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WO2001055142A1 - Isothiazole derivatives and their use as pesticides - Google Patents

Isothiazole derivatives and their use as pesticides Download PDF

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Publication number
WO2001055142A1
WO2001055142A1 PCT/GB2001/000325 GB0100325W WO0155142A1 WO 2001055142 A1 WO2001055142 A1 WO 2001055142A1 GB 0100325 W GB0100325 W GB 0100325W WO 0155142 A1 WO0155142 A1 WO 0155142A1
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WO
WIPO (PCT)
Prior art keywords
optionally substituted
alkyl
alkoxy
haloalkyl
cyano
Prior art date
Application number
PCT/GB2001/000325
Other languages
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
Original Assignee
Syngenta Limited
PILKINGTON, Joan
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB0002037A external-priority patent/GB0002037D0/en
Priority claimed from GB0002035A external-priority patent/GB0002035D0/en
Application filed by Syngenta Limited, PILKINGTON, Joan filed Critical Syngenta Limited
Priority to AU30348/01A priority Critical patent/AU3034801A/en
Publication of WO2001055142A1 publication Critical patent/WO2001055142A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

  • the present invention relates to azole derivatives, to processes for preparing them, to fungicidal, insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them, to methods of using them to combat fungal diseases (especially fungal diseases of plants) and to methods of using them to combat and control insect, acarine, mollusc and nematode pests.
  • Azole and azine derivatives are disclosed in WO95/31448, WO97/18198, WO98/02424, WO98/05670 and WO98/17630.
  • the present invention provides a compound of formula (I):
  • A is optionally substituted C 1-6 alkylene, optionally substituted C 2-6 alkenylene, optionally substituted C 2-6 alkynylene, optionally substituted cycloalkylene, optionally substituted C ]-6 alkylenoxy, optionally substituted oxy(C 1 . 6 )alkylene, optionally substituted C 1-6 alkylenethio, optionally substituted thio(C ⁇ _ 6 )alkylene, optionally substituted C J-6 alkylenamino, optionally substituted amino(C 1-6 )alkylene, optionally substituted [C ⁇ -6 alkyleneoxy(C 1 .
  • B is N, N-oxide or CR 7 ;
  • R 1 is hydrogen, halogen, optionally substituted C 1-6 alkyl, optionally substituted C 2 _ alkenyl, optionally substituted C 2-6 alkynyl, optionally substituted C ⁇ _ 6 alkoxy, optionally substituted C
  • R 2 is hydrogen, halogen, optionally substituted C 1-6 alkyl, optionally substituted C 2 .
  • R 1 and R 2 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated, carbocylic or heterocyclic ring which may contain one or two heteroatoms selected from O, N or S and which is optionally substituted by C 1-6 alkyl, C 1-6 haloalkyl or halogen;
  • R 3 , R 4 and R 5 are, independently, hydrogen, halogen, optionally substituted C ⁇ -6 alkyl
  • R 7 is hydrogen, halogen, nitro, cyano, optionally substituted C 1-8 alkyl, optionally substituted C 2-6 alkenyl, optionally substituted C 2 . 6 alkynyl, optionally substituted C 3-7 cycloalkyl, optionally substituted C 1-6 alkoxycarbonyl, optionally substituted C 1-6 alkylcarbonyl, optionally substituted C ⁇ -6 alkylaminocarbonyl, optionally substituted di(C 1-6 )alkylaminocar- bonyl, optionally substituted phenyl or optionally substituted heteroaryl;
  • R 8 is optionally substituted C MO alkyl, optionally substituted [C 2-6 alkenyl(C 1-6 )alkyl], optionally substituted [C 2-6 alkynyl(C 1-6 )alkyl], optionally substituted C 3-7 cycloalkyl, amino, optionally substituted C 1-6 alkylamino, optionally substituted di(C 1-6 )alky
  • R 9 is optionally substituted C MO alkyl, optionally substituted [C 2 . 6 alkenyl(C 1-6 )alkyl], optionally substituted [C 2-6 alkynyl(C 1-6 )alkyl], optionally substituted C 3-7 cycloalkyl, optionally substituted C ⁇ -10 alkylcarbonyl, optionally substituted C MO alkoxycarbonyl, optionally substituted Cwo alkylaminocarbonyl, optionally substituted di(C 1-1 o)alkylamino- carbonyl or optionally substituted phenoxycarbonyl);
  • R 10 and R u are, independently, optionally substituted C MO alkyl, optionally substituted C 1-6 alkoxy, optionally substituted [C 2-6 alkenyl(C 1-6 )alkyl], optionally substituted [C 2-6 alkynyl- (C 1-6 )alkyl], optionally substituted C 3-7 cycloalkyl, optionally substituted C ⁇ -10 alkylcarbonyl, optionally substituted C O alkoxycarbonyl, formyl, optionally substituted C MO alkylaminocarbonyl, optionally substituted di(C M o)alkylaminocarbonyl, hydroxy, amino, optionally substituted C 1-6 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 MO alkoxycarbonyloxy, optionally substituted phen
  • R is hydrogen, optionally substituted C 1-10 alkyl, optionally substituted C 1-6 alkoxy, optionally substituted [C 2 _ 6 alkenyl(C ⁇ - 6 )alkyl], optionally substituted [C 2 . 6 alkynyl (C ⁇ -6 )alkyl], optionally substituted C 3-7 cycloalkyl, optionally substituted C MO alkylcarbonyl, optionally substituted C O alkoxycarbonyl, formyl, optionally substituted C 1-10 alkylaminocarbonyl, optionally substituted di(C M o)alkylaminocarbonyl, hydroxy, amino, optionally substituted C ⁇ -6 alkylamino, optionally substituted di(C 1- )alkylamino, optionally substituted phenoxycarbonyl, optionally substituted C ⁇ _ 6 alkylthio, optionally substituted C ⁇ -6 alkyl- sulfinyl, optionally substituted C 1-6 alkylsulfonyl,
  • R 14 is hydrogen, cyano, nitro, optionally substituted C 1-6 alkyl, optionally substituted C 3-7 cycloalkyl, optionally substituted (C 2-6 )al
  • R 15 is hydrogen, cyano, optionally substituted Cj -8 alkyl, optionally substituted [C . 6 alkenyl(C 1-6 )alkyl], optionally substituted [C -6 alkynyl(C 1 . 6 )alkyl], optionally substituted C 3-7 cycloalkyl, optionally substituted [C 3-7 cycloalkyl(C 1-6 )alkyl], C 1-6 alkoxy(C 1-6 )alkyl, optionally substituted C 1-6 alkoxycarbonyl, optionally substituted C 1-6 alkylcarbonyl, optionally substituted C 1-6 alkylaminocarbonyl, optionally substituted di(C 1-6 )alkylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl;
  • R 16 and R 21 are, independently, hydrogen, optionally substituted phenyl (C 1-2 )alkyl or optionally substituted C 1-2 o alkyl;
  • R 17 and R 22 are independently hydrogen, optionally substituted phenyl or optionally substituted C 1-6 alkyl;
  • R 19 and R 20 are, independently, hydrogen, optionally substituted C 1-2 o alkyl, optionally substituted C 3-7 cycloalkyl, optionally substituted [C 2-2 o alkenyl(C 1-6 )alkyl], optionally substituted [C 2-2 o alkynyl(C 1-6 )alkyl], optionally substituted C 1-20 alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted C 1-2 o alkylcarbonyl, optionally substituted C ⁇ -2 o alkylsulfonyl or optionally substituted phenylsulfonyl.
  • One group of preferred compounds of formula (I) is a group (G) wherein A is optionally substituted C ⁇ - 6 alkylene, optionally substituted C 2-6 alkenylene, optionally substituted C 2-6 alkynylene, optionally substituted C 1-6 alkylenoxy, optionally substituted oxy(C 1- )alkylene, optionally substituted C 1-6 alkylenethio, optionally substituted thio- (C 1-6 )alkylene, optionally substituted C ⁇ -6 alkylenamino, optionally substituted amino- (C 1-6 )alkylene, optionally substituted [C 1-6 alkyleneoxy(C 1- 6)alkylene], optionally substituted [C 1-6 alkylenethio(C 1 - 6 )alkylene], optionally substituted [C ⁇ -6 alkylenesulfinyl(Ci_ 6 )alkylene], optionally substituted [C 1-6 alkylenesulfonyl(C ⁇ -6 )alkylene] or optional
  • Y is O, S or NR 14 ;
  • Z is O, S or NR 15 ;
  • 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 C 1-6 alkylthio, optionally substituted C 3-7 cycloalkyl, cyano, nitro or SF 5 ;
  • R 7 is hydrogen, halogen, nitro, cyano, optionally substituted C 1-8 alkyl, optionally substituted C 2-6 alkenyl, optionally substituted C 2-6 alkynyl, optionally substituted C 3-7 cycloalkyl, optionally substituted C 1-6 alkoxycarbonyl, optionally substituted C 1-6 alkylcarbonyl, optionally substituted C 1-6 alkylaminocarbonyl, optionally substituted di(C 1-6 )alkylamino- carbonyl, optionally substituted phenyl or optionally substituted heteroaryl;
  • R 8 is optionally substituted C O alkyl, optionally substituted [C 2-6 alkenyl (C ⁇ 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 MO alkoxycarbonyl, formyl, optionally substituted C 1-10 alkylaminocarbonyl, optionally substituted di- (C M o)alkylaminocarbonyl, amino, optionally substituted C 1-6 alkylamino, optionally substituted di(C 1-6 )alkylamino, optionally substituted phenoxycarbonyl, tri(C ⁇ -4 )alkylsilyl, aryldi-
  • R 9 is optionally substituted C MO alkyl, optionally substituted [C 2 . 6 alkenyl(C 1-6 )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 MO alkoxycarbonyl, optionally substituted C MO alkylaminocarbonyl, optionally substituted di(C ⁇ . ⁇ o)alkyl- aminocarbonyl or optionally substituted phenoxycarbonyl); R 10 and R 11 are, independently, optionally substituted C MO alkyl, optionally substituted C ⁇ -6 alkoxy, optionally substituted [C 2-6 alkenyl(C 1-6 )alkyl], optionally substituted [C 2-6 alkynyl(C ⁇ -6 )alkyl], optionally substituted C 3 .
  • R 14 is hydrogen, cyano, nitro, optionally substituted C 1-6 alkyl, optionally substituted C 3-7 cycloalkyl, optionally substituted (C 2-6 )alkenyl(C 1 . 6 )alkyl, optionally substituted (C 2- 6)alkynyl(C 1-6 )alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted C 1-6 alkylcarbonyl, optionally substituted Ci- 6 alkoxycarbonyl, optionally substituted Cj -6 alkylamino, optionally substituted di(C] -6 )alkylamino, optionally substituted C ⁇ -6 alkylcarbonylamino, optionally substituted C 1-6 alkoxycarbonylamino, optionally substituted C 1-6 alkoxy, optionally substituted C ⁇ -6 alkylthio, optionally substituted C 1-6 alkylsulfinyl, optionally substituted C 1-6 alkylsulfony
  • R 17 and R 22 are independently hydrogen, optionally substituted phenyl or optionally substituted C 1-6 alkyl;
  • the compounds of formula (I) may exist in different geometric or optical isomers or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
  • R 27 and R 28 are, independently, hydrogen, C 1-8 alkyl, C 3 . 7 cycloalkyl, C 2 . 6 alkenyl(C 1-6 )alkyl, C 2-6 alkynyl(C 1-6 )alkyl, C 2 .
  • 6 haloalkyl C 1-6 alkoxy(C ⁇ - 6 )alkyl, C 1-6 alkoxycarbonyl(Ci- )alkyl, carboxy(C 1-6 )alkyl or phenyl(C 1-2 )alkyl; or R 27 and R 28 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 .
  • 6 alkyl groups; R 29 and R 30 are, independently, hydrogen, C 1-8 alkyl, C 3 .
  • Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, rc-propyl, n-butyl, n-pentyl, n-hexyl, iso-p ⁇ opyl, n-butyl, sec-butyl, iso-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 C 1-6 alkyl or halogen), C 5-7 cycloalkenyl (itself optionally substituted with C 1- alkyl or halogen), hydroxy, C MO alkoxy, C O alkoxy(CMo)alkoxy, tri(C 1-4 )alkylsilyl(C 1-6 )alkoxy, C 1-6 alkoxy- carbonyl(C M o)alkoxy, C MO haloalkoxy, aryl(C 1-4 )alkoxy (where the aryl group is optionally substituted), C 3 , cycloalkyloxy (where the cycloalkyl group is optionally substituted with C 1-6 alkyl or halogen), C MO alkenyloxy, C O alkynyloxy, SH, C ⁇ -10 alkylthi
  • 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.
  • acyl is optionally substituted C 1- alkylcarbonyl (for example acetyl), optionally substituted C 2 . alkenylcarbonyl, optionally substituted C 2-6 alkynylcarbonyl, optionally substituted arylcarbonyl (for example benzoyl) or optionally substituted heteroarylcarbonyl.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF 3 , CF 2 C1, CF 3 CH 2 or CHF 2 CH 2 .
  • Aryl includes naphthyl, anthracyl, fluorenyl and indenyl but is preferably phenyl.
  • heteroaryl refers to an aromatic ring containing up to 10 atoms including one or more heteroatoms (preferably one or two heteroatoms) selected from O, S and N.
  • 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
  • heterocyclyl When present, the optional substituents on heterocyclyl include C 1-6 alkyl as well as those optional substituents given above for an alkyl moiety.
  • Cycloalkyl includes cyclopropyl, cyclopentyl and cyclohexyl.
  • Cycloalkenyl includes cyclopentenyl and cyclohexenyl.
  • cycloalkyl or cycloalkenyl include C 1-3 alkyl as well as those optional substituents given above for an alkyl moiety.
  • Carbocyclic rings include aryl, cycloalkyl and cycloalkenyl groups.
  • the optional substituents on aryl or heteroaryl are selected, independently, from halogen, nitro, cyano, NCS-, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy- (C 1-6 )alkyl, C 2- alkenyl, C 2-6 haloalkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl (itself optionally substituted with C 1-6 alkyl or halogen), C 5-7 cycloalkenyl (itself optionally substituted with C 1-6 alkyl or halogen), hydroxy, C 1-10 alkoxy, C 1-10 alkoxy(C 1-10 )alkoxy, tri(C 1-4 )alkyl- silyl(C 1-6 )alkoxy, C 1-6 alkoxycarbonyl(CM 0 )alkoxy, C O haloalkoxy, aryl(C ⁇ - )alkoxy (where the aryl group is optionally,
  • C 3- cycloalkylthio (where the cycloalkyl group is optionally substituted with C 1-6 alkyl or halogen), tri(C 1- )alkylsilyl(C ⁇ -6)alkylthio, arylthio (where the aryl group is optionally substituted), C 1-6 alkylsulfonyl, C ⁇ -6 haloalkylsulfonyl, C 1-6 alkylsulfinyl, C 1-6 haloalkylsulfinyl, arylsulfonyl (where the aryl group is optionally substituted), tri(C ⁇ -4)alkylsilyl, aryldi(C 1- )alkylsilyl, (C 1- )alkyldiarylsilyl, triarylsilyl, C MO alkylcarbonyl, HO 2 C, C MO alkoxycarbonyl, aminocarbonyl, C 1-6 alkylaminocarbon
  • Haloalkenyl groups are alkenyl groups which are substituted with one or more of the same or different halogen atoms
  • dialkylamino substituents include those where the dialkyl groups together with the N atom to which they are attached form a five, six or seven- membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which is optionally substituted by one or two independently selected (C 1-6 )alkyl groups.
  • heterocyclic rings are formed by joining two groups on an N atom, the resulting rings are suitably pyrrolidine, piperidine, thiomorpholine and morpholine each of which may be substituted by one or two independently selected (C 1-6 ) alkyl groups.
  • the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, HO 2 C, C O alkoxy (itself optionally substituted by C MO alkoxy), aryl(C 1- )alkoxy, C MO alkylthio, C MO alkylcarbonyl, C MO alkoxycarbonyl, d. 6 alkylaminocarbonyl, di(C 1-6 alkylaminocarbonyl, (C 1 .
  • the optional substituents on alkenyl or alkynyl include one or more of halogen, aryl and C 3-7 cycloalkyl.
  • heterocyclyl is optionally substituted by C 1-6 alkyl.
  • the optional substituents for cycloalkyl include halogen, cyano and C 1-3 alkyl.
  • the optional substituents for cycloalkenyl include C 1-3 alkyl, halogen and cyano.
  • the present invention provides a compound of formula (IA):
  • One group of preferred compounds of formula (IA) is a group (GA) wherein
  • A is d. 6 alkylene, C 1-6 alkenylene, C 1-6 alkylenoxy, oxy(C 1-6 )alkylene, C 1-6 alkylenamino or
  • B is N or CR 7 ;
  • Z is O, S or NR 15 ;
  • R 1 is hydrogen, halogen, C 1-6 alkyl, C 2 . 6 alkenyl, C 2-6 alkynyl, C 1-6 cyanoalkyl, C 1-6 haloalkyl, C ⁇ . 6 alkoxy, d- 6 haloalkoxy, C 1-6 alkylthio, C 1-6 haloalkylthio, C 3-6 cycloalkyl, C 3-7 cycloalkyl(C 1-4 )alkyl, C 1-6 alkoxy(C 1- )alkyl, cyano, nitro or SF 5 ;
  • R 2 is hydrogen, halogen, C ⁇ -6 alkyl, C -6 alkenyl, d_ 6 alkynyl, C ⁇ -6 haloalkyl, C 1-6 alkoxy,
  • R 3 , R 4 and R 5 are independently selected from hydrogen, halogen, C ⁇ -6 alkyl, C ⁇ -6 alkoxy, C ⁇ -6 haloalkoxy, C 1-6 alkylthio, C 1-6 haloalkylthio, C ⁇ -6 alkylsulfinyl, C ⁇ . 6 haloalkylsulfinyl, C 1-6 alkylsulfonyl, d.6 haloalkylsulfonyl, C ⁇ .
  • R 6 is cyano, C ⁇ -8 alkyl, C ⁇ -6 haloalkyl, C], 6 cyanoalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 3-7 halocycloalkyl, C 3-7 cyanocycloalkyl, C 1-3 alkyl(C 3-7 )cycloalkyl, C 1-3 alkyl (C 3-7 )halocycloalkyl, C5-6 cycloalkenyl, C 3-7 cycloalkyl(d- 6 )alkyl, C 5-6 cycloalkenyl(d.
  • Ci- 6 alkylcarbonyl(Ci -6 )alkyl Ci- 6 alkylcarbonyl(Ci -6 )alkyl, C 2-6 alkenylcarbonyl(C ⁇ .6)alkyl, C 2-6 alkynylcarbonyl(C ⁇ -6 )alkyl, C 1-6 alkoxycarbonyl(C 1-6 )alkyl, C 3-6 alkenyloxycarbonyl(C 1-6 )alkyl, C 3-6 alkynyl- oxycarbonyl(d- 6 )alkyl, aryloxycarbonyl(C 1 .
  • R 7 is hydrogen, halogen, nitro, cyano, C 1-8 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 2-6 haloalkenyl, C 3-7 cycloalkyl(C 1-6 )alkyl, C ⁇ -6 alkoxy- (C 1-6 )alkyl, C 1-6 alkoxycarbonyl, C 1-6 alkylcarbonyl, C 1-6 alkylaminocarbonyl, di(d ⁇ alkylaminocarbonyl, d- 6 alkoxycarbonyl(C 1-6 )alkyl, C 1-6 alkylcarbonyl(C 1-6 )alkyl, C 1-6 alkyl- aminocarbonyl(C 1-6 )alkyl, di(C 1-6 )alkylaminocarbonyl(C 1-6 )alkyl, phenyl (
  • R 9 is C MO alkyl, benzyloxymethyl, benzoyloxymethyl, C ⁇ -6 alkoxy(C 1-6 )alkyl, C 2 - 6 alkenyl- (C 1-6 )alkyl (especially allyl), C 2- 6 alkynyl(C 1-6 )alkyl (especially propargyl), C 1-10 alkylcarbonyl or C MO alkoxycarbonyl (especially wobutoxycarbonyl);
  • R 15 is hydrogen, C 1-8 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 2-6 alkenyl, C 2- alkynyl, C 3-7 cycloalkyl, C 2-6 haloalkenyl, C 3 . 7 cycloalkyl(C 1-6 )alkyl, C ⁇ .
  • R 16 and R 21 are, independently, Cue alkyl or phenyl(C 1-2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d_ 6 alkyl, C ⁇ -6 haloalkyl, C 1-6 alkoxy or d_ 6 haloalkoxy);
  • R 18 is hydrogen, C 1-8 alkyl, C e haloalkyl, C 1-6 cyanoalkyl, C 2- 6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy(C 1-6 )alkyl, phenyl(C 1-4 )alkyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d- 6 alkyl, C 1-6 haloalkyl, d- 6 alkoxy or Ci- 6 haloalkoxy), heteroaryl- (C 1-4 )alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, d_ 6 alkyl, C 1-6 haloalkyl, d-6 alkoxy or C 1-6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, C 1-6 alkyl, C 1-6 haloalkyl, C
  • N C(CH 3 ) 2 ;
  • R 19 and R 20 are, independently, hydrogen, d. 8 alkyl, C 3 . 7 cycloalkyl, C 3-6 alkenyl, C 3-6 alkynyl, C 3-7 cycloalkyl(C ⁇ -4 )alkyl, C 2-6 haloalkyl, C 1-6 alkoxy(C 1-6 )alkyl, C 1-6 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 heteroatoms selected from O, N or S and which may be optionally substituted by one or two C l alkyl groups;
  • R 22 is d- 6 alkyl, C 1-6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, C 1-6 alkyl, C 1-6 haloalkyl, d- 6 alkoxy or d-6 haloalkoxy);
  • R 25 is hydrogen, C 1-6 alkyl, C 1-6 haloalkyl, C ⁇ -6 alkoxy, cyano, d -6 alkoxycarbonyl, C 1-6 alkylcarbonyl or NR 29 R 30 ;
  • R 26 is d. 6 alkyl or optionally substituted phenyl(C 1-2 )alkyl;
  • R 27 and R 28 are, independently, hydrogen, C 1-8 alkyl or phenyl (optionally substituted by halo, nitro, cyano, C 1-6 alkyl, d_6 haloalkyl, d ⁇ alkoxy or C 1-6 haloalkoxy); and
  • R 29 and R 30 are, independently, hydrogen, C 1-8 alkyl, C 3-7 cycloalkyl, C 3-6 alkenyl, C 3-6 alkynyl, C 2-6 haloalkyl, C ⁇ -6 alkoxy(C 1- 6)alkyl, C 1-6 alkoxycarbonyl(C 1-6 )alkyl, carboxy- (C 1-6 )alkyl or phenyl(C 1-2 )alkyl; or 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 may be optionally substituted by one or two C 1-6 alkyl groups.
  • Another group of preferred compounds of formula (IA) is a group where A, B, Z, R 1 ,
  • R 13 is cyano, nitro, C ⁇ -6 alkyl, C 1-6 haloalkyl, C 3-7 cycloalkyl, C 3-7 cycloalkyl(d -6 )alkyl, CH 2 (C 2-6 )alkenyl, CH 2 (C 2-6 )alkynyl, phenyl (optionally substituted by halo, nitro, cyano, Ci- 6 alkyl, C 1-6 haloalkyl, C 1-6 alkoxy or d-6 haloalkoxy), heteroaryl (optionally substituted by O 01/55142 17
  • halo nitro, cyano, C 1-6 alkyl, C!. haloalkyl, Ci- 6 alkoxy or C 1-6 haloalkoxy), Ci- 6 alkylcarbonyl, C 1-6 alkoxycarbonyl, d-6 alkylamino, di(C 1-6 )alkylamino, C 1-6 alkylcarbonylamino, Ci- 6 alkoxycarbonylamino, C 1-6 alkoxy, C ⁇ _6 alkylthio, C ⁇ _ 6 alkylsulfinyl, C 1-6 alkylsulfonyl, C 1-6 haloalkylthio, C 1-6 haloalkylsulfinyl, C 1-6 haloalkylsulfonyl, arylthio, arylsulfinyl, arylsulfonyl or OCO(C 1-6 )alkyl.
  • R 27 and R 28 are, independently, hydrogen, C 1-8 alkyl or phenyl (which may be optionally substituted by halo, nitro, cyano, C ⁇ -6 alkyl, Ci- 6 haloalkyl, C ⁇ -6 alkoxy or d.6 haloalkoxy);
  • R 24 is hydrogen, C 1-6 alkyl or d, 6 haloalkyl;
  • R 25 is hydrogen, d- 6 alkyl, C e haloalkyl, C ⁇ -6 alkoxy, cyano, d- alkoxycarbonyl, C 1-6 alkyl- carbonyl or NR 29 R 30 ; and
  • R 29 and R 30 are, independently,
  • 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 may be optionally substituted by one or two d- alkyl groups.
  • A is more preferably C alkylene (optionally substituted by halogen, C 1-3 alkyl or Cu alkoxy, -C(O)- or C 1-4 alkyleneoxy (which may be optionally substituted by C 1-3 alkyl).
  • A is C 1-2 alkyl-substituted C 1-4 alkylene, fluoro- substituted C alkylene, methoxy-substituted C 1- alkylene, -C(O)- or C 2- alkyleneoxy; still more preferably A is C 1-2 alkyl-substituted C 1-4 alkylene, fluoro-substituted C ⁇ - alkylene or methoxy-substituted C 1-4 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; even further preferred that A is CHF, CH(OCH 3 ) or CH(CH 3 ); and yet further preferred that either A is CHF or CH(CH 3 ) or A is CH 2 , CH(CH 3 ) or CH 2 O.
  • Y is preferably O or S.
  • Y is more preferably O.
  • Z is preferably O or S.
  • Z is more preferably O.
  • R 1 is hydrogen, halogen, d- 6 alkyl, Ci- 6 cyanoalkyl, Ci- 6 haloalkyl, C 3-7 cycloalkyl(C 1-4 )alkyl, Ci-6 alkoxy(d- 6 )alkyl, C 2-6 alkenyl, C 2 _ 6 alkynyl, d- 6 alkoxy, d- 6 haloalkoxy, d- 6 alkylthio, d- haloalkylthio, C 3 _6 cycloalkyl, cyano, nitro or SF 5 .
  • R 1 is more preferably hydrogen, halogen, d- 6 alkyl, C 2-6 alkenyl, Ci.
  • R 1 is hydrogen, halogen, d_ 6 alkyl, C ⁇ _ 6 haloalkyl, d- 6 alkoxy(Ci- 6 )alkyl, C 2-6 alkenyl, d-6 alkoxy, d. 6 haloalkoxy, d- 6 alkylthio, d- 6 haloalkylthio, C 3 . 6 cycloalkyl or cyano.
  • R 1 is halogen, d-6 alkyl, Ci. 6 haloalkyl, d- 6 alkoxy or d- 6 haloalkoxy.
  • R is hydrogen, halogen, Ci- 6 alkyl, Ci- 6 haloalkyl, d- 6 alkoxy (d_ 6 )alkyl, d- 6 alkoxy, C b haloalkoxy, d-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 d_ 6 alkyl, d-6 haloalkyl or halogen.
  • R 2 is even more preferably hydrogen, halogen, d- 6 alkyl, d- 6 haloalkyl, Ci- 6 alkoxy, Cue haloalkoxy, d- 6 alkoxy(d_6)alkyl, C ⁇ . 6 alkylthio or SF 5 ; or R and R together with the atoms to which they are attached form a benzene ring optionally substituted by d- 6 alkyl, Ci- 6 haloalkyl or halogen; or alternatively the ring may be a cyclopentane ring.
  • R 2 is hydrogen, halogen, d. 6 alkyl, d. 6 haloalkyl, d- 6 alkoxy(Ci- 6 )alkyl, C ⁇ -6 alkoxy, d_6 haloalkoxy; or R 1 and R 2 together with the atoms to which they are attached form a cyclopentane ring optionally substituted by C ⁇ _ 6 alkyl, d- 6 haloalkyl or halogen.
  • R 2 is most preferably halogen, d -6 alkyl, d -6 haloalkyl, C ⁇ -6 alkoxy, d- 6 alkoxy(C ⁇ - 6 )alkyl or Ci- 6 haloalkoxy.
  • R 3 , R 4 and R 5 are, independently, hydrogen, halogen, Ci. 6 alkyl, Ci- 6 haloalkyl, C ⁇ _6 alkoxy, d-6 haloalkoxy, d_6 alkylthio, Ci. 6 haloalkylthio, d- 6 alkylsulfinyl, C ⁇ - 6 haloalkylsulfinyl, d-6 alkylsulfonyl, C ⁇ _6 haloalkylsulfonyl, cyano, nitro, Ci- 6 alkylcarbonyl or Ci-6 alkoxycarbonyl.
  • R 3 , R 4 and R 5 are, independently, hydrogen, halogen or d- 3 alkyl. It is even more preferred that R 3 , R 4 and R 5 are, independently, hydrogen or halogen
  • R 6 is cyano, d_ 8 alkyl, C ⁇ _ 8 haloalkyl, d. 8 cyanoalkyl, C 3 . 7 cycloalkyl(C ⁇ - 6 )alkyl, C 5 . 6 cycloalkenyl(C 1 .6)alkyl, d.6 alkoxy(C ⁇ -6)alkyl, C 3 . 6 alkenyloxy(Ci -6 )alkyl, C 3-6 alkynyloxy(Ci- 6 )alkyl, aryloxy(Ci- 6 )alkyl, Ci.
  • heterocyclyl(Ci. 4 )alkyl where the heterocyclyl group is optionally substituted by halo, cyano, d- 6 alkyl, Ci-6 haloalkyl, C ⁇ - 6 alkoxy or d- 6 haloalkoxy), C 2 .
  • R 22 is phenyl (optionally substituted by halo, nitro, cyano, Ci.6 alkyl, d_ 6 haloalkyl, C ⁇ .
  • R 19 and R 20 are, independently, hydrogen, d. 8 alkyl, C 3 - 7 cycloalkyl(C ⁇ - 4 )alkyl, C 2 . 6 haloalkyl, C 1-6 alkoxy(C ⁇ . 6 )alkyl, C 3 . 7 cycloalkyl, C 3 . 6 alkenyl, C . 6 alkynyl or d_6 alkoxycarbonyl; and R 21 is phenyl(d.
  • R 6 is d- 8 alkyl, C ⁇ _ 8 haloalkyl, C ⁇ . 8 cyanoalkyl, C 3 . 7 cycloalkyl(Cj- 6 )alkyl, C 5 _ 6 cycloalkenyl(C ⁇ _ 6 )alkyl, d- 6 alkoxy(C ⁇ - 6 )alkyl, C 3 . 6 alkenyloxy(Ci- 6 )alkyl, C 3 . 6 alkynyloxy(Ci- 6 )alkyl, aryloxy(Ci_ 6 )alkyl, d. 6 carboxyalkyl, Ci.
  • alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C ⁇ _ 6 alkyl, d- 6 haloalkyl, C ⁇ _ 6 alkoxy or C 1-6 haloalkoxy), heteroaryl(C 1-4 )alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C ⁇ -6 alkyl, C ⁇ _ 6 haloalkyl, C ⁇ _ 6 alkoxy or C ⁇ _ 6 haloalkoxy), heterocyclyl- (Ci.
  • alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, d- 6 alkyl, d_ 6 haloalkyl, d- 6 alkoxy or C ⁇ _6 haloalkoxy), C 2 _ 6 alkenyl, C 2 _ 6 haloalkenyl, Ci- 6 cyanoalkenyl, C 5 - 6 cycloalkenyl, aminocarbonyl(C 2 _ 6 )alkenyl, d- ⁇ alkylaminocarbonyl- (d- 6 )alkenyl, di(C 16 )alkylaminocarbonyl(C 1 -6)alkenyl, phenyl(C 2 .
  • alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d- 6 alkyl, C ⁇ _ 6 haloalkyl, Ci- 6 alkoxy or Ci- 6 haloalkoxy), C 2 . 6 alkynyl, aminocarbonyl(C 2 _ 6 )alkynyl, alkylaminocarbonyl (C ⁇ - 6 )alkynyl, di(Ci- 6 )alkylaminocarbonyl(C 1 . 6 )alkynyl, C . 7 cycloalkyl, C 3 . 7 halocycloalkyl, C 3 . 7 cyanocycloalkyl, d.
  • R 18 is C ⁇ -8 alkyl or d. 6 haloalkyl
  • R 22 is phenyl (optionally substituted by halo, nitro, cyano, d_ 6 alkyl, d. 6 haloalkyl, C ⁇ _ 6 alkoxy or C ⁇ -6 haloalkoxy), Ci. 6 alkyl or d_6 haloalkyl
  • R 19 and R 20 are, independently, hydrogen, d -8 alkyl, C 3 .
  • R 21 is phenyl(d. 2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d_ 6 alkyl, d- 8 haloalkyl, Ci- 6 alkoxy or d- 6 haloalkoxy) or Ci.6 alkyl.
  • R 6 is more preferably C ⁇ _ 8 alkyl, C 1-8 haloalkyl, d. 6 cyanoalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-7 cycloalkyl, C 3-7 halocycloalkyl, C 3-7 cyanocycloalkyl, C 1-3 alkyl(C 3-7 )cycloalkyl, C 1-3 alkyl(C 3-7 )halocycloalkyl, C 5 . 6 cycloalkenyl, C 3 . cycloalkyl(Ci.
  • phenyl group is optionally substituted by halo, nitro, cyano, d- 6 alkyl, d. 6 haloalkyl, d- 6 alkoxy or d- 6 haloalkoxy
  • heteroaryl optionally substituted by halo, nitro, cyano, d_ 6 alkyl, haloalkyl, Ci-6 alkoxy or d_6 haloalkoxy
  • heterocyclyl wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Ci- 6 alkyl, d- 6 haloalkyl, d- 6 alkoxy or C ⁇ _ 6 haloalkoxy
  • heteroaryl(C ⁇ C ⁇ .
  • heteroaryl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, Ci- 6 haloalkyl, C ⁇ -6 alkoxy or d- 6 haloalkoxy
  • heterocyclyl(C 1- )alkyl wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C 1-6 alkyl, Ci-6 haloalkyl, Ci-6 alkoxy or d- haloalkoxy
  • R 18 O, C ⁇ _ 8 alkylthio, R 19 R 20 N or R 21 ON C(R 22 ); where R 18 is d_ 8 alkyl, d.
  • R 22 is d. 6 alkyl, d- 6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, Ci- 6 alkyl, d- 6 haloalkyl, d_ 6 alkoxy or C ⁇ _ 6 haloalkoxy);
  • R 19 and R 20 are, independently, hydrogen, C ⁇ _ 8 alkyl, C 3 . 7 cycloalkyl, C -6 alkenyl, C 3- 6 alkynyl, C 3-7 cycloalkyl(Ci -4 )alkyl, C 2-6 haloalkyl, d. 6 alkoxy(d.
  • R 6 alkyl, d- 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 heteroatoms selected from O, N or S and which may be optionally substituted by one or two C ⁇ _ 6 alkyl groups; and R 21 is d- 6 alkyl or phenyl(d.
  • R 6 is more preferably C 1-8 alkyl, C ⁇ -8 haloalkyl, C ⁇ -8 cyanoalkyl, C 3-7 cycloalkyl, C 1-3 alkyl(C 3-7 )cycloalkyl, d.
  • heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C ⁇ -6 alkyl, C ⁇ -6 haloalkyl, d-6 alkoxy or Cue haloalkoxy) or R 19 R 20 N; where R 19 and R 20 are, independently, C ⁇ . 8 alkyl or together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two C ⁇ _ 6 alkyl groups.
  • R 6 is C 1-8 alkyl, C 1-8 haloalkyl, d. 8 cyanoalkyl, d. 6 alkoxy (Ci- 6 ) alkyl, C 3 . 7 cycloalkyl, d- 3 alkyl (C 3 . 7 ) cycloalkyl, heterocyclyl (optionally substituted by halo, nitro, cyano, d. 6 alkyl, d-6 haloalkyl, d_ 6 alkoxy or C ⁇ . 6 haloalkoxy) or di(C i -8 )alkylamino.
  • R 6 is C ⁇ -8 alkyl, C ⁇ _ 8 haloalkyl, Cj- 8 cyanoalkyl, C ⁇ _ 6 alkoxy (d. 6 ) alkyl, C . 7 cycloalkyl, d. 3 alkyl (C 3 . 7 ) cycloalkyl, heterocyclyl (optionally substituted by Ci- 6 alkyl) or di(Ci. 8 )alkylamino.
  • R 6 is most preferably C ⁇ - 8 alkyl, C]- 8 haloalkyl, d. 8 cyanoalkyl, C 3 . 7 cycloalkyl, C ⁇ -3 alkyl(C 3 . 7 )cycloalkyl, d. 6 alkoxy(d. 6 )alkyl or R 19 R 20 N; where R 19 andR 20 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 Ci- 6 alkyl groups. It is preferred that R is hydrogen, halogen, nitro, cyano, C 1-8 alkyl, Ci- 6 haloalkyl,
  • R 7 is hydrogen, halogen, C ⁇ _ 8 alkyl or Ci- 6 haloalkyl.
  • R 8 is C MO alkyl, C MO haloalkyl, C 2-6 alkenyl(C ⁇ - 6 )alkyl, C 2 . 6 alkynyl(Ci_6)alkyl, C 3-7 cycloalkyl, Ci-6 alkylamino, di(C 1-6 )alkylamino or phenyl(C ⁇ -4 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d- 6 alkyl, C ⁇ . 6 haloalkyl, d- 6 alkoxy or Ci- haloalkoxy),
  • R 8 is C ⁇ - 6 alkyl, C ⁇ _6 haloalkyl, C 2 _6 alkenyl(d_ 6 )alkyl, C _ 6 alkynyl(C 1 . 6 )alkyl or benzyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d. alkyl, d-6 haloalkyl, d-6 alkoxy or Ci-6 haloalkoxy). It is preferred that R 9 is C MO alkyl, C MO haloalkyl, C 2 .6 alkenyl(d. 6 )alkyl, C 2 .
  • R 9 is C MO alkyl, d- 6 haloalkyl, C 2 . 6 alkenyl(C ⁇ _ 6 )alkyl, C 2 .
  • R 9 is even more preferably C MO alkyl, d- 6 alkylthio(C ⁇ _ 6 )alkyl, C 2 . 6 alkenyl- (Ci- 6 )alkyl (especially allyl), C 2-6 alkynyl(C 1-6 )alkyl (especially propargyl), benzyl, d- 6 alkoxycarbonyl(Ci- 6 )alkyl or C MO alkoxycarbonyl (especially w ⁇ butoxycarbonyl).
  • R 9 is most preferably C MO alkyl, C ⁇ -6 alkylthio(Ci_ 6 )alkyl, C 2 _ 6 alkenyl(C]. 6 )alkyl (especially allyl), C 2 . 6 alkynyl(d-6)alkyl (especially propargyl), benzyl or d_ 6 alkoxycarbonyl(Ci- 6 )alkyl.
  • R 10 is CM O alkyl, C 2 . 6 alkenyl(Ci- 6 )alkyl, C 2 . 6 alkynyl(Ci. 6 )alkyl, C 3-7 cycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, C 1-6 alkyl, d_ 6 haloalkyl, Ci- 6 alkoxy or Ci-6 haloalkoxy), CM O haloalkyl, d. alkoxy(d- 6 )alkyl, C 3 .
  • R 10 is d-6 alkyl, C 2 . 6 alkenyl(C ⁇ - 6 )alkyl, C 2 . 6 alkynyl- (Ci. 6 )alkyl, C 3 . 7 cycloalkyl, phenyl, d-6 haloalkyl, d_ 6 alkoxy(Ci. 6 )alkyl, Ci- 6 alkylcarbonylamino, Ci- alkoxycarbonylamino, C ⁇ _ 6 alkoxy, d_ 6 alkylamino, di(Ci. 6 )alkylamino, hydroxy, phenoxy, hydroxy(Ci. 6 )alkyl, hydroxy(Ci- 6 )alkylamino or carboxy(C i _ 6 ) alkoxy.
  • R 11 is Ci. 10 alkyl, C 2 _6 alkenyl(d- 6 )alkyl, C 2 - 6 alkynyl(Ci- 6 )alkyl, C 3 . 7 cycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, Ci. 6 alkyl, d. 6 haloalkyl, Ci- 6 alkoxy or Ci- 6 haloalkoxy), CM O haloalkyl, Ci. 6 alkoxy(d- 6 )alkyl or C 3-7 cycloalkyl- (Ci. 6 )alkyl.
  • R 11 is Ci-io alkyl, C 2 . 6 alkenyl(Ci -6 )alkyl, C 2 _ 6 alkynyl(Ci. 6 )alkyl, C 3 . 7 cycloalkyl, phenyl, Ci. 10 haloalkyl, C ⁇ _ 6 alkoxy(Ci. 6 )alkyl or C 3 . 7 cycloalkyl(d. 6 )alkyl.
  • R 12 is hydrogen, d.io alkyl, C 2 . 6 alkenyl(d. 6 )alkyl, C 2 . 6 alkynyl(Ci. 6 )alkyl, C 3 . cycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, d_ 6 alkyl, d- 6 haloalkyl, d- alkoxy or d-6 haloalkoxy), C O haloalkyl, d_ 6 alkoxy(C ⁇ - 6 )alkyl or C 3 . 7 cycloalkyl(d- 6 )alkyl. It is more preferred that R 12 is hydrogen, d.
  • R 12 is even more preferably hydrogen, C ⁇ -6 alkyl or C ⁇ _ 6 alkoxy (C ⁇ - 6 )alkyl; most preferably hydrogen.
  • R 13 is C MO alkyl, C 2 .6 alkenyl(C 1 _6)alkyl, C 2 . 6 alkynyl(C ⁇ - 6 )alkyl, C 3 . 7 cycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, Cue alkyl, Ci- 6 haloalkyl, d-6 alkoxy or d_ 6 haloalkoxy), d- 10 haloalkyl, d- 6 alkoxy(C ⁇ - 6 )alkyl, C 3 .
  • R 13 is Ci-6 alkyl, C 2 _6 alkenyl(d- 6 )alkyl, C 2 . alkynyl(Ci. 6 )- alkyl, C 3 . 7 cycloalkyl, phenyl, d- 6 haloalkyl, C ⁇ _ 6 alkoxy(Ci- 6 )alkyl, d_ 6 alkylcarbonylamino, Ci-6 alkoxycarbonylamino, Ci_ alkoxy, C ⁇ _ alkylamino, di(d. 6 )alkylamino, hydroxy, phenoxy, hydroxy(d.
  • R' 4 is cyano, nitro, d- 6 alkyl, Ci. 6 haloalkyl, C 3 . 7 cycloalkyl(C ⁇ . 6 )alkyl, C 3-7 cycloalkyl, (C 2 . 6 )alkenylCH 2 , (C 2 .
  • Ci-6 haloalkyl C ⁇ _ 6 alkoxy or Ci-6 haloalkoxy
  • Ci- 6 alkylcarbonyl Ci- 6 alkoxycarbonyl
  • Ci- 6 alkylamino di(C ⁇ _ 6 )- alkylamino, d.6 alkylcarbonylamino
  • Ci-6 alkoxycarbonylamino Ci- 6 alkoxy, C ⁇ _ 6 alkylthio, Ci-6 haloalkylthio, Ci-6 alkylsulfinyl, C ⁇ .
  • R 15 is hydrogen, C ⁇ . 8 alkyl, Cue haloalkyl, C ⁇ _ 6 cyanoalkyl, C 2 . 6 alkenylCH 2 , C 2 .6 haloalkenylCH 2 , C 2 . 6 alkynylCH 2 , C 3 . 7 cycloalkyl, C 3 . 7 cycloalkyl(d- 6 )- alkyl, d-6 alkoxy(C ⁇ . 6 )alkyl, d_6 alkoxycarbonyl, d_ 6 alkylcarbonyl, Ci.
  • R 15 is hydrogen, C ⁇ 8 alkyl or d- 6 haloalkyl.
  • Table 2 provides 330 compounds of formula (2):
  • R° and M are as defined in Table 2.
  • Table 3 provides 330 compounds of formula (3):
  • Table 4 provides 330 compounds of formula (4):
  • Table 5 provides 330 compounds of formula (5):
  • Table 6 provides 330 compounds of formula (6):
  • Table 7 provides 330 compounds of formula (7):
  • Table 9 provides 330 compounds of formula (9):
  • Table 10 provides 330 compounds of formula (10):
  • Table 11 provides 330 compounds of formula (11):
  • Table 12 provides 330 compounds of formula (12):
  • Table 13 provides 330 compounds of formula (13):
  • Table 14 provides 330 compounds of formula (14):
  • Table 15 provides 330 compounds of formula (15):
  • Table 16 provides 330 compounds of formula (16):
  • Table 17 provides 330 compounds of formula (17):
  • Table 18 provides 330 compounds of formula (18):
  • Table 20 provides 330 compounds of formula (20):
  • Table 21 provides 330 compounds of formula (21):
  • Table 22 provides 330 compounds of formula (22):
  • Table 23 provides 330 compounds of formula (23): O 01/55142
  • Table 24 provides 330 compounds of formula (24):
  • Table 25 provides 330 compounds of formula (25):
  • Table 26 provides 330 compounds of formula (26):
  • Table 27 provides 330 compounds of formula (27):
  • Table 29 provides 330 compounds of formula (29):
  • Table 30 provides 330 compounds of formula (30):
  • Table 31 provides 330 compounds of formula (31):
  • Table 32 provides 330 compounds of formula (32):
  • Table 33 provides 330 compounds of formula (33):
  • Table 34 provides 330 compounds of formula (34):
  • Table 35 provides 330 compounds of formula (35):
  • Table 36 provides 330 compounds of formula (36):
  • Table 37 provides 330 compounds of formula (37):
  • Table 38 provides 330 compounds of formula (38):
  • Table 39 provides 330 compounds of formula (39):
  • Table 40 provides 330 compounds of formula (40):
  • Table 41 provides 330 compounds of formula (41):
  • Table 42 provides 330 compounds of formula (42):
  • Table 43 provides 330 compounds of formula (43):
  • Table 44 provides 330 compounds of formula (44):
  • Table 45 provides 330 compounds of formula (45):
  • Table 47 provides 330 compounds of formula (47):
  • Table 48 provides 330 compounds of formula (48):
  • Table 49 provides 330 compounds of formula (49):
  • Table 50 provides 330 compounds of formula (50):
  • Table 51 provides 330 compounds of formula (51):
  • Table 52 provides 330 compounds of formula (52):
  • Table 53 provides 330 compounds of formula (53):
  • Table 54 provides 330 compounds of formula (54):
  • Table 55 provides 330 compounds of formula (55):
  • Table 56 provides 330 compounds of formula (56):
  • Table 57 provides 330 compounds of formula (57):
  • Table 58 provides 330 compounds of formula (58):
  • Table 59 provides 330 compounds of formula (59):
  • Table 60 provides 330 compounds of formula (60):
  • Table 61 provides 330 compounds of formula (61):
  • Table 62 provides 330 compounds of formula (62):
  • Table 63 provides 330 compounds of formula (63):
  • Table 64 provides 330 compounds of formula (64):
  • Table 65 provides 330 compounds of formula (65):
  • Table 66 provides 330 compounds of formula (66):
  • Table 67 provides 330 compounds of formula (67):
  • Table 68 provides 330 compounds of formula (68):
  • Table 69 provides 330 compounds of formula (69):
  • Table 70 provides 330 compounds of formula (70):
  • Table 71 provides 330 compounds of formula (71):
  • Table 72 provides 330 compounds of formula (72):
  • Table 73 provides 330 compounds of formula (73):
  • Table 74 provides 330 compounds of formula (74):
  • Table 75 provides 330 compounds of formula (75):
  • Table 76 provides 330 compounds of formula (76):
  • Table 77 provides 330 compounds of formula (77):
  • Table 78 provides 330 compounds of formula (78):
  • Table 79 shows selected melting point and selected NMR data, all with CDCI 3 as the solvent (unless otherwise stated; if a mixture of solvents is present, this is indicated as, for example, (CDCI 3 / d ⁇ -DMSO)), (no attempt is made to list all characterising data in all cases) for compounds of Tables 1 to 78.
  • the compounds of the invention may be made in a variety of ways.
  • a compound of formula (II), wherein R 35 is hydrogen with an alkylating or acylating agent, optionally in the presence of a base and a phase transfer catalyst, provides a compound of formula (la), wherein R 9 is an alkyl or acyl group.
  • suitable alkylating agents include, but are not restricted to, alkyl halides (such as methyl iodide) and alkyl sulfates (such as dimethylsulfate).
  • Suitable acylating agents include anhydrides (such as acetic anhydride), acid chlorides (such as acetyl chloride or benzoyl chloride) and chloroformates (such as ethyl chloroformate).
  • Suitable bases include organic bases (such as triethylamine or pyridine), alkali metal alkoxides (such as potassium tert-butoxide) and inorganic bases (such as sodium hydride or sodium hydroxide).
  • Suitable phase transfer catalysts may be selected by reference to the literature (see, for example, J. March, Advanced Organic Chemistry, Third Edition, John Wiley and Sons, New York, 1985, pages 320-322 and references therein).
  • R 9 is an alkyl group with a nucleophile, for example an alcohol (suitable alcohols include, but are not restricted to, ethanol or methanol) or an amine, optionally in the presence of a base and a phase transfer catalyst or in the presence of a mercuric salt (such as mercuric chloride), provides, respectively, a compound of formula (Ib) or (Ic).
  • a nucleophile for example an alcohol (suitable alcohols include, but are not restricted to, ethanol or methanol) or an amine, optionally in the presence of a base and a phase transfer catalyst or in the presence of a mercuric salt (such as mercuric chloride), provides, respectively, a compound of formula (Ib) or (Ic).
  • a nucleophile for example an alcohol (suitable alcohols include, but are not restricted to, ethanol or methanol) or an amine, optionally in the presence of a base and a phase transfer catalyst or in the presence of a mercuri
  • a compound of formula (la) may be reacted with an alcohol or an amine, O-alkylhydroxylamine or hydrazine, optionally in the presence of a mercuric salt (such as mercuric chloride), according to known procedures to give a compound of formula (Ib) or (Ic), respectively where R 8 , R 10 and R 11 are, independently, hydrogen, optionally substituted alkyl, alkenyl, alkynyl, amino, substituted amino or alkoxy.
  • R 10 when R 10 is hydrogen, it may be reacted further with an alkylating or acylating agent under conditions previously described to give further substituted compounds of formula (Ic).
  • a compound of formula (IT) may be prepared by reacting a compound of formula (Ha) 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-bis0 ⁇ r ⁇ -tolyl)-l,3-dithia-2,4- diphosphetane-2,4-disulfide (Davy reagent -tolyl) or phosphorus pentasulfide in a suitable solvent such as toluene or fluorobenzene.
  • a suitable thionating agent such as 2,4-bis(4-methoxyphenyl)-l,3-dithia
  • a compound of formula (Ila) may be reacted with a chlorinating agent, for example phosphorus oxychloride or phosphorous pentachloride, to give a compound of formula (IH) which can be further reacted with a thiol, an alcohol or an amine, optionally in the presence of a base, to give, respectively, a compound of formula (la), (Ib), or (Ic).
  • a chlorinating agent for example phosphorus oxychloride or phosphorous pentachloride
  • a compound of formula (Ila) wherein A is optionally substituted alkylene, alkenylene, alkylenoxy, alkylenamino or alkylenethio may be prepared by reacting a compound of formula (IV) with an appropriate a compound of formula (N), where X is hydroxy, alkoxy or aryloxy in the presence of a known coupling agent such as 1,3- dicyclohexylcarbodiimide or l-(3-dimethylaminopropyl)-3-ethylcarbodiimide.
  • a compound of formula (N), where X is hydroxy may first be converted to an acid chloride or anhydride suitable for reaction with an amine to form an amide (such procedures are well known to those skilled in the art and are described, for example in J. March, Advanced O 01/55142 - 63 -
  • Compounds of formula (IN) are known compounds, or may be prepared from commercially available starting materials by methods described in the literature (see, for example, C. Oliver Kappe, Robert Flammang, and Curt Wentrup, Heterocycles, Vol. 37, No. 3, 1615, (1994), A. Adams and R. Slack, J. Chem. Soc, 3061, (1959) and Ronald Ehackler, Kenneth W. Burow, Jr., Sylvester V. Kaster and David I. Wickiser, J. Heterocyclic Chem, 26, 1575, (1989), Ronald Ehackler, Glen P Jourdan, Peter L Johnson, Brian R Thoreen and Jack G Samaritoni, PCT Int.
  • Benzothiophenes may be made from appropriate thiophenols by processes similar to those described by Robert D Schuetz and Richard L Titus (J. Heterocycl. Chem., 4, No 4, 465 (1967); suitable thiophenols are known compounds or may be prepared by known methods.
  • Benzofurans may be made from ⁇ rt/zo-halophenols as described by Henning Lutjens and Peter J Scammells, Tetrahedron Letters 39 (1998), 6581-6584, Terence C. Owen et ah, Tetrahedron Letters 30, No. 13, 1597 (1989) and Fred G O 01/55142 64
  • Indoles may be prepared form ⁇ rt/r ⁇ -haloanilines according to the method of Cheng-yi Chen et al., J. Org. Chem., 1997, 62, 2676, Takao Sakamoto et al., J. Org. Chem., 1997, 62, 6507 and Alan D. Adams et al., WO9827974.
  • Appropriate ⁇ rt&osubstituted phenols and anilines may be prepared by known methods from commercially available starting materials.
  • a compound of formula (Na) may be prepared by treating a compound of formula (NI) with an optionally substituted haloalkyl ester or an ⁇ , ⁇ unsaturated ester, preferably in the presence of a base such as potassium carbonate.
  • a compound of formula (Nil) can be reacted with appropriate malonate, alkane or alkene derivatives in the presence of suitable catalysts, for example palladium (0) derivatives, to give a compound of formula (V).
  • a compound of formula (VET) may be made from a compound of formula (lib) by treatment with N,N-dimethyl-formamide 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 (VET) may be treated subsequently with a secondary amine (HNR 29 R 30 ) to give a compound of formula (DC); a compound of formula (lib) may be treated in an analogous manner with trialkylorthoformates to afford a compound of formula (X), where R d is C 1-6 alkyl.
  • a compound of formula (V) (where A is CH 2 O and X is O-alkyl) may be further derivatised by deprotonation with a suitable base (such as lithium hexamethyl disilazide) followed by reaction with an electrophile such as an alkyl halide, alkyl sulphate or a halogenating agent [such as N-chlorosuccinamide or l-chloromethyl-4-fluoro-l,4- diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate)] and this procedure may be carried out more than once to generate further compounds of formula (Ha).
  • a suitable base such as lithium hexamethyl disilazide
  • an electrophile such as an alkyl halide, alkyl sulphate or a halogenating agent [such as N-chlorosuccinamide or l-chloromethyl-4-fluoro-l,4- diazoniabicyclo
  • a compound of formula (IN) can be reacted with a diazing agent such as tert-butyl nitrite in the presence of copper oxide to give a compound of formula (XI) which can then be further reacted with a compound of formula (V) (where X is chlorine) to give a compound of formula (Id).
  • a diazing agent such as tert-butyl nitrite in the presence of copper oxide
  • 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.
  • Damalinia spp. and Linognathus spp. bits and sucking lice
  • Meloidogyne spp. root knot nematodes
  • Globodera spp. and Heterodera spp. cyst nematodes
  • Pratylenchus spp. lesion nematodes
  • Rhodopholus spp. banana burrowing nematodes
  • Tylenchulus spp. citrus nematodes
  • Haemonchus contortus barber pole worm
  • Caenorhabditis elegans_ vinegar eelworm
  • 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 grised) on rice and wheat and other Pyricularia spp.
  • 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; Cochli
  • Botrytis cinerea grey mould
  • Botrytis cinerea grey mould
  • Alternaria spp. on vegetables (for example carrots), oil-seed rape, apples, tomatoes, potatoes, cereals (for example wheat) and other hosts
  • Venturia spp. including Venturia inaequalis (scab)) on apples, pears, stone fruit, tree nuts and other hosts
  • Cladosporium spp. on a range of hosts including cereals (for example wheat) and tomatoes
  • a compound of formula (I) may move acropetally, basipetally or locally in plant tissue to be active against one or more fungi. Moreover, a compound of formula (I) may be volatile enough to be active in the vapour phase against one or more fungi on the plant.
  • the invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a pest, a locus of pest, or to a plant susceptible to attack by a pest, and a method of combating and controlling fungi which comprises applying a fungicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a plant, to a seed of a plant, to the locus of the plant or seed, to soil or to any other growth medium (for example a nutrient solution).
  • the compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
  • plant as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes protectant, curative, systemic, eradicant and antisporulant treatments.
  • the compounds of formula (I) are preferably used for agricultural, horticultural and turfgrass purposes in the form of a composition.
  • a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA).
  • SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula (I).
  • the composition is generally used for the control of pests or fungi such that a compound of formula (I) is applied at a rate of from O.lg to 10kg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 1kg per hectare.
  • a compound of formula (I) When used in a seed dressing, a compound of formula (I) is used at a rate of 0.000 lg to lOg (for example O.OOlg or 0.05g), preferably 0.005g to lOg, more preferably 0.005g to 4g, per kilogram of seed.
  • the present invention provides an insecticidal, acaricidal, nematicidal, molluscicidal or fungicidal composition comprising an insecticidally, acaricidally, nematicidally, molluscicidally or fungicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor.
  • the composition is preferably an insecticidal, acaricidal, nematicidal or fungicidal composition.
  • the invention provides a method of combating and controlling pests or fungi at a locus which comprises treating the pests or fungi or the locus of the pests or fungi with an insecticidally, acaricidally, nematicidally, molluscicidally or fungicidally effective amount of a composition comprising a compound of formula (I).
  • the compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
  • compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations.
  • DP dustable powders
  • SP soluble powders
  • SG water soluble granules
  • WP water dispersible granules
  • GR granules
  • SL soluble concentrates
  • OL oil miscible liquids
  • UL ultra
  • Dustable powders may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
  • solid diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers
  • Soluble powders may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • water-soluble organic solids such as a polysaccharide
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary.
  • a hard core material such as sands, silicates, mineral carbonates, sulphates or phosphates
  • Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils.
  • One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • Dispersible Concentrates may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).
  • Emulsifiable concentrates or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents).
  • Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C 8 -do fatty acid dimethylamide) and chlorinated hydrocarbons.
  • aromatic hydrocarbons such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark
  • ketones such as cycl
  • An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.
  • Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion.
  • Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of formula (I) is present initially in either the water or the solvent/SFA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs.
  • An ME may be either an oil-in- water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation.
  • An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
  • SC Suspension concentrates
  • SCs may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I).
  • SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound.
  • One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle.
  • a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
  • Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example n-butane).
  • a compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
  • a compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
  • Capsule suspensions may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor.
  • the polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure.
  • the compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment.
  • a compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
  • a composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)).
  • additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).
  • a compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS).
  • DS powder for dry seed treatment
  • SS water soluble powder
  • WS water dispersible powder for slurry treatment
  • CS capsule suspension
  • the preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above.
  • Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
  • Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di- wopropyl- and tri-wopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (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 octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
  • Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carb
  • a compound of formula (I) may be applied by any of the known means of applying pesticidal or fungicidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.
  • a locus of the pests such as a habitat of the pests, or a growing plant liable to infestation by the pest
  • a compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
  • compositions for use as aqueous preparations are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use.
  • These concentrates which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
  • a compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers).
  • fertilisers for example nitrogen-, potassium- or phosphorus-containing fertilisers.
  • Suitable formulation types include granules of fertiliser.
  • the mixtures suitably contain up to 25% by weight of the compound of formula (I).
  • the invention therefore also provides a fertiliser composition comprising a fertiliser and a compound of formula (I).
  • compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.
  • the resulting composition may have a broader spectrum of activity or a greater level of intrinsic activity than the compound of formula (I) alone. Further the other fungicide may have a synergistic effect on the fungicidal activity of the compound of formula (I).
  • the compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components.
  • the particular additional active ingredient will depend upon the intended utility of the composition.
  • Suitable pesticides include the following: a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate; b) Organophosphates, such as, profenofos, sulprofos, acephat
  • 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),
  • the compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
  • synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.
  • Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
  • 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 PDCTM.
  • 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.
  • EXAMPLE 1 This Example illustrates the preparation of N-(4-chloro-3-methylisothiazol-5-yl)thio(2- [2,2-dimethylpropyl] benzoxazol-5-yl)acetamide.
  • Step 1 Preparation of 5-amino-4-chloro-3-methylisothiazole.
  • Nitric acid (69% by weight, 16M, 20ml) was added dropwise to a solution of methyl (4-hydroxyphenyl)acetate [from step 2] (50.0g, 0.3mole) in acetic acid (500ml), maintaining the temperature of the reaction below 15°C by external cooling. (An induction period was observed for this reaction.) Once gas chromatographic analysis had confirmed that the reaction was complete, the mixture was carefully quenched into water (21) with vigorous stirring. An emulsion formed which subsequently crystallised. After filtration, washing with water and drying, the desired product was obtained as a yellow powder.
  • Step 5 Preparation of methyl [3-(2,2-dimethylpropionamido)-4- hydroxyphenyl]acetate._
  • Step 6 Preparation of methyl [(2,2-dimethylpropyl)-5-benzoxazolyl]acetate.
  • p ⁇ r -Toluenesulphonic acid 1.5g
  • toluene 120ml
  • a Dean & StarkTM assembly fitted to remove water.
  • the solution was cooled to ⁇ 80°C and methyl [3-(2,2-dimethylpropionamido)-4-hydroxy-phenyl]acetate [from step 5] (20.0g, 0.07mole) was added portionwise.
  • Step 7 Preparation of [(2,2-dimethylpropyl)-5-benzoxazolyI]acetic acid.
  • Step 8 Preparation of N-(4-chloro-3-methylisothiazol-5-yl)-[2-(2,2- dimethylpropyl)benzoxazol-5-yI]acetamide.
  • Step 9 Preparation of N-(4-chloro-3-methylisothiazoI-5-yl)thio(2-[2,2- dimethylpropyl] benzoxazoI-5-yl)acetamide.
  • N-(4-chloro-3-methylisothiazol-5-yl)-(2-[2,2-dimethylpropyl]benzoxazol-5-yl)- acetamide [from step 8] (lOg) was heated to 75-80°C in dry fluorobenzene (150ml) with stirring under an atmosphere of nitrogen. The solution was treated portion-wise over 2hour with 2,4-bis(p-tolylthio)-l,3,2,4-dithiadiphosphetane-2,4-disulfide (18g), heated to reflux for a further 5hour and was then allowed to cool to ambient temperature.
  • Example 2 The product from Example 1 (5.00g) was stirred under an atmosphere of nitrogen in dry tetrahydrofuran (THF) (50ml) whilst sodium bis(trimethylsilyl)amide (12.7ml of a l.OM solution in THF) was added. The mixture was stirred at ambient temperature for 30minutes and then methyl iodide (0.79ml) was added. The mixture was heated at 45 °C for 3hours and then allowed to stand at ambient temperature overnight. The reaction mixture was partitioned between ethyl acetate and water. The organic layers were dried (magnesium sulfate), filtered and the solvent was evaporated under reduced pressure.
  • THF dry tetrahydrofuran
  • Compound No. 77 of Table No. 1 as a light brown gum; Compound No. 37 of Table No. 1 as a yellow gum; and Compound No. 17 of Table No. 1 as an orange solid.
  • Example 2 The product from Example 1 (0.30g) was stirred under an atmosphere of nitrogen in acetone (5ml) containing anhydrous potassium carbonate (0.15g) and was then treated with a solution of chloromethyl methylsulfide (0.075g) in acetone (2ml). The mixture was heated to 55°C for hour, allowed to cool to ambient temperature and was then filtered. The insoluble material was washed with further acetone and the combined filtrate was evaporated under reduced pressure. The residual oil was fractionated by chromatography (silica; hexane: diethyl ether at 10:1 to 4:1 by volume) to give the required product as a brown gum (0.18g).
  • EXAMPLE 5 This Example illustrates the preparation of Compound No. 257 of Table No. 1.
  • the product from Example 2 (0.20g) was dissolved in ethanol (5ml) and allylamine (0.18ml) was added. The mixture was stirred at ambient temperature for 24hours. The solvent was removed under reduced pressure and the solid residue was triturated (hexane:ethyl acetate at 4: 1 by volume) and the triturating solvents were evaporated to give a yellow oil. This oil was purified by column chromatography to give the required product as an orange oil (0.12g). Using similar procedures, the following compounds were prepared individually:
  • Example 2 The product from Example 2 (0.20g) was dissolved in acetic acid (5ml) and aniline (0.22ml) was added. The mixture was stirred at ambient temperature for 24hours. The solvent was removed under reduced pressure and the residue was purified by column chromatography (silica gel, eluting with ethyl acetate:hexane at 1:7 by volume) to give the required product as a brown solid (0.079g).
  • Example 2 The product from Example 2 (0.30g) was dissolved in methyl anthranilate (5 ml) and the mixture was allowed to stir at ambient temperature for 3 days and then at 40°C for one further day. The solvent was removed under reduced pressure and the residue was purified by column chromatography (silica gel, eluting with ethyl acetate: hexane at 1:9 by volume) to give the required product as a pink solid (0.138g).
  • EXAMPLE 8 This Example illustrates the preparation of Compound No. 217 of Table No. 1.
  • the product from Example 1 (0.20g) was dissolved in tetrahydrofuran (5 ml) and 2-hydroxyethylhydrazine (0.067ml) and mercury (U) chloride (0.115g) were added.
  • the mixture was stirred at 40°C for 4hours, then at ambient temperature overnight and then at 50°C for a further 4hours.
  • the reaction mixture was filtered through a pad of Hi-FloTM and the solvent was removed under reduced pressure.
  • the residue was purified by column chromatography (silica gel, eluting with ethyl acetate followed by methanol) to give the required product as a brown gum (0.050g).
  • EXAMPLE 9 This Example illustrates the preparation of Compound No. 367 of Table No. 1.
  • the product from Example 2 (0.20g) was dissolved in ethanol (5ml) and hydroxylamine hydrochloride (0.102g) and triethylamine (0.27ml) were added.
  • the mixture was stirred at ambient temperature for 24hours.
  • the solvent was removed under reduced pressure and the residue was triturated (hexane:ethyl acetate at 4: 1 by volume) to leave a solid.
  • the solid was dissolved in ethyl acetate, filtered and washed with water.
  • the organic layer was dried (magnesium sulfate), filtered and evaporated under reduced pressure to give the required product as a yellow solid (0.072g).
  • EXAMPLE 10 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.
  • results from these tests are displayed in Table 80, 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.
  • This Example illustrates the fungicidal properties of compounds of formula (I).
  • the compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.
  • Test compounds were individually formulated as a solution either in acetone or acetone/ethanol (1: 1 by volume) which was diluted in deionised water to a concentration of lOOppm (that is, lmg of compound in a final volume of 10ml) immediately before use.
  • lOOppm concentration of lmg of compound in a final volume of 10ml
  • TWEEN 20 0.1% by volume
  • TWEEN is a registered trade mark.
  • Individual compounds of formula (I) were applied as a foliar (Folr) application (where the chemical solution was applied to the foliage of the test plants by spraying the plant to maximum droplet retention.)
  • the Phytophthora infestans lycopersici, Puccinia recondita and Pyricularia oryzae plants were inoculated with a calibrated fungal spore suspension.
  • the Uncinula necator plants were inoculated using a 'blowing' inoculation technique.
  • Phytophthora infestans lycopersici Assessments were performed on a single leaf of each of the replicate plants for Uncinula necator. For Puccinia recondita and Pyricularia recondita assessments were carried out collectively on the plants in each replicate pot.
  • the disease level present (that is, the percentage leaf area covered by actively sporulating disease) was assessed visually. For each treatment, the assessed values for all its replicates were meaned to provide mean disease values. Untreated control plants were assessed in the same manner. The data were then processed by the method, described hereinafter, to provide PRCO (Percentage Reduction from Control) values.
  • PRCO Percentage Reduction from Control
  • the PRCO is then rounded to the nearest whole number; therefore, in this particular example, the PRCO result is 71. It is possible for negative PRCO values to be obtained.
  • PHYTIN Phytophthora infestans lycopersici
  • PUCCRT Puccinia recondita
  • PYRIOR Pyricularia oryzae
  • UNCINE Uncinula necator

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Abstract

A compound of formula (I), where B is N, N-oxide or CR7; M is OC(=Y), N=C(OR8), N=C(SR9), N=C(NR10R11) or N(R?12)C(=NR13¿) where O or N is the atom of attachment to the isothiazole group; Y is O, S or NR14; Z is O, S or NR15; and A and the various R groups are defined organic radicals, and their preparation and use and compositions containing them.

Description

ISOTHIAZOLE DERIVATIVES AND THEIR USE AS PESTICIDES
The present invention relates to azole derivatives, to processes for preparing them, to fungicidal, insecticidal, acaricidal, molluscicidal and nematicidal compositions comprising them, to methods of using them to combat fungal diseases (especially fungal diseases of plants) and to methods of using them to combat and control insect, acarine, mollusc and nematode pests.
Azole and azine derivatives are disclosed in WO95/31448, WO97/18198, WO98/02424, WO98/05670 and WO98/17630. The present invention provides a compound of formula (I):
Figure imgf000003_0001
where A is optionally substituted C1-6 alkylene, optionally substituted C2-6 alkenylene, optionally substituted C2-6 alkynylene, optionally substituted cycloalkylene, optionally substituted C]-6 alkylenoxy, optionally substituted oxy(C1.6)alkylene, optionally substituted C1-6 alkylenethio, optionally substituted thio(Cι_6)alkylene, optionally substituted CJ-6 alkylenamino, optionally substituted amino(C1-6)alkylene, optionally substituted [Cι-6 alkyleneoxy(C1.6)alkylene], optionally substituted [C1-6 alkylenethio(C1-6)alkylene], optionally substituted
Figure imgf000003_0002
optionally substituted [ .6 alkylenesulfonyl(C1-6)alkylene] or optionally substituted [Cι-6 alkyleneamino(C1-6)alkylene]; B is N, N-oxide or CR7;
M is OC(=Y), N=C(OR8), N=C(SR9), N=C(NR10Rπ) or N(R12)C(=NR13) where O or N is the atom of attachment to the isothiazole group; Y is O, S or NR14; Z is O, S or NR15;
R1 is hydrogen, halogen, optionally substituted C1-6 alkyl, optionally substituted C2_ alkenyl, optionally substituted C2-6 alkynyl, optionally substituted Cι_6 alkoxy, optionally substituted C|-6 alkylthio, optionally substituted C3_7 cycloalkyl, cyano, nitro or SF5; R2 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 C1-6 alkylthio, optionally substituted C1-6 alkylsulfinyl, optionally substituted C1-6 alkylsulfonyl, cyano, nitro, formyl, optionally substituted C1-6 alkylcarbonyl, optionally substituted C1-6 alkoxycarbonyl, SF5 or RI6ON=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 C1-6 alkyl, C1-6 haloalkyl or halogen; R3, R4 and R5 are, independently, hydrogen, halogen, optionally substituted Cι-6 alkyl, optionally substituted C1-6 alkoxy, optionally substituted C1-6 alkylthio, optionally substituted C1-6 alkylsulfinyl, optionally substituted Cι-6 alkylsulfonyl, cyano, nitro, optionally substituted C1-6 alkylcarbonyl, optionally substituted -β alkoxycarbonyl or SF5; R6 is hydrogen, halogen, cyano, optionally substituted C1-2o alkyl, optionally substituted C2-20 alkenyl, optionally substituted C2-20 alkynyl, optionally substituted C3- cycloalkyl, optionally substituted C5-6 cycloalkenyl, formyl, optionally substituted C1-20 alkoxycarbonyl, optionally substituted C1-2o alkylcarbonyl, aminocarbonyl, optionally substituted C1-20 alkylaminocar- bonyl, optionally substituted di(C1-2o)alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylamino- carbonyl, optionally substituted N-(Ci-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 C1-2o alkylsulfinyl, optionally substituted C1-2o alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl, R18O, R19R20N or R21ON=C(R22);
R7 is hydrogen, halogen, nitro, cyano, optionally substituted C1-8 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted C3-7 cycloalkyl, optionally substituted C1-6 alkoxycarbonyl, optionally substituted C1-6 alkylcarbonyl, optionally substituted Cι-6 alkylaminocarbonyl, optionally substituted di(C1-6)alkylaminocar- bonyl, optionally substituted phenyl or optionally substituted heteroaryl; R8 is optionally substituted CMO alkyl, optionally substituted [C2-6 alkenyl(C1-6)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 C1-10 alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, formyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(C1-10)alkyl- aminocarbonyl, amino, optionally substituted phenoxycarbonyl, tri(C1- )alkylsilyl, aryldi- (Cι-4)alkylsilyl, (Cι-4)alkyldiarylsilyl or triarylsilyl;
R9 is optionally substituted CMO alkyl, optionally substituted [C2.6 alkenyl(C1-6)alkyl], optionally substituted [C2-6 alkynyl(C1-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted Cι-10 alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, optionally substituted Cwo alkylaminocarbonyl, optionally substituted di(C1-1o)alkylamino- carbonyl or optionally substituted phenoxycarbonyl);
R10 and Ru are, independently, optionally substituted CMO alkyl, optionally substituted C1-6 alkoxy, optionally substituted [C2-6 alkenyl(C1-6)alkyl], optionally substituted [C2-6 alkynyl- (C1-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted Cι-10 alkylcarbonyl, optionally substituted C O alkoxycarbonyl, formyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(CMo)alkylaminocarbonyl, hydroxy, amino, optionally substituted C1-6 alkylamino, optionally substituted di(C1-6)alkylamino, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylamino, optionally substituted CMO alkylcarbonyloxy, optionally substituted CMO alkoxycarbonyloxy, optionally substituted phenoxycarbonyloxy, optionally substituted CMoalkylaminocarbonyloxy, optionally substituted di(CMo)alkylaminocarbonyloxy, optionally substituted CMO alkylcarbonylamino, optionally substituted C O alkoxycarbonylamino, optionally substituted phenoxycarbonylamino, optionally substituted C1-10 alkylaminocarbonylamino, optionally substituted di(CMo)alkylaminocarbonylamino or optionally substituted phenoxycarbonyl;
R is hydrogen, optionally substituted C1-10 alkyl, optionally substituted C1-6 alkoxy, optionally substituted [C2_6 alkenyl(Cι-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 C1-10 alkylaminocarbonyl, optionally substituted di(CMo)alkylaminocarbonyl, hydroxy, amino, optionally substituted Cι-6 alkylamino, optionally substituted di(C1- )alkylamino, optionally substituted phenoxycarbonyl, optionally substituted Cι_6 alkylthio, optionally substituted Cι-6 alkyl- sulfinyl, optionally substituted C1-6 alkylsulfonyl, optionally substituted C1-6 aryl, optionally substituted C1-6 arylthio, optionally substituted C1-6 arylsulfinyl, optionally substituted C e arylsulfonyl or R36R37NS; R36 and R37 are, independently, optionally substituted C1-6 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 C1-6 alkyl groups; R13 is hydrogen, hydroxy, cyano, nitro, optionally substituted CMO 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 C1-6 alkylcarbonyl, optionally substituted Cι.6 alkoxycarbonyl, optionally substituted C1-6 alkylamino, optionally substituted di(C1- 6)alkylamino, optionally substituted C1-6 alkylcarbonylamino, optionally substituted C1-6 alkoxycarbonylamino, optionally substituted Cι-6 alkoxy, optionally substituted C1-6 alkylthio, optionally substituted C1-6 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 CMO alkylaminocarbonyloxy, optionally substituted di(CMo)alkylaminocarbonyloxy, optionally substituted phenoxycarbonylamino, optionally substituted CMO alkylaminocarbonylamino, optionally substituted di(C1-1o)alkylaminocarbonylamino or optionally substituted C1-6 alkylcarbonyloxy; R14 is hydrogen, cyano, nitro, optionally substituted C1-6 alkyl, optionally substituted C3-7 cycloalkyl, optionally substituted (C2-6)alkenyl(C1-6)alkyl, optionally substituted (C2- 6)alkynyl(C1- )alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted C1-6 alkylcarbonyl, optionally substituted Cι-6 alkoxycarbonyl, optionally substituted Cι-6 alkylamino, optionally substituted di(C1-6)alkylamino, optionally substituted C1-6 alkylcarbonylamino, optionally substituted C1-6 alkoxycarbonylamino, optionally substituted Cι-6 alkoxy, optionally substituted C1-6 alkylthio, optionally substituted Cι-6 alkylsulfinyl, optionally substituted C1-6 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or optionally substituted C1-6 alkylcarbonyloxy;
R15 is hydrogen, cyano, optionally substituted Cj-8 alkyl, optionally substituted [C .6 alkenyl(C1-6)alkyl], optionally substituted [C -6 alkynyl(C1.6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted [C3-7 cycloalkyl(C1-6)alkyl], C1-6 alkoxy(C1-6)alkyl, optionally substituted C1-6 alkoxycarbonyl, optionally substituted C1-6 alkylcarbonyl, optionally substituted C1-6 alkylaminocarbonyl, optionally substituted di(C1-6)alkylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl;
R16 and R21 are, independently, hydrogen, optionally substituted phenyl (C1-2)alkyl or optionally substituted C1-2o alkyl;
R17 and R22 are independently hydrogen, optionally substituted phenyl or optionally substituted C1-6 alkyl; R18 is hydrogen, optionally substituted C1-2o alkyl, optionally substituted [C2-2o alkenyl- (C1-6)alkyl], optionally substituted [C2-20 alkynyl(Cι-6) alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, (C1-6)alkylCH=N, optionally substituted arylCH=N, optionally substituted [aryl(C1-6)alkyl]CH=N, optionally substituted heteroarylCH=N, optionally substituted [heterocyclyl(C1-6)alkyl]CH=N, optionally substituted arylC(CH3)=N, optionally substituted heteroarylC(CH3)=N or optionally substituted di(C1.6)alkylC=N; and R19 and R20 are, independently, hydrogen, optionally substituted C1-2o alkyl, optionally substituted C3-7 cycloalkyl, optionally substituted [C2-2o alkenyl(C1-6)alkyl], optionally substituted [C2-2o alkynyl(C1-6)alkyl], optionally substituted C1-20 alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted C1-2o alkylcarbonyl, optionally substituted Cι-2o alkylsulfonyl or optionally substituted phenylsulfonyl.
One group of preferred compounds of formula (I) is a group (G) wherein A is optionally substituted Cι-6 alkylene, optionally substituted C2-6 alkenylene, optionally substituted C2-6 alkynylene, optionally substituted C1-6 alkylenoxy, optionally substituted oxy(C1- )alkylene, optionally substituted C1-6 alkylenethio, optionally substituted thio- (C1-6)alkylene, optionally substituted Cι-6 alkylenamino, optionally substituted amino- (C1-6)alkylene, optionally substituted [C1-6 alkyleneoxy(C1-6)alkylene], optionally substituted [C1-6 alkylenethio(C1-6)alkylene], optionally substituted [Cι-6 alkylenesulfinyl(Ci_6)alkylene], optionally substituted [C1-6 alkylenesulfonyl(Cι-6)alkylene] or optionally substituted [C1-6 - alkyleneamino(Cj- )alkylene]; B is N, N-oxide or CR7;
M is OC(=Y), N=C(OR8), N=C(SR9) or N=C(NR10RU) where O or N is the atom of attachment to the isothiazole group; - o -
Y is O, S or NR14;
Z is O, S or NR15;
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 C1-6 alkylthio, optionally substituted C3-7 cycloalkyl, cyano, nitro or SF5;
R2 is hydrogen, halogen, optionally substituted C1-6 alkyl, optionally substituted C2. alkenyl, optionally substituted C2-6 alkynyl, optionally substituted C1-6 alkoxy, optionally substituted Ci-6 alkylthio, optionally substituted C1-6 alkylsulfinyl, optionally substituted C1-6 alkylsulfonyl, cyano, nitro, formyl, R16ON=C(R17), optionally substituted C1-6 alkylcarbonyl, optionally substituted C1-6 alkoxycarbonyl or SF5; or R1 and R2 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated ring carbocylic or heterocyclic ring which may contain one or two heteroatoms selected from O, N or S and which may be optionally substituted by C1- alkyl, C1-6 haloalkyl or halogen; R3, R4 and R5 are, independently, hydrogen, halogen, optionally substituted C1- alkyl, optionally substituted C1-6 alkoxy, optionally substituted Cι-6 alkylthio, optionally substituted C1-6 alkylsulfinyl, optionally substituted C1-6 alkylsulfonyl, cyano, nitro, optionally substituted C1-6 alkylcarbonyl, optionally substituted C1-6 alkoxycarbonyl or SF5; R6 is hydrogen, halogen, cyano, optionally substituted C1-2o alkyl, optionally substituted C2.2o alkenyl, optionally substituted C2-2o alkynyl, optionally substituted C3-7 cycloalkyl, optionally substituted Cs-6 cycloalkenyl, formyl, optionally substituted C1-20 alkoxycarbonyl, optionally substituted C1-2o alkylcarbonyl, aminocarbonyl, optionally substituted C1-2o alkylaminocarbonyl, optionally substituted di(C1-20)alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-alkyl-N-arylaminocarbonyl, optionally substituted diarylaminocarbonyl, optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted alkylheteroarylaminocarbonyl, optionally substituted diheteroarylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, R18O, HS, optionally substituted C1-20 alkylthio, optionally substituted C1-20 alkylsulfinyl, optionally substituted C1-2o alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl, R19R20N or R21ON=C(R22); O 01/55142 _ 7 _ P
R7 is hydrogen, halogen, nitro, cyano, optionally substituted C1-8 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted C3-7 cycloalkyl, optionally substituted C1-6 alkoxycarbonyl, optionally substituted C1-6 alkylcarbonyl, optionally substituted C1-6 alkylaminocarbonyl, optionally substituted di(C1-6)alkylamino- carbonyl, optionally substituted phenyl or optionally substituted heteroaryl;
R8 is optionally substituted C O alkyl, optionally substituted [C2-6 alkenyl (C^alkyl], optionally substituted [C2-6 alkynyl(C1-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted CMO alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, formyl, optionally substituted C1-10 alkylaminocarbonyl, optionally substituted di- (CMo)alkylaminocarbonyl, amino, optionally substituted C1-6 alkylamino, optionally substituted di(C1-6)alkylamino, optionally substituted phenoxycarbonyl, tri(Cι-4)alkylsilyl, aryldi-
(C1- )alkylsilyl, (Cj-4)alkyldiarylsilyl or triarylsilyl;
R9 is optionally substituted CMO alkyl, optionally substituted [C2.6 alkenyl(C1-6)alkyl], optionally substituted [C2-6 alkynyl(C1-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted CMO alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(Cι.ιo)alkyl- aminocarbonyl or optionally substituted phenoxycarbonyl); R10 and R11 are, independently, optionally substituted CMO alkyl, optionally substituted Cι-6 alkoxy, optionally substituted [C2-6 alkenyl(C1-6)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 or optionally substituted phenoxycarbonyl;
R14 is hydrogen, cyano, nitro, optionally substituted C1-6 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 C1-6 alkylcarbonyl, optionally substituted Ci-6 alkoxycarbonyl, optionally substituted Cj-6 alkylamino, optionally substituted di(C]-6)alkylamino, optionally substituted Cι-6 alkylcarbonylamino, optionally substituted C1-6 alkoxycarbonylamino, optionally substituted C1-6 alkoxy, optionally substituted Cι-6 alkylthio, optionally substituted C1-6 alkylsulfinyl, optionally substituted C1-6 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or C1-6acyloxy; R15 is hydrogen, cyano, optionally substituted C1-8 alkyl, optionally substituted [C2-6 alkenyl(C1-6)alkyl], optionally substituted [C2- alkynyl(C1-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted [C3-7 cycloalkyl(C1-6)alkyl], C1-6 alkoxy(C1-6)alkyl, optionally substituted C1-6 alkoxycarbonyl, optionally substituted C1-6 alkylcarbonyl, optionally substituted C1-6 alkylaminocarbonyl, optionally substituted di(C1-6)alkyl- aminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl; R16 and R21 are, independently, hydrogen, optionally substituted phenyl(C1-2)alkyl or optionally substituted C1-2o alkyl;
R17 and R22 are independently hydrogen, optionally substituted phenyl or optionally substituted C1-6 alkyl; R18 is hydrogen, optionally substituted Cι-2o alkyl, optionally substituted [C2-2o alkenyl- (C1-6)alkyl], optionally substituted [C2-2o alkynyl(C1-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted [heterocyclyl(C1-6)alkylCH=N] or di(C1-6)alkylC=N; and R19 and R20 are, independently, hydrogen, optionally substituted Cι-20 alkyl, optionally substituted C3-7 cycloalkyl, optionally substituted [C2-2o alkenyl(C1-6)alkyl], optionally substituted [C2-2o alkynyl(C1-6)alkyl], optionally substituted C1-2o alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted Cι_2o alkylcarbonyl, optionally substituted Cι-2o 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 heteroatoms selected from O, N or S and which may be optionally substituted by one or two -6 alkyl groups.
Another group of preferred compounds of formula (I) is a group where A, B, Z, R1, R2, R3, R4, R5 and R6 are as defined above for a group (G); provided that A is not CH2 or CH2O; and M is NR12C(=X) where N is the atom of attachment to the isothiazole group; X is O, S or NR13; R12 is hydrogen, optionally substituted CMO alkyl, optionally substituted [C2_ alkenyl(C1-6)alkyl], optionally substituted [C2- alkynyl(C1-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted C O alkylcarbonyl, optionally substituted C O alkoxycarbonyl, formyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(C1-10)alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted Cι-6 alkylthio, optionally substituted C1-6 alkylsulfinyl, optionally substituted C1-6 alkylsulfonyl, optionally substituted C1-6 arylthio, optionally substituted d-6 arylsulfinyl, optionally substituted C1-6 arylsulfonyl or R36R37NS; R36 and R37 are, independently, optionally substituted C1-6 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; and R is hydrogen, cyano, nitro, optionally substituted C1-6 alkyl, optionally substituted C3-7 cycloalkyl, optionally substituted (C2-6)alkenyl(C1-6)alkyl, optionally substituted (C -6)alkynyl(C1-6)alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted - alkylcarbonyl, optionally substituted C1-6 alkoxycarbonyl, optionally substituted C1-6 alkylamino, optionally substituted d^ . 6)alkylamino, optionally substituted C1-6 alkylcarbonylamino, optionally substituted Cι-6 alkoxycarbonylamino, optionally substituted C1-6 alkoxy, optionally substituted Cι-6 alkylthio, optionally substituted Cι-6 alkylsulfinyl, optionally substituted d-β alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or C1-6 acyloxy.
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, C1-6 alkyl, C1-6 haloalkyl, Cι-6 cyanoalkyl, C1-6 alkoxy(C1-6) alkyl, Cι-6 alkoxy, cyano, =O, =NR23 and =CR24R25; and, especially, one or more of halogen, C1-6 alkyl, C1-6 haloalkyl, Cι-6 cyanoalkyl, C1-6 alkoxy(C1-6) alkyl, C1-6 alkoxy, cyano, =O, =NR23 and =CR24R25; wherein R23 is C1-6 alkyl, -6 haloalkyl, OR26 or NR27R28; where R24 and R25 are, independently, hydrogen, C1-6 alkyl, C1-6 alkoxy, C1-6 haloalkyl, cyano, C1-6 alkoxycarbonyl, C1-6 alkylcarbonyl or NR29R30; R26 is .6 alkyl, Cι-6 haloalkyl or phenyl(C1-2)alkyl; R27 and R28 are, independently, hydrogen, C1-8 alkyl, C3.7 cycloalkyl, C2.6 alkenyl(C1-6)alkyl, C2-6 alkynyl(C1-6)alkyl, C2.6 haloalkyl, C1-6 alkoxy(Cι-6)alkyl, C1-6 alkoxycarbonyl(Ci- )alkyl, carboxy(C1-6)alkyl or phenyl(C1-2)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 .6 alkyl groups; R29 and R30 are, independently, hydrogen, C1-8 alkyl, C3.7 cycloalkyl, C2-6 alkenyl- (C1-6)alkyl, C2-6 alkynyl(C1-6)alkyl, C2-6 haloalkyl, C1- alkoxy(C1-6)alkyl, C1- alkoxy- carbonyl(C1-6)alkyl, carboxy(C1-6)alkyl or phenyl(C1-2)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 Cι-6 alkyl groups.
Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, rc-propyl, n-butyl, n-pentyl, n-hexyl, iso-pτopyl, n-butyl, sec-butyl, iso-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 C1-6 alkyl or halogen), C5-7 cycloalkenyl (itself optionally substituted with C1- alkyl or halogen), hydroxy, CMO alkoxy, C O alkoxy(CMo)alkoxy, tri(C1-4)alkylsilyl(C1-6)alkoxy, C1-6 alkoxy- carbonyl(CMo)alkoxy, CMO haloalkoxy, aryl(C1-4)alkoxy (where the aryl group is optionally substituted), C3, cycloalkyloxy (where the cycloalkyl group is optionally substituted with C1-6 alkyl or halogen), CMO alkenyloxy, C O alkynyloxy, SH, Cι-10 alkylthio, CMO haloalkylthio, aryl(C1-4)alkylthio (where the aryl group is optionally substituted), C3-7 cycloalkylthio (where the cycloalkyl group is optionally substituted with C1-6 alkyl or halogen), tri(C1.4)alkylsilyl(C1-6)alkylthio, arylthio (where the aryl group is optionally substituted), C1-6 alkylsulfonyl, C1-6 haloalkylsulfonyl, Cι-6 alkylsulfinyl, C1-6 haloalkylsulfmyl, arylsulfonyl (where the aryl group may be further optionally substituted), tri(C1- )alkylsilyl, aryldi(C1-4)alkylsilyl, (C1, )alkyldiarylsilyl, triarylsilyl, CMO alkylcarbonyl, HO2C, CMO alkoxycarbonyl, aminocarbonyl, C1- alkylaminocarbonyl, di(d.6 alkylaminocarbonyl, N-(C1-3 alkyl)-N-(C1-3 alkoxy)aminocarbonyl, C1-6 alkylcarbonyloxy, arylcarbonyloxy (where the aryl group is optionally substituted), di(C1-6)alkylaminocarbonyloxy, aryl (itself optionally substituted), heteroaryl (itself optionally substituted), heterocyclyl (itself optionally substituted with Cι-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 C1-6 alkyl or halogen), amino, C1-6 alkylamino, di(C1_6)alkylamino, C1-6 alkylcarbonylamino and N-(Cι-6)alkylcarbonyl-N-(Cι-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 C1- alkylcarbonyl (for example acetyl), optionally substituted C2. alkenylcarbonyl, optionally substituted C2-6 alkynylcarbonyl, optionally substituted arylcarbonyl (for example benzoyl) or optionally substituted heteroarylcarbonyl.
Halogen is fluorine, chlorine, bromine or iodine.
Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF3, CF2C1, CF3CH2 or CHF2CH2. Aryl includes naphthyl, anthracyl, fluorenyl and indenyl but is preferably phenyl.
The term heteroaryl refers to an aromatic ring containing up to 10 atoms including one or more heteroatoms (preferably one or two heteroatoms) selected from O, S and N. Examples of such rings include pyridine, pyrimidine, furan, quinoline, quinazoline, pyrazole, thiophene, thiazole, oxazole and isoxazole. The terms heterocycle and heterocyclyl refer to a non-aromatic ring containing up to
10 atoms including one or more (preferably one or two) heteroatoms selected from O, S and N. Examples of such rings include 1,3-dioxolane, tetrahydrofuran and morpholine.
When present, the optional substituents on heterocyclyl include C1-6 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 C1-3 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-, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy- (C1-6)alkyl, C2- alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C3-7 cycloalkyl (itself optionally substituted with C1-6 alkyl or halogen), C5-7 cycloalkenyl (itself optionally substituted with C1-6 alkyl or halogen), hydroxy, C1-10 alkoxy, C1-10 alkoxy(C1-10)alkoxy, tri(C1-4)alkyl- silyl(C1-6)alkoxy, C1-6 alkoxycarbonyl(CM0)alkoxy, C O haloalkoxy, aryl(Cι- )alkoxy (where the aryl group is optionally substituted), C3-7 cycloalkyloxy (where the cycloalkyl group is optionally substituted with C1-6 alkyl or halogen), C O alkenyloxy, C1-10 alkynyloxy, SH, C O alkylthio, CMO haloalkylthio, aryl (C ^alkylthio (where the aryl group may be O 01/55142 _ 12 _
further optionally substituted), C3- cycloalkylthio (where the cycloalkyl group is optionally substituted with C1-6 alkyl or halogen), tri(C1- )alkylsilyl(Cι-6)alkylthio, arylthio (where the aryl group is optionally substituted), C1-6 alkylsulfonyl, Cι-6 haloalkylsulfonyl, C1-6 alkylsulfinyl, C1-6 haloalkylsulfinyl, arylsulfonyl (where the aryl group is optionally substituted), tri(Cι-4)alkylsilyl, aryldi(C1- )alkylsilyl, (C1- )alkyldiarylsilyl, triarylsilyl, CMO alkylcarbonyl, HO2C, CMO alkoxycarbonyl, aminocarbonyl, C1-6 alkylaminocarbonyl, di(C1-6 alkylaminocarbonyl, N-(Cι-3 alkyl)-N-(Cj-3 alkoxy)aminocarbonyl, d_6 alkylcarbonyloxy, arylcarbonyloxy (where the aryl group is optionally substituted), di(Cι-6)alkylamino- carbonyloxy, aryl (itself optionally substituted), heteroaryl (which itself may be further optionally substituted), heterocyclyl (itself optionally substituted with d_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 Cι-6 alkyl or halogen), amino, C1-6 alkylamino, di(C1-6)alkylamino, Cι-6 alkylcarbonylamino and N-(C1.6)alkylcarbonyl-N-(C1-6)alkylamino. For substituted phenyl moieties, heterocyclyl and heteroaryl groups it is preferred that one or more substituents are independently selected from halogen, d-6 alkyl, Cι_6 haloalkyl, d-6 alkoxy(d.6)alkyl, C1-6 alkoxy, d_6 haloalkoxy, Cι-6 alkylthio, d-6 haloalkylthio, Cι-6 alkylsulfinyl, C1-6 haloalkylsulfinyl, d-6 alkylsulfonyl, C1-6 haloalkylsulfonyl, C2-6 alkenyl, C2- haloalkenyl, C2-6 alkynyl, C3-7 cycloalkyl, nitro, cyano, CO2H, d_6 alkylcarbonyl, C1-6 alkoxycarbonyl, R3,R3 N or R33R34NC(O); wherein R31, R32, R33 and R34 are, independently, hydrogen or C1-6 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 (C1-6)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 (C1-6) alkyl groups. Preferably the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, HO2C, C O alkoxy (itself optionally substituted by CMO alkoxy), aryl(C1- )alkoxy, CMO alkylthio, CMO alkylcarbonyl, CMO alkoxycarbonyl, d.6 alkylaminocarbonyl, di(C1-6 alkylaminocarbonyl, (C1.6)alkylcarbonyloxy, optionally substituted phenyl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl, heterocyclyloxy, C3- cycloalkyl (itself optionally substituted with (C1-6)alkyl or halogen), C3-7 cycloalkyloxy, Cs-7 cycloalkenyl, Cι-6 alkylsulfonyl, C1-6 alkylsulfinyl, tri(C1-4)alkylsilyl, tri(C1-4)alkylsilyl(C1-6)alkoxy, aryldi(C1-4)alkylsilyl, (C1-4)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 C1-6 alkyl.
Preferably the optional substituents for cycloalkyl include halogen, cyano and C1-3 alkyl.
Preferably the optional substituents for cycloalkenyl include C1-3 alkyl, halogen and cyano.
In a further aspect, the present invention provides a compound of formula (IA):
wherein A, B, M, Z, R1, R2, R3, R4, R5 and R6 are as defined above for a compound of formula (I).
One group of preferred compounds of formula (IA) is a group (GA) wherein
A is d.6 alkylene, C1-6 alkenylene, C1-6 alkylenoxy, oxy(C1-6)alkylene, C1-6 alkylenamino or
C1-6 alkylenethio, each of which is optionally substituted by C1-3 alkyl, C1-3 haloalkyl, C1-3 cyanoalkyl, halogen, C1-3 alkoxy, C1-6 alkoxycarbonyl, cyano, =O, =NR23 or =CR2 R25;
B is N or CR7;
M is N=C(SR9) where N is the atom of attachment to the isothiazole group;
Z is O, S or NR15;
R1 is hydrogen, halogen, C1-6 alkyl, C2.6 alkenyl, C2-6 alkynyl, C1-6 cyanoalkyl, C1-6 haloalkyl, Cι.6 alkoxy, d-6 haloalkoxy, C1-6 alkylthio, C1-6 haloalkylthio, C3-6 cycloalkyl, C3-7 cycloalkyl(C1-4)alkyl, C1-6 alkoxy(C1- )alkyl, cyano, nitro or SF5;
R2 is hydrogen, halogen, Cι-6 alkyl, C -6 alkenyl, d_6 alkynyl, Cι-6 haloalkyl, C1-6 alkoxy,
C1-6 alkoxy (Cι-6)alkyl, Cι-6 haloalkoxy, Cι_6 alkylthio, C1- haloalkylthio, C1- alkylsulfinyl, d_6 haloalkylsulfinyl, Cι_6 alkylsulfonyl, Cι-6 haloalkylsulfonyl, C1-6 haloalkyl, cyano, nitro, formyl, CH=NOR16, C1-6 alkylcarbonyl, C1-6 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 ring carbocylic or heterocyclic ring which may contain one or two heteroatoms selected from O, N or S and which may be optionally substituted by C1-6 alkyl, C1-6 haloalkyl or halogen;
R3, R4 and R5 are independently selected from hydrogen, halogen, Cι-6 alkyl, Cι-6 alkoxy, Cι-6 haloalkoxy, C1-6 alkylthio, C1-6 haloalkylthio, Cι-6 alkylsulfinyl, Cι.6 haloalkylsulfinyl, C1-6 alkylsulfonyl, d.6 haloalkylsulfonyl, Cι.6 haloalkyl, cyano, nitro, Cι_6 alkylcarbonyl, C1-6 alkoxycarbonyl or SF5; R6 is cyano, Cι-8 alkyl, Cι-6 haloalkyl, C],6 cyanoalkyl, C2-6 alkenyl, C2-6 alkynyl, C3-7 cycloalkyl, C3-7 halocycloalkyl, C3-7 cyanocycloalkyl, C1-3 alkyl(C3-7)cycloalkyl, C1-3 alkyl (C3-7)halocycloalkyl, C5-6 cycloalkenyl, C3-7 cycloalkyl(d-6)alkyl, C5-6 cycloalkenyl(d. 6)alkyl, C2-6 haloalkenyl, d-6 cyanoalkenyl, C1-6 alkoxy(C1-6)alkyl, C3-6 alkenyloxy - (d-6)alkyl, C3-6 alkynyloxy(C1-6)alkyl, aryloxy(C1-6)alkyl, formyl, Cι.6 carboxyalkyl, Ci-6 alkylcarbonyl(Ci-6)alkyl, C2-6 alkenylcarbonyl(Cι.6)alkyl, C2-6 alkynylcarbonyl(Cι-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, C3-6 alkenyloxycarbonyl(C1-6)alkyl, C3-6 alkynyl- oxycarbonyl(d-6)alkyl, aryloxycarbonyl(C1.6)alkyl, C1-6 alkylthio(C1-6)alkyl, C1-6 alkylsulfinyl(Cι-6)alkyl, C1-6 alkylsulfonyl(C1.6)alkyl, aminocarbonyl(Cι-6)alkyl, amino- carbonyl(C2-6)alkenyl, aminocarbonyl(C2-6)alkynyl, C1-6 alkylaminocarbonyl(C1_6)alkyl, di(C1-6)alkylaminocarbonyl(C1-6)alkyl, C1-6alkylaminocarbonyl(Cι-6)alkenyl, di(C1-6)alkyl- aminocarbonyl(C \ -6)alkenyl, alkylaminocarbonyl(C ] -6)alkynyl, di(C 1 -6)alkylamino- carbonyl(C1-6)alkynyl, Cι-6 alkoxycarbonyl, Cι-6 alkylcarbonyl, aminocarbonyl, C1-6 alkylaminocarbonyl, di(C1-6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, Cι-6 alkyl, d_6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), phenyl(Cι- )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, Cι-6 alkoxy or C1-6 haloalkoxy), phenyl(C2-4)alkenyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, Cι-6 alkoxy or C1-6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Cι-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1- haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heteroaryl(C1-4)alkyl (where the heteroaryl may be substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), heterocyclyl(C1-4)alkyl (where the heterocyclyl may be substituted by halo, cyano, d-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or C1-6 haloalkoxy), R18O, Cι-8 alkylthio, R19R20N or R21ON=C(R22);
R7 is hydrogen, halogen, nitro, cyano, C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C2-6 alkenyl, C2-6 alkynyl, C3-7 cycloalkyl, C2-6 haloalkenyl, C3-7 cycloalkyl(C1-6)alkyl, Cι-6 alkoxy- (C1-6)alkyl, C1-6 alkoxycarbonyl, C1-6 alkylcarbonyl, C1-6 alkylaminocarbonyl, di(d ^alkylaminocarbonyl, d-6 alkoxycarbonyl(C1-6)alkyl, C1-6 alkylcarbonyl(C1-6)alkyl, C1-6 alkyl- aminocarbonyl(C1-6)alkyl, di(C1-6)alkylaminocarbonyl(C1-6)alkyl, phenyl (optionally substituted by halo, nitro, cyano, C1-6 alkyl, d.6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy), phenyl(C1-6)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, d-6 haloalkyl, C1-6 alkoxy or d-6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Ci-6 alkyl, C1-6 haloalkyl, Cue alkoxy or Cι.6 haloalkoxy) or hetero- aryl(C1-6)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C1-6 alkyl, d_6 haloalkyl, d-6 alkoxy or Cue haloalkoxy); R9 is CMO alkyl, benzyloxymethyl, benzoyloxymethyl, Cι-6alkoxy(C1-6)alkyl, C2-6 alkenyl- (C1-6)alkyl (especially allyl), C2-6 alkynyl(C1-6)alkyl (especially propargyl), C1-10 alkylcarbonyl or CMO alkoxycarbonyl (especially wobutoxycarbonyl);
R15 is hydrogen, C1-8 alkyl, C1-6 haloalkyl, C1-6 cyanoalkyl, C2-6 alkenyl, C2- alkynyl, C3-7 cycloalkyl, C2-6 haloalkenyl, C3.7 cycloalkyl(C1-6)alkyl, Cι. alkoxy(C1-6)alkyl, d-6 alkoxycarbonyl, C1-6 alkylcarbonyl, C1-6 alkylaminocarbonyl, di(Cι-6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, C1-6 alkyl, d-6 haloalkyl, C1-6 alkoxy or d. haloalkoxy) or heteroaryl (optionally substituted by halo, nitro, cyano, Cι_6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or d_6 haloalkoxy);
R16 and R21 are, independently, Cue alkyl or phenyl(C1-2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d_6 alkyl, Cι-6 haloalkyl, C1-6 alkoxy or d_6 haloalkoxy);
R18 is hydrogen, C1-8 alkyl, C e haloalkyl, C1-6 cyanoalkyl, C2-6 alkenyl, C2-6 alkynyl, C1-6 alkoxy(C1-6)alkyl, phenyl(C1-4)alkyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, C1-6 haloalkyl, d-6 alkoxy or Ci-6 haloalkoxy), heteroaryl- (C1-4)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, d_6 alkyl, C1-6 haloalkyl, d-6 alkoxy or C1-6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or Cι-6 haloalkoxy), heterocyclyl- (C1- )alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, - d-6 alkyl, d-6 haloalkyl, C1-6 alkoxy or Ci-6 haloalkoxy), C1-6 alkoxycarbonyl(C1-6)alkyl or
N=C(CH3)2;
R19 and R20 are, independently, hydrogen, d.8 alkyl, C3.7 cycloalkyl, C3-6 alkenyl, C3-6 alkynyl, C3-7 cycloalkyl(Cι-4)alkyl, C2-6 haloalkyl, C1-6 alkoxy(C1-6)alkyl, C1-6 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 heteroatoms selected from O, N or S and which may be optionally substituted by one or two Cl alkyl groups; R22 is d-6 alkyl, C1-6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, C1-6 alkyl, C1-6 haloalkyl, d-6 alkoxy or d-6 haloalkoxy); R23 is Cl alkyl, OR26 or NR27R28; R24 is hydrogen, Ci-6 alkyl or C1-6 haloalkyl;
R25 is hydrogen, C1-6 alkyl, C1-6 haloalkyl, Cι-6 alkoxy, cyano, d-6 alkoxycarbonyl, C1-6 alkylcarbonyl or NR29R30; R26 is d.6 alkyl or optionally substituted phenyl(C1-2)alkyl;
R27 and R28 are, independently, hydrogen, C1-8 alkyl or phenyl (optionally substituted by halo, nitro, cyano, C1-6 alkyl, d_6 haloalkyl, d^ alkoxy or C1-6 haloalkoxy); and
R29 and R30 are, independently, hydrogen, C1-8 alkyl, C3-7 cycloalkyl, C3-6 alkenyl, C3-6 alkynyl, C2-6 haloalkyl, Cι-6 alkoxy(C1-6)alkyl, C1-6 alkoxycarbonyl(C1-6)alkyl, carboxy- (C1-6)alkyl or phenyl(C1-2)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 may be optionally substituted by one or two C1-6 alkyl groups. Another group of preferred compounds of formula (IA) is a group where A, B, Z, R1,
R2, R3, R4, R5 and R6 are as defined above for a group (GA); provided that A is not CH2 or CH2O; and M is NR12C(=X) where N is the atom of attachment to the isothiazole group; X is O, S or NR13; R12is hydrogen, CMO alkyl, benzyloxymethyl, benzoyloxymethyl, Ci-όalkoxy- (C1-6)alkyl, C2-6 alkenyl(C1-6)alkyl (especially allyl), C2.6 alkynyl(d.6)alkyl (especially propargyl), CMO alkylcarbonyl or CMO alkoxycarbonyl (especially wobutoxycarbonyl); and R13 is cyano, nitro, Cι-6 alkyl, C1-6 haloalkyl, C3-7 cycloalkyl, C3-7 cycloalkyl(d-6)alkyl, CH2(C2-6)alkenyl, CH2(C2-6)alkynyl, phenyl (optionally substituted by halo, nitro, cyano, Ci-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy or d-6 haloalkoxy), heteroaryl (optionally substituted by O 01/55142 17
halo, nitro, cyano, C1-6 alkyl, C!. haloalkyl, Ci-6 alkoxy or C1-6 haloalkoxy), Ci-6 alkylcarbonyl, C1-6 alkoxycarbonyl, d-6 alkylamino, di(C1-6)alkylamino, C1-6 alkylcarbonylamino, Ci-6 alkoxycarbonylamino, C1-6 alkoxy, Cι_6 alkylthio, Cι_6 alkylsulfinyl, C1-6 alkylsulfonyl, C1-6 haloalkylthio, C1-6 haloalkylsulfinyl, C1-6 haloalkylsulfonyl, arylthio, arylsulfinyl, arylsulfonyl or OCO(C1-6)alkyl.
It is preferred that A is C1-6 alkylene, C1-6 alkenylene, C1-6 alkylenoxy, oxy(C1-6)alkylene or Ci-6 alkylenamino, each of which is optionally substituted by C1-3 alkyl, C1-3 haloalkyl, C1-3 cyanoalkyl, halogen, C1-3 alkoxy, d-6 alkoxycarbonyl, cyano, =O, =NR23 or =CR24R25; where R23 is d-6 alkyl, OR26 or NR27R28; R26 is d.6 alkyl or phenyl(Cι,2)alkyl (where the phenyl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, d-6 haloalkyl, C1-6 alkoxy or d-6 haloalkoxy); R27 and R28 are, independently, hydrogen, C1-8 alkyl or phenyl (which may be optionally substituted by halo, nitro, cyano, Cι-6 alkyl, Ci-6 haloalkyl, Cι-6 alkoxy or d.6 haloalkoxy); R24 is hydrogen, C1-6 alkyl or d,6 haloalkyl; R25 is hydrogen, d-6 alkyl, C e haloalkyl, Cι-6 alkoxy, cyano, d- alkoxycarbonyl, C1-6 alkyl- carbonyl or NR29R30; and R29 and R30 are, independently, hydrogen, C1-8 alkyl, C3-7 cycloalkyl, C3-6 alkenyl, C3-6 alkynyl, C2-6 haloalkyl, Ci-6 alkoxy(Cι-6)alkyl, Cι-6 alkoxycarbonyl(C1-6)alkyl, carboxy(Cι.6)alkyl or phenyl(C1-2)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 may be optionally substituted by one or two d- alkyl groups.
A is more preferably C alkylene (optionally substituted by halogen, C1-3 alkyl or Cu alkoxy, -C(O)- or C1-4 alkyleneoxy (which may be optionally substituted by C1-3 alkyl).
It is even more preferred that A is C1-2 alkyl-substituted C1-4 alkylene, fluoro- substituted C alkylene, methoxy-substituted C1- alkylene, -C(O)- or C2- alkyleneoxy; still more preferably A is C1-2 alkyl-substituted C1-4 alkylene, fluoro-substituted Cι- alkylene or methoxy-substituted C1-4 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; even further preferred that A is CHF, CH(OCH3) or CH(CH3); and yet further preferred that either A is CHF or CH(CH3) or A is CH2, CH(CH3) or CH2O.
B is preferably N. M is preferably N=C(OR8), N=C(SR9) or N(R12)C(=NR13); M is more preferably N=C(OR8) or N=C(SR9); and M is most preferably N=C(SR9).
Y is preferably O or S.
Y is more preferably O. Z is preferably O or S.
Z is more preferably O.
It is preferred that R1 is hydrogen, halogen, d-6 alkyl, Ci-6 cyanoalkyl, Ci-6 haloalkyl, C3-7 cycloalkyl(C1-4)alkyl, Ci-6 alkoxy(d-6)alkyl, C2-6 alkenyl, C2_6 alkynyl, d-6 alkoxy, d-6 haloalkoxy, d-6 alkylthio, d- haloalkylthio, C3_6 cycloalkyl, cyano, nitro or SF5. R1 is more preferably hydrogen, halogen, d-6 alkyl, C2-6 alkenyl, Ci.6 haloalkyl, d-6 alkoxy, Ci- haloalkoxy, Ci-6 alkylthio, Cι_6 haloalkylthio, C3.6 cycloalkyl, cyano, nitro or SF5.
It is even more preferred that R1 is hydrogen, halogen, d_6 alkyl, Cι_6 haloalkyl, d-6 alkoxy(Ci-6)alkyl, C2-6 alkenyl, d-6 alkoxy, d.6 haloalkoxy, d-6 alkylthio, d-6 haloalkylthio, C3.6 cycloalkyl or cyano.
It is most preferred that R1 is halogen, d-6 alkyl, Ci.6 haloalkyl, d-6 alkoxy or d-6 haloalkoxy.
It is preferred that R2 is hydrogen, halogen, Ci-6 alkyl, d-6 haloalkyl, Ci-6 alkoxy(Ci-6)alkyl, C2-6 alkenyl, d_6 alkynyl, d_6 alkoxy, C1-6 haloalkoxy, Cι_6 alkylthio, Ci-6 haloalkylthio, d-6 alkylsulfinyl, d-6 haloalkylsulfinyl, d-6 alkylsulfonyl, d-6 haloalkylsulfonyl, cyano, nitro, formyl, Ci-6 alkylcarbonyl, Ci-6 alkoxycarbonyl, SF5 or CH=NOR16; 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 d-6 alkyl, C1-6 haloalkyl or halogen; where R16 is phenyl(C1-2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, d-6 haloalkyl, d-6 alkoxy or Ci-6 haloalkoxy) or C1-6 alkyl.
It is more preferred that R is hydrogen, halogen, Ci-6 alkyl, Ci-6 haloalkyl, d-6 alkoxy (d_6)alkyl, d-6 alkoxy, C b haloalkoxy, d-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 d_6 alkyl, d-6 haloalkyl or halogen.
R2 is even more preferably hydrogen, halogen, d-6 alkyl, d-6 haloalkyl, Ci-6 alkoxy, Cue haloalkoxy, d-6 alkoxy(d_6)alkyl, Cι.6 alkylthio or SF5; or R and R together with the atoms to which they are attached form a benzene ring optionally substituted by d-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, d.6 alkyl, d.6 haloalkyl, d-6 alkoxy(Ci-6)alkyl, Cι-6 alkoxy, d_6 haloalkoxy; or R1 and R2 together with the atoms to which they are attached form a cyclopentane ring optionally substituted by Cι_6 alkyl, d-6 haloalkyl or halogen.
R2 is most preferably halogen, d-6 alkyl, d-6 haloalkyl, Cι-6 alkoxy, d-6 alkoxy(Cι-6)alkyl or Ci-6 haloalkoxy.
It is preferred that R3, R4 and R5 are, independently, hydrogen, halogen, Ci.6 alkyl, Ci-6 haloalkyl, Cι_6 alkoxy, d-6 haloalkoxy, d_6 alkylthio, Ci.6 haloalkylthio, d-6 alkylsulfinyl, Cι-6 haloalkylsulfinyl, d-6 alkylsulfonyl, Cι_6 haloalkylsulfonyl, cyano, nitro, Ci-6 alkylcarbonyl or Ci-6 alkoxycarbonyl.
It is more preferred that R3, R4 and R5 are, independently, hydrogen, halogen or d-3 alkyl. It is even more preferred that R3, R4 and R5 are, independently, hydrogen or halogen
(especially fluorine).
It is preferred that R6 is cyano, d_8 alkyl, Cι_8 haloalkyl, d.8 cyanoalkyl, C3.7 cycloalkyl(Cι-6)alkyl, C5.6 cycloalkenyl(C1.6)alkyl, d.6 alkoxy(Cι-6)alkyl, C3.6 alkenyloxy(Ci-6)alkyl, C3-6 alkynyloxy(Ci-6)alkyl, aryloxy(Ci-6)alkyl, Ci.6 carboxyalkyl, d-6 alkylcarbonyl(d.6)alkyl, C2-6 alkenylcarbonyl(C1-6)alkyl, C2-6 alkynylcarbonyl(Ci-6)alkyl, Ci-6 alkoxycarbonyl(Ci-6)alkyl, C3-6 alkenyloxycarbonyl(Ci.6)alkyl, C3-6 alkynyloxycarbonyl(Ci.6)alkyl, aryloxycarbonyl(Ci-6)alkyl, Cι-6 alkylthio(Ci-6)alkyl, d-6 alkylsulfinyl(Ci-6)alkyl, Ci.6 alkylsulfonyl(Cι.6)alkyl, aminocarbonyl(d-6)alkyl, d^ alkyl- aminocarbonyl(C1-6)alkyl, di(Cι-6)alkylaminocarbonyl(C1-6)alkyl, phenyl(CM)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d-6 haloalkyl, d-6 alkoxy or C1-6 haloalkoxy), heteroaryl(CM)alkyl (where the heteroaryl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Cι.6 haloalkyl, Cι_6 alkoxy or d-6 haloalkoxy), heterocyclyl(Ci.4)alkyl (where the heterocyclyl group is optionally substituted by halo, cyano, d-6 alkyl, Ci-6 haloalkyl, Cι-6 alkoxy or d-6 haloalkoxy), C2.6 alkenyl, C2_6 haloal- kenyl, d-6 cyanoalkenyl, C5-6 cycloalkenyl, aminocarbonyl(C2_6)alkenyl, d-6 alkylamino- carbonyl(Ci-6)alkenyl, di(Ci.6)alkylaminocarbonyl(Cι-6)alkenyl, phenyl-(C2^)alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, d- haloalkyl, d_6 alkoxy or d-6 haloalkoxy), C2-6 alkynyl, aminocarbonyl-(C2_6)alkynyl, alkylaminocarbonyl(Ci.6)alkynyl, di(Cι.6)alkylaminocarbonyl(Cι-6)alkynyl, C3-7 cycloalkyl, C3-7 halocycloalkyl, C -7 cyanocycloalkyl, C1-3 alkyl(C3-7)cycloalkyl, C1-3 alkyl(C3.7)- halocycloalkyl, C5-6 cycloalkenyl, formyl, Ci_6 alkoxycarbonyl, Ci-6 alkylcarbonyl, amino- carbonyl, d.6 alkylaminocarbonyl, di(Cι-6)alkylaminocarbonyl, phenyl (optionally sub- stituted by halo, nitro, cyano, d-6 alkyl, Ci_6 haloalkyl, d.6 alkoxy or Cι-6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Cι_6 alkyl, Ci-6 haloalkyl, d_6 alkoxy or Ci-6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, Cι.6 alkyl, Ci-6 haloalkyl, d.6 alkoxy or d-6 haloalkoxy), Ci.8 alkylthio, R18O, R19R20N or R21ON=C(R22); where R18 is hydrogen, d_8 alkyl, Ci_6 haloalkyl, Cι_6 cyanoalkyl, Ci-6 alkoxy(d-6)alkyl,
Figure imgf000022_0001
(wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Cι_6 haloalkyl, d-6 alkoxy or Ci.6 haloalkoxy), heteroaryl(Cι- )alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Cι_6 alkyl, d-6 haloalkyl, d.6 alkoxy or Cι-6 haloalkoxy), heterocyclyl (d.4)alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Cι_6 alkyl, C e haloalkyl, Ci.6 alkoxy or C1.6 haloalkoxy), d.6 alkoxycarbonyl(Ci.6)alkyl, C2.6 alkenyl, C2.6 alkynyl or N=C(CH3)2; R22 is phenyl (optionally substituted by halo, nitro, cyano, Ci.6 alkyl, d_6 haloalkyl, Cι.6 alkoxy or C1-6 haloalkoxy), Ci.6 alkyl or d-6 haloalkyl; R19 and R20 are, independently, hydrogen, d.8 alkyl, C3-7cycloalkyl(Cι-4)alkyl, C2.6 haloalkyl, C1-6 alkoxy(Cι.6)alkyl, C3.7 cycloalkyl, C3.6 alkenyl, C .6 alkynyl or d_6 alkoxycarbonyl; and R21 is phenyl(d.2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d.6 alkyl, Ci-6 haloalkyl, Cι.6 alkoxy or Ci-6 haloalkoxy) or d-6 alkyl.
It is further preferred that R6 is d-8 alkyl, Cι_8 haloalkyl, Cι.8 cyanoalkyl, C3.7 cycloalkyl(Cj-6)alkyl, C5_6 cycloalkenyl(Cι_6)alkyl, d-6 alkoxy(Cι-6)alkyl, C3.6 alkenyloxy(Ci-6)alkyl, C3.6 alkynyloxy(Ci-6)alkyl, aryloxy(Ci_6)alkyl, d.6 carboxyalkyl, Ci.6 alkylcarbonyl(Cι-6)alkyl, C2.6 alkenylcarbonyl(d-6)alkyl, C2.6 alkynylcarbonyl(Cι.6)alkyl, Ci-6 alkoxycarbonyl(Ci_6)alkyl, C3.6 alkenyloxycarbonyl(Ci_6)alkyl, C3_6 alkynyloxycarbonyl- (Ci.6)alkyl, aryloxycarbonyl(Cι.6)alkyl, Cι.6 alkylthio(d-6)alkyl, d.6 alkylsulfinyl(Ci-6)alkyl, Ci-6 alkylsulfonyl(C1-6)alkyl, aminocarbonyl(Cι-6)alkyl, Ci-6 alkylaminocarbonyl(Cι-6)alkyl, di(Cι-6)alkylaminocarbonyl(Cι-6)alkyl, phenyl (Cι. )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Cι_6 alkyl, d-6 haloalkyl, Cι_6 alkoxy or C1-6 haloalkoxy), heteroaryl(C1-4)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Cι-6 alkyl, Cι_6 haloalkyl, Cι_6 alkoxy or Cι_6 haloalkoxy), heterocyclyl- (Ci.4)alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, d_6 haloalkyl, d-6 alkoxy or Cι_6 haloalkoxy), C2_6 alkenyl, C2_6 haloalkenyl, Ci-6 cyanoalkenyl, C5-6 cycloalkenyl, aminocarbonyl(C2_6)alkenyl, d-ό alkylaminocarbonyl- (d-6)alkenyl, di(C16)alkylaminocarbonyl(C1-6)alkenyl, phenyl(C2.4)alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, Cι_6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy), C2.6 alkynyl, aminocarbonyl(C2_6)alkynyl, alkylaminocarbonyl (Cι-6)alkynyl, di(Ci-6)alkylaminocarbonyl(C1.6)alkynyl, C .7 cycloalkyl, C3.7 halocycloalkyl, C3.7 cyanocycloalkyl, d.3 alkyl(C3.7)cycloalkyl, d.3 alkyl(C3.7)halocyclo- alkyl, phenyl (optionally substituted by halo, nitro, cyano, d_6 alkyl, d-6 haloalkyl, d-6 alkoxy or d-6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, d-6 alkyl, d-6 haloalkyl, d-6 alkoxy or d_6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, d.6 alkyl, C1-6 haloalkyl, d-6 alkoxy or d-6 haloalkoxy), C1-8 alkylthio, R18O, R19R20N or R21ON=C(R22); where R18 is Cι-8 alkyl or d.6 haloalkyl; R22 is phenyl (optionally substituted by halo, nitro, cyano, d_6 alkyl, d.6 haloalkyl, Cι_6 alkoxy or Cι-6 haloalkoxy), Ci.6 alkyl or d_6 haloalkyl; R19 and R20 are, independently, hydrogen, d-8 alkyl, C3.7 cycloalkyl(Cι^)alkyl, C2.6 haloalkyl, Cι_6 alkoxy(C1-6)alkyl, C3-7 cycloalkyl, C3-6 alkenyl, C3_6 alkynyl or Ci.6 alkoxycarbonyl; and R21 is phenyl(d.2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d_6 alkyl, d-8 haloalkyl, Ci-6 alkoxy or d-6 haloalkoxy) or Ci.6 alkyl.
R6 is more preferably Cι_8 alkyl, C1-8 haloalkyl, d.6 cyanoalkyl, C2-6 alkenyl, C2-6 alkynyl, C3-7 cycloalkyl, C3-7 halocycloalkyl, C3-7 cyanocycloalkyl, C1-3 alkyl(C3-7)cycloalkyl, C1-3 alkyl(C3-7)halocycloalkyl, C5.6 cycloalkenyl, C3. cycloalkyl(Ci.6)alkyl, C5_6 cycloalkenyl (d-6)alkyl, C2_6 haloalkenyl, d-6 cyanoalkenyl, d-6 alkoxy(Cι-6)alkyl, C3.6 alkenyloxy(d_6)alkyl, C3_6 alkynyloxy(d-6)alkyl, aryloxy(Ci-6)alkyl, d-6 carboxyalkyl, Ci.6 alkylcarbonyl(Cι.6)alkyl, C2_6 alkenylcarbonyl(d.6)alkyl, C2.6 alkynylcarbonyl(Ci.6)alkyl, Ci-6 alkoxycarbonyl(Ci_6)alkyl, C3.6 alkenyloxycarbonyl(Ci-6)alkyl, C3-6 alkynyloxycarbonyl- (Ci-6)alkyl, aryloxycarbonyl(Ci.6)alkyl, Ci. alkylthio(Ci.6)alkyl, Ci-6 alkylsulfinyl(Cι.6)alkyl, Ci-6 alkylsulfonyl(Ci-6)alkyl, aminocarbonyl(Cι-6)alkyl, aminocarbonyl(C2.6)alkenyl, aminocarbonyl(C2.6)alkynyl, d-6 alkylaminocarbonyl(Ci-6)alkyl, di(Ci-6)alkylaminocarbonyl- (Ci-6)alkyl, Cι_6 alkylaminocarbonyl(d-6)alkenyl, di(d-6)alkylaminocarbonyl(Cι-6)alkenyl, alkylaminocarbonyl(Cι_6)alkynyl, di(Ci-6)alkylaminocarbonyl(Ci.6)alkynyl, phenyl
(optionally substituted by halo, nitro, cyano, C1.6 alkyl, Cι_6 haloalkyl, d-6 alkoxy or d_6 haloalkoxy), phenyl(C1.4)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Cι.6 alkyl, Cι-6 haloalkyl, Ci-6 alkoxy or Cι-6 haloalkoxy), phenyl(C2- )alkenyl, „,„ M /eβ1 „
WO 01/55142 - 22 -
(wherein the phenyl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, d.6 haloalkyl, d-6 alkoxy or d-6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, d_6 alkyl,
Figure imgf000024_0001
haloalkyl, Ci-6 alkoxy or d_6 haloalkoxy), heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d-6 haloalkyl, d-6 alkoxy or Cι_6 haloalkoxy), heteroaryl(Cι.4)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, Ci-6 haloalkyl, Cι-6 alkoxy or d-6 haloalkoxy), heterocyclyl(C1- )alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C1-6 alkyl, Ci-6 haloalkyl, Ci-6 alkoxy or d- haloalkoxy), R18O, Cι_8 alkylthio, R19R20N or R21ON=C(R22); where R18 is d_8 alkyl, d.6 haloalkyl; R22 is d.6 alkyl, d-6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d-6 haloalkyl, d_6 alkoxy or Cι_6 haloalkoxy); R19 and R20 are, independently, hydrogen, Cι_8 alkyl, C3.7 cycloalkyl, C -6 alkenyl, C3-6 alkynyl, C3-7 cycloalkyl(Ci-4)alkyl, C2-6 haloalkyl, d.6 alkoxy(d.6)alkyl, d- 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 heteroatoms selected from O, N or S and which may be optionally substituted by one or two Cι_6 alkyl groups; and R21 is d-6 alkyl or phenyl(d.2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, Cue haloalkyl, Cι_ alkoxy or d-6 haloalkoxy); and R6 is more preferably C1-8 alkyl, Cι-8 haloalkyl, Cι-8 cyanoalkyl, C3-7 cycloalkyl, C1-3 alkyl(C3-7)cycloalkyl, d.6 alkoxy(Ci-6)alkyl, heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, Cι-6 alkyl, Cι-6 haloalkyl, d-6 alkoxy or Cue haloalkoxy) or R19R20N; where R19 and R20 are, independently, Cι.8 alkyl or together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two Cι_6 alkyl groups.
It is even more preferred that R6 is C1-8 alkyl, C1-8 haloalkyl, d.8 cyanoalkyl, d.6 alkoxy (Ci-6) alkyl, C3.7 cycloalkyl, d-3 alkyl (C3.7) cycloalkyl, heterocyclyl (optionally substituted by halo, nitro, cyano, d.6 alkyl, d-6 haloalkyl, d_6 alkoxy or Cι.6 haloalkoxy) or di(C i -8)alkylamino. It is yet more preferred that R6 is Cι-8 alkyl, Cι_8 haloalkyl, Cj-8 cyanoalkyl, Cι_6 alkoxy (d.6) alkyl, C .7 cycloalkyl, d.3 alkyl (C3.7) cycloalkyl, heterocyclyl (optionally substituted by Ci-6 alkyl) or di(Ci.8)alkylamino.
R6 is most preferably Cι-8 alkyl, C]-8 haloalkyl, d.8 cyanoalkyl, C3.7 cycloalkyl, Cι-3 alkyl(C3.7)cycloalkyl, d.6 alkoxy(d.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 Ci-6 alkyl groups. It is preferred that R is hydrogen, halogen, nitro, cyano, C1-8 alkyl, Ci-6 haloalkyl,
Ci-6 cyanoalkyl, C3.7 cycloalkyl(d.6)alkyl, Cι_6 alkoxy(Ci-6)alkyl, d-6 alkoxycarbonyl- (d.6)alkyl, d_6 alkylcarbonyl(d-6)alkyl, Cι_6 alkylaminocarbonyl(Ci.6)alkyl, di(Ci-6)alkylamino-carbonyl(Ci-6)alkyl, phenyl(d_6)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, d_6 haloalkyl, Ci-6 alkoxy or d_ haloalkoxy), heteroaryl(Ci-6)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, d_6 haloalkyl, d-6 alkoxy or d_6 haloalkoxy), C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C3-7 cycloalkyl, Ci-6 alkoxycarbonyl, Ci-6 alkylcarbonyl, Cι-6 alkylaminocarbonyl, di(Cι-6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Ci-6 haloalkyl, Ci-6 alkoxy or d_6 haloalkoxy) or heteroaryl (optionally substituted by halo, nitro, cyano, d_6 alkyl, Ci-6 haloalkyl, d.6 alkoxy or d_6 haloalkoxy).
It is more preferred that R7 is hydrogen, halogen, Cι_8 alkyl or Ci-6 haloalkyl. It is preferred that R8 is CMO alkyl, CMO haloalkyl, C2-6 alkenyl(Cι-6)alkyl, C2.6 alkynyl(Ci_6)alkyl, C3-7 cycloalkyl, Ci-6 alkylamino, di(C1-6)alkylamino or phenyl(Cι-4)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, Cι.6 haloalkyl, d-6 alkoxy or Ci- haloalkoxy),
It is more preferred that R8 is Cι-6 alkyl, Cι_6 haloalkyl, C2_6 alkenyl(d_6)alkyl, C _6 alkynyl(C1.6)alkyl or benzyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d. alkyl, d-6 haloalkyl, d-6 alkoxy or Ci-6 haloalkoxy). It is preferred that R9 is CMO alkyl, CMO haloalkyl, C2.6 alkenyl(d.6)alkyl, C2.6 alkynyl(d-6)alkyl, C3.7 cycloalkyl, CMO alkylthio(Ci-io)alkyl, CMO alkoxycarbonyl, d.10 alkoxycarbonyl(CMo)alkyl or
Figure imgf000025_0001
(wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d-6 haloalkyl, d_6 alkoxy or d_6 haloalkoxy), It is more preferred that R9 is CMO alkyl, d-6 haloalkyl, C2.6 alkenyl(Cι_6)alkyl, C2.6 alkynyl(Ci-6)alkyl, Ci_6 alkylthio(Cι.6)alkyl, CMO alkoxycarbonyl, d.6 alkoxycarbonyl- (Ci_6)alkyl or benzyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Cι_6 alkyl, Cι_6 haloalkyl, Cι.6 alkoxy or Cι_6 haloalkoxy).
R9 is even more preferably CMO alkyl, d-6 alkylthio(Cι_6)alkyl, C2.6 alkenyl- (Ci-6)alkyl (especially allyl), C2-6 alkynyl(C1-6)alkyl (especially propargyl), benzyl, d-6 alkoxycarbonyl(Ci-6)alkyl or CMO alkoxycarbonyl (especially wøbutoxycarbonyl).
R9 is most preferably CMO alkyl, Cι-6 alkylthio(Ci_6)alkyl, C2_6 alkenyl(C].6)alkyl (especially allyl), C2.6 alkynyl(d-6)alkyl (especially propargyl), benzyl or d_6 alkoxycarbonyl(Ci-6)alkyl.
It is preferred that R10 is CMO alkyl, C2.6 alkenyl(Ci-6)alkyl, C2.6 alkynyl(Ci.6)alkyl, C3-7 cycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, C1-6 alkyl, d_6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy), CMO haloalkyl, d. alkoxy(d-6)alkyl, C3.7 cycloalkyl- (Cι_6)alkyl, Ci-6 alkylcarbonylamino, Cι_6 alkoxycarbonylamino, d-6 alkylaminocarbonyl- amino, Ci- alkylcarbonyloxy, Ci-6 alkoxycarbonyloxy, Cι_6 alkylaminocarbonyloxy, Ci-6 alkoxy, Ci-6 alkylamino, di(Ci-6)alkylamino, hydroxy, phenoxy (optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d_6 haloalkyl, d_6 alkoxy or d-6 haloalkoxy), hydroxy- (C1-6)alkyl, hydroxy(Ci_6)alkylamino or carboxy(Cι.6)alkoxy.
It is more preferred that R10 is d-6 alkyl, C2.6 alkenyl(Cι-6)alkyl, C2.6 alkynyl- (Ci.6)alkyl, C3.7 cycloalkyl, phenyl, d-6 haloalkyl, d_6 alkoxy(Ci.6)alkyl, Ci-6 alkylcarbonylamino, Ci- alkoxycarbonylamino, Cι_6 alkoxy, d_6 alkylamino, di(Ci.6)alkylamino, hydroxy, phenoxy, hydroxy(Ci.6)alkyl, hydroxy(Ci-6)alkylamino or carboxy(C i _6) alkoxy.
It is preferred that R11 is Ci.10 alkyl, C2_6 alkenyl(d-6)alkyl, C2-6 alkynyl(Ci-6)alkyl, C3.7 cycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, Ci.6 alkyl, d.6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy), CMO haloalkyl, Ci.6 alkoxy(d-6)alkyl or C3-7 cycloalkyl- (Ci.6)alkyl.
It is more preferred that R11 is Ci-io alkyl, C2.6 alkenyl(Ci-6)alkyl, C2_6 alkynyl(Ci.6)alkyl, C3.7 cycloalkyl, phenyl, Ci.10 haloalkyl, Cι_6 alkoxy(Ci.6)alkyl or C3.7 cycloalkyl(d.6)alkyl.
It is preferred that R12 is hydrogen, d.io alkyl, C2.6 alkenyl(d.6)alkyl, C2.6 alkynyl(Ci.6)alkyl, C3. cycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, d_6 alkyl, d-6 haloalkyl, d- alkoxy or d-6 haloalkoxy), C O haloalkyl, d_6 alkoxy(Cι-6)alkyl or C3.7 cycloalkyl(d-6)alkyl. It is more preferred that R12 is hydrogen, d.10 alkyl, C2_6 alkenyl(Cι.6)alkyl, C2.6 alkynyl(Ci.6)alkyl, C3. cycloalkyl, phenyl, CMO haloalkyl, Cι-6 alkoxy(C1-6)alkyl or C3.7 cycloalkyl(Cι.6)alkyl.
R12 is even more preferably hydrogen, Cι-6 alkyl or Cι_6 alkoxy (Cι-6 )alkyl; most preferably hydrogen.
It is preferred that R13 is CMO alkyl, C2.6 alkenyl(C1_6)alkyl, C2.6 alkynyl(Cι-6)alkyl, C3.7 cycloalkyl, phenyl (optionally substituted by halo, nitro, cyano, Cue alkyl, Ci-6 haloalkyl, d-6 alkoxy or d_6 haloalkoxy), d-10 haloalkyl, d-6 alkoxy(Cι-6)alkyl, C3.7 cycloalkyl- (d-6)alkyl, Cue alkylcarbonylamino, Ci-6 alkoxycarbonylamino, d-6 alkylaminocarbonyl- amino, d-6 alkylcarbonyloxy, Cι_6 alkoxycarbonyloxy, d-6 alkylaminocarbonyloxy, Cue alkoxy, Ci-6 alkylamino, di(Cι_6)alkylamino, hydroxy, phenoxy (optionally substituted by halo, nitro, cyano, d,6 alkyl, d-6 haloalkyl, d-6 alkoxy or d_6 haloalkoxy), hydroxy(Cι_6)- alkyl, hydroxy(Ci-6)alkylamino or carboxy(Ci.6)alkoxy. It is more preferred that R13 is Ci-6 alkyl, C2_6 alkenyl(d-6)alkyl, C2. alkynyl(Ci.6)- alkyl, C3.7 cycloalkyl, phenyl, d-6 haloalkyl, Cι_6 alkoxy(Ci-6)alkyl, d_6 alkylcarbonylamino, Ci-6 alkoxycarbonylamino, Ci_ alkoxy, Cι_ alkylamino, di(d.6)alkylamino, hydroxy, phenoxy, hydroxy(d.6)alkyl, hydroxy(Cι-6)alkylamino or carboxy(Ci_6)alkoxy. It is preferred that R'4 is cyano, nitro, d-6 alkyl, Ci.6 haloalkyl, C3.7 cycloalkyl(Cι.6)alkyl, C3-7 cycloalkyl, (C2.6)alkenylCH2, (C2.6)alkynylCH2, phenyl (optionally substituted by halo, nitro, cyano, Cι_6 alkyl, Ci.6 haloalkyl, Ci-6 alkoxy or Cι_6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Cι_6 alkyl, d.6 haloalkyl, Cι_6 alkoxy or Ci-6 haloalkoxy), Ci-6 alkylcarbonyl, d-6 alkoxycarbonyl, Ci-6 alkylamino, di(Cι_6)- alkylamino, d.6 alkylcarbonylamino, Ci-6 alkoxycarbonylamino, Ci-6 alkoxy, Cι_6 alkylthio, Ci-6 haloalkylthio, Ci-6 alkylsulfinyl, Cι.6 haloalkylsulfinyl, Ci_6 alkylsulfonyl, d-6 haloalkylsulfonyl, arylthio, arylsulfinyl, arylsulfonyl or (d_6)alkylcarbonyloxy.
It is preferred that R15 is hydrogen, Cι.8 alkyl, Cue haloalkyl, Cι_6 cyanoalkyl, C2.6 alkenylCH2, C2.6 haloalkenylCH2, C2.6 alkynylCH2, C3.7 cycloalkyl, C3.7 cycloalkyl(d-6)- alkyl, d-6 alkoxy(Cι.6)alkyl, d_6 alkoxycarbonyl, d_6 alkylcarbonyl, Ci.6alkyl- aminocarbonyl, di(Ci.6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, d-6 alkyl, d-6 haloalkyl, d_6 alkoxy or d-6 haloalkoxy) or heteroaryl (optionally substituted by halo, nitro, cyano, d-6 alkyl, Ci.6 haloalkyl, Ci-6 alkoxy or Ci_6 haloalkoxy). It is more preferred that R15 is hydrogen, Cμ8 alkyl or d-6 haloalkyl. The compounds in Tables 1 to 78 below illustrate compounds of the invention. Table 1 provides
Figure imgf000027_0001
wherein M and R6 are as defined in Table 1. Table 1
Figure imgf000028_0001
Table 1 Continued
Figure imgf000029_0001
Table 1 Continued
Figure imgf000030_0001
Table 1 Continued
Figure imgf000031_0001
Table 1 Continued
Figure imgf000032_0001
Table 1 Continue
Figure imgf000033_0001
Table 1 Continued
Figure imgf000034_0001
Table 1 Continued
Figure imgf000035_0001
Table 1 Continued
Figure imgf000036_0001
Table 2 provides 330 compounds of formula (2):
Figure imgf000037_0001
wherein R° and M are as defined in Table 2.
Table 2
Figure imgf000037_0002
Table 2 Continued
Figure imgf000038_0001
Table 2 Continued
Figure imgf000039_0001
Table 2 Continued
Figure imgf000040_0001
Table 2 Continued
Figure imgf000041_0001
Table 2 Continued
Figure imgf000042_0001
Table 2 Continued
Figure imgf000043_0001
Table 2 Continued
Figure imgf000044_0001
Table 3 provides 330 compounds of formula (3):
Figure imgf000045_0001
wherein M and R are as defined in Table 2.
Table 4 provides 330 compounds of formula (4):
Figure imgf000045_0002
wherein M and R6 are as defined in Table 2.
Table 5 provides 330 compounds of formula (5):
Figure imgf000045_0003
wherein M and R6 are as defined in Table 2.
Table 6 provides 330 compounds of formula (6):
Figure imgf000045_0004
wherein M and R are as defined in Table 2.
Table 7 provides 330 compounds of formula (7):
Figure imgf000045_0005
wherein M and R are as defined in Table 2. Table 8 provides 330 compounds of formula (8):
Figure imgf000046_0001
wherein M and R are as defined in Table 2.
Table 9 provides 330 compounds of formula (9):
Figure imgf000046_0002
wherein M and R are as defined in Table 2.
Table 10 provides 330 compounds of formula (10):
Figure imgf000046_0003
wherein M and R6 are as defined in Table 2.
Table 11 provides 330 compounds of formula (11):
Figure imgf000046_0004
wherein M and R are as defined in Table 2.
Table 12 provides 330 compounds of formula (12):
Figure imgf000046_0005
wherein M and R6 are as defined in Table 2.
Table 13 provides 330 compounds of formula (13):
Figure imgf000047_0001
wherein M and R6 are as defined in Table 2.
Table 14 provides 330 compounds of formula (14):
Figure imgf000047_0002
wherein M and R6 are as defined in Table 2.
Table 15 provides 330 compounds of formula (15):
Figure imgf000047_0003
wherein M and R6 are as defined in Table 2.
Table 16 provides 330 compounds of formula (16):
Figure imgf000047_0004
wherein M and R6 are as defined in Table 2.
Table 17 provides 330 compounds of formula (17):
Figure imgf000047_0005
wherein M and R6 are as defined in Table 2.
Table 18 provides 330 compounds of formula (18):
Figure imgf000048_0001
wherein M and R are as defined in Table 2.
Table 19 provides 330 compounds of formula (19):
Figure imgf000048_0002
wherein M and R are as defined in Table 2.
Table 20 provides 330 compounds of formula (20):
Figure imgf000048_0003
wherein M and R are as defined in Table 2.
Table 21 provides 330 compounds of formula (21):
Figure imgf000048_0004
wherein M and R6 are as defined in Table 2.
Table 22 provides 330 compounds of formula (22):
Figure imgf000048_0005
wherein M and R6 are as defined in Table 2.
Table 23 provides 330 compounds of formula (23): O 01/55142
- 47 -
Figure imgf000049_0001
wherein M and R are as defined in Table 2.
Table 24 provides 330 compounds of formula (24):
Figure imgf000049_0002
wherein M and R are as defined in Table 2.
Table 25 provides 330 compounds of formula (25):
Figure imgf000049_0003
wherein M and R6 are as defined in Table 2.
Table 26 provides 330 compounds of formula (26):
Figure imgf000049_0004
wherein M and R are as defined in Table 2.
Table 27 provides 330 compounds of formula (27):
Figure imgf000049_0005
wherein M and R are as defined in Table 2.
Table 28 provides 330 compounds of formula (28):
Figure imgf000050_0001
wherein M and R are as defined in Table 2.
Table 29 provides 330 compounds of formula (29):
Figure imgf000050_0002
wherein M and R are as defined in Table 2.
Table 30 provides 330 compounds of formula (30):
Figure imgf000050_0003
wherein M and R are as defined in Table 2.
Table 31 provides 330 compounds of formula (31):
Figure imgf000050_0004
wherein M and R are as defined in Table 2.
Table 32 provides 330 compounds of formula (32):
Figure imgf000050_0005
wherein M and R are as defined in Table 2.
Table 33 provides 330 compounds of formula (33):
Figure imgf000051_0001
wherein M and R are as defined in Table 2.
Table 34 provides 330 compounds of formula (34):
Figure imgf000051_0002
wherein M and R are as defined in Table 2.
Table 35 provides 330 compounds of formula (35):
Figure imgf000051_0003
wherein M and R6 are as defined in Table 2.
Table 36 provides 330 compounds of formula (36):
Figure imgf000051_0004
wherein M and R are as defined in Table 2.
Table 37 provides 330 compounds of formula (37):
Figure imgf000051_0005
wherein M and R are as defined in Table 2.
Table 38 provides 330 compounds of formula (38):
Figure imgf000052_0001
wherein M and R are as defined in Table 2.
Table 39 provides 330 compounds of formula (39):
Figure imgf000052_0002
wherein M and R are as defined in Table 2.
Table 40 provides 330 compounds of formula (40):
Figure imgf000052_0003
wherein M and R6 are as defined in Table 2.
Table 41 provides 330 compounds of formula (41):
Figure imgf000052_0004
wherein M and R are as defined in Table 2.
Table 42 provides 330 compounds of formula (42):
Figure imgf000052_0005
wherein M and R are as defined in Table 2.
Table 43 provides 330 compounds of formula (43):
Figure imgf000053_0001
wherein M and R are as defined in Table 2.
Table 44 provides 330 compounds of formula (44):
Figure imgf000053_0002
wherein M and R are as defined in Table 2.
Table 45 provides 330 compounds of formula (45):
Figure imgf000053_0003
wherein M and R6 are as defined in Table 2.
Table 46 provides 330 compounds of formula (46):
Figure imgf000053_0004
wherein M and R6 are as defined in Table 2.
Table 47 provides 330 compounds of formula (47):
Figure imgf000053_0005
wherein M and R are as defined in Table 2.
Table 48 provides 330 compounds of formula (48):
Figure imgf000054_0001
wherein M and R are as defined in Table 2.
Table 49 provides 330 compounds of formula (49):
Figure imgf000054_0002
wherein M and R are as defined in Table 2.
Table 50 provides 330 compounds of formula (50):
Figure imgf000054_0003
wherein M and R6 are as defined in Table 2.
Table 51 provides 330 compounds of formula (51):
Figure imgf000054_0004
wherein M and R are as defined in Table 2.
Table 52 provides 330 compounds of formula (52):
Figure imgf000054_0005
wherein M and R6 are as defined in Table 2.
Table 53 provides 330 compounds of formula (53):
Figure imgf000055_0001
wherein M and R are as defined in Table 2.
Table 54 provides 330 compounds of formula (54):
Figure imgf000055_0002
wherein M and R6 are as defined in Table 2.
Table 55 provides 330 compounds of formula (55):
Figure imgf000055_0003
wherein M and R6 are as defined in Table 2.
Table 56 provides 330 compounds of formula (56):
Figure imgf000055_0004
wherein M and R are as defined in Table 2.
Table 57 provides 330 compounds of formula (57):
wherein M and R are as defined in Table 2.
Table 58 provides 330 compounds of formula (58):
Figure imgf000056_0001
wherein M and R are as defined in Table 2.
Table 59 provides 330 compounds of formula (59):
Figure imgf000056_0002
wherein M and R are as defined in Table 2.
Table 60 provides 330 compounds of formula (60):
Figure imgf000056_0003
wherein M and R are as defined in Table 2.
Table 61 provides 330 compounds of formula (61):
Figure imgf000056_0004
wherein M and R are as defined in Table 2.
Table 62 provides 330 compounds of formula (62):
Figure imgf000056_0005
wherein M and R are as defined in Table 2.
Table 63 provides 330 compounds of formula (63):
Figure imgf000057_0001
wherein M and R are as defined in Table 2.
Table 64 provides 330 compounds of formula (64):
Figure imgf000057_0002
wherein M and R are as defined in Table 2.
Table 65 provides 330 compounds of formula (65):
Figure imgf000057_0003
wherein M and R are as defined in Table 2.
Table 66 provides 330 compounds of formula (66):
Figure imgf000057_0004
wherein M and R are as defined in Table 2.
Table 67 provides 330 compounds of formula (67):
Figure imgf000057_0005
wherein M and R6 are as defined in Table 2.
Table 68 provides 330 compounds of formula (68):
Figure imgf000058_0001
wherein M and R6 are as defined in Table 2.
Table 69 provides 330 compounds of formula (69):
Figure imgf000058_0002
wherein M and R are as defined in Table 2.
Table 70 provides 330 compounds of formula (70):
Figure imgf000058_0003
wherein M and R6 are as defined in Table 2.
Table 71 provides 330 compounds of formula (71):
Figure imgf000058_0004
wherein M and R are as defined in Table 2.
Table 72 provides 330 compounds of formula (72):
Figure imgf000058_0005
wherein M and R6 are as defined in Table 2.
Table 73 provides 330 compounds of formula (73):
Figure imgf000059_0001
wherein M and R are as defined in Table 2.
Table 74 provides 330 compounds of formula (74):
Figure imgf000059_0002
wherein M and R are as defined in Table 2.
Table 75 provides 330 compounds of formula (75):
Figure imgf000059_0003
wherein M and R are as defined in Table 2.
Table 76 provides 330 compounds of formula (76):
Figure imgf000059_0004
wherein M and R are as defined in Table 2.
Table 77 provides 330 compounds of formula (77):
Figure imgf000059_0005
wherein M and R are as defined in Table 2.
Table 78 provides 330 compounds of formula (78):
Figure imgf000060_0001
wherein M and R >6 are as defined in Table 2.
The following abbreviations are used throughout this description: m.p. = melting point ppm = parts per million s = singlet br = broad d = doublet dd = doublet of doublets t = triplet q = quartet m = multiplet
Table 79 shows selected melting point and selected NMR data, all with CDCI3 as the solvent (unless otherwise stated; if a mixture of solvents is present, this is indicated as, for example, (CDCI3 / dβ-DMSO)), (no attempt is made to list all characterising data in all cases) for compounds of Tables 1 to 78.
TABLE 79
Figure imgf000061_0001
Table 79 Continued
Figure imgf000062_0001
The compounds of the invention may be made in a variety of ways.
Treatment of a compound of formula (II), wherein R35 is hydrogen, with an alkylating or acylating agent, optionally in the presence of a base and a phase transfer catalyst, provides a compound of formula (la), wherein R9 is an alkyl or acyl group. Examples of suitable alkylating agents include, but are not restricted to, alkyl halides (such as methyl iodide) and alkyl sulfates (such as dimethylsulfate). Suitable acylating agents include anhydrides (such as acetic anhydride), acid chlorides (such as acetyl chloride or benzoyl chloride) and chloroformates (such as ethyl chloroformate). Suitable bases include organic bases (such as triethylamine or pyridine), alkali metal alkoxides (such as potassium tert-butoxide) and inorganic bases (such as sodium hydride or sodium hydroxide). Suitable phase transfer catalysts may be selected by reference to the literature (see, for example, J. March, Advanced Organic Chemistry, Third Edition, John Wiley and Sons, New York, 1985, pages 320-322 and references therein).
Figure imgf000063_0001
(la) (ϋ)
Treatment of a compound of formula (la), wherein R9 is an alkyl group with a nucleophile, for example an alcohol (suitable alcohols include, but are not restricted to, ethanol or methanol) or an amine, optionally in the presence of a base and a phase transfer catalyst or in the presence of a mercuric salt (such as mercuric chloride), provides, respectively, a compound of formula (Ib) or (Ic).
Figure imgf000063_0002
(lb) (Ic) Alternatively, a compound of formula (la) may be reacted with an alcohol or an amine, O-alkylhydroxylamine or hydrazine, optionally in the presence of a mercuric salt (such as mercuric chloride), according to known procedures to give a compound of formula (Ib) or (Ic), respectively where R8, R10 and R11 are, independently, hydrogen, optionally substituted alkyl, alkenyl, alkynyl, amino, substituted amino or alkoxy. In the case of a compound of formula (Ic), when R10 is hydrogen, it may be reacted further with an alkylating or acylating agent under conditions previously described to give further substituted compounds of formula (Ic).
A compound of formula (IT) may be prepared by reacting a compound of formula (Ha) 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-bis0^αrα-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.
Figure imgf000064_0001
Alternatively, a compound of formula (Ila) may be reacted with a chlorinating agent, for example phosphorus oxychloride or phosphorous pentachloride, to give a compound of formula (IH) which can be further reacted with a thiol, an alcohol or an amine, optionally in the presence of a base, to give, respectively, a compound of formula (la), (Ib), or (Ic).
A compound of formula (Ila) wherein A is optionally substituted alkylene, alkenylene, alkylenoxy, alkylenamino or alkylenethio may be prepared by reacting a compound of formula (IV) with an appropriate a compound of formula (N), where X is hydroxy, alkoxy or aryloxy in the presence of a known coupling agent such as 1,3- dicyclohexylcarbodiimide or l-(3-dimethylaminopropyl)-3-ethylcarbodiimide. Alternatively, a compound of formula (N), where X is hydroxy, may first be converted to an acid chloride or anhydride suitable for reaction with an amine to form an amide (such procedures are well known to those skilled in the art and are described, for example in J. March, Advanced O 01/55142 - 63 -
Organic Chemistry, Third Edition, John Wiley and Sons, New York, 1985, pps 370-376 and references therein) and then reacted with a compound of formula (IN).
Figure imgf000065_0001
(V) (IN) (U-a)
Compounds of formula (IN) are known compounds, or may be prepared from commercially available starting materials by methods described in the literature (see, for example, C. Oliver Kappe, Robert Flammang, and Curt Wentrup, Heterocycles, Vol. 37, No. 3, 1615, (1994), A. Adams and R. Slack, J. Chem. Soc, 3061, (1959) and Ronald E Hackler, Kenneth W. Burow, Jr., Sylvester V. Kaster and David I. Wickiser, J. Heterocyclic Chem, 26, 1575, (1989), Ronald E Hackler, Glen P Jourdan, Peter L Johnson, Brian R Thoreen and Jack G Samaritoni, PCT Int. Appl., WO9304580 Al, and references therein). The syntheses of substituted benzimidazoles, benzoxazoles and benzthiazoles are well known (see for example, Alan R. Katritzky and Charles W. Rees, Comprehensive Heterocyclic Chemistry, Volume 6, Pergamon Press, 1984; Helmut M Hugel, Synth. Commun., 15 (12), 1075-1080, (1985); J. Scheigetz, R. Zamboni and B. Roy, Synth. Commun, 25 (18) 2791-2086, (1985); David Dunwell, Delme Evans, Terence A. Hicks, J. Med. Chem., 1975, 18, No. 1, 53; Abdou O.Abdelhamid, Cyril Parkanyi, S.M. Khaledur Rashid and Winston D. Lloyd, J. Heterocyclic Chem.; 25, 403, (1988); Teruyuki Kondo, Sungbong Yang, Keun-Tae Huh, Masanobu Kobayashi, Shinju Kotachi and Yoshihisa Watanabe, Chemistry Letters, 1275, 1991; Dale L. Boger, J. Org. Chem., 43 No. 11, 2296, (1978) and similar processes may be utilised in the synthesis of a compound of formula (V) from appropriate starting materials. Benzothiophenes may be made from appropriate thiophenols by processes similar to those described by Robert D Schuetz and Richard L Titus (J. Heterocycl. Chem., 4, No 4, 465 (1967); suitable thiophenols are known compounds or may be prepared by known methods. Benzofurans may be made from σrt/zo-halophenols as described by Henning Lutjens and Peter J Scammells, Tetrahedron Letters 39 (1998), 6581-6584, Terence C. Owen et ah, Tetrahedron Letters 30, No. 13, 1597 (1989) and Fred G O 01/55142 64
Schreiber and Robert Stevenson, J.C.S. Perkin 1, 90, 1977. Indoles may be prepared form ørt/rø-haloanilines according to the method of Cheng-yi Chen et al., J. Org. Chem., 1997, 62, 2676, Takao Sakamoto et al., J. Org. Chem., 1997, 62, 6507 and Alan D. Adams et al., WO9827974. Appropriate ørt&osubstituted phenols and anilines may be prepared by known methods from commercially available starting materials.
In a further approach, a compound of formula (Na) may be prepared by treating a compound of formula (NI) with an optionally substituted haloalkyl ester or an α,β unsaturated ester, preferably in the presence of a base such as potassium carbonate.
Figure imgf000066_0001
(Na) (NI)
A compound of formula (Nil) can be reacted with appropriate malonate, alkane or alkene derivatives in the presence of suitable catalysts, for example palladium (0) derivatives, to give a compound of formula (V).
Figure imgf000066_0002
(vπ)
A compound of formula (VET) may be made from a compound of formula (lib) by treatment with N,N-dimethyl-formamide 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 imgf000066_0003
(lib) (vm) A compound of formula (VET) may be treated subsequently with a secondary amine (HNR29R30) to give a compound of formula (DC); a compound of formula (lib) may be treated in an analogous manner with trialkylorthoformates to afford a compound of formula (X), where Rd is C1-6 alkyl.
Figure imgf000067_0001
(IX) (X)
A compound of formula (V) (where A is CH2O and X is O-alkyl) may be further derivatised by deprotonation with a suitable base (such as lithium hexamethyl disilazide) followed by reaction with an electrophile such as an alkyl halide, alkyl sulphate or a halogenating agent [such as N-chlorosuccinamide or l-chloromethyl-4-fluoro-l,4- diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate)] and this procedure may be carried out more than once to generate further compounds of formula (Ha).
A compound of formula (IN) can be reacted with a diazing agent such as tert-butyl nitrite in the presence of copper oxide to give a compound of formula (XI) which can then be further reacted with a compound of formula (V) (where X is chlorine) to give a compound of formula (Id).
Figure imgf000067_0002
(XI) (Id)
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 lotus (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, Reticuliterm.es flavipes, R. speratu, R. virginicus, R. hesperus, and R. santonensis) and the Termitidae (for example Globitermes sulphureus), Solenopsis geminata (fire ant), Monomorium pharaonis (pharaoh's ant),
Damalinia spp. and Linognathus spp. (biting and sucking lice), Meloidogyne spp. (root knot nematodes), Globodera spp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesion nematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulus spp. (citrus nematodes), Haemonchus contortus (barber pole worm), Caenorhabditis elegans_ (vinegar eelworm), Trichostrongylus spp. (gastro intestinal nematodes) and Deroceras reticulatum (slug). The compounds of formula (I) are also active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae (Magnaporthe grised) 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 cingulatd), black rot or frogeye leaf spot (Botryosphaeria obtusa), Brooks fruit spot (Mycosphaerella pomϊ), Cedar apple rust (Gymnosporangiumjuniperi-virginianae), sooty blotch (Gloeodes pomigena), flyspeck (Schizothyrium pomi) and white rot (Botryosphaeria dothideά)) 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; Laetisariafuciformis 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 solution). The compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
The term "plant" as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes protectant, curative, systemic, eradicant and antisporulant treatments.
As fungicides, the compounds of formula (I) are preferably used for agricultural, horticultural and turfgrass purposes in the form of a composition.
In order to apply a compound of formula (I) as an insecticide, acaricide, nematicide or molluscicide to a pest, a locus of pest, or to a plant susceptible to attack by a pest, or, as a fungicide to a plant, to a seed of a plant, to the locus of the plant or seed, to soil or to any other growth medium, a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA). SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula (I). The composition is generally used for the control of pests or fungi such that a compound of formula (I) is applied at a rate of from O.lg to 10kg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 1kg per hectare. When used in a seed dressing, a compound of formula (I) is used at a rate of 0.000 lg to lOg (for example O.OOlg or 0.05g), preferably 0.005g to lOg, more preferably 0.005g to 4g, per kilogram of seed. In another aspect the present invention provides an insecticidal, acaricidal, nematicidal, molluscicidal or fungicidal composition comprising an insecticidally, acaricidally, nematicidally, molluscicidally or fungicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor. The composition is preferably an insecticidal, acaricidal, nematicidal or fungicidal composition.
In a still further aspect the invention provides a method of combating and controlling pests or fungi at a locus which comprises treating the pests or fungi or the locus of the pests or fungi with an insecticidally, acaricidally, nematicidally, molluscicidally or fungicidally effective amount of a composition comprising a compound of formula (I). The compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
The compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I). Dustable powders (DP) may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder. Soluble powders (SP) may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG). Wettable powders (WP) may be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).
Granules (GR) may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent). Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).
Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C8-do fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of formula (I) is present initially in either the water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs. An ME may be either an oil-in- water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example n-butane). A compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps. A compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment. A compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)). Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).
A compound of formula (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 di- wopropyl- and tri-wopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulphosuccinamates, paraffin or olefine sulphonates, taurates and lignosulphonates. Suitable SFAs of the amphoteric type include betaines, propionates and glycinates. Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins. Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
A compound of formula (I) may be applied by any of the known means of applying pesticidal or fungicidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.
A compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
A compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers). Suitable formulation types include granules of fertiliser. The mixtures suitably contain up to 25% by weight of the compound of formula (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). 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- 1 ,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide ( AC382042) , N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide, acibenzolar (CGA245704), alanycarb, aldimorph, anilazine, azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S, bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, ca ropamid, 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-wo-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-rsøpropyl, 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 PDC™.
Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.
The invention is illustrated by the following Examples:
EXAMPLE 1 This Example illustrates the preparation of N-(4-chloro-3-methylisothiazol-5-yl)thio(2- [2,2-dimethylpropyl] benzoxazol-5-yl)acetamide.
Step 1 - Preparation of 5-amino-4-chloro-3-methylisothiazole.
5-Amino-3-methylisothiazole hydrochloride (250g, 1.66 mole) was suspended in dichloromethane( 1.251) and stirred at 8°C. Sulfuryl chloride(146.8ml, 1.83 mole) was added dropwise over lhour and during this addition the temperature of the reaction mixture was maintained between 10 and 15°C. As the sulfuryl chloride was added the suspended particles dissolved and a dark oil began to fall out of solution. The resultant two-phase mixture was stirred at 10°C for 15minute. The mixture was cooled to below 10°C and quenched by careful addition of aqueous potassium carbonate solution (367.3g, 2.66 mole, of potassium carbonate in 1 litre of water). The two phases were separated and the aqueous layer extracted with dichloromethane (600ml+400ml). The combined organic layers were dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated in vacuo. The residue was slurried in hexane (~500ml) for lhour, filtered and dried to give 5-amino-4- chloro-3-methyl-isothiazole as a red-brown-solid (228.7g, 93%), m.p. 69-71°C. 1H NMR (CDC13) δ: 2.3(3H,s); 4.6(2H, br.s)ppm. Step 2 - Preparation of methyl (4-hydroxyphenyl)acetate. Hydrogen chloride was bubbled through a solution of (4-hydroxyphenyl) acetic acid (25g , 0.16mole) in methanol (100ml) at room temperature. An exotherm resulted in the solution refluxing for about lOminutes. The mixture was allowed to cool to room temperature and the solvent was evaporated in vacuo to afford methyl (4- hydroxyphenyl)acetate as a yellow oil (27.5g) which crystallised on seeding, m.p. 46-52°C.
1H NMR (CDC13) δ: 3.57(2H,s); 3.71(3H,s); 6.0(lH,br); 6.76(2H,m); 7.10(2H,m)pρm. Step 3 - Preparation of methyl (4-hydroxy-3-nitrophenyl)acetate.
Nitric acid (69% by weight, 16M, 20ml) was added dropwise to a solution of methyl (4-hydroxyphenyl)acetate [from step 2] (50.0g, 0.3mole) in acetic acid (500ml), maintaining the temperature of the reaction below 15°C by external cooling. (An induction period was observed for this reaction.) Once gas chromatographic analysis had confirmed that the reaction was complete, the mixture was carefully quenched into water (21) with vigorous stirring. An emulsion formed which subsequently crystallised. After filtration, washing with water and drying, the desired product was obtained as a yellow powder.
Η NMR (CDC13) δ: 3.63(2H,s); 3.72(3H,s); 7.14(lH,d); 7.52(lH,dd); 8.02(lH,d); 10.5(lH,s)ppm. Step 4 - Preparation of methyl (3-amino-4-hydroxyphenyl)acetate.
Methyl (4-hydroxy-3-nitrophenyl)acetate [from step 3] (48.9g, 0.23mole) and 5% palladium on carbon were suspended in methanol and the resulting mixture was hydrogenated until all the starting material had been consumed. The reaction mixture was filtered to remove the catalyst and the filter-cake was washed with methanol. The combined filtrate and washings were concentrated in vacuo, affording methyl (3-amino-4- hydroxyphenyl)acetate as a solid (41.0g). 1H NMR (d6-DMSO) δ: 3.51(2H,s); 4.45(2H,b); 6.20(lH,dd); 6.40(lH,d); 6.49(lH,d);
8.87(lH,br)ppm.
Step 5 - Preparation of methyl [3-(2,2-dimethylpropionamido)-4- hydroxyphenyl]acetate._
Sodium hydrogen carbonate (19g, 0.23mole) was suspended in 1,2-dimethoxyethane (180ml), and methyl (3-amino-4-hydroxyphenyl)acetate [from step 4] (26.3g, 0.145mole) was added. To this mixture was added, dropwise, a solution of t-butyl acetyl chloride in 1,2- dimethoxyethane (45ml), over 2hour. Once the addition was complete, the mixture was stirred at room temperature for lhour. The mixture was filtered, the inorganic solid washed with ethyl acetate (3x50ml) and the filtrate and washings were combined and concentrated. Trituration of the product with hexane gave methyl [3-(2,2-dimethylpropionamido)-4- hydroxyphenyl]acetate (40.1g) as an off-white solid, m.p. 112-113°C.
1H NMR (CDC13) δ: l.l(9H,s); 2.30(2H,s); 3.51(2H,s); 3.70(3H,s); 6.9-7.0(3H,m); 7.55(lH,b); 8.85(lH,br)ppm.
Step 6 - Preparation of methyl [(2,2-dimethylpropyl)-5-benzoxazolyl]acetate. pαr -Toluenesulphonic acid (1.5g) in toluene (120ml) was stirred and heated to reflux with a Dean & Stark™ assembly fitted to remove water. After lhour at reflux the solution was cooled to ~80°C and methyl [3-(2,2-dimethylpropionamido)-4-hydroxy-phenyl]acetate [from step 5] (20.0g, 0.07mole) was added portionwise. The reaction mixture was then heated at reflux for 6 hours, cooled, diluted with hexane (200ml) and filtered through a plug of silica gel, eluting with ethyl acetate. The filtrate was evaporated in vacuo to give methyl [(2,2-dimethylpropyl)-5-benzoxazolyl]acetate (17.5 g) as an oil.
1H NMR (CDC13) δ: l.l(9H,s); 2.8(2H,s); 3.7(3H,s); 3.74(2H,s); 7.4(3H,m)ppm. Step 7 - Preparation of [(2,2-dimethylpropyl)-5-benzoxazolyI]acetic acid. Methyl [(2,2-dimethylpropyl)-5-benzoxazolyl]acetate [from step 6] (5.00g, 0.0185mole) was dissolved in methanol (5ml) and then a solution of sodium hydroxide (0.8 lg, 0.0204mole) in water (5ml) was added slowly over 20minute, maintaining the temperature below 25°C by external cooling. Once the addition was complete, the mixture was allowed to stir at room temperature for lhour. The reaction mixture was poured slowly into water (50ml) and concentrated hydrochloride acid was added until the pH of the mixture was below pH6. The mixture was stirred for lhour then filtered and the solid was washed thoroughly with water and dried. Trituration with hexane gave [(2,2-dimethylpropyl)-5- benzoxazolyl] acetic acid (4.5 lg) as a white solid, m.p. 108-109°C.
1H NMR (CDC13) δ: 1.05(9H,s); 2.80(2H,s); 3.77(2H,s); 7.42(3H,m)ppm. Step 8 - Preparation of N-(4-chloro-3-methylisothiazol-5-yl)-[2-(2,2- dimethylpropyl)benzoxazol-5-yI]acetamide.
[2-(2,2-Dimethylpropyl)-5-benzoxazolyl]acetic acid [from step 7] (0.800g, 0.003mole) was suspended in dichloromethane (10ml) and N,N-dimethylformamide (one drop) and oxalyl chloride (0.45 lg, 0.004mole) were added sequentially. The mixture was stirred for 2hour and then the solvent was removed in vacuo. The residue was taken up in xylene (10ml), 5-amino-4-chloro-3-methylisothiazole [from step 1] (0.829g, O.OOόmole) was added and then the mixture was heated under reflux for 2hour. The mixture was cooled to room temperature, diluted with ethyl acetate and washed with brine. The organic solution was dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo. The residue was further purified by flash column chromatography on silica gel, eluting with a 2:1 mixture of hexane: ethyl acetate, to give N-(4-chloro-3-methylisothiazol-5-yl)-[2-(2,2- dimethylpropyl)-benzoxazol-5-yl] acetamide (0.325g) as a pale orange solid, m.p. 144-145°C. 1H NMR (CDCI3) δ: l.l(9H,s); 2.35(3H,s); 2.85(2H,s); 3.95(2H,s); 7.25(lH,dd);
7.55(lH,d); 7.65(lH,d); 8.1(lH,br)ppm.
Step 9 - Preparation of N-(4-chloro-3-methylisothiazoI-5-yl)thio(2-[2,2- dimethylpropyl] benzoxazoI-5-yl)acetamide.
N-(4-chloro-3-methylisothiazol-5-yl)-(2-[2,2-dimethylpropyl]benzoxazol-5-yl)- acetamide [from step 8] (lOg) was heated to 75-80°C in dry fluorobenzene (150ml) with stirring under an atmosphere of nitrogen. The solution was treated portion-wise over 2hour with 2,4-bis(p-tolylthio)-l,3,2,4-dithiadiphosphetane-2,4-disulfide (18g), heated to reflux for a further 5hour and was then allowed to cool to ambient temperature. The mixture was filtered, the insoluble material was washed with fluorobenzene and the combined filtrate was diluted with hexane (100m) and was then applied to a short column of silica. The column was eluted with hexane then mixtures of hexane and ethyl acetate (ratio 10:1 to 6:1). The fractions containing the desired product were combined and then evaporated under reduced pressure to give the required product (5.1g) as a pale yellow solid, m.p.l67-168°C. 1H NMR (CDCI3) δ: 1.10(9H,s); 2.40(3H,s); 2.85(2H,s); 4.45(2H,s); 7.30(lH,dd); 7.58(lH,d); 7.68(lH,d); 9.32(lH,br)ppm.
EXAMPLE 2 This Example illustrates the preparation of Compound No.7 of Table No. 1.
The product from Example 1 (5.00g) was stirred under an atmosphere of nitrogen in dry tetrahydrofuran (THF) (50ml) whilst sodium bis(trimethylsilyl)amide (12.7ml of a l.OM solution in THF) was added. The mixture was stirred at ambient temperature for 30minutes and then methyl iodide (0.79ml) was added. The mixture was heated at 45 °C for 3hours and then allowed to stand at ambient temperature overnight. The reaction mixture was partitioned between ethyl acetate and water. The organic layers were dried (magnesium sulfate), filtered and the solvent was evaporated under reduced pressure. The residual oil was purified by chromatography (Zorbax SilTMlOO with hexane: ethyl acetate at 9:1 by volume) to give the required product as an orange solid (3.68g). Using similar procedures, the following compounds were prepared individually:
Compound No. 77 of Table No. 1 as a light brown gum; Compound No. 37 of Table No. 1 as a yellow gum; and Compound No. 17 of Table No. 1 as an orange solid.
EXAMPLE 3 This Example illustrates the preparation of Compound No. 27 of Table No. 1.
The product from Example 1 (0.30g) was stirred under an atmosphere of nitrogen in acetone (5ml) containing anhydrous potassium carbonate (0.15g) and was then treated with a solution of chloromethyl methylsulfide (0.075g) in acetone (2ml). The mixture was heated to 55°C for hour, allowed to cool to ambient temperature and was then filtered. The insoluble material was washed with further acetone and the combined filtrate was evaporated under reduced pressure. The residual oil was fractionated by chromatography (silica; hexane: diethyl ether at 10:1 to 4:1 by volume) to give the required product as a brown gum (0.18g).
Using similar procedures, the following compounds were prepared individually: Compound No. 67 of Table No. 1 as a yellow gum; Compound No. 47 of Table No. 1 as a brown gum; Compound No. 57 of Table No. 1 as a brown gum; Compound No. 37 of Table No. 75 as a brown gum; and Compound No. 87 of Table No. 1 as a brown gum. EXAMPLE 4 This Example illustrates the preparation of Compound No. 157 of Table No. 1. Sodium (1 lmg) was dissolved in 2-butyn-l-ol (5ml) with stirring over 30minutes. The product from Example 2 (0.20g) was added and stirring was continued at ambient temperature for 3hours. The solvent was removed under reduced pressure and the residue was partitioned between ethyl acetate and water. The organic layers were dried (magnesium sulfate), filtered and evaporated under reduced pressure. The residue was purified by column chromatography (silica; hexane:ethyl acetate at 9:1 by volume) to give the required product as an orange gum (0.147g). Using similar procedures, the following compounds were prepared individually:
Compound No. 107 of Table No. 1 as a yellow gum; Compound No. 177 of Table No. 1 as a yellow gum; Compound No. 127 of Table No. 1 as a yellow gum; Compound No. 117 of Table No. 1 as a brown gum; Compound No. 137 of Table No. 1 as a yellow oil; Compound No. 147 of Table No. 1 as a yellow oil; and Compound No. 167 of Table No. 1 as a yellow oil.
EXAMPLE 5 This Example illustrates the preparation of Compound No. 257 of Table No. 1. The product from Example 2 (0.20g) was dissolved in ethanol (5ml) and allylamine (0.18ml) was added. The mixture was stirred at ambient temperature for 24hours. The solvent was removed under reduced pressure and the solid residue was triturated (hexane:ethyl acetate at 4: 1 by volume) and the triturating solvents were evaporated to give a yellow oil. This oil was purified by column chromatography to give the required product as an orange oil (0.12g). Using similar procedures, the following compounds were prepared individually:
Compound No. 197 of Table No. 1 as a yellow gum and Compound No. 207 of Table No. 1 as a yellow gum.
EXAMPLE 6 This Example illustrates the preparation of Compound No. 397 of Table No. 1.
The product from Example 2 (0.20g) was dissolved in acetic acid (5ml) and aniline (0.22ml) was added. The mixture was stirred at ambient temperature for 24hours. The solvent was removed under reduced pressure and the residue was purified by column chromatography (silica gel, eluting with ethyl acetate:hexane at 1:7 by volume) to give the required product as a brown solid (0.079g).
EXAMPLE 7 This Example illustrates the preparation of Compound No. 247 of Table No. 1.
The product from Example 2 (0.30g) was dissolved in methyl anthranilate (5 ml) and the mixture was allowed to stir at ambient temperature for 3 days and then at 40°C for one further day. The solvent was removed under reduced pressure and the residue was purified by column chromatography (silica gel, eluting with ethyl acetate: hexane at 1:9 by volume) to give the required product as a pink solid (0.138g).
EXAMPLE 8 This Example illustrates the preparation of Compound No. 217 of Table No. 1. The product from Example 1 (0.20g) was dissolved in tetrahydrofuran (5 ml) and 2-hydroxyethylhydrazine (0.067ml) and mercury (U) chloride (0.115g) were added. The mixture was stirred at 40°C for 4hours, then at ambient temperature overnight and then at 50°C for a further 4hours. The reaction mixture was filtered through a pad of Hi-Flo™ and the solvent was removed under reduced pressure. The residue was purified by column chromatography (silica gel, eluting with ethyl acetate followed by methanol) to give the required product as a brown gum (0.050g).
Using similar procedures, the following compounds were prepared individually: Compound No. 237 of Table No. 1 as a white solid; Compound No. 387 of Table No. 1 as a fawn solid; Compound No. 337 of Table No. 1 as a brown gum; Compound No. 347 of Table No. 1 as a brown oil; Compound No. 377 of Table No. 1 as a colourless oil; and Compound No. 357 of Table No. 1 as a white solid.
EXAMPLE 9 This Example illustrates the preparation of Compound No. 367 of Table No. 1. The product from Example 2 (0.20g) was dissolved in ethanol (5ml) and hydroxylamine hydrochloride (0.102g) and triethylamine (0.27ml) were added. The mixture was stirred at ambient temperature for 24hours. The solvent was removed under reduced pressure and the residue was triturated (hexane:ethyl acetate at 4: 1 by volume) to leave a solid. The solid was dissolved in ethyl acetate, filtered and washed with water. The organic layer was dried (magnesium sulfate), filtered and evaporated under reduced pressure to give the required product as a yellow solid (0.072g).
EXAMPLE 10 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 80, 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 80
Figure imgf000088_0001
EXAMPLE 11
This Example illustrates the fungicidal properties of compounds of formula (I). The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.
Plants were grown in John Innes Potting Compost (No.l or 2) in 4cm diameter, 3.5cm depth minipots. The test compounds were individually formulated as a solution either in acetone or acetone/ethanol (1: 1 by volume) which was diluted in deionised water to a concentration of lOOppm (that is, lmg of compound in a final volume of 10ml) immediately before use. When foliar sprays were applied to monocotyledonous crops, TWEEN 20 (0.1% by volume) was added. TWEEN is a registered trade mark. Individual compounds of formula (I) were applied as a foliar (Folr) application (where the chemical solution was applied to the foliage of the test plants by spraying the plant to maximum droplet retention.)
These tests were carried out against Uncinula necator (UNCTNE), on vines; Phytophthora infestans lycopersici (PHYTIN) on tomatoes; Puccinia recondita (PUCCRT), on wheat; and Pyricularia oryzae (PYRIOR) on rice. Each treatment was applied to two or more replicate plants for Phytophthora infestans lycopersici and Uncinula necator. For tests on Puccinia recondita and Pyricularia oryzae two replicate pots each containing 6 to 10 plants were used for each treatment. The plants were inoculated one day before (Erad) or one day after (Prot) chemical application. The Phytophthora infestans lycopersici, Puccinia recondita and Pyricularia oryzae plants were inoculated with a calibrated fungal spore suspension. The Uncinula necator plants were inoculated using a 'blowing' inoculation technique.
After chemical application and inoculation, the plants were incubated under high humidity conditions and then put into an appropriate environment to allow infection to proceed, until the disease was ready for assessment. The time period between chemical application and assessment varied from five to fourteen days according to the disease and environment. However, each individual disease was assessed after the same time period for all compounds. Assessments were performed on each of two leaves on each of the replicate plants for
Phytophthora infestans lycopersici. Assessments were performed on a single leaf of each of the replicate plants for Uncinula necator. For Puccinia recondita and Pyricularia recondita assessments were carried out collectively on the plants in each replicate pot.
The disease level present (that is, the percentage leaf area covered by actively sporulating disease) was assessed visually. For each treatment, the assessed values for all its replicates were meaned to provide mean disease values. Untreated control plants were assessed in the same manner. The data were then processed by the method, described hereinafter, to provide PRCO (Percentage Reduction from Control) values.
An example of a typical calculation is as follows:
Mean disease level for treatment A = 25% Mean disease level on untreated controls = 85% PRCO = 100 - { Mean disease level for treatment A } x 100 {Mean disease level on untreated controls}
= 100 - (25 x 100) = 70.6
85
The PRCO is then rounded to the nearest whole number; therefore, in this particular example, the PRCO result is 71. It is possible for negative PRCO values to be obtained.
TABLE 81
Figure imgf000090_0001
Key to Table 81;
PHYTIN = Phytophthora infestans lycopersici PUCCRT = Puccinia recondita PYRIOR = Pyricularia oryzae UNCINE = Uncinula necator

Claims

A compound of formula (I):
Figure imgf000091_0001
where A is optionally substituted d_6 alkylene, optionally substituted C2.6 alkenylene, optionally substituted C2.6 alkynylene, optionally substituted cycloalkylene, optionally substituted Ci-6 alkylenoxy, optionally substituted oxy(d-6)alkylene, optionally substituted d-6 alkylenethio, optionally substituted thio(Ci.6)alkylene, optionally substituted d.6 alkylenamino, optionally substituted amino(Cι-6)alkylene, optionally substituted [Ci_ alkyleneoxy(Ci-6)alkylene], optionally substituted [Cι_6 alkylenethio- (Ci_6)alkylene], optionally substituted [Ci_6 alkylenesulfinyl(Ci_6)-alkylene], optional-ly substituted [Ci_6 alkylenesulfonyl(Ci-6)alkylene] or optionally substituted [d-6 al-kyleneamino(d-6)alkylene]; B is N, N-oxide or CR7; M is OC(=Y), N=C(OR8), N=C(SR9), N=C(NR10Rπ) or N(R12)C(=NR13) where O or N is the atom of attachment to the isothiazole group; Y is O, S or NR14; Z is O, S or NR15;
R1 is hydrogen, halogen, optionally substituted d-6 alkyl, optionally substituted C2_6 alkenyl, optionally substituted C2_6 alkynyl, optionally substituted d_6 alkoxy, optionally substituted d-6 alkylthio, optionally substituted C3.7 cycloalkyl, cyano, nitro or SF5; R2 is hydrogen, halogen, optionally substituted d-6 alkyl, optionally substituted C2.6 alkenyl, optionally substituted C2.6 alkynyl, optionally substituted Cue alkoxy, optionally substituted C].6 alkylthio, optionally substituted Cι-6 alkylsulfinyl, optionally substituted Cι_6 alkylsulfonyl, cyano, nitro, formyl, optionally substituted d_6 alkylcarbonyl, optionally substituted d-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 Ci-6 alkyl, Ci-6 haloalkyl or halogen;
R3, R4 and R5 are, independently, hydrogen, halogen, optionally substituted d- alkyl, optionally substituted d- alkoxy, optionally substituted Ci-6 alkylthio, optionally substituted Cι_6 alkylsulfinyl, optionally substituted Ci- alkylsulfonyl, cyano, nitro, optionally substituted Cι.6 alkylcarbonyl, optionally substituted Ci-6 alkoxycarbonyl or SF5;
R6 is hydrogen, halogen, cyano, optionally substituted Cι.20 alkyl, optionally substituted C2-2o alkenyl, optionally substituted C2.20 alkynyl, optionally substituted C3.7 cycloalkyl, optionally substituted C5.6 cycloalkenyl, formyl, optionally substituted d_2o alkoxycarbonyl, optionally substituted Cι_2o alkylcarbonyl, aminocarbonyl, optionally substituted Cι_20 alkylaminocarbonyl, optionally substituted di(Cι_2o)alkylaminocarbonyl, optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-(Cι_6)alkyl- N-arylaminocarbonyl, optionally substituted diarylaminocarbonyl, optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted N-(d_ 6)alkyl-N-heteroarylaminocarbonyl, optionally substituted diheteroarylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, SH, optionally substituted d_2o alkylthio, optionally substituted d.20 alkylsulfinyl, optionally substituted Cι-2o alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl, R18O, RI9R20N or R21ON=C(R22); R7 is hydrogen, halogen, nitro, cyano, optionally substituted C1-8 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted C3.7 cycloalkyl, optionally substituted C].6 alkoxycarbonyl, optionally substituted Ci-6 alkylcarbonyl, optionally substituted d-6 alkylaminocarbonyl, optionally substituted di(d_
6)alkylaminocarbonyl, optionally substituted phenyl or optionally substituted heteroaryl;
R8 is optionally substituted Ci.10 alkyl, optionally substituted [C2-6 alkenyl- (Ci_6)alkyl], optionally substituted [C2.6 alkynyl(Ci-6)alkyl], optionally substituted C3.7 cycloalkyl, amino, optionally substituted d_6 alkylamino, optionally substituted di(Ci-6)alkyl-amino, optionally substituted Ci-io alkylcarbonyl, optionally substituted C o alkoxy-carbonyl, formyl, optionally substituted CMO alkylaminocarbonyl, optionally sub-stituted di- (Ci-io)alkylaminocarbonyl, amino, optionally substituted phenoxy-carbonyl, tri(d.4)alkylsilyl, aryldi(C1-4)alkylsilyl, (C1-4)alkyldiarylsilyl or triarylsilyl; R9 is optionally substituted C O alkyl, optionally substituted [C2_6 alkenyl- (Ci.6)alkyl], optionally substituted [C2_6 alkynyl(Ci-6)alkyl], optionally substituted C3. cycloalkyl, optionally substituted Ci-ι0 alkylcarbonyl, optionally substituted CMO alkoxycarbonyl, optionally substituted C O alkylaminocarbonyl, optionally substituted di(CMo)-alkylaminocarbonyl or optionally substituted phenoxycarbonyl);
R10 and R11 are, independently, optionally substituted CMO alkyl, optionally substituted d-6 alkoxy, optionally substituted [C2.6 alkenyl(d.6)alkyl], optionally substituted [C2.6 alkynyl(d_6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted CMO alkylcarbonyl, optionally substituted Ci-io alkoxycarbonyl, formyl, optionally substituted C O alkylaminocarbonyl, optionally substituted di(C1.1o)-alkylaminocarbonyl, hydroxy, amino, optionally substituted Cι.6 alkylamino, optionally substituted di- (Ci.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- (Ci.io)alkylaminocarbonyloxy, optionally substituted CMO alkylcarbonylamino, optionally substituted C O alkoxycarbonylamino, optionally substituted phenoxycarbonylamino, optionally substituted C O alkylaminocarbonyl-amino, optionally substituted di(d. ιo)alkylaminocarbonylamino or optionally substituted phenoxycarbonyl; R12 is hydrogen, optionally substituted CMO alkyl, optionally substituted d-6 alkoxy, optionally substituted [C2_6 alkenyl(d-6)alkyl], optionally substituted [C2-6 alkyny(Ci-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted d-io alkyl-carbonyl, optionally substituted C O alkoxycarbonyl, formyl, optionally substituted CMO alkylaminocarbonyl, optionally substituted di(Ci-io)alkylaminocarbonyl, hydroxy, amino, optionally substituted d_6 alkylamino, optionally substituted di(Ci-6)-alkylamino, optionally substituted phenoxycarbonyl, optionally substituted Ci-6 alkylthio, optionally substituted d-6 alkylsulfinyl, optionally substituted Ci-6 alkylsulfonyl, optionally substituted Cι_6 aryl, optionally substituted d-6 arylthio, optionally substituted Ci-6 arylsulfinyl, optionally substituted d-6 arylsulfonyl or R36R37NS; R36 and R37 are, independently, optionally substituted d-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 Ci-6 alkyl groups; R13 is hydrogen, hydroxy, cyano, nitro, optionally substituted CMO alkyl, optionally substituted C3-7 cycloalkyl, optionally substituted (C2_6)alkenyl-
(Ci_6)alkyl, optionally substituted (C2.6)alkynyl(d.6)alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted - Ci-6 alkylcarbonyl, optionally substituted d.6 alkoxycarbonyl, optionally substituted Ci-6 alkylamino, optionally substituted di(Ci-6)alkylamino, optionally substituted Ci-6 alkylcarbonylamino, optionally substituted d-6 alkoxycarbonylamino, optionally substituted d_6 alkoxy, optionally substituted Ci_6 alkylthio, optionally substituted d-6 alkylsulfinyl, optionally substituted Ci-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 CMO alkylaminocarbonyloxy, optionally substituted di(d. io)alkylaminocarbonyloxy, optionally substituted phenoxycarbonylamino, optionally substituted Ci-io alkyl-aminocarbonylamino, optionally substituted di(C1.io)alkylaminocarbonylamino or optionally substituted d_6 alkylcarbonyloxy;
R14 is hydrogen, cyano, nitro, optionally substituted d_6 alkyl, optionally substituted C3. cycloalkyl, optionally substituted (C2.6)alkenyl(Cι_6)alkyl, optionally substituted (C2.6)alkynyl(Ci.6)alkyl, optionally substituted phenyl, optionally substituted heter-oaryl, optionally substituted Ci-6 alkylcarbonyl, optionally substituted d-6 alkoxycarbonyl, optionally substituted Ci.6 alkylamino, optionally substituted di- (Cι-6)alkylamino, optionally substituted -6 alkylcarbonylamino, optionally substituted Ci.6 alkoxycarbonylamino, optionally substituted d. alkoxy, optionally substituted Ci-6 alkylthio, optionally substituted Cι_6 alkylsulfinyl, optionally substituted d-6 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or optionally substituted d-6 alkylcarbonyloxy;
R15 is hydrogen, cyano, optionally substituted d-8 alkyl, optionally substituted [C2_6 alkenyl(Cι_6)alkyl], optionally substituted [C2-6 alkynyl(Ci-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted [C3.7 cycloalkyl(d-6)alkyl], d-6 alkoxy(d.6)alkyl, optionally substituted Ci-6 alkoxycarbonyl, optionally substituted Ci-6 alkylcarbonyl, optionally substituted d-6 alkylaminocarbonyl, optionally substituted di(C]-6)alkylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl;
R16 and R21 are, independently, hydrogen, optionally substituted phenyl- (C1-2)alkyl or optionally substituted d_2o alkyl;
R17 and R22 are independently hydrogen, optionally substituted phenyl or optionally substituted Cι_6 alkyl;
R18 is hydrogen, optionally substituted d. o alkyl, optionally substituted [C2.2o alkenyl(Cι_6)alkyl], optionally substituted [C2.2o alkynyl(Cι_6) alkyl], optionally substituted C3. cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted heterocyclyl, (d-6)alkylCH=N, optionally substituted arylCH=N, optionally substituted [aryl(Ci-6)alkyl]CH=N, optionally substituted heteroarylCH=N, optionally substituted [heterocyclyl(Ci_6)alkyl]CH=N, optionally substituted arylC(CH3)=N, optionally substituted heteroarylC(CH3)=N or optionally substituted di-
(C1.6)alkylC=N; and
R19 and R20 are, independently, hydrogen, optionally substituted d_2o alkyl, optionally substituted C3.7 cycloalkyl, optionally substituted [C2.2o alkenyl-
(Ci-6)alkyl], optionally substituted [C2-2o alkynyl(Ci-6)alkyl], optionally substituted Ci_2o alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted d-2o alkylcarbonyl, optionally substituted C1-2o alkylsulfonyl or optionally substituted phenylsulfonyl.
A compound according to claim 1 which is a compound of formula IA
Figure imgf000096_0001
wherein A, B, M, Z, R1, R2, R3, R4, R5 and R6 are as defined in claim 1 for a compound of formula (I).
3. A compound according to claim 1 or claim 2 wherein A is Ci.6 alkylene, d-6 alkenylene, d_6 alkylenoxy, oxy(d-6)alkylene or Ci.6 alkylenamino, each of which is optionally substituted by Cι_3 alkyl, d-3 haloalkyl, Cι-3 cyanoalkyl, halogen, C1-3 alkoxy, Ci-6 alkoxycarbonyl, cyano, =O, =NR23 or =CR2 R25; where R23 is d-6 alkyl, OR26 or NR27R28; R26 is Ci-6 alkyl or phenyl(d.2)alkyl (where the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Cι_6 haloalkyl, d-6 alkoxy or Cι_6 haloalkoxy); R27 and R28 are, independently, hydrogen, C].8 alkyl or phenyl (which may be optionally substituted by halo, nitro, cyano, d-6 alkyl, d- haloalkyl, d-6 alkoxy or Ci-6 haloalkoxy); R24 is hydrogen, d-6 alkyl or Ci_6 haloalkyl; R25 is hydrogen, d. 6 alkyl, d-6 haloalkyl, d_6 alkoxy, cyano, d_6 alkoxycarbonyl, Ci.6 alkylcarbonyl or NR29R30; and R29 and R30 are, independently, hydrogen, C1-8 alkyl, C3.7 cycloalkyl, C3_6 alkenyl, C3.6 alkynyl, C2_6 haloalkyl, Ci-6 alkoxy-
(Ci_6)alkyl, Ci_6 alkoxycarbonyl(d.6)alkyl, carboxy(d.6)alkyl or phenyl- (Cι.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 may be optionally substituted by one or two d-6 alkyl groups.
A compound according to any precedding claim wherein M is N=C(OR ), N=C(SR9) or N(R12)C(=NR13) where R8, R9, R12 and R13 are as defined in claim 1.
5. A compound according to any precedding claim wherein R1 is hydrogen, halogen, Ci-6 alkyl, d-6 cyanoalkyl, d-6 haloalkyl, C3.7 cycloalkyl(C1_4)alkyl, Ci-6 alkoxy-(Ci.6)alkyl, C2.6 alkenyl, C2-6 alkynyl, d-6 alkoxy, d-6 haloalkoxy, d_6 alkylthio, d-6 haloalkylthio, C3_6 cycloalkyl, cyano, nitro or SF5.
6. A compound according to any precedding claim wherein R2 is hydrogen, halogen, d_6 alkyl, d_6 haloalkyl, d-6 alkoxy(Ci.6)alkyl, C2.6 alkenyl, d.6 alkynyl, Cι_6 alkoxy, d-6 haloalkoxy, d_6 alkylthio, Ci.6 haloalkylthio, d.6 alkylsulfinyl, d_6 haloalkylsulfinyl, Ci-6 alkylsulfonyl, Ci-6 haloalkylsulfonyl, cyano, nitro, formyl, Ci-6 alkylcarbonyl, d-6 alkoxycarbonyl, SF5 or CH=NOR16; 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 d-6 alkyl, C1-6 haloalkyl or halogen; where R16 is phenyl(d-2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci.6 alkyl, Ci-6 haloalkyl, C1-6 alkoxy or Ci-6 haloalkoxy) or d-6 alkyl.
7. A compound according to any precedding claim wherein R3, R4 and R5 are, independently, hydrogen, halogen, Ci-6 alkyl, Cι_6 haloalkyl, d-6 alkoxy, d-6 haloalkoxy, d-6 alkylthio, d.6 haloalkylthio, d_6 alkylsulfinyl, d_6 haloalkylsulfinyl, d_6 alkylsulfonyl, Ci-6 haloalkylsulfonyl, cyano, nitro, d_6 alkylcarbonyl or Ci.6 alkoxycarbonyl.
8. A compound according to any precedding claim wherein R6 is cyano, d_8 alkyl, d.8 haloalkyl, d.8 cyanoalkyl, C3.7 cycloalkyl(d_6)alkyl, C5-6 cycloalkenyl(Ci_6)alkyl, d-6 alkoxy(Ci-6)alkyl, C3.6 alkenyloxy(d.6)alkyl, C3-6 alkynyloxy(Cι.6)alkyl, aryloxy(Ci-6)alkyl, Cι.6 carboxyalkyl, d-6 alkylcarbonyl(Ci_6)alkyl, C2.6 alkenylcarbonyl(Cι_6)alkyl, C2_6 alkynylcarbonyl(Ci.6)alkyl, d-6 alkoxycarbonyl (d-6)alkyl, C3.6 alkenyloxycarbonyl(Ci-6)alkyl, C3.6 alkynyloxycarbonyl(C1.6)alkyl, aryloxycarbonyl(Ci_6)alkyl, d_6 alkylthio(Ci-6)alkyl, d-6 alkylsurfinyl(Cι. 6)alkyl, Ci-6 alkylsulfonyl(C1-6)alkyl, aminocarbonyl(Ci-6)alkyl, d_6 alkylaminocarbonyl(Ci-6) alkyl, di(Cι.6)alkylaminocarbonyl(Ci-6)alkyl, phenyl(C1- )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d-6 haloalkyl, d-6 alkoxy or Cι_6 haloalkoxy), heteroaryl(C1- )alkyl (where the heteroaryl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, d-6 haloalkyl, C1-6 alkoxy or Ci- haloalkoxy), heterocyclyl(C1- )alkyl (where the heterocyclyl group is optionally substituted by halo, cyano, Ci-6 alkyl, C1-6 haloalkyl, Cι_6 alkoxy or Ci-6 haloalkoxy), C2-6 alkenyl, C2-6 haloalkenyl, d_6 cyanoalkenyl, C5-6 cycloalkenyl, aminocarbonyl(C2_6)alkenyl, d-6 alkylaminocarbonyl(d.6)alkenyl, di(d. 6)alkyl-aminocarbonyl(Ci-6)alkenyl, phenyl(C2.4)alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Cι_6 alkyl, d-6 haloalkyl, Ci- alkoxy or d-6 haloalkoxy), C2.6 alkynyl, aminocarbonyl(C2.6)alkynyl, alkylaminocarbonyl(d-6)-alkynyl, di(Cι-6)alkylaminocarbonyl(Ci-6)alkynyl, C3_7 cycloalkyl, C3_7 halocycloalkyl, C3.7 cyanocycloalkyl, C1-3 alkyl(C3_ )cycloalkyl, Ci_3 alkyl(C3_ )halocycloalkyl, C5-6 cycloalkenyl, formyl, Ci-6 alkoxycarbonyl, Cι_6 alkylcarbonyl, aminocarbonyl, d-6 alkylaminocarbonyl, di(Ci.6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, d_6 alkyl, d-6 haloalkyl, d_6 alkoxy or Cι_6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, d-6 alkyl, Ci-6 haloalkyl, d_6 alkoxy or d-6 haloalkoxy), heterocyclyl (optionally substituted by halo, nitro, cyano, d-6 alkyl, d_6 haloalkyl, d-6 alkoxy or d_6 haloalkoxy), Cι_8 alkylthio, R18O, R,9R20N or R21ON=C(R22); where R18 is hydrogen, d.8 alkyl, Ci_6 haloalkyl, Ci-6 cyanoalkyl, Ci.6 alkoxy(Ci_6)alkyl, phenyl(d^)alkyl, (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d-6 haloalkyl, d. alkoxy or d-6 haloalkoxy), heteroaryl(C1.4)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Cι_6 haloalkyl, d-6 alkoxy or d-6 haloalkoxy), heterocyclyl(d. 4 4)alkyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, ccyyaannoo, Ci- alkyl, d-6 haloalkyl, d^ alkoxy or d-6 haloalkoxy), d-6 alkoxycarbonyl(Ci.6)alkyl, C2.6 alkenyl, C2.6 alkynyl or N=C(CH3)2; R22 is phenyl (optionally substituted by halo, nitro, cyano, d-6 alkyl, d_6 haloalkyl, Ci-6 alkoxy or Cι_6 haloalkoxy), Ci-6 alkyl or d-6 haloalkyl; R19 and R20 are, independently, hydrogen, d_8 alkyl, C3-7cycloalkyl(C1- )alkyl, C2_6 haloalkyl, Ci-6 alkoxy(Ci_6)alkyl, C3.7 cycloalkyl, C3-6 alkenyl, C3_6 alkynyl or d-6
91 alkoxycarbonyl; and R is phenyl(Cι-2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d.6 haloalkyl, d.6 alkoxy or d-6 haloalkoxy) or d-6 alkyl.
9. 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.
10. 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.
11. A method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying to a pest, to a locus of a pest, or to a plant susceptible to attack by a pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I) as claimed in claim 1.
PCT/GB2001/000325 2000-01-28 2001-01-26 Isothiazole derivatives and their use as pesticides WO2001055142A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6703347B2 (en) * 2000-01-28 2004-03-09 Syngenta Limited Isothiazole derivatives and their use as pesticides
WO2009007098A1 (en) * 2007-07-11 2009-01-15 Syngenta Participations Ag Isothiazole and pyrazole derivatives as fungicides

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995031448A1 (en) * 1994-05-17 1995-11-23 Dowelanco N-(5-isothiazolyl)amide pesticides
WO1998002424A1 (en) * 1996-07-16 1998-01-22 Bayer Aktiengesellschaft Substituted n-(5-isothiazolyl) thioamides
WO1998018198A1 (en) * 1996-10-18 1998-04-30 A. Ahlstrom Corporation Active rectifier circuit

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995031448A1 (en) * 1994-05-17 1995-11-23 Dowelanco N-(5-isothiazolyl)amide pesticides
WO1998002424A1 (en) * 1996-07-16 1998-01-22 Bayer Aktiengesellschaft Substituted n-(5-isothiazolyl) thioamides
WO1998018198A1 (en) * 1996-10-18 1998-04-30 A. Ahlstrom Corporation Active rectifier circuit

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6703347B2 (en) * 2000-01-28 2004-03-09 Syngenta Limited Isothiazole derivatives and their use as pesticides
EP1686128A3 (en) * 2000-01-28 2007-01-24 Syngenta Limited Isothiazole derivatives and their use as pesticides
WO2009007098A1 (en) * 2007-07-11 2009-01-15 Syngenta Participations Ag Isothiazole and pyrazole derivatives as fungicides
US8377953B2 (en) 2007-07-11 2013-02-19 Syngenta Crop Protection Llc Isothiazole and pyrazole derivatives as fungicides

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