WO2008091594A2 - Mélanges fongicides - Google Patents

Mélanges fongicides Download PDF

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Publication number
WO2008091594A2
WO2008091594A2 PCT/US2008/000813 US2008000813W WO2008091594A2 WO 2008091594 A2 WO2008091594 A2 WO 2008091594A2 US 2008000813 W US2008000813 W US 2008000813W WO 2008091594 A2 WO2008091594 A2 WO 2008091594A2
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methyl
composition
component
compound
alkyl
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PCT/US2008/000813
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WO2008091594A3 (fr
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John Anthony Bruhn
Robert James Pasteris
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E. I. Du Pont De Nemours And Company
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Publication of WO2008091594A2 publication Critical patent/WO2008091594A2/fr
Publication of WO2008091594A3 publication Critical patent/WO2008091594A3/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles

Definitions

  • This invention relates to fungicidal mixtures of certain carboxamide derivatives, their iV-oxides and salts, and to compositions comprising such mixtures and methods for using such mixtures as fungicides.
  • This invention relates to a fungicidal composition (i.e. combination) comprising (a) at least one compound selected from the compounds of Formula 1 (including all geometric and stereoisomers), ⁇ f-oxides, and salts thereof,
  • R 1 is an optionally substituted phenyl or 5- or 6-membered heteroaromatic ring;
  • A is CH 2 or NH;
  • W 1 is O or S;
  • X is a radical selected from
  • G is an optionally substituted 5-membered heteroaromatic ring or 5-membered saturated or partially saturated heterocyclic ring;
  • W 2 is O or S
  • Q is -NQ a Q b ;
  • Q a is H, C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, C 5 -C 10 alkylcycloalkylalkyl, C 1 -C 3 haloalkyl, C 2 -C 3 haloalkenyl, cyano, hydroxy, C 1 -C 3 alkoxy, C 2 -C 3 alkoxyalkyl, C 1 -C 3 hydroxyalkyl, C 2 -C 3 alkylcarbonyl, C 2 -C 3 alkoxycarbonyl, C 2 -C 3 alkylaminocarbonyl or C 3 -C 5 dialkylaminocarbonyl;
  • R 5 is H, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, C 5 -C 10 alkylcycloalkylalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, cyano, nitro, C 2 -C 4 alkoxyalkyl, C 1 -C 4 hydroxyalkyl, C 2 -C 4 alkylcarbonyl, C 2 -C 6 alk
  • R 6 is an optionally substituted phenyl, benzyl, naphthalenyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkenyl or 5- or 6-membered heteroaromatic ring; and R 15 is H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 4 cycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, C 5 -C 10 alkylcycloalkylalkyl, C 1 -C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 3 -C 4 halocycloalkyl or C 2 -
  • Q a and R 5 are taken together with the atoms connecting them to form an optionally substituted 5- to 7-membered ring containing as ring members 2 to 7 carbon atoms and optionally 1 to 3 heteroatoms selected from up to 1 O, up to 1 S and up to 2 N; or
  • Q a and R 6 are taken together with the atoms connecting them to form an optionally substituted 5- to 7-membered ring containing as ring members 2 to 7 carbon atoms and optionally 1 to 3 heteroatoms selected from up to 1 O, up to 1 S and up to 2 N; or R 5 and R 15 are taken together with the carbon atom to which they are bonded to form an optionally substituted 5- to 7-membered ring containing as ring members 2 to 7 carbon atoms and optionally 1 to 3 heteroatoms selected from up to 1 O, up to 1 S and up to 1 N; or
  • R 5 and R 6 are taken together with the carbon atom to which they are bonded to form an optionally substituted 5- to 7-membered ring containing as ring members 2 to
  • This invention also 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 or other plant parts, a fungicidally effective amount of the aforesaid composition.
  • compositions, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • plant includes members of Kingdom Plantae, particularly seed plants (Spermatopsida), at all life stages, including young plants (e.g., germinating seeds developing into seedlings) and mature, reproductive stages (e.g., plants producing flowers and seeds).
  • Portions of plants include geotropic members typically growing beneath of 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 or bud of a vegetative propagation unit such as tuber, corm or rhizome.
  • 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.
  • 1-2 alkyl indicates that one or two of the available positions for that substituent may be alkyl which are independently selected.
  • 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 can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkylene denotes a straight-chain or branched alkanediyl.
  • alkylene examples include CH2, CH 2 CH 2 , CH(CH 3 ), CH 2 CH 2 CH 2 and CH 2 CH(CH 3 ).
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl.
  • alkoxyalkyl examples include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group.
  • alkylsulfinyl examples include CH 3 S(O), CH 3 CH 2 S(O), CH 3 CH 2 CH 2 S(O), (CH 3 ) 2 CHS(O) and the different butylsulf ⁇ nyl, pentylsulfinyl and hexylsulfinyl isomers.
  • alkylsulfonyl examples include CH 3 S(O) 2 , CH 3 CH 2 S(O) 2 , CH 3 CH 2 CH 2 S(O) 2 , (CH 3 ) 2 CHS(O) 2 and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers.
  • Alkylamino "dialkylamino”, “alkenylthio”, “alkenylsulfinyl”, “alkenylsulfonyl”, “alkynylthio”, “alkynylsulfinyl”, “alkynylsulfonyl”, and the like, are defined analogously to the above examples.
  • “Trialkylsilyl” includes three branched and/or straight-chain alkyl radicals attached to and linked through a silicon atom such as trimethylsilyl, triethylsilyl and t-butyl- dimethylsilyl.
  • Aromatic indicates that each of the ring atoms is essentially in the same plane and has a /?-orbital perpendicular to the ring plane, and in which (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.
  • 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.
  • saturated ring denotes a ring in which no ring member is bonded to an adjacent ring member through a double bond.
  • saturated ring system denotes a ring system in which no ring member is bonded to an adjacent ring member through a double bond.
  • a “partially saturated ring” (alternatively described as a “partially unsaturated ring”) is intermediate between a saturated ring and a fully unsaturated ring (which may be aromatic).
  • partially saturated ring (which may be carbocyclic or heterocyclic unless otherwise stated) denotes a ring comprising at least one ring member bonded to an adjacent ring member through a double bond and also comprising at least one ring member bonded to an adjacent ring member through a single bond that conceptually could be replaced by a double bond to form a less saturated ring.
  • partially saturated bicyclic ring system denotes a bicyclic ring system (which may be carbocyclic or heterocyclic unless otherwise stated) comprising at least one ring member bonded to an adjacent ring member through a double bond and also comprising at least one ring member bonded to an adjacent ring member through a single bond that conceptually could be replaced by a double bond to form a less saturated ring system.
  • bicyclic ring system examples include tetrahydronaphthalene, tetrahydroquinoline and tetrahydroisoquinoline.
  • partially saturated tricyclic ring system denotes a tricyclic ring system (which may be carbocyclic or heterocyclic unless otherwise stated) comprising at least one ring member bonded to an adjacent ring member through a double bond and also comprising at least one ring member bonded to an adjacent ring member through a single bond that conceptually could be replaced by a double bond to form a less saturated ring system.
  • one component ring may be aromatic, and in a partially saturated tricyclic ring system, one or two component rings may be aromatic, provided that in a nonaromatic ring component at least one ring member is bonded to am adjacent ring member through a single bond that conceptually could be replaced by a double bond to form a less saturated ring system.
  • bicyclic ring system denotes a ring system containing two rings that share two or more common atoms. If the common atoms are adjacent (i.e. there is a bond between the bridgehead carbons), the bicyclic ring system is a "fused bicyclic ring system". If the common atoms are not adjacent (i.e. there is no bond between the bridgehead carbons), the ring system is a "bridged bicyclic ring system".
  • Present Embodiment 50 depicts a variety of illustrative fused bicyclic and tricyclic ring systems as the Qb component of Q. However, Q b can also be a bridged bicyclic or tricyclic ring system.
  • carbocyclic ring denotes a ring or ring system wherein the atoms forming the ring backbone are selected only from carbon.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • a carbocyclic ring can be a saturated, partially saturated, or fully unsaturated ring.
  • H ⁇ ckel's rule When a fully unsaturated carbocyclic ring satisfies H ⁇ ckel's rule, then said ring is also called an "aromatic ring".
  • a carbocyclic ring that does not satisfy H ⁇ ckel's rule is described as a "nonaromatic carbocyclic ring”.
  • heterocyclic ring denotes 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 heterocyclic ring can be a saturated, partially saturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies H ⁇ ckel's rule, then said ring is also called a "heteroaromatic ring” or "aromatic heterocyclic ring”.
  • a heterocyclic ring that does not satisfy H ⁇ ckel's rule is described as a "nonaromatic heterocyclic ring".
  • saturated heterocyclic ring denotes a heterocyclic ring in which no ring member is bonded to an adjacent ring member through a double bond.
  • partially saturated heterocyclic ring denotes a heterocyclic ring comprising at least one ring member bonded to an adjacent ring member through a double bond and also comprising at least one ring member bonded to an adjacent ring member through a single bond that conceptually could be replaced by a double bond to form a less saturated heterocyclic ring.
  • heterocyclic rings and ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • a compound of Formula 1 when a compound of Formula 1 is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • Synthetic methods for the preparation of iV-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and /n-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
  • halogen either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine.
  • 1-2 halogen indicates that one or two of the available positions for that substituent may be halogen which are independently selected. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 .
  • haloalkynyl examples include HC ⁇ CCHCl, CF 3 C ⁇ C, CC1 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CCl 3 S, CF 3 S, CCl 3 CH 2 S and ClCH 2 CH 2 CH 2 S.
  • haloalkylsulfinyl examples include CF 3 S(O), CCl 3 S(O), CF 3 CH 2 S(O) and CF 3 CF 2 S(O).
  • haloalkylsulfonyl examples include CF 3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 and CF 3 CF 2 S(O) 2 .
  • Cj-C: The total number of carbon atoms in a substituent group is indicated by the "Cj-C:" prefix where i and j are numbers from 1 to 10.
  • C j -C 4 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
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, for example, CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • alkylcarbonyl include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • the dotted line in Formula 1 represents that the bond indicated can be a single bond or double bond.
  • a group contains a substituent which can be hydrogen, for example Q a , R 5 or R 15 , then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
  • a variable group is shown to be optionally attached to a position, for example (R 2 ) n wherein n may be O, then hydrogen may be at the position even if not recited in the variable group definition.
  • a position on a group is said to be "not substituted” or "unsubstituted”
  • hydrogen atoms are attached to take up any free valency.
  • R 1 , R 2 , R 5 , R 6 , R 15 , R 16 , R 16a , G, Q a and Q b refers to groups that are unsubstituted or have at least 1 non-hydrogen substituent. These groups may be substituted with as many optional substituents as can be accommodated by replacing a hydrogen atom with a non-hydrogen substituent on any available carbon or nitrogen atom. Commonly, the number of optional substituents (when present) ranges from 1 to 3.
  • R 1 is an optionally substituted phenyl or 5- or 6-membered heteroaromatic ring
  • G is an optionally substituted 5-membered heteroaromatic ring or 5- membered saturated or partially saturated heterocyclic ring
  • Q a and Q b are taken together with the nitrogen atom to which they are bonded to form an optionally substituted 5- to 7- membered saturated or partially saturated heterocyclic ring
  • R ⁇ is an optionally substituted phenyl, benzyl, naphthalenyl, C3-C6 cycloalkyl, C3-C6 cycloalkenyl or 5- or 6- membered heteroaromatic ring
  • Q-2 through Q-85 are optionally substituted.
  • substituted in connection with these R 1 , G, R 6 , Q a and Q b groups refers to groups that have at least one non-hydrogen substituent that does not extinguish the fungicidal activity. Since these groups are optionally substituted, they need not have any non-hydrogen substituents.
  • heterocyclic substituent name with the letter “o” (e.g., “piperidino”, “pyrrolidino”, “isoquinolino”, “isoindolo”) means that the heterocyclic substituent is bonded to the remainder of the molecule through the nitrogen atom of the heterocycle.
  • locant descriptors may be omitted;
  • pyrazol-1-yl means “lH-pyrazol-1-yl” according to the Chemical Abstracts system of nomenclature.
  • pyridyl is synonymous with "pyridinyl”. The order of listing substituents may be different from the Chemical Abstracts system if the difference does not affect the meaning.
  • Examples of compounds of Formula 1 include compounds wherein
  • R 1 is a phenyl or 5- or 6-membered heteroaromatic ring, optionally substituted with 1 to 2 substituents independently selected from R 4 ; each R 4 is independently C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 1Q cycloalkylalkyl, C 4 -C10 alkylcycloalkyl, C5-C 1Q alkylcycloalkylalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, hydroxy, amino, cyano, nitro, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -
  • G is a 5-membered heteroaromatic ring or 5-membered saturated or partially saturated heterocyclic ring, each ring optionally substituted with up to 2 substituents selected from R 3 on carbon ring members and selected from R 1 1 on nitrogen ring members; each R 3 is independently C1-C3 alkyl, C 1 -C 3 haloalkyl or halogen;
  • R 11 is C 1 -C 3 alkyl
  • Q is a radical selected from Q-I through Q-85 as described in connection with Embodiment 50 described hereinafter.
  • R 3a is independently H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl or halogen (more particularly H, C 1 -
  • R l la is H or C 1 -C 3 alkyl
  • R 6 is one of H-I through H-46 as described in connection with Embodiment 65 described hereinafter
  • R 12 is H or C 1 -C 3 alkyl.
  • each R 4 is independently C 1 -C 3 alkyl, C2 ⁇ C 3 alkenyl, C2-C3 alkynyl, cyclopropyl, C 1 -C3 haloalkyl, C2-C3 haloalkenyl, C2-C3 haloalkynyl, halocyclopropyl, halogen, cyano, nitro, C 1 -C2 alkoxy or C 1 -C2 haloalkoxy;
  • R 5 is C 1 -C4 alkyl, C2-C4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 4 cycloalkyl, C 1 -C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 3 -C 4 halocycloalkyl, cyano or C 2 -C 4 alkoxyalkyl; and
  • each R 8 is independently H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 3 -
  • each R 9 is independently C 1 -C 3 alkyl, cyclopropyl, C 1 -C 3 haloalkyl, halocyclopropyl, halogen, hydroxy, C 2 -C 3 alkylcarbonyloxy, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy;
  • R 10 is H or methyl;
  • each R 16 is independently C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 2 -
  • each R 13 is independently C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, cyclopropyl, C 1 -C 3 haloalkyl, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, halocyclopropyl, halogen, cyano, nitro, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy.
  • Examples of the compounds of the Paragraph B above include compounds wherein X is one of X 1 , X 2 and X 3 ; and each R 2 is independently C 1 -C 2 alkv l. C 1 -C 2 haloalkyl, C 1 - C 2 alkoxy, halogen, cyano or hydroxy; Q a is H or CH 3 ; and R 15 is H or CH3.
  • Examples of the compounds of the Paragraph C above include compounds wherein R 1 is one of U-I through U-3, U-Il, U-13, U-20, U-22, U-23, U-36, U-37 through U-39 and
  • each R 4 is independently halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy.
  • G is G-I, G-2, G-3, G-I, G-8, G-IO, G-I l, G-14, G-15, G-23, G-24, G-26, G-27, G-28, G-30, G-36, G-37, G-38 or G-49 through G-55;
  • R 3a is H, CH 3 , Cl or Br; and R 11 is H or CH 3 .
  • G is G-I, G-2, G-7, G-8, G-14, G-15, G-23, G-24, G-26, G-27, G-36, G-37, G-38, G-49 or G-50 (including e.g., where G is unsubstituted).
  • R 5 is C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 4 cycloalkyl, C 1 - C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 3 -C 4 halocycloalkyl, cyano or C 2 - C 4 alkoxyalkyl; R 6 is H-I, H-20, H-32, H-45 or H-46; each R 7 is independently halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl
  • Q is Q-I, Q-2, Q-8, Q-14, Q-23, Q-41, Q-59 or Q-62;
  • Q a is methyl;
  • R 5 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl or cyano;
  • R 6 is H-I or H-45;
  • R 12 is H or CH 3 ; each R 7 is independently F, Cl, Br, OCH 3 or methyl;
  • R l 5 is H;
  • R 8 is CH 3 , OCH 3 or OH; and
  • R 10 is H or CH 3 .
  • Additional examples of the compounds of Paragraph C include compounds wherein W 1 and W 2 are independently O; Q a is CH 3 ; m, j, n and p are all independently 0 or 1; R 3a is
  • each R 7 is independently F, Cl, Br, OCH 3 or methyl
  • each R 8 is independently C 1 -C 2 alkyl, C 1 -C 2 alkoxy or hydroxy
  • each R 9 is independently F, Cl, Br, hydroxy, OCH 3 or CH 3 .
  • R 1 is U-I or U-50; each R 4 is independently halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl or C 1 -C 2 alkoxy; G is G-I, G-2, G-15, G-26, G-27, G-36, G- 37 or G-38; Q is Q-I, Q-2 , Q-8, Q-23 or Q-41; R 5 is C 1 -C 4 alkyl, C 2 -C 4 alkenyl or cyano; R 6 is H-45; and each R 4 is independently connected to the 3- or 5-position of U-I, each R 4 is independently connected to the 3- and 5-position of U-I, each R 4 is independently connected to the 2- or 3-position of U-50, or each R 4 is independently connected to the 2- and 5- position of U-50 (e.g., compounds where X is X 1 and G is G-I; X is X 1 and G is G-2; X is X 1 and G is G is G is
  • each R 4 is independently connected to the 3- or 5- position of U-I
  • k is 1 and R 4 is connected to the 3- or 5-position of U-I
  • each R 4 is independently connected to the 3- and 5-position of U-I
  • k is 2 and an independently selected R 4 is connected to each of the 3- and 5-positions of U-I
  • each R 4 is independently connected to the 2- or 3-position of U-50
  • k is 1 and R 4 is connected to the 3- or 5- position of U-50
  • each R 4 is independently connected to the 2- and 5-position of U-50
  • k is 2 and an independently selected R 4 is connected to each of the 2- and 5-positions of U-50.
  • Compounds of Formula 1 suitable for use in accordance with this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the compounds may be present as a mixture of stereoisomers, individual stereoisomers, or as optically active forms.
  • Formula 1 when Q is Q-I, and R 5 , R 6 and R 15 of Q-I in Formula 1 are different, then Formula 1 possesses a chiral center at the carbon atom to which they are commonly bonded.
  • This invention comprises racemic mixtures.
  • this invention includes compounds of Formula 1 that are enriched compared to the racemic mixture in an enantiomer of Formula 1.
  • enantiomeric excess which is defined as (2x-l)-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).
  • the more fungicidally active enantiomer is believed to be that wherein R 15 is a hydrogen, the hydrogen atom attached to the carbon atom identified with an asterisk (*) is below the plane defined by the 3 non-hydrogen atoms attached to the carbon atom identified with the asterisk (*) as in Formula 1' (with the aromatic ring of Q-2 through Q-74 positioned with respect to the carbon atom identified with an asterisk (*) in a manner analogous to R 6 in Q-I in Formula 1')-
  • R 5 is CH 3
  • R 6 is phenyl and R 15 is H
  • Formula 1' has the R configuration at the carbon atom to which R ⁇ , R 6 and R 1 ⁇ are commonly bonded.
  • compositions of this invention of Formula 1 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.
  • the substituents R 4 , R 5 , R 7 , R 8 , R 9 , R 13 , R 15 , R 16 , R 16a , Q a , Q b and X 1 through X 8 may themselves contain chiral centers.
  • This invention comprises racemic mixtures as well as enriched and essentially pure stereoconfigurations at these additional chiral centers.
  • This invention comprises mixtures of conformational isomers.
  • this invention includes compounds of Formula 1 that are enriched compared to the mixture of a conformer of Formula 1.
  • salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms.
  • the compounds forming the present mixtures and compositions contain acidic or basic moieties, a wide variety of salts can be formed, and these salts are useful in the present mixtures and compositions for controlling plant diseases caused by fungal plant pathogens
  • salts 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 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.
  • organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium.
  • Methyl benzimidazole carbamate (MBC) fungicides (bl) (Fungicide Resistance Action Committee (FRAC) code 1) inhibit mitosis by binding to ⁇ -tubulin during microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure.
  • Methyl benzimidazole carbamate fungicides include benzimidazole and thiophanate fungicides.
  • the benzimidazoles include benomyl, carbendazim, fuberidazole and thiabendazole.
  • the thiophanates include thiophanate and thiophanate-methyl.
  • Diacarboximide fungicides (b2) (Fungicide Resistance Action Committee (FRAC) code 2) are proposed to inhibit a lipid peroxidation in fungi through interference with NADH cytochrome c reductase. Examples include chlozolinate, iprodione, procymidone and vinclozolin.
  • DMI Demethylation inhibitor
  • FRAC Fungicide Resistance Action Committee
  • DMI fungicides are divided between several chemical classes: azoles (including triazoles and imidazoles), pyrimidines, piperazines and pyridines.
  • the triazoles include azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole and uniconazole.
  • the imidazoles include clotrimazole, imazalil, oxpoconazole, prochloraz, pefurazoate and triflumizole.
  • the pyrimidines include fenarimol and nuarimol.
  • the piperazines include triforine.
  • the pyridines include pyrifenox.
  • Phenylamide fungicides include acylalanine, oxazolidinone and butyrolactone fungicides.
  • the acylalanines include benalaxyl, benalaxyl-M, furalaxyl, metalaxyl and metalaxyl-M/mefenoxam.
  • the oxazolidinones include oxadixyl.
  • the butyrolactones include ofurace.
  • Amine/morpholine fungicides (also known as non-DMI sterol biosynthesis inhibitors) include morpholine, piperidine and spiroketal-amine fungicides.
  • the morpholines include aldimorph, dodemorph, fenpropimorph, tridemorph and trimorphamide.
  • the piperidines include fenpropidin and piperalin.
  • the spiroketal-amines include spiroxamine.
  • Phospholipid biosynthesis inhibitor fungicides (b6) (Fungicide Resistance Action Committee (FRAC) code 6) inhibit growth of fungi by affecting phospholipid biosynthesis.
  • Phospholipid biosynthesis fungicides include phophorothiolate and dithiolane fungicides.
  • the phosphorothiolates include edifenphos, iprobenfos and pyrazophos.
  • the dithiolanes include isoprothiolane.
  • Carboxamide fungicides (b7) (Fungicide Resistance Action Committee (FRAC) code 7) inhibit Complex II (succinate dehydrogenase) fungal respiration by disrupting a key enzyme in the Krebs Cycle (TCA cycle) named succinate dehydrogenase. Inhibiting respiration prevents the fungus from making ATP, and thus inhibits growth and reproduction.
  • Carboxamide fungicides include benzamide, furan carboxamide, oxathiin carboxamide, thiazole carboxamide, pyrazole carboxamide and pyridine carboxamide.
  • the Benzamides include benodanil, flutolanil and mepronil.
  • the furan carboxamides include fenfuram.
  • the oxathiin carboxamide include carboxin and oxycarboxin.
  • the thiazole carboxamides include thifluzamide.
  • the pyrazole carboxamides include furametpyr, penthiopyrad, bixafen, N-[2-(lS,2R)-[l, l'-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-l- methyl-lH-pyrazole-4-carboxamide and N-[2-(l,3-dimethylbutyl)phenyl]-5-fluoro-l,3- dimethyl-lH-pyrazole-4-carboxamide.
  • the pyridine carboxamide include boscalid.
  • ⁇ ydroxy(2-amino-)pyrimidine fungicides (b8) (Fungicide Resistance Action Committee (FRAC) code 8) inhibit nucleic acid synthesis by interfering with adenosine deaminase. Examples include bupirimate, dimethirimol and ethirimol.
  • fungicides (b9) (Fungicide Resistance Action Committee (FRAC) code 9) are proposed to inhibit biosynthesis of the amino acid methionine and to disrupt the secretion of hydrolytic enzymes that lyse plant cells during infection. Examples include cyprodinil, mepanipyrim and pyrimethanil.
  • QoI Quality of infrared fungicides
  • FRAC Field Action Committee
  • Quinone outside inhibitor fungicides include methoxyacrylate, methoxycarbamate, oximinoacetate, oximinoacetamide, oxazolidinedione, dihydrodioxazine, imidazolinone and benzylcarbamate fungicides.
  • the methoxyacrylates include azoxystrobin, enestroburin (SYP-Z071) and picoxystrobin.
  • the methoxycarbamates include pyraclostrobin.
  • the oximinoacetates include kresoxim-methyl and trifloxystrobin.
  • the oximinoacetamides include dimoxystrobin, metominostrobin, orysastrobin, ⁇ -[methoxyimino]-N-methyl-2-[[[l-[3-(trifluoromethyl)phenyl]- ethoxy]imino]methyl]benzeneacetamide and 2-[[[3-(2,6-dichlorophenyl)-l-methyl-2-propen- l-y]idene]amino]oxy]methyl]- ⁇ -(methoxyimino)- ⁇ methylbenzeneacetamide.
  • the oxazolidinediones include famoxadone.
  • the dihydrodioxazines include fluoxastrobin.
  • the imidazolinones include fenamidone.
  • the benzylcarbamates include pyribencarb.
  • Phenylpyrrole fungicides (bl2)
  • FRAC Field Resistance Action Committee
  • Quinoline fungicides (bl3) (Fungicide Resistance Action Committee (FRAC) code 13) are proposed to inhibit signal transduction by affecting G-proteins in early cell signaling. They have been shown to interfere with germination and/or appressorium formation in fungi that cause powder mildew diseases. Quinoxyfen is an example of this class of fungicide. "Lipid peroxidation inhibitor fungicides (bl4)” (Fungicide Resistance Action
  • Lipid peroxidation fungicides include aromatic carbon and 1,2,4-thiadiazole fungicides.
  • the aromatic carbons include biphenyl, chloroneb, dicloran, quintozene, tecnazene and tolclofos-methyl.
  • the 1,2,4-thiadiazoles include etridiazole.
  • MBI-R Melanin biosynthesis inhibitors-reductase
  • FRAC Federal Action Committee
  • 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 (MBI-D) fungicides (bl6) (Fungicide Resistance Action Committee (FRAC) code 16.1) inhibit the naphthal reduction step in melanin biosynthesis.
  • Melanin is required for host plant infection by some fungi.
  • Melanin biosynthesis inhibitors-reductase fungicides include isobenzofuranone, pyrroloquinolinone and triazolobenzothiazole fung
  • Melanin biosynthesis inhibitors-dehydratase fungicides include cyclopropanecarboxamide, carboxamide and propionamide fungicides.
  • the cyclopropanecarboxamides include carpropamid.
  • the carboxamides include diclocymet.
  • the propionamides include fenoxanil.
  • Hydroxyanilide fungicides (bl7)
  • FRAC Field Resistance Action Committee
  • Squalene-epoxidase inhibitor fungicides include thiocarbamate and allylamine fungicides.
  • the thiocarbamates include pyributicarb.
  • the allylamines include naftifine and terbinafine.
  • Examples include polyoxin.
  • FRAC Function III mitochondrial respiration in fungi by affecting ubiquinol reductase. Reduction of ubiquinol is blocked at the "quinone inside" (Qi) site of the cytochrome bc ⁇ complex, which is located in the inner mitochondrial membrane of fungi. Inhibiting mitochondrial respiration prevents normal fungal growth and development.
  • Quinone inside inhibitor fungicides include cyanoimidazole and sulfamoyltriazole fungicides.
  • the cyanoimidazoles include cyazofamid.
  • the sulfamoyltriazoles include amisulbrom.
  • Benzamide fungicides (b22) (Fungicide Resistance Action Committee (FRAC) code 22) inhibit mitosis by binding to ⁇ -tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure. Examples include zoxamide.
  • Enopyranuronic acid antibiotic fungicides (b23) (Fungicide Resistance Action Committee (I 7 RAC) code 23) inhibit growth of fungi by affecting protein biosynthesis. Examples include blasticidin-S.
  • Halopyranosyl antibiotic fungicides (b24)
  • FRAC Field Resistance Action Committee
  • Glucopyranosyl antibiotic protein synthesis fungicides (b25)
  • FRAC Field Resistance Action Committee
  • FRAC Food Resistance Action Committee
  • Action Committee (FRAC) code 29) inhibit fungal respiration by uncoupling oxidative phosphorylation. Inhibiting respiration prevents normal fungal growth and development.
  • This class includes 2,6-dinitroanilines such as fluazinam, pyrimidonehydrazones such as ferimzone and dinitrophenyl crotonates such as dinocap, meptyldinocap and binapacryl.
  • 2,6-dinitroanilines such as fluazinam, pyrimidonehydrazones such as ferimzone and dinitrophenyl crotonates such as dinocap, meptyldinocap and binapacryl.
  • Organic tin fungicides (b30) (Fungicide Resistance Action Committee (FRAC) code
  • ATP adenosine triphosphate
  • examples include fentin acetate, fentin chloride and fentin hydroxide.
  • Carboxylic acid fungicides (b31)" (Fungicide Resistance Action Committee (FRAC) code 31) inhibit growth of fungi by affecting deoxyribonucleic acid (DNA) topoisomerase type II (gyrase). Examples include oxolinic acid.
  • Heteroaromatic fungicides (b32) (Fungicide Resistance Action Committee (FRAC) code 32) are proposed to affect DNA/ribonucleic acid (RNA) synthesis.
  • Heteroaromatic fungicides include isoxazole and isothiazolone fungicides.
  • the isoxazoles include hymexazole and the isothiazolones include octhilinone.
  • Phosphonate fungicides (b33) (Fungicide Resistance Action Committee (FRAC) code 33) include phosphorous acid and its various salts, including fosetyl-aluminum.
  • Phthalamic acid fungicides (b34) include teclofthalam.
  • Benzotriazine fungicides (b35) include triazoxide.
  • Benzene-sulfonamide fungicides (b36) include flusulfamide.
  • Phyridazinone fungicides (b37) include diclomezine.
  • Thiophene-carboxamide fungicides (b38)
  • FRAC Field Resistance Action Committee
  • CAA Carboxylic acid amide
  • Carboxylic acid amide fungicides include cinnamic acid amide, valinamide carbamate and mandelic acid amide fungicides.
  • the cinnamic acid amides include dimethomorph and flumorph.
  • the valinamide carbamates include benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb and valiphenal.
  • the mandelic acid amides include mandipropamid, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-l-yl]oxy]-3-methoxyphenyl]-ethyl]- 3-methyl-2-[(methylsulfonyl)amino]butanamide and 7V-[2-[4-[[3-(4-chlorophenyl)-2-propyn- l-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide.
  • Tetracycline antibiotic fungicides (Ml)
  • FRAC Fluorescence Activated Cell Death Antigen deficiency
  • fungi inhibit growth of fungi by affecting complex 1 nicotinamide adenine dinucleotide (NADH) oxidoreductase. Examples include oxytetracycline.
  • Thiocarbamate fungicides (b42) (Fungicide Resistance Action Committee (FRAC) code 42) include methasulfocarb.
  • Benzamide fungicides (b43) (Fungicide Resistance Action Committee (FRAC) code 43) inhibit growth of fungi by derealization of spectrin-like proteins. Examples include acylpicolide fungicides such as fluopicolide and fluopyram. "Host plant defense induction fungicides (b44)” (Fungicide Resistance Action
  • Host plant defense induction fungicides include benzo-thiadiazole, benzisothiazole and thiadiazole-carboxamide fungicides.
  • the benzo-thiadiazoles include acibenzolar-S-methyl.
  • the benzisothiazoles include probenazole.
  • the thiadiazole-carboxamides include tiadinil and isotianil. "Multi-site contact fungicides (b45)" inhibit fungal growth through multiple sites of action and have contact/preventive activity.
  • This class of fungicides includes: “copper fungicides (M5.1) (Fungicide Resistance Action Committee (FRAC) code Ml)", “sulfur fungicides (b45.2) (Fungicide Resistance Action Committee (FRAC) code M2)' ⁇ “dithiocarbamate fungicides (M5.3) (Fungicide Resistance Action Committee (FRAC) code M3)", “phthalimide fungicides (b45.4) (Fungicide Resistance Action Committee (FRAC) code M4)", "chloronitrile fungicides (M5.5) (Fungicide Resistance Action Committee (FRAC) code M5)' ⁇ “sulfamide fungicides (b45.6) (Fungicide Resistance Action Committee (FRAC) code M6)", "guanidine fungicides (b45.7) (Fungicide Resistance Action Committee (FRAC) code M7)” “triazines fungicides (b45.8) (Fungicide Resistance Action Committee (FRAC) code M8)” and "quinone fungicides (b45.9)
  • Copper fungicides are inorganic compounds containing copper, typically in the copper(II) oxidation state; examples include copper oxychloride, copper sulfate and copper hydroxide, including compositions such as Bordeaux mixture (tribasic copper sulfate).
  • Sulfur fungicides are inorganic chemicals containing rings or chains of sulfur atoms; examples include elemental sulfur.
  • Dithiocarbamate fungicides contain a dithiocarbamate molecular moiety; examples include mancozeb, metiram, propineb, ferbam, maneb, thiram, zineb and ziram.
  • Phthalimide fungicides contain a phthalimide molecular moiety; examples include folpet, captan and captafol.
  • Chloronitrile fungicides contain an aromatic ring substituted with chloro and cyano; examples include chlorothalonil.
  • Sulfamide fungicides include dichlofluanid and tolyfluanid.
  • Guanidine fungicides include dodine, guazatine, iminoctadine albesilate and iminoctadine triacetate.
  • Triazines fungicides include anilazine.
  • Quinone fungicides include dithianon.
  • “Fungicides other than fungicides of component (a) and components (bl) through (b45); (b46)” include certain fungicides considered to have an unknown mode of action. These include: “thiazole carboxamide fungicide (b46.1) (Fungicide Resistance Action Committee (FRAC) code U5)", “phenyl-acetamide fungicide (b46.2) (Fungicide Resistance Action Committee (FRAC) code U6)", "quinazolinone fungicide (b46.3) (Fungicide Resistance Action Committee (FRAC) code U7)” and “benzophenone fungicide (b46.4) (Fungicide Resistance Action Committee (FRAC) code U8)".
  • the thiazole carboxamides include ethaboxam.
  • the phenyl-acetamides include cyflufenamid and N- [[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]- methylene]benzeneacetamide.
  • the quinazolinones include proquinazid and 2-butoxy-6-iodo- 3-propyl-4H-l-benzopyran-4-one.
  • the benzophenones include metrafenone.
  • the (b46) group also includes bethoxazin, neo-asozin (ferric methanearsonate), pyrrolnitrin, quinomethionate, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-l-yl]oxy]-3- methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide, ⁇ f-[2-[4-[[3-(4- chlorophenyl)-2-propyn-l-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-
  • the present invention comprises compositions of one or more compounds selected from Formula 1, iV-oxides and salts thereof, with one or more compounds or salts thereof selected from (b) as described in the Summary of the Invention.
  • Embodiment 1 The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein A is C ⁇ 2.
  • Embodiment 2 The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein A is NH.
  • Embodiment 3 The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein W 1 is O.
  • Embodiment 4. The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein W 1 is S.
  • Embodiment 5. The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein W 2 is O.
  • Embodiment 6. The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein W 2 is S.
  • Embodiment 7. The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein R 2 is methyl.
  • Embodiment 8 The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein n is 0 or 1.
  • Embodiment 9. The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein n is 0.
  • Embodiment 10 The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein X is X 1 , X 2 or X3.
  • Embodiment 11 The composition of Embodiment 10 wherein X is X 1 or X 2 and each ring is saturated.
  • Embodiment 12 The composition of Embodiment 10 wherein X is X 1 .
  • Embodiment 13 The composition of Embodiment 12 wherein X is X 1 and the ring is saturated.
  • Embodiment 14 The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein R 1 is one of U-I through U-50;
  • k is 0, 1 or 2; provided that when U is U-4, U-I l through U-15, U-24 through U-26, U-31 and U-35, and an R 4 radical is attached to a nitrogen atom of the ring, said R 4 radical is C j -
  • Embodiment 15 The composition of Embodiment 14 wherein R 1 is selected from U-I through U-5, U-8, U-I l, U-13, U-15, U-20 through U-28, U-31, U-36 through
  • Embodiment 16 The composition of Embodiment 15 wherein R 1 is selected from U-I through U-3, U-5, U-8, U-13, U-20, U-22, U-23, U-25 through U-28, U-36 through U-39 and U-50.
  • Embodiment 17 The composition of Embodiment 16 wherein R 1 is selected from U-I through U-3, U-13, U-20, U-22, U-23, U-36 through U-39 and U-50.
  • Embodiment 18 The composition of Embodiment 17 wherein R 1 is U-I or U-50.
  • Embodiment 19 The composition of Embodiment 18 wherein R 1 is U-I. Embodiment 19a.
  • component (a) is a compound of Formula 1 or a salt thereof, and Embodiments 18 and 19 wherein X is X 1 , X 2 or X 3 , each R 2 is independently C 1 -C 3 alkyl, G is an optionally substituted 5-membered heteroaromatic ring containing 1 to 3 heteroatoms selected from 0 to 1 O, 0 to 1 S and 0 to 3 N, Q a is CH 3 , Q b is radical selected from
  • R 5 is CJ-CO alkyl, C2-C6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 - C6 halocycloalkyl, cyano, nitro, C2-C 4 alkoxyalkyl, Cj-C 4 hydroxyalkyl, C2-C4 alkylcarbonyl, C 2 -Cg alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C 3 -Cg dialkylaminocarbonyl or C3-C6 trialkylsilyl, and R 6 is an optionally substituted phenyl, naphthalenyl or 5- or 6-membere
  • Embodiment 21 The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein R 1 is a phenyl or 5- or 6-membered heteroaromatic ring, optionally substituted with 1 to 2 substituents independently selected from R 4 and each R 4 is independently C 1 - C 3 alkyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, cyclopropyl, C 1 -C 3 haloalkyl, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, halocyclopropyl, halogen, cyano, nitro, C j -C 2 alkoxy, C 1 -C 2 haloalkoxy, C 1 -C 2 alkylthio, C 1 -C 2 haloalkylthio, C 1 -C 2 alkoxyalkyl, C2 ⁇ C 3 alky
  • Embodiment 22 The composition of Embodiment 21 wherein each R 4 is independently C 1 -C 3 alkyl, C2 ⁇ C 3 alkenyl, C 2 -C 3 alkynyl, cyclopropyl, C 1 -C 3 haloalkyl, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, halocyclopropyl, halogen, cyano, nitro, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy.
  • Embodiment 23 The composition of Embodiment 22 wherein each R 4 is independently halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy.
  • Embodiment 24 The composition of Embodiment 23 wherein each R 4 is independently halogen, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl or C 1 -C 2 alkoxy.
  • Embodiment 25 The composition of Embodiment 24 wherein each R 4 is independently Cl, Br, I, methyl, ethyl, trifluoromethyl or methoxy.
  • Embodiment 26 The composition of Embodiment 25 wherein at least one R 4 is Cl.
  • Embodiment 27 The composition of Embodiment 25 wherein at least one R 4 is Br.
  • Embodiment 28 The composition of Embodiment 25 wherein at least one R 4 is methyl.
  • Embodiment 29 The composition of Embodiment 25 wherein at least one R 4 is ethyl.
  • Embodiment 30 The composition of Embodiment 25 wherein at least one R 4 is trifluoromethyl.
  • Embodiment 31 The composition of Embodiment 25 wherein at least one R 4 is methoxy.
  • Embodiment 32 The composition of Embodiment 19 wherein each R 4 is independently connected to the 3- or 5-position of U-I (i.e. k is 1, and R 4 is connected to the 3- or 5-position of U-I).
  • Embodiment 32a The composition of Embodiment 19a wherein each R 4 is independently connected to the 3- or 5-position of U-I (i.e.
  • each R 4 is independently C 1 -C 6 alkyl, C 2 -CO alkenyl, C 2 -CO alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 - C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, hydroxy, amino, cyano, nitro, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C 1 -C4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylthio, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulf
  • Embodiment 33 The composition of Embodiment 19 wherein each R 4 is independently connected to the 3- and 5-position of U-I (i.e. k is 2, and an independently selected R 4 is connected to the 3- and 5-positions of U-I).
  • each R 4 is independently C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, hydroxy, amino, cyano, nitro, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsul
  • Embodiment 34 The composition of Embodiment 20 wherein each R 4 is independently connected to the 2- or 3-position of U-50 (i.e. k is 1, and R 4 is connected to the 2- or 3-position of U-50).
  • Embodiment 35 The composition of Embodiment 20 wherein each R 4 is independently connected to the 2- and 5-position of U-50 (i.e. k is 2, and an independently selected R 4 is connected to each of 2- and 5-positions of U-50).
  • Embodiment 36 The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein G is one of G-I through G-55;
  • Embodiment 37 The composition of Embodiment 36 wherein G is selected from G-I through G-3, G-7, G-8, G-10, G-I l, G-14, G-15, G-23, G-24, G-26 through G-
  • Embodiment 38 The composition of Embodiment 37 wherein G is selected from G-I, G-2, G-7, G-8, G-14, G-15, G-23, G-24, G-26, G-27, G-36 through G-38, G-49,
  • Embodiment 39 The composition of Embodiment 38 wherein G is selected from G-I,
  • G-2 G-15, G-26, G-27, G-36, G-37 and G-38.
  • Embodiment 40 The composition of Embodiment 39 wherein G is selected from G-I, G-2, G-15, G-26 and G-36.
  • Embodiment 41 The composition of Embodiment 40 wherein G is G-I.
  • G is G-I.
  • Embodiment 42 The composition of Embodiment 39 wherein G is G-2.
  • G is G-2.
  • Embodiment 43 The composition of Embodiment 36 wherein G is G-15.
  • G is G-15.
  • Embodiment 44 The composition of Embodiment 36 wherein G is G-26.
  • G is G-26.
  • Embodiments 1 through 35 Embodiments 46 through 96, Embodiments Al through A4, and Embodiments A6 through A 13.
  • Embodiment 45 The composition of Embodiment 36 wherein G is G-36.
  • G G-36.
  • Embodiment 46 The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein G is a 5- membered heteroaromatic ring or 5-membered saturated or partially saturated heterocyclic ring, each ring optionally substituted with up to 2 substituents selected from R 3 on carbon ring members and selected from R 1 1 on nitrogen ring members; each R 11 is independently C 1 -C3 alkyl; each R 3 is independently C j - C 3 alkyl or halogen.
  • G is a 5- membered heteroaromatic ring or 5-membered saturated or partially saturated heterocyclic ring, each ring optionally substituted with up to 2 substituents selected from R 3 on carbon ring members and selected from R 1 1 on nitrogen ring members; each R 11 is independently C 1 -C3 alkyl; each R 3 is independently C j - C 3 alkyl or halogen.
  • Embodiment 47 The composition of Embodiment 46 wherein R 3 is methyl.
  • Embodiment 48 The composition of any one of Embodiments 36 through 45 wherein G is unsubstituted.
  • Embodiment 49 The composition of Embodiment 36 wherein R 3a is H and R l la is H or methyl.
  • Embodiment 50 The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein Q is selected from Q-I through Q-85;
  • R 15 is as described above, and for Q-2 through Q-75, each R 8 is independently attached to the carbon atoms of the nonaromatic carbocyclic ring or heterocyclic ring of the Q group, and each R 9 is independently attached to the carbon atoms of phenyl or heteroaromatic ring of the Q group; each R 8 is independently H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 3 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, hydroxy, amino, cyano, nitro, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C
  • R 16a is H, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 alkylcycloalkyl, C5-C 10 alkylcycloalkylalkyl, C 1 -C 6 haloalkyl, C 3 -C 6 haloalkenyl, C 3 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfonyl, amino, C 1 -C 4 alkylamino, C 2 -Cg dialkylamino, C 3 -C 6 cycloalkylamin
  • R 6 is a phenyl, benzyl, naphthalenyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkenyl or 5- or 6- membered heteroaromatic ring, each optionally substituted with 1 to 3 substituents selected from R 7 on carbon ring members and R 12 on nitrogen ring members; each R 7 is independently CI-CG alkyl, C 2 -CG alkenyl, C 2 -Cg alkynyl, C 3 -Cg cycloalkyl, C4-C10 cycloalkylalkyl, C 4 -CjO alkylcycloalkyl, C5-C 1 0 alkylcycloalkylalkyl, CJ-CG haloalkyl, C 2 -Cg haloalkenyl, C 2 -Cg haloalkynyl,
  • Embodiment 51 The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein Q is selected from Q-I through Q-4, Q-8 through Q-10, Q-12, Q-14, Q-22 through Q-
  • Embodiment 52 The composition of Embodiment 51 wherein Q is Q-I, Q-2, Q-8,
  • Embodiment 53 The composition of Embodiment 52 wherein Q is Q-I, Q-2, Q-8, Q-
  • Embodiment 54 The composition of Embodiment 53 wherein Q is Q-I.
  • Embodiment 55 The composition of Embodiment 53 wherein Q is Q-2.
  • Embodiment 56 The composition of Embodiment 53 wherein Q is Q-8.
  • Embodiment 57 The composition of Embodiment 53 wherein Q is Q-23.
  • Embodiment 58 The composition of Embodiment 53 wherein Q is Q-41.
  • Embodiment 59 The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein R ⁇ is C 1 -
  • Embodiment 60 The composition of Embodiment 59 wherein R 5 is C j -C 4 alkyl, C 2 -
  • Embodiment 61 The composition of Embodiment 60 wherein R 5 is C 1 -C 4 alkyl, C 1 -
  • Embodiment 62 The composition of Embodiment 61 wherein R 5 is C1-C 4 alkyl, C2-
  • Embodiment 63 The composition of Embodiment 62 wherein R 5 is C1-C3 alkyl.
  • Embodiment 65 The composition of Embodiment 50 wherein R 6 is one of H-I through H-46;
  • each R 7 is independently Cj-Cg alkyl, C2-Cg alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C 4 -C 1 0 cycloalkylalkyl, C 4 -C10 alkylcycloalkyl, C5-C10 alkylcycloalkylalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C3 ⁇ C 6 halocycloalkyl, halogen, hydroxy, amino, cyano, nitro, C1-C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylthio, C 1 -C 4
  • Embodiment 66 The composition of Embodiment 65 wherein R 6 is H-I, H-20, H-32, H-45 or H-46.
  • Embodiment 67 The composition of Embodiment 66 wherein R 6 is H-I or H-45.
  • Embodiment 68 The composition of Embodiment 67 wherein R 6 is H-45.
  • Embodiment 69 The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein Q b is CR 5 R 6 R 15 ; R 6 is a phenyl, benzyl, naphthalenyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkenyl or 5- or 6-membered heteroaromatic ring, each optionally substituted with 1 to 3 substituents selected from R 7 on carbon ring members and R 12 on nitrogen ring members; each R 7 is independently C j -C 3 alkyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, cyclopropyl, C 1 -C 3 haloalkyl, C 2 -C 3 haloalkenyl, C 2 - C 3 haloalkynyl, halocyclopropyl, halogen, cyano, nitro, hydroxy,
  • Embodiment 70 The composition of Embodiment 69 wherein each R 7 is independently C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, cyclopropyl, C 1 -C 3 haloalkyl, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, halocyclopropyl, halogen, cyano, nitro, hydroxy, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy.
  • Embodiment 71 The composition of Embodiment 70 wherein each R 7 is independently halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, hydroxy, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy.
  • Embodiment 72 The composition of Embodiment 71 wherein each R 7 is independently halogen, hydroxy, C 1 -C 2 alkoxy or C 1 -C 3 alkyl.
  • Embodiment 73 The composition of Embodiment 72 wherein each R 7 is independently F, Cl, Br, hydroxy, methoxy or methyl.
  • Embodiment 74 The composition of Embodiment 65 wherein p is 0.
  • Embodiment 75 The composition of Embodiment 65 wherein R 12 is H or C 1 -C 2 alkyl.
  • Embodiment 76 The composition of Embodiment 75 wherein R 12 is methyl.
  • Embodiment 77 The composition of Formula 1 wherein R 15 is H, C 1 -C 4 alkyl, C 2 - C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 4 cycloalkyl or C 1 -C 4 haloalkyl.
  • Embodiment 78 The composition of Embodiment 77 wherein R 15 is H or C 1 -C 3 alkyl.
  • Embodiment 79 The composition of Embodiment 78 wherein R 15 is H.
  • Embodiment 80 The composition of Formula 1 wherein Q a is H or C 1 -C 3 alkyl.
  • Embodiment 81 The composition of Embodiment 80 wherein Q a is H or methyl.
  • Embodiment 82 The composition of Embodiment 81 wherein Q a is methyl.
  • each R 8 is independently H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 3 -C 4 alkynyl, C 3 -C 6 cycloalkyl, Cj-C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, hydroxy, amino, cyano, nitro, C 1 -C 4 alkoxy or C 2 -C 4 alkylcarbonyloxy.
  • Embodiment 84 The composition of Embodiment 83 wherein each R 8 is independently H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 3 -C 4 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 4 haloalkyl, C 3 -C 6 halocycloalkyl, halogen, hydroxy, amino, cyano, nitro, C 1 -C 4 alkoxy or C 2 -C 4 alkylcarbonyloxy.
  • Embodiment 85 The composition of Embodiment 84 wherein each R 8 is independently H, C 1 -C 3 alkyl, hydroxy, C 1 -C 3 alkoxy or C 2 -C 3 alkylcarbonyloxy.
  • Embodiment 86 The composition of Embodiment 85 wherein R 8 is H, methyl, methoxy or hydroxy.
  • Embodiment 87 The composition of Embodiment 50 wherein m is 0 or 1.
  • Embodiment 88 The composition of Embodiment 87 wherein m is 0.
  • Embodiment 89 The composition of Embodiment 50 wherein each R 9 is independently C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, cyclopropyl, C 1 -C 3 haloalkyl, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, halocyclopropyl, halogen, cyano, nitro, hydroxy, C 2 -C 3 alkylcarbonyloxy, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy, C 1 -C 2 alkylthio, C 1 -C 2 haloalkylthio, C 2 -C 3 alkoxyalkyl, C 2
  • Embodiment 90 The composition of Embodiment 89 wherein each R 9 is independently C 1 -C 3 alkyl, cyclopropyl, C 1 -C 3 haloalkyl, halocyclopropyl, halogen, hydroxy, C 2 -C 3 alkylcarbonyloxy, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy.
  • Embodiment 91 The composition of Embodiment 90 wherein each R 9 is independently C 1 -C 3 alkyl, hydroxy, C 1 -C 2 alkoxy or halogen.
  • Embodiment 92 The composition of Embodiment 92.
  • Embodiment 91 wherein each R 9 is independently methyl, F, Cl, Br, hydroxy or methoxy.
  • Embodiment 93 The composition of Embodiment 50 wherein j is 0 or 1.
  • Embodiment 94 The composition of Embodiment 93 wherein j is 0.
  • Embodiment 95 The composition of Embodiment 50 wherein each R 10 is H or methyl.
  • Embodiment 96 The composition described in the Summary of the Invention wherein component (a) is a compound of Formula 1 or a salt thereof, wherein Q is Q-I through Q-75 and Q-83 through Q-85 and Q has the orientation depicted above in Embodiment 50, and wherein R 1 ⁇ has an orientation below the plane defined by the 3 non-hydrogen atoms attached to the carbon atom identified with the asterisk (*) (e.g., for Q-I, Formula 1').
  • Embodiment 97 The composition of Embodiment 50 wherein each R 1 ⁇ is independently C 1 -C 3 alkyl, C2-C3 alkenyl, C2-C3 alkynyl, cyclopropyl, C 1 -C 3 haloalkyl, C2-C3 haloalkenyl, C2-C3 haloalkynyl, halocyclopropyl, halogen, cyano, nitro, C 1 -C 2 alkoxy or C1-C2 haloalkoxy; or a phenyl or benzyl ring, optionally substituted with up to 3 substituents selected from R 13 .
  • Embodiment 98 The composition of Embodiment 50 wherein R 16a is H, C 1 -C 3 alkyl, allyl, propargyl, cyclopropyl or C 1 -C 3 haloalkyl; or a phenyl or benzyl ring, optionally substituted with up to 3 substituents selected from R 13 .
  • Embodiment 99 A compound of Embodiment 50 wherein when Q is Q-76, Q-77,
  • Embodiment 100 The composition of Embodiment 99 wherein m is 1.
  • Embodiment 101 The composition of Embodiment 50 wherein when Q is Q-78 and
  • Embodiment 102 The composition of Embodiment 50 wherein when Q is Q-78 and
  • R 16a is H, then m is 1.
  • Embodiment 103 The composition of Embodiment 50 wherein when Q is Q-78, then R 16a is other than H and m is 0.
  • Embodiment Al Combinations of Embodiments 1-103 are illustrated by: Embodiment Al.
  • component (a) is a compound of Formula 1 or a salt thereof, wherein n is 0; R 1 is a phenyl or 5- or 6-membered heteroaromatic ring, optionally substituted with 1 to 2 substituents independently selected from R 4 ; and each R 4 is independently C 1 -Cg alkyl, C 2 -C 6 alkenyl, C2-C6 alkynyl, C 3 -C 6 cycloalkyl, C 1 -C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 6 halocycloalkyl, halogen, hydroxy, amino, cyano, nitro, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio,
  • Embodiment A2 The composition of Embodiment Al wherein W 1 is O and W 2 is O.
  • Embodiment A3 The composition of Embodiment A2 wherein A is CH 2 .
  • Embodiment A4 The composition of Embodiment A3 wherein X is X 1 or X 2 .
  • Embodiment A5 The composition of Embodiment A4 wherein G is G-I, G-2, G-15,
  • Embodiment A6 The composition of Embodiment A5 wherein G is unsubstituted.
  • Embodiment A7 The composition of Embodiment A6 wherein Q is Q-I, Q-2, Q-8, Q- 23 or Q-41 and Q a is H or C 1 -C 3 alkyl.
  • Embodiment A8 The composition of Embodiment A7 wherein R 5 is Cj-C 3 alkyl, R 6 is H-45, R 15 is H, and p is 0.
  • Embodiment A9. The composition of Embodiment A7 wherein j is 0, m is 0 or 1, and
  • R 8 is H, methyl, methoxy or hydroxy.
  • Embodiment AlO The composition of any one of Embodiments A8 and A9 wherein RMs U-l or U-50.
  • Embodiment Al 1 The composition of Embodiment AlO wherein each R 4 is independently Cl, Br, methyl, ethyl, trifluoromethyl or methoxy.
  • Embodiment A12 The composition of Embodiment Al l wherein Q is Q-I, Q a is methyl, R 5 is C ] -C 2 alkyl, R 15 is H, and the carbon atom to which R 5 and R 6 are attached is a stereocenter with the R configuration.
  • Embodiment A13 The composition of Embodiment Al l wherein Q is Q-2, Q-8, Q-23 or Q-41, Q a is methyl, R 15 is H, and the carbon atom identified with the asterisk
  • (*) is a stereocenter having a configuration described as R, provided that when m is 1, R 8 is hydroxy or methoxy and the R 8 group is attached to the carbon adjacent to the carbon atom identified with an asterisk (*), then the carbon atom identified with the asterisk (*) is a stereocenter having a configuration described as S.
  • Embodiment A14 The composition of Embodiment Al wherein component (a) is selected from the group consisting of
  • Embodiment Bl The composition described in the Summary of the Invention
  • component (b) includes at least one (bl) compound selected from benomyl, carbendazim and thiophanate-methyl.
  • Embodiment B2 The composition described in the Summary of the Invention
  • component (b) includes at least one (b2) compound selected from procymidone, iprodione and vinclozolin.
  • Embodiment B The composition described in the Summary of the Invention
  • component (b) includes at least one (b3) compound selected from epoxiconazole, fluquinconazole, triadimenol, simeconazole, ipconazole, triforine, cyproconazole, difenconazole, flusilazole, flutriafol, metconazole, myclobutanil, prochloraz, propiconazole, prothioconazole, tebuconazole and tetraconazole.
  • component (b) includes at least one (b3) compound selected from epoxiconazole, fluquinconazole, triadimenol, simeconazole, ipconazole, triforine, cyproconazole, difenconazole, flusilazole, flutriafol, metconazole, myclobutanil, prochloraz, propiconazole, prothioconazole, tebuconazole and t
  • Embodiment B3a The composition described in the Summary of the Invention
  • component (b) includes at least one (b3) compound selected from epoxiconazole and prothioconazole.
  • Embodiment B3b The composition described in the Summary of the Invention
  • component (b) includes at least one (b3) compound selected from cyproconazole, difenconazole, flusilazole, myclobutanil, propiconazole, tebuconazole and tetraconazole.
  • Embodiment B The composition described in the Summary of the Invention
  • component (b) includes at least one (b4) compound selected from metalaxyl, metalaxyl-M, benalaxyl, benalaxyl-M, furalaxyl, ofurace and oxadixyl.
  • Embodiment B4a The composition described in the Summary of the Invention
  • component (b) includes at least one (M) compound selected from mefenoxam, metalaxyl, metalaxyl M, benalaxyl, furalaxyl, ofurace and oxadixyl.
  • Embodiment B5 The composition described in the Summary of the Invention (including but not limited to composition of Embodiments 1 through 103 and Al through A14) wherein component (b) includes at least one (b5) compound selected from aldimorph, dodemorph, fenpropimorph, tridemorph, trimorphamide. fenpropidin, piperalin and spiroxamine.
  • Embodiment B5a The composition described in the Summary of the Invention (including but not limited to composition of Embodiments 1 through 103 and Al through A 14) wherein component (b) includes at least one (b5) compound selected from spiroxamine.
  • Embodiment B6 The composition described in the Summary of the Invention
  • component (b) includes at least one (b6) compound selected from edifenphos and isoprothiolane.
  • Embodiment B7 The composition described in the Summary of the Invention
  • component (b) includes at least one (b7) compound selected from boscalid, penthiopyrad, bixafen, carboxin and oxycarboxin.
  • Embodiment B7a The composition described in the Summary of the Invention
  • component (b) includes at least one (b7) compound selected from bixafen.
  • Embodiment B7b The composition described in the Summary of the Invention
  • component (b) includes at least one (b7) compound selected from boscalid, penthiopyrad, carboxin and oxycarboxin.
  • component (b) includes at least one (b8) compound selected from ethirimol.
  • Embodiment B9 The composition described in the Summary of the Invention
  • component (b) includes at least one (b9) compound selected from cyprodinil.
  • Embodiment BlO The composition described in the Summary of the Invention
  • component (b) includes at least one (blO) compound selected from diethofencarb.
  • Embodiment BI l The composition described in the Summary of the Invention
  • component (b) includes at least one (bll) compound selected from azoxystrobin, pyraclostrobin, kresoxim-methyl, trifloxystrobin, picoxystrobin, pyribencarb, famoxadone, fenamidone, enestrobin, dimoxystrobin, metominostrobin, orysastrobin and fluoxastrobin.
  • component (b) includes at least one (bll) compound selected from azoxystrobin, pyraclostrobin, kresoxim-methyl, trifloxystrobin, picoxystrobin, pyribencarb, famoxadone, fenamidone, enestrobin, dimoxystrobin, metominostrobin, orysastrobin and fluoxastrobin.
  • component (b) includes at least one (bll) compound selected from azoxystrobin, pyraclostrobin, kresoxim-methyl,
  • component (b) includes at least one (bl l) compound selected from azoxystrobin, pyraclostrobin, kresoxim-methyl, trifloxystrobin, picoxystrobin, pyribencarb, famoxadone, fenamidone, discostrobin, enestrobin, dimoxystrobin, metominostrobin, orysastrobin and fluoxastrobin.
  • component (b) includes at least one (bl l) compound selected from azoxystrobin, pyraclostrobin, kresoxim-methyl, trifloxystrobin, picoxystrobin, pyribencarb, famoxadone, fenamidone, discostrobin, enestrobin, dimoxystrobin, metominostrobin, orysastrobin and fluoxastrobin.
  • Embodiment B 12 The composition described in the Summary of the Invention
  • component (b) includes at least one (bl2) compound selected from fenpiclonil and fludioxonil.
  • component (b) includes at least one (bl3) compound selected from quinoxyfen.
  • Embodiment B 14 The composition described in the Summary of the Invention
  • component (b) includes at least one (bl4) compound selected from chloroneb.
  • Embodiment B15 The composition described in the Summary of the Invention
  • component (b) includes at least one (bl5) compound selected from pyroquilon and tricyclazole.
  • Embodiment B16 The composition described in the Summary of the Invention
  • Embodiment B includes at least one (bl6) compound selected from carpropamid.
  • component (b) includes at least one (bl7) compound selected from fenhexamid.
  • Embodiment B 18. The composition described in the Summary of the Invention
  • component (b) includes at least one (bl8) compound selected from pyributicarb.
  • Embodiment B 19 The composition described in the Summary of the Invention
  • component (b) includes at least one (bl9) compound selected from polyoxin.
  • Embodiment B20 The composition described in the Summary of the Invention (including but not limited to composition of Embodiments 1 through 103 and Al through A14) wherein component (b) includes at least one (b20) compound selected from pencycuron.
  • Embodiment B21 The composition described in the Summary of the Invention
  • component (b) includes at least one (b21) compound selected from cyazofamid and amisulbrom.
  • Embodiment B22 The composition described in the Summary of the Invention
  • component (b) includes at least one (b22) compound selected from zoxamide.
  • Embodiment B23 The composition described in the Summary of the Invention
  • component (b) includes at least one (b23) compound selected from blasticidin-S.
  • Embodiment B24 The composition described in the Summary of the Invention
  • component (b) includes at least one (b24) compound selected from kasugamycin.
  • Embodiment B25 The composition described in the Summary of the Invention (including but not limited to composition of Embodiments 1 through 103 and Al through A14) wherein component (b) includes at least one (b25) compound selected from streptomycin.
  • Embodiment B26 The composition described in the Summary of the Invention
  • component (b) includes at least one (b26) compound selected from validamycin.
  • Embodiment B27 The composition described in the Summary of the Invention
  • component (b) includes at least one (b27) compound selected from cymoxanil.
  • Embodiment B28 The composition described in the Summary of the Invention
  • component (b) includes at least one (b28) compound selected from propamacarb, propamacarb-hydrochloride, prothiocarb and iodocarb.
  • component (b) includes at least one (b28) compound selected from propamacarb, propamacarb-hydrochloride, prothiocarb and iodocarb.
  • Embodiment B28a The composition described in the Summary of the Invention
  • component (b) includes at least one (b28) compound selected from propamacarb.
  • Embodiment B29 The composition described in the Summary of the Invention
  • component (b) includes at least one (b29) compound selected from fluazinam, binapacryl, ferimzone, meptyldinocap and dinocap.
  • Embodiment B29a The composition described in the Summary of the Invention
  • component (b) includes at least one compound selected from (b29) compound such as fluazinam and dinocap.
  • Embodiment B30 The composition described in the Summary of the Invention
  • component (b) includes at least one (b30) compound selected from fentin acetate.
  • Embodiment B31 The composition described in the Summary of the Invention (including but not limited to composition of Embodiments 1 through 103 and Al through A 14) wherein component (b) includes at least one (b31) compound selected from oxolinic acid.
  • Embodiment B32 The composition described in the Summary of the Invention
  • component (b) includes at least one (b32) compound selected from hymexazole.
  • Embodiment B33 The composition described in the Summary of the Invention
  • component (b) includes at least one (b33) compound selected from phosphorous acid and its various salts, including fosetyl- aluminum.
  • component (b) includes at least one (b33) compound selected from phosphorous acid and its various salts, including fosetyl- aluminum.
  • Embodiment B34 The composition described in the Summary of the Invention
  • component (b) includes at least one (b34) compound selected from teclofthalam.
  • Embodiment B35 The composition described in the Summary of the Invention
  • component (b) includes at least one (b35) compound selected from triazoxide.
  • Embodiment B36 The composition described in the Summary of the Invention
  • component (b) includes at least one (b36) compound selected from flusulfamide.
  • Embodiment B37 The composition described in the Summary of the Invention
  • component (b) includes at least one (b37) compound selected from diclomezine.
  • Embodiment B38 The composition described in the Summary of the Invention
  • component (b) includes at least one (b38) compound selected from silthiofam.
  • Embodiment B39 The composition described in the Summary of the Invention (including but not limited to composition of Embodiments 1 through 103 and Al through A 14) wherein component (b) includes at least one (b39) compound selected from diflumetorim.
  • Embodiment B40 The composition described in the Summary of the Invention
  • component (b) includes at least one (b40) compound selected from dimethomorph, benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, valiphenal, mandipropamid and flumorph.
  • component (b) includes at least one (b40) compound selected from dimethomorph, benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, valiphenal, mandipropamid and flumorph.
  • component (b) includes at least one (b40) compound selected from dimethomorph, benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, valiphenal, mandipropamid and flumorph.
  • Embodiment B41 The composition described in the Summary of the Invention
  • component (b) includes at least one (b41) compound selected from oxytetracycline.
  • Embodiment B42 The composition described in the Summary of the Invention
  • component (b) includes at least one (b42) compound selected from methasulfocarb.
  • Embodiment B43 The composition described in the Summary of the Invention
  • component (b) includes at least one (b43) compound selected from fluopicolide and fluopyram.
  • Embodiment B44 The composition described in the Summary of the Invention
  • component (b) includes at least one (b44) compound selected from acibenzolar-S-methyl.
  • Embodiment B45 The composition described in the Summary of the Invention
  • component (b) includes at least one (b45) compound selected from copper oxychloride, copper sulfate, copper hydroxide, Bordeaux composition (tribasic copper sulfide), elemental sulfur, mancozeb, metiram, propineb, ferbam, maneb, thiram, zineb, ziram, folpet, captan, captafol and chlorothalonil.
  • component (b) includes at least one (b45) compound selected from copper oxychloride, copper sulfate, copper hydroxide, Bordeaux composition (tribasic copper sulfide), elemental sulfur, mancozeb, metiram, propineb, ferbam, maneb, thiram, zineb, ziram, folpet, captan, captafol and chlorothalonil.
  • component (b) includes at least one (b45) compound selected from copper oxychloride, copper sulfate, copper hydroxide, Bordeaux composition (tri
  • component (b) includes at least one (b45) compound selected from copper sulfate, copper hydroxide, Bordeaux composition (tribasic copper sulfide), copper hydroxide, elemental sulfur, mancozeb, metiram, propineb, ferbam, maneb, thiram, zineb, ziram, folpet, captan, captafol and chlorothalonil.
  • component (b) includes at least one (b45) compound selected from copper sulfate, copper hydroxide, Bordeaux composition (tribasic copper sulfide), copper hydroxide, elemental sulfur, mancozeb, metiram, propineb, ferbam, maneb, thiram, zineb, ziram, folpet, captan, captafol and chlorothalonil.
  • Embodiment B45b The composition described in the Summary of the Invention
  • component (b) includes at least one (b45) compound selected from the group consisting of copper fungicides (b45.1), sulfur fungicides (b45.2), dithiocarbamate fungicides (b45.3), phthalimide fungicides
  • Embodiment B46 The composition described in the Summary of the Invention
  • component (b) includes at least one (b46) compound selected from ethaboxam, cyflufenamid, proquinazid, metrafenone, ⁇ f-[2-[4-[[3-
  • Embodiment B46a The composition described in the Summary of the Invention
  • component (b) includes at least one (b46) compound selected from ethaboxam and proquinazid.
  • component (b) includes at least one (b46) compound selected from ethaboxam and proquinazid.
  • Embodiment B46b The composition described in the Summary of the Invention
  • component (b) includes at least one (b46) compound selected from the group consisting of thiazole carbamate fungicides (b46.1), quinazolinone and its related fungicides (M6.3) and 5-chloro-6-(2,4,6- trifluorophenyl)-7-(4-methylpiperidin-l-yl)[l,2,4]triazolo[l,5- ⁇ ]pyrimidine.
  • component (b) includes at least one (b46) compound selected from the group consisting of thiazole carbamate fungicides (b46.1), quinazolinone and its related fungicides (M6.3) and 5-chloro-6-(2,4,6- trifluorophenyl)-7-(4-methylpiperidin-l-yl)[l,2,4]triazolo[l,5- ⁇ ]pyrimidine.
  • Embodiment B47 The composition described in the Summary of the Invention
  • component (b) includes at least one compound selected from (b46), fungicides other than fungicides of component (a) and components (b3), (M), (b5), (b7), (bl 1), (bl2), (bl3), (b21), (b27), (b28), (b29), (b33), (MO)
  • X 1 and X is linked to the G thiazole ring at the 2 position of said thiazole ring.
  • X 1 and X is linked to the G thiazole ring at the 2 position of said thiazole ring.
  • X 1 and X is linked to the G oxazole ring at the 2 position of said oxazole ring.
  • X 1 and X is linked to the G oxazole ring at the 2 position of said oxazole ring.
  • X 1 and X is linked to the G thiazole ring at the 2 position of said thiazole ring.
  • X 1 and X is linked to the G thiazole ring at the 2 position of said thiazole ring.
  • X 1 and X is linked to the G oxazole ring at the 2 position of said oxazole ring.
  • X 1 and X is linked to the G oxazole ring at the 2 position of said oxazole ring.
  • G is the thiazole ring
  • Q is Q-8 and X is X 2 and X is linked to the G thiazole ring at the 2 position of said thiazole ring.
  • embodiments of these compounds within Embodiments 1 through 11, Embodiments 14 through 35, Embodiment 41, Embodiments 59 through 82, Embodiment 96, Embodiments Al through A4, Embodiment A6, Embodiment A8 and Embodiments AlO through A12.
  • fungicidal compositions of the present invention comprising a fungicidally effective amount of a composition of Embodiments 1 to 103, Al to A 14, and Bl to B47 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • Embodiments of the invention further include methods for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a fungicidally effective amount of a composition of Embodiments 1 to 103, Al to A14, and Bl to B47 (e.g., as a composition described herein).
  • compositions include those where component (a) and component (b) are present in a fungicidally effective amount and the weight ratio of component (a) to component (b) is from about 100:1 to 1:500 (e.g., from about 100:1 to about 1:500). These compositions are particularly effective for controlling plant diseases caused by Oomycete fungal plant pathogens.
  • compositions where the weight ratio of component (a) to component (b) is from about 125:1 to about 1:125 (e.g., from about 25:1 to about 1:25). Of particular note are compositions where the weight ratio of component (a) to component (b) is from about 5:1 to 1:5.
  • the compounds of Formula 1 can be prepared by one or more of the following methods and variations as described in Schemes 1-22.
  • the definitions of R 1 , R 2 , A, W 1 , W 2 , X, G, Q a , Qb and n in the compounds of Formulae 1-46 below are as defined above in the Summary of the Invention unless otherwise noted.
  • Compounds of Formulae la-Ik are various subsets of the compounds of Formula 1.
  • Compounds of Formulae 19a-19b are various subsets of the compounds of Formula 19.
  • Compounds of Formulae 23a, 26a and 27a are various subsets of the compounds of Formula 23, 26 and 27 respectively.
  • compounds of Formula 1 can be prepared by coupling of an acid chloride of Formula 2 with an amine of Formula 3 in the presence of an acid scavenger to provide the compound of Formula Ia.
  • Typical acid scavengers include amine bases such as triethylamine, diisopropylethylamine and pyridine.
  • Other scavengers include hydroxides such as sodium and potassium hydroxide and carbonates such as sodium carbonate and potassium carbonate.
  • polymer-supported acid scavengers such as polymer-bound diisopropylethylamine and polymer-bound N,N- dimethylaminopyridine.
  • amides of Formula Ia can be converted to thioamides of Formula Ib using a variety of standard thiating reagents such as phosphorus pentasulfide or 2,4-bis(4-methoxyphenyl)-l ,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson's reagent).
  • standard thiating reagents such as phosphorus pentasulfide or 2,4-bis(4-methoxyphenyl)-l ,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson's reagent).
  • W 1 is O
  • the conversion of W 2 from O to S may be accompanied by conversion of W 1 from O to S.
  • the amines of Formula 3 are known or can be prepared by methods known to one skilled in the art.
  • compounds of Formula Ic wherein A is methylene can be prepared by coupling of an acid chloride of Formula 5 with an amine of Formula 6 in the presence of an acid scavenger, as described for Scheme 1 above.
  • Acid salts of the Formula 6 amines can also be used in this reaction, provided at least 2 equivalents of the acid scavenger is present, as known to one skilled in the art.
  • Typical acids used to form salts with amines include hydrochloric acid, oxalic acid and trifluoroacetic acid.
  • amides of Formula Ic can be converted to thioamides of Formula Id using a variety of standard thiating reagents such as phosphorus pentasulfide or 2,4-bis(4-methoxyphenyl)-l,3-dithia-
  • compounds of Formula Ic can also be prepared by coupling of an acid of Formula 7 with an amine of Formula 6 (or its acid salt) in the presence of a dehydrative coupling reagent, analogous to the procedure described in Scheme 2 above.
  • the acids of Formula 7 are known or can be prepared by methods known to one skilled in the art.
  • R 1 CH 2 COOH where R 1 is a heteroaromatic ring linked through nitrogen can be prepared by reacting the corresponding R 1 H compound with a haloacetic acid or ester in the presence of base; see, for example, US Patent 4,084,955.
  • Adapa Synthetic Communications 2003, 33, 59-63 and references sited therein; or from R 1 Br or R 1 I by palladium catalyzed coupling with ?-butyl acetate or diethyl malonate followed by ester hydrolysis; see, for example, W. A. Moradi and S. L. Buchwald, J. Am. Chem. Soc. 2001, 123, 7996-8002 and J. F. Hartwig et al., /. Am. Chem. Soc. 2002, 124, 12557-12565.
  • the reaction is carried out in the presence of a base such as sodium hydride or potassium carbonate in a solvent such as tetrahydrofuran, N,iV-dimethylformamide or acetonitrile at 0 to 80 °C.
  • a base such as sodium hydride or potassium carbonate
  • a solvent such as tetrahydrofuran, N,iV-dimethylformamide or acetonitrile at 0 to 80 °C.
  • the haloacetamide of Formula 9 can be prepared by the reaction of an amine of Formula 6 with a haloacetyl halide or a haloacetic acid or its anhydride, analogous to the amide-forming reactions described in Schemes 3 and 4, respectively.
  • Compounds of Formula Ie and If wherein A is NH, where R 1 is phenyl or a 5- or 6- membered heteroaromatic ring linked via a carbon atom, can be prepared by reaction of an isocyanate or an isothiocyanate of Formula 10 with an amine of Formula 6, respectively, as depicted in Scheme 6. This reaction is typically carried out at an ambient temperature in an aprotic solvent such as dichloromethane or acetonitrile.
  • Compounds of Formula Ie and If can also be prepared by the reaction of an amine of Formula 11 with a carbamoyl or thiocarbamoyl chloride or imidazole of Formula 12 as shown in Scheme 7.
  • Z 2 is chlorine
  • the reaction is typically carried out in the presence of an acid scavenger.
  • Typical acid scavengers include amine bases such as triethylamine, diisopropylethylamine and pyridine.
  • Other scavengers include hydroxides such as sodium and potassium hydroxide and carbonates such as sodium carbonate and potassium carbonate.
  • the carbamoyl or thiocarbamoyl chlorides of Formula 12 can be prepared from amines of Formula 6 by treatment with phosgene or thiophosgene, respectively, or their equivalents, while carbamoyl or thiocarbamoyl imidazoles of Formula 12 (wherein Z 2 is imidazol-1-yl) can be prepared from amines of Formula 6 by treatment with l.l'-carbonyldiimidazole or l,l'-thiocarbonyldiimidazole, respectively, according to general methods known to one skilled in the art.
  • Scheme 7
  • Certain compounds of Formula Ig where G is linked to the piperidine ring via a carbon atom can be prepared from compounds of Formula Ih by catalytic hydrogenation as shown in Scheme 8.
  • Typical conditions involve exposing a compound of Formula Ih to hydrogen gas at a pressure of 14 to 100 psi (96 to 689 kPa), preferably 40 to 50 psi (276 to 345 kPa), in the presence of a metal catalyst such as palladium supported on an inert carrier such as activated carbon, in a weight ratio of 5 to 20 % of metal to carrier, suspended in a solvent such as ethanol at an ambient temperature.
  • a metal catalyst such as palladium supported on an inert carrier such as activated carbon
  • Certain compounds of Formula Ig where G is linked to the piperidine ring via a nitrogen atom can be prepared by displacement of an appropriate leaving group Z 3 on a piperidine of Formula 13 with a nitrogen-containing heterocycle of Formula 14 in the presence of a base as depicted in Scheme 9.
  • Suitable bases include sodium hydride or potassium carbonate and the reaction is carried out in a solvent such as N,N- dimethylformamide or acetonitrile at 0 to 80 0 C.
  • Suitable leaving groups in the piperidines of Formula 13 include bromine, iodine, mesylate (OMs, OS(O) 2 CH 3 ), triflate (OS(O) 2 CF 3 ) and the like, and can be prepared from the corresponding piperidine compounds of Formula 13 where 7? is OH, as known to one skilled in the art.
  • compounds of Formula Ii can be converted to compounds of Formula Ij using a variety of standard thiating reagents such as phosphorus pentasulfide or 2,4-bis(4- methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson's reagent).
  • standard thiating reagents such as phosphorus pentasulfide or 2,4-bis(4- methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson's reagent).
  • W 2 is O
  • the compounds of Formula 16 where Z 4 is triflate can be prepared from the corresponding compounds of Formula 16 where Z 4 is OH by methods known to one skilled in the art.
  • the acid compounds of Formula 4 can be prepared by saponification of the corresponding ester compounds of Formula 17 using an alkali metal hydroxide such as LiOH, NaOH or KOH usually in the presence of water along with a co-solvent such as tetrahydrofuran and/or methanol to aid solubility of the ester as shown in Scheme 11.
  • the reaction is typically run at O to 60 0 C with the resultant carboxylate salt being converted to the free acid by addition of a slight excess of a mineral acid such as hydrochloric acid or sulfuric acid.
  • the ester compounds of Formula 17 can be prepared from the amine compounds of Formula 18 by methods analogous to those described above for the preparation of compounds of Formula 1 as outlined in Scheme 12.
  • the amine compounds of Formula 18 can be prepared from the protected amine compounds of Formula 19 where PG is an acid-labile amine protecting group such as a t- butoxycarbonyl (t-Boc) or a benzyloxycarbonyl (Cbz) group as shown in Scheme 13.
  • PG is an acid-labile amine protecting group such as a t- butoxycarbonyl (t-Boc) or a benzyloxycarbonyl (Cbz) group as shown in Scheme 13.
  • the protecting group is removed by treating with an acid such as trifluoroacetic acid or gaseous HCl in the presence of a solvent such as dichloromethane or dioxane.
  • the amine can be isolated as its acid salt or converted in a subsequent step to the free amine by treatment with a base, as known to one skilled in the art.
  • R 40 is Q-C 4 alkyl
  • PG is an acid-labile protecting group
  • the amines of Formula 6 can be prepared from the protected amines of Formula 20 where PG is an acid-labile amine protecting group such as a t-butoxycarbonyl (t-Boc) or a benzyloxycarbonyl (Cbz) group as depicted in Scheme 14 by methods analogous to those described above for the preparation of compounds of Formula 18 as outlined in Scheme 13.
  • PG is an acid-labile amine protecting group such as a t-butoxycarbonyl (t-Boc) or a benzyloxycarbonyl (Cbz) group as depicted in Scheme 14 by methods analogous to those described above for the preparation of compounds of Formula 18 as outlined in Scheme 13.
  • the protected amines of Formula 20 can be prepared from the acid or acid chloride compounds of Formula 21 by methods analogous to those described above for the preparation of compounds of Formula 1 as outlined in Scheme 15.
  • the compounds of Formula 21 where R 41 is OH can be obtained from compounds of Formula 19 by saponification, analogous to methods described for Scheme 11.
  • R 41 is Cl or OH
  • PG is an acid-labile protecting group.
  • Many compounds of Formula 19 are known or can be prepared by methods known to one skilled in the art starting with the intermediates such as, but not limited to, those depicted in Exhibit 1.
  • the synthetic literature is extensive for the formation of 5-membered heteroaromatic rings or 5-membered partially saturated heterocyclic rings (for example, G-I through G-55); see, for example, Comprehensive Heterocyclic Chemistry, Vol. 4-6, A. R. Katritzky and C. W. Rees editors, Pergamon Press, New York, 1984; Comprehensive Heterocyclic Chemistry II, Vol. 2-4, A. R. Katritzky, C. W. Rees, and E. F.
  • the compounds of Formula 19a where G is linked to the tetrahydropyridine ring via a carbon atom can be prepared by reacting the cyclic boronates of Formula 30 with the heteroaromatic compounds of Formula 31 where Z 6 is a halogen, preferably Br or I, or a triflate group as shown in Scheme 16.
  • the reaction is carried out in the presence of a catalytic amount of palladium such as PdC ⁇ dppf (PdC ⁇ -IJ'- bis(diphenylphosphino)ferrocene) and a base such as potassium acetate in a solvent such as dioxane at 80 to 100 °C, similar to that reported for the coupling of boronates of Formula 30 with aryl halides and triflates by P. R. Eastwood, Tetrahedron Letters 2000, 41, 3705-3708.
  • the use of palladium in the synthesis of heterocycles is well known; see, for example, J. J. Li and G. W.
  • PG is an acid-labile protecting group
  • Z 6 is Cl, Br, I or OTf
  • R 40 is C 1 -C4 alkyl.
  • G 1 is G-25 through G-30
  • the compound of Formula 33 can be obtained by the route shown in Scheme 19 from the amino piperidine of Formula 23a; see, for example, Bioorganic & Medicinal Chemistry Letters 2001, 11(18), 2475-2479 and J. Org. Chem. 1985, 50(21), 4006-4014.
  • the compound of Formula 46 can also be prepared from the N-benzyl hydrazino piperidine of Formula 27a as shown in Scheme 20; see, for example, Bioorganic & Medicinal Chemistry Letters 1999, 9(9), 1285-1290 and J. Het. Chem., 1993, 30(4), 865- 872.
  • Scheme 20 See, for example, Bioorganic & Medicinal Chemistry Letters 1999, 9(9), 1285-1290 and J. Het. Chem., 1993, 30(4), 865- 872.
  • the compound of Formula 37 can also be obtained by the route shown in Scheme 21 from the amino piperidine of Formula 23a; see, for example, Bioorganic & Medicinal Chemistry Letters 2001, 11(18), 2475-2479 and Organic Letters 2002, 4(23), 4133-4134.
  • Step B Preparation of l-(l,l-dimethylethyl) 4-(4-carboxy-2-thiazolyl)-l-piperidine- carboxylate
  • the oil was dissolved in 15 mL of tetrahydrofuran and added dropwise to a suspension of lithium aluminum hydride (7.82 g, 206 mmol) in 25 mL of tetrahydrofuran that had been cooled to 0 °C.
  • the reaction mixture was refluxed overnight, cooled to 0 °C and quenched by the sequential addition of 8 mL of water, 8 mL of 15 % aqueous NaOH solution and 24 mL of water.
  • the mixture was filtered through Celite®, diatomaceous filter aid, the resulting solid was washed with hot ethyl acetate, and the combined filtrates and washings were concentrated under reduced pressure to give 7.06 g of the title compound as a yellow oil.
  • 1,1-Dimethylethyl 4-[4-[[methyl[(l/?)-l-phenylpropyl]amino]carbonyl]-2-thiazolyl]-l- piperidinecarboxylate (i.e. the product of Example 1, Step D) (3.6 g, 8.1 mmol) was dissolved in 100 mL of ether and treated with 20 mL of 4 N HCl in dioxane. The reaction mixture was stirred at ambient temperature for 4 h during which time a precipitate formed and was collected. The mother liquid was concentrated under reduced pressure, treated with 20 mL of 4 N HCl in dioxane, stirred at ambient temperature for 1 h and concentrated under reduced pressure.
  • N-Methyl-N-[(l ⁇ )-l-phenylpropyl]-2-(4-piperidinyl)-4-thiazolecarboxamide i.e. the product of Example 1, Step E
  • 206 mg, 0.6 mmol was dissolved in 4 mL of dry dichloromethane.
  • Step B Preparation of N-methyl-2-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl]-4-piperidinyl]-yV-[(l/?)-l-phenylpropyl]-4-thiazolecarboxamide iV-Methyl-N-[(l/?)-l-phenylpropyl]-2-(4-piperidinyl)-4-thiazolecarboxamide (i.e. the product of Example 1, Step E) (150 mg, 0.44 mmol) was dissolved in 3 mL of dry dichloromethane. To this solution was added triethylamine (30 ⁇ L, 0.22 mmol), 5-methyl-3-
  • the dichloromethane/hexanes/ethyl acetate solution was concentrated under reduced pressure, and the residue was purified by preparative reverse phase High Pressure Liquid Chromatography (HPLC) using a solvent gradient going from 100 % water to 100 % acetonitrile to give 85 mg of the title product, a compound of the present invention, as an oil.
  • HPLC High Pressure Liquid Chromatography
  • Step B Preparation of 2-[l-[(2,5-dichlorophenyl)acetyl]-4-piperidinyl]- ⁇ f-methyl-./V-
  • N-Methyl- ⁇ T-[(l/?)-l-phenylpropyl]-2-(4-piperidinyl)-4-thiazolecarboxamide (i.e. the product of Example 1, Step E) (171 mg, 0.5 mmol) was dissolved in 3 mL of dry dichloromethane. To this was added triethylamine (35 ⁇ L, 0.25 mmol), 2,5- dichlorobenzeneacetic acid (102 mg, 0.5 mmol) (i.e.
  • Step A Preparation of 1,1-dimethylethyl 4-[5-(methoxycarbonyl)-2-thiazolyl]-l- piperazinecarboxylate
  • 1,1-Dimethylethyl 1 -piperazinecarboxylate (1.86 g, 10 mmol), methyl 2-bromo-5- thiazolecarboxylate (2.0 g, 9.0 mmol), diazabicycloundecene (1.5 mL, 10 mmol) and a catalytic amount of potassium iodide (2 mg) were dissolved in 10 mL of dry dimethyl sulfoxide and stirred at ambient temperature for 1 h to give a precipitate. An additional 10 mL of dimethyl sulfoxide was added, the mixture was heated briefly to dissolve the solids, and the mixture was stirred at ambient temperature for 40 minutes and then at 50 °C for 2 h.
  • Step B Preparation of l-(l,l-dimethylethyl) 4-(5-carboxy-2-thiazolyl)-l -piperazinecarboxylate
  • Step C Preparation of 1,1-dimethylethyl 4-[5-[[methyl[(l/?)-l-phenylethyl]amino]- carbonyl]-2-thiazolyl]-l-piperazinecarboxylate
  • Step E Preparation of 2-[4-[(2,5-dimethylphenyl)acetyl]-l-piperazinyl]-./V-methyl-./V-
  • reaction mixture was stirred at ambient temperature for 3 days, concentrated under reduced pressure, diluted with ethyl acetate, washed with 1 N aqueous hydrochloric acid, saturated aqueous sodium bicarbonate solution and brine, dried over magnesium sulfate and concentrated under reduced pressure to give a dark oil. Purification by silica gel chromatography using 25-100 % ethyl acetate in hexanes as eluant gave 9.12 g of the title compound as an oil.
  • Step B Preparation of N-methyl-2-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl]-4-piperidinyl]-N-[(l/?)-l-phenylethyl]-4-thiazolecarboxamide
  • reaction mixture was then dissolved in 10 mL of acetonitrile, and 1.O mL of triethylamine was added. Meanwhile, a solution of 310 mg (1.49 mmol) of 5-methyl-3-(trifluoromethyl)-lH-pyrazole-l -acetic acid in 10 mL of acetonitrile was treated with 1.0 mL of a solution of 1-propanephosphonic acid cyclic anhydride (50 % in ethyl acetate), stirred at room temperature for 15 minutes, then combined with the above amine solution.
  • 1-propanephosphonic acid cyclic anhydride 50 % in ethyl acetate
  • the resulting formamide (4.54 g, 26 mmol) was dissolved in 50 mL of tetrahydrofuran and added dropwise to a suspension of lithium aluminum hydride (1.1 g, 29 mmol) in 20 mL of tetrahydrofuran that had been cooled to 0 °C.
  • the reaction mixture was refluxed overnight, then cooled to 0 °C and quenched by the sequential addition of 1.1 mL of water, 1.1 mL of
  • Step B Preparation of 1,1-dimethylethyl 4-[4-[(methyl[(lfl)-l,2,3,4-tetrahydro-l- naphthalenyl]amino]carbonyl]-2-thiazolyl]-l-piperidinecarboxylate
  • Step C Preparation of N-methyl-2-(4-piperidinyl)-N-[(l/?)-l,2,3,4-tetrahydro-l- naphthalenyl]-4-thiazolecarboxamide monohydrochloride 1,1-Dimethylethyl 4-[4-[(methyl[(l/?)-l,2,3,4-tetrahydro-l-naphthalenyl]amino]- carbonyl]-2-thiazolyl]-l-piperidinecarboxylate (i.e.
  • Step D General preparation of 2-[l-[(substituted-phenyl)acetyl]-4-piperidinyl]-//- methyl- ⁇ f-[(l/?)-l,2,3,4-tetrahydro-l-naphthalenyl]-4-thiazolecarboxamide and N-methyl-2- [ 1 - [ [substituted- lH-pyrazol- 1 -yl] acetyl] -4-piperi dinyl]-N- [(l/?)-l,2,3,4-tetrahydro-l-naphthalenyl]-4-thiazolecarboxamide A mixture of iV-methyl-2-(4-piperidinyl)-iV-[(li?)-l,2,3,4-tetrahydro-l-naphthalenyl]- 4-thiazolecarboxamide monohydrochloride (i.e.
  • reaction mixture was partitioned between 1 N aqueous hydrochloric acid and dichloromethane, and the organic layer was washed with 1 N aqueous hydrochloric acid, water and brine, dried over MgSC ⁇ and concentrated under reduced pressure to give 6.58 g of the title compound.
  • Step B Preparation of 1,1-dimethylethyl 4-[4,5-dihydro-4-(methoxycarbonyl)-2- oxazolyl]-l-piperidinecarboxylate
  • reaction mixture was stirred until homogeneous, and 4.59 g (29.87 mmol) of carbon tetrachloride was added dropwise over 5 minutes.
  • the reaction mixture was stirred for 2.5 h at room temperature, cooled to 0 °C and diluted with 170 mL of ethyl acetate followed by 50 mL of saturated aqueous sodium bicarbonate solution.
  • the mixture was stirred for 10 minutes, poured into 120 mL of water, and the organic layer was separated, washed with brine, dried over MgSC ⁇ and concentrated under reduced pressure to give a yellow oil.
  • the oil was purified by silica gel chromatography using 75-100 % ethyl acetate in hexanes as eluant to give 2.95 g of the title compound as an oil containing traces of triphenylphosphine.
  • Step C Preparation of 1,1-dimethylethyl 4-[4-(methoxycarbonyl)-2-oxazolyl]-l- piperidinecarboxylate To a solution of 1,1-dimethylethyl 4-[4,5-dihydro-4-(methoxycarbonyl)-2-oxazolyl]-l- piperidinecarboxylate (i.e.
  • Step D Preparation of l-(l,l-dimethylethyl) 4-(4-carboxy-2-oxazolyl)-l-piperidine- carboxylate
  • 1,1 -Dimethyl ethyl 4-[4-(methoxycarbonyl)-2-oxazolyl]-l-piperidinecarboxylate i.e. the product of Example 7, Step C
  • 1.41 g, 4.55 mmol was dissolved in 12 mL tetrahydrofuran, and 8 mL of water was added.
  • the reaction mixture was cooled to 0 °C with vigorous stirring.
  • a l N aqueous sodium hydroxide solution (9.1 mL) was added dropwise, and the reaction mixture was stirred at room temperature for 2 h.
  • the mixture was diluted with saturated sodium chloride solution (10 mL), 30 mL of diethyl ether was added and the aqueous phase was acidified to pH 3-4 by dropwise addition of 20 % citric acid solution. The precipitated solid was filtered and dried to give 1.21 g of the title compound.
  • Step E Preparation of 1,1-dimethylethyl 4-[4-[[methyl[(l/?)-l-phenylpropyl]amino]- carbonyl]-2-oxazolyl]-l-piperidinecarboxylate A mixture of l-(l,l-dimethylethyl) 4-(4-carboxy-2-oxazolyl)-l-piperidinecarboxylate
  • the reaction mixture was poured into 4 mL of 1 N aqueous hydrochloric acid, and the organic layer was washed with 1 N aqueous hydrochloric acid, water and brine, dried (MgSO 4 ) and concentrated under reduced pressure.
  • the residue was purified by silica gel chromatography using 25-75 % of ethyl acetate in hexanes as eluant to give 209 mg of the title compound as an oil.
  • Step F Preparation of N-methyl-2-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl]-4-piperidinyl]-N-[(l/?)-l-phenylpropyl]-4-oxazolecarboxamide 1,1-Dimethylethyl 4-[4-[[methyl[(l/?)-l-phenylpropyl]amino]carbonyl]-2-oxazolyl]-l- piperidinecarboxylate (i.e.
  • Step B Preparation of N-methyl-2-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl]-4-piperidinyl]-iV-[(17?)-l,2,3,4-tetrahydro-l-naphthalenyl]-4- oxazolecarboxamide 1,1-Dimethylethyl 4-[4-[[methyl[(l#)-l,2,3,4-tetrahydro-l-naphthalenyl]amino]- carbonyl]-2-oxazolyl]-l-piperidinecarboxylate (i.e.
  • Step A Preparation of methyl l-[(2,5-dimethylphenyl)acetyl]-4-piperidine- carboxylate
  • a solution of 2.86 g (20 mmol) of methyl isonipecotate and 2.53 g (2.5 mmol) of triethylamine in 10 mL of dry dichloromethane was cooled to 0 °C, and a solution of 4.02 g (22 mmol) of 2,5-dimethylphenylacetyl chloride in 5 mL of dichloromethane was added dropwise. The mixture was stirred at room temperature for 16 h and then poured into 20 mL of water.
  • Methyl l-[(2,5-dimethylphenyl)acetyl]-4-piperidinecarboxylate (i.e. the product of Example 9, Step A) (4.95 g, 17.1 mmol) was dissolved in 20 mL of tetrahydrofuran, and 15 mL of water was added. With vigorous stirring the reaction mixture was cooled to 0 °C, and 35 mL of a 1 N aqueous sodium hydroxide solution was added dropwise.
  • reaction mixture was stirred at room temperature for 1 h, diluted with 20 mL of brine, washed with diethyl ether (3 x 20 mL), and the aqueous phase was acidified with 1 N aqueous hydrochloric acid to pH 3-4. The precipitate was collected and dried to give 4.08 g of the title compound.
  • reaction mixture was stirred until homogeneous, and carbon tetrachloride (1.59 g, 10.32 mmol) was added dropwise over 5 minutes.
  • the reaction mixture was stirred for 2.5 h at room temperature, cooled to 0 °C and diluted with 50 mL of ethyl acetate followed by 15 mL of saturated aqueous sodium bicarbonate solution.
  • the mixture was stirred for 10 minutes, poured into 40 mL of water, and the organic layer was separated, washed with brine, dried over MgSC»4 and concentrated under reduced pressure to give 6 g of a yellow oil.
  • Step E Preparation of methyl 2-[l-[(2,5-dimethylphenyl)acetyl]-4-piperidinyl]-4- oxazolecarboxylate
  • methyl 2-[l-[(2,5-dimethylphenyl)acetyl]-4-piperidinyl]-4,5-dihydro- 4-oxazolecarboxylate i.e. the product of Example 9, Step D
  • l,8-diazabicyclo[5.4.0]undec-7-ene 508 mg, 3.34 mmol.
  • Methyl 2-[l-[(2,5-dimethylphenyl)acetyl]-4-piperidinyl]-4-oxazolecarboxylate i.e. the product of Example 9, Step E
  • 665 mg, 1.87 mmol was dissolved in 5 mL tetrahydrofuran, and 3.3 mL of water was added.
  • the reaction mixture was cooled to 0 0 C with vigorous stirring.
  • a l N aqueous sodium hydroxide solution (3.7 mL) was added dropwise, and the reaction mixture was stirred at room temperature for 2 h.
  • Step G Preparation of 2-[l-[(2,5-dimethylphenyl)acetyl]-4-piperidinyl]-N-methyl-iV-
  • Step E Preparation of ethyl 3,5-dichloro-lH-pyrazole-l-acetate A suspension of 3,5-dichloro-lH-pyrazole (690 mg, 5.0 mmol) (i.e. the product of
  • Step G Preparation of 2-[l-[(3,5-dichloro-lH-pyrazol-l-yl)acetyl]-4-piperidinyl]- ⁇ f- methyl-N-[(l/?)-l,2,3,4-tetrahydro-l-naphthalenyl]-4-thiazolecarboxamide
  • a solution of 3,5-dichloro-lH-pyrazol-l -acetic acid 70 mg, 0.36 mmol
  • Step B Preparation of 5-chloro-N,N-dimethyl-3-(trifluoromethyl)-lH-pyrazole-l- sulfonamide Under a nitrogen atmosphere, ⁇ f, ⁇ f-dirnethyl-3-(trifluoromethyl)-lH-pyrazole-l- sulfonamide (4.0 g, 16 mmol) (i.e. the product of Example 13, Step A) in tetrahydrofuran (25 mL) was cooled to -78 0 C was then treated with rc-butyllithium (2 M solution in cyclohexane, 8.6 mL, 17.2 mmol) dropwise.
  • Step F Preparation of 2-[l-[[5-chloro-3-(trifluoromethyl)-lH-pyrazol-l-yl]acetyl]-4- piperidinyl]-N-methyl-N-[(l/?)-l,2,3,4-tetrahydro-l-naphthalenyl]-4- thiazolecarboxamide
  • Step B Preparation of 2-[l-[[3,5-bis(trifluoromethyl)-lH-pyrazol-l-yl]acetyl]-4- piperidinyl]-N-methyl-iV-[(li?)-l,2,3,4-tetrahydro-l-naphthalenyl]-4- thiazolecarboxamide
  • reaction mixture was added to a stirred suspension of ⁇ f-methyl-2-(4-piperidinyl)-/V-[(l/?)-l,2,3,4- tetrahydro-l-naphthalenyl]-4-thiazolecarboxamide monohydrochloride (i.e. the product of Example 6, Step C) (210 mg, 0.53 mmol), triethylamine (0.5 mL, 3.75 mmol) in ethyl acetate (5 mL). The reaction mixture was then stirred at room temperature for 12 h. The resulting suspension was concentrated in vacuo and purified by MPLC on silica gel using ethyl acetate/hexanes as eluant to give 110 mg of the title product, a compound of the present invention, as an oil.
  • Step B Preparation of ethyl 3,5-diethyl-lH-pyrazole-l-acetate
  • Example 15 Step B) in tetrahydrofuran (10 mL) was treated with sodium hydroxide (1.0 g) in water (7.5 mL). The reaction mixture was then stirred at room temperature overnight. The reaction mixture was concentrated under reduced pressure and washed with diethyl ether.
  • Step D Preparation of 2-[l-[(3,5-diethyl-lH-pyrazol-l-yl)acetyl]-4-piperidinyl]-W- methyl-yV-[(l/?)-l,2,3,4-tetrahydro-l-naphthalenyl]-4-thiazolecarboxamide
  • a solution of 3,5-diethyl-lH-pyrazol-l-acetic acid (135mg, 0.74 mmol) (i.e.
  • Example 6 Step C) (210 mg, 0.53 mmol), triethylamine (0.5 mL, 3.75 mmol) in ethyl acetate (5 mL). The reaction mixture was then stirred at room temperature for 12 h. The resulting suspension was concentrated in vacuo and purified by MPLC on silica gel using ethyl acetate/hexanes as eluant to give 60 mg of the title product, a compound of the present invention, as an oil.
  • Step C Preparation of 5-ethyl-3-(trifluoromethyl)-lH-pyrazole-l -acetic acid
  • Ethyl 5-ethyl-3-(trifluoromethyl)-lH-pyrazole-l-acetate (1.34 g, 7.5 mmol) i.e. the product of Example 16, Step B
  • tetrahydrofuran 5 mL
  • sodium hydroxide 0.5 g
  • water 3.5 mL
  • the reaction mixture was then stirred at room temperature overnight.
  • the reaction mixture was concentrated under reduced pressure and washed with diethyl ether.
  • the resulting aqueous layer was acidified with concentrated hydrochloric acid to give a white precipitate.
  • the precipitate was filtered and dried in air to give 690 mg of the title compound.
  • Step D Preparation of 2-[l-[[5-ethyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]acetyl]-4- piperidinyl]-N-methyl-N-[(l/?)-l,2,3,4-tetrahydro-l-naphthalenyl]-4- thiazolecarboxamide
  • reaction mixture was added to a stirred suspension of iV-methyl-2-(4-piperidinyl)-iV-[(l/?)-l, 2,3,4- tetrahydro-l-naphthalenyl]-4-thiazolecarboxamide monohydrochloride (i.e. the product of Example 6 Step C) (219 mg, 0.56 mmol), triethylamine (0.5 mL, 3.75 mmol) in ethyl acetate (5 mL). The reaction mixture was then stirred at room temperature for 12 h. The resulting suspension was concentrated in vacuo and purified by silica gel MPLC using ethyl acetate/hexanes as eluant to give 200 mg of the title product, a compound of the present invention, as an oil.
  • Step C Preparation of ethyl l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl]-4-piperidinylcarboxylate
  • reaction mixture was poured in 50 mL of water, and the organic layer was subsequently washed with water, 1 M aqueous hydrochloric acid, water, saturated aqueous solution of sodium bicarbonate and brine.
  • the separated organic layers were dried (MgSO 4 ) and evaporated in vacuo to give 3.2 g of the title compound.
  • Step D Preparation of l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]acetyl]-4- piperidinylcarboxylic acid
  • Step E Preparation of N-[(15)-l-(hydroxymethyl)-2-[methyl[(l/?)-l,2,3,4-tetrahydro- l-naphthalenyl]amino]-2-oxoethyl]-l-[[5-methyl-3-(trifluoromethyl)-lH- pyrazol-l-yl]acetyl]-4-piperidinecarboxamide
  • Step F Preparation of 7V-methyl-2-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl]-4-piperidinyl]-N-[(li?)-l,2,3,4-tetrahydro-l-naphthalenyl]-4- oxazolinecarboxamide
  • Step B Preparation of 1,1-dimethylethyl 4-[3-(methoxycarbonyl)-lH-pyrazol-l-yl]-
  • Step E Preparation of l-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]acetyl]-4- piperidinyl]-lH-pyrazole-3-carboxylic acid
  • Step F Preparation of iV-methyl-l-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl]-4-piperidinyl]-iV-[(l/?)-l,2,3,4-tetrahydro-l-naphthalenyl]-lH- pyrazole-3-carboxamide
  • the crude product was purified by medium-pressure liquid chromatography on silica gel using 75-100 % of ethyl acetate in hexanes as eluant to give 55 mg of the title compound, a compound of the present invention, as an oil.
  • Step B Preparation of ethyl-2-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl]-4-piperidinyl]-4-thiazolecarboxylate 5-Methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]acetic acid (7.58 g, 36.4 mmol) (i.e. the product of Example 2, Step A) was dissolved in 100 mL of dichloromethane. To the reaction mixture, 1 drop of ⁇ f. ⁇ f-dimethylformamide was added and the reaction mixture was cooled to 0 °C.
  • Step C Preparation of 2-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]acetyl]-
  • reaction mixture was cooled again to 0 °C and treated with 1 N aqueous hydrochloric acid (36.3 mL, 36.3 mmol).
  • 1 N aqueous hydrochloric acid (36.3 mL, 36.3 mmol).
  • the resulting precipitate was filtered, washed with water and dried in a vacuum oven at 100 °C to give 10.95 g of the title compound as a white solid.
  • Step D Preparation of 2-[l-[[5-rnethyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]acetyl]- 4-piperidinyl]-4-thiazolecarbonyl chloride
  • Step E Preparation of N-[(l/?)-2,3-dihydro-lH-inden-l-yl]-N-methyl-2-[l-[[5- methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]acetyl]-4-piperidinyl]-4- thiazolecarboxamide 2-[l-[[5-Methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]acetyl]-4-piperidinyl]-4- thiazolecarbonyl chloride (210 mg, 0.5 mmol) (i.e.
  • the collected dichloromethane solution was evaporated in vacuo and purified by medium-pressure liquid chromatography on silica gel using 50-100 % of ethyl acetate in 1-chlorobutane as eluant to give 214 mg of the title compound, a compound of the present invention, as a white foam.
  • reaction mixture was stirred at room temperature for 16 h, diluted with 4 mL of dichloromethane, and washed with water, 1 N aqueous hydrochloric acid, water, saturated solution of sodium bicarbonate and brine.
  • the filtered reaction mixture was dried over magnesium sulfate and concentrated in vacuo to give 215 mg of the title compound, a compound of the present invention, as a white foam.
  • reaction mixture was stirred at room temperature for 16 h, diluted with 4 mL of dichloromethane, and washed with water, 1 N aqueous hydrochloric acid, water, saturated solution of sodium bicarbonate and brine.
  • the filtered reaction mixture was dried over magnesium sulfate and concentrated in vacuo to give 300 mg of the title compound, a compound of the present invention, as a white foam.
  • the crude product was purified by medium-pressure liquid chromatography on silica gel using 60-100 % of ethyl acetate in hexanes as eluant to give 242 mg of the title compound, a compound of the present invention, as white foam.
  • the reaction mixture was stirred at room temperature for 16 h, diluted with 2 mL of dichloromethane, and washed with water, 1 N aqueous hydrochloric acid, water, saturated solution of sodium bicarbonate and brine.
  • the filtered reaction mixture was dried over sodium sulfate and concentrated in vacuo.
  • the crude product was purified by medium-pressure liquid chromatography on silica gel using 60-100 % of ethyl acetate in hexanes as eluant to give 70 mg of the title compound, a compound of the present invention, as white foam.
  • the reaction mixture was stirred at room temperature for 16 h, poured into 100 mL of 1 M aqueous hydrochloric acid, and filtered.
  • the filtered aqueous layer was washed with dichloromethane, basified with NaOH pellets to p ⁇ 13, and then extracted with dichloromethane.
  • the extract was washed with brine, dried over magnesium sulfate and evaporated in vacuo to give a gummy yellow solid.
  • the solid was slurried in diethyl ether, filtered, washed with diethyl ether and air dried to give 2.15 g of the title compounds as white powder.
  • Step B Preparation of N-methyl-2-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl]-4-piperidinyl]-N-[(l ⁇ ,45)-l,2,3,4-tetrahydro-4-hydroxy-l- naphthalenyl]-4-thiazolecarboxamide and its enantiomer
  • the reaction mixture was stirred at room temperature for 1 h, diluted with dichloromethane, and washed with water, 1 N aqueous hydrochloric acid, water, saturated solution of sodium bicarbonate and brine.
  • the filtered reaction mixture was dried over magnesium sulfate and concentrated in vacuo.
  • the crude product was purified by medium-pressure liquid chromatography on silica gel using 0- 20 % of acetone in ethyl acetate as eluant to give 700 mg of the title compounds, compounds of the present invention, as an off-white powder.
  • reaction mixture was filtered through Celite® diatomaceous filter aid, and purified by medium-pressure liquid chromatography on silica gel using 20 % acetone in ethyl acetate as eluant to give 70 mg of the title compound, a compound of the present invention, as a white foam.
  • the resulting residue was diluted with diethyl ether and allowed to stand at room temperature for 16 h.
  • the precipitate formed was filtered, the filtrate was washed with saturated aqueous solution of sodium bicarbonate, dried over magnesium sulfate and concentrated under reduced pressure.
  • the reaction residue was diluted with diethyl ether and extracted with 1 N aqueous hydrochloric acid.
  • the aqueous extract was basified with 50 % aqueous solution of sodium hydroxide to p ⁇ 9 and immediately extracted with diethyl ether.
  • Step B Preparation of N-methyl-2-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl]-4-piperidinyl]-N-[(li?,4/?)-l,2,3,4-tetrahydro-4-hydroxy-l- naphthalenyl]-4-thiazolecarboxamide and its enantiomer
  • (l/?,4/?)-l,2,3,4-tetrahydro-4-(methylamino)-l-naphthalenol and its enantiomer 70 mg, 0.39 mmol
  • the filtered reaction mixture was dried over magnesium sulfate and concentrated in vacuo.
  • the crude product was purified by medium-pressure liquid chromatography on silica gel using 0-20 % of acetone in ethyl acetate as eluant to give 160 mg of the title compounds, compounds of the present invention, as a white foam.
  • Step A Preparation of 1,1-dimethylethyl 4-[4-(ethoxycarbonyl)-2-thiazolyl]-l- piperazinecarboxylate
  • 1,1 -Dimethyl ethyl 1 -piperazinecarboxylate (1.86 g, 10 mmol), methyl 2-chloro-5- thiazolecarboxylate (1.92 g, 10.0 mmol), diazabicycloundecene (1.5 mL, 10 mmol) and a catalytic amount of potassium iodide (2 mg) were dissolved in 10 mL of dry dimethyl sulfoxide and warmed to 80 0 C for 16 h. The warm solution was added dropwise with stirring to 200 mL of cold water. The reaction mixture was extracted with diethyl ether.
  • Step B Preparation of ethyl 2-(l-piperazinyl)-4-thiazolecarboxylate monohydrochloride
  • Step C Preparation of ethyl-2-[4-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl]-l-piperazinyl]-4-thiazolecarboxylate
  • Step D Preparation of 2-[4-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]acetyl]-l- piperazinyl]-4-thiazolecarboxylic acid
  • Step E Preparation of iV-methyl-2-[4-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl]-l-piperazinyl]-N-[(li?)-l,2,3,4-tetrahydro-l-naphthalenyl]-4- thiazolecarboxamide
  • Step A Preparation of 1,1-dimethylethyl 4-bromo-4-[4-(ethoxycarbonyl)-2- thiazolyl]-l-piperidinecarboxylate
  • reaction mixture was then cooled, filtered, concentrated in vacuo, and purified by medium-pressure liquid chromatography on silica gel using 0-20 % of ethyl acetate in 1-chlorobutane as eluant to give 1.9 g of the title compound as an oil.
  • Step D Preparation of ethyl 2-[l,2,3,6-tetrahydro-l-[[5-methyl-3-(trifluoromethyl)- lH-pyrazol-l-yl]acetyl]-4-pyridinyl]-4-thiazolecarboxylate 5-Methyl-3-(trifluoromethyl)-lH-pyrazole-l-acetyl chloride (1.05 g, 2.5 mmol)
  • the reaction mixture was diluted with dichloromethane, washed with 1 N aqueous hydrochloric acid, water, saturated aqueous solution of sodium bicarbonate and brine, and dried over magnesium sulfate. The filtered residue was evaporated in vacuo to give 1.0 g of a white foam.
  • the resulting foam was purified by medium-pressure liquid chromatography on silica gel eluting with 0-50 % ethyl acetate in 1-chlorobutane to give 0.67 g of the title compound as a yellow oil which solidified on standing.
  • the extract was dried over magnesium sulfate and concentrated in vacuo to give 0.61 g of a tan solid.
  • the resulting solid was dissolved in 25 mL of dichloromethane and treated with 0.5 mL of oxalyl chloride and 5 ⁇ L of TV.iV-dimethylformamide. The reaction mixture was stirred at room temperature for 3 h, and then concentrated in vacuo to give a tan foam.
  • Step A Preparation of 1,1-dimethylethyl 4-[4-(ethoxycarbonyl)-2H-l,2,3-triazol-2- yl]-l-piperidinecarboxylate
  • Step B Preparation of ethyl 2-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl]-4-piperidinyl]-2H-l,2,3-triazole-4-carboxylate
  • Trifluoroacetic acid (3 mL) was added to 1,1-dimethylethyl 4-[4-(ethoxycarbonyl)- 2H-l,2,3-triazol-2-yl]-l-piperidinecarboxylate (0.41 g, 1.3 mmol) (i.e. the product of Example 32, Step A).
  • the reaction mixture was stirred for 45 minutes.
  • the reaction mixture was then concentrated in vacuo.
  • the resulting mixture was treated with saturated aqueous sodium bicarbonate and the aqueous layer was extracted three times with dichloromethane.
  • reaction mixture was then added to a solution of ethyl 4-piperidinyl-2H-l,2,3-triazole-4-carboxylate (0.23 g) and triethylamine (0.20 mL, 1.4 mmol) in dichloromethane (10 mL) at 0 °C.
  • the reaction mixture was stirred at room temperature overnight.
  • the organic layer was washed with saturated aqueous sodium bicarbonate, dried (Na 2 SO 4 ) and the solvent was removed with a rotary evaporator.
  • the residue was purified by medium pressure liquid chromatography (MPLC) using 35 to 60 % ethyl acetate in hexanes as eluant to afford 0.35 g of the title compound as a white solid.
  • MPLC medium pressure liquid chromatography
  • the aqueous layer was washed with diethyl ether and the aqueous layer was acidified with concentrated hydrochloric acid to p ⁇ 1, and extracted with dichloromethane and then chloroform. The combined organic layers were dried (Na 2 SO 4 ) and concentrated in vacuo to afford 0.27 g of the title compound as a white solid.
  • Step D Preparation of N-methyl-2-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yI]acetyl]-4-piperidinyl]-N-[(lR)-l,2,3,4-tetrahydro-l-naphthalenyl]-2H- 1 ,2,3-triazole-4-carboxamide
  • Step B Preparation of ethyl l-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl]-4-piperidinyl]-lH-pyrazole-4-carboxylate
  • Step B Preparation of 1,1-dimethylethyl 4-[4-
  • This amine was reacted with the acid chloride formed from 5-methyl-3-(trifluoromethyl)-lH-pyrazole-l-acetic acid (0.18 g, 0.88 mmol) and oxalyl chloride (0.10 mL, 1.15 mmol) in the presence of triethylamine (0.16 mL, 1.15 mmol) to afford 0.24 g of the title compound as a white solid.
  • Step C Preparation of l-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]acetyl]-4- piperidinyl]-lH-pyrazole-4-carboxylic acid
  • Step D Preparation of N-methyl-l-[l-[[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl]-4-piperidinyl]-N-[(l/?)-l,2,3,4-tetrahydro-l-naphthalenyl]-lH- pyrazole-4-carboxamide
  • Step D l-[l-[[5-methyl-3-
  • Tables IA to 10 list specific compounds of Formula 1 useful in the fungicidal mixtures, compositions and methods of the present invention. These compounds are to be construed as illustrative and not limiting of the disclosure in any way. The following abbreviations are used in the Tables which follow: n means normal, i means iso, c means cyclo, t means tertiary, s means secondary, Ac means acetyl, Me means methyl, Et means ethyl, Pr means propyl, i-Pr means isopropyl, c-Pr means cyclopropyl, Bu means butyl, Pen means pentyl, Hex means hexyl, and CN means cyano. A dash (-) indicates no substituents.
  • the invention includes but is not limited to the following exemplary species of component (a) compounds.

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Abstract

La présente invention concerne une composition fongicide comprenant (a) au moins un composé choisi parmi les composés N-oxydes de formule 1, et des sels de ceux-ci, (insérer la formule 1 ici) R1, R2, A, G, Q, W1, W2, X et n étant autrement tels que définis dans la description, et (b) au moins un composé fongicide supplémentaire. L'invention concerne également un procédé pour contrôler les maladies des plantes causées par des pathogènes de plantes de type fongique comprenant l'application à la plante ou à une partie de celle-ci, ou à la graine de la plante, d'une quantité efficace sur le plan fongique de la composition précédemment citée.
PCT/US2008/000813 2007-01-24 2008-01-18 Mélanges fongicides WO2008091594A2 (fr)

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