susceptible to attack by a pest, or, as a fungicide to a plant, to a seed of a plant, to the locus of the plant or seed, to soil or to any other growth medium, a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA). SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula (I). The composition is generally used for the control of pests or fungi such that a compound of formula (I) is applied at a rate of from O.lg to 10kg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 1kg per hectare.
When used in a seed dressing, a compound of formula (I) is used at a rate of 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.
In another aspect the present invention provides an insecticidal, acaricidal, nematicidal, molluscicidal or fungicidal composition comprising an insecticidally, acaricidally, nematicidally, molluscicidally or fungicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor. The composition is preferably an insecticidal, acaricidal, nematicidal or fungicidal composition.
In a still further aspect the invention provides a method of combating and controlling pests or fungi at a locus which comprises treating the pests or fungi or the locus of the pests or fungi with an insecticidally, acaricidally, nematicidally, molluscicidally or fungicidally effective amount of a composition comprising a compound of formula (I). The compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
The compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula
(I)-
Dustable powders (DP) may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
Soluble powders (SP) may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG). Wettable powders (WP) may be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).
Granules (GR) may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank). Emulsifiable concentrates (EC) or oil-in- water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methyl- cyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol),
N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C8-C10 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 «-butane). A compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as «-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
A compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound. Capsule suspensions (CS) may be prepared in a manner similar to the preparation of
EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coa- cervation procedure. The compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment. A compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)). Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).
A compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS). The preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type. Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dode- cylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di-wopropyl- 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 (pre- dominately 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 octyl- phenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite). A compound of formula (I) may be applied by any of the known means of applying pesticidal or fungicidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.
A compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
A compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers). Suitable formulation types include granules of fertiliser. The mixtures suitably contain up to 25% by weight of the compound of formula (I). The invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula (I).
The compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity. By including another fungicide, the resulting composition may have a broader spectrum of activity or a greater level of intrinsic activity than the compound of formula (I) alone. Further the other fungicide may have a synergistic effect on the fungicidal activity of the compound of formula (I). The compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition. Examples of suitable pesticides include the following: a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate; b) Organophosphates, such as, profenofos, sulprofos, acephate, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon; c) Carbamates (including aryl carbamates), such as pirimicarb, triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl or oxamyl; d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron, flufenoxuron or chlorfluazuron; e) Organic tin compounds, such as cyhexatin, fenbutatin oxide or azocyclotin; f) Pyrazoles, such as tebufenpyrad and fenpyroximate; g) Macrolides, such as avermectins or milbemycins, for example abamectin, emamectin benzoate, ivermectin, milbemycin, spinosad or azadirachtin; h) Hormones or pheromones; i) Organochlorine compounds such as endosulfan, benzene hexachloride, DDT, chlordane or dieldrin; j) Amidines, such as chlordimeform or amitraz; k) Fumigant agents, such as chloropicrin, dichloropropane, methyl bromide or metam;
1) Chloronicotinyl compounds such as imidacloprid, thiacloprid, acetamiprid, nitenpyram or thiamethoxarn; 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- 1 - 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 (MOΝ65500), N-( 1 -cyano- 1 ,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide (AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide, acibenzolar (CGA245704), alanycarb, aldimorph, anilazine, azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S, bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulphate, copper tallate and Bordeaux mixture, cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulphide 1,1 '-dioxide, dichlofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O,O-di-ts,o-propyl-iS'-benzyl thiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethirimol, ethyl(Z)-N-benzyl-N([methyl(methyl-thioethylideneaminooxycarbonyl)amino]thio)-
-β-alaninate, etridiazole, famoxadone, fenamidone (RPA407213), fenarimol, fenbuconazole, fenfuram, fenhexamid (KBR2738), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos, iprodione, iprovalicarb (SZX0722), isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054, LY211795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metconazole, metiram, metiram-zinc, metominostrobin, myclobutanil, neoasozin, nickel dimethyldithiocarbamate, nitrothal-wopropyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-Al, phosphorus acids, phthalide, picoxy- strobin (ZA1963), polyoxin D, polyram, probenazole, prochloraz, procymidone, prop- amocarb, propiconazole, propineb, propionic acid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, sipconazole (F-155), sodium pentachlorophenate, spiroxamine, streptomycin, sulphur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamid, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl, thiram, timiben- conazole, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tri- cyclazole, tridemorph, trifloxystrobin (CGA279202), triforine, triflumizole, triticonazole, validamycin A, vapam, vinclozolin, zineb and ziram.
The compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
Examples of suitable synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole. Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
An example of a rice selective herbicide which may be included is propanil. An example of a plant growth regulator for use in cotton is PIX™.
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 illustrates the preparation of N-(4-chloro-3-methylisothiazol-5-yl)-[2-
(2,2-dimethylpropyl)-benzoxazol-5-yl]acetamide..
Step l
Preparation of 5-amino-4-chloro-3-methylisothiazole. 5-Amino-3-methylisothiazole hydrochloride (250g, 1.66mole) was suspended in dichloromethane(l .251) and stirred at 8°C. Sulfuryl chloride( 146.8ml, 1.83mole) was added dropwise over lhour and during this addition the temperature of the reaction mixture was maintained between 10 and 15°C. As the sulfuryl chloride was added the suspended particles dissolved and a dark oil began to fall out of solution. The resultant two-phase mixture was stirred at 10°C for 15minute. The mixture was cooled to below 10°C and quenched by careful addition of aqueous potassium carbonate solution (367.3g, 2.66mole, of potassium carbonate in 11 of water). The two phases were separated and the aqueous layer extracted with dichloromethane (600ml+400ml). The combined organic layers were dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated in vacuo. The residue was slurried in hexane (~500ml) for lhour, filtered and dried to give 5-amino-4-chloro-3- methyl-isothiazole as a red-brown-solid (228.7g, 93%), m.p. 69-71°C. 'H NMR (CDC13) δ: 2.3 (3H,s); 4.6(2H, bs)ppm.
Step 2 Preparation of methyl (4-hydroxyphenyl)acetate.
Hydrogen chloride was bubbled through a solution of (4-hydroxyphenyl) acetic acid (25g , O.lόmole) in methanol (100ml) at room temperature. An exotherm resulted in the solution refluxing for about lOminute. The mixture was allowed to cool to room temperature and the solvent was evaporated in vacuo to afford methyl (4-hydroxyphenyl)-acetate as a yellow oil (27.5g) which crystallised on seeding, m.p. 46-52°C.
Η NMR (CDC13) δ: 3.57(2H,S); 3.71(3H,s); 6.0(lH,b); 6.76 (2H,m); 7.10(2H,m)ppm. Step 3
Preparation of methyl (4-hydroxy-3-nitrophenyl)acetate.
Nitric acid (69% by weight, 16M, 20ml) was added dropwise to a solution of methyl (4-hydroxyphenyl)acetate [from step 2] (50.0g, 0.3mole) in acetic acid (500ml), maintaining the temperature of the reaction below 15°C by external cooling. (An induction period was observed for this reaction.) Once gas chromatographic analysis had confirmed that the reaction was complete, the mixture was carefully quenched into water (21) with vigorous stirring. An emulsion formed which subsequently crystallised. After filtration, washing with water and drying, the desired product was obtained as a yellow powder.
Η NMR (CDC13) δ: 3.63(2H,s); 3.72(3H,s); 7.14(lH,d); 7.52(lH,dd); 8.02(lH,d); 10.5(lH,s)ppm. Step 4 Preparation of methyl (3-amino-4-hydroxyphenyl)acetate.
Methyl (4-hydroxy-3-nitrophenyl)acetate [from step 3] (48.9g, 0.23mole) and 5% palladium on carbon were suspended in methanol and the resulting mixture was hydrogen- nated until all the starting material had been consumed. The reaction mixture was filtered to remove the catalyst and the filter-cake was washed with methanol. The combined filtrate and washings were concentrated in vacuo, affording methyl (3-amino-4-hydroxyphenyl)- acetate as a solid (41.0g).
Η NMR (d6-DMSO) δ: 3.51(2H,s); 4.45(2H,b); 6.20(lH,dd); 6.40(lH,d); 6.49(lH,d); 8.87(lH,b)ppm. Step 5
Preparation of methyl [3-(2,2-dimethylpropionamido)-4-hydroxy phenyl] acetate.
Sodium hydrogen carbonate (19 g, 0.23mole) was suspended in 1 ,2-dimethoxyethane (180ml), and methyl (3-amino-4-hydroxyphenyl)acetate [from step 4] (26.3g, 0.145mole) was added. To this mixture was added, dropwise, a solution of t-butyl acetyl chloride in 1 ,2- dimethoxyethane (45ml) over 2hour. Once the addition was complete, the mixture was stirred at room temperature for lhour. The mixture was filtered, the inorganic solid washed with ethyl acetate (3x50ml) and the filtrate and washings were combined and concentrated. Trituration of the product with hexane gave methyl [3-(2,2-dimethylpropionamido)-4- hydroxyphenyljacetate (40. lg) as an off-white solid, m.p. 112-113°C. ΗNMR (CDC13) δ: l.l(9H,s); 2.30(2H,s); 3.51(2H,s); 3.70(3H,s); 6.9-7.0(3H,m);
7.55(lH,br); 8.85(lH,br)ppm.
Step 6
Preparation of methyl [(2,2-dimethyIpropyl)-5-benzoxazolyl] acetate. rα-Toluenesulphonic acid (1.5g) in toluene (120ml) was stirred and heated to reflux with a Dean & Stark™ assembly fitted to remove water. After lhour at reflux the solution was cooled to ca.80°C and methyl [3-(2,2-dimethylpropionamido)-4-hydroxy- phenyljacetate [from step 5] (20.0g, 0.07mole) was added portionwise. The reaction mixture was then heated at reflux for 6hour, cooled, diluted with hexane (200ml) and filtered through a plug of silica gel, eluting with ethyl acetate. The filtrate was evaporated in vacuo to give methyl [(2,2-dimethylpropyl)-5-benzoxazolyl]acetate (17.5g) as an oil. 'H NMR (CDCI3) δ: l.l(9H,s); 2.8(2H,s); 3.7(3H,s); 3.74(2H,s); 7.4(3H,m)ppm. Step 7 Preparation of [(2,2-dimethylpropyl)-5-benzoxazolyl]acetic acid.
Methyl [(2,2-dimethylpropyl)-5-benzoxazolyl]acetate [from step 6] (5.00g, 0.0185mole) was dissolved in methanol (5ml) and then a solution of sodium hydroxide (0.81g, 0.0204mole) in water (5ml) was added slowly over 20minute, maintaining the temperature below 25°C by external cooling. Once the addition was complete, the mixture was allowed to stir at room temperature for lhour. The reaction mixture was poured slowly into water (50ml) and concentrated hydrochloride acid was added until the pH of the mixture was below pH6. The mixture was stirred for lhour then filtered and the solid was washed thoroughly with water and dried. Trituration with hexane gave [(2,2-dimethylpropyl)-5- benzoxazolyl] acetic acid (4.5 lg) as a white solid, m.p.108-109°C.
'H NMR (CDC13) δ: 1.05(9H,s); 2.80(2H,s); 3.77(2H,s); 7.42(3H,m)ppm.
Step 8
Preparation of N-(4-chloro-3-methylisothiazol-5-yl)-[2-(2,2-dimethylpropyl)- benzoxazol-5-y I] acetamide.
[2-(2,2-Dimethylpropyl)-5-benzoxazolyl]acetic acid [from step 7] (0.800g, 0.003mole) was suspended in dichloromethane (10ml) and N,N-dimethylformamide (one drop) and oxalyl chloride (0.45 lg, 0.004mole) were added sequentially. The mixture was stirred for 2hour and then the solvent was removed in vacuo. The residue was taken up in xylene (10ml), 5-amino-4-chloro-3-methylisothiazole [from step 1] (0.829g, 0.006mole) was added and then the mixture was heated under reflux for 2hour. The mixture was cooled to room temperature, diluted with ethyl acetate and washed with brine. The organic solution was dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo. The residue was further purified by flash column chromatography on silica gel, eluting with a 2:1 mixture of hexane: ethyl acetate, to give N-(4-chloro-3-methylisothiazol-5- yl)-[2-(2,2-dimethylpropyl)-benzoxazol-5-yl]acetamide (0.325g) as a pale orange solid, m.p. 144-145°C. 'H NMR (CDC13) δ: l.l(9H,s); 2.35(3H,s); 2.85(2H,s); 3.95(2H,s); 7.25(lH,dd);
7.55(lH,d); 7.65(lH,d); 8.1(lH,b)ppm. EXAMPLE 2 This Example illustrates the preparation of Compound No.17 of Table No.1. N-(4-Chloro-3-methylisothiazol-5-yl)-(2-[2,2-dimethylpropyl]benzoxazol-5-yl)- acetamide [from Example 1] (0.38g) in dry tetrahydrofuran (3ml) was stirred at ambient temperature under an atmosphere of nitrogen and treated with sodium bis(trimethyl- silyl)amide (1.1ml of 1M solution in tetrahydrofuran ). The mixture was stirred for 0.25hour, 2-(trimethylsilyl)ethoxymethyl chloride (0.185g) in dry tetrahydrofuran (0.5ml) was added and then the reaction mixture was stirred for 20hour. The solvent was evaporated under reduced pressure and the residue fractionated by chromatography (silica; hexane/ethyl acetate at 10: 1 by volume) to give the required product (0.105g) as a pale yellow gum.
The following compounds were each prepared individually using a similar procedure. Compound No.7 of Table No.l. was prepared as a pale yellow gum. Compound No.37 of Table No.l. was prepared from α-chlorobenzyl ethyl ether (Reference: J. Med. Chem. (1974), 77,702 and references within), as a colourless oil. Compound No.47 of Table No.1. was prepared from n-octyl chloromethyl ether.
Compound No.297 of Table No.l. was prepared from (-) chloromethyl menthyl ether.
Compound No. 307 of Table No.l. was prepared from (+) chloromethyl menthyl ether. EXAMPLE 3
This Example illustrates the preparation of Compound No.27 of Table No.1. N-(4-Chloro-3-methylisothiazol-5-yl)-(2-[2,2-dimethylpropyl]benzoxazol-5-yl)- acetamide (0.38g) in dry tetrahydrofuran (3ml) was stirred at ambient temperature under an atmosphere of nitrogen and treated with sodium bis(trimethylsilyl)amide (1.1ml of 1M solution in tetrahydrofuran ). The mixture was stirred for 0.25hour and then chloromethyl pivaloate (0.22g) in tetrahydrofuran (0.5ml) was added. The reaction was stirred at ambient temperature for 18hour then dry N,N-dimethylformamide (3 ml) was added followed by sodium iodide (0.020g). The mixture was heated to 80-90°C with stirring for 1 lhour then allowed to cool to ambient temperature. The reaction was poured into water, extracted with diethyl ether (20ml), dried (magnesium sulfate) then the ether extract was evaporated under reduced pressure onto silica. The residual solid was added to a short column of silica then eluted with hexane/ethyl acetate (10:1 to 5:1 by volume) and the fractions containing the desired product were combined and evaporated under reduced pressure to give an oil. This oil was further fractionated by HPLC (silica, hexane/ethyl acetate at 5:1 by volume) to give the required product as a colourless oil, 0.035g. EXAMPLE 4
This Example illustrates the preparation of d2-chloromethyl ethyl ether. Step l Preparation of diethoxy-d2-methane.
Montmorillonite K10 (1.0 g) was added to a mixture of paraformaldehyde-d2 (5.0 g) in ethanol (45.7 ml). The mixture was stirred and heated to reflux for 95 hours. The mixture was allowed to cool and was filtered through a plug of Hyflo Super Cel® diatomaceous earth with ethanol (5 ml) to give a solution of the desired product in ethanol (21.16 g, produc ethanol 1 :5.5 as assessed by Η NMR) Step 2 Preparation of d2-chIoromethyl ethyl ether.
The solution obtained from step 1 (21.16 g) was treated with benzoyl chloride (51.4 ml) and concentrated sulfuric acid (0.62 g), and the mixture was heated to 100°C for 6.5 hours. The mixture was allowed to cool and the reaction mixture was distilled at atmospheric pressure (66-96°C) to give the desired product (1.56 g) as a colourless oil. EXAMPLE 5
This Example illustrates the preparation of Compound No.397 of Table No.l. N-(4-Chloro-3-methylisothiazol-5-yl)-(2-[2,2-dimethylpropyl]benzoxazol-5-yl)- acetamide [from Example 1] (0.15 g) was dissolved in methyl isobutyl ketone (2 ml) and anhydrous potassium carbonate (66 mg) and 2-chloroethyl vinyl ether (0.12 ml) were added. The mixture was heated to 80°C for 2 hours. Potassium iodide (200 mg) was added and the mixture was heated for a further 18hours. The reaction mixture was allowed to cool and was passed through a plug of silica eluting with ethyl acetate/hexane 1 :2. The solvents were evaporated and the residue purified by column chromatography (silica eluting with ethyl acetate hexane 1 :7) to give the desired product (18 mg) as an orange oil. The following compounds were each prepared individually using a similar procedure.
Compound No.127 of Table No.l was prepared as an orange oil. Compound No.137 of Table No.l was prepared as a yellow oil.
Compound No.147 of Table No.l was prepared as an orange oil.
Compound No.157 of Table No.l was prepared as an orange oil.
Compound No.167 of Table No.1 was prepared as a yellow oil. Compound No.177 of Table No.1 was prepared as an orange oil.
Compound No.187 of Table No.l was prepared as a brown oil.
Compound No.197 of Table No.l was prepared as an orange oil.
Compound No.317 of Table No.l was prepared as an orange oil.
Compound No.327 of Table No.l was prepared as an orange oil. Compound No.337 of Table No.l was prepared as an orange oil.
Compound No.207 of Table No.l was prepared as an yellow gum.
Compound No.347 of Table No.l was prepared as an orange oil.
Compound No.367 of Table No.l was prepared as a brown solid.
Compound No.377 of Table No.1 was prepared as a pale yellow oil. Compound No.387 of Table No.l was prepared as an orange oil.
Compound No.77 of Table No.l was prepared as an orange oil.
EXAMPLE 6 This Example illustrates the preparation of Compound No.57 of Table No.l. N-(4-Chloro-3-methylisothiazol-5-yl)-(2-[2,2-dimethylpropyl]benzoxazol-5-yl)- acetamide [from Example 1] (0.50g) was dissolved in dichloromethane (12 ml) and cooled to 2°C. Aqueous 50% sodium hydroxide solution (1 ml), bromomethyl acetate (0.65 ml), benzyltriethylammonium chloride (10 mg) and potassium iodide (25 mg) were added and the mixture was stirred at 2°C for 2 hours and then at ambient temperature for 3 hours. Magnesium sulfate was added to remove the water, and the mixture was filtered through a sinter with dichloromethane which was then evaporated under reduced pressure. The residue was purified by chromatography (silica; hexane/ethyl acetate at 2:1 by volume) to give the required product (54.8 mg) as a yellow oil.
The following compounds were each prepared individually using a similar procedure. Compound No.357 of Table No.1 was prepared as a yellow solid.
Compound No .217 of Table No.l was prepared as a colourless oil. Compound No.67 of Table No.l was prepared as a yellow oil. O 01/55141 QA
- 84 -
EXAMPLE 7 This Example illustrates the preparation of Compound No.97 of Table No.l. N-(4-Chloro-3-methylisothiazol-5-yl)-(2-[2,2-dimethylpropyl]benzoxazol-5-yl)- acetamide [from Example 1] (0.37g) was dissolved in chloromethyl allyl ether (0.8 ml, prepared by an analogous method to that described in example 4) and triethylamine (0.28 ml) was added. The mixture was heated to 70°C for 90 minutes. The mixture was allowed to cool and saturated aqueous sodium bicarbonate solution (10 ml) was added. The mixture was extracted with ethyl acetate (4 x 5 ml). The combined organic layers were dried (magnesium sulfate), filtered and evaporated under reduced pressure, and the residue was purified by column chromatography (silica eluting with ethyl acetate/hexane 1:1) to give the desired product (90 mg) as a yellow oil.
The following compounds were each prepared individually using a similar procedure. Compound No.407 of Table No.l was prepared as a yellow gum. Compound No.87 of Table No.1 was prepared as a pale yellow gum.
Compound No.107 of Table No.l was prepared as a yellow oil. Compound No.227 of Table No.l was prepared as a pale yellow oil.
EXAMPLE 8 This Example illustrates the preparation of Compound No.117 of Table No.1.
N-(4-Chloro-3-methylisothiazol-5-yl)-(2-[2,2-dimethylpropyl]benzoxazol-5-yl)- acetamide [from Example 1] (0.57g) was dissolved in dichloromethane (8 ml) and N,0- bis(trimethylsilyl)acetamide (0.34 g) was added, followed by d2-chloromethyl ethyl ether [from Example 4] (0.29 g). The mixture was stirred at ambient temperature for 65 hours. The mixture was diluted with dichloromethane (25 ml) and washed with saturated aqueous sodium bicarbonate solution (2 x 20 ml), dried (magnesium sulfate), filtered and evaporated. The residue was purified by column chromatography (silica eluting with hexane followed by hexane/ethyl acetate 4:1) to give the desired product (0.45 g) as a yellow oil.
The following compounds were each prepared individually using a similar procedure. Compound No.247 of Table No.1 was prepared as a pale yellow oil.
Compound No.257 of Table No.l was prepared as a pale yellow oil. Compound No.237 of Table No.l was prepared as a pale yellow oil.
EXAMPLE 9 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, SYNPERONIC NP8, until the liquid composition contained the required concentration of the compound. SYNPERONIC is a registered trade mark.
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.
In each test against peach potato aphids (Myzus persicae), Chinese cabbage leaves were infested with aphids, the infested leaves were sprayed with a test composition and pest mortality was assessed after three days. Similar tests were conducted against, independently, two-spotted spider mites
(Tetranychus urticae), fruit flies (Drosophila melanogaster), tobacco budworms (Heliothis virescens), diamond back moth (Plutella xylostella) and corn root worm (Diabrotica bait eat a).
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 88, 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.
Table 88
Figure imgf000087_0001
EXAMPLE 10 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 concen-tration of lOOppm (that is, lmg of compound in a final volume of 10ml) immediately before use. When foliar sprays were applied to monocotyledonous crops, TWEEN 20 (0.1 % by volume) was added. TWEEN is a registered trade mark.
Individual compounds of formula (I) were applied as a foliar (Folr) application (where the chemical solution was applied to the foliage of the test plants by spraying the plant to maximum droplet retention.)
These tests were carried out against Uncinula necator (UNCINE), on vines; Phytophthora infestans lycopersici (PHYTIN) on tomatoes; Puccinia recondita (PUCCRT), on wheat; and Pyricularia oryzae (PYRIOR) on rice. Each treatment was applied to two or more replicate plants for Phytophthora infestans lycopersici and Uncinula necator. For tests on Puccinia recondita and Pyricularia oryzae two replicate pots each containing 6 to 10 plants were used for each treatment. The plants were inoculated one day before (Erad) or one day after (Prot) chemical application. The Phytophthora infestans lycopersici, Puccinia recondita and Pyricularia oryzae plants were inoculated with a calibrated fungal spore suspension. The Uncinula necator plants were inoculated using a 'blowing' inoculation technique.
After chemical application and inoculation, the plants were incubated under high humidity conditions and then put into an appropriate environment to allow infection to proceed, until the disease was ready for assessment. The time period between chemical application and assessment varied from five to fourteen days according to the disease and environment. However, each individual disease was assessed after the same time period for all compounds. Assessments were performed on each of two leaves on each of the replicate plants for
Phytophthora infestans lycopersici. Assessments were performed on a single leaf of each of the replicate plants for Uncinula necator. For Puccinia recondita and Pyricularia recondita assessments were carried out collectively on the plants in each replicate pot.
The disease level present (that is, the percentage leaf area covered by actively sporula- ting 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 asses-sed 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.
PRCO results are shown in Table 89.
TABLE 89
Figure imgf000089_0001
Key to Table 89
PHYTIN = Phytophthora infestans lycopersici PUCCRT = Puccinia recondita PYRIOR = Pyricularia oryzae EXAMPLE 11
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 techniques employed were as follows.
Plants were grown either in John Innes Potting Compost (No.1 or 2) in 4cm diameter, 3.5cm depth minipots or on an artificial, cellulose based growing medium. The test compounds were individually formulated as a solution either in acetone or acetone/ethanol (1:1 by volume) which was diluted in reverse osmosis 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 (Prot) application (where the chemical solution was applied to the foliage of the test plants by spraying the foliage to maximum droplet retention) or as a systemic (Syst) application (where the chemical was added to a small beaker in which the test plant pots were standing).
These tests were carried out against Plasmopara viticola (PLASVI) on vines; Phytophthora infestans lycopersici (PHYTIN) on tomatoes; and Blumeria graminis f.sp. tritici (ERYSGT), Stagonospora nodorum (LEPTNO) and Puccinia triticina (PUCCRT) on wheat. Each treatment was applied to two or more replicate plants for Plasmopara viticola and Phytophthora infestans lycopersici and in all tests where the cellulose growing medium was employed. In minipot tests on Blumeria graminis f.sp. tritici, Stagonospora nodorum and Puccinia triticina, two replicate pots each containing 6 to 10 plants were used for each treatment. The plants were inoculated with a calibrated fungal spore either όhours or one day after chemical application.
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 Blumeria graminis f.sp. tritici plants were inoculated using a 'shake' inoculation technique. For Plasmopara viticola, the plants were reincubated under high humidity conditions for 24hours prior to assessment. The time period between chemical application and assessment varied from five to nine days according to the disease and environment. However, each individual disease was assessed after the same time period for all the compounds tested against that particular disease.
Assessments were performed on a single leaf of each of the two replicate plants for Plasmopara viticola and on each of two leaves on each of the replicate plants for Phytophthora infestans lycopersici. For Blumeria graminis f.sp. tritici, Stagonospora nodorum and Puccinia triticina, assessments were carried out collectively on the plants in each replicate minipot or cellulose medium.
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 either of two alternative methods, described below, each providing its own PRCO (Percentage Reduction from Control) value. All assessments on plants grown on cellulose media (and some grown in soil) used method 1. METHOD 1 This method uses banded assessment values.
The mean disease values are banded in the manner shown below. If the disease level value falls exactly mid- way between two of the points, the result will be the lower of the two points.
0 = 0% disease present 10 = 5.1-10%) disease present
1 = 0.1-1% disease present 20 = 10.1-20%) disease present
3 = 1.1-3% disease present 30 = 20.1-30% disease present
5 = 3.1-5% disease present 60 = 30.1-60%) disease present
90 = 60.1-100%) disease present
An example of a typical banded calculation is as follows:
Mean disease level for treatment A = 25% Therefore banded mean disease level for treatment A = 30 Mean disease level on untreated controls = 85%) Therefore banded mean disease level on untreated controls = 90
PRCO = 100 - { Banded mean disease level for treatment A } x 100 O 01/55141
91
{Banded mean disease level on untreated controls}
100 - (30 x 100) = 66.7 90
The PRCO is then rounded to the nearest whole number; therefore, in this particular example, the PRCO result is 67.
METHOD 2
This method uses unhanded assessment values (that is, the mean disease values are used in the PRCO calculation without a banding step).
An example of a typical unhanded 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. Results are displayed in Table 90.
TABLE 90
Figure imgf000092_0001
Key to Table 90
LEPTNO = Stagonospora nodorum
PLASVI = Plasmopara viticola
PHYTIN = Phytophthora infestans lycopersici

Claims

1. A compound of formula (I) :
Figure imgf000093_0001
wherein n is 0 or 1 ; B is N, N-oxide or CR5; Y is O, S or NR6; Z is O, S or NR7; R1 is hydrogen, halogen, optionally substituted C,.6 alkyl, optionally substituted C2.6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted C^ alkoxy, optionally substituted C1-6 alkylthio, optionally substituted C3.7 cycloalkyl, cyano, nitro or SF5;
R2 is hydrogen, halogen, optionally substituted C,.6 alkyl, optionally substituted C 2-6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted C,_6 alkoxy, optionally substituted C,^ alkylthio, optionally substituted C,.6 alkylsulfinyl, optionally substituted C,.6 alkylsulfonyl, cyano, nitro, formyl, optionally substituted C,_6 alkylcarbonyl, optionally substituted C,_6 alkoxycarbonyl, SF5 or R8ON=C(R9); or R1 and R2 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 hetero-cyclic ring which may contain one or two heteroatoms selected from O, N or S and which is optionally substituted by C,^ alkyl, C,^ haloalkyl or halogen; R3 is optionally substituted aryl, optionally substituted arylcarbonyl, optionally substituted Cj.,0 alkyl [but not C,,6 alkyl, CH2(CM haloalkyl), C,_6 cyanoalkyl, C,.6 alkoxy(C1.6)alkyl, C,.6 alkylthio(C1.6)alkyl, C,.6 alkoxy(CM)alkoxy(C1.6)alkyl, C,.6 alkylcarbonyl(C!.6)alkyl, C,.6 alkoxy carbonyl(C,.6)alkyl or optionally substituted phenyl(C,.4)alkyl], optionally substituted [C2.6 alkenyl(C,.6)alkyl] [but not C3.6 alkenyl], optionally substituted [C2.6 alkynyl(C,.6)alkyl] [but not C3.6 alkynyl], optionally substituted C3.7 cycloalkyl, optionally substituted C,.10 alkylcarbonyl [ but not C,.6 alkylcarbonyl], optionally substituted C,.I0 alkoxycarbonyl [but not C,_6 alkoxycarbonyl], optionally substituted C 0 alkylaminocarbonyl [but not C,.6 alkylaminocarbonyl], optionally substituted di(C1.10)alkylaminocarbonyl [but not di(C,.6)alkylaminocarbonyl], optionally substituted C,.6 alkylthio, optionally substituted C,.6 alkylsulfinyl, optionally substituted C,_6 alkylsulfonyl [but not S(O),Rβ; where Ra is C,_6 alkyl or C,.6 haloalkyl and r is 0, 1 or 2]; or Rl0RπNS(O)p; p is 0, 1 or 2;
R4 is hydrogen, halogen, cyano, optionally substituted C^ alkyl, optionally substituted C2.20 alkenyl, optionally substituted C2.20 alkynyl, optionally substituted C3.7 cycloalkyl, optionally substituted C5.6 cycloalkenyl, formyl, optionally substituted .20 alkoxycarbonyl, optionally substituted C,.20 alkylcarbonyl, aminocarbonyl, optionally substituted C,.20 alkylaminocarbonyl, optionally substituted di-
(C,_20)alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-(C,.6)alkyl-N-arylaminocarbonyl, optionally substituted diarylaminocarbonyl, optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted N-(C,.6)alkyl-N-heteroarylaminocarbonyl, optionally substituted diheteroarylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, SH, optionally substituted C,.20 alkylthio, optionally substituted C,.20 alkylsulfinyl, optionally substituted C,.20 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl, R120, R13R14N or R15ON=C(R16); R5 is hydrogen, halogen, nitro, cyano, optionally substituted C,.g alkyl, optionally substituted C2.6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted C3.7 cycloalkyl, optionally substituted Cw alkoxycarbonyl, optionally substituted C1-6 alkylcarbonyl, optionally substituted C^ alkylaminocarbonyl, optionally substituted di(C,.6)alkylaminocarbonyl, optionally substituted phenyl or optionally substituted heteroaryl;
R6 is hydrogen, cyano, nitro, optionally substituted C,_6 alkyl, optionally substituted C3.7 cycloalkyl, optionally substituted (C2.6)alkenyl(C,.6)alkyl, optionally substituted (C2.6)alkynyl(C1.6)alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted Cj.6 alkylcarbonyl, optionally substituted C,.6 alkoxycarbonyl, optionally substituted C,_6 alkylamino, optionally substituted di - (C1.6)alkylamino, optionally substituted C,.6 alkylcarbonylamino, optionally substituted Cj.6 alkoxycarbonylamino, optionally substituted C,.6 alkoxy, optionally substituted C,_6 alkylthio, optionally substituted C,.6 alkylsulfinyl, optionally substituted C,.6 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or C,.6alkylcarbonyloxy; R7 is hydrogen, cyano, optionally substituted C,.g alkyl, optionally substituted [C2.6 alkenyl(C,.6)alkyl], optionally substituted [C2.6 alkynyl(C,.6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted [C3.7 cycloalkyl(C,.6)alkyl], C,_6 alkoxy(C,.6)alkyl, optionally substituted C,.6 alkoxycarbonyl, optionally substituted C,.6 alkylcarbonyl, optionally substituted C,.6 alkylaminocarbonyl, optionally substituted di(C,.6)alkylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl;
R8 and R15 are, independently, hydrogen, optionally substituted phenyl (C,.2)alkyl or optionally substituted C,.20 alkyl;
R9 and R16 are, independently, hydrogen, optionally substituted phenyl or optionally substituted C,_6 alkyl; R10 and R11 are, independently, optionally substituted C,.6 alkyl; or R10 and R11 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 and S and which is optionally substituted by one or two independently selected C,.6 alkyl groups; R12 is hydrogen, optionally substituted C].20 alkyl, optionally substituted [C2.20 alkenyl(C!.6)alkyl], optionally substituted [C2_20 alkynyl(C,.6) alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, (C,.6)alkylCH=N, optionally substituted arylCH=N, optionally substituted [aryl(C,.6)alkyl]CH=N, optionally substituted heteroarylCH=N, optionally substituted [heterocyclyl(C,.6)alkyl]CH=N, optionally substituted arylC(CH3)=N, optionally substituted heteroarylC(CH3)=N or optionally substituted di(C,.6)alkylC=N; and
R13 and R14 are, independently, hydrogen, optionally substituted C,.20 alkyl, optionally substituted C3.7 cycloalkyl, optionally substituted [C2.20 alkenyl(C,.6)alkyl], optionally substituted [C2.20 alkynyl(C1.6)alkyl], optionally substituted C,.20 alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted C,.20 alkylcarbonyl, optionally substituted C,.20 alkylsulfonyl or optionally substituted phenylsulfonyl.
2. A compound according to claim 1 wherein the compound is of formula I A
Figure imgf000096_0001
wherein n, B, Y, Z, R1, R2, R3 and R4 are as defined in claim 1 for a compound of formula (I).
3. A compound according to claim 1 or claim 2 wherein n is 0.
4. A compound according to any preceding claim wherein R1 is hydrogen, halogen, Cj.6 alkyl, C^ cyanoalkyl, C,.6 haloalkyl, C3.7 cycloalkyl(C,.4)alkyl, CL6 alkoxy -
(Cι.6)alkyl, C2.6 alkenyl, C2.6 alkynyl, CL6 alkoxy, CL6 haloalkoxy, C,.6 alkylthio, C,.6 haloalkylthio, C3.6 cycloalkyl, cyano, nitro or SF5.
5. A compound according to any preceding claim wherein R2 is hydrogen, halogen, C,_ 6 alkyl, C,^ haloalkyl, C,^ alkoxy (C,.6)alkyl, C2.6 alkenyl, C,.6 alkynyl, C,_6 alkoxy, C,. 6 haloalkoxy, C,_6 alkylthio, C,.6 haloalkylthio, C,_6 alkylsulfinyl, C 6 haloalkylsulfinyl, C,.6 alkylsulfonyl, C,_6 haloalkylsulfonyl, cyano, nitro, formyl, C,_6 alkylcarbonyl, C,.6 alkoxycarbonyl, SF5 or CH=NOR8; or R1 and R2 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 C,^ alkyl, C,.6 haloalkyl or halogen; where R8 is phenyl(C,.2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C 6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,^ haloalkoxy) or C,.6 alkyl.
6. A compound according to any preceding claim wherein R3 is C7.10 alkyl, C 6 alky lcarbonyloxy (C , -6)alkyl, di(C , .6)alky laminocarbonyloxy (C j.6)alky 1, benzoyl- oxymethyl (where the phenyl ring is optionally substituted with halogen or CM alkyl), C,_6 alkoxy (C,.6)alkyl (where the alkyl group is substituted by aryl or CM alkoxycarbonyl), tri(CM)alkylsilyl(C1.6)alkoxy(C1.6)alkyl, C3.7 cycloalkyloxy- (C 6) alkyl (where the cycloalkyl group is optionally substituted with C,.6 alkyl), C7.10 alkoxy(Cj.6)alkyl, C,^ haloalkyloxymethyl, C2.6 alkenyloxy (CM)alkyl, C2.6 alkynyloxy(C )alkyl, benzyloxy(C )alkyl (where the phenyl ring is optionally substituted with halogen or CM alkyl), C3.7 cycloalkyl(CM)alkyl, heteroaryl -(C,_3) alkyl (where the heteroaryl group is optionally substituted with halogen or C,.3 alkyl), tri(CM)alkylsilyl(C,^)alkyl, C2.6 haloalkenyl(C!.6)alkyl, C alkoxycarbonyl(C2.6) alkenyl(C1.6)alkyl, aryl(C2.6)alkenyl(C1.6)alkyl, tri(CM)alkylsilyl(C2.6)alkynyl(C1.6) alkyl or C7.10 alkylcarbonyl.
7. A compound according to any preceding claim wherein R4 is cyano, Cj.8 alkyl, C,.g haloalkyl, C,.8 cyanoalkyl, C3.7 cycloalkyl(C,.6)alkyl, C5.6 cycloalkenyl(C,.6)alkyl, -C,.6 alkoxy(C!.6)alkyl, C„ alkenyloxy(C, alkyl, C3.6 alkynyloxy (C,.6)alkyl, aryloxy(C,.6) alkyl, C,.6 carboxyalkyl, C,.6 alkylcarbony C^alkyl, C2.6 alkenylcarbonyl(C,.6)alkyl, C2.6 alkynylcarbonyl(C,^)alkyl, Cι_6 alkoxycarbonyl- (Cw)alkyl, C3.6 alkenyl oxycarbonyl(C!.6)alkyl, C3.6
Figure imgf000097_0001
aryloxycarbonyl(C,.6) alkyl, C,.6 alkylthio(C,.6)alkyl, C 6 alkylsulfmyl(C,.6)alkyl, C,.6 alkylsulfonyl(C,.6) alkyl, aminocarbonyl(C,.6)alkyl, C^ alkylaminocarbonyl- (C^^alkyl, d^C^) alkylaminocarbonyl(C!.6)alkyl, phenyl(C1.4)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,_6 haloalkyl, C,.6 alkoxy or
C,.6 haloalkoxy), heteroaryl(C1.4)alkyl (where the heteroaryl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or C1-6 haloalkoxy), heterocyclyl(C )alkyl (where the heterocyclyl group is optionally substituted by halo, cyano, C,.6 alkyl, C,.6 haloalkyl, C 6 alkoxy or C,.6 haloalkoxy), C2.6 alkenyl, C2.6 haloalkenyl, C,.6 cyanoalkenyl, C5^ cycloalkenyl, aminocarbonyl- (C2.6)alkenyl, C,.6 alkylaminocarbonyl(C,.6)alkenyl, di(C,.6)alkyl-aminocarbonyl
(C^) alkenyl, phenyl(CM)alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, CN6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), C2.6 alkynyl, aminocarbonyl(C2^)alkynyl, alkylaminocarbonyl(C1.6)alkynyl, di(C,.6)alkylaminocarbonyl(C1.6)alkynyl, C3.7 cycloalkyl, C3.7 halocycloalkyl, C3.7 cyanocycloalkyl, C1-3 alkyl(C3.7)cycloalkyl, C,.3 alkyl(C3.7)halocycloalkyl, C5.6 cycloalkenyl, formyl, C,.6 alkoxycarbonyl, C,_6 alkylcarbonyl, aminocarbonyl, CL6 alkylaminocarbonyl, di(C,.6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, C].6 alkyl, C,^ haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, C,_6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or .6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, C,.6 alkyl,
C,.6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), C s alkylthio, RI O, RI3R14N or R15ON=C(R16); where R12 is hydrogen, C,.g alkyl, C,_6 haloalkyl, C,^ cyanoalkyl, C,.6 alkoxy(C!.6)alkyl, phenyl(CM)alkyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, CL6 alkoxy or C,.6 haloalkoxy), heteroaryl(CM)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,.6 haloalkyl, C,.6 alkoxy or C,.6 haloalkoxy), heterocyclyl(CM)alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C,.6 alkyl, C,_6 haloalkyl, C,.6 alkoxy or CL6 haloalkoxy), C,.6 alkoxycarbonyl(C1.6)alkyl, CΪJ6 alkenyl, C2.6 alkynyl or N=C(CH3)2; R16 is phenyl (optionally substituted by halo, nitro, cyano, CL6 alkyl, C,_6 haloalkyl,
C,.6 alkoxy or C^ haloalkoxy), Cj.6 alkyl or CL6 haloalkyl; R13 and R14 are, independently, hydrogen, Cμ8 alkyl, C3.7cycloalkyl(C,.4)alkyl, C2.6 haloalkyl, C,.6 alkoxy(C!.6)alkyl, C3.7 cycloalkyl, C3.6 alkenyl, C3.6 alkynyl or C,_6 alkoxycarbonyl; and R15 is phenyl(C,.2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C^ alkyl, C,^ haloalkyl, C,_6 alkoxy or C,.6 haloalkoxy) or C,.6 alkyl.
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.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002059120A1 (en) * 2001-01-26 2002-08-01 Syngenta Limited Process for the preparation of isothiazole derivatives
US6703347B2 (en) * 2000-01-28 2004-03-09 Syngenta Limited Isothiazole derivatives and their use as pesticides
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US6703347B2 (en) * 2000-01-28 2004-03-09 Syngenta Limited Isothiazole derivatives and their use as pesticides
EP1686128A3 (en) * 2000-01-28 2007-01-24 Syngenta Limited Isothiazole derivatives and their use as pesticides
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JP2006525337A (en) * 2003-04-30 2006-11-09 エフ　エム　シー　コーポレーション Insecticidal (dihalopropenyl) phenylalkyl-substituted benzoxazole and benzothiazole derivatives
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US7576224B2 (en) 2003-04-30 2009-08-18 Fmc Corporation Insecticidal (dihalopropenyl) phenylalkyl substituted dihydrobenzofuran and dihydrobenzopyran derivatives
US7585891B2 (en) 2003-04-30 2009-09-08 Fmc Corporation Pesticidal (dihalopropenyl)phenylalkyl substituted benzodioxolane and benzodioxole derivatives
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US8080558B2 (en) 2007-10-29 2011-12-20 Natco Pharma Limited 4-(tetrazol-5-yl)-quinazoline derivatives as anti-cancer agent

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