WO2015191382A1 - Tétrazolinones fongicides - Google Patents

Tétrazolinones fongicides Download PDF

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WO2015191382A1
WO2015191382A1 PCT/US2015/034383 US2015034383W WO2015191382A1 WO 2015191382 A1 WO2015191382 A1 WO 2015191382A1 US 2015034383 W US2015034383 W US 2015034383W WO 2015191382 A1 WO2015191382 A1 WO 2015191382A1
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compound
alkyl
methyl
haloalkyl
formula
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Kimberly Katherine Marcus
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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
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings

Definitions

  • This invention relates to certain tetrazolinones, their N-oxides, salts and compositions, and methods of their use as fungicides.
  • This invention is directed to compounds of Formula 1 (including all stereoisomers), N-oxides, and salts thereof, agricultural compositions containing them and their use as fungicides:
  • each R 1 and R 2 is independently hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3
  • R 3 is hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy or
  • W is O or S
  • R 4a is hydrogen, hydroxy, halogen, cyano, C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, C2 ⁇ Cg
  • R b is hydrogen, C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, C2 ⁇ Cg alkoxyalkyl, C ⁇ -Cg alkoxy or C ⁇ -Cg haloalkoxy; or
  • R 4a and R ⁇ are taken together with the carbon atom to which they are attached to form a C3 ⁇ Cg cycloalkyl ring or C3 ⁇ Cg halocycloalkyl ring;
  • Z is a 5- or 6-membered heterocyclic ring selected from Z-l through Z-40
  • alkylcarbonyloxy C 4 -C 10 cycloalkylcarbonyloxy, C ⁇ -Cg alkylthio, C 3 -C 8 cycloalkylthio, C ⁇ -Cg alkylsulfinyl, C ⁇ -Cg alkylsulfonyl, C 3 -C 8
  • cycloalkylsulfonyl C ⁇ -Cg alkylamino, C 2 -C 8 dialkylamino, C 3 -C 8 cycloalkylamino, C 2 -C 8 alkylcarbonylamino, C ⁇ -Cg alkylsulfonylamino, C ⁇ -C f alkylaminosulfonyl or C 2 -C 8 dialkylaminosulfonyl; or
  • each G A is independently phenyl, naphthalenyl, benzyl, benzyloxy, benzoyl, phenoxy or phenylsulfonyl, each optionally substituted with up to 5 substituents independently selected from R 6 ; or
  • each R 6 is independently selected from R 6a on carbon atom ring members and
  • each R 6a is independently selected from halogen, cyano, hydroxy, amino,
  • haloalkylsulfinyl C ⁇ -Cg alkylsulfonyl, C ⁇ -Cg haloalkylsulfonyl, C3 ⁇ Cg cycloalkylsulfonyl, C3-C10 trialkylsilyl, C ⁇ -Cg alkylamino, C2 ⁇ Cg dialkylamino, C ⁇ -C ⁇ haloalkylamino, C2 ⁇ Cg halodialkylamino, C3 ⁇ Cg cycloalkylamino, C2 ⁇ Cg alkylcarbonylamino, C2 ⁇ Cg haloalkylcarbonylamino, C ⁇ -Cg alkylsulfonylamino, C ⁇ -C ⁇ haloalkylsulfonylamino or G B ;
  • each R 6b is independently selected from cyano, hydroxy, C ⁇ -Cg alkyl, C ⁇ -Cg
  • haloalkyl C ⁇ -Cg alkoxy, C2 ⁇ Cg alkylcarbonyl, C2 ⁇ Cg alkoxycarbonyl or C3-C6 cycloalkyl;
  • each R 7 is hydrogen, C1-C3 alkyl, C3 ⁇ Cg cycloalkyl or C1-C3 haloalkyl;
  • each R 8 is hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkylcarbonyl or C2-C3 haloalkylcarbonyl;
  • each R 9 is hydrogen, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkylcarbonyl or C2-C3 haloalkylcarbonyl;
  • each G B is independently a phenyl, benzyloxy, phenoxy, benzylthio, phenylthio or a 5- or 6-membered heteroaromatic ring each optionally substituted with up to 3 substituents independently selected from the group consisting of halogen, cyano, nitro, C j -Cg alkyl, C2-Cg alkenyl, C2-Cg alkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 alkylcycloalkyl, C ⁇ -C ⁇ haloalkyl, C2-C6 haloalkenyl, C ⁇ -Cg alkoxy, C ⁇ -C ⁇ haloalkoxy and C ⁇ -C ⁇ alkylthio;
  • n 1 , 2 or 3;
  • this invention relates to a compound of Formula 1 including all geometric and stereoisomers, an N-oxide or a salt thereof.
  • This invention also relates to a fungicidal composition
  • a fungicidal composition comprising (a) a compound of the invention (i.e. in a fungicidally effective amount); and (b) 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) a compound of the invention; and (b) 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).
  • the aforedescribed method can also be described as a method for protecting a plant or plant seed from diseases caused by fungal pathogens comprising applying a fungicidally effective amount of a compound of Formula 1, an N-oxide, or a salt thereof (e.g., as a composition described herein), to the plant (or portion thereof) or plant seed (directly or through the environment (e.g., growing medium) of the plant or plant seed).
  • a fungicidally effective amount of a compound of Formula 1, an N-oxide, or a salt thereof e.g., as a composition described herein
  • compositions, mixture, 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, mixture, process, method, article, or apparatus.
  • transitional phrase consisting essentially of is used to define a composition, method or apparatus that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention.
  • 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 terms “fungal pathogen” and “fungal plant pathogen” include pathogens in the Ascomycota, Basidiomycota and Zygomycota phyla, and the fungal-like Oomycota class that are the causal agents of a broad spectrum of plant diseases of economic importance, affecting ornamental, turf, vegetable, field, cereal and fruit crops.
  • “protecting a plant from disease” or “control of a plant disease” includes preventative action (interruption of the fungal cycle of infection, colonization, symptom development and spore production) and/or curative action (inhibition of colonization of plant host tissues).
  • MOA mode of action
  • FRAC Fungicide Resistance Action Committee
  • A nucleic acid synthesis
  • B mitosis and cell division
  • C respiration
  • D amino acid and protein synthesis
  • E signal transduction
  • F lipid synthesis and membrane integrity
  • G sterol biosynthesis in membranes
  • H cell wall biosynthesis in membranes
  • I melanin synthesis in cell wall
  • P host plant defense induction, multi-site contact activity and unknown mode of action.
  • Each MOA class consists of one or more groups based either on individual validated target sites of action, or in cases where the precise target site is unknown, based on cross resistance profiles within a group or in relation to other groups.
  • Each of these groupings within a FRAC-defmed MO A, whether the target site is known or unknown, is designated by a FRAC code. Additional information on target sites and FRAC codes can be obtained from publicly available databases maintained, for example, by FRAC.
  • cross resistance refers to a phenomenon wherein a pathogen evolves resistance to one fungicide and in addition acquires resistance to others.
  • additional fungicides are typically, but not always, in the same chemical class or have the same target site of action, or can be detoxified by the same mechanism.
  • 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 ethenyl, 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 ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl also includes moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkylene denotes a straight-chain or branched alkanediyl.
  • alkylene examples include CH 2 , CH 2 CH 2 , CH(CH 3 ), CH 2 CH 2 CH 2 , CH 2 CH(CH 3 ), and the different butylene isomers.
  • Alkynylene denotes a straight-chain or branched alkynediyl containing one triple bond. Examples of “alkynylene” include C ⁇ C, CH 2 C ⁇ C, C ⁇ CCH 2 , and the different butynylene isomers.
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl. 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 .
  • Alkoxyalkoxy denotes alkoxy substitution on alkoxy.
  • Alkenyloxy includes straight-chain or branched alkenyloxy moieties.
  • alkynyloxy includes straight-chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HC ⁇ CCH 2 0, CH 3 C ⁇ CCH 2 0 and CH 3 C ⁇ CCH 2 CH 2 0.
  • 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. Examples of “alkylsulfinyl” include CH 3 S(0)-, CH 3 CH 2 S(0)-, CH 3 CH 2 CH 2 S(0)-, (CH 3 ) 2 CHS(0)- and the different butylsulfmyl, pentylsulfmyl and hexylsulfmyl isomers.
  • alkylsulfonyl examples include CH 3 S(0) 2 -, CH 3 CH 2 S(0) 2 -, CH 3 CH 2 CH 2 S(0) 2 -, (CH 3 ) 2 CHS(0) 2 -, and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers.
  • Alky lthio alkyl denotes alkylthio substitution on alkyl.
  • alkylthioalkyl examples include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 .
  • Alkylthioalkoxy denotes alkylthio substitution on alkoxy.
  • Alkyldithio denotes branched or straight-chain alkyldithio moieties. Examples of “alkyldithio” include CH 3 SS-, CH 3 CH 2 SS-, CH 3 CH 2 CH 2 SS-, (CH 3 ) 2 CHSS- and the different butyldithio and pentyldithio isomers.
  • Cyanoalkyl denotes an alkyl group substituted with one cyano group. Examples of “cyanoalkyl” include NCCH 2 , NCCH 2 CH 2 and CH 3 CH(CN)CH 2 .
  • Alkylamino "dialkylamino”, “alkenylthio”, “alkenylsulfmyl”, “alkenylsulfonyl”, “alkynylthio”, “alkynylsulfmyl”, “alkynylsulfonyl”, and the like, are defined analogously to the above examples.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • alkylcycloalkyl denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, z ' -propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl.
  • cycloalkylalkyl denotes cycloalkyl substitution on an alkyl moiety.
  • cycloalkylalkyl examples include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.
  • cycloalkoxy denotes cycloalkyl linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy.
  • Cycloalkylalkoxy denotes cycloalkylalkyl linked through an oxygen atom attached to the alkyl chain.
  • cycloalkylalkoxy examples include cyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moieties bonded to straight-chain or branched alkoxy groups.
  • Cyanocycloalkyl denotes a cycloalkyl group substituted with one cyano group.
  • Examples of “cyanocycloalkyl” include 4-cyanocyclohexyl and 3-cyanocyclopentyl.
  • Cycloalkenyl includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- and 1,4-cyclohexadienyl.
  • halogen either alone or in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” or “alkyl substituted with halogen” include F 3 C-, C1CH 2 -, CF 3 CH 2 - and CF 3 CC1 2 -.
  • halocycloalkyl haloalkoxy
  • haloalkyl haloalkoxy
  • haloalkylthio CC1 3 S-, CF 3 S-, CC1 3 CH 2 S- and C1CH 2 CH 2 CH 2 S-.
  • haloalkylsulfmyl examples include CF 3 S(0)-, CC1 3 S(0)-, CF 3 CH 2 S(0)- and CF 3 CF 2 S(0)-.
  • haloalkylsulfonyl examples include CF 3 S(0) 2 -, CC1 3 S(0) 2 -, CF 3 CH 2 S(0) 2 - and CF 3 CF 2 S(0) 2 -.
  • haloalkynyl examples include HC ⁇ CCHC1-, CF 3 C ⁇ C-, CC1 3 C ⁇ C- and FCH 2 C ⁇ CCH 2 -.
  • haloalkoxyalkoxy examples include CF 3 OCH 2 0-, C1CH 2 CH 2 0CH 2 CH 2 0-, Cl 3 CCH 2 OCH 2 0- as well as branched alkyl derivatives.
  • 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.
  • C1-C4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2 -
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 )-, CH 3 OCH 2 CH 2 - or CH 3 CH 2 OCH 2 -
  • C4 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 -.
  • C 2 -C 8 alkoxycarbonyl designates 2 to 8 carbon ester functional groups wherein the carbonyl carbon is part of the carbon count.
  • 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 5 ) m , m is 1, 2 or 3. Further, when the subscript indicates a range, e.g. (R)i_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 , 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 6 )k wherein k 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 "not substituted” or “unsubstituted”, then hydrogen atoms are attached to take up any free valency.
  • 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 "bicyclic ring system” and “fused bicyclic ring system” denote a ring system consisting of two fused rings which can be “ortho-fused", “bridged bicyclic” or “spirobicyclic”.
  • An "ortho-fused bicyclic ring system” denotes a ring system wherein the two constituent rings have two adjacent atoms in common.
  • a “bridged bicyclic ring system” is formed by bonding a segment of one or more atoms to nonadjacent ring members of a ring.
  • a “spirobicyclic ring system” is formed by bonding a segment of two or more atoms to the same ring member of a ring.
  • the term “fused heterobicyclic ring system” denotes a fused bicyclic ring system in which at least one ring atom is not carbon.
  • Carbocyclic ring denote a ring or ring system wherein the atoms forming the ring backbone are selected only from carbon.
  • 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.
  • a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs.
  • a carbocyclic ring or heterocyclic ring can be a saturatedor unsaturated ring.
  • “Saturated” refers to a ring having a backbone consisting of atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms. Unless otherwise stated, an “unsaturated ring” may be partially unsaturated or fully unsaturated.
  • partially unsaturated ring denotes a ring comprising at least one ring member bonded to an adjacent ring member through a double bond and which conceptually potentially accommodates a number of non-cumulated double bonds between adjacent ring members (i.e. in its fully unsaturated counterpart form) greater than the number of double bonds present (i.e. in its partially unsaturated form).
  • heterocyclic rings and ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen atom on said carbon or nitrogen.
  • Aromatic indicates that each of the ring atoms is essentially in the same plane and has a / ⁇ -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 Huckel's rule.
  • aromatic ring system denotes a carbocyclic or heterocyclic ring system in which at least one ring of the ring system is aromatic. When a fully unsaturated carbocyclic ring satisfies Huckel's rule, then said ring is also called an "aromatic ring" or "aromatic carbocyclic ring".
  • 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 denotes a carbocyclic ring 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.
  • optionally substituted in connection with the heterocyclic rings 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.
  • optionally substituted is used interchangeably with the phrase “substituted or unsubstituted” or with the term “(un)substituted.” 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.
  • Stereoisomers are isomers of identical constitution but differing in the arrangement of their atoms in space and include enantiomers, diastereomers, cis-trans isomers (also known as geometric isomers) and atropisomers. Atropisomers result from restricted rotation about single bonds where the rotational barrier is high enough to permit isolation of the isomeric species.
  • 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. For a comprehensive discussion of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.
  • This invention comprises racemic mixtures (equal amounts of the enantiomers), compounds that are enriched compared to the racemic mixture in an enantiomer and compounds that are the essentially pure enantiomers of compounds of Formula 1.
  • enantiomeric excess which is defined as (2 ⁇ -1) ⁇ 100 %, where x is the mole fraction of the dominant enantiomer in the mixture (e.g., an ee of 20 % corresponds to a 60:40 ratio of enantiomers).
  • compositions of this invention have at least a 50 % enantiomeric excess; more preferably at least a 75 % enantiomeric excess; still more preferably at least a 90 % enantiomeric excess; and the most preferably at least a 94 % enantiomeric excess of the more active isomer.
  • enantiomerically pure embodiments of the more active isomer are enantiomerically pure embodiments of the more active isomer.
  • Compounds of Formula 1 can comprise additional chiral centers.
  • substituents and other molecular constituents such as R 5 and R 6 may themselves contain chiral centers.
  • This invention comprises racemic mixtures as well as enriched and essentially pure stereoconfigurations at these additional chiral centers.
  • Compounds of this invention can exist as one or more conformational isomers due to restricted rotation about the amide bond (e.g., R 5 equal to C(0)-NH2) in Formula 1.
  • This invention comprises mixtures of conformational isomers.
  • this invention includes compounds that are enriched in one conformer relative to others.
  • This invention comprises all stereoisomers, conformational isomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
  • 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.
  • N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as t-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethyldioxirane
  • salts of 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, N-oxides and agriculturally suitable salts thereof.
  • Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts.
  • Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types).
  • polymorph refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice.
  • polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co- crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability.
  • beneficial effects e.g., suitability for preparation of useful formulations, improved biological performance
  • Embodiments of the present invention as described in the Summary of the Invention include the following (where Formula 1 as used in the following Embodiments includes N- oxides and salts thereof) and reference to "a compound of Formula 1" includes the definitions of substituents specified in the Summary of the Invention unless further defined in the Embodiments:
  • Embodiment 1 A compound of Formula 1 wherein R 1 is hydrogen, halogen, cyano, C!-C 3 alkyl, -C3 alkoxy, -C3 haloalkyl, -C3 haloalkoxy, C 3 -C 4 cycloalkyl, C3-C6 trialkylsilyl or C3-C6 halotrialkylsilyl.
  • Embodiment 2 A compound of Embodiment 1 wherein R 1 is halogen, cyano, C1-C2 alkyl, C1-C2 alkoxy, C1-C2 haloalkyl or C1-C2 haloalkoxy.
  • Embodiment 3 A compound of Embodiment 2 wherein R 1 is halogen, cyano, C1-C2 alkyl or C1-C2 haloalkyl.
  • Embodiment 4 A compound of Embodiment 3 wherein R 1 is F, CI or methyl.
  • Embodiment 5 A compound of Embodiment 4 wherein R 1 is methyl.
  • Embodiment 6 A compound of Formula 1 or any one of Embodiments 1 through 5 either alone or in combination, wherein R 2 is hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy or C1-C3 haloalkyl.
  • Embodiment 7 A compound of Embodiment 6 wherein R 2 is hydrogen, halogen,
  • Embodiment 8 A compound of Embodiment 7 wherein R 2 is hydrogen or halogen.
  • Embodiment 9. A compound of Embodiment 8 wherein R 2 is hydrogen.
  • Embodiment 10 A compound of Formula 1 or any one of Embodiments 1 through 9 either alone or in combination, wherein R 3 is C1-C2 alkyl, C1-C2 haloalkyl, C ⁇ -
  • Embodiment 11 A compound of Embodiment 10 wherein R 3 is C1-C2 alkyl or C1-C2 haloalkyl.
  • Embodiment 12 A compound of Embodiment 11 wherein R 3 is methyl.
  • Embodiment 13 A compound of Formula 1 or any one of Embodiments 1 through 12 either alone or in combination, wherein W is O.
  • Embodiment 14 A compound of Formula 1 or any one of Embodiments 1 through 13 either alone or in combination, wherein R a and R ⁇ are taken alone (i.e. R a and R ⁇ are not taken together with the carbon atom to which they are attached to form a ring).
  • Embodiment 15 A compound of Formula 1 or any one of Embodiments 1 through 14 either alone or in combination, wherein when R a is hydrogen, halogen, cyano,
  • Embodiment 15 a A compound of Embodiment 15 wherein when R a is hydrogen or methyl.
  • Embodiment 16 A compound of Embodiment 15a wherein when R 4a is hydrogen.
  • Embodiment 17. A compound of Formula 1 or any one of Embodiments 1 through 16 either alone or in combination, wherein R ⁇ is hydrogen, C1-C3 alkyl or C1-C3 haloalkyl.
  • Embodiment 17a A compound of Embodiment 17 wherein R ⁇ is hydrogen or methyl.
  • Embodiment 18 A compound of Embodiment 17a wherein when R ⁇ is hydrogen.
  • Embodiment 19 A compound of Formula 1 or any one of Embodiments 1 through 13 either alone or in combination, wherein when R a and R ⁇ are taken together with the carbon atom to which they are attached to form a ring, then the ring is a cy clopropy 1 ring .
  • Embodiment 20 A compound of Formula 1 or any one of Embodiments 1 through 19 either alone or in combination, wherein Z is selected from Z-1 through Z-14.
  • Embodiment 21 A compound of Embodiment 20 wherein Z is selected from Z-1, Z-2, Z-3, Z-7, Z-9, Z-10, Z-l l, Z-12 or Z-14.
  • Embodiment 22 A compound of Embodiment 21 wherein Z is selected from Z-1, Z-2,
  • Embodiment 23 A compound of Embodiment 22 wherein Z is Z-1.
  • Embodiment 24 A compound of Embodiment 22 wherein Z is Z-2.
  • Embodiment 25 A compound of Embodiment 22 wherein Z is Z-7.
  • Embodiment 26 A compound of Embodiment 22 wherein Z is Z-10.
  • Embodiment 27 A compound of Formula 1 or any one of Embodiments 1 through 26 either alone or in combination, wherein each R 5 is independently halogen, C ⁇ -C ⁇ alkyl, C3-C8 cycloalkyl, C ⁇ -Cg haloalkyl, C ⁇ -Cg alkoxy, C ⁇ -Cg haloalkoxy, or QA.
  • Embodiment 28 A compound of Embodiment 27 wherein R 5 is G A .
  • Embodiment 28a A compound of Formula 1 or any one of Embodiments 1 through 28 either alone or in combination, wherein m is 1 or 2.
  • Embodiment 28b A compound of Embodiment 28a wherein m is 1.
  • Embodiment 29 A compound of Formula 1 or any one of Embodiments 1 through 28b either alone or in combination, wherein each G A is phenyl or benzyl;
  • k 0, 1, 2 or 3;
  • p 0, 1, 2, 3, 4 or 5.
  • Embodiment 30 A compound of Embodiment 29 wherein G A is phenyl, G-35, G-47 or G-48.
  • Embodiment 31 A compound of Embodiment 30 wherein G A is phenyl or G-48.
  • Embodiment 32 A compound of Embodiment 31 wherein G A is phenyl.
  • Embodiment 33 A compound of Embodiment 31 wherein G A is G-48.
  • haloalkylcarbonyl C 4 -C 10 cycloalkylcarbonyl, C 2 -C 8 alkoxycarbonyl, C 4 -C 10 cycloalkoxycarbonyl, C 2 -C 8 alkylaminocarbonyl, C3-C10
  • dialkylaminocarbonyl C4-C10 cycloalkylaminocarbonyl, C ⁇ -Cg alkoxy, C ⁇ -Cg haloalkoxy, C3 ⁇ C 8 cycloalkoxy and C3-C10 trialkylsilyl.
  • Embodiment 35 A compound of Embodiment 34 wherein each R 6a is independently halogen, C j -Cg alkyl, C 3 -C 6 cycloalkyl, C j -Cg haloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 haloalkylcarbonyl, -Cg alkoxy, C j -Cg haloalkoxy, C 3 -C 6 cycloalkoxy and C3-C6 trialkylsilyl.
  • Embodiment 35 a A compound of Embodiment 35 wherein each R 6a is independently halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy.
  • Embodiment 36 A compound of Formula 1 or any one of Embodiments 1 through 35a either alone or in combination, wherein each R 6 ⁇ is independently C1-C4 alkyl or C 2 -C4 alkylcarbonyl.
  • Embodiment 37 A compound of Formula 1 or any one of Embodiments 1 through 36 either alone or in combination, wherein m is 1 or 2.
  • Embodiment 38 A compound of Embodiments 37 wherein m is 1.
  • Embodiment 39 A compound of Formula 1 or any one of Embodiments 1 through 38 either alone or in combination, wherein k is 1 or 2.
  • Embodiment 40 A compound of Formula 1 or any one of Embodiments 1 through 39 either alone or in combination, wherein p is 0 or 1.
  • 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 1-40 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention.
  • Embodiment A A compound of Formula 1 wherein
  • R 1 is halogen, cyano, C1-C2 alkyl, C1-C2 alkoxy, C1-C2 haloalkyl or C1-C2 haloalkoxy;
  • R 2 is hydrogen, halogen, cyano, C1-C3 alkyl, C1-C3 alkoxy or C1-C3
  • R 3 is C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy or C3 cycloalkyl;
  • R 4a is hydrogen, halogen, cyano, C1-C3 alkyl or C1-C3 haloalkyl;
  • R 4b is hydrogen, -C3 alkyl or -C3 haloalkyl
  • W is O
  • Z is selected from Z-l through Z-14;
  • each R 5 is independently halogen, C ⁇ -Cg alkyl, C3-C8 cycloalkyl, C ⁇ -Cg haloalkyl, C ⁇ -Cg alkoxy, C ⁇ -Cg haloalkoxy, or G A ;
  • n 1 or 2;
  • each G A is phenyl or benzyl; or a 5- or 6-membered heteroaromatic ring
  • G-l through G-58 selected from G-l through G-58; or an 8-, 9-, 10- or 11-membered fused heterobicyclic ring system selected from G-59 through G-83;
  • each R 6a is independently halogen, cyano, hydroxy, amino,
  • -C(R 7 ) N-R 8 , Ci-Cg alkyl, C 3 -C 8 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C ⁇ -Cg haloalkyl, C2 ⁇ Cg alkylcarbonyl, C2 ⁇ Cg
  • haloalkylcarbonyl C4-C10 cycloalkylcarbonyl, C2 ⁇ Cg alkoxycarbonyl, C4-C10 cycloalkoxycarbonyl, C2 ⁇ Cg alkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, C4-C10 cycloalkylaminocarbonyl, C ⁇ -Cg alkoxy, C ⁇ -Cg haloalkoxy, C3 ⁇ Cg cycloalkoxy and C3-C10 trialkylsilyl; and
  • each R 6 ⁇ is independently C 1-C4 alkyl or C2-C4 alkylcarbonyl.
  • Embodiment B A compound of Embodiment A wherein R 1 is halogen, cyano, C1-C2 alkyl or C1-C2 haloalkyl;
  • R 2 is hydrogen, halogen, cyano, methyl or trifluoromethyl
  • R 3 is C!-C 2 1 or C i-C 2 haloalkyl
  • R a is hydrogen or methyl
  • R 4 ⁇ is hydrogen or methyl
  • Z is selected from Z-l, Z-2, Z-3, Z-7, Z-9, Z-10, Z-l 1, Z-12 or Z-14.
  • Embodiment C A compound of Embodiment B wherein
  • R 1 is F, CI or methyl
  • R 2 is hydrogen or halogen
  • R 4a is hydrogen
  • R b is hydrogen
  • Z is selected from Z-l, Z-2, Z-7 or Z-10;
  • R 5 is G A ;
  • n 1;
  • G A is phenyl, G-35, G-47 or G-48;
  • each R 6a is independently halogen, C ⁇ -Cg alkyl, C3-C6 cycloalkyl, C ⁇ -Cg haloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C ⁇ -C ⁇ alkoxy, C ⁇ -C ⁇ haloalkoxy, C3-C6 cycloalkoxy and C3-C6 trialkylsilyl.
  • Embodiment D A compound of Embodiment C wherein
  • R 1 is methyl
  • R 2 is hydrogen
  • R 3 is methyl
  • G A is phenyl or G-48.
  • each R 6a is independently halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy.
  • Specific embodiments include compounds of Formula 1 selected from the group consisting of:
  • This invention provides a fungicidal composition
  • a fungicidal composition comprising a compound of Formula 1 (including all stereoisomers, N-oxides, and salts thereof), and at least one other fungicide.
  • a compound of Formula 1 including all stereoisomers, N-oxides, and salts thereof
  • at least one other fungicide are compositions comprising a compound corresponding to any of the compound embodiments described above.
  • This invention provides a fungicidal composition
  • a fungicidal composition comprising a compound of Formula 1 (including all stereoisomers, N-oxides, and salts thereof) (i.e. in a fungicidally effective amount), and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • a compound of Formula 1 including all stereoisomers, N-oxides, and salts thereof
  • additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • This invention provides a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed, a fungicidally effective amount of a compound of Formula 1 (including all stereoisomers, N-oxides, and salts thereof).
  • a compound of Formula 1 including all stereoisomers, N-oxides, and salts thereof.
  • embodiment of such methods are methods comprising applying a fungicidally effective amount of a compound corresponding to any of the compound embodiments describe above.
  • the compounds are applied as compositions of this invention.
  • compounds of Formula 1 can be prepared by the well-known Suzuki reaction via Pd-catalyzed cross-coupling of an aromatic iodide or bromide of Formula 2 wherein X 1 is Br or I with a substituted unsaturated heterocyclic boronic acid or ester of Formula 3.
  • Suzuki reactions conditions see, for example, Suzuki et al, Chemical Re iew, 1995, 95, 2457-2483.
  • catalysts are useful for this type of transformation; particularly useful as a catalyst is tetrakis(triphenylphosphine)- palladium(O).
  • Solvents such as tetrahydrofuran, acetonitrile, diethyl ether, dioxane and N,N-dimethylformamide are suitable.
  • the boronic acids and esters of Formula 3 are either commercially available or can be prepared by known methods.
  • Compounds of Formula 1 wherein Z is a N-linked substituted unsaturated heterocyclic ring can be prepared via a copper-catalyzed cross-coupling reaction using compounds of Formula 4.
  • Buchwald et al Accounts of Chemical Research, 1998, 31 ⁇ 2), 805-818 and Hartwig, Angew. Chem. Int. Ed., 1998, 37, 2046-2067.
  • a compound of Formula 2b (i.e., Formula 2 wherein W is sulfur) may be prepared from a compound of Formula 2a (i.e., Formula 2 wherein W is oxygen) by treatment with Lawesson's reagent, P2S5, or P4S JO- Thioamide formation reactions of this type are typically conducted in an aprotic solvent such as toluene or p- dioxane at elevated temperatures between 40 °C and the boiling point of the solvent. Reactions of this type are well known in the literature; see, for example, March and Smith,
  • a compound of Formula 2a (i.e., Formula 2 wherein W is oxygen) may be prepared from a compound of Formula 5 by reaction with a tetrazolinone of Formula 6.
  • Substitution reactions of this type may be carried out in solvents such as N,N- dimethylformamide, N-methylpyrrolidinone, methanol, or benzene at temperatures ranging from around room temperature to the boiling point of the solvent and in the presence of a base such as potassium hydroxide, potassium carbonate, sodium hydroxide, or sodium carbonate.
  • solvents such as N,N- dimethylformamide, N-methylpyrrolidinone, methanol, or benzene at temperatures ranging from around room temperature to the boiling point of the solvent and in the presence of a base such as potassium hydroxide, potassium carbonate, sodium hydroxide, or sodium carbonate.
  • a base such as potassium hydroxide, potassium carbonate, sodium hydroxide, or sodium carbonate.
  • a compound of Formula 2a (i.e., Formula 2 wherein W is oxygen) may be prepared from a compound of Formula 2c (i.e., Formula 2 wherein W is oxygen and R 3 is H) by reaction with a reagent of Formula 7 wherein X 3 is a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a methanesulfonate group, a methoxysulfonate group, a /?-toluenesulfonate group, or a trifluoromethylsulfonate group.
  • a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a methanesulfonate group, a methoxysulfonate group, a /?-toluenesulfonate group, or a trifluoromethylsulfonate group.
  • Reactions of this type are typically carried out in a solvent such as N, N-dimethylformamide, acetonitrile, or water, in the presence of a base such as potassium carbonate, sodium carbonate, or sodium hydroxide, at temperatures ranging from ambient temperature to the boiling point of the solvent.
  • a reagent of Formula 7 is commercially available or may be prepared by methods known in the literature (e.g. iodomethane).
  • X 3 is CI, Br, I, OS0 2 Me, OTs, OS0 2 CF 3
  • a compound of Formula 2c (i.e., Formula 2 wherein R 3 is H and W is oxygen) may be prepared from an isocyanate compound of Formula 8 by reaction with an azide of Formula 9, wherein X 4 is sodium or a trimethylsilyl group, in a solvent such as N, N-dimethylformamide, tetrahydrofuran, or toluene at temperatures ranging from around 0 °C to the boiling point of the solvent.
  • Suitable azides of Formula 9 for this reaction are commercially available and include trimethylsilyl azide and sodium azide.
  • Lewis acids such as aluminum trichloride or boron trifluoride may be used in the reaction. For typical reaction conditions, see, for example, US6548450.
  • a compound of Formula 8 can be prepared from a compound of Formula 5 wherein X 2 is a chlorine or bromine atom by reaction with a cyanate reagent such as silver cyanate, potassium cyanate or tetraethylammonium cyanate in a solvent such as tetrahydrofuran, toluene, dichloromethane, diethylether, N, N-dimethylformamide or acetone at a temperature ranging from room temperature to boiling point of solvent.
  • a cyanate reagent such as silver cyanate, potassium cyanate or tetraethylammonium cyanate
  • a solvent such as tetrahydrofuran, toluene, dichloromethane, diethylether, N, N-dimethylformamide or acetone
  • a compound of Formula 8 may be prepared from an amine of Formula 10 by treatment with a reagent such as phosgene, diphosgene, or triphosgene in the presence of a base such as triethylamine, sodium hydrogencarbonate, or pyridine in a solvent such as dichloromethane, ethyl acetate, toluene, or tetrahydrofuran at a temperature ranging from about 0 °C to the boiling point of the solvent.
  • a reagent such as phosgene, diphosgene, or triphosgene
  • a base such as triethylamine, sodium hydrogencarbonate, or pyridine
  • a solvent such as dichloromethane, ethyl acetate, toluene, or tetrahydrofuran at a temperature ranging from about 0 °C to the boiling point of the solvent.
  • An amine of Formula 10a (i.e., a compound of Formula 10 wherein R a and R ⁇ are H) may be accessed by the reduction of a nitrile compound of Formula 11, as depicted in Scheme 7.
  • a reduction of this type may be carried out using a reducing agent such as lithium aluminum hydride, Raney nickel, or sodium borohydride in the presence of nickel(II) chloride in a solvent such as methanol, ethanol, or tetrahydrofuran at a temperature ranging from about 0 °C to the boiling point of the solvent.
  • Nitrile compounds of Formula 11 are either commercially available or may be readily prepared by methods known in the literature.
  • benzylic alcohols of Formula 13 may be converted to benzyl halides of Formula 5a by treatment with a reagent such as thionyl chloride, phosphorus 10 pentachloride, phosphorus trichloride, phosphorus oxychloride, phosphorus tribromide, or hydrogen bromide.
  • a reagent such as thionyl chloride, phosphorus 10 pentachloride, phosphorus trichloride, phosphorus oxychloride, phosphorus tribromide, or hydrogen bromide.
  • Sydnones of Formula 14 can be prepared as shown in Scheme 10.
  • the intermediate compound of Formula 16 is prepared by a copper-catalyzed cross-coupling reaction between glycine (17) and a compound of Formula 18 wherein X 5 is bromine or iodine according to the general procedure of S. Roettger et al, J. Combinatorial Chem. 2007, 9, 204-9.
  • the sydnone of Formula 14 can then be prepared from the compound of Formula 16 by many procedures published in the literature, including C. J. Thoman et al, Organic Syntheses 1965, Vol. 45, pages 96-99.
  • Compounds of Formula 18 are either commercially available or can be prepared by a variety of methodologies known in the art of organic synthesis.
  • Compounds of Formula 18 (wherein R 5 is G A and G A is G-59 through G- 83) can be prepared according to the following procedures: in World Patent Publication WO 2009/062289 (G-59, G-62, G-65 and G-66), T. Muraki et al, Tetrahedron Lett. 1996, 37, 2441-2444 (G-62), T. Hideo et al, J. Chem. Soc, Perkin Transactions 1 1997, 5, 787-793 (G-62 and G-64), S.
  • a variety of general methods known in the art are useful for preparing compounds of Formula 4. Illustrative of these methods is the method depicted in Scheme 11 for preparing compounds of Formula 4a (i.e. Formula 4 wherein Z is Z-l and m is 1).
  • a compound of Formula 4a is prepared by the well-known Suzuki reaction involving palladium-catalyzed cross-coupling of an aromatic halide of Formula 18 wherein X 5 is Br or I with a commercially available pyrazole boronic acid of Formula 19.
  • a pyrazole ring is used to illustrate the method of Scheme 11, one skilled in the art recognizes that the Suzuki reaction can be used with other unsaturated heterocyclic boronic acids.
  • Suzuki reaction conditions see, for example, Suzuki et al, Chemical Review 1995, 95, 2457-2483.
  • a method for the preparation of compounds of Formula 4b (i.e., Formula 4 wherein Z is Z-10) is shown in Scheme 12.
  • a source of azide ion such as sodium azide or trimethylsilylazide in a polar solvent such as dimethylsulfoxide, N, N-dimethylformamide, or ethanol
  • An example of the use of trimethylsilylazide/tetrabutylammonium fluoride combination can be found in J. Med. Chem. 2004, 47, 4645.
  • Methods for preparing compounds of Formula 20 are known in the literature.
  • Another method for preparing compounds of Formula 1 utilizes the strategy of building the Z ring from an acyl group.
  • Compounds of Formula 21 can be prepared from compounds of Formula 2 by reaction with acetic anhydride in the presence of a palladium catalyst as shown in Scheme 13.
  • a palladium catalyst as shown in Scheme 13.
  • Compounds of Formula 21 can also be prepared as shown in Scheme 14.
  • the method first involves reacting a compound of Formula 2 with a vinyl ether of Formula 22 in the presence of a palladium catalyst according to the general procedures reported in the literature (see, for example, Xiao et al., J. Organic Chem. 2006, 71, 7467-7470).
  • certain compounds of Formula la can be prepared by first reacting a compound of Formula 21 with N,N-dimethylformamide dimethyl acetal (DMF-DMA) at temperatures ranging from about 40 to about 100 °C in a lower alkanol solvent such as methanol or ethanol, which can optionally comprise water, to provide an intermediate compound of Formula 23.
  • a lower alkanol solvent such as methanol or ethanol, which can optionally comprise water
  • certain compounds of Formula lb can be prepared from a compound of Formula la by reaction with a compound of Formula 18.
  • the reaction is optionally run in the presence of a catalyst, typically comprising palladium or copper.
  • a catalyst typically comprising palladium or copper.
  • compounds of Formula lb can be prepared by reacting a compound of Formula la with a boronic ester of Formula 24 in the presence of a suitable copper salt.
  • a suitable copper salt For leading references see Chan et al., in Boronic Acids, 205-240, D. G. Hall, Ed., Wiley- VCH.
  • Compounds of Formula Id are prepared from compounds of Formula 21 as shown in Scheme 19.
  • Compounds of Formula Id are prepared by reaction compounds of Formula 26 with hydrazine in a lower alcohol solvent, such as methanol, in the presence of a suitable base, such as sodium hydroxide, at a temperature between ambient and the reflux temperature of the solvent.
  • a suitable base such as sodium hydroxide
  • Compounds of Formula 26 can be prepared by reacting compounds of Formula 21 with dimethylamine hydrochloride and formaldehyde in the presence of a lower alcohol solvent, such as ethanol, at a temperature between ambient and the reflux temperature of the solvent.
  • a lower alcohol solvent such as ethanol
  • compounds of Formula le can be prepared from a compound of Formula If (Formula 1 wherein Z is Z-11 and Z-12 and R 5 is H).
  • a compound of Formula If is reacted with a compound of Formula 18 in the presence of iron(III) acetylacetonate (Fe(acac)3), copper oxide and cesium carbonate in N,N-dimethylformamide at temperatures ranging from about 25 to about 150 °C as described by TaiUefer et al, Angew. Chem. Int. Ed. 2007, 46, 934-936.
  • mixtures of regioisomers of Formula le are obtained from these reactions. Purification of the regioisomers is achieved by chromatography.
  • trimethylsilyl substituted alkynes of Formula 27 are obtained by contacting a compound of Formula 2 with ethynyltrimethylsilane in the presence of a suitable palladium catalyst (such as, for example, tetrakis(triphenylphosphine)palladium or dichlorobis(triphenylphosphine)palladium) and in the presence of a suitable copper catalyst (such, as for example, copper(I) iodide).
  • a suitable palladium catalyst such as, for example, tetrakis(triphenylphosphine)palladium or dichlorobis(triphenylphosphine)palladium
  • a suitable copper catalyst such, as for example, copper(I) iodide
  • the mole ratio of ethynyltrimethylsilane to the compound of Formula 2 is typically from about 1.1 to about 5, and the mole ratios of the palladium catalyst and the copper catalyst to the compound of Formula 2 are each about 0.005 to about 0.1.
  • the reaction is preferably run in the presence of a suitable amine base such as, for example, an amine base comprising triethylamine, N,N-diisopropylethylamine, diethylamine or piperidine.
  • the reaction is preferably conducted in the presence of a solvent. However, in some cases the reaction can be carried out without solvent other than the compound of Formula 2, the ethynyltrimethylsilane and the amine base.
  • a preferred procedure involves use of a suitable solvent including, for example, tetrahydrofuran, toluene or N,N-dimethylformamide.
  • a suitable solvent including, for example, tetrahydrofuran, toluene or N,N-dimethylformamide.
  • a solvent is a mixture of the suitable solvent with the amine base.
  • the solvent comprises the amine base or a combination of the amine base and the suitable solvent, the amine base is typically in large stoichiometric excess relative to the compound of Formula 2.
  • step 2 of Scheme 21 removal of the trimethylsilane group to give an alkyne of
  • Formula 28 is achieved by treating a compound Formula 27 with an alkali metal hydroxide or carbonate such as potassium hydroxide, sodium hydroxide or potassium carbonate in methanol or ethanol.
  • an alkali metal hydroxide or carbonate such as potassium hydroxide, sodium hydroxide or potassium carbonate in methanol or ethanol.
  • the mole ratio of the base to the compound of Formula 27 is from about 0.001 to about 5.
  • the reaction is preferably conducted in a suitable organic solvent.
  • the method is most satisfactorily conducted at a temperature ranging from about 0 °C to the reflux temperature of the solvent, and most preferably from about 25 to 30 °C.
  • other disilylating conditions known in the art can be used, such as treatment with tetrabutylammonium fluoride in solvents such as tetrahydrofuran and chloroform (optimally comprising water).
  • Suitable azide sources include, for example, sodium azide and trimethylsilyl azide.
  • the mole ratio of the azide source relative to the compound of Formula 28 is typically from about 1 to about 3.
  • suitable copper(I) salts comprise one or more compounds selected from the group consisting of copper(I) iodide, copper(I) bromide and copper(I) chloride.
  • a copper(II) salt can be used in combination with a mild reducing agent, for example copper(II) sulfate with sodium ascorbate.
  • the mole ratio of the copper(I) salt to the compound of Formula 28 is typically from about 0.05 to about 0.2.
  • the reaction is typically run in a solvent such as N,N-dimethylformamide, tetrahydrofuran, methanol, tert-butanol, dimethyl sulfoxide (optionally comprising water), at temperatures from about 25 to 100 °C.
  • a solvent such as N,N-dimethylformamide, tetrahydrofuran, methanol, tert-butanol, dimethyl sulfoxide (optionally comprising water), at temperatures from about 25 to 100 °C.
  • a solvent such as N,N-dimethylformamide, tetrahydrofuran, methanol, tert-butanol, dimethyl sulfoxide (optionally comprising water)
  • a compound of Formula lg i.e., Formula 1 wherein W is oxygen and R a and R ⁇ are H
  • a compound of Formula lh i.e., Formula 1 wherein W is oxygen, R 4a and R 4 b are H, and R 3 is H
  • isocyanate compounds of Formula 29 can be prepared from amine compounds of Formula 30 according to methods cited for the preparation of compounds of Formula 8 in Scheme 6.
  • amine compounds of Formula 30 can be prepared from nitrile compounds of Formula 31 according to the methods cited for the preparation of compounds of Formula 10a in Scheme 7.
  • compounds of Formula 31 can be prepared from phenyl halides of Formula 32 according to the methods cited for the preparation of compounds of Formula 1 in Scheme 1.
  • Compounds of Formula 32 are commercially available or may be prepared by methods known in the literature.
  • the reaction mixture was then cooled to room temperature and diluted with water (20 mL).
  • the aqueous phase was extracted with ethyl acetate (3 x 30 mL).
  • the combined organic phases were washed with water and saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated under vacuum.
  • the residue was purified by column chromatography on silica gel, with 2:3 ethyl acetate/petroleum ether as eluent, to afford the title compound as an off white solid (4.5 g).
  • Step B Preparation of 5-[3-(2,4-dimethoxyphenyl)-lH-pyrazol-l-yl]-2- methylbenzenemethanamine
  • Step C Preparation of 3-(2,4-dimethoxyphenyl)- 1 -[3-(isocyanatomethyl)-4- methylphenyl]- lH-pyrazole
  • Step D Preparation of l-[[5-[3-(2,4-dimethoxyphenyl)-lH-pyrazol-l-yl]-2- methylphenyl]methyl]-l,2-dihydro-5H-tetrazol-5-one
  • Step E Preparation of l-[[5-[3-(2,4-dimethoxyphenyl)-lH-pyrazol-l-yl]-2- methylphenyljmethyl] - 1 ,4-dihydro-4-methyl-5H-tetrazol-5 -one
  • n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, SEt means ethylthio, -CN means cyano and -NO2 means nitro.
  • Substituents R 6al and R 6a2 are substituents on the G A ring portion of Formula 1 (in Tables 1A-34H below) wherein substituent R 6al is in an ortho position and substituent R 6a2 is in a para position relative to the position of attachment to the Z ring portion of Formula 1.
  • the present disclosure also includes Tables 2A through 34A, each of which is constructed the same as Table 1 A above except that the row heading in Table 1 A (i.e. "R 6al is F") below the Markush structure is replaced with the respective row heading shown below.
  • R 6al is F
  • R 6a2 and R 1 are as defined in Table 1A above.
  • the first entry in Table 2A specifically discloses l-[[5-[l- (2-chloro-4-fluorophenyl)- lH-pyrazol-3-yl]-2-methylphenyl]methyl]- 1 ,4-dihydro-4-methyl- 5H-tetrazol-5-one.
  • Table Table Headings Table Table Headings
  • R 6al is Br 20A R 6al is O(n-Pr)
  • R 6al is CN 21A R 6al is OCF 3
  • R 6al is OH 22A
  • R 6al is OCHF 2
  • R 6a l is Me 24A
  • R 6al is OCH 2 C ⁇ CH
  • R 6a l is Et 25A
  • R 6al is OCH 2 C ⁇ CCH 3
  • R 6al is z-Pr 27A R 6al is OCH 2 OCH 3
  • R 6al is c .
  • Pr 28A R 6al is OCH 2 CH 2 OCH 3
  • R 6al is SMe
  • R 6al is C ⁇ CH 3 OA R 6al SEt
  • R 6al is C ⁇ CCH 3 31A
  • R 6a l is CH 2 OCH 3
  • R 6a l is CF 3 32A
  • R 6al is CH 2 OCH 2 CH 3
  • R 6al is CHF 2 33A
  • R 6al is OCH 2 CF 3
  • R 6al is CH 2 C1 34A R 6al is OCF 2 CF 2 H
  • Table IB is identical to Table 1A, except that the chemical structure in the Table IB heading is replaced with the followin structure:
  • the first compound in Table IB is the structure shown immediately above wherein R 6al is F; R 6a2 is F and R 1 is Me.
  • Tables 2B through 34B are constructed in a similar manner as Tables 2A through 34A.
  • Table IC is identical to Table 1A, except that the chemical structure in the Table IC heading is replaced with the following structure:
  • the first compound in Table 1C is the structure shown immediately above wherein R 6al is F; R 6a2 is F and R 1 is Me.
  • Tables 2C through 34C are constructed in a similar manner as Tables 2A through 34A.
  • Table ID is identical to Table 1A, except that the chemical structure in the Table ID heading is replaced with the following structure:
  • the first compound in Table ID is the structure shown immediately above wherein R 6al is F; R 6a2 is F and R 1 is Me.
  • Tables 2D through 34D are constructed in a similar manner as Tables 2A through 34A.
  • Table IE is identical to Table 1A, except that the chemical structure in the Table IE heading is replaced with the following structure:
  • the first compound in Table IE is the structure shown immediately above wherein R 6al is F; R 6a2 is F and R 1 is Me.
  • Tables 2E through 34E are constructed in a similar manner as Tables 2A through 34A.
  • Table IF is identical to Table 1A, except that the chemical structure in the Table IF heading is replaced with the following structure:
  • the first compound in Table IF is the structure shown immediately above wherein R 6al is F; R 6a2 is F and R 1 is Me.
  • Tables 2F through 34F are constructed in a similar manner as Tables 2A through 34A.
  • Table 1G is identical to Table 1A, except that the chemical structure in the Table 1G heading is replaced with the followin structure:
  • the first compound in Table 1G is the structure shown immediately above wherein R 6al is F; R 6a2 is F and R 1 is Me.
  • Tables 2G through 34G are constructed in a similar manner as Tables 2A through 34A.
  • Table IH is identical to Table 1A, except that the chemical structure in the Table IH heading is replaced with the followin structure:
  • the first compound in Table IH is the structure shown immediately above wherein R 6al is F; R 6a2 is F and R 1 is Me.
  • Tables 2H through 34H are constructed in a similar manner as Tables 2A through 34A.
  • a compound of Formula 1 of this invention (including N-oxides and salts thereof) 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 serve as a carrier.
  • a composition i.e. formulation
  • additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serve 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, oil-in-water emulsions, flowable concentrates 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, oil-in-water emulsion, flowable concentrate 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, but occasionally another suitable medium like an aromatic or paraffmic hydrocarbon or vegetable oil. Spray volumes can range 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,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), alkyl phosphates (e.g., triethyl phosphate), 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, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone
  • Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C 6 -C 2 2), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, 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, grapeseed, 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.
  • alkylated fatty acids e.g., methylated, ethylated, butylated
  • 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.
  • surfactants also known as “surface-active agents”
  • surface-active agents generally modify, most often reduce, the surface tension of the liquid.
  • surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.
  • 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
  • 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 diquaternary 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 ⁇ can be wet milled using media mills to obtain particles with average diameters below 3 ⁇ .
  • 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 um 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.
  • One embodiment of the present invention relates to a method for controlling fungal pathogens, comprising diluting the fungicidal composition of the present invention (a compound of Formula 1 formulated with surfactants, solid diluents and liquid diluents or a formulated mixture of a compound of Formula 1 and at least one other fungicide) with water, and optionally adding an adjuvant to form a diluted composition, and contacting the fungal pathogen or its environment with an effective amount of said diluted composition.
  • the fungicidal composition of the present invention a compound of Formula 1 formulated with surfactants, solid diluents and liquid diluents or a formulated mixture of a compound of Formula 1 and at least one other fungicide
  • a spray composition formed by diluting with water a sufficient concentration of the present fungicidal composition can provide sufficient efficacy for controlling fungal pathogens
  • adjuvant products can also be added to spray tank mixtures.
  • additional adjuvants are commonly known as “spray adjuvants” or “tank- mix adjuvants”, and include any substance mixed in a spray tank to improve the performance of a pesticide or alter the physical properties of the spray mixture.
  • Adjuvants can be anionic or nonionic surfactants, emulsifying agents, petroleum-based crop oils, crop-derived seed oils, acidifiers, buffers, thickeners or defoaming agents.
  • Adjuvants are used to enhancing efficacy (e.g., biological availability, adhesion, penetration, uniformity of coverage and durability of protection), or minimizing or eliminating spray application problems associated with incompatibility, foaming, drift, evaporation, volatilization and degradation.
  • adjuvants are selected with regard to the properties of the active ingredient, formulation and target (e.g., crops, insect pests).
  • the amount of adjuvants added to spray mixtures is generally in the range of about 2.5% to 0.1 % by volume.
  • the application rates of adjuvants added to spray mixtures are typically between about 1 to 5 L per hectare.
  • Representative examples of spray adjuvants include: Adigor® (Syngenta) 47% methylated rapeseed oil in liquid hydrocarbons, Silwet® (Helena Chemical Company) polyalkyleneoxide modified heptamethyltrisiloxane and Assist® (BASF) 17% surfactant blend in 83% paraffin based mineral oil.
  • compositions formulated for seed treatment generally comprise a film former or adhesive agent. Therefore typically a seed coating composition of the present invention comprises a biologically effective amount of a compound of Formula 1 and a film former or adhesive agent. Seed can be coated by spraying a flowable suspension concentrate directly into a tumbling bed of seeds and then drying the seeds. Alternatively, other formulation types such as wetted powders, solutions, suspoemulsions, emulsifiable concentrates and emulsions in water can be sprayed on the seed. This process is particularly useful for applying film coatings on seeds. Various coating machines and processes are available to one skilled in the art. Suitable processes include those listed in P. Kosters et al, Seed Treatment: Progress and Prospects, 1994 BCPC Mongraph No. 57, and references listed therein.
  • Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0%> sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%
  • Compound 1 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; 90.0% U.S.S. No. 25-50 sieves)
  • Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0%> sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%
  • Compound 1 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%
  • Compound 1 10.0% butyl polyoxyethylene/polypropylene block copolymer 4.0%> stearic acid/polyethylene glycol copolymer 1.0%) styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1%
  • Compound 1 10.0% imidacloprid 5.0% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1%
  • Water-soluble and water-dispersible formulations are typically diluted with water to form aqueous compositions before application.
  • Aqueous compositions for direct applications to the plant or portion thereof typically contain at least about 1 ppm or more (e.g., from 1 ppm to 100 ppm) of the compound(s) of this invention.
  • a flowable suspension formulated for seed treatment typically comprises from about 0.5 to about 70% of the active ingredient, from about 0.5 to about 30% of a film- forming adhesive, from about 0.5 to about 20% of a dispersing agent, from 0 to about 5% of a thickener, from 0 to about 5% of a pigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0 to about 1% of a preservative, and from 0 to about 75% of a volatile liquid diluent.
  • 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 Ascomycota, Basidiomycota, Zygomycota phyla, and the fungal-like Oomycata class. 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 but are not limited to those listed in Table 1.
  • names for both the sexual/teleomorph/perfect stage as well as names for the asexual/anamorph/imperfect stage (in parentheses) are listed where known. Synonymous names for pathogens are indicated by an equal sign.
  • the sexual/teleomorph/perfect stage name Phaeosphaeria nodorum is followed by the corresponding asexual/anamorph/imperfect stage name Stagnospora nodorum and the synonymous older name Septoria nodorum.
  • brassicae Guignardia bidweUii, Venturia inaequalis, Pyrenophora tritici-repentis
  • Dreschlera tritici-repentis Helminthosporium tritici-repentis
  • Pyrenophora teres Helminthosporium teres
  • Corynespora cassiicola Phaeosphaeria nodorum
  • Phaeospora nodorum Septoria nodorum
  • Erysiphales the powdery mildews
  • Botryotinia fuckeliana Botrytis cinerea
  • Oculimacula yallundae Tapesia yallundae
  • anamorph Helgardia herpotrichoides Pseudocercosporella herpetrichoides), Monilinia fructicola, Sclerotinia sclerotiorum, Sclerotinia minor, and Sclerotinia homoeocarpa;
  • Ascomycete pathogens including Magnaporthe grisea, Gaeumannomyces graminis, Rhynchosporium secalis, and anthracnose pathogens such as Glomerella acutata
  • Basidiomycetes in the order Urediniales including Puccinia recondita, P.
  • Basidiomycetes in the order Polyporales such as Athelia rolfsii (Sclerotium rolfsii);
  • Oomycetes in the order Pythiales including Phytophthora infestans, P. megasperma, P. parasitica, P. sojae, P. cinnamomi and P. capsici, and Pythium pathogens such as Pythium aphanidermatum, P. graminicola, P. irregulare, P. ultimum and . dissoticum;
  • Peronospora hyoscyami Peronospora tabacina
  • P. manshurica Hyaloperonospora parasitica
  • Pseudoperonospora cubensis and Bremia lactucae and other genera and species closely related to all of the above pathogens.
  • compositions or combinations also have activity against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae, and other related species.
  • bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae, and other related species.
  • the compounds of the invention are useful for improving (i.e. increasing) the ratio of beneficial to harmful microorganisms in contact with crop plants or their propagules (e.g., seeds, corms, bulbs, tubers, cuttings) or in the agronomic environment of the crop plants or their propagules.
  • Plant and seed varieties and cultivars can be obtained by conventional propagation and breeding methods or by genetic engineering methods. Genetically modified plants or seeds (transgenic plants or seeds) are those in which a heterologous gene (transgene) has been stably integrated into the plant's or seed's genome. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
  • Genetically modified plant cultivars which can be treated according to the invention include those that are resistant against one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, cold temperature, soil salinity, etc.), or that contain other desirable characteristics. Plants can be genetically modified to exhibit traits of, for example, herbicide tolerance, insect-resistance, modified oil profiles or drought tolerance. Useful genetically modified plants containing single gene transformation events or combinations of transformation events are listed in Table 2. Additional information for the genetic modifications listed in Table 2 can be obtained from publicly available databases maintained, for example, by the U.S. Department of Agriculture.
  • Tl through T37 are used in Table 2 for traits.
  • a "-" means the entr is not avail ble.
  • Alfalfa cp4 epsps (aroA:CP4) Alfalfa cp4 epsps (aroA:CP4) Alfalfa cp4 epsps (aroA:CP4) Canola* te
  • Canola* cp4 epsps (aroA:CP4); goxv247 Canola* cp4 epsps (aroA:CP4); goxv247
  • Canola* cp4 epsps (aroA:CP4) Canola* phyA
  • Carnation 1 1 (7442) FLO-07442-4 T8; T9 surB; dfr; hfl (G '5'h)
  • Carnation 1400A (1 1400) FLO-1 1400-2 T8; T9 surB; dfr; bp40 (G '5'h)
  • treating a seed means contacting the seed with a biologically effective amount of a compound of this invention, which is typically formulated as a composition of the invention.
  • This seed treatment protects the seed from soil-borne disease pathogens and generally can also protect roots and other plant parts in contact with the soil of the seedling developing from the germinating seed.
  • the seed treatment may also provide protection of foliage by translocation of the compound of this invention or a second active ingredient within the developing plant. Seed treatments can be applied to all types of seeds, including those from which plants genetically transformed to express specialized traits will germinate.
  • Representative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis toxin or those expressing herbicide resistance such as glyphosate acetyltransferase, which provides resistance to glyphosate. Seed treatments with compounds of this invention can also increase vigor of plants growing from the seed.
  • Compounds of this invention and their compositions, both alone and in combination with other fungicides, nematicides and insecticides, are particularly useful in seed treatment for crops including, but not limited to, maize or corn, soybeans, cotton, cereal (e.g., wheat, oats, barley, rye and rice), potatoes, vegetables and oilseed rape.
  • crops including, but not limited to, maize or corn, soybeans, cotton, cereal (e.g., wheat, oats, barley, rye and rice), potatoes, vegetables and oilseed rape.
  • the compounds of this invention are useful in treating postharvest diseases of fruits and vegetables caused by fungi and bacteria. These infections can occur before, during and after harvest. For example, infections can occur before harvest and then remain dormant until some point during ripening (e.g., host begins tissue changes in such a way that infection can progress); also infections can arise from surface wounds created by mechanical or insect injury.
  • the compounds of this invention can reduce losses (i.e. losses resulting from quantity and quality) due to postharvest diseases which may occur at any time from harvest to consumption.
  • Treatment of postharvest diseases with compounds of the invention can increase the period of time during which perishable edible plant parts (e.g, fruits, seeds, foliage, stems, bulbs, tubers) can be stored refrigerated or un- refrigerated after harvest, and remain edible and free from noticeable or harmful degradation or contamination by fungi or other microorganisms.
  • Treatment of edible plant parts before or after harvest with compounds of the invention can also decrease the formation of toxic metabolites of fungi or other microorganisms, for example, mycotoxins such as aflatoxins.
  • 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, fruits, 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. Control of postharvest pathogens which infect the produce before harvest is typically accomplished by field application of a compound of this invention, and in cases where infection occurs after harvest the compounds can be applied to the harvested crop as dips, sprays, fumigants, treated wraps and box liners.
  • Rates of application for these compounds can be influenced by factors such as the plant diseases to be controlled, the plant species to be protected, ambient moisture and temperature and should be determined under actual use conditions.
  • a fungicidally effective amount can be influenced by factors such as the plant diseases to be controlled, the plant species to be protected, ambient moisture and temperature and should be determined under actual use conditions.
  • One skilled in the art can easily determine through simple experimentation the fungicidally effective amount necessary for the desired level of plant disease control.
  • 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 0.001 g (more typically about 0.1 g) 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 compound of Formula 1 (in a fungicidally effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount) 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.
  • one aspect of the present invention is a fungicidal composition
  • a fungicidal composition comprising (i.e. a mixture or combination of) a compound of Formula 1, an N-oxide, or a salt thereof (i.e. component a), and at least one other fungicide (i.e. component b).
  • 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 fungicidally effective amount of at least one additional fungicidal active ingredient having a similar spectrum of control but a different site of action.
  • composition which in addition to the Formula 1 compound of component (a), includes as component (b) at least one fungicidal compound selected from the group consisting of the FRAC-defined mode of action (MOA) classes (A) nucleic acid synthesis, (B) mitosis and cell division, (C) respiration, (D) amino acid and protein synthesis, (E) signal transduction, (F) lipid synthesis and membrane integrity, (G) sterol biosynthesis in membranes, (H) cell wall biosynthesis in membranes, (I) melanin synthesis in cell wall, (P) host plant defense induction, multi-site contact activity and unknown mode of action.
  • MOA FRAC-defined mode of action
  • FRAC-recognized or proposed target sites of action along with their FRAC target site codes belonging to the above MOA classes are (Al) R A polymerase I, (A2) adenosine deaminase, (A3) DNA/RNA synthesis (proposed), (A4) DNA topoisomerase, (B1-B3) B- tubulin assembly in mitosis, (B4) cell division (proposed), (B5) derealization of spectrin- like proteins, (CI) complex I NADH odxido-reductase, (C2) complex II: succinate dehydrogenase, (C3) complex III: cytochrome bcl (ubiquinol oxidase) at Qo site, (C4) complex III: cytochrome bcl (ubiquinone reductase) at Qi site, (C5) uncouplers of oxidative phosphorylation, (C6) inhibitors of oxidative phosphorylation, ATP synthase, (
  • composition which in addition to the Formula 1 compound of component (a), includes as component (b) at least one fungicidal compound selected from the group consisting of the classes (bl) methyl benzimidazole carbamate (MBC) fungicides; (b2) dicarboximide fungicides; (b3) demethylation inhibitor (DMI) fungicides; (b4) phenylamide fungicides; (b5) amine/morpholine fungicides; (b6) phospholipid biosynthesis inhibitor fungicides; (b7) succinate dehydrogenase inhibitor fungicides; (b8) hydroxy(2- amino-)pyrimidine fungicides; (b9) anilinopyrimidine fungicides; (blO) N-phenyl carbamate fungicides; (bl 1) quinone outside inhibitor (Qol) fungicides; (bl2) phenylpyrrole fungicides; (bl3) azanaphthalene fungicide
  • Methyl benzimidazole carbamate (MBC) fungicides 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.
  • b2 "Dicarboximide fungicides" (FRAC code 2) inhibit a MAP/histidine kinase in osmotic signal transduction.
  • Examples include chlozolinate, iprodione, procymidone and vinclozolin.
  • DMI Demethylation inhibitor
  • FRAC code 3 Step 3
  • SBI Sterol Biosynthesis Inhibitors (SBI): Class I) inhibit C14-demethylase, which plays a role in sterol production.
  • Sterols such as ergosterol, are needed for membrane structure and function, making them essential for the development of functional cell walls. Therefore, exposure to these fungicides results in abnormal growth and eventually death of sensitive fungi.
  • DMI fungicides are divided between several chemical classes: azoles (including triazoles and imidazoles), pyrimidines, piperazines, pyridines and triazolinthiones.
  • the triazoles include azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, , quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, uniconazole-P, a-( l- chlorocyclopropyl)-a ⁇ [2-(2,2-dichlorocyclopropyl)ethyl]- ⁇ H ⁇ 1 ,
  • the imidazoles include econazole, imazalil, oxpoconazole, prochloraz, pefurazoate and triflumizole.
  • the pyrimidines include fenarimol, nuarimol and triarimol.
  • the piperazines include triforine.
  • the pyridines include buthiobate, pyrifenox, pyrisoxazole (3-[(3R)-5-(4-chlorophenyl)-2,3- dimethyl-3-isoxazolidinyl]pyridine, mixture of 3R,5R- and S ⁇ S-isomers) and (aS)-[3-(4- chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol.
  • the triazolinthiones include prothioconazole and 2-[2-(l-chlorocyclopropyl)-4-(2,2- dichlorocyclopropyl)-2-hydroxybutyl]-l ,2-dihydro-3H-l ,2,4-triazole-3-thione.
  • 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.
  • 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 (also known as kiralaxyl), furalaxyl, metalaxyl and metalaxyl-M (also known as mefenoxam).
  • the oxazolidinones include oxadixyl.
  • the butyrolactones include ofurace.
  • Amine/morpholine fungicides include morpholine, piperidine and spiroketal-amine fungicides.
  • the morpho lines include aldimorph, dodemorph, fenpropimorph, tridemorph and trimorphamide.
  • the piperidines include fenpropidin and piperalin.
  • the spiroketal-amines include spiroxamine.
  • Phospholipid biosynthesis inhibitor fungicides 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.
  • SDHI fungicides include phenylbenzamide, furan carboxamide, oxathiin carboxamide, thiazole carboxamide, pyrazole-4-carboxamide, pyridine carboxamide,, phenyl oxoethyl thiophene amides and pyridinylethyl benzamides
  • 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-4-carboxamides include benzovindiflupyr (N-[9-(dichloromethylene)- 1 ,2,3 ,4-tetrahydro- 1 ,4- methanonaphthalen-5 -yl] -3 -(difluoromethyl)- 1 -methyl- 1 H-pyrazole-4-carboxamide), bixafen, fluxapyroxad (3 -(difluoromethyl)- 1 -methyl-N-(3 ',4',5 '-trifluoro [1,1 '-biphenyl] -2- yl)-lH-pyrazole-4-carboxamide), furametpyr, isopyrazam (3 -( difluoromethyl)-!- methyl- ⁇ - [l s 23,4-tetrahydro-9-(l-methylet ⁇
  • the phenyl oxoethyl thiophene amides include isofetamid (N-[l,l-dimethyl-2-[2- methyl-4-(l -methylethoxy)phenyl]-2-oxoethyl]-3-methyl-2-thiophenecarboxamide).
  • the pyridinylethyl benzamides include fluopyram.
  • fungicides (FRAC code 9) are proposed to inhibit biosynthesis of the amino acid methionine and to disrupt the secretion of hydro lytic enzymes that lyse plant cells during infection. Examples include cyprodinil, mepanipyrim and pyrimethanil.
  • FRAC code 10 "N-Phenyl carbamate fungicides” (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.
  • Quinone outside inhibitor fungicides include methoxyacrylate, methoxycarbamate, oximinoacetate, oximinoacetamide and dihydrodioxazine fungicides (collectively also known as strobilurin fungicides), and oxazolidinedione, imidazolinone and benzylcarbamate fungicides.
  • the methoxyacrylates include azoxystrobin, coumoxystrobin (methyl (aE)-2-[[(3-butyl-4-methyl-2-oxo-2H-l- benzopyran-7-yl)oxy]methyl] -a-(methoxymethylene)benzeneacetate), enoxastrobin (methyl (aE)-2-[[[(E)-[(2E)-3-(4-chlorophenyl)-l-methyl-2-propen-l-ylidene]amino]oxy]methyl]-a- (methoxymethylene)benzeneaceate) (also known as enestroburin), flufenoxystrobin (methyl (aE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-a-
  • the methoxycarbamates include pyraclostrobin ,pyrametostrobin (methyl N-[2-[[(l ,4-dimethyl-3 -phenyl- lH-pyrazol-5- yl)oxy]methyl]phenyl]-N-methoxycarbamate) and triclopyricarb (methyl N-methoxy-N-[2- [[(3,5,6-trichloro-2-pyridinyl)oxy]methyl]phenyl]carbamate).
  • the oximinoacetates include kresoxim-methyl, and trifloxystrobin.
  • the oximinoacetamides include dimoxystrobin, fenaminstrobin ((aE)-2-[[[(E)-[(2E)-3-(2,6-dichlorophenyl)- l-methyl-2-propen- 1 - ylidene]amino]oxy]methyl]-a-(methoxyimino)-N-methylbenzeneacetamide),
  • the dihydrodioxazines include fluoxastrobin.
  • the oxazolidinediones include famoxadone.
  • the imidazolinones include fenamidone.
  • the benzylcarbamates include pyribencarb.
  • Class (bl 1) also includes mandestrobin (2- [(2,5 -dimethylphenoxy)methyl] -a-methoxy-N-benzeneacetamide) .
  • Azanaphthalene fungicides include aryloxyquino lines and quinazolinones.
  • the aryloxyquinolines include quinoxyfen.
  • the quinazolinones include proquinazid.
  • 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 hydrocarbon and 1 ,2,4-thiadiazole fungicides.
  • the aromatic hydrocarboncarbon fungicides include biphenyl, chloroneb, dicloran, quintozene, tecnazene and tolclofos-methyl.
  • the 1 ,2,4-thiadiazoles include etridiazole.
  • Melanin biosynthesis inhibitors-reductase fungicides include isobenzofuranone, pyrroloquinolinone and triazolobenzothiazole fungicides.
  • the isobenzofuranones include fthalide.
  • the pyrroloquinolinones include pyroquilon.
  • the triazolobenzothiazoles include tricyclazole.
  • Melanin biosynthesis inhibitors-dehydratase fungicides include cyclopropanecarboxamide, carboxamide and propionamide fungicides.
  • the cyclopropanecarboxamides include carpropamid.
  • the carboxamides include diclocymet.
  • the propionamides include fenoxanil.
  • SBI Sterol Biosynthesis Inhibitor
  • Class III fungicides FRAC code 17
  • SBI Class III inhibitors include hydroxyanilide fungicides and amino-pyrazolinone fungicides.
  • Hydroxyanilides include fenhexamid.
  • Amino-pyrazolinones include fenpyrazamine (S-2- propen-l-yl 5-amino-2,3-dihydro-2-(l-methylethyl)-4-(2-methylphenyl)-3-oxo-lH-pyrazole-
  • Squalene-epoxidase inhibitor fungicides include thiocarbamate and allylamine fungicides.
  • the thiocarbamates include pyributicarb.
  • the allylamines include naftifme and terbinafme.
  • Benzamide and thiazole carboxamide fungicides 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.
  • the benzamides include zoxamide.
  • the thiazole carboxamides include ethaboxam.
  • Glucopyranosyl antibiotic protein synthesis fungicides
  • FRAC code 25 "Glucopyranosyl antibiotic: protein synthesis fungicides” inhibit growth of fungi by affecting protein biosynthesis. Examples include streptomycin.
  • Glucopyranosyl antibiotic: trehalase and inositol biosynthesis fungicides inhibit trehalase and inositol biosynthesis. Examples include validamycin.
  • FRAC code 28 "Carbamate fungicides" (FRAC code 28) are considered multi-site inhibitors of fungal growth. They are proposed to interfere with the synthesis of fatty acids in cell membranes, which then disrupts cell membrane permeability. Propamacarb, iodocarb, and prothiocarb are examples of this fungicide class.
  • Carboxylic acid fungicides inhibit growth of fungi by affecting deoxyribonucleic acid (DNA) topoisomerase type II (gyrase). Examples include oxolinic acid.
  • Heteroaromatic fungicides (Fungicide Resistance Action Committee (FRAC) code 32) are proposed to affect DNA/ribonucleic acid (R A) synthesis. Heteroaromatic fungicides include isoxazoles and isothiazolones. The isoxazoles include hymexazole and the isothiazolones include octhilinone.
  • FRAC code 33 "Phosphonate fungicides" (FRAC code 33) include phosphorous acid and its various salts, including fosetyl-aluminum.
  • Thiophene-carboxamide fungicides (FRAC code 38) are proposed to affect ATP production. Examples include silthiofam.
  • Carboxylic acid amide (CAA) fungicides inhibit cellulose synthase which prevents growth and leads to death of the target fungus.
  • Carboxylic acid amide fungicides include cinnamic acid amide, valinamide and other carbamate, and mandelic acid amide fungicides.
  • the cinnamic acid amides include dimethomorph, flumorph and pyrimorph (3 -(2-chloro-4-pyridinyl)-3-[4-( 1,1 -dimethyl ethyl)phenyl]-l -(4- morpholinyl)-2-propene-l-one).
  • valinamide and other carbamates include benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, tolprocarb (2,2,2-trifluoroethyl N- [( 1 S)-2 -methyl- 1 - [ [(4-methylbenzoyl)amino]methyl]propyl] carbamate) and valifenalate (methyl N-[(l-methylethoxy)carbonyl]-L-valyl-3-(4-chlorophenyl)-P-alaninate) (also known as 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- 1 -yl]oxy]-3-methoxyphenyl]- ethyl] -3 -methyl-2- [(ethylsulfonyl)amino]butanamide.
  • Benzamide fungicides inhibit growth of fungi by derealization of spectrin-like proteins.
  • Examples include pyridinylmethyl benzamide fungicides such as fluopicolide (now FRAC code 7, pyridinylethyl benzamides).
  • Microbial fungicides disrupt fungal pathogen cell membranes.
  • Microbial fungicides include Bacillus species such as Bacillus amyloliquefaciens strains QST 713, FZB24, MB 1600, D747 and the fungicidal lipopeptides which they produce.
  • Q X I fungicides include triazolopyrimidylamines such as ametoctradin (5- ethyl-6-octyl[ 1 ,2,4]triazolo[ 1 ,5-a]pyrimidin-7-amine).
  • Plant extract fungicides are proposed to act by cell membrane disruption. Plant extract fungicides include terpene hydrocarbons and terpene alcohols such as the extract from Melaleuca alternifolia (tea tree).
  • Host plant defense induction fungicides include benzothiadiazoles, benzisothiazole and thiadiazole-carboxamide fungicides.
  • the benzothiadiazoles include acibenzolar-S-methyl.
  • the benzisothiazoles include probenazole.
  • the thiadiazole- carboxamides include tiadinil and isotianil.
  • (b48) Multi-site contact fungicides” inhibit fungal growth through multiple sites of action and have contact/preventive activity.
  • This class of fungicides includes: (b48.1) “copper fungicides” (FRAC code Ml)", (b48.2) “sulfur fungicides” (FRAC code M2), (b48.3) “dithiocarbamate fungicides” (FRAC code M3), (b48.4) "phthalimide fungicides” (FRAC code M4), (b48.5) “chloronitrile fungicides” (FRAC code M5), (b48.6) “sulfamide fungicides” (FRAC code M6), (b48.7) multi-site contact “guanidine fungicides” (FRAC code M7), (b48.8) “triazine fungicides” (FRAC code M8), (b48.9) “quinone fungicides” (FRAC code M9), (b48.10) "quinoxaline
  • 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.
  • Multi-site contact “guanidine fungicides” include, guazatine, iminoctadine albesilate and iminoctadine triacetate.
  • Triazine fungicides include anilazine.
  • Quinone fungicides include dithianon.
  • Quinoxaline fungicides include quinomethionate (also known as chinomethionate).
  • Maleimide fungicides include fluoroimide.
  • the phenyl-acetamides include cyflufenamid and N- [[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]-methylene]- benzeneacetamide.
  • the aryl-phenyl ketones include benzophenones such as metrafenone, and benzoylpyridines such as pyriofenone (5-chloro-2-methoxy-4-methyl-3-pyridinyl)(2,3,4- trimethoxy-6-methylphenyl)methanone).
  • the quanidines include dodine.
  • the thiazolidines include flutianil ((2Z)-2-[[2-fluoro-5-(trifluoromethyl)phenyl]thio]-2-[3-(2-methoxyphenyl)-
  • the pyrimidinonehydrazones include ferimzone.
  • the (b49.6) class includes oxathiapiprolin (l-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3- isoxazolyl]-2-thiazolyl]- 1 -piperidinyl]-2-[5-methyl-3-(trifluoromethyl)- lH-pyrazol- 1 - yljethanone) and its R-enantiomer which is l-[4-[4-[5i?-(2,6-difluorophenyl)-4,5-dihydro-
  • the (b49) class also includes bethoxazin, flometoquin (2-ethyl-3,7-dimethyl-6-[4- (trifluoromethoxy)phenoxy]-4-quinolinyl methyl carbonate), fluoroimide, neo-asozin (ferric methanearsonate), picarbutrazox (1,1-dimethylethyl N-[6-[[[[((Z)-l -methyl- lH-tetrazol- 5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate), pyrrolnitrin, quinomethionate, tebufloquin (6-(l,l-dimethylethyl)-8-fluoro-2,3-dimethyl-4-quinolinyl acetate), tolnifanide (N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methyl
  • Additional "Fungicides other than fungicides of classes (1) through (46)" whose mode of action may be unknown, or may not yet be classified include a fungicidal compound selected from components (b49.7) through (b49.12), as shown below.
  • Component (b49.7) relates to a compound of Formula b49.7
  • Examples of a compound of Formula b49.7 include (b49.7a) (2-chloro-6-fluorophenyl)- methyl 2-[l-[2-[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl]-4-piperidinyl]-4-thiazole- carboxylate (Registry Number 1299409-40-7) and (b49.7b) (li?)-l,2,3,4-tetrahydro- 1 -naphthalenyl 2-[ 1 -[2-[3,5-bis(difluoromethyl)- lH-pyrazol-1 -yl]acetyl]-4-piperidinyl]- 4-thiazolecarboxylate (Registry Number 1299409-42-9).
  • Methods for preparing compounds of Formula b46.2 are described in PCT Patent Publications WO 2009/132785 and WO 2011/051243.
  • Com onent (b49.8) relates to a compound of Formula b49.8
  • Rb2 i s CH 3 , CF 3 or CHF 2 wherein Rb2 i s CH 3 , CF 3 or CHF 2 ; Rb3 i s CH 3 , CF 3 or CHF 2 ; Rb i s halogen or
  • n 0, 1, 2 or 3.
  • Examples of a compound of Formula b49.8 include (b49.8a) l-[4-[4-[5-[(2,6- difluorophenoxy)methy 1] -4,5 -dihydro-3 -isoxazolyl]-2-thiazolyl]- 1 -piperdinyl] -2- [5 -methyl- 3-(trifluoromethyl)-lH-pyrazol-l-yl]ethanone.
  • Methods for preparing compounds of Formula b49.8 are described in PCT Patent Application PCT/US11/64324.
  • Component (b4799) relates to a compound of Formula b49.9
  • Examples of a compound of Formula b49.9 include (b49.9a) [[4-methoxy-2- [[[(3S,7R,8R,9S)-9-methyl-8-(2-methyl- 1 -oxopropoxy)-2,6-dioxo-7-(phenylmethyl)- 1 ,5- dioxonan-3 -yl] amino]carbonyl] -3 -pyridinyl]oxy]methyl 2-methylpropanoate (Registry Number 517875-34-2), (b49.9b) (3 l S,6 l S,7i?,8i?)-3-[[[3-(acetyloxy)-4-methoxy-2-pyridinyl]- carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-l,5-dioxonan-7-yl 2-methyl- propanoate (Registry Number 234112-93-7), (b49.9c)
  • Component (b49.10) relates to a com ound of Formula b49.10
  • R ⁇ 6 is H or F
  • R ⁇ 7 is -CF2CHFCF3 or -CF2CF2H.
  • Examples of a compound of Formula b49.10 are (b49.10a) 3-(difluoromethyl)-N-[4-fiuoro-2-(l,l,2,3,3,3-hexafluoro- propoxy)phenyl]-l -methyl- lH-pyrazole-4-carboxamide (Registry Number 1172611-40-3) and (b49.1 Ob) 3-(difluoromethyl)-l -methyl-N-[2-(l , 1 ,2,2-tetrafluoroethoxy)phenyl]- 1H- pyrazole-4-carboxamide (Registry Number 923953-98-4).
  • Compounds of Formula 49.10 can be prepared by methods described in PCT Patent Publication WO 2007/017450.
  • Component b49.11 relates a compound of Formula b49.11
  • R b8 is halogen, C1-C4 alkoxy or C2-C4 alkynyl
  • R b9 is ⁇ , halogen or -C4 alkyl
  • Pv bl ° is C!-C 12 alkyl, -C ⁇ haloalkyl, -C ⁇ alkoxy, C 2 -C 12 alkoxyalkyl, C 2 - C 2 alkenyl, C 2 -Cj 2 alkynyl, C4-Cj 2 alkoxyalkenyl, C4-Cj 2 alkoxyalkynyl, Cj-
  • R bl 1 is methyl or -Ybl3.
  • R bl2 is C!-C 2 alkyl
  • Y bl3 is CH 2 , O or S.
  • Examples of compounds of Formula b49.11 include (b49.11a) 2-[(3-bromo-6- quinolinyl)oxy]-N-(l,l-dimethyl-2-butyn-l-yl)-2-(methylthio)acetamide, (b49.1 lb) 2-[(3- ethynyl-6-quinolinyl)oxy] -N-[ 1 -(hydroxymethyl)- 1 -methyl-2-propyn- 1 -yl] -2-(methylthio)- acetamide, (b49.11c) N-( 1 , 1 -dimethyl-2-butyn- 1 -yl)-2- [(3 -ethynyl-6-quinolinyl)oxy] -2- (methylthio)acetamide, (b49.1 Id) 2-[(3-bromo-8-methyl-6-quinolinyl)oxy]-N-(l,l-dimethyl- 2-propyn
  • Component 49.12 relates to N-[4-[[3-[(4-chlorophenyl)methyl]-l,2,4-thiadiazol-5- yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide, which is believed to inhibit C24-methyl transferase involved in the biosynthesis of sterols.
  • 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 (49).
  • 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 (49).
  • 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.
  • component (b) fungicides include acibenzolar-S-methyl, aldimorph, ametoctradin, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl (including benalaxyl-M), benodanil, benomyl, benthiavalicarb (including benthiavalicarb-isopropyl), benzovindiflupyr, bethoxazin, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, captafol, captan, carbendazim, carboxin, carpropamid, chloroneb, chlorothalonil, chlozolinate, clotrimazole, copper hydroxide, copper oxychloride, copper sulfate, coumoxystrobin, c
  • 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 anilazine, azaconazole, benodanil, benzovindiflupyr, bitertanol, bixafen, boscalid, bromuconazole, buthiobate, captafol, captan, carboxin, chlorothalonil, clotrimazole, copper salts, copper hydroxide, copper oxychloride, cyproconazole, dichlofluanid, difenoconazole, diniconazole, dithianon, econazole, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fenfuram, ferbam, fluopyram, fluoroimide, fluqui
  • a fungicide selected from the group anilazine, azaconazole
  • invertebrate pest control compounds or agents such as abamectin, acephate, acetamiprid, acrinathrin, afidopyropen
  • cyclopropanecarboxylate amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin, carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyantraniliprole (3 -bromo- 1 -(3 -chloro-2-pyridinyl)-N- [4-cyano-2-methyl-6- [(methylamino)carbonyl]phenyl]- lH-pyrazole-5-carboxamide), cyclaniliprole (3-bromo-N- [2 ⁇ bromo-4-c-hloro-6- [ [( 1 -cy clopropylethy Damiiio] carbonyljphenyl]
  • Bacillus thuringiensis subsp. kurstaki and the encapsulated delta-endotoxins of Bacillus thuringiensis (e.g., Cellcap, MPV, MPVII); entomopathogenic fungi, such as green muscardine fungus; and entomopathogenic virus including baculovirus, nucleopolyhedro virus (NPV) such as HzNPV, AfNPV; and granulosis virus (GV) such as CpGV.
  • NPV nucleopolyhedro virus
  • 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).
  • 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.
  • combinations of a compound of the invention with other biologically active compounds or agents can result in a less-than-additive (i.e. safening) effect on organisms beneficial to the agronomic environment.
  • a compound of the invention may safen a herbicide on crop plants or protect a beneficial insect species (e.g., insect predators, pollinators such as bees) from an insecticide.
  • Fungicides of note for formulation with compounds of Formula 1 to provide mixtures useful in seed treatment include but are not limited to amisulbrom, azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil, cyproconazole, difenoconazole, dimethomorph, fluazinam, fludioxonil, flufenoxystrobin, fluquinconazole, fluopicolide, fluoxastrobin, flutriafol, fluxapyroxad, ipconazole, iprodione, metalaxyl, mefenoxam, metconazole, myclobutanil, paclobutrazole, penflufen, picoxystrobin, prothioconazole, pyraclostrobin, sedaxane, silthiofam, tebuconazole, thiabendazole, thiophanate-methyl, thiram, trifloxystrobin and
  • Invertebrate pest control compounds or agents with which compounds of Formula 1 can be formulated to provide mixtures useful in seed treatment include but are not limited to abamectin, acetamiprid, acrinathrin, afidopyropen, amitraz, avermectin, azadirachtin, bensultap, bifenthrin, buprofezin, cadusafos, carbaryl, carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole, cyfluthrin, beta- cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha- cypermethrin, zeta-cypermethrin, cyrom
  • Compositions comprising compounds of Formula 1 useful for seed treatment can further comprise bacteria and fungi that have the ability to provide protection from the harmful effects of plant pathogenic fungi or bacteria and/or soil born animals such as nematodes.
  • Bacteria exhibiting nematicidal properties may include but are not limited to Bacillus firmus, Bacillus cereus, Bacillius subtiliis and Pasteuria penetrans.
  • a suitable Bacillus firmus strain is strain CNCM 1-1582 (GB-126) which is commercially available as BioNemTM.
  • a suitable Bacillus cereus strain is strain NCMM 1-1592. Both Bacillus strains are disclosed in US 6,406,690.
  • Other suitable bacteria exhibiting nematicidal activity are B.
  • Bacteria exhibiting fungicidal properties may include but are not limited to B. pumilus strain GB34.
  • Fungal species exhibiting nematicidal properties may include but are not limited to Myrothecium verrucaria, Paecilomyces lilacinus and Purpureocillium lilacinum.
  • Seed treatments can also include one or more nematicidal agents of natural origin such as the elicitor protein called harpin which is isolated from certain bacterial plant pathogens such as Erwinia amylovora.
  • harpin elicitor protein
  • An example is the Harpin-N-Tek seed treatment technology available as N-HibitTM Gold CST.
  • Seed treatments can also include one or more species of legume-root nodulating bacteria such as the microsymbiotic nitrogen- fixing bacteria Bradyrhizobium japonicum.
  • These inocculants can optionally include one or more lipo-chitooligosaccharides (LCOs), which are nodulation (Nod) factors produced by rhizobia bacteria during the initiation of nodule formation on the roots of legumes.
  • LCOs lipo-chitooligosaccharides
  • Nod nodulation
  • the Optimize® brand seed treatment technology incorporates LCO Promoter TechnologyTM in combination with an inocculant.
  • Seed treatments can also include one or more isoflavones which can increase the level of root colonization by mycorrhizal fungi.
  • Mycorrhizal fungi improve plant growth by enhancing the root uptake of nutrients such as water, sulfates, nitrates, phosphates and metals.
  • isoflavones include, but are not limited to, genistein, biochanin A, formononetin, daidzein, glycitein, hesperetin, naringenin and pratensein.
  • Formononetin is available as an active ingredient in mycorrhizal inocculant products such as PHC Colonize® AG.
  • Seed treatments can also include one or more plant activators that induce systemic acquired resistance in plants following contact by a pathogen.
  • a plant activator which induces such protective mechanisms is acibenzolar-S-methyl.
  • test suspensions for Tests A-C were first dissolved in acetone in an amount equal to 10 % of the final volume and then suspended at the desired concentration (in ppm) in acetone and purified water (50/50 mix by volume) containing the surfactant Trem® 014 (polyhydric alcohol esters) added at the rate of 9 drops/liter. The resulting test suspensions were then used in Tests A-C. Spraying a 250 ppm test suspension to the point of run-off on the test plants was the equivalent of a rate of lOOO g/ha.
  • test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore dust of Erysiphe graminis f. sp. tritici, (the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20 °C for 8 days, after which time disease ratings were visually made.
  • test suspension was sprayed to the point of run-off on wheat seedlings.
  • seedlings were inoculated with a spore suspension of Puccinia recondita f. sp. tritici, (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20 °C for 24 h, and then moved to a growth chamber at 20 °C for 7 days, after which time disease ratings were visually made.
  • test suspension was sprayed to the point of run-off on wheat seedlings.
  • seedlings were inoculated with a spore suspension of Septoria tritici (the causal agent of wheat leaf blotch) and incubated in a saturated atmosphere at 24 °C for 48 h, and then moved to a growth chamber at 20 °C for 19 days, after which time disease ratings were visually made.
  • Results for Tests A-C are given in Table A. In the Table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls). A dash (-) indicates no test results. All results are for 250 ppm except where followed by an "*", which indicates 50 ppm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne des composés de formule (1), y compris tous leurs stéréo-isomères, N-oxides et sels. Dans cette formule, R1, R2, R3, R4a, R4b, W et Z sont tels que définis dans la description. La présente invention concerne en outre des compositions contenant les composés de formule (1), et des procédés pour lutter contre les maladies des végétaux causées par un agent pathogène fongique, consistant à appliquer une quantité efficace d'un composé ou d'une composition selon l'invention.
PCT/US2015/034383 2014-06-11 2015-06-05 Tétrazolinones fongicides Ceased WO2015191382A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11993580B1 (en) 2022-12-02 2024-05-28 Neumora Therapeutics, Inc. Methods of treating neurological disorders

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999007687A1 (fr) * 1997-08-05 1999-02-18 Agrevo Uk Limited Derives pesticides de 4-benzyl-1,2,4-triazolin-5-one
EP1103548A1 (fr) * 1998-08-03 2001-05-30 Sumitomo Chemical Company Limited Derives de triazolone, leur utilisation, et produits intermediaires obtenus a partir de ces derives
EP1238975A1 (fr) * 1999-12-08 2002-09-11 Sumitomo Chemical Company, Limited Composes de difluoromethyltriazolone, utilisation de ces composes et intermediaires pour leur fabrication
WO2008122375A2 (fr) * 2007-04-10 2008-10-16 Bayer Cropscience Ag Dérivés d'arzlisoxayoline insecticides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999007687A1 (fr) * 1997-08-05 1999-02-18 Agrevo Uk Limited Derives pesticides de 4-benzyl-1,2,4-triazolin-5-one
EP1103548A1 (fr) * 1998-08-03 2001-05-30 Sumitomo Chemical Company Limited Derives de triazolone, leur utilisation, et produits intermediaires obtenus a partir de ces derives
EP1238975A1 (fr) * 1999-12-08 2002-09-11 Sumitomo Chemical Company, Limited Composes de difluoromethyltriazolone, utilisation de ces composes et intermediaires pour leur fabrication
WO2008122375A2 (fr) * 2007-04-10 2008-10-16 Bayer Cropscience Ag Dérivés d'arzlisoxayoline insecticides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11993580B1 (en) 2022-12-02 2024-05-28 Neumora Therapeutics, Inc. Methods of treating neurological disorders
US12371414B2 (en) 2022-12-02 2025-07-29 Neumora Therapeutics, Inc. Methods of treating neurological disorders

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