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WO2001055140A1 - Isothiazole derivatives and their use as pesticides - Google Patents

Isothiazole derivatives and their use as pesticides Download PDF

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Publication number
WO2001055140A1
WO2001055140A1 PCT/GB2001/000308 GB0100308W WO0155140A1 WO 2001055140 A1 WO2001055140 A1 WO 2001055140A1 GB 0100308 W GB0100308 W GB 0100308W WO 0155140 A1 WO0155140 A1 WO 0155140A1
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Prior art keywords
optionally substituted
alkyl
alkoxy
formula
haloalkyl
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PCT/GB2001/000308
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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 AU2001230338A priority Critical patent/AU2001230338A1/en
Publication of WO2001055140A1 publication Critical patent/WO2001055140A1/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

Definitions

  • the present invention relates to azine and 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
  • Azole and azine derivatives are disclosed in WO95/31448, WO97/18198, WO98/02424, WO98/05670 and WO98/17630.
  • the present invention provides a compound of formula (I):
  • n 0 or 1 ;
  • A is optionally substituted C ⁇ - alkylene, optionally substituted C 2-6 alkenylene, optionally substituted C 2 _ alkynylene, optionally substituted cycloalkylene, optionally substituted C ⁇ - 6 alkylenoxy, optionally substituted oxy(C ⁇ -6 )alkylene, optionally substituted C ⁇ _ 6 alkylenethio, optionally substituted thio( ⁇ alkylene, optionally substituted C ⁇ _ alkyl enamino, optionally substituted amino(C ⁇ _ 6 )alkylene, optionally substituted [C ⁇ -6 alkyleneoxy(C ⁇ _ 6 )alkylene], optionally substituted [ .6 alkylenethio(C ⁇ .
  • E is N, N-oxide or CR 2 ;
  • G, J, L and Q are, independently, N, N-oxide or CR 6 provided that neither are all N nor are all CR 6 ; where more than one of G, J, L and Q is CR 6 , R can be the same or different;
  • Y is O, S or NR 13 ;
  • R 1 is hydrogen, halogen, optionally substituted C 1-6 alkyl, optionally substituted C 2-6 alkenyl, optionally substituted C 2-6 alkynyl, optionally substituted C 1-6 alkoxy, optionally substituted d_ 6 alkylthio, optionally substituted C 3-7 cycloalkyl, cyano, nitro or SF 5 ;
  • R 2 is hydrogen, halogen, optionally substituted - 6 alkyl, optionally substituted C . 6 alkenyl, optionally substituted C 2-6 alkynyl, optionally substituted C ⁇ -6 alkoxy, optionally substituted C !
  • R 3 , R 4 and R 5 are, independently, hydrogen, halogen, optionally substituted C 1- alkyl, optionally substituted Ci- 6 alkoxy, optionally substituted C 1-6 alkylthio, optionally substituted Ci- 6 alkylsulfinyl, optionally substituted C ⁇ -6 alkylsulfonyl, cyano, nitro, optionally substituted C ⁇ -6 alkylcarbonyl, optionally substituted C ⁇ _6 alkoxycarbonyl or SF 5 ;
  • R 6 is hydrogen, halogen, cyano, optionally substituted C 1-20 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 1-2 o alkoxycarbonyl, optionally substituted C ⁇ _ 20 alkylcarbonyl, aminocarbonyl, optionally
  • R 9 is optionally substituted C MO alkyl, optionally substituted [C 2-6 alkenyl(C]_ 6 )alkyl], optionally substituted [C 2-6 alkynyl(C 1-6 )alkyl], optionally substituted C 3-7 cycloalkyl, optionally substituted C MO alkylcarbonyl, optionally substituted C ⁇ -10 alkoxycarbonyl, optionally substituted C MO alkylaminocarbonyl, optionally substituted di(C ⁇ _ ⁇ o)alkylamino- carbonyl or optionally substituted phenoxycarbonyl);
  • R 10 and R 11 are, independently, optionally substituted C 1-10 alkyl, optionally substituted C 1-6 alkoxy, optionally substituted [C 2-6 alkenyl(C 1 . 6 )alkyl], optionally substituted [C . 6 alkynyl(C 1-6 )alkyl], optionally substituted C 3-7 cycloalkyl, optionally substituted C O alkylcarbonyl, optionally substituted C MO alkoxycarbonyl, formyl, optionally substituted C MO alkylaminocarbonyl, optionally substituted di(C ⁇ -10 )alkylaminocarbonyl, hydroxy, amino, optionally substituted C 1- alkylamino, optionally substituted di(C 1 _ 6 )alkylamino, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylamino, optionally substituted C MO alkylcarbonyloxy, optionally substituted C O alkoxycarbonyloxy, optionally substituted
  • R 17 and R 22 are independently hydrogen, optionally substituted phenyl or optionally substituted Q. 6 alkyl;
  • R 19 and R 20 are, independently, hydrogen, optionally substituted Q_ 20 alkyl, optionally substituted C 3-7 cycloalkyl, optionally substituted [C -2 o alkenyl(C ⁇ _ 6 )alkyl], optionally substituted [C 2- o alkynyl(Q_. 6 )alkyl], optionally substituted Q -2 o alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted Q.
  • One group of preferred compounds of formula (I) is that group where n is 0 or 1 ;
  • A is optionally substituted Q_ 6 alkylene, optionally substituted C 2 _ 6 alkenylene, optionally substituted Q_ 6 alkynylene, optionally substituted Q_6 alkylenoxy, optionally substituted oxy(Q- 6 )alkylene, optionally substituted Q_6 alkylenethio, optionally substituted thio(C ⁇ .
  • E is N, N-oxide or CR 2 ;
  • R 1 is hydrogen, halogen, optionally substituted Q_6 alkyl, optionally substituted C 2 _ 6 alkenyl, optionally substituted C 2-6 alkynyl, optionally substituted Q. 6 alkoxy, optionally substituted Q -6 alkylthio, optionally substituted C 3 . 7 cycloalkyl, cyano, nitro or SF 5 ;
  • R and R together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated 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 Q_ 6 alkyl, Q_ 6 haloalkyl or halogen;
  • R 3 , R 4 and R 5 are, independently, hydrogen, halogen, optionally substituted . 6 alkyl, optionally substituted Q.6 alkoxy, optionally substituted Q_6 alkylthio, optionally substituted Q.
  • alkylsulfinyl optionally substituted Q_ 6 alkylsulfonyl, cyano, nitro, optionally substituted Q- 6 alkylcarbonyl, optionally substituted Q-6 alkoxycarbonyl or SF 5 ;
  • R 6 is hydrogen, halogen, cyano, optionally substituted Q -2 o alkyl, optionally substituted C 2 .
  • 20 alkenyl, optionally substituted Q- 2 o alkynyl, optionally substituted C 3 .
  • alkylaminocarbonyl optionally substituted di(Q_ o)alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-alkyl-N-arylaminocarbonyl, optionally substituted diarylaminocarbonyl, optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted alkylheteroarylaminocarbonyl, optionally substituted diheteroarylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, R 18 O, HS, optionally substituted C 1-2 o alkylthio, optionally substituted C].
  • R 21 ON C(R 22 ); where any two adjacent groups of G, J, L and Q are CR 6 , the two adjacent R 6 groups together with the carbon atoms to which they are attached may together form a five-, six- or seven-membered saturated or unsaturated ring, which may contain one or two hetero atoms selected from O, N or S and which may be optionally substituted by Q. 6 alkyl, Q_ 6 alkoxy, Q_ 6 haloalkyl or halogen; R 7 is Q. 6 alkyl;
  • R 8 is optionally substituted C MO alkyl, optionally substituted [C 2 _ 6 alkenyl(Q- 6 )alkyl], optionally substituted [C 2 _ 6 alkynyl(C ⁇ - 6 )alkyl], optionally substituted C 3 - 7 cycloalkyl, optionally substituted C MO alkylcarbonyl, optionally substituted Q_ ⁇ 0 alkoxycarbonyl, formyl, optionally substituted Q_ ⁇ o alkylaminocarbonyl, optionally substituted di(Q_ 10 )- alkylaminocarbonyl, , amino, optionally substituted Q-6 alkylamino, optionally substituted di(Q- 6 )alkylamino, optionally substituted phenoxycarbonyl, tri(Q. )alkylsilyl, aryldi(Q_ 4 )- alkylsilyl, (C ⁇ -4 )alkyldiarylsilyl or triarylsilyl;
  • R 9 is optionally substituted Q.io alkyl, optionally substituted [Q_ 6 alkenyl(Q. 6 )alkyl], optionally substituted [C 2 . 6 alkynyl(Q_ 6 )alkyl], optionally substituted C 3 . 7 cycloalkyl, optionally substituted C MO alkylcarbonyl, optionally substituted C MO alkoxycarbonyl, optionally substituted Q.io alkylaminocarbonyl, optionally substituted di(Q_ 1 o)-alkylaminocarbonyl or optionally substituted phenoxycarbonyl);
  • R 10 and R 11 are, independently optionally substituted C O alkyl, optionally substituted Q -6 alkoxy, optionally substituted [C _6 alkenyl(Q_ 6 )alkyl], optionally substituted [C 2-6 alkynyl(Q- 6 )alkyl], optionally substituted C 3 .
  • R 12 is hydrogen, optionally substituted C MO alkyl, optionally substituted [C 2 . 6 alkenyl(Q- 6 )alkyl], optionally substituted [C 2-6 alkynyl(Ci -6 )alkyl], optionally substituted - o -
  • cycloalkyl optionally substituted Q_ 10 alkylcarbonyl, optionally substituted C MO alkoxycarbonyl, formyl, optionally substituted C MO alkylaminocarbonyl, optionally substituted di(Q_ ⁇ o)alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted Q- 6 alkylthio, optionally substituted Q_6 alkylsulfinyl, optionally substituted Q_ 6 alkylsulfonyl, optionally substituted Q. 6 arylthio, optionally substituted Q_ 6 arylsulfinyl, optionally substituted Q -6 arylsulfonyl or R 36 R 37 NS;
  • R 13 is hydrogen, cyano, nitro, optionally substituted Q. 6 alkyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted (C 2 . 6 )alkenyl(Q. 6 )alkyl, optionally substituted (C 2 . 6 )alkynyl(Q- 6 )alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted Q. 6 alkylcarbonyl, optionally substituted Q_ 6 alkoxycarbonyl, optionally substituted Q.6 alkylamino, optionally substituted di(Q_ 6 )alkylamino, optionally substituted Q_ 6 alkylcarbonylamino, optionally substituted Q.
  • R 14 and R 15 are, independently, hydrogen, halogen, cyano, nitro, optionally substituted Q- 6 alkyl, optionally substituted C 2 _6 alkenyl, optionally substituted C 2 _ 6 alkynyl or optionally substituted Q_ alkoxy;
  • R 16 and R 21 are, independently, hydrogen, optionally substituted phenyl (Q. 2 )alkyl or optionally substituted Q_ 20 alkyl;
  • R 17 and R 22 are independently hydrogen, optionally substituted phenyl or optionally substituted Q- 6 alkyl;
  • R , 18 is hydrogen, optionally substituted Q. 2 o alkyl, optionally substituted [C . 2 o alkenyl (C
  • R 19 and R 20 are, independently, hydrogen, optionally substituted Q. o alkyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted [C 2 . o alkenyl(C ⁇ _ 6 )alkyl], optionally substituted [C 2 .
  • 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 23 is Q. 6 alkyl, Q. 6 haloalkyl, OR 26 or NR 27 R 28 ; where R 24 and R 25 are, independently, hydrogen, Q. 6 alkyl, Q. alkoxy, Q. 6 haloalkyl, cyano, Q.6 alkoxycarbonyl, Q -6 alkylcarbonyl or NR 2 R 30 ; R 26 is Q. 6 alkyl, Q_ 6 haloalkyl or phenyl(Q -2 )alkyl; R 27 and R 28 are, independently, hydrogen, Q_ 8 alkyl, C 3 . 7 cycloalkyl, C 2 .
  • R 29 and R 30 are, independently, hydrogen, Q_ g alkyl, C 3 . 7 cycloalkyl, C 2 . alkenyl(Q_ 6 )alkyl, C 2 _ 6 alkynyl (Q- 6 )alkyl, _ 6 haloalkyl, Q. 6 alkoxy(C ⁇ . 6 )alkyl, Q_ 6 alkoxycarbonyl(Q_ 6 )alkyl, carboxy(C ⁇ .
  • R 29 and R 30 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 Q.6 alkyl groups.
  • Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, «-hexyl, s ⁇ -propyl, n-butyl, sec-butyl, wo-butyl, tert-butyl or neo-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 Q_ 6 alkyl or halogen), C 5 . 7 cycloalkenyl (itself optionally substituted with Q.
  • Alkenyl and alkynyl moieties can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)- or (Z)-configuration. Examples are vinyl, allyl and propargyl.
  • the optional substituents on alkenyl or alkynyl include those optional substituents given above for an alkyl moiety.
  • acyl is optionally substituted Q -6 alkylcarbonyl (for example acetyl), optionally substituted Q- 6 alkenylcarbonyl, optionally substituted C 2 . 6 alkynylcarbonyl, optionally substituted arylcarbonyl (for example benzoyl) or optionally substituted heteroarylcarbonyl.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF 3 , CF 2 C1, CF 3 CH 2 or CHF 2 CH .
  • 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 Q_ 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 Q. 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-, Q.6 alkyl, Q. 6 haloalkyl, Q- 6 alkoxy(Q. 6 )alkyl, - 6 alkenyl, C 2 _ 6 haloalkenyl, .6 alkynyl, C 3 . 7 cycloalkyl (itself optionally substituted with Q_ 6 alkyl or halogen), C 5 .
  • substituents are independently selected from halogen, Q- 6 alkyl, Q_ 6 haloalkyl, Q. 6 alkoxy(Q_ 6 )alkyl, Q- 6 alkoxy, Q_6 haloalkoxy, Q_ 6 alkylthio, Q_ 6 haloalkylthio, Q- 6 alkylsulfinyl, Q.
  • 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
  • (Q. 6 )alkyl groups When heterocyclic rings are formed by joining two groups on an N atom, the resulting rings are suitably pyrrolidine, piperidine, thiomorpholine and morpholine each of which may be substituted by one or two independently selected (Q. 6 ) alkyl groups.
  • the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, HO 2 C, C MO alkoxy (itself optionally substituted by C O alkoxy), aryl(Q_ )alkoxy, C M O alkylthio, Q_ ⁇ 0 alkylcarbonyl, C MO alkoxycarbonyl, Q -6 alkylaminocarbonyl, di(Q_ 6 alkylaminocarbonyl, (Q. 6 )alkylcarbonyloxy, optionally substituted phenyl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl, heterocyclyloxy, C 3 .
  • heterocyclyl is optionally substituted by Q. 6 alkyl.
  • the optional substituents for cycloalkyl include halogen, cyano and Q. 3 alkyl.
  • the optional substituents for cycloalkenyl include Q. 3 alkyl, halogen and cyano.
  • the present invention provides a compound of formula (LA):
  • A is Q- alkylene (optionally substituted by halogen C ⁇ _ 3 alkyl, Q_ 3 alkoxy, hydroxy or halogen), -C(O)- or C ⁇ - 4 alkyleneoxy (optionally substituted by Q- 3 alkyl,
  • A is yet more preferably Q_ alkylene (optionally substituted by halogen, Q -3 alkyl or
  • A is Q_ alkyl-substituted Q_ alkylene, fluoro- substituted Q. alkylene, methoxy-substituted Q. alkylene, -C(O)- or Q_ 4 alkyleneoxy; still more preferably A is Q_ 2 alkyl-substituted C ⁇ _ alkylene, fluoro-substituted C]_ alkylene or methoxy-substituted Q- alkylene.
  • A is CH(CH 3 )CH 2 , CH 2 CH(CH 3 ), CH(CH 3 ), CHF, CH(OCH 3 ) or CH(CH 3 )O; even further preferred that A is CH(CH 3 )CH 2 , CH 2 CH(CH 3 ), CH(CH 3 ), CHF or CH(CH 3 )O; especially preferred that A is CHF, CH(OCH 3 ) or CH(CH 3 ); and most preferably A is CHF or CH(CH 3 ).
  • D is preferably S.
  • E is N or CR 2 where R 2 is hydrogen, halogen, Q. alkyl, Q_ 6 haloalkyl, Q. 6 alkoxy, Q. 6 haloalkoxy, Q.6 alkoxy(Q.6)alkyl, Q. 6 alkylthio or SF 5 ; or R 1 and R 2 together with the atoms to which they are attached form a benzene ring optionally substituted by Q. 6 alkyl,Q -6 haloalkyl or halogen.
  • G, J, L and Q are, independently, N, N-oxide or CR 6 with the proviso that neither are all N, nor are all N-oxide and nor are all CR 6 ; where more than one of G, J, L and Q is CR 6 , R 6 can be the same or different.
  • G, J, L and Q are, independently, N or CR 6 with the proviso that neither are all N nor are all CR 6 ; where more than one of G, J, L and Q is CR 6 , R 6 can be the same or different.
  • R 12 is hydrogen, Q. 4 alkyl, . 4 alkoxy(Q. 4 )alkyl, benzyloxymethyl or benzoyloxymethyl.
  • Y is preferably O or S. More preferably Y is O.
  • Preferred values of R 1 are hydrogen, halogen, Q_6 alkyl, _6 alkenyl, . 6 alkynyl, Q.
  • R 1 is more preferably hydrogen, halogen, Q. 6 alkyl, Q. 6 alkenyl, Q. 6 haloalkyl, Q_ 6 alkoxy, Q_ 6 haloalkoxy, Q- 6 alkylthio, Q. 6 haloalkylthio, - 6 cycloalkyl, cyano, nitro or SF 5 ;
  • R 1 is halogen, Q. 6 alkyl, Q. 6 haloalkyl, Q_ 6 alkoxy or Q. 6 haloalkoxy.
  • R 2 is preferably hydrogen, halogen, Q_ 6 alkyl, C 2 - 6 alkenyl, Q. 6 alkynyl, Q. haloalkyl, Ci.6 alkoxy, Q. 6 alkoxy (Q. 6 )alkyl, Q. 6 haloalkoxy, Q. 6 alkylthio, Q. 6 haloalkylthio, Q- 6 alkylsulfinyl, Ci_ 6 haloalkylsulfmyl, Q_ alkylsulfonyl, Ci.
  • R 2 is hydrogen, halogen, Q_ 6 alkyl, Q- 6 haloalkyl, Q_ 6 alkoxy (Q- 6 )alkyl, Q_ 6 alkoxy, Q_ 6 haloalkoxy, Q_ 6 alkylthio or 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 Q. 6 alkyl, Q. 6 haloalkyl or halogen.
  • R 2 is even more preferably hydrogen, halogen, Q_ 6 alkyl, Q- 6 haloalkyl, Q- 6 alkoxy, Ci. 6 haloalkoxy, Q. 6 alkoxy(Q-6)alkyl, Q. 6 alkylthio or SF 5 ; or R 1 and R 2 together with the atoms to which they are attached form a benzene ring optionally substituted by Q. 6 alkyl, Ci- 6 haloalkyl or halogen; or alternatively the ring may be a cyclopentane ring.
  • R 2 is hydrogen, halogen, Q- 6 alkyl, Q- 6 haloalkyl, Q. 6 alkoxy(Q- 6 )alkyl, Ci. 6 alkoxy, Q.6 haloalkoxy, or R 1 and R 2 together with the atoms to which they are attached form a cyclopentane ring optionally substituted by Q_ 6 alkyl, Q_ 6 haloalkyl or halogen.
  • R 2 is most preferably halogen, Q. 6 alkyl, Q_6 haloalkyl, Q. 6 alkoxy, Q. 6 alkoxy(Q_ 6 )alkyl or Q. 6 haloalkoxy.
  • R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, Q_ 6 alkyl, Q. 6 alkoxy, Q- 6 haloalkoxy, Q- 6 alkylthio, Q.6 haloalkylthio, Q. 6 alkylsulfinyl, Q. 6 haloalkylsulfinyl, Q- 6 alkylsulfonyl, . 6 haloalkylsulfonyl, Q. 6 haloalkyl, cyano, nitro, Q- 6 alkylcarbonyl, Q_ 6 alkoxycarbonyl or SF 5 .
  • R 3 , R 4 and R 5 are independently hydrogen, Q -3 alkyl or halogen.
  • R 3 , R 4 and R 5 are independently, hydrogen or halogen (especially fluorine); it is more especially preferred that each of R , R and R 5 is hydrogen.
  • R 6 is cyano, Q -8 alkyl, Q -8 haloalkyl, Q. 8 cyanoalkyl, Q_ 7 cycloalkyl (C ⁇ -6)alkyl, Q_ 6 cycloalkenyl(Q-6)alkyl, Q. alkoxy(Q_6)alkyl, C 3 . 6 alkenyloxy(Q- 6 )alkyl, C 3 . 6 alkynyloxy(Q- 6 )alkyl, aryloxy(C ⁇ . 6 )alkyl, Q. 6 carboxyalkyl, Q. 6 alkylcarbonyl(C ⁇ . 6 )alkyl, C _ 6 alkenylcarbonyl(Q.
  • heteroaryl (Q_ )alkyl where the heteroaryl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q- 6 alkoxy or Q_ 6 haloalkoxy
  • heterocyclyl (Q_ )alkyl where the heterocyclyl group is optionally substituted by halo, cyano, Q_ 6 alkyl, Q. 6 haloalkyl, Q.6 alkoxy or Q. 6 haloalkoxy
  • R 6 is Q_ 8 alkyl, Q. 8 haloalkyl, Q. 8 cyanoalkyl, Q.
  • R 6 is more preferably . 8 alkyl, Q -8 haloalkyl, Q_ 8 cyanoalkyl, C 2 . 6 alkenyl, _ 6 alkynyl, C 3 . 7 cycloalkyl, C 3 . 7 halocycloalkyl, Q- 7 cyanocycloalkyl, C ⁇ _ 3 alkyl(C 3 _ )cycloalkyl, Ci_ 3 alkyl(Q_ 7 )halocycloalkyl, C 5 .
  • alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q- 6 alkyl, Q- 6 haloalkyl, Q -6 alkoxy or C ⁇ - 6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q- 6 haloalkyl, Q_ 6 alkoxy or Ci- 6 haloalkoxy), heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q_6 haloalkyl, Q_ alkoxy or Q_ 6 haloalkoxy), heteroaryl(Q- 4 )alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q_ 6 haloalkyl, Ci-6 alkoxy or Q_ 6 haloalkoxy), hetero
  • R is Q. 8 alkyl, Q. 8 haloalkyl, . 8 cyanoalkyl, Q_ 6 alkoxy (Q- ⁇ ) alkyl, Q- 7 cycloalkyl, Q- 3 alkyl (C 3 . 7 ) cycloalkyl, heterocyclyl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q- 6 haloalkyl, Q_ 6 alkoxy or Q_ 6 haloalkoxy) or di(Q_ 8 )alkylamino.
  • R 6 is Q. 8 alkyl, Q. 8 haloalkyl, Q_ 8 cyanoalkyl, Q- 6 alkoxy (Q_ 6 ) alkyl, Q. cycloalkyl, Q_ 3 alkyl (C 3 . 7 ) cycloalkyl, heterocyclyl (optionally substituted by Q. 6 alkyl) or di(Ci. 8 )alkylamino.
  • R 6 is yet more preferably Q_ 8 alkyl, Q_ 8 haloalkyl, C ⁇ - 8 cyanoalkyl, Q. 7 cycloalkyl,
  • R 6 is most preferably Q_ 8 alkyl, Q_ 6 haloalkyl, Q_ 6 alkoxy, Q. 7 cycloalkyl or Q. cyclalkyl(Q. 7 ) alkyl.
  • R 8 is C MO alkyl, C O haloalkyl, _ 6 alkenyl (Q_ 6 )alkyl, - 6 alkynyl(Q_ 6 )alkyl, C 3 _ 7 cycloalkyl, Q.6 alkylamino, di(Q.6)alkylamino or phenyl(Q_ 4 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q. 6 haloalkyl, Q_ 6 alkoxy or Q. 6 haloalkoxy). It is more preferred that R is Q_ 6 alkyl, Q. 6 haloalkyl, .
  • R 9 is C O alkyl, C O haloalkyl, C 2-6 alkenyl(Q_ 6 )alkyl, _ 6 alkynyl(Q_ 6 )alkyl, C 3 . 7 cycloalkyl, C MO alkylthio(Q_ ⁇ 0 )alkyl, Q.io alkoxycarbonyl, C MO alkoxycarbonyl(Q_ ⁇ o)alkyl or phenyl(Q.
  • R 9 is Q.io alkyl, Q.6 haloalkyl, _ 6 alkenyl(Q- 6 )alkyl, - 6 alkynyl (Ci_ 6 )alkyl, Q_ 6 alkylthio(Q_ 6 )alkyl, C MO alkoxycarbonyl, Q_ 6 alkoxycarbonyl(Q- 6 )alkyl or benzyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q_ 6 haloalkyl, Q-6 alkoxy or Q. 6 haloalkoxy).
  • R 9 is even more preferably C MO alkyl, Q.6 alkyl thio(C ⁇ . 6 )alkyl, _ 6 alkenyl(Q_ 6 )alkyl (especially allyl), C 2 . 6 alkynyl(C ⁇ . 6 )alkyl (especially propargyl), benzyl, Q. 6 alkoxycarbonyl(C ⁇ - 6 )alkyl or Q.io alkoxycarbonyl (especially w ⁇ butoxycarbonyl).
  • R 9 is most preferably C MO alkyl, Q.6 alkylthio(Q. 6 )alkyl, C 2 _ 6 alkenyl(Q_ 6 )alkyl
  • R 10 is Q.io alkyl, C 2-6 alkenyl(Q_ 6 )alkyl, C 2-6 alkynyl(Q. 6 )alkyl, C 3-7 cycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q. 6 haloalkyl, Q. 6 alkoxy or Q_ 6 haloalkoxy), Q_ ⁇ o haloalkyl, C ⁇ _ 6 alkoxy(Q_ 6 )alkyl, C 3 .
  • cycloalkyl(C ⁇ _ ⁇ )alkyl Ci- 6 alkylcarbonylamino, Q_ 6 alkoxycarbonylamino, C ⁇ _ 6 alkylaminocarbonylamino, Q. 6 alkylcarbonyloxy, Ci-6 alkoxycarbonyloxy, C ⁇ _6 alkylaminocarbonyloxy, Q. 6 alkoxy, Q. 6 alkylamino, di(Q_ 6 )alkylamino, hydroxy, phenoxy (optionally substituted by halo, nitro, cyano, Q. 6 alkyl, Q_ 6 haloalkyl, C ⁇ . 6 alkoxy or Q. 6 haloalkoxy), hydroxy(Ci_ 6 )alkyl, hydroxy(C i _ 6 )alkylamino or carboxy(C i . 6 )alkoxy.
  • R 10 is Q_6 alkyl, C 2 .6 alkenyl(C ⁇ . 6 )alkyl, C 2 . 6 alkynyl(Q_ 6 )- alkyl, C 3 . 7 cycloalkyl, phenyl, Q.6 haloalkyl, Q. 6 alkoxy(C].6)alkyl, C ⁇ _ 6 alkylcarbonylamino, Q. 6 alkoxycarbonylamino, Q.
  • R 1 ' is C MO alkyl, C 2 . 6 alkenyl(Q. 6 )alkyl, C 2 . 6 alkynyl(Q. 6 )alkyl,
  • R 11 is Q_ ⁇ o alkyl, . 6 alkenyl (Q ⁇ )alkyl, C 2 . 6 alkynyl(C]. 6 )alkyl, C 3 . 7 cycloalkyl, phenyl, CMO haloalkyl, Q_ 6 alkoxy(Q. 6 )alkyl or C 3 . 7 cycloalkyl(Q. 6 )alkyl.
  • R 12 is hydrogen, CM O alkyl, C 2 _ 6 alkenyl(C ⁇ _ 6 )alkyl, C 2 . 6 alkynyl- (Q- 6 )alkyl, C 3 . 7 cycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, Q. 6 alkyl, Q_ 6 haloalkyl, Ci. 6 alkoxy or Q.6 haloalkoxy), C O haloalkyl, Q. 6 alkoxy(Q. 6 )alkyl or C 3-7 cycloalkyl(C ⁇ . 6 )alkyl.
  • R 12 is hydrogen, C M O alkyl, _ 6 alkenyl(Q_ 6 )alkyl, C _ 6 alkynyl(C ⁇ _6)alkyl, C 3 . 7 cycloalkyl, phenyl, Ci.io haloalkyl, Q. alkoxy (Q. 6 ) alkyl benzyloxymethyl or benzoyloxymethyl or C 3 . 7 cycloalkyl(Q. 6 )alkyl.
  • R 12 is even more preferebly hydrogen, Q_ 6 alkyl, Ci. alkoxy(Q. 6 )alkyl, benzyloxymethyl or benzoyloxymethyl.
  • R 12 is most preferably hydrogen, Q_ 6 alkyl or Cj- 6 alkoxy (Q. 6 )alkyl.
  • R 13 is preferably cyano, nitro, Q_ 6 alkyl, Q. 6 haloalkyl, C 3-7 cycloalkyl, C 3 . 7 cycloalkyl(Q_ 6 )alkyl, CH 2 (C 2 . ⁇ ) alkenyl, CH 2 (C 2 _ 6 )alkynyl, phenyl (optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q. 6 haloalkyl, Q_ 6 alkoxy or C). 6 haloalkoxy) heteroaryl (optionally substituted by halo, nitro, cyano, Q. 6 alkyl, Q_6 haloalkyl, Q_ 6 alkoxy or Q.
  • R 13 is CM O alkyl, Q. 6 alkenyl(C ⁇ _6)alkyl, C 2 . 6 alkynyl (C ⁇ _ 6 )alkyl, Q. 7 cycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, Q. 6 alkyl, Q. 6 haloalkyl, Q. 6 alkoxy or Q. 6 haloalkoxy), CM O haloalkyl, Q. 6 alkoxy(Q. 6 )alkyl, Q_ 7 cycloalkyl(Q.
  • R 13 is Ci.6 alkyl, -6 alkenyl(Q. 6 )alkyl, C 2 . 6 alkynyl(Q. 6 )alkyl, C 3 . 7 cycloalkyl, phenyl, Q- 6 haloalkyl, Q. 6 alkoxy(C ⁇ . 6 )alkyl, Q_ 6 alkylcarbonylamino, Q_ 6 alkoxycarbonylamino, C ⁇ _6 alkoxy, C ⁇ _ 6 alkylamino, di(Q. 6 )alkylamino, hydroxy, phenoxy, hydroxy(C ⁇ . 6 )alkyl, hydroxy(Q_ 6 )alkylamino or carboxy(Ci_ 6 )alkoxy.
  • R 14 and R 15 independently, are hydrogen, halogen, Q. 6 alkyl, Q_ 6 haloalkyl - 6 alkenyl, Ci. 6 alkynyl, Q_ 6 alkoxy or C ⁇ -6 haloalkoxy.
  • R 16 and R 21 independently, are, Q_6 alkyl or phenyl(C ⁇ -2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q. 6 alkyl, Q. 6 haloalkyl, Q. 6 alkoxy or C i . 6 haloalkoxy) .
  • R 17 is hydrogen or Q. 3 alkyl.
  • R 18 is preferably hydrogen, Q. 8 alkyl, Q.6 haloalkyl, Q. 6 cyanoalkyl, C 2 . 6 alkenyl, . 6 alkynyl, Q. 6 alkoxy(Q_ 6 )alkyl, phenyl (Q_ )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), heteroaryl(Q_ )alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, . 6 alkyl, .
  • heterocyclyl optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q-6 haloalkyl, . 6 alkoxy or Q- 6 haloalkoxy
  • heterocyclyl(Q. 4 )alkyl wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q. 6 haloalkyl, Q.6 alkoxy or Q_ haloalkoxy
  • Q. 6 alkoxycarbonyl(Q. 6 )alkyl or N C(CH 3 ) 2 .
  • R is hydrogen, Q_ 8 alkyl, Q. 6 haloalkyl, Q. 6 cyanoalkyl, Q. 6 alkoxy(Q. 6 )alkyl, phenyl(Q_ 4 )alkyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q- 6 alkyl, Q. 6 haloalkyl, Q_6 alkoxy or Q. 6 haloalkoxy), heteroaryl(Q_ 4 )- alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Q. alkyl, . 6 haloalkyl, Q. 6 alkoxy or Q.
  • R 19 and R 20 independently, are, hydrogen, Q.g alkyl, Q. 7 cycloalkyl, _ 6 alkenyl, _ 6 alkynyl, Q_ cycloalkyl(Q. )alkyl, -6 haloalkyl, Q_ 6 alkoxy(Q_ 6 )alkyl, Q- 6 alkoxycarbonyl; or R 19 and R 20 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q- 6 alkyl groups. More preferably R 19 and R 20 are, independently, hydrogen, Q.
  • R 19 and R 20 are, independently, Q. 8 alkyl.
  • R 21 is phenyl (Q. 2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_ 6 alkyl, Q. 6 haloalkyl, Q_6 alkoxy or Q_ 6 haloalkoxy) or Q_ 6 alkyl.
  • R 22 is Q- 6 alkyl, Q_6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, Q- 6 alkyl, Q_ 6 haloalkyl, Q.6 alkoxy or Q_ 6 haloalkoxy).
  • R 23 is Q. 6 alkyl, OR 26 or NR 27 R 28 .
  • R 24 is preferably hydrogen, Q. 6 alkyl or Q. 6 haloalkyl.
  • R 25 is hydrogen, Q_6 alkyl, Q. 6 haloalkyl, Q. 6 alkoxy, cyano, Q. 6 alkoxycarbonyl, C ⁇ _ 6 alkylcarbonyl or NR R .
  • R 26 is Q_ 6 alkyl or optionally substituted phenyl(Q. 2 )alkyl.
  • R 27 and R 28 independently, are, hydrogen, Q. 8 alkyl or phenyl (optional substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q_ 6 alkoxy or Q. 6 haloalkoxy).
  • R 29 and R 30 independently, are, hydrogen, Q. 8 alkyl, Q_ 7 cycloalkyl, Q_ 6 alkenyl, C 3 - 6 alkynyl, C 2 - 6 haloalkyl, Q_ 6 alkoxy(C ⁇ . 6 )alkyl, C ⁇ - 6 alkoxycarbonyl(Q. 6 )alkyl, carboxy(Q. 6 )alkyl or phenyl(C ⁇ _ 2 )alkyl; or R and R together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q. 6 alkyl groups.
  • R 36 and R 37 independently, are, hydrogen, Q. 6 alkyl, CH 2 (Q- 4 haloalkyl), Q- 6 cyanoalkyl, Q. 6 alkoxy(Q. 6 )alkyl, Q_6 alkylthio(Q- 6 )alkyl, Q.6 alkoxy(Q_ 6 )alkoxy(Q. 6 )-alkyl, phenyl(Q.
  • R 36 and R 7 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q_ 6 alkyl groups.
  • optionally substituted isothiazolyl optionally subsituted pyridyl, optionally substituted pyrimidinyl, optionally substituted quinazolinyl and optionally substituted quinolinyl groups in which the optional substituents are chosen from halo, Q- 6 alkyl, Q- 6 haloalkyl, Q_ 6 alkoxy, Q.6 alkoxy(C ⁇ . 6 )alkyl or Q-6 haloalkoxy.
  • Table 1 provides 160 compounds of formula (1):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 2 provides 160 compounds of formula (2):
  • R , R and R are as defined in Table 1.
  • Table 3 provides 160 compounds of formula (3):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • R , R and R are as defined in Table 1.
  • Table 8 provides 160 compounds of formula (8):
  • R , R " and R are as defined in Table 1.
  • Table 9 provides 144 compounds of formula (9):
  • R 1 , R 12 and R 6 are as defined in Table 4.
  • Table 10 provides 160 compounds of formula (10):
  • R 1 , R 1 " " and R are as defined in Table 1.
  • Table 11 provides 160 compounds of formula (11):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 13 provides 160 compounds of formula (13):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • R , R and R are as defined in Table 4.
  • Table 15 provides 160 compounds of formula (15):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 16 provides 160 compounds of formula (16):
  • Table 17 provides 160 compounds of formula (17):
  • R 1 , R 1 and R are as defined in Table 1.
  • Table 18 provides 160 compounds of formula (18):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • R 1 , R 12 and R 6 are as defined in Table 4.
  • Table 20 provides 160 compounds of formula (20):
  • R , R and R are as defined in Table 1.
  • Table 22 provides 160 compounds of formula (22):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 23 provides 160 compounds of formula (23):
  • R , R 12 and R are as defined in Table 1.
  • R 1 , R 12 and R 6 are as defined in Table 4.
  • Table 25 provides 160 compounds of formula (25):
  • R , R and R are as defined in Table 1.
  • Table 26 provides 160 compounds of formula (26):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 28 provides 160 compounds of formula (28):
  • R 1 , R 12 and R are as defined in Table 1.
  • Table 29 provides 160 compounds of formula (29):
  • R , R and R are as defined in Table 1.
  • Table 30 provides 144 compounds of formula (30):
  • R 1 , R 12 and R 6 are as defined in Table 4.
  • Table 31 provides 160 compounds of formula (31):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 32 provides 160 compounds of formula (32):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 33 provides 160 compounds of formula (33):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 34 provides 160 compounds of formula (34):
  • R 1 , R 12 and R 6 are as defined in Table 4.
  • Table 36 provides 160 compounds of formula (36):
  • R . 1 , R , 12 and R are as defined in Table 1.
  • Table 37 provides 160 compounds of formula (37):
  • R , R " and R are as defined in Table 1.
  • Table 38 provides 160 compounds of formula (38):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 39 provides 160 compounds of formula (39):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 40 provides 144 compounds of formula (40):
  • R 1 , R 12 and R 6 are as defined in Table 4.
  • Table 41 provides 160 compounds of formula (41):
  • R , 1 , R12 and R are as defined in Table 1.
  • Table 42 provides 160 compounds of formula (42):
  • R . 1 , R .12 and R are as defined in Table 1.
  • Table 43 provides 160 compounds of formula (43):
  • R . 1 , r R1 " and R are as defined in Table 1.
  • Table 44 provides 160 compounds of formula (44):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 45 provides 144 compounds of formula (45):
  • R , ⁇ , R .12 and R are as defined in Table 4.
  • Table 46 provides 160 compounds of formula (46):
  • R , R and R are as defined in Table 1.
  • Table 47 provides 160 compounds of formula (47):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 48 provides 160 compounds of formula (48):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 50 provides 144 compounds of formula (50):
  • R 1 , R 12 and R 6 are as defined in Table 4.
  • Table 51 provides 160 compounds of formula (51):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 52 provides 160 compounds of formula (52):
  • R ⁇ and R are as defined in Table 1.
  • Table 53 provides 160 compounds of formula (53):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 54 provides 160 compounds of formula (54):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 55 provides 160 compounds of formula (55):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 56 provides 160 compounds of formula (56):
  • R , R , 12 and R are as defined in Table 1.
  • Table 57 provides 160 compounds of formula (57):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 59 provides 160 compounds of formula (59):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 60 provides 160 compounds of formula (60):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 61 provides 160 compounds of formula (61):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 62 provides 160 compounds of formula (62):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 63 provides 160 compounds of formula (63):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 64 provides 160 compounds of formula (64):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 65 provides 160 compounds of formula (65):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 66 provides 160 compounds of formula (66):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 67 provides 160 compounds of formula (67):
  • R , 1 , R .12 and R are as defined in Table 1.
  • Table 68 provides 160 compounds of formula (68):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 69 provides 160 compounds of formula (69):
  • R , R , 12 and R are as defined in Table 1.
  • Table 70 provides 160 compounds of formula (70):
  • R , R and R are as defined in Table 1.
  • Table 71 provides 160 compounds of formula (71):
  • Table 73 provides 160 compounds of formula (73):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 74 provides 160 compounds of formula (74):
  • R , 1 , r R12 and R are as defined in Table 1.
  • Table 75 provides 160 compounds of formula (75):
  • R , ⁇ , R , 12 and R are as defined in Table 1.
  • Table 76 provides 160 compounds of formula (76):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 77 provides 160 compounds of formula (77):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 78 provides 160 compounds of formula (78):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 79 provides 160 compounds of formula (79):
  • R , 1 , R> 12 and R are as defined in Table 1.
  • Table 80 provides 160 compounds of formula (80):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 81 provides 160 compounds of formula (81):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 82 provides 160 compounds of formula (82):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 83 provides 160 compounds of formula (83):
  • R , R and R are as defined in Table 1.
  • Table 84 provides 160 compounds of formula (84):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 85 provides 160 compounds of formula (85):
  • R , 1 , D R12 and R are as defined in Table 1.
  • Table 86 provides 160 compounds of formula (86): wherein R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 87 provides 160 compounds of formula (87):
  • R , ⁇ , R , 12 and R are as defined in Table 1.
  • Table 88 provides 160 compounds of formula (88):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 89 provides 160 compounds of formula (89):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 90 provides 160 compounds of formula (90):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 91 provides 160 compounds of formula (91): wherein R 1 , R 12 and R are as defined in Table 1.
  • Table 92 provides 160 compounds of formula (92):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 93 provides 160 compounds of formula (93):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 94 provides 160 compounds of formula (94):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 95 provides 160 compounds of formula (95):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 96 provides 160 compounds of formula (96): wherein R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 97 provides 160 compounds of formula (97):
  • R , ⁇ , R , 12 and R are as defined in Table 1.
  • Table 98 provides 160 compounds of formula (98):
  • R , R and R are as defined in Table 1.
  • Table 99 provides 160 compounds of formula (99):
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 100 provides 160 compounds of formula (100):
  • R 1 , R 12 and R are as defined in Table 1.
  • Table 101 provides 160 compounds of formula (101): wherein R 1 , R 12 and R 6 are as defined in Table 101.
  • Table 102 provides 160 compounds of formula (102):
  • R 1 , R 12 and R 6 are as defined in Table 101.
  • Table 103 provides 160 compounds of formula (103):
  • R , R and R are as defined in Table 101.
  • Table 104 provides 160 compounds of formula (104):
  • R 1 , R 12 and R° are as defined in Table 101.
  • Table 105 provides 160 compounds of formula (105):
  • R 1 , R 12 and R 6 are as defined in Table 101.
  • Table 106 provides 1 0 compounds of formula (106):
  • R 1 , R 12 and R 6 are as defined in Table 101.
  • Table 107 provides 160 compounds of formula (107):
  • R , R and R are as defined in Table 101.
  • Table 108 provides 160 compounds of formula (108):
  • R , ⁇ , R , 12 and R are as defined in Table 101.
  • Table 109 provides 160 compounds of formula (109):
  • R 1 , R 12 and R 6 are as defined in Table 101.
  • Table 110 provides 160 compounds of formula (110):
  • R 1 , R 12 and R 6 are as defined in Table 101.
  • Table 111 provides 64 Compounds of formula (111):
  • R 1 , R 12 , R a and R b are as defined in Table 111.
  • Table 112 provides 64 Compounds of formula (112):
  • R , 1 1 , r R> 12 , D Ra a and R D are as defined in Table 111.
  • Table 113 provides 64 Compounds of formula (113):
  • R 1 , R 12 , R a and R b are as defined in Table 111.
  • Table 114 provides 64 Compounds of formula (114):
  • R 1 , R 12 , R a and R b are as defined in Table 111.
  • Table 115 provides 64 Compounds of formula (115):
  • r R> 12 , r R,a a and R D are as defined in Table 111.
  • Table 116 provides 64 Compounds of formula (116):
  • R , 1 1 , R> 1 , ⁇ R_> a and R D are as defined in Table 111.
  • Table 117 provides 64 Compounds of formula (117):
  • R 1 , R 12 , R a and R b are as defined in Table 111.
  • Table 118 provides 64 Compounds of formula (118):
  • R , 1 1 , R, 12 , r R,a a and R D are as defined in Table 111.
  • Table 119 provides 64 Compounds of formula (119):
  • R 1 , R 12 , R a and R b are as defined in Table 111.
  • Table 120 provides 160 compounds of formula (120)
  • Table 121 provides 160 compounds of formula (121)
  • Table 122 provides 160 compounds of formula (122)
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 123 provides 160 compounds of formula (123)
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 124 provides 160 compounds of formula (124)
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 125 provides 160 compounds of formula (125)
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 127 provides 160 compounds of formula (127)
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 128 provides 160 compounds of formula (128)
  • R , R and R are as defined in Table 1.
  • Table 129 provides 160 compounds of formula (129)
  • R , R , 12 and R are as defined in Table 1.
  • Table 130 provides 160 compounds of formula (130)
  • R 1 , R 12 and R are as defined in Table 1.
  • Table 131 provides 160 compounds of formula (131)
  • R 1 , R 12 and R are as defined in Table 1.
  • Table 132 provides 160 compounds of formula (132)
  • R 1 , R 12 and R 6 are as defined in Table 1.
  • Table 134 provides 160 compounds of formula (134)
  • R 1 , R 12 and R are as defined in Table 1.
  • Table 135 shows selected NMR data, all with CDC1 3 , as the solvent (unless otherwise stated; if a mixture of solvents is present, this is indicated as, for example (CDC1 3 / d f ,- DMSO)), (no attempt is made to list all characterising data in all cases) for compounds of Tables 1 to 134.
  • the compounds of the invention may be made in a variety of ways.
  • a compound of formula (I) which is a compound of formula (IB) (wherein Y is oxygen and R 1 , R 3 , R 4 , R 5 , R 12 , A, D, E, G, J, L and Q are as defined above in relation to formula (I), except that R 12 is not H) may be made from a compound of formula (2) [wherein Y is oxygen and R 1 , R 3 , R 4 , R 5 , A, D, E, G, J, L and Q are as defined above in relation to formula (I)] by treatment with an alkylating agent (such as an alkyl halide, chloromethyl alkyl ether, dialkyl sulfate or trialkyloxonium salt), an acylating agent (such as an acid chloride) or a similar reagent (such as a carbamoyl chloride, or sulfenyl chloride), optionally in the presence of a base and optionally in the presence of a catalyst such as a phase
  • a compound of formula (IB) may be separated from a compound of formula (3) and purified by routine techniques such as recrystallisation, chromatography or trituration with a suitable solvent.
  • a compound of formula (IB) (where R , 1'2 is alkoxyalkyl or acyloxyalkyl) may also be prepared from a compound of formula (2) by sequential reaction with formaldehyde and an alkylating or acylating agent.
  • a compound of formula (2) [where Y is oxygen; and D, E, G, J, L, Q, R 1 , R 3 , R 4 and R 5 are as defined above in relation to formula (I)] and A is optionally substituted alkylene, alkenylene, alkynylene, alkylenoxy, alkylenamino or alkylenethio) may be prepared by reacting a compound of formula (4) (where D, E, and R 1 are as defined above in relation to formula I) with an appropriate compound of formula (5) (where A is optionally substituted alkylene, alkenylene, alkynylene, alkylenoxy, alkylenamino or alkylenethio; G, J, L, Q, R 3 , R 4 and R 5 are as defined above in relation to formula (I); and X is hydroxy) preferably in the presence of a suitable coupling reagent (such as 1,3-dicyclohexylcarbodiimide, 1,3- diisopropylcarbod
  • Compounds of formula (5) may be prepared in a number of ways, the preferred method is dependent on the nature of the fused benzheterocyclic ring and on the nature of the moiety A-C(O)-X .
  • the moiety A-C(O)-X may be attached by reacting a suitable reagent V-A-C(O)-X with a preformed compound of formula (6):
  • Certain compounds of formula (5) are amenable to modification to give further analogues.
  • X is an alkoxy moiety and A is an alkylene moiety
  • a compound of formula (5) undergoes reactions typical of aliphatic esters.
  • a compound of formula (5c) [where W is a single bond or suitable group (such as CH 2 ); X is .
  • R 3 , R 4 , R 5 , G, J, L and Q are as defined above for a compound of formula (I)] may be reacted with a suitable base (such as lithium diisopropylamide, sodium hydride or lithium hexamethyldisilazide) in a suitable solvent (such as tetrahydrofuran) and then treated with an alkylating agent (such as an alkyl halide), a halogenating agent (such as an N- chlorosuccinimide or N-fluorobenzenesulfonimide) or another electrophilic agent of formula Rf-LG (where LG designates a suitable leaving group, such as a halide) to introduce a new substituent R f .
  • a suitable base such as lithium diisopropylamide, sodium hydride or lithium hexamethyldisilazide
  • a suitable solvent such as tetrahydrofuran
  • an alkylating agent such as an alkyl
  • a compound of formula (5) bearing fragments which are sufficiently chemically reactive undergoes reactions typical of those fragments.
  • a compound of formula (5d) [wherein W is as defined as for a compound of formula (5c), X is C]. 6 alkoxy and R 3 , R 4 , R 5 , G, J, L and Q are as defined above for a compound of formula (I)] will undergo certain reactions typical of ⁇ -ketoesters.
  • a compound of formula (5d) may be reduced by metal hydrides (such as sodium borohydride) in a suitable solvent (such as ethanol) to give a corresponding alcohol of formula (5e):
  • Quinazolines may be formed from ort/zo-acylated amines, using similar procedures to those described, for example, by J. Siegal and B.E. Christensen, JACS, 73, 5777 (1951) and K. Schofield, T. Swain and R.S. Theobold, J. Chem. Soc. 1924 (1952). Cinnolines may be prepared from ⁇ rt/i ⁇ -aminophenylacetylenes by processes described by S.F.
  • the fused heterocyclic ring may be formed by ring synthesis from a suitably substituted benzene of formula(9) [where atoms or groups Q 1 and G 1 are suitable precursors for the formation of the desired heterocyclic ring and where the the benzene ring already bears the required substituent A- CO-X (where X is preferably an alkoxy moiety)] by processes analogous to those utilised in the preparation of compounds of formula (6): ring synthesis
  • a compound of formula (2) [wherein Y is sulfur and R 1 , R 3 , R 4 , R 5 , A, D, E, G, J, L and Q are as defined above in relation to formula (I)] may be prepared by reacting a compound of formula (2) [wherein Y is oxygen and R 1 , R 3 , R 4 , R 5 , A, D, E, G, J, L and Q 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(p ⁇ r ⁇ -tolyl)-l,3-dithia-2,4-
  • a compound of formula (10) (wherein R 1 , R 3 , R 4 , R 5 , D, E, G, J, L and Q are as defined above in relation to formula (I) may be made from a compound of formula (11) [wherein R 1 , R 3 , R 4 , R 5 , D, E, G, J, L and Q 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.
  • This invention covers isolated isomers together with mixtures of isomers.
  • a compound of formula (10) may be treated subsequently with an amine (HNR 27r R>28 ) ⁇
  • a compound of formula (11) may be treated in an analogous manner with a trialkyloithoformate (HC(OR 6 ) 3 ) [where R 26 is as defined for a compound of formula (I)] to afford a compound of formula (13) [wherein R 1 , R 3 , R 4 , R 5 , R 26 , D, E, G, J, L and Q are as defined above in relation to formula (I)].
  • HC(OR 6 ) 3 wherein R 26 is as defined for a compound of formula (I)]
  • a compound of formula (10), (12) or (13) may also be oxidised to a compound of formula (10) (where W is a single bond) under known conditions.
  • a compound of formula (2) (wherein Y is sulfur) may be treated with an electrophile (such as an alkyl halide, dialkyl sulfate, or trialkyloxonium salt), optionally in the presence of a base to give a compound of formula (14) [where R 9 is alkyl; and R 1 , R 3 , R 4 , R 5 , A, D, E, G, J, L and Q are as defined above in relation to formula (I)].
  • an electrophile such as an alkyl halide, dialkyl sulfate, or trialkyloxonium salt
  • a compound of formula (I) which is a compound of formula (IC) [wherein E is CR 2 ; and R 1 , R 2 , R 3 , R 4 , R 5 , A, D, G, J, L and Q are as defined above in relation to formula (I)] may be prepared by reacting a compound of formula (15) [where E is CR 2 and D, R 1 and R 2 are as defined above in relation to formula (I)] with an appropriate compound of formula (5) (where A, G, J, L, Q, R 3 , R 4 and R 5 are as defined above in relation to formula (I) and X is hydroxy) preferably in the presence of a suitable coupling reagent (such as 1 ,3- dicyclohexylcarbodiimide, 1,3-diisopropylcarbodiimide, l-(3-dimethylaminopropyl)-3- ethylcarbodiimide or 1 , 1 ' -carbonyldiimidazo
  • Compounds of formula (15) are known compounds or may be made from known compounds by known methods.
  • the compounds of formula (I) can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests.
  • the pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies).
  • pest species which may be controlled by the compounds of formula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp.
  • Capsids Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp.
  • the compounds of formula (I) are also active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae (Magnaporthe grisea) on rice and wheat and other Pyricularia spp. on other hosts; Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts (for example turf, rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental plants); Erysiphe cichoracearum on cucurbits (for example melon); Erysiphe graminis (powdery mildew) on barley, wheat, rye and turf and other powdery mildews on various hosts, such as Sphaerotheca macularis on hops, Sphaerotheca fusca (Sphaerothe
  • 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.
  • 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 ina
  • 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.
  • downy mildews such as Bremia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts, Pseudoperonospora humuli on hops and Pseudoperonospora cub
  • mice such as wheat and barley, peanuts, vegetables, cotton and turf; Sclerotinia spp. on turf, peanuts, potatoes, oil-seed rape and other hosts; Sclerotium spp. on turf, peanuts and other hosts; Gibberella fujikuroi on rice; Colletotrichum spp. on a range of hosts including turf, coffee and vegetables; Laetisaria fuciformis on turf; Mycosphaerella spp. on bananas, peanuts, citrus, pecans, papaya and other hosts; Diaporthe spp. on citrus, soybean, melon, pears, lupin and other hosts; Elsinoe spp.
  • Verticillium spp. on a range of hosts including hops, potatoes and tomatoes; Pyrenopeziza spp. on oil-seed rape and other hosts; Oncobasidium theobromae on cocoa causing vascular streak dieback; Fusarium spp., Typhula spp., Microdochium nivale, Ustilago spp., Urocystis spp., Tilletia spp. and Claviceps purpurea on a variety of hosts but particularly wheat, barley, turf and maize; Ramularia spp.
  • 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 01/551 . 7Q .
  • any other growth medium for example a nutrient 01/551 . 7Q .
  • the compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
  • plant as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes protectant, curative, systemic, eradicant and antisporulant treatments.
  • the compounds of formula (I) are preferably used for agricultural, horticultural and turfgrass purposes in the form of a composition.
  • a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA).
  • SFAs are chemicals which are able to modify the properties of an interface (for example, liquid solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula (I).
  • the composition is generally used for the control of pests or fungi such that a compound of formula (I) is applied at a rate of from 0. lg tolOkg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 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 0.00 lg 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 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 _ 80 _
  • 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 O 01/55140 g l
  • 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 SOLNESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLNESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), ⁇ -alkylpyrrolidones (such as ⁇ -methylpyrrolidone or ⁇ -octylpyrrolidone), dimethyl amides of fatty acids (such as C 8 -C ⁇ 0 fatty acid dimethylamide) and chlorinated hydrocarbons.
  • aromatic hydrocarbons such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLNESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLNESSO is a Registered Trade Mark
  • 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
  • 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 ..
  • 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).
  • DS powder for dry seed treatment
  • SS water soluble powder
  • WS water dispersible powder for slurry treatment
  • CS capsule suspension
  • the preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above.
  • Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
  • Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium diisopropyl- and tri-wopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these
  • 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 OA
  • octylphenol nonylphenol or octylcresol
  • partial esters derived from long chain fatty acids or hexitol anhydrides condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
  • Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
  • hydrophilic colloids such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose
  • swelling clays such as bentonite or attapulgite
  • a compound of formula (I) may be applied by any of the known means of applying pesticidal or fungicidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.
  • a locus of the pests such as a habitat of the pests, or a growing plant liable to infestation by the pest
  • a compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
  • compositions for use as aqueous preparations are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use.
  • These concentrates which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
  • a compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers).
  • fertilisers for example nitrogen-, potassium- or phosphorus-containing fertilisers.
  • Suitable formulation types include granules of fertiliser.
  • the mixtures suitably contain up to 25% by weight of the compound of formula (I).
  • the invention therefore also provides a fertiliser composition
  • 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
  • pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the composition.
  • selective insecticides for particular crops for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed.
  • insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).
  • acaricidal ovo-larvicides such as clofentezine, flubenzimine, hexythiazox or tetradifon
  • acaricidal motilicides such as dicofol or propargite
  • acaricides such as bromopropylate or chlorobenzilate
  • growth regulators such
  • fungicidal compounds which may be included in the composition of the invention are (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy- iminoacetamide (SSF-129), 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole- 1-sulphonamide, ⁇ -[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]- ⁇ -butyrolactone, 4-chloro- 2-cyano-N,N-dimethyl-5-/?-tolylimidazole-l-sulfonamide (IKF-916, cyamidazosulfamid), 3-5-dichloro-N-(3-chloro- 1 -ethyl- 1 -methyl-2-oxopropyl)-4-methylbenzamide (RH-7281 , zoxamide), N-allyl
  • 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.
  • This Example illustrates the preparation of Compound No. 1 of Table No. 96.
  • Step 2 Preparation of N-(4-chloro-3-methyIisothiazol-5-yl)-(2,3-dimethylquinoxalin-6- yl)-acetamide
  • Oxalyl chloride (0.178g, 0.0014mol) was added dropwise to a suspension of the acid
  • Step 2 Preparation of N-(4-chloro-3-methylisothiazol-5-yl)-4-aminophenyIacetamide Sodium methoxide (0.227 g, 0.0042 mol) was added to a solution of 5-amino-4- chloro-3-methylisothiazole (0.25 g, 0.0017 mol) in tetrahydrofuran (15 ml) and the mixture stirred at room temperature for 10 minutes.
  • Step 3 Preparation of N-(4-chloro-3-methylisothiazol-5-yl)-(2-methyIquinolin-6- yl)acetamide
  • aniline prepared in Step 2 (0.204 g, 0.0007 mol), p r ⁇ -chloranil (0.268 g , 0.0011 mol), crotonaldehyde (0.102 g, 0.0015 mol), concentrated hydrochloric acid (0.091 ml) and n-butanol (5 ml) were heated at 95 °C for 1 hour, then cooled to room temperature.
  • 2-Isopropylacrolein (0.92 ml, 0.00788 mol) was added dropwise, with stirring, to a mixture of 3-aminophenylacetic acid (0.915 g, 0.0061 mol), concentrated aqueous hydrochloric acid solution (1.51ml) and chloranil (1.64g, 0.0073mol) in n-butanol (15ml) at 80°C. Once the addition was complete the mixture was heated at gentle reflux for 1 hour, then cooled and allowed to stand at room temperature for 3days. The solvent was removed in vacuo, the residue diluted with ether and saturated aqueous sodium bicarbonate solution added until the solution was basic.
  • the mixture was diluted with water, the solids removed by filtration through HYFLO [HYFLO is a registered trademark] diatomaceous earth and the filtrate partitioned.
  • the aqueous phase was extracted with diethyl ether and the combined organic solutions were brine, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo.
  • the residue was triturated with a small quantity of dichloromethane, and then purified by column chromatography on silica gel, eluting with dichloromethane. Fractions containing the desired product were combined and the solvent evaporated in vacuo.
  • Step 2 Preparation of N-(4-chloro-3-methylisothiazoI-5-yl)-[3-(l-methyIethyl)quinolin-
  • HYFLO is a registered trademark] diatomaceous earth, washing with water and with ethyl acetate.
  • the filtrate was partitioned, and the aqueous phase extracted with ethyl acetate.
  • the organic solutions were combined, washed with dilute aqueous sodium hydroxide solution and water, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo.
  • HYFLO is a registered trademark] diatomaceous earth
  • the filtrate was washed with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated in vacuo.
  • the residue was purified by flash column chromatography on silica gel, eluting with ethyl acetate : hexane 1:5 to give ethyl [2-(2,2- dimethylpropyl)quinoxalin-6-yl] acetate as an orange oil.
  • 5-Amino-4-chloro-3-methylisothiazole (0.67 g, 0.0045 mol) was added to a stirred suspension of sodium methoxide (0.54 g, 0.010 mol) in tetrahydrofuran (20 ml) and the mixture stirred at room temperature for 15 minutes.
  • Ethyl [2-(2,2-dimethylpropyl)quinoxalin- 6-yl] acetate (1.18 g, 0.0045 mol) was added and the mixture stirred at room temeperature for 4 hours, then allowed to stand at room temperature overnight. The mixture was poured into aqueous citric acid solution and extracted with ethyl acetate.
  • EXAMPLE 5 This Example illustrates the preparation of Compound No. 77 of Table No. 91.
  • Step 1 Preparation of ethyl [2-(2,2-dimethylpropyl)quinoxalin-6-yl]fluoroacetate.
  • Lithium bis(trimethylsilyl)amide (1.15 Molar solution in tetrahydrofuran, 1.7ml, 0.002mol) was added dropwise to a solution of ethyl [2-(2,2-dimethylpropyl)quinoxalin-6-yl] acetate (0.50g, 0.0017mol) in tetrahydrofuran (10ml) at -70°C, and the mixture stirred for Vi hour.
  • EXAMPLE 7 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. 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.
  • 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 136, 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 136 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;
  • EXAMPLE 8 This Example illustrates the fungicidal properties of compounds of formula (I). The 5 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 0 (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
  • 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 6hours 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.
  • 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 [Banded mean disease level on untreated controls ⁇
  • This method uses unbanded 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.
  • ERYSGT Blumeria graminis f.sp. tritici
  • LEPTNO Stagonospora nodorum
  • PHYTIN Phytophthora infestans lycopersici
  • PLASVI Plasmopara viticola
  • PUCCRT Puccinia triticina

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Abstract

A compound of formula (I) wherein n is 0 or 1; D is S, NR?7, CR14=CR15, CR14=N; CR14¿=N(O), N=CR15 or N(O)=CR15; E is N, N-oxide or CR2; G, J, L and Q are, independently, N, N-oxide or CR6 provided that neither are all N nor are all CR6; where more than one of G, J, L and Q is CR6, R6 can be the same or different; M is OC(=Y), N=C(OR8), N=C(SR9), N=C(NR10R11) or N(R12)C(=Y) where O or N is the atom of attachment to the ring containing E and D; Y is O, S or NR13; and A and the various R groups are defined organic radicals; their preparation and use and compositions containing them.

Description

ISOTHIAZOLE DERIVATIVES AM) THEIR USE AS PESTICIDES
The present invention relates to azine and azole derivatives, to processes for preparing them, to fungicidal, insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them, to methods of using them to combat fungal diseases
(especially fungal diseases of plants) and to methods of using them to combat and control insect, acarine, mollusc and nematode pests.
Azole and azine derivatives are disclosed in WO95/31448, WO97/18198, WO98/02424, WO98/05670 and WO98/17630. The present invention provides a compound of formula (I):
Figure imgf000003_0001
wherein n is 0 or 1 ;
A is optionally substituted Cι- alkylene, optionally substituted C2-6 alkenylene, optionally substituted C2_ alkynylene, optionally substituted cycloalkylene, optionally substituted Cι-6 alkylenoxy, optionally substituted oxy(Cι-6)alkylene, optionally substituted Cι_6 alkylenethio, optionally substituted thio( ^alkylene, optionally substituted Cι_ alkyl enamino, optionally substituted amino(Cι_6)alkylene, optionally substituted [Cι-6 alkyleneoxy(Cι_6)alkylene], optionally substituted [ .6 alkylenethio(Cι.6)alkylene], optionally substituted [Cι-6 alkylenesulfιnyl(Cι-6)alkylene], optionally substituted [Cι-6 alkylenesulfonyl(Cι_ )alkylene] or optionally substituted [Cι_6 alkyleneamino(Cι_6)alkylene];
D is S, NR7, CR,4=CR15, CR14=N, CR,4=N(O), N=CR15 or N(O)=CR15;
E is N, N-oxide or CR2;
G, J, L and Q are, independently, N, N-oxide or CR6 provided that neither are all N nor are all CR6; where more than one of G, J, L and Q is CR6, R can be the same or different;
M is OC(=Y), N=C(OR8), N=C(SR9), N=C(NRI0Rπ) or N(R12)C(=Y) where O or N is the atom of attachment to the ring containing E and D;
Y is O, S or NR13; R1 is hydrogen, halogen, optionally substituted C1-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted C1-6 alkoxy, optionally substituted d_6 alkylthio, optionally substituted C3-7 cycloalkyl, cyano, nitro or SF5; R2 is hydrogen, halogen, optionally substituted -6 alkyl, optionally substituted C .6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted Cι-6 alkoxy, optionally substituted C!_6 alkylthio, optionally substituted C1-6 alkylsulfinyl, optionally substituted Cι_ alkylsulfonyl, cyano, nitro, formyl, optionally substituted
Figure imgf000004_0001
alkylcarbonyl, optionally substituted Cι.6 alkoxycarbonyl, SF5 or R16ON=C(R17); 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 Cι_6 alkyl, C]_6 haloalkyl or halogen;
R3, R4 and R5 are, independently, hydrogen, halogen, optionally substituted C1- alkyl, optionally substituted Ci-6 alkoxy, optionally substituted C1-6 alkylthio, optionally substituted Ci-6 alkylsulfinyl, optionally substituted Cι-6 alkylsulfonyl, cyano, nitro, optionally substituted Cι-6 alkylcarbonyl, optionally substituted Cι_6 alkoxycarbonyl or SF5; R6 is hydrogen, halogen, cyano, optionally substituted C1-20 alkyl, optionally substituted C2-20 alkenyl, optionally substituted C2-20 alkynyl, optionally substituted C3-7 cycloalkyl, optionally substituted C5-6 cycloalkenyl, formyl, optionally substituted C1-2o alkoxycarbonyl, optionally substituted Cι_20 alkylcarbonyl, aminocarbonyl, optionally substituted C1-20 alkylaminocarbonyl, optionally substituted di(C1-20)alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-(C1-6)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 diheteroarylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, SH, optionally substituted C1-20 alkylthio, optionally substituted Cι-20 alkylsulfinyl, optionally substituted Cι_20 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl, R18O, R19R20N or R21ON=C(R22); where any two adjacent groups of G, J, L and Q are CR6, the two adjacent R6 groups together with the carbon atoms to which they are attached may together form a five-, six- or seven-membered saturated or unsaturated ring, which may contain one or two heteroatoms selected from O, N or S and which may be optionally substituted by C]-6 alkyl, C1-6 alkoxy, C1-6 haloalkyl or halogen; R7 is C1-6 alkyl; R8 is optionally substituted CMO alkyl, optionally substituted [C2-6 alkenyl(C1- )alkyl], optionally substituted [C2-6 alkynyl(C1-6)alkyl], optionally substituted C3-7 cycloalkyl, amino, optionally substituted C1-6 alkylamino, optionally substituted di(C1_6)alkylamino, optionally substituted CMO alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, formyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted diC . 10)alkylaminocarbonyl, amino, optionally substituted phenoxycarbonyl, tri(Cι- )alkylsilyl, aryldi(C1- )alkylsilyl, (C1- )alkyldiarylsilyl or triarylsilyl;
R9 is optionally substituted CMO alkyl, optionally substituted [C2-6 alkenyl(C]_6)alkyl], optionally substituted [C2-6 alkynyl(C1-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted CMO alkylcarbonyl, optionally substituted Cι-10 alkoxycarbonyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(Cι_ιo)alkylamino- carbonyl or optionally substituted phenoxycarbonyl);
R10 and R11 are, independently, optionally substituted C1-10 alkyl, optionally substituted C1-6 alkoxy, optionally substituted [C2-6 alkenyl(C1.6)alkyl], optionally substituted [C .6 alkynyl(C1-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted C O alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, formyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(Cι-10)alkylaminocarbonyl, hydroxy, amino, optionally substituted C1- alkylamino, optionally substituted di(C1_6)alkylamino, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylamino, optionally substituted CMO alkylcarbonyloxy, optionally substituted C O alkoxycarbonyloxy, optionally substituted phenoxycarbonyloxy, optionally substituted CMO alkylaminocarbonyloxy, optionally substituted di(Cι.ι0)alkylaminocarbonyloxy, optionally substituted CMO alkylcarbonylamino, optionally substituted CMO alkoxycarbonylamino, optionally substituted phenoxycarbonylamino, optionally substituted CMO alkylaminocarbonylamino, optionally substituted di(CMo)alkylaminocarbonylamino or optionally substituted phenoxycarbonyl; R is hydrogen, optionally substituted CMO alkyl, optionally substituted Cι-6 alkoxy, optionally substituted [C2-6 alkenyl(Cj-6)alkyl], optionally substituted [C2-6 alkynyl (Cι.6)- alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted CMO alkylcarbonyl, optionally substituted C O alkoxycarbonyl, formyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(CMo)alkylaminocarbonyl, hydroxy, amino, optionally substituted Cι_6 alkylamino, optionally substituted di(Cι_6)alkylamino, optionally substituted phenoxycarbonyl, optionally substituted _ alkylthio, optionally substituted C1-6 alkylsulfinyl, optionally substituted C1-6 alkylsulfonyl, optionally substituted C1-6 aryl, optionally substituted C1-6 arylthio, optionally substituted C1-6 arylsulfinyl, optionally substituted C1-6 arylsulfonyl or R36R37NS(O)q; q is 0, 1 or 2; R36 and R37 are, independently, optionally substituted Ci-6 alkyl; or R36 and R37 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Cι_ alkyl groups; R13 is hydrogen, hydroxy, cyano, nitro, optionally substituted C O alkyl, optionally substituted C3-7 cycloalkyl, optionally substituted (C2-6)alkenyl(C1.6)alkyl, optionally substituted (C2-6)alkynyl(C1_6)alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted -6 alkylcarbonyl, optionally substituted Cι-6 alkoxycarbonyl, optionally substituted Ci-6 alkylamino, optionally substituted di(Q_6)alkyl- amino, optionally substituted Ci-6 alkylcarbonylamino, optionally substituted Ci_ alkoxycarbonylamino, optionally substituted Cι_6 alkoxy, optionally substituted C]_6 alkylthio, optionally substituted -6 alkylsulfinyl, optionally substituted Cι_6 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylamino, optionally substituted CMO alkoxycarbonyloxy, optionally substituted phenoxycarbonyloxy,optionally substituted Cj.ϊo lkylaminocarbonyloxy, optionally substituted di(CMo)alkylaminocarbonyloxy, optionally substituted phenoxycarbonylamino, optionally substituted CMO alkylaminocarbonylamino, optionally substituted di(Q.ιo)alkyl- aminocarbonylamino or optionally substituted C1-6 alkylcarbonyl oxy; R14 and R15 are, independently, hydrogen, halogen, cyano, nitro, optionally substituted Q_6 alkyl, optionally substituted C2_6 alkenyl, optionally substituted -6 alkynyl or optionally substituted Q_6 alkoxy; R16 and R21 are, independently, hydrogen, optionally substituted phenyl (Q_2)alkyl or optionally substituted Q-2o alkyl;
R17 and R22 are independently hydrogen, optionally substituted phenyl or optionally substituted Q.6 alkyl;
R18 is hydrogen, optionally substituted Q-2o alkyl, optionally substituted [Q-2o alkenyl (C 1-6)- alkyl], optionally substituted [C2-2o alkynyl (Q-ό) alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, (Q-6)alkylCH=N, optionally substituted arylCH=N, optionally substituted [aryl(Q,6)alkyl]CH=N, optionally substituted heteroarylCH=N, optionally substituted [heterocyclyl(Q-6)alkyl]CH=N, optionally substituted arylC(CH3)=N, optionally substituted heteroarylC(CH3)=N or optionally substituted di(Q.6)alkylC=N; and R19 and R20 are, independently, hydrogen, optionally substituted Q_20 alkyl, optionally substituted C3-7 cycloalkyl, optionally substituted [C -2o alkenyl(Cι_6)alkyl], optionally substituted [C2- o alkynyl(Q_.6)alkyl], optionally substituted Q-2o alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted Q.2o alkylcarbonyl, optionally substituted Q-2o alkylsulfonyl or optionally substituted phenylsulfonyl; provided that when E is CR2 and M is N(R12)C(=Y) (where Y is O or S) then D is not CR14=CR15.
One group of preferred compounds of formula (I) is that group where n is 0 or 1 ; A is optionally substituted Q_6 alkylene, optionally substituted C2_6 alkenylene, optionally substituted Q_6 alkynylene, optionally substituted Q_6 alkylenoxy, optionally substituted oxy(Q-6)alkylene, optionally substituted Q_6 alkylenethio, optionally substituted thio(Cι.6)- alkylene, optionally substituted Q-6 alkylenamino, optionally substituted amino(Q_6)- alkylene, optionally substituted [Ci-6 alkyleneoxy(Q-6)alkylene], optionally substituted [Cι_6 alkylenethio(Cι_6)alkylene], optionally substituted [Q.6 alkylenesulfinyl(Cι-6)alkylene], optionally substituted [Q-6 alkylenesulfonyl(Cι.6)alkylene] or optionally substituted [Q-6 alkyleneamino(C 1 _6)alkylene] ;
D is S, NR7, CR14=CR15, CR14=N, CR14=N(O), N=CR15 or N(O)=CR15; E is N, N-oxide or CR2;
G, J, L and Q are independently N, N-oxide or CR6 with the proviso that neither are all N nor are all CR6; where more than one of G, J, L and Q is CR6, R6 can be the same or different; M is OC(=Y), N(R12)C(=Y), N=C(OR8), N=C(SR9) or N=C(NR10Rπ) where O or N is the atom of attachment to the ring containing E and D; Y is O, S or NR13;
R1 is hydrogen, halogen, optionally substituted Q_6 alkyl, optionally substituted C2_6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted Q.6 alkoxy, optionally substituted Q-6 alkylthio, optionally substituted C3.7 cycloalkyl, cyano, nitro or SF5;
R2 is hydrogen, halogen, optionally substituted Q_6 alkyl, optionally substituted -6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted Q-6 alkoxy, optionally substituted Q_6 alkylthio, optionally substituted Q-6 alkylsulfinyl, optionally substituted Q-6 alkylsulfonyl, cyano, nitro, formyl, R16ON=C(R17), optionally substituted Q.6 alkylcarbonyl, optionally substituted CΪ-6 alkoxycarbonyl or SF5; or R and R together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated 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 Q_6 alkyl, Q_6 haloalkyl or halogen; R3, R4 and R5 are, independently, hydrogen, halogen, optionally substituted .6 alkyl, optionally substituted Q.6 alkoxy, optionally substituted Q_6 alkylthio, optionally substituted Q. alkylsulfinyl, optionally substituted Q_6 alkylsulfonyl, cyano, nitro, optionally substituted Q-6 alkylcarbonyl, optionally substituted Q-6 alkoxycarbonyl or SF5; R6 is hydrogen, halogen, cyano, optionally substituted Q-2o alkyl, optionally substituted C2.20 alkenyl, optionally substituted Q-2o alkynyl, optionally substituted C3.7 cycloalkyl, optionally substituted -6 cycloalkenyl, formyl, optionally substituted Q-20 alkoxycarbonyl, optionally substituted Q_2o alkylcarbonyl, aminocarbonyl, optionally substituted Q.2o alkylaminocarbonyl, optionally substituted di(Q_ o)alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-alkyl-N-arylaminocarbonyl, optionally substituted diarylaminocarbonyl, optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted alkylheteroarylaminocarbonyl, optionally substituted diheteroarylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, R18O, HS, optionally substituted C1-2o alkylthio, optionally substituted C].2o alkylsulfinyl, optionally substituted Q-2o alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl , R19R20N or
R21ON=C(R22); where any two adjacent groups of G, J, L and Q are CR6, the two adjacent R6 groups together with the carbon atoms to which they are attached may together form a five-, six- or seven-membered saturated or unsaturated ring, which may contain one or two hetero atoms selected from O, N or S and which may be optionally substituted by Q.6 alkyl, Q_6 alkoxy, Q_6 haloalkyl or halogen; R7 is Q.6 alkyl;
R8 is optionally substituted CMO alkyl, optionally substituted [C2_6 alkenyl(Q-6)alkyl], optionally substituted [C2_6 alkynyl(Cι-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted CMO alkylcarbonyl, optionally substituted Q_ι0 alkoxycarbonyl, formyl, optionally substituted Q_ιo alkylaminocarbonyl, optionally substituted di(Q_10)- alkylaminocarbonyl, , amino, optionally substituted Q-6 alkylamino, optionally substituted di(Q-6)alkylamino, optionally substituted phenoxycarbonyl, tri(Q. )alkylsilyl, aryldi(Q_4)- alkylsilyl, (Cι-4)alkyldiarylsilyl or triarylsilyl;
R9 is optionally substituted Q.io alkyl, optionally substituted [Q_6 alkenyl(Q. 6)alkyl], optionally substituted [C2.6 alkynyl(Q_6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted CMO alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, optionally substituted Q.io alkylaminocarbonyl, optionally substituted di(Q_ 1o)-alkylaminocarbonyl or optionally substituted phenoxycarbonyl);
R10 and R11 are, independently optionally substituted C O alkyl, optionally substituted Q-6 alkoxy, optionally substituted [C _6 alkenyl(Q_6)alkyl], optionally substituted [C2-6 alkynyl(Q-6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted Q.io alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, formyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(Q-ιo)alkylaminocarbonyl, hydroxy, amino, optionally substituted Q_6 alkylamino, optionally substituted di(Q_6)alkylamino, or optionally substituted phenoxycarbonyl;
R12 is hydrogen, optionally substituted CMO alkyl, optionally substituted [C2.6 alkenyl(Q-6)alkyl], optionally substituted [C2-6 alkynyl(Ci-6)alkyl], optionally substituted - o -
η cycloalkyl, optionally substituted Q_10 alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, formyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(Q_ιo)alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted Q-6 alkylthio, optionally substituted Q_6 alkylsulfinyl, optionally substituted Q_6 alkylsulfonyl, optionally substituted Q.6 arylthio, optionally substituted Q_6 arylsulfinyl, optionally substituted Q-6 arylsulfonyl or R36R37NS;
R13 is hydrogen, cyano, nitro, optionally substituted Q.6 alkyl, optionally substituted C3.7 cycloalkyl, optionally substituted (C2.6)alkenyl(Q.6)alkyl, optionally substituted (C2. 6)alkynyl(Q-6)alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted Q.6 alkylcarbonyl, optionally substituted Q_6 alkoxycarbonyl, optionally substituted Q.6 alkylamino, optionally substituted di(Q_6)alkylamino, optionally substituted Q_6 alkylcarbonylamino, optionally substituted Q.6 alkoxycarbonylamino, optionally substituted Cι.6 alkoxy, optionally substituted Q.6 alkylthio, optionally substituted Q_6 alkylsulfinyl, optionally substituted Q.6 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or Q_6 acyloxy;
R14 and R15 are, independently, hydrogen, halogen, cyano, nitro, optionally substituted Q-6 alkyl, optionally substituted C2_6 alkenyl, optionally substituted C2_6 alkynyl or optionally substituted Q_ alkoxy; R16 and R21 are, independently, hydrogen, optionally substituted phenyl (Q.2)alkyl or optionally substituted Q_20 alkyl;
R17 and R22 are independently hydrogen, optionally substituted phenyl or optionally substituted Q-6 alkyl;
R , 18 is hydrogen, optionally substituted Q.2o alkyl, optionally substituted [C .2o alkenyl (C
6)alkyl], optionally substituted [C .20 alkynyl (Q.6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, (Q_6)alkylCH=N or di(Q.6)alkylC=N; R19 and R20 are, independently, hydrogen, optionally substituted Q. o alkyl, optionally substituted C3.7 cycloalkyl, optionally substituted [C2. o alkenyl(Cι_6)alkyl], optionally substituted [C2.2o alkynyl(Q_6)alkyl], optionally substituted Cι_ o alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted Q.2o alkylcarbonyl, optionally substituted Q_ o alkylsulfonyl or optionally substituted phenylsulfonyl; or R19 and R20 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q.6 alkyl groups; and R36 and R37 are, independently, optionally substituted Q.6 alkyl or R36 and R37 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 .6 alkyl groups; provided that when E is CR2 and M is N(R12)C(=Y) (where Y is O or S) then D is not CR,4=CR15.
The compounds of formula (I) may exist in different geometric or optical isomers or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
When present, optional substituents on alkylene, alkenylene or alkynylene moieties include (subject to valency constraints) one or more of hydroxy, halogen, Q_6 alkyl, Q-6 haloalkyl, Q.6 cyanoalkyl, Q.6 alkoxy(Q.6) alkyl, Q_6 alkoxy, cyano, =O, =NR23 and =CR24R25; and, especially, one or more of halogen, Q.6 alkyl, Q_6 haloalkyl, Q_6 cyanoalkyl, Q.6 alkoxy(Q.6) alkyl, Q.6 alkoxy, cyano, =O, =NR23 and =CR24R25; wherein R23 is Q.6 alkyl, Q.6 haloalkyl, OR26 or NR27R28; where R24 and R25 are, independently, hydrogen, Q.6 alkyl, Q. alkoxy, Q.6 haloalkyl, cyano, Q.6 alkoxycarbonyl, Q-6 alkylcarbonyl or NR2 R30; R26 is Q.6 alkyl, Q_6 haloalkyl or phenyl(Q-2)alkyl; R27 and R28 are, independently, hydrogen, Q_8 alkyl, C3.7 cycloalkyl, C2.6 alkenyl(Q_6)alkyl, C2.6 alkynyl(Q_6)alkyl, C2_6 haloalkyl, Q.6 alkoxy(Q.6)alkyl, Q_6 alkoxycarbonyl(Q_6)alkyl, carboxy(Q_6)alkyl or phenyl(Q_2)alkyl; or R27 and R28 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 Q.6 alkyl groups; R29 and R30 are, independently, hydrogen, Q_g alkyl, C3.7 cycloalkyl, C2. alkenyl(Q_6)alkyl, C2_6 alkynyl (Q-6)alkyl, _6 haloalkyl, Q.6 alkoxy(Cι.6)alkyl, Q_6 alkoxycarbonyl(Q_6)alkyl, carboxy(Cι.6)alkyl or phenyl(Q_2)alkyl; or R29 and R30 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 Q.6 alkyl groups. Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, «-hexyl, sø-propyl, n-butyl, sec-butyl, wo-butyl, tert-butyl or neo-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 Q_6 alkyl or halogen), C5.7 cycloalkenyl (itself optionally substituted with Q.6 alkyl or halogen), hydroxy, CMO alkoxy, CMO alkoxy(Q.ιo)alkoxy, tri(C1-4)alkylsilyl(Q-6)alkoxy, Q.6 alkoxycarbonyl(Q-10)alkoxy, Q-10 haloalkoxy, aryl(Q_ )alkoxy (where the aryl group is optionally substituted), C3_7 cycloalkyloxy (where the cycloalkyl group is optionally substituted with Q-6 alkyl or halogen), .io alkenyloxy, C O alkynyloxy, SH, CMO alkylthio, Q.10 haloalkylthio, aryl(Q- )alkylthio (where the aryl group is optionally substituted), C3-7 cycloalkylthio (where the cycloalkyl group is optionally substituted with Q-6 alkyl or halogen), tri(Q-4)alkylsilyl(Q-6)alkylthio, arylthio (where the aryl group is optionally substituted), Q_6 alkylsulfonyl, Q_6 haloalkylsulfonyl, Q-6 alkylsulfinyl, Q_6 haloalkylsulfmyl, arylsulfonyl (where the aryl group may be further optionally substituted), tri(Q.4)alkylsilyl, aryldi(C1^)alkylsilyl, (Q.4)alkyldiarylsilyl, triarylsilyl, CMO alkylcarbonyl, HO2C, CMO alkoxycarbonyl, aminocarbonyl, Cι_6 alkylaminocarbonyl, di(Q_6 alkylaminocarbonyl, N-(C1.3 alkyl)-N-(Cι.3 alkoxy)aminocarbonyl, Q_6 alkylcarbonyloxy, arylcarbonyloxy (where the aryl group is optionally substituted), di(Q.6)alkylaminocarbonyloxy, aryl (itself optionally substituted), heteroaryl (itself optionally substituted), heterocyclyl (itself optionally substituted with Q_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 Q-6 alkyl or halogen), amino, Q_6 alkylamino, di(Q-6)alkylamino, Q_6 alkylcarbonylamino and N-(Q.6)alkylcarbonyl-N-(Q.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 (Z)-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 Q-6 alkylcarbonyl (for example acetyl), optionally substituted Q-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 CHF2CH .
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 Q_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 Q.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-, Q.6 alkyl, Q.6 haloalkyl, Q-6 alkoxy(Q.6)alkyl, -6 alkenyl, C2_6 haloalkenyl, .6 alkynyl, C3.7 cycloalkyl (itself optionally substituted with Q_6 alkyl or halogen), C5.7 cycloalkenyl (itself optionally substituted with Q_6 alkyl or halogen), hydroxy, Q_io alkoxy, Q.io alkoxy(Q-ι0)alkoxy, tri(Q_4)alkylsilyl(Q_6)alkoxy, Q_6 alkoxycarbonyl(Q_10)alkoxy, C O haloalkoxy, aryl(Q_4)alkoxy (where the aryl group is optionally substituted), Q_7 cycloalkyloxy (where the cycloalkyl group is optionally substituted with Q-6 alkyl or halogen), Q.io alkenyloxy, Q.io alkynyloxy, SH, Q-io alkylthio, Q.io haloalkylthio, aryl(Q.4)alkylthio (where the aryl group may be further optionally substituted), Q_7 cycloalkylthio (where the cycloalkyl group is optionally substituted with Q-6 alkyl or halogen), tri(Q_4)alkylsilyl(Q-6)alkylthio, arylthio (where the aryl group is optionally substituted), Q.6 alkylsulfonyl, Q.6 haloalkylsulfonyl, Q-6 alkylsulfinyl, Q-6 haloalkylsulfmyl, arylsulfonyl (where the aryl group is optionally substituted), tri(Q.4)alkylsilyl, aryldi(Q-4)alkylsilyl, (Q-4)alkyldiarylsilyl, triarylsilyl, C O alkylcarbonyl, HO2C, Ci_ιo alkoxycarbonyl, aminocarbonyl, Q-6 alkylaminocarbonyl, di(Q-6 alkylaminocarbonyl, N-(Cι_3 alkyl)-N-(Q.3 alkoxy)aminocarbonyl, Ci_6 alkylcarbonyloxy, arylcarbonyloxy (where the aryl group is optionally substituted), di(Cι-6)alkylaminocarbonyloxy, aryl (itself optionally substituted), heteroaryl (which itself may be further optionally substituted), heterocyclyl (itself optionally substituted with Ci-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 Q_6 alkyl or halogen), amino, Q_6 alkylamino, di(Q_6)alkylamino, Q_6 alkylcarbonylamino and N-(Q.6)alkylcarbonyl-N-(Q-6)alkylamino.
For substituted phenyl moieties, heterocyclyl and heteroaryl groups it is preferred that one or more substituents are independently selected from halogen, Q-6 alkyl, Q_6 haloalkyl, Q.6 alkoxy(Q_6)alkyl, Q-6 alkoxy, Q_6 haloalkoxy, Q_6 alkylthio, Q_6 haloalkylthio, Q-6 alkylsulfinyl, Q.6 haloalkylsulfmyl, Q_6 alkylsulfonyl, Q_6 haloalkylsulfonyl, -6 alkenyl, _6 haloalkenyl, -6 alkynyl, C3.7 cycloalkyl, nitro, cyano, CO2H, Q.6 alkylcarbonyl, Q.6 alkoxycarbonyl, R31R32N or R33R34NC(O); wherein R31, R32, R33 and R34 are, independently, hydrogen or Q_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
(Q.6)alkyl groups. When heterocyclic rings are formed by joining two groups on an N atom, the resulting rings are suitably pyrrolidine, piperidine, thiomorpholine and morpholine each of which may be substituted by one or two independently selected (Q.6) alkyl groups. Preferably the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, HO2C, CMO alkoxy (itself optionally substituted by C O alkoxy), aryl(Q_ )alkoxy, CM O alkylthio, Q_ι0 alkylcarbonyl, CMO alkoxycarbonyl, Q-6 alkylaminocarbonyl, di(Q_6 alkylaminocarbonyl, (Q.6)alkylcarbonyloxy, optionally substituted phenyl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl, heterocyclyloxy, C3.7 cycloalkyl (itself optionally substituted with (Q_6)alkyl or halogen), Q- cycloalkyloxy, Q_7 cycloalkenyl, Q_6 alkylsulfonyl, Q-6 alkylsulfinyl, tri(Q- )alkylsilyl, tri(Ci.4)alkylsilyl(Ci.6)alkoxy, aryldi(Cι-4)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 Q.6 alkyl.
Preferably the optional substituents for cycloalkyl include halogen, cyano and Q.3 alkyl. Preferably the optional substituents for cycloalkenyl include Q.3 alkyl, halogen and cyano.
In a further aspect, the present invention provides a compound of formula (LA):
Figure imgf000015_0001
wherein A, D, E, G, J, L, M, Q, R1, R3, R4 and R5 are as defined above for a compound of formula (I).
A is preferably Ci.6 alkylene, Q_6 alkenylene, Q_6 alkylenoxy, oxy(Q.6)alkylene, Q.6 alkylenamino or Q-6 alkylenethio, each of which is optionally substituted by Q_3 alkyl, Q.3 haloalkyl, Cι_3 cyanoalkyl, halogen, Cι_3 alkoxy, Q_6 alkoxycarbonyl, cyano, hydroxy, =O,
=NR23 or =CR24R25. More preferably A is Q- alkylene (optionally substituted by halogen Cι_3 alkyl, Q_3 alkoxy, hydroxy or halogen), -C(O)- or Cι-4 alkyleneoxy (optionally substituted by Q-3 alkyl,
Q-3 alkoxy, hydroxy or halogen).
A is yet more preferably Q_ alkylene (optionally substituted by halogen, Q-3 alkyl or
Cι_3 alkoxy), -C(O)- or C1- alkyleneoxy (which may be optionally substituted by Q_3 alkyl). It is even more preferred that A is Q_ alkyl-substituted Q_ alkylene, fluoro- substituted Q. alkylene, methoxy-substituted Q. alkylene, -C(O)- or Q_4 alkyleneoxy; still more preferably A is Q_2 alkyl-substituted Cι_ alkylene, fluoro-substituted C]_ alkylene or methoxy-substituted Q- alkylene. It is further preferred that A is CH(CH3)CH2, CH2CH(CH3), CH(CH3), CHF, CH(OCH3) or CH(CH3)O; even further preferred that A is CH(CH3)CH2, CH2CH(CH3), CH(CH3), CHF or CH(CH3)O; especially preferred that A is CHF, CH(OCH3) or CH(CH3); and most preferably A is CHF or CH(CH3). D is preferably S.
Preferably E is N or CR2 where R2 is hydrogen, halogen, Q. alkyl, Q_6 haloalkyl, Q.6 alkoxy, Q.6 haloalkoxy, Q.6 alkoxy(Q.6)alkyl, Q.6 alkylthio or SF5; or R1 and R2 together with the atoms to which they are attached form a benzene ring optionally substituted by Q.6 alkyl,Q-6 haloalkyl or halogen. Preferably G, J, L and Q are, independently, N, N-oxide or CR6 with the proviso that neither are all N, nor are all N-oxide and nor are all CR6; where more than one of G, J, L and Q is CR6, R6 can be the same or different.
More preferably G, J, L and Q are, independently, N or CR6 with the proviso that neither are all N nor are all CR6; where more than one of G, J, L and Q is CR6, R6 can be the same or different.
M is preferably N(R12)C(=Y) or N=C(SR9) where O or N is the atom of attachment to the ring containing E and D.
More preferably, M is N(R12)C(=O) where N is the atom of attachment to the ring containing E and D. M is even more preferably NR12C(=O). and R12 is hydrogen, Q_6 alkyl, Q.6 alkoxy(Q.6 )alkyl, benzyloxymethyl or benzoyloxymethyl.where R12 is hydrogen, Q.4 alkyl, .4 alkoxy(Q.4)alkyl, benzyloxymethyl or benzoyloxymethyl. Y is preferably O or S. More preferably Y is O. Preferred values of R1 are hydrogen, halogen, Q_6 alkyl, _6 alkenyl, .6 alkynyl, Q.
6 cyanoalkyl, Q_6 haloalkyl, Q.6 alkoxy, Q_6 haloalkoxy, Q.6 alkylthio, Q_6 haloalkylthio, . cycloalkyl, C3.7 cycloalkyl(Q.4)alkyl, Q_6 alkoxy(Q.6)alkyl, cyano, nitro or SF5.
R1 is more preferably hydrogen, halogen, Q.6 alkyl, Q.6 alkenyl, Q.6 haloalkyl, Q_6 alkoxy, Q_6 haloalkoxy, Q-6 alkylthio, Q.6 haloalkylthio, -6 cycloalkyl, cyano, nitro or SF5;
It is most preferred that R1 is halogen, Q.6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Q.6 haloalkoxy. R2 is preferably hydrogen, halogen, Q_6 alkyl, C2-6 alkenyl, Q.6 alkynyl, Q. haloalkyl, Ci.6 alkoxy, Q.6 alkoxy (Q.6)alkyl, Q.6 haloalkoxy, Q.6 alkylthio, Q.6 haloalkylthio, Q-6 alkylsulfinyl, Ci_6 haloalkylsulfmyl, Q_ alkylsulfonyl, Ci.6 haloalkylsulfonyl, cyano, nitro, formyl, CH=NOR16, Ci_6 alkylcarbonyl, Q-6 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 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 Q_6 alkyl, Q_6 haloalkyl or halogen.
It is further preferred that R2 is hydrogen, halogen, Q_6 alkyl, Q-6 haloalkyl, Q_6 alkoxy (Q-6)alkyl, Q_6 alkoxy, Q_6 haloalkoxy, Q_6 alkylthio or SF5; or R1 and R2 together with the atoms to which they are attached form a cyclopentane or benzene ring optionally substituted by Q.6 alkyl, Q.6 haloalkyl or halogen.
R2 is even more preferably hydrogen, halogen, Q_6 alkyl, Q-6 haloalkyl, Q-6 alkoxy, Ci.6 haloalkoxy, Q.6 alkoxy(Q-6)alkyl, Q.6 alkylthio or SF5; or R1 and R2 together with the atoms to which they are attached form a benzene ring optionally substituted by Q.6 alkyl, Ci-6 haloalkyl or halogen; or alternatively the ring may be a cyclopentane ring.
It is further preferred that R2 is hydrogen, halogen, Q-6 alkyl, Q-6 haloalkyl, Q.6 alkoxy(Q-6)alkyl, Ci.6 alkoxy, Q.6 haloalkoxy, or R1 and R2 together with the atoms to which they are attached form a cyclopentane ring optionally substituted by Q_6 alkyl, Q_6 haloalkyl or halogen.
R2 is most preferably halogen, Q.6 alkyl, Q_6 haloalkyl, Q.6 alkoxy, Q.6 alkoxy(Q_6)alkyl or Q.6 haloalkoxy.
Preferably R3, R4 and R5 are independently selected from hydrogen, halogen, Q_6 alkyl, Q.6 alkoxy, Q-6 haloalkoxy, Q-6 alkylthio, Q.6 haloalkylthio, Q.6 alkylsulfinyl, Q.6 haloalkylsulfinyl, Q-6 alkylsulfonyl, .6 haloalkylsulfonyl, Q.6 haloalkyl, cyano, nitro, Q-6 alkylcarbonyl, Q_6 alkoxycarbonyl or SF5.
It is more preferred that R3, R4 and R5 are independently hydrogen, Q-3 alkyl or halogen.
Even more preferably R3, R4 and R5 are independently, hydrogen or halogen (especially fluorine); it is more especially preferred that each of R , R and R5 is hydrogen.
It is preferred that R6 is cyano, Q-8 alkyl, Q-8 haloalkyl, Q.8 cyanoalkyl, Q_7 cycloalkyl (Cι-6)alkyl, Q_6 cycloalkenyl(Q-6)alkyl, Q. alkoxy(Q_6)alkyl, C3.6 alkenyloxy(Q-6)alkyl, C3.6 alkynyloxy(Q-6)alkyl, aryloxy(Cι.6)alkyl, Q.6 carboxyalkyl, Q.6 alkylcarbonyl(Cι.6)alkyl, C _6 alkenylcarbonyl(Q.6)alkyl, C2.6 alkynylcarbonyl(C].6)alkyl, Cι.6 alkoxycarbonyl(Ci.6)alkyl, C3.6 alkenyloxycarbonyl(Q_6)alkyl, C3.6 alkynyloxycarbonyl(Cι.6)alkyl, aryloxycarbonyl(Q-6)alkyl, Q.6 alkylthio(Q_6)alkyl, Ci-6 alkylsulfinyl(Ci_6)alkyl, Q_6 alkylsulfonyl(Ci_6)alkyl, aminocarbonyl(Q-6)alkyl, Q.6 alkylaminocarbonyl (C i .6)alkyl, di(C i .6)alkylaminocarbonyl(C i .6)alkyl, phenyl(C i .4)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), heteroaryl (Q_ )alkyl (where the heteroaryl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q-6 alkoxy or Q_6 haloalkoxy), heterocyclyl (Q_ )alkyl (where the heterocyclyl group is optionally substituted by halo, cyano, Q_6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), C2.6 alkenyl, Q.6 haloalkenyl, Q_6 cyanoalkenyl, -6 cycloalkenyl, aminocarbonyl(C2_6)alkenyl, Q_6 alkylaminocarbonyl(Q-6)alkenyl, di(Q-6)alkylaminocarbonyl(Q.6)alkenyl, phenyl(C2_4)alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q-6 alkyl, Q_6 haloalkyl, Q-6 alkoxy or Q_6 haloalkoxy), Q-6 alkynyl, aminocarbonyl(C2-6)alkynyl, alkylaminocarbonyl(Q-6)alkynyl, di(Ci_6)alkylaminocarbonyl(Cι-6)alkynyl, C3-7 cycloalkyl, C3.7 halocycloalkyl, C3-7 cyanocycloalkyl, Cι_3 alkyl(C3-7)cycloalkyl, Q_3 alkyl(C3.7)halocycloalkyl, C5.6 cycloalkenyl, formyl, Q_6 alkoxycarbonyl, Ci-6 alkylcarbonyl, aminocarbonyl, Q-6 alkylaminocarbonyl, di(Q_6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q-6 alkoxy or Q.6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q_6 haloalkyl, Q-6 alkoxy or Ci-6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q.6 haloalkoxy), Q.8 alkylthio, R,8O, R19R20N or R21ON=C(R22). It is further preferred that R6 is Q_8 alkyl, Q.8 haloalkyl, Q.8 cyanoalkyl, Q.7 cycloalkyl(Q-6)alkyl, C5_6 cycloalkenyl(Q.6)alkyl, Q.6 alkoxy(Q.6)alkyl, C3_6 alkenyloxy(Q.6)alkyl, C3.6 alkynyloxy(Q_6)alkyl, aryloxy(Q.6)alkyl, Cι-6 carboxyalkyl, Q_6 alkylcarbonyl(Q.6)alkyl, C .6 alkenylcarbonyl(Q_6)alkyl, C2.6 alkynylcarbonyl(C!-6)alkyl, Q.6 alkoxycarbonyl(Q_6)alkyl, C3-6 alkenyloxycarbonyl(Q_6)alkyl, C3_6 alkynyloxycarbonyl- (Cι.6)alkyl, aryloxycarbonyl(Cι-6)alkyl, Q-6 a]kylthio(Q_6)alkyl, Q-6 alkylsulfinyl(Q-6)alkyl, C)_6 alkylsulfonyl(Cι_6)alkyl, aminocarbonyl(Q-6)alkyl, Cι-6 alkylaminocarbonyl(Q-6)alkyl, di(Ci_6)alkylaminocarbonyl(Cι-6)alkyl, phenyl(C1.4)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Q.6 haloalkoxy), heteroaryl(Q_4)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Ci-6 alkoxy or Q-6 haloalkoxy), heterocyclyl- (Q-4)alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q. 6 alkyl, Q_6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), C2.6 alkenyl, _6 haloalkenyl, Q.6 cyanoalkenyl, _6 cycloalkenyl, aminocarbonyl(C2-6)alkenyl, Q.6 alkylaminocarbonyl(Q.6)- alkenyl, di(Q6)alkylaminocarbonyl(Q.6)alkenyl, phenyl(C2_4)alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q-6 haloalkyl, Q_6 alkoxy or Ci-6 haloalkoxy), -6 alkynyl, aminocarbonyl(Q_6)alkynyl, alkylaminocarbonyl(Q_6)alkynyl, di(Ci-6)alkylaminocarbonyl(Cι.6)alkynyl, C3_7 cycloalkyl, C3-7 halocycloalkyl, C3.7 cyanocycloalkyl, Q-3 alkyl(C3_7)cycloalkyl, Cι-3 alkyl(C3_7)halocycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q-6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Q-6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), Q_8 alkylthio, R18O, R19R20N or R21ON=C(R22). R6 is more preferably .8 alkyl, Q-8 haloalkyl, Q_8 cyanoalkyl, C2.6 alkenyl, _6 alkynyl, C3.7 cycloalkyl, C3.7 halocycloalkyl, Q-7 cyanocycloalkyl, Cι_3 alkyl(C3_ )cycloalkyl, Ci_3 alkyl(Q_7)halocycloalkyl, C5.6 cycloalkenyl, C3.7 cycloalkyl(Cι.6)alkyl, _6 cycloalkenyl(Cι-6)alkyl, C2_6 haloalkenyl, Q_6 cyanoalkenyl, Q.6 alkoxy(Q.6)alkyl, C3_6 alkenyloxy(Q_6)alkyl, C3_6 alkynyloxy(Cι.6)alkyl, aryloxy(Ci-6)alkyl, Q-6 carboxyalkyl, Q.6 alkylcarbonyl(Cι.6)alkyl, C2_6 alkenylcarbonyl(Cι_6)alkyl, C2_6 alkynylcarbonyl(Q_6)alkyl, C1.6 alkoxycarbonyl(Cι_6)alkyl, C3_6 alkenyloxycarbonyl(Q_6)alkyl, C3.6 alkynyloxycarbonyl(Q.6)alkyl, aryloxycarbonyl(Cι_6)alkyl, C1. alkyl thio(Q.6)alkyl, Q-6 alkylsulfinyl(Cι-6)alkyl, Cι_6 alkylsulfonyl(Q.6)alkyl, aminocarbonyl (Q.6)alkyl, aminocarbonyl(C2-6)alkenyl, aminocarbonyl(C2_6)alkynyl, Q-6 alkylaminocarbonyl(Q_6)alkyl, di(Cι.6)alkylaminocarbonyl(Q_6)alkyl, Cι.6 alkylaminocarbonyl(Cι.6)alkenyl, di(Cι.6)alkylaminocarbonyl(Cι.6)alkenyl, alkylaminocarbonyl(Q.6)alkynyl, di(Q.6)alkylaminocarbonyl(Q_6)alkynyl, phenyl (optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q-6 alkoxy or Q_6 haloalkoxy), phenyl(Q_4)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q-6 alkyl, Q.6 haloalkyl, Q_ alkoxy or C ι.6 haloalkoxy), phenyl(Q. )alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q-6 alkyl, Q-6 haloalkyl, Q-6 alkoxy or Cι-6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q-6 haloalkyl, Q_6 alkoxy or Ci-6 haloalkoxy), heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_ alkoxy or Q_6 haloalkoxy), heteroaryl(Q-4)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Ci-6 alkoxy or Q_6 haloalkoxy), heterocyclyl (Q.4)alkyl
(wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q-6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), R18O, Q_8 alkylthio, R19R20N or R21ON=C(R22); and R6 is still more preferably Q_8 alkyl, Q.8 haloalkyl, Q_8 cyanoalkyl, C3.7 cycloalkyl, Q-3 alkyl(C3_7)cycloalkyl, Ci-6 alkoxy(Ci_6)alkyl, heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Ci-6 haloalkyl, Q. alkoxy or Q.6 haloalkoxy) or R19R20N.
It is even more preferred that R is Q.8 alkyl, Q.8 haloalkyl, .8 cyanoalkyl, Q_6 alkoxy (Q-ό) alkyl, Q-7 cycloalkyl, Q-3 alkyl (C3.7) cycloalkyl, heterocyclyl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q-6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy) or di(Q_8)alkylamino.
It is yet more preferred that R6 is Q.8 alkyl, Q.8 haloalkyl, Q_8 cyanoalkyl, Q-6 alkoxy (Q_6) alkyl, Q. cycloalkyl, Q_3 alkyl (C3.7) cycloalkyl, heterocyclyl (optionally substituted by Q.6 alkyl) or di(Ci.8)alkylamino.
R6 is yet more preferably Q_8 alkyl, Q_8 haloalkyl, Cι-8 cyanoalkyl, Q.7 cycloalkyl,
Q-3 alkyl(C3.7)cycloalkyl, Q.6 alkoxy(Q.6)alkyl or R19R20N; where R19 andR20 are, independently, Ci_8 alkyl or together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one further heteroatom selected from O, N or S and which may be optionally substituted by one or two Q_6 alkyl groups. R6 is most preferably Q_8 alkyl, Q_6 haloalkyl, Q_6 alkoxy, Q.7 cycloalkyl or Q. cyclalkyl(Q.7) alkyl.
It is preferred that R8 is CMO alkyl, C O haloalkyl, _6 alkenyl (Q_6)alkyl, -6 alkynyl(Q_6)alkyl, C3_7 cycloalkyl, Q.6 alkylamino, di(Q.6)alkylamino or phenyl(Q_4)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Q.6 haloalkoxy). It is more preferred that R is Q_6 alkyl, Q.6 haloalkyl, .6 alkenyl (Q-ό)alkyl, -6 alkynyl (Q_6)alkyl or benzyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Ci.6 haloalkyl, Q. alkoxy or Q_6 haloalkoxy).
It is preferred that R9 is C O alkyl, C O haloalkyl, C2-6 alkenyl(Q_6)alkyl, _6 alkynyl(Q_6)alkyl, C3.7 cycloalkyl, CMO alkylthio(Q_ι0)alkyl, Q.io alkoxycarbonyl, CMO alkoxycarbonyl(Q_ιo)alkyl or phenyl(Q. )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q-6 haloalkyl, Q-6 alkoxy or Q_6 haloalkoxy), It is more preferred that R9 is Q.io alkyl, Q.6 haloalkyl, _6 alkenyl(Q-6)alkyl, -6 alkynyl (Ci_6)alkyl, Q_6 alkylthio(Q_6)alkyl, CMO alkoxycarbonyl, Q_6 alkoxycarbonyl(Q-6)alkyl or benzyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q-6 alkoxy or Q.6 haloalkoxy).
R9 is even more preferably CMO alkyl, Q.6 alkyl thio(Cι.6)alkyl, _6 alkenyl(Q_ 6)alkyl (especially allyl), C2.6 alkynyl(Cι.6)alkyl (especially propargyl), benzyl, Q.6 alkoxycarbonyl(Cι-6)alkyl or Q.io alkoxycarbonyl (especially wøbutoxycarbonyl). R9 is most preferably CMO alkyl, Q.6 alkylthio(Q.6)alkyl, C2_6 alkenyl(Q_6)alkyl
(especially allyl), C2-6 alkynyl (Q.6)alkyl (especially propargyl), benzyl or Q_6 alkoxycarbonyl(Q.6)alkyl.
It is preferred that R10 is Q.io alkyl, C2-6 alkenyl(Q_6)alkyl, C2-6 alkynyl(Q.6)alkyl, C3-7 cycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q_6 haloalkoxy), Q_ιo haloalkyl, Cι_6 alkoxy(Q_6)alkyl, C3. cycloalkyl(Cι_ δ)alkyl, Ci-6 alkylcarbonylamino, Q_6 alkoxycarbonylamino, Cι_6 alkylaminocarbonylamino, Q.6 alkylcarbonyloxy, Ci-6 alkoxycarbonyloxy, Cι_6 alkylaminocarbonyloxy, Q.6 alkoxy, Q. 6 alkylamino, di(Q_6)alkylamino, hydroxy, phenoxy (optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q_6 haloalkyl, Cι.6 alkoxy or Q.6 haloalkoxy), hydroxy(Ci_6)alkyl, hydroxy(C i _6)alkylamino or carboxy(C i .6)alkoxy.
It is more preferred that R10 is Q_6 alkyl, C2.6 alkenyl(Cι.6)alkyl, C2.6 alkynyl(Q_6)- alkyl, C3.7 cycloalkyl, phenyl, Q.6 haloalkyl, Q.6 alkoxy(C].6)alkyl, Cι_6 alkylcarbonylamino, Q.6 alkoxycarbonylamino, Q.6 alkoxy, Q_6 alkylamino, di(Q_6)alkylamino, hydroxy, phenoxy, hydroxy(Q_6)alkyl, hydroxy(Cι_6)alkylamino or carboxy(Q_6)alkoxy. It is preferred that R1 ' is CMO alkyl, C2.6 alkenyl(Q.6)alkyl, C2.6 alkynyl(Q.6)alkyl,
C3.7 cycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, Q-6 alkyl, Q_6 haloalkyl, .6 alkoxy or Q.6 haloalkoxy), Q.10 haloalkyl, Q.6 alkoxy(Q.6)alkyl or C3-7 cycloalkyl(Cι. 6)alkyl.
It is more preferred that R11 is Q_ιo alkyl, .6 alkenyl (Q^)alkyl, C2.6 alkynyl(C].6)alkyl, C3.7 cycloalkyl, phenyl, CMO haloalkyl, Q_6 alkoxy(Q.6)alkyl or C3.7 cycloalkyl(Q.6)alkyl.
It is preferred that R12 is hydrogen, CMO alkyl, C2_6 alkenyl(Cι_6)alkyl, C2.6 alkynyl- (Q-6)alkyl, C3.7 cycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q_6 haloalkyl, Ci.6 alkoxy or Q.6 haloalkoxy), C O haloalkyl, Q.6 alkoxy(Q.6)alkyl or C3-7 cycloalkyl(Cι.6)alkyl. It is more preferred that R12 is hydrogen, CMO alkyl, _6 alkenyl(Q_6)alkyl, C _6 alkynyl(Cι_6)alkyl, C3.7 cycloalkyl, phenyl, Ci.io haloalkyl, Q. alkoxy (Q.6) alkyl benzyloxymethyl or benzoyloxymethyl or C3.7 cycloalkyl(Q.6)alkyl.
R12 is even more preferebly hydrogen, Q_6 alkyl, Ci. alkoxy(Q.6 )alkyl, benzyloxymethyl or benzoyloxymethyl. R12 is most preferably hydrogen, Q_6 alkyl or Cj-6 alkoxy (Q.6 )alkyl.
R13 is preferably cyano, nitro, Q_6 alkyl, Q.6 haloalkyl, C3-7 cycloalkyl, C3.7 cycloalkyl(Q_6)alkyl, CH2(C2.ό) alkenyl, CH2(C2_6)alkynyl, phenyl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or C).6 haloalkoxy) heteroaryl (optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q.6 haloalkoxy), Q_6 alkylcarbonyl, Q. alkoxycarbonyl, Q_6 alkylamino, di(Q_6)alkylamino, Ci. alkylcarbonylamino, Q.6 alkoxycarbonylamino, Cι_6 alkoxy, Q_6 alkylthio, Q. alkylsulfinyl, Ci.6 alkylsulfonyl, Q_6 haloalkylthio, Q.6 haloalkylsulfinyl, Q_6 haloalkylsulfonyl, arylthio, arylsulfinyl, arylsulfonyl or OCO(Q_6)alkyl.
It is preferred that R13 is CMO alkyl, Q.6 alkenyl(Cι_6)alkyl, C2.6 alkynyl (Cι_6)alkyl, Q.7 cycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), CMO haloalkyl, Q.6 alkoxy(Q.6)alkyl, Q_7 cycloalkyl(Q. 6)alkyl, Q_6 alkylcarbonylamino, Q_6 alkoxycarbonylamino, Cι_6 alkylaminocarbonylamino, Ci-6 alkylcarbonyloxy, Cι.6 alkoxycarbonyloxy, Q_6 alkylaminocarbonyloxy, Cι_6 alkoxy, Cι_ 6 alkylamino, di(Q_6)alkylamino, hydroxy, phenoxy (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q-6 haloalkoxy), hydroxy(Cι_6)alkyl, hydroxy(C].6)alkylamino or carboxy(Cι_6)alkoxy. It is more preferred that R13 is Ci.6 alkyl, -6 alkenyl(Q.6)alkyl, C2.6 alkynyl(Q. 6)alkyl, C3.7 cycloalkyl, phenyl, Q-6 haloalkyl, Q.6 alkoxy(Cι.6)alkyl, Q_6 alkylcarbonylamino, Q_6 alkoxycarbonylamino, Cι_6 alkoxy, Cι_6 alkylamino, di(Q.6)alkylamino, hydroxy, phenoxy, hydroxy(Cι.6)alkyl, hydroxy(Q_6)alkylamino or carboxy(Ci_6)alkoxy.
Preferably R14 and R15 independently, are hydrogen, halogen, Q.6 alkyl, Q_6 haloalkyl -6 alkenyl, Ci.6 alkynyl, Q_6 alkoxy or Cι-6 haloalkoxy.
Preferably R16 and R21 independently, are, Q_6 alkyl or phenyl(Cι-2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or C i .6 haloalkoxy) .
Preferably R17 is hydrogen or Q.3 alkyl.
R18 is preferably hydrogen, Q.8 alkyl, Q.6 haloalkyl, Q.6 cyanoalkyl, C2.6 alkenyl, .6 alkynyl, Q.6 alkoxy(Q_6)alkyl, phenyl (Q_ )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), heteroaryl(Q_ )alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, .6 alkyl, .6 haloalkyl, .6 alkoxy or Q-6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q-6 haloalkyl, .6 alkoxy or Q-6 haloalkoxy), heterocyclyl(Q.4)alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q_ haloalkoxy), Q.6 alkoxycarbonyl(Q.6)alkyl or N=C(CH3)2.
More preferably R is hydrogen, Q_8 alkyl, Q.6 haloalkyl, Q.6 cyanoalkyl, Q.6 alkoxy(Q.6)alkyl, phenyl(Q_4)alkyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q-6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Q.6 haloalkoxy), heteroaryl(Q_4)- alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Q. alkyl, .6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), heterocyclyl (Q_4)alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q_6 haloalkoxy), Q.6 alkoxycarbonyl(Q_6)alkyl, Q_6 alkenyl, Q.6 alkynyl or N=C(CH3)2; Even more preferably R is Q.8 alkyl, Q.6 haloalkyl;
Preferably R19 and R20 independently, are, hydrogen, Q.g alkyl, Q.7 cycloalkyl, _6 alkenyl, _6 alkynyl, Q_ cycloalkyl(Q. )alkyl, -6 haloalkyl, Q_6 alkoxy(Q_6)alkyl, Q-6 alkoxycarbonyl; or R19 and R20 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q-6 alkyl groups. More preferably R19 and R20 are, independently, hydrogen, Q.8 alkyl, Q_7 cycloalkyl, -6 alkenyl, C3.6 alkynyl, Q-7 cycloalkyl(Q_4)alkyl, Q.6 haloalkyl, Q_6 alkoxy(Q.6)alkyl or Q.6 alkoxycarbonyl.
Even more preferably R19 and R20 are, independently, Q.8 alkyl.
Preferably R21 is phenyl (Q.2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Q_6 haloalkoxy) or Q_6 alkyl.
Preferably R22 is Q-6 alkyl, Q_6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, Q-6 alkyl, Q_6 haloalkyl, Q.6 alkoxy or Q_6 haloalkoxy).
Preferably R23 is Q.6 alkyl, OR26 or NR27R28.
R24 is preferably hydrogen, Q.6 alkyl or Q.6 haloalkyl. Preferably R25 is hydrogen, Q_6 alkyl, Q.6 haloalkyl, Q.6 alkoxy, cyano, Q.6 alkoxycarbonyl, Cι_6 alkylcarbonyl or NR R .
Preferably R26 is Q_6 alkyl or optionally substituted phenyl(Q.2)alkyl. Preferably R27 and R28 independently, are, hydrogen, Q.8 alkyl or phenyl (optional substituted by halo, nitro, cyano, Q_6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Q.6 haloalkoxy).
Preferably R29 and R30 independently, are, hydrogen, Q.8 alkyl, Q_7 cycloalkyl, Q_6 alkenyl, C3-6 alkynyl, C2-6 haloalkyl, Q_6 alkoxy(Cι.6)alkyl, Cι-6 alkoxycarbonyl(Q.6)alkyl, carboxy(Q.6)alkyl or phenyl(Cι_2)alkyl; or R and R together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q.6 alkyl groups.
Preferably R36 and R37 independently, are, hydrogen, Q.6 alkyl, CH2(Q-4 haloalkyl), Q-6 cyanoalkyl, Q.6 alkoxy(Q.6)alkyl, Q_6 alkylthio(Q-6)alkyl, Q.6 alkoxy(Q_6)alkoxy(Q. 6)-alkyl, phenyl(Q.4)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_ alkyl, Q_6 haloalkyl, Q_6 alkoxy or Q-6 haloalkoxy), heteroaryl(Q_4)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q.6 haloalkyl, Q_6 alkoxy or Ci-6 haloalkoxy), heterocyclyl(Q. )alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q-6 haloalkyl, Q.6 alkoxy or Q-6 haloalkoxy); or R36 and R 7 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q_6 alkyl groups.
More preferred optionally substituted rings of formula (where Z is the point of attachment to M)
Figure imgf000025_0001
include optionally substituted isothiazolyl, optionally subsituted pyridyl, optionally substituted pyrimidinyl, optionally substituted quinazolinyl and optionally substituted quinolinyl groups in which the optional substituents are chosen from halo, Q-6 alkyl, Q-6 haloalkyl, Q_6 alkoxy, Q.6 alkoxy(Cι.6)alkyl or Q-6 haloalkoxy. Especially preferred substituted rings of formula
Figure imgf000025_0002
are:
Figure imgf000026_0001
Particularly preferred optionally substituted fused rings of the formula
Figure imgf000026_0002
are
Figure imgf000026_0003
Figure imgf000026_0004
The compounds in Tables 1 to 134 illustrate compounds of the invention. Table 1 provides 160 compounds of formula (1):
Figure imgf000027_0001
wherein R1, R12 and R6 are as defined in Table 1.
Table 1
Figure imgf000027_0002
Table 1 Continued
Figure imgf000028_0001
Table 1 Continued
Figure imgf000029_0001
Figure imgf000030_0001
Table 1 Continued
Figure imgf000031_0003
Table 2 provides 160 compounds of formula (2):
Figure imgf000031_0001
wherein R , R and R are as defined in Table 1.
Table 3 provides 160 compounds of formula (3):
Figure imgf000031_0002
wherein R1, R12 and R6 are as defined in Table 1.
Figure imgf000032_0002
Figure imgf000032_0001
m
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0002
Figure imgf000035_0001
Figure imgf000036_0001
wherein R , R and R are as defined in Table 1.
Table 8 provides 160 compounds of formula (8):
Figure imgf000036_0002
wherein R , R " and R are as defined in Table 1.
Table 9 provides 144 compounds of formula (9):
Figure imgf000036_0003
wherein R1, R12 and R6 are as defined in Table 4.
Table 10 provides 160 compounds of formula (10):
Figure imgf000036_0004
wherein R1, R1"" and R are as defined in Table 1.
Table 11 provides 160 compounds of formula (11):
Figure imgf000036_0005
wherein R , R ~ and R are as defined in Table 1. Table 12 provides 160 compounds of formula (12):
Figure imgf000037_0001
wherein R1, R12 and R6 are as defined in Table 1.
Table 13 provides 160 compounds of formula (13):
Figure imgf000037_0002
wherein R1, R12 and R6 are as defined in Table 1.
Table 14 provides 144 compounds of formula (14):
Figure imgf000037_0003
wherein R , R and R are as defined in Table 4.
Table 15 provides 160 compounds of formula (15):
Figure imgf000037_0004
wherein R1, R12 and R6 are as defined in Table 1.
Table 16 provides 160 compounds of formula (16):
Figure imgf000038_0001
wherein R
Figure imgf000038_0002
are as defined in Table 1.
Table 17 provides 160 compounds of formula (17):
Figure imgf000038_0003
wherein R1, R1 and R are as defined in Table 1.
Table 18 provides 160 compounds of formula (18):
Figure imgf000038_0004
wherein R1, R12 and R6 are as defined in Table 1.
Table 19 provides 144 compounds of formula (19):
Figure imgf000038_0005
wherein R1, R12 and R6 are as defined in Table 4.
Table 20 provides 160 compounds of formula (20):
Figure imgf000038_0006
wherein R1, R12 and R6 are as defined in Table 1. Table 21 provides 160 compounds of formula (21):
Figure imgf000039_0001
wherein R , R and R are as defined in Table 1.
Table 22 provides 160 compounds of formula (22):
Figure imgf000039_0002
wherein R1, R12 and R6 are as defined in Table 1.
Table 23 provides 160 compounds of formula (23):
Figure imgf000039_0003
wherein R , R12 and R are as defined in Table 1.
Table 24 provides 144 compounds of formula (24):
Figure imgf000039_0004
wherein R1, R12 and R6 are as defined in Table 4.
Table 25 provides 160 compounds of formula (25):
Figure imgf000039_0005
O 01/55140 O
- JO -
wherein R , R and R are as defined in Table 1.
Table 26 provides 160 compounds of formula (26):
Figure imgf000040_0001
wherein R1, R12 and R6 are as defined in Table 1. Table 27 provides 160 compounds of formula (27):
Figure imgf000040_0002
wherein R1, R12 and R6 are as defined in Table 1.
Table 28 provides 160 compounds of formula (28):
Figure imgf000040_0003
wherein R1, R12 and R are as defined in Table 1.
Table 29 provides 160 compounds of formula (29):
Figure imgf000040_0004
wherein R , R and R are as defined in Table 1.
Table 30 provides 144 compounds of formula (30):
Figure imgf000041_0001
wherein R1, R12 and R6 are as defined in Table 4.
Table 31 provides 160 compounds of formula (31):
Figure imgf000041_0002
wherein R1, R12 and R6 are as defined in Table 1.
Table 32 provides 160 compounds of formula (32):
Figure imgf000041_0003
wherein R1, R12 and R6 are as defined in Table 1.
Table 33 provides 160 compounds of formula (33):
Figure imgf000041_0004
wherein R1, R12 and R6 are as defined in Table 1.
Table 34 provides 160 compounds of formula (34):
Figure imgf000041_0005
wherein R1, R12 and R6 are as defined in Table 1. Table 35 provides 144 compounds of formula (35):
Figure imgf000042_0001
wherein R1, R12 and R6 are as defined in Table 4.
Table 36 provides 160 compounds of formula (36):
Figure imgf000042_0002
wherein R . 1 , R , 12 and R are as defined in Table 1.
Table 37 provides 160 compounds of formula (37):
Figure imgf000042_0003
wherein R , R " and R are as defined in Table 1.
Table 38 provides 160 compounds of formula (38):
Figure imgf000042_0004
wherein R1, R12 and R6 are as defined in Table 1.
Table 39 provides 160 compounds of formula (39):
Figure imgf000042_0005
wherein R1, R12 and R6 are as defined in Table 1.
Table 40 provides 144 compounds of formula (40):
Figure imgf000043_0001
wherein R1, R12 and R6 are as defined in Table 4.
Table 41 provides 160 compounds of formula (41):
Figure imgf000043_0002
wherein R , 1 , R12 and R are as defined in Table 1.
Table 42 provides 160 compounds of formula (42):
Figure imgf000043_0003
wherein R . 1 , R .12 and R are as defined in Table 1.
Table 43 provides 160 compounds of formula (43):
Figure imgf000043_0004
wherein R . 1 , r R1 " and R are as defined in Table 1.
Table 44 provides 160 compounds of formula (44):
Figure imgf000044_0001
wherein R1, R12 and R6 are as defined in Table 1.
Table 45 provides 144 compounds of formula (45):
Figure imgf000044_0002
wherein R ,ι , R .12 and R are as defined in Table 4.
Table 46 provides 160 compounds of formula (46):
Figure imgf000044_0003
wherein R , R and R are as defined in Table 1.
Table 47 provides 160 compounds of formula (47):
Figure imgf000044_0004
wherein R1, R12 and R6 are as defined in Table 1.
Table 48 provides 160 compounds of formula (48):
Figure imgf000044_0005
wherein R , R , 12 ~ and R are as defined in Table 1. Table 49 provides 160 compounds of formula (49):
Figure imgf000045_0001
wherein R1, R12 and R6 are as defined in Table 1.
Table 50 provides 144 compounds of formula (50):
Figure imgf000045_0002
wherein R1, R12 and R6 are as defined in Table 4.
Table 51 provides 160 compounds of formula (51):
Figure imgf000045_0003
wherein R1, R12 and R6 are as defined in Table 1.
Table 52 provides 160 compounds of formula (52):
Figure imgf000045_0004
wherein R , R ~ and R are as defined in Table 1.
Table 53 provides 160 compounds of formula (53):
Figure imgf000046_0001
wherein R1, R12 and R6 are as defined in Table 1.
Table 54 provides 160 compounds of formula (54):
Figure imgf000046_0002
wherein R1, R12 and R6 are as defined in Table 1.
Table 55 provides 160 compounds of formula (55):
Figure imgf000046_0003
wherein R1, R12 and R6 are as defined in Table 1.
Table 56 provides 160 compounds of formula (56):
Figure imgf000046_0004
wherein R , R , 12 and R are as defined in Table 1.
Table 57 provides 160 compounds of formula (57):
Figure imgf000046_0005
wherein R , 1 , r R> 12 and R are as defined in Table 1. Table 58 provides 160 compounds of formula (58):
Figure imgf000047_0001
wherein R1, R12 and R6 are as defined in Table 1.
Table 59 provides 160 compounds of formula (59):
Figure imgf000047_0002
wherein R1, R12 and R6 are as defined in Table 1.
Table 60 provides 160 compounds of formula (60):
Figure imgf000047_0003
wherein R1, R12 and R6 are as defined in Table 1.
Table 61 provides 160 compounds of formula (61):
Figure imgf000047_0004
wherein R1, R12 and R6 are as defined in Table 1.
Table 62 provides 160 compounds of formula (62):
wherein R1, R12 and R6 are as defined in Table 1.
Table 63 provides 160 compounds of formula (63):
Figure imgf000048_0001
wherein R1, R12 and R6 are as defined in Table 1.
Table 64 provides 160 compounds of formula (64):
Figure imgf000048_0002
wherein R1, R12 and R6 are as defined in Table 1. Table 65 provides 160 compounds of formula (65):
Figure imgf000048_0003
wherein R1, R12 and R6 are as defined in Table 1.
Table 66 provides 160 compounds of formula (66):
Figure imgf000048_0004
wherein R1, R12 and R6 are as defined in Table 1.
Table 67 provides 160 compounds of formula (67):
Figure imgf000049_0001
wherein R , 1 , R .12 and R are as defined in Table 1.
Table 68 provides 160 compounds of formula (68):
Figure imgf000049_0002
wherein R1, R12 and R6 are as defined in Table 1.
Table 69 provides 160 compounds of formula (69):
Figure imgf000049_0003
wherein R , R , 12 and R are as defined in Table 1.
Table 70 provides 160 compounds of formula (70):
Figure imgf000049_0004
wherein R , R and R are as defined in Table 1.
Table 71 provides 160 compounds of formula (71):
Figure imgf000049_0005
wherein R , R , 12 and R are as defined in Table 1. Table 72 provides 160 compounds of formula (72):
Figure imgf000050_0001
wherein Rl, R51 and R6 are as defined in Table 1
Table 73 provides 160 compounds of formula (73):
Figure imgf000050_0002
wherein R1, R12 and R6 are as defined in Table 1.
Table 74 provides 160 compounds of formula (74):
Figure imgf000050_0003
wherein R , 1 , r R12 and R are as defined in Table 1.
Table 75 provides 160 compounds of formula (75):
Figure imgf000050_0004
wherein R ,ι , R , 12 and R are as defined in Table 1.
Table 76 provides 160 compounds of formula (76):
Figure imgf000050_0005
wherein R1, R12 and R6 are as defined in Table 1.
Table 77 provides 160 compounds of formula (77):
Figure imgf000051_0001
wherein R1, R12 and R6 are as defined in Table 1.
Table 78 provides 160 compounds of formula (78):
Figure imgf000051_0002
wherein R1, R12 and R6 are as defined in Table 1.
Table 79 provides 160 compounds of formula (79):
Figure imgf000051_0003
wherein R , 1 , R> 12 and R are as defined in Table 1.
Table 80 provides 160 compounds of formula (80):
Figure imgf000051_0004
wherein R1, R12 and R6 are as defined in Table 1.
Table 81 provides 160 compounds of formula (81):
Figure imgf000052_0001
wherein R1, R12 and R6 are as defined in Table 1.
Table 82 provides 160 compounds of formula (82):
Figure imgf000052_0002
wherein R1, R12 and R6 are as defined in Table 1.
Table 83 provides 160 compounds of formula (83):
Figure imgf000052_0003
wherein R , R and R are as defined in Table 1.
Table 84 provides 160 compounds of formula (84):
Figure imgf000052_0004
wherein R1, R12 and R6 are as defined in Table 1.
Table 85 provides 160 compounds of formula (85):
Figure imgf000052_0005
wherein R , 1 , D R12 and R are as defined in Table 1.
Table 86 provides 160 compounds of formula (86):
Figure imgf000053_0001
wherein R1, R12 and R6 are as defined in Table 1.
Table 87 provides 160 compounds of formula (87):
Figure imgf000053_0002
wherein R ,ι , R , 12 and R are as defined in Table 1.
Table 88 provides 160 compounds of formula (88):
Figure imgf000053_0003
wherein R1, R12 and R6 are as defined in Table 1.
Table 89 provides 160 compounds of formula (89):
Figure imgf000053_0004
wherein R1, R12 and R6 are as defined in Table 1.
Table 90 provides 160 compounds of formula (90):
Figure imgf000053_0005
wherein R1, R12 and R6 are as defined in Table 1.
Table 91 provides 160 compounds of formula (91):
Figure imgf000054_0001
wherein R1, R12 and R are as defined in Table 1.
Table 92 provides 160 compounds of formula (92):
Figure imgf000054_0002
wherein R1, R12 and R6 are as defined in Table 1.
Table 93 provides 160 compounds of formula (93):
Figure imgf000054_0003
wherein R1, R12 and R6 are as defined in Table 1.
Table 94 provides 160 compounds of formula (94):
Figure imgf000054_0004
wherein R1, R12 and R6 are as defined in Table 1.
Table 95 provides 160 compounds of formula (95):
Figure imgf000054_0005
wherein R1, R12 and R6 are as defined in Table 1.
Table 96 provides 160 compounds of formula (96):
Figure imgf000055_0001
wherein R1, R12 and R6 are as defined in Table 1.
Table 97 provides 160 compounds of formula (97):
Figure imgf000055_0002
wherein R ,ι , R , 12 and R are as defined in Table 1.
Table 98 provides 160 compounds of formula (98):
Figure imgf000055_0003
wherein R , R and R are as defined in Table 1.
Table 99 provides 160 compounds of formula (99):
Figure imgf000055_0004
wherein R1, R12 and R6 are as defined in Table 1.
Table 100 provides 160 compounds of formula (100):
Figure imgf000055_0005
wherein R1, R12 and R are as defined in Table 1.
Table 101 provides 160 compounds of formula (101):
Figure imgf000056_0001
wherein R1, R12 and R6 are as defined in Table 101.
Table 101
Figure imgf000056_0002
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0005
Table 102 provides 160 compounds of formula (102):
Figure imgf000060_0001
wherein R1, R12 and R6 are as defined in Table 101.
Table 103 provides 160 compounds of formula (103):
Figure imgf000060_0002
wherein R , R and R are as defined in Table 101.
Table 104 provides 160 compounds of formula (104):
Figure imgf000060_0003
wherein R1, R12 and R° are as defined in Table 101.
Table 105 provides 160 compounds of formula (105):
Figure imgf000060_0004
wherein R1, R12 and R6 are as defined in Table 101.
Table 106 provides 1 0 compounds of formula (106):
Figure imgf000061_0001
wherein R1, R12 and R6 are as defined in Table 101.
Table 107 provides 160 compounds of formula (107):
Figure imgf000061_0002
wherein R , R and R are as defined in Table 101.
Table 108 provides 160 compounds of formula (108):
Figure imgf000061_0003
wherein R ,ι , R , 12 and R are as defined in Table 101.
Table 109 provides 160 compounds of formula (109):
Figure imgf000061_0004
wherein R1, R12 and R6 are as defined in Table 101.
Table 110 provides 160 compounds of formula (110):
Figure imgf000062_0001
wherein R1, R12 and R6 are as defined in Table 101.
Table 111 provides 64 Compounds of formula (111):
Figure imgf000062_0002
wherein R1, R12, Ra and Rb are as defined in Table 111.
Table 111
Figure imgf000062_0003
Figure imgf000063_0001
Table 112 provides 64 Compounds of formula (112):
Figure imgf000064_0001
wherein R , 11, r R> 12 , D Raa and RD are as defined in Table 111.
Table 113 provides 64 Compounds of formula (113):
Figure imgf000064_0002
wherein R1, R12, Ra and Rb are as defined in Table 111.
Table 114 provides 64 Compounds of formula (114):
Figure imgf000064_0003
wherein R1, R12, Ra and Rb are as defined in Table 111.
Table 115 provides 64 Compounds of formula (115):
Figure imgf000064_0004
wherein r R> 12 , r R,aa and RD are as defined in Table 111.
Table 116 provides 64 Compounds of formula (116):
Figure imgf000064_0005
wherein R , 11, R> 1 , τ R_> a and RD are as defined in Table 111.
Table 117 provides 64 Compounds of formula (117):
Figure imgf000065_0001
wherein R1, R12, Ra and Rb are as defined in Table 111.
Table 118 provides 64 Compounds of formula (118):
Figure imgf000065_0002
wherein R , 11, R, 12 , r R,aa and RD are as defined in Table 111.
Table 119 provides 64 Compounds of formula (119):
Figure imgf000065_0003
wherein R1 , R12, Ra and Rb are as defined in Table 111.
Table 120 provides 160 compounds of formula (120)
Figure imgf000065_0004
wherein R , 1 , r R> 12 and R are as defined in Table 1
Table 121 provides 160 compounds of formula (121)
Figure imgf000066_0001
wherein R
Figure imgf000066_0002
are as defined in Table 1.
Table 122 provides 160 compounds of formula (122)
Figure imgf000066_0003
wherein R1, R12 and R6 are as defined in Table 1.
Table 123 provides 160 compounds of formula (123)
Figure imgf000066_0004
wherein R1, R12 and R6 are as defined in Table 1.
Table 124 provides 160 compounds of formula (124)
Figure imgf000066_0005
wherein R1, R12 and R6 are as defined in Table 1.
Table 125 provides 160 compounds of formula (125)
Figure imgf000066_0006
wherein R1, R12 and R6 are as defined in Table 1. Table 126 provides 160 compounds of formula (126)
Figure imgf000067_0001
wherein R1, R12 and R6 are as defined in Table 1.
Table 127 provides 160 compounds of formula (127)
Figure imgf000067_0002
wherein R1, R12 and R6 are as defined in Table 1.
Table 128 provides 160 compounds of formula (128)
Figure imgf000067_0003
wherein R , R and R are as defined in Table 1.
Table 129 provides 160 compounds of formula (129)
Figure imgf000067_0004
wherein R , R , 12 and R are as defined in Table 1.
Table 130 provides 160 compounds of formula (130)
Figure imgf000067_0005
wherein R1, R12 and R are as defined in Table 1.
Table 131 provides 160 compounds of formula (131)
Figure imgf000068_0001
wherein R1, R12 and R are as defined in Table 1.
Table 132 provides 160 compounds of formula (132)
Figure imgf000068_0002
wherein R1, R12 and R6 are as defined in Table 1. Table 133 provides 160 compounds of formula (133)
Figure imgf000068_0003
wherein R1, R12 and R6 are as defined in Table 1.
Table 134 provides 160 compounds of formula (134)
Figure imgf000068_0004
wherein R1, R12 and R are as defined in Table 1.
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 135 shows 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 / df,- DMSO)), (no attempt is made to list all characterising data in all cases) for compounds of Tables 1 to 134.
Table 135
Figure imgf000069_0001
Table 135 Continued
Figure imgf000070_0001
The compounds of the invention may be made in a variety of ways.
For example, a compound of formula (I) which is a compound of formula (IB) (wherein Y is oxygen and R1, R3, R4, R5, R12, A, D, E, G, J, L and Q are as defined above in relation to formula (I), except that R12 is not H) may be made from a compound of formula (2) [wherein Y is oxygen and R1, R3, R4, R5, A, D, E, G, J, L and Q are as defined above in relation to formula (I)] by treatment with an alkylating agent (such as an alkyl halide, chloromethyl alkyl ether, dialkyl sulfate or trialkyloxonium salt), an acylating agent (such as an acid chloride) or a similar reagent (such as a carbamoyl chloride, or sulfenyl chloride), optionally in the presence of a base and optionally in the presence of a catalyst such as a phase-transfer catalyst. Frequently these reactions give rise to a mixture of a compound of formula (IB), together with a compound of formula (3), as an isomeric product. Certain compounds of formula (3) are novel and have similar insecticidal and and fungicidal propoerties as the compounds of formula I and as such form a further aspect of the invention. A compound of formula (IB) may be separated from a compound of formula (3) and purified by routine techniques such as recrystallisation, chromatography or trituration with a suitable solvent.
Figure imgf000071_0001
(2) (IB) (3) A compound of formula (IB) (where R , 1'2 is alkoxyalkyl or acyloxyalkyl) may also be prepared from a compound of formula (2) by sequential reaction with formaldehyde and an alkylating or acylating agent.
A compound of formula (2) [where Y is oxygen; and D, E, G, J, L, Q, R1, R3, R4 and R5 are as defined above in relation to formula (I)] and A is optionally substituted alkylene, alkenylene, alkynylene, alkylenoxy, alkylenamino or alkylenethio) may be prepared by reacting a compound of formula (4) (where D, E, and R1 are as defined above in relation to formula I) with an appropriate compound of formula (5) (where A is optionally substituted alkylene, alkenylene, alkynylene, alkylenoxy, alkylenamino or alkylenethio; G, J, L, Q, R3, R4 and R5 are as defined above in relation to formula (I); and X is hydroxy) preferably in the presence of a suitable coupling reagent (such as 1,3-dicyclohexylcarbodiimide, 1,3- diisopropylcarbodiimide, l-(3-dimethylaminopropyl)-3-ethylcarbodiimide or 1,1'- carbonyldiimidazole) or with a suitable acid halide of formula (5) (where X is halogen), acid anhydride of formula (5) [where X is OC(O)alkyl] or ester of formula (5) (where X is alkoxy, substituted alkoxy or aryloxy, especially methoxy) optionally in the presence of a base such as triethylamine or sodium methoxide and in a suitable solvent (such as 1,1,2,2- tetrachloroethane, tetrahydrofuran, N,N-dimethylacetamide or mesitylene). A compound of formula (2) (where A is optionally substituted oxyalkylene) may be prepared in an analogous manner starting from a compound of formula (4) and a suitable chloroformate of formula (5) (where X is chlorine).
Figure imgf000072_0001
(4) (5) (2)
Compounds of formula (4) are known compounds or may be made from known compounds by known methods.
Compounds of formula (5) may be prepared in a number of ways, the preferred method is dependent on the nature of the fused benzheterocyclic ring and on the nature of the moiety A-C(O)-X . For example, the moiety A-C(O)-X may be attached by reacting a suitable reagent V-A-C(O)-X with a preformed compound of formula (6):
Figure imgf000072_0002
(7) (6) (5)
Examples of such procedures include (but are not restricted to):
(i) The coupling of a compound of formula (6) [where Z is hydroxy and R3, R4, R5, G, J, L and Q are as defined above for a compound of formula (I)] to a suitably functionalised alkyl halide [such as a haloalkyl ester of formula (7a), where A' is an optionally substituted alkylene, X is alkoxy and V is a halogen (such as bromine)] under basic conditions to give a compound of formula (5a):
Figure imgf000072_0003
(7a) (6) (5a)
(ii) The coupling of a suitably functionalised alkane (such as a malonate), alkene (such as an acrylate) or an alkyne with a suitable fused heterocyclic halide of formula (6) (where Z is chlorine, bromine or iodine, especially bromine or iodine) under transition-metal (especially Cu and Pd) mediated cross-coupling conditions. An example of this type of transformation is the reaction between a compound of formula (8) (where Rx and Ry are as defined above for substituents on alkenylene, A" is a single bond or optionally substituted alkylene and X is Cι_6 alkoxy) and a compound of formula (6) [where Z is bromine or iodine and R , R4, R5, G, J, L and Q are as defined above for a compound of formula (1)] under Pd(0) catalysis to give a compound of formula (5b):
Figure imgf000073_0001
(8) (6) (5b) (iii) The direct alkylation or acylation under, for example, Friedel-Craft conditions.
Certain compounds of formula (5) are amenable to modification to give further analogues. For example, when X is an alkoxy moiety and A is an alkylene moiety, a compound of formula (5) undergoes reactions typical of aliphatic esters. Thus a compound of formula (5c) [where W is a single bond or suitable group (such as CH2); X is .6 alkoxy; and R3, R4, R5, G, J, L and Q are as defined above for a compound of formula (I)] may be reacted with a suitable base (such as lithium diisopropylamide, sodium hydride or lithium hexamethyldisilazide) in a suitable solvent (such as tetrahydrofuran) and then treated with an alkylating agent (such as an alkyl halide), a halogenating agent (such as an N- chlorosuccinimide or N-fluorobenzenesulfonimide) or another electrophilic agent of formula Rf-LG (where LG designates a suitable leaving group, such as a halide) to introduce a new substituent Rf . This procedure may be repeated to introduce a second substituent Rε, which may be the same or different to Rf:
Figure imgf000073_0002
(5c) As expected, a compound of formula (5) bearing fragments which are sufficiently chemically reactive undergoes reactions typical of those fragments. For example, a compound of formula (5d) [wherein W is as defined as for a compound of formula (5c), X is C].6 alkoxy and R3, R4, R5, G, J, L and Q are as defined above for a compound of formula (I)] will undergo certain reactions typical of α-ketoesters. Thus a compound of formula (5d) may be reduced by metal hydrides (such as sodium borohydride) in a suitable solvent (such as ethanol) to give a corresponding alcohol of formula (5e):
Figure imgf000074_0001
(5d) (5e)
These compounds may be individually converted to a compound of formula (I) by similar procedures to those outlined previously.
The syntheses of substituted benzazines such as quinolines, quinoxalines, quinazolines, cinnolines and benzotriazines are described in the chemical literature (see, for example, Alan R. Katritzky and Charles W. Rees, Comprehensive Heterocyclic Chemistry, Vol. 3, Pergamon Press, 1984), and many of these methods may be useful in preparing a compound of formula (6) from known compounds. For example, treatment of phenylenediamines with α-dicarbonyl compounds, or with α-bromoketones, in the presence of an oxidant, as described by Cheesman and Werstiuk [Adv. Heterocyclic Chem., 22, 367, (1978)] yield quinoxalines. Syntheses of quinolines from anilines is well documented [see for example, Song et al., J. Heterocyclic Chem., 30, 17, (1993); Meth-Cohn et al., JCS Perkin 1, 1537, (1981) and references therein]. Quinazolines may be formed from ort/zo-acylated amines, using similar procedures to those described, for example, by J. Siegal and B.E. Christensen, JACS, 73, 5777 (1951) and K. Schofield, T. Swain and R.S. Theobold, J. Chem. Soc. 1924 (1952). Cinnolines may be prepared from ørt/iø-aminophenylacetylenes by processes described by S.F. Vasilevsky et al., Synth. Commun. 24, No 12, 1733 (1994) and benzotriazines may be made by a modified Bamberger reaction similar to that described by Raja H Attallah and Musa Z Nazer, Tetrahedron Lett., 38, No 12, 1793 (1982)
In an alternative approach to a compound of formula (5), the fused heterocyclic ring may be formed by ring synthesis from a suitably substituted benzene of formula(9) [where atoms or groups Q1 and G1 are suitable precursors for the formation of the desired heterocyclic ring and where the the benzene ring already bears the required substituent A- CO-X (where X is preferably an alkoxy moiety)] by processes analogous to those utilised in the preparation of compounds of formula (6): ring synthesis
Figure imgf000075_0001
Figure imgf000075_0002
(9) (5) This methodology may be extended to the following transformation:
Figure imgf000075_0003
rιngsyπthesιs
Figure imgf000075_0004
Compounds of formula (9) are known compounds or may be made from known compounds by known methods.
A compound of formula (2) [wherein Y is sulfur and R1, R3, R4, R5, A, D, E, G, J, L and Q are as defined above in relation to formula (I)] may be prepared by reacting a compound of formula (2) [wherein Y is oxygen and R1, R3, R4, R5, A, D, E, G, J, L and Q 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(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 (10) (wherein R1, R3, R4, R5, D, E, G, J, L and Q are as defined above in relation to formula (I) may be made from a compound of formula (11) [wherein R1, R3, R4, R5, D, E, G, J, L and Q 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. This invention covers isolated isomers together with mixtures of isomers.
Figure imgf000075_0005
(11) (10) A compound of formula (10) may be treated subsequently with an amine (HNR 27r R>28 )^
[where R ,27 and R ,28 are as defined above in relation to a compound of formula (I)] to give a compound of formula (12) [wherein R1, R3, R4, R5, R27, R28, D, E, G, J, L and Q are as defined above in relation to formula (I)]. A compound of formula (11) may be treated in an analogous manner with a trialkyloithoformate (HC(OR 6)3) [where R26 is as defined for a compound of formula (I)] to afford a compound of formula (13) [wherein R1, R3, R4, R5, R26, D, E, G, J, L and Q are as defined above in relation to formula (I)].
Figure imgf000076_0001
(12) (13)
A compound of formula (10), (12) or (13) may also be oxidised to a compound of formula (10) (where W is a single bond) under known conditions.
A compound of formula (2) (wherein Y is sulfur) may be treated with an electrophile (such as an alkyl halide, dialkyl sulfate, or trialkyloxonium salt), optionally in the presence of a base to give a compound of formula (14) [where R9 is alkyl; and R1, R3, R4, R5, A, D, E, G, J, L and Q are as defined above in relation to formula (I)].
Figure imgf000076_0002
(14) Such a compound may be further treated with a compound of formula R^R1 'NH, (where R10 and R11 are, independently, optionally substituted C 0 alkyl) to give a compound of formula (I) [where M is N=C(NR10Rπ) and R10 and R11 are, independently, optionally substituted CMO alkyl] or with a compound of formula R OH [where R is as defined for above for a compound of formula (I) (except that R is not amino)] to give a compound of formula (I) [where M is N=C(OR ) and R is as defined for above for a compound of formula (I) (except that R8 is not amino)] by known methods.
A compound of formula (I) which is a compound of formula (IC) [wherein E is CR2; and R1, R2, R3, R4, R5, A, D, G, J, L and Q are as defined above in relation to formula (I)] may be prepared by reacting a compound of formula (15) [where E is CR2 and D, R1 and R2 are as defined above in relation to formula (I)] with an appropriate compound of formula (5) (where A, G, J, L, Q, R3, R4 and R5 are as defined above in relation to formula (I) and X is hydroxy) preferably in the presence of a suitable coupling reagent (such as 1 ,3- dicyclohexylcarbodiimide, 1,3-diisopropylcarbodiimide, l-(3-dimethylaminopropyl)-3- ethylcarbodiimide or 1 , 1 ' -carbonyldiimidazole) by known methods .
Figure imgf000077_0001
(15) (5) (IC)
Compounds of formula (15) are known compounds or may be made from known compounds by known methods.
The compounds of formula (I) can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests. The pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies).
Examples of pest species which may be controlled by the compounds of formula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp.
(capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips), Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis (boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (white flies), Bemisia tabaci (white fly), Ostrinia nubilalis (European corn borer), Spodoptera littoralis (cotton leafworm), Heliothis virescens (tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpa zea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pieris brassicae (white butterfly), Plutella xylostella (diamond back moth), Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locusta_ migratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp. (rootworms), Panonychus ulmi (European red mite), Panonychus citri (citrus red mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpus spp. (flat mites), Boophilus microplus (cattle tick), Dermacentor variabilis (American dog tick), Ctenocephalides felis (cat flea), Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), termites of the Mastotermitidae (for example Mastotermes spp.), the Kalotermitidae (for example Neotermes spp.), the Rhinotermitidae (for example Coptotermes formosanus, Reticulitermes βavipes, R. speratu, R. virginicus, R. hesperus, and R. santonensis) and the Termitidae (for example Globitermes sulphureus), Solenopsis geminata (fire ant), Monomorium pharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. (biting and sucking lice), Meloidogyne spp. (root knot nematodes), Globodera spp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulus spp. (citrus nematodes), Haemonchus contortus (barber pole worm), Caenorhabditis elegan _ (vinegar eelworm), Trichostrongylus spp. (gastro intestinal nematodes) and Deroceras reticulatum (slug).
The compounds of formula (I) are also active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae (Magnaporthe grisea) on rice and wheat and other Pyricularia spp. on other hosts; Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts (for example turf, rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental plants); Erysiphe cichoracearum on cucurbits (for example melon); Erysiphe graminis (powdery mildew) on barley, wheat, rye and turf and other powdery mildews on various hosts, such as Sphaerotheca macularis on hops, Sphaerotheca fusca (Sphaerotheca fuliginea) on cucurbits (for example cucumber), Leveillula taurica on tomatoes, aubergine and green pepper, Podosphaera leucotricha on apples and Uncinula necator on vines; Cochliobolus spp., Helminthosporium spp., Drechslera spp. (Pyrenophora spp.), Rhynchosporium spp., Mycosphaerella graminicola (Septoria tritici) and Phaeosphaeria nodorum (Stagonospora nodorum or Septoria nodorum), Pseudocercosporella herpotrichoides and Gaeumannomyces graminis on cereals (for example wheat, barley, rye), turf and other hosts; Cercospora arachidicola and
Cercosporidium personatum on peanuts and other Cercospora spp. on other hosts, for example sugar beet, bananas, soya beans and rice; Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables, vines and other hosts and other Botrytis spp. on other hosts; Alternaria spp. on vegetables (for example carrots), oil-seed rape, apples, tomatoes, potatoes, cereals (for example wheat) and other hosts; Venturia spp. (including Venturia inaequalis (scab)) on apples, pears, stone fruit, tree nuts and other hosts; Cladosporium spp. on a range of hosts including cereals (for example wheat) and tomatoes; Monilinia spp. on stone fruit, tree nuts and other hosts; Didymella spp. on tomatoes, turf, wheat, cucurbits and other hosts; Phoma spp. on oil-seed rape, turf, rice, potatoes, wheat and other hosts; Aspergillus spp. and Aureobasidium spp. on wheat, lumber and other hosts; Ascochyta spp. on peas, wheat, barley and other hosts; Stemphylium spp. (Pleospora spp.) on apples, pears, onions and other hosts; summer diseases (for example bitter rot (Glomerella cingulata), black rot or frogeye leaf spot (Botryosphaeria obtusa), Brooks fruit spot (Mycosphaerella 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; Gibberella fujikuroi on rice; Colletotrichum spp. on a range of hosts including turf, coffee and vegetables; Laetisaria fuciformis on turf; Mycosphaerella spp. on bananas, peanuts, citrus, pecans, papaya and other hosts; Diaporthe spp. on citrus, soybean, melon, pears, lupin and other hosts; Elsinoe spp. on citrus, vines, olives, pecans, roses and other hosts; Verticillium spp. on a range of hosts including hops, potatoes and tomatoes; Pyrenopeziza spp. on oil-seed rape and other hosts; Oncobasidium theobromae on cocoa causing vascular streak dieback; Fusarium spp., Typhula spp., Microdochium nivale, Ustilago spp., Urocystis spp., Tilletia spp. and Claviceps purpurea on a variety of hosts but particularly wheat, barley, turf and maize; Ramularia spp. on sugar beet, barley and other hosts; post-harvest diseases particularly of fruit (for example Penicillium digitatum, Penicillium italicum and Trichoderma viride on oranges, Colletotrichum musae and Gloeosporium musarum on bananas and Botrytis cinerea on grapes); other pathogens on vines, notably Eutypa lata, Guignardia bidwellii, Phellinus igniarus, Phomopsis viticola, Pseudopeziza tracheiphila and Stereum hirsutum; other pathogens on trees (for example Lophodermium seditiosum) or lumber, notably Cephaloascus fragrans, Ceratocystis spp., Ophiostoma piceae, Penicillium spp., Trichoderma pseudokoningii, Trichoderma viride, Trichoderma harzianum, Aspergillus niger, Leptographium lindbergi and Aureobasidium pullulans; and fungal vectors of viral diseases (for example Polymyxa graminis on cereals as the vector of barley yellow mosaic virus (B YMV) 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 01/551 . 7Q .
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 0. lg tolOkg 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 0.00 lg 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 _ 80 _
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 O 01/55140 g l
solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).
Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLNESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLNESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), Ν-alkylpyrrolidones (such as Ν-methylpyrrolidone or Ν-octylpyrrolidone), dimethyl amides of fatty acids (such as C8-Cι0 fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water. Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of formula (I) is present initially in either the water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product. Aerosol formulations comprise a compound of formula (I) and a suitable propellant
(for example n-butane). A compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
A compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment. A compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution ..
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on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I). Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).
A compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS). The preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.
Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium diisopropyl- and tri-wopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally 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 OA
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octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
A compound of formula (I) may be applied by any of the known means of applying pesticidal or fungicidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.
A compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
A compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers). Suitable formulation types include granules of fertiliser. The mixtures suitably contain up to 25% by weight of the compound of formula (I).
The invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula (I). The compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.
By including another fungicide, the resulting composition may have a broader spectrum of activity or a greater level of intrinsic activity than the compound of formula (I) alone. Further the other fungicide may have a synergistic effect on the fungicidal activity of the compound of formula (I).
The compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition. Examples of suitable pesticides include the following: a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate; b) Organophosphates, such as, profenofos, sulprofos, acephate, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon; c) Carbamates (including aryl carbamates), such as pirimicarb, triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl or oxamyl; d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron, flufenoxuron or chlorfluazuron; e) Organic tin compounds, such as cyhexatin, fenbutatin oxide or azocyclotin; f) Pyrazoles, such as tebufenpyrad and fenpyroximate; g) Macrolides, such as avermectins or milbemycins, for example abamectin, emamectin benzoate, ivermectin, milbemycin, spinosad or azadirachtin; h) Hormones or pheromones; i) Organochlorine compounds such as endosulfan, benzene hexachloride, DDT, chlordane or dieldrin; j) Amidines, such as chlordimeform or amitraz; k) Fumigant agents, such as chloropicrin, dichloropropane, methyl bromide or metam; 1) Chloronicotinyl compounds such as imidacloprid, thiacloprid, acetamiprid, nitenpyram or thiamethoxam; m) Diacylhydrazines, such as tebufenozide, chromafenozide or methoxyfenozide; n) Diphenyl ethers, such as diofenolan or pyriproxifen; o) Indoxacarb; p) Chlorfenapyr; or q) Pymetrozine.
In addition to the major chemical classes of pesticide listed above, other pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the composition. For instance, selective insecticides for particular crops, for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed. Alternatively insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron). O 01/55140 ._
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Examples of fungicidal compounds which may be included in the composition of the invention are (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy- iminoacetamide (SSF-129), 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole- 1-sulphonamide, α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone, 4-chloro- 2-cyano-N,N-dimethyl-5-/?-tolylimidazole-l-sulfonamide (IKF-916, cyamidazosulfamid), 3-5-dichloro-N-(3-chloro- 1 -ethyl- 1 -methyl-2-oxopropyl)-4-methylbenzamide (RH-7281 , zoxamide), N-allyl-4,5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide (MOΝ65500), N- (1 -cyano- l,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide (AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide, acibenzolar (CGA245704), alanycarb, 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, 0,0-di-j.rø-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethirimol, ethyl(Z)-N-benzyl-N([methyl(methyl-thioethylideneaminooxycarbonyl)amino]thio)-
-β-alaninate, etridiazole, famoxadone, fenamidone (RPA407213), fenarimol, fenbuconazole, fenfuram, fenhexamid (KBR2738), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos, iprodione, iprovalicarb (SZX0722), isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054, LY211795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metconazole, metiram, metiram-zinc, metominostrobin, myclobutanil, neoasozin, nickel dimethyldithiocarbamate, nitrothal- isopropyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-Al, phosphorus acids, phthalide, picoxystrobin (ZA1963), polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, propionic acid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, sipconazole (F-155), sodium pentachlorophenate, spiroxamine, streptomycin, sulphur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamid, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl, thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin (CGA279202), triforine, triflumizole, triticonazole, validamycin A, vapam, vinclozolin, zineb and ziram. The compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
Examples of suitable synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.
Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
An example of a rice selective herbicide which may be included is propanil. An example of a plant growth regulator for use in cotton is 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. O 01/55140 . 89 _
EXAMPLE 1
This Example illustrates the preparation of Compound No. 1 of Table No. 96.
Step 1 - Preparation of (2,3-dimethylquinoxalin-6-yl)acetic acid
3,4-Diaminophenylacetic acid (0.30g, 0.0018mol) and 2,3-butanedione (0.155g, 0.0018mol) were heated in ethanol at 65°C for lhour. The mixture was cooled to room temperature, the solvent removed in vacuo and the residue triturated sequentially with water and diethyl ether to give (2,3-dimethylquinoxalin-6-yl)acetic acid (0.28 g) as a brown solid. 1H NMR (CDC13) δ ppm: 2.60(s,6H); 3.76(s,2H); 7.56(dd,lH); 7.76(d,lH); 7.83(d,lH)
Step 2 - Preparation of N-(4-chloro-3-methyIisothiazol-5-yl)-(2,3-dimethylquinoxalin-6- yl)-acetamide Oxalyl chloride (0.178g, 0.0014mol) was added dropwise to a suspension of the acid
(0.28g, 0.0013mol) prepared in Step 1 above in 1,2-dichloroethane (5ml) and the mixture stirred at room temperature for lhour, then heated to reflux. A solution of 5-amino-4-chloro- 3-methylisothiazole (0.193g, 0.0013mol) in xylene (5ml) was added and the mixture heated at reflux for 1.5hours. The mixture was cooled to room temperature and partitioned between ethyl acetate and saturated aqueous sodium bicarbonate solution. The organic extract was dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo. The residue was taken up in diethyl ether and further purified by flash column chromatography to give Compound 6, N-(4-chloro-3-methylisothiazol-5-yl)-(2,3-dimethylquinoxalin-6-yl)- acetamide (0.035g) as a yellow powder. 1H ΝMR (CDC13) δ ppm: 2.36(s,3H); 2.72(s,3H); 2.73(s,3H); 4.08(s,2H);
7.61(dd,lH); 7.90(d,lH); 7.98(d,lH); 8.89(s,lH).
EXAMPLE 2 This Example illustrates the preparation of Compound No. 1 of Table No. 1. Step 1 - Preparation of methyl 4-aminophenylacetate 4-Aminophenylacetic acid (lOOg) was suspended in methanol (1000ml) and gaseous hydrogen chloride was passed through until the mixture was saturated. The mixture was heated at 50°C for 2hours and was then allowed to cool to room temperature. The solvent was evaporated in vacuo, the residue taken up aqueous sodium bicarbonate solution and extracted with ethyl acetate. The organic extract was washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo to afford methyl 4-aminophenylacetate as a pale brown liquid.
1H NMR (CDC13) δ ppm: 3.5(s,2H); 3.7(s,3H): 6.65(m,2H); 7.05(m,2H). Step 2 - Preparation of N-(4-chloro-3-methylisothiazol-5-yl)-4-aminophenyIacetamide Sodium methoxide (0.227 g, 0.0042 mol) was added to a solution of 5-amino-4- chloro-3-methylisothiazole (0.25 g, 0.0017 mol) in tetrahydrofuran (15 ml) and the mixture stirred at room temperature for 10 minutes. A solution of methyl 4-aminophenylacetate (0.277 g, 0.0017 mol) in tetrahydrofuran (2 ml) was added and the mixture kept at room temperature for 3 days. The mixture was poured into water, acidified with aqueous citric acid and extracted with ethyl acetate. The organic extract was washed sequentially with water and brine, dried over magnesium sulfate, filtered and the filtrate evaporated in vacuo. The residue was further purified by column chromatography, eluting initially with 1 : 1 ethyl acetate : hexane and then with 2 : 1 ethyl acetate : hexane to give N-(4-chloro-3-methylisothiazol-5- yl)-4-aminophenylacetamide (0.242 g) as a pale orange-buff solid.
1H ΝMR (CDC13) δ ppm: 2.38(s,3H); 3.77(s,2H); 3.80(br,2H); 6.75(d,2H), 7.12 (d,2H); 8.1(br,lH).
Step 3 - Preparation of N-(4-chloro-3-methylisothiazol-5-yl)-(2-methyIquinolin-6- yl)acetamide The aniline prepared in Step 2 (0.204 g, 0.0007 mol), p rα-chloranil (0.268 g , 0.0011 mol), crotonaldehyde (0.102 g, 0.0015 mol), concentrated hydrochloric acid (0.091 ml) and n-butanol (5 ml) were heated at 95 °C for 1 hour, then cooled to room temperature. Further quantities of pαra-chloranil (0.268 g , 0.0011 mol) and crotonaldehyde (0.102 g, 0.0015 mol) were added and the mixture heated at 100 °C for 30 minutes, then cooled to room temperature. The solvent was evaporated in vacuo, the residue taken up in ethyl acetate and extracted with aqueous sodium bicarbonate solution. The organic extract was washed sequentially with water and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated. Trituration with a mixture of diethyl ether and pentane gave N-(4-chloro- 3-methylisothiazol-5-yl)-(2-methylquinolin-6-yl)acetamide, as a khaki solid, m.p. 205 °C. 1H ΝMR (CDCl3/ dό-DMSO) δ ppm: 2.39(s,3H), 2.76(s,3H); 4.12(s,2H);
7.31(d,lH); 7.67(dd,lH); 7.76(d,lH); 7.98(d,lH); 8.04(d,lH); 10.70(s,lH). EXAMPLE 3 This Example illustrates the preparation of Compound No. 4 of Table No. 26. Step 1 - Preparation of n-butyl [3-(l-methylethyl)quinoIin-7-yl]acetate
2-Isopropylacrolein (0.92 ml, 0.00788 mol) was added dropwise, with stirring, to a mixture of 3-aminophenylacetic acid (0.915 g, 0.0061 mol), concentrated aqueous hydrochloric acid solution (1.51ml) and chloranil (1.64g, 0.0073mol) in n-butanol (15ml) at 80°C. Once the addition was complete the mixture was heated at gentle reflux for 1 hour, then cooled and allowed to stand at room temperature for 3days. The solvent was removed in vacuo, the residue diluted with ether and saturated aqueous sodium bicarbonate solution added until the solution was basic. The mixture was diluted with water, the solids removed by filtration through HYFLO [HYFLO is a registered trademark] diatomaceous earth and the filtrate partitioned. The aqueous phase was extracted with diethyl ether and the combined organic solutions were brine, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo. The residue was triturated with a small quantity of dichloromethane, and then purified by column chromatography on silica gel, eluting with dichloromethane. Fractions containing the desired product were combined and the solvent evaporated in vacuo. The residue was further purified by vacuum distillation (using a Kugelrohr apparatus), collecting the fraction distilling at 235-250 °C (0.1-0.2 mmHg), to give n-butyl [3-(l-methylethyl)quinolin-7-yl]acetate (0.579 g) as a yellow oil. 1H NMR (CDC13) δ ppm: 0.92(t,3H); 1.37(m,2H); 1.39(d,6H); 1.62(m,2H);
3.16(m,lH); 3.85(s,2H); 4.12(t,3H); 7.55(dd,lH); 7.80(d,lH); 8.03(d,lH); 8.07(d,lH);
8.85(d,lH).
Step 2 - Preparation of N-(4-chloro-3-methylisothiazoI-5-yl)-[3-(l-methyIethyl)quinolin-
7-yl]acetamide. Potassium tert-butoxide (1 Molar solution in tetrahydrofuran, 2.01 ml, 0.00201 mol) was added dropwise to a solution of 5-amino-4-chloro-3-methylisothiazole (0.273 g, 0.00184 mol) in tetrahydrofuran (12 ml) and the mixture stirred at room temperature for 25 minutes. A solution of ra-butyl [3-(l-methylethyl)quinolin-7-yl]acetate (0.4768 g, 0.00167 mol) in tetrahydrofuran (4 ml) was added and the mixture stirred at room temeperature for 3 hours. The mixture was poured into saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The organic extracts were combined, washed with water and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo. Trituration with a mixture of diethyl ether and pentane gave N-(4-chloro-3-methylisothiazol- 5-yl)-[3-(l-methylethyl)quinolin-7-yl]acetamide (0.2656 g) as a tan solid, m.p. 175-178 °C
1H ΝMR (CDC13) δ pp : 1.40(d,6H); 2.36(s,3H); 3.16(m,lH); 4.09(s, 2H); 7.52(dd,lH); 7.86(d,lH); 7.98(d,lH); 8.05(d,lH); 8.53(br,lH); 8.87(d,lH) EXAMPLE 4
This Example illustrates the preparation of Compound Νo.7 of Table No. 91. Step 1 - Preparation of 6-bromoquinoxaline.
A mixture of 4-bromo-l,2-phenylenediamine(17.61 g, 0.094 mol), 8.8M aqueous glyoxal solution (11 ml, 0.094 mol) and sodium bisulfite (20.0 g, 0.19 mol) was stirred and heated in water (130 ml) at 70 °C for 3 hours. The mixture was allowed to cool to room temperature overnight. Potassium carbonate (13.2 g, 0.094 mol) was added and the mixture stirred at room temperature for Vi hour. The mixture was filtered through Hyflo® diatomaceous earth, washing with water and with ethyl acetate. The filtrate was partitioned, and the aqueous phase extracted with ethyl acetate. The organic solutions were combined, washed with water and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo to give 6-bromoquinoxaline (12.7 g) as a brown solid. 1H NMR (CDCI3) δ ppm: 7.82(dd,lH); 7.97(d,lH); 8.28(d,lH); 8.82(s,2H) Step 2 - Preparation of 2-(2,2-dimethylpropyl)-6-bromoquinoxaIine and 2-(2,2- dimethylpropyl)-7-bromoquinoxaline A solution of ammonium persulfate (14 g, 0.06 mol) in water (65 ml) was added to a mixture of 6-bromoquinoxaline (6.4 g, 0.031 mol), silver nitrate (1.02 g, 0.006 mol) and tert- butylacetic acid (7.5 ml, 0.06 mol) in 10% aqueous sulfuric acid (30 mL) at 70 °C. An exotherm was noticed, the temperature rising to 95 °C, before falling to 80 °C. The mixture was stirred and maintained at 80 °C by external heating for 2 hours. The mixture was cooled to room temperature, and allowed to stand overnight, and then heated at 75 °C for a further 2 hours. The mixture was cooled, poured onto a mixture of ice and concentrated aqueous ammonia solution.
The mixture was filtered through HYFLO [HYFLO is a registered trademark] diatomaceous earth, washing with water and with ethyl acetate. The filtrate was partitioned, and the aqueous phase extracted with ethyl acetate. The organic solutions were combined, washed with dilute aqueous sodium hydroxide solution and water, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, gradient eluting with ethyl acetate : hexane (1: 15 to neat ethyl acetate) to give 2-(2,2-dimethylpropyl)-6-bromoquinoxaline and 2-(2,2- dimethylpropyl)-7-bromoquinoxaline. 2-(2,2-dimethylpropyl)-6-bromoquinoxaline: 1H NMR (CDC13) δ ppm: 1.04(s,9H); 2.90(s,2H); 7.82(dd,lH); 7.94(d,lH); 8.26(d,lH); 8.69(s,lH)
2-(2,2-dimethylρropyl)-7-bromoquinoxaline: 1H NMR (CDC13) δ ppm: 0.94(s,9H);
2.82(s,2H); 7.68(dd,lH); 7.84(d,lH); 8.17(d,lH); 8.61(s,lH)
Step 3 - Preparation of ethyl [2-(2,2-dimethylpropyl)quinoxalin-6-yI]acetate
A mixture of 2-(2,2-dimethylpropyl)-6-bromoquinoxaline (1.00 g, 0.00358 mol), palladium acetate (0.04 g, 0.00018 mol), tri-tert-butyl phosphine (0.036 g, 0.00018 mol), potassium tert-butoxide (0.422 g, 0.00377 mol) and ethyl trimethylsilyl malonate (0.88 ml, 0.0043 mol) were heated together in toluene (10 ml) at 85 °C, under an atmosphere of nitrogen, for 1 hour. The mixture was cooled to room temperature, filtered through HYFLO [HYFLO is a registered trademark] diatomaceous earth, and the filter cake washed with diethyl ether. The filtrate was washed with water and brine, dried over anhydrous magnesium sulfate, filtered and evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with ethyl acetate : hexane 1:5 to give ethyl [2-(2,2- dimethylpropyl)quinoxalin-6-yl] acetate as an orange oil.
1H NMR (CDC13) δ ppm: 1.02(s,9H); 1.28(t,3H); 2.91(s,2H); 3.86(s,2H); 4.19(q,2H); 7.69(dd,lH); 7.96(s,lH); 8.03(d,lH); 8.69(s,lH)
Step 4 - Preparation of N-(4-chloro-3-methylisothiazol-5-yl)-[2-(2,2- dimethylpropyl)quinoxalin-6-yl]acetamide
5-Amino-4-chloro-3-methylisothiazole (0.67 g, 0.0045 mol) was added to a stirred suspension of sodium methoxide (0.54 g, 0.010 mol) in tetrahydrofuran (20 ml) and the mixture stirred at room temperature for 15 minutes. Ethyl [2-(2,2-dimethylpropyl)quinoxalin- 6-yl] acetate (1.18 g, 0.0045 mol) was added and the mixture stirred at room temeperature for 4 hours, then allowed to stand at room temperature overnight. The mixture was poured into aqueous citric acid solution and extracted with ethyl acetate. The organic extracts were combined, washed with water and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo. The residue was triturated with diethyl ether and pentane to give N-(4-chloro-3-methylisothiazol-5-yl)-[2-(2,2-dimethylpropyl)quinoxalin-6- yl]acetamide (0.837 g) as an off-white solid, m.p. 203-207°C. O 01/55140 n .
- 94 -
1H NMR (CDCI3) δ ppm: 1.03(s,9H); 2.38(s,3H); 2.93(s,2H); 4.12(s,2H); 7.72(dd,lH); 8.04(d,lH); 8.12(d,lH); 8.19(br,lH); 8.73(s,lH).
EXAMPLE 5 This Example illustrates the preparation of Compound No. 77 of Table No. 91. A mixture of N-(4-chloro-3-methylisothiazol-5-yl)-[2-(2,2-dimethylpropyl)quinoxalin-6- yl]acetamide (0.350 g, 0.0009 mol), chloromethyl ethyl ether (0.21 ml, 0.00225 mol), 52% aqueous sodium hydroxide solution (0.35 ml) and benzyl triethylammonium chloride (0.011 g, 0.00005 mol) in dichloromethane (10 ml) was stirred at 5 °C for 2 hours, and then allowed to warm to room temperature over V2 hour. The mixture was dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo.
The residue was purified by flash column chromatography on silica gel, eluting with ethyl acetate : hexane 3: 1 to give N-(4-chloro-3-methylisothiazol-5-yl)-N-ethoxymethyl-[2-(2,2- dimethylpropyl)quinoxalin-6-yl]acetamide (0.087 g) as a yellow gum. Further elution with ethyl acetate : hexane 1 : 1 gave N-(4-chloro-2-ethoxymethyl-3-methylisothiazol-5-ylidene)- [2-(2,2-dimethylpropyl)quinoxalin-6-yl]acetamide(0.126 g) as a white solid, m.p. 134-137 °C N-(4-chloro-3-methylisothiazol-5-yl)-N-ethoxymethyl-[2-(2,2-dimethylpropyl)quinoxalin-6- yljacetamide :
1H ΝMR (CDC13) δ ppm: 1.03(s,9H); 1.22(t,3H); 2.52(s,3H); 2.91(s,3H); 3.63(q,2H); 3.84(br,2H); 5.12(br,2H); 7.57(br,lH); 7.79(br,lH); 8.01(d,lH); 8.68(s,lH) N-(4-chloro-2-ethoxymethyl-3-methylisothiazol-5-ylidene)-[2-(2,2- dimethylpropyl)quinoxalin-6-yl]acetamide:
1H ΝMR (CDC13) δ ppm: 1.02(s,9H); 1.16(t,3H); 2.56(s,3H); 2.89(s,2H); 3.52 (q,2H); 4.31(s,2H); 5.21(s,2H); 7.78(dd,lH); 8.02(d,lH); 8.03(s,lH); 8.67(s,lH).
EXAMPLE 6
This Example illustrates the preparation of Compound No. 7 of Table No. 94. Step 1 - Preparation of ethyl [2-(2,2-dimethylpropyl)quinoxalin-6-yl]fluoroacetate.
Lithium bis(trimethylsilyl)amide (1.15 Molar solution in tetrahydrofuran, 1.7ml, 0.002mol) was added dropwise to a solution of ethyl [2-(2,2-dimethylpropyl)quinoxalin-6-yl] acetate (0.50g, 0.0017mol) in tetrahydrofuran (10ml) at -70°C, and the mixture stirred for Vi hour. A slurry of l-chloromethyl-4-fluoro-l,4-diazoniabicyclo[2,2,2]octane bis(tetrafluoroborate) (0.673 g, 0.0019 mol) in tetrahydrofuran was added portionwise at -70 °C, and once the addition was complete the mixture was allowed to warm to room temperature and stirred for 1 hour. The mixture was quenched with water, acidifed with 2M aqueous hydrochloric acid and extracted with ethyl acetate. The organic extract was washed with water and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with dichloromethane : hexane 2: 1 to give ethyl [2-(2,2-dimethylpropyl)quinoxalin-6-yl]fluoroacetate as a colourless oil.
1H NMR (CDC13) δ ppm: 1.03(s,9H); 1.28(t,lH); 2.92(s,3H); 4.28(m,2H); 6.00(d,lH); 7.82(dd,lH); 8.12(d,lH); 8.19(s,lH); 8.73(s,lH) Step 2 - Preparation of N-(4-chloro-3-methylisothiazol-5-yl)-[2-(2,2- dimethylpropyl)quinoxalin-6-yl]fluoroacetamide
Potassium tert-butoxide (1.0 Molar solution in tetrahydrofuran, 0.48 ml, 0.00048mol) was added dropwise to a solution of 5-amino-4-chloro-3-methylisothiazole (0.071 g, 0.00048 mol) in tetrahydrofuran and the mixture stirred at room temperature for 15 minutes. A solution of ethyl [2-(2,2-dimethylpropyl)quinoxalin-6-yl]fluoroacetate (1.18 g, 0.0045 mol) in tetrahydrofuran was added and the mixture stirred at room temeperature for 1 hour. A second portion of potassium tert-butoxide (0.2 ml) solution was added and the mixture stirred for a further Yι hour. The mixture was quenched with water, poured into aqueous citric acid solution and extracted with ethyl acetate. The organic extracts were combined, washed with water and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo. The residue was purified by column chromatography on silica gel, eluting with ethyl acetate : hexane 1:2 and then with ethyl acetate : hexane 1:1 to give an orange foam. Trituration with diethyl ether gave N-(4-chloro-3-methylisothiazol-5-yl)-[2- (2,2-dimethylpropyl)quinoxalin-6-yl]fluoroacetamide (0.076 g) as a white solid, m.p. 158- 160 °C.
1H ΝMR (CDC13) δ ppm: 1.04(s,9H); 2.45(s,3H); 2.94(s,2H); 6.32(d,lH); 7.87(dd,lH); 8.16(d,lH); 8.24(s,lH); 8.75(s,lH); 9.09(br,lH).
EXAMPLE 7 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 balteata).
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 136, 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 136
Figure imgf000099_0001
EXAMPLE 8 This Example illustrates the fungicidal properties of compounds of formula (I). The 5 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.l 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 0 (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 5 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). 9g
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 6hours 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 [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 unbanded assessment values (that is, the mean disease values are used in the PRCO calculation without a banding step).
An example of a typical unbanded 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 137.
TABLE 137
Figure imgf000102_0001
Key to Table 137
ERYSGT = Blumeria graminis f.sp. tritici
LEPTNO = Stagonospora nodorum
PHYTIN = Phytophthora infestans lycopersici
PLASVI = Plasmopara viticola
PUCCRT = Puccinia triticina

Claims

A compound of formula (I):
Figure imgf000103_0001
wherein n is 0 or 1 ;
A is optionally substituted .6 alkylene, optionally substituted C2.6 alkenylene, optionally substituted C2.6 alkynylene, optionally substituted cycloalkylene, optionally substituted Cι_6 alkylenoxy, optionally substituted oxy(C1.6)alkylene, optionally substituted Cι-6 alkylenethio, optionally substituted thio(C1.6)alkylene, optionally substituted Q.6 alkylenamino, optionally substituted amino(Cι_6)alkylene, optionally substituted [ -6 alkyleneoxy(Q.6)alkylene], optionally substituted [Q.6 alkylenethio(Q.6)alkylene], optionally substituted [Cι.6 alkylenesulfinyl(Q. 6)alkylene], optionally substituted [Q_6 alkylenesulfonyl(C1.6)alkylene] or optionally substituted [Q_6 alkyleneamino(Cι.6)alkylene];
D is S, NR7, CR14=CR15, CR14=N, CR14=N(O), N=CR15 or N(O)=CR15;
E is N, N-oxide or CR2;
G, J, L and Q are, independently, N, N-oxide or CR6 provided that neither are all N nor are all CR6; where more than one of G, J, L and Q is CR6, R6 can be the same or different;
M is OC(=Y), N=C(OR8), N=C(SR9), N=C(NR10Rπ) or N(R12)C(=Y) where O or N is the atom of attachment to the ring containing E and D;
Y is O, S or NR13; R1 is hydrogen, halogen, optionally substituted Q.6 alkyl, optionally substituted C2_6 alkenyl, optionally substituted C2_6 alkynyl, optionally substituted .6 alkoxy, optionally substituted Q_6 alkylthio, optionally substituted C3.7 cycloalkyl, cyano, nitro or SF5; R2 is hydrogen, halogen, optionally substituted Ci-6 alkyl, optionally substituted C2_6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted Q.6 alkoxy, optionally substituted Q_6 alkylthio, optionally substituted Q.6 alkylsulfinyl, optionally substituted Ci.6 alkylsulfonyl, cyano, nitro, formyl, optionally substituted C e alkylcarbonyl, optionally substituted Q_6 alkoxycarbonyl, SF5 or R16ON=C(R17); 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 Q_6 alkyl, Q_6 haloalkyl or halogen; R3, R4 and R5 are, independently, hydrogen, halogen, optionally substituted Q.6 alkyl, optionally substituted Q.6 alkoxy, optionally substituted Q.6 alkylthio, optionally substituted Q.6 alkylsulfinyl, optionally substituted Q_6 alkylsulfonyl, cyano, nitro, optionally substituted Q_6 alkylcarbonyl, optionally substituted Q. alkoxycarbonyl or SF5; R6 is hydrogen, halogen, cyano, optionally substituted Q.2o alkyl, optionally substituted C2.20 alkenyl, optionally substituted C2-20 alkynyl, optionally substituted C3.7 cycloalkyl, optionally substituted C5.6 cycloalkenyl, formyl, optionally substituted Q.20 alkoxycarbonyl, optionally substituted Q_20 alkylcarbonyl, aminocarbonyl, optionally substituted Q.20 alkylaminocarbonyl, optionally substituted di(Q.2o)alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-(Q.6)alkyl-N-arylaminocarbonyl, optionally substituted diarylaminocarbonyl, optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted N-(Q.6)alkyl-N-heteroarylaminocarbonyl, optionally substituted diheteroarylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, SH, optionally substituted Q.20 alkylthio, optionally substituted Q.2o alkylsulfinyl, optionally substituted Q_20 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl, R18O, RI9R20N or R21ON=C(R22); where any two adjacent groups of G, J, L and Q are CR , the two adjacent R6 groups together with the carbon atoms to which they are attached may together form a five-, six- or seven- membered saturated or unsaturated ring, which may contain one or two heteroatoms selected from O, N or S and which may be optionally substituted by Q.6 alkyl, Q.6 alkoxy, Q.6 haloalkyl or halogen; R7 is Q.6 alkyl; R8 is optionally substituted CMO alkyl, optionally substituted [C2-6 alkenyl (Q.6)alkyl], optionally substituted [C2_6 alkynyl(Q.6)alkyl], optionally substituted C3.7 cycloalkyl, amino, optionally substituted Q_6 alkylamino, optionally substituted di(Q. 6)alkylamino, optionally substituted C O alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, formyl, optionally substituted Q.10 alkylaminocarbonyl, optionally substituted di(CMo)alkylaminocarbonyl, amino, optionally substituted phenoxycarbonyl, tri(Q-4)alkylsilyl, aryldi(Q.4)alkylsilyl, (Q.4)alkyldiarylsilyl or triarylsilyl;
R9 is optionally substituted Q.io alkyl, optionally substituted [C2.6 alkenyl(Q.6)alkyl], optionally substituted [C .6 alkynyl(Q.6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted CMO alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(Q. ιo)alkylaminocarbonyl or optionally substituted phenoxycarbonyl); R10 and R11 are, independently, optionally substituted CMO alkyl, optionally substituted Q_6 alkoxy, optionally substituted [C2_6 alkenyl(Q_6)alkyl], optionally substituted [C2.6 alkynyl(Q_6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted CMO alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, formyl, optionally substituted C O alkylaminocarbonyl, optionally substituted di(Q. ιo)alkylaminocarbonyl, hydroxy, amino, optionally substituted Q. alkylamino, optionally substituted di(Q.6)alkylamino, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylamino, optionally substituted CMO alkylcarbonyloxy, optionally substituted Q_10 alkoxycarbonyloxy, optionally substituted phenoxycarbonyloxy, optionally substituted Q-io alkylaminocarbonyloxy, optionally substituted di(Q. ιo)alkylaminocarbonyloxy, optionally substituted C O alkylcarbonylamino, optionally substituted CMO alkoxycarbonylamino, optionally substituted phenoxycarbonylamino, optionally substituted Q.io alkylaminocarbonylamino, optionally substituted di(Q_ ιo)alkylaminocarbonylamino or optionally substituted phenoxycarbonyl;
R12 is hydrogen, optionally substituted CMO alkyl, optionally substituted Q.6 alkoxy, optionally substituted [C2_6 alkenyl(Q_6)alkyl], optionally substituted [C2_6 alkynyl(Cι-6)alkyl], optionally substituted C3_7 cycloalkyl, optionally substituted CM O alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, formyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(Q. 1o)alkylaminocarbonyl, hydroxy, amino, optionally substituted Q.6 alkylamino, optionally substituted di(Q.6)alkylamino, optionally substituted phenoxycarbonyl, optionally substituted Q.6 alkylthio, optionally substituted Q.6 alkylsulfinyl, optionally substituted Q.6 alkylsulfonyl, optionally substituted Q_6 aryl, optionally substituted Q_6 arylthio, optionally substituted Q.6 arylsulfinyl, optionally substituted Q.6 arylsulfonyl or R36R37NS(O)q; q is 0, 1 or 2; R36 and R37 are, independently, optionally substituted Q_6 alkyl; or R and R 7 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q_6 alkyl groups;
R is hydrogen, hydroxy, cyano, nitro, optionally substituted CMO alkyl, optionally substituted C3.7 cycloalkyl, optionally substituted (C2.6)alkenyl(Q.6)alkyl, optionally substituted (C2_6)alkynyl(Q.6)alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted Q.6 alkylcarbonyl, optionally substituted
Q. alkoxycarbonyl, optionally substituted Q.6 alkylamino, optionally substituted di(Q.6)alkylamino, optionally substituted C1-6 alkylcarbonylamino, optionally substituted Q. alkoxycarbonylamino, optionally substituted .6 alkoxy, optionally substituted .6 alkylthio, optionally substituted Q.6 alkylsulfinyl, optionally substituted Q_6 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylamino, optionally substituted CM O alkoxycarbonyloxy, optionally substituted phenoxycarbonyloxy,optionally substituted Q-io alkylaminocarbonyloxy, optionally substituted di(Q-ιo)alkylaminocarbonyloxy, optionally substituted phenoxycarbonylamino, optionally substituted CMO alkylaminocarbonylamino, optionally substituted di(CM0)alkylaminocarbonylamino or optionally substituted Q_6 alkylcarbonyl oxy; R14 and R15 are, independently, hydrogen, halogen, cyano, nitro, optionally substituted Q.6 alkyl, optionally substituted C2_6 alkenyl, optionally substituted C2.6 alkynyl or optionally substituted Q_6 alkoxy;
R16 and R21 are, independently, hydrogen, optionally substituted phenyl (Q.2)alkyl or optionally substituted Q. o alkyl;
R17 and R22 are independently hydrogen, optionally substituted phenyl or optionally substituted Q.6 alkyl;
R18 is hydrogen, optionally substituted Q-20 alkyl, optionally substituted [C2-2o alkenyl(Q_6)alkyl], optionally substituted [C2.20 alkynyl(Cι.6) alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, (Q.6)alkylCH=N, optionally substituted arylCH=N, optionally substituted [aryl(Q.6)alkyl]CH=N, optionally substituted heteroarylCH=N, optionally substituted [heterocyclyl(Q.6)alkyl]CH=N, optionally substituted arylC(CH3)=N, optionally substituted heteroarylC(CH3)=N or optionally substituted di(Q.6)alkylC=N; and
R19 and R20 are, independently, hydrogen, optionally substituted Q-20 alkyl, optionally substituted C3-7 cycloalkyl, optionally substituted [C2-2o alkenyl(Q_6)alkyl], optionally substituted [C2.20 alkynyl(Cι-6)alkyl], optionally substituted Q.20 alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted Q-2o alkylcarbonyl, optionally substituted Q-2o alkylsulfonyl or optionally substituted phenylsulfonyl; provided that when E is CR2 and M is N(R12)C(=Y) (where Y is O or S) then D is not CR14=CR15.
A compound according to claim 1 of formula IA
Figure imgf000107_0001
wherein A, D, E, G, J, L, M, Q, R1, R3, R4 and R5 are as defined in claim 1 for a compound of formula (I). WO 01/55140 t n£ PCT/GB
- 106 -
3. A compound according to claim 1 or claim 2 wherein A is Q.6 alkylene, Q_6 alkenylene, Q-6 alkylenoxy, oxy(Q.6)alkylene, Q.6 alkylenamino or Q_6 alkylenethio, each of which is optionally substituted by Q.3 alkyl, Q-3 haloalkyl, Q.3 cyanoalkyl, halogen, Q-3 alkoxy, Q_6 alkoxycarbonyl, cyano, hydroxy, =O, =NR23 or =CR24R25 where R23, R24 and R25 are as defined in claim 1.
4. A compound according to any preceding claim wherein M is N(R12)C(=Y) or N=C(SR9) where O or N is the atom of attachment to the ring containing E and D and Y, R12 and R9 are as defined in claim I.
5. A compound according to any preceding claim wherein G, J, L and Q are, independently, N or CR6 with the proviso that neither are all N nor are all CR6; where more than one of G, J, L and Q is CR6, R can be the same or different and have a value as defined in claim 1.
6. A compound according to any preceding claim wherein R , R and R are independently selected from hydrogen, halogen, Q.6 alkyl, Q_6 alkoxy, Q_6 haloalkoxy, Q_6 alkylthio, Q_6 haloalkylthio, Q_6 alkylsulfinyl, Q.6 haloalkylsulfinyl, Q.6 alkylsulfonyl, Q_6 haloalkylsulfonyl, Q.6 haloalkyl, cyano, nitro, Q.6 alkylcarbonyl, Q_ alkoxycarbonyl or SF5.
7. A compound according to any preceding claim wherein R6 is cyano, Q.8 alkyl, Q_8 haloalkyl, Q.8 cyanoalkyl, Q.7 cycloalkyl(Q.6)alkyl, C5-6 cycloalkenyl(Q_6)alkyl, Q_ 6 alkoxy(Q_6)alkyl, C3.6 alkenyloxy(Q.6)alkyl, -6 alkynyloxy(Q_6)alkyl, aryloxy- (Q_6)alkyl, Q-6 carboxyalkyl, Q_6 alkylcarbonyl(Q_6)alkyl, C2.6 alkenylcarbonyl-
(Q.6)alkyl, C2-6 alkynylcarbonyl(Q-6)alkyl, Q_6 alkoxycarbonyl(Q_6)alkyl, C3_6 alkenyloxycarbonyl(Q-6)alkyl, -6 alkynyloxycarbonyl(Q_6)alkyl, aryloxycarbonyl(Q.6)alkyl, Q.6 alkylthio(Cι_6)alkyl, Q_6 alkylsulfinyl(Q_6)alkyl, Q-6 alkylsulfonyl(Cι-6)alkyl, aminocarbonyl(Ci-6)alkyl, Q_6 alkylaminocarbonyl(Q. 6)alkyl, di(Cι-6)alkylaminocarbonyl(Cι_6)alkyl, phenyl (Q_4)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q-6 haloalkyl, Q.6 alkoxy or Ci-6 haloalkoxy), heteroaryl(Q-4)alkyl (where the heteroaryl group is optionally substituted by halo, nitro, cyano, Q-6 alkyl, Q.6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy), heterocyclyl(Q.4)alkyl (where the heterocyclyl group is optionally substituted by halo, cyano, Q.6 alkyl, Q.6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), C2.6 alkenyl, C2_6 haloalkenyl, Q-6 cyanoalkenyl, C5_6 cycloalkenyl, aminocarbonyl- (C2-6)alkenyl, C1.6 alkylaminocarbonyl(C1.6)alkenyl, di(Q.6)alkylaminocarbonyl-
(Q.6)alkenyl, phenyl(C2-4)alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q_6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), .6 alkynyl, aminocarbonyl(C2_6)alkynyl, alkylaminocarbonyl(Cι.6)alkynyl, di(Ci-6)alkylaminocarbonyl(Q.6)alkynyl, C3.7 cycloalkyl, C3.7 halocycloalkyl, C3.7 cyanocycloalkyl, Ci.3 alkyl(C3.7)cycloalkyl, Q.3 alkyl(C3-7)halocycloalkyl, C5_6 cycloalkenyl, formyl, Q_6 alkoxycarbonyl, Q_6 alkylcarbonyl, aminocarbonyl, Q.6 alkylaminocarbonyl, di(Cι-6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, Q.6 alkyl, Q_6 haloalkyl, Q.6 alkoxy or Q.6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Q_6 alkyl, Q_6 haloalkyl, Q_6 alkoxy or Cι.6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano,
Q.6 alkyl, Q.6 haloalkyl, Q_ alkoxy or Ci.6 haloalkoxy), Q.8 alkylthio, R18O, R19R20N or R21ON=C(R22) where R18, R19, R20, R21 and R22 are as defined in claim 1.
8. A compound according to any preceding claim wherein R1 is hydrogen, halogen, Q_6 alkyl, .6 alkenyl, _6 alkynyl, Q.6 cyanoalkyl, Q.6 haloalkyl, Q_6 alkoxy, Q_6 haloalkoxy, Ci.6 alkylthio, Q.6 haloalkylthio, .6 cycloalkyl, C3.7 cycloalkyl- (Cι_4)alkyl, Ci.6 alkoxy(Cι.6)alkyl, cyano, nitro or SF5.
- 108 -
9. A compound of formula (3)
Figure imgf000110_0001
wherein A, G, J, L, Q, D, E, Y, R , R , R and R are as defined in claim 1, and R is optionally substituted CMO alkyl, optionally substituted Q_6 alkoxy, optionally substituted [C _6 alkenyl(Q_6)alkyl], optionally substituted [C2_6 alkynyl(Q.6)alkyl], optionally substituted C3_7 cycloalkyl, optionally substituted Q.io alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, formyl, optionally substituted Q.io alkylaminocarbonyl, optionally substituted di(Q.ιo)alkylaminocarbonyl, hydroxy, amino, optionally substituted Q_6 alkylamino, optionally substituted di- (Q.6)alkylamino, optionally substituted phenoxycarbonyl, optionally substituted Q.6 alkylthio, optionally substituted Q.6 alkylsulfinyl, optionally substituted Q.6 alkylsulfonyl, optionally substituted Q. aryl, optionally substituted Q- arylthio, optionally substituted Q-6 arylsulfinyl, optionally substituted Q.6 arylsulfonyl or R36R37NS(O)q; q is 0, 1 or 2; R36 and R37 are, independently, optionally substituted Q.6 alkyl; or R and R together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further hetero atoms selected from O, N or S and which may be optionally substituted by one or two Q-6 alkyl groups.
10. 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.
11. 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.
2. 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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