WO2001090105A1 - Isothiazoles as pesticides - Google Patents

Isothiazoles as pesticides Download PDF

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Publication number
WO2001090105A1
WO2001090105A1 PCT/GB2001/002312 GB0102312W WO0190105A1 WO 2001090105 A1 WO2001090105 A1 WO 2001090105A1 GB 0102312 W GB0102312 W GB 0102312W WO 0190105 A1 WO0190105 A1 WO 0190105A1
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WO
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Prior art keywords
alkyl
optionally substituted
formula
compound
alkoxy
Prior art date
Application number
PCT/GB2001/002312
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 Chritopher 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
Application filed by Syngenta Limited, PILKINGTON, Joan filed Critical Syngenta Limited
Priority to AU58618/01A priority Critical patent/AU5861801A/en
Publication of WO2001090105A1 publication Critical patent/WO2001090105A1/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):
  • q is 0 or 1 ;
  • B is CR 3 and Z is O, S or NR° or B is N and Z is NR >7'.;
  • Y is O, S or NR 8 ;
  • R 1 is hydrogen, halogen, optionally substituted d-6 alkyl, optionally substituted C 2 - 6 alkenyl, optionally substituted C 2 - 6 alkynyl, optionally substituted C ⁇ - 6 alkoxy, optionally substituted d- 6 alkylthio, optionally substituted C 3 .
  • R 5 is hydrogen, halogen, nitro, cyano, optionally substituted d- 8 alkyl, optionally substituted C 2 - 6 alkenyl, optionally substituted C 2 - 6 alkynyl, optionally substituted C 3 - 7 cycloalkyl, optionally substituted Ci-6 alkoxycarbonyl, optionally substituted Ci- 6 alkylcarbonyl, optionally substituted Ci-6 alkylaminocarbonyl, optionally substituted di(Ci- 6 )alkylamino
  • R 7 is substituted Ci-s alkyl, optionally substituted [C 2 - 6 alkenyl(Ci- 6 )alkyl], optionally substituted [C 2 - 6 alkynyl(Ci- 6 )alkyl], substituted C 3 - 7 cycloalkyl, substituted [C 3 - 7 cycloalkyl(Ci- 6 )alkyl], substituted d- 6 alkoxycarbonyl, substituted d- 6 alkylcarbonyl, substituted Ci- 6 alkylaminocarbonyl, optionally substituted di(Ci- 6 )alkylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl;
  • R 7 is substituted Ci-s alkyl, optionally substituted [C 2 - 6 alkenyl(Ci- 6 )alkyl], optionally substituted [C
  • R 16 is Ci- 6 alkyl
  • R 17 is d-6 alkyl or optionally substituted phenyl(C ⁇ - 2 )- alkyl
  • R 18 is Ci- 6 alkyl
  • R 19 and R 20 are, independently, hydrogen, optionally substituted d- 6 alkyl or optionally substituted phenyl
  • p and r are, independently, 0, 1 or 2.
  • the compounds of formula (I) may exist in different geometric or optical isomers or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
  • Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, w ⁇ -propyl, n-butyl, sec-butyl, is ⁇ -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 Ci- 6 alkyl or halogen), C5-- 7 cycloalkenyl (itself optionally substituted with d- 6 alkyl or halogen), hydroxy, d- 10 alkoxy, d-10 alkoxy(Ci- 10 )alkoxy, tri(Ci- )alkylsilyl(d-6)alkoxy, d- 6 alkoxycarbonyl (Ci-io)alkoxy, d-io haloalkoxy, aryl(d- 4 )alkoxy (where the aryl group is optionally substituted), C 3 - cycloalkyloxy (where the cycloalkyl group is optionally substituted with Ci- 6 alkyl or halogen), d-i 0 alkenyloxy,
  • Alkenyl and alkynyl moieties can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)- or ⁇ -configuration. Examples are vinyl, allyl and propargyl.
  • the optional substituents on alkenyl or alkynyl include those optional substituents given above for an alkyl moiety.
  • acyl is optionally substituted d-6 alkylcarbonyl (for example acetyl), optionally substituted C 2 -6 alkenylcarbonyl, optionally substituted C 2 - 6 alkynylcarbonyl, optionally substituted arylcarbonyl (for example benzoyl) or optionally substituted heteroarylcarbonyl.
  • d-6 alkylcarbonyl for example acetyl
  • C 2 -6 alkenylcarbonyl optionally substituted C 2 - 6 alkynylcarbonyl
  • arylcarbonyl for example benzoyl
  • heteroarylcarbonyl for example benzoyl
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF 3 , CF 2 C1, CF 3 CH 2 or CHF 2 CH 2 .
  • Aryl includes naphthyl, anthracyl, fluorenyl and indenyl but is preferably phenyl.
  • heteroaryl refers to an aromatic ring containing up to 10 atoms including one or more heteroatoms (preferably one or two heteroatoms) selected from O, S and N. 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 d-e 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 Cj- 3 alkyl as well as those optional substituents given above for an alkyl moiety.
  • Carbocyclic rings include aryl, cycloalkyl and cycloalkenyl groups.
  • the optional substituents on aryl or heteroaryl are selected, independently, from halogen, nitro, cyano, NCS-, d- 6 alkyl, d- 6 haloalkyl, d- 6 alkoxy(Ci- 6 )alkyl, C 2 - 6 alkenyl, C 2 -6 haloalkenyl, C 2 - 6 alkynyl, C 3 - 7 cycloalkyl (itself optionally substituted with Ci-6 alkyl or halogen), C 5 - 7 cycloalkenyl (itself optionally substituted with d- 6 alkyl or halogen), hydroxy, d- 10 alkoxy, Ci-io alkoxy(C ⁇ - 10 )alkoxy, tri(Ci- 4 )alkylsilyl(d- 6 )alkoxy, Ci-6 alkoxycarbonyl(Ci- 10 )alkoxy, d-io haloalkoxy, aryl
  • substituents are independently selected from halogen, d-6 alkyl, d-6 haloalkyl, Ci- 6 alkoxy(Ci- 6 )alkyl, Ci-6 alkoxy, C ⁇ - 6 haloalkoxy, d- 6 alkylthio, d-e haloalkylthio, d- 6 alkylsulfinyl, d- 6 haloalkylsulfinyl, d- 6 alkylsulfonyl, d- 6 haloalkylsulfonyl, C 2 - 6 alkenyl, C 2 - 6 haloalkenyl, C 2 -6 alkynyl, C 3 - 7 cycloalkyl, nitro, cyano, CO 2 H, d- 6 alkylcarbonyl, d- 6 alkoxycarbonyl, R 21 R 22
  • 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 (d- 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 (d- 6 ) alkyl groups.
  • the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, HO C, d-io alkoxy (itself optionally substituted by Ci-io alkoxy), aryl(C ⁇ - ) alkoxy, aryl(Ci- )alkylthio, d-io alkylthio, d- 10 alkylcarbonyl, Ci- 10 alkoxycarbonyl, Ci-6 alkylaminocarbonyl, di(Ci- 6 alkylaminocarbonyl, (Ci- 6 )alkylcarbonyloxy, optionally substituted phenyl, aryl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl, heterocyclyloxy, C 3 - 7 cycloalkyl (itself optionally substituted with (d-6)alkyl or halogen), C 3 - 7 cycloalkyl(itself optionally substituted with (
  • the optional substituents on alkenyl or alkynyl include one or more of halogen, aryl, d- 6 alkyl, C 3 - 7 cycloalkyl, C 5 - 7 cycloalkenyl (itself optionally substituted by d- 6 alkyl) and Ci- 6 alkoxycarbonyl.
  • heterocyclyl is optionally substituted by C ⁇ - 6 alkyl.
  • the optional substituents for cycloalkyl include halogen, cyano, d- 3 alkyl, d- 3 alkyl(C 2 - 4 )alkenyl and phenyl (itself optionally substituted by halogen).
  • the optional substituents for cycloalkenyl include d- 3 alkyl, halogen and cyano.
  • the present invention provides a compound of formula (IA):
  • More preferred compounds of formula (I) are compounds of formula (IA) or (IB) wherein q is 0; B is CR 5 ; Y is O, S or NR 8 ; Z is O, S or NR 6 ; R 1 is hydrogen, halogen, d- 6 alkyl, C 2 - 6 alkenyl, C 2 - 6 alkynyl, d- 6 cyanoalkyl, d-6 haloalkyl, d- 6 alkoxy, d- 6 haloalkoxy, Ci- 6 alkylthio, d- 6 haloalkylthio, C 3 - 6 cycloalkyl, C 3 - 7 cycloalkyl(Ci- 4 )alkyl, C ⁇ - 6 alkoxy(Ci- 6 )alkyl, cyano, nitro or
  • R 8 is cyano, nitro, d- 6 alkyl, d- 6 haloalkyl, C 3 - 7 cycloalkyl, C 3 - 7 cycloalkyl(Ci- 6 )alkyl, CH
  • R 16 is d- 6 alkyl
  • R 17 is Ci- 6 alkyl or optionally substituted phenyl(d- 2 )- alkyl
  • R 18 is d- 6 alkyl
  • R 19 and R 20 are, independently, hydrogen, optionally substituted - 6 alkyl or optionally substituted phenyl
  • p is 0, 1 or 2.
  • a further group of preferred compounds of formula (I) is provided by compounds of formula (IC) wherein q is 0; B is CR 5 ; Y is O, S or NR 8 ; Z is O, S or NR 6 ; R 1 is hydrogen, halogen, d- 6 alkyl, C 2 - 6 alkenyl, C 2 - 6 alkynyl, d- 6 cyanoalkyl, d- 6 haloalkyl, d- 6 alkoxy, Ci- 6 haloalkoxy, C ⁇ - 6 alkylthio, C ⁇ - 6 haloalkylthio, C 3 - 6 cycloalkyl, C 3 - 7 cycloalkyl(C !
  • R 1 and R 2 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated ring carbocylic or heterocyclic ring which may contain one or two hetero atoms selected from O, N or S and which may be optionally substituted by C ⁇ - 6 alkyl, Ci-6 haloalkyl or halogen;
  • R 3 is hydrogen, d- 6 alkyl, Ci- 6 alkoxy(Ci- 6 )alkyl, C 3 - 6 alkenyl, C 3 - 6 alkynyl, d- 6 alkylcarbonyl or Ci- 6 alkoxycarbonyl;
  • R 4 is hydrogen or methyl;
  • R 5 is hydrogen, halogen, nitro, cyano, d- 8 alkyl, Ci- 6 haloalkyl, d- 6 cyanoalkyl, C 2 - 6 alkenyl, C 2 - 6 alkyny
  • R 8 is cyano, nitro, d- 6 alkyl, d- 6 haloalkyl, C 3 - 7 cycloalkyl, C 3 . 7 cycloalkyl(Ci.
  • R 10 is d- 6 alkyl or phenyl(Ci- 2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci- 6 alkyl, d- 6 haloalkyl, d- 6 alkoxy or Ci- 6 haloalkoxy
  • 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 R 1 is hydrogen, halogen, d- 6 alkyl, Ci- 6 cyanoalkyl, d- 6 haloalkyl,
  • R 1 is more preferably hydrogen, halogen, d- 6 alkyl, C 2 - 6 alkenyl, d- 6 haloalkyl, Ci- 6 alkoxy, d-6 haloalkoxy, d- 6 alkylthio, d-e haloalkylthio, C 3 - 6 cycloalkyl, cyano, nitro or SF 5 .
  • R 1 is hydrogen, halogen, d- 6 alkyl, d- 6 haloalkyl, Ci- 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 most preferably halogen, Ci-6 alkyl, Ci-6 haloalkyl, Ci. 6 alkoxy or d_ 6 haloalkoxy. It is preferred that R 2 is hydrogen, halogen, d- 6 alkyl, Ci- 6 haloalkyl, d- 6 alkoxy(C 1 -6)alkyl, C 2 - 6 alkenyl, d- 6 alkynyl, Ci- 6 alkoxy, d- 6 haloalkoxy, d- 6 alkylthio, Ci- 6 haloalkylthio, Ci-6 alkylsulfinyl, d- 6 haloalkylsulfinyl, d- 6 alkylsulfonyl, d.
  • 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 d- 6 alkyl, d-6 haloalkyl or halogen; where R 10 is phenyl(d.
  • R 2 is hydrogen, halogen, d_6 alkyl, d-6 haloalkyl, Ci. 6 alkoxy (d. 6 )alkyl, d_ 6 alkoxy, d- 6 haloalkoxy, Ci-6 alkylthio or SF5; 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, Ci-6 haloalkyl or halogen.
  • R 2 is even more preferably hydrogen, halogen, d-6 alkyl, d- 6 haloalkyl, d- 6 alkoxy, Ci- 6 haloalkoxy, C ⁇ _ 6 alkoxy(C 1 -6)alkyl, d- 6 alkylthio or SF 5 ; or R 1 and R 2 together with the atoms to which they are attached form a benzene ring optionally substituted by Ci- 6 alkyl, d- 6 haloalkyl or halogen; or alternatively the ring may be a cyclopentane ring.
  • R 2 is hydrogen, halogen, d-6 alkyl, d- 6 haloalkyl, C ⁇ - 6 alkoxy(Ci- 6 )alkyl, Ci-6 alkoxy, Ci-6 haloalkoxy, or R 1 and R 2 together with the atoms to which they are attached form a cyclopentane ring optionally substituted by d- 6 alkyl, d- 6 haloalkyl or halogen.
  • R 2 is most preferably halogen, Ci-6 alkyl, d- 6 haloalkyl, d- 6 alkoxy, d- 6 alkoxy(Ci- 6 )alkyl or Ci-6 haloalkoxy.
  • R 3 is preferably hydrogen, d-6 alkyl, Ci-6alkoxy(Ci-6)alkyl, C 3 -6 alkenyl (especially allyl), C 3 -6 alkynyl (especially propargyl), d. 6 alkylcarbonyl or Ci-6 alkoxycarbonyl (especially s butoxycarbonyl).
  • R 3 is more preferably hydrogen, d-e alkyl or Ci- 6 alkoxy(C ⁇ . 6 )alkyl.
  • R 4 is preferably d- 8 alkyl, C ⁇ - 6 haloalkyl, d- 6 cyanoalkyl, C 2 - 6 alkenyl, C 2 - 6 alkynyl, C 3 - 7 cycloalkyl, C 3 - 7 halocycloalkyl, C 3 - 7 cyanocycloalkyl, Ci- 3 alkyl(C 3 - 7 )cycloalkyl, C ⁇ - 3 alkyl(C 3 - 7 )halocycloalkyl, C 3 - 6 cycloalkyl(Ci- 6 )alkyl, C 5 - 6 cycloalkenyl, C 5 - 6 cycloalkenyl(Ci- 6 )alkyl, C 2 .
  • R 4 is more preferably d- 8 alkyl, d- 6 haloalkyl, Ci- 6 cyanoalkyl, C 2 - 6 alkenyl, C 2 - 6 alkynyl, C 3 - 7 cycloalkyl, C 3 - 7 halocycloalkyl, C 3 - 7 cyanocycloalkyl, C ⁇ - 3 alkyl(C 3 - 7 )cycloalkyl, Ci- 3 alkyl(C 3 - 7 )halocycloalkyl, C 3 . 6 cycloalkyl(Ci-6)alkyl, C 5 - 6 cycloalkenyl, C 5 .
  • R 5 is preferably hydrogen, halogen, nitro, cyano, d- 8 alkyl, d- 6 haloalkyl, d- 6 cyanoalkyl, C 3 - 7 cycloalkyl(Ci- 6 )alkyl, d- 6 alkoxy(Ci- 6 )alkyl, Ci- 6 alkoxycarbonyl (Ci- 6 )alkyl, Ci- 6 alkylcarbonyl(Ci- 6 )alkyl, Ci- 6 alkylaminocarbonyl(Ci- 6 )alkyl, di(d-e)alkylamino- carbonyl(C ⁇ - 6 )alkyl, phenyl(d-6)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C ⁇ - 6 alkyl, Ci- 6 haloalkyl, d- 6 alkoxy or d-6 haloalkoxy), heteroaryl(C
  • R 5 is more preferably hydrogen, halogen, nitro, cyano, d- 8 alkyl or d- 6 haloalkyl.
  • R 5 is even more preferably hydrogen, halogen, cyano, d- alkyl or d- 3 haloalkyl.
  • R 5 is most preferably hydrogen, halogen, d- 3 alkyl or d- 3 haloalkyl.
  • R 6 is hydrogen, d- 8 alkyl, d- 6 haloalkyl, d- 6 cyanoalkyl, CH 2 (C 2 - 6 )alkenyl, CH 2 (C 2 . 6 )haloalkenyl, CH 2 (C 2 . 6 )alkynyl, C 3 - 7 cycloalkyl, C 3 - 7 cycloalkyl(C ⁇ - 6 )alkyl, Ci. 6 alkoxy(Ci-6)alkyl, C ⁇ _ alkoxycarbonyl, C ⁇ .
  • R 6 is hydrogen, C ⁇ - 8 alkyl or C ⁇ - 6 haloalkyl.
  • R 7 is preferably substituted d- 8 alkyl, optionally substituted [C 2 . 6 alkenyl(Ci- 6 )alkyl], optionally substituted [C 2 - 6 alkynyl(d- 6 )alkyl], substituted C 3 - 7 cycloalkyl, substituted [C 3 - 7 cycloalkyl(C ⁇ - 6 )alkyl], substituted Ci- 6 alkoxycarbonyl, substituted Ci- 6 alkylcarbonyl, substituted d.
  • R 7 is not Ci-e haloalkyl, d-6 cyanoalkyl, C 2 - 6 alkenyl, C 2 -6 alkynyl or C 2 - 6 haloalkenyl.
  • R 8 is cyano, nitro, Ci-6 alkyl, d-6 haloalkyl, C 3 - 7 cycloalkyl(Ci. 6 )alkyl, C 3 . 7 cycloalkyl, CH 2 (C 2 - 6 )alkenyl, CH 2 (C 2 - 6 )alkynyl, phenyl (optionally substituted by halo, nitro, cyano, d-6 alkyl, Ci-6 haloalkyl, Ci- 6 alkoxy or Ci- 6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Ci- 6 alkyl, Ci- 6 haloalkyl, d- 6 alkoxy or Ci-6 haloalkoxy), Ci-6 alkylcarbonyl, d-6 alkoxycarbonyl, d-6 alkylamino, di(Ci-6)alkylamino, d-6 alkylcarbonylamino,
  • Table 1 provides 72 compounds of formula (IA) wherein q is 0; Y is O; Z is O; R 4 is hydrogen; and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 2 provides 72 compounds of formula (IA) wherein q is 0; Y is O; Z is O; R 4 is methyl; and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 3 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R 4 is ethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 4 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R 4 is n-propyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 5 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R 4 is wopropyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 6 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R 4 is n-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 7 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R 4 is sec-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 8 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R 4 is w ⁇ butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 9 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R 4 is tert-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 10 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R 4 is neopentyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 11 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R 4 is 2,2,2-trifluoroethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 12 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R 4 is pentafluoroethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 13 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R 4 is heptafluoropropyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 14 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R 4 is methyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 15 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R 4 is ethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 16 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R 4 is ra-propyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 17 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R 4 is wopropyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 18 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R 4 is n-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 19 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R 4 is sec-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 20 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R 4 is z obutyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 21 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R 4 is tert-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 22 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R 4 is neopentyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 23 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R 4 is 2,2,2-trifluoroethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 24 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R 4 is pentafluoroethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 25 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R 4 is heptafluoropropyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 26 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R 4 is
  • Table 27 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is methyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 28 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is ethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 29 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is n-propyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 30 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is zsopropyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 31 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH 3 ,
  • R 4 is n-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 32 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is sec-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 33 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is .sobutyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 34 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is tert-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 35 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is neopentyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 36 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is 2,2,2-trifiuoroethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 37 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH 3 ,
  • R 4 is pentafluoroethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 38 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is heptafluoropropyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 39 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R 4 is methyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 40 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R 4 is ethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 41 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R 4 is n-propyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 42 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R 4 is zsopropyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 43 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R 4 is n-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 44 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R 4 is sec-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 45 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R 4 is zsobutyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 46 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R 4 is tert-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 47 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R 4 is rae ⁇ pentyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 48 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R 4 is 2,2,2-trifluoroethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 49 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R 4 is pentafluoroethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 50 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R 4 is heptafluoropropyl and R 1 , R 2 , R 3 and B are as defined in Table 1
  • Table 51 provides 72 compounds of formula (IB) wherein q is 0; Y is O; Z is O; R 4 is methyl; and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 52 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R 4 is ethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 53 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R 4 is n-propyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 54 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R 4 is z's ⁇ propyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 55 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R 4 is n-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 56 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R 4 is sec-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 57 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R 4 is z's ⁇ butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 58 provides 72 compounds of formula (IB) wherem q is 0, Y is O, Z is O, R 4 is tert-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 59 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R 4 is ncopentyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 60 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R 4 is 2,2,2-trifluoroethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 61 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R 4 is pentafluoroethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 62 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R 4 is heptafluoropropyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 63 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R 4 is methyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 64 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R 4 is ethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 65 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R 4 is n-propyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 66 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R 4 is zs ⁇ propyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 67 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R 4 is zz-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 68 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R 4 is sec-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 69 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R 4 is zs ⁇ butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 70 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R 4 is tert-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 71 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R 4 is ne ⁇ pentyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 72 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R 4 is 2,2,2-trifluoroethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 73 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R 4 is pentafluoroethyl and R , R , R and B are as defined in Table 1.
  • Table 74 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R 4 is heptafluoropropyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 75 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R 4 is 2-methylpropen-l-yl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 76 provides 72 compounds of formula (IB) wherem q is 0, Y is O, Z is N-CH 3 , R 4 is methyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 77 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is ethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 78 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is n-propyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 79 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH 3 ,
  • R 4 is z ' s ⁇ propyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 80 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is R-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 81 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is sec-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 82 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is z ' s ⁇ butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 83 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is tert-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 84 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is rce ⁇ pentyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 85 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH 3 ,
  • R 4 is 2,2,2-trifluoroethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 86 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is pentafluoroethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 87 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH 3 , R 4 is heptafluoropropyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 88 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R 4 is methyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 89 provides 72 compounds of formula (IB) wherem q is 0, Y is O, Z is NH, R 4 is ethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 90 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R 4 is n-propyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 91 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R 4 is z ' s ⁇ propyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 92 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R 4 is n-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 93 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R 4 is sec-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 94 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R 4 is z's ⁇ butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 95 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R 4 is tert-butyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 96 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R 4 is Re ⁇ pentyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 97 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R 4 is 2,2,2-trifluoroethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 98 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R 4 is pentafluoroethyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 99 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R 4 is heptafluoropropyl and R 1 , R 2 , R 3 and B are as defined in Table 1.
  • Table 100 provides 48 compounds of formula (IC) wherein q is 0, Y is O, Z is N-R 7 , B is CH, R 4 is H and R 1 , R 2 , R 3 and R 7 are as defined in Table 100.
  • Table 101 provides 48 compounds of formula (IC) wherein q is 0, Y is O, Z is N-R 7 B 4 is CH 3 and R 1 , R 2 , R 3 and R 7 are as defined in Table 100.
  • m.p. melting point
  • ppm parts per million
  • d doublet
  • dd doublet of doublets
  • t triplet
  • q quartet
  • m multiplet
  • Table 102 shows selected melting point and selected NMR data, all with CDC1 3 as the solvent (unless otherwise stated; if a mixture of solvents is present, this is indicated as, for example, (CDC1 3 / de-DMSO)), (no attempt is made to list all characterising data in all cases) for compounds of Tables 1-101.
  • a compound of formula (I) (wherein Y is oxygen) may be prepared by coupling an aminoisothiazole with a suitably substituted benzofuran, benzothiophene, indole or benzimidazole.
  • Suitable aminoisothiazoles are known compounds, or may be prepared from commercially available starting materials by methods described in the literature (for example, see the following documents and references therein: 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)]; Ronald E. hackler, Kenneth W. Burrow Jr., Sylvester V. Raster and David I. Wickiser [J. Heterocyclic Chem., 26, 1575, (1989)] and Ronald Ehackler, Glen P Jourdan, Peter L Johnson, Brian Thoreen and Jack Samaratoni [WO9304580 Al]).
  • a compound of formula (IDA) [which is a compound of formula (DDT) wherein q is 1; X is alkoxy; and B, Z, and R 4 are as defined above in relation to a compound of formula (I)] may be made from a compound of formula (IN) [wherein B, Z, and R 4 are as defined above in relation to a compound of formula (I)] under known conditions:
  • a compound of ormula (IDA) may be prepared by conversion of an appropriately substituted phenoxyacetic acid or phenoxyacetic ester, using a ring-synthesis method as described for the synthesis of a compound of formula (IN) below.
  • a compound of formula (IHB) [which is a compound of formula (El) wherein q is 0;
  • X is hydroxy or alkoxy; and B, Z and R 4 are as defined above in relation to a compound of formula (I)] may be made from a compound of formula (N) [wherein Hal is chlorine, bromine or iodine; and B, Z and R 4 are as defined above in relation to a compound of formula (I)] by reaction with a suitably functionalised alkane (such as a derivative of malonic acid) under transition-metal (especially palladium) mediated cross-coupling conditions, followed by known procedures required to convert the cross-coupled product into a compound of formula (N).
  • a suitably functionalised alkane such as a derivative of malonic acid
  • transition-metal especially palladium
  • a compound of formula (N) [wherein Hal is bromine] may be reacted with a derivative of malonic acid (such as diethyl malonate or ethyl trimethylsilyl malonate) under palladium catalysed cross-coupling conditions [see, for example, John F. Hartwig et al., J. Am. Chem. Soc, 121, 1473 (1999)] and the product obtained is then hydrolysed and decarboxylated to give a compound of formula (IHB).
  • malonic acid such as diethyl malonate or ethyl trimethylsilyl malonate
  • a compound of formula (DIB) may be prepared by conversion of an appropriately substituted phenylacetic acid or phenylacetic ester, using a ring-synthesis method as described for the synthesis of a compound of formula (N) below.
  • the syntheses of compounds of formula (IN) and formula (N) are well known (see for example, Alan R. Katritzky and Charles W. Rees [Comprehensive Heterocyclic Chemistry, Nol.4, Pergamon Press, 1984]) and similar methods may be utilised in the syntheses of compounds of formula (B); the examples given below represent just a few of the methods available for their syntheses.
  • 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)] or from aryl fluorides by the method of Alexander J. Bridges, Arthur Lee, Emmanuel C. Manduakor and C. Eric Scwartz [Tetrahedron Letters, 33, 7499-7502 (1992)]; suitable thiophenols and aryl fluorides are known compounds or may be prepared by known methods.
  • Benzofurans may be made, for example, from ⁇ rt/t ⁇ -halophenols as described by Henning Lutjens and Peter J Scammells [Tetrahedron Letters 39 (1998), 6581-6584], Terence C Owen et al. [Tetrahedron Letters 30, No 13, 1597 (1989)] and Fred G Schreiber and Robert Stevenson [J.C.S. Perkin 1, 90, 1977] or from ⁇ rtz ⁇ -hydroxybenzyl halides by the method of A Hercouet and M Le Corre [Tetrahedron, Vol 37, No 16, 2867 (1981)].
  • Indoles may be made from ⁇ rt/. ⁇ -substituted anilines according to the methods of Cheng-yi Chen et al. [J. Org. Chem. 1997, 62, 2676], Takao Sakamoto et al. [J. Org. Chem. 1997, 62, 6507], CE. Castro et al. [J.Org. Chem., 1966, 31, 4071] and Alan D. Adams et al. [WO9827974].
  • Appropriate ⁇ rt/z ⁇ -substituted phenols and anilines are known compounds or may be prepared from known compounds by methods familiar to those skilled in the art.
  • a compound of formula (I) [wherein Y is sulphur] may be prepared by reacting a compound of formula (I) [wherein Y is oxygen] with a suitable thionating agent (such as 2,4-bis(4-methoxyphenyl)- 1 ,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson' s reagent), 2,4-bis(methylthio)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Davy reagent methyl), 2,4-bis(p ⁇ ra-tolyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Davy reagent p-tolyl) or phosphorus pentasulfide) in a suitable solvent (such as toluene or fluorobenzene).
  • a suitable thionating agent
  • a compound of formula (I) [wherein R is H and Y is oxygen] may be treated with an alkylating agent (such as an alkyl halide, dialkyl sulfate or trialkyloxonium salt), with a sulphenylating agent (such as a sulfenyl chloride), with a sulfonylating agent (such as a sulfonyl chloride) or with an acylating agent (such as an acid chloride), optionally in the presence of a base, to give a compound of formula (I) [where Y is oxygen and R 3 is not H].
  • an alkylating agent such as an alkyl halide, dialkyl sulfate or trialkyloxonium salt
  • a sulphenylating agent such as a sulfenyl chloride
  • a sulfonylating agent such as a sulfonyl chloride
  • an acylating agent such as an acid
  • a compound of formula (I) [where Y is oxygen and R 3 is alkoxymethyl] may be prepared from a compound of formula (I) [where Y is oxygen and R 3 is H] by sequential reaction with formaldehyde and an alkylating agent; likewise, a compound of formula (I) [where Y is oxygen and R is acyloxymethyl] may be prepared by using an acylating agent instead of an alkylating agent.
  • 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), Fra ⁇ kliniella occidentalis (thrip), Thrips spp.
  • the compounds of formula (I) are also active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae (Magnaporthe grisea) on rice and wheat and other Pyricularia spp. on other hosts; Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts (for example turf, rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental plants); Erysiphe cichoracearum on cucurbits (for example melon); Erysiphe graminis (powdery mildew) on barley, wheat, rye and turf and other powdery mildews on various hosts, such as Sphaerotheca macularis on hops, Sphaerotheca fusca (Sphaerothe
  • Botrytis cinerea grey mould
  • Botrytis cinerea grey mould
  • Botrytis cinerea grey mould
  • Altemaria spp. on vegetables (for example carrots), oil-seed rape, apples, tomatoes, potatoes, cereals (for example wheat) and other hosts
  • Venturia spp. including Venturia inaequalis (scab)) on apples, pears, stone fruit, tree nuts and other hosts
  • Cladosporium spp. on a range of hosts including cereals (for example wheat) and tomatoes
  • a compound of formula (I) may move acropetally, basipetally or locally in plant tissue to be active against one or more fungi. Moreover, a compound of formula (I) may be volatile enough to be active in the vapour phase against one or more fungi on the plant.
  • the invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a pest, a locus of pest, or to a plant susceptible to attack by a pest, and a method of combating and controlling fungi which comprises applying a fungicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a plant, to a seed of a plant, to the locus of the plant or seed, to soil or to any other growth medium (for example a nutrient solution).
  • the compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
  • plant as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes protectant, curative, systemic, eradicant and antisporulant treatments.
  • the compounds of formula (I) are preferably used for agricultural, horticultural and turfgrass purposes in the form of a composition.
  • a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA).
  • SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting).
  • all compositions both solid and liquid formulations
  • the composition is generally used for the control of pests or fungi such that a compound of formula (I) is applied at a rate of from O.lg tolOkg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to lkg per hectare.
  • a compound of formula (I) When used in a seed dressing, a compound of formula (I) is used at a rate of O.OOOlg to lOg (for example O.OOlg or 0.05g), preferably 0.005g to lOg, more preferably 0.005g to 4g, per kilogram of seed.
  • O.OOOlg to lOg for example O.OOlg or 0.05g
  • 0.005g to lOg more preferably 0.005g to 4g
  • 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.
  • the formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).
  • Dustable powders may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
  • solid diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers
  • Soluble powders may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • water-soluble organic solids such as a polysaccharide
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary.
  • a hard core material such as sands, silicates, mineral carbonates, sulphates or phosphates
  • Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils.
  • One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • DC Dispersible Concentrates
  • a compound of formula (I) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether.
  • organic solvent such as a ketone, alcohol or glycol ether.
  • surface active agent for example to improve water dilution or prevent crystallisation in a spray tank.
  • Emulsifiable concentrates or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents).
  • Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLNESSO 100, SOLNESSO 150 and SOLNESSO 200; SOLNESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), ⁇ - alkylpyrrolidones (such as ⁇ -methylpyrrolidone or ⁇ -octylpyrrolidone), dimethyl amides of fatty acids (such as C 8 -C 10 fatty acid dimethylamide) and chlorinated hydrocarbons.
  • aromatic hydrocarbons such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLNESSO 100, SOLNESSO 150 and SOLNESSO 200; SOLNESSO is a Registered Trade Mark
  • ketones such
  • An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.
  • Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion.
  • Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of formula (I) is present initially in either the water or the solvent/SFA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs.
  • An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation.
  • An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
  • SC Suspension concentrates
  • SCs may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I).
  • SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound.
  • One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle.
  • a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
  • Aerosol formulations comprise a compound of formula (I) and a suitable propellant
  • a compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as «-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
  • a suitable medium for example water or a water miscible liquid, such as «-propanol
  • a compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
  • Capsule suspensions may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor.
  • the polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure.
  • the compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment.
  • a compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
  • a composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)).
  • additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).
  • a compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS).
  • DS powder for dry seed treatment
  • SS water soluble powder
  • WS water dispersible powder for slurry treatment
  • CS capsule suspension
  • 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- z's ⁇ propyl- and tri-z ' s ⁇ propyl-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 te
  • 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).
  • hydrophilic colloids such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose
  • swelling clays such as bentonite or attapulgite
  • a compound of formula (I) may be applied by any of the known means of applying pesticidal or fungicidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.
  • a locus of the pests such as a habitat of the pests, or a growing plant liable to infestation by the pest
  • a compound of formula (I) may also be injected into plants or sprayed onto vegetation using electro dynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
  • compositions for use as aqueous preparations are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use.
  • These concentrates which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
  • a compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers).
  • fertilisers for example nitrogen-, potassium- or phosphorus-containing fertilisers.
  • Suitable formulation types include granules of fertiliser.
  • the mixtures suitably contain up to 25% by weight of the compound of formula (I).
  • the invention therefore also provides a fertiliser composition
  • a fertiliser composition comprising a fertiliser and a compound of formula (I).
  • the compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.
  • the resulting composition may have a broader spectrum of activity or a greater level of intrinsic activity than the compound of formula (I) alone. Further the other fungicide may have a synergistic effect on the fungicidal activity of the compound of formula (I).
  • the compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components.
  • the particular additional active ingredient will depend upon the intended utility of the composition.
  • Suitable pesticides include the following: a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate; b) Organophosphates, such as, profenofos, sulprofos, acephat
  • pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the composition.
  • selective insecticides for particular crops for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed.
  • insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).
  • acaricidal ovo-larvicides such as clofentezine, flubenzimine, hexythiazox or tetradifon
  • acaricidal motilicides such as dicofol or propargite
  • acaricides such as bromopropylate or chlorobenzilate
  • growth regulators such
  • fungicidal compounds which may be included in the composition of the invention are (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy- iminoacetamide (SSF-129), 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole- 1-sulphonamide, -[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]- ⁇ -butyrolactone, 4-chloro- 2-cyano-NJV-dimethyl-5- ⁇ -tolylimidazole-l-sulfonamide (IKF-916, cyamidazosulfamid), 3-5-dichloro-N-(3-chloro-l-ethyl-l-methyl-2-oxopro ⁇ yl)-4-methylbenzamide (RH-7281, zoxamide), N-allyl-4,5,-(
  • synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.
  • Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
  • An example of a rice selective herbicide which may be included is propanil.
  • An example of a plant growth regulator for use in cotton is PIXTM.
  • Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type.
  • other formulation types may be prepared.
  • one active ingredient is a water insoluble solid and the other a water insoluble liquid
  • the resultant composition is a suspoemulsion (SE) formulation.
  • Step 1 preparation of methyl 4-hvdroxy-3-iodophenylacetate.
  • Iodine 3.g, 12mmol
  • potassium iodate 1.3g, 6mmol
  • aqueous acetic acid from 15ml of water and 60ml of glacial acetic acid
  • the solvent was removed in vacuo and then the residue was taken up in diethyl ether and washed sequentially with saturated aqueous sodium bicarbonate solution and sodium bisulfite solution, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo.
  • the residue was purified by flash column chromatography on silica gel, eluting with a mixture of ethyl acetate and dichloromethane to give methyl 4-hydroxy-3-iodophenylacetate (3.6g).
  • Step 3 preparation of [ N-(4-chloro-3-methylisothiazol-5-yl)-(2-pro ⁇ ylbenzofuran-5- yPacetamide.
  • 5-Amino-4-chloro-3-methylisothiazole (0.176g, 1.18mmol) was added to a suspension of sodium methoxide (0.146g, 2.70mmol) in tetrahydrofuran (5ml) and the mixture was stirrred at room temperature for 20minutes.
  • a solution of methyl (2-propylbenzofuran-5-yl)acetate (0.25 g, 1.08mmol) in tetrahydrofuran (2ml) was added dropwise and once the addition was complete the mixture was stirred at room temperature for 4hours. The mixture was quenched with water, made acidic with saturated aqueous ammonium chloride solution and extracted with ethyl acetate.
  • Example 4 illustrates the preparation of Compound No. 6 of Table No. 4.
  • CompoundNo. 1 of Table No. 4 (0.25g, 0.72mmol), prepared as in Example 1, was dissolved in dichloromethane (4ml) and N,O-bis(trimethylsilyl)acetamide (0.173g, 0.86mmol) was added. The mixture was stirred at room temperature for 15minutes and then a solution of chloromethyl ethyl ether (0.136g, 1.44mmol) was added. The mixture was stirred at room temperature for 20hours, quenched with saturated aqueous sodium bicarbonate solution and extracted with ethyl acetate.
  • Step 2 preparation of 2-hvdroxy-5-bromobenzyl bromide.
  • Step 4 preparation of 5-bromo-2-heptafluoropropylbenzofuran.
  • Triethylamine (0.92g, 0.009mol) was added and the mixture was heated to reflux for 2hours. The mixture was cooled to room temperature, filtered and the filtrate was evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with dichloromethane, and was purified further by flash column chromatography on silica gel, eluting with hexane to give 5-bromo-2-heptafluoropropylbenzofuran (l.Og).
  • Ethyl trimethylsilyl malonate (0.39g, 0.0019mol) was added to a mixture of 5-bromo- 2-heptafluoropropylbenzofuran (0.577g, 0.0016mol) and palladium acetate (0.018g, O.OOOlmol) in toluene (7ml) and the mixture was stirred at room temperature.
  • Potassium tert-butoxide (Imolar solution in tetrahydrofuran; 1.67ml)
  • tri-tert-butylphosphine Imolar solution in toluene; 0.16ml
  • Step 5 preparation of [ N-(4-chloro-3-methylisothiazol-5-yl -(2- heptafluoropropylbenzofuran-5-yl)acetamide.
  • 5-Amino-4-chloro-3-methylisothiazole (0.224g, 0.0015mol) was added to a suspension of sodium methoxide (0.192g, 0.0036mol) in tetrahydrofuran (5ml) and the mixture was stirrred at room temperature for 20minutes.
  • EXAMPLE 4 This Example illustrates the preparation of Compound No.l of Table No.69. Step 1 - preparation of methyl 6-bromobenzothiophene-2-carboxylate. Sodium hydride (60% dispersion in oil; 0.59g, 0.0015mol) was weighed into a round- bottomed flask, washed twice with hexane and then dimethylsulfoxide (15ml) and methyl thioglycollate (0.97ml, 0.01 lmol) were introduced. The mixture was stirred for lOminutes and 4-bromo-2-fluorbenzaldehyde (2.0g, O.Olmol) was added.
  • 4-bromo-2-fluorbenzaldehyde 2.0g, O.Olmol
  • Diisobutylaluminium hydride (1 molar solution in heptane; 9.5ml) was added dropwise to a solution of methyl 6-bromobenzothiophene-2-carboxylate (1.17g, 0.0043mol) in toluene (120ml) at -78°C and once the addition was complete the mixture was stirred for 15rninutes, quenched with dilute aqueous hydrochloric acid and then extracted with ethyl acetate. The organic extract was washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo.
  • Step 3 preparation of 6-bromobenzothiophene-2-carboxaldehvde.
  • a solution of dimethylsulfoxide (0.58ml, 0.008mol) in dichloromethane (5ml) was added dropwise to a solution of oxalyl chloride (0.36ml, 0.004mol) in dichloromethane (15ml) at -78°C and the mixture was stirred for 5minutes, during which time the temperature rose to -60°C.
  • Step 4 preparation of 6-bromo-2-(2-methylprop-l-enyl benzothiophene.
  • n-Butyllithium 2.5molar solution in hexanes; 2.25ml
  • isopropyltriphenylphosphonium iodide (2.56g, 0.006mol) in tetrahydrofuran
  • Ethyl trimethylsilyl malonate (0.20g, O.OOlmol) was added to a mixture of 6-bromo-2- (2-methylpropyl)benzothiophene (0.229g, 0.00085mol) and palladium acetate (0.0095g, 0.0004mol) in toluene (2.3ml) and the mixture was stirred at room temperature.
  • Potassium tert-butoxide (Imolar solution on tetrahydrofuran; 0.89ml) and tri-tert-butylphosphine (0.0086g, 0.000043mol) were added sequentially. Nitrogen gas was bubbled through the reaction mixture for 15minutes and then the mixture was stirred and heated at 80°C for 90minutes.
  • Step 7 preparation of T N- ( 4-chloro-3-methylisothiazol-5-yl)-.2-(2- methylpropyl benzothiophen-6-yl acetamide.
  • 5-Amino-4-chloro-3-methylisothiazole (0.079g, 0.0005mol) was added to a suspension of sodium methoxide (0.029g, 0.0005mol) in tetrahydrofuran (0.5ml) and the mixture was stirrred at room temperature for 20minutes.
  • a solution of ethyl [2-(2- methylpropyl)benzothiophen-6-yl]acetate (0.134g, 0.0005mol) in tetrahydrofuran (1ml) was added dropwise and, once the addition was complete, the mixture was stirred at room temperature overnight. The mixture was quenched with water, made acidic with dilute aqueous hydrochloric acid solution and extracted with ethyl acetate.
  • Step 1 preparation of methyl 4-amino-3-iodophenylacetate.
  • Methyl 4-aminophenylacetate (5.0g, 0.03mol) was dissolved in a mixture of glacial acetic acid (100ml) and water (26ml) and the resulting solution was cooled in an ice bath to below 5°C.
  • Potassium iodate (1.3g, 0.006mol) and iodine (3.1g, 0.012mol) were added and the mixture was stirred for lhour and then the cooling bath was removed and the mixture was stirred at room temperature for a further l ⁇ hours.
  • the mixture was poured into water and extracted with ethyl acetate.
  • Step 2 preparation of methyl 4-amino-3-(4-methylpent-l-vnyl)phenylacetate.
  • a mixture of methyl 4-amino-3-iodophenylacetate (2.0g, 0.007mol), 4-methyl-l- pentyne (0.4ml, 0.0034mol), co ⁇ er(I) iodide (0.0065g, O.00035mol) and dichlorobis(triphenylphosphine)palladium( ⁇ ) (0.24g, 00035mol) was stirred in diethylamine (50ml) at 60 °C for 3hours and was then allowed to stand at room temperature overnight.
  • Step 3 preparation of methyl [2-(2-methylpropyl)indol-5-yl] acetate.
  • a mixture of methyl 4-amino-3-(4-methylpent-l-ynyl)phenylacetate (1.04g, 0.0042mol) and co ⁇ per(I) iodide (1.60g, 0.0085mol) in N,N-dimethylformamide (30ml) was stirred and heated at 110°C for 3hours and was then cooled to room temperature.
  • the mixture was partitioned between water and ethyl acetate and the organic extract was filtered through Hyflo Super Cel® diatomaceous earth, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo.
  • Step 4 preparation of ⁇ N-(4-chloro-3-methylisothiazol-5-yl)-r2-(2-methyl ⁇ ropyl)- indol-5-yllacetamide I .
  • 5-Amino-4-chloro-3-methylisothiazole (0.22g, 0.0015mol) was added to a suspension of sodium methoxide (0.18g, 0.003mol) in tetrahydrofuran (5ml) and the mixture was stirrred at room temperature for 30minutes.
  • a solution of methyl [2-(2-methylpropyl)indol-5- yl]acetate (0.325g, 0.0013mol)in tetrahydrofuran (5ml) was added dropwise and, once the addition was complete, the mixture was stirred at room temperature for 4hours. The mixture was partitioned between water and extracted with ethyl acetate.
  • EXAMPLE 6 This Example illustrates the pesticidal/insecticidal properties of compounds of formula (I).
  • the activities of individual compounds of formula (I) were determined using a variety of pests.
  • the pests were treated with a liquid composition containing 500 parts per million (ppm) by weight of a compound of formula (I).
  • Each composition was made by dissolving the compound in an acetone and ethanol (50:50 by volume) mixture and diluting the solution with water containing 0.05% by volume of a wetting agent, SYNPERONIC NP8, until the liquid composition contained the required concentration of the compound.
  • SYNPERONIC is a registered trade mark.
  • test procedure adopted with regard to each pest was essentially the same and comprised supporting a number of the pests on a medium, which was usually a substrate, a host plant or a foodstuff on which the pests feed, and treating either or both the medium and the pests with a composition. Pest mortality was assessed usually between two and five days after treatment.
  • Tests were also conducted against root knot nematodes (Meloidogyne incognita) using an in vitro test in which nematodes were suspended in a liquid composition which had been prepared as described above except that it contained a concentration of 12.5ppm by weight of a compound of formula (I) and it contained no SYNPERONIC NP8.
  • results from these tests are displayed in Table 103, in which each mortality (score) is designated as 9, 5 or 0 wherein 9 indicates 80-100% mortality, 5 indicates 40-79% mortality and 0 indicates less than 40% mortality; and Dm represents Drosophila melanogaster, Mp represents Myzus persicae; Hv represents Heliothis virescens; Px represents Plutella xylostella; Tu represents Tetranychus urticae; Db represents Diabrotica balteata; and Mi represents Meloidogyne incognita.
  • EXAMPLE 7 This Example illustrates the fungicidal properties of compounds of formula (I). The compounds were tested against a variety of foliar fungal diseases of plants. The techniques employed were as follows.
  • Test compounds were individually formulated as a solution either in acetone or acetone/ethanol (1 : 1 by volume) which was diluted in reverse osmosis water to a concentration of lOOppm (that is, lmg of compound in a final volume of 10ml) immediately before use.
  • lOOppm concentration of lmg of compound in a final volume of 10ml
  • the plants were incubated under high humidity conditions and then put into an appropriate environment to allow infection to proceed, until the disease was ready for assessment.
  • the Blumeria graminis f.sp. tritici plants were inoculated using a 'shake' inoculation technique.
  • the plants were reincubated under high humidity conditions for 24hours prior to assessment.
  • the time period between chemical application and assessment varied from five to nine days according to the disease and environment. However, each individual disease was assessed after the same time period for all the compounds tested against that particular disease.
  • Phytophthora infestans lycopersici For Blumeria graminis f.sp. tritici, Stagonospora nodorum and Puccinia triticina, assessments were carried out collectively on the plants in each replicate minipot or cellulose medium. The disease level present (that is, the percentage leaf area covered by actively sporulating disease) was assessed visually. For each treatment, the assessed values for all its replicates were meaned to provide mean disease values. Untreated control plants were assessed in the same manner. The data were then processed by either of two alternative methods, described below, each providing its own PRCO (Percentage Reduction from Control) value. All assessments on plants grown on cellulose media (and some grown in soil) used method 1. METHOD 1
  • This method uses banded assessment values.
  • PRCO 100 - ⁇ Banded mean disease level for treatment A ⁇ x 100 ⁇ Banded mean disease level on untreated controls ⁇
  • the PRCO is then rounded to the nearest whole number; therefore, in this particular example, the PRCO result is 67.
  • This method uses unhanded assessment values (that is, the mean disease values are used in the PRCO calculation without a banding step).
  • PRCO 100 - ⁇ Mean disease level for treatment A ⁇ x 100 ⁇ Mean disease level on untreated controls ⁇
  • the PRCO is then rounded to the nearest whole number; therefore, in this particular example, the PRCO result is 71.
  • Results are displayed in Table 104.
  • ERYSGT Blumeria graminis f.sp. tritici
  • LEPTNO Stagonospora nodorum
  • PLASNI Plasmopara viticola
  • PHYTIN Phytophthora infestans lycopersici
  • PUCCRT Puccinia recondita

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Abstract

A compound of formula (I) where q is 0 or 1; B is CR5 and Z is O, S or NR6 or B is N and Z is NR7; Y is O, S or NR8; and the various R groups are defined radicals; and their use and compositions containing them.

Description

ISOTHIAZOLES 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 imgf000002_0001
wherein q is 0 or 1 ; B is CR3 and Z is O, S or NR° or B is N and Z is NR >7'.; Y is O, S or NR8; R1 is hydrogen, halogen, optionally substituted d-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted Cι-6 alkoxy, optionally substituted d-6 alkylthio, optionally substituted C3.7 cycloalkyl, cyano, nitro or SF5; R2 is hydrogen, halogen, optionally substituted Ci-6 alkyl, optionally substituted C -6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted d-6 alkoxy, optionally substituted d-6 alkylthio, optionally substituted Ci-6 alkylsulfinyl, optionally substituted d-6 alkylsulfonyl, cyano, nitro, formyl, C(R9)=NOR10, optionally substituted d-6 alkylcarbonyl, optionally substituted Ci-6 alkoxycarbonyl or SF5; or R1 and R2 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated ring carbocylic or heterocyclic ring which may contain one or two hetero atoms selected from O, N or S and which may be optionally substituted by d-6 alkyl, d-6 haloalkyl or halogen; R3 is hydrogen, d-6 alkyl, CH2(Ci-4 haloalkyl), Cw cyanoalkyl, C3-6 alkenyl, C3-6 alkynyl, d-6 alkoxy(Cι-6)alkyl, d-6 alkylthio (C1-6)alkyl, d-e alkoxy(C1-6)alkoxy(C1-6)alkyl, Ci-6 alkylcarbonyl, Ci-6 alkoxycarbonyl, formyl, d-6 alkylcarbonyl(Cι-6)alkyl, d-6 alkoxycarbonyl(Ci-6)alkyl, Ci-6 alkylaminocarbonyl, di(Ci-6)alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted phenyl(Ci- )alkyl or S(O)rRπ; R4 is hydrogen, halogen, cyano, d-8 alkyl, Ci-6 haloalkyl, d-6 cyanoalkyl, C2-6 alkenyl, C2.6 alkynyl, C3-7 cycloalkyl, C3-7 halocycloalkyl, C3.7 cyanocycloalkyl, Ci-3 alkyl(C3-7)cycloalkyl, Ci-3 alkyl (C3-7) halocycloalkyl, C3-6 cycloalkyl(Cι.6)alkyl, C5-6 cycloalkenyl, C5-6 cycloalkenyl (d-6)alkyl, C2-6 haloalkenyl, Ci-6 cyanoalkenyl, Ci-6 alkoxy(C1-6)alkyl, formyl, Ci-6 carboxyalkyl, d-6 alkylcarbonyl(d-6)alkyl, Ci-6 alkoxycarbonyl(Ci-6)alkyl, Ci-6 alkylthio (d-6)alkyl, d-6 alkylsulfinyl(d-6)alkyl, d-6 alkylsulfonyl(d-6)alkyl, aminocarbonyl(Ci-6)alkyl, Ci-6 alkylaminocarbonyl(Ci-6)alkyl, di(Ci-6)alkylaminocarbonyl(d-6)alkyl, Ci-6 alkoxycarbonyl, d-6 alkylcarbonyl, aminocarbonyl, _6 alkylaminocarbonyl, di(Ci-6)alkylaminocarbonyl, optionally substituted phenyl, optionally substituted phenyl(Ci-4)alkyl, optionally substituted phenyl(C2. )alkenyl, optionally substituted heteroaryl, optionally substituted heteroaryl(d-4)alkyl, optionally substituted heterocyclyl, optionally substituted heterocyclyl(d- )alkyl, a group OR12, a group SH, a group S(O)pR13, a group NR14R15, a group C(R16)=NOR17 or a group C(R18)=NNR19R20; R5 is hydrogen, halogen, nitro, cyano, optionally substituted d-8 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted C3-7 cycloalkyl, optionally substituted Ci-6 alkoxycarbonyl, optionally substituted Ci-6 alkylcarbonyl, optionally substituted Ci-6 alkylaminocarbonyl, optionally substituted di(Ci-6)alkylaminocarbonyl, optionally substituted phenyl or optionally substituted heteroaryl; R6 is hydrogen, cyano, optionally substituted d-8 alkyl, optionally substituted [C2-6 alkenyl(d-6)alkyl], optionally substituted [C2-6 alkynyl(d-6)alkyl], optionally substituted C3-7 cycloalkyl, optionally substituted [C3-7 cycloalkyl(Ci-6)alkyl], Cι-6 alkoxy(Ci.6)alkyl, optionally substituted Ci-6 alkoxycarbonyl, optionally substituted Ci-6 alkylcarbonyl, optionally substituted Ci-6 alkylaminocarbonyl, optionally substituted di(Ci-6)alkylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl; R7 is substituted Ci-s alkyl, optionally substituted [C2-6 alkenyl(Ci-6)alkyl], optionally substituted [C2-6 alkynyl(Ci-6)alkyl], substituted C3-7 cycloalkyl, substituted [C3-7 cycloalkyl(Ci-6)alkyl], substituted d-6 alkoxycarbonyl, substituted d-6 alkylcarbonyl, substituted Ci-6 alkylaminocarbonyl, substituted di(C1-6)alkylaminocarbonyl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl; provided that R7 is not d-6 haloalkyl, Ci-e cyanoalkyl, C2-6 alkenyl, C2-6 alkynyl or C2-6 haloalkenyl; R is hydrogen, cyano, nitro, optionally substituted Ci-6 alkyl, optionally substituted C3-7 cycloalkyl, optionally substituted (C2.6)alkenyl(Ci-6)alkyl, optionally substituted (C2-6)alkynyl(Ci-6)alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted Ci-6 alkylcarbonyl, optionally substituted C3-6 alkoxycarbonyl, optionally substituted d-6 alkylamino, optionally substituted di(Ci-6)alkylamino, optionally substituted Ci-6 alkylcarbonylamino, optionally substituted Ci-6 alkoxycarbonylamino, optionally substituted d-6 alkoxy, optionally substituted Ci-6 alkylthio, optionally substituted Cι-6 alkylsulfinyl, optionally substituted Cι-6 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or Ci-6 acyloxy; R9 is hydrogen, optionally substituted phenyl or optionally substituted Cι-6 alkyl; R10 is hydrogen, optionally substituted phenyl (d-2)alkyl or optionally substituted d- o
1 1 1 alkyl; R is d-6 alkyl, Ci-6 haloalkyl or optionally substituted phenyl; R is hydrogen, d-6 alkyl, Ci-6 haloalkyl, C3_6 alkenyl, d-4 cyanoalkyl, d-6 alkoxycarbonyl (Ci-6)alkyl, optionally substituted phenyl, optionally substituted phenyl(Cι_4)alkyl, optionally substituted heteroaryl, N=C(CH3)2; R13 is d-6 alkyl, Ci-6 haloalkyl, C3-6 alkenyl, cyano, d- cyanoalkyl, Ci-6 alkoxycarbonyl(Ci-6)alkyl, optionally substituted phenyl, optionally substituted phenyl(d-4)alkyl or optionally substituted heteroaryl; R14 and R15 are, independently, hydrogen, d-8 alkyl, C3-7 cycloalkyl, C3-6 alkenyl, C3-6 alkynyl, C -6 haloalkyl, d-6 alkoxy (Ci-6)alkyl, Ci-6 alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, d-6 alkylcarbonyl, d-6 alkylSO2, optionally substituted phenylSO2 or optionally substituted phenyl(Ci. )alkyl; R16 is Ci-6 alkyl; R17 is d-6 alkyl or optionally substituted phenyl(Cι-2)- alkyl; R18 is Ci-6 alkyl; R19 and R20 are, independently, hydrogen, optionally substituted d-6 alkyl or optionally substituted phenyl; and p and r are, independently, 0, 1 or 2.
The compounds of formula (I) may exist in different geometric or optical isomers or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds. Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, wσ-propyl, n-butyl, sec-butyl, is ø-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 Ci-6 alkyl or halogen), C5--7 cycloalkenyl (itself optionally substituted with d-6 alkyl or halogen), hydroxy, d-10 alkoxy, d-10 alkoxy(Ci-10)alkoxy, tri(Ci- )alkylsilyl(d-6)alkoxy, d-6 alkoxycarbonyl (Ci-io)alkoxy, d-io haloalkoxy, aryl(d-4)alkoxy (where the aryl group is optionally substituted), C3- cycloalkyloxy (where the cycloalkyl group is optionally substituted with Ci-6 alkyl or halogen), d-i0 alkenyloxy, d-10 alkynyloxy, SH, Ci-10 alkylthio, d-10 haloalkylthio, aryl(Ci- )alkylthio (where the aryl group is optionally substituted), C3-7 cycloalkylthio (where the cycloalkyl group is optionally substituted with Ci-β alkyl or halogen), tri(Cι-4)alkylsilyl(C1-6)alkylthio, arylthio (where the aryl group is optionally substituted), Ci-6 alkylsulfonyl, Ci-6 haloalkylsulfonyl, d-6 alkylsulfinyl, d.6 haloalkylsulfinyl, arylsulfonyl (where the aryl group may be further optionally substituted), tri(Ci-4)alkylsilyl, aryldi(Cι-4)alkylsilyl, (Ci-4)alkyldiarylsilyl, triarylsilyl, Ci-10 alkylcarbonyl, HO2C, Ci-io alkoxycarbonyl, aminocarbonyl, Ci-6 alkylaminocarbonyl, di(d-6 alkylaminocarbonyl, N-(Cι-3 alkyl)-N-(Ci-3 alkoxy)aminocarbonyl, Ci-6 alkylcarbonyloxy, arylcarbonyloxy (where the aryl group is optionally substituted), di(d-6)alkylaminocarbonyloxy, aryl (itself optionally substituted), heteroaryl (itself 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 Ci-6 alkyl or halogen), amino, Ci-6 alkylamino, di(Ci-6)alkylamino, d-6 alkylcarbonylamino and N-(Ci-6)alkylcarbonyl-N-(d-6)alkylamino.
Alkenyl and alkynyl moieties can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)- or ©-configuration. Examples are vinyl, allyl and propargyl.
When present, the optional substituents on alkenyl or alkynyl include those optional substituents given above for an alkyl moiety.
In the context of this specification acyl is optionally substituted d-6 alkylcarbonyl (for example acetyl), optionally substituted C2-6 alkenylcarbonyl, optionally substituted C2-6 alkynylcarbonyl, optionally substituted arylcarbonyl (for example benzoyl) or optionally substituted heteroarylcarbonyl.
Halogen is fluorine, chlorine, bromine or iodine.
Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF3, CF2C1, CF3CH2 or CHF2CH2.
Aryl includes naphthyl, anthracyl, fluorenyl and indenyl but is preferably phenyl. The term heteroaryl refers to an aromatic ring containing up to 10 atoms including one or more heteroatoms (preferably one or two heteroatoms) selected from O, S and N. Examples of such rings include pyridine, pyrimidine, furan, quinoline, quinazoline, pyrazole, thiophene, thiazole, oxazole and isoxazole. The terms heterocycle and heterocyclyl refer to a non-aromatic ring containing up to
10 atoms including one or more (preferably one or two) heteroatoms selected from O, S and N. Examples of such rings include 1,3-dioxolane, tetrahydrofuran and morpholine.
When present, the optional substituents on heterocyclyl include d-e 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 Cj-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-, d-6 alkyl, d-6 haloalkyl, d-6 alkoxy(Ci-6)alkyl, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C3-7 cycloalkyl (itself optionally substituted with Ci-6 alkyl or halogen), C5-7 cycloalkenyl (itself optionally substituted with d-6 alkyl or halogen), hydroxy, d-10 alkoxy, Ci-io alkoxy(Cι-10)alkoxy, tri(Ci-4)alkylsilyl(d-6)alkoxy, Ci-6 alkoxycarbonyl(Ci-10)alkoxy, d-io haloalkoxy, aryl(Cι-4)alkoxy (where the aryl group is optionally substituted), C3- cycloalkyloxy (where the cycloalkyl group is optionally substituted with Ci-6 alkyl or halogen), d-io alkenyloxy, Ci-io alkynyloxy, SH, Cι-10 alkylthio, Ci-10 haloalkylthio, aryl(Cι-4)alkylthio (where the aryl group may be further optionally substituted), C3-7 cycloalkylthio (where the cycloalkyl group is optionally substituted with Ci-β alkyl or halogen), tri(C1-4)alkylsilyl(C1-6)alkylthio, arylthio (where the aryl group is optionally substituted), d-6 alkylsulfonyl, Ci-6 haloalkylsulfonyl, Ci-6 alkylsulfϊnyl, d-6 haloalkylsulfinyl, arylsulfonyl (where the aryl group is optionally substituted), tri(d-4)alkylsilyl, aryldi(d-4)alkylsilyl, (d-4)alkyldiarylsilyl, triarylsilyl, d-10 alkylcarbonyl, HO2C, Ci-10 alkoxycarbonyl, aminocarbonyl, d-6 alkylaminocarbonyl, di(d-6 alkyl)aminocarbonyl, N-(d-3 alkyl)-N-(d-3 alkoxy)aminocarbonyl, d-6 alkylcarbonyloxy, arylcarbonyloxy (where the aryl group is optionally substituted), di(C1.6)alkylaminocarbonyloxy, 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 d-6 alkyl or halogen), amino, Ci-6 alkylamino, di(Cι-6)alkylamino, Ci-6 alkylcarbonylamino and N-(C1.6)alkylcarbonyl-N-(C1-6)alkylamino.
For substituted aryl moieties, heterocyclyl and heteroaryl groups it is preferred that one or more substituents are independently selected from halogen, d-6 alkyl, d-6 haloalkyl, Ci-6 alkoxy(Ci-6)alkyl, Ci-6 alkoxy, Cι-6 haloalkoxy, d-6 alkylthio, d-e haloalkylthio, d-6 alkylsulfinyl, d-6 haloalkylsulfinyl, d-6 alkylsulfonyl, d-6 haloalkylsulfonyl, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl, C3-7 cycloalkyl, nitro, cyano, CO2H, d-6 alkylcarbonyl, d-6 alkoxycarbonyl, R21R22N or R23R24NC(O), wherein R21, R22, R23 and R24 are, independently, hydrogen or d-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 (d-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 (d-6) alkyl groups.
Preferably the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, HO C, d-io alkoxy (itself optionally substituted by Ci-io alkoxy), aryl(Cι- ) alkoxy, aryl(Ci- )alkylthio, d-io alkylthio, d-10 alkylcarbonyl, Ci-10 alkoxycarbonyl, Ci-6 alkylaminocarbonyl, di(Ci-6 alkylaminocarbonyl, (Ci-6)alkylcarbonyloxy, optionally substituted phenyl, aryl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy, heterocyclyl, heterocyclyloxy, C3-7 cycloalkyl (itself optionally substituted with (d-6)alkyl or halogen), C3-7 cycloalkyl(itself optionally substituted with (Ci-6)alkyl or halogen)oxy, C3- cycloalkyl (itself optionally substituted with (d-6)alkyl or halogen)thio, C5-7 cycloalkenyl, Ci-6 alkylsulfonyl, d-6 alkylsulfinyl, tri(Cι-4)alkylsilyl, tri(Ci-4)alkylsilyl(Ci-6)alkoxy, tri(Ci- )alkylsilyl(Ci-6) alkylthio, aryldi(Ci-4)alkylsilyl, (Ci-4)alkyldiarylsilyl, triarylsilyl, phenoxy (itself optionally substituted by halogen, Ci-4 alkyl or heteroaryloxy (itself optionally substituted by halogen)), C7-lυ bicycloalkane, C7-io bicycloalkene and (C S alkylcarbonyl)(Ci-4 alkyl)amino.
Preferably the optional substituents on alkenyl or alkynyl include one or more of halogen, aryl, d-6 alkyl, C3-7 cycloalkyl, C5-7 cycloalkenyl (itself optionally substituted by d-6 alkyl) and Ci-6 alkoxycarbonyl.
It is more preferred that heterocyclyl is optionally substituted by Cι-6 alkyl.
Preferably the optional substituents for cycloalkyl include halogen, cyano, d-3 alkyl, d-3 alkyl(C2-4)alkenyl and phenyl (itself optionally substituted by halogen).
Preferably the optional substituents for cycloalkenyl include d-3 alkyl, halogen and cyano.
In a further aspect, the present invention provides a compound of formula (IA):
Figure imgf000008_0001
where q, B, Y, Z, R1, R2, R3 and R4 are as defined above for a compound of formula (I). In another aspect, the present invention provides a compound of formula (IB):
Figure imgf000008_0002
where q, B, Y, Z, R1, R2, R3 and R4 are as defined above for a compound of formula (I). In a yet further aspect, the present invention provides a compound of formula (IC):
Figure imgf000009_0001
where q, B, Y, Z, R1, R2, R3 and R4 are as defined above for a compound of formula (I). More preferred compounds of formula (I) are compounds of formula (IA) or (IB) wherein q is 0; B is CR5; Y is O, S or NR8; Z is O, S or NR6; R1 is hydrogen, halogen, d-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, d-6 cyanoalkyl, d-6 haloalkyl, d-6 alkoxy, d-6 haloalkoxy, Ci-6 alkylthio, d-6 haloalkylthio, C3-6 cycloalkyl, C3-7 cycloalkyl(Ci-4)alkyl, Cι-6 alkoxy(Ci-6)alkyl, cyano, nitro or SF5; R2 is hydrogen, halogen, d-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, d-6 haloalkyl, d-6 alkoxy, Ci-6 alkoxy(d-6)alkyl, d-6 haloalkoxy, Ci-6 alkylthio, Ci-6 haloalkylthio, Cι-6 alkylsulfinyl, Ci-6 haloalkylsulfinyl, d-6 alkylsulfonyl, Ci-6 haloalkylsulfonyl, d-6 haloalkyl, cyano, nitro, formyl, CH=NOR10, d-6 alkylcarbonyl, Ci-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 hetero atoms selected from O, N or S and which may be optionally substituted by Ci-6 alkyl, Ci-6 haloalkyl or halogen; R3 is hydrogen, d-6 alkyl, Ci-6alkoxy(Ci-6)alkyl, C3-6 alkenyl, C3-6 alkynyl, d-6 alkylcarbonyl or Ci-6 alkoxycarbonyl; R4 is halogen, cyano, d-8 alkyl, Ci_6 haloalkyl, Ci-6 cyanoalkyl, C2-6 alkenyl, C2-e alkynyl, C3-7 cycloalkyl, C3- halocycloalkyl, C3-7 cyanocycloalkyl, d-3 alkyl(C3-7) cycloalkyl, Ci-3 alkyl(C3-7)halocycloalkyl, C3-6 cycloalkyl(Ci-6)alkyl, C5-6 cycloalkenyl, C5-6 cycloalkenyl(C1-6)alkyl, C2-6 haloalkenyl, Ci-6 cyanoalkenyl, Ci-6 alkoxy(d-6)alkyl, d-6 carboxyalkyl, d-6 alkylcarbonyl(d-6)alkyl, Ci-6 alkoxycarbonyl(C1-6)alkyl, Ci-6 alkylthio(Ci-6)alkyl, Ci-β alkylsulfinyl(Ci-6)alkyl, d-6 alkylsulfonyl(C1-6)alkyl, aminocarbonyl(C1-6) alkyl, d-6 alkylaminocarbonyl(d-6)alkyl, di(Ci-6)alkylaminocarbonyl(Ci-6)alkyl, d-6 alkoxycarbonyl, Ci-6 alkylcarbonyl, aminocarbonyl, d-6 alkylaminocarbonyl, di(d.6) alkylaminocarbonyl, optionally substituted phenyl, optionally substituted phenyl(d-4)alkyl, optionally substituted phenyl(C2. )alkenyl, optionally substituted heteroaryl, optionally substituted heteroaryl(d-4)alkyl, optionally substituted heterocyclyl, optionally substituted heterocyclyl(d-4)alkyl, a group OR12, a group S(O)pR13, a group NR14R15, a group C(R16)=NOR17 or a group C(R18)=NNR19R20; R5 is hydrogen, halogen, nitro, cyano, d-8 alkyl, d-6 haloalkyl, Ci.6 cyanoalkyl, C2-6 alkenyl, C2-6 alkynyl, C3-7 cycloalkyl, C2-6 haloalkenyl, C3_7 cycloalkyl(d.6)alkyl, Cι-6 alkoxy(Cι-6)alkyl, Ci-6 alkoxycarbonyl, d-6 alkylcarbonyl, d-6 alkylaminocarbonyl, di(d- 6)alkylaminocarbonyl, d-6 alkoxycarbonyl(d-6)alkyl, Ci-6 alkylcarbonyl(Cι-6)alkyl, Ci-6 alkylaminocarbonyl(Cι-6) alkyl, di(Ci-6)alkylaminocarbonyl(d-6)alkyl, phenyl (optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d- haloalkyl, Cι-6 alkoxy or Ci-6 haloalkoxy), phenyl(Ci-6)alkyl (wherem the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Ci-6 haloalkyl, d-6 alkoxy or d-6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, d_6 alkyl, Ci-6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy) or heteroaryl(d-6)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); R6 is hydrogen, d-8 alkyl, Ci-6 haloalkyl, Ci-6 cyanoalkyl, C2-6 alkenyl, C2-β alkynyl, C3-7 cycloalkyl, C2-6 haloalkenyl, C3.7 cycloalkyl(d-6)alkyl, Ci-6 alkoxy(Ci-6)alkyl, d-6 alkoxycarbonyl, d-6 alkylcarbonyl, Ci-6 alkylaminocarbonyl, di(Ci-6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d-6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy) or heteroaryl (optionally substituted by halo, nitro, cyano, d-6 alkyl, Ci-6 haloalkyl, Ci-6 alkoxy or d-6 haloalkoxy); R8 is cyano, nitro, d-6 alkyl, d-6 haloalkyl, C3-7 cycloalkyl, C3-7 cycloalkyl(Ci-6)alkyl, CH2(C2-6)alkenyl, CH2(C2-6)alkynyl, phenyl (optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Ci-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 Ci-6 haloalkoxy), Ci-6 alkylcarbonyl, d-6 alkoxycarbonyl, Ci-6 alkylamino, di(Ci-6)alkylamino, Ci-6 alkylcarbonylamino, Ci-6 alkoxycarbonylamino, d-6 alkoxy, d-6 alkylthio, d-6 alkylsulfinyl, d-6 alkylsulfonyl, d-6 haloalkylthio, d-e haloalkylsulfinyl, Ci-6 haloalkylsulfonyl, arylthio, arylsulfinyl, arylsulfonyl or OCO(d-6) alkyl; R10 is Ci-6 alkyl or 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); R12 is hydrogen, Ci-6 alkyl, d-6 haloalkyl, C3-6 alkenyl, d-4 cyanoalkyl, Ci-6 alkoxycarbonyl(d-6)alkyl, optionally substituted phenyl, optionally substituted phenyl(Ci-4)alkyl, optionally substituted heteroaryl, N=C(CH3)2; R13 is Ci-6 alkyl, d-6 haloalkyl, C3-6 alkenyl, cyano, d-4 cyanoalkyl, Cw alkoxycarbonyl(d-6) alkyl, optionally substituted phenyl, optionally substituted phenyl(d- )alkyl or optionally substituted heteroaryl; R14 and R15 are, independently, hydrogen, d-8 alkyl, C3-7 cycloalkyl, C3-6 alkenyl, C3-6 alkynyl, C2-6 haloalkyl, d-6 alkoxy(C1-6)alkyl, Ci-6 alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, Ci-6 alkylcarbonyl, d-6 alkylSO2, optionally substituted phenylSO2 or optionally substituted phenyl(Ci.4)alkyl; R16 is d-6 alkyl; R17 is Ci-6 alkyl or optionally substituted phenyl(d-2)- alkyl; R18 is d-6 alkyl; R19 and R20 are, independently, hydrogen, optionally substituted -6 alkyl or optionally substituted phenyl; and p is 0, 1 or 2.
A further group of preferred compounds of formula (I) is provided by compounds of formula (IC) wherein q is 0; B is CR5; Y is O, S or NR8; Z is O, S or NR6; R1 is hydrogen, halogen, d-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, d-6 cyanoalkyl, d-6 haloalkyl, d-6 alkoxy, Ci-6 haloalkoxy, Cι-6 alkylthio, Cι-6 haloalkylthio, C3-6 cycloalkyl, C3-7 cycloalkyl(C!-4)alkyl, d-6 alkoxy(d-6)alkyl, cyano, nitro or SF5; R2 is hydrogen, halogen, d-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, Cι-6 haloalkyl, Ci-6 alkoxy, d-6 alkoxy(Ci-6)alkyl, Ci-6 haloalkoxy, d-6 alkylthio, d-6 haloalkylthio, Ci-6 alkylsulfinyl, d-6 haloalkylsulfinyl, d-6 alkylsulfonyl, Ci-6 haloalkylsulfonyl, Ci-6 haloalkyl, cyano, nitro, formyl, CH=NOR10, Ci-6 alkylcarbonyl, d.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 hetero atoms selected from O, N or S and which may be optionally substituted by Cι-6 alkyl, Ci-6 haloalkyl or halogen; R3 is hydrogen, d-6 alkyl, Ci-6alkoxy(Ci-6)alkyl, C3-6 alkenyl, C3-6 alkynyl, d-6 alkylcarbonyl or Ci-6 alkoxycarbonyl; R4 is hydrogen or methyl; R5 is hydrogen, halogen, nitro, cyano, d-8 alkyl, Ci-6 haloalkyl, d-6 cyanoalkyl, C2-6 alkenyl, C2-6 alkynyl, C3-7 cycloalkyl, C2.6 haloalkenyl, C3- cycloalkyl(Ci-6)alkyl, d-6 alkoxy(Ci-6)alkyl, Ci-6 alkoxycarbonyl, Ci-6 alkylcarbonyl, Ci-6 alkylaminocarbonyl, di(Ci-6)alkylaminocarbonyl, d-6 alkoxycarbonyl- (Ci-6)alkyl, d-6 alkylcarbonyl(Ci-6)alkyl, Ci-6 alkylaminocarbonyl(Ci-6)alkyl, di(Ci-6)alkylaminocarbonyl(Ci-6) alkyl, phenyl (optionally substituted by halo, nitro, cyano, d-6 alkyl, Ci-6 haloalkyl, d-6 alkoxy or Cι-6 haloalkoxy), phenyl(d-6)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d.6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, d-6 alkyl, d-6 haloalkyl, Ci-6 alkoxy or d-6 haloalkoxy) or heteroaryl(Ci-6)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d-6 haloalkyl, Ci-6 alkoxy or d-6 haloalkoxy); R6 is hydrogen, d-8 alkyl, d.6 haloalkyl, d_6 cyanoalkyl, C2.6 alkenyl, C2.6 alkynyl, C3-7 cycloalkyl, C2.6 haloalkenyl, C3_7 cycloalkyl(Ci.6)alkyl, Ci-5 alkoxy(d-6)alkyl, Ci-6 alkoxycarbonyl, Ci-6 alkylcarbonyl, Ci-6 alkylaminocarbonyl, di(d-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, Cι-6 alkoxy or Ci-6 haloalkoxy); R8 is cyano, nitro, d-6 alkyl, d-6 haloalkyl, C3-7 cycloalkyl, C3.7 cycloalkyl(Ci.6)alkyl, CH2(C2-6)alkenyl, CH2(C2-6)alkynyl, phenyl (optionally substituted by halo, nitro, cyano, d-6 alkyl, d-6 haloalkyl, d-6 alkoxy or Ci-6 haloalkoxy) heteroaryl (optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d-6 haloalkyl, d-6 alkoxy or Ci-6 haloalkoxy), d-6 alkylcarbonyl, d.6 alkoxycarbonyl, Ci.6 alkylamino, di(d.6)alkylamino, Ci- alkylcarbonylamino, Ci-6 alkoxycarbonylamino, Cι-6 alkoxy, Cι-6 alkylthio, Ci-6 alkylsulfinyl, d-6 alkylsulfonyl, Ci-6 haloalkylthio, Ci-6 haloalkylsulfinyl, -e haloalkylsulfonyl, arylthio, arylsulfinyl, arylsulfonyl or OCO(d-6) alkyl; and R10 is d-6 alkyl or phenyl(Ci-2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d-6 haloalkyl, d-6 alkoxy or Ci-6 haloalkoxy). q is preferably 0. B is preferably CR5.
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, d-6 haloalkyl,
C3-7 cycloalkyl(Ci-4)alkyl, Cι-6 alkoxy(Ci-6)alkyl, C2-6 alkenyl, C2-6 alkynyl, Ci-6 alkoxy, d-6 haloalkoxy, Ci-β alkylthio, d-6 haloalkylthio, C3-6 cycloalkyl, cyano, nitro or SF5.
R1 is more preferably hydrogen, halogen, d-6 alkyl, C2-6 alkenyl, d-6 haloalkyl, Ci-6 alkoxy, d-6 haloalkoxy, d-6 alkylthio, d-e haloalkylthio, C3-6 cycloalkyl, cyano, nitro or SF5. It is even more preferred that R1 is hydrogen, halogen, d-6 alkyl, d-6 haloalkyl, Ci-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.
R1 is most preferably halogen, Ci-6 alkyl, Ci-6 haloalkyl, Ci.6 alkoxy or d_6 haloalkoxy. It is preferred that R2 is hydrogen, halogen, d-6 alkyl, Ci-6 haloalkyl, d-6 alkoxy(C1-6)alkyl, C2-6 alkenyl, d-6 alkynyl, Ci-6 alkoxy, d-6 haloalkoxy, d-6 alkylthio, Ci-6 haloalkylthio, Ci-6 alkylsulfinyl, d-6 haloalkylsulfinyl, d-6 alkylsulfonyl, d.6 haloalkylsulfonyl, cyano, nitro, formyl, d-6 alkylcarbonyl, d_6 alkoxycarbonyl or CH=NOR10; 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, d-6 haloalkyl or halogen; where R10 is phenyl(d.2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, d-6 alkyl, d_6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy) or Ci-6 alkyl.
It is more preferred that R2 is hydrogen, halogen, d_6 alkyl, d-6 haloalkyl, Ci.6 alkoxy (d.6)alkyl, d_6 alkoxy, d-6 haloalkoxy, Ci-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, Ci-6 haloalkyl or halogen.
R2 is even more preferably hydrogen, halogen, d-6 alkyl, d-6 haloalkyl, d-6 alkoxy, Ci-6 haloalkoxy, Cι_6 alkoxy(C1-6)alkyl, d-6 alkylthio or SF5; or R1 and R2 together with the atoms to which they are attached form a benzene ring optionally substituted by Ci-6 alkyl, d-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, Cι-6 alkoxy(Ci-6)alkyl, Ci-6 alkoxy, Ci-6 haloalkoxy, or R1 and R2 together with the atoms to which they are attached form a cyclopentane ring optionally substituted by d-6 alkyl, d-6 haloalkyl or halogen. R2 is most preferably halogen, Ci-6 alkyl, d-6 haloalkyl, d-6 alkoxy, d-6 alkoxy(Ci-6)alkyl or Ci-6 haloalkoxy.
R3 is preferably hydrogen, d-6 alkyl, Ci-6alkoxy(Ci-6)alkyl, C3-6 alkenyl (especially allyl), C3-6 alkynyl (especially propargyl), d.6 alkylcarbonyl or Ci-6 alkoxycarbonyl (especially s butoxycarbonyl). R3 is more preferably hydrogen, d-e alkyl or Ci-6alkoxy(Cι.6)alkyl.
R4 is preferably d-8 alkyl, Cι-6 haloalkyl, d-6 cyanoalkyl, C2-6 alkenyl, C2-6 alkynyl, C3-7 cycloalkyl, C3-7 halocycloalkyl, C3-7 cyanocycloalkyl, Ci-3 alkyl(C3-7)cycloalkyl, Cι-3 alkyl(C3-7)halocycloalkyl, C3-6 cycloalkyl(Ci-6)alkyl, C5-6 cycloalkenyl, C5-6 cycloalkenyl(Ci-6)alkyl, C2.6 haloalkenyl, d-6 cyanoalkenyl, d.6 alkoxy(C1.6)alkyl, Ci-6 alkylcarbonyl(Ci-6)alkyl, Ci.6 alkoxycarbonyl(Ci-6)alkyl, d-6 alkylthio(d-6)alkyl, d.6 alkylsulfinyl(Ci-6)alkyl, Ci-6 alkylsulfonyl(d-6)alkyl, Cw alkoxycarbonyl, d-6 alkylcarbonyl, optionally substituted phenyl or optionally substituted heterocyclyl. R4 is more preferably d-8 alkyl, d-6 haloalkyl, Ci-6 cyanoalkyl, C2-6 alkenyl, C2-6 alkynyl, C3-7 cycloalkyl, C3-7 halocycloalkyl, C3-7 cyanocycloalkyl, Cι-3 alkyl(C3-7)cycloalkyl, Ci-3 alkyl(C3-7)halocycloalkyl, C3.6 cycloalkyl(Ci-6)alkyl, C5-6 cycloalkenyl, C5.6 cycloalkenyl(d_6)alkyl, C2.6 haloalkenyl, Ci-6 cyanoalkenyl, Ci-6 alkoxy(d-6)alkyl or optionally substituted phenyl.
R5 is preferably hydrogen, halogen, nitro, cyano, d-8 alkyl, d-6 haloalkyl, d-6 cyanoalkyl, C3-7 cycloalkyl(Ci-6)alkyl, d-6 alkoxy(Ci-6)alkyl, Ci-6 alkoxycarbonyl (Ci-6)alkyl, Ci-6 alkylcarbonyl(Ci-6)alkyl, Ci-6 alkylaminocarbonyl(Ci-6)alkyl, di(d-e)alkylamino- carbonyl(Cι-6)alkyl, phenyl(d-6)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Cι-6 alkyl, Ci-6 haloalkyl, d-6 alkoxy or d-6 haloalkoxy), heteroaryl(Ci-6)alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d-6 haloalkyl, Cι-6 alkoxy or Ci.6 haloalkoxy), C2-6 alkenyl, C2-6 haloalkenyl, C2.6 alkynyl, C .7 cycloalkyl, Ci.6 alkoxycarbonyl, Ci-6 alkylcarbonyl, Ci_6 alkylaminocarbonyl, di(Ci-6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, _6 alkyl, Ci-6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy) or heteroaryl
(optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Ci-6 haloalkyl, d.6 alkoxy or Ci_6 haloalkoxy).
R5 is more preferably hydrogen, halogen, nitro, cyano, d-8 alkyl or d-6 haloalkyl. R5 is even more preferably hydrogen, halogen, cyano, d- alkyl or d-3 haloalkyl. R5 is most preferably hydrogen, halogen, d-3 alkyl or d-3 haloalkyl.
It is preferred that R6 is hydrogen, d-8 alkyl, d-6 haloalkyl, d-6 cyanoalkyl, CH2(C2-6)alkenyl, CH2(C2.6)haloalkenyl, CH2(C2.6)alkynyl, C3-7 cycloalkyl, C3-7 cycloalkyl(Cι-6)alkyl, Ci.6 alkoxy(Ci-6)alkyl, Cι_ alkoxycarbonyl, Cι.6 alkylcarbonyl, d-6 alkylaminocarbonyl, di(C1-6)alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, d-6 alkyl, Ci-e haloalkyl, d-6 alkoxy or d.6 haloalkoxy) or heteroaryl
(optionally substituted by halo, nitro, cyano, Ci-6 alkyl, d-6 haloalkyl, d_6 alkoxy or d-6 haloalkoxy).
It is more preferred that R6 is hydrogen, Cι-8 alkyl or Cι-6 haloalkyl. R7 is preferably substituted d-8 alkyl, optionally substituted [C2.6 alkenyl(Ci-6)alkyl], optionally substituted [C2-6 alkynyl(d-6)alkyl], substituted C3-7 cycloalkyl, substituted [C3-7 cycloalkyl(Cι-6)alkyl], substituted Ci-6 alkoxycarbonyl, substituted Ci-6 alkylcarbonyl, substituted d.6 alkylaminocarbonyl, substituted di(Cι-6)alkylaminocarbonyl, optionally substituted -6 alkylsulfonyl or optionally substituted arylsulfonyl; provided that R7 is not Ci-e haloalkyl, d-6 cyanoalkyl, C2-6 alkenyl, C2-6 alkynyl or C2-6 haloalkenyl.
It is preferred that R8 is cyano, nitro, Ci-6 alkyl, d-6 haloalkyl, C3-7 cycloalkyl(Ci.6)alkyl, C3.7 cycloalkyl, CH2(C2-6)alkenyl, CH2(C2-6)alkynyl, phenyl (optionally substituted by halo, nitro, cyano, d-6 alkyl, Ci-6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Ci-6 haloalkyl, d-6 alkoxy or Ci-6 haloalkoxy), Ci-6 alkylcarbonyl, d-6 alkoxycarbonyl, d-6 alkylamino, di(Ci-6)alkylamino, d-6 alkylcarbonylamino, Ci-6 alkoxycarbonylamino, Ci-6 alkoxy, Ci-6 alkylthio, d-6 haloalkylthio, d-6 alkylsulfinyl, Ci-6 haloalkylsulfinyl, d-6 alkylsulfonyl, Ci-6 haloalkylsulfonyl, arylthio, arylsulfinyl, arylsulfonyl or (d-6)alkylcarbonyloxy.
The compounds in Tables 1-101 illustrate compounds of the invention.
Table 1 provides 72 compounds of formula (IA) wherein q is 0; Y is O; Z is O; R4 is hydrogen; and R1, R2, R3 and B are as defined in Table 1.
Table 1
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Table 2 provides 72 compounds of formula (IA) wherein q is 0; Y is O; Z is O; R4 is methyl; and R1, R2, R3 and B are as defined in Table 1. Table 3 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R4 is ethyl and R1, R2, R3 and B are as defined in Table 1.
Table 4 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R4 is n-propyl and R1, R2, R3 and B are as defined in Table 1. Table 5 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R4 is wopropyl and R1, R2, R3 and B are as defined in Table 1.
Table 6 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R4 is n-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 7 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R4 is sec-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 8 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R4 is wøbutyl and R1, R2, R3 and B are as defined in Table 1.
Table 9 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R4 is tert-butyl and R1, R2, R3 and B are as defined in Table 1. Table 10 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R4 is neopentyl and R1, R2, R3 and B are as defined in Table 1.
Table 11 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R4 is 2,2,2-trifluoroethyl and R1, R2, R3 and B are as defined in Table 1.
Table 12 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R4 is pentafluoroethyl and R1, R2, R3 and B are as defined in Table 1.
Table 13 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is O, R4is heptafluoropropyl and R1, R2, R3 and B are as defined in Table 1.
Table 14 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R4 is methyl and R1, R2, R3 and B are as defined in Table 1. Table 15 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R4 is ethyl and R1, R2, R3 and B are as defined in Table 1.
Table 16 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R4 is ra-propyl and R1, R2, R3 and B are as defined in Table 1.
Table 17 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R4 is wopropyl and R1 , R2, R3 and B are as defined in Table 1.
Table 18 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R4 is n-butyl and R1, R2, R3 and B are as defined in Table 1. Table 19 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R4 is sec-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 20 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R4 is z obutyl and R1, R2, R3 and B are as defined in Table 1. Table 21 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R4 is tert-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 22 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R4 is neopentyl and R1, R2, R3 and B are as defined in Table 1.
Table 23 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R4 is 2,2,2-trifluoroethyl and R1 , R2, R3 and B are as defined in Table 1.
Table 24 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R4 is pentafluoroethyl and R1, R2, R3 and B are as defined in Table 1.
Table 25 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R4 is heptafluoropropyl and R1, R2, R3 and B are as defined in Table 1. Table 26 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is S, R4 is
2-methylprop-l-enyl and R1, R2, R3 and B are as defined in Table 1.
Table 27 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH3, R4 is methyl and R1, R2, R3 and B are as defined in Table 1.
Table 28 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH3, R4 is ethyl and R1 , R2, R3 and B are as defined in Table 1.
Table 29 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH3, R4 is n-propyl and R1, R2, R3 and B are as defined in Table 1.
Table 30 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH3, R4 is zsopropyl and R1, R2, R3 and B are as defined in Table 1. Table 31 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH3,
R4 is n-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 32 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH3, R4 is sec-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 33 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH3, R4 is .sobutyl and R1, R2, R3 and B are as defined in Table 1.
Table 34 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH3, R4 is tert-butyl and R1, R2, R3 and B are as defined in Table 1. Table 35 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH3, R4 is neopentyl and R1, R2, R3 and B are as defined in Table 1.
Table 36 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH3, R4 is 2,2,2-trifiuoroethyl and R1, R2, R3 and B are as defined in Table 1. Table 37 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH3,
R4 is pentafluoroethyl and R1, R2, R3 and B are as defined in Table 1.
Table 38 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is N-CH3, R4is heptafluoropropyl and R1, R2, R3 and B are as defined in Table 1.
Table 39 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R4 is methyl and R1, R2, R3 and B are as defined in Table 1.
Table 40 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R4 is ethyl and R1, R2, R3 and B are as defined in Table 1.
Table 41 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R4 is n-propyl and R1, R2, R3 and B are as defined in Table 1. Table 42 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R4 is zsopropyl and R1, R2, R3 and B are as defined in Table 1.
Table 43 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R4 is n-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 44 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R4 is sec-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 45 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R4 is zsobutyl and R1, R2, R3 and B are as defined in Table 1.
Table 46 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R4 is tert-butyl and R1, R2, R3 and B are as defined in Table 1. Table 47 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R4 is raeσpentyl and R1, R2, R3 and B are as defined in Table 1.
Table 48 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R4 is 2,2,2-trifluoroethyl and R1, R2, R3 and B are as defined in Table 1.
Table 49 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R4 is pentafluoroethyl and R1, R2, R3 and B are as defined in Table 1.
Table 50 provides 72 compounds of formula (IA) wherein q is 0, Y is O, Z is NH, R4 is heptafluoropropyl and R1, R2, R3 and B are as defined in Table 1 Table 51 provides 72 compounds of formula (IB) wherein q is 0; Y is O; Z is O; R4 is methyl; and R1, R2, R3 and B are as defined in Table 1.
Table 52 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R4 is ethyl and R1, R2, R3 and B are as defined in Table 1. Table 53 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R4 is n-propyl and R1, R2, R3 and B are as defined in Table 1.
Table 54 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R4 is z'søpropyl and R1, R2, R3 and B are as defined in Table 1.
Table 55 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R4 is n-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 56 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R4 is sec-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 57 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R4 is z'søbutyl and R1, R2, R3 and B are as defined in Table 1. Table 58 provides 72 compounds of formula (IB) wherem q is 0, Y is O, Z is O, R4 is tert-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 59 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R4 is ncopentyl and R1, R2, R3 and B are as defined in Table 1.
Table 60 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R4 is 2,2,2-trifluoroethyl and R1 , R2, R3 and B are as defined in Table 1.
Table 61 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R4 is pentafluoroethyl and R1, R2, R3 and B are as defined in Table 1.
Table 62 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is O, R4is heptafluoropropyl and R1, R2, R3 and B are as defined in Table 1. Table 63 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R4 is methyl and R1, R2, R3 and B are as defined in Table 1.
Table 64 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R4 is ethyl and R1, R2, R3 and B are as defined in Table 1.
Table 65 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R4 is n-propyl and R1, R2, R3 and B are as defined in Table 1.
Table 66 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R4 is zsøpropyl and R1, R2, R3 and B are as defined in Table 1. Table 67 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R4 is zz-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 68 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R4 is sec-butyl and R1, R2, R3 and B are as defined in Table 1. Table 69 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R4 is zsσbutyl and R1, R2, R3 and B are as defined in Table 1.
Table 70 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R4 is tert-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 71 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R4 is neøpentyl and R1, R2, R3 and B are as defined in Table 1.
Table 72 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R4 is 2,2,2-trifluoroethyl and R1, R2, R3 and B are as defined in Table 1.
Table 73 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R4 is pentafluoroethyl and R , R , R and B are as defined in Table 1. Table 74 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R4 is heptafluoropropyl and R1, R2, R3 and B are as defined in Table 1.
Table 75 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is S, R4 is 2-methylpropen-l-yl and R1, R2, R3 and B are as defined in Table 1.
Table 76 provides 72 compounds of formula (IB) wherem q is 0, Y is O, Z is N-CH3, R4 is methyl and R1 , R2, R3 and B are as defined in Table 1.
Table 77 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH3, R4 is ethyl and R1, R2, R3 and B are as defined in Table 1.
Table 78 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH3, R4 is n-propyl and R1, R2, R3 and B are as defined in Table 1. Table 79 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH3,
R4 is z'sσpropyl and R1, R2, R3 and B are as defined in Table 1.
Table 80 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH3, R4 is R-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 81 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH3, R4 is sec-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 82 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH3, R4 is z'søbutyl and R1, R2, R3 and B are as defined in Table 1. Table 83 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH3, R4 is tert-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 84 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH3, R4 is rceøpentyl and R1, R2, R3 and B are as defined in Table 1. Table 85 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH3,
R4 is 2,2,2-trifluoroethyl and R1, R2, R3 and B are as defined in Table 1.
Table 86 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH3, R4 is pentafluoroethyl and R1, R2, R3 and B are as defined in Table 1.
Table 87 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is N-CH3, R4 is heptafluoropropyl and R1 , R2, R3 and B are as defined in Table 1.
Table 88 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R4 is methyl and R1, R2, R3 and B are as defined in Table 1.
Table 89 provides 72 compounds of formula (IB) wherem q is 0, Y is O, Z is NH, R4 is ethyl and R1, R2, R3 and B are as defined in Table 1. Table 90 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R4 is n-propyl and R1, R2, R3 and B are as defined in Table 1.
Table 91 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R4 is z'søpropyl and R1, R2, R3 and B are as defined in Table 1.
Table 92 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R4 is n-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 93 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R4 is sec-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 94 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R4 is z'søbutyl and R1, R2, R3 and B are as defined in Table 1. Table 95 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R4 is tert-butyl and R1, R2, R3 and B are as defined in Table 1.
Table 96 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R4 is Reøpentyl and R1, R2, R3 and B are as defined in Table 1.
Table 97 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R4 is 2,2,2-trifluoroethyl and R1 , R2, R3 and B are as defined in Table 1.
Table 98 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R4 is pentafluoroethyl and R1, R2, R3 and B are as defined in Table 1. Table 99 provides 72 compounds of formula (IB) wherein q is 0, Y is O, Z is NH, R4 is heptafluoropropyl and R1, R2, R3 and B are as defined in Table 1.
Table 100 provides 48 compounds of formula (IC) wherein q is 0, Y is O, Z is N-R7, B is CH, R4 is H and R1, R2, R3 and R7 are as defined in Table 100. Table 100
Figure imgf000024_0001
Figure imgf000025_0001
Table 101 provides 48 compounds of formula (IC) wherein q is 0, Y is O, Z is N-R7 B 4 is CH3 and R1, R2, R3 and R7 are as defined in Table 100. 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 102 shows selected melting point and selected NMR data, all with CDC13 as the solvent (unless otherwise stated; if a mixture of solvents is present, this is indicated as, for example, (CDC13 / de-DMSO)), (no attempt is made to list all characterising data in all cases) for compounds of Tables 1-101.
Table 102
Figure imgf000026_0001
Table 102
Figure imgf000027_0001
The compounds of the invention may be made in a variety of ways. For example, a compound of formula (I) (wherein Y is oxygen) may be prepared by coupling an aminoisothiazole with a suitably substituted benzofuran, benzothiophene, indole or benzimidazole. For instance, the coupling of a 5-aminoisothiazole of formula (H) (where R1 and R2 are as defined above in relation to formula (I)) with an acylating agent (such as an acid chloride, carboxylic acid or ester) of formula (HI) [where B, Z, R4 and q are as defined above in relation to formula (I) and X is hydroxy, chlorine, alkoxy (preferably methoxy or ethoxy) or aryloxy (preferably phenoxy or pentafluorophenoxy)] under known conditions leads to a compound of formula of formula (ID) [which is a compound of formula (I) where Y is O and R3 is H].
Figure imgf000028_0001
(II) (III) (ID)
Suitable aminoisothiazoles are known compounds, or may be prepared from commercially available starting materials by methods described in the literature (for example, see the following documents and references therein: 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)]; Ronald E. Hackler, Kenneth W. Burrow Jr., Sylvester V. Raster and David I. Wickiser [J. Heterocyclic Chem., 26, 1575, (1989)] and Ronald E Hackler, Glen P Jourdan, Peter L Johnson, Brian Thoreen and Jack Samaratoni [WO9304580 Al]).
A compound of formula (IDA) [which is a compound of formula (DDT) wherein q is 1; X is alkoxy; and B, Z, and R4 are as defined above in relation to a compound of formula (I)] may be made from a compound of formula (IN) [wherein B, Z, and R4 are as defined above in relation to a compound of formula (I)] under known conditions:
Figure imgf000028_0002
(IV) (|II >
Alternatively, a compound of ormula (IDA) may be prepared by conversion of an appropriately substituted phenoxyacetic acid or phenoxyacetic ester, using a ring-synthesis method as described for the synthesis of a compound of formula (IN) below. A compound of formula (IHB) [which is a compound of formula (El) wherein q is 0;
X is hydroxy or alkoxy; and B, Z and R4 are as defined above in relation to a compound of formula (I)] may be made from a compound of formula (N) [wherein Hal is chlorine, bromine or iodine; and B, Z and R4 are as defined above in relation to a compound of formula (I)] by reaction with a suitably functionalised alkane (such as a derivative of malonic acid) under transition-metal (especially palladium) mediated cross-coupling conditions, followed by known procedures required to convert the cross-coupled product into a compound of formula (N). For example, a compound of formula (N) [wherein Hal is bromine] may be reacted with a derivative of malonic acid (such as diethyl malonate or ethyl trimethylsilyl malonate) under palladium catalysed cross-coupling conditions [see, for example, John F. Hartwig et al., J. Am. Chem. Soc, 121, 1473 (1999)] and the product obtained is then hydrolysed and decarboxylated to give a compound of formula (IHB).
Figure imgf000029_0001
(V) (MB)
Alternatively, a compound of formula (DIB) may be prepared by conversion of an appropriately substituted phenylacetic acid or phenylacetic ester, using a ring-synthesis method as described for the synthesis of a compound of formula (N) below. The syntheses of compounds of formula (IN) and formula (N) are well known (see for example, Alan R. Katritzky and Charles W. Rees [Comprehensive Heterocyclic Chemistry, Nol.4, Pergamon Press, 1984]) and similar methods may be utilised in the syntheses of compounds of formula (B); the examples given below represent just a few of the methods available for their syntheses. 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)] or from aryl fluorides by the method of Alexander J. Bridges, Arthur Lee, Emmanuel C. Manduakor and C. Eric Scwartz [Tetrahedron Letters, 33, 7499-7502 (1992)]; suitable thiophenols and aryl fluorides are known compounds or may be prepared by known methods. Benzofurans may be made, for example, from ørt/tø-halophenols as described by Henning Lutjens and Peter J Scammells [Tetrahedron Letters 39 (1998), 6581-6584], Terence C Owen et al. [Tetrahedron Letters 30, No 13, 1597 (1989)] and Fred G Schreiber and Robert Stevenson [J.C.S. Perkin 1, 90, 1977] or from ørtzø-hydroxybenzyl halides by the method of A Hercouet and M Le Corre [Tetrahedron, Vol 37, No 16, 2867 (1981)]. Indoles may be made from ørt/.ø-substituted anilines according to the methods of Cheng-yi Chen et al. [J. Org. Chem. 1997, 62, 2676], Takao Sakamoto et al. [J. Org. Chem. 1997, 62, 6507], CE. Castro et al. [J.Org. Chem., 1966, 31, 4071] and Alan D. Adams et al. [WO9827974]. Appropriate ørt/zø-substituted phenols and anilines are known compounds or may be prepared from known compounds by methods familiar to those skilled in the art. A compound of formula (I) [wherein Y is sulphur] may be prepared by reacting a compound of formula (I) [wherein Y is oxygen] with a suitable thionating agent (such as 2,4-bis(4-methoxyphenyl)- 1 ,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson' s reagent), 2,4-bis(methylthio)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Davy reagent methyl), 2,4-bis(pαra-tolyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Davy reagent p-tolyl) or phosphorus pentasulfide) in a suitable solvent (such as toluene or fluorobenzene).
A compound of formula (I) [wherein R is H and Y is oxygen] may be treated with an alkylating agent (such as an alkyl halide, dialkyl sulfate or trialkyloxonium salt), with a sulphenylating agent (such as a sulfenyl chloride), with a sulfonylating agent (such as a sulfonyl chloride) or with an acylating agent (such as an acid chloride), optionally in the presence of a base, to give a compound of formula (I) [where Y is oxygen and R3 is not H]. Alternatively, a compound of formula (I) [where Y is oxygen and R3 is alkoxymethyl] may be prepared from a compound of formula (I) [where Y is oxygen and R3 is H] by sequential reaction with formaldehyde and an alkylating agent; likewise, a compound of formula (I) [where Y is oxygen and R is acyloxymethyl] may be prepared by using an acylating agent instead of an alkylating agent.
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), Fraήkliniella 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), Luciϊlia spp. (blowflies), Blattella germanica (cockroach), Periplaneta americana (cockroach), Blatta orientalis (cockroach), termites of the Mastotermitidae (for example Mastotermes spp.), the Kalotermitidae (for example Neotermes spp.), the Rhinotermitidae (for example Coptotermes formosanus, Reticulitermes 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), Caenorhάbditis elegansfyinegax eelworm), Trichostrongylus spp. (gastro intestinal nematodes) and Deroceras reticulatum (slug).
The compounds of formula (I) are also active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae (Magnaporthe grisea) on rice and wheat and other Pyricularia spp. on other hosts; Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts (for example turf, rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental plants); Erysiphe cichoracearum on cucurbits (for example melon); Erysiphe graminis (powdery mildew) on barley, wheat, rye and turf and other powdery mildews on various hosts, such as Sphaerotheca macularis on hops, Sphaerotheca fusca (Sphaerotheca fuliginea) on cucurbits (for example cucumber), Leveillula taurica on tomatoes, aubergine and green pepper, Podosphaera leucotricha on apples and Uncinula necator on vines; Cochliobolus spp., Helminthosporium spp., Drechslera spp. (Pyrenophora spp.), Rhynchosporium spp., Mycosphaerella graminicola (Septoria tritici) and Phaeosphaeria nodorum (Stagonospora nodorum or Septoria nodorum), Pseudocercosporella herpotrichoides and Gaeumannomyces graminis on cereals (for example wheat, barley, rye), turf and other hosts; Cercospora arachidicola and Cercosporidium personatum on peanuts and other Cercospora spp. on other hosts, for example sugar beet, bananas, soya beans and rice; Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables, vines and other hosts and other Botrytis spp. on other hosts; Altemaria 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; Monϊlinia 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 (Glomereϊla cingulata), black rot or frogeye leaf spot (Botryosphaeria obtusa), Brooks fruit spot (Mycosphaerella pomi), Cedar apple rust (Gymnosporangium juniperi- virginianae), sooty blotch (Gloeodes pomigena), flyspeck (Schizothyrium pomi) and white rot (Botryosphaeria dothidea)) on apples and pears; Plasmopara viticola on vines; other downy mildews, such as Bremia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts, Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on cucurbits; Pythium spp. (including Pythium ultimum) on turf and other hosts; Phytophthora infestans on potatoes and tomatoes and other Phytophthora spp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco, cocoa and other hosts; Thanatephorus cucumeris on rice and turf and other Rhizoctonia spp. on various hosts such as wheat and barley, peanuts, vegetables, cotton and turf; Sclerotinia spp. on turf, peanuts, potatoes, oil-seed rape and other hosts; Sclerotium spp. on turf, peanuts and other hosts; Gibberella fujikuroi on rice; Colletotrichum spp. on a range of hosts including turf, coffee and vegetables; Laetisaria fuciformis on turf; Mycosphaerella spp. on bananas, peanuts, citrus, pecans, papaya and other hosts; Diaporthe spp. on citrus, soybean, melon, pears, lupin and other hosts; Elsinoe spp. on citrus, vines, olives, pecans, roses and other hosts; Verticillium spp. on a range of hosts including hops, potatoes and tomatoes; Pyrenopeziza spp. on oil-seed rape and other hosts; Oncobasidium theobromae on cocoa causing vascular streak dieback; Fusarium spp., Typhula spp., Microdochium nivale, Ustilago spp., Urocystis spp., Tilletia spp. and Claviceps purpurea on a variety of hosts but particularly wheat, barley, turf and maize; Ramularia spp. on sugar beet, barley and other hosts; post-harvest diseases particularly of fruit (for example Penicillium digitatum, Penicillium italicum and Trichoderma viride on oranges, Colletotrichum musae and Gloeosporium musarum on bananas and Botrytis cinerea on grapes); other pathogens on vines, notably Eutypa lota, 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, Aspergϊllus 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 YMN) 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 tolOkg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to lkg per hectare.
When used in a seed dressing, a compound of formula (I) is used at a rate of O.OOOlg 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 SOLNESSO 100, SOLNESSO 150 and SOLNESSO 200; SOLNESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), Ν- alkylpyrrolidones (such as Ν-methylpyrrolidone or Ν-octylpyrrolidone), dimethyl amides of fatty acids (such as C8-C10 fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water. Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of formula (I) is present initially in either the water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product. Aerosol formulations comprise a compound of formula (I) and a suitable propellant
(for example 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 «-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- z'søpropyl- and tri-z'søpropyl-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 electro dynamic 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) Jhdoxacarb; 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, -[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone, 4-chloro- 2-cyano-NJV-dimethyl-5-^-tolylimidazole-l-sulfonamide (IKF-916, cyamidazosulfamid), 3-5-dichloro-N-(3-chloro-l-ethyl-l-methyl-2-oxoproρyl)-4-methylbenzamide (RH-7281, zoxamide), N-allyl-4,5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide (MOΝ65500), _V- (1-cyano-l ,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide (AC382042), N-(2-methoxy-5-ρyridyl)-cyclopropane carboxamide, acibenzolar (CGA245704), alanycarb, aldimorph, anilazine, azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S, bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulphate, copper tallate and Bordeaux mixture, cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulphide l,l'-dioxide, dichlofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, O,O-di-z'sø-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-thioethylideneaminooxyc_ιrbonyl)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-z'søpropyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-Al, phosphorus acids, phthalide, picoxystrobin (ZA1963), polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, propionic acid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, sipconazole (F-155), sodium pentachlorophenate, spiroxamine, streptomycin, sulphur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamid, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl, thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin (CGA279202), triforine, triflumizole, triticonazole, validamycin A, vapam, vinclozolin, zineb and ziram. The compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
Examples of suitable synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.
Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
An example of a rice selective herbicide which may be included is propanil. An example of a plant growth regulator for use in cotton is PIX™.
Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.
The invention is illustrated by the following Examples:
EXAMPLE 1 This Example illustrates the preparation of Compound No.1 of Table No.4.
Step 1 - preparation of methyl 4-hvdroxy-3-iodophenylacetate. Iodine (3.1g, 12mmol) and potassium iodate (1.3g, 6mmol) were added to a solution of methyl 4-hydroxyphenylacetate (5.0g, 30mmol) in aqueous acetic acid (from 15ml of water and 60ml of glacial acetic acid) and the mixture was stirred at room temperature for 30hours. The solvent was removed in vacuo and then the residue was taken up in diethyl ether and washed sequentially with saturated aqueous sodium bicarbonate solution and sodium bisulfite solution, dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with a mixture of ethyl acetate and dichloromethane to give methyl 4-hydroxy-3-iodophenylacetate (3.6g).
1H NMR (CDC13) δ: 3.52(s,2H); 3.71(s,3H); 5.36(s,lH); 6.93(d,lH); 7.17(dd,lH); 7.59(d,lH)ppm. Step 2 - preparation of methyl (2-propylbenzofuran-5-yl acetate.
A mixture of methyl 4-hydroxy-3-iodophenylacetate (0.50g, 1.71mmol), 1-pentyne (0.125g, 1.78mmol) and cuprous oxide (0.155g,1.07mmol) in pyridine (7ml) was placed in a sealed tube and the mixture was heated at 120°C for 20hours. The mixture was cooled to room temperature, filtered and the filtrate was evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with a mixture of ethyl acetate:hexane 15:85 to give methyl(2-propylbenzofuran-5-yl)acetate (0.30g).
1H NMR (CDCI3) δ: 1.00(t,3H); 1.77(m,2H); 2.73(t,2H); 3.69(s,3H); 3.69(s,2H); 6.34(s,lH); 7.12(dd,lH); 7.37(m,2H)ppm.
Step 3 - preparation of [ N-(4-chloro-3-methylisothiazol-5-yl)-(2-proρylbenzofuran-5- yPacetamide.
5-Amino-4-chloro-3-methylisothiazole (0.176g, 1.18mmol) was added to a suspension of sodium methoxide (0.146g, 2.70mmol) in tetrahydrofuran (5ml) and the mixture was stirrred at room temperature for 20minutes. A solution of methyl (2-propylbenzofuran-5-yl)acetate (0.25 g, 1.08mmol) in tetrahydrofuran (2ml) was added dropwise and once the addition was complete the mixture was stirred at room temperature for 4hours. The mixture was quenched with water, made acidic with saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The organic extract was washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo to give Compound No. 1 of Table No. 4 (0.34g) as a colourless solid. EXAMPLE 2
This Example illustrates the preparation of Compound No. 6 of Table No. 4. CompoundNo. 1 of Table No. 4 (0.25g, 0.72mmol), prepared as in Example 1, was dissolved in dichloromethane (4ml) and N,O-bis(trimethylsilyl)acetamide (0.173g, 0.86mmol) was added. The mixture was stirred at room temperature for 15minutes and then a solution of chloromethyl ethyl ether (0.136g, 1.44mmol) was added. The mixture was stirred at room temperature for 20hours, quenched with saturated aqueous sodium bicarbonate solution and extracted with ethyl acetate. The organic extract was washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, initially eluting with ethyl acetate : hexane 15:85 and then with ethyl acetate:hexane 2:3 to give Compound No. 6 of Table No. 4 (0.15g) as a yellow oil and N-(2-ethoxyoxymethyl-4-chloro-3- methylisothiazolin-5-ylidene)-2-(propylbenzofuran-5-yl)acetamide (0.07g) as a solid, m.p.92- 93°C.
EXAMPLE 3 This Example illustrates the preparation of Compound No. 1 of Table No. 13. Step 1 - preparation of 2-hvdroxy-5-bromobenzyl alcohol.
Sodium borohydride (0.40g, O.Olmol) was added to a solution of 5-bromosalicylaldehyde (0.20g, O.Olmol) in tetrahydrofuran (30ml) and the mixture was stirred at room temperature for 4hours. The reaction was quenched by addition of dilute aqueous hydrochloric acid solution and the mixture extracted with ethyl acetate. The organic extract was dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo to give 2-hydroxy-5-bromobenzyl alcohol (1.95g) as a white solid, which was used without further purification in the next step.
Step 2 - preparation of 2-hvdroxy-5-bromobenzyl bromide.
A solution of triphenylphosphine (2.45g, 0.009mol) in diethyl ether (15ml) was added dropwise to a chilled (ice-bath) mixture of 2-hydroxy-5-bromobenzyl alcohol (1.95g,
0.009mol) and 1,2-dibromotetrachloroethane (3.05g, 0.009mol) in diethyl ether. Once the addition was complete, the cooling bath was removed and the mixture stirred at room temperature for 2hours. The reaction mixture was filtered and the filtrate evaporated in vacuo to afford 2-hydroxy-5-bromobenzyl bromide (2.65g), which was used without further purification in the next step. Step 3 - preparation of (2-hvdroxy-5-bromobenzyl triphenylphosphonium bromide.
A mixture of triphenylphosphine (2.56g, 0.009mol) and 2-hydroxy-5-bromobenzyl bromide (2.6g, 0.009mol) in toluene (30ml) was stirred and heated at 100°C for 2hours. The mixture was cooled to room temperature and the precipitate was collected by filtration to yield (2-hydroxy-5-bromobenzyl)triphenylphosphonium bromide (4.25g) which was used without further purification in the next step.
Step 4 - preparation of 5-bromo-2-heptafluoropropylbenzofuran.
A solution of heptafluoropropionyl chloride (1.06g, 0.0045mol) in chloroform (5ml) was added dropwise to a stirred slurry of (2-hydroxy-5-bromobenzyl)triphenyl phosphonium bromide (1.6g, 0.003mol) in chloroform (30ml) and the mixture was stirred at room temperature for 30minutes and then at 50°C for 2hours (during this time the solid dissolved). The mixture was cooled to room temperature then toluene (60ml) was added and the reaction mixture was concentrated in vacuo until a volume of approximately 30ml remained. Triethylamine (0.92g, 0.009mol) was added and the mixture was heated to reflux for 2hours. The mixture was cooled to room temperature, filtered and the filtrate was evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with dichloromethane, and was purified further by flash column chromatography on silica gel, eluting with hexane to give 5-bromo-2-heptafluoropropylbenzofuran (l.Og).
1H NMR (CDC13) δ: 7.20(s,lH); 7.48(d,lH); 7.56(d,lH); 7.83(s,lH)ppm. Step 5 - preparation of ethyl (2-heptafluoropropylbenzofuran-5-yl)acetate.
Ethyl trimethylsilyl malonate (0.39g, 0.0019mol) was added to a mixture of 5-bromo- 2-heptafluoropropylbenzofuran (0.577g, 0.0016mol) and palladium acetate (0.018g, O.OOOlmol) in toluene (7ml) and the mixture was stirred at room temperature. Potassium tert-butoxide (Imolar solution in tetrahydrofuran; 1.67ml) and tri-tert-butylphosphine (Imolar solution in toluene; 0.16ml) were added sequentially. Nitrogen gas was bubbled through the reaction mixture for lOminutes and then the mixture was stirred and heated at 90°C for 90minutes. The mixture was cooled to room temperature and filtered through Hyflo Super Cel® diatomaceous earth. The filtrate was washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with ethyl acetate:hexane 3:37 to give ethyl (2-heptafluoropropylbenzofuran-5-yl)acetate (0.5 lg). 1H NMR (CDCI3) δ: 1.28(t,3H); 3.73 (s,2H); 4.18(q,2H); 7.22(s,lH); 7.38(d,lH); 7.55(d,lH); 7.61(s,lH)ppm.
Step 5 - preparation of [ N-(4-chloro-3-methylisothiazol-5-yl -(2- heptafluoropropylbenzofuran-5-yl)acetamide. 5-Amino-4-chloro-3-methylisothiazole (0.224g, 0.0015mol) was added to a suspension of sodium methoxide (0.192g, 0.0036mol) in tetrahydrofuran (5ml) and the mixture was stirrred at room temperature for 20minutes. A solution of ethyl (2-heptafluoropropylbenzofuran-5-yl)acetate (0.5 lg, 0.0014mol) in tetrahydrofuran (3ml) was added dropwise and once the addition was complete the mixture was stirred at room temperature for 3hours. The mixture was quenched with water, made acidic with saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The organic extract was washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with ethyl acetate:hexane 1:3 to give Compound No.l of Table No.13 (0.52g) as a colourless solid, m.p. 136-137°C.
EXAMPLE 4 This Example illustrates the preparation of Compound No.l of Table No.69. Step 1 - preparation of methyl 6-bromobenzothiophene-2-carboxylate. Sodium hydride (60% dispersion in oil; 0.59g, 0.0015mol) was weighed into a round- bottomed flask, washed twice with hexane and then dimethylsulfoxide (15ml) and methyl thioglycollate (0.97ml, 0.01 lmol) were introduced. The mixture was stirred for lOminutes and 4-bromo-2-fluorbenzaldehyde (2.0g, O.Olmol) was added. The temperature of the reaction rose to 40°C and the mixture was stirred for 15minutes before being poured onto a stirred ice-water mixture. The precipitate was collected by filtration, and purified by flash column chromatography on silica gel, eluting with ethyl acetate:hexane 1:1 to give methyl 6-bromobenzothiophene-2-carboxylate (2.16g) as a white solid.
1H NMR (CDC13) δ: 3.96(s,3H); 7.53(dd,lH); 7.74(d,lH); 7.97-8.04(m,2H)ppm. Step 2 - preparation of 6-bromo-2-(hvdroxymethyl)benzothiophene. Diisobutylaluminium hydride (1 molar solution in heptane; 9.5ml) was added dropwise to a solution of methyl 6-bromobenzothiophene-2-carboxylate (1.17g, 0.0043mol) in toluene (120ml) at -78°C and once the addition was complete the mixture was stirred for 15rninutes, quenched with dilute aqueous hydrochloric acid and then extracted with ethyl acetate. The organic extract was washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with ethyl acetate:hexane 1:4 to give 6-bromo- 2-(hydroxymethyl)benzothiophene (0.90g) as a white solid. 1H NMR (CDC13) δ: 1.96 (br,lH); 4.94(br.s,2H); 7.2(s,lH); 7.45(dd,lH); 7.60(d,lH);
7.96 (br.s,lH)pρm.
Step 3 - preparation of 6-bromobenzothiophene-2-carboxaldehvde. A solution of dimethylsulfoxide (0.58ml, 0.008mol) in dichloromethane (5ml) was added dropwise to a solution of oxalyl chloride (0.36ml, 0.004mol) in dichloromethane (15ml) at -78°C and the mixture was stirred for 5minutes, during which time the temperature rose to -60°C. A solution of 6-bromo-2-(hydroxymethyl) benzothiophene (0.90g, 0.0037mol) in a mixture of dichloromethane (7ml) and dimethylsulfoxide (0.5ml) was added dropwise, maintaining the temperature below -60°C by external cooling. The mixture was stirred for 30minutes, triethylamine (2.6ml, 0.019mol) was added and the mixture was stirred at -60°C for a further 5minutes and then allowed to warm to room temperature and stirred for 3hours. The mixture was poured into water and extracted with dichloromethane. The organic extract was dried over anhydrous magnesium sulfate, filtered and the filtrate evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with ethyl acetate:hexane 1:4 to give 6-bromobenzothiophene-2-carboxaldehyde (0.786g) as a cream solid.
1HNMR (CDC13) δ: 7.55(d,lH); 7.79(d,lH); 7.97(s,lH); 8.07(s,lH); 10.06(s,lH)ppm.
Step 4 - preparation of 6-bromo-2-(2-methylprop-l-enyl benzothiophene. n-Butyllithium (2.5molar solution in hexanes; 2.25ml) was added dropwise to a solution of isopropyltriphenylphosphonium iodide (2.56g, 0.006mol) in tetrahydrofuran
(43ml) at -25°C and the mixture was stirred for 5minutes and then allowed to warm to -5°C. A solution of 6-bromobenzothiophene-2-carboxaldehyde (0.71g, 0.003mol) in tetrahydrofuran (20ml) was added dropwise and, once the addition was complete, the mixture was allowed to warm to 5°C and was stirred for 2hours. The mixture was quenched by addition of dilute aqueous hydrochloric acid and extracted with ethyl acetate. The organic extract was washed with water and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with ethyl acetate:hexane 1:4 to give 6-bromo-2-(2- methylprop- 1 -enyl)-benzothiophene (0.545g) .
1H NMR (CDC13) δ: 1.96(s,3H); 2.06(s,3H); 6.40(s,lH); 7.03(s,lH); 7.40(d,lH); 7.54(d,lH); 8.88(s,lH)ppm. Step 5 - preparation of 6-bromo-2-(2-methylpropyl)benzothiophene.
A solution of 6-bromo-2-(2-methylprop-l-enyl)benzothiophene (0.44g, 0.0016mol) in ethanol (20ml) was hydrogenated (at 4bar pressure of hydrogen) over a catalytic amount of 3% platinum on carbon. Once the reaction was complete, as judged by thin layer chromatography, the catalyst was removed by filtration through Hyflo Super Cel® diatomaceous earth and the filtrate was evaporated in vacuo. The residue was further purified by flash column chromatography on silica gel, eluting with diethyl etheπhexane 1:9 to give 6-bromo-2-(2-methylpropyl)benzothiophene (0.229g).
1H NMR (CDC13) δ: 0.98(d,6H); 1.98(m,lH); 2.76(d,2H); 6.95(s,lH); 7.41(d,lH); 7.53(d,lH); 7.89(d,lH)ppm. Step 6 - preparation of ethyl r2-(2-methylpropyl)benzothiophen-6-yriacetate.
Ethyl trimethylsilyl malonate (0.20g, O.OOlmol) was added to a mixture of 6-bromo-2- (2-methylpropyl)benzothiophene (0.229g, 0.00085mol) and palladium acetate (0.0095g, 0.0004mol) in toluene (2.3ml) and the mixture was stirred at room temperature. Potassium tert-butoxide (Imolar solution on tetrahydrofuran; 0.89ml) and tri-tert-butylphosphine (0.0086g, 0.000043mol) were added sequentially. Nitrogen gas was bubbled through the reaction mixture for 15minutes and then the mixture was stirred and heated at 80°C for 90minutes. The mixture was cooled to room temperature and filtered through Hyflo Super Cel® diatomaceous earth. The filtrate was washed with water and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with diethyl etheπhexane 1:9 to give ethyl [2-(2-methylpropyl) benzothiophen-6-yl] acetate (0.146g).
1H NMR (CDC13) δ: 0.98(d,6H); 1.26(t,3H); 1.98(m,lH); 2.76(d,lH); 3.68(s,2H); 4.06(q,2H); 6.95(s,lH); 7.24(d,lH); 7.61(d,lH); 7.67(s,lH)ppm.
Step 7 - preparation of T N-(4-chloro-3-methylisothiazol-5-yl)-.2-(2- methylpropyl benzothiophen-6-yl acetamide.
5-Amino-4-chloro-3-methylisothiazole (0.079g, 0.0005mol) was added to a suspension of sodium methoxide (0.029g, 0.0005mol) in tetrahydrofuran (0.5ml) and the mixture was stirrred at room temperature for 20minutes. A solution of ethyl [2-(2- methylpropyl)benzothiophen-6-yl]acetate (0.134g, 0.0005mol) in tetrahydrofuran (1ml) was added dropwise and, once the addition was complete, the mixture was stirred at room temperature overnight. The mixture was quenched with water, made acidic with dilute aqueous hydrochloric acid solution and extracted with ethyl acetate. The organic extract was washed with water and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo . The residue was purified by flash column chromatography on silica gel, eluting with ethyl acetate :hexane 1:4 to give Compound No.l of Table No.69.
EXAMPLE 5 This Example illustrates the preparation of Compound No.1 of Table No.45.
Step 1 - preparation of methyl 4-amino-3-iodophenylacetate. Methyl 4-aminophenylacetate (5.0g, 0.03mol) was dissolved in a mixture of glacial acetic acid (100ml) and water (26ml) and the resulting solution was cooled in an ice bath to below 5°C. Potassium iodate (1.3g, 0.006mol) and iodine (3.1g, 0.012mol) were added and the mixture was stirred for lhour and then the cooling bath was removed and the mixture was stirred at room temperature for a further lδhours. The mixture was poured into water and extracted with ethyl acetate. The organic extract was washed with saturated aqueous bicarbonate solution and saturated aqueous sodium bisulfite solution, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo. The residue was purified by chromatography on silica gel (gradient elution, hexane and ethyl acetate) to give methyl 4-amino-3-iodophenylacetate (6.0g) as an orange oil.
1H NMR (CDC13) δ: 3.48(s,2H); 3.69(s,3H); 4.07(br,2H); 6.7(d,lH); 7.07(dd,lH); 7.56(d,lH)ppm.
Step 2 - preparation of methyl 4-amino-3-(4-methylpent-l-vnyl)phenylacetate. A mixture of methyl 4-amino-3-iodophenylacetate (2.0g, 0.007mol), 4-methyl-l- pentyne (0.4ml, 0.0034mol), coρρer(I) iodide (0.0065g, O.00035mol) and dichlorobis(triphenylphosphine)palladium(π) (0.24g, 00035mol) was stirred in diethylamine (50ml) at 60 °C for 3hours and was then allowed to stand at room temperature overnight. The reaction mixture was partititoned between brine and ethyl acetate and the organic extract was dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo. Purification by column chromatography on silica gel gave methyl 4-amino-3-(4-methylpent- l-ynyl)phenylacetate (1.34g) as a brown oil. 1HNMR (CDCI3) δ: 1.06(d,6H); 1.87(m,lH); 2.37(d,lH); 3.48(s,2H); 3.69(s,3H); 4.16(br,2H); 6.64(d,lH); 7.0(dd,lH); 7.18(d,lH)ppm.
Step 3 - preparation of methyl [2-(2-methylpropyl)indol-5-yl] acetate. A mixture of methyl 4-amino-3-(4-methylpent-l-ynyl)phenylacetate (1.04g, 0.0042mol) and coρper(I) iodide (1.60g, 0.0085mol) in N,N-dimethylformamide (30ml) was stirred and heated at 110°C for 3hours and was then cooled to room temperature. The mixture was partitioned between water and ethyl acetate and the organic extract was filtered through Hyflo Super Cel® diatomaceous earth, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo. The residue was purified by flash column chromatography on silica gel (ethyl acetate / hexane gradient elution) to give methyl [2-(2-methylpropyl)indol-5-yl]acetate (0.65g) as a yellow oil.
1HNMR (CDC13) δ: 0.97 (d,6H); 1.98 (m,lH); 2.61 (d,2H); 3.68(s,3H); 3.70(s,2H); 6.19(m,lH); 7.02(dd,lH); 7.23(d,lH); 7.42(d,lH); 7.85(br,lH)ppm.
Step 4 - preparation of {N-(4-chloro-3-methylisothiazol-5-yl)-r2-(2-methylρropyl)- indol-5-yllacetamide I .
5-Amino-4-chloro-3-methylisothiazole (0.22g, 0.0015mol) was added to a suspension of sodium methoxide (0.18g, 0.003mol) in tetrahydrofuran (5ml) and the mixture was stirrred at room temperature for 30minutes. A solution of methyl [2-(2-methylpropyl)indol-5- yl]acetate (0.325g, 0.0013mol)in tetrahydrofuran (5ml) was added dropwise and, once the addition was complete, the mixture was stirred at room temperature for 4hours. The mixture was partitioned between water and extracted with ethyl acetate. The organic extract was washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate was evaporated in vacuo. The residue was purified by flash column chromatography on silica gel, eluting with ethyl acetate / hexane (gradient elution) to give Compound No.l of Table No.45 (0.176g).
EXAMPLE 6 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 balteatd). 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 103, 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 103
Figure imgf000053_0001
EXAMPLE 7 This Example illustrates the fungicidal properties of compounds of formula (I). The compounds were tested against a variety of foliar fungal diseases of plants. The techniques employed were as follows.
Plants were grown either in John Lines Potting Compost (No.l or 2) in 4cm diameter, 3.5cm depth minipots or on an artificial, cellulose based growing medium. The test compounds were individually formulated as a solution either in acetone or acetone/ethanol (1 : 1 by volume) which was diluted in reverse osmosis water to a concentration of lOOppm (that is, lmg of compound in a final volume of 10ml) immediately before use. When foliar sprays were applied to monocotyledonous crops, TWEEN 20 (0.1% by volume) was added. TWEEN is a registered trade mark.
Individual compounds of formula (I) were applied as a foliar (Prot) application (where the chemical solution was applied to the foliage of the test plants by spraying the foliage to maximum droplet retention) or as a systemic (Syst) application (where the chemical was added to a small beaker in which the test plant pots were standing).
These tests were carried out against Plasmopara viticola (PLASNI) on vines; Phytophthora infestans ly coper sici (PHYTIΝ) on tomatoes; and Blumeria graminis f.sp. tritici (ERYSGT), Stagonospora nodorum (LEPTΝO) and Puccinia triticina (PUCCRT) on wheat. Each treatment was applied to two or more replicate plants for Plasmopara viticola and Phytophthora infestans lycopersici and in all tests where the cellulose growing medium was employed. In minipot tests on Blumeria graminis f.sp. tritici, Stagonospora nodorum and Puccinia triticina, two replicate pots each containing 6 tolO plants were used for each treatment. The plants were inoculated with a calibrated fungal spore either 6hours or one day after chemical application.
After chemical application and inoculation, the plants were incubated under high humidity conditions and then put into an appropriate environment to allow infection to proceed, until the disease was ready for assessment. The Blumeria graminis f.sp. tritici plants were inoculated using a 'shake' inoculation technique. For Plasmopara viticola, the plants were reincubated under high humidity conditions for 24hours prior to assessment. The time period between chemical application and assessment varied from five to nine days according to the disease and environment. However, each individual disease was assessed after the same time period for all the compounds tested against that particular disease.
Assessments were performed on a single leaf of each of the two replicate plants for Plasmopara viticola and on each of two leaves on each of the replicate plants for
Phytophthora infestans lycopersici. For Blumeria graminis f.sp. tritici, Stagonospora nodorum and Puccinia triticina, assessments were carried out collectively on the plants in each replicate minipot or cellulose medium. The disease level present (that is, the percentage leaf area covered by actively sporulating disease) was assessed visually. For each treatment, the assessed values for all its replicates were meaned to provide mean disease values. Untreated control plants were assessed in the same manner. The data were then processed by either of two alternative methods, described below, each providing its own PRCO (Percentage Reduction from Control) value. All assessments on plants grown on cellulose media (and some grown in soil) used method 1. METHOD 1
This method uses banded assessment values.
The mean disease values are banded in the manner shown below. If the disease level value falls exactly mid-way between two of the points, the result will be the lower of the two points. 0 = 0% disease present 10 = 5.1-10% disease present
1 = 0.1-1% disease present 20 = 10.1-20% disease present 3 = 1.1-3% disease present 30 = 20.1-30% disease present 5 = 3.1-5% disease present 60 = 30.1-60% disease present
90 = 60.1-100% disease present
An example of a typical banded calculation is as follows:
Mean disease level for treatment A = 25% Therefore banded mean disease level for treatment A = 30 Mean disease level on untreated controls = 85% Therefore banded mean disease level on untreated controls = 90
PRCO = 100 - { Banded mean disease level for treatment A } x 100 {Banded mean disease level on untreated controls}
= 100 - (30 x 100) = 66.7 90
The PRCO is then rounded to the nearest whole number; therefore, in this particular example, the PRCO result is 67.
METHOD 2
This method uses unhanded assessment values (that is, the mean disease values are used in the PRCO calculation without a banding step).
An example of a typical unhanded calculation is as follows:
Mean disease level for treatment A = 25% Mean disease level on untreated controls = 85%
PRCO = 100 - { Mean disease level for treatment A } x 100 {Mean disease level on untreated controls}
= 100 - (25 x 100) = 70.6 85 The PRCO is then rounded to the nearest whole number; therefore, in this particular example, the PRCO result is 71.
It is possible for negative PRCO values to be obtained. Results are displayed in Table 104.
TABLE 104
Figure imgf000056_0001
Key to Table 104:
ERYSGT = Blumeria graminis f.sp. tritici LEPTNO = Stagonospora nodorum PLASNI = Plasmopara viticola PHYTIN = Phytophthora infestans lycopersici PUCCRT = Puccinia recondita

Claims

A compound of formula (I):
Figure imgf000057_0001
wherein q is 0 or 1 ; B is CR5 and Z is O, S or NR6 or B is N and Z is NR7; Y is O, S or NR8; R1 is hydrogen, halogen, optionally substituted Ci-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted Ci-6 alkoxy, optionally substituted Ci-6 alkylthio, optionally substituted C3-7 cycloalkyl, cyano, nitro or SF5; R2 is hydrogen, halogen, optionally substituted Ci-6 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted Ci-6 alkoxy, optionally substituted Ci-6 alkylthio, optionally substituted Ci.6 alkylsulfinyl, optionally substituted d_6 alkylsulfonyl, cyano, nitro, formyl, C(R9)=NOR10, optionally substituted d-6 alkylcarbonyl, optionally substituted Ci_6 alkoxycarbonyl or SF5; or R1 and R2 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated ring carbocylic or heterocyclic ring which may contain one or two hetero atoms selected from O, N or S and which may be optionally substituted by d_6 alkyl, d-6 haloalkyl or halogen; R3 is hydrogen, d-6 alkyl, CH2(d-4 haloalkyl), d-6 cyanoalkyl, C3.6 alkenyl, C3-6 alkynyl, Ci-e alkoxy(Cι-e)alkyl, Cι-6 alkylthio(d-6)alkyl, Ci-6 alkoxy(Ci-6)alkoxy(Ci-6)alkyl, d-6 alkylcarbonyl, Cι-6 alkoxycarbonyl, formyl, Ci_6 alkylcarbonyl(Ci-6)alkyl, d-6 alkoxycarbonyl(d-6)alkyl, Ci_6 alkylaminocarbonyl, di(C1-6)alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted phenyl(d-4)alkyl or S(O)rRπ; R4 is hydrogen, halogen, cyano, d,8 alkyl, Ci-6 haloalkyl, Ci-6 cyanoalkyl, C2-6 alkenyl, C2-6 alkynyl, C3-7 cycloalkyl, C3-7 halocycloalkyl, C3-7 cyanocycloalkyl, d.3 alkyl(C3.7)cycloalkyl, Cι_3 alkyl(C3-7) halocycloalkyl, C3-6 cycloalkyl(Ci-6)alkyl, C5-6 cycloalkenyl, C5.6 cycloalkenyl(d-6) -alkyl, C2-6 haloalkenyl, d-6 cyanoalkenyl, d-6 alkoxy(Ci-6)alkyl, formyl, Ci-6 carboxyalkyl, Ci-6 alkylcarbonyl(Cι-6)alkyl, d-e alkoxycarbonyl(C1.6)alkyl, d-6 alkylthio(Cι-6)alkyl, d-6 alkylsulfinyl(Ci-6)alkyl, Ci-6 alkylsulfonyl(Ci-6)alkyl, aminocarbonyl(Ci_6)alkyl, d-6 alkylaminocarbonyl(Ci-6)alkyl, di(Ci-6)alkylaminocarbonyl(Ci-6)alkyl, Ci-6 alkoxycarbonyl, Ci-6 alkylcarbonyl, aminocarbonyl, Ci-6 alkylaminocarbonyl, di(Cι-6)alkylaminocarbonyl, optionally substituted phenyl, optionally substituted phenyl(d-4)alkyl, optionally substituted phenyl(C2-4)alkenyl, optionally substituted heteroaryl, optionally substituted heteroaryl(Ci-4)alkyl, optionally substituted heterocyclyl, optionally substituted heterocyclyl(Ci-4)alkyl, a group OR12, a group SH, a group S(O)pR13, a group NR14R15, a group C(R16)=NOR17 or a group C(R18)=NNR19R20; R5 is hydrogen, halogen, nitro, cyano, optionally substituted d.8 alkyl, optionally substituted C2-6 alkenyl, optionally substituted C2-6 alkynyl, optionally substituted C3-7 cycloalkyl, optionally substituted Ci-6 alkoxycarbonyl, optionally substituted Ci-6 alkylcarbonyl, optionally substituted d.6 alkylaminocarbonyl, optionally substituted di(Ci.6)alkylaminocarbonyl, optionally substituted phenyl or optionally substituted heteroaryl; R6 is hydrogen, cyano, optionally substituted d-8 alkyl, optionally substituted [C2-6 alkenyl(Ci-6)alkyl], optionally substituted [C2-6 alkynyl(Ci-6)alkyl], optionally substituted C3.7 cycloalkyl, optionally substituted [C3.7 cycloalkyl(d-6) alkyl], Ci-6 alkoxy(Ci-6)alkyl, optionally substituted d-6 alkoxycarbonyl, optionally substituted Ci-6 alkylcarbonyl, optionally substituted Ci-6 alkylaminocarbonyl, optionally substituted di(Cι-6)alkylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl; R7 is substituted d-8 alkyl, optionally substituted [C2-6 alkenyl(Ci-6)alkyl], optionally substituted [C2-6 alkynyl(d-6)alkyl], substituted C3-7 cycloalkyl, substituted [C3-7 cycloalkyl(d-6)a-kyl], substituted Ci-6 alkoxycarbonyl, substituted Ci-6 alkylcarbonyl, substituted Ci-6 alkylaminocarbonyl, substituted di- (Cι-6)alkylaminocarbonyl, optionally substituted alkylsulfonyl or optionally substituted arylsulfonyl; provided that R7 is not Ci-6 haloalkyl, d_6 cyanoalkyl, C2.6 alkenyl, C2-6 alkynyl or C2-6 haloalkenyl ;R8 is hydrogen, cyano, nitro, optionally substituted d-6 alkyl, optionally substituted C - 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 d-6 alkylcarbonyl, optionally substituted d-6 alkoxycarbonyl, optionally substituted Ci-6 alkylamino, optionally substituted di(Ci-6)alkylamino, optionally substituted d-6 alkylcarbonylamino, optionally substituted Cι_6 alkoxycarbonylamino, optionally substituted Ci_6 alkoxy, optionally substituted d-6 alkylthio, optionally substituted Ci-6 alkylsulfinyl, optionally substituted d-6 alkylsulfonyl, optionally substituted arylthio, optionally substituted arylsulfinyl, optionally substituted arylsulfonyl or d-6 acyloxy; R9 is hydrogen, optionally substituted phenyl or optionally substituted Ci-6 alkyl; R10 is hydrogen, optionally substituted phenyl (Cι-2)alkyl or optionally substituted Cι-2o alkyl; R11 is d-6 alkyl, d-6 haloalkyl or optionally substituted phenyl; R12 is hydrogen, Ci-6 alkyl, d-6 haloalkyl, C3-6 alkenyl, Cι-4 cyanoalkyl, Cι-6 alkoxycarbonyl(Cι-6)alkyl, optionally substituted phenyl, optionally substituted phenyl(Ci-4)alkyl, optionally substituted heteroaryl, N=C(CH3)2; R13 is Ci-6 alkyl, d-6 haloalkyl, C3-6 alkenyl, cyano, d-4 cyanoalkyl, Ci-6 alkoxycarbonyl(d-6)alkyl, optionally substituted phenyl, optionally substituted phenyl(Ci-4)alkyl or optionally substituted heteroaryl; R14 and R15 are, independently, hydrogen, d-8 alkyl, C3-7 cycloalkyl, C3-6 alkenyl, C -6 alkynyl, C2-6 haloalkyl, Cι-6 alkoxy(Ci.6)alkyl, Ci-6 alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, Ci.6 alkylcarbonyl, Ci-6 alkylSO , optionally substituted phenylSO2 or optionally substituted phenyl(d-4) alkyl; R16 is d-6 alkyl; R17 is d-6 alkyl or optionally substituted phenyl(d_2)alkyl; R18 is Ci-6 alkyl; R19 and R20 are, independently, hydrogen, optionally substituted d-6 alkyl or optionally substituted phenyl; and p and r are, independently, 0, 1 or 2.
A compound of formula (I) according to claim 1 which is a compound of formula (IA):
Figure imgf000059_0001
wherein q, B, Y, Z, R .1 , r R>2 , τ R.3 and R are as claimed in claim 1.
A compound of formula (I) according to claim 1 which is a compound of formula (IB):
Figure imgf000060_0001
wherein q, B, Y, Z, R .1 , R r 2 , r R>3 a „„nd , r R>4 are as claimed in claim 1.
4. A compound of formula (I) according to claim 1 which is a compound of formula (IC):
Figure imgf000060_0002
wherein q, B, Y, Z, R1, R2, R3 and R4 are as claimed in claim 1.
A compound according to any preceding claim where R is hydrogen, halogen, Ci-6 alkyl, Ci-6 cyanoalkyl, Ci-6 haloalkyl, C3-7 cycloalkyKd-^alkyl, d-6 alkoxy(Cι- 6)alkyl, C2-6 alkenyl, C2.6 alkynyl, d.6 alkoxy, Ci-e haloalkoxy, d-6 alkylthio, d.6 haloalkylthio, C3_6 cycloalkyl, cyano, nitro or SF5.
A compound according to any preceding claim where R is hydrogen, halogen, Ci.6 alkyl, d.6 haloalkyl, d_6 alkoxy(Cι.6)alkyl, C2-6 alkenyl, d-6 alkynyl, d-6 alkoxy, Ci-6 haloalkoxy, Ci-6 alkylthio, Ci-6 haloalkylthio, Ci-6 alkylsulfinyl, d.6 haloalkylsulfinyl, d_6 alkylsulfonyl, d-6 haloalkylsulfonyl, cyano, nitro, formyl, Ci-6 alkylcarbonyl, d-6 alkoxycarbonyl or CH=NOR10; 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, d-6 haloalkyl or halogen; where R is phenyl(Cι_2)alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, Ci-6 alkyl, Cι-6 haloalkyl, Ci-6 alkoxy or Ci-6 haloalkoxy) or Ci-6 alkyl.
7. A compound according to any preceding claim where R3 is hydrogen, Ci-6 alkyl, C1-6alkoxy(C1-6)alkyl, C3.6 alkenyl, C3-6 alkynyl, d-6 alkylcarbonyl or d-6 alkoxycarbonyl.
8. A compound according to any preceding claim where R4 is d-8 alkyl, Ci-e haloalkyl, d-6 cyanoalkyl, C2-6 alkenyl, C2-6 alkynyl, C3-7 cycloalkyl, C3-7 halocycloalkyl, C3-7 cyanocycloalkyl, Cι-3 alkyl(C3-7)cycloalkyl, C!-3 alkyl(C3-7)halocycloalkyl, C3-6 cycloalkyl(Ci-6)alkyl, C5-6 cycloalkenyl, C5.6 cycloalkenyl(Cι-6)alkyl, C2-6 haloalkenyl, Ci-6cyanoalkenyl, Cι-6 alkoxy(Cι-e)alkyl, d-6 alkylcarbonyl(Ci-6)alkyl, Ci-6 alkoxycarbonyl(Ci-6)alkyl, d-6 alkylthio(Cι-6)alkyl, d-6 alkylsulfinyl(Ci.6)alkyl, Ci-6 alkylsulfonyl(Cι-6)alkyl, d-6 alkoxycarbonyl, Ci-6 alkylcarbonyl, optionally substituted phenyl or optionally substituted heterocyclyl.
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, a compound of formula (IA) as claimed in claim 2, a compound of formula (IB) as claimed in claim 3 or a compound of formula (IC) as claimed in claim 4; 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, a compound of formula (IA) as claimed in claim 2, a compound of formula (IB) as claimed in claim 3 or a compound of formula (IC) as claimed in claim 4.
1. 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, a compound of formula (IA) as claimed in claim 2, a compound of formula (IB) as claimed in claim 3 or a compound of formula (IC) as claimed in claim 4.
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US7973069B2 (en) 2004-07-14 2011-07-05 Ptc Therapeutics, Inc. Methods for treating hepatitis C

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WO1998005670A1 (en) * 1996-07-31 1998-02-12 Bayer Aktiengesellschaft Substituted n-isothiazolyl-(thio)amides
WO1999010334A1 (en) * 1997-08-22 1999-03-04 Bayer Aktiengesellschaft Acylated 5-aminoisothiazoles as pesticides and fungicides
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WO1995031448A1 (en) * 1994-05-17 1995-11-23 Dowelanco N-(5-isothiazolyl)amide pesticides
WO1998005670A1 (en) * 1996-07-31 1998-02-12 Bayer Aktiengesellschaft Substituted n-isothiazolyl-(thio)amides
WO1999010334A1 (en) * 1997-08-22 1999-03-04 Bayer Aktiengesellschaft Acylated 5-aminoisothiazoles as pesticides and fungicides
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WO2000063207A1 (en) * 1999-04-20 2000-10-26 Syngenta Limited Pesticidal indazole or benzotriazole derivatives

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Publication number Priority date Publication date Assignee Title
WO2005040162A1 (en) * 2003-10-27 2005-05-06 Basf Aktiengesellschaft 5-(2-arylacetamido)isothiazole compounds i
US7973069B2 (en) 2004-07-14 2011-07-05 Ptc Therapeutics, Inc. Methods for treating hepatitis C

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