WO2001055135A1 - Derives d'azine utilises comme pesticides - Google Patents

Derives d'azine utilises comme pesticides Download PDF

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Publication number
WO2001055135A1
WO2001055135A1 PCT/GB2001/000310 GB0100310W WO0155135A1 WO 2001055135 A1 WO2001055135 A1 WO 2001055135A1 GB 0100310 W GB0100310 W GB 0100310W WO 0155135 A1 WO0155135 A1 WO 0155135A1
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Prior art keywords
alkyl
haloalkyl
alkoxy
formula
cyano
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PCT/GB2001/000310
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English (en)
Inventor
Sarah Armstrong
Nigel John Barnes
Susan Patricia Barnett
Eric Daniel Clarke
Patrick Jelf Crowley
Torquil Eoghan Macleod Fraser
David John Hughes
Christopher John Mathews
Roger Salmon
Stephen Christopher Smith
Russell Viner
William Guy Whittingham
John Williams
Alan John Whittle
William Roderick Mound
Christopher John Urch
Brian Leslie Pilkington
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Syngenta Limited
PILKINGTON, Joan
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Priority to AU2001230340A priority Critical patent/AU2001230340A1/en
Publication of WO2001055135A1 publication Critical patent/WO2001055135A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to azine derivatives, to processes for preparing them, to fungicidal, insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them, to methods of using them to combat fungal diseases (especially fungal diseases of plants) and to methods of using them to combat and control insect, acarine, mollusc and nematode pests.
  • B is N or CR 18 ;
  • E is CR 12 ;
  • Y is O, S
  • R 1 is hydrogen, halogen, C,_ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, C,. 6 cyanoalkyl, C ⁇ haloalkyl, C ⁇ alkoxy, Cj. 6 haloalkoxy, C,. 6 alkylthio, C 6 haioalkylthio, C 3 ⁇ cycloalkyl, C 3. cycloalkyl(C M )alkyl, C,. 6 alkoxyCC ⁇ alkyl, cyano, nitro or SF 5 ;
  • R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, C,. 6 alkyl, C '1-6 alkoxy, C,_ 6 haloalkoxy, C ⁇ alkylthio, C,. 6 haioalkylthio, C t . 6 alkylsulfmyl, C, 1-6 haloalkylsulfmyl, C j.6 alkylsulfonyl, C,. 6 haloalkylsulfonyl, C j . 6 haloalkyl, cyano, nitro, C, .6 alkylcarbonyl, C,_ 6 alkoxycarbonyl or SF 5 ;
  • R 6 is C,. 8 alkyl, C,. g haloalkyl, C,. g cyanoalkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, C 3 . 7 cycloalkyl, C 3 . 7 halocycloalkyl, C 3 . 7 cyanocycloalkyl, Cj. 3 alkyl(C 3 . 7 )cycloalkyl, C,. 3 alkyl(C 3.7 )halocycloalkyl, C 5 . 6 cycloalkenyl, C 3 . 7 cycloalky ⁇ C ⁇ alkyl, C 5 . 6 cycloalkenyl(C,.
  • heteroaryl optionally substituted by halo, nitro, cyano, C,_ 6 alkyl, C, .6 haloalkyl, C 6 alkoxy or C ⁇ 6 haloalkoxy
  • heterocyclyl wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C ⁇ alkyl, C 6 haloalkyl, C, .6 alkoxy or C 1-6 haloalkoxy
  • heteroaryl(C M )alkyl wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C,_ 6 alkyl, C,.
  • R 27 is C, .5 alkyl, .6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C, .6 haloalkyl, C j . 6 alkoxy or C,. 6 haloalkoxy); R 27 is C,_ 6 alkyl, C,_ 6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, C, ⁇ alkyl, C 1-6 haloalkyl, C,. 6 alkoxy or C, .6 haloalkoxy); R and R are, independently, hydrogen, C,.
  • R 8 and R 9 are independently selected from hydrogen, halogen, cyano, nitro, C,_ 6 alkyl, C 1-6 haloalkyl, C,. 6 alkoxy(C,. 6 )alkyl, C 2 . 6 alkenyl, C 2 . 6 haloalkenyl, C 2 . 6 alkynyl, C,. 6 alkoxy or C , . 6 haloalkoxy ;
  • R is hydrogen, halogen, C,_ 6 alkyl, C 2 . 6 alkenyl, C,. 6 alkynyl, C,. 6 haloalkyl, C 1-6 alkoxy, C x _ 6 alkoxy (C,. 6 )alkyl, C,. 6 haloalkoxy, C t . 6 alkylthio, C ⁇ haioalkylthio, C ⁇ alkylsulfinyl, C,_ 6 haloalkylsulfmyl, C L6 alkylsulfonyl, C,.
  • R 17 is hydrogen, C [ . 6 alkyl, C,. 6 haloalkyl, C, ⁇ alkoxy, cyano, C]_ 6 alkoxycarbonyl, C,. 6 alkylcarbonyl orNR 6 R 47 ;
  • R 18 is hydrogen, halogen, nitro, cyano, C,. 8 alkyl, C,. 6 haloalkyl, C,. 6 cyanoalkyl, C 2.6 alkenyl, C 2 . 6 alkynyl, C 3 . 7 cycloalkyl, C 2 ⁇ haloalkenyl, C 3 . 7 cycloalky ⁇ C ⁇ alkyl, C,. 5 alkoxy(C,. 6 )alkyl, C 6 alkoxycarbonyl, C,. 6 alkylcarbonyl, C,. 6 alkylaminocarbonyl, di(C 1.6 )alkylaminocarbonyl, C,. 6 alkoxycarbonyl(C ! .
  • R 22 is C,. 6 alkyl or optionally substituted phenyl(C, .2 )alkyl;
  • R 23 and R 24 are, independently, hydrogen, C,. 8 alkyl or phenyl (optionally substituted by halo, nitro, cyano, C,_ 6 alkyl, C,. 6 haloalkyl, C,. 6 alkoxy or C,_ 6 haloalkoxy);
  • R 26 is hydrogen, C,. g alkyl, C,. 6 haloalkyl, C,. 6 cyanoalkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, C 6 alkoxy (Chalky 1, phenyl(C M )alkyl , (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,_ 6 alkyl, C,. 6 haloalkyl, C ⁇ alkoxy or C,_ 6 haloalkoxy), heteroaryl(C M )alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C,_ 6 alkyl, C,.
  • 6 haloalkyl C]. 6 alkoxy or C, ⁇ haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, C 1-6 alkyl, C,. 6 haloalkyl, C,. 6 alkoxy or C,. 6 haloalkoxy), heterocyclyl(C )alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,. 6 haloalkyl, C w alkoxy or C 1-6 haloalkoxy), C,.
  • R 27 is C,. 6 alkyl, C,. 6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano,
  • R 28 and R 29 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,. 6 )alkyl, C,. 6 alkoxycarbonyl;
  • R 31 and R 32 are, independently, C, ⁇ alkyl or pheny ⁇ C ⁇ alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,. 5 alkyl, C,. 6 haloalkyl, C,_ 6 alkoxy or C j . 6 haloalkoxy);
  • R 46 and R 47 are, independently, hydrogen, C N8 alkyl, C 3 . 7 cycloalkyl, C 3 . 6 alkenyl, C 3.6 alkynyl, C 2.6 haloalkyl, C x . 6 alkoxy(C, ⁇ )alkyl, C,. 6 alkoxycarbonyl(C 1 . 6 )alkyl, carboxy(C ] . 6 )alkyl or pheny ⁇ C ⁇ alkyl; or R 46 and R 47 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two C,. 6 alkyl groups; and
  • R 51 is hydrogen, C,. 10 alkyl, C 1 . 6 alkylcarbonyloxy(C,. 6 )alkyl, benzoyloxymethyl (where the phenyl ring may be optionally substituted with halogen or C M alkyl), C,_ 6 alkoxy(C, .6 )alkyl (where the alkyl group may be optionally substituted by aryl or C, .4 alkoxycarbonyl), C 2 . 6 alkenyloxy(C M )alkyl, C 2 . 6 alkynyloxy(C,. 4 )alkyl, benzyloxy(C,.
  • 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.
  • Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, tt-propyl, «-butyl, H-pentyl, w-hexyl, w ⁇ -propyl, «-butyl, sec-butyl, zs ⁇ -butyl, tert-butyl or ⁇ eo-pentyl.
  • 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.
  • acyl is C,. 6 alkylcarbonyl (for example acetyl), C 2-6 alkenylcarbonyl, C 2 . 6 alkynylcarbonyl, arylcarbonyl (for example benzoyl) or heteroary lcarbony 1.
  • 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. It is preferred that heterocyclyl is optionally substituted by C,_ 6 alkyl. Cycloalkyl includes cyclopropyl, cyclopentyl and cyclohexyl.
  • Cycloalkenyl includes cyclopentenyl and cyclohexenyl.
  • Carbocyclic rings include aryl, cycloalkyl and cycloalkenyl groups. It is to be understood that dialkylamino substituents include those where the dialkyl groups together with the N atom to which they are attached form a five, six or seven- membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two C, ⁇ alkyl groups.
  • heterocyclic rings are formed by joining two groups on an N atom
  • the resulting rings are suitably pyrrolidine, piperidine, thiomorpholine and morpholine each of which may be substituted by one or two (C,. 6 )alkyl groups.
  • phenyl(C 2 ⁇ ,)alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,_ 6 alkyl, C,. 6 haloalkyl, C 1-6 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,.
  • A is C ⁇ 6 alkylene (optionally substituted by C ⁇ alkyl, halogen, C, .3 haloalkyl, C 1-3 cyanoalkyl, C,. 6 alkoxycarbonyl), -C(O)- or C,. 6 alkyleneoxy.
  • A is C M alkylene -C(O)- or C,. 4 alkyleneoxy; or alternatively is C,_ 4 alkylene (optionally substituted by C 1-3 alkyl or by halogen). Even more preferably A is CH 2 CH(CH 3 ), CHF or CH 2 O.
  • A is CH 2 or is CH(CH 3 ) or is CHF.
  • N is the atom of attachment to the ring containing E and D and R 51 is hydrogen, C M alkyl, C alkoxy (C,. 4 )alkyl, benzyloxymethyl or benzoyloxymethyl.
  • Z is preferably O.
  • B is N.
  • E is CR 12 where R 12 is hydrogen, halogen, C,. 6 alkyl, C,_ 6 haloalkyl, C,_ 6 alkoxy, C,. 6 haloalkoxy, C,_ 6 alkoxy (C ⁇ alkyl, C,. 6 alkylthio or SF 5 ; or R 1 and R 12 together with the atoms to which they are attached form a benzene ring optionally substituted by C, .6 alkyl C w haloalkyl or halogen.
  • R 8 and R 9 are independently selected from hydrogen, halogen, cyano, nitro, C,. 6 alkyl, C x . 6 haloalkyl, C 2 . 6 alkenyl, C 2 . 6 haloalkenyl, C 2 . 6 alkynyl, C,. 6 alkoxy, C, .6 haloalkoxy.
  • R 8 and R 9 are independently selected from hydrogen, halogen, C,_ 6 alkyl, C ⁇ haloalkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, C,. 6 alkoxy or C,. 6 haloalkoxy.
  • R 8 and R 9 are independently selected from hydrogen or C 1-3 alkyl.
  • R 51 is hydrogen, C,. 6 alkyl, C,. 6 alkylcarbonyloxymethyl, C ⁇ alkoxymethyl, C 2.6 alkenyl(C, .6 )alkyl, C 2 . 6 alkynyl(C ] ⁇ )alkyl, benzyloxymethyl or benzoyloxymethyl. Yet more preferably R 51 is hydrogen, C,_ 6 alkyl, C 1-6 alkoxy (C 1 . 6 )alkyl, benzyloxymethyl or benzoyloxymethyl; or is C,. 6 alkylcarbonyloxymethyl.
  • R 51 is hydrogen, C M alkyl, C,. 6 alkylcarbonyloxymethyl or C,_ 4 alkoxymethyl.
  • R 1 is hydrogen, halogen, C L6 alkyl, C 2 . 6 alkenyl, C,. 6 haloalkyl, C, .6 alkoxy, C, .6 haloalkoxy, C,. 6 alkylthio, C,. 6 haioalkylthio, C 3 . 6 cycloalkyl, cyano, nitro or SF 5 .
  • R 1 is hydrogen, halogen, C,. 6 alkyl, C 2 . 6 alkenyl, C, ⁇ haloalkyl, C, ⁇ alkoxy, C L6 haloalkoxy, C,. 6 alkylthio, C]. 6 haioalkylthio, C 3 . 6 cycloalkyl, alkoxy(C,. 6 )alkyl, cyano or nitro.
  • R 1 is halogen, C ⁇ alkyl, C,. 6 haloalkyl, C, ⁇ alkoxy or C ⁇ haloalkoxy.
  • R 3 , R 4 and R 5 are independently hydrogen, C,. 3 alkyl or halogen.
  • R 3 , R 4 and R 5 are independently, hydrogen, or halogen (especially fluorine) but most preferably each is hydrogen.
  • R 6 is alkyl, C,. g haloalkyl, C,. 8 cyanoalkyl, C 3 . 7 cycloalkyl(C,. 6 )alkyl, C 5.6 cycloalkeny ⁇ C j . ⁇ alkyl, C,. 6 alkoxy(C,. 6 )alkyl, C 3 . 6 alkenyloxy(C w )alkyl, C 3 . 6 alkynyloxy(C ⁇ )alkyl, aryloxy(C 1 . 6 )alkyl, C,. 6 carboxyalkyl, C]_ 6 alkylcarbony ⁇ C ⁇ alkyl, C 2.6 alkenylcarbonyl(C,.
  • heteroaryl which may be optionally substituted by halo, nitro, cyano, C,_ 6 alkyl, C w haloalkyl, Cj. 6 alkoxy or C,. 6 haloalkoxy
  • heterocyclyl which may be optionally substituted by halo, nitro, cyano, C, ⁇ alkyl, C, .6 haloalkyl, C 6 alkoxy or C, ⁇ haloalkoxy
  • C,. g alkylthio, R 26 O, R 28 R 29 N or R 31 ON C(R 27 ); where R 26 is .g alkyl or C,.
  • R 27 is phenyl (which may be optionally substituted by halo, nitro, cyano, C 6 alkyl, C,_ 6 haloalkyl, Cj. 6 alkoxy or C ⁇ haloalkoxy), C, .6 alkyl or C, .6 haloalkyl;
  • R 28 and R 29 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 .
  • R 31 is phenyl(C 1-2 )alkyl (wherein the phenyl group may be optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,_ 6 haloalkyl, C x _ 6 alkoxy or C w haloalkoxy) or C 1-6 alkyl.
  • R 6 is C,. g alkyl, C,. 8 haloalkyl, C x . s cyanoalkyl, C 3 . 7 cycloalkyl, C,_ 3 alkyl (C 3.7 ) cycloalkyl, C,. 6 alkoxy (C,. 6 ) alkyl, heterocyclic (optionally substituted by halo, nitro, cyano, C, .6 alkyl, C,. 6 haloalkyl, C,. 6 alkoxy or C,. 6 haloalkoxy) or R 28 R 2 N where R 28 andR 29 are independently C,.
  • R 6 is C,. 8 alkyl, C,_ 8 haloalkyl, C ] _ 8 cyanoalkyl, C ].6 alkoxy (C j.6 ) alkyl, C 3.7 cycloalkyl, C ⁇ alkyl (C 3 .
  • R 6 is C 1-g alkyl or C,. g haloalkyl.
  • R 12 is hydrogen, halogen, C,. 6 alkyl, C,. 6 haloalkyl, C, ⁇ alkoxy (C, .6 )alkyl, C 2 . 6 alkenyl, C,_ 6 alkynyl, C 6 alkoxy, C x . 6 haloalkoxy, C,. 6 alkylthio, C,. 6 haioalkylthio, C, .6 alkylsulfinyl, C,. 6 haloalkylsulfinyl, C,.
  • R 1 and R 12 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated, carbocylic or heterocyclic ring which may contain one or two heteroatoms selected from O, N or S and which may be optionally substituted by C, .6 alkyl, C j.6 haloalkyl or halogen; and R 32 is phenyl(C 1 .
  • R 12 is hydrogen, halogen, C ⁇ alkyl, C ⁇ haloalkyl, C, .6 alkoxy (C,. 6 )alkyl, C,. 6 alkoxy, C,. 6 haloalkoxy, C ⁇ alkylthio, or R 1 and R 12 together with the atoms to which they are attached form a cyclopentane or benzene ring optionally substituted by C, .6 alkyl, C,_ 6 haloalkyl or halogen.
  • R 12 is hydrogen, halogen, C,_ 6 alkyl, C,. 6 haloalkyl, C,. 6 alkoxy(C, .6 )alkyl, C,.
  • R 18 is hydrogen, halogen, nitro, cyano, C,. g alkyl or C w haloalkyl. More preferably R 18 is hydrogen, halogen, C,. 3 alkyl or C,. 3 haloalkyl.
  • Table 1 provides 80 compounds of formula:
  • Table 2 provides 80 compounds of formula:
  • Table 3 provides 80 compounds of formula:
  • Table 4 provides 80 compounds of formula:
  • Table 5 provides 80 compounds of formula:
  • Table 6 provides 80 compounds of formula:
  • Table 8 provides 80 compounds of formula:
  • Table 9 provides 80 compounds of formula:
  • Table 10 provides 80 compounds of formula:
  • Table 11 provides 80 compounds of formula:
  • Table 12 provides 80 compounds of formula:
  • Table 13 provides 80 compounds of formula:
  • Table 14 provides 80 compounds of formula:
  • Table 15 provides 80 compounds of formula:
  • Table 16 provides 80 compounds of formula:
  • Table 17 provides 80 compounds of formula:
  • Table 18 provides 80 compounds of formula:
  • Table 19 provides 80 compounds of formula:
  • Table 20 provides 80 compounds of formula:
  • Table 21 provides 80 compounds of formula: wherein D, E, Rl and R6 are as defined in Table 1.
  • Table 22 provides 80 compounds of formula:
  • Table 23 provides 80 compounds of formula:
  • Table 24 provides 80 compounds of formula:
  • Table 25 provides 80 compounds of formula:
  • Table 27 provides 80 compounds of formula:
  • Table 28 provides 80 compounds of formula:
  • Table 29 provides 80 compounds of formula:
  • Table 30 provides 80 compounds of formula: wherein D, E, Rl and R6 are as defined in Table 1.
  • Table 31 provides 80 compounds of formula:
  • Table 32 provides 80 compounds of formula:
  • Table 33 provides 80 compounds of formula:
  • Table 34 provides 80 compounds of formula:
  • Table 35 provides 80 compounds of formula:
  • Table 36 provides 80 compounds of formula:
  • Table 37 provides 80 compounds of formula:
  • Table 38 provides 80 compounds of formula:
  • Table 39 provides 80 compounds of formula:
  • Table 40 provides 80 compounds of formula:
  • Table 41 provides 80 compounds of formula:
  • Table 42 provides 80 compounds of formula:
  • Table 43 provides 80 compounds of formula: wherein D, E, Rl and R6 are as defined in Table 1.
  • Table 44 provides 80 compounds of formula:
  • Table 45 provides 80 compounds of formula:
  • Table 46 provides 80 compounds of formula: R1 i Hx J- wherein D, E, Rl and R6 are as defined in Table 1.
  • Table 47 provides 80 compounds of formula:
  • Table 48 provides 80 compounds of formula:
  • Table 49 provides 80 compounds of formula:
  • Table 50 provides 80 compounds of formula:
  • Table 51 provides 80 compounds of formula:
  • Table 52 provides 80 compounds of formula:
  • Table 53 provides 80 compounds of formula:
  • Table 54 provides 80 compounds of formula:
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  • Table 59 provides 80 compounds of formula:
  • Table 60 provides 80 compounds of formula:
  • Table 61 provides 80 compounds of formula:
  • Table 62 provides 80 compounds of formula:
  • Table 63 provides 80 compounds of formula:
  • Table 64 provides 80 compounds of formula:
  • Table 65 provides 80 compounds of formula:
  • Table 66 provides 80 compounds of formula:
  • Table 67 provides 80 compounds of formula:
  • Table 68 provides 80 compounds of formula:
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  • Table 70 provides 80 compounds of formula:
  • Table 71 provides 80 compounds of formula:
  • Table 72 provides 80 compounds of formula:
  • Table 73 provides 80 compounds of formula:
  • Table 74 provides 80 compounds of formula:
  • Table 75 provides 80 compounds of formula:
  • Table 76 provides 80 compounds of formula:
  • Table 77 provides 80 compounds of formula:
  • Table 78 provides 80 compounds of formula:
  • Table 79 provides 80 compounds of formula:
  • Table 80 provides 80 compounds of formula: wherein D, E, Rl and R6 are as defined in Table 1.
  • Table 81 provides 80 compounds of formula:
  • Table 82 provides 80 compounds of formula:
  • Table 83 provides 80 compounds of formula:
  • Table 84 provides 80 compounds of formula:
  • Table 85 provides 80 compounds of formula:
  • Table 86 provides 80 compounds of formula:
  • Table 87 provides 80 compounds of formula:
  • Table 88 provides 80 compounds of formula:
  • Table 89 provides 80 compounds of formula:
  • Table 90 provides 80 compounds of formula:
  • Table 91 provides 80 compounds of formula:
  • Table 92 provides 80 compounds of formula:
  • Table 93 provides 80 compounds of formula:
  • Table 94 provides 80 compounds of formula:
  • Table 95 provides 80 compounds of formula:
  • Table 96 provides 80 compounds of formula:
  • Table 97 provides 80 compounds of formula:
  • Table 99 provides 80 compounds of formula:
  • Table 100 provides 80 compounds of formula:
  • Table 101 provides 80 compounds of formula:
  • Table 102 provides 80 compounds of formula:
  • Table 103 provides 80 compounds of formula:
  • Table 104 provides 80 compounds of formula:
  • Table 105 provides 80 compounds of formula:
  • Table 106 provides 80 compounds of formula:
  • Table 107 provides 80 compounds of formula: wherein D, E, Rl and R6 are as defined in Table 1.
  • Table 108 provides 80 compounds of formula:
  • Table 109 provides 80 compounds of formula:
  • Table 110 provides 80 compounds of formula:
  • Table 111 provides 80 compounds of formula:
  • Table 112 provides 80 compounds of formula:
  • Table 113 provides 80 compounds of formula:
  • Table 114 provides 80 compounds of formula:
  • Table 115 provides 80 compounds of formula:
  • Table 116 provides 80 compounds of formula: wherein D, E, Rl and R6 are as defined in Table 1.
  • Table 117 provides 80 compounds of formula:
  • Table 118 provides 80 compounds of formula:
  • Table 119 provides 80 compounds of formula:
  • Table 120 provides 80 compounds of formula:
  • Table 121 provides 80 compounds of formula:
  • Table 122 provides 80 compounds of formula:
  • Table 123 provides 80 compounds of formula:
  • Table 124 provides 80 compounds of formula:
  • Table 125 provides 80 compounds of formula: wherein D, E, Rl and R6 are as defined in Table 1.
  • Table 126 provides 80 compounds of formula:
  • Table 127 provides 80 compounds of formula:
  • Table 128 provides 80 compounds of formula:
  • Table 129 provides 80 compounds of formula:
  • Table 130 provides 80 compounds of formula:
  • Table 131 provides 80 compounds of formula:
  • Table 132 provides 80 compounds of formula:
  • Table 133 provides 80 compounds of formula:
  • Table 134 provides 80 compounds of formula:
  • Table 135 provides 80 compounds of formula:
  • Table 136 provides 80 compounds of formula:
  • Table 137 provides 80 compounds of formula:
  • Table 138 provides 80 compounds of formula:
  • Table 139 provides 80 compounds of formula:
  • Table 140 provides 80 compounds of formula:
  • Table 141 provides 80 compounds of formula:
  • Table 142 provides 80 compounds of formula:
  • Table 143 provides 80 compounds of formula:
  • Table 144 provides 80 compounds of formula:
  • Table 145 provides 80 compounds of formula:
  • Table 146 provides 80 compounds of formula:
  • Table 147 provides 80 compounds of formula:
  • Table 148 provides 80 compounds of formula:
  • Table 149 provides 80 compounds of formula:
  • Table 150 provides 80 compounds of formula:
  • Table 151 provides 80 compounds of formula:
  • Table 153 provides 80 compounds of formula:
  • Table 154 provides 80 compounds of formula:
  • Table 155 provides 80 compounds of formula:
  • Table 156 provides 80 compounds of formula:
  • the compounds of the invention may be made in a variety of ways.
  • a base such as triethylamine
  • Compounds of formula III are known compounds or may be made from known compounds by known methods.
  • Suitable thiophenols are known compounds or may be prepared by known methods.
  • Benzofurans may be made from ortho-halophenols as described by Henning Lutjens and Peter J Scammells, Tetrahedron Letters 39 (1998), 6581-6584, Terence C Owen et al., Tetrahedron Letters 30, No 13, 1597 (1989) and Fred G Schreiber and Robert Stevenson J.C.S. Perkin 1, 90, 1977.
  • Indoles may be made from ortho-haloanilines according to the methods of Cheng-yi Chen et al., J. Org. Chem. 1997, 62, 2676, Takao Sakamoto et al., J. Org. Chem.
  • a compound of formula V (where B, D, E, Z, R 1 R 3 , R 4 , R 5 , R 6 and R 51 are as defined above in relation to formula I) may be prepared by reacting a compound of formula II (where B, D, E, Z, R 1 R 3 , R 4 , R 5 , R 6 and R 51 are as defined above in relation to formula I) with a suitable thionating agent such as 2,4-bis(4-methoxyphenyl)-l,3-dithia-2,4-diphosphetane- 2,4-disulfide (Lawesson's reagent), 2,4-bis(methylthio)-l,3-dithia-2,4-diphosphetane-2,4- disulfide (Davy reagent methyl), 2,4-bis(para-tolyl)-l ,3-dithia-2,4-diphosphetane-2,4- disulfide (Davy reagent p
  • Compounds of formula VI may be made from compounds of formula VII (where B, D, E, Z, R 1 R 3 , R 4 , R 5 , R 6 and R 51 are as defined above in relation to formula I) by treatment with N,N-dimethylformamide dialkyl acetal in a suitable solvent such as toluene or N,N-dimethylformamide. Frequently this reaction produces a mixture of E and Z isomers which are sometimes separable by standard techniques such as flash column chromatography and recrystallisation.
  • Compounds II or V may be treated with an electrophile (such as an alkyl halide, dialkyl sulfate, chloromethylether, trialkyloxonium salt or alkyl chloroformate) optionally in the presence of a base.
  • an electrophile such as an alkyl halide, dialkyl sulfate, chloromethylether, trialkyloxonium salt or alkyl chloroformate
  • Compounds VIII (where B, D, E, Z, R 1 R 3 , R 4 , R 5 , R 6 and R 53 are as defined above in relation to formula I) may be reacted with alcohols, hydroxylamines, amines and hydrazines, optionally in the presence of a mercuric salt (such as mercuric chloride), according to known procedures to give compounds IX (where B, D, E, Z, R 1 R 3 , R 4 , R 5 , R 6 and R 52 are as defined above in relation to formula I) and X (where B, D, E, Z, R 1 R ⁇ R 4 , R 5 , R 6 , R 54 and R 55 are as defined above in relation to formula I) respectively.
  • a mercuric salt such as mercuric chloride
  • An alternative method for making compounds II involves the acylation of a compound of formula XI (where A, D, E, R 1 , R 3 , R 4 , R 5 and R 51 are as defined above in relation to formula I) followed by cyclisation, optionally in the presence of an acidic catalyst such as para-toluene sulfonic acid in a suitable solvent such as xylene or 1 ,1 ,2,2- tetrachloroethane .
  • Compounds XI (where A, D, E, R 1 , R 3 , R 4 , R 5 and R 51 are as defined above in relation to formula I) may be prepared from compounds XII (where A, D, E, R 1 , R 3 , R 4 , R 5 and R 51 are as defined above in relation to formula I) by a sequential procedure of nitration followed by reduction, using known procedures.
  • compounds XII may be prepared by the dealkylation of compounds XIII (where A, D, E, R 1 , R 3 , R 4 , R 5 and R 51 are as defined above in relation to formula I) where R is an alkyl group (especially methyl) or substituted alkyl group (especially benzyl) under standard conditions.
  • Compounds XIII (where A, D, E, R 1 , R 3 , R 4 , R 5 and R 51 are as defined above in relation to formula I) may be prepared from compounds III (where D, E, R 1 , and R 51 are as defined above in relation to formula I) by processes analogous to those already described for compounds II. Heteroaryl N-oxides can be prepared using known methods.
  • the compounds of formula (I) can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. 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 sulphureus
  • 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).
  • all compositions both solid and liquid formulations
  • the composition is generally used for the control of pests or fungi such that a compound of formula (I) is applied at a rate of from O.lg tolOkg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 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 (I).
  • Dustable powders may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
  • solid diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers
  • Soluble powders may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • water-soluble organic solids such as a polysaccharide
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary.
  • a hard core material such as sands, silicates, mineral carbonates, sulphates or phosphates
  • Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils.
  • One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • DC Dispersible Concentrates
  • a compound of formula (I) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether.
  • organic solvent such as a ketone, alcohol or glycol ether.
  • surface active agent for example to improve water dilution or prevent crystallisation in a spray tank.
  • Emulsifiable concentrates or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents).
  • Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C 8 -C 10 fatty acid dimethylamide) and chlorinated hydrocarbons.
  • aromatic hydrocarbons such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark
  • ketones such as cycl
  • An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.
  • Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion.
  • Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of formula (I) is present initially in either the water or the solvent/SFA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs.
  • An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation.
  • An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
  • SC Suspension concentrates
  • SCs may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I).
  • SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound.
  • One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle.
  • a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
  • Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example n-butane).
  • a compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
  • a suitable medium for example water or a water miscible liquid, such as n-propanol
  • a compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
  • Capsule suspensions may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor.
  • the polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure.
  • the compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment.
  • a compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
  • a composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)).
  • additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).
  • a compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS).
  • DS powder for dry seed treatment
  • SS water soluble powder
  • WS water dispersible powder for slurry treatment
  • CS capsule suspension
  • compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
  • Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di- isopropyl- and tri-isopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3 -carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric
  • Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.
  • Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
  • Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carb
  • a compound of formula (I) may be applied by any of the known means of applying pesticidal or fungicidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.
  • a locus of the pests such as a habitat of the pests, or a growing plant liable to infestation by the pest
  • a compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
  • Compositions for use as aqueous preparations are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use.
  • These concentrates which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
  • a compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers).
  • fertilisers for example nitrogen-, potassium- or phosphorus-containing fertilisers.
  • Suitable formulation types include granules of fertiliser.
  • the mixtures suitably contain up to 25% by weight of the compound of formula (I).
  • the invention therefore also provides a fertiliser composition
  • 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.
  • the resulting composition may have a broader spectrum of activity or a greater level of intrinsic activity than the compound of formula (I) alone. Further the other fungicide may have a synergistic effect on the fungicidal activity of the compound of formula (I).
  • the compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide. fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components.
  • the particular additional active ingredient will depend upon the intended utility of the composition.
  • Suitable pesticides include the following: a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate; b) Organophosphates, such as, profenofos, sulprofos, acephat
  • fenobucarb propoxur, methomyl or oxamyl
  • Benzoyl ureas such as diflubenzuron, triflumuron, hexaflumuron, flufenoxuron or chlorfluazuron
  • Organic tin compounds such as cyhexatin, fenbutatin oxide or azocyclotin
  • f) Pyrazoles such as tebufenpyrad and fenpyroximate
  • Macrolides such as avermectins or milbemycins, for example abamectin, emamectin benzoate, ivermectin, milbemycin, spinosad or azadirachtin
  • Hormones or pheromones i) Organochlorine compounds such as endosulfan, benzene hexachloride, DDT, chlordane or dieldrin
  • pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the composition.
  • selective insecticides for particular crops for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed.
  • insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).
  • acaricidal ovo-larvicides such as clofentezine, flubenzimine, hexythiazox or tetradifon
  • acaricidal motilicides such as dicofol or propargite
  • acaricides such as bromopropylate or chlorobenzilate
  • growth regulators such
  • fungicidal compounds which may be included in the composition of the invention are (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy- iminoacetamide (SSF- 129), 4-bromo-2-cyano-N,N-dimethyl-6-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
  • SE suspoemulsion
  • This Example illustrates the pesticidal/insecticidal properties of compounds of formula (I).
  • the activities of individual compounds of formula (I) were determined using a variety of pests.
  • the pests were treated with a liquid composition containing 500 parts per million (ppm) by weight of a compound.
  • Each composition was made by dissolving the compound in an acetone and ethanol (50:50 by volume) mixture and diluting the solution with water containing 0.05% by volume of a wetting agent, SYNPERONIC NP8, until the liquid composition contained the required concentration of the compound.
  • test procedure adopted with regard to each pest was essentially the same and comprised supporting a number of the pests on a medium which was usually a substrate, a host plant or a foodstuff on which the pests feed, and treating either or both the medium and the pests with a composition. Pest mortality was assessed usually between two and five days after treatment.
  • results of the tests against peach aphid are presented below.
  • Chinese cabbage leaves were infested with aphids, the infested leaves were sprayed with the test composition, and the mortality assessed after three days.
  • the results indicate a grading of mortality (score) designated as 9, 5 or 0 wherein 9 indicates 80-100% mortality, 5 indicates 40-79% mortality and 0 indicates less than 40% mortality.

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

Abstract

L'invention concerne un composé représenté par la formule (I) dans laquelle B représente N ou CR18; D représente CR8=CR9; E représente CR12; M représente N(R51)C(=Y), où N représente l'atome de fixation à l'anneau contenant E et D; Y représente O ou S; Z représente O et lorsque B représente CR18 Z peut également représenter S; et A et les divers groupes R sont des radicaux organiques définis. L'invention concerne également la préparation et l'utilisation de tels composés, ainsi que des compositions les contenant.
PCT/GB2001/000310 2000-01-28 2001-01-26 Derives d'azine utilises comme pesticides WO2001055135A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001230340A AU2001230340A1 (en) 2000-01-28 2001-01-26 Azine derivatives as pesticides

Applications Claiming Priority (2)

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GB0002029.7 2000-01-28
GB0002029A GB0002029D0 (en) 2000-01-28 2000-01-28 Chemical compounds

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PCT/GB2001/000310 WO2001055135A1 (fr) 2000-01-28 2001-01-26 Derives d'azine utilises comme pesticides

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008524157A (ja) * 2004-12-15 2008-07-10 ドムペ・ファ．ル．マ・ソチエタ・ペル・アツィオーニ ２−アリールプロピオン酸誘導体及びそれを含有する医薬組成物

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7781478B2 (en) 2004-07-14 2010-08-24 Ptc Therapeutics, Inc. Methods for treating hepatitis C

Citations (10)

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Publication number Priority date Publication date Assignee Title
WO1993004580A1 (fr) * 1991-09-03 1993-03-18 Dowelanco Pesticides a base d'arylacetamides n-(4-pyridyle ou 4-quinoleinyle)
EP0623282A1 (fr) * 1993-05-05 1994-11-09 Shell Internationale Researchmaatschappij B.V. Procédés et composés pesticides
EP0640597A1 (fr) * 1993-08-24 1995-03-01 BASF Aktiengesellschaft Isoxazoles et/ou isothiazoles, substitués par un groupe acylamino, leur preparation et utilisation
WO1995031448A1 (fr) * 1994-05-17 1995-11-23 Dowelanco Pesticides de n-(5-isothiazolyle)amide
WO1996008475A1 (fr) * 1994-09-13 1996-03-21 Novartis Ag Derives pesticides de la pyridine
DE19542372A1 (de) * 1995-11-14 1997-05-15 Bayer Ag Acylierte 5-Aminoisothiazole
WO1998002424A1 (fr) * 1996-07-16 1998-01-22 Bayer Aktiengesellschaft N-(5-isothiazolyl)-thioamides substitues
WO1998005670A1 (fr) * 1996-07-31 1998-02-12 Bayer Aktiengesellschaft N-isothiazolyl-(thio)amides substitues
WO1998017630A1 (fr) * 1996-10-17 1998-04-30 Bayer Aktiengesellschaft Derives d'amide et leur utilisation comme parasiticides
WO2000006566A1 (fr) * 1998-07-30 2000-02-10 Syngenta Limited Derives de benzoxazole, benzthiazole et benzimidazole

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993004580A1 (fr) * 1991-09-03 1993-03-18 Dowelanco Pesticides a base d'arylacetamides n-(4-pyridyle ou 4-quinoleinyle)
EP0623282A1 (fr) * 1993-05-05 1994-11-09 Shell Internationale Researchmaatschappij B.V. Procédés et composés pesticides
EP0640597A1 (fr) * 1993-08-24 1995-03-01 BASF Aktiengesellschaft Isoxazoles et/ou isothiazoles, substitués par un groupe acylamino, leur preparation et utilisation
WO1995031448A1 (fr) * 1994-05-17 1995-11-23 Dowelanco Pesticides de n-(5-isothiazolyle)amide
WO1996008475A1 (fr) * 1994-09-13 1996-03-21 Novartis Ag Derives pesticides de la pyridine
DE19542372A1 (de) * 1995-11-14 1997-05-15 Bayer Ag Acylierte 5-Aminoisothiazole
WO1997018198A1 (fr) * 1995-11-14 1997-05-22 Bayer Aktiengesellschaft 5-aminoisothiazoles acyles avec effet insecticide, produits intermediaires et procede de production correspondant
WO1998002424A1 (fr) * 1996-07-16 1998-01-22 Bayer Aktiengesellschaft N-(5-isothiazolyl)-thioamides substitues
WO1998005670A1 (fr) * 1996-07-31 1998-02-12 Bayer Aktiengesellschaft N-isothiazolyl-(thio)amides substitues
WO1998017630A1 (fr) * 1996-10-17 1998-04-30 Bayer Aktiengesellschaft Derives d'amide et leur utilisation comme parasiticides
WO2000006566A1 (fr) * 1998-07-30 2000-02-10 Syngenta Limited Derives de benzoxazole, benzthiazole et benzimidazole

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008524157A (ja) * 2004-12-15 2008-07-10 ドムペ・ファ．ル．マ・ソチエタ・ペル・アツィオーニ ２−アリールプロピオン酸誘導体及びそれを含有する医薬組成物

Also Published As

Publication number Publication date
WO2001055137A1 (fr) 2001-08-02
AU2001230340A1 (en) 2001-08-07
GB0002029D0 (en) 2000-03-22
AU2867101A (en) 2001-08-07

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