EP2274284A2 - Azoles substitués fongicides - Google Patents

Azoles substitués fongicides

Info

Publication number
EP2274284A2
EP2274284A2 EP09743637A EP09743637A EP2274284A2 EP 2274284 A2 EP2274284 A2 EP 2274284A2 EP 09743637 A EP09743637 A EP 09743637A EP 09743637 A EP09743637 A EP 09743637A EP 2274284 A2 EP2274284 A2 EP 2274284A2
Authority
EP
European Patent Office
Prior art keywords
imidazole
chloro
ring
methyl
difluoro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09743637A
Other languages
German (de)
English (en)
Inventor
Thomas Paul Selby
James Francis Bereznak
John Joseph Bisaha
Amy X. Ding
Vijayagopal Gopalsamuthiram
Mary Ann Hanagan
Jeffrey Keith Long
Andrew Edmund Taggi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP2274284A2 publication Critical patent/EP2274284A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members 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
    • C07D233/68—Halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members 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
    • C07D233/88—Nitrogen atoms, e.g. allantoin
    • 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
    • C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
    • 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
    • C07D401/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D403/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D409/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D417/04—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 directly linked by a ring-member-to-ring-member bond

Definitions

  • This invention relates to certain azoles, their JV-oxides, salts and compositions, and methods of their use as fungicides.
  • This invention is directed to compounds of Formula 1 (including all geometric and stereoisomers), //-oxides, and salts thereof, agricultural compositions containing them and their use as fungicides:
  • Z is N or CR 4 ;
  • Q 3 is a phenyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R 5c ; or a 5- to
  • each R 5a , R 5b and R 5c is independently halogen, cyano, hydroxy, nitro, C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, C 1 -C 7 haloalkyl, C 2 -C 7 haloalkenyl, C 3 -C 7 cycloalkyl, C 3 -C 7 halocycloalkyl, C 4 -C 1Q alkylcycloalkyl, C 4 -C 1Q cycloalkylalkyl, C 6 -C 14 cycloalkylcycloalkyl, C 3 -C 7
  • RlO and R l 1 [ s independently H, C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, C 1 -C 7 haloalkyl, C 2 -C 7 haloalkenyl, C 3 -C 7 cycloalkyl or C 3 -C 7 halocycloalkyl; each R 12 is independently H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkylcarbonyl,
  • each R 13a and R 13b is independently H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl,
  • the compound is not a compound of F-I through F-4, as shown below
  • the compound is not 4- [2-ethyl-l-(4-methoxyphenyl)-lH-imidazol-5-yl] -pyridine, 4-[l-(4-methoxyphenyl)-2-methyl-lH-imidazol-5-yl]pyridine or 3,5-dichloro-2- (4-iodo-5-phenyl-lH-l,2,3-triazol-l-yl)pyridine; and (e) when J is Q 2 , X is CR 2 , Y is N and Z is N, then R 2 is other than ⁇ . More particularly, this invention pertains to a compound of Formula 1 (including all geometric and stereoisomers), an JV-oxide or a salt thereof.
  • This invention also relates to a fungicidal composition
  • a fungicidal composition comprising a fungicidally effective amount of a compound of Formula 1 (or an JV-oxide or salt thereof) and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • This invention also relates to a fungicidal composition
  • a fungicidal composition comprising a mixture of a compound of Formula 1 (or an JV-oxide or salt thereof) and at least one other fungicide (e.g., at least one other fungicide having a different site of action).
  • This invention further relates to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed, a fungicidally effective amount of a compound of the invention (e.g., as a composition described herein).
  • compositions comprising, “comprising,” “includes,” “including,” “has,” “having”, “contains” or “containing” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • plant includes members of Kingdom Plantae, particularly seed plants (Spermatopsida), at all life stages, including young plants (e.g., germinating seeds developing into seedlings) and mature, reproductive stages (e.g., plants producing flowers and seeds). Portions of plants include geotropic members typically growing beneath the surface of the growing medium (e.g., soil), such as roots, tubers, bulbs and corms, and also members growing above the growing medium, such as foliage (including stems and leaves), flowers, fruits and seeds.
  • seedling used either alone or in a combination of words means a young plant developing from the embryo of a seed.
  • the term “broadleaf ' used either alone or in words such as “broadleaf crop” means dicot or dicotyledon, a term used to describe a group of angiosperms characterized by embryos having two cotyledons.
  • alkylating agent refers to a chemical compound in which a carbon-containing radical is bound through a carbon atom to leaving group such as halide or sulfonate, which is displaceable by bonding of a nucleophile to said carbon atom.
  • alkylating does not limit the carbon-containing radical to alkyl; the carbon-containing radicals in alkylating agents include the variety of carbon-bound substituent radicals specified, for example, for R 2 , R 3 and R 4 .
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, /-propyl, or the different butyl, pentyl, hexyl or heptyl isomers.
  • Alkenyl includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl, hexenyl and heptenyl isomers.
  • Alkenyl also includes polyenes such as 1 ,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl, hexynyl and heptynyl isomers.
  • Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkylene denotes a straight-chain or branched alkanediyl.
  • alkylene examples include CH 2 , CH 2 CH 2 , CH(CH 3 ), CH 2 CH 2 CH 2 , CH 2 CH(CH 3 ) and the different butylene, pentylene and hexylene isomers.
  • Alkynylene denotes a straight-chain or branched alkynediyl containing one triple bond. Examples of “alkynylene” include CH 2 C ⁇ C, C ⁇ CCH 2 and the different butynylene, pentynylene and hexynylene isomers.
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy, hexyloxy and heptyloxy isomers.
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio, hexylthio and heptylthio isomers.
  • Alkylsulfmyl includes both enantiomers of an alkylsulfinyl group.
  • Alkylamino includes an NH radical substituted with straight-chain or branched alkyl. Examples of “alkylamino” include CH 3 CH 2 NH, CH 3 CH 2 CH 2 NH, and (CH 3 ) 2 CHCH 2 NH. Examples of “dialkylamino” include (CH 3 ) 2 N, (CH 3 CH 2 CH 2 ) 2 N and CH 3 CH 2 (CH 3 )N.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl.
  • alkoxyalkyl examples include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkylthioalkyl denotes alkylthio substitution on alkyl.
  • alkylthioalkyl examples include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 ;
  • alkylsulfmylalkyl and “alkylsulfonylalkyl” include the corresponding sulfoxides and sulfones, respectively.
  • alkylamino alkyl denotes alkylamino substitution on alkyl.
  • alkylaminoalkyl include CH 3 NHCH 2 , CH 3 NHCH 2 CH 2 , CH 3 CH 2 NHCH 2 , CH 3 CH 2 CH 2 CH 2 NHCH 2 and CH 3 CH 2 NHCH 2 CH 2 .
  • dialkylaminoalkyl include ((CH 3 ) 2 CH) 2 NCH 2 , (CH 3 CH 2 CH 2 ) 2 NCH 2 and CH 3 CH 2 (CH 3 )NCH 2 CH 2 .
  • Hydroxyalkyl denotes an alkyl group substituted with one hydroxy group. Examples of “hydroxyalkyl” include HOCH 2 CH 2 , CH 3 CH 2 (OH)CH and HOCH 2 CH 2 CH 2 CH 2 .
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
  • alkylcycloalkyl denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, z-propylcyclobutyl, methylcyclopentyl and methylcyclohexyl.
  • cycloalkylalkyl denotes cycloalkyl substitution on an alkyl moiety.
  • examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.
  • cycloalkylcycloalkyl denotes cycloalkyl substitution on another cycloalkyl ring, wherein each cycloalkyl ring independently has from 3 to 7 carbon atom ring members.
  • cycloalkylcycloalkyl examples include cyclopropylcyclopropyl (such as l,l'-bicyclopropyl-l-yl, 1,1'- bicyclopropyl-2-yl), cyclohexylcyclopentyl (such as 4-cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as l,l'-bicyclohexyl-l-yl), and the different cis- and trans- cycloalkylcycloalkyl isomers, (such as (li?,25)-l,l'-bicyclopropyl-2-yl and ( ⁇ R,2R)- ⁇ ,Y- bicyclopropyl-2-yl).
  • cyclopropylcyclopropyl such as l,l'-bicyclopropyl-l-yl, 1,1'- bicyclopropyl-2-yl
  • cycloalkoxy denotes cycloalkyl attached to and linked through an oxygen atom including, for example, cyclopentyloxy and cyclohexyloxy.
  • cycloalkylene denotes a cycloalkanediyl ring.
  • cycloalkylene examples include cyclopropylene, cyclobutylene, cyclopentylene and cyclohexylene.
  • cycloalkenylene denotes a cycloalkenediyl ring containing one olefmic bond.
  • Examples of “cycloalkenylene” include cylopropenediyl and cyclpentenediyl.
  • alkylene examples include CH 2 , CH 2 CH 2 , CH(CH 3 ), CH 2 CH 2 CH 2 ,
  • Trialkylsilyl includes 3 branched and/or straight-chain alkyl radicals attached to and linked through a silicon atom, such as trimethylsilyl, triethylsilyl and tert-butyldimethylsilyl.
  • halogen either alone or in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” or “alkyl substituted with halogen” include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, F 2 CHCH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CCl 3 S, CF 3 S, CCl 3 CH 2 S and ClCH 2 CH 2 CH 2 S.
  • halocycloalkyl examples include
  • Cj-C j The total number of carbon atoms in a substituent group is indicated by the "Cj-C j " prefix where i and j are numbers from 1 to 14.
  • C ⁇ -C 4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C 3 alkoxyalkyl designates, for example, CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • the number of optional substituents may be restricted by an expressed limitation.
  • the phrase “optionally substituted with up to 3 substituents selected from R 5a on carbon ring members” means that 0, 1, 2 or 3 substituents can be present (if the number of potential connection points allows).
  • the phrase “optionally substituted with up to 5 substituents selected from R 5a on carbon ring members” means that 0, 1, 2, 3, 4 or 5 substituents can be present if the number of available connection points allows.
  • said substituents are independently selected from the group of defined substituents (e.g., (R v ) r wherein r is 1, 2, 3, 4 or 5 in Exhibit 1).
  • substituents are independently selected from the group of defined substituents (e.g., (R v ) r wherein r is 1, 2, 3, 4 or 5 in Exhibit 1).
  • a "ring” as a component of Formula 1 is carbocyclic or heterocyclic.
  • the term “ring system” as a component of Formula 1 denotes two fused rings (e.g., two phenyl rings fused to form naphthalenyl).
  • nonaromatic includes rings that are fully saturated as well as partially or fully unsaturated, provided that none of the rings are aromatic.
  • a "fully unsaturated heterocycle” includes both aromatic and nonaromatic heterocycles.
  • aromatic indicates that each of the ring atoms of a fully unsaturated ring is essentially in the same plane and has a /?-orbital perpendicular to the ring plane, and that (4n + T) ⁇ electrons, where n is a positive integer, are associated with the ring to comply with H ⁇ ckel's rule.
  • carbocyclic ring denotes a ring or ring system wherein the atoms forming the ring backbone are selected only from carbon.
  • a carbocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring.
  • saturated carbocyclic refers to a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.
  • heterocyclic ring or “heterocycle” denote a ring in which at least one atom forming the ring backbone is not carbon (e.g., N, O or S). Typically a heterocyclic ring contains no more than 4 N atoms, no more than 2 O atoms and no more than 2 S atoms. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies H ⁇ ckel's rule, then said ring is also called a "heteroaromatic ring” or “aromatic heterocyclic ring”.
  • heterocyclic ring system or “heteroaromatic bicyclic ring system” denote a ring system in which at least one atom forming the ring backbone is not carbon (e.g., N, O or S) and at least one ring is aromatic. Unless otherwise indicated, heterocyclic rings and heteroaromatic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • substituents are optional, 0 to 5 substituents may be present, limited only by the number of available points of attachment.
  • the ring members selected from up to 2 O, up to 2 S and up to 4 N atoms are optional, provided at least one ring member is not carbon (e.g., N, O or S).
  • the nitrogen atom ring members may be oxidized as //-oxides, because compounds relating to Formula 1 also include iV-oxide derivatives.
  • Examples of a 5- to 6-membered fully unsaturated heterocyclic ring include the rings A-I through A-31 illustrated in Exhibit 1, and examples of an 8- to 10-membered heteroaromatic bicyclic ring system include the ring systems A-31 through A-72 illustrated in Exhibit 2.
  • the relative the variable (R v ) r is any substituent as defined in the Summary of the Invention for Q 1 , Q 2 and Q 3 (e.g., a Q 1 ring or ring system is optionally substituted with R 5a on carbon ring members and cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminoalkyl and C 3 -C 6 dialkylaminoalkyl on nitrogen atom ring members) and r is an integer from 0 to 5, limited by the number of available positions on each depicted ring or ring system.
  • substituents are optional, 0 to 5 substituents may be present, limited only by the number of available points of attachment.
  • the ring members selected from up to 2 O, up to 2 S and up to 4 N atoms are optional, provided at least one ring member is not carbon (e.g., N, O or S).
  • the nitrogen atom ring members may be oxidized as iV-oxides, because compounds relating to Formula 1 also include iV-oxide derivatives.
  • Examples of a 5- to 6-membered fully unsaturated heterocyclic ring in W 1 , W 2 and W 3 include the rings A-I through A-31 illustrated in Exhibit 1 wherein (R v ) r is any substituent as defined in the Summary of the Invention for W 1 , W 2 or W 3 (e.g., a W 1 ring is optionally substituted with R 5a on carbon ring members and cyano, C j -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminoalkyl and C 3 -C 6 dialkylaminoalkyl on nitrogen atom ring members) and r is an integer from 0 to 5, limited
  • R v groups are shown in the structures A-I through A-72, it is noted that they do not need to be present since they are optional substituents. Note that when R v is H attached to an atom, this is the same as if said atom is unsubstituted. The nitrogen atoms that require substitution to fill their valence are substituted with H or R v . Note that when the attachment point between (R v ) r and the depicted ring or ring system is illustrated as floating, (R v ) r can be attached to any available carbon atom or nitrogen atom of the depicted ring or ring system.
  • the depicted ring or ring system can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the depicted ring or ring system by replacement of a hydrogen atom.
  • Compounds of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the compounds of the invention may be present as a mixture of stereoisomers or as individual stereoisomers (e.g., in optically active form).
  • Atropisomers which are conformational isomers that occur when rotation about a single bond in a molecule is restricted as a result of steric interaction with other parts of the molecule and the substituents at both ends of the single bond are unsymmetrical.
  • atropisomerism occurs at a single bond in Formula 1 when the rotational barrier is high enough (about ⁇ G > 25 kcal moH) that separation of isomers at ambient temperature becomes possible.
  • one atropisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other atropisomer or when separated from the other atropisomer.
  • Atropisomers can be found in March, Advanced Organic Chemistry, 4th Ed. 1992, 101-102 and Gawronski et al, Chirality 2002, 14, 689-702.
  • This invention includes compounds or compositions that are enriched in an atropisomer of Formula 1 compared to other atropisomers of the compounds. Also included are the essentially pure atropisomers of compounds of Formula 1.
  • nitrogen-containing heterocycles can form JV-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form TV-oxides.
  • tertiary amines can form JV-oxides.
  • Synthetic methods for the preparation of iV-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as t-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethyldioxirane.
  • salts of the compounds of Formula 1 are useful for control of plant diseases caused by fungal plant pathogens (i.e. are agriculturally suitable).
  • the salts of the compounds of Formula 1 include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • the present invention comprises compounds selected from Formula 1, JV-oxides and agriculturally suitable salts thereof.
  • Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts.
  • Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types).
  • polymorph refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice.
  • polymorphs can have the same chemical composition, they can also differ in composition due the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability.
  • a polymorph of a compound represented by Formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound represented by Formula 1.
  • Preparation and isolation of a particular polymorph of a compound represented by Formula 1 can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures.
  • Embodiments of the present invention as described in the Summary of the Invention include those described below.
  • Formula 1 includes iV-oxides and salts thereof, and reference to "a compound of Formula 1" includes the definitions of substituents specified in the Summary of the Invention unless further defined in the
  • Embodiment 1 A compound of Formula 1 wherein J is Q 2 .
  • Embodiment 2. A compound of Formula 1 wherein J is R 1 .
  • Embodiment 3 A compound of Formula 1 or Embodiment 2 wherein R 1 is C 1 -C 3 alkyl.
  • Embodiment 4 A compound of Embodiment 3 wherein R 1 is methyl.
  • Embodiment 5 A compound of Formula 1 or any one of Embodiments 1 through 4 wherein X is CR 2 or CQ 3 .
  • Embodiment 6 A compound of Embodiment 5 wherein X is CR 2 .
  • Embodiment 6a A compound of Embodiment 5 wherein X is CQ 3 .
  • Embodiment 7. A compound of Formula 1 or any one of Embodiments 1 through 6a wherein Y is N.
  • Embodiment 8. A compound of Formula 1 or any one of Embodiments 1 through 6a wherein Y is CR 3 .
  • Embodiment 9 A compound of Formula 1 or any one of Embodiments 1 through 8 wherein Z is CR 4 .
  • Embodiment 10 A compound of Formula 1 or any one of Embodiments 1 through 8 wherein Z is N.
  • Embodiment 11 A compound of Formula 1 wherein J is Q 2 , X is CR 2 , Y is N and Z is CR 4 , or J is R 1 , X is CQ 3 , Y is CR 3 and Z is N, or J is Q 2 , X is CR 2 , Y is N and Z is N.
  • Embodiment 12 A compound of Embodiment 11 wherein J is Q 2 , X is CR 2 , Y is N and Z is CR 4 or J is R 1 , X is CQ 3 , Y is CR 3 and Z is N.
  • Embodiment 13 A compound of Embodiment 12 wherein J is Q 2 , X is CR 2 , Y is N and
  • Embodiment 15 A compound of Embodiment 14 wherein Q 1 is a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 3 substituents independently selected from R 5a on carbon atom ring members and selected from cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl,
  • Embodiment 16 A compound of Embodiment 15 wherein Q 1 is a phenyl or pyridinyl ring, optionally substituted with up to 3 substituents independently selected from
  • Embodiment 17 A compound of Embodiment 16 wherein Q 1 is a pyridinyl ring attached to Formula 1 at the 3 -position of the pyridinyl ring and optionally substituted with up to 3 substituents independently selected from R 5a .
  • Embodiment 18 A compound of Embodiment 16 wherein Q 1 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 5a .
  • Embodiment 19 A compound of Embodiment 16 wherein Q 1 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 5a .
  • Embodiment 20 A compound of Embodiment 19 wherein W 1 is a phenyl or
  • Embodiment 21 A compound of Embodiment 20 wherein W 1 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 5a .
  • Embodiment 23 A compound of Embodiment 22 wherein Q 2 is a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 3 substituents independently selected from R 5 ⁇ on carbon atom ring members and selected from cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminoalkyl and C 3 -C 6 dialkylaminoalkyl on nitrogen atom ring members; or C(R 7a R 7
  • Embodiment 24 A compound of Embodiment 23 wherein Q 2 is a phenyl or pyridinyl ring, optionally substituted with up to 3 substituents independently selected from R5b.
  • Embodiment 25 A compound of Embodiment 24 wherein Q 2 is a pyridinyl ring attached to Formula 1 at the 3 -position of the pyridinyl ring and optionally substituted with up to 3 substituents independently selected from R 5 ⁇ .
  • Embodiment 26 A compound of Embodiment 24 wherein Q 2 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 5 ⁇ .
  • Embodiment 27 A compound of Embodiment 24 wherein Q 2 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 5 ⁇ .
  • Embodiment 27a A compound of Formula 1 or any one of Embodiments 1 through 27 wherein when each Q 1 and Q 2 is independently a phenyl or pyridinyl ring, then one of the Q 1 and Q 2 rings is substituted with 2 or 3 substituents and the other of the Q 1 and Q 2 rings is substituted with 1 or 2 substituents.
  • Embodiment 28 A compound of Formula 1 or any one of Embodiments 1 through 27 wherein at least one R 5a substituent is attached at an ortho position of the Q 1 ring.
  • Embodiment 29 A compound of Formula 1 or any one of Embodiments 1 through 28 wherein two R 5a substituents are attached at ortho positions of the Q 1 ring.
  • Embodiment 30 A compound of Formula 1 or any one of Embodiments 1 through 29 wherein at least one R 5 ⁇ substituent is attached at an ortho position of the Q 2 ring.
  • Embodiment 31 A compound of Formula 1 or any one of Embodiments 1 through 30 wherein two R 5 ⁇ substituents are attached at ortho positions of the Q 2 ring.
  • Embodiment 32 A compound of Formula 1 or any one of Embodiments 1 through 23 wherein W 2 is a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring optionally substituted with up to 3 substituents independently selected from R 5 b on carbon atom ring members and selected from cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminoalky
  • Embodiment 33 A compound of Embodiment 32 wherein W 2 is a phenyl or pyridinyl ring, optionally substituted with up to 3 substituents independently selected from R5b.
  • Embodiment 34 A compound of Embodiment 33 wherein W 2 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 5 ⁇ .
  • Embodiment 35 A compound of Embodiment 32 wherein W 2 is a phenyl or pyridinyl ring, optionally substituted with up to 3 substituents independently selected from R 5 ⁇ .
  • Embodiment 36 A compound of Embodiment 35 wherein Q 3 is a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 3 substituents independently selected from R 5c on carbon atom ring members and selected from cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminoalkyl and C 3 -C 6 dialkylaminoalkyl on nitrogen atom ring members; or C(R 7a R 7b
  • Embodiment 37 A compound of Embodiment 36 wherein Q 3 is a phenyl or pyridinyl ring, optionally substituted with up to 3 substituents independently selected from R5c.
  • Embodiment 38 A compound of Embodiment 37 wherein Q 3 is a pyridinyl ring attached to Formula 1 at the 3 -position of the pyridinyl ring and optionally substituted with up to 3 substituents independently selected from R 5c .
  • Embodiment 39 A compound of Embodiment 37 wherein Q 3 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 5c .
  • Embodiment 40 Embodiment 40.
  • Embodiment 41 A compound of Embodiment 40 wherein W 3 is a phenyl or pyridinyl ring, optionally substituted with up to 3 substituents independently selected from R 5C .
  • Embodiment 42 A compound of Embodiment 41 wherein W 3 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 5c .
  • Embodiment 44 A compound of Embodiment 43 wherein each R 2 , R 3 and R 4 is independently H, halogen, cyano or C 1 -C 3 alkyl.
  • Embodiment 45 A compound of Embodiment 44 wherein each R 2 , R 3 and R 4 is independently Cl, Br, I or C 1 -C 2 alkyl.
  • Embodiment 46 A compound of Embodiment 45 wherein each R 2 , R 3 and R 4 is independently Cl, Br or methyl.
  • Embodiment 47 A compound of Formula 1 or any one of Embodiments 1 through 46 wherein each R 5a , R 5 ⁇ and R 5c is independently halogen, cyano, C 1 -C 3 alkyl,
  • Embodiment 48 A compound of Embodiment 47 wherein each R 5a , R 5 ⁇ and R 5c is independently halogen, cyano, C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio or C 1 -C 3 alkylamino.
  • Embodiment 49 A compound of Embodiment 48 wherein each R 5a , R 5 ⁇ and R 5c is independently halogen, cyano, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl or C 1 -C 3 alkoxy.
  • Embodiment 50 A compound of Embodiment 49 wherein each R 5a , R 5 ⁇ and R 5c is independently F, Cl, Br, cyano, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl or C 1 -C 2 alkoxy.
  • Embodiment 51 A compound of Embodiment 48 wherein each R 5a , R 5 ⁇ and R 5c is independently halogen, cyano, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl or C 1 -C 3 alkoxy.
  • Embodiment 52. A compound of Formula 1 or any one of Embodiments 1 through 47 wherein each U is independently O or NR 12 .
  • Embodiment 53 A compound of Embodiment 52 wherein each U is independently O or NH.
  • Embodiment 54 A compound of Formula 1 or any one of Embodiments 1 through 47 wherein each V is C 2 -C 4 alkylene.
  • Embodiment 55 A compound of Formula 1 or any one of Embodiments 1 through 47 wherein each T is independently NR 13a R 13b or OR 14 .
  • Embodiment 55 a A compound of Formula 1 or any one of Embodiments 1 through 55 wherein each R 13a and R 13 ⁇ is independently H, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl.
  • Embodiment 55b A compound of Formula 1 or any one of Embodiments 1 through 55 wherein each R 13a and R 13 ⁇ is independently H, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl.
  • Embodiment 56 A compound of Formula 1 or any one of Embodiments 1 through 55b independently when an instance of R 7a is not taken together with the carbon atom to which the instance of R 7a is attached and a geminal instance of R 7 ⁇ to form a carbocyclic ring (i.e. R 7a is taken alone) then the instance of R 7a is H, cyano or methyl.
  • Embodiment 56a A compound of Embodiment 56 wherein each R 7a is independently H or methyl.
  • Embodiment 57 A compound of Embodiment 56a wherein each R 7a is H.
  • Embodiment 58 A compound of Formula 1 or any one of Embodiments 1 through 57 wherein independently when an instance of R 7 ⁇ is not taken together with the carbon atom to which the instance of R 7 ⁇ is attached and a geminal instance of R 7a to form a carbocyclic ring (i.e. R 7 ⁇ is taken alone) then the instance of R 7 ⁇ is independently H or methyl.
  • Embodiment 59 A compound of Embodiment 58 wherein each R 7 ⁇ is H.
  • Embodiment 59a A compound of Formula 1 or any one of Embodiments 1 through 59 wherein when a pair of R 7a and R 7 ⁇ attached to the same carbon atom are taken together with the carbon atom to form a carbocyclic ring, the ring is a cyclopropyl ring.
  • Embodiment 60 A compound of Formula 1 or any one of Embodiments 1 through 59a wherein each pair of R 7a and R 7 ⁇ attached to the same carbon atom are not taken together to form a carbocyclic ring (i.e. R 7a and R 7 ⁇ are taken alone).
  • Embodiment 61 A compound of Formula 1 or any one of Embodiments 1 through 60 wherein each R 8 , R 9a , R 9b , R 10 and R 11 is independently H, C 1 -C 2 alkyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl or C 1 -C 2 haloalkyl.
  • Embodiment 62 A compound of Embodiment 61 wherein each R 8 , R 9a , R 9 ⁇ , R l ° and
  • R 1 * is independently H or methyl.
  • Embodiment 63a A compound of Formula 1 or any one Embodiments 1 through 62 wherein when J is Q 2 , X is CR 2 , Y is N and Z is CR 4 and Q 1 is a phenyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R 5a ; or a 5- to 6-membered fully unsaturated heterocyclic ring or an 8- to 10-membered heteroaromatic bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2
  • R 4 is halogen and Q 2 is a phenyl ring or 2-pyridinyl ring substituted with halogen at an ortho position, then said phenyl ring or 2-pyridinyl ring is also substituted with R 5 ⁇ at a meta position.
  • Embodiment 64a A compound of Formula 1 or any one Embodiments 1 through 62 wherein when J is Q 2 , X is CR 2 , Y is N and Z is CR 4 and Q 2 is a phenyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R 5b ; or a 5- to 6-membered fully unsaturated heterocyclic ring or an 8- to 10-membered heteroaromatic bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2
  • Embodiment 65 A compound of Formula 1 or any one of Embodiments 1 through 62 wherein when J is Q 2 , X is CR 2 , Y is N and Z is CR 4 , then
  • Embodiment 65 a A compound of Formula 1 of Embodiment 65 wherein when R 2 is halogen and Q 1 is a phenyl ring substituted with halogen at an ortho position, then Q 2 is neither phenyl nor substituted phenyl; and when R 4 is halogen and Q 2 is a phenyl ring substituted with halogen at an ortho position, then Q 1 is neither phenyl nor substituted phenyl.
  • Embodiments of this invention can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1 but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1.
  • embodiments of this invention including Embodiments l-65a above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention.
  • Embodiment Al Combinations of Embodiments l-65a are illustrated by: Embodiment Al .
  • Q 1 is a phenyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 3 substituents independently selected from R 5a ; or a 5- to 6-membered fully unsaturated heterocyclic ring containing ring members selected from carbon atoms and up to 3 heteroatoms independently selected from up to 2 O, up to 2 S and up to
  • W 1 is a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring optionally substituted with up to 3 substituents independently selected from R 5a on carbon atom ring members and selected from cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminoalkyl and C 3 -C 6 dialkylaminoalkyl on nitrogen atom ring members;
  • W 2 is a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring optionally substituted with up to 3 substituents independently selected from R 5b on carbon atom ring members and selected from cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminoalkyl and C 3 -C 6 dialkylaminoalkyl on nitrogen atom ring members;
  • Q 3 is a phenyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 3 substituents
  • W 3 is a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring optionally substituted with up to 3 substituents independently selected from R 5c on carbon atom ring members and selected from cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C
  • Q 1 is a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 3 substituents independently selected from R 5a on carbon atom ring members and selected from cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminoalkyl and C 3 -C 6 dialkylaminoalkyl on nitrogen atom ring members; or C(R 7a R 7b )W ! ;
  • W 1 is a phenyl or pyridinyl ring optionally substituted with up to 3 substituents independently selected from R 5a ;
  • Q 2 is a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 3 substituents independently selected from R 5b on carbon atom ring members and selected from cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminoalkyl and C 3 -C 6 dial
  • W 2 is a phenyl or pyridinyl ring optionally substituted with up to 3 substituents independently selected from R 5b ;
  • Q 3 is a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 3 substituents independently selected from R 5c on carbon atom ring members and selected from cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminoalkyl and C 3 -C 6 dial
  • each R 5a , R 5b and R 5c is independently halogen, cyano, C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 1 -C 3 haloalkyl, C 3 cycloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkylthio, C 1 -C 3 alkylamino, C 2 -C 4 dialkylamino C 2 -C 4 alkylcarbonyl, C 2 -C 4 alkoxycarbonyl, C 2 -C 4 alkylcarbonylamino or -U-V-T;
  • U is O or NH;
  • V is C 2 -C 4 alkylene;
  • T is NR 13a R 13b or OR 14 ;
  • each R 7a and R 7b is independently H or methyl; each R 8 , R 9a , R 9b
  • Embodiment A3 A compound of Embodiment A2 wherein Q 1 is a phenyl or pyridinyl ring optionally substituted with up to 3 substituents independently selected from R 5a ; Q 2 is a phenyl or pyridinyl ring optionally substituted with up to 3 substituents independently selected from R 5b ; and Q 3 is a phenyl or pyridinyl ring optionally substituted with up to 3 substituents independently selected from R 5c .
  • Embodiment A4 A compound of Embodiment A3 wherein each R 2 , R 3 and R 4 is independently H, halogen, cyano or C 1 -C 3 alkyl; and each R 5a , R 5b and R 5c is independently halogen, cyano, C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio or C 1 -C 3 alkylamino.
  • Embodiment A5 A compound of Embodiment A4 wherein J is Q 2 ; X is CR 2 ; Y is N;
  • Z is CR 4 ; each R 2 and R 4 is independently Cl, Br, I or C 1 -C 2 alkyl; each R 5a and R 5b is independently F, Cl, Br, cyano, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl or C 1 -C 2 alkoxy; and one of the Q 1 and Q 2 rings is substituted with 2 to 3 substituents and the other of the Q 1 and Q 2 rings is substituted with 1 to 2 substituents.
  • Specific embodiments include compounds of Formula 1 selected from the group consisting of:
  • Another aspect of the present invention relates to compounds of Formula IP (including all geometric and stereoisomers), iV-oxides, and salts thereof, agricultural compositions containing them and their use as fungicides:
  • X is N, CR 2 Or CQ 3 ;
  • Y is N or CR 3 ;
  • Z is N or CR 4 ;
  • Q 1 is a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring, or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R 5a ;
  • Q 2 is a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring, or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R 5b ;
  • Q 3 is a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring, or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 5 substituents independently selected from R 5c ;
  • R 1 is C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, C 3 -C 7 cycloalkyl, C 1 -C 7 haloalkyl, C 2 -C 7 haloalkenyl, C ⁇ C 1Q alkylcycloalkyl or C ⁇ C 1Q cycloalkylalkyl; each R 2 , R 3 and R 4 is independently ⁇ , halogen, cyano, nitro, C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 7 -C 7 alkynyl, C 3 -C 7 cycloalkyl, C 1 -C 7 haloalkyl, C 2 -C 7 haloalkenyl, C 1 -C 7 alkoxy, C 1 -C 7 haloalkoxy, C 1 -C 7 alkylthio, C 1 -C 7 alkylsulfmyl,
  • this aspect of the present invention pertains to a compound of Formula IP (including all geometric and stereoisomers), an JV-oxide or a salt thereof.
  • a fungicidal composition comprising (a) a compound selected from Formula IP, //-oxides and salts thereof; and (b) at least one other fungicide. Also related to this aspect is a fungicidal composition comprising (a) a fungicidally effective amount of a compound selected from Formula IP, //-oxides and salts thereof; and (b) at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • Also related to this aspect is a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed, a fungicidally effective amount of a compound selected from Formula IP, JV-oxides and salts thereof (e.g., as a composition described herein).
  • Embodiments of this aspect include Embodiments Bl through B53 described below.
  • Formula IP includes iV-oxides and salts thereof, and reference to "a compound of Formula IP" includes the definitions of substituents specified above for Formula IP unless further defined in the Embodiments.
  • Embodiment B 1. A compound of Formula IP wherein J is Q 2 .
  • Embodiment B2. A compound of Formula IP wherein J is R 1 .
  • Embodiment B3. A compound of Formula IP or Embodiment Bl wherein R 1 is C 1 -C 2 alkyl.
  • Embodiment B4 A compound of Formula IP wherein X is CR 2 .
  • Embodiment B5. A compound of Formula IP wherein X is CQ 3 .
  • Embodiment B6. A compound of Formula IP wherein Y is N.
  • Embodiment B7 A compound of Formula IP wherein Y is CR 3 .
  • Embodiment B8. A compound of Formula IP wherein Z is CR 4 .
  • Embodiment B9. A compound of Formula IP wherein Z is N.
  • Embodiment BlO. A compound of Formula IP wherein Q 1 is a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring, or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 3 substituents independently selected from R 5a .
  • Q 2 is a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring, or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 3 substituents independently selected from R 5 ⁇ .
  • Embodiment B 13 A compound of Embodiment BlO wherein Q 1 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 5a .
  • Embodiment B 14 A compound of Embodiment BI l wherein Q 2 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 5 ⁇ Embodiment B 15.
  • Embodiment B 16 A compound of Embodiment B13 wherein Q 1 is a phenyl ring optionally substituted with up to 2 substituents independently selected from R 5a .
  • Embodiment B 17. A compound of Embodiment B 14 wherein Q 2 is a phenyl ring optionally substituted with up to 2 substituents independently selected from R 5 ⁇ .
  • Embodiment B 18 A compound of Embodiment B15 wherein Q 3 is a phenyl ring optionally substituted with up to 2 substituents independently selected from R 5c .
  • Embodiment B 19 A compound of Embodiment B16 wherein Q 1 is a phenyl ring optionally substituted with up to 1 substituent selected from R 5a .
  • Embodiment B20. A compound of Embodiment B17 wherein Q 2 is a phenyl ring optionally substituted with up to 1 substituent selected from R 5 ⁇ .
  • Embodiment B21. A compound of Embodiment Bl 8 wherein Q 3 is a phenyl ring optionally substituted with up to 1 substituent selected from R 5c .
  • Embodiment B22 A compound of Formula IP or Embodiment B13 wherein Q 1 is a phenyl ring substituted with up to 3 substituents independently selected from R 5a attached at ortho and/or para positions.
  • Embodiment B23 A compound of Formula IP or Embodiment B 14 wherein Q 2 is a phenyl ring substituted with up to 3 substituents independently selected from R 5b attached at ortho and/or para positions.
  • Embodiment B24 A compound of Formula IP or Embodiment B 15 wherein Q 3 is a phenyl ring substituted with up to 3 substituents independently selected from R 5c attached at ortho and/or para positions.
  • Embodiment B25 A compound of Formula IP or Embodiment B22 wherein Q 1 is a phenyl ring substituted with 3 substituents independently selected from R 5a attached at ortho and para positions.
  • Embodiment B26 A compound of Formula IP or Embodiment B23 wherein Q 2 is a phenyl ring substituted with 3 substituents independently selected from R 5b attached at ortho and para positions.
  • Embodiment B27 A compound of Formula IP or Embodiment B24 wherein Q 3 is a phenyl ring substituted with 3 substituents independently selected from R 5c attached at ortho and para positions.
  • Embodiment B28 A compound of Formula IP or Embodiment B22 wherein Q 1 is a phenyl ring substituted with up to 2 substituents independently selected from R 5a attached at ortho and/or para positions.
  • Embodiment B29 A compound of Formula IP or Embodiment B23 wherein Q 2 is a phenyl ring substituted with up to 2 substituents independently selected from R 5b attached at ortho and/or para positions.
  • Embodiment B30 A compound of Formula IP or Embodiment B24 wherein Q 3 is a phenyl ring substituted with up to 2 substituents independently selected R 5c attached at ortho and/or para positions.
  • Embodiment B31 A compound of Formula IP or Embodiment B28 wherein Q 1 is a phenyl ring substituted with 2 substituents independently selected from R 5a attached at one ortho position and the para position.
  • Embodiment B32 A compound of Formula IP or Embodiment B29 wherein Q 2 is a phenyl ring substituted with 2 substituents independently selected from R 5b attached at one ortho position and the para position.
  • Embodiment B33 A compound of Formula IP or Embodiment B30 wherein Q 3 is a phenyl ring substituted with 2 substituents independently selected from R 5c attached at one ortho position and the para position.
  • Embodiment B34 A compound of Formula IP or Embodiment B28 wherein Q 1 is a phenyl ring substituted with 2 substituents independently selected from R 5a attached at ortho positions.
  • Embodiment B35 A compound of Formula IP or Embodiment B29 wherein Q 2 is a phenyl ring substituted with 2 substituents independently selected from R 5 ⁇ attached at ortho positions.
  • Embodiment B36 A compound of Formula IP or Embodiment B30 wherein Q 3 is a phenyl ring substituted with 2 substituents independently selected from R 5c attached at ortho positions.
  • Embodiment B37 A compound of Formula IP wherein Q 1 is a phenyl ring substituted with 2 substituents independently selected from R 5a attached at one meta position and the para position.
  • Embodiment B38 A compound of Formula IP wherein Q 2 is a phenyl ring substituted with 2 substituents independently selected from R 5 ⁇ attached at one meta position and the para position.
  • Embodiment B39 A compound of Formula IP wherein Q 3 is a phenyl ring substituted with 2 substituents independently selected from R 5c attached at one meta position and the para position.
  • Embodiment B40 A compound of Formula IP or Embodiment B 19 wherein Ql is a phenyl ring substituted with up to 1 substituent selected from R 5a attached at the para position.
  • Embodiment B41 A compound of Formula IP or Embodiment B21 wherein Q ⁇ is a phenyl ring substituted with up to 1 substituent selected from R 5c attached at the para position.
  • Embodiment B42 A compound of Formula IP or Embodiment B40 wherein Q 1 is a phenyl ring substituted with 1 substituent selected from R 5a attached at the para position.
  • Embodiment B43 A compound of Formula IP or Embodiment B40 wherein Q 1 is a phenyl ring substituted with 1 substituent selected from R 5a attached at the para position.
  • Embodiment B44. A compound of Formula IP or Embodiment B41 wherein Q 3 is a phenyl ring substituted with 1 substituent selected from R 5c attached at the para position.
  • Embodiment B45. A compound of Formula IP wherein each R 2 , R 3 and R 4 is independently H, halogen, cyano, C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 3 cycloalkyl or C 1 -C 3 haloalkyl.
  • Embodiment B46 A compound of Embodiment B45 wherein each R 2 , R 3 and R 4 is independently H, halogen or C 1 -C 3 alkyl.
  • Embodiment B47 A compound of Embodiment B46 wherein each R 2 , R 3 and R 4 is independently H, Cl, Br, I or C 1 -C 2 alkyl.
  • Embodiment B48 A compound of Embodiment B47 wherein R 2 is selected from H, Cl,
  • Embodiment B49 A compound of Embodiment B47 wherein R 3 is selected from H, Cl,
  • Embodiment B50 A compound of Embodiment B47 wherein R 4 is selected from H, Cl,
  • Embodiment B51 A compound of Formula IP wherein each R 5a , R 5 ⁇ and R 5c is independently halogen, cyano, nitro, C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 3 cycloalkyl,
  • C 1 -C 3 haloalkyl C 2 -C 3 haloalkenyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, C 1 -C 3 haloalkylthio, C 1 -C 3 haloalkoxy or C 1 -C 6 haloalkylthio.
  • Embodiment B52 A compound of Embodiment B51 wherein each R 5a , R 5 ⁇ and R 5c is independently halogen, cyano, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl or C 1 -C 3 alkoxy.
  • Embodiment B53 A compound of Embodiment B52 wherein each R 5a , R 5 ⁇ and R 5c is independently halogen, CH 3 , OCH 3 or CF 3 .
  • Embodiments B1-B53 above as well as any other embodiments described herein relevant to Formula IP can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula IP but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula IP.
  • Embodiments B1-B53 above as well as any other embodiments described herein relevant to Formula IP, and any combination thereof pertain to the compositions and methods relating to compounds of Formula IP.
  • counterparts of Embodiments 1- 62 wherein "Formula 1" is replaced by "Formula IP” to the extent that these counterpart embodiments limit the definition of substituents on Formula IP.
  • counterparts of Embodiments B1-B53 wherein "Formula IP” is replaced by "Formula 1" to the extent that these counterpart embodiments limit the definition of substituents on Formula 1.
  • Embodiment Cl A compound of Formula IP wherein
  • Q 1 is independently a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring, or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 3 substituents independently selected from R 5a ;
  • Q 2 is independently a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring, or a naphthalenyl ring system, each ring or ring system optionally substituted with up to 3 substituents independently selected from R 5 b;
  • Q 3 is independently a phenyl, thienyl, pyridinyl, pyridazinyl, pyrimidinyl or pyrazolyl ring, or a naphthalenyl ring system, each ring or ring system optionally substituted with
  • each R 5a , R 5 ⁇ and R 5c is independently halogen, cyano, nitro, C 1 -C 7 alkyl, C 2 -C 7 alkenyl, C 2 -C 7 alkynyl, C 3 -C 7 cycloalkyl, C 1 -C 7 haloalkyl,
  • Embodiment C3 A compound of Embodiment C2 wherein each R 2 and R 4 is independently H, halogen, cyano, C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 3 cycloalkyl or C 1 -C 3 haloalkyl; and each R 5a and R 5 ⁇ is independently halogen, cyano, nitro, C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 3 cycloalkyl, C 1 -C 3 haloalkyl, C 2 -C 3 haloalkenyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio, C 1 -C 3 haloalkylthio, C 1 -C 3 haloalkoxy or
  • Embodiment C4 A compound of Embodiment C3 wherein
  • Q 1 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 5a;
  • Q 2 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 5 ⁇ ;
  • each R 2 and R 4 is independently H, halogen or C 1 -C 3 alkyl;
  • each R 5a and R 5b is independently halogen, cyano, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl or C 1 -C 3 alkoxy.
  • each R 2 and R 4 is independently H, Cl, Br, I or C 1 -C 2 alkyl; and each R 5a and R 5b is independently halogen, CH 3 , OCH 3 or CF 3 .
  • Embodiment C7 A compound of Embodiment Cl wherein X is CQ 3 ; Y is CR 3 ;
  • R 3 is H, Cl, Br or CH 3 ; Z is N;
  • R 1 is C 1 -C 2 alkyl.
  • compounds of Formula 1 or Formula IP including geometric and stereoisomers, iV-oxides, and salts thereof (including but not limited to Embodiments 1-62, A1-A5, Bl-53 and C1-C6, above) wherein when Q 1 is a phenyl ring which is not substituted by R 5a at either ortho positions, then when X is N or CR 2 and Q 2 is a phenyl ring, the Q 2 phenyl ring is substituted by at least one R 5 * 5 at an ortho position.
  • This invention provides a fungicidal composition
  • a fungicidal composition comprising a compound of Formula 1 or Formula IP (including all geometric and stereoisomers, iV-oxides, and salts thereof), and at least one other fungicide.
  • a compound of Formula 1 or Formula IP including all geometric and stereoisomers, iV-oxides, and salts thereof
  • at least one other fungicide are compositions comprising a compound corresponding to any of the compound embodiments described above.
  • This invention provides a fungicidal composition
  • a fungicidal composition comprising a fungicidally effective amount of a compound of Formula 1 or Formula IP (including all geometric and stereoisomers, iV-oxides, and salts thereof), and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • a compound of Formula 1 or Formula IP including all geometric and stereoisomers, iV-oxides, and salts thereof
  • additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • This invention provides a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed, a fungicidally effective amount of a compound of Formula 1 or Formula IP (including all geometric and stereoisomers, iV-oxides, and salts thereof).
  • a compound of Formula 1 or Formula IP including all geometric and stereoisomers, iV-oxides, and salts thereof.
  • embodiment of such methods are methods comprising applying a fungicidally effective amount of a compound corresponding to any of the compound embodiments describe above.
  • the compounds are applied as compositions of this invention.
  • Compounds of Formula Ia (Formula 1 wherein J is Q 2 , X is CR 2 , Y is N and Z is CR 4 ) can be prepared by halogenation or alkylation of compounds of Formula Ib (i.e. Formula 1 wherein J is Q 2 , X is CR 2 , R 2 is H, Y is N and Z is CR 4 ) as illustrated in Scheme 1.
  • halogenation can be achieved using a variety of halogenating reagents known in the art such as elemental halogen (e.g., CI 2 , Br 2 , I 2 ), sulfuryl chloride, iodine monochloride or a JV-halosuccinimide (e.g., NBS, NCS, NIS) in an appropriate solvent such as ⁇ /, ⁇ /-dimethylformamide, carbon tetrachloride, acetonitrile, dichloromethane or acetic acid.
  • elemental halogen e.g., CI 2 , Br 2 , I 2
  • sulfuryl chloride iodine monochloride
  • iodine monochloride iodine monochloride
  • JV-halosuccinimide e.g., NBS, NCS, NIS
  • Alkylation is achieved by reacting a compound of Formula Ib with a metalating agent, followed by an alkylating agent of formula R 2 -Lg (wherein Lg is a leaving group such as Cl, Br, I or a sulfonate, for example, /?-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate).
  • Suitable metalating agents include, for example, as n-butyl lithium (n-BuL ⁇ ), lithium diisopropylamide (LDA) or sodium hydride (NaH).
  • alkylation and “alkylating agent” are not limited to R 2 being an alkyl group, and include in addition to alkyl such groups as alkylthio, haloalkyl, alkenyl, haloalkenyl, alkynyl, and the like.
  • alkyl such groups as alkylthio, haloalkyl, alkenyl, haloalkenyl, alkynyl, and the like.
  • alkyl such groups as alkylthio, haloalkyl, alkenyl, haloalkenyl, alkynyl, and the like.
  • Compounds of Formula Ia can be subjected to various nucleophilic and metallation reactions to add substituents or modify existing substituents, and thus provide other functionalized compounds of Formula Ia.
  • compounds of Formula Ia wherein R 2 and/or R 4 are halogen can undergo nucleophilic displacements to provide compounds of Formula Ia wherein R 2 and/or R 4 are groups linked to the imidazole ring through an O, S or N atom (e.g., displacements with alkoxides, thiolates and amines).
  • compounds of Formula Ia wherein R 2 and/or R 4 are iodo can be used to prepare the corresponding thiocyanate (-SCN) derivatives of Formula Ia.
  • Typical conditions involve contacting the iodo compound of Formula Ia with a thiocyanating agent such as K[Cu(SCN) 2 ], which is generated in situ from equimolar amounts of copper(I) thiocyanate and potassium thiocyanate.
  • the reaction is typically carried out in a polar solvent such as ⁇ /, ⁇ /-dimethylformamide, dimethylacetamide, 1,4-dioxane or dimethylsulfoxide at a temperature between about room temperature and the reflux temperature of the solvent.
  • the reaction can also be carried out at higher temperatures using a microwave reactor.
  • Suzuki et al. Synthetic Communications 1996, 2(5(18), 3413- 3419.
  • compounds of Formula Ia wherein R 2 and/or R 4 are bromo or iodo can be cross-coupled with compounds of formulae R 2 -Met or R 4 -Met (wherein Met is Sn, Zn, B(OH) 2 , Mg, Li, Cu or other suitable counterions) in the presence of a palladium or nickel catalyst to produce compounds of Formula Ia wherein R 2 and/or R 4 are cyano, alkyl, alkenyl, haloalkenyl, alkynyl, and the like.
  • Preferred catalysts include but are not limited to Pd(PPh 3 ) 4 , PdCl 2 (PPh 3 ) 2 , PdCl 2 (diphenylphosphinoferrocene), NiCl 2 (PPh 3 ) 2 and tetrakis(tri-2-furylphosphino)palladium.
  • the exact conditions for each reaction will depend upon the catalyst used and the counterions in the compound of formulae R 2 -Met or R 4 -Met.
  • the presence of a base (such as an alkali carbonate, tertiary amine or alkali fluoride) is necessary for reactions involving compounds of formulae R 2 -Met or R 4 -Met where Met is B(OH) 2 .
  • Examples 13, 16, 17, 18, 19 and 31 illustrate various cross-coupling reactions for the preparation of certain compounds of Formula Ia.
  • compounds of Formula Ia can alternatively be prepared by halogenation of a compound of Formula 2 preferentially at the 4-position of the imidazole ring to provide a compound of Formula Ic (Formula 1 wherein J is Q 2 , X is CR 2 , Y is N, Z is CR 4 and R 4 is H) wherein R 2 is halogen, which can then be treated with a second equivalent of the same or different halogenating reagent to provide a compound of Formula Ia wherein R 2 and R 4 are halogen.
  • Step C of Examples 1 and 34 see Step C of Examples 1 and 34.
  • compounds of Formula Ia wherein R 4 is halogen, alkyl, alkylthio, haloalkyl, alkenyl, haloalkenyl, alkynyl, and the like can be prepared from compounds of Formula Ic by metallation with a reagent such as n-butyllithium (n-BuLi), lithium diisopropylamide (LDA) or sodium hydride (NaH) in a solvent such as tetrahydrofuran, dioxane or toluene at temperatures ranging from about 0 0 C to room temperature.
  • a solvent such as tetrahydrofuran, dioxane or toluene at temperatures ranging from about 0 0 C to room temperature.
  • the anion is then contacted with an electrophile resulting in the introduction of an R 4 group onto Formula Ic, thus providing a compound of Formula Ia.
  • electrophile e.g., halogenating agent or R -Lg
  • Synthesis of compounds of Formula Ib can be achieved as outlined in Scheme 3.
  • a compound of Formula 3 is JV-arylated with halides of formula Q 2 X 1 wherein X 1 is I, Cl, Br or F.
  • X 1 is I, Cl, Br or F.
  • a suitable copper source e.g., copper(I) iodide or copper(I) triflate
  • a metal carbonate base e.g., potassium or cesium carbonate
  • a suitable solvent such as xylenes, dioxane or acetonitrile
  • compounds of Formula 4 can be converted directly to Formula Ib by reaction with a halide of formula Q 1 X 1 in the presence of palladium(II) acetate and a triarylphosphine ligand and cesium fluoride in a solvent such as dioxane, tetrahydrofuran or acetonitrile at the reflux temperature of the solvent.
  • a solvent such as dioxane, tetrahydrofuran or acetonitrile
  • lithiation of a compound of Formula 4 with n-butyllithium (n-BuLi) or lithium diisopropylamide (LDA), followed by treatment of the anion with trialkylorganostannyl chlorides or boronic acids (or esters) provides compounds of Formula 5.
  • Treatment of compounds Formula 5 with a halide of formula Q 1 X 1 using well-known transition metal-catalyzed cross coupling reaction conditions provides Formula Ib compounds. Typically the reaction is run in the present of a palladium catalyst.
  • L is (alkyl) 3 Sn or B(OH) 2
  • n-butyl lithium n-BuLi
  • LDA lithium diisopropylamide
  • NaH sodium hydride
  • the anion is then contacted with an electrophile resulting in the introduction of an R 4 group onto Formula 6, thus providing a compound of Formula Ib.
  • the electrophile can be a halogen derivative such as JV-chlorosuccinimide (NCS),
  • NBS ⁇ /-bromosuccinimide
  • NIS TV-iodosuccinimide
  • hexachloroethane or
  • the electrophile can be an alkylating agent of the formula R 4 -Lg (wherein Lg is a leaving group such as Cl, Br, I or a sulfonate, for example, /?-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate) where R 4 is alkyl, alkylthio, haloalkyl, alkenyl, haloalkenyl, alkynyl, and the like.
  • the terms "alkylation” and “alkylating agent” are not limited to R 4 being an alkyl group.
  • Example 4 illustrates the method of Scheme 4 using LDA and iodomethane.
  • compounds of Formula Ib can be prepared by reacting JV-chloroamidines of Formula 7 with enamines of Formula 8.
  • cyclization proceeds through the intermediacy of an in szYw-generated 4-morpholino-4,5- dihydroimidazole which undergoes elimination of the morpholino group to provide the compounds of Formula Ib.
  • the reaction is run in the presence of a base such as pyridine, 4-(dimethylamino)pyridine or a trialkylamine and in a suitable solvent, such as dichloromethane, trichloromethane, carbon tetrachloride or toluene, at temperatures ranging from about 0 0 C to the reflux temperature of the solvent.
  • imidazole rings of Formula Ib can also be prepared by numerous other methods described in the chemistry literature.
  • the general method described by Wiglenda et al., Journal of Medicinal Chemistry 2007, 50(1), 1475-1484 can be used to prepare compounds of Formula Ib; the method can also be readily adapted to prepare Formula Ib compounds wherein each Q 1 and/or Q 2 is an optionally substituted benzyl group.
  • Compounds of Formula 7 can be easily synthesized from amidines and JV-chlorosuccinimide according to the procedure given by Pocar et al., Tetrahedron Letters 1976, 21, 1839-1842.
  • Enamines of Formula 8 can be prepared by known methods; for example, see van der Gen et al., Tetrahedron Letters 1979, 26, 2433-2436.
  • compounds of Formula Ic can be prepared by reacting an imine of Formula 9 with a substituted /?-toluenesulfonylmethyl isocyanide of Formula 10 or a substituted benzotriazol-1-ylmethyl isocyanide of Formula 11 in the presence of a suitable base such as potassium carbonate, potassium tert-butoxide, sodium hydroxide, sodium hydride, te/t-butylamine or l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in an appropriate solvent such as methanol, dioxane, tetrahydrofuran, dimethylsulfoxide,
  • a suitable base such as potassium carbonate, potassium tert-butoxide, sodium hydroxide, sodium hydride, te/t-butylamine or l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in an appropriate solvent such as methanol, dioxane,
  • Imines of Formula 9 can be readily prepared by contacting an amine of Formula Q 2 NH 2 with an aldehyde of formula Q 1 CHO under dehydrative conditions such as heating in toluene or xylenes with use of a Dean-Stark trap to remove water formed in the reaction.
  • an acid catalyst such as /?-toluenesulfonic acid can be added to the reaction mixture to promote elimination of water.
  • Step A of Examples 1, 3, 9, 34 and 37 illustrate the preparation of a compound of Formula 9.
  • Compounds of Formula 10 can be prepared from the unsubstituted
  • the substituted benzotriazol-1-ylmethyl isocyanides of Formula 11 can be prepared by contacting benzotriazol-1-yl-methyl isocyanide with a compound of formula R 2 X 1 (wherein X 1 is halogen) in the presence of a base such as potassium carbonate, sodium hydride or potassium tert-butoxide.
  • a base such as potassium carbonate, sodium hydride or potassium tert-butoxide.
  • a base such as potassium carbonate, sodium hydride or potassium tert-butoxide.
  • Halogenation at the 2-position of the imidazole ring of Formula Ic can be achieved using methods analogous to those already described for Scheme 2 to provide compounds of Formula Ia wherein R 2 is halogen. Examples 12, 15, 30, 35 and 38 illustrate this halogenation method.
  • Aminonitriles of Formula 12 are readily available from amines of formula Q 2 NH 2 , aldehydes of formula Q 1 CHO and a cyanide source by means of the Strecker reaction.
  • a variety of solvents and cyanide sources can be employed.
  • the presence of a Lewis acid such as indium(III) chloride can be advantageous.
  • a Lewis acid such as indium(III) chloride.
  • Methanaminium salts of Formula 13 are commercially available, for example, chloromethylenedimethyliminium chloride (i.e. R 2 and X 1 are Cl) can be obtained from commercial sources. Compounds of Formula 13 can also be synthesized by methods documented in the chemistry literature.
  • the 2-imidazolecarboxaldehyde of Formula Ia 1 can be reduced with sodium borohydride in methanol to provide the corresponding compound of Formula Ia 2 (i.e. Formula Ia wherein R 4 is 2-hydroxymethyl).
  • R 4 is 2-hydroxymethyl
  • Example 21 Treatment of the 2-hydroxymethyl compound of Formula Ia 2 with diethylaminosulfur trifluoride (DAST) results in the 2-fluoromethyl derivative of Formula Ia 3 (i.e. Formula Ia wherein R 4 is -CH 2 F).
  • DAST diethylaminosulfur trifluoride
  • 2-halomethyl analogs of Formula Ia 3 can be prepared using methods described in the chemistry literature.
  • 2-bromomethyl analogs of Formula Ia 3 can be prepared by treating 2-hydroxymethyl compounds of Formula Ia 2 with hydrobromic acid in a solvent such as glacial acetic acid using the method described by Beukers et al., Journal of Medicinal Chemistry 2004, 47(15), 3707-3709.
  • the 2-imidazolecarboxaldehyde can be treated with hydroxylamine hydrochloride to provide the oxime of Formula Ia 4 (i.e. Formula Ia wherein R 4 is oxime functionality).
  • R 4 is oxime functionality
  • compounds of Formula Id can be prepared as outlined in Scheme 11.
  • compounds of Formula 15 are first halogenated analogous to the method described in Scheme 2 to provide the compounds of Formula 16, which can then be coupled with a boronic acid of formula Q 3 B(OH) 2 using well-known Suzuki palladium-catalyzed cross coupling reaction conditions.
  • Many catalysts are useful for the Suzuki reaction; particularly useful catalysts include tetrakis(triphenylphosphine)palladium(0) and [1,1'- bis(diphenylphosphino)ferrocene]dichloropalladium(II).
  • Solvents such as tetrahydrofuran, acetonitrile, diethyl ether and dioxane are suitable.
  • compounds of Formula Id can be prepared by introduction of the R 1 substituent via alkylation of the pyrazole ring with an alkylating agent R i -Lg wherein Lg is a leaving group such as Cl, Br, I or a sulfonate such as /?-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate.
  • R i -Lg wherein Lg is a leaving group such as Cl, Br, I or a sulfonate such as /?-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate.
  • alkylation and “alkylating agent” are not limited to R 1 being an alkyl group and include in addition to alkyl such groups as alkylthio, haloalkyl, alkenyl, haloalkenyl, alkynyl, and the like.
  • Alkylation of pyrazoles using potassium carbonate in N,N-dimethylformamide or acetone are described by Kitazaki et al, Chem. Pharm. Bull. 2000, 48(12), 1935-1946 and Jeon et al., Journal of Fluorine Chemistry 2007, 128, 1191-1197.
  • reaction can be run in a variety of solvents, but typically optimal yields are obtained when the reaction is run in ethanol at a temperature between about room temperature and the reflux temperature of the solvent.
  • General procedures for this type of reaction are well documented in the chemical literature; for example, see Maya et al, Bioorganic & Medicinal Chemistry 2005, 13(6), 297-2107; and Domagala et al., Journal of Heterocyclic Chemistry 1989, 26, 1147-1158.
  • the method of Scheme 13 is also illustrated in Step C of Example 39.
  • alkylhydrazines i.e. R 1 NFINF ⁇
  • R 1 is other than hydrogen
  • these reactions result in mixtures of 1- and 2-substituted pyrazole regioisomers which can be separated using chromatography.
  • Compounds of Formula 18 can be prepared from ketones of Formula 19 and ⁇ /, ⁇ /-dimethylformamide dimethyl acetal using the method described by Maya et al., Bioorganic & Medicinal Chemistry 2005, 13(6), 297-2107. The reaction is typically conducted in a solvent such as benzene, toluene or xylenes at a temperature between about room temperature and the reflux temperature of the solvent. The method of Scheme 14 is illustrated in Step B of Example 39.
  • Ketones of Formula 19 can be prepared by reaction of acid chlorides of Formula 20 with the desired aromatic species of formula Q 1 -H under Friedel-Crafts condensation reaction conditions. Friedel-Crafts reactions are documented in a variety of published references including Lutjens et al., Journal of Medicinal Chemistry 2003, 46(10), 1870- 1877; PCT Patent Publication WO 2005/037758; and J. March, Advanced Organic Chemistry, McGraw-Hill, New York, p 490 and references cited within. The method of Scheme 15 is also illustrated in Step A of Example 39.
  • amines of Formula 24 can be converted to diazonium salts and then reacted with a copper salt (e.g., copper(I) halide, copper(II) halide or copper(I) cyanide) in the presence of an acid to provide compounds of Formula Id.
  • a copper salt e.g., copper(I) halide, copper(II) halide or copper(I) cyanide
  • the diazonium salt formed from the amine of Formula 24 is generated under standard conditions, for example, strong acid (e.g., hydrochloric acid or hydrobromic acid)
  • the cyclization reaction proceeds through the intermediacy of an in szYw-generated 4-metallotriazole which when treated with an electrophile of formula R 2 -Lg (wherein Lg is a leaving group such as Cl, Br, I or a sulfonate, for example, /?-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate) provides the corresponding compound of Formula Ie.
  • the reaction is run in an aprotic solvent, such as tetrahydrofuran, at temperature between about 0 0 C to the reflux temperature of the solvent.
  • an aprotic solvent such as tetrahydrofuran
  • R is a wherein M is MgX or Li lower alkyl group
  • compounds of Formula 1 and the intermediates described above can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation and reduction reactions to add or modify substituents for formation of further compounds of Formula 1.
  • Compounds wherein R 2 , R 3 , R 4 , R 5a , R 5 ⁇ or R 5c is halogen (preferably bromide or iodide) are particularly useful intermediates for transition metal-catalyzed cross-coupling reactions to prepare compounds of Formula 1.
  • R 5 ⁇ and R 5c substituents attached to the rings and ring systems of Q 1 , Q 2 and Q 3 may be more conveniently incorporated after forming the central azole ring with the rings or ring systems of Q 1 , Q 2 and Q 3 attached.
  • R 5a , R 5 ⁇ and/or R 5c is halogen or another suitable leaving group
  • the leaving group can be replaced using various electrophilic, nucleophilic and organometallic reactions known in the art to introduce other functional groups as R 5a , R 5 * 5 and R 5c .
  • Example 29 demonstrates the preparation of a compound of Formula Ia wherein R 5a is cyano (-CN) starting from the corresponding compound of Formula Ia wherein R 5a is bromo.
  • Example 43 illustrates the preparation of a compound of Formula Ia wherein R 5 ⁇ is thiocyanate (-SCN) starting from the corresponding compound of Formula Ia wherein R 5 ⁇ is iodo.
  • compounds of Formula 1 wherein a ring or ring system of Q 1 , Q 2 or Q 3 is substituted with an R 5a , R 5 ⁇ or R 5c substituent which is -U-V-T (as defined in the Summary of the Invention) can be prepared from the corresponding compounds of Formula 1 wherein R 5a , R 5 ⁇ or R 5c is a halogen or other suitable leaving group, such as by the general method described in PCT Patent Publication WO 2007/149448 (see Scheme 15 therein).
  • the solvent system was solvent A: water with 0.05% trifluoroacetic acid by volume/volume, and solvent B: acetonitrile with 0.05% trifluoroacetic acid by volume/volume (gradient started at 0 minutes with 90% solvent A and 10% solvent B and increased solvent B to 90% over 20 minutes, flow rate was 1 mL/minute). Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated.
  • the mass spectra value given in the following Examples is the molecular weight of the highest isotopic abundance parent ion (M+ 1) formed by addition of H + (molecular weight of 1) to the molecule, observed by mass spectrometry using electrospray ionization (ESI).
  • ESI electrospray ionization
  • reaction mixture was stirred at -50 0 C for 1.5 h, and then a solution of iodomethane (1.47 g, 10.3 mmol) in tetrahydrofuran (16 mL) was added.
  • the reaction mixture was slowly warmed to room temperature, stirred for 4 h, and then concentrated under reduced pressure.
  • the resulting residue was diluted with dichloromethane (50 mL), washed with water (20 mL) and saturated aqueous sodium chloride solution (20 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • the reaction mixture was diluted with ethyl acetate (40 mL), washed with water (20 mL) and saturated aqueous sodium chloride solution (20 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • the resulting material was purified by silica gel chromatography using methanol-dichloromethane (1 : 9) as eluant to provide the title compound, a compound of the present invention, as an off- white solid (0.20 g, 95.3 area % purity by ⁇ PLC) melting at 132-134 0 C.
  • Example 9 the product of Example 9) (0.280 g, 0.78 mmol) and hexachloroethane (1.10 g, 4.7 mmol) in tetrahydrofuran (5 mL) at -78 0 C was added lithium diisopropylamide (1.0 M in tetrahydrofuran, 0.390 mL, 0.78 mmol).
  • Step B Preparation of 4-chloro-5-(2,6-difluoro-4-methoxyphenyl)-l-(3- fluorophenyl)- lH-imidazole
  • 2,6- ⁇ -[(3-fluorophenyl)amino)]-4-methoxybenzeneacetonitrile i.e. the product of Step A
  • dichloromethane 20 mL
  • ⁇ /-(chloromethylene)- ⁇ /-methylmethanaminium chloride (1.60 g, 12.5 mmol).
  • reaction mixture was diluted with saturated aqueous sodium carbonate solution, and the resulting aqueous mixture was extracted with dichloromethane.
  • Step A Preparation of 2,6- ⁇ -[(4-fluorophenyl)amino)]-3-methoxybenzeneacetonitrile
  • a mixture of 4-fluoroaniline (1.17 g, 10.6 mmol), 2,6-difluoro-3- methoxybenzaldehyde (2.0Og, 11.6 mmol), potassium cyanide (2.80 g, 42.4 mmol) and indium chloride (2.30 g, 10.4 mmol) in tetrahydrofuran (50 mL) was stirred at room temperature overnight.
  • the reaction mixture was diluted with water (about 100 mL) and extracted with ethyl acetate.
  • Step B Preparation of 4-bromo-5-(2,6-difluoro-3-methoxyphenyl)-l-(4- fluorophenyl)- lH-imidazole
  • N-bromosuccinimide (0.250 g, 1.40 mmol) was added to the reaction mixture and the mixture was again heated at 60 0 C overnight, after which time more N-bromosuccinimide (0.250 g, 1.40 mmol) was added and the mixture was again heated at 60 0 C overnight.
  • the reaction mixture was diluted with saturated aqueous sodium carbonate solution, and the aqueous mixture was extracted with dichloromethane. The combined organic layers were dried over magnesium sulfate, filtered and concentrated under reduced pressure.
  • Ethynyltrimethyl silane (0.216 g, 2.2 mmol) was added to the reaction mixture, stirring was continued for 2 h, and then the mixture was heated at reflux overnight. More dichlorobis(triphenylphosphine)palladium (0.147 g, 0.21 mmol) and ethynyltrimethylsilane (0.216 g, 2.2 mmol) were added to the reaction mixture, and the mixture was heated at reflux for 4 h.
  • the reaction mixture was diluted with saturated aqueous sodium carbonate solution and extracted with ethyl acetate, and the combined organic layers were washed with saturated aqueous ethylenediaminetetraacetic acid, dried over magnesium sulfate, filtered and concentrated under reduced pressure.
  • the resulting material was purified by medium pressure liquid chromatography on silica gel (0 to 100% gradient of ethyl acetate in hexanes as eluant) to provide the title compound as a solid (0.244 g).
  • Step B Preparation of 4-chloro-5-(2,6-difluorophenyl)-2-ethynyl-l-(3-fluorophenyl)- lH-imidazole
  • 2-bromo-4-chloro-5-(2,6-difluorophenyl)-l-(3-fluorophenyl)-lH- imidazole i.e. the product of Step A
  • a solution of sodium hydroxide and methanol 1%, w/w, 2 mL
  • ⁇ /, ⁇ /-dimethylformamide (0.47 mL, 6.0 mmol) was added. After an additional 1 h of stirring at 0 0 C, the reaction mixture was allowed to warm to room temperature. After 1 h, the reaction mixture was diluted with aqueous citric acid solution (20%, 30 mL) and extracted with diethyl ether (100 mL). The organic layers were dried over magnesium sulfate, filtered and concentrated under reduced pressure. The resulting material was purified by flash column chromatography on silica gel (0 to 20% gradient of ethyl acetate in n-butyl chloride as eluant) to provide the title compound, a compound of the present invention, as a pale- yellow solid (0.397 g).
  • the reaction mixture was diluted with ethyl acetate and washed with water (2x), and the ethyl acetate mixture was neutralized by the addition of saturated aqueous sodium bicarbonate solution.
  • the aqueous mixture was extracted with ethyl acetate (2x), and the combined organic layers were washed with saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate, filtered and concentrated under reduced pressure.
  • the resulting material was purified by medium pressure liquid chromatography on silica gel (0 to 100% gradient of ethyl acetate in hexanes as eluant) to provide the title compound, a compound of the present invention, as a solid (0.470 g).
  • 1H NMR (CDCl 3 ) ⁇ 7.32 (m, 3H), 7.15 (m, 2H), 6.86 (dd, 2H), 3.70 (s, 2H), 3.66 (s, 3H).
  • the resulting material was purified by medium pressure liquid chromatography on silica gel (0 to 100% gradient of ethyl acetate in hexanes as eluant) to provide the title compound, a compound of the present invention, as a solid (0.037 g).
  • the resulting material was purified by medium pressure liquid chromatography on silica gel (0 to 100% gradient of ethyl acetate in hexanes as eluant) to provide the title compound, a compound of the present invention, as a solid (0.063 g).
  • reaction mixture was concentrated under reduced pressure, and the resulting material was purified by medium pressure liquid chromatography on silica gel (0 to 100% gradient of ethyl acetate in hexanes as eluant) to provide the title compound, a compound of the present invention, as a solid (0.088 g).
  • reaction mixture was allowed to warm to room temperature, and stirred overnight. More tribromoborane (1 M in dichloromethane, 1.4 mL, 1.40 mmol) was added to the reaction mixture at room temperature, and stirring was continued for 4 h. Hydrochloric acid (1 N, 8.0 mL) was added to the reaction mixture, and then the aqueous mixture was brought to a basic pH by the addition of saturated aqueous sodium carbonate solution. The aqueous mixture was extracted with ethyl acetate, and the extract was dried over magnesium sulfate, filtered and concentrated under reduced pressure.
  • Step A Preparation of phenylmethyl ⁇ /-[3-[4-[4-chloro-2-methyl-l-(4-methylphenyl)- lH-imidazol-5-yl]-3,5-difluorophenoxy]propyl]- ⁇ /-methylcarbamate A mixture of 4-[4-chloro-2-methyl-l-(4-methylphenyl)-lH-imidazol-5-yl]-3,5- difluorophenol (i.e.
  • Example 32 the product of Example 32 (0.200 g, 0.598 mmol) and 4 A molecular sieves (1.55 g) in N, ⁇ /-dimethylformamide (3 mL) was stirred at room temperature for 3 h, and then a solution of phenylmethyl ⁇ /-(3-chloropropyl)- ⁇ /-methylcarbamate (prepared by the method described in PCT Publication WO 2007/149448) (0.434 g, 1.80 mmol) and tetrabutylammonium iodide (0.044 g, 0.120 mmol) in ⁇ /, ⁇ /-dimethylformamide (1 mL) was added.
  • phenylmethyl ⁇ /-(3-chloropropyl)- ⁇ /-methylcarbamate prepared by the method described in PCT Publication WO 2007/149448
  • tetrabutylammonium iodide 0.044 g, 0.120 mmol
  • Step B Preparation of 3-[4-[4-chloro-2-methyl- 1 -(4-methylphenyl)- lH-imidazol-5- yl]-3 ,5 -difluorophenoxy] -//-methyl- 1 -propanamide hydrochloride
  • Step A Preparation of N-[(2,6-difluoro-4-methoxyphenyl)methylene]-6- (trifluoromethyl)-3 -pyridinamine
  • Step C Preparation of 5-[4-chloro-5-(2,6-difluoro-4-methoxyphenyl)- lH-imidazol- 1 - yl]-2-(trifluoromethyl)pyridine A mixture of 5-[5-(2,6-difluoro-4-methoxyphenyl)-lH-imidazol-l-yl]-2-
  • Step A Preparation of ⁇ /-[(6-chloro-3-pyridinyl)methylene]-2,6-difluoro-4- methoxybenzenamine
  • Step A Preparation of l-(4-chlorophenyl)-2-(2,6-difluorophenyl)ethanone A mixture of 2,6-difluorophenylacetic acid (5.63 g, 31.1 mmol) and thionyl chloride
  • Step B) the product of Step B) (0.22 g, 0.66 mmol), 3-fiuorophenylboronic acid (0.18 g, 1.32 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.02 g, 0.02 mmol), 2- dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.04 g, 0.09 mmol), and potassium phosphate (0.43 g, 2.0 mmol), and the mixture was then heated at 100 0 C overnight. The reaction mixture was allowed to cool to room temperature, and then concentrated under reduced pressure.
  • the resulting material was purified by medium pressure liquid chromatography on silica gel (5:95 to 30:70 gradient of ethyl acetate in hexanes as eluant) to provide a solid.
  • the solid was triturated with n-butyl chloride, filtered and air-dried to provide the title compound, a compound of the present invention, as an off-white solid (0.08 g)- 1 H NMR (CDCl 3 ): ⁇ 7.45-7.38 (m, IH), 7.28-7.20 (m, 2H), 7.04-6.79 (m, 4H), 3.71 (s, 3H),
  • the reaction mixture was diluted with water (50 mL) and extracted with hexanes (50 mL). The aqueous layer was then acidified to pH 4 with aqueous hydrochloric acid (3 N) solution and extracted with diethyl ether (3 x 100 mL). The combined diethyl ether layers were washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated under reduced pressure to provide a tan solid (4.6 g).
  • Step B Preparation of 5-bromo-4-(2-chloro-4-fluorophenyl)- 1 ,3-dimethyl- IH- pyrazole
  • 4-(2-chloro-4-fluorophenyl)-l,3-dimethyl-lH-pyrazol-5-amine i.e. the product of Step A
  • acetonitrile 50 mL
  • copper(II) bromide 3.94 g, 17.7 mmol
  • reaction mixture was cooled to about 0 0 C with an ice-water bath, and then tert-butyi nitrite (90% technical grade, 2.33 mL, 17.7 mmol) was added dropwise over 5 minutes.
  • the reaction mixture was allowed to warm slowly to room temperature.
  • Aqueous hydrochloric acid solution (1 N, 20 mL) and ethyl acetate (20 mL) were added to the reaction mixture, and then the mixture was filtered through a pad (2 cm) of Celite® (diatomaceous filter aid).
  • the Celite® pad was washed with ethyl acetate (20 mL), the layers were separated, and the organic layer was washed with aqueous hydrochloric acid (1 N) solution and saturated aqueous sodium chloride solution, dried over magnesium sulfate, and concentrated under reduced pressure to provide the title compound as an orange-brown semisolid.
  • the reaction mixture was heated at reflux for 3 h and then cooled to room temperature and aqueous hydrochloric acid solution (1 N, 3 rnL) was added.
  • the aqueous mixture was extracted with ethyl acetate (20 mL), and the organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, and concentrated under reduced pressure to provide an oily material.
  • the oily material was purified by silica gel (5 g) column chromatography (3 to 100% ethyl acetate in hexanes as eluant) to provide the title compound, a compound of the present invention, as a yellow oil (118 mg).
  • Step B Preparation of 4-chloro-l-(4-chlorophenyl)-5-(2,4-difluorophenyl)-lH-l,2,3- triazole
  • ethylmagnesium chloride 2 M in tetrahydrofuran, 1.2 mL, 2.39 mmol
  • l-ethynyl-2,4-difluorobenzene 0.300 g, 2.17 mmol
  • the reaction mixture was heated at 50 0 C for 15 minutes and then allowed to cool to room temperature.
  • a solution of l-azido-4-chlorobenzene i.e.
  • Step A) the product of Step A) (0.328 g, 2.39 mmol) in tetrahydrofuran (1 mL) was added to the reaction mixture, followed by heating at 50 0 C. After 1 h, hexachloroethane (1.03 g, 4.34 mmol) was added to the reaction mixture. After 2 h, the reaction mixture was allowed to cool to room temperature, and hydrochloric acid (2 M in diethyl ether, 2 mL) was added.
  • Q 2 is 4-Cl-Ph, R 2 is Cl and R 4 is Me.
  • Q 2 is 4-Cl-Ph, R 2 is Cl and R 4 is Me.
  • the present disclosure also includes Tables IA through 934A, each of which is constructed the same as Table 1 above except that the row heading in Table 1 (i.e. "Q 2 is 4-Cl-Ph, R 2 is Cl and R 4 is Me") is replaced with the respective row heading shown below.
  • Table IA the row heading is "Q 2 is 4-Cl-Ph, R 2 is Br and R 4 is Me", and (R 5a ) m is as defined in Table 1 above.
  • the first entry in Table IA specifically discloses 4-bromo-l-(4-chlorophenyl)-5-(2,6-difluorophenyl)-lH-imidazole.
  • Tables 2A through 934A are constructed similarly.
  • IA Q 2 is 4-Cl-Ph, R 2 is Br and R 4 is Me.
  • Q 2 is 4-Cl-Ph, R 2 is Cl and R 4 is CFH 2 .
  • Q 2 is 4-Cl-Ph, R 2 is I and R 4 is Me.
  • Q 2 is 4-Cl-Ph, R 2 is Me and R 4 is Me.
  • Q 2 is 4-Cl-Ph, R 2 is Me and R 4 is Cl.
  • Q 2 is 4-Cl-Ph, R 2 is Me and R 4 is Br.
  • Q 2 is 4-Cl-Ph, R 2 is Me and R 4 is I.
  • Q 2 is 4-Cl-Ph, R 2 is Me and R 4 is MeO.
  • Q 2 is 4-Cl-Ph, R 2 is MeO and R 4 is Me.
  • HA Q 2 is 4-Cl-Ph, R 2 is Br and R 4 is Cl.
  • Q 2 is 4-Cl-Ph, R 2 is Cl and R 4 is Br.
  • Q 2 is 4-Cl-Ph, R 2 is Cl and R 4 is Cl.
  • Q 2 is 4-Cl-Ph, R 2 is Me and R 4 is MeS.
  • Q 2 is 4-Cl-Ph, R 2 is MeS and R 4 is Me.
  • Q 2 is 4-Cl-Ph, R 2 is Et and R 4 is Br.
  • Q 2 is 4-Cl-Ph, R 2 is Me and R 4 is Et.
  • Q 2 is 4-Cl-Ph, R 2 is Me and R 4 is CN.
  • Q 2 is 4-Cl-Ph, R 2 is Me and R 4 is H.
  • Q 2 is 4-Cl-Ph, R 2 is Cl and R 4 is H.
  • Q 2 is 4-Cl-Ph, R 2 is Br and R 4 is H.
  • Q 2 is 3 -Cl-Ph, R 2 is Cl and R 4 is Me.
  • Q 2 is 3 -Cl-Ph, R 2 is Br and R 4 is Me.
  • Q 2 is 3 -Cl-Ph, R 2 is Me and R 4 is Me.
  • Q 2 is 3 -Cl-Ph, R 2 is Br and R 4 is Br.
  • Q 2 is 3 -Cl-Ph, R 2 is Br and R 4 is Cl.
  • Q 2 is 3 -Cl-Ph, R 2 is Cl and R 4 is Cl.
  • Q 2 is 4-F-Ph, R 2 is Cl and R 4 is CFH 2 .
  • Q 2 is 4-F-Ph, R 2 is Br and R 4 is Me.
  • Q 2 is 4-F-Ph, R 2 is I and R 4 is Me.
  • Q 2 is 4-F-Ph, R 2 is Me and R 4 is Me.
  • Q 2 is 4-F-Ph, R 2 is Me and R 4 is Cl.
  • Q 2 is 4-F-Ph, R 2 is Me and R 4 is Br.
  • Q 2 is 4-F-Ph, R 2 is Me and R 4 is I.
  • Q 2 is 4-F-Ph, R 2 is Br and R 4 is Br.
  • Q 2 is 4-F-Ph, R 2 is Br and R 4 is Cl.
  • Q 2 is 4-F-Ph, R 2 is Me and R 4 is H.
  • Q 2 is 4-F-Ph, R 2 is Cl and R 4 is H.
  • Q 2 is 4-F-Ph, R 2 is Br and R 4 is H.
  • Q 2 is 3-F-Ph, R 2 is Cl and R 4 is CFH 2 .
  • 57A Q 2 is 3-F-Ph, R 2 is Br and R 4 is Me.
  • 58A Q 2 is 3-F-Ph, R 2 is I and R 4 is Me.
  • 59A Q 2 is 3-F-Ph, R 2 is Me and R 4 is Me.
  • 61A Q 2 is 3-F-Ph, R 2 is Me and R 4 is Br.
  • Q 2 is 3-F-Ph, R 2 is Br and R 4 is Cl.
  • 67A Q 2 is 3-F-Ph, R 2 is Me and R 4 is H.
  • 74A Q 2 is 3-CF 2 HO-Ph, R 2 is Me and R 4 is Me.
  • Q 2 is 3-CF 2 HO-Ph, R 2 is Me and R 4 is Cl.
  • 76A Q 2 is 3-CF 2 HO-Ph, R 2 is Me and R 4 is Br.
  • 77A Q 2 is 3-CF 2 HO-Ph, R 2 is Me and R 4 is I.
  • 81A Q 2 is 3-CF 2 HO-Ph, R 2 is Cl and R 4 is Cl.
  • 82A Q 2 is 3-CF 2 HO-Ph, R 2 is Me and R 4 is H.
  • Q 2 is 4-Me-Ph, R 2 is Cl and R 4 is Me.
  • Q 2 is 4-Me-Ph, R 2 is Cl and R 4 is CFH 2 .
  • 87A Q 2 is 4-Me-Ph, R 2 is Br and R 4 is Me.
  • 89A Q 2 is 4-Me-Ph, R 2 is Me and R 4 is Me.
  • 91A Q 2 is 4-Me-Ph, R 2 is Me and R 4 is Br.
  • 92A Q 2 is 4-Me-Ph, R 2 is Me and R 4 is I.
  • Q 2 is 4-Me-Ph, R 2 is Cl and R 4 is Br.
  • 96A Q 2 is 4-Me-Ph, R 2 is Cl and R 4 is Cl.
  • 97A Q 2 is 4-Me-Ph, R 2 is Me and R 4 is H.
  • 98A Q 2 is 4-Me-Ph, R 2 is Cl and R 4 is H.
  • Q 2 is 4-Me-Ph, R 2 is Br and R 4 is H.
  • IOOA Q 2 is 3-Me-Ph, R 2 is Cl and R 4 is Me. Table Row Heading
  • Q 2 is 3-Me-Ph, R 2 is Cl and R 4 is CFH 2 .
  • 106A Q 2 is 3-Me-Ph, R 2 is Me and R 4 is Br.
  • 107A Q 2 is 3-Me-Ph, R 2 is Me and R 4 is I.
  • 109A Q 2 is 3-Me-Ph, R 2 is Br and R 4 is Cl.
  • HOA Q 2 is 3-Me-Ph, R 2 is Cl and R 4 is Br.
  • H iA Q 2 is 3-Me-Ph, R 2 is Cl and R 4 is Cl.
  • Q 2 is 3-Me-Ph, R 2 is Me and R 4 is H.
  • 113A Q 2 is 3-Me-Ph, R 2 is Cl and R 4 is H.
  • 114A Q 2 is 3-Me-Ph, R 2 is Br and R 4 is H.
  • 116A Q 2 is 4-Et-Ph, R 2 is Cl and R 4 is CFH 2 .
  • 117A Q 2 is 4-Et-Ph, R 2 is Br and R 4 is Me.
  • 118A Q 2 is 4-Et-Ph, R 2 is I and R 4 is Me.
  • Q 2 is 4-Et-Ph, R 2 is Me and R 4 is Me.
  • Q 2 is 4-Et-Ph, R 2 is Me and R 4 is Cl.
  • 121A Q 2 is 4-Et-Ph, R 2 is Me and R 4 is Br.
  • Q 2 is 4-Et-Ph, R 2 is Me and R 4 is I.
  • 123A Q 2 is 4-Et-Ph, R 2 is Br and R 4 is Br.
  • 124A Q 2 is 4-Et-Ph, R 2 is Br and R 4 is Cl.
  • 125A Q 2 is 4-Et-Ph, R 2 is Cl and R 4 is Br.
  • 127A Q 2 is 4-Et-Ph, R 2 is Me and R 4 is H.
  • Q 2 is 4-Et-Ph, R 2 is Cl and R 4 is H.
  • Q 2 is 4-Et-Ph, R 2 is Br and R 4 is H.
  • 131A Q 2 is 4-Cl, 3-F-Ph, R 2 is Cl and R 4 is CFH 2 .
  • 132A Q 2 is 4-Cl, 3-F-Ph, R 2 is Br and R 4 is Me.
  • 133A Q 2 is 4-Cl, 3-F-Ph, R 2 is I and R 4 is Me.
  • 134A Q 2 is 4-Cl, 3-F-Ph, R 2 is Me and R 4 is Me.
  • Q 2 is 4-Cl, 3-F-Ph, R 2 is Me and R 4 is Cl.
  • 136A Q 2 is 4-Cl, 3-F-Ph, R 2 is Me and R 4 is Br.
  • 138A Q 2 is 4-Cl, 3-F-Ph, R 2 is Br and R 4 is Br.
  • Q 2 is 4-Cl, 3-F-Ph, R 2 is Cl and R 4 is Br.
  • Q 2 is 4-Cl, 3-F-Ph, R 2 is Me and R 4 is H.
  • 143A Q 2 is 4-Cl, 3-F-Ph R 2 is Cl and R 4 is H.
  • 144A Q 2 is 4-Cl, 3-F-Ph, R 2 is Br and R 4 is H.
  • 146A Q 2 is 2-Cl, 4-F-Ph, R 2 is Cl and R 4 is CFH 2 .
  • Q 2 is 2-Cl, 4-F-Ph, R 2 is Br and R 4 is Me.
  • a Q 2 is 2-Cl, 4-F-Ph, R 2 is Me and R 4 is Me.
  • Q 2 is 2-Cl, 4-F-Ph, R 2 is Me and R 4 is Cl.
  • 151A Q 2 is 2-Cl, 4-F-Ph, R 2 is Me and R 4 is Br.
  • 152A Q 2 is 2-Cl, 4-F-Ph, R 2 is Me and R 4 is I.
  • 154A Q 2 is 2-Cl, 4-F-Ph, R 2 is Br and R 4 is Cl.
  • 155A Q 2 is 2-Cl, 4-F-Ph, R 2 is Cl and R 4 is Br.
  • 156A Q 2 is 2-Cl, 4-F-Ph, R 2 is Cl and R 4 is Cl.
  • 157A Q 2 is 2-Cl, 4-F-Ph, R 2 is Me and R 4 is H.
  • 158A Q 2 is 2-Cl, 4-F-Ph R 2 is Cl and R 4 is H.
  • 159A Q 2 is 2-Cl, 4-F-Ph, R 2 is Br and R 4 is H.
  • Q 2 is 4-F, 3-Me-Ph, R 2 is Cl and R 4 is Me.
  • Q 2 is 4-F, 3-Me-Ph, R 2 is Cl and R 4 is CFH 2 .
  • Q 2 is 4-F, 3-Me-Ph, R 2 is Br and R 4 is Me.
  • Q 2 is 4-F, 3-Me-Ph, R 2 is I and R 4 is Me.
  • 164A Q 2 is 4-F, 3-Me-Ph, R 2 is Me and R 4 is Me.
  • Q 2 is 4-F, 3-Me-Ph, R 2 is Me and R 4 is Cl.
  • 166A Q 2 is 4-F, 3-Me-Ph, R 2 is Me and R 4 is Br.
  • 167A Q 2 is 4-F, 3-Me-Ph, R 2 is Me and R 4 is I.
  • 168A Q 2 is 4-F, 3-Me-Ph, R 2 is Br and R 4 is Br.
  • Q 2 is 4-F, 3-Me-Ph, R 2 is Br and R 4 is Cl.
  • Q 2 is 4-F, 3-Me-Ph, R 2 is Cl and R 4 is Br.
  • Q 2 is 4-F, 3-Me-Ph, R 2 is Cl and R 4 is Cl.
  • 172A Q 2 is 4-F, 3-Me-Ph, R 2 is Me and R 4 is H.
  • Q 2 is 4-F, 3-Me-Ph, R 2 is Cl and R 4 is H.
  • 174A Q 2 is 4-F, 3-Me-Ph, R 2 is Br and R 4 is H.
  • a Q 2 is 3,4-di-F-Ph, R 2 is Cl and R 4 is Me.
  • 177A Q 2 is 3,4-di-F-Ph, R 2 is Br and R 4 is Me.
  • 179A Q 2 is 3,4-di-F-Ph, R 2 is Me and R 4 is Me.
  • Q 2 is 3,4-di-F-Ph, R 2 is Me and R 4 is Cl.
  • Q 2 is 3,4-di-F-Ph, R 2 is Me and R 4 is Br.
  • Q 2 is 3,4-di-F-Ph, R 2 is Me and R 4 is I.
  • Q 2 is 3,4-di-F-Ph, R 2 is Br and R 4 is Br.
  • 185A Q 2 is 3,4-di-F-Ph, R 2 is Cl and R 4 is Br.
  • 187A Q 2 is 3,4-di-F-Ph, R 2 is Me and R 4 is H.
  • 188A Q 2 is 3,4-di-F-Ph, R 2 is Cl and R 4 is H.
  • 190A Q 2 is 3,4-di-Cl-Ph, R 2 is Cl and R 4 is Me.
  • Q 2 is 3,4-di-Cl-Ph, R 2 is Cl and R 4 is CFH 2 .
  • a Q 2 is 3,4-di-Cl-Ph, R 2 is Br and R 4 is Me.
  • Q 2 is 3,4-di-Cl-Ph, R 2 is I and R 4 is Me.
  • Q 2 is 3,4-di-Cl-Ph, R 2 is Me and R 4 is Me.
  • 196A Q 2 is 3,4-di-Cl-Ph, R 2 is Me and R 4 is Br.
  • Q 2 is 3,4-di-Cl-Ph, R 2 is Cl and R 4 is Br.
  • 201A Q 2 is 3,4-di-Cl-Ph, R 2 is Cl and R 4 is Cl.
  • 202A Q 2 is 3,4-di-Cl-Ph, R 2 is Me and R 4 is H.
  • 204A Q 2 is 3,4-di-Cl-Ph, R 2 is Br and R 4 is H.
  • Q 2 is 3,5-di-MeO-Ph, R 2 is Cl and R 4 is CFH 2 .
  • 207A Q 2 is 3,5-di-MeO-Ph, R 2 is Br and R 4 is Me.
  • Q 2 is 3,5-di-MeO-Ph, R 2 is Me and R 4 is Me.
  • 210A Q 2 is 3,5-di-MeO-Ph, R 2 is Me and R 4 is Cl.
  • 211A Q 2 is 3,5-di-MeO-Ph, R 2 is Me and R 4 is Br. Table Row Heading
  • Q 2 is 3,5-di-MeO-Ph, R 2 is Br and R 4 is Br.
  • Q 2 is 3,5-di-MeO-Ph, R 2 is Cl and R 4 is Br.
  • 216A Q 2 is 3,5-di-MeO-Ph, R 2 is Cl and R 4 is Cl.
  • Q 2 is 3,5-di-MeO-Ph, R 2 is Mt ; and R 4 is H.
  • Q 2 is 3,5-di-MeO-Ph, R 2 is Cl and R 4 is H.
  • Q 2 is 3,5-di-MeO-Ph, R 2 is Br and R 4 is H.
  • Q 2 is 2-Cl, 3,5-di-MeO-Ph, R 2 is Cl and R 4 is Me.
  • Q 2 is 2-Cl, 3,5-di-MeO-Ph, R 2 is Cl and R 4 is CFH 2 .
  • 222A Q 2 is 2-Cl, 3,5-di-MeO-Ph, R 2 is Br and R 4 is Me.
  • Q 2 is 2-Cl, 3,5-di-MeO-Ph, R 2 is I and R 4 is Me.
  • 224A Q 2 is 2-Cl, 3,5-di-MeO-Ph, R 2 is Me and R 4 is Me.
  • 225A Q 2 is 2-Cl, 3,5-di-MeO-Ph, R 2 is Me and R 4 is Cl.
  • Q 2 is 2-Cl, 3,5-di-MeO-Ph, R 2 is Me and R 4 is Br.
  • Q 2 is 2-Cl, 3,5-di-MeO-Ph, R 2 is Me and R 4 is I.
  • Q 2 is 2-Cl, 3,5-di-MeO-Ph, R 2 is Br and R 4 is Br.
  • Q 2 is 2-Cl, 3,5-di-MeO-Ph, R 2 is Br and R 4 is Cl.
  • 230A Q 2 is 2-Cl, 3,5-di-MeO-Ph, R 2 is Cl and R 4 is Br.
  • IA Q 2 is 2-Cl, 3,5-di-MeO-Ph, R 2 is Cl and R 4 is Cl.
  • 233A Q 2 is 2-Cl, 3,5-di-MeO-Ph, R 2 is Cl and R 4 is H.
  • Q 2 is 2-Cl, 3,5-di-MeO-Ph, R 2 is Br and R 4 is H.
  • 235A Q 2 is 4-Cl, 3,5-di-MeO-Ph, R 2 is Cl and R 4 is Me.
  • Q 2 is 4-Cl, 3,5-di-MeO-Ph, R 2 is Cl and R 4 is CFH 2 .
  • Q 2 is 4-Cl, 3,5-di-MeO-Ph, R 2 is Br and R 4 is Me.
  • Q 2 is 4-Cl, 3,5-di-MeO-Ph, R 2 is I and R 4 is Me.
  • Q 2 is 4-Cl, 3,5-di-MeO-Ph, R 2 is Me and R 4 is Me.
  • 240A Q 2 is 4-Cl, 3,5-di-MeO-Ph, R 2 is Me and R 4 is Cl.
  • Q 2 is 4-Cl, 3,5-di-MeO-Ph, R 2 is Me and R 4 is Br.
  • Q 2 is 4-Cl, 3,5-di-MeO-Ph, R 2 is Me and R 4 is I.
  • 243A Q 2 is 4-Cl, 3,5-di-MeO-Ph, R 2 is Br and R 4 is Br.
  • Q 2 is 4-Cl, 3,5-di-MeO-Ph, R 2 is Br and R 4 is Cl.
  • Q 2 is 4-Cl, 3,5-di-MeO-Ph, R 2 is Cl and R 4 is Br.
  • Q 2 is 4-Cl, 3,5-di-MeO-Ph, R 2 is Cl and R 4 is Cl.
  • Q 2 is 4-Cl, 3,5-di-MeO-Ph, R 2 is Me and R 4 is H.
  • Q 2 is 4-Cl, 3,5-di-MeO-Ph, R 2 is Br and R 4 is H.
  • Q 2 is 4-Cl-Bn, R 2 is Cl and R 4 is Me.
  • Q 2 is 4-Cl-Bn, R 2 is Cl and R 4 is CFH 2 .
  • Q 2 is 4-Cl-Bn, R 2 is Br and R 4 is Me.
  • Q 2 is 4-Cl-Bn, R 2 is I and R 4 is Me.
  • Q 2 is 4-Cl-Bn, R 2 is Me and R 4 is Me.
  • 255A Q 2 is 4-Cl-Bn, R 2 is Me and R 4 is Cl.
  • 256A Q 2 is 4-Cl-Bn, R 2 is Me and R 4 is Br.
  • Q 2 is 4-Cl-Bn, R 2 is Me and R 4 is I.
  • Q 2 is 4-Cl-Bn, R 2 is Br and R 4 is Br.
  • Q 2 is 4-Cl-Bn, R 2 is Br and R 4 is Cl.
  • 260A Q 2 is 4-Cl-Bn, R 2 is Cl and R 4 is Br.
  • Q 2 is 4-Cl-Bn, R 2 is Cl and R 4 is Cl.
  • Q 2 is 4-Cl-Bn, R 2 is Me and R 4 is H.
  • Q 2 is 4-Cl-Bn, R 2 is Cl and R 4 is H.
  • 264A Q 2 is 4-Cl-Bn, R 2 is Br and R 4 is H.
  • Q 2 is 4-F-Bn, R 2 is Cl and R 4 is Me.
  • Q 2 is 4-F-Bn, R 2 is Cl and R 4 is CFH 2 .
  • Q 267A Q 2 is 4-F-Bn, R 2 is Br and R 4 is Me.
  • Q 2 is 4-F-Bn, R 2 is I and R 4 is Me.
  • Q 2 is 4-F-Bn, R 2 is Me and R 4 is Me.
  • 270A Q 2 is 4-F-Bn, R 2 is Me and R 4 is Cl.
  • Q 2 is 4-F-Bn, R 2 is Me and R 4 is Br.
  • Q 2 is 4-F-Bn, R 2 is Me and R 4 is I.
  • Q 2 is 4-F-Bn, R 2 is Br and R 4 is Br.
  • Q 2 is 4-F-Bn, R 2 is Br and R 4 is Cl.
  • 275A Q 2 is 4-F-Bn, R 2 is Cl and R 4 is Br.
  • Q 2 is 4-F-Bn, R 2 is Cl and R 4 is Cl.
  • Q 277A Q 2 is 4-F-Bn, R 2 is Me and R 4 is H.
  • Q 2 is 4-F-Bn, R 2 is Cl and R 4 is H.
  • Q 2 is 4-F-Bn, R 2 is Br and R 4 is H.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Cl and R 4 is CFH 2 .
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Br and R 4 is Me.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is I and R 4 is Me.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Me and R 4 is Me.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Me and R 4 is Cl.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Me and R 4 is Br.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Me and R 4 is I.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Me and R 4 is MeO.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is MeO and R 4 is Me.
  • 290A Q 2 is 6-Cl-3-pyridinyl, R 2 is Br and R 4 is Br.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Br and R 4 is Cl.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Cl and R 4 is Br.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Cl and R 4 is Cl.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Me and R 4 is MeS.
  • Q 2 is 6-Cl-3-pyridinyl
  • R 2 is MeS
  • R 4 is Me.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Et and R 4 is Br.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Et and R 4 is Cl.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Et and R 4 is Me.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Me and R 4 is Et.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Cl and R 4 is Et.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Me and R 4 is CN.
  • Q 2 is 6-Cl-3-pyridinyl, R 2 is Me and R 4 is H.
  • 303A Q 2 is 6-Cl-3-pyridinyl, R 2 is Cl and R 4 is H.
  • 304A Q 2 is 6-Cl-3-pyridinyl, R 2 is Br and R 4 is H.
  • Q 2 is 6-Me-3-pyridinyl, R 2 is Cl and R 4 is CFH 2 .
  • Q 2 is 6-Me-3-pyridinyl, R 2 is Br and R 4 is Me.
  • Q 2 is 6-Me-3-pyridinyl, R 2 is I and R 4 is Me.
  • a Q 2 is 6-Me-3-pyridinyl, R 2 is Me and R 4 is Me.
  • Q 2 is 6-Me-3-pyridinyl, R 2 is Me and R 4 is Br.
  • Q 2 is 6-Me-3-pyridinyl, R 2 is Me and R 4 is I.
  • Q 2 is 6-Me-3-pyridinyl, R 2 is Br and R 4 is Br.
  • Q 2 is 6-Me-3-pyridinyl, R 2 is Br and R 4 is Cl.
  • Q 2 is 6-Me-3-pyridinyl, R 2 is Cl and R 4 is Br.
  • Q 2 is 6-Me-3-pyridinyl, R 2 is Me and R 4 is H.
  • Q 2 is 6-Me-3-pyridinyl, R 2 is Cl and R 4 is H.
  • Q 2 is 6-Me-3-pyridinyl, R 2 is Br and R 4 is H.
  • 320A Q 2 is 6-MeO-3-pyridinyl, R 2 is Cl and R 4 is Me.
  • Q 2 is 6-MeO-3-pyridinyl, R 2 is Cl and R 4 is CFH 2 .
  • Q 2 is 6-MeO-3-pyridinyl, R 2 is Br and R 4 is Me.
  • Q 2 is 6-MeO-3-pyridinyl, R 2 is I and R 4 is Me.
  • Q 2 is 6-MeO-3-pyridinyl, R 2 is Me and R 4 is Me.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des composés de la formule 1, comprenant tous les isomères géométriques et stéréo-isomères, N-oxydes et leurs sels, INSERER FORMULE 1 ICI, dans laquelle J est Q2 ou R1; X est N, CR2 ou CQ3; Y est N ou CR3; Z est N ou CR4 et Q1, Q2, Q3, R1, R2 et R3 sont tels que définis dans la description. L'invention concerne également des compositions contenant les composés de la formule 1 et des procédés de lutte, contre une maladie de plante provoquée par un pathogène fongique, qui comporte l'application d'une quantité efficace d'un composé ou d'une composition de l'invention.
EP09743637A 2008-05-08 2009-05-07 Azoles substitués fongicides Withdrawn EP2274284A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US12699008P 2008-05-08 2008-05-08
PCT/US2009/042922 WO2009137538A2 (fr) 2008-05-08 2009-05-06 Azoles substitués fongicides
PCT/US2009/043096 WO2009137651A2 (fr) 2008-05-08 2009-05-07 Azoles substitués fongicides

Publications (1)

Publication Number Publication Date
EP2274284A2 true EP2274284A2 (fr) 2011-01-19

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EP09743637A Withdrawn EP2274284A2 (fr) 2008-05-08 2009-05-07 Azoles substitués fongicides

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EP (1) EP2274284A2 (fr)
AR (1) AR071769A1 (fr)
CL (1) CL2009001094A1 (fr)
PE (1) PE20091953A1 (fr)
TW (1) TW200950698A (fr)
UY (1) UY31811A (fr)
WO (2) WO2009137538A2 (fr)

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TWI504350B (zh) 2010-09-01 2015-10-21 Du Pont 殺真菌吡唑及其混合物
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EP3010908A1 (fr) 2013-02-20 2016-04-27 E. I. du Pont de Nemours and Company Pyrazoles fongicides
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Publication number Publication date
WO2009137538A3 (fr) 2012-04-19
AR071769A1 (es) 2010-07-14
PE20091953A1 (es) 2010-01-09
WO2009137651A3 (fr) 2012-04-26
TW200950698A (en) 2009-12-16
UY31811A (es) 2010-01-05
WO2009137538A2 (fr) 2009-11-12
WO2009137651A8 (fr) 2010-03-18
WO2009137651A2 (fr) 2009-11-12
CL2009001094A1 (es) 2010-10-08

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