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WO2008103357A1 - 1,2,4-triazoles tricycliques fongicides - Google Patents

1,2,4-triazoles tricycliques fongicides Download PDF

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Publication number
WO2008103357A1
WO2008103357A1 PCT/US2008/002191 US2008002191W WO2008103357A1 WO 2008103357 A1 WO2008103357 A1 WO 2008103357A1 US 2008002191 W US2008002191 W US 2008002191W WO 2008103357 A1 WO2008103357 A1 WO 2008103357A1
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Prior art keywords
compound
halogen
alkyl
independently selected
optionally substituted
Prior art date
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PCT/US2008/002191
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English (en)
Inventor
James Francis Bereznak
Dominic Ming-Tak Chan
Detlef Geffken
Mary Ann Hanagan
Gerald Edward Lepone
Robert James Pasteris
Steven Lewis Swann, Jr.
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
    • C07D471/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
    • C07D487/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14—Ortho-condensed systems

Definitions

  • This invention relates to certain 1,2,4-triazoles, their N-oxides, salts and compositions, and methods of their use as fungicides.
  • One area of need is for compounds that are useful for controlling plant diseases caused by Ascomycete fungal plant pathogens, such as powdery mildew diseases of cereal, broadleaf and fruit crops.
  • World Patent Application WO 1997/02262 discloses certain pyrimidinones of Formula i as fungicides.
  • each R 1 and R 2 is independently CJ-CJO alkyl; W is O, S or NH; each R 3 and R 4 is independently hydrogen, halogen or C j -C 4 alkyl; and Q is O, S or NH.
  • This invention is directed to compounds of Formula 1 including all geometric and stereoisomers, ⁇ f-oxides, and salts thereof, agricultural compositions containing them and their use as fungicides:
  • W is O, S(O) n , NR 5 or a direct bond; n is 0, 1 or 2; Q is O, S or NR 6 ;
  • R 1 is C 1 -C 10 alkyl, C 3 -C 7 cycloalkyl, C 3 -C 10 alkenyl, C 3 -C 10 alkynyl, C 2 -C 10 alkoxyalkyl, C 2 -C 10 alkylthioalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, C5-C 10 alkylcycloalkylalkyl, Cg-C 12 cycloalkylcycloalkyl,
  • C 2 -C 10 alkylsulfonylalkyl C 4 -C 10 alkenyloxyalkyl, C 4 -C 10 alkynyloxyalkyl, C 4 -C 10 alkenylthioalkyl, C 4 -C 10 alkynylthioalkyl, C 4 -C 10 alkoxyalkenyl, C 4 -C 10 alkylthioalkenyl, C 4 -C 10 trialkylsilylalkyl or C 1 -C 10 alkoxy, each optionally substituted with one or more substituents independently selected from halogen; or
  • R 1 is NR 7 R 8 ;
  • R 2 is C 1 -C 10 alkyl, C 3 -C 7 cycloalkyl, C 3 -C 10 alkenyl, C 3 -C 10 alkynyl, C 2 -C 10 alkoxyalkyl, C 2 -C 10 alkylthioalkyl, C 2 -C 10 alkylsulfonylalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10 cycloalkylalkyl, C5-C 10 alkylcycloalkylalkyl, C 4 -C 10 alkenyloxyalkyl, C 4 -C 10 alkynyloxyalkyl, C 4 -C 10 alkenylthioalkyl, C 4 -C 10 alkynylthioalkyl, C 4 -C 10 alkoxyalkenyl, C 4 -C 10 alkylthioalkenyl or C 4 -C 10 trialkylsilylalkyl,
  • R 3 is hydrogen, halogen, nitro, cyano or NR 26 R 27 ; or C 1 -Cg alkyl, C2-Cg alkenyl, C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyl, C 1 -C 8 alkoxy, C 3 -C 8 alkenyloxy, C 3 -C 8 alkynyloxy, C 1 -C 8 alkylthio, C 1 -C 8 alkylsulfonyl or C 2 -C 8 alkoxyalkyl, each optionally substituted with one or more substituents independently selected from halogen; or a phenyl ring optionally substituted with one or more substituents independently selected from R 28 ; R 4 is hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy;
  • R 6 is hydrogen; or C 1 -C 1Q alkyl, C 3 -C 10 alkenyl, C 3 -C 10 alkynyl, C 3 -C 7 cycloalkyl,
  • each R 9 is independently C 2 -C 4 alkoxycarbonyl, C 2 -C 4 dialkylamino, halogen,
  • R 20 J R22 > R 24, R 26 and R 29 is independently hydrogen or C 1 -C 4 alkyl; each R8, Rl l, R 14 , Rl6, R l9, R 2l ; R23, R 25 5 R 27 and R 30 is independently hydrogen, C 1 -C 8 alkyl or C 1 -C 4 haloalkyl; or each R 7 and R 8 , R 10 and R 11 , R 13 and R 14 , R 18 and R 19 , R 20 and R 21 , R 22 and R 23 , R 24 and R 25 , R 26 and R 27 , and R 29 and R 30 are independently taken together as -CH 2 CH 2 CH 2 CH 2 -, -CH 2 (CH 2 ) 3 CH 2 -, -CH 2 CH 2 OCH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 CH(CH 3 )CH 2 - or -CH 2 CH(CH 3 )OCH(CH 3 )CH 2 -; R 17 is hydrogen, C 1
  • this invention pertains to a compound of Formula 1 including all geometric and stereoisomers, an iV-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 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 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, 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.
  • the term “alkylating agent” refers to a chemical compound in which a carbon-containing radical is bound through a carbon atom to a leaving group such as halide or sulfonate, which is displaceable by bonding of a nucleophile to said carbon atom. Unless otherwise indicated, the term “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 R 1 and R 2 .
  • 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 or hexyl isomers.
  • alkenyl includes straight-chain or branched alkenes such as 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain or branched alkynes such as 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on straight-chain or branched alkyl moieties. Examples of “alkoxyalkyl” 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 .
  • Alkoxyalkenyl denotes alkoxy substitution on straight-chain or branched alkenyl moieties.
  • alkylthioalkenyl denotes alkylthio substitution on straight-chain or branched alkenyl moieties. Examples of “alkylthioalkenyl” include
  • Alkynyloxy includes straight-chain or branched alkynyloxy moieties.
  • alkynyloxy examples include HC ⁇ CCH 2 0, CH 3 C ⁇ CCH 2 O and CH 3 C ⁇ CCH 2 CH 2 O.
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group.
  • alkylsulfinyl examples include CH 3 S(O)-, CH 3 CH 2 S(O)-, CH 3 CH 2 CH 2 S(O)-, (CH 3 ) 2 CHS(O)- and the different butylsulfinyl, pentylsulf ⁇ nyl and hexylsulfinyl isomers.
  • alkylsulfonyl examples include CH 3 S(O) 2 -, CH 3 CH 2 S(O) 2 -, CH 3 CH 2 CH 2 S(O) 2 -, (CH 3 ) 2 CHS(O) 2 -, and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers.
  • Alkylsulfonylalkyl denotes alkylsulfonyl substitution on alkyl.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” 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 .
  • Dialkylamino denotes an amino group substituted with two alkyl groups. Examples of “dialkylamino” include (CH 3 ) 2 N. and (CH 3 CH 2 ) 2 N.
  • alkynylthioalkyl and the like are defined analogously to the above examples.
  • Trialkylsilylalkyl denotes a branched or straight-chain alkyl substituted with a trialkylsilyl group.
  • 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.
  • Examples of “trialkylsilylalkyl” include (CH 3 ) 3 SiCH 2 ,
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • alkylcycloalkyl denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, /-propylcyclobutyl, 3-methylcyclopentyl and 4-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.
  • alkylcycloalkylalkyl denotes alkylcycloalkyl substitution on an alkyl moiety. Examples of alkylcycloalkylalkyl include ethylcyclopropylmethyl, i-propylcyclobutylethyl, and 3- methylcyclopentylpropyl .
  • cycloalkylcycloalkyl denotes cycloalkyl substitution on another cycloalkyl ring, wherein each cycloalkyl ring independently has from 3 to 6 carbon ring members.
  • cycloalkylcycloalkyl radicals include cyclopropylcyclopropyl (such as 1,1'- bicyclopropyl-1-yl, l,l'-bicyclopropyl-2-yl), cyclohexylcyclopentyl (such as 4- cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as l,l'-bicyclohexyl-l-yl), and the different cis- or trans-cycloalkylcycloalkyl isomers, (such as (l/?,25)-l,l'-bicyclopropyl-2-yl and ( IR,2R)- 1 , 1 '-bicyclopropy
  • halogen either alone or in compound words such as “haloalkyl”, or when used in descriptions of groups optionally substituted with one or more substituents independently selected from halogen, includes: fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, or when used in descriptions of groups optionally substituted with one or more substituents independently selected from halogen, said groups may be partially or fully substituted with halogen atoms which may be the same or different. Examples of haloalkyl or alkyl optionally substituted with one or more substituents independently selected from halogen include F 3 C-, ClCH 2 -, CF 3 CH 2 - and CF 3 CCl 2 -.
  • haloalkoxy and the like, are defined analogously to the term “haloalkyl”.
  • haloalkoxy include CF 3 O-, CCl 3 CH 2 O-, HCF 2 CH 2 CH 2 O- and CF 3 CH 2 O-.
  • a "ring” or “ring system” as a component of Formula 1 is carbocyclic or heterocyclic.
  • the term “ring system” denotes two or more fused rings.
  • the terms tricyclic and fused tricyclic when used in connection with a ring system denote a ring system consisting of three fused rings, in which either ring can be saturated, partially unsaturated, or fully unsaturated, unless otherwise indicated.
  • carbocyclic ring carbocycle or carbocyclic ring system denote a ring or ring system wherein the atoms forming the ring backbone are selected only from carbon. Unless otherwise indicated, a carbocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated carbocyclic ring satisfies Huckel's rule, then said ring is also called an "aromatic 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 denote a ring or ring system in which at least one atom forming the ring backbone is not carbon, e.g., nitrogen, oxygen or sulfur. Typically a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies Hiickel's rule, then said ring is also called a "heteroaromatic ring” or aromatic heterocyclic ring. Unless otherwise indicated, heterocyclic rings and ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • Aromatic indicates that each of the ring atoms is essentially in the same plane and has a p-orbital perpendicular to the ring plane, and that (4n + 2) ⁇ electrons, where n is a positive integer, are associated with the ring to comply with H ⁇ ckel's rule.
  • aromatic ring system denotes a carbocyclic or heterocyclic ring system in which at least one ring of the ring system is aromatic.
  • aromatic carbocyclic ring system denotes a carbocyclic ring system in which at least one ring of the ring system is aromatic.
  • aromatic heterocyclic ring system denotes a heterocyclic ring system in which at least one ring of the ring system is aromatic.
  • nonaromatic ring system denotes a carbocyclic or heterocyclic ring system that may be fully saturated, as well as partially or fully unsaturated, provided that none of the rings in the ring system are aromatic.
  • nonaromatic carbocyclic ring system in which no ring in the ring system is aromatic.
  • nonaromatic heterocyclic ring system denotes a heterocyclic ring system in which no ring in the ring system is aromatic.
  • C 1 -C4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl
  • C 2 alkoxyalkyl designates CH3OCH2
  • C3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), 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 .
  • substituents When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents (e.g., (R 9 ) r wherein r is 1, 2, or 3). Further, when the subscript indicates a range, e.g. (R) j _ j , then the number of substituents may be selected from the integers between i and j inclusive. When a group contains a substituent which can be hydrogen, for example R 3 or R 4 then when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
  • variable group When a variable group is shown to be optionally attached to a position, for example (R 9 ) r wherein r may be 0, then hydrogen may be at the position even if not recited in the variable group definition.
  • hydrogen atoms When one or more positions on a group are said to be "unsubstituted”, then hydrogen atoms are attached to take up any free valency.
  • R 1 , R 2 , R 3 , R 6 and R 9 refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the unsubstituted analog. As used herein, the following definitions shall apply unless otherwise indicated.
  • an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of the other. Commonly, the number of optional substituents (when present) ranges from 1 to 5.
  • each R 1 and R 2 can independently be (among others) C J -C 1Q alkyl substituted with a 3-, 4-, 5- or 6-membered heterocyclic ring optionally substituted with up to 3 substituents independently selected from R 9 .
  • optionally substituted 3-, 4-, 5- or 6-membered heterocyclic rings include the rings Y-I through Y-74 illustrated in Exhibit 1 wherein R 9 is any substituent as defined in the Summary of the Invention and r is an integer from 0 to 3.
  • R 9 groups are shown in the structures Y-I through Y-74, it is noted that they do not need to be present since they are optional substituents.
  • (R 9 ) r can be attached to any available carbon or nitrogen atom of the Y group.
  • the nitrogen atoms that require a substitutent to fill their valence are substituted with either H or R 9 .
  • some Y groups can only be substituted with less than three R 9 groups (e.g., Y-16 through Y-18, Y-20 through Y-24, Y-52, Y-53, and Y-65 through Y-67).
  • G together with the two carbon atoms to which it is attached forms a 5- or 6-membered ring substituted with R 3 and R 4 wherein each R 3 and R 4 is any substituent as defined in the Summary of the Invention.
  • G is a heterocyclic ring examples of said ring, hereafter identified as a G ring, include the rings illustrated as G-I to G-39 in Exhibit 2.
  • R 3 and R 4 can be attached to any available carbon or nitrogen atom of the G ring.
  • the nitrogen atoms that require a substitutent to fill their valence are substituted with either R 3 or R 4 .
  • G rings can only be substituted with one R 3 or R 4 group; in those cases the G ring is substituted with R 3 (e.g., G-10 through G-13, G-26 and G-27 are substituted only with R 3 ).
  • R 3 e.g., G-10 through G-13, G-26 and G-27 are substituted only with R 3 .
  • the G ring encompasses the portion of the molecule enclosed in the brackets, and the wavy line indicates that the G ring is attached to the remainder of Formula 1.
  • 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, individual stereoisomers or as an optically active form.
  • nitrogen containing heterocycles can form N-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 N-oxides.
  • nitrogen containing heterocycles which can form N-oxides.
  • tertiary amines can form N-oxides.
  • Synthetic methods for the preparation of ⁇ f-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 r-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as r-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethyldioxirane.
  • salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms.
  • 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.
  • salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention comprises compounds selected from Formula 1, iV-oxides and agriculturally suitable salts thereof.
  • Embodiments of the present invention as described in the Summary of the Invention include (where Formula 1 as used in the following Embodiments includes TV-oxides and salts thereof):
  • Embodiment 1 A compound of Formula 1 wherein W is O or S(O) n .
  • Embodiment 2. A compound of Embodiment 1 wherein W is O or S.
  • Embodiment 3. A compound of Embodiment 2 wherein W is O.
  • Embodiment 4. A compound of Formula 1 wherein W is NR 5 .
  • Embodiment 5. A compound of Formula 1 wherein R 5 is hydrogen.
  • Embodiment 6 A compound of Formula 1 wherein W is a direct bond.
  • Embodiment 7. A compound of Formula 1 wherein Q is O or S.
  • Embodiment 8. A compound of Embodiment 7 wherein Q is O.
  • Embodiment 9. A compound of Formula 1 wherein G together with the two carbon atoms to which it is attached forms a phenyl, thiophene, pyridine, thiazole, oxazole or pyrimidine ring.
  • Embodiment 10 A compound of Embodiment 9 wherein G together with the two carbon atoms to which it is attached forms a phenyl, thiophene or pyridine ring.
  • Embodiment 11 A compound of Embodiment 10 wherein G together with the two carbon atoms to which it is attached forms a phenyl ring.
  • Embodiment 12. A compound of Formula 1 wherein R 1 is C 1 -Cg alkyl, C 3 -C 5 cycloalkyl, C 3 -Cg alkenyl, C 3 -Cg alkynyl, C2-Cg alkoxyalkyl, C2-Cg alkylthioalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 5 -C 10 alkylcycloalkylalkyl, Cg-C 10 cycloalkylcycloalkyl, C 4 -C 8 alkenyloxyalkyl or C 1 -C 8 alkoxy, each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 12A A compound of Embodiment 12 wherein R 1 is C 1 -C 8 alkyl, C 3 -C 5 cycloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 2 -C 8 alkoxyalkyl, C 2 -C 8 alkylthioalkyl, C 4 -C 8 cycloalkylalkyl, C 5 -C 10 alkylcycloalkylalkyl, C 4 -C 8 alkenyloxyalkyl or C 1 -C 8 alkoxy, each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 13 A compound of Embodiment 12 wherein R 1 is C 1 -C 8 alkyl, C 3 -C 5 cycloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 2 -C 8 alkoxyalkyl, C 2 -
  • R 1 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 8 alkoxyalkyl, C 4 -C 8 cycloalkylalkyl,
  • Embodiment 13A A compound of Embodiment 13 wherein R 1 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 8 alkoxyalkyl, C 4 -Cg cycloalkylalkyl or
  • Embodiment 14 A compound of Embodiment 13 wherein R 1 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 4 -C 8 cycloalkylalkyl or C 6 cycloalkylcycloalkyl, each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 14A A compound of Embodiment 14 wherein R 1 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl or C 4 -C 8 cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 14B A compound of Embodiment 14A wherein R 1 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl or C 4 -C 8 cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 14C A compound of Embodiment 14B wherein R 1 is CpCg alkyl optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 15 A compound of Formula 1 wherein R 1 is NR 7 R 8 .
  • Embodiment 16 A compound of Formula 1 wherein each R 7 , R 10 , R 12 , R 13 , R 15 , R 18 ,
  • R 20 , R 22 , R 24 , R 26 and R 29 is hydrogen.
  • Embodiment 17 A compound of Formula 1 wherein each R 8 , R n , R 14 , R 16 , R 19 , R 21 , R 23 , R 2 S, R 27 and R 30 is C 1 -C 8 alkyl.
  • Embodiment 18 A compound of Formula 1 wherein R 1 is a phenyl, pyridinyl, furanyl or thienyl ring, each ring optionally substituted up to 3 substituents independently selected from R 9 .
  • Embodiment 19 A compound of Embodiment 18 wherein R 1 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 9 .
  • C 1 -C 6 alkyl C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 1 -C 6 alkyloxy or C 1 -C 6 alkylthio, each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 22 A compound of Embodiment 21 wherein R 9 is C 2 -C 4 dialkylamino, halogen, trifluoromethyl, methyl, ethyl, methoxy or methylthio.
  • Embodiment 23 A compound of Formula 1 wherein R 1 is C 1 -C 1Q alkyl substituted with cyano, or a 5- or 6-membered heterocyclic ring containing 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs, each heterocyclic ring optionally substituted with up to 3 substituents independently selected from R 9 .
  • Embodiment 24 A compound of Embodiment 23 wherein R 1 is C 1 -C 8 alkyl substituted with cyano.
  • Embodiment 25 A compound of Embodiment 23 wherein R 1 is C 1 -C 10 alkyl substituted with a 5- or 6-membered heterocyclic ring selected from the group consisting of thiophene, furan, thiazole, oxazole, isothiazole, isoxazole, pyrrole, pyrazole, imidazole, tetrahydrofuran, 1,3-dioxolane, dihydrooxazole, dihydroimidazole, dihydropyrazole, dihydroisoxazole, pyridine, dihydrooxazine, tetrahydropyran or morpholine, each heterocyclic ring optionally substituted up to 3 substituents independently selected from R 9 .
  • R 1 is C 1 -C 10 alkyl substituted with a 5- or 6-membered heterocyclic ring selected from the group consisting of thiophene, furan, thiazole, oxazole
  • Embodiment 28 A compound of Formula 1 wherein R 2 is CpC 8 alkyl, C 3 -Cg alkenyl, C 3 -C 8 alkynyl, C 2 -C 8 alkoxyalkyl, C 2 -C 8 alkylthioalkyl, C 4 -C 8 alkylcycloalkyl, C 4 -C 8 cycloalkylalkyl, C5-C 1 0 alkylcycloalkylalkyl or C 4 -C 8 alkenyloxyalkyl, each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 28A A compound of Embodiment 28 wherein R 2 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 2 -C 8 alkoxyalkyl, C 2 -C 8 alkylthioalkyl, C 4 -C 8 cycloalkylalkyl, C 5 -C 10 alkylcycloalkylalkyl or C 4 -C 8 alkenyloxyalkyl, each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 29 A compound of Embodiment 28 wherein R 2 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 8 alkoxyalkyl, C 4 -C 8 alkylcycloalkyl, C 4 -C 8 cycloalkylalkyl or C 5 -C 10 alkylcycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen.
  • R 2 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 8 alkoxyalkyl, C 4 -C 8 alkylcycloalkyl, C 4 -C 8 cycloalkylalkyl or C 5 -C 10 alkylcycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 29 A A compound of Embodiment 29 wherein R 2 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 8 alkoxyalkyl, C 4 -C 8 cycloalkylalkyl or C 5 -C 10 alkylcycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 30 A compound of Embodiment 29 wherein R 2 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 4 -C 8 alkylcycloalkyl or C 4 -C 8 cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 30A A compound of Embodiment 30 wherein R 2 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl or C 4 -C 8 cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 30B A compound of Embodiment 30A wherein R 2 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl or C 4 -C 8 cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen Embodiment 3OC. A compound of Embodiment 30B wherein R 2 is Cj-Cg alkyl optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 31 A compound of Formula 1 wherein R 2 is phenyl optionally substituted with up to 3 substituents independently selected from R 9 .
  • Embodiment 32 A compound of Formula 1 wherein R 2 is C 1 -C 1 Q alkyl substituted with cyano or a 5- or 6-membered heterocyclic ring containing 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs, each heterocyclic ring optionally substituted with up to 3 substituents independently selected from R 9 .
  • Embodiment 33 A compound of Embodiment 32 wherein R 2 is C 1 -Cg alkyl substituted with cyano.
  • Embodiment 34 A compound of Embodiment 32 wherein R 2 is C 1 -Cg alkyl substituted with cyano.
  • a compound of Embodiment 32 wherein R 2 is C 1 -C 1Q alkyl substituted with a 5- or 6-membered heterocyclic ring selected from the group consisting of thiophene, furan, thiazole, oxazole, isothiazole, isoxazole, pyrrole, pyrazole, imidazole, tetrahydrofuran, 1,3-dioxolane, dihydrooxazole, dihydroimidazole, dihydropyrazole, dihydroisoxazole, pyridine, dihydrooxazine, tetrahydropyran or morpholine, each heterocyclic ring optionally substituted with up to 3 substituents independently selected from R 9 .
  • Embodiment 35 A compound of Formula 1 wherein R 3 is hydrogen, halogen or cyano;
  • Embodiment 36 A compound of Embodiment 35 wherein R 3 is hydrogen, halogen or cyano; or C 1 -C 4 alkyl, ethynyl or C 1 -C 4 alkoxy each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 37 A compound of Embodiment 35 wherein R 3 is hydrogen, halogen or cyano; or C 1 -C 4 alkyl, ethynyl or C 1 -C 4 alkoxy each optionally substituted with one or more substituents independently selected from halogen.
  • a compound of Embodiment 36 wherein R 3 is hydrogen, halogen, cyano, C 1 -C 4 alkyl, ethynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy.
  • Embodiment 38. A compound of Embodiment 37 wherein R 3 is hydrogen or halogen.
  • Embodiment 39 A compound of Embodiment 38 wherein R 3 is halogen.
  • Embodiment 40 A compound of Embodiment 39 wherein R 4 is hydrogen or halogen.
  • Embodiment 41 A compound of Formula 1 wherein G together with the two carbon atoms to which it is attached forms a phenyl ring substituted at the 7- position with R 3 and R 3 is other than hydrogen.
  • Embodiment 42 A compound of Embodiment 41 wherein R 3 is halogen or cyano; or C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkynyl, C 1 -C 8 alkoxy, C 1 -C 8 alkylthio, C 1 -C 8 alkylsulfonyl or C 2 -C 8 alkoxyalkyl, each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 43 A compound of Embodiment 42 wherein R 3 is halogen or cyano; or C 1 -C 4 alkyl, ethynyl or C 1 -C 4 alkoxy each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment 44 A compound of Embodiment 43 wherein R 3 is halogen or cyano.
  • Embodiment 45. A compound of Embodiment 44 wherein R 3 is halogen.
  • Embodiment 46 A compound of Formula 1 wherein G together with the two carbon atoms to which it is attached forms a phenyl ring substituted at the 7- position with R 3 and at the 9-position with R 4 , and R 3 and R 4 are other than hydrogen.
  • Embodiment 47 A compound of Embodiment 46 wherein R 3 and R 4 are independently halogen or cyano.
  • Embodiment 48 A compound of Embodiment 47 wherein R 3 and R 4 are independently halogen.
  • Embodiment 49. A compound of Formula 1 wherein R 3 and R 4 are other than hydrogen.
  • 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 1-49 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention. Combinations of Embodiments 1—49 are illustrated by:
  • Embodiment A A compound of Formula 1, N-oxides and salts thereof, wherein
  • R 1 is C 1 -C 8 alkyl, C 3 -C 5 cycloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 2 -C 8 alkoxyalkyl, C 2 -C 8 alkylthioalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 5 -C 1Q alkylcycloalkylalkyl, Cg-C 1 Q cycloalkylcycloalkyl, C 4 -C 8 alkenyloxyalkyl or C 1 -C 8 alkoxy, each optionally substituted with one or more substituents independently selected from halogen; or R 1 is a phenyl, pyridiny
  • N CR 18 R 19 and NR 2 OR 21 ;
  • Embodiment B A compound of Embodiment A wherein
  • R 1 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 8 alkoxyalkyl, C 4 -C 8 cycloalkylalkyl, C 4 -C 8 alkylcycloalkyl, C 5 -C 10 alkylcycloalkylalkyl or C 6 cycloalkylcycloalkyl each optionally substituted with one or more substituents independently selected from halogen; or R 1 is phenyl optionally substituted with up to 3 substituents independently selected from R 9 ;
  • R 2 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 8 alkoxyalkyl, C 4 -C 8 alkylcycloalkyl, C 4 -C 8 cycloalkylalkyl or C 5 -C 10 alkylcycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen; or R 2 is phenyl optionally substituted with up to 3 substituents independently selected from R 9 ;
  • R 3 is hydrogen, halogen, cyano, C 1 -C 4 alkyl, ethynyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl or C 1 -C 4 haloalkoxy; and each R9 is independently C 2 -C 4 dialkylamino, halogen, trifluoromethyl, methyl, ethyl, methoxy or methylthio.
  • Embodiment C A compound of Embodiment B wherein
  • W is O or S;
  • R 1 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 4 -C 8 cycloalkylalkyl or
  • R 2 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 4 -C 8 alkylcycloalkyl or
  • Embodiment D A compound of Embodiment C wherein
  • Q is O or S; G together with the two carbon atoms to which it is attached forms a phenyl ring;
  • R 1 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl or C 4 -C 8 cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen;
  • R 2 is C 1 -C 8 alkyl, C 3 -C 8 alkenyl or C 4 -C 8 cycloalkylalkyl, each optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment E A compound of Embodiment D wherein
  • R 1 is C 1 -C 8 alkyl optionally substituted with one or more substituents independently selected from halogen;
  • R 2 is C 1 -C 8 alkyl optionally substituted with one or more substituents independently selected from halogen.
  • Embodiment F A compound of Embodiment E wherein
  • Specific embodiments include compounds of Formula 1 selected from the group consisting of:
  • Embodiments 1 through 49 and Embodiments A through F other than compounds wherein R 1 is C 4 -Ci 0 alkylcycloalkyl or C 6 -C 12 cycloalkylcycloalkyl, or R 2 is C 4 -C 10 alkylcycloalkyl, where applicable.
  • 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 (including all geometric and stereoisomers, N-oxides, and salts thereof), and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • compositions comprising a compound corresponding to any of the compound embodiments described above.
  • 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 (including all geometric and stereoisomers, N-oxides, and salts thereof).
  • methods comprising applying a fungicidally effective amount of a compound corresponding to any of the compound embodiments describe above.
  • embodiments where the compounds are applied as compositions of this invention.
  • compounds of the Formula Ia can be prepared by N-alkylation of compounds of Formula 2.
  • compounds of Formula 2 are first contacted with a base, followed by an alkylating agent of Formula 3 wherein X 1 is a nucleophic reaction leaving group such as halide (e.g., Cl, Br, I).
  • halide e.g., Cl, Br, I
  • a compound of Formula 2 typically comprises contacting Formula 2 with a base and then a compound of Formula 3, it is not critical for the successful outcome of the reaction.
  • a compound of Formula 2, a base, and a compound of Formula 3 can be combined simultaneously.
  • the reaction is typically run in an inert solvent (e.g., N,N- dimethylformamide) at temperatures between about -20 and 60 0 C.
  • Suitable bases comprise, for example, alkali metal (such as lithium, sodium, or potassium) hydrides, hydroxides or carbonates (e.g., NaOH, KOH, Na 2 CO 3 , K 2 CO 3 ).
  • the method of Scheme 1 is illustrated in Step D of Example 1, Step B of Example 2, Step C of Example 3, Step B of Example 4, Step D of Example 6 and Step B of Example 9.
  • compounds of Formula 2 can be prepared by reacting hydrazino carboxylic acids or esters of Formula 4 with substituted ⁇ f-cyanocarbonimidates of
  • the reaction is typically conducted in a solvent such as an alcohol (e.g., methanol, ethanol or propanol) or iV,N-dimethylformamide, at temperatures between about
  • a solvent such as an alcohol (e.g., methanol, ethanol or propanol) or iV,N-dimethylformamide, at temperatures between about
  • Suitable bases comprise, for example, triethylamine, l,8-diazabicyclo(5.4.0)undec-7-ene, potassium carbonate or sodium carbonate.
  • the method of Scheme 2 is illustrated in Step C of Example 1, Step A of Example 2, Step B of Example 3 and Step A of Example 4. This type of transformation is also document in the chemical literature see, for example,
  • Hydrazino carboxylic acids or esters of Formula 4 can be prepared from the corresponding amino carboxylic acids or esters by methods well document in the art. For leading references, see PCT Patent Publication WO 2002/102359, and Stephenson, Emily F. M., Organic Syntheses 1949, Collective Volume 3, 54-8. An example of the method described in WO 2002/102359 is illustrated in Step B of Example 1.
  • Substituted N-cyanocarbonimidates of Formula 5 are commercially available and can be prepared by methods described in the literature.
  • compounds of Formula 5 wherein WR 2 is OCgH 5 , OCH3 or SCH 3 can be commercially obtained and can also be prepared by reacting dialkyl imidocarbonates with cyanogen halides (e.g., Br) as described in U.S. patent 5,237,084, or by reacting dialkyl imidocarbonates with cyanamide according to the general method of Han, Bo et. al., Organic Letters 2004, 6(21), 3691-3694.
  • An example of the method described in Organic Letters 2004, 6(21), 3691-3694 is illustrated in Step A of Example 1, and an example of the method described U.S. 5,237,084 is illustrated in Step A of Example 3.
  • compounds of Formula 2 can also be synthesized from triazole carboxamides of Formula 6 via a cyclization reaction.
  • the method is typically conducted in the presence of a base (e.g., potassium carbonate) and a catalyst (e.g., potassium iodide is particularly useful when X 2 is Br or Cl).
  • a base e.g., potassium carbonate
  • a catalyst e.g., potassium iodide is particularly useful when X 2 is Br or Cl.
  • the method of Scheme 3 is illustrated in Step C of Example 6.
  • triazole carboxamides of Formula 6 can be prepared by reacting carboxylic acids or acid chlorides of Formula 7 with aminotriazoles of Formula 8. Using N- ⁇ -dimethylaminopropyO-AT-ethylcarbodiimide hydrochlori de-mediated coupling conditions (typically at room temperature), kinetic reaction control prevails and this method provides the less stable amides of Formula 9.
  • a base e.g., potassium carbonate
  • a solvent e.g., N,N-dimethylformamide
  • the method of Scheme 4 is illustrated in Step A and Step B of Example 6.
  • substituted aminotriazoles of Formula 8 are commercially available, for example compounds of Formula 8 wherein WR2 is SMe, CH3, CF3, or cyclopropyl can be commercial obtained.
  • compounds of Formula 8 can be prepared by one of several methods, for example, by reacting an aminoguanidine sulfate with an acid according to the general method of Lipinski, Christopher et al., Journal of Medicinal Chemistry 1985, 25(11), 1628-36.
  • carboxylic acids or acid chlorides of Formula 7 can be converted to compounds of Formula 2 by reacting with aminotriazoles of Formula 8.
  • This reaction works particularly well when X 2 is adjacent to the heteroatom of a heterocycle, for example when G forms a pyridine ring.
  • the reaction is typically run in a solvent (e.g., ⁇ f,N-dimethylformamide), and in the presence of a base (e.g., potassium carbonate), metal catalyst (e.g., copper powder), and an iodide catalyst (e.g., potassium iodide) according to the general method described in German patent application
  • a solvent e.g., ⁇ f,N-dimethylformamide
  • a base e.g., potassium carbonate
  • metal catalyst e.g., copper powder
  • an iodide catalyst e.g., potassium iodide
  • compounds of Formula Ic are treated with metal alkoxides (e.g., NaOMe, NaOEt or NaOPr) in a solvent, such as the corresponding alcohols (e.g., methanol, ethanol or propanol), tetrahydrofuran, iV,iV-dimethylfbrmamide or dimethylsulfoxide at temperatures between about O and 150 °C.
  • a solvent such as the corresponding alcohols (e.g., methanol, ethanol or propanol), tetrahydrofuran, iV,iV-dimethylfbrmamide or dimethylsulfoxide at temperatures between about O and 150 °C.
  • the metal alkoxides are commercially available and can be prepared by reacting the desired alcohol with a base, such as alkali metal (e.g., lithium, sodium or potassium) hydrides or sodium.
  • alkali metal e.g., lithium, sodium or potassium
  • compounds of Formula Ib may be
  • Sulfoxides and sulfones of Formula Ic (wherein n is 1 or 2) can be prepared by treatment of the corresponding sulfides of Formula Id with an oxidizing reagent, for example, m-chloroperoxybenzoic acid. Oxidation reactions of this type are well documented; see, for example, March, J. Advanced Organic Chemistry; 3 rd ed., John Wiley: New York, (1985), 1089 and references cited within. The method of Scheme 7 for the preparation of a sulfone is illustrated in Step A of Example 7 and Step C of Example 9.
  • n 1 or 2
  • thiols of Formula 10 can be obtained from thiols of Formula 10 as shown in Scheme 8.
  • the thiol of Formula 10 is first selectively alkylated by reacting with an alkylating agent of Formula 11 wherein X 3 is a nucleophic reaction leaving group such as halide (e.g., Cl, Br, I) or sulfonate (e.g., mesylate, triflate, p- toluenesulfonate), and a base such as, for example, triethylamine, potassium carbonate, sodium hydroxide or sodium hydride.
  • halide e.g., Cl, Br, I
  • sulfonate e.g., mesylate, triflate, p- toluenesulfonate
  • a base such as, for example, triethylamine, potassium carbonate, sodium hydroxide or sodium hydride.
  • the reaction is typically run in an inert solvent (e.g., iV,N-dimethylformamide) at temperatures ranging between about -20 0 C and the normal boiling point of the solvent.
  • an inert solvent e.g., iV,N-dimethylformamide
  • N-alkylation of compounds of Formula 12 can be achieved using methods analogous to those already described for Scheme 1.
  • Compounds of Formula 10 can be prepared by condensation of hydrazino carboxylic acids or esters of Formula 4 with iV-cyanothioiminocarbonates of Formula 13 as depicted in Scheme 9. Conditions for the method of Scheme 9 are analogous to those already described for the method of Scheme 2.
  • N-cyanothioiminocarbonates of Formula 13 can be prepared from cyanamide, carbon disulfide and potassium hydroxide according to the general method described in PCT Patent Publication WO 1994/26724.
  • Z is S(O) n Me, Cl or Br, wherein Q is O and W is NR 5 and n is 0, 1 or 2
  • one or more equivalents of Formula 15 amine can be used relative to Formula 14.
  • one equivalent of an amine of Formula 15 and an acid scavenger e.g., triethylamine
  • the reaction can be run with or without solvent, including using Formula 15 amine as the solvent, at temperatures ranging between about room temperature and the normal boiling point of the solvent. It is understood by one skilled in the art, that when an amine of Formula 15 is used as a solvent it will be in large stoichiometric excess relative to Formula 14. In cases where the boiling point of the amine at atmospheric pressure is low, the reaction can be maintained above atmospheric pressure to facilitate running the reaction at temperatures higher then the normal boiling point of the amine.
  • the preferred reaction conditions will depend on the Z group. For general methods, see U.S. patent 3,867,384.
  • Amines of Formula 15 are commercially available or can be prepared by well known methods, see, for example, March, J. Advanced Organic Chemistry; 3 rd ed., John Wiley: New York, (1985), 1153-1154 and references cited within.
  • Compounds of Formula 14 wherein Z is S(O) n Me can be prepared by the methods already described for Schemes 7, 8 and 9.
  • Compounds of Formula 14 wherein Z is Cl or Br can be synthesized from compounds of Formula 16 as outlined in Scheme 11 using Sandmeyer reaction conditions. In this method the diazonium salt of the compound of Formula 16 is generated and then reacted with a copper salt (e.g., CuCl) in the presence of an acid.
  • the diazonium salt of Formula 16 is generated under standard conditions, for example, strong acid and sodium nitrite or using non-aqueous conditions.
  • amines of Formula 16 can be prepared by a modification of the methods already described for Schemes 1 and 2.
  • the hydrazino carboxylic acids or esters of Formula 4 are reacted with sodium dicyanamide to provide the amines of Formula 17, which are then alkylated to give compounds of Formula 16.
  • Step A of Example 5 illustrates the preparation of a compound of Formula 17, and Step B of Example 5 illustrates the preparation of a compound of the Formula 16 according to the method of Scheme 12.
  • compounds of Formula Ih can be prepared by treatment of compounds of Formula Ia with phosphorus pentasulfide or Lawesson's reagent in an inert solvent such as dioxane at temperatures ranging from between about 0 °C and the normal boiling point of the solvent.
  • an inert solvent such as dioxane
  • R 3 and R 4 are shown in Schemes 1 through 14, one skilled in the art will recognize that for some compounds of Formula 1 each R 3 or R 4 substituent may be more conveniently introduced after the formation of the fused tricyclic ring system.
  • compounds of Formula 1 in which G forms a fused thiophene ring can be halogenated on the thiophene ring to give the corresponding mono or dihalo substituted compounds of Formula 1 (R 3 is halogen, or R 3 and R 4 are both halogen).
  • Other R 3 and R 4 substituents can be introduced by displacement of a leaving group such as halogen.
  • Step A Preparation of dimethyl cyanocarbonimidate A stirred solution cyanamide (7.75 g, 0.18 mol) and tetramethyl orthocarbonate (25 g,
  • Step C Preparation of 7-iodo-2-methoxy[l,2,4]triazolo[l,5- ⁇ ]quinazolin-5(lH)-one To a stirred solution of dimethyl cyanocarbonimidate (i.e. the product of Step A)
  • the combined organic extracts were washed with water (3 x 30 mL), dried (MgSC ⁇ ), filtered, and concentrated under reduced pressure to provide an oil.
  • the oil was purified by flash column chromatography using a Supelco (division of Sigma-Aldrich Co., 595 North Harrison Road, Bellefonte, PA 16823, U.S.A.) tube prepacked with 10 g of silica gel (50 ⁇ m particle diameter, 70 A pore size) and as eluant ethyl acetate-hexanes (starting with 1:9 and ending with 1:1).
  • the fractions were concentrated under reduced pressure and the residue triturated with hexanes to provide the title compound, a compound of the present invention, as a white solid (17 mg) melting at 132-134 °C.
  • Step B Preparation of 4-(cyclopropylmethyl)-2-ethoxy[l,2,4]triazolo[l,5- ⁇ ]quinazolin-5(4H)-one
  • the reaction mixture was cooled to 0 °C, the p ⁇ was adjusted to 3 by adding concentrated sulfuric acid and the mixture was heated at 60 °C for 4 h. After cooling, the resulting precipitate was collected by filtration, washed with methylene chloride (3 x 10 mL), water (2 x 10 mL) and dried to provide the crude product as a gray solid (1.1 g).
  • the combined filtrates were concentrated and extracted with ethyl acetate (3 x 15 mL). The combined organic extracts were washed with water, brine, dried (MgSC ⁇ ), filtered and concentrated to provide the title product as a tan solid (92 mg).
  • Step C Preparation of 7-iodo-2-propoxy-4-propyl[l,2,4]triazolo[l,5- ⁇ ]quinazolin- 5(4H)-one
  • a mixture of 7-iodo-2-propoxy[l,2,4]triazolo[l,5- ⁇ ]quinazolin-5(lH)-one i.e. the product of Step B) (50 mg, 0.14 mmol), potassium carbonate (37 mg, 0.27 mmol), 1-iodopropane (16 ⁇ L, 27.6 mg, l ⁇ mmol) and anhydrous N ⁇ V-dimethylformamide (0.5 mL) was stirred at room temperature for 3 h.
  • reaction mixture was diluted with water (5 mL) and filtered through a Chem Elut cartridge packed with diatomaceous earth (manufactured by Varian) using ethyl acetate as eluant.
  • the solvent was evaporated under reduced pressure to provide the title compound, a compound of the present invention, as a white solid (37 mg) melting at 122-125 °C.
  • Step A Preparation of 7-iodo-2-(methylthio)-4-propyl[l,2,4]triazolol[l,5- ⁇ ]quinazolin-5(4H)-one
  • Step A Preparation of 7-iodo-2-(methylthio)[l,2,4]triazolo[l,5- ⁇ ]quinazolin-5(lH)- one
  • 2-hydrazino-5-iodobenzoic acid monohydrochloride i.e. the product of Example 1, Step B
  • dimethyl cyanocarbonimidodithioate i.e. the product of Example 1, Step B
  • Step B Preparation of 7-iodo-2-(methylthio)-4-propyl[l,2,4]triazolol[l,5- ⁇ ]quinazolin-5(4H)-one
  • Step B Preparation of 2-amino-7-iodo-4-propyl[l,2,4]triazolo[l,5- ⁇ ]quinazolin- 5(4H)-one
  • Step C Preparation of 2-chloro-7-iodo-4-propyl[l,2,4]triazolo[l,5- ⁇ ]quinazolin- 5(4H)-one
  • Tert-butyl nitrite 144 mg, 1.36 mmol
  • 2-amino-7-iodo-4-propyl[l,2,4]triazolo[l,5- ⁇ ]quinazolin-5(4H)-one i.e. the product of Step B) (500 mg, 1.36 mmol) and trifluoroacetic acid (10 mL).
  • reaction mixture was added to a solution of copper(I) chloride (50 mg, 0.51 mmol) and concentrated hydrochloric acid (3 mL) at 0 °C.
  • the reaction mixture was allowed to warm to room temperature. After 3 h, the reaction mixture was poured into ice water and the p ⁇ was adjusted to 8 by adding sodium carbonate.
  • the aqueous mixture was extracted with ethyl acetate (3 x 135 mL), the combined organic extracts washed with brine, dried (MgSC ⁇ ), filtered and concentrated under reduced pressure to give a green solid.
  • the solid was purified by flash column chromatography using a Supelco (division of Sigma-Aldrich Co., 595 North Harrison Road, Bellefonte, PA 16823, U.S.A.) tube prepacked with 10 g of silica gel (50 ⁇ m particle diameter, 70 A pore size) and as eluant 1: 1 ethyl acetate-hexanes to provide the title compound as light tan solid (114 mg) melting at 161-164 °C.
  • Supelco division of Sigma-Aldrich Co., 595 North Harrison Road, Bellefonte, PA 16823, U.S.A.
  • Step A Preparation of l-[(2,5-dichloro-3-thienyl)carbonyl]-3-(methylthio)-lH-l,2,4- triazol-5-amine
  • Step B Preparation of 2,5-dichloro-N-[5-(methylthio)-lH-l,2,4-triazol-3-yl]-3- thiophenecarboxamide
  • Step C Preparation of 7-chloro-2-(methylthio)thieno[3,2-e][l,2,4]triazolo[l,5- ⁇ ]pyrimidin-5(lH)-one
  • a mixture of the 2,5-dichloro-N-[5-(methylthio)-lH-l,2,4-triazol-3-yl]-3- thiophenecarboxamide i.e.
  • Step B the product of Step B, and 1.38 g prepared by the method of Step B) (14.52 g, 46.3 mmol), potassium carbonate (12.79 g, 92.7 mmol), potassium iodide (1.43 g, 8.6 mmol) and N ⁇ -dimethylformamide (150 mL) was heated at 130 °C. After 24 h, the reaction mixture was slowly added to a stirred solution of hydrochloric acid (IN) and the p ⁇ was adjusted to 2. The resulting solid precipitate was collected by filtration, washed with water and dried in a vacuum oven at 50 °C to provide the title compound as a white solid (10.41 g) melting at > 220 °C.
  • reaction mixture was cooled, diluted with water (50 mL) and the p ⁇ was adjusted to 2 by the addition of hydrochloric acid (1 N). The resulting orange solid was collected by filtration to provide the title compound (958 mg) melting at >250 °C.
  • Step C Preparation of 2-(methylsulfonyl)-4-propylpyrido[3,2-e][l,2,4]triazolo[l,5- ⁇ ]pyrimidin-5(4H)-one A solution of 2-(methylthio)-4-propylpyrido[3,2-e][l,2,4]triazolo[l,5- ⁇ ]pyrirnidin-
  • CN means cyano
  • NO2 means nitro
  • Ph means phenyl
  • Me means methyl
  • Et means ethyl
  • /-Pr means isopropyl
  • n means normal
  • c means cyclo
  • OMe means methoxy
  • CF 3 means trifluoromethyl
  • SMe means methylthio.
  • G together with the two carbon atoms to which it is attached forms a 5- or 6-membered ring substituted with R 3 and R 4 wherein each R 3 and R 4 is any substituent as defined in the Summary of the Invention.
  • G ring examples of said rings, hereafter identified as a G ring, include the rings illustrated as G-I to G-39 in Exhibit 2 in the Details of the Invention above.
  • G-I a fused 5- or 6-membered heterocyclic ring
  • R 3 is 6-Br and R 4 is H
  • the structure would be as follows:
  • the numbering system for the G rings is as indicated in Exhibit 2 in the Details of the Invention.
  • R 1 and R 2 include CpC j o alkyl substituted with a 3-, 4-, 5- or 6-membered heterocyclic ring containing 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs, each heterocyclic ring optionally substituted with up to 3 substituents independently selected from R 9 .
  • R 1 or R 2 is CJ-CI Q alkyl substituted with a 3-, 4-, 5- or 6-membered heterocyclic ring
  • the heterocyclic ring is indicated by a Y-number and said Y-number corresponds to the Y groups illustrated in Exhibit 1 in the Details of the Invention above.
  • R 1 is CH 2 CH 2 CH(CH 3 )CH 2 CH 2 (Y-I) and Y-I is substituted with R 9 wherein R 9 is 2,3-di- CH 3
  • R 1 would be represents as illustrated below:
  • CH 2 CH CHCH 2 OCH 3 OCH 2 CH 2 CH 3
  • Q is O
  • W is O
  • R 2 is n-Pr
  • R 3 is 7-1 and R 4 is H
  • Q is O
  • W is O
  • R 2 is n-Pr
  • 1 * 3 is 7-1
  • R 4 is 9-1.
  • CH 2 CH CHCH 2 OCH 3
  • CH 2 CH CHCH 2 SCH 3 CH 2 CH 2 Si(CH 3 ) 3 OCH 2 CH 2 CH 3
  • Q is O, W is S, R 2 is n-Pr, R 3 is 7-1 and R 4 is H.
  • Q is O
  • W is NR 5
  • R 5 is H
  • R 2 is n-Pr
  • R 3 is 7-1
  • R' * is H.
  • CH 2 C CCl CH 2 OCH 3 CH 2 OCH 2 CH 3 CH 2 OCF 3
  • CH 2 CH CHCH 2 OCH 3
  • CH 2 CH CHCH 2 SCH 3 CH 2 CH 2 Si(CH 3 ) 3 OCH 2 CH 2 CH 3
  • Q is O
  • W is a direct bond
  • R 1 is n-Pr
  • R 3 is 7-Br
  • R 4 is H.
  • Q is O
  • W is O
  • R 1 is n-Pr
  • R 3 is 7-1 and R 4 is H.
  • CH 2 (tetrahydro-2-furanyl) N C(CH 3 ) 2 N(CH 3 ) 2 NHCH 2 CH 2 CH 3
  • Q is O, W is a direct bond, Rl is n-Pr, R 3 is 7-1 and R 4 s H.
  • Q is O, W is a direct bond, R 1 is n-Pr, R 3 is 7-1 and R 4 is 9-1.
  • Q is O, W is S, R 1 is n-Pr, R 3 is 7-1 and R 4 is H.
  • CH 2 CH 2 SCH 2 CH CH 2 CH 2 CH 2 SCH 2 C ⁇ CH CH 2 CH 2 Si(CH 3 ) 3 Ph
  • Q is O
  • W is NR 5
  • R 5 is H
  • R 1 is n-Pr
  • R 3 is 7-1
  • R 4 is H.
  • Q is O
  • W is O
  • R 1 is CH 2 (tetrahyrdro-2-furanyl)
  • R 3 is 7-1 and R 4 is H.
  • CH 2 CH 2 SCH 2 CH CH 2 CH 2 CH 2 SCH 2 C ⁇ CH CH 2 CH 2 Si(CH 3 ) 3 Ph
  • CH 2 (tetrahydro-2-furanyl) N C(CH 3 ) 2 N(CH 3 ) 2 NHCH 2 CH 2 CH 3
  • Q is O
  • W is S
  • R 1 is CH 2 (tetrahyrdro-2-furanyl)
  • R 3 is 7-1
  • R 4 is H.
  • Q is O, W is a direct bond, R 1 is CH (tetrahyrdro-2-furanyl), R 3 is 7-1 and R 4 is H.
  • R2 is CH (tetrahyrdro-2-furanyl)
  • Q is O
  • W is O
  • R 1 is CH (tetrahyrdro-2-furanyl)
  • R 3 is 7-1 and R 4 is 9-1.
  • Q O
  • W S
  • R 1 CH 2 (tetrahyrdro-2-furanyl)
  • R 3 7-1
  • R 4 9-1.
  • Q is O, W is a direct bond, R 1 is CH 2 (tetrahyrdro-2-furanyl), R 3 is 7-1 and R 4 is 9-1.
  • Q is O
  • W is O
  • R 1 is n -propyl and R ⁇ is ⁇ -propyl.
  • G-I 6-1 H G-I 6-CF 3 H G-I 7-C ⁇ CH 6-Br
  • G-4 6-1 H G-4 6-CF 3 H G-4 6-1 7-CH 2 CH 3
  • G-23 7-CH CH 2 H G-24 6-CH 3 H G-25 H H R3 R4 R3 R 4 R3 R4
  • Q is O
  • W is O
  • RI is n-propyl
  • R ⁇ is n-propyl
  • G is G-2, Q is O, W is O, R 2 is n-propyl, R 3 is 7-Br and R 4 is H.
  • CH 2 CH CHCH 2 OCH 3
  • CH 2 CH CHCH 2 SCH 3 CH 2 CH 2 Si(CH 3 ) 3 OCH 2 CH 2 CH 3
  • G is G-2, Q is O, W is NH, R 2 is n-propyl, R 3 is 7-Br and R 4 is H.
  • G is G-2, Q is O, W is S, R 2 is ⁇ -propyl, R 3 is 7-Br and R 4 is H.
  • G is G-16, Q is O, W is S, R 2 is n-propyl, R 3 is 7-1 and R 4 is H.
  • CH 2 CH CHCH 2 OCH 3
  • CH 2 CH CHCH 2 SCH 3 CH 2 CH 2 Si(CH 3 ) 3 OCH 2 CH 2 CH 3
  • G is G- 1 , Q is O, W is NH 1 R 2 is n-propyl, R 3 is 7-Br and R 4 is H.
  • CH 2 (tetrahydro-2-furanyl) N C(CH 3 ) 2 N(CH 3 ) 2 NHCH 2 CH 2 CH 3
  • G is G-I, Q is 0, W is a direct bond, R 1 is n-propyl, R 3 is 7-1 and R 4 is H.
  • G is G- 16, Q is O, W is O, R 1 is n-propyl, R 3 is 7-1 and R 4 is H.
  • CH 2 CH 2 SCH 2 CH CH 2 CH 2 CH 2 SCH 2 C ⁇ CH CH 2 CH 2 Si(CH 3 ) 3 Ph
  • N C(CH 3 ) 2
  • G is G- 16, Q is O, W is NH, R 1 is /i-propyl, R 3 is 7-1 and R 4 is H.
  • Q is O, R 1 is ⁇ -propyl, R 3 is 7-1, R 4 is H and Y is substituted 1 to 3 substituents selected from the group R 9 , when R 9 is a dash ("-") then Y is unsubstituted (i.e. a ring bearing only hydrogens).
  • a compound of this invention will generally be used as a fungicidal active ingredient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as a carrier.
  • a composition i.e. formulation
  • additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as a carrier.
  • the formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like, which optionally can be thickened into gels.
  • aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion and suspo-emulsion.
  • nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.
  • compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film- forming solutions or flowable suspensions are particularly useful for seed treatment.
  • Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated”). Encapsulation can control or delay release of the active ingredient.
  • An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.
  • Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water. Spray volumes can range from about from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting. Liquid and solid formulations can be applied onto seeds of crops and other desirable vegetation as seed treatments before planting to protect developing roots and other subterranean plant parts and/or foliage through systemic uptake.
  • the formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate.
  • Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.
  • Liquid diluents include, for example, water, N ⁇ V-dimethylalkanamides (e.g., iV ⁇ V-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., iV-methylpyrrolidinone), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, triacetin, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-
  • Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C6-C 22 X such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grape seed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof.
  • plant seed and fruit oils e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grape seed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel
  • animal-sourced fats e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil
  • Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
  • the solid and liquid compositions of the present invention often include one or more surfactants. When added to a liquid, surfactants (also known as "surface-active agents”) generally modify, most often reduce, the surface tension of the liquid.
  • surfactants can be useful as wetting agents, dispersants, emulsif ⁇ ers or defoaming agents.
  • surfactants can be classified as nonionic, anionic or cationic.
  • Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide
  • Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of e
  • Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquatemary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.
  • amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amine
  • Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.
  • compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants).
  • formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes.
  • Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes.
  • formulation auxiliaries and additives include those listed in McCutcheon's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.
  • the compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent.
  • Solutions, including emulsifiable concentrates can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water.
  • Active ingredient slurries, with particle diameters of up to 2,000 ⁇ m can be wet milled using media mills to obtain particles with average diameters below 3 ⁇ m.
  • Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 ⁇ m range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques.
  • Pellets can be prepared as described in U.S. 4,172,714.
  • Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493.
  • Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030.
  • Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
  • Compound 10 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%
  • Compound 16 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; 90.0%
  • Compound 9 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%
  • Compound 9 20.00% polyvinylpyrrolidone- vinyl acetate copolymer 5.00% montan acid wax 5.00% calcium ligninsulfonate 1.00% polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol (POE 20) 2.00% polyorganosilane 0.20% colorant red dye 0.05% water 65.75%
  • the compounds of this invention are useful as plant disease control agents.
  • the present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed to be protected, an effective amount of a compound of the invention or a fungicidal composition containing said compound.
  • the compounds and/or compositions of this invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops.
  • pathogens include: Oomycetes, including Phytophthora diseases such as Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora cinnamomi and Phytophthora capsici, Pythium diseases such as Pythium aphanidermatum, and diseases in the Peronosporaceae family such as Plasmopara viticola, Peronospora spp. (including Peronospora tabacina and Peronospora parasitica), Pseudoperonospora spp.
  • Phytophthora diseases such as Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora cinnamomi and Phytophthora capsici
  • Pythium diseases such as Pythium aphanidermatum
  • diseases in the Peronosporaceae family such as
  • Botrytis diseases such as Botrytis cinerea, Monilinia fructicola, Sclerotinia diseases such as Sclerotinia sclerotiorum, Magnaporthe grisea, Phomopsis viticola, Helminthosporium diseases such as Helminthosporium tritici repentis, Pyrenophora teres, anthracnose diseases such as Glomerella or Colletotrichum spp.
  • Puccinia spp. such as Colletotrichum graminicola and Colletotrichum orbiculare, and Gaeumannomyces graminis; Basidiomycetes, including rust diseases caused by Puccinia spp. (such as Puccinia recondita, Puccinia striiformis, Puccinia hordei, Puccinia graminis and Puccinia arachidis), Hemileia vastatrix and Phakopsora pachyrhizi; other pathogens including Rhizoctonia spp.
  • Puccinia recondita Puccinia striiformis, Puccinia hordei, Puccinia graminis and Puccinia arachidis
  • Hemileia vastatrix and Phakopsora pachyrhizi other pathogens including Rhizoctonia spp.
  • compositions or combinations also have activity against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae, and other related species.
  • the compounds and/or compositions of this invention are particularly advantageous for controling diseases caused by Ascomycete fungal plant pathogens. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include: Ascomycetes, including powdery mildew diseases such as Erysiphe spp. (including Erysiphe graminis and Erysiphe polygoni), Uncinula necatur, Sphaerotheca fuligena and Podosphaera leucotricha, and other related species.
  • Ascomycetes including powdery mildew diseases such as Erysiphe spp. (including Erysiphe graminis and Erysiphe polygoni), Uncinula necatur, Sphaerotheca fuligena and Podosphaera leucotricha, and other related species.
  • Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing.
  • the compounds can also be applied to seeds to protect the seeds and seedlings developing from the seeds.
  • the compounds can also be applied through irrigation water to treat plants.
  • Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than about 1 g/ha to about 5,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from about 0.1 to about 10 g per kilogram of seed.
  • Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including fungicides, insecticides, nematocides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • fungicides insecticides, nematocides, bactericides, acaricides, herbicides, herbicide safeners
  • growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus
  • the present invention also pertains to a composition
  • a composition comprising a fungicidally effective amount of a compound of Formula 1 and a biologically effective amount of at least one additional biologically active compound or agent and can further comprise at least one of a surfactant, a solid diluent or a liquid diluent.
  • the other biologically active compounds or agents can be formulated in compositions comprising at least one of a surfactant, solid or liquid diluent.
  • one or more other biologically active compounds or agents can be formulated together with a compound of Formula 1, to form a premix, or one or more other biologically active compounds or agents can be formulated separately from the compound of Formula 1, and the formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.
  • compositions which in addition to the compound of Formula 1 include at least one fungicidal compound selected from the group consisting of the classes (1) methyl benzimidazole carbamate (MBC) fungicides; (2) dicarboximide fungicides; (3) demethylation inhibitor (DMI) fungicides; (4) phenylamide fungicides; (5) amine/morpholine fungicides; (6) phospholipid biosynthesis inhibitor fungicides; (7) carboxamide fungicides; (8) hydroxy(2-amino-)pyrimidine fungicides; (9) anilinopyrimidine fungicides; (10) N-phenyl carbamate fungicides; (11) quinone outside inhibitor (QoI) fungicides; (12) phenylpyrrole fungicides; (13) quinoline fungicides; (14) lipid peroxidation inhibitor fungicides; (15) melanin biosynthesis inhibitors-reductase (MBI-R) fungicides; (15)
  • Methyl benzimidazole carbamate (MBC) fungicides (Fungicide Resistance Action Committee (FRAC) code 1) inhibit mitosis by binding to ⁇ -tubulin during microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure.
  • Methyl benzimidazole carbamate fungicides include benzimidazole and thiophanate fungicides.
  • the benzimidazoles include benomyl, carbendazim, fuberidazole and thiabendazole.
  • the thiophanates include thiophanate and thiophanate-methyl.
  • DMI fungicides are divided between several chemical classes: azoles (including triazoles and imidazoles), pyrimidines, piperazines and pyridines.
  • the triazoles include azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole and uniconazole.
  • the imidazoles include clotrimazole, imazalil, oxpoconazole, prochloraz, pefurazoate and triflumizole.
  • the pyrimidines include fenarimol and nuarimol.
  • the piperazines include triforine.
  • the pyridines include pyrifenox. Biochemical investigations have shown that all of the above mentioned fungicides are DMI fungicides as described by K. H. Kuck et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, H. Lyr (Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.
  • Phenylamide fungicides are specific inhibitors of RNA polymerase in Oomycete fungi. Sensitive fungi exposed to these fungicides show a reduced capacity to incorporate uridine into rRNA. Growth and development in sensitive fungi is prevented by exposure to this class of fungicide.
  • Phenylamide fungicides include acylalanine, oxazolidinone and butyrolactone fungicides.
  • the acylalanines include benalaxyl, benalaxyl-M, furalaxyl, metalaxyl and metalaxyl- M/mefenoxam.
  • the oxazolidinones include oxadixyl.
  • the butyrolactones include ofurace. (5) "Amine/morpholine fungicides" (Fungicide Resistance Action Committee (FRAC) code 5) inhibit two target sites within the sterol biosynthetic pathway, ⁇ 8 ⁇ ⁇ 7 isomerase and ⁇ 14 reductase.
  • FRAC Field Resistance Action Committee
  • Amine/morpholine fungicides include morpholine, piperidine and spiroketal-amine fungicides.
  • the morpholines include aldimorph, dodemorph, fenpropimorph, tridemorph and trimorphamide.
  • the piperidines include fenpropidin and piperalin.
  • the spiroketal-amines include spiroxamine.
  • "Phospholipid biosynthesis inhibitor fungicides" Fungicide Resistance Action Committee (FRAC) code 6) inhibit growth of fungi by affecting phospholipid biosynthesis.
  • Phospholipid biosynthesis fungicides include phophorothiolate and dithiolane fungicides.
  • the phosphorothiolates include edifenphos, iprobenfos and pyrazophos.
  • the dithiolanes include isoprothiolane.
  • Carboxamide fungicides (Fungicide Resistance Action Committee (FRAC) code 7) inhibit Complex II (succinate dehydrogenase) fungal respiration by disrupting a key enzyme in the Krebs Cycle (TCA cycle) named succinate dehydrogenase. Inhibiting respiration prevents the fungus from making ATP, and thus inhibits growth and reproduction.
  • Carboxamide fungicides include benzamides, furan carboxamides, oxathiin carboxamides, thiazole carboxamides, pyrazole carboxamides and pyridine carboxamides.
  • the benzamides include benodanil, flutolanil and mepronil.
  • the furan carboxamides include fenfuram.
  • the oxathiin carboxamides include carboxin and oxycarboxin.
  • the thiazole carboxamides include thifluzamide.
  • the pyrazole carboxamides include furametpyr, penthiopyrad, bixafen, N-[2-(15,2/?)-[l,r-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)- 1 -methyl- lH-pyrazole-4-carboxamide and ⁇ f-[2-(l,3-dimethylbutyl)phenyl]-5-fluoro-l,3- dimethyl-lH-pyrazole-4-carboxamide.
  • the pyridine carboxamides include boscalid.
  • ⁇ ydroxy(2-amino-)pyrimidine fungicides inhibit nucleic acid synthesis by interfering with adenosine deaminase. Examples include bupirimate, dimethirimol and ethirimol.
  • FRAC code 10
  • FRAC code 10
  • inhibit mitosis by binding to ⁇ -tubulin and disrupting microtubule assembly.
  • Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure. Examples include diethofencarb.
  • QoI Quality of the virus
  • FRAC Field Action Committee
  • Quinone outside inhibitor fungicides include methoxyacrylate, methoxycarbamate, oximinoacetate, oximinoacetamide, oxazolidinedione, dihydrodioxazine, imidazolinone and benzylcarbamate fungicides.
  • the methoxyacrylates include azoxystrobin, enestroburin (SYP-Z071) and picoxystrobin.
  • the methoxycarbamates include pyraclostrobin.
  • the oximinoacetates include kresoxim-methyl and trifloxystrobin.
  • the oximinoacetamides include dimoxystrobin, metominostrobin, orysastrobin, ⁇ -[methoxyimino]-N-methyl-2-[[[l-[3-(trifluoromethyl)phenyl]ethoxy]imino]- methyl]benzeneacetamide and 2-[[[3-(2,6-dichlorophenyl)-l-methyl-2-propen- 1-ylidene]- amino]oxy]methyl]-a-(methoxyimino)-iV-methylbenzeneacetamide.
  • the oxazolidinediones include famoxadone.
  • the dihydrodioxazines include fluoxastrobin.
  • the imidazolinones include fenamidone.
  • the benzylcarbamates include pyribencarb.
  • Lipid peroxidation inhibitor fungicides are proposed to inhibit lipid peroxidation which affects membrane synthesis in fungi. Members of this class, such as etridiazole, may also affect other biological processes such as respiration and melanin biosynthesis.
  • Lipid peroxidation fungicides include aromatic carbon and 1,2,4-thiadiazole fungicides.
  • the aromatic carbon fungicides include biphenyl, chloroneb, dicloran, quintozene, tecnazene and tolclofos- methyl.
  • the 1,2,4-thiadiazole fungicides include etridiazole.
  • MMI-R Melanin biosynthesis inhibitors-reductase fungicides
  • FRAC Field Action Committee
  • MBI-D Melanin biosynthesis inhibitors-dehydratase fungicides
  • FRAC Field Action Committee
  • scytalone dehydratase in melanin biosynthesis Melanin in required for host plant infection by some fungi.
  • Melanin biosynthesis inhibitors-dehydratase fungicides include cyclopropanecarboxamide, carboxamide and propionamide fungicides.
  • the cyclopropanecarboxamides include carpropamid.
  • the carboxamides include diclocymet.
  • the propionamides include fenoxanil.
  • Squalene-epoxidase inhibitor fungicides include thiocarbamate and allylamine fungicides.
  • the thiocarbamates include pyributicarb.
  • the allylamines include naftifine and terbinafme.
  • Polyoxin fungicides (Fungicide Resistance Action Committee (FRAC) code 19) inhibit chitin synthase. Examples include polyoxin.
  • Quinone inside inhibitor (QiI) fungicides (Fungicide Resistance Action Committee (FRAC) code 21) inhibit Complex IE mitochondrial respiration in fungi by affecting ubiquinol reductase. Reduction of ubiquinol is blocked at the "quinone inside" (Qi) site of the cytochrome bc ⁇ complex, which is located in the inner mitochondrial membrane of fungi. Inhibiting mitochondrial respiration prevents normal fungal growth and development.
  • Quinone inside inhibitor fungicides include cyanoimidazole and sulfamoyltriazole fungicides.
  • the cyanoimidazoles include cyazofamid.
  • the sulfamoyltriazoles include amisulbrom.
  • Benzamide fungicides (Fungicide Resistance Action Committee (FRAC) code 22) inhibit mitosis by binding to ⁇ -tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure. Examples include zoxamide.
  • FRAC Food Resistance Action Committee
  • Oxidative phosphorylation uncoupling fungicides inhibit fungal respiration by uncoupling oxidative phosphorylation. Inhibiting respiration prevents normal fungal growth and development.
  • This class includes 2,6-dinitroani lines such as fluazinam, pyrimidonehydrazones such as ferimzone and dinitrophenyl crotonates such as dinocap, meptyldinocap and binapacryl.
  • Carboxylic acid fungicides (Fungicide Resistance Action Committee (FRAC) code 31) inhibit growth of fungi by affecting deoxyribonucleic acid (DNA) topoisomerase type ⁇ (gyrase). Examples include oxolinic acid.
  • Heteroaromatic fungicides include isoxazole and isothiazolone fungicides.
  • the isoxazoles include hymexazole and the isothiazolones include octhilinone.
  • Thiophene-carboxamide fungicides (Fungicide Resistance Action Committee (FRAC) code 38) are proposed to affect ATP production. Examples include silthiofam. (39) "Pyrimidinamide fungicides” (Fungicide Resistance Action Committee (FRAC) code 39) inhibit growth of fungi by affecting phospholipid biosynthesis and include diflumetorim.
  • Carboxylic acid amide (CAA) fungicides are proposed to inhibit phospholipid biosynthesis and cell wall deposition. Inhibition of these processes prevents growth and leads to death of the target fungus.
  • Carboxylic acid amide fungicides include cinnamic acid amide, valinamide carbamate and mandelic acid amide fungicides.
  • the cinnamic acid amides include dimethomorph and flumorph.
  • the valinamide carbamates include benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb and valiphenal.
  • the mandelic acid amides include mandipropamid, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-l-yl]oxy]-3-methoxyphenyl]ethyl]- 3-methyl-2-[(methylsulfonyl)amino]butanamide and N-[2-[4-[[3-(4-chlorophenyl)-2-propyn- l-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide. (41) 'Tetracycline antibiotic fungicides" (Fungicide Resistance Action Committee
  • FRAC code 41
  • FRAC code 41
  • NADH complex 1 nicotinamide adenine dinucleotide
  • Examples include oxytetracycline.
  • acylpicolide fungicides such as fluopicolide and fluopyram.
  • Host plant defense induction fungicides include benzo-thiadiazole, benzisothiazole and thiadiazole-carboxamide fungicides.
  • the benzo-thiadiazoles include acibenzolar-S-methyl.
  • the benzisothiazoles include probenazole.
  • the thiadiazole-carboxamides include tiadinil and isotianil.
  • Multi-site contact fungicides inhibit fungal growth through multiple sites of action and have contact/preventive activity.
  • This class of fungicides includes: (45.1) “copper fungicides" (Fungicide Resistance Action Committee (FRAC) code Ml)", (45.2) “sulfur fungicides” (Fungicide Resistance Action Committee (FRAC) code M2), (45.3) “dithiocarbamate fungicides” (Fungicide Resistance Action Committee (FRAC) code M3), (45.4) "phthalimide fungicides” (Fungicide Resistance Action Committee (FRAC) code M4), (45.5) "chloronitrile fungicides” (Fungicide Resistance Action Committee (FRAC) code M5), (45.6) “sulfamide fungicides” (Fungicide Resistance Action Committee (FRAC) code M6), (45.7) "guanidine fungicides” (Fungicide Resistance Action Committee (FRAC) code M7), (45.8) “triazine fungicides” (Fungicides)
  • Copper fungicides are inorganic compounds containing copper, typically in the copper(II) oxidation state; examples include copper oxychloride, copper sulfate and copper hydroxide, including compositions such as Bordeaux mixture (tribasic copper sulfate).
  • Sulfur fungicides are inorganic chemicals containing rings or chains of sulfur atoms; examples include elemental sulfur.
  • Dithiocarbamate fungicides contain a dithiocarbamate molecular moiety; examples include mancozeb, metiram, propineb, ferbam, maneb, thiram, zineb and ziram.
  • Phthalimide fungicides contain a phthalimide molecular moiety; examples include folpet, captan and captafol.
  • Chloronitrile fungicides contain an aromatic ring substituted with chloro and cyano; examples include chlorothalonil.
  • Sulfamide fungicides include dichlofluanid and tolyfluanid.
  • Guanidine fungicides include dodine, guazatine, iminoctadine albesilate and iminoctadine triacetate.
  • Triazine fungicides include anilazine.
  • Quinone fungicides include dithianon.
  • Fungicides other than fungicides of classes (1) through (45) include certain fungicides whose mode of action may be unknown. These include: (46.1) “thiazole carboxamide fungicides” (Fungicide Resistance Action Committee (FRAC) code U5), (46.2) “phenyl-acetamide fungicides” (Fungicide Resistance Action Committee (FRAC) code U6), (46.3) “quinazolinone fungicides” (Fungicide Resistance Action Committee (FRAC) code U7) and (46.4) "benzophenone fungicides” (Fungicide Resistance Action Committee (FRAC) code U8).
  • the thiazole carboxamides include ethaboxam.
  • the phenyl-acetamides include cyflufenamid and N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3- difluorophenyl]-methylene]benzeneacetamide.
  • the quinazolinones include proquinazid and 2-butoxy-6-iodo-3-propyl-4H-l-benzopyran-4-one.
  • the benzophenones include metrafenone.
  • the (b46) class also includes bethoxazin, neo-asozin (ferric methanearsonate), pyrrolnitrin, quinomethionate, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-l-yl]oxy]-3-methoxy- phenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide, N-[2-[4-[[3-(4-chloro- phenyl)-2-propyn-l-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]- butanamide, 2-[[2-fluoro-5-(trifluoromethyl)phenyl]thio]-2-[3-(2-methoxyphenyl)-2-thiazo- lidinylidene]acetonitrile, 3-
  • a mixture comprising a compound of Formula 1 and at least one fungicidal compound selected from the group consisting of the aforedescribed classes (1) through (46).
  • a composition comprising said mixture (in fungicidally effective amount) and further comprising at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • a mixture comprising a compound of Formula 1 and at least one fungicidal compound selected from the group of specific compounds listed above in connection with classes (1) through (46).
  • a composition comprising said mixture (in fungicidally effective amount) and further comprising at least one additional surfactant selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • insecticides such as abamectin, acephate, acetamiprid, amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin, carbofuran, cartap, chlorantraniliprole (DPX-E2Y45), chlorfenapyr, chlorfluazuron, chlo ⁇ yrifos, chlo ⁇ yrifos-methyl, chromafenozide, clothianidin, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin, diafenthiuron, dia
  • Bacillus thuringiensis e.g., Cellcap, MPV, MPVII
  • entomopathogenic fungi such as green muscardine fungus
  • entomopathogenic virus including baculovirus, nucleopolyhedro virus (NPV) such as HzNPV, AfNPV
  • GV granulosis virus
  • Compounds of this invention and compositions thereof can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis delta-endotoxins).
  • the effect of the exogenously applied fungicidal compounds of this invention may be synergistic with the expressed toxin proteins.
  • the weight ratio of these various mixing partners (in total) to the compound of Formula 1 is typically between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (for example ratios between about 1:30 and about 30:1).
  • weight ratios between about 1:300 and about 300:1 for example ratios between about 1:30 and about 30:1.
  • One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It will be evident that including these additional components may expand the spectrum of diseases controlled beyond the spectrum controlled by the compound of Formula 1 alone.
  • combinations of a compound of this invention with other biologically active (particularly fungicidal) compounds or agents can result in a greater-than-additive (i.e. synergistic) effect. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable.
  • synergism of fungicidal active ingredients occurs at application rates giving agronomically satisfactory levels of fungal control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load.
  • a combination of a compound of Formula 1 with at least one other fungicidal active ingredient is such a combination where the other fungicidal active ingredient has different site of action from the compound of Formula 1.
  • a combination with at least one other fungicidal active ingredient having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management.
  • a composition of the present invention can further comprise a biologically effective amount of at least one additional fungicidal active ingredient having a similar spectrum of control but a different site of action.
  • compositions which in addition to compound of Formula 1 include at least one compound selected from the group consisting of (1) alkylenebis(dithiocarbamate) fungicides; (2) cymoxanil; (3) phenylamide fungicides; (4) pyrimidinone fungicides; (5) chlorothalonil; (6) carboxamides acting at complex II of the fungal mitochondrial respiratory electron transfer site; (7) quinoxyfen; (8) metrafenone; (9) cyflufenamid; (10) cyprodinil; (11) copper compounds; (12) phthalimide fungicides; (13) fosetyl-aluminum; (14) benzimidazole fungicides; (15) cyazofamid; (16) fluazinam; (17) iprovalicarb; (18) propamocarb; (19) validomycin; (20) dichlorophenyl dicarboximide fungicides; (21) zoxamide; (22) fluopicoli
  • M forms a fused phenyl, thiophene or pyridine ring;
  • R 1 1 is C j -C 6 alkyl;
  • R 12 is C 1 -C 6 alkyl or C 1 -C 6 alkoxy;
  • R 13 is halogen;
  • R 14 is hydrogen or halogen.
  • Pyrimidinone fungicides are described in PCT Patent Application Publication WO 94/26722 and U.S. Patents 6,066,638, 6,245,770, 6,262,058 and 6,277,858.
  • pyrimidinone fungicides selected from the group: 6-bromo-3-propyl-2-propyloxy- 4(3H)-quinazolinone, 6,8-diiodo-3-propyl-2-propyloxy-4(3H)-quinazolinone, 6-iodo- 3-propyl-2-propyloxy-4(3H)-quinazolinone (proquinazid), 6-chloro-2-propoxy-3-propyl- thieno[2,3-c ⁇ pyrimidin-4(3H)-one, 6-bromo-2-propoxy-3-propylthieno[2,3-rf]pyrimidin- 4(3H)-one, 7-bromo-2-propoxy-3-propylthi
  • Sterol biosynthesis inhibitors control fungi by inhibiting enzymes in the sterol biosynthesis pathway.
  • Demethylase-inhibiting fungicides have a common site of action within the fungal sterol biosynthesis pathway, involving inhibition of demethylation at position 14 of lanosterol or 24-methylene dihydrolanosterol, which are precursors to sterols in fungi. Compounds acting at this site are often referred to as demethylase inhibitors, DMI fungicides, or DMIs.
  • the demethylase enzyme is sometimes referred to by other names in the biochemical literature, including cytochrome P-450 (14DM). The demethylase enzyme is described in, for example, J. Biol. Chem.
  • DMI fungicides are divided between several chemical classes: azoles (including triazoles and imidazoles), pyrimidines, piperazines and pyridines.
  • the triazoles include azaconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole and unicon
  • the imidazoles include clotrimazole, econazole, imazalil, isoconazole, miconazole, oxpoconazole, prochloraz and triflumizole.
  • the pyrimidines include fenarimol, nuarimol and triarimol.
  • the piperazines include triforine.
  • the pyridines include buthiobate and pyrifenox. Biochemical investigations have shown that all of the above mentioned fungicides are DMI fungicides as described by K. ⁇ . Kuck et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, ⁇ . Lyr (Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.
  • bc ⁇ Complex Fungicides (group 28) have a fungicidal mode of action which inhibits the bc ⁇ complex in the mitochondrial respiration chain.
  • the bc ⁇ complex is sometimes referred to by other names in the biochemical literature, including complex IQ of the electron transfer chain, and ubihydroquinone:cytochrome c oxidoreductase. This complex is uniquely identified by Enzyme Commission number ECl.10.2.2.
  • the bc ⁇ complex is described in, for example, J. Biol. Chem. 1989, 264, 14543-48; Methods Enzymol. 1986, 126, 253-71; and references cited therein.
  • Strobilurin fungicides such as azoxystrobin, dimoxystrobin, enestroburin (SYP-Z071), fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin are known to have this mode of action (H. Sauter et al., Angew. Chem. Int. Ed. 1999, 38, 1328-1349).
  • Other fungicidal compounds that inhibit the bc ⁇ complex in the mitochondrial respiration chain include famoxadone and fenamidone.
  • Alkylenebis(dithiocarbamate)s include compounds such as mancozeb, maneb, propineb and zineb.
  • Phenylamides (group (3)) include compounds such as metalaxyl, benalaxyl, furalaxyl and oxadixyl.
  • Carboxamides include compounds such as boscalid, carboxin, fenfuram, flutolanil, furametpyr, mepronil, oxycarboxin, thifluzamide, penthiopyrad and ⁇ f-[2-(l,3-dimethylbutyl)phenyl]-5-fluoro-l,3-dimethyl-lH- pyrazole-4-carboxamide (PCT Patent Publication WO 2003/010149), and are known to inhibit mitochondrial function by disrupting complex II (succinate dehydrogenase) in the respiratory electron transport chain.
  • complex II succinate dehydrogenase
  • Copper compounds include compounds such as copper oxychloride, copper sulfate and copper hydroxide, including compositions such as Bordeaux mixture (tribasic copper sulfate).
  • Phthalimides include compounds such as folpet and captan.
  • Benzimidazole fungicides include benomyl and carbendazim.
  • Dichlorophenyl dicarboximide fungicides include chlozolinate, dichlozoline, iprodione, isovaledione, myclozolin, procymidone and vinclozolin.
  • Non-DMI sterol biosynthesis inhibitors include morpholine and piperidine fungicides.
  • the morpholines and piperidines are sterol biosynthesis inhibitors that have been shown to inhibit steps in the sterol biosynthesis pathway at a point later than the inhibitions achieved by the DMI sterol biosynthesis (group (27)).
  • the morpholines include aldimorph, dodemorph, fenpropimorph, tridemorph and trimorphamide.
  • the piperidines include fenpropidin
  • Preferred for better control of plant diseases caused by fungal plant pathogens are mixtures of a compound of this invention with a fungicide selected from the group: azoxystrobin, kresoxim-methyl, trifloxystrobin, pyraclostrobin, picoxystrobin, dimoxystrobin, metominostrobin/fenominostrobin, quinoxyfen, metrafenone, cyflufenamid, fenpropidine, fenpropimorph, cyproconazole, epoxiconazole, flusilazole, metconazole, propiconazole, proquinazid, prothioconazole, tebuconazole, triticonazole, famoxadone and penthiopyrad.
  • azoxystrobin kresoxim-methyl
  • trifloxystrobin e.g., pyraclostrobin
  • picoxystrobin dimoxystrobin
  • Specifically preferred mixtures are selected from the group: combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with azoxystrobin, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with kresoxim-methyl, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with trifloxystrobin, combinations of Compound 7, Compound 8, Compound 9, Compound 10, Compound 11 or Compound 16 with pyraclostrobin, combinations of Compound 7, Compound 8, Compound
  • TESTS demonstrate the control efficacy of compounds of this invention on specific pathogens.
  • the pathogen control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-D for compound descriptions.
  • the following abbreviations are used in the Index Tables: Me means methyl, Et means ethyl, n-Pr means normal propyl, c means cyclo, Ph means phenyl.
  • the abbreviation "Ex.” stands for "Example” and is followed by a number indicating in which example the compound is prepared.
  • a dash (“-") indicates a direct bond.

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Abstract

La présente invention concerne des composés de formule 1, y compris les formes géométriques et stéréomères, N-oxydes, et sels de ceux-ci, dans laquelle: W est O, S(O)?n#191, NR5 ou une liaison directe; n est 0, 1 or 2; Q est O, S ou NR6; G forme avec les deux atomes de carbone auquel il est lié un noyau de 5 à 6 chaînons ; et R1, R2, R3, R4, R5, et R6 sont tels que définis dans la description. L'invention concerne également des compositions contenant les composés de formule (1) ainsi que des procédés de lutte contre la maladie des plantes entraînée par un agent pathogène fongique comprenant l'application d'une quantité efficace d'un composé ou d'une composition selon l'invention.
PCT/US2008/002191 2007-02-21 2008-02-20 1,2,4-triazoles tricycliques fongicides Ceased WO2008103357A1 (fr)

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US9394311B2 (en) 2012-05-30 2016-07-19 Hoffmann-La Roche Inc. Triazolo compounds as PDE10 inhibitors
CN103214519A (zh) * 2013-04-02 2013-07-24 武汉工程大学 O-乙基-s-正丙基-（3-乙基-2-氰基亚胺-1-咪唑）磷酸酯的合成工艺
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US10112951B2 (en) 2016-02-12 2018-10-30 Eli Lilly And Company PDE1 inhibitor
US10138244B2 (en) 2016-08-25 2018-11-27 Eli Lilly And Company Triazolopyrazinone derivative useful as a human PDE1 inhibitor
US11180503B2 (en) 2017-08-02 2021-11-23 Eli Lilly And Company [1,2,4]Triazolo[4,3-A]pyrazin-6(5H)-one derivatives
US11401274B2 (en) 2017-08-10 2022-08-02 Eli Lilly And Company [1,2,4]Triazolo derivatives as PDE1 inhibitors for the treatment of diabetes
WO2023284807A1 (fr) * 2021-07-16 2023-01-19 中国药科大学 Composé contenant un squelette de tétrahydronaphthyridone ou de tétrahydropyridopyrimidinone, son procédé de préparation et son utilisation pharmaceutique

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