WO2004018438A2 - Microbiocidal (e.g. fungicidal) 1,2,3-triazole derivatives - Google Patents

Microbiocidal (e.g. fungicidal) 1,2,3-triazole derivatives Download PDF

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Publication number
WO2004018438A2
WO2004018438A2 PCT/EP2003/009111 EP0309111W WO2004018438A2 WO 2004018438 A2 WO2004018438 A2 WO 2004018438A2 EP 0309111 W EP0309111 W EP 0309111W WO 2004018438 A2 WO2004018438 A2 WO 2004018438A2
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Prior art keywords
alkyl
optionally substituted
alkoxy
halogen
independently selected
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PCT/EP2003/009111
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French (fr)
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WO2004018438A3 (en
Inventor
Josef Ehrenfreund
Hans Tobler
Harald Walter
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Syngenta Participations Ag
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Priority claimed from GB0219612A external-priority patent/GB0219612D0/en
Priority claimed from GB0310464A external-priority patent/GB0310464D0/en
Priority to MXPA05001819A priority Critical patent/MXPA05001819A/en
Priority to AT03792351T priority patent/ATE516275T1/en
Priority to BR0313686-8A priority patent/BR0313686A/en
Priority to EP03792351A priority patent/EP1539717B1/en
Priority to JP2005501204A priority patent/JP4643441B2/en
Priority to AU2003253417A priority patent/AU2003253417A1/en
Application filed by Syngenta Participations Ag filed Critical Syngenta Participations Ag
Priority to US10/524,721 priority patent/US7531559B2/en
Priority to CA002494263A priority patent/CA2494263A1/en
Publication of WO2004018438A2 publication Critical patent/WO2004018438A2/en
Publication of WO2004018438A3 publication Critical patent/WO2004018438A3/en
Priority to IL16622505A priority patent/IL166225A0/en
Priority to CR7696A priority patent/CR7696A/en
Priority to US12/463,449 priority patent/US7956194B2/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/36—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D411/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D411/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D411/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/08—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/08—Bridged systems

Definitions

  • the present invention relates to novel 1,2,3-triazole derivatives which have microbiocidal activity, in particular fungicidal activity.
  • the invention also relates to novel intermediates used in the preparation of these compounds, to agrochemical compositions which comprise at least one of the novel compounds as active ingredient and to the use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.
  • the present invention provides a compound of formula (I):
  • A is an ⁇ rt/zo-substituted ring selected from formulae (Al) to (A22);
  • (A22) Q is a single or a double bond
  • X is O, N(R 18 ), S or (CR 19 R 20 )(CR 21 R 22 ) m (CR 23 R 24 ) n
  • R 1 is halogen, cyano, nitro, C ⁇ - 4 alkyl, C ⁇ . 4 haloalkyl, C ⁇ . alkoxy, C ⁇ _ 4 haloalkoxy or optionally substituted C 2 . 4 alkenyl, optionally substituted C 2 .
  • R 2 is C alkyl, C haloalkyl, C ⁇ - 4 alkoxy(C ⁇ . 4 )alkyl or C ⁇ - 4 alkylthio(C ⁇ . 4 )alkyl or [optionally substituted aryl](C ⁇ _ 4 )alkyl- or [optionally substituted aryl]oxy(C ⁇ - 4 )alkyl- (where the optionally substituted aryl moieties may each have up to 3 substituents, each independently selected from halogen and C,.
  • C 3 -s cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from C M alkyl, halogen, C M alkoxy and C M haloalkoxy) and C 4 .
  • 8 cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from C alkyl, halogen, C ⁇ 4 alkoxy and C M haloalkoxy), Si(CH 3 ) 3 and C 4 .
  • 8 cycloalkenyl (itself optionally substituted by up to 3 substituents, each independently selected from C alkyl, halogen, C M alkoxy and C haloalkoxy)], C 3 .
  • 8 cycloalkyl [optionally substituted by up to 3 substituents, each independently selected from halogen, C M alkyl, C haloalkyl, C M alkoxy, C haloalkoxy, C M thioalkyl, C 3 .
  • CM haloalkyl C M alkoxy(C )alkyl, C ⁇ . 4 haloalkoxy(C ⁇ _ 4 )alkyl or Si(C alkyl) 3 ;
  • R 26 and R 27 are each, independently, hydrogen, halogen, CM alkyl or CM haloalkyl;
  • R 28 is hydrogen, CM alkyl or CM haloalkyl;
  • m is 0 or 1;
  • n is 0 or 1;
  • p is 0 or 1; and Z is CM alkylene.
  • Halogen is fluoro, chloro, bromo or iodo.
  • Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, ra-butyl, «-pentyl, n-hexyl, zso-propyl, see-butyl, iso-butyl, tert-butyl, Heo-pentyl, n-heptyl, 1,3-dimethylbutyl, 1,3-dimethylpentyl, l-methyl-3 -ethyl-butyl or 1 ,3,3-trimethylbutyl.
  • Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same or different halogen atoms and are, for example, CF 3 , CF 2 C1, CHF , CH 2 F, CC1 3 , CF 3 CH 2 , CHF 2 CH 2 , CH 2 FCH 2 , CH 3 CHF or CH 3 CF 2 .
  • Alkenyl and alkynyl moieties can be in the form of straight or branched chains.
  • the alkenyl moieties, where appropriate, can be of either the (E)- or (Z -configuration. Examples are vinyl, allyl, ethynyl and propargyl.
  • Alkylidene moieties can be in the form of straight or branched chains.
  • Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Cycloalkenyl includes cyclobutenyl, cyclopentenyl, cyclohexenyl and cycloheptenyl.
  • Bicycloalkyl includes bicyclo[l,l,l]pentyl, bicyclo[2,l,l]hexyl, bicyclo[2,2,l]heptyl, bicyclo[2,2,2]octyl, bicyclo[3,2,l]octyl and bicyclo[3,2,2]nonyl.
  • Aryl includes phenyl, naphthyl, anthracyl, fluorenyl and indanyl but is preferably phenyl.
  • A is as defined above provided that it is not (Al).
  • R is as defined above provided that it is not an aliphatic, saturated or unsaturated group [in which the group contains three to thirteen carbon atoms and at least one silicon atom and, optionally, one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, and the group is optionally substituted by up to four independently selected halogen atoms].
  • A is as defined above provided that it is not (Al) when R 6 is an aliphatic, saturated or unsaturated group [in which the group contains three to thirteen carbon atoms and at least one silicon atom and, optionally, one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, and the group is optionally substituted by up to four independently selected halogen atoms].
  • R 6 is an aliphatic, saturated or unsaturated group [in which the group contains three to thirteen carbon atoms and at least one silicon atom and, optionally, one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, and the group is optionally substituted by up to four independently selected halogen atoms].
  • Q is a single bond.
  • n is 0.
  • m is 0.
  • A is selected from formulae (Al), (A2), (A3), (A16), (A17), (A18), (A19), (A20) and (A22).
  • A is selected from formulae (Al), (A2), (A18), (A19) and (A22). Even more preferably A is selected from one of the following ortho-substituted rings:
  • R , 13 and R .14 are each, independently, selected from H and C M alkyl.
  • X is O, NR 18 or (CR 19 R 20 )(CR 21 R 22 ) m (CR 23 R 24 ) n .
  • X is O or (CR 19 R 20 )(CR 21 R 22 ) m (CR 23 R 24 ) n .
  • X is (CR 19 R 20 )(CR 2, R 22 ) m (CR 23 R 24 ) n .
  • X is (CR 19 R 20 ).
  • R 1 is C alkyl, C M haloalkyl, NO 2 , CN or OCF 3 . More preferably R 1 is CHF 2 , CF 3 , CH 2 F, CF 2 C1, CH 3 or C 2 H 5 .
  • R 1 is CHF 2 , CF 3 , CH 2 F, CF 2 C1 or CH 3 .
  • R 1 is CHF 2 , CF 3 or CH 2 F.
  • R is C ⁇ _ 4 alkyl, C M haloalkyl, C M alkoxy(C ⁇ _ 4 )alkyl or C alkylthio(C ⁇ . )alkyl. More preferably R 2 is CH 3 , CF 3 , C 2 H 5 , CH 2 OCH 3 or CH 2 SCH 3 .
  • R 2 is CH 3 or C 2 H 5 .
  • R 2 is CH 3 .
  • R 3 is H.
  • each R is, independently, H, halogen, C ⁇ - 4 alkyl or C M alkoxy. More preferably each R 4 is, independently, H, Cl, Br, CH 3 or CH 3 O.
  • each R 4 is, independently, H, Cl or CH 3 .
  • each R 4 is H.
  • R 5 is H, C]. 6 alkyl, C ⁇ _ 4 alkoxy or CM alkoxy(C ⁇ _ )alkyl. More preferably R 5 is H, methyl, OC(CH 3 ) 3 or CH 2 OCH 3 .
  • R 5 is H or methyl.
  • R 6 is chosen from C - ⁇ 0 alkyl, C 3 - 9 haloalkyl, C 3 . 7 cycloalkyl [optionally substituted by C cycloalkyl (itself optionally substituted by C ⁇ . 2 alkyl) or by up to two C M alkyl groups], an aliphatic group [which contains three to ten carbon atoms and at least one silicon atom and, optionally, one oxygen atom], thienyl [optionally substituted by halo], furyl [optionally substituted by halo], pyridyl [optionally substituted by halo], oxazolyl, isoxazolyl and
  • R 6 is C 3 . alkyl, C 3 . 6 cycloalkyl [optionally substituted by C M alkyl or a C 3 cycloalkyl (itself optionally substituted by Ci. 2 alkyl)], an aliphatic group (which contains three to eight carbon atoms and at least one silicon atom) or
  • R 7 is H, F or CH 3 .
  • R 8 is H.
  • R 9 is H.
  • R 10 is H.
  • R 11 is H.
  • R 12 is H.
  • R 13 , R 14 , R 15 , R 16 are each, independently, H, CH 3 , C 2 H 5 , CF 3 , CH 3 O, C(O)CH 3 or CH 3 OCH 2 . More preferably R 13 , R 14 , R 15 , R 16 are each, independently, H or CH 3 .
  • R 17 is H.
  • R 18 is H, CH 3 , C 2 H 5 , C(O)OC ⁇ - 4 alkyl (optionally substituted with halogen or C ⁇ - 4 alkoxy) or COH.
  • R 18 is C(O)OC]. alkyl (optionally substituted with halogen or CM alkoxy) or COH. Even more preferably R 18 is C(O)OC ⁇ - 4 alkyl (optionally substituted with halogen or
  • R 18 is C(O)OC alkyl.
  • R 19 and R 20 are, independently, H, CH 3 , C 2 H 5 , «-C 3 H 7 , z ' -C 3 H 7 , t-C 4 H , CH(C 2 H 5 ) , CH 2 -cyclopropyl or cyclopentyl; or R 19 and R 20 together with the carbon atom to which they are attached form a 3-membered carbocyclic ring.
  • R 21 is H or CH 3 .
  • R 22 is H or CH 3 .
  • R 23 is H or CH 3 .
  • R 24 is H or CH 3 .
  • R and R are as defined above for a compound of formula (I) and Y is halogen, hydroxy or C1. 5 alkoxy, are useful as intermediates in the preparation of compounds of formula (I).
  • the present invention provides a compound of formula (13) where R 1 and R 2 are as defined above for a compound of formula (I) and Y is halogen, hydroxy or C ⁇ _ 5 alkoxy; provided that when R 1 is chloro and R 2 is 4-CH 3 O-C 6 H -CH 2 -, Y is not C 2 H 5 O; when R 1 is CH 3 O and R 2 is CH 3 , Y is not C 2 H 5 O; when R 1 is bromo and R 2 is CH 3 OCH 2 , Y is not CH 3 O; and when R 1 is CH 3 and R 2 is C 2 H 5 , Y is not OH.
  • Y is hydroxy, chloro, fluoro or C ⁇ . 3 alkoxy.
  • Anilines of formula (Ilia) are novel when R 13 , R 14 , R 15 , R 16 , Q and X are as defined above for a compound of formula (I); provided that when R 13 , R 14 , R 15 and R 16 are each H then X is not CH when Q is a double bond and X is not CH 2 CH 2 when Q is a single bond or a double bond; and when R 13 is CH 3 , R 14 is OCH 3 and R 15 and R 16 are both H then X is not CH 2 CH 2 when Q is a single bond.
  • the present invention provides a compound of formula (IHa) where R 13 , R 14 , R 15 , R 16 , Q and X are as defined above for a compound of formula (I); provided that when R 13 , R 14 , R 15 and R 16 are each H then X is not CH 2 when Q is a double bond and X is not CH 2 CH 2 when Q is a single bond or a double bond; and when R 13 is CH 3 , R 14 is OCH 3 and R 15 and R 16 are both H then X is not CH 2 CH 2 when Q is a single bond.
  • the compounds of formula (I), (If) and (Ilia) may exist as different geometric or optical isomers or in different tautomeric forms.
  • This invention covers, for each formula, all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
  • Table 1 provides 59 compounds of formula (II) wherein R 1 , R 2 and Y are as defined in Table 1.
  • Table X represents Table 2 [when X is 2], Table 3 [when X is 3], Table 4 [when X , Table 5 [when X is 5], Table 6 [when X is 6] and represents Table 7 [when X is 7].
  • Table 2 provides 457 compounds of formula (1-2):
  • R 2 , R 3 , R 6 and R 7 are as defined in Table 2.
  • Table 3 provides 457 compounds of formula (1-3):
  • R , R , R and R are as defined in Table 3.
  • Table 4 provides 457 compounds of formula (1-4):
  • R 2 , R 3 , R 6 and R 7 are as defined in Table 4.
  • Table 5 provides 457 compounds of formula (1-5):
  • R 2 , R 3 , R 6 and R 7 are as defined in Table 6.
  • Table 7 provides 457 compounds of formula (1-7):
  • R 2 , R 3 , R 6 and R 7 are as defined in Table 7.
  • Table Y represents Table 8 [when Y is 8], Table 9 [when Y is 9], Table 10 [when Y is 10], Table 11 [when Y is 11], Table 12 [when Y is 12], Table 13 [when Y is 13], Table 14 [when Y is 14], Table 15 [when Y is 15], Table 16 [when Y is 16], Table 17 [when Y is 17], Table 18 [when Y is 18] and represents Table 19 [when Y is 19].
  • Table 8 provides 364 compounds of formula (1-8):
  • R 2 , R 3 , and R 6 are as defined in Table 9.
  • Table 10 provides 364 compounds of formula (I- 10):
  • R , R , and R are as defined in Table 10.
  • Table 11 provides 364 compounds of formula (I-l 1):
  • R 2 , R 3 , and R 6 are as defined in Table 11.
  • Table 12 provides 364 compounds of formula (1-12):
  • R 2 , R 3 , and R 6 are as defined in Table 14.
  • Table 15 provides 364 compounds of formula (1-15):
  • R , R , and R are as defined in Table 15.
  • Table 16 provides 364 compounds of formula (1-16):
  • R 2 , R 3 , and R 6 are as defined in Table 18.
  • Table 19 provides 364 compounds of formula (1-19):
  • R 2 , R 3 , and R 6 are as defined in Table 19.
  • Table Z represents Table 20 [when Z is 20], Table 21 [when Z is 21], Table 22 [when Z is 22], Table 23 [when Z is 23], Table 24 [when Z is 24] and represents Table 25 [when Z is 25].
  • Table 20 provides 182 compounds of formula (1-20):
  • R • 2 , R and A are as defined in Table 20.
  • Table 21 provides 182 compounds of formula (1-21):
  • R 2 , R 3 and A are as defined in Table 21.
  • Table 22 provides 182 compounds of formula (1-22):
  • R 2 , R 3 and A are as defined in Table 22.
  • Table 23 provides 182 compounds of formula (1-23):
  • R 2 , R 3 and A are as defined in Table 24.
  • Table 25 provides 182 compounds of formula (1-25):
  • R 2 , R 3 and A are as defined in Table 25.
  • Table 26 provides 133 compounds of formula (TJJa) where R 1J , R 1 , R 1D , R 10 , Q and X are as defined in Table 26.
  • Table ZZ represents Table 27 (when ZZ is 27) and represents Table 28 (when ZZ is
  • Table 27 provides 42 compounds of formula (1-27) where R 1 , R 2 , R 3 and R 6 are as defined in Table 9.
  • Table 28 provides 42 compounds of formula (1-28) where R 1 , R 2 , R 3 and R 6 are as defined in Table 10.
  • Table 29 shows selected melting point data for compounds of Tables 1 to 28.
  • the compounds according to formula (I) may be prepared according to the following reaction schemes.
  • C ⁇ - 5 alkyl] ⁇ each of which is a compound of formula (IT), as defined above ⁇ maybe prepared by a reaction sequence starting with a l,2,3-triazole-4,5-dicarboxylic acid diester of formula A [Y.Tanaka et al., Tetrahedron, 29, 3271 (1973)] [where each R' is, independently, C ⁇ - 5 alkyl] (preferably the dimethyl ester).
  • a with an alkylating agent such as R 2 -halo (where R 2 is as defined above for formula (13); and halo is preferably iodo) or an appropriate sulphate, sulphonate or carbonate ester] in the presence of a base [such as K 2 CO 3 , Na 2 CO 3 or NEt 3 ] in a suitable solvent [such as acetonitrile, DMF or dimethylacetamide] at ambient to elevated temperatures furnishes a mixture of regioisomers, of formulae B and C, which may be separated by conventional methods.
  • an alkylating agent such as R 2 -halo (where R 2 is as defined above for formula (13); and halo is preferably iodo) or an appropriate sulphate, sulphonate or carbonate ester
  • a base such as K 2 CO 3 , Na 2 CO 3 or NEt 3
  • a suitable solvent such as acetonitrile, DMF or dimethylacetamide
  • a base such as KOH, NaOH or LiOH
  • a protic solvent such as methanol
  • a fluorinating agent such as DAST (diethylamino sulphur trifloride) or, preferably, SF 4
  • hydrofluoric acid gives a 5-CF 3 -l,2,3-triazole-4-carboxylic acid ester of formula E.
  • a chlorinating agent such as thionyl chloride or phosgene
  • an acid chloride of formula F which may be reduced catalytically in an inert solvent [for example ethyl acetate or THF] in the presence of a base [for example Hunig base] to give an aldehyde-ester of formula G (modified Rosenmund conditions).
  • Metal hydride reduction of a compound of formula G [for example by NaBH 4 or LiBH 4 ] in methanol provides a 5-hydroxymethyl-l ,2,3-triazole of formula J, from which a 5-fluoromethyl derivative of formula K may be obtained by fluorination under mild conditions, preferably with DAST at low temperatures (0 to -78°C) in an inert solvent [such as dichloromethane].
  • Chlorination of compound of formula D [for example by thionyl chloride] followed by treatment with ammonia, preferably in a protic solvent [such as water, methanol or ethanol] furnishes an amide of formula M from which a 5-cyano- 1,2,3- triazole of formula N may be obtained by means of a dehydrating agent [such as phosphorylchloride] .
  • a protic solvent such as water, methanol or ethanol
  • a 5-hydroxy-l,2,3-triazole of formula O_ may be obtained.
  • an alkylating agent such as methyl iodide, dimethylsulphate or dimethylcarbonate
  • a base for example NaH, K 2 CO 3 or Na 2 CO 3
  • a polar solvent for example DMF, DMSO or CH 3 CN
  • a 5-methoxy-l,2,3-triazole of formula R which may be converted to a trichloromethoxy derivative of formula S with a chlorinating agent [such as chlorine] in the presence of azoisobutyronitrile (AIBN) or ultra-violet irradiation at elevated temperature.
  • AIBN azoisobutyronitrile
  • a 5-trifluoromethoxy-l,2,3-triazole of formula T may be prepared.
  • a compound of formula U may also be obtained by treatment of a compound of formula P or V with NaNU 2 in an polar solvent [such as DMF, sulpholane or N-methylpyrrolidone] at elevated temperatures.
  • Transformations of a compound of formula (II') [where R and R are as defined in formula (I); Y is OR'; and R' is C 1 - 5 alkyl] to give a compound of formula (II) [where R 1 and R 2 are as defined in formula (I) and Y is halo or hydroxy] includes saponification with a base [such as KOH or NaOH] in a protic solvent [such as methanol, ethanol or water], at ambient or elevated temperature to give a l,2,3-triazole-4-carboxylic acid of formula W.
  • a base such as KOH or NaOH
  • a protic solvent such as methanol, ethanol or water
  • a compound of formula (IHa) may be obtained according to scheme 4:
  • R 13 , R 14 , R 15 , R 16 and X are as defined above for a compound of formula (I)) [obtained through Diels-Alder addition of an in situ generated benzyne, for example, starting from a 6-nitroanthranilic acid as described by L.Paquette et al, J. Amer. Chem. Soc. 99, 3734 (1977) or from other suitable benzyne precursers (see H. Pellissier et al. Tetrahedron, 59, 701 (2003) with a 5-7 membered cyclic 1,4-diene according to, or by analogy to,
  • R 6 is an aliphatic or alicyclic, saturated or unsaturated group [in which the group contains three to thirteen carbon atoms and at least one silicon atom and, optionally, one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, and the group is optionally substituted by up to four independently selected halogen atoms] and R 7"10 are as defined in formula (I) may be prepared by analogy with literature examples. References include e.g. E.A.Chernyshew et al., Bull. Acad. Sci.
  • anilines comprises compounds of formula (lTlc)
  • R' represents C 2 - alkyl, C 2 - haloalkyl or C 3 - 6 cycloalkyl (itself optionally substituted by up to 3 substituents, independently selected from halo, C ⁇ _ alkyl, C ⁇ - 3 haloalkyl and C ⁇ - haloalkoxy).
  • a compound of formula (Hlc) may be prepared by a reaction sequence starting with a crossed aldol condensation of benzaldehyde with a ketone of formula CH 3 C(O)R' [where R' is as defined above for a compound of formula (Hlc)] in the presence of NaOH or KOH in a solvent (such as water or ethanol) and usually under reflux conditions or alternatively by reaction of benzaldehyde with a Wittig reagent under standard conditions.
  • a solvent such as water or ethanol
  • a compound of formula (I) [where A, R 1 and R 2 are as defined above and R 3 is H] may be synthesized by reacting a compound of formula (II') [where R 1 and R 2 are as defined above and R' is C1-5 alkyl] with an aniline of formula (HI) [where A is as defined above for a compound of formula (I)] in the presence of NaN(TMS) 2 at -10 °C to ambient temperature, preferably in dry THF, as described by J.Wang et al, Synlett, 2001, 1485.
  • aa c compound of formula (I) [where A, R and R are as defined above and R is H] may be prepared by reacting a compound of formula (H) [where R and R are as defined above and Y is OH] with a compound of formula (HI) [where A is as defined above for a compound of formula (I)] in the presence of an activating agent [such as BOP-C1] and two equivalents of a base [such as NEt 3 ] or by reacting a compound of formula (H) [where Y is Cl, Br or F] with a compound of formula (IH) in the presence of one equivalent of a base [such as NEt 3 , NaHCO 3 , KHCO 3 , Na 2 CO 3 or K 2 CO 3 ] in a solvent [such as dichloromethane, ethyl acetate or DMF] preferably at -10 to 30°C.
  • a base such as NEt 3 , NaHCO 3 , KHCO 3 , Na 2
  • a compound of formula (I) [where R .3 i ⁇ s as defined above for formula (I), except that it is not hydrogen] may be prepared by reacting a compound of formula (I) [where R 3 is hydrogen] with a species Y-R [where R is as defined for formula (I), except that it is not hydrogen; and Y is halogen, preferably Cl, Br or I; or Y is such that Y-R 3 is an anhydride: that is, when R 3 is COR*, Y is OCOR*] in the presence of a base [for example NaH, NEt 3 , NaHCO 3 or K 2 CO 3 ] in an appropriate solvent [such as ethyl acetate] or in a biphasic mixture [such as dichloromethane/water mixturte], at -10 to 30°C.
  • a base for example NaH, NEt 3 , NaHCO 3 or K 2 CO 3
  • an appropriate solvent such as ethyl acetate
  • novel compounds of formula (I) have, for practical purposes, a very advantageous spectrum of activities for protecting plants against diseases that are caused by fungi as well as by bacteria and viruses.
  • the compounds of formula (I) can be used in the agricultural sector and related fields of use as active ingredients for controlling plant pests.
  • the novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous cultivated plants.
  • the compounds of formula I can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later, for example from phytopathogenic microorganisms.
  • compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • the compounds according to present invention may be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management, etc.
  • the compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium,
  • Ascomycetes classes e.g. Venturia and Erysiphe, Podosphaera, Monilinia,
  • novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus).
  • target crops to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco
  • the compounds of formula (I) are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances.
  • the methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
  • Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO97/33890.
  • the compounds of formula (I) are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds.
  • further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
  • the compounds of formula (I) can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities.
  • Mixing components which are particularly preferred are azoles, such as azaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, fiusilazole, flutriafol, hexaconazole, imazalil, imiben- conazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carbin
  • flumorph dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb, IKF-916 (cyazofamid), kasugamycin, methasulfocarb, metrafenone, nicobifen, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin, zoxamide (RH7281).
  • a preferred method of applying a compound of formula (I), or an agrochemical composition which contains at least one of said compounds, is foliar application.
  • the frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen.
  • the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field.
  • the compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
  • a formulation that is, a composition containing the compound of formula (I)] and, if desired, a solid or liquid adjuvant, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
  • extenders for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
  • the agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula I, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.
  • Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from lOg to 1kg a.i./ha, most preferably from 20g to 600g a.i./ha.
  • convenient dosages are from lOmg to lg of active substance per kg of seeds.
  • EXAMPLE 1 This Example illustrates the preparation of Compound No. 1.15 [2-methyl-5- trifluoromethyl-2H-l,2,3-triazole-4-carboxylic acid methyl ester] and Compound No. 1.13 [2-methyl-5-trifluoromethyl-2H-l ,2,3-triazole-4-carboxylic acid].
  • l,2,3-Triazole-4,5-dicarboxylic acid dimethyl ester Y. Tanaka et al.
  • EXAMPLE 2 This Example illustrates the preparation of Compound No.1.03 [2-methyl-5- difluoromethyl-2H-l,2,3-triazole-5-carboxylic acid methyl ester]. a) Preparation of 5-Chlorocarbonyl-2-methyl-2H-l,2,3-triazole-4-carboxylic acid methyl ester.
  • EXAMPLE 3 This Example illustrates the preparation of Compound No.1.50 [2-methyl-5- fluoromethyl-2H-l,2,3-triazole-5-carboxylic acid methyl ester]. a) Preparation of 5-hydroxymethyl-2-methyl-2H-l,2.3-triazole-4-carboxylic acid methyl ester.
  • Example B-l Action against Puccinia recondita / wheat (Brownrust on wheat)
  • Example B-2 Action against Podosphaera leucotricha / apple (Powdery mildew on apple) 5 week old apple seedlings cv. Mclntosh are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after, the application apple plants are inoculated by shaking plants infected with apple powdery mildew above the test plants. After an incubation period of 12 days at 22°C and 60%r.h. under a light regime of 14/10hours (light/dark) the disease incidence is assessed.
  • Example B-3 Action against Venturia inaequalis / apple (Scab on apple)
  • Example B-4 Action against Erysiphe graminis / barley (Powdery mildew on barley) 1 week old barley plants cv. Regina are treated with the formulated test compound
  • Example B-5 Action against Botrytis cinerea / grape (Botrytis on grapes) 5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the grape plants are inoculated by spraying a spore suspension (lxl 0 6 conidia/ml) on the test plants. After an incubation period of 4 days at 21°C and 95%or.h. in a greenhouse the disease incidence is assessed. Compounds 2.029, 3.017 and 3.219 each show good activity in this test ( ⁇ 50% disease incidence).
  • Example B-6 Action against Botrytis cinerea / tomato (Botrytis on tomatoes)
  • Example B-7 Action against Septoria nodorum / wheat (Septoria leaf spot on wheat) 1 week old wheat plants cv. Arina are treated with the formulated test compound
  • Example B-8 Action against Helminthosporium teres / barley (Net blotch on barley)
  • Example B-9 Action against Alternaria solani / tomato (Early blight on tomatoes) 4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02%> active ingredient) in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (2xl0 5 conidia/ml) on the test plants. After an incubation period of 3 days at 20°C and 95%>r.h. in a growth chamber the disease incidence is assessed.
  • Example B-10 Action against Uncinula necator / grape (Powdery mildew on grapes) 5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02%> active ingredient) in a spray chamber. One day after application, the grape plants are inoculated by shaking plants infected with grape powdery mildew above the test plants. After an incubation period of 7 days at 26°C and 60%r.h. under a light regime of 14/lOhours (light/dark) the disease incidence is assessed.

Abstract

A compound of formula (1):where A is an ortho-substituted ring selected from a number of specified rings; R1 is halogen, cyano, nitro, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy or C 1-4 haloalkoxy or optionally substituted C 2-4 alkenyl, optionally substituted C 2-4 alkynyl or optionally substituted SO2(C 1-4)alkyl (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen and C 1-4 alkoxy); R 2 is C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy(C 1-4)alkyl or C 1-4 alkyltbio(C 1-4)alkyl or [optionally substituted aryl](C 1-4)alkyl- or [optionally substituted aryl]oxy(C l-4)a1kyl(where the optionally substituted aryl moieties may each have up to 3 substituents, each independently selected from halogen and C 1-4 alkoxy); R 3 is hydrogen, CH2C =CR4, CH2CR4=C(H)R4, CH=C=CH2 or COR5 or optionally substituted C 1-4 alkyl, optionally substituted C 1-4 alkoxy or optionally substituted (C I-4) alkylC(=O)O (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen and C 1-4 alkoxy, C 1-4 alkyl, C 1-2 haloalkoxy, bydroxy, cyano, carboxyl, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl and ethylsulfonyl), The compound of Formula (I) have microbiocidal activity, in particular fungicidal activity.

Description

CHEMICAL COMPOUNDS
The present invention relates to novel 1,2,3-triazole derivatives which have microbiocidal activity, in particular fungicidal activity. The invention also relates to novel intermediates used in the preparation of these compounds, to agrochemical compositions which comprise at least one of the novel compounds as active ingredient and to the use of the active ingredients or compositions in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.
The present invention provides a compound of formula (I):
Figure imgf000002_0001
where A is an σrt/zo-substituted ring selected from formulae (Al) to (A22);
Figure imgf000002_0002
Figure imgf000002_0003
(A2) (A3) (A4)
Figure imgf000002_0004
(A5) (A6) <A7)
Figure imgf000003_0001
(A8) (A9)
Figure imgf000003_0002
(A10) (Al l)
Figure imgf000003_0003
(A12) (A13) (A14) (A15)
Figure imgf000003_0004
Figure imgf000004_0001
(A22) Q is a single or a double bond; X is O, N(R18), S or (CR19R20)(CR21R22)m(CR23R24)n; R1 is halogen, cyano, nitro, Cι-4 alkyl, Cι.4 haloalkyl, Cι. alkoxy, Cι_4 haloalkoxy or optionally substituted C2.4 alkenyl, optionally substituted C2.4 alkynyl or optionally substituted SO2(Cι_4 )alkyl (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen and C alkoxy); R2 is C alkyl, C haloalkyl, Cι-4 alkoxy(Cι.4)alkyl or Cι-4 alkylthio(Cι.4)alkyl or [optionally substituted aryl](Cι_4)alkyl- or [optionally substituted aryl]oxy(Cι-4)alkyl- (where the optionally substituted aryl moieties may each have up to 3 substituents, each independently selected from halogen and C,.4 alkoxy); R3 is hydrogen, CH2C ≡€R4, CH2CR4=C(H)R4, CH-C^CH^ or COR5 or optionally substituted CM alkyl, optionally substituted C alkoxy or optionally substituted (CM) alkylC(=O)O (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen, CM alkoxy, CM alkyl, Cι_2 haloalkoxy, hydroxy, cyano, carboxyl, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl and ethylsulfonyl); each R4 is, independently, hydrogen, halogen, CM alkyl, C haloalkyl, CM alkoxy or CM alkoxy(Cι- )alkyl; R5 is hydrogen or optionally substituted Cι_6 alkyl, optionally substituted Cι_4 alkoxy, optionally substituted CM alkoxy(Cι_4)alkyl, optionally substituted CM alkylthio(Cι_4)alkyl or optionally substituted aryl (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen, Cι.6 alkoxy, Cι_6 haloalkoxy, cyano, hydroxy, methoxycarbonyl and ethoxycarbonyl); R6 is phenyl [optionally substituted by up to 3 substituents, each independently selected from halogen, cyano, nitro, CM alkyl, Cι-4 haloalkyl, C alkoxy, CM haloalkoxy, Cι- haloalkylthio, C(H)=N-OH, C(H)=N-O(C].6 alkyl), C(d.6 alkyl)=N-OH, C(Cι.6 alkyl)=N-O-(Cι_6 alkyl), (Z)pC≡CR25 and (Z)PCR28=CR26R27], a 5-6 membered heterocyclic ring [in which the ring contains 1 to 3 heteroatoms (each independently chosen from oxygen, sulphur and nitrogen) and the ring is optionally substituted by up to 3 substituents, each independently selected from halogen, cyano, nitro, C alkyl, CM haloalkyl, C alkoxy, CM haloalkoxy, C(H)=N-O-(Cι.6 alkyl) and C(d.6 alkyl)=N-O-(Cι.6 alkyl)], C3..2 alkyl [optionally substituted by up to 6 substituents, each independently selected from halogen, cyano, C alkoxy, C thioalkyl, COO-CM alkyl, =N-OH, =N-O-(C alkyl),
C3-s cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from CM alkyl, halogen, CM alkoxy and CM haloalkoxy) and C4.8 cycloalkenyl (itself optionally substituted by up to 3 substituents, each independently selected from CM alkyl, halogen, C alkoxy and CM haloalkoxy)], C2-ι2 alkenyl [optionally substituted by up to 6 substituents, each independently selected from halogen, cyano, C alkoxy, C thioalkyl, COO-(Cι_4 alkyl), -N-OH, =N-O-(Cι_4 alkyl), C3-8 cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from Cι-4 alkyl, halogen, Cι-4 alkoxy and Cι-4 haloalkoxy) and C4-8 cycloalkenyl (itself optionally substituted by up to 3 substituents, each independently selected from C alkyl, halogen, CM alkoxy and C haloalkoxy)], C2_ι2 alkynyl [optionally substituted by up to 6 substituents, each independently selected from halogen, cyano, CM alkoxy, C thioalkyl, COO-Cι_4 alkyl, =N-OH, =N-O-(C alkyl), C3.8 cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from C alkyl, halogen, Cμ4 alkoxy and CM haloalkoxy), Si(CH3)3 and C4.8 cycloalkenyl (itself optionally substituted by up to 3 substituents, each independently selected from C alkyl, halogen, CM alkoxy and C haloalkoxy)], C3.8 cycloalkyl [optionally substituted by up to 3 substituents, each independently selected from halogen, CM alkyl, C haloalkyl, CM alkoxy, C haloalkoxy, CM thioalkyl, C3.6 cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from Cι-4 alkyl, halogen, CM alkoxy and C haloalkoxy) and phenyl (itself optionally substituted by up to five independently selected halogen atoms)], C4.8 cycloalkenyl [optionally substituted by up to 3 substituents, each independently selected from halogen, CM alkyl, CM haloalkyl, C alkoxy, CM haloalkoxy, C thioalkyl, C3.6 cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from C],4 alkyl, halogen, CM alkoxy and C haloalkoxy) and phenyl (itself optionally substituted by up to five independently selected halogen atoms)], C6.ι2 bicycloalkyl [optionally substituted by up to 3 substituents, each independently selected from halogen, CM alkyl and CM haloalkyl] or an aliphatic, saturated or unsaturated group [in which the group contains three to thirteen carbon atoms and at least one silicon atom and, optionally, one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, and the group is optionally substituted by up to four independently selected halogen atoms]; R7, R8, R9, R10, Rn and R12 are each, independently, hydrogen, halogen, cyano, nitro, Cμ4 alkyl, C haloalkyl, C alkoxy, d-4 haloalkoxy, C thioalkyl or C thiohaloalkyl; R13, R14, R15, R16 and R17 are each, independently, hydrogen, halogen, CM alkyl, C(O)CH3, CM haloalkyl, C alkoxy, Ci_4 haloalkoxy, CM thioalkyl, C thiohaloalkyl, hydroxymethyl or CM alkoxymethyl; R18 is hydrogen, CM alkyl, CM alkoxy(Cι_4)alkyl, formyl, C(=O)Cι-4 alkyl (optionally substituted by halogen or Cι-4-alkoxy) or C(=O)O-Cι-6 alkyl (optionally substituted by halogen, CM alkoxy or CN); R19, R20, R21, R22, R23 and R24 are each, independently, Cι.6 alkyl, Cι-6 alkenyl [both optionally substituted by halogen, hydroxy, =O, CM alkoxy, O-C(O)-Cι-4 alkyl, aryl or a 3-7 membered carbocyclic ring (itself optionally substituted by up to three methyl groups)], a 3-7 membered carbocyclic ring (optionally substituted by up to three methyl groups and optionally containing one heteroatom selected from nitrogen and oxygen), hydrogen, halogen, hydroxy or Cι-4 alkoxy; or R19R20 together with the carbon atom to which they are attached form a carbonyl-group, a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups), Cι-6 alkylidene (optionally substituted by up to three methyl groups) or C3.6 cycloalkylidene (optionally substituted by up to three methyl groups); R is hydrogen, halogen, C alkyl,
CM haloalkyl, CM alkoxy(C )alkyl, Cι.4 haloalkoxy(Cι_4)alkyl or Si(C alkyl)3; R26 and R27 are each, independently, hydrogen, halogen, CM alkyl or CM haloalkyl; R28 is hydrogen, CM alkyl or CM haloalkyl; m is 0 or 1; n is 0 or 1; p is 0 or 1; and Z is CM alkylene. Halogen is fluoro, chloro, bromo or iodo.
Each alkyl moiety is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, ra-butyl, «-pentyl, n-hexyl, zso-propyl, see-butyl, iso-butyl, tert-butyl, Heo-pentyl, n-heptyl, 1,3-dimethylbutyl, 1,3-dimethylpentyl, l-methyl-3 -ethyl-butyl or 1 ,3,3-trimethylbutyl. Haloalkyl moieties are alkyl moieties which are substituted by one or more of the same or different halogen atoms and are, for example, CF3, CF2C1, CHF , CH2F, CC13, CF3CH2, CHF2CH2, CH2FCH2, CH3CHF or CH3CF2. Alkenyl and alkynyl moieties can be in the form of straight or branched chains. The alkenyl moieties, where appropriate, can be of either the (E)- or (Z -configuration. Examples are vinyl, allyl, ethynyl and propargyl.
Alkylidene moieties can be in the form of straight or branched chains. Alkylidene includes methylidene [CH2=C], ethylidene [CH3C(H)=C], «-propylidene, t-propylidene [(CH3)2C=C], «-butylidene, t-butylidene, 2-butylidene, n-pentylidene, z-pentylidene, neø-pentylidene, 2-pentylidene, «-hexylidene, 2-hexylidene, 3-hexylidene, t-hexylidene and neo-hexylidene.
Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
Cycloalkenyl includes cyclobutenyl, cyclopentenyl, cyclohexenyl and cycloheptenyl. Cycloalkylidene includes cyclopropylidene [c(C3H4)=C], cyclobutylidene, cyclopentylidene and cyclohexylidene.
Bicycloalkyl includes bicyclo[l,l,l]pentyl, bicyclo[2,l,l]hexyl, bicyclo[2,2,l]heptyl, bicyclo[2,2,2]octyl, bicyclo[3,2,l]octyl and bicyclo[3,2,2]nonyl. Aryl includes phenyl, naphthyl, anthracyl, fluorenyl and indanyl but is preferably phenyl.
In one aspect of the invention, A is as defined above provided that it is not (Al). In another aspect of the invention, R is as defined above provided that it is not an aliphatic, saturated or unsaturated group [in which the group contains three to thirteen carbon atoms and at least one silicon atom and, optionally, one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, and the group is optionally substituted by up to four independently selected halogen atoms].
In a further aspect of the invention, A is as defined above provided that it is not (Al) when R6 is an aliphatic, saturated or unsaturated group [in which the group contains three to thirteen carbon atoms and at least one silicon atom and, optionally, one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, and the group is optionally substituted by up to four independently selected halogen atoms]. Preferably Q is a single bond. Preferably n is 0.
Preferably m is 0. Preferably A is selected from formulae (Al), (A2), (A3), (A16), (A17), (A18), (A19), (A20) and (A22).
More preferably A is selected from formulae (Al), (A2), (A18), (A19) and (A22). Even more preferably A is selected from one of the following ortho-substituted rings:
Figure imgf000008_0001
where R , 13 and R .14 are each, independently, selected from H and CM alkyl. Preferably X is O, NR18 or (CR19R20)(CR21R22)m(CR23R24)n.
More preferably X is O or (CR19R20)(CR21R22)m(CR23R24)n.
Even more preferably X is (CR19R20)(CR2,R22)m(CR23R24)n.
Most preferably X is (CR19R20).
Preferably R1 is C alkyl, CM haloalkyl, NO2, CN or OCF3. More preferably R1 is CHF2, CF3, CH2F, CF2C1, CH3 or C2H5.
Even more preferably R1 is CHF2, CF3, CH2F, CF2C1 or CH3.
Most preferably R1 is CHF2, CF3 or CH2F.
Preferably R is Cι_4 alkyl, CM haloalkyl, CM alkoxy(Cι_4)alkyl or C alkylthio(Cι. )alkyl. More preferably R2 is CH3, CF3, C2H5, CH2OCH3 or CH2SCH3.
Even more preferably R2 is CH3 or C2H5.
Most preferably R2 is CH3.
Preferably R3 is hydrogen, CH2C≡CR4, CH2CR4=C(H)R4, CH=C=CH2 or COR5.
More preferably R3 is H, CH2C≡€H, CH=C=CH2, CH2CH=CH2 or COCH3. Still more preferably R3 is H, CH2C ≡€H, CH=C=CH2 or CH2CH-CH2.
Even more preferably R3 is H, CH2C ≡CH or CH=C=CH2.
Most preferably R3 is H.
Preferably each R is, independently, H, halogen, Cι-4 alkyl or CM alkoxy. More preferably each R4 is, independently, H, Cl, Br, CH3 or CH3O.
Still more preferably each R4 is, independently, H, Cl or CH3.
Most preferably each R4 is H.
Preferably R5 is H, C].6 alkyl, Cι_4 alkoxy or CM alkoxy(Cι_ )alkyl. More preferably R5 is H, methyl, OC(CH3)3 or CH2OCH3.
Even more preferably R5 is H or methyl.
Preferably R6 is chosen from C -ι0 alkyl, C3-9 haloalkyl, C3.7 cycloalkyl [optionally substituted by C cycloalkyl (itself optionally substituted by Cι.2 alkyl) or by up to two CM alkyl groups], an aliphatic group [which contains three to ten carbon atoms and at least one silicon atom and, optionally, one oxygen atom], thienyl [optionally substituted by halo], furyl [optionally substituted by halo], pyridyl [optionally substituted by halo], oxazolyl, isoxazolyl and
Figure imgf000009_0001
where Rc and Rd are, independently, H, Cl, Br, F, I, CN, NO2, C alkyl, CF3, SCF3, OCF3, CH=NOH, CH=N-OC,,6 alkyl, C≡CH, C≡C-Si(CH3)3, C(H)-CH2 or C(H)=CH(C alkyl).
More preferably R6 is C3. alkyl, C3.6 cycloalkyl [optionally substituted by CM alkyl or a C3 cycloalkyl (itself optionally substituted by Ci.2 alkyl)], an aliphatic group (which contains three to eight carbon atoms and at least one silicon atom) or
Figure imgf000009_0002
where Re is Cl, Br, F, CF3, OCF3, CH=N-OCM alkyl, C≡CH, C≡C-Si(CH3)3 or C(H)=CH2 [in one aspect it is preferred that Re is Cl, Br, F, CF3, OCF3, CH=N-OC alkyl, C≡CH or C(H)=CH2]. Even more preferably R6 is chosen from one of the following moieties:
Figure imgf000010_0001
where Re is Cl, Br, F, CF3, C≡CH, C≡C-Si(CH3)3 or CH=N-OC alkyl [in one aspect it is preferred that Re is Cl, Br, F, CF3, C≡CH or CH=N-OC alkyl]. Preferably R7 is H, F or CH3. Preferably R8 is H. Preferably R9 is H. Preferably R10 is H. Preferably R11 is H.
Preferably R12 is H.
Preferably R13, R14, R15, R16 are each, independently, H, CH3, C2H5, CF3, CH3O, C(O)CH3 or CH3OCH2. More preferably R13, R14, R15, R16 are each, independently, H or CH3. Preferably R17 is H.
Preferably R18 is H, CH3, C2H5, C(O)OCι-4 alkyl (optionally substituted with halogen or Cι-4 alkoxy) or COH.
More preferably R18 is C(O)OC]. alkyl (optionally substituted with halogen or CM alkoxy) or COH. Even more preferably R18 is C(O)OCι-4 alkyl (optionally substituted with halogen or
CM alkoxy).
Most preferably R18 is C(O)OC alkyl.
Preferably R19 and R20 are each, independently, H, halogen, Cι-5 alkyl, Cι_3 alkoxy, CH2O, C3.6 cycloalkyl, CH2O-C(=O)CH3, CH2-C3.6 cycloalkyl or benzyl; or R19 and R20 together with the carbon atom to which they are attached form a carbonyl group, a 3-5 membered carbocyclic ring, C1-5 alkylidene or C3.6 cycloalkylidene. More preferably R19 and R20 are, independently, H, CH3, C2H5, «-C3H7, z'-C3H7, t-C4H , CH(C2H5) , CH2-cyclopropyl or cyclopentyl; or R19 and R20 together with the carbon atom to which they are attached form a 3-membered carbocyclic ring.
Preferably R21 is H or CH3.
Preferably R22 is H or CH3.
Preferably R23 is H or CH3.
Preferably R24 is H or CH3.
Compounds of formula (II):
Figure imgf000011_0001
1 9 where R and R are as defined above for a compound of formula (I) and Y is halogen, hydroxy or C1.5 alkoxy, are useful as intermediates in the preparation of compounds of formula (I).
Some compounds of formula (IT) are already known in the literature [B.Iddon et al. J.Chem. Soc. PerkinTrans. 1, 1341 (1996); M.Begtrup et al., Acta Chemica Scand., 19, 2022 (1965); D.R.Buckle et al., J.Chem.Res, Syn. 10, 292 (1982); and A.Peratoner et al., Sci.Fis.Mat.Nat.Rend 5, 16 (1907)] but others are novel.
Therefore, in another aspect the present invention provides a compound of formula (13) where R1 and R2 are as defined above for a compound of formula (I) and Y is halogen, hydroxy or Cι_5 alkoxy; provided that when R1 is chloro and R2 is 4-CH3O-C6H -CH2-, Y is not C2H5O; when R1 is CH3O and R2 is CH3, Y is not C2H5O; when R1 is bromo and R2 is CH3OCH2, Y is not CH3O; and when R1 is CH3 and R2 is C2H5, Y is not OH.
Preferably Y is hydroxy, chloro, fluoro or Cι.3 alkoxy.
Some compounds of formula (IHa) are also novel but some are described in the literature [see, for example, L. A Paquette et al., J Amer. Chem Soc. 99, 3734 (1977); H. Plieninger et al., Chem. Ber. 109, 2121 (1976); Kasansski et al., Zh. Obshch.Khim. (1959), 29, 2588; and A. J. Kirby et al, J. Chem. Soc, Per/tin Trans. 2, 1997, 1081].
Figure imgf000012_0001
Anilines of formula (Ilia) are novel when R13, R14, R15, R16, Q and X are as defined above for a compound of formula (I); provided that when R13, R14, R15 and R16 are each H then X is not CH when Q is a double bond and X is not CH2CH2 when Q is a single bond or a double bond; and when R13 is CH3, R14 is OCH3 and R15 and R16 are both H then X is not CH2CH2 when Q is a single bond.
Therefore, in a further aspect, the present invention provides a compound of formula (IHa) where R13, R14, R15, R16, Q and X are as defined above for a compound of formula (I); provided that when R13, R14, R15 and R16 are each H then X is not CH2 when Q is a double bond and X is not CH2CH2 when Q is a single bond or a double bond; and when R13 is CH3, R14 is OCH3 and R15 and R16 are both H then X is not CH2CH2 when Q is a single bond.
The compounds of formula (I), (If) and (Ilia) may exist as different geometric or optical isomers or in different tautomeric forms. This invention covers, for each formula, all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
The compounds in Tables 1 to 28 below illustrate compounds of the invention. Table 1 provides 59 compounds of formula (II) wherein R1, R2 and Y are as defined in Table 1. Table 1
Figure imgf000012_0002
Figure imgf000013_0001
Figure imgf000014_0001
Table X represents Table 2 [when X is 2], Table 3 [when X is 3], Table 4 [when X , Table 5 [when X is 5], Table 6 [when X is 6] and represents Table 7 [when X is 7].
Table X
Figure imgf000014_0002
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Table 2 provides 457 compounds of formula (1-2):
Figure imgf000023_0001
wherein R2, R3, R6 and R7 are as defined in Table 2.
Table 3 provides 457 compounds of formula (1-3):
Figure imgf000023_0002
wherein R , R , R and R are as defined in Table 3.
Table 4 provides 457 compounds of formula (1-4):
Figure imgf000023_0003
wherein R2, R3, R6 and R7 are as defined in Table 4.
Table 5 provides 457 compounds of formula (1-5):
Figure imgf000023_0004
wherein R2, R3, R6 and R7 are as defined in Table 5. Table 6 provides 457 compounds of formula (1-6):
Figure imgf000024_0001
wherein R2, R3, R6 and R7 are as defined in Table 6.
Table 7 provides 457 compounds of formula (1-7):
Figure imgf000024_0002
wherein R2, R3, R6 and R7 are as defined in Table 7.
Table Y represents Table 8 [when Y is 8], Table 9 [when Y is 9], Table 10 [when Y is 10], Table 11 [when Y is 11], Table 12 [when Y is 12], Table 13 [when Y is 13], Table 14 [when Y is 14], Table 15 [when Y is 15], Table 16 [when Y is 16], Table 17 [when Y is 17], Table 18 [when Y is 18] and represents Table 19 [when Y is 19].
Table Y
Figure imgf000024_0003
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0003
Table 8 provides 364 compounds of formula (1-8):
Figure imgf000031_0001
wherein R2, R3,.and R6 are as defined in Table 8. Table 9 provides 364 compounds of formula (1-9):
Figure imgf000031_0002
wherein R2, R3, and R6 are as defined in Table 9.
Table 10 provides 364 compounds of formula (I- 10):
Figure imgf000032_0001
wherein R , R , and R are as defined in Table 10.
Table 11 provides 364 compounds of formula (I-l 1):
Figure imgf000032_0002
wherein R2, R3, and R6 are as defined in Table 11.
Table 12 provides 364 compounds of formula (1-12):
Figure imgf000032_0003
wherein R2, R3, and R are as defined in Table 12. Table 13 provides 364 compounds of formula (1-13):
Figure imgf000032_0004
wherein R2, R3, and R6 are as defined in Table 13. Table 14 provides 364 compounds of formula (1-14):
Figure imgf000033_0001
wherein R2, R3, and R6 are as defined in Table 14.
Table 15 provides 364 compounds of formula (1-15):
Figure imgf000033_0002
wherein R , R , and R are as defined in Table 15.
Table 16 provides 364 compounds of formula (1-16):
Figure imgf000033_0003
wherein R2, R3, and R6 are as defined in Table 16. Table 17 provides 364 compounds of formula (1-17):
Figure imgf000033_0004
wherein R , R , and R are as defined in Table 17. Table 18 provides 364 compounds of formula (1-18):
Figure imgf000034_0001
wherein R2, R3, and R6 are as defined in Table 18.
Table 19 provides 364 compounds of formula (1-19):
Figure imgf000034_0002
wherein R2, R3, and R6 are as defined in Table 19.
Table Z represents Table 20 [when Z is 20], Table 21 [when Z is 21], Table 22 [when Z is 22], Table 23 [when Z is 23], Table 24 [when Z is 24] and represents Table 25 [when Z is 25].
Table Z
Figure imgf000034_0003
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Table 20 provides 182 compounds of formula (1-20):
Figure imgf000046_0002
wherein R • 2 , R and A are as defined in Table 20.
Table 21 provides 182 compounds of formula (1-21):
Figure imgf000046_0003
wherein R2, R3 and A are as defined in Table 21.
Table 22 provides 182 compounds of formula (1-22):
Figure imgf000046_0004
wherein R2, R3 and A are as defined in Table 22.
Table 23 provides 182 compounds of formula (1-23):
Figure imgf000046_0005
wherein R , R and A are as defined in Table 23. Table 24 provides 182 compounds of formula (1-24):
Figure imgf000047_0001
wherein R2, R3 and A are as defined in Table 24.
Table 25 provides 182 compounds of formula (1-25):
Figure imgf000047_0002
wherein R2, R3 and A are as defined in Table 25.
Table 26 provides 133 compounds of formula (TJJa) where R1J, R1 , R1D, R10, Q and X are as defined in Table 26. Q is shown to be either a single bond (-) or a double bond (=).
Table 26
Figure imgf000047_0003
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Table ZZ represents Table 27 (when ZZ is 27) and represents Table 28 (when ZZ is
28).
Table ZZ
Figure imgf000050_0002
Figure imgf000051_0003
Table 27 provides 42 compounds of formula (1-27) where R1, R2, R3 and R6 are as defined in Table 9.
Figure imgf000051_0001
Table 28 provides 42 compounds of formula (1-28) where R1, R2, R3 and R6 are as defined in Table 10.
Figure imgf000051_0002
Throughout this description, temperatures are given in degrees Celsius; "NMR" means nuclear magnetic resonance spectrum; MS stands for mass spectrum; "%" is percent by weight, unless corresponding concentrations are indicated in other units; "syn' refers to a syn configuration of the relevant substituent with respect to the annellated benzene ring; and "anti" refers to an anti configuration of the relevant substituent with respect to the anellated benzene ring.
The following abbreviations are used throughout this description: m.p. = melting point b.p.= boiling point, s = singlet br = broad d = doublet dd = doublet of doublets t = triplet q = quartet m = multiplet ppm = parts per million
Table 29 shows selected melting point data for compounds of Tables 1 to 28.
Table 29
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
The compounds according to formula (I) may be prepared according to the following reaction schemes.
(a) Preparation of a compound of formula (II).
Schemes 1, 2 and 3 demonstrate that a compound of formula E, H, K, L, N, O, P, R,
S. X, TJ, V, W, Y or Z [where R1 and R2 are as defined above for formula (II); and R' is
Cι-5 alkyl] {each of which is a compound of formula (IT), as defined above} maybe prepared by a reaction sequence starting with a l,2,3-triazole-4,5-dicarboxylic acid diester of formula A [Y.Tanaka et al., Tetrahedron, 29, 3271 (1973)] [where each R' is, independently, Cι-5 alkyl] (preferably the dimethyl ester).
Scheme 1
Figure imgf000055_0001
Treatment of A with an alkylating agent [such as R2-halo (where R2 is as defined above for formula (13); and halo is preferably iodo) or an appropriate sulphate, sulphonate or carbonate ester] in the presence of a base [such as K2CO3, Na2CO3 or NEt3] in a suitable solvent [such as acetonitrile, DMF or dimethylacetamide] at ambient to elevated temperatures furnishes a mixture of regioisomers, of formulae B and C, which may be separated by conventional methods. Saponification of a compound of formula B with up to one equivalent of a base [such as KOH, NaOH or LiOH] in a protic solvent [such as methanol], preferably under reflux conditions, provides a mono-ester of formula D. Subsequent reaction of a compound of formula D with a fluorinating agent [such as DAST (diethylamino sulphur trifloride) or, preferably, SF4] in the presence of hydrofluoric acid gives a 5-CF3-l,2,3-triazole-4-carboxylic acid ester of formula E. Alternatively, treatment of a compound of formula D with a chlorinating agent [such as thionyl chloride or phosgene] under standard conditions results in an acid chloride of formula F which may be reduced catalytically in an inert solvent [for example ethyl acetate or THF] in the presence of a base [for example Hunig base] to give an aldehyde-ester of formula G (modified Rosenmund conditions). Fluorination of a compound of formula G by means of D AST, dimethoxy-DAST or SF4 in the presence of hydrofluoric acid, optionally with solvent, preferably at elevated temperatures, forms a 5-difluoromethyl-l,2,3-triazole-4-carboxylic acid ester of formula H.
Metal hydride reduction of a compound of formula G [for example by NaBH4 or LiBH4] in methanol provides a 5-hydroxymethyl-l ,2,3-triazole of formula J, from which a 5-fluoromethyl derivative of formula K may be obtained by fluorination under mild conditions, preferably with DAST at low temperatures (0 to -78°C) in an inert solvent [such as dichloromethane].
Alternatively, hydride reduction of a compound of formula J by conventional methods [for example via its mesylate, tosylate or iodide] results in a 5-methyl-l- ,2,3- triazole of formula L.
Chlorination of compound of formula D [for example by thionyl chloride] followed by treatment with ammonia, preferably in a protic solvent [such as water, methanol or ethanol] furnishes an amide of formula M from which a 5-cyano- 1,2,3- triazole of formula N may be obtained by means of a dehydrating agent [such as phosphorylchloride] .
Scheme 2
Figure imgf000057_0001
Further transformations to prepare a compound of formula (IT) [where R1 and R2 are as defined above for formula (I); Y is OR' and R' is Cι_5 alkyl] include aHofmann rearrangement of an amide of formula M with NaOBr or NaOCl in the presence of NaOH to give a 5-amino-l,2,3-triazole of formula O.
Diazotation of a compound of formula O by means of sodium nitrite under aqueous acidic conditions [for example sulphuric acid] or with a nitrite ester [for example (t)-amyl nitrite] in an organic solvent [for example acetone, dichloromethane or THF] in the presence of a halogenide [such as CuCl or CuBr] gives a 5-halo-l,2,3-triazole of formula P [where halo is Cl or Br] which on treatment with a fluorinating agent [such as KF or CsF], preferably in DMF or N-methylpyrrolidone at elevated temperatures, results in a 5-fluoro-l,2,3-triazole of formula V.
By diazotation of a compound of formula O and subsequent acidic aqueous hydrolysis under heating, a 5-hydroxy-l,2,3-triazole of formula O_ may be obtained. Treatment of a compound of formula O_ with an alkylating agent [such as methyl iodide, dimethylsulphate or dimethylcarbonate] and a base [for example NaH, K2CO3 or Na2CO3] in a polar solvent [for example DMF, DMSO or CH3CN] gives a 5-methoxy-l,2,3-triazole of formula R which may be converted to a trichloromethoxy derivative of formula S with a chlorinating agent [such as chlorine] in the presence of azoisobutyronitrile (AIBN) or ultra-violet irradiation at elevated temperature. By treatment of a compound of formula S with a fluorinating agent [for example KF or SbF3] a 5-trifluoromethoxy-l,2,3-triazole of formula T may be prepared. Oxidation of a compound of formula O with [for example sodium perborate] or treatment according to A. Sudalai et al. [ Angew. Chem. Int. Ed. 40, 405 (2001)] leads to a 5-nitro derivative of formula U. Alternatively, a compound of formula U may also be obtained by treatment of a compound of formula P or V with NaNU2 in an polar solvent [such as DMF, sulpholane or N-methylpyrrolidone] at elevated temperatures.
Scheme 3
Figure imgf000058_0001
i W Y
o
F
N. ,N N
R2 z
Transformations of a compound of formula (II') [where R and R are as defined in formula (I); Y is OR'; and R' is C1-5 alkyl] to give a compound of formula (II) [where R1 and R2 are as defined in formula (I) and Y is halo or hydroxy] includes saponification with a base [such as KOH or NaOH] in a protic solvent [such as methanol, ethanol or water], at ambient or elevated temperature to give a l,2,3-triazole-4-carboxylic acid of formula W. Chlorination of a compound of formula W under standard conditions [for example with thionyl chloride, phosgene or oxalyl chloride] yields an acid chloride of formula Y. Fluorination of a compound of formula W with D AST or SF4 under mild conditions
[low to ambient temperatures], preferably in an inert solvent [such as dichloromethane] gives an acid fluoride of formula Z.
(b) Preparation of a compound of formula (III). A compound of formula (HI)
H2N-A (III) where A is as defined above for a compound of formula (I), is useful as an intermediate in the preparation of a compound of formula (I). Most o-substituted amino-aryls and amino-heteroaryls of formula (III) are known from the literature, but some are novel.
A compound of formula (IHa) may be obtained according to scheme 4:
Figure imgf000059_0001
Treatment of an ort/zo-substituted nitrobenzonorbornadiene of formula AA (where
R13, R14, R15, R16 and X are as defined above for a compound of formula (I)) [obtained through Diels-Alder addition of an in situ generated benzyne, for example, starting from a 6-nitroanthranilic acid as described by L.Paquette et al, J. Amer. Chem. Soc. 99, 3734 (1977) or from other suitable benzyne precursers (see H. Pellissier et al. Tetrahedron, 59, 701 (2003) with a 5-7 membered cyclic 1,4-diene according to, or by analogy to,
L.Paquette et al, J. Amer. Chem. Soc. 99, 3734 (1977), D. Gravel et al. Can. J. Chem. 69, 1193 (1991), J.R. Malpass et al. Tetrahedron, 48, 861 (1992), D.E. Lewis et al. Synthetic Communications, 23, 993 (1993), R.N. Warrener et al. Molecules, 6, 353 (2001), R.N. Warrener et al. Molecules, 6, 194 (2001) or I. Fleming et al. J. Chem. Soc, Perkin Trans.1, 2645 (1998)] with Zn, in the presence of ammonium chloride or an aluminium amalgam, in a protic solvent [such ethanol or water] gives an aniline of formula CC, whilst catalytic hydrogenation of a compound of formula AA with, for example, RaNi, Pd/C or Rh/C in the presence of a solvent [for example THF, ethyl acetate, methanol or ethanol] affords an aniline of formula BB. Compounds of formula (nib)
Figure imgf000059_0002
where R6 is an aliphatic or alicyclic, saturated or unsaturated group [in which the group contains three to thirteen carbon atoms and at least one silicon atom and, optionally, one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, and the group is optionally substituted by up to four independently selected halogen atoms] and R7"10 are as defined in formula (I) may be prepared by analogy with literature examples. References include e.g. E.A.Chernyshew et al., Bull. Acad. Sci. USSR ,1960, 1323; K.T.Kang et al., Tetrahedron Letters, 32, 4341 (1991), Synthetic Comm., 24, 1507 (1994); M.Murata et al, Tetrahedron Letters 40, 9255 (1999); A.Falcou et al., Tetrahedron 56, 225 (2000); A.Arcadi et al., Tetrahedron Letters 27, 6397 (1986); KCNicolaou et al., Chem.Eur. J. 1, 31 (1995); N.Chatani et al., JOrg. Chem. 60, 834 (1995); T. Stuedemann et al., Tetrahedron 54, 1299 (1998); P.F.Hurdlik et al., J. Org. Chem. 54, 5613 (1989); K.Karabelas et al., J. Org. Chem. 51, 5286 (1986); TJeffery, Tetrahedron Letters 40, 1673 (1999) and Tetrahedron Letters 41, 8445 (2000); KOlofson et al., J. Org. Chem. 63, 5076 (1998); H.Uirata et al, Bull. Chem. Soc. Jap. 57, 607 (1984); and G.Maas et al., Tetrahedron 49, 881 (1983); and references cited therein. Recent reviews for the introduction of Si-containing functionalities into phenyl derivatives can be found in "The Chemistry of Organosilicon Compounds", Vols. 1-3, S.Patai, Z.Rappaport and Z.Rappaport, Y.Apeloid eds., Wiley 1989, 1998, 2001 and "Houben-Weyl Science and Synthesis", Organometallics Vol. 4, I.Fleming ed., G.Thieme 2002.
Another group of anilines comprises compounds of formula (lTlc)
Figure imgf000060_0001
where R' represents C2- alkyl, C2- haloalkyl or C3-6 cycloalkyl (itself optionally substituted by up to 3 substituents, independently selected from halo, Cι_ alkyl, Cι-3 haloalkyl and Cι- haloalkoxy).
A compound of formula (Hlc) may be prepared by a reaction sequence starting with a crossed aldol condensation of benzaldehyde with a ketone of formula CH3C(O)R' [where R' is as defined above for a compound of formula (Hlc)] in the presence of NaOH or KOH in a solvent (such as water or ethanol) and usually under reflux conditions or alternatively by reaction of benzaldehyde with a Wittig reagent under standard conditions. The resulting ,β -unsaturated ketone of formula (IN) [where R' is as defined above for a compound (file)]:
Figure imgf000061_0001
may then be converted into a compound of formula (V) [where R' is as defined above for a compound (Die)]:
Figure imgf000061_0002
by reacting first with hydrazine hydrate in ethanol under reflux conditions and then heating (in the range of from 150 to 250°C) in the presence of KOH (distilling off the solvent). After nitration with HΝO3-H O or HNO3-acetic anhydride in a cooled vessel (in the range of from -30°C to 0°C), the resulting olp -mixture of a nitrobenzene of formula (VI) [where R' is as defined above for a compound (Die)]:
Figure imgf000061_0003
may then be separated and catalytically reduced (Pt/C/ H2 or Ra-Ni H2) in a solvent (such as methanol, ethanol of THF) at ambient temperature to give a compound of formula
(iπc).
Alternatively the synthesis of a compound of formula (Did) [where R,a is hydrogen or methyl]
Figure imgf000061_0004
may be accomplished by a reaction sequence started by a Wittig reaction of o-nitrobenzaldehyde with an ylide, prepared from a cyclopropylmethyltriphenylphosphonium bromide in the presence of a strong base [such as NaH] in a solvent [such as DMSO], in the range of 0-85°C. The resulting E/Z-mixture of a compound of formula (Vπ)
Figure imgf000062_0001
[where R , ' .a is hydrogen or methyl] may be converted to a compound of formula (V1JJ-)
Figure imgf000062_0002
by the application of the Simmons Smith reaction (Zn-Cu, CH2I2, ether as a solvent) to the olefin group of a compound of formula (VII) to give a compound of formula (VDI). The reduction of the nitro moiety of a compound of formula (VDI) to give a compound of formula (Hlc) may be performed by using the same conditions as described above for a compound of formula (VI). (c) Preparation of a compound of formula (I).
Scheme 5
Figure imgf000062_0003
or) (')
A compound of formula (I) [where A, R1 and R2 are as defined above and R3 is H] may be synthesized by reacting a compound of formula (II') [where R1 and R2 are as defined above and R' is C1-5 alkyl] with an aniline of formula (HI) [where A is as defined above for a compound of formula (I)] in the presence of NaN(TMS)2 at -10 °C to ambient temperature, preferably in dry THF, as described by J.Wang et al, Synlett, 2001, 1485. Scheme 6
Figure imgf000063_0001
1 ^
Alternatively ,, aa c compound of formula (I) [where A, R and R are as defined above and R is H] may be prepared by reacting a compound of formula (H) [where R and R are as defined above and Y is OH] with a compound of formula (HI) [where A is as defined above for a compound of formula (I)] in the presence of an activating agent [such as BOP-C1] and two equivalents of a base [such as NEt3] or by reacting a compound of formula (H) [where Y is Cl, Br or F] with a compound of formula (IH) in the presence of one equivalent of a base [such as NEt3, NaHCO3, KHCO3, Na2CO3 or K2CO3] in a solvent [such as dichloromethane, ethyl acetate or DMF] preferably at -10 to 30°C.
Scheme 7
Figure imgf000063_0002
(l) [R3 = H] (I) [R3 as defined above but not H]
A compound of formula (I) [where R .3 i ■s as defined above for formula (I), except that it is not hydrogen] may be prepared by reacting a compound of formula (I) [where R3 is hydrogen] with a species Y-R [where R is as defined for formula (I), except that it is not hydrogen; and Y is halogen, preferably Cl, Br or I; or Y is such that Y-R3 is an anhydride: that is, when R3 is COR*, Y is OCOR*] in the presence of a base [for example NaH, NEt3, NaHCO3 or K2CO3] in an appropriate solvent [such as ethyl acetate] or in a biphasic mixture [such as dichloromethane/water mixturte], at -10 to 30°C.
Surprisingly, it has now been found that the novel compounds of formula (I) have, for practical purposes, a very advantageous spectrum of activities for protecting plants against diseases that are caused by fungi as well as by bacteria and viruses.
The compounds of formula (I) can be used in the agricultural sector and related fields of use as active ingredients for controlling plant pests. The novel compounds are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous cultivated plants. The compounds of formula I can be used to inhibit or destroy the pests that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later, for example from phytopathogenic microorganisms.
It is also possible to use compounds of formula (I) as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
Furthermore the compounds according to present invention may be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage, in hygiene management, etc. The compounds of formula (I) are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium,
Plasmopara). Outstanding activity has been observed against powdery mildew (Erysiphe spp.). Furthermore, the novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus). Within the scope of present invention, target crops to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.
The compounds of formula (I) are used in unmodified form or, preferably, together with the adjuvants conventionally employed in the art of formulation. To this end they are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances. As with the type of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects. Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO97/33890.
The compounds of formula (I) are normally used in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession with further compounds. These further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
The compounds of formula (I) can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities. Mixing components which are particularly preferred are azoles, such as azaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, fiusilazole, flutriafol, hexaconazole, imazalil, imiben- conazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carbinole, such as ancymidol, fenarimol, nuarimol; 2-amino-pyrimidines, such as bupirimate, dimethirimol, ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil; pyrroles, such as fenpiclonil, fludioxonil; phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl; benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozoline; carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine; strobilurines, such as azoxystrobin, kresoxim-methyl, metomi- nostrobin, SSF-129, trifloxystrobin, picoxystrobin, BAS 500F (proposed name pyraclostrobin), BAS 520; dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halomethylthiotetrahydrophthalimides, such as captafol, captan, dichlofluanid, fluoromides, folpet, tolyfluanid; Cu-compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper; nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl; organo-p-derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl; various others, such as acibenzolar-S-methyl, anilazine, benthiavalicarb, blasticidin-S, chinomethionate, chloroneb, chlorothalonil, cyflufenamid, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, SYP-LI90
(proposed name: flumorph), dithianon, ethaboxam, etridiazole, famoxadone, fenamidone, fenoxanil, fentin, ferimzone, fluazinam, flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb, IKF-916 (cyazofamid), kasugamycin, methasulfocarb, metrafenone, nicobifen, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin, zoxamide (RH7281).
A preferred method of applying a compound of formula (I), or an agrochemical composition which contains at least one of said compounds, is foliar application. The frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field. The compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation. A formulation [that is, a composition containing the compound of formula (I)] and, if desired, a solid or liquid adjuvant, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface active compounds (surfactants).
The agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula I, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.
Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from lOg to 1kg a.i./ha, most preferably from 20g to 600g a.i./ha. When used as seed drenching agent, convenient dosages are from lOmg to lg of active substance per kg of seeds.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations.
The following non-limiting Examples illustrate the above-described invention in more detail.
EXAMPLE 1 This Example illustrates the preparation of Compound No. 1.15 [2-methyl-5- trifluoromethyl-2H-l,2,3-triazole-4-carboxylic acid methyl ester] and Compound No. 1.13 [2-methyl-5-trifluoromethyl-2H-l ,2,3-triazole-4-carboxylic acid]. a) Preparation of 2-methyl-2H-1.2,3-triazole-4,5-dicarboxylic acid dimethylester and l-methyl-lH-l,2,3-triazole-4,5-dicarboxyric acid dimethylester. l,2,3-Triazole-4,5-dicarboxylic acid dimethyl ester (Y. Tanaka et al. Tetrahedron 29, 3271 (1973)) (74.06g; 0.40mol), potassium carbonate (110.57g; 0.80mol) and methyl iodide (73.81g; 0.52mol) were reacted in acetonitrile (1000ml) at 40°C for 20minutes and then for 20hours at ambient temperature. The mixture was poured onto ice-water and extracted with ether to give the crude product (70.66g) as a mixture of isomers. Separation on silica gel in ethyl acetate-hexane (2:3) yielded 36.51g (46%) of 2-methyl- 2H-l,2,3-triazole-4,5-dicarboxylic acid dimethylester [m.p. 86-87°C; 1H-NMR (300 MHz, DMSO-d6), δ(ppm): 4.27(s,3H), 3.88(s,6H)] and 26.92g (34%) of l-methyl-lH-1,2,3- triazole-4,5-dicarboxylic dimethylester [m.p. 63-64°C; 1H-NMR (300MHz, DMSO-d6), δ(ppm): 4.19(s,3H), 3.93(s,3H), 3.87(s,3H)]. b) Preparation of 2-methyl-2H-l,2,3-triazole-4,5-dicarboxylic acid monomethyl ester To a solution of 2-methyl-2H-l,2,3-triazole-4,5-dicarboxylic acid dimethylester (1.2g; 6mmol) in 30ml methanol was added 358mg KOH (assay 86%; 5.5mmol). The mixture was heated at reflux temperature for 48hours. The solvent was evaporated and the residue was then taken into water and extracted with ethyl acetate (3 times). The combined organic phases contained non-reacted starting material. The aqueous phase was acidified with 2N HC1 (pH2-3) and extracted with ethyl acetate (3 times). The extracts were combined, dried (anhydrous MgSO4) and evaporated to dryness to give 803mg (72%) of the desired compound (m.p. 125-126°C; 1H-NMR (300 MHz, DMSO-d6), δ(ppm): 13.7(br.s,lH, exchangable with D2O), 4.24(s,3H), 3.84(s,3H). c) Preparation of 2-methyl-5-trifluoromethyl-2H-l,2,3-triazole-4-carboxylic acid methyl ester [Compound Number 1.151.
2-Methyl-2H-l,2,3-triazole-4,5-dicarboxylic acid monomethyl ester (2.9g; 15.66mmol) and dichloromethane (160ml) were placed in an 0.31itre monel autoclave. Under an inert atmosphere and cooling with dry ice, gaseous HF (27g) was introduced at -50°C followed by gaseous SF4 (distilled, 6.9g; 64.23mmol). The autoclave was heated to 80°C for 6hours. The maximum pressure amounted 9.8bar. After cooling to ambient temperature the reaction mixture was poured onto ice-dichloromethane and adjusted to pH7 with aqueous NaHCO3. Extraction with dichloromethane (3 times), drying over Na SO4 and evaporation under reduced pressure afforded the crude product. Purification by Kugelrohr-distillation at 3mbar and ca.180°C gave 2.8g (85%) of Compound No.1.15 as a yellowish liquid.
1H-NMR (300 MHz, CDC13), δ(ppm): 4.29(s,3H), 3.97(s,3H);
19F-NMR (235 MHz, CDC13), δ (ppm): -61.7.
13C-NMR (125 MHz, CDC13), δ(ppm): 159.05, 139.65 (q, J (S)F = 40.8 Hz), 137.20, 119.63 (q, JCF = 269.4 Hz, CF3), 52.96, 43.01. d) Preparation of 2-methyl-5-trifluoromethyl-2H-l,2,3-triazole-4-carboxylic acid [Compound Number 1.131
A solution of 2-methyl-5-trifluoromethyl-2H-l,2,3-triazole-4-carboxylic acid methyl ester [Compound Number 1.15] (2.09g; O.Olmol) and KOH (86 %; 0.783g; 1.2eq.) in THF (50ml) was heated at reflux temperature for 3.5 hours. The solution was evaporated, the residue was dissolved in water and acidified to pH 1-2 with HC1 (1M). Evaporation of the aqueous solution followed by continuous extration in ethylacetate for 20 hours gave of Compound No 1.13 (2.1 lg; 100%) as a crystalline solid. 1H-NMR (400 MHz, DMSO-d6), δ(ppm): 4.19(s,3H). 19F-NMR (235 MHz, DMSO-d6), δ (ppm): -59.3.
13C-NMR (125 MHz, DMSO-d6), δ(ppm): 160.74, 144.08, 135.81 (q, Jc(5)F = 38.1 Hz), 120.63 (q, JCF = 268.4 Hz, CF3), 42.20.
EXAMPLE 2 This Example illustrates the preparation of Compound No.1.03 [2-methyl-5- difluoromethyl-2H-l,2,3-triazole-5-carboxylic acid methyl ester]. a) Preparation of 5-Chlorocarbonyl-2-methyl-2H-l,2,3-triazole-4-carboxylic acid methyl ester.
Methyl 2-methyl-l,2,3-triazole-4,5-dicarboxylate (2.3g; 0.01 lmol) was reacted with oxalyl chloride (1.46ml; 0.014mol) plus two drops of DMF in dichloromethane (20ml) at 20°C. When the vigourous reaction ceased the temperature was raised to reflux for 15hours. The mixture was evaporated to dryness to give 2.7g of the acid chloride as a solid. 1H-NMR (300 MHz, CDC13), δ (ppm): 4.48(s, H), 4.0(s,3H). b Preparation of 5-formyl-2-methyl-2H-l,2.3-triazole-4-carboxylic acid methyl ester.
To a solution of freshly prepared 5-Chlorocarbonyl-2-methyl-2H-l,2,3-triazole-4- carboxylic acid methyl ester (2.7g; ca.l3mmol) in THF (270 ml) was added ethyl- diisopropyl-amine (1.88g; l.leq.). The mixture was hydrogenated in the presence of 2.7g 10%o Pd/C at 0-5°C at normal pressure for 2V2 hours and subsequently filtered from the catalyst. The clear solution was evaporated to give the crude as a solid which was dissolved again in ethyl acetate and stirred for a couple of minutes with silica gel. After filtration and evaporation 1.77 g (84%) of pure product as off-white crystals were obtained [m.p. 107-108°C; 1H-NMR (300 MHz, CDC13), δ (ppm): 10.43(s,lH), 4.33(s,3H), 4.01(s,3H)]. c Preparation of 2-methyl-5-difluoromethyl-2H-l,2.3-triazole-5-carboxylic acid methyl ester. [Compound No.1.03.]
5-Formyl-2-methyl-2H-l,2,3-triazole-4-carboxylic acid methyl ester (600mg; 3.5mmol) in 0.5ml CHC13 were reacted with (bis(2-methoxyethyl)amino) sulfurtrifluoride (1350mg; ό.lmmol) at ambient temperature to 50°C for 6days. The resulting orange solution was carefully quenched with 6ml of a saturated aqueous NaHCO3 solution (vigorous reaction) and extracted with ethyl acetate (twice). The combined organic phases were washed with aqueous NaHCO3-solution, dried over anhydrous MgSO and evaporated to give 351mg (52%) of colourless crystals. 1H-NMR (300MHz, CDC13), δ (ppm): 7.15(t, JHF = 53.5 Hz, 1H, H-CF2),
4.30(s,3H), 3.98(s,3H); 19F-NMR (235 MHz, CDC13), δ (ppm): -116.1; 13C-NMR (125MHz, CDC13), δ (ppm): 160.0, 143.6(t, JC(5)F = 25.6 Hz), 137.2, 108.0(t, J(CF)= 237.8 Hz, CHF2), 52.6, 42.7].
EXAMPLE 3 This Example illustrates the preparation of Compound No.1.50 [2-methyl-5- fluoromethyl-2H-l,2,3-triazole-5-carboxylic acid methyl ester]. a) Preparation of 5-hydroxymethyl-2-methyl-2H-l,2.3-triazole-4-carboxylic acid methyl ester.
2.6g (13.3mmol) of 5-formyl-2-methyl-2H-l,2,3-triazole-4-carboxylic acid methyl ester (see Example 2a) in methanol (100ml) was treated with NaBH (601mg) under stirring for lhour at ambient temperature. The reaction mixture was quenched with saturated aqueous ammonium chloride solution, extracted with ethyl acetate, dried with Na SO4 and evaporated to give the crude as an oil. Purification on silica gel in ethyl acetate : hexane (2:1) yielded 1.85g (81%) of the crystalline ρroduct,m.p. 112-113°C. 1H-NMR (300MHz, CDC13), δ (ppm): 4.86(d, J= 6.9 Hz, 1H), 4.22(s,3H),
3.98(s,3H), 3.53(t; J= 6.9 Hz, exchangeable with D2O). b Preparation of 2-methyl-5-fluoromethyl-2H-l,2,3-triazole-5-carboxylic acid methyl ester. [Compound No.1.50.]
A solution of 5-hydroxymethyl-2-methyl-2H-l,2,3-triazole-4-carboxylic acid methyl ester (200mg; l.lmmol) in CH2CI2 (15ml) was reacted with 0.26ml diethylamino sulfur trifluoride (2mmol) for 15minutes at -40°C followed by 15hours at ambient temperature. After evaporation, the crude product was purified on silica gel in ethyl acetate : hexane (3:1) to give 181mg (95%) of the desired product, m.p. 64-66°C. 1H-NMR (300MHz, CDC13), δ (ppm): 5.66(d, JHF = 47.5 Hz, 2H, H2-CF), 4.26(s,3H), 3.96(s,3H). 19F-NMR (235 MHz, CDCI3), δ (ppm): -214.
!3C-NMR (125MHz, CDC13), δ (ppm): 161.6, 145.86 (d, JC(5)F= 18.7 Hz) , 137.09, 74.82(d, JCF = 166.6 Hz, CH F), 52.2, 42.3.
EXAMPLE 4 This Example illustrates the preparation of Compound No.3.017 [5-difluoromethyl-2-methyl-2H-l,2,3-triazole-4-carboxylic acid (4λ-chloro-biphenyl-2- yl)-amide].
To a solution of 2-methyl-5-difluoromethyl-2H-l,2,3-triazole-5-carboxylic acid methyl ester (300mg; 1.57mmol) and 4,-chloro-biphenyl-2-ylamine (320mg; 1.57mmol) in THF (3ml) was added sodium bis(trimethylsilyl)-amide (0.88ml 2M in THF; 1.76mmol; 1.12eq.) by syringe at 0°C over 1.5minutes. The reaction mixture was stirred at 0°C for 15minutes and then at ambient temperature for 22 hours. It was then poured on cold saturated NH C1 solution and extracted with ethyl acetate. After washing with brine it was dried (anhydrous MgSO4) and evaporated to dryness to give a solid, which was triturated with hexane. The colourless crystalline product was filtered and dried: 300mg (53%) [m.p. 155-156°C; IH-NMR (300MHz, CDC13), δ (ppm): 8.5(br, exchangeable with D2O, 1H), 8.4 (d, 1H), 7.5-7.2(m,7H), 7.38 (t, JHF = 52.5 Hz,lH, CHF2), 4.2(s,3H), LC-MS: 363(M+H)].
EXAMPLE 5
This Example illustrates the preparation of Compound No.2.219 [2-methyl-5- trifluoromethyl-2H-l,2,3-triazole-4-carboxylic acid [2-(l,3-dimethyl-butyl)-phenyl]- amide].
To a solution of 2-methyl-5-trifluoromethyl-2H- 1,2,3 -triazole-4-carboxylic acid methyl ester (150mg; 0.75mmol) and 2-(l,3-dimethyl-butyl)-phenylamine (133mg; 0.75mmol) in 1.5ml THF was added sodium bis(trimethylsilyl)-amide (0.638ml 2M in THF; 1.7eq.) by syringe at ambient temperature. The reaction mixture was stirred for 20hours and was then poured on cold saturated NH C1 solution and extracted with ethyl acetate. After washing with brine it was dried (anhydrous MgSO ) and evaporated to dryness to give the crude product, which was purified on silica gel in cyclohexane-ethyl acetate (18:1) The crystalline product was triturated in hexane, filtered and dried in vacuo to yield 130mg (49%) of Compound No. 2.219 [mp 94.6-95.4°C; IH-NMR (300MHz, CDC13), δ (ppm): 8.5(br.s, exchangeable with D2O,lH), 8.0(d,lH), 7.3-7.15(m,3H),
4.33(s,3H), 3.0(m,lH), 1.55-1.35(m,3H), 1.26(d,3H), 0.9(2d,6H); LC-MS: 355.6(M+H)].
EXAMPLE 6 This Example illustrates the preparation of Compound No.26.014 [1,8-Dimethyl- l l-oxa-tricyclo[6.2.1.0*2.7*]undeca-2,4,6-trien-3-yl-amine]. A solution of l,4-dimethyl-5-nitro-l,4-dihydro-l,4-epoxynaphthalene (5.49g;
25.27mmol) (see T. Nishiyama et al, Rikagaku-hen, 28, 37-43 (2000)) in 55ml THF was hydrogenated in the presence of RaNi (l.lg) at ambient temparature. Hydrogen uptake was 2.231itre (97%) after 18hours. After filtering off the catalyst, the filtrate was evaporated and taken into ether, washed with aqueous NaHCθ3-solution and dried (NaSO4) to give 4.60g of crude product, as an oil. Trituration with hexane and a trace of ether furnished a total of 4.5g (94%) of reddish crystalline product, m.p.92-93°C.
Η-NMR (300 MHz, CDCI3), δ (ppm): 7.05(t,lH), 6.7(t,2H), ca.5(br,exchangeable with D2O, 2H), 2.0(s,3H), 1.9(m,2H), 1.8(s,3H), 1.7(m,lH), 1.5(m,lH). EXAMPLE 7
This Example illustrates the preparation of Compound No.26.001 [1,8-Dimethyl- l l-oxa-tricyclo[6.2.1.0*2.7*]undeca-2,4,6,9-tetraen-3-yl-amine].
To l,4-dimethyl-5-nitro-l,4-dihydro-l,4-epoxynaphthalene (4.22g; 19.43mmol) (see Example 6) in ethanol (60ml) was added a solution of ammoniumchloride (2.08g) in H2O (5.2ml) at 47°C. Under vigorous stirring, zinc powder (9.10g; 0.14mol) was added in portions over a period of 5minutes. The suspension was heated to reflux for S ∑hours followed by filtration through Hyflo™ to give a clear yellow filtrate. After evaporation, the crude product amounted 4.57g, as a viscous oil. Column chromatography on silica gel in ethyl acetate-hexane (1 :4) gave 1.24g (34%) of the desired product, as brownish crystals, m.p. 92-96°C. 1H-NMR (300 MHz, CDC13), δ(ppm): 6.85 and 6.7(two m, 2x2H), 6.47(t,lH), ca.5-3 (br., exchangeable with D2O,2H), 2.07(s,3H), 1.85(s,3H).
FORMULATION EXAMPLES FOR COMPOUNDS OF FORMULA (I)
Working procedures for preparing formulations of the compounds of formula I such as Emulsifiable Concentrates, Solutions, Granules, Dusts and Wettable Powders are described in WO97/33890.
BIOLOGICAL EXAMPLES: FUNGICIDAL ACTIONS
Example B-l : Action against Puccinia recondita / wheat (Brownrust on wheat)
1 week old wheat plants cv. Anna are treated with the formulated test compound (0.02%> active ingredient) in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (lxl05uredospores/ml) on the test plants.
After an incubation period of 2 days at 20°C and 95%r.h. the plants are kept in a greenhouse for 8days at 20°C and 60%>r.h. The disease incidence is assessed lOdays after inoculation. Infestation is prevented virtually completely (0-5% infestation) with each of
Compounds 2.273, 3.219, 3.273, 3.321, 8.189, 9.189, 20.017, 20.022, 21.017 and 21.022.
Example B-2: Action against Podosphaera leucotricha / apple (Powdery mildew on apple) 5 week old apple seedlings cv. Mclntosh are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after, the application apple plants are inoculated by shaking plants infected with apple powdery mildew above the test plants. After an incubation period of 12 days at 22°C and 60%r.h. under a light regime of 14/10hours (light/dark) the disease incidence is assessed.
Compounds 2.005, 3.017, 3.219 and 9.189 each exhibit strong efficacy (<20% infestation). Example B-3: Action against Venturia inaequalis / apple (Scab on apple)
4 week old apple seedlings cv. Mclntosh are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the apple plants are inoculated by spraying a spore suspension (4x10 conidia/ml) on the test plants. After an incubation period of 4 days at 21°C and 95%>r.h. the plants are placed for 4 days at 21°C and 60%>r.h. in a greenhouse. After another 4 day incubation period at
21°C and 95%r.h. the disease incidence is assessed.
Compounds 3.017, 3.219 and 9.189 each exhibit strong efficacy (<20% infestation). Example B-4: Action against Erysiphe graminis / barley (Powdery mildew on barley) 1 week old barley plants cv. Regina are treated with the formulated test compound
(0.02%) active ingredient) in a spray chamber. One day after application, the barley plants are inoculated by shaking powdery mildew infected plants above the test plants. After an incubation period of 6 days at 20°C / 18°C (day/night) and 60%>r.h. in a greenhouse the disease incidence is assessed.
Compounds 2.017, 2.029, 2.273, 3.005, 3.017, 3.029, 3.067, 3.070, 3.219, 3.273,
3.321, 3.407, 8.189, 9.189 and 21.017 each exhibit strong efficacy (<20% infestation).
Example B-5: Action against Botrytis cinerea / grape (Botrytis on grapes) 5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the grape plants are inoculated by spraying a spore suspension (lxl 06 conidia/ml) on the test plants. After an incubation period of 4 days at 21°C and 95%or.h. in a greenhouse the disease incidence is assessed. Compounds 2.029, 3.017 and 3.219 each show good activity in this test (<50% disease incidence).
Example B-6: Action against Botrytis cinerea / tomato (Botrytis on tomatoes)
4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (lxl05conidia/ml) on the test plants. After an incubation period of 4 days at 20°C and 95%r.h. in a growth chamber the disease incidence is assessed.
Compounds 2.029, 3.005, 3.029, 3.067, 3.070, 3.219, 3.273, 9.189 and 20.017 each exhibit good efficacy (<50%> disease incidence). Example B-7: Action against Septoria nodorum / wheat (Septoria leaf spot on wheat) 1 week old wheat plants cv. Arina are treated with the formulated test compound
(0.02%) active ingredient) in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (5xl05conidia/ml) on the test plants. After an incubation period of 1 day at 20°C and 95%>r.h. the plants are kept for 10 days at 20°C and 60%>r.h. in a greenhouse. The disease incidence is assessed 11 days after inoculation. Compounds 3.273 and 9.189 each show good activity in this test (<50% disease incidence). Example B-8: Action against Helminthosporium teres / barley (Net blotch on barley)
1 week old barley plants cv. Regina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the barley plants are inoculated by spraying a spore suspension (3xl04conidia/ml) on the test plants. After an incubation period of 4 days at 20°C and 95%>r.h. in a greenhouse the disease incidence is assessed.
Compounds 2.005, 2.017, 2.029, 2.067, 2.070, 2.273, 3.005, 3.017, 3.029, 3.067, 3.070, 3.219, 3.407, 9.189 and 21.017 each show good activity in this test (<20% disease incidence). Example B-9: Action against Alternaria solani / tomato (Early blight on tomatoes) 4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02%> active ingredient) in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (2xl05conidia/ml) on the test plants. After an incubation period of 3 days at 20°C and 95%>r.h. in a growth chamber the disease incidence is assessed.
Compounds 2.005, 2.029, 3.005, 3.017, 3.029 and 9.189 each show good activity in this test (<20% disease incidence).
Example B-10: Action against Uncinula necator / grape (Powdery mildew on grapes) 5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02%> active ingredient) in a spray chamber. One day after application, the grape plants are inoculated by shaking plants infected with grape powdery mildew above the test plants. After an incubation period of 7 days at 26°C and 60%r.h. under a light regime of 14/lOhours (light/dark) the disease incidence is assessed.
Compounds 3.017, 3.219 and 9.189 each show good activity in this test (<20% disease incidence).

Claims

CLAΓMS
A compound of formula (I):
Figure imgf000076_0001
where A is an ørt/zo-substituted ring selected from formulae (Al) to (A22);
Figure imgf000076_0002
Figure imgf000076_0003
(A2) (A3) (A4)
Figure imgf000076_0004
(AS) (A6) (A7)
,R R'
N. *- = N. s
R R
(AS) (A9)
Figure imgf000077_0001
(A10) (All)
Figure imgf000077_0002
(A12) (A13) (A14) (A15)
Figure imgf000077_0003
Figure imgf000077_0004
r r
Q is a single or a double bond; X is O, N(R18), S or CR19R20)(CR21R22)m(CR23R24)n; R1 is halogen,, cyano, nitro, CM alkyl, C,.4 haloalkyl, C alkoxy, C haloalkoxy or optionally substituted C - alkenyl, . optionally substituted C2_4 alkynyl or optionally substituted SO (Cι.4 )alkyl (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen and C alkoxy); R2 is CM alkyl, C haloalkyl, CM alkoxy(Cι_4)alkyl or CM alkylthio(CM)alkyl or [optionally substituted aryl](Cι-4)alkyl- or [optionally substituted aryl]oxy(Cι-4)alkyl- (where the optionally substituted aryl moieties may each have up to 3 substituents, each independently selected from halogen and C alkoxy); R3 is hydrogen,
CH2C ≡€R4, CH2CR4=C(H)R4, CH=C=CH2 or COR5 or optionally substituted C alkyl, optionally substituted C alkoxy or optionally substituted (CM) alkylC(=O)O (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen, C alkoxy, C alkyl, Cι_2 haloalkoxy, hydroxy, cyano, carboxyl, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl and ethylsulfonyl); each R4 is, independently, hydrogen, halogen, Cι_4 alkyl, C haloalkyl, CM alkoxy or C alkoxy(Cι-4)alkyl; R5 is hydrogen or optionally substituted Cι_6 alkyl, optionally substituted C alkoxy, optionally substituted C alkoxy(Cι- )alkyl, optionally substituted CM alkylthio(C1_4)alkyl or optionally substituted aryl (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen, Cι-6 alkoxy, Cι_6 haloalkoxy, cyano, hydroxy, methoxycarbonyl and ethoxycarbonyl); R6 is phenyl [optionally substituted by up to 3 substituents, each independently selected from halogen, cyano, nitro, CM alkyl, CM haloalkyl, CM alkoxy, CM haloalkoxy, CM haloalkylthio, C(H)=N-OH, C(H)=N-O(Cι_6 alkyl), C(C,_6 alkyl)=N-OH,
C(Cι-6 alkyl)=N-O-(Cι-6 alkyl), (Z)PC≡CR25 and (Z)PCR28=CR26R27], a 5-6 membered heterocyclic ring [in which the ring contains 1 to 3 heteroatoms (each independently chosen from oxygen, sulphur and nitrogen) and the ring is optionally substituted by up to 3 substituents, each independently selected from halogen, cyano, nitro, -4 alkyl, C haloalkyl, C alkoxy, CM haloalkoxy,
C(H)=N-O-(Cι_6 alkyl) and C(Cι-6 alkyl)=N-O-(Cι-6 alkyl)], C3-,2 alkyl [optionally substituted by up to 6 substituents, each independently selected from halogen, cyano, CM alkoxy, Cι-4 thioalkyl, COO-Cι-4 alkyl, =N-OH, =N-O-(CM alkyl), C3-8 cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from CM alkyl, halogen, CM alkoxy and Cι_4 haloalkoxy) and C4.8 cycloalkenyl (itself optionally substituted by up to 3 substituents, each independently selected from C alkyl, halogen, C alkoxy and C haloalkoxy)],
C2-.2 alkenyl [optionally substituted by up to 6 substituents, each independently selected from halogen, cyano, Cι_4 alkoxy, CM thioalkyl, COO-(Cι-4 alkyl), =N-OH, =N-O-(CM alkyl), C3.8 cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from CM alkyl, halogen, CM alkoxy and CM haloalkoxy) and C4.8 cycloalkenyl (itself optionally substituted by up to 3 substituents, each independently selected from CM alkyl, halogen, .4 alkoxy and CM haloalkoxy)], C2-12 alkynyl [optionally substituted by up to 6 substituents, each independently selected from halogen, cyano, CM alkoxy, C thioalkyl, COO-CM alkyl, =N-OH, =N-O-(CM alkyl), C3.8 cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from CM alkyl, halogen, C alkoxy and C haloalkoxy), Si(CH3)3 and C4-8 cycloalkenyl (itself optionally substituted by up to 3 substituents, each independently selected from C alkyl, halogen, CM alkoxy and CM haloalkoxy)], C3_8 cycloalkyl [optionally substituted by up to 3 substituents, each independently selected from halogen, Cι-4 alkyl, CM haloalkyl, Cι_4 alkoxy, CM haloalkoxy, C thioalkyl,
C3.6 cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from Cι_4 alkyl, halogen, C alkoxy and CM haloalkoxy) and phenyl (itself optionally substituted by up to five independently selected halogen atoms)], C4.8 cycloalkenyl [optionally substituted by up to 3 substituents, each independently selected from halogen, CM alkyl, C haloalkyl, CM alkoxy,
CM haloalkoxy, CM thioalkyl, C3_6 cycloalkyl (itself optionally substituted by up to 3 substituents, each independently selected from CM alkyl, halogen, CM alkoxy and CM haloalkoxy) and phenyl (itself optionally substituted by up to five independently selected halogen atoms)], C6-i2 bicycloalkyl [optionally substituted by up to 3 substituents, each independently selected from halogen, CM alkyl and
CM haloalkyl] or an aliphatic, saturated or unsaturated group [in which the group contains three to thirteen carbon atoms and at least one silicon atom and, optionally, one to three heteroatoms, each independently selected from oxygen, nitrogen and sulphur, and the group is optionally substituted by up to four independently selected halogen atoms]; R7, R8, R9, R10, R11 and R12 are each, independently, hydrogen, halogen, cyano, nitro, CM alkyl, CM haloalkyl, C alkoxy, CM haloalkoxy, C thioalkyl or C thiohaloalkyl; R13, R14, R15, R16 and R17 are each, independently, hydrogen, halogen, CM alkyl, C(O)CH3, Cι_ haloalkyl, CM alkoxy, CM haloalkoxy, C thioalkyl, CM thiohaloalkyl, hydroxymethyl or Cι_ alkoxymethyl; R is hydrogen, CM alkyl, C alkoxy(Cι-4)alkyl, formyl, C(=O)CM alkyl (optionally substituted by halogen or CM alkoxy) or C(=O)O-Cι-6 alkyl (optionally substituted by halogen, Cι_
4 alkoxy or CN); R19, R20, R21, R22, R23 and R24 are each, independently, Cι-6 alkyl, Cι_6 alkenyl [both optionally substituted by halogen, hydroxy, =O, Cι-4 alkoxy, O- C(O)-Cι-4 alkyl, aryl or a 3-7 membered carbocyclic ring (itself optionally substituted by up to three methyl groups)], a 3-7 membered carbocyclic ring (optionally substituted by up to three methyl groups and optionally containing one heteroatom selected from mtrogen and oxygen), hydrogen, halogen, hydroxy or Ci. 4 alkoxy; or R19R20 together with the carbon atom to which they are attached form a carbonyl-group, a 3-5 membered carbocyclic ring (optionally substituted by up to three methyl groups), Cι-6 alkylidene (optionally substituted by up to three methyl groups) or C3.6 cycloalkylidene (optionally substituted by up to three methyl groups); R is hydrogen, halogen, CM alkyl, CM haloalkyl, CM alkoxy(Cι-4)alkyl, Cι-4haloalkoxy(Cι.4)alkyl or Si(C1.4 alkyl)3; R26 and R27 are each, independently, hydrogen, halogen, C alkyl or CM haloalkyl; R28 is hydrogen, CM alkyl or Cι_4 haloalkyl; m is 0 or 1; n is 0 or 1; p is 0 or 1; and Z is CM alkylene.
2. A compound of formula (I) as claimed in claim 1 where A is selected from formulae (Al), (A2), (A3), (A16), (A17), (A18), (A19), (A20) and (A22).
3. A compound of formula (I) as claimed in claim 1 or 2 where R1 is CM alkyl, C haloalkyl, NO2, CN or OCF3.
4. A compound of formula (I) as claimed in claim 1, 2 or 3 where R2 is CM alkyl, C haloalkyl, C alkoxy(Cι_4)alkyl or Cι_4 alkylthio(Cι-4)alkyl.
5. A compound of formula (I) as claimed in claim 1, 2, 3 or 4 where R3 is hydrogen, CH2C =€R4, CH2CR4=C(H)R4, CH=C=CH2 or COR5.
6. A compound of formula (H) :
Figure imgf000081_0001
where R1 and R2 are as defined in claim 1 and Y is halogen, hydroxy or Cι-5 alkoxy; provided that when R1 is chloro and R2 is 4-CH3O-C6H4-CH2-, Y is not C2H5O; when R1 is CH3O and R2 is CH3, Y is not C2H5O; when R1 is bromo and R2 is CH3OCH2 Y is not CH3O; and when R1 is CH3 and R2 is C2H5, Y is not OH.
7. A compound of formula (Ifla)
Figure imgf000081_0002
where R13, R14, R15, R16, X and Q are as defined in claim 1 ; provided that when
R13, R14, R15 and R16 are each H then X is not CH2 when Q is a double bond and X is not CH2CH2 when Q is a single bond or a double bond;and when R13 is CH3, R14 is OCH3 and R15 and R16 are both H then X is not CH2CH2 when Q is a single bond. A composition for controlling microorganisms and preventing attack and infestation of plants therewith, wherein the active ingredient is a compound of formula (I) as claimed in claim 1 together with a suitable carrier.
A method of controlling or preventing infestation of cultivated plants by phytopathogenic microorganisms by application of a compound of formula (I) as claimed in claim 1 to plants, to parts thereof or the locus thereof.
PCT/EP2003/009111 2002-08-22 2003-08-18 Microbiocidal (e.g. fungicidal) 1,2,3-triazole derivatives WO2004018438A2 (en)

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CR7696A CR7696A (en) 2002-08-22 2005-02-17 MICROBIOCIDES (FOR EXAMPLE FUNGICIDES) DERIVED FROM 1-2-3 TRIAZOLS
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