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WO2001055138A1 - Derives d'azole, leur preparation et utilisation - Google Patents

Derives d'azole, leur preparation et utilisation Download PDF

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Publication number
WO2001055138A1
WO2001055138A1 PCT/GB2001/000331 GB0100331W WO0155138A1 WO 2001055138 A1 WO2001055138 A1 WO 2001055138A1 GB 0100331 W GB0100331 W GB 0100331W WO 0155138 A1 WO0155138 A1 WO 0155138A1
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Prior art keywords
optionally substituted
alkyl
alkoxy
haloalkyl
cyano
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PCT/GB2001/000331
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English (en)
Inventor
Sarah Armstrong
Nigel John Barnes
Susan Patricia Barnett
Eric Daniel Clarke
Patrick Jelf Crowley
Torquil Eoghan Macleod Fraser
David John Hughes
Christopher John Mathews
Roger Salmon
Stephen Christopher Smith
Russell Viner
William Guy Whittingham
John Williams
Alan John Whittle
William Roderick Mound
Christopher John Urch
Brian Leslie Pilkington
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Syngenta Ltd
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Syngenta Ltd
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Priority to AU2001230354A priority Critical patent/AU2001230354A1/en
Publication of WO2001055138A1 publication Critical patent/WO2001055138A1/fr
Anticipated expiration legal-status Critical
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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):
  • n is 0 or 1 ;
  • B is N, N-oxide or CR 8 ;
  • Y is O, S or NR 9 ;
  • Z is O, S or NR 10 ;
  • R 1 is hydrogen, halogen, optionally substituted C 6 alkyl, optionally substituted C 2 . 6 alkenyl, optionally substituted C 2 . 6 alkynyl, optionally substituted C,. 6 alkoxy, optionally substituted C,_ 6 alkylthio, optionally substituted C 3 . 7 cycloalkyl, cyano, nitro or SF 5 ;
  • R 2 is hydrogen, halogen, optionally substituted C,. 6 alkyl, optionally substituted C 2.6 alkenyl, optionally substituted C 2 . 6 alkynyl, optionally substituted C ⁇ alkoxy, optionally substituted C, .6 alkylthio, optionally substituted C,_ 6 alkylsulfinyl, optionally substituted C,.
  • R 1 and R 2 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated, carbocylic or heterocyclic ring which may contain one or two heteroatoms selected from O, N or S and which is optionally substituted by C,. 6 alkyl, C ⁇ haloalkyl or halogen; R 3 is hydrogen, optionally substituted C l0 alkyl, optionally substituted [C 2 .
  • R 4 , R 5 and R 6 are, independently, hydrogen, halogen, optionally substituted C,_ 6 alkyl, optionally substituted C]_ 6 alkoxy, optionally substituted C,.
  • R 4 , R 5 and R 6 are hydrogen, halogen, cyano, optionally substituted C,. 20 alkyl, optionally substituted C 2.20 alkenyl, optionally substituted C 2 . 20 alkynyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted C 5 .
  • R 8 is hydrogen, halogen, nitro, cyano, optionally substituted C ⁇ _ & alkyl, optionally substituted C 2.6 alkenyl, optionally substituted C 2 . 6 alkynyl, optionally substituted C 3 .
  • R 9 is hydrogen, cyano, nitro, optionally substituted C,_ 6 alkyl, optionally substituted C 3.7 cycloalkyl, optionally substituted (C 2 . 6 )alkenyl(C 1 .
  • R 10 is hydrogen, cyano, optionally substituted C,. g alkyl, optionally substituted [C 2-6 alkenyl(C, .6 )alkyl], optionally substituted [C 2 . 6 alkyny ⁇ C ⁇ alkyl], optionally substituted C 3.7 cycloalkyl, optionally substituted [C 3 . 7 cycloalkyl(C, ⁇ )alkyl], C,. 6 alkoxy(C, .6 )alkyl, optionally substituted C,. 6 alkoxycarbonyl, optionally substituted C,.
  • R 11 and R 18 are, independently, hydrogen, optionally substituted phenyl (C,. 2 )alkyl or optionally substituted C ⁇ _ 20 alkyl;
  • R 12 and R 19 are, independently, hydrogen, optionally substituted phenyl or optionally substituted C,_ 6 alkyl;
  • R 13 and R 14 are, independently, optionally substituted Cj. 6 alkyl; or R 13 and R 14 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N and S and which is optionally substituted by one or two independently selected C,. 6 alkyl groups;
  • R' 5 is hydrogen, optionally substituted C,. 20 alkyl, optionally substituted [C 2 . 20 alkenyl- (C,. 6 )alkyl], optionally substituted [C 2 .
  • R 16 and R 17 are, independently, hydrogen, optionally substituted C, .20 alkyl, optionally substituted C 3 _ 7 cycloalkyl, optionally substituted [C 2 . 20 alkenyl(C,. 6 )alkyl], optionally substituted [C 2 . 20 alkynyl(C,. 6 )alkyl], optionally substituted C,. 20 alkoxycarbonyl, optionally substituted phenoxycarbonyl, formyl, optionally substituted . ⁇ alkylcarbonyl, optionally substituted C,. 20 alkylsulfonyl or optionally substituted phenylsulfonyl.
  • One group of preferred compounds is a group where n is 0 or 1 ; B is N, N-oxide or CR 8 ; Y is O, S or NR 9 ; Z is O, S or NR 10 ;
  • R 1 is hydrogen, halogen, optionally substituted C,. 6 alkyl, optionally substituted C 2 _ 6 alkenyl, optionally substituted C 2 . 6 alkynyl, optionally substituted C,. 6 alkoxy, optionally substituted C, .6 alkylthio, optionally substituted C 3 . 7 cycloalkyl, cyano, nitro or SF 5 ;
  • R 3 is hydrogen, optionally substituted C M0 alkyl, optionally substituted [C 2.6 alkenyl- optionally substituted [C 2 . 6 alkynyl(C ⁇ _ 6 )alkyl], optionally substituted C 3.7 cycloalkyl, optionally substituted C,. ]0 alkylcarbonyl, optionally substituted C l 0 alkoxycarbonyl, formyl, optionally substituted C,.
  • alkylaminocarbonyl optionally substituted di(C 1 ., 0 )alkylaminocarbonyl, optionally substituted phenoxycarbonyl, optionally substituted C j _ 6 alkylthio, optionally substituted C, ⁇ alkylsulfinyl, optionally substituted C 6 alkylsulfonyl, optionally substituted C ⁇ arylthio, optionally substituted C, .6 arylsulfinyl, optionally substituted C,. 6 arylsulfonyl or R 1 R I4 NS;
  • R 4 , R 5 and R 6 are, independently, hydrogen, halogen, optionally substituted C,_ 6 alkyl, optionally substituted C ⁇ alkoxy, optionally substituted C,. 6 alkylthio, optionally substituted C,. 6 alkylsulfinyl, optionally substituted C,. 6 alkylsulfonyl, cyano, nitro, optionally substituted C,. 6 alkylcarbonyl, optionally substituted C,. 6 alkoxycarbonyl or SF 5 , provided that at least one of R 4 , R 5 and R 6 is not hydrogen;
  • R 7 is hydrogen, halogen, cyano, optionally substituted C,_ 20 alkyl, optionally substituted C 2 _ 20 alkenyl, optionally substituted C 2 . 20 alkynyl, optionally substituted C 3.7 cycloalkyl, optionally substituted C 5 . 6 cycloalkenyl, formyl, optionally substituted C,. 20 alkoxycarbonyl, optionally substituted C,. 20 alkylcarbonyl, aminocarbonyl, optionally substituted C,. 20 alkylaminocarbonyl, optionally substituted di(C,.
  • alkylaminocarbonyl optionally substituted aryloxycarbonyl, optionally substituted arylcarbonyl, optionally substituted arylaminocarbonyl, optionally substituted N-alkyl-N-arylaminocarbonyl, optionally substituted diary laminocarbonyl, optionally substituted heteroaryloxycarbonyl, optionally substituted heteroarylcarbonyl, optionally substituted heteroarylaminocarbonyl, optionally substituted alkylheteroarylaminocarbonyl, optionally substituted diheteroarylaminocarbonyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted heterocyclyl, R 15 O, HS, optionally substituted C,.
  • R 8 is hydrogen, halogen, nitro, cyano, optionally substituted C, ⁇ alkyl, optionally substituted C 2.6 alkenyl, optionally substituted C 2 . 6 alkynyl, optionally substituted C 3 . 7 cycloalkyl, optionally substituted C,. 6 alkoxycarbonyl, optionally substituted C,. 6 alkylcarbonyl, optionally substituted C,. 6 alkylaminocarbonyl, optionally substituted di(C,.
  • R 9 is hydrogen, cyano, nitro, optionally substituted C,_ 6 alkyl, optionally substituted C 3.7 cycloalkyl, optionally substituted (C 2 _ 6 )alkenyl(C,. 6 )alkyl, optionally substituted (C 2 _ 6 ) alkynyl(C,. 6 )alkyl, optionally substituted phenyl, optionally substituted heteroaryl, optionally substituted C 6 alkylcarbonyl, optionally substituted C ⁇ 6 alkoxycarbonyl, optionally substituted C,. 6 alkylamino, optionally substituted di(C 1 .
  • R is hydrogen, cyano, optionally substituted C,_ 8 alkyl, optionally substituted [C 2-6 alkenyl(C,.
  • R n and R 18 are, independently, hydrogen, optionally substituted phenyl (C, .2 )alkyl or optionally substituted C,. 20 alkyl;
  • R 12 and R 19 are, independently, hydrogen, optionally substituted phenyl or optionally substituted C,_ 6 alkyl;
  • R 13 and R 14 are, independently, optionally substituted C w alkyl or R 13 and R 14 together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two C,_ 6 alkyl groups;
  • 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.
  • optional substituents on alkylene, alkenylene or alkynylene moieties include (subject to valency constraints) one or more of hydroxy, halogen, C,_ 6 alkyl, C,_ 6 haloalkyl, C,. 6 cyanoalkyl, C,. 6 alkoxy(C,.
  • R 23 is C [.6 alkyl, C 6 haloalkyl or phenyl(C ⁇ _ 2 )alkyl;
  • R 24 and R 25 are, independently, hydrogen, C,_ 8 alkyl, C 3 . 7 cycloalkyl, C 2 . 6 alkenyl(C ⁇ _ 6 )alkyl.
  • R are, independently, hydrogen, C,. 8 alkyl, C 3 . 7 cycloalkyl, C 2 . 6 alkenyl(C,. 6 )alkyl, C 2-6 alkynyl(C,. 6 )alkyl, C 2 . 6 haloalkyl, C,_ 6 alkoxy(C,- 6 )alkyl, C ⁇ alkoxycarbonyl(C ⁇ Jalkyl, carboxy (C ⁇ alkyl or phenyl(C ⁇ .
  • each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl,
  • the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, NCS-, C 3 . 7 cycloalkyl (itself optionally substituted with C ] . 6 alkyl or halogen), C 5.7 cycloalkenyl (itself optionally substituted with C,_ 6 alkyl or halogen), hydroxy, C ⁇ . 10 alkoxy, C,. 10 alkoxy(C 0 )alkoxy, tri(C M )alkylsilyl(C 1 . 5 )alkoxy, C,.
  • Alkenyl and alkynyl moieties can be in the form of straight or branched chains, and the alkenyl moieties, where appropriate, can be of either the (E)- or (ZJ-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 C,. 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.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF 3 , CF 2 C1, CF 3 CH 2 or CHF 2 CH 2 .
  • Aryl includes naphthyl, anthracyl, fluorenyl and indenyl but is preferably phenyl.
  • heteroaryl refers to an aromatic ring containing up to 10 atoms including one or more heteroatoms (preferably one or two heteroatoms) selected from O, S and N.
  • heteroatoms preferably one or two heteroatoms
  • examples of such rings include pyridine, pyrimidine, furan, quinoline, quinazoline, pyrazole, thiophene, thiazole, oxazole and isoxazole.
  • heterocycle and heterocyclyl refer to a non-aromatic ring containing up to 10 atoms including one or more (preferably one or two) heteroatoms selected from O, S and N. Examples of such rings include 1,3-dioxolane, tetrahydrofuran and morpholine.
  • the optional substituents on heterocyclyl include C,. 6 alkyl as well as those optional substituents given above for an alkyl moiety.
  • Cycloalkyl includes cyclopropyl, cyclopentyl and cyclohexyl.
  • Cycloalkenyl includes cyclopentenyl and cyclohexenyl.
  • cycloalkyl or cycloalkenyl include C,_ 3 alkyl as well as those optional substituents given above for an alkyl moiety.
  • Carbocyclic rings include aryl, cycloalkyl and cycloalkenyl groups.
  • the optional substituents on aryl or heteroaryl are selected, independently, from halogen, nitro, cyano, NCS-, C,_ 6 alkyl, C,. 6 haloalkyl, C,_ 6 alkoxy(C ! . 6 )alkyl, C 2 . 6 alkenyl, C 2 . 6 haloalkenyl, C 2 . 6 alkynyl, C 3 . 7 cycloalkyl (itself optionally substituted with C,. 6 alkyl or halogen), C 5 .
  • substituents are independently selected from halogen, C, .6 alkyl, C,_ 6 haloalkyl, C t.6 alkoxy(C,. 6 )alkyl, C,. 6 alkoxy, C,_ 6 haloalkoxy, C,. 6 alkylthio, C 6 haloalkylthio, C,. 6 alkylsulfinyl, C ⁇ haloalkylsulfmyl, C 6 alkylsulfonyl, C,.
  • Haloalkenyl groups are alkenyl groups which are substituted with one or more of the same or different halogen atoms
  • dialkylamino substituents include those where the dialkyl groups together with the N atom to which they are attached form a five, six or seven- membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which is optionally substituted by one or two independently selected (C ⁇ ⁇ alkyl groups.
  • heterocyclic rings are formed by joining two groups on an N atom, the resulting rings are suitably pyrrolidine, piperidine, thiomorpholine and morpholine each of which may be substituted by one or two independently selected (C,_ 6 ) alkyl groups.
  • the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, HO 2 C, C,. ]0 alkoxy (itself optionally substituted by C 0 alkoxy), aryl(C M )alkoxy, C,. 10 alkylthio, C 0 alkylcarbonyl, C lA0 alkoxycarbonyl, C,. 6 alkylaminocarbonyl, di(C,_ 6 alkylaminocarbonyl, (C,.
  • alkenyl or alkynyl include one or more of halogen, aryl and C 3 . 7 cycloalkyl. It is more preferred that heterocyclyl is optionally substituted by C,. 6 alkyl.
  • the optional substituents for cycloalkyl include halogen, cyano and C,. ; alkyl.
  • the optional substituents for cycloalkenyl include C,. 3 alkyl, halogen and cyano.
  • the present invention provides a compound of formula (IA):
  • n, B, Y, Z, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined above for a compound of formula (I).
  • One group of preferred compounds of formula (I A) is a group where B is N or CR 8 ; Y is O, S or NR 9 ; Z is O, S or NR 10 ;
  • R 1 is hydrogen, halogen, C ⁇ 6 alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, C,_ 6 cyanoalkyl, C, ⁇ haloalkyl, C, .6 alkoxy, C ⁇ haloalkoxy, C,_ 6 alkylthio, C L6 haloalkylthio, C 3 . 6 cycloalkyl, C 3. - cycloalkyl(C, ⁇ )alkyl, C, .6 alkoxy(C 1 . 6 )alkyl, cyano, nitro or SF 5 ;
  • R 2 is hydrogen, halogen, C,. 6 alkyl, C 2 . 6 alkenyl, C,_ 6 alkynyl, C ⁇ haloalkyl, C, ⁇ alkoxy, C,. 6 alkoxy (C,. 6 )alkyl, C 6 haloalkoxy, C L6 alkylthio, C,. 6 haloalkylthio, C, ⁇ alkylsulfinyl, C ⁇ _ 6 haloalkylsulfinyl, C ⁇ alkylsulfonyl, C ⁇ haloalkylsulfonyl, C ⁇ haloalkyl, cyano, nitro, formyl, CH ⁇ NOR 11 , 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 heteroatoms selected from O, N or S and which may be optionally substituted by C,_ 6 alkyl, C,. 6 haloalkyl or halogen;
  • R 3 is hydrogen, C 0 alkyl, benzyloxymethyl, benzoyloxymethyl, C,. 6 alkoxy (C,. 6 )alkyl, C 2.6 alkeny ⁇ ⁇ alkyl (especially allyl), C 2 . 6 alkynyl(C,. 6 )alkyl (especially propargyl), C, . , 0 alkylcarbonyl or C 0 alkoxycarbonyl (especially wobutoxycarbonyl);
  • R 4 , R 5 and R 6 are, independently, selected from hydrogen, halogen, C,_ 6 alkyl, C w alkoxy, C,_ 6 haloalkoxy, C,. 6 alkylthio, C,. 6 haloalkylthio, C,. 6 alkylsulfinyl, C 6 haloalkylsulfinyl, C, proposition 6 alkylsulfonyl, C,. 6 haloalkylsulfonyl, C,. 6 haloalkyl, cyano, nitro, C,_ 6 alkylcarbonyl, C,_ 6 alkoxycarbonyl or SF 5 , provided that at least one of R 4 , R 5 and R 6 is not hydrogen;
  • R 7 is cyano, C, .g alkyl, C t . 6 haloalkyl, C,_ 6 cyanoalkyl, C 2 . 6 alkenyl, C 2.6 alkynyl, C 3.7 cycloalkyl, C 3 . 7 halocycloalkyl, C 3 . 7 cyanocycloalkyl, C 1 . 3 alkyl(C 3 . 7 )cycloalkyl, C,. 3 alkyl- (C 3.7 )halocycloalkyl, C 5 . 6 cycloalkenyl, C 3 . 7 cycloalkyl(C ⁇ 6 )alkyl, C 5 . 6 cycloalkenyl(C,.
  • (C, .6 )alkyl aryloxycarbony ⁇ C ⁇ alkyl, C,_ 6 alkylthio(C ] . 6 )alkyl, C,. 6 alkylsulfinyl(C,. 6 )alkyl, C, .6 alkylsulfonyl(C,. 6 )alkyl, aminocarbonyl(C,_ 6 )alkyl, aminocarbonyl(C 2 . 6 )alkenyl, aminocarbonyl(C 2 . 6 )alkynyl, C,_ 6 alkylaminocarbony ⁇ C ⁇ alkyl, di(C,. 6 )alkyl- aminocarbonyl(C,.
  • heteroaryl(C,. 4 )alkyl where the heteroaryl may be substituted by halo, nitro, cyano, C,_ 6 alkyl, C,. 6 haloalkyl, C,. 6 alkoxy or C ⁇ haloalkoxy
  • heterocyclyl(C M )alkyl where the heterocyclyl may be substituted by halo, cyano, C 6 alkyl, C x _ 6 haloalkyl, C,. 6 alkoxy or C,. 6 haloalkoxy
  • R 15 O, C,.coordinating alkylthio, R 16 R 17 N or R 18 ON C(R 19 );
  • R 8 is hydrogen, halogen, nitro, cyano, C,_ 8 alkyl, C,_ 6 haloalkyl, C,. 6 cyanoalkyl, C 2.6 alkenyl, C 2 . 6 alkynyl, C 3 . 7 cycloalkyl, C 2 . 6 haloalkenyl, C 3 . 7 cycloalkyl(C ! . 6 )alkyl, C,. 6 alkoxy(C,. 6 )alkyl, C, ⁇ alkoxycarbonyl, C,.
  • phenyl(C 1 . 6 )alkyl wherein the phenyl group is optionally substituted by halo, nitro, cyano, C, .6 alkyl, C,. 6 haloalkyl, C,_ 6 alkoxy or C ⁇ haloalkoxy
  • heteroaryl optionally substituted by halo, nitro, cyano, C, ⁇ alkyl, C 6 haloalkyl, C,. 6 alkoxy or C, ⁇ haloalkoxy
  • heteroaryl- (C, .6 )alkyl wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C, .6 haloalkyl, C,_ 6 alkoxy or C 6 haloalkoxy
  • the heteroaryl group is optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C, .6 haloalkyl, C,_
  • R 9 is cyano, nitro, C,_ 6 alkyl, C,_ 6 haloalkyl, C 3 . 7 cycloalkyl, C 3 . 7 cycloalkyl(C,. 6 )alkyl, CH 2 (C 2.6 )alkenyl, CH 2 (C 2 . 6 )alkynyl, phenyl (optionally substituted by halo, nitro, cyano, C,.
  • R 10 is hydrogen, C,. g alkyl, C,. 6 haloalkyl, C,. 6 cyanoalkyl, C 2 . 6 alkenyl, C 2 _ 6 alkynyl, C 3.7 cycloalkyl, C 2.6 haloalkenyl, C 3 . 7 cycloalky ⁇ C ⁇ alkyl, C,. 6 alkoxy(C,. 6 )alkyl, C, .6 alkoxycarbonyl, C, .6 alkylcarbonyl, C,. 6 alkylaminocarbonyl, di(C,. 6 )alkylaminocarbonyl, phenyl (optionally substituted by halo, nitro, cyano, C,.
  • R 11 and R 18 are, independently, C,. 6 alkyl or phenyl(C,. 2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,. 6 haloalkyl, C,_ 6 alkoxy or C,. 6 haloalkoxy);
  • R 15 is hydrogen, C,_ 8 alkyl, C 6 haloalkyl, C 6 cyanoalkyl, C 2 . 6 alkenyl, C 2.6 alkynyl, C, .6 alkoxy (C,. 6 )alkyl, phenyl(C M )alkyl , (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C, .6 alkyl, C ⁇ haloalkyl, C,_ 6 alkoxy or C,_ 6 haloalkoxy), heteroaryl- (C, .4 )alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C,.
  • R 16 and R 17 are, independently, hydrogen, C,. g alkyl, C 3 . 7 cycloalkyl, C 3 . 6 alkenyl, C 3.6 alkynyl, C 3 . 7 cycloalkyl(C,. 4 )alkyl, C 2 . 6 haloalkyl, C,. 6 alkoxy(C,. 6 )alkyl, C,. 6 alkoxycarbonyl, or R 16 and R 17 together with the N atom to which they are attached form a five, six or seven- membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two C,. 6 alkyl groups; and
  • R 19 is C,. 6 alkyl, C,. 6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, C, .6 alkyl, C,_ 6 haloalkyl, Cj_ 6 alkoxy or C 6 haloalkoxy).
  • n is preferably 0.
  • B is preferably N.
  • Y is preferably O or S.
  • Y is more preferably O.
  • Z is preferably O or S._
  • Z is more preferably O.
  • R 1 is hydrogen, halogen, C,_ 6 alkyl, C,. 6 cyanoalkyl, C,_ 6 haloalkyl, C 3.7 cycloalkyl(C )alkyl, C,. 6 alkoxy C ⁇ alkyl, C 2 . 6 alkenyl, C 2 . 6 alkynyl, C,_ 6 alkoxy, C, .6 haloalkoxy, C 6 alkylthio, C,. 6 haloalkylthio, C 3 . 6 cycloalkyl, cyano, nitro or SF 5 .
  • R 1 is more preferably hydrogen, halogen, C,. 6 alkyl, C 2 . 6 alkenyl, C,.
  • R 1 is hydrogen, halogen, C,. 6 alkyl, C 6 haloalkyl, C 6 alkoxy(C !.6 )alkyl, C 2.6 alkenyl, C w alkoxy, C,. 6 haloalkoxy, C,. 6 alkylthio, C ⁇ haloalkylthio, C 3.6 cycloalkyl or cyano. It is most preferred that R 1 is halogen, C,_ 6 alkyl, C 6 haloalkyl, C,. 6 alkoxy or C,_ 6 haloalkoxy.
  • R 2 is hydrogen, halogen, C ⁇ alkyl, C 6 haloalkyl, C]. 6 alkoxy(C ! . 6 )alkyl, C 2 . 6 alkenyl, C, ⁇ alkynyl, C ⁇ alkoxy, C ⁇ haloalkoxy, C,. 6 alkylthio, C, .6 haloalkylthio, C, .6 alkylsulfinyl, C,_ 6 haloalkylsulfinyl, C,_ 6 alkylsulfonyl, C, ⁇ haloalkylsulfonyl, cyano, nitro, formyl, C,. 6 alkylcarbonyl, C,_ 6 alkoxycarbonyl, SF 5 or
  • R 1 and R 2 together with the atoms to which they are attached may be joined to form a five, six or seven-membered saturated or unsaturated, carbocylic or heterocyclic ring which may contain one or two heteroatoms selected from O, N or S and which is optionally substituted by C,_ 6 alkyl, C,. 6 haloalkyl or halogen; where R 11 is phenyl(C,. 2 )alk ⁇ l (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,_ 6 alkyl, C j . 6 haloalkyl, C,. 6 alkoxy or C,. 6 haloalkoxy) or C,_ 6 alkyl.
  • R 2 is hydrogen, halogen, C,_ 6 alkyl, C,. 6 haloalkyl, C,. 6 alkoxy (C, .6 )alkyl, C,. 6 alkoxy, C,. 6 haloalkoxy, C . 6 alkylthio or SF 5 ; or R 1 and R 2 together with the atoms to which they are attached form a cyclopentane or benzene ring optionally substituted by C, .6 alkyl, C, ⁇ haloalkyl or halogen.
  • R 2 is even more preferably hydrogen, halogen, C,_ 6 alkyl, C,. 6 haloalkyl, C, ⁇ alkoxy,
  • R 2 is hydrogen, halogen, C ⁇ alkyl, C,_ 6 haloalkyl, C, ⁇ alkoxy (C,. 6 )alkyl, C,. 6 alkoxy, C,_ 6 haloalkoxy, or R 1 and R 2 together with the atoms to which they are attached form a cyclopentane ring optionally substituted by C,_ 6 alkyl, C, ⁇ haloalkyl or halogen.
  • R 2 is most preferably halogen, C,. 6 alkyl, C ⁇ haloalkyl, C,. 6 alkoxy, C, ⁇ alkoxy(C ! . 6 )alkyl or C,. 6 haloalkoxy. It is preferred that R 3 is hydrogen, C 0 alkyl, C ⁇ alkylcarbonyloxy(C ! . 6 )alkyl, benzoyloxymethyl (where the phenyl ring is optionally substituted with halogen or C alkyl), C,_ 6 alkoxy(C,. 6 )alkyl (where the alkyl group is optionally substituted by aryl or C M alkoxycarbonyl), C 2 .
  • R 3 is hydrogen, C 6 alkyl, C,. 6 alkylcarbonyloxymethyl, benzoyloxymethyl (where the phenyl ring is optionally substituted with halogen or C alkyl), C,. 6 alkoxymethyl, C 2 . 6 alkenyloxymethyl, C 2 . 6 alkynyloxymethyl, benzyloxymethyl (where the phenyl ring is optionally substituted with halogen or C,_ 4 alkyl), C 2.6 alkynyl(C ] . 6 )alkyl (especially propargyl) or C,. 10 alkylcarbonyl.
  • R 3 is more preferably hydrogen, C,. 6 alkyl, C, ⁇ alkoxy(C, .6 )alkyl, C, . ⁇ alkylcarbonyloxymethyl, benzyloxymethyl or benzoyloxymethyl.
  • R 3 is even more preferably hydrogen, C,_ 6 alkyl, C,. 6 alkoxy(C,. 6 )alkyl, benzyloxymethyl or benzoyloxymethyl.
  • R 4 , R 5 and R 6 are, independently, hydrogen, halogen, C, .6 alkyl, C j.6 haloalkyl, C,. 6 alkoxy, C,. 6 haloalkoxy, C,_ 6 alkylthio, C x _ 6 haloalkylthio, C,. 6 alkylsulfinyl, C L6 haloalkylsulfinyl, C,. 6 alkylsulfonyl, C,. 6 haloalkylsulfonyl, cyano, nitro, C,_ 6 alkylcarbonyl or C 6 alkoxycarbonyl, provided that at least one of R 4 , R 5 and R 6 is not hydrogen.
  • R 4 , R 5 and R 6 are preferably, independently, hydrogen, C,. 3 alkyl or halogen, provided that at least one of R 4 , R 5 and R 6 is not hydrogen.
  • R 4 , R 5 and R 6 are more preferably, independently, hydrogen or halogen (especially fluorine), provided that at least one of R 4 , R 5 and R 6 is not hydrogen.
  • R 4 , R 5 and R 6 is fluorine.
  • R 7 is cyano, C,. g alkyl, C,_ g haloalkyl, C,_ 8 cyanoalkyl, C 3.7 cycloalkyl(C, .6 )alkyl, C 5.6 cycloalkeny ⁇ C ⁇ alkyl, C,. 6 alkoxy(C, .6 )alkyl, C 3 . 6 alkenyloxy(C,. 6 )alkyl, C 3 . 6 alkynyloxy(Cj. 6 )alkyl, aryloxy (C,. 6 )alkyl, C,. 6 carboxyalkyl, C, .6 alkylcarbonyl(C,.
  • heteroaryl group is optionally substituted by halo, nitro, cyano, C,_ 6 alkyl, C,_ 6 haloalkyl, C,. 6 alkoxy or C,. 6 haloalkoxy
  • heterocyclyl(C M )alkyl where the heterocyclyl group is optionally substituted by halo, cyano, C,_ 6 alkyl, C,. 6 haloalkyl, C,_ 6 alkoxy or C,_ 6 haloalkoxy
  • C 2 6 alkenyl, C 2.6 haloalkenyl, C,.
  • heteroaryl(C M )alkyl wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,_ 6 haloalkyl, C, ⁇ alkoxy or C,. 6 haloalkoxy
  • heterocyclyl(C, .4 )alkyl wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C ⁇ alkyl, C,_ 6 haloalkyl, C,. 6 alkoxy or C,. 6 haloalkoxy), C,.
  • R 19 is phenyl (optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,. 6 haloalkyl, C,. 6 alkoxy or Cj_ 6 haloalkoxy), C,. 6 alkyl or C,. 6 haloalkyl;
  • R 16 and R 17 are, independently, hydrogen, C ⁇ 8 alkyl,
  • R 18 is phenyl(C,. 2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,. 6 haloalkyl, C,. 6 alkoxy or C,. 6 haloalkoxy) or C,. 6 alkyl.
  • R 7 is more preferably Cj.g alkyl, C,. 8 haloalkyl, C,. g cyanoalkyl, C 2 . 6 alkenyl, C 2.6 alkynyl, C 3.7 cycloalkyl, C 3 . 7 halocycloalkyl, C 3 . 7 cyanocycloalkyl, C,_ 3 alkyl(C 3 . 7 )cycloalkyl, C j . 3 alkyl(C 3.7 )halocycloalkyl, C 5 ⁇ cycloalkenyl, C 3 . 7 cycloalkyl(C,. 6 )alkyl, C 5 .
  • phenyl(C 2 ⁇ ,)alkenyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C w alkyl, C ⁇ haloalkyl, C,. 6 alkoxy or Cj. 6 haloalkoxy), heteroaryl (optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,. 6 haloalkyl, C,.
  • heterocyclyl (wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C ⁇ alkyl, C w haloalkyl, C,_ 6 alkoxy or C, ⁇ haloalkoxy), heteroaryl(C ] _ 4 )alkyl (wherein the heteroaryl group is optionally substituted by halo, nitro, cyano, C,_. 6 alkyl, C ⁇ . 6 haloalkyl, C,. 6 alkoxy or C,. 5 haloalkoxy), heterocyclyl(C M )alkyl
  • heterocyclyl group is optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,_ 6 haloalkyl, C,. 6 alkoxy or C,. 6 haloalkoxy
  • R 15 O, C,. 8 alkylthio, R 16 R 17 N or R ,8 ON C(R 19 );
  • R 15 is C % alkyl, C 6 haloalkyl
  • R 19 is C,. 6 alkyl, C,. 6 haloalkyl or phenyl (optionally substituted by halo, nitro, cyano, C,- 6 alkyl, C,. 6 haloalkyl, C,. 6 alkoxy or C,.
  • R 16 and R 17 are, independently, hydrogen, C,_ 8 alkyl, C 3 . 7 cycloalkyl, C 3 . 6 alkenyl, C 3 . 6 alkynyl, C 3 . 7 cycloalkyl(C,. 4 )alkyl, C 2 . 6 haloalkyl, C,. 6 alkoxy(C,. 6 )alkyl, C,.
  • R 16 and R 17 together with the N atom to which they are attached form a five, six or seven- membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which may be optionally substituted by one or two C,_ 6 alkyl groups; and R 18 is C, .6 alkyl or phenyl(C ] . 2 )alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C ⁇ alkyl, C ⁇ _ 6 haloalkyl, C ⁇ 6 alkoxy or C,_ 6 haloalkoxy); and R 7 is more preferably C]. 8 alkyl, C,.
  • R 7 is C,. g alkyl, C,. 8 haloalkyl, C,. g cyanoalkyl, C 3.7 cycloalkyl(C,. 6 )alkyl, C 5 . 6 cycloalkeny ⁇ C ⁇ alkyl, C,. 6 alkoxy ⁇ alkyl, C 3.6 alkenyloxy(C !.6 )alkyl, C 3 . 6 aryloxy(C,. 6 )alkyl, C,. 6 carboxyalkyl, C ⁇ 6 alkylcarbonyl(C,. 6 )alkyl, C 2 . 6 alkenylcarbonyl(C,. 6 )alkyl, C 2 .
  • heterocyclyl-(C,. 4 )alkyl wherein the heterocyclyl group is optionally substituted by halo, nitro, cyano, C,_ 6 alkyl, C,. 6 haloalkyl, C ⁇ . 6 alkoxy or C,. 6 haloalkoxy), C 2 . 6 alkenyl, C 2 . 6 haloalkenyl, C w cyanoalkenyl, C 5 . 6 cycloalkenyl, aminocarbonyl(C 2 . 6 )alkenyl, C,.
  • R 19 is phenyl (optionally substituted by halo, nitro, cyano, C ⁇ alkyl, C,. 6 haloalkyl, C,. 6 alkoxy or C,. 6 haloalkoxy), C,. 6 alkyl or C ⁇ haloalkyl;
  • R 16 and R 17 are, independently, hydrogen, C,. g alkyl, C 3.7 cycloalkyl(C )alkyl, C 2 ⁇ haloalkyl, C,. 6 alkoxy (C,. 6 )alkyl, C 3 . 7 cycloalkyl, C 3 . 6 alkenyl, C ⁇ alkynyl or C,.
  • R 18 is pheny ⁇ . ⁇ alkyl (wherein the phenyl group is optionally substituted by halo, nitro, cyano, C,_ 6 alkyl, C,. 6 haloalkyl, C, .6 alkoxy or C, .6 haloalkoxy) or C,. 6 alkyl.
  • R 7 is C,. g alkyl, C,. g haloalkyl, C,. g cyanoalkyl, C,_ 6 alkoxy (C,_ 6 ) alkyl, C 3 . 7 cycloalkyl, C,. 3 alkyl (C 3 . 7 ) cycloalkyl, heterocyclyl (optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,. 6 haloalkyl, C,. 6 alkoxy or C,. 6 haloalkoxy) or
  • R 7 is C s alkyl, C,. g haloalkyl, C,. g cyanoalkyl, C, ⁇ alkoxy (C,_ 6 ) alkyl, C 3 . 7 cycloalkyl, C,. 3 alkyl (C 3 . 7 ) cycloalkyl, heterocyclyl (optionally substituted by C _ 6 alkyl) or di(C,. 8 )alkylamino.
  • R 7 is most preferably C,. g alkyl, C ⁇ haloalkyl, C,. g cyanoalkyl, C 3 .
  • R 16 R 17 N are, independently, C, .g alkyl or together with the N atom to which they are attached form a five, six or seven- membered heterocyclic ring which may contain one further heteroatom selected from O, N or S and which may be optionally substituted by one or two C,_ 6 alkyl groups.
  • R 8 is hydrogen, halogen, nitro, cyano, C ] _ 8 alkyl, C,_ 6 haloalkyl, C, .6 cyanoalkyl, C 3 .
  • R 8 is hydrogen, halogen, C]. 8 alkyl or C,. 6 haloalkyl. It is preferred that R 9 is cyano, nitro, C,_ 6 alkyl, C t . 6 haloalkyl, C 3.7 cycloalkyl- (C, ⁇ )alkyl, C 3.7 cycloalkyl, CH 2 (C 2 . 6 )alkenyl, CH 2 (C 2 . 6 )alkynyl, phenyl (optionally substituted by halo, nitro, cyano, C,. 6 alkyl, C,..
  • R is hydrogen, C,. 8 alkyl, C,. 6 haloalkyl, C,. 6 cyanoalkyl, C 2-6 alkenyl, C 2 . 6 haloalkenyl, C 2 . 6 alkynyl, C 3 . 7 cycloalkyl, C 3 . 7 cycloalkyl(C 1 . 6 )alkyl, C j . 6 alkoxy(C, .6 )alkyl, C,_ 6 alkoxycarbonyl, C,. 6 alkylcarbonyl, C,.
  • R 10 is hydrogen, C,. g alkyl or C,. 6 haloalkyl.
  • Table 1 provides 160 compounds of formula (1):
  • R 1 , R 3 and R 7 are as defined in Table 1
  • Table 2 provides 160 compounds of formula (2):
  • R 1 , R 3 and R 7 are as defined in Table 1.
  • Table 3 provides 160 compounds of formula (3):
  • R 1 , R 3 and R 7 are as defined in Table 1.
  • Table 4 provides 160 compounds of formula (4):
  • Table 5 provides 160 compounds of formula (5):
  • R 1 , R 3 and R 7 are as defined in Table 1.
  • Table 6 provides 160 compounds of formula (6):
  • R 1 , R 3 and R 7 are as defined in Table 1.
  • Table 7 provides 160 compounds of formula (7): (7) wherein R 1 , R 3 and R 7 are as defined in Table 1.
  • Table 8 provides 160 compounds of formula (8):
  • R 1 , R 3 and R 7 are as defined in Table 1.
  • Table 9 provides 160 compounds of formula (9):
  • Table 10 provides 160 compounds of formula (10):
  • R 1 , R 3 and R 7 are as defined in Table 1.
  • Table 11 provides 160 compounds of formula (11):
  • R 1 , R 3 and R 7 are as defined in Table 1.
  • Table 12 provides 160 compounds of formula (12): (12) wherein R 1 , R 3 and R 7 are as defined in Table 1.
  • Table 13 provides 160 compounds of formula (13):
  • R 1 , R 3 and R 7 are as defined in Table 1.
  • Table 14 provides 160 compounds of formula (14):
  • R 1 , R 3 and R 7 are as defined in Table 1.
  • Table 15 provides 160 compounds of formula (15):
  • R 1 , R 3 and R 7 are as defined in Table 1.
  • Table 16 provides 80 compounds of formula (16):
  • Table 17 provides 80 compounds of formula (17):
  • R 3 and R 7 are defined in Table 16.
  • Table 18 provides 80 compounds of formula (18):
  • R 3 and R 7 are defined in Table 16.
  • Table 19 provides 80 compounds of formula (19):
  • R 3 and R 7 are defined in Table 16.
  • Table 20 provides 80 compounds of formula (20):
  • Table 21 provides 80 compounds of formula (21):
  • R 3 and R 7 are defined in Table 16.
  • Table 22 provides 80 compounds of formula (22) wherein R 3 and R 7 are defined in Table 16.
  • Table 23 provides 80 compounds of formula (23):
  • R 3 and R 7 are defined in Table 16.
  • Table 24 shows selected melting point and selected NMR data, all with CDC1 3 as the solvent (unless otherwise stated; if a mixture of solvents is present, this is indicated as, for example, (CDC1 3 / d 6 -DMSO)), (no attempt is made to list all characterising data in all cases) for compounds of Tables 1 to 23.
  • a compound of formula (I) (wherein Y is O) may be prepared by reacting a compound of formula (II) with an appropriate a compound of formula (III) (where X is alkoxy or aryloxy), optionally in the presence of a base such as sodium methoxide, or with a compound of formula (III) (where X is hydroxy) in the presence of a known coupling agent such as 1,3-dicyclohexylcarbodiimide or l-(3-dimethylaminopropyl)-3-ethylcarbodiimide.
  • a known coupling agent such as 1,3-dicyclohexylcarbodiimide or l-(3-dimethylaminopropyl)-3-ethylcarbodiimide.
  • the compound of formula (III) (where X is hydroxy) may first be converted to an acid chloride or anhydride suitable for reaction with an amine to form an amide, and then reacted with a compound of formula (II) to yield (I); such procedures are well known to those skilled in the art and are described, for example in J. March, Advanced Organic Chemistry, Third Edition, John Wiley and Sons, New York, 1985, pps 370-376 and references therein.
  • a compound of formula (I) (where Y is S) may be prepared by reacting a compound of formula (I) (where Y is O) with a suitable thionating agent such as 2,4-bis(4- methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson's reagent), 2,4- bis(methylthio)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Davy reagent methyl), 2,4- bis(p ⁇ r ⁇ -tolyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Davy reagent j ⁇ -tolyl) or phosphorus pentasulfide in a suitable solvent such as toluene or fluorobenzene.
  • a suitable thionating agent such as 2,4-bis(4-
  • thiophenols are known compounds or may be prepared by known methods.
  • Benzofurans may be made from ⁇ rt/zo-halophenols as described by Henning Lufjens and Peter J Scammells, Tetrahedron Letters 39 (1998), 6581-6584, Terence C. Owen et al, Tetrahedron Letters 30, No. 13, 1597 (1989) and Fred G Schreiber and Robert Stevenson, J.C.S. Perkin 1, 90, 1977.
  • Indoles may be prepared from ortb ⁇ -haloanilines according to the method of Cheng-yi Chen et al, J. Org.
  • a compound of formula (IV) can be reacted with a suitable derivative of acetic acid (such as a haloacetic ester) to provide a compound of formula (III).
  • a suitable derivative of acetic acid such as a haloacetic ester
  • a compound of formula (V), in particular where halo is bromine, can be reacted with an appropriate malonate derivative in the presence of suitable catalysts, for example palladium (0) derivatives, and the resulting malonate hydrolysed and decarboxylated to give a compound of formula (III).
  • suitable catalysts for example palladium (0) derivatives
  • a compound of formula (VI) (where R' may be hydrogen or, preferably, C,_ 6 alkyl) (fluorophenyl acetic acid derivatives are known) may be nitrated under standard conditions to give a compound of formula (VII), which, following standard reaction conditions known to those skilled in the art (methoxode displacment, demethylation and reduction) may be converted to a compound of formula (VIII) which itself may be converted to, for example, a benzoxazole, so leading to the formation of a compound of formula (I) (where B is N and Z is O).
  • a compound of formula (VII) may be reduced (for example by catalytic hydrogenation) to give a compound of formula (IX), which may in turn be acylated.
  • the resulting compound of formula (X) is then treated sequentially with a thionating agent (such as Lawesson's reagent) and a base to give a compound of formula (XI).
  • a compound of formula (XI) may be converted to a compound of formula (I) (where B is N; and Z is S) using methods described above.
  • a compound of formula (I) (wherein R 3 is H and Y is oxygen) with an alkylating or acylating agent, optionally in the presence of a base and a phase transfer catalyst, provides a compound of formula (I) (wherein R 3 is an acyl or alkyl group and Y is oxygen).
  • suitable alkylating agents include, but are not restricted to, alkyl halides (such as methyl iodide), haloalkyl ethers (such as chloromethyl ethyl ether) and alkyl sulfates (such as dimethyl sulfate).
  • Suitable acylating agents include anhydrides (such as acetic anhydride), acid chlorides (such as acetyl chloride or benzoyl chloride) and chloroformates (such as ethyl chloroformate).
  • Suitable bases include organic bases (such as triethylamine or pyridine), alkali metal alkoxides (such as potassium tert-butoxide) and inorganic bases (such as sodium hydride or sodium hydroxide).
  • Suitable phase transfer catalysts may be selected by reference to the literature (see, for example, J. March, Advanced Organic Chemistry, Third Edition, John Wiley and Sons, New York, 1985, pages 320-322 and references therein).
  • a compound of formula (I) (wherein Y is sulfur and R 3 is H) may be treated with an electrophile (such as an alkyl halide, alkyl sulfate or trialkyloxonium salt) optionally in the presence of a base to give a compound of formula (XII) (wherein Y is sulfur and R 20 is alkyl).
  • an electrophile such as an alkyl halide, alkyl sulfate or trialkyloxonium salt
  • Such a compound may be further treated with a compound of formula R 9 -NH 2 (where R 9 is as defined above for a compound of formula (I)), optionally in the presence of a mercuric salt (such as mercuric chloride), according to known procedures to give a compound of formula (I) wherein R 3 is H and Y is NR 9 ).
  • Such a compound may be treated with an alkylating agent, an acylating agent or similar electrophile to give a compound of formula (I) [where R3 is as defined above for a compound of formula (I) (except that R 3 is not H) and Y is NR 9 ].
  • the compounds of formula (I) can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Hemiptera, Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera, Hymenoptera and Isoptera and also other invertebrate pests, for example, acarine, nematode and mollusc pests. Insects, acarines, nematodes and molluscs are hereinafter collectively referred to as pests.
  • the pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, companion animals, forestry and the storage of products of vegetable origin (such as fruit, grain and timber); those pests associated with the damage of man-made structures and the transmission of diseases of man and animals; and also nuisance pests (such as flies).
  • pest species which may be controlled by the compounds of formula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids), Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper), Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp. (stinkbugs), Frankliniella occidentalis (thrip), Thrips spp.
  • Damalinia spp. and Linognathus spp. bits and sucking lice
  • Meloidogyne spp. root knot nematodes
  • Globodera spp. and Heterodera spp. cyst nematodes
  • Pratylenchus spp. lesion nematodes
  • Rhodopholus spp. banana burrowing nematodes
  • Tylenchulus spp. citrus nematodes
  • Haemonchus contortus barber pole worm
  • Caenorhabditis elegans vinegar eelworm
  • Trichostrongylus spp. gastro intestinal nematodes
  • 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 (Sphaerothe
  • Cercosporidium personatum on peanuts and other Cercospora spp. on other hosts for example sugar beet, bananas, soya beans and rice; Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables, vines and other hosts and other Botrytis spp. on other hosts; Alternaria spp. on vegetables (for example carrots), oil-seed rape, apples, tomatoes, potatoes, cereals (for example wheat) and other hosts; Venturia spp. (including Venturia inaequalis (scab)) on apples, pears, stone fruit, tree nuts and other hosts; Cladosporium spp. on a range of hosts including cereals (for example wheat) and tomatoes; Monilinia spp.
  • Botrytis cinerea grey mould
  • Alternaria spp. on vegetables for example carrots), oil-seed rape, apples, tomatoes, potatoes, cereals (for example wheat) and other hosts
  • Venturia spp. including Venturia ina
  • a compound of formula (I) may move acropetally, basipetally or locally in plant tissue to be active against one or more fungi. Moreover, a compound of formula (I) may be volatile enough to be active in the vapour phase against one or more fungi on the plant.
  • the invention therefore provides a method of combating and controlling insects, acarines, nematodes or molluscs which comprises applying an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a pest, a locus of pest, or to a plant susceptible to attack by a pest, and a method of combating and controlling fungi which comprises applying a fungicidally effective amount of a compound of formula (I), or a composition containing a compound of formula (I), to a plant, to a seed of a plant, to the locus of the plant or seed, to soil or to any other growth medium (for example a nutrient solution).
  • the compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
  • plant as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes protectant, curative, systemic, eradicant and antisporulant treatments.
  • the compounds of formula (I) are preferably used for agricultural, horticultural and turfgrass purposes in the form of a composition.
  • a compound of formula (I) is usually formulated into a composition which includes, in addition to the compound of formula (I), a suitable inert diluent or carrier and, optionally, a surface active agent (SFA).
  • SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula (I).
  • the composition is generally used for the control of pests or fungi such that a compound of formula (I) is applied at a rate of from O.lg to 10kg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 1kg per hectare.
  • a compound of formula (I) When used in a seed dressing, a compound of formula (I) is used at a rate of 0.000 lg to lOg (for example 0.00 lg or 0.05g), preferably 0.005g to lOg, more preferably 0.005g to 4g, per kilogram of seed.
  • the present invention provides an insecticidal, acaricidal, nematicidal, molluscicidal or fungicidal composition
  • an insecticidal, acaricidal, nematicidal, molluscicidal or fungicidal composition comprising an insecticidally, acaricidally, nematicidally, molluscicidally or fungicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor.
  • the composition is preferably an insecticidal, acaricidal, nematicidal or fungicidal composition.
  • the invention provides a method of combating and controlling pests or fungi at a locus which comprises treating the pests or fungi or the locus of the pests or fungi with an insecticidally, acaricidally, nematicidally, molluscicidally or fungicidally effective amount of a composition comprising a compound of formula (I).
  • the compounds of formula (I) are preferably used against insects, acarines, nematodes or fungi.
  • compositions can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations.
  • the formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula
  • Dustable powders may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
  • solid diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers
  • Soluble powders may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility /solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • water-soluble organic solids such as a polysaccharide
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary.
  • a hard core material such as sands, silicates, mineral carbonates, sulphates or phosphates
  • Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils.
  • One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • DC Dispersible Concentrates
  • a compound of formula (I) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether.
  • organic solvent such as a ketone, alcohol or glycol ether.
  • surface active agent for example to improve water dilution or prevent crystallisation in a spray tank.
  • Emulsifiable concentrates or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents).
  • Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as C 8 -C ⁇ 0 fatty acid dimethylamide) and chlorinated hydrocarbons.
  • aromatic hydrocarbons such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark
  • ketones such as
  • An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.
  • Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion.
  • Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of formula (I) is present initially in either the water or the solvent/SFA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs.
  • An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation.
  • An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
  • SC Suspension concentrates
  • SCs may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I).
  • SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound.
  • One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle.
  • a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
  • Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example ⁇ -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 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
  • compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
  • Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di- wopropyl- and tri-wopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (
  • Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.
  • Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
  • Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carb
  • a compound of formula (I) may be applied by any of the known means of applying pesticidal or fungicidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.
  • a locus of the pests such as a habitat of the pests, or a growing plant liable to infestation by the pest
  • a compound of formula (I) may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
  • Compositions for use as aqueous preparations are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use.
  • These concentrates which may include DCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
  • a compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers).
  • fertilisers for example nitrogen-, potassium- or phosphorus-containing fertilisers.
  • Suitable formulation types include granules of fertiliser.
  • the mixtures suitably contain up to 25% by weight of the compound of formula (I).
  • the invention therefore also provides a fertiliser composition
  • a fertiliser composition comprising a fertiliser and a compound of formula (I).
  • the compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.
  • the resulting composition may have a broader spectrum of activity or a greater level of intrinsic activity than the compound of formula (I) alone. Further the other fungicide may have a synergistic effect on the fungicidal activity of the compound of formula (I).
  • the compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components.
  • the particular additional active ingredient will depend upon the intended utility of the composition.
  • Suitable pesticides include the following: a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or 5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl- 3-(2-oxofhiolan-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-trifluoromethyl- benzimidazole-1-sulphonamide, ⁇ -[N-(3-chloro-2,6-xylyl)-2-methoxy- acetamido]- ⁇ -butyrolactone, 4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole- 1 - sulfonamide (IKF-916, cyamidazosulfamid), 3-5-dichloro-N-(3-chloro-l -ethyl- l-methyl-2- oxopropyl)-4-methylbenzamide (RH-7281, zox
  • the compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
  • suitable synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.
  • Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
  • An example of a rice selective herbicide which may be included is propanil.
  • An example of a plant growth regulator for use in cotton is PIXTM.
  • Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type.
  • other formulation types may be prepared.
  • one active ingredient is a water insoluble solid and the other a water insoluble liquid
  • SE suspoemulsion
  • Stage2 Preparation of methyl 2,4-difluoro-5-nitrophenylacetate (and 2,4-difluoro-5- nitrophenylacetic acid).
  • Stage 4 The product from Stage 3 (4g) was dissolved in dry dichloromethane (150ml) and cooled to -70°C with stirring under an atmosphere of nitrogen. To the solution was added dropwise boron tribromide in dichloromethane (49.2ml of IM solution) then the mixture was stirred for lhour at -60°C. The reaction mixture was allowed to warm to -23°C, maintained at this temperature for lhour and then allowed to warm to 0°C, at which it was maintained for 1.5hours. Diethylether (150ml) was added to the mixture followed by a saturated aqueous solution of sodium hydrogen carbonate (200ml).
  • Stage 5 Preparation of methyl 5-amino-2-fluoro-4-hydroxyphenylacetate.
  • the product from Stage 4 (3.38g) was dissolved in methanol (30ml) containing
  • Stage 6 Preparation of methyl (6-fluoro-2-methylbenzoxazol-5-yl) acetate.
  • the product from Stage 5 (0.50g) was dissolved in trimethylorthoacetate (10ml) and heated to reflux with stirring for 2hours then allowed to cool to ambient temperature and stored for 18hours.
  • Stage 7 Preparation of N-(4-chloro-3-methylisothiazol-5-yl)-(6-fluoro-2- methylbenzoxazol-5-yl)acetamide.
  • Stage 3 Preparation of N-(4-chloro-3-methylisothiazol-5-yl)-(6-fluoro-2(2,2- dimethylpropyl)benzoxazol-5-yl)acetamide.
  • the product from Stage 2 (0.10g) in dry tetrahydrofuran (1.5ml) was added to 5- amino-4-chloro-3-methylisothiazole (0.10g) which had been pre-treated with sodium methoxide (0.085g) in tetrahydrofuran (1ml). The mixture was stirred at ambient temperature for 0.5hour then stored at ambient for lday.
  • 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 25, 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; and Mi represents Meloidogyne incognita.
  • This Example illustrates the fungicidal properties of compounds of formula (I).
  • the compounds were tested against a variety of foliar fungal diseases of plants. The techniques employed were as follows. Plants were grown either in John Innes Potting Compost (No.1 or 2) in 4cm diameter,
  • 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. Assessments were performed on a single leaf of each of the two replicate plants for
  • This method uses banded assessment values.
  • the mean disease values are banded in the manner shown below. If the disease level value falls exactly mid-way between two of the points, the result will be the lower of the two points.
  • PRCO 100 - ⁇ Banded mean disease level for treatment A ⁇ x 100 ⁇ Banded mean disease level on untreated controls ⁇
  • This method uses 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:
  • the PRCO is then rounded to the nearest whole number; therefore, in this particular example, the PRCO result is 71.
  • ERYSGT Blumeria graminis f.sp. tritici
  • PLASVI Plasmopara viticola
  • PUCCRT Puccinia recondita

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  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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Abstract

L'invention concerne un composé de la formule (I), dans laquelle n est égal à 0 ou 1; B représente N, N-oxyde ou CR8; Y représente O, S ou NR9; Z représente O, S ou NR?10; et R1, R2, R3, R4, R5, R6 et R7¿ sont des radicaux organiques. L'invention concerne également leur préparation et utilisation ainsi que les compositions les contenant.
PCT/GB2001/000331 2000-01-28 2001-01-26 Derives d'azole, leur preparation et utilisation Ceased WO2001055138A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001230354A AU2001230354A1 (en) 2000-01-28 2001-01-26 Azole derivatives, their preparation and use

Applications Claiming Priority (2)

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GB0002041A GB0002041D0 (en) 2000-01-28 2000-01-28 Chemical compounds
GB0002041.2 2000-01-28

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007020460A1 (fr) * 2005-08-19 2007-02-22 Syngenta Participations Ag Procédé chimique
US7973069B2 (en) 2004-07-14 2011-07-05 Ptc Therapeutics, Inc. Methods for treating hepatitis C

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998005670A1 (fr) * 1996-07-31 1998-02-12 Bayer Aktiengesellschaft N-isothiazolyl-(thio)amides substitues
WO2000006566A1 (fr) * 1998-07-30 2000-02-10 Syngenta Limited Derives de benzoxazole, benzthiazole et benzimidazole

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998005670A1 (fr) * 1996-07-31 1998-02-12 Bayer Aktiengesellschaft N-isothiazolyl-(thio)amides substitues
WO2000006566A1 (fr) * 1998-07-30 2000-02-10 Syngenta Limited Derives de benzoxazole, benzthiazole et benzimidazole

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7973069B2 (en) 2004-07-14 2011-07-05 Ptc Therapeutics, Inc. Methods for treating hepatitis C
WO2007020460A1 (fr) * 2005-08-19 2007-02-22 Syngenta Participations Ag Procédé chimique
JP2009504721A (ja) * 2005-08-19 2009-02-05 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト 化学工程

Also Published As

Publication number Publication date
GB0002041D0 (en) 2000-03-22
AU2001230354A1 (en) 2001-08-07

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