EP0836384A1 - Arthropodicidal and fungicidal cyclic amides - Google Patents

Arthropodicidal and fungicidal cyclic amides

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Publication number
EP0836384A1
EP0836384A1 EP96919422A EP96919422A EP0836384A1 EP 0836384 A1 EP0836384 A1 EP 0836384A1 EP 96919422 A EP96919422 A EP 96919422A EP 96919422 A EP96919422 A EP 96919422A EP 0836384 A1 EP0836384 A1 EP 0836384A1
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EP
European Patent Office
Prior art keywords
alkyl
chr
haloalkyl
alkoxy
optionally substituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96919422A
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German (de)
French (fr)
Inventor
Richard James Brown
Dominic Ming-Tak Chan
Michael Henry Howard, Jr.
Dilon Jancey Daniel
David Alan Clark
Thomas Paul Selby
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication of EP0836384A1 publication Critical patent/EP0836384A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • 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
    • A01N43/80—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 1,2
    • 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
    • A01N43/82—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 three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • This invention relates to certain cyclic amides, their N-oxides, agriculturally suitable salts and compositions, and methods of their use as fungicides and arthropodicides.
  • the control of plant diseases caused by fungal plant pathogens is extremely important in achieving high crop efficiency. Plant disease damage to ornamental, vegetable, field, cereal, and fruit crops can cause significant reduction in productivity and thereby result in increased costs to the consumers.
  • the control of arthropod pests is also extremely important in achieving high crop efficiency. Arthropod damage to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer.
  • the control of arthropod pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.
  • WO 95/14009 discloses cyclic amides of Formula i as fungicides:
  • A is O; S; ⁇ ; ⁇ R 5 ; or CR 14 ;
  • G is C or ⁇ ; provided that when G is C, A is O, S or ⁇ R 5 and the floating double bond is attached to G; and when G is ⁇ , A is ⁇ or CR 14 and the floating double bond is attached to A;
  • W is O or S
  • X is OR 1 ; S ⁇ rnR 1 ; or halogen
  • R 1 , R 2 , and R 5 are each independently, in part, H or C ⁇ -C 6 alkyl; R 3 and R 4 are each independently, in part, H; halogen; cyano; nitro; Ci-Cg alkyl;
  • R 7 is, in part, H; C j -Cg alkyl; haloalkyl; or C j -C 6 alkoxy;
  • Z is, in part, an optionally substituted phenyl, 3 to 14-membered nonaromatic heterocyclic ring system or 5 to 14-membered aromatic heterocyclic ring system;
  • R 14 is H; halogen; C r C 6 alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl;
  • This publication does not disclose use of the compounds as arthropodicides. Furthermore, this publication does not disclose compounds where the optional substituents on Z are themselves substituted with C2-Cg alkenyl, C2-Cg haloalkenyl, C 2 -C 6 alkynyl, C 2 -Cg haloalkynyl, C3-C6 alkenyloxy, C3-C6 haloalkenyloxy, C1-C 4 alkylthio, C1-C4 haloalkylthio, C1-C4 alkylsulfinyl, C1-C 4 haloalkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C3-C6 alkenylthio, C3-C6 haloalkenylthio, or SF 5 .
  • E is selected from: i) 1,2-phenylene optionally substituted with one of R 3 , R 4 , or both R 3 and
  • A is O; S; N; NR 5 ; or CR 14 ;
  • G is C or N; provided that when G is C, then A is O, S or NR 5 and the floating double bond is attached to G; and when G is N, then A is N or CR 1 and the floating double bond is attached to A;
  • W is O; S; NH; N(C r C 6 alkyl); or NO(C r C 6 alkyl);
  • X is H; OR 1 ; SCO ⁇ R 1 ; halogen; C r C 6 alkyl; C r C 6 haloalkyl; C 3 -C 6 cycloalkyl; cyano; NH 2 ; NHR 1 ; N(C r C 6 alkyfjR 1 ; NH(C r C 6 alkoxy); or N(C 1 -C 6 alkoxy)R 1 ; R 1 is C r C 6 alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; ⁇ -C ⁇ haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; or C 2 -C alkoxycarbonyl;
  • R 2 is H; C r C 6 alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; C2-Cg haloalkynyl; ⁇ -C 6 cycloalkyl; C 2 -C 4 alkylcarbonyl; C 2 -C 4 alkoxycarbonyl; hydroxy; C1-C2 alkoxy; or acetyloxy;
  • R 3 and R 4 are each independently halogen; cyano; nitro; hydroxy; Ci-Cg alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; C 2 -C 6 haloalkynyl; C Cg alkoxy; Ci-Cg haloalkoxy; C 2 -C6 alkenyloxy; C 2 -C6 alkynyloxy; C Cg alkylthio; C1-C6 alkylsulfinyl; Ci-Cg alkylsulfonyl; formyl; C 2 -C 6 alkylcarbonyl; C 2 -C 6 alkoxycarbonyl; NH 2 C(O);
  • R 5 is H; C r C 6 alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; C 2 -C 6 haloalkynyl; C 3 -C 6 cycloalkyl; C 2 -C alkylcarbonyl; or C -C alkoxycarbonyl;
  • -CR 6 CR 6 -; -C ⁇ C-; -CHR 5 O-; -OCHR 15 -; -CHR 15 S(O) n -; -S(O) n CHR 15 -;
  • Y linkage is defined such that the moiety depicted on the left side of the linkage is bonded to E and the moiety on the right side of the linkage is bonded to Z;
  • Z 1 is H or -A 3 -Z; WUs O or S;
  • a 1 is O; S; NR 15 ; or a direct bond;
  • a 2 is O; NR 15 ; or a direct bond;
  • N(C r C 6 alkyl) 2 cyano; nitro; SiR 19 R 20 R 21 ; or GeR 19 R 20 R 21 ;
  • R 9 is H; 1-2 halogen; C r C 6 alkyl; C r C 6 haloalkyl; C r C 6 alkoxy; C r C 6 haloalkoxy; C 2 -C6 alkenyl; C 2 -C6 haloalkenyl; C 2 -Cg alkynyl; Ci-Cg alkylthio; C r C 6 haloalkylthio; C r C 6 alkylsulfinyl; C ⁇ -C 6 alkylsulfonyl;
  • N(C r C 6 alkyl) 2 ; -C(R 18 ) NOR 17 ; cyano; nitro; SF 5 ; SiR 22 R 23 R 24 ; or
  • R 9 is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R 1 J , R 12 , or both R 1 1 and R 12 ; each R 10 is independently halogen; C1-C4 alkyl; C ⁇ -C haloalkyl; C ⁇ -C 4 alkoxy; nitro; or cyano; or when R 9 and an R 10 are attached to adjacent atoms on Z, R 9 and said adjacently attached R 10 can be taken together as -OCH 2 O- or -OCH 2 CH 2 O-; each CH 2 group of said taken together R 9 and R 10 optionally substituted with 1-2 halogen; or when Y and an R 10 are attached to adjacent atoms on Z and Y is
  • R 7 and said adjacently attached R 10 can be taken together as -(CH ) r -J- such that J is attached to Z; J is -CH 2 -; -CH 2 CH 2 -; -OCH 2 -; -CH 2 O-; -SCH 2 -; -CH 2 S-; -N(R 16 )CH 2 -; or
  • R 11 and R 12 are each independently 1-2 halogen; C ⁇ -C alkyl; C r C haloalkyl;
  • each R 15 is independently H; C j -C3 alkyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C1-C4 alkyl,
  • R 16 , R 17 , and R 18 are each independently H; C r C 3 alkyl; C 3 -C 6 cycloalkyl; or phenyl optionally substituted with halogen, C1-C4 alkyl, C1-C 4 haloalkyl,
  • R 19 , R 2 0, R 2 1, R 22 , R 23 , and R 24 are each independently C r C 6 alkyl; C 2 -C 6 alkenyl; C 1 -C4 alkoxy; or phenyl; each R 25 is independently C j -C 4 alkyl; C j -C 4 haloalkyl; C 2 -C 4 alkenyl; C ] -C 4 alkoxy; or phenyl; each R 26 is independently H; C r C 6 alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -Cg alkynyl; C 2 -C6 haloalkynyl; C3- cycloalkyl; or phenyl or benzyl, each optionally substituted on the
  • This invention provides a method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound of Formula I including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, provided that:
  • E 1,2-phenylene optionally substituted with one of R 3 , R 4 , or both R 3 and R 4 ;
  • X is OR 1 , SCOmR 1 or halogen;
  • R 9 is SiR 22 R 23 R 24 or GeR 22 R 23 R 24 ; then Z is other than phenyl or a 5 to 14-membered aromatic heterocyclic ring system each substituted with R 9 and optionally substituted with one or more R 10 ;
  • This invention also provides selected compounds of Formula I which are considered particularly effective fungicides and arthropodicides.
  • this invention provides compounds of Formula IA including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, and agricultural compositions containing them and their use as fungicides and arthropodicides:
  • E is 1,2-phenylene optionally substituted with one of R 3 , R 4 , or both R 3 and R 4 ;
  • A is O or N;
  • G is C or N; provided that when G is C, then A is O and the floating double bond is attached to G; and when G is N, then A is N and the floating double bond is attached to A;
  • W is O;
  • X is OR 1 ;
  • R 1 is C1-C3 alkyl;
  • R 2 is H or C r C 2 alkyl
  • R 3 and R 4 are each independently halogen; cyano; nitro; Ci-Cg alkyl; Cj-Cg haloalkyl; C j -Cg alkoxy; or C ⁇ -C 6 haloalkoxy; C r C 6 alkylsulfonyl; C 2 -C6 alkylcarbonyl; C 2 -C 6 alkoxycarbonyl; (C r C 4 alkyl)NHC(O); (C1-C4 alkyl) 2 NC(O); benzoyl; or phenylsulfonyl;
  • Z is selected from the group 2-thiazolyl; 1,2,4-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,4-thiadiazolyl; 1,3,4-thiadiazolyl; and pyrazinyl; each group substituted with R 9 and optionally substituted with one or more R 10 ;
  • R 9 is H; halogen; C r C 6 alkyl; C r C 6 haloalkyl; C r C 6 alkoxy; C ⁇ -C 6 haloalkoxy; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; C r C 6 alkylthio; C r C 6 haloalkylthio; C j -Cg alkylsulfinyl; C j -Cg alkylsulfonyl; C3-C6 cycloalkyl; C 3 -C 6 alkenyloxy
  • R 17 and R 18 are each independently H; C1-C3 alkyl; C3 ⁇ C 6 cycloalkyl; or phenyl optionally substituted with halogen, C r C 4 alkyl, C r C 4 haloalkyl, C1-C 4 alkoxy, C -C4 haloalkoxy, nitro or cyano;
  • R 22 , R 23 , and R 24 are each independently C r C 6 alkyl; C 2 -C 6 alkenyl; C1-C4 alkoxy; or phenyl; each R 25 is independently C r C alkyl; C1-C4 haloalkyl; C 2 -C 4 alkenyl; C C 4 alkoxy; or phenyl; each R 26 is independently H; C r C 6 alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 al
  • This invention also provides certain compounds of Formula I which are useful as fungicides and arthropodicides.
  • this invention provides compounds of Formula IB including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, and agricultural compositions containing them and their use as fungicides and arthropodicides:
  • E is selected from: i) 1,2-phenylene optionally substituted with one of R 3 , R 4 , or both R 3 and R 4 ; ii) a naphthalene ring, provided that when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, the naphthalene ring optionally substituted with one of R 3 , R 4 , or both R 3 and R 4 ; and iii) a ring system selected from 5 to 12-membered monocyclic and fused bicyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each fused bicyclic ring system optionally containing one nonaromatic ring that optionally includes one or two Q as ring members and optionally includes one or two ring members independently selected from C
  • G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, each aromatic heterocyclic ring system optionally substituted with one of R 3 , R 4 , or both R 3 and R 4 ;
  • A is O; S; N; NR 5 ; or CR 14 ;
  • G is C or N; provided that when G is C, then A is O, S or NR 5 and the floating double bond is attached to G; and when G is N, then A is N or CR 14 and the floating double bond is attached to A; W is O; S; NH; N(C r C 6 alkyl); or NO(C r C 6 alkyl);
  • X is H; OR 1 ; SCO ⁇ R 1 ; halogen; C r C 6 alkyl; C r C 6 haloalkyl; C 3 -C 6 cycloalkyl; cyano; NH 2 ; NHR 1 ; N(C r C 6 alkyl)!* 1 ; NH(C r C 6 alkoxy); or
  • R 1 is C r C 6 alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; C -C 6 haloalkynyl; C 3 -C 6 cycloalkyl; C 2 -C alkylcarbonyl; or C 2 -C alkoxycarbonyl;
  • R 2 is H; C r C 6 alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; C 2 -Cg haloalkynyl; C 3 -C 6 cycloalkyl; C 2 -C 4 alkylcarbonyl; C -C 4 alkoxycarbonyl; hydroxy; C ⁇ -C alkoxy; or acetyloxy; R 3 and R 4 are each independently halogen; cyano; nitro; hydroxy; C ⁇ -C 6 alkyl; C 2 -C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; C 2 -C 6 haloalkynyl; C ⁇ -C 6 alkoxy; C r C 6 haloalkoxy; C 2
  • W 1 is O or S
  • a 1 is O; S; NR 15 ; or a direct bond
  • a 2 is O; NR 15 ; or a direct bond
  • each R 6 is independently H; 1-2 CH 3 ; C 2 -C 3 alkyl; C r C 3 alkoxy; C 3 -C 6 cycloalkyl; formylamino; C 2 -C 4 alkylcarbonylamino; C -C 4 alkoxycarbonylamino; NH 2 C(O)NH; (C r C 3 alkyl)NHC(O)NH;
  • each R 7 is independently H; C r C 6 alkyl; C r C 6 haloalkyl; C r C 6 alkoxy; C r C 6 haloalkoxy; C ⁇ -C 6 alkylthio; C r C 6 alkylsulfinyl; C r C 6 alkylsulfonyl; C r C 6 haloalkylthio; Cj-Cg haloalkylsulfinyl; C r C 6 haloalkylsulfonyl; C 2 -C 6 alkenyl; C 2 -Cg haloalkenyl; C 2 -C6 alkynyl; C -C 6 haloalkynyl; C3 ⁇ C 6 cycloalkyl; C -C alkylcarbonyl; C 2 -C4 alkoxycarbonyl; halogen; cyano; nitro; hydroxy;
  • each Q is independently selected from the group -CHR 13 -, -NR 13 -, -O-, and
  • R 8 is H; 1-2 halogen; C r C 6 alkyl; C r C 6 haloalkyl; C r C 6 alkoxy; C r C 6 haloalkoxy; C 2 -Cg alkenyl; C 2 -C 6 haloalkenyl; C 2 - alkynyl; Ci-Cg alkylthio; Ci-Cg haloalkylthio; Ci-Cg alkylsulfinyl; Ci-Cg alkylsulfonyl; C 3 -C 6 cycloalkyl; C 3 -C 6 alkenyloxy; CO 2 (C r C 6 alkyl); NH(C r C 6 alkyl);
  • R 9 is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy each substituted with R 1 1 and optionally substituted with R 12 ; each R 10 is independently halogen; Cj-C alkyl; C1-C4 haloalkyl; C1-C4 alkoxy; nitro; or cyano; or when R 9 and an R 10 are attached to adjacent atoms on Z, R 9 and said adjacently attached R 10 can be taken together as -OCH 2 O- or -OCH 2 CH 2 O-; each CH 2 group of said taken together R 9 and R 10 optionally substituted with 1-2 halogen; or when Y and an R 10
  • R 7 and said adjacently attached R 10 can be taken together as -(CH 2 ) r -J- such that J is attached to Z; J is -CH 2 -; -CH 2 CH 2 -; -OCH 2 -; -CH 2 O-; -SCH 2 -; -CH 2 S-; -N(R 16 )CH 2 -; or
  • R 11 is C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; C 2 -C 6 haloalkynyl; C 2 -C 6 alkoxyalkyl; C 2 -C 6 alkyl thioalkyl; C 3 -C 6 alkoxy alkynyl; C7-C10 tetrahydropyranyloxyalkynyl; benzyloxymethyl; C3-C 6 alkenyloxy; C 3 -C 6 haloalkenyloxy; C3-C6 alkynyloxy; C3-C6 haloalkynyloxy; C 2 -C 6 alkoxyalkoxy; C5-C9 trialkylsilylalkoxyalkoxy; C 2 -Cg alkylthioalk
  • R 12 is 1-2 halogen; C r C 4 alkyl; C r C 4 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -Cg alkynyl; C2-C 6 haloalkynyl; C 2 -C 6 alkoxyalkyl; C 2 -C 6 alkylthioalkyl; C 3 -C
  • each R 15 is independently H; -C3 alkyl; C 3 -C 6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C r C 4 alkyl,
  • R 16 is H; C j -C 3 alkyl; C 3 -C 6 cycloalkyl; or phenyl optionally substituted with halogen, C r C 4 alkyl, C r C haloalkyl, C1-C4 alkoxy, C
  • R 19 , R 20 , and R 21 are each independently C r C 6 alkyl; C 2 -C 6 alkenyl; C r C 4 alkoxy; or phenyl; each R 25 is independently C r C 4 alkyl; C r C 4 haloalkyl; C 2 -C 4 alkenyl; C r C 4 alkoxy; or phenyl; each R 26 is independently H; C r C 6 alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; C 2 -C 6 haloalkynyl; C 3 -C 6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C--C 4 alkyl, C1-C4 haloalkyl, CpC 4 alkoxy, C
  • E is 1,2-phenylene optionally substituted with one of R 3 , R 4 , or both R 3 and R 4 ;
  • A is O; S; N; NR 5 ; or CR 14 ;
  • G is C or N; provided that when G is C, then A is O, S or NR 5 and the floating double bond is attached to G; and when G is N, then A is N or CR 14 and the floating double bond is attached to A;
  • W is O; S; NH; N(C r C 6 alkyl); or NO(C r C 6 alkyl);
  • X is OR 1 ; SCO ⁇ R 1 ; or halogen
  • R 1 is C r C 6 alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; C 2 -C6 haloalkynyl; C3-C 6 cycloalkyl; C 2 -C 4 alkylcarbonyl; or C 2 -C 4 alkoxycarbonyl;
  • R 2 is H; C r C 6 alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; 2 -C ⁇ haloalkynyl; C3-C6 cycloalkyl; C 2 -C 4 alkylcarbonyl; C 2 -C 4 alkoxycarbonyl; hydroxy; C*-C 2 alkoxy; or acetyloxy; R 3 and R 4 are each independently halogen; cyano; nitro; hydroxy; C*-C 6 alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; C 2 -C 6 haloalkynyl; C j -Cg alkoxy; C r C 6 haloalkoxy; C
  • N(C r C 6 alkyl) 2 cyano; nitro; SiR 19 R ⁇ R 21 ; or GeR 19 R 2 ⁇ R2 l ; each R 10 is independently halogen; C C alkyl; C1-C4 haloalkyl; C r C 4 alkoxy; nitro; or cyano;
  • R 14 is H; halogen; C r C 6 alkyl; C r C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl; C 2 -C 6 alkynyl; C 2 -C 6 haloalkynyl; or C 3 -C 6 cycloalkyl;
  • R 19 , R 20 and R 21 are each independently C r C 6 alkyl; C 2 -C 6 alkenyl; C r C 4 alkoxy; or phenyl; each R 25 is independently C1-C4 alkyl; C1-C4 haloalkyl; C 2 -C 4 alkenyl; C1-C4 alkoxy; or phenyl; and m is 0, 1 or 2.
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, .-propyl, or the different butyl, pentyl or hexyl isomers.
  • 1-2 CH3 indicates that the substituent can be methyl or, when there is a hydrogen attached to the same atom, the substituent and said hydrogen can both be methyl.
  • Alkenyl includes straight-chain or branched alkenes such as vinyl, 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 alkanediyl. Examples of “alkylene” include CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 CH 2 .
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkoxyalkoxy denotes alkoxy substitution on alkoxy.
  • Alkenyloxy includes straight-chain or branched alkenyloxy moieties.
  • alkynyloxy includes straight-chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HC ⁇ CCH 2 O, CH 3 OCCH 2 O and CH 3 C ⁇ CCH 2 CH 2 O.
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylfhio, butylthio, pentylthio and hexylthio isomers.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 .
  • Alkylthioalkylthio denotes alkylthio substitution on alkylthio.
  • alkylthioalkoxy denotes alkylthio substitution on alkoxy.
  • Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group. Examples of “alkylsulfinyl” include CH 3 S(O), CH 3 CH 2 S(O), CH 3 CH 2 CH 2 S(O), (CH 3 ) 2 CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers.
  • alkylsulfonyl examples include CH3S(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.
  • Alkenylthio is defined analogously to the above examples.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • Cycloalkenyl includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- and 1,4-cyclohexadienyl.
  • Trialkylsilylalkoxyalkoxy denotes trialkylsilylalkoxy substitution on alkoxy. Examples of “trialkylsilylalkoxyalkoxy” includes, for example,
  • aromatic carbocyclic ring system includes fully aromatic carbocycles and carbocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied).
  • nonaromatic carbocyclic ring system denotes fully saturated carbocycles as well as partially or fully unsaturated carbocycles where the H ⁇ ckel rule is not satisfied by any of the rings in the ring system.
  • aromatic heterocyclic ring system includes fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied .
  • nonaromatic heterocyclic ring system denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles where the H ⁇ ckel rule is not satisfied by any of the rings in the ring system.
  • the heterocyclic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides .
  • 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.
  • alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • haloalkenyl “haloalkynyl", “haloalkoxy”, and the like, are defined analogously to the term “haloalkyl”.
  • 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 CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 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 .
  • the total number of carbon atoms in a substituent group is indicated by the "C--Cj" prefix where i and j are numbers from 1 to 10.
  • C1-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl.
  • alkylcarbonyl examples include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • stereoisomers 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 present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • the salts of the compounds of the invention include acid- addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • the salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a phenol.
  • organic bases e.g., pyridine, ammonia, or triethylamine
  • inorganic bases e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium
  • Preferred methods for reasons of better activity and/or ease of synthesis are: Preferred 1. Methods for controlling arthropods using compounds of Formula I above, and N-oxides and agriculturally suitable salts thereof, wherein:
  • E is selected from the group 1,2-phenylene; 1,5-, 1,6-, 1,7-, 1,8-, 2,6-, 2,7-, 1,2-, and 2,3-naphthalenediyl; lH-pyrrole-1,2-, 2,3- and 3,4-diyl; 2,3- and 3,4-furandiyl; 2,3- and 3,4-thiophenediyl; lH-pyrazole-1,5-, 3,4- and 4,5-diyl; lH-imidazole-1,2-, 4,5- and 1,5-diyl; 3,4- and 4,5-isoxazolediyl; 4,5-oxazolediyl; 3,4- and
  • each aromatic ring system optionally substituted with one of R 3 , R 4 , or both R 3 and R 4 ;
  • W is O;
  • R 1 is C1-C3 alkyl or C r C 3 haloalkyl
  • 5 R 2 is H; C r C 6 alkyl; C r C 6 haloalkyl; or C 3 -C 6 cycloalkyl;
  • R 3 and R 4 are each independently halogen; cyano; nitro; Ci-Cg alkyl;
  • -CH CH-; -C ⁇ C-; -CH 2 O-; -OCH 2 -; -CH 2 S(O) n -; -S(O) n CH 2 -;
  • R 7 is H; C r C 6 alkyl; C r C 6 haloalkyl; C r C 6 alkoxy; C r C 6 alkylthio;
  • R 7 and said adjacently attached R 10 can be taken 20 together as -(CH 2 ) r -J- such that J is attached to Z;
  • Z is selected from the group C ⁇ -C 10 alkyl; C 3 -Cg cycloalkyl; phenyl; naphthalenyl; anthracenyl; phenanthrenyl; lH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; lH-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; lH-l,2,3-triazolyl; 2H-l,2,3-triazolyl; 25 1H- 1 ,2,4-triazolyl; 4H- 1 ,2,4-triazolyl; 1 ,2,3-oxadiazolyl;
  • 1,3,4-thiadiazolyl lH-tetrazolyl; 2H-tetrazolyl; pyridinyl; pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4-triazinyl; 30 1,2,4,5-tetrazinyl; lH-indolyl; benzofuranyl; benzo[ ?]thiophenyl; lH-indazolyl; lH-benzimidazolyl; benzoxazolyl; benzothiazolyl; quinolinyl; isoquinolinyl; cinnolinyl; phthalazinyl; quinazolinyl; quinoxalinyl; 1,8-naphthyridinyl; pteridinyl; 2,3-dihydro-lH-indenyl;
  • E is selected from the group 1,2-phenylene; 1,6-, 1,7-, 1,2-, and 2,3-naphfhalenediyl; 2,3- and 3,4-furandiyl; 2,3- and
  • Z is selected from the group phenyl; naphthalenyl; 2-thiazolyl;
  • R 7 is ⁇ ; C r C 6 alkyl; C r C 6 haloalkyl; C r C 6 alkoxy; C r C 6 alkylthio;
  • E is 1 ,2-phenylene optionally substituted with one of R 3 , R 4 , or both R 3 and R 4 ;
  • A is O or N;
  • X is OR 1 ;
  • R 1 is C ⁇ -C 3 alkyl
  • R 2 is H or C r C2 alkyl
  • -CH CH-; -C ⁇ C-; -CH 2 O-; -OCH 2 -; -CH 2 S(O) n -; -S(O) n CH 2 -; or a direct bond;
  • Z is selected from the group 2-thiazolyl; 1,2,4-oxadiazolyl;
  • Z is selected from the group 2-thiazolyl; 1,2,4-oxadiazolyl; and
  • Y is -O-
  • R 9 is phenyl optionally substituted with one of R 11 , R 12 , or both R 1 1 and R 12 .
  • Most preferred are methods of Preferred 5 where the compound is selected from the group:
  • SiR 22 R 23 R 24 ; or GeR 22 R 23 R 24 ; or R 9 is phenyl, benzyl, phenoxy, pyridinyl, thienyl, furanyl, or pyrimidinyl each optionally substituted with one of R 11 , R 12 , or both R 11 and R 12 .
  • Preferred 2A Compounds of Preferred IA wherein:
  • Z is selected from the group 2-thiazolyl; 1,2,4-oxadiazolyl;
  • Y is -O-
  • R 9 is phenyl optionally substituted with one of R 11 , R 12 , or both R 11 and R 12 .
  • Preferred IA selected from the group: 4-[2-[[3-[3,5-bis(trifluoromethyl)phenyl]-l,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4- dihydro-5-methoxy-2-methyl-3H- 1 ,2,4-triazol-3-one; 4-[2-[[3-[3,5-bis(trifluoromethyl)phenyl]-l,2,4-thiadiazol-5-yl]oxy]-6- methylphenyl]-2,4-dihydro-5-methoxy-2-methyl-3H-l,2,4-triazol-3-one; 4-[2-[[3-( 1 , 1 -dimethylethyl)- 1 ,2,4-thiadiazol-5-yl]oxy]-6-methylphenyl]-2,4- dihydro-5-methoxy
  • This invention also relates to fungicidal compositions comprising fungicidally effective amounts of the compounds of Formula IA and at least one of a surfactant, a solid diluent or a liquid diluent.
  • a surfactant a solid diluent or a liquid diluent.
  • the preferred compositions of the present invention are those which comprise the above preferred compounds of Formula IA.
  • 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 seedling, a fungicidally effective amount of the compounds of Formula IA and the compositions described herein.
  • the preferred methods of use are those involving the above preferred compounds of Formula IA.
  • This invention also relates to arthropodicidal compositions comprising arthropodicidally effective amounts of the compounds of Formula IA and at least one of a surfactant, a solid diluent or a liquid diluent.
  • the preferred compositions of the present invention are those which comprise the above preferred compounds of Formula IA.
  • This invention also relates to a method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of the compounds of Formula IA and the compositions described herein.
  • the preferred methods of use are those involving the above preferred compounds of Formula IA.
  • Preferred compounds of Formula IB for reasons of better fungicidal or arthropodicidal activity and/or ease of synthesis are:
  • W is O
  • R 1 is C ⁇ -C 3 alkyl or C r C 3 haloalkyl
  • R 2 is ⁇ ; C r Cg alkyl; C r C 6 haloalkyl; or C 3 -C 6 cycloalkyl;
  • R 3 and R 4 are each independently halogen; cyano; nitro; Cj-C alkyl; 20 C r C 6 haloalkyl; C r C 6 alkoxy; C r C 6 haloalkoxy; C r C 6 alkylthio;
  • Ci-Cg alkylsulfonyl C 2 -Cg alkylcarbonyl; C2-C alkoxycarbonyl; (C r C 4 alkyl)N ⁇ C(O); (C r C 4 alkyl) 2 NC(O); benzoyl; or phenylsulfonyl;
  • R 7 is H; C r C 6 alkyl; C r C 6 haloalkyl; C r C 6 alkoxy; C r C 6 alkylthio; C2-Cg alkenyl; C 2 -Cg alkynyl; C 3 -Cg cycloalkyl; halogen; or cyano; 30 or when Y and an R 10 are attached to adjacent atoms on Z and Y is
  • R 7 and said adjacently attached R 10 can be taken together as -(CH 2 ) r -J- such that J is attached to Z;
  • Z is selected from the group C r C 10 alkyl; C 3 -C 8 cycloalkyl; phenyl; 35 naphthalenyl; anthracenyl; phenanthrenyl; lH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; lH-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; lH-l,2,3-triazolyl; 2H-l,2,3-triazolyl; lH-l,2,4-triazolyl; 4H-l,2,4-triazolyl; 1,2,3-oxadiazolyl;
  • E is selected from the group 1,2-phenylene; 1,6-, 1,7-, 1,2-, and
  • Preferred 3B Compounds of Preferred 2B wherein: E is 1,2-phenylene optionally substituted with one of R 3 , R 4 , or both R 3 and R 4 ; A is O or N; X is OR 1 ; R 1 is C1-C3 alkyl; R 2 is H or C r C 2 alkyl;
  • -CH CH-; -C ⁇ C-; -CH 2 O-; -OCH 2 -; -CH 2 S(O) n -; -S(O) n CH 2 -; or a direct bond;
  • Z is selected from the group 2-thiazolyl; 1,2,4-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,4-thiadiazolyl; and 1,3,4-thiadiazolyl; each group substituted with R 9 and optionally substituted with R 10 ; and R 15 is H; C!-C 3 alkyl; or cyclopropyl.
  • Preferred 4B Compounds of Preferred 3B wherein: R 1 is methyl; R 2 is methyl;
  • Preferred 5B Compounds of Preferred 4B wherein:
  • Z is selected from the group 2-thiazolyl; 1,2,4-oxadiazolyl; and
  • R 9 is phenyl substituted with R 1 1 and optionally substituted with R 12 .
  • Most preferred are compounds of Preferred 5B selected from the group: 4-[2-[[3-(3-ethynylphenyl)-l,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4-dihydro-5- methoxy-2-methyl-3H- 1 ,2,4-triazol-3-one; and [3-[5-[2-(l ,5-dihydro-3-methoxy- l-methyl-5-oxo-4H- 1 ,2,4-triazol-4- yl)phenoxy]- 1 ,2,4-thiadiazol-3-yl]phenyl] trifluoromethanesulfonate.
  • This invention also relates to fungicidal compositions comprising fungicidally effective amounts of the compounds of Formula IB and at least one of a surfactant, a solid diluent or a liquid diluent.
  • fungicidal compositions comprising fungicidally effective amounts of the compounds of Formula IB and at least one of a surfactant, a solid diluent or a liquid diluent.
  • the preferred compositions of the present invention are those which comprise the above preferred compounds of Formula IB .
  • 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 seedling, a fungicidally effective amount of the compounds of Formula IB and the compositions described herein.
  • the preferred methods of use are those involving the above preferred compounds of Formula IB.
  • This invention also relates to arthropodicidal compositions comprising arthropodicidally effective amounts of the compounds of Formula IB and at least one of a surfactant, a solid diluent or a liquid diluent.
  • the preferred compositions of the present invention are those which comprise the above preferred compounds of Formula IB.
  • This invention also relates to a method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of the compounds of Formula IB and the compositions described herein.
  • the preferred methods of use are those involving the above preferred compounds of Formula IB.
  • R 1 is C r C 3 alkyl or C r C 3 haloalkyl
  • R 2 is ⁇ ; C r C 6 alkyl; C r C 6 haloalkyl; or C 3 -C 6 cycloalkyl
  • R 3 and R 4 are each independently halogen; cyano; nitro; C--Cg alkyl;
  • C j -Cg haloalkyl C--Cg alkoxy; C j -Cg haloalkoxy; Ci-Cg alkylthio; C Cg alkylsulfonyl; C 2 -Cg alkylcarbonyl; C 2 -Cg alkoxycarbonyl; (C r C 4 alkyl)NHC(O); (C r C 4 alkyl) 2 NC(O); benzoyl; or phenylsulfonyl.
  • Preferred 2C Compounds of Preferred 1C wherein: A is O or N; X is OR 1 or halogen; R 1 is C ⁇ -C 3 alkyl; R 2 is H or C 1 -C 2 alkyl; and
  • R 3 and R 4 are each independently halogen; C1-C3 alkyl; C j -C3 alkoxy; or C1 -C3 alkylthio.
  • Preferred 3C Compounds of Preferred 2C wherein: A is N; R 1 is methyl;
  • R 2 is methyl
  • R 3 and R 4 are each independently halogen or methyl.
  • Most preferred are compounds of Preferred 3C selected from the group: 2,4-dihydro-4-(2-hydroxyphenyl)-5-methoxy-2-methyl-3H-l,2,4-triazol-3-one; 2,4-dihydro-4-(2-hydroxy-6-methylphenyl)-5-methoxy-2-methyl-3H- 1 ,2,4- triazol-3-one;
  • the compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-33.
  • One skilled in the art will recognize that compounds of Formula IA and IB are encompassed by Formula I and, therefore, can be prepared by these procedures.
  • the definitions of E, A, G, W, X, R!-R 27 , Y, Z 1 , W 1 , A ⁇ A 3 , Z, Q, J, m, n, p, r and s in the compounds of Formulae 1-58 below are as defined above in the Summary of the Invention.
  • Compounds of Formulae Ia-Im are various subsets of the compounds of Formula I, and all substituents for Formulae Ia-Im are as defined above for Formula I.
  • a compound of Formula I wherein R 2 is H may exist as tautomer la or lb, or both la and lb.
  • the present invention comprises all tautomeric forms of compounds of Formula I.
  • Procedures 1) to 5 describe syntheses involving construction of the amide ring after the formation of the aryl moiety (E-Y-Z).
  • Procedure 5) describes syntheses of the aryl moiety (E-Y-Z) with the amide ring already in place.
  • the compounds of Formula I are prepared by treating compounds of Formula 1 with an appropriate alkyl transfer reagent in an inert solvent with or without additional acidic or basic reagents or other reagents (Scheme 1).
  • Suitable solvents are selected from the group consisting of polar aprotic solvents such as acetonitrile, dimethylformamide or dimethyl sulfoxide; ethers such as tetrahydrofuran, dimethoxyethane, or diethyl ether; ketones such as acetone or 2-butanone; hydrocarbons such as toluene or benzene; and halocarbons such as dichloromethane or chloroform.
  • polar aprotic solvents such as acetonitrile, dimethylformamide or dimethyl sulfoxide
  • ethers such as tetrahydrofuran, dimethoxyethane, or diethyl ether
  • ketones such as acetone or 2-butanone
  • a protic cosolvent such as methanol.
  • compounds of Formula I can also be prepared by contacting carbonyl compounds of Formula 1 with alkyl trichloroacetimidates of Formula 3 and a Lewis acid catalyst.
  • Suitable Lewis acids include trimethylsilyl triflate and tetrafluoroboric acid.
  • the alkyl trichloroacetimidates can be prepared from the appropriate alcohol and trichloroacetonitrile as described in the literature (J. Danklmaier and H. Honig, Synth. Commun., (1990), 20, 203).
  • Compounds of Formula I can also be prepared from compounds of Formula 1 by treatment with a trialkyloxonium tetrafluoroborate (i.e., Meerwein's salt) of Formula 4 (Method 3).
  • a trialkyloxonium tetrafluoroborate i.e., Meerwein's salt
  • the use of trialkyloxonium salts as powerful alkylating agents is well known in the art (see U. Schollkopf, U. Groth, C. Deng, Angew. Chem., Int. Ed. Engl, (1981), 20, 798).
  • alkylating agents which can convert carbonyl compounds of Formula 1 to compounds of Formula I are dialkyl sulfates such as dimethyl sulfate, haloalkyl sulfonates such as methyl trifluoromethanesulfonate, and alkyl halides such as iodomethane and propargyl bromide (Method 4). These alkylations can be conducted with or without additional base.
  • Appropriate bases include alkali metal alkoxides such as potassium tert-butoxide, inorganic bases such as sodium hydride and potassium carbonate, or tertiary amines such as triethylamine, pyridine, l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and triethylenediamine.
  • alkali metal alkoxides such as potassium tert-butoxide
  • inorganic bases such as sodium hydride and potassium carbonate
  • tertiary amines such as triethylamine, pyridine, l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and triethylenediamine.
  • X OH
  • X OH
  • the nucleophiles of Formula 6 are N-substituted hydroxylamines (HO- ⁇ HR 2 ) and substituted hydrazines (H ⁇ (R 5 )- ⁇ HR 2 ). Examples of such nucleophiles are N-methylhydroxylamine and methylhydrazine.
  • the malonate esters of Formula 5 can be prepared by methods described hereinafter.
  • T 0(C!-C4 alkyl), Cl, 1-imidazDlyl
  • Esters of Formula 5a can be prepared from copper (I)-catalyzed reaction of malonate esters of Formula 7 with substituted aryl halides of Formula 8 according to methods adapted from A. Osuka, T. Kobayashi and H. Suzuki, Synthesis, (1983), 67 and M. S. Malamas, T. C. Hohman, and J. Millen, J. Med. Chem., 1994, 37, 2043-2058, and illustrated in Scheme 3. Procedures to prepare compounds of Formula 8 are described below (see Scheme 32).
  • Malonate esters of Formula 5a can also be prepared from diester carboxylic acids of Formula 5b after modification of the carboxylic acid functional group to the appropriate Y and Z group.
  • a copper (I)-catalyzed coupling of malonates of Formula 7 with orthobromocarboxylic acids of Formula 8a can be used to prepare compounds of Formula 5b as shown in Scheme 3.
  • Methods to prepare compounds of Formula 8a are common in the art (see P. Beak, V. Snieckus, Ace. Chem. Res., (1982), 15, 306 and Org. React., (1979), 26, 1 and references therein).
  • R C ⁇ -C 4 alkyl
  • the malonate esters of Formula 5a can be prepared by treating aryl acetic acid esters of Formula 9 with a dialkyl carbonate or alkyl chloroformate in the presence of a suitable base such as, but not limited to, sodium metal or sodium hydride (Scheme 4).
  • a suitable base such as, but not limited to, sodium metal or sodium hydride
  • R C 1 -C alkyl
  • Esters of Formula 9 can be prepared from acid-catalyzed alcoholysis of aryl acetonitriles of Formula 10 or esterification of aryl acetic acids of Formula 11 as illustrated in Scheme 5 (see Org. Synth., Coll. Vol. I, (1941), 270).
  • esters of formula 9 can be prepared by palladium (O)-catalyzed cross coupling reaction of aryl iodides of Formula 8 with a Reformatsky reagent or an alkoxy(trialkylstannyl)acetylene followed by hydration (Scheme 5).
  • a Reformatsky reagent or an alkoxy(trialkylstannyl)acetylene followed by hydration (Scheme 5).
  • Aryl acetic acid esters of Formula 9a can also be prepared by copper (I)-catalyzed condensation of aryl halides of Formula 12 with compounds of Formula 13 as described in EP-A-307,103 and illustrated below in Scheme 6.
  • esters of Formula 9 can also be prepared by forming the Y 2 bridge using conventional nucleophilic substitution chemistry (Scheme 7). Displacement of an appropriate leaving group (Lg) in electrophiles of Formula 15 or 16 with a nucleophilic ester of Formula 14 affords compounds of Formula 9b.
  • a base for example sodium hydride, is used to generate the corresponding alkoxide or thioalkoxide of the compound of Formula 14.
  • R C!-C 4 alkyl
  • Y 2 O, S, OCHR 15 SCHR 15 , CHR 15 0, CHR 15 S, NR 15
  • esters of Formula 9 can also be prepared by forming the Y 3 bridge from substituted hydroxylamine 9d and carbonyl compounds 14a.
  • the hydroxylamine 9d is in turn prepared from esters 9c. This method has been described in EP-A-600,835 and illustrated in Scheme 8.
  • Compounds of Formula I can also be prepared by reaction of Formula 17 compounds with alkali metal alkoxides (R ⁇ M+ alkali metal thioalkoxides (R ⁇ 'M " ), or an amine derivative in a suitable solvent (Scheme 9).
  • the leaving group Lg 1 in the amides of Formula 17 are any group known in the art to undergo a displacement reaction of this type. Examples of suitable leaving groups include chlorine, bromine, and sulfonyl and sulfonate groups. Examples of suitable inert solvents are dimethylformamide or dimethyl sulf oxide, dimethoxyethane methanol.
  • NC -Cg alkyOR 1 NH(C ⁇ -Cg alkoxy), or
  • Lg l Br, -SC ⁇ V, or -OSO2V
  • V C r Cg alkyl, -C haloalkyl, or4-CH 3 -CgH4
  • compounds of Formula 1 wherein X is OH by reaction with halogenating agents such as thionyl chloride or phosphorus oxybromide to form the corresponding ⁇ -halo-substituted derivatives (Scheme 10).
  • halogenating agents such as thionyl chloride or phosphorus oxybromide
  • compounds of Formula lb can be treated with an alkylsulfonyl halide or haloalkylsulfonyl anhydride, such as methanesulfonyl chloride, -toluenesulfonyl chloride, and trifluoromethanesulfonyl anhydride, to form the corresponding ⁇ -alkylsulfonate of Formula 17a.
  • the reaction with the sulfonyl halides may be performed in the presence of a suitable base (e.g., triethylamine).
  • sulfonyl compounds of Formula 17b can be prepared by oxidation of the corresponding thio compound of Formula 18 using well-known methods for the oxidation of sulfur (see Schrenk, K. In The Chemistry of Sulphones and Sulphoxides; Patai, S. et al., Eds.; Wiley: New York, 1988). Suitable oxidizing reagents include meta-chloro-peroxybenzoic acid, hydrogen peroxide and Oxone® (KHSO5).
  • V C j -Cg alkyl, C j -Cg haloalkyl, or 4-CH 3 -CgH 4
  • the diacyl compound of Formula 19 is treated with excess thionyl halide, for example excess thionyl chloride.
  • the product formed first is the ring-closed compound of Formula 20 which can be isolated or converted in situ to the compound of Formula 17c; see P. Molina, A. Tarraga, A. Espinosa, Synthesis, (1989), 923 for a description of this process.
  • the hydrazides of Formula 19 can be prepared as illustrated in Scheme 13. Condensation of the isocyanate of Formula 21 with the hydrazine of Formula H NNR 2 R 27 in an inert solvent such as tetrahydrofuran affords the hydrazide.
  • R 27 alkyl
  • R C 1 -C 4 alkyl
  • Ketene dithioacetals of Formula 22a can be prepared by condensing arylacetic acid esters of Formula 9 with carbon disulfide in the presence of a suitable base, followed by reaction with two equivalents of an R ⁇ -halide, such as iodomethane or propargyl bromide (Scheme 15).
  • the carbonylating agents of Formula 24 are carbonyl or thiocarbonyl transfer reagents such as phosgene, thiophosgene, diphosgene
  • the compounds of Formula 24 can be alkyl chloroformates or dialkyl carbonates. Some of these carbonylating reactions may require the addition of a base to effect reaction.
  • Appropriate bases include alkali metal alkoxides such as potassium t -butoxide, inorganic bases such as sodium hydride and potassium carbonate, tertiary amines such as triethylamine and triethylenediamine, pyridine, or l,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
  • alkali metal alkoxides such as potassium t -butoxide
  • inorganic bases such as sodium hydride and potassium carbonate
  • tertiary amines such as triethylamine and triethylenediamine
  • pyridine or l,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
  • Suitable solvents include polar aprotic solvents such as acetonitrile, dimethylformamide, or dimethyl sulfoxide; ethers such as tetrahydrofuran, dimethoxyethane, or diethyl ether; ketones such as acetone or 2-butanone; hydrocarbons such as toluene or benzene; or halocarbons such as dichloromethane or chloroform.
  • the reaction temperature can vary between 0°C and 150°C and the reaction time can be from 1 to 72 hours depending on the choice of base, solvent, temperature, and substrates.
  • N-Amino-ureas of Formula 23 can be prepared as illustrated in Scheme 17. Treatment of an arylamine of Formula 25 with phosgene, thiophosgene,
  • N,N'-carbonyldiimidazole, or N,N'-thiocarbonyldiimidazole produces the isocyanate or isothiocyanate of Formula 26.
  • a base can be added for reactions with phosgene or thiophosgene.
  • Subsequent treatment of the iso(thio)cyanate with an R 2 -substituted hydrazine produces the N-amino-urea of Formula 23.
  • 2-halocarboxylic acid chlorides 2-halocarboxylic acid esters or 2-haloacyl imidazoles.
  • the initial acylation on the arylamino nitrogen is followed by an intramolecular displacement of the 2-halo group to effect cyclization.
  • Base may be added to accelerate the acylation and/or the subsequent cyclization.
  • Suitable bases include triethylamine and sodium hydride.
  • Formula le compounds can be prepared by reaction of Formula 26 isocyanates with Formula 28a esters. As described above, base may be added to accelerate the reaction and subsequent cyclization to Formula le compounds.
  • the ureas of Formula 27 can be prepared by either of the methods illustrated in Scheme 19.
  • an isocyanate or isothiocyanate of Formula 26 can be condensed with an amine of Formula R 2 -NH 2 to form the urea.
  • the arylamine and iso(thio)cyanates of Formulae 25 and 26, respectively, are commercially available or prepared by well-known methods.
  • isothiocyanates can be prepared by methods described in J. Heterocycl. Chem., (1990), 27, 407.
  • Isocyanates can be prepared as described in March, j. Advanced Organic
  • thionating reagents such as P 2 S5 or Lawesson's reagent (2,4-bis(4-methoxyphenyl)-l,3-dithia-2,4- diphosphetane-2,4-disulfide
  • aryl halides of Formula 29 can be prepared by radical halogenation of the corresponding alkyl compound (i.e., H instead of halogen in Formula 29), or by acidic cleavage of the corresponding methylether (i.e., OMe instead of halogen in Formula 29).
  • Other aryl halides of Formula 29 can be prepared from the appropriate alcohols of Formula 30 by well known halogenation methods in the art (see Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry; 3rd ed., Part B, Plenum: New York, (1990), p 122).
  • R C ⁇ -C alkyl 32: P P OR ⁇
  • the olefins of Formula lg can be converted to the saturated compounds of Formula Ih by hydrogenation over a metal catalyst such as palladium on carbon as is well-known in the art (Rylander, Catalytic Hydrogenation in Organic Synthesis; Academic: New York, 1979).
  • Formula li alkynes can be prepared by halogenation/dehalogenation of Formula lg olefins using procedures well-known in the art (March, J. Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985), p 924). Additionally, Formula li alkynes can be prepared by well-known reaction of aryl halides with alkyne derivatives in the presence of catalysts such as nickel or palladium (see J. Organomet. Chem., (1975), 93 253-257).
  • the olefin of Formula lg can also be prepared by reversing the reactivity of the reactants in the Wittig or Horner-Emmons condensation.
  • 2-alkylaryl derivatives of Formula 33 can be converted into the corresponding dibromo-compound of Formula 34 as illustrated in Scheme 23 (see Synthesis, (1988), 330).
  • the dibromo- compound can be hydrolyzed to the carbonyl compound of Formula 35, which in turn can be condensed with a phosphorus-containing nucleophile of Formula 36 or 37 to afford the olefin of Formula lg.
  • compounds of Formula 35 can be prepared by oxidation of the corresponding alcohols of Formula 30.
  • Vinylhalides of Formula Ij can be prepared by reacting phosphorus reagents of Formulae 37a or 37b with carbonyl compounds of Formula 35 (Scheme 23).
  • the preparations of halides of Formula 37a from the appropriate diethylphosphonoacetate are described by McKenna and Khawli in J. Org. Chem., (1986), 51, 5467.
  • the thiono esters of Formula 37b can be prepared from esters of Formula 37a by converting the carbonyl oxygen of the ester to a thiocarbonyl (see Chem. Rev., (1984), 84, 17 and Tetrahedron Lett., (1984), 25, 2639).
  • Carbamates of Formula II can be prepared by reacting aryl alcohols of Formula 30 with isocyanates of Formula 39 (Scheme 25). A base such as triethylamine can be added to catalyze the reaction. As shown, carbamates of Formula II can be further alkylated to provide the carbamates of Formula Im.
  • the compounds of the present invention are prepared by combinations of reactions as illustrated in the Schemes 1-25 in which Z is a moiety as described in the summary.
  • Preparation of the compounds containing the radical Z as described in the summary, substituted with L can be accomplished by one skilled in the art by the appropriate combination of reagents and reaction sequences for a particular Z-L.
  • Such reaction sequences can be developed based on known reactions available in the chemical art. For a general reference, see March, J. Advanced Organic Chemistry; 3rd ed., John Wiley:
  • H 2 NOHor 0 C 7-Z H 2 NOH.
  • HO base* HO-N CR 7 -Z
  • Compounds of Formula 40 can be prepared from compounds of Formula 39a (Scheme 27) by Friedel-Crafts acylation with compounds of Formula 42. (See Olah, G. "Friedel-Crafts and Related Reactions," Interscience, New York (1963-1964) for a general review). Compounds of Formula 40 may also be prepared by reaction of acyl halides, anhydrides, esters, or amides of Formula 45 with organometallic reagents of Formula 44. (See March, J.
  • the organometallic compounds of Formula 44 may be prepared by reductive metallation or halogen-metal exchange of a halogen-containing compound of Formula 43 using, for example, magnesium or an organolithium reagent, or by deprotonation of compounds of Formula 39a using a strong base such as a lithioamide or an organolithium reagent, followed by transmetallation.
  • R C!-C4 alkyl
  • Compounds of Formula 43 may be prepared by reaction of compounds of Formula 39a (Scheme 28) with, for example, bromine or chlorine, with or without additional catalysts, under free-radical or aromatic electrophilic halogenation conditions, depending on the nature of Z.
  • Alternative sources of halogen such as N- halosuccinimides, tert-butyl hypohalites or SO 2 Cl 2 , may also be used. (See March, J.
  • Compounds of Formula 48 can be prepared from compounds of Formula 40b by treatment with peracids such as perbenzoic or peracetic acid, or with other peroxy compounds in the presence of an acid catalysts, followed by hydrolysis of the resultant ester.
  • peracids such as perbenzoic or peracetic acid
  • Compounds of Formula 52 can be prepared from compounds of Formula 48 by conversion to the dialkylthiocarbamates of Formula 50 followed by rearrangement to Formula 51 and subsequent hydrolysis. See M. S. Newman and H. A. Karnes, J. Org. Chem. (1966), 31, 3980-4.
  • R C ⁇ -C 4 alkyl
  • Compounds of Formula 53 can be converted to compounds of Formulae 43, 48 or 52 via the diazonium compounds 54, by treatment with nitrous acid followed by subsequent reaction (Scheme 30). See reviews by Hegarty , pt. 2, pp 511-91 and Schank, pt. 2, pp 645-657, in Patai, "The Chemistry of Diazonium and Diazo Groups," Wiley, New York (1978).
  • Treatment of Formula 54 compounds with cuprous halides or iodide ions yield compounds of Formula 43.
  • Treatment of Formula 54 compounds with cuprous oxide in the presence of excess cupric nitrate provides compounds of Formula 48. (Cohen, Dietz, and Miser, J. Org. Chem., (1977), 42, 2053).
  • Treatment of Formula 54 compounds with (S2)" 2 yields compounds of Formula 52.
  • Compounds of Formula 53 can be prepared from compounds of Formula 39a by nitration, followed by reduction (Scheme 31).
  • nitrating agents are available (see Schofield, " Aromatic Nitration," Cambridge University Press, Cambridge (1980)). Reduction of nitro compounds can be accomplished in a number of ways (see March, J. Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985), pp 1 103-4 and references therein).
  • Iodides of Formula 8 can be prepared from compounds of Formula 58 by the methods described above in Schemes 21-25 for various Y-Z combinations.
  • Compounds of Formula 58 can in turn be prepared from compounds of Formula 57 by functional group interconversions which are well known to one skilled in the art.
  • the compounds of Formula 57 can be prepared by treating compounds of Formula 56 with an organolithium reagent such as rc-BuLi or LDA followed by trapping the intermediate with iodine (Beak, P., Snieckus, V. Ace. Chem. Res., (1982), 15, 306).
  • T 4 CO2H, CONR 2 , CONHR,
  • Compounds of Formula Lg-Z may be prepared according to literature procedures, for example, Comprehensive Heterocyclic Chemistry, Pergamon Press, vol. 6, 1984, pp 463-511 or J. Org. Chem. (1973), 38, 469 or J. Het. Chem. (1979), 961 for the preparation of 1,2,4-thiadiazoles, U.S. 5,166,165 or J. Chem. Soc, Perkin Trans. 1 (1983), 967 for the preparation of 1,3,4-oxadiazoles and 1,3,4-thiadiazoles, EP 446,010 or J. Med. Chem. (1992), 35, 3691 for the preparation of 1,2,4-oxadiazoles.
  • R 9 may be introduced via a palladium(0)-catalyzed cross coupling reaction with the appropriate nucleophile containing R 9 , such as arylboronic acids, aryl or alkyl zinc reagents, and substituted acetylenes.
  • R 9 may be introduced via a palladium(0)-catalyzed cross coupling reaction with the appropriate nucleophile containing R 9 , such as arylboronic acids, aryl or alkyl zinc reagents, and substituted acetylenes.
  • R 9 may be introduced via a palladium(0)-catalyzed cross coupling reaction with the appropriate nucleophile containing R 9 , such as arylboronic acids, aryl or alkyl zinc reagents, and substituted acetylenes.
  • Step E Preparation of 4-r2-rr3-f3.5-bis('trifluoromethyl)phenyll-1.2.4-thiadiazol-
  • Step A Preparation of ethyl 3-(trifluoromethoxy)benzenecarboximidate hydrochloride To a solution of 3-(trifluoromethoxy)benzonitrile (10 g. 53.4 mmol) in ethyl ether (55 mL) is added absolute ethanol (3.3 mL). The solution is cooled to 0 °C and saturated with dry HC1 gas. The reaction mixture is then left to stand at ambient temperature for 7 days after which time it is filtered under a stream of dry nitrogen to give the title compound of Step A (10.99 g) as a white solid.
  • Step C Preparation of 5-cMoro-3-r3-(t ⁇ ifluoromethoxy)phenyl ⁇ l- 1.2.4-thiadiazole
  • Step B To a solution of the title compound of Step B (10.36 g, 43.06 mmol) in water (100 mL) is added methylene chloride (200 mL), benzyltriethylammonium chloride (0.8 g) and perchloromethyl mercaptan (4.7 mL, 32.6 mmol) and the mixture is cooled in an ice bath. With efficient stirring, sodium hydroxide (6.89 g) in water (100 mL) is then added drop wise such that the internal temperature does not exceed 10 °C. After the addition is complete, the cooling bath is removed and the reaction mixture stirred for a further 1.5 h. The organic layer is then separated, dried over magnesium sulfate and concentrated.
  • methylene chloride 200 mL
  • benzyltriethylammonium chloride 0.8 g
  • perchloromethyl mercaptan 4.7 mL, 32.6 mmol
  • Step D Preparation of 2.4-dihydro-5-methoxy-2-methyl-4-[2-l 3-r3-
  • Step B Preparation of 2-(4-chlorophenyl)-5-(mefhylsulfonyl)- 1.3.4-oxadiazole
  • Step C Preparation of 4-r2-IT5-f4-chloropheny ⁇ - 1.3.4-oxadiazol-2- yl1oxy1phenvn-2.4-dihydro-5-methoxy-2-methyl-3H-1.2.4-triazol-3-one
  • potassium carbonate 406 mg
  • Step B The mixture was stirred overnight before being diluted with methylene chloride and washed with water.
  • the aqueous phase was re-extracted with methylene chloride and the combined organic phases were dried over magnesium sulfate and the solution was concentrated under reduced pressure.
  • Example 4 To a solution of the title compound of Example 4 (307 mg, 0.71 mmol) in DMF (4 mL) was added copper(I) iodide (14 mg), triethylamine (0.347 mL), 3,3-dimethyl-l- butyne (0.219 mL) and bis(triphenylphosphine)palladium(II) chloride (25 mg). The mixture was stirred for 40 h at ambient temperature before being diluted with ethyl acetate, washed with IN ⁇ C1 and dried over magnesium sulfate.
  • Example 6 The mixture was stirred overnight at ambient temperature before being diluted with ethyl ether. The resulting mixture was washed with a saturated aqueous solution of ethylenediaminetetraacetic acid, a saturated aqueous solution of Na ⁇ CU3, and a saturated aqueous solution of NaCl and then was dried over magnesium sulfate. The solution was concentrated and the material was crystallized from ethanol to give the title compound of Example 6 (315 mg), a compound of the invention, as a solid melting at 133-134 °C.
  • Example 7 Recrystallization from ethanol afforded the title compound of Example 7 (153 mg), a compound of the invention, as a white solid melting at 177-178 °C. l R NMR (CDC1 3 ) ⁇ 8.29 (s,l ⁇ ), 8.15 (d,lH), 7.62 (m,lH), 7.57 (m,2H), 7.49 (m,2H), 7.4 (t,lH), 3.78 (s,3H), 3.37 (s,3H).
  • Step B Preparation of r3-[5-r2-d.5-dihydro-3-methoxy-l-methyl-5-oxo-4H- l. ⁇ -triazol ⁇ -yDphenoxyl-l. ⁇ -thiadiazol-S-yllphenyll benzoate
  • methylene chloride 112 mL
  • triethylamine 6.1 mL
  • 4-(dimethylamino)pyridine 206 mg
  • benzoyl chloride 4.5 mL
  • Step A To a solution of the title compound of Step A (4.01 g, 36 mmol) in water (89 mL) and methylene chloride (177 mL) was added benzyltriethylammonium chloride (675 mg) and perchloromethyl mercaptan (4.0 mL) and the mixture was cooled in an ice bath. A solution of sodium hydroxide (4.36 g) in water (89 mL) was then added such that the internal temperature did not exceed 10 °C. Upon complete addition, the cooling bath was removed and the mixture was stirred for 3 h. The layers were separated and the organic layer was dried over magnesium sulfate.
  • Step B Purification by column chromatography (petroleum ether and then 1-chlorobutane) gave the title compound of Step B.
  • Step C Preparation of 4-r2-rr3-(2-furanyl -1.2.4-thiadiazol-5-vnoxy1phenyll-2.4- dihydro-5-methoxy-2-methyl-3H- 1.2.4-triazol-3-one
  • potassium carbonate 289 mg
  • Step B Preparation of 4-r2- r3-('2.5-dichloro-3-thienylV1.2.4-thiadiazol-5- ylloxy]phenyl1-2,4-dihydro-5-methoxy-2-methyI-3H-1.2.4-triazol-3-one
  • potassium carbonate (1.21 g)
  • the mixture was stirred at ambient temperature for 30 h at which point extra potassium carbonate (0.6 g) was added.
  • Step B Preparation of 5-chloro-3-f 1.1 -dimefhylethylV 1.2.4-thiadiazole
  • Step C Preparation of 4-r2-fr3-f 1.1 -dimethylethylV 1 ,2.4-thiadiazol-5- ylloxy1phenyl1-2.4-dihydro-5-methoxy-2-methyl-3H-1.2.4-triazol-3-one
  • the resulting dark solution was stirred for 22 h at room temperature and an additional 1.5 mL of the organozinc reagent was then added to complete the reaction.
  • the reaction mixture was partitioned between 100 mL of ethyl acetate and 50 mL of diluted aqueous hydrochloric acid. The aqueous layer was extracted with 50 mL of ethyl acetate and the combined organic layers were dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude product.
  • Step B Preparation of 2-chloro-5-(4-chlorophenyl)- 1 ,3,4-thiadiazole
  • Step C Preparation of 4-r2-[T5-f4-chlorophenyl)- 3,4-thiadiazol-2- yl1oxylphenyl1-2,4-dihydro-5-methoxy-2 methyl-3H- 1 ,2,4-triazol-3-one
  • the title compound of Step B (0.46 g, 2 mmol)
  • the title compound of Step D in Example 1 (0.44 g, 2 mmol)
  • potassium carbonate 0.8 g, 5.8 mmol
  • Step B Preparation of 5-bromo-2-chloro-4-r3-ftrifluoromethvL)phenyl1thiazole
  • Step B The title compound of Step B (3 g) was dissolved in 50 mL of acetonitrile and to this solution was added with stirring 2.5 g of copper(II) chloride followed by 2 mL of tert-butylnitrite (dropwise). Nitrogen evolution was evident and the reaction exothermically warmed to approximately 30 °C. The dark reaction mixture was stirred for 45 min and was then partitioned between 200 mL of ethyl acetate and 200 mL of distilled water. The organic layer was separated, washed with IN aqueous HC1, water, and then saturated aqueous NaCl. The organic layer was dried over MgSO 4 and then was concentrated under reduced pressure to give a dark oil/solid residue.
  • Step C The main component was isolated by flash chromatography on silica gel using 5-10% ethyl acetate in hexanes as eluant to give 2.4 g of the title compound of Step C as a red tinted solid melting at 52-55 °C.
  • Step D Preparation of 4-f2-[r5-bromo-4-13-ftrifluoromethyl)phenyl " l-2- thiazolyl1oxylphenyll-2.4-dihydro-5-methoxy-2-methyl-3H-1.2.4-triazol-
  • Step B Preparation of 5-chloro-2.4-dihydro-4-(2-methoxy-6-methylphenyl')-2- methyl-3H- 1 ,2.4-triazol-3-one
  • the title compound of Step A (100.0 g, 447.9 mmol) was suspended in ethyl acetate (1 L) and added dropwise, via mechanical pump, over 3.5 h to a stirring solution of phosgene ( 177 g, 1.79 moles) in ethyl acetate (1.5 L) which was heated at reflux. After the addition was complete, the mixture was heated at reflux for a further 3 h, cooled to room temperature and stirred overnight.
  • Step C Preparation of 5-chloro-2.4-dihydro-4-(2-hydroxy-6-methylphenyl)-2- methyl-3H- 1 ,2.4-triazol-3-one
  • benzene 200 mL
  • aluminum chloride 23.7 g, 178 mmol
  • Step C Preparation of 2.4-dihydro-4-( " 2-hydroxy-6-methylphenylV5-methoxy-2- methyl-3H- 1.2.4-triazol-3-one
  • Step A Preparation of 2.4-dihydro-5-methoxy-2-methyl-4-[2-[rtris(l- methylethyl silylloxylphenyll-3H- 1.2.4-triazol-3-one
  • DMF 100 mL
  • triisopropylsilyl chloride 13.3 mL, 61.9 mmol
  • Step B Preparation of 4-
  • a solution of the title compound of Step A (2.16 g, 5.72 mmol) in anhydrous tetrahydrofuran was cooled to -78 °C and terr-butyllithium (4.0 mL, 1.7 M solution in pentane, 6.8 mmol) was added dropwise.

Abstract

Uses of compounds of Formula (I), and their N-oxides and agriculturally suitable salts, as arthropodicides are disclosed, wherein E is an optionally substituted 1,2-phenylene, and optionally substituted naphthalene ring, or a ring system selected from certain 5 to 12-membered monocyclic and fused bicyclic aromatic heterocyclic ring systems as defined in the disclosure; A is O; S; N; NR?5; or CR14¿; G is C or N; provided that when G is C, then A is O, S or NR5 and the floating double bond is attached to G; and when G is N, then A is N or CR14 and the floating double bond is attached to A; W is O; S; NH; N(C¿1?-C6 alkyl); or NO(C1-C6 alkyl); X is H; OR?1¿; S(O)¿mR?1; halogen; C¿1?-C6 alkyl; C1-C6 haloalkyl; C3-C6 cycloalkyl; cyano; NH2; NHR?1; N(C¿1-C6 alkyl)R1; NH(C¿1?-C6 alkoxy); or N(C1-C6 alkoxy)R?1; R2¿ is H; C¿1?-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; C2-C4 alkoxycarbonyl; hydroxy; C1-C2 alkoxy; or acetyloxy; R?1, R5¿, Y, Z, R14 and m are as defined in the disclosure. Also diclosed are compounds and compositions of Formula (IA) as defined in the disclosure and their use as arthropodicides and fungicides, and compounds and compositions of Formula (IB) as defined in the disclosure and their use as arthropodicides and fungicides. Also disclosed are compounds of Formula (II) as defined in the disclosure which are useful as intermediates for the preparation of the fungicides and arthropodicides of this invention where Y is oxygen and E is 1,2-phenylene.

Description

TITLE ARTHROPODICIDAL AND FUNGICIDAL CYCLIC AMIDES BACKGROUND OF THE INVENTION This invention relates to certain cyclic amides, their N-oxides, agriculturally suitable salts and compositions, and methods of their use as fungicides and arthropodicides.
The control of plant diseases caused by fungal plant pathogens is extremely important in achieving high crop efficiency. Plant disease damage to ornamental, vegetable, field, cereal, and fruit crops can cause significant reduction in productivity and thereby result in increased costs to the consumers. The control of arthropod pests is also extremely important in achieving high crop efficiency. Arthropod damage to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of arthropod pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.
WO 95/14009 discloses cyclic amides of Formula i as fungicides:
i wherein
A is O; S; Ν; ΝR5; or CR14;
G is C or Ν; provided that when G is C, A is O, S or ΝR5 and the floating double bond is attached to G; and when G is Ν, A is Ν or CR14 and the floating double bond is attached to A;
W is O or S;
X is OR1; S^rnR1; or halogen;
R1, R2, and R5 are each independently, in part, H or Cι-C6 alkyl; R3 and R4 are each independently, in part, H; halogen; cyano; nitro; Ci-Cg alkyl;
Cj-Cg haloalkyl; Cj-C6 alkoxy; or C C6 haloalkoxy; Y is, in part, -O-; -CR6=CR6-; -C≡C-; -CHR60-; -OCHR6-; -CHR60-N=C(R7)-; -(R7)C=N-OCH(R6)-; -C(R7)=N-O-; -O-N=C(R7)-; or a direct bond; R6 is independently H or C1-C3 alkyl;
R7 is, in part, H; Cj-Cg alkyl; haloalkyl; or Cj -C6 alkoxy; Z is, in part, an optionally substituted phenyl, 3 to 14-membered nonaromatic heterocyclic ring system or 5 to 14-membered aromatic heterocyclic ring system; R14 is H; halogen; CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl;
C2-Cg alkynyl; C2-Cg haloalkynyl; or C3-C6 cycloalkyl; and m is 0, 1 or 2.
This publication does not disclose use of the compounds as arthropodicides. Furthermore, this publication does not disclose compounds where the optional substituents on Z are themselves substituted with C2-Cg alkenyl, C2-Cg haloalkenyl, C2-C6 alkynyl, C2-Cg haloalkynyl, C3-C6 alkenyloxy, C3-C6 haloalkenyloxy, C1-C4 alkylthio, C1-C4 haloalkylthio, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C3-C6 alkenylthio, C3-C6 haloalkenylthio, or SF5.
SUMMARY OF THE INVENTION This invention involves compounds of Formula I including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof:
I wherein E is selected from: i) 1,2-phenylene optionally substituted with one of R3, R4, or both R3 and
R4; ii) a naphthalene ring, provided that when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, the naphthalene ring optionally substituted with one of R3, R4, or both R3 and R4; and iii) a ring system selected from 5 to 12-membered monocyclic and fused bicyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each fused bicyclic ring system optionally containing one nonaromatic ring that optionally includes one or two Q as ring members and optionally includes one or two ring members independently selected from C(=O) and S(O)2, provided that G is attached to an aromatic ring, and when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, each aromatic heterocyclic ring system optionally substituted with one of R3, R4, or both R3 and R4;
A is O; S; N; NR5; or CR14;
G is C or N; provided that when G is C, then A is O, S or NR5 and the floating double bond is attached to G; and when G is N, then A is N or CR1 and the floating double bond is attached to A;
W is O; S; NH; N(CrC6 alkyl); or NO(CrC6 alkyl);
X is H; OR1; SCO^R1; halogen; CrC6 alkyl; CrC6 haloalkyl; C3-C6 cycloalkyl; cyano; NH2; NHR1 ; N(CrC6 alkyfjR1 ; NH(CrC6 alkoxy); or N(C1-C6 alkoxy)R1; R1 is CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; ^-C^ haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; or C2-C alkoxycarbonyl;
R2 is H; CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-Cg haloalkynyl; ^-C6 cycloalkyl; C2-C4 alkylcarbonyl; C2-C4 alkoxycarbonyl; hydroxy; C1-C2 alkoxy; or acetyloxy;
R3 and R4 are each independently halogen; cyano; nitro; hydroxy; Ci-Cg alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C Cg alkoxy; Ci-Cg haloalkoxy; C2-C6 alkenyloxy; C2-C6 alkynyloxy; C Cg alkylthio; C1-C6 alkylsulfinyl; Ci-Cg alkylsulfonyl; formyl; C2-C6 alkylcarbonyl; C2-C6 alkoxycarbonyl; NH2C(O);
(CrC4 alkyl)NHC(O); (CrC4 alkyl)2NC(O); Si(R25)3; Ge(R25)3; (R25)3Si-C=C-; or phenyl, phenylethynyl, benzoyl, or phenylsulfonyl each substituted with R8 and optionally substituted with one or more R10; or when E is 1 ,2-phenylene and R3 and R4 are attached to adjacent atoms, R3 and R4 can be taken together as C3-C5 alkylene, C3-C5 haloalkylene, C3-C5 alkenylene or C3-C5 haloalkenylene each optionally substituted with 1-2
CrC3 alkyl; R5 is H; CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; C2-C alkylcarbonyl; or C -C alkoxycarbonyl;
Y is -O-; -S(O)n-; -NR15-; -C(=O)-; -CH(OR15)-; -CHR6-; -CHR6CHR6-;
-CR6=CR6-; -C≡C-; -CHR 5O-; -OCHR15-; -CHR15S(O)n-; -S(O)nCHR15-;
-CHR15O-N=C(R7)-; -(R7)C=N-OCH(R15)-; -C(R7)=N-O-; -O-N=C(R7)-;
-CHR15OC(=O)N(R15)-; -CHR15OC(=S)N(R15)-; -CHR15OC(=O)O-; -CHR15OC(=S)O-; -CHR1 OC(=O)S-; -CHR15OC(=S)S-;
-CHR15SC(=O)N(R15)-; -CHR15SC(=S)N(R15)-; -CHR15SC(=O)O-;
-CHR15SC(=S)O-; -CHR15SC(=O)S-; -CHR15SC(=S)S-;
-CHR15SC(=NR15)S-; -CHR15N(R15)C(=O)N(R15)-;
-CHR15O-N(R15)C(=O)N(R15)-; -CHR15O-N(R15)C(=S)N(R15)-; -CHR15O-N=C(R7)NR15-; -CHR15O-N=C(R7)OCH ;
-CHR15O-N=C(R7)-N=N-; -CHR15O-N=C(R7)-C(=O)-;
-CHR15O-N=C(R7)-C(=N-A2-Z1)-A1-;
-CHRl5O-N=C(R7)-C(R7)=N-A2-A3-; -CHR15O-N=C(-C(R7)=N-A2-Z1)-;
-CHR15O-N=C(R7)-CH2O-; -CHR15O-N=C(R7)-CH2S-; -O-CH2CH2O-N=C(R7)-; -CHR15O-C(R15)=C(R7)-; -CHR15O-C(R7)=N-;
-CHR15S-C(R7)=N-; -C(R7)=N-NR15-; -CH=N-N=C(R7)-;
-CHR15N(R15)-N=C(R7)-; -CHR15N(COCH3)-N=C(R7)-;
-OC(=S)NR15C(=O)-; -CHR6-C(=W1)-A1-; -CHR6CHR6-C(=W1)-A1-;
-CR^CR^C^W^-A1-; -C≡C-C(=W1)-A1-; -N=CR6-C(=W1)-A1-; or a direct bond; and the directionality of the Y linkage is defined such that the moiety depicted on the left side of the linkage is bonded to E and the moiety on the right side of the linkage is bonded to Z; Z1 is H or -A3-Z; WUs O or S; A1 is O; S; NR15; or a direct bond;
A2 is O; NR15; or a direct bond; A3 is -C(=O)-; -S(O)2-; or a direct bond; each R6 is independently H; 1-2 CH3; C2-C3 alkyl; CrC3 alkoxy; C3-C6 cycloalkyl; formylamino; C -C4 alkylcarbonylamino; C2-C4 alkoxycarbonylamino; NH2C(O)NH; (CrC3 alkyl)NHC(O)NH; (C C3 alkyl)2NC(O)NH; N(CrC3 alkyl)2; piperidinyl; mo holinyl; 1-2 halogen; cyano; or nitro; each R7 is independently H; C*-C6 alkyl; CrC6 haloalkyl; Ci-Cg alkoxy; Cj-C6 haloalkoxy; CrC6 alkylthio; CrC6 alkylsulfinyl; CrC6 alkylsulfonyl; CrC6 haloalkylthio; CrC6 haloalkylsulfmyl; C C6 haloalkylsulfonyl; C2-C6 alkenyl; C2-Cg haloalkenyl; C2-Cg alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; C2-C4 alkoxycarbonyl; halogen; cyano; nitro; hydroxy; amino; NH(Cι-Cg alkyl); N^-Cg alkyl)2; or moφholinyl; each Z is independently selected from: i) CJ-CJO alkyl, C2-CIQ alkenyl, and C2-CJO alkynyl each substituted with R9 and optionally substituted with one or more R10; ϋ) C3-C cycloalkyl, C3-Cg cycloalkenyl and phenyl each substituted with R9 and optionally substituted with one or more R10; iii) a ring system selected from 3 to 14-membered monocyclic, fused bicyclic and fused tricyclic nonaromatic heterocyclic ring systems and 5 to
14-membered monocyclic, fused bicyclic and fused tricyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each nonaromatic or aromatic heterocyclic ring system substituted with R9 and optionally substituted with one or more R10; iv) a multicyclic ring system selected from 8 to 14-membered fused-bicyclic and fused-tricyclic ring systems which are an aromatic carbocyclic ring system, a nonaromatic carbocyclic ring system, or a ring system containing one or two nonaromatic rings that each include one or two Q as ring members and one or two ring members independently selected from C(=O) and S(O)2, and any remaining rings as aromatic carbocyclic rings, each multicyclic ring system substituted with R9 and optionally substituted with one or more R10; and v) adamantyl substituted with R9 and optionally substituted with one or more R-0; each Q is independently selected from the group -CHR13-, -NR13-, -O-, and -S(O)p-; R8 is H; 1-2 halogen; CrC6 alkyl; CrC6 haloalkyl; CrC6 alkoxy; CrC6 haloalkoxy; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; CrC6 alkylthio; C«-C6 haloalkylthio; C\-C6 alkylsulfinyl; CrC6 alkylsulfonyl;
C3-C6 cycloalkyl; C3-C6 alkenyloxy; CO2(CrC6 alkyl); NH(CrC6 alkyl);
N(CrC6 alkyl)2; cyano; nitro; SiR19R20R21; or GeR19R20R21; R9 is H; 1-2 halogen; CrC6 alkyl; CrC6 haloalkyl; CrC6 alkoxy; CrC6 haloalkoxy; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-Cg alkynyl; Ci-Cg alkylthio; CrC6 haloalkylthio; CrC6 alkylsulfinyl; Cι-C6 alkylsulfonyl;
C3-C6 cycloalkyl; C3-C6 alkenyloxy; CO2(CrC6 alkyl); NH(CrC6 alkyl);
N(CrC6 alkyl)2; -C(R18)=NOR17; cyano; nitro; SF5; SiR22R23R24; or
GeR22R 3R24; or R9 is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R1 J, R12, or both R1 1 and R12; each R10 is independently halogen; C1-C4 alkyl; Cι-C haloalkyl; Cι-C4 alkoxy; nitro; or cyano; or when R9 and an R10 are attached to adjacent atoms on Z, R9 and said adjacently attached R10 can be taken together as -OCH2O- or -OCH2CH2O-; each CH2 group of said taken together R9 and R10 optionally substituted with 1-2 halogen; or when Y and an R10 are attached to adjacent atoms on Z and Y is
-CHR15O-N=C(R7)-, -O-N=C(R7)-, -O-CH2CH2O-N=C(R7)-, -CHR15O-C(R15)=C(R7)-, -CH=N-N=C(R7)-, -CHR15N(R15)-N=C(R7)- or
-CHR15N(COCH3)-N=C(R7)-, R7 and said adjacently attached R10 can be taken together as -(CH )r-J- such that J is attached to Z; J is -CH2-; -CH2CH2-; -OCH2-; -CH2O-; -SCH2-; -CH2S-; -N(R16)CH2-; or
-CH2N(R16)-; each CH2 group of said J optionally substituted with 1 to 2 CH3;
R11 and R12 are each independently 1-2 halogen; Cι-C alkyl; CrC haloalkyl;
C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C2-C6 alkoxyalkyl; C2-C6 alkylthioalkyl; C3-C6 alkoxyalkynyl; C7-Cι0 tetrahydropyranyloxyalkynyl; benzyloxymethyl; C1-C4 alkoxy; C1-C4 haloalkoxy; C3-C6 alkenyloxy; C3-C6 haloalkenyloxy; C3-C6 alkynyloxy;
C3-C6 haloalkynyloxy; C2-C6 alkoxyalkoxy; C5-C9 trialkylsilylalkoxyalkoxy;
C2-C6 alkylthioalkoxy; CrC4 alkylthio; CrC4 haloalkylthio; CrC4 alkylsulfinyl; CrC haloalkylsulfinyl; C1-C4 alkylsulfonyl; CrC4 haloalkylsulfonyl; C3-C6 alkenylthio; C3-C6 haloalkenylthio; C2-C6 alkylthioalkylthio; nitro; cyano; thiocyanato; hydroxy; N(R2^)2; SF5;
Si(R25)3; Ge(R25)3; (R25)3Si-C≡C-; OSi(R 5)3; OGe(R2 )3; C(=O)R26; C(=S)R26; C(=O)OR26; C(=S)OR26; C(=O)SR26; C(=S)SR26;
C(=O)N(R26)2; C(=S)N(R26)2; OC(=O)R26; OC(=S)R26; SC(=O)R26;
SC(=S)R26; N(R 6)C(=O)R26; N(R 6)C(=S)R26; OC(=O)OR27;
OC(=O)SR27; OC(=O)N(R26)2; SC(=O)OR27; SC(=O)SR27; S(O)2OR26; S(O)2N(R26)2; OS(O)2R27; N(R26)S(O)2R27; or phenyl, phenoxy, benzyl, benzyloxy, phenylsulfonyl, phenylethynyl or pyridinylethynyl, each optionally substituted with halogen, C1-C4 alkyl, CrC haloalkyl, C!-C alkoxy, C1-C4 haloalkoxy, nitro or cyano; each R13 is independently H; Cj-Cg alkyl; C Cg haloalkyl; or phenyl optionally substituted with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, CJ-C4 haloalkoxy, nitro or cyano; R14 is H; halogen; CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl;
C2-Cg alkynyl; C2-C6 haloalkynyl; or C3~C6 cycloalkyl; each R15 is independently H; Cj-C3 alkyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C1-C4 alkyl,
C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano; or when Y is -CHR15N(R15)C(=O)N(R15)-, the two R15 attached to nitrogen atoms on said group can be taken together as -(CH2)S-; or when Y is -CHR15O-N=C(R7)NR15-, R7 and the adjacently attached R15 can be taken together as -CH2-(CH2)S-; -O-(CH2)s-; -S-(CH2)S-; or
-N(C]-C3 alkyl)-(CH2)s-; with the directionality of said linkage defined such that the moiety depicted on the left side of the linkage is bonded to the carbon and the moiety on the right side of the linkage is bonded to the nitrogen; R16, R17, and R18 are each independently H; CrC3 alkyl; C3-C6 cycloalkyl; or phenyl optionally substituted with halogen, C1-C4 alkyl, C1-C4 haloalkyl,
C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano; R19, R20, R21, R22, R23, and R24 are each independently CrC6 alkyl; C2-C6 alkenyl; C1-C4 alkoxy; or phenyl; each R25 is independently C j -C4 alkyl; C j -C4 haloalkyl; C2-C4 alkenyl; C ] -C4 alkoxy; or phenyl; each R26 is independently H; CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-Cg alkynyl; C2-C6 haloalkynyl; C3- cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, CrC4 alkyl, CrC4 haloalkyl, CrC alkoxy, C1-C4 haloalkoxy, nitro or cyano; each R27 is independently Cj-Cg alkyl; Cj-Cg haloalkyl; C2-C6 alkenyl; C2-Cg haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C j-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano; m, n and p are each independently 0, 1 or 2; r is 0 or 1 ; and s is 2 or 3.
This invention provides a method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound of Formula I including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, provided that:
(i) when E is 1,2-phenylene optionally substituted with one of R3, R4, or both R3 and R4; X is OR1, SCOmR1 or halogen; Y is -O-, -S(O)n-, -ΝR15-, -C(=O)-,-CH(OR15)-, -CHR6-, -CHR6CHR6-, -CR6=CR6-, -C≡C-, -CHR15O-, -OCHR15-, -CHR15S(O)n-, -S(O)nCHR15-,
-CHR15O-Ν=C(R7)-, -(R )C=N-OCH(R15)-, -C(R7)=N-O-, -O-N=C(R7)-, -CHR15OC(=O)N(R15)- or a direct bond; and R9 is SiR22R23R24 or GeR22R23R24; then Z is other than phenyl or a 5 to 14-membered aromatic heterocyclic ring system each substituted with R9 and optionally substituted with one or more R10;
(ii) when E is a naphthalene ring optionally substituted with one of R3, R4, or both R3 and R4; R3 or R4 is Si(R25)3 or Ge(R25)3; and Y is -O-, -S(O)n-, -C(=O)-, -CHR6-, -CHR6CHR6-, -CR6=CR6-, -C≡C-, -OCHR15-, -S(O)nCHR15- or a direct bond; then Z is other than CrC10 alkyl, C2-C10 alkenyl or C2-Cιo alkynyl each substituted with R9 and optionally substituted with one or more R10; and (iii) when E is a naphthalene ring optionally substituted with one of R3, R4, or both R3 and R4; R3 or R4 is Si(R 5)3 or Ge(R2 )3; and Y is -S(O)n-, -C(=O)-, -C≡C- or a direct bond; then Z is other than phenyl substituted with R9 and optionally substituted with one or more R10.
This invention also provides selected compounds of Formula I which are considered particularly effective fungicides and arthropodicides. Specifically, this invention provides compounds of Formula IA including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, and agricultural compositions containing them and their use as fungicides and arthropodicides:
IA wherein
E is 1,2-phenylene optionally substituted with one of R3, R4, or both R3 and R4; A is O or N; G is C or N; provided that when G is C, then A is O and the floating double bond is attached to G; and when G is N, then A is N and the floating double bond is attached to A; W is O; X is OR1; R1 is C1-C3 alkyl;
R2 is H or CrC2 alkyl;
R3 and R4 are each independently halogen; cyano; nitro; Ci-Cg alkyl; Cj-Cg haloalkyl; Cj-Cg alkoxy; or Cι-C6 haloalkoxy; CrC6 alkylsulfonyl; C2-C6 alkylcarbonyl; C2-C6 alkoxycarbonyl; (CrC4 alkyl)NHC(O); (C1-C4 alkyl)2NC(O); benzoyl; or phenylsulfonyl;
Y is -O-; -S(O)n-; -NR15-; -C(=O)-; -CH(OR15)-; -CH2-; -CH2CH2-; -CH=CH-; -C≡C-; -CH2O-; -OCH2-; -CH2S(O)n-; -S(O)nCH2-; or a direct bond; and the directionality of the Y linkage is defined such that the moiety depicted on the left side of the linkage is bonded to E and the moiety on the right side of the linkage is bonded to Z;
Z is selected from the group 2-thiazolyl; 1,2,4-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,4-thiadiazolyl; 1,3,4-thiadiazolyl; and pyrazinyl; each group substituted with R9 and optionally substituted with one or more R10; R9 is H; halogen; CrC6 alkyl; CrC6 haloalkyl; CrC6 alkoxy; Cι-C6 haloalkoxy; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; CrC6 alkylthio; CrC6 haloalkylthio; Cj-Cg alkylsulfinyl; Cj-Cg alkylsulfonyl; C3-C6 cycloalkyl; C3-C6 alkenyloxy; CO2(CrC6 alkyl); NH(CrC6 alkyl); N(CrC6 alkyl)2; -C(R18)=NOR17; cyano; nitro; SF5; SiR 2R23R24; or GeR22R 3R24; or R9 is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R1 -, R12, or both R1 * and R12; provided that when Z is pyrazinyl, then R9 is other than H or C--C6 haloalkyl; each R10 is independently halogen; C*-C4 alkyl; C1-C4 haloalkyl; C1-C4 alkoxy; nitro; or cyano; or when R9 and an R10 are attached to adjacent atoms on Z, R9 and said adjacently attached R10 can be taken together as -OCH2O- or -OCH2CH2O-; each CH2 group of said taken together R9 and R10 optionally substituted with 1-2 halogen; R11 and R12 are each independently 1-2 halogen; -C4 alkyl; C1-C4 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C2-C6 alkoxyalkyl; C2-Cg alkyl thioalkyl; C3-C6 alkoxy alkynyl; C7-C10 tetrahydropyranyloxy alkynyl; benzyloxymethyl; C1-C4 alkoxy; C1-C4 haloalkoxy; C3-C6 alkenyloxy; C3-Cg haloalkenyloxy; C3-Cg alkynyloxy;
C3-C6 haloalkynyloxy; C2-C6 alkoxyalkoxy; C5-C9 trialkylsilylalkoxyalkoxy; C2-C6 alkylthioalkoxy ; C l -C4 alkylthio; C j -C4 haloalkylthio; C j -C4 alkylsulfinyl; C1-C4 haloalkylsulfinyl; C1-C4 alkylsulfonyl; C1-C4 haloalkylsulfonyl; C3-C6 alkenylthio; C3-Cg haloalkenylthio; C2-C6 alkylthioalkylthio; nitro; cyano; thiocyanato; hydroxy; N(R26)2; SF5;
Si(R25)3; Ge(R 5)3; (R2 )3Si-C≡C-; OSi(R2 )3; OGe(R25)3; C(=O)R26; C(=S)R26; C(=O)OR 6; C(=S)OR 6; C(=O)SR26; C(=S)SR26;
C(=O)N(R26)2; C(=S)N(R26)2; OC(=O)R26; OC(=S)R26; SC(=O)R26;
SC(=S)R26; N(R26)C(=O)R26; N(R26)C(=S)R26; OC(=O)OR27;
OC(=O)SR27; OC(=O)N(R 6)2; SC(=O)OR27; SC(=O)SR27; S(O)2OR26;
S(O)2N(R26)2; OS(O)2R27; N(R 6)S(O)2R27; or phenyl, phenoxy, benzyl, benzyloxy, phenylsulfonyl, phenylethynyl or pyridinylethynyl, each optionally substituted with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, CrC haloalkoxy, nitro or cyano; R15 is H; C1-C3 alkyl; or cyclopropyl;
R17 and R18 are each independently H; C1-C3 alkyl; C3~C6 cycloalkyl; or phenyl optionally substituted with halogen, CrC4 alkyl, CrC4 haloalkyl, C1-C4 alkoxy, C -C4 haloalkoxy, nitro or cyano; R22, R23, and R24 are each independently CrC6 alkyl; C2-C6 alkenyl; C1-C4 alkoxy; or phenyl; each R25 is independently CrC alkyl; C1-C4 haloalkyl; C2-C4 alkenyl; C C4 alkoxy; or phenyl; each R26 is independently H; CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C*-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1 -C haloalkoxy, nitro or cyano; each R27 is independently Ci-Cg alkyl; Ci-Cg haloalkyl; C -C alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, Cj-C4 alkyl, C1-C4 haloalkyl, Ct-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano; and n is 0, l or 2. This invention also provides certain compounds of Formula I which are useful as fungicides and arthropodicides. Specifically, this invention provides compounds of Formula IB including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, and agricultural compositions containing them and their use as fungicides and arthropodicides:
IB wherein
E is selected from: i) 1,2-phenylene optionally substituted with one of R3, R4, or both R3 and R4; ii) a naphthalene ring, provided that when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, the naphthalene ring optionally substituted with one of R3, R4, or both R3 and R4; and iii) a ring system selected from 5 to 12-membered monocyclic and fused bicyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each fused bicyclic ring system optionally containing one nonaromatic ring that optionally includes one or two Q as ring members and optionally includes one or two ring members independently selected from C(=O) and S(O)2, provided that G is attached to an aromatic ring, and when
G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, each aromatic heterocyclic ring system optionally substituted with one of R3, R4, or both R3 and R4; A is O; S; N; NR5; or CR14;
G is C or N; provided that when G is C, then A is O, S or NR5 and the floating double bond is attached to G; and when G is N, then A is N or CR14 and the floating double bond is attached to A; W is O; S; NH; N(CrC6 alkyl); or NO(CrC6 alkyl); X is H; OR1 ; SCO^R1 ; halogen; CrC6 alkyl; CrC6 haloalkyl; C3-C6 cycloalkyl; cyano; NH2; NHR1; N(CrC6 alkyl)!*1; NH(CrC6 alkoxy); or
N(CrC6 alkoxy)R1; R1 is CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C -C6 haloalkynyl; C3-C6 cycloalkyl; C2-C alkylcarbonyl; or C2-C alkoxycarbonyl;
R2 is H; CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-Cg haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; C -C4 alkoxycarbonyl; hydroxy; Cι-C alkoxy; or acetyloxy; R3 and R4 are each independently halogen; cyano; nitro; hydroxy; Cι-C6 alkyl; C2 -C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; Cι-C6 alkoxy; CrC6 haloalkoxy; C2-C6 alkenyloxy; C2-C6 alkynyloxy; Cι-C6 alkylthio; Cι-C6 alkylsulfinyl; Cj-Cg alkylsulfonyl; formyl;
C2-C6 alkylcarbonyl; C2-C6 alkoxycarbonyl; NH2C(O);
(CrC4 alkyl)NHC(O); (CrC4 alkyl)2NC(O); Si(R25)3; Ge(R25)3; (R25)3Si-C≡C-; or phenyl, phenylethynyl, benzoyl, or phenylsulfonyl each substituted with R8 and optionally substituted with one or more R10; or when E is 1,2-phenylene and R3 and R4 are attached to adjacent atoms, R3 and R4 can be taken together as C3-C5 alkylene, C3-C5 haloalkylene, C3-C5 alkenylene or C3-C5 haloalkenylene each optionally substituted with 1-2 CrC3 alkyl;
R5 is H; CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-Cg haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; or C2-C4 alkoxycarbonyl; Y is -O-; -S(O)n-; -NR15-; -C(=O)-; -CH(OR15)-; -CHR6-; -CHR^CHR6-; -CR6=CR6-; -C≡C-; -CHR15O-; -OCHR15-; -CHR15S(O)n-; -S(O)nCHR15-;
-CHR15O-N=C(R7)-; -(R7)C=N-OCH(R15)-; -C(R7)=N-O-; -O-N=C(R7)-; -CHR15OC(=O)N(R15)-; -CHR15OC(=S)N(R15)-; -CHR15OC(=O)O-;
-CHR15OC(=S)O-; -CHR15OC(=O)S-; -CHR15OC(=S)S-;
-CHR15SC(=O)N(R15)-; -CHR15SC(=S)N(R15)-; -CHR15SC(=O)O-;
-CHR15SC(=S)O-; -CHR15SC(=O)S-; -CHR15SC(=S)S-; -CHR15SC(=NR15)S-; -CHR15N(R15)C(=O)N(R15)-;
-CHR15O-N(R15)C(=O)N(R15)-; -CHR15O-N(R15)C(=S)N(R15)-;
-CHR15O-N=C(R7)NR15-; -CHR15O-N=C(R7)OCH2-;
-CHR15O-N=C(R7)-N=N-; -CHR15O-N=C(R7)-C(=O)-;
-CHR15O-N=C(R7)-C(=N-A2-Z1)-A1-; -CHR15O-N=C(R7)-C(R7)=N-A2-A3-; -CHR15O-N=C(-C(R7)=N-A2-Z1)-;
-CHR15O-N=C(R7)-CH2O-; -CHR15O-N=C(R7)-CH2S-;
-O-CH2CH2O-N=C(R7)-; -CHR15O-C(R15)=C(R7)-; -CHR15O-C(R7)=N-;
-CHR15S-C(R7)=N-; -C(R7)=N-NR15-; -CH-=N-N=C(R7)-;
-CHR15N(R15)-N=C(R7)-; -CHR15N(COCH3)-N=C(R7)-; -OC(=S)NR15C(=O)-; -CHR6-C(=W1)-A1-; -CHR6CHR6-C(=W1)-A1-;
-CR6=CR6-C(=W1)-A1-; -C≡C-C(=W1)-A1-; -N=CR6-C(=W1)-A1-; or a direct bond; and the directionality of the Y linkage is defined such that the moiety depicted on the left side of the linkage is bonded to E and the moiety on the right side of the linkage is bonded to Z; Z1 is H or -A3-Z;
W1 is O or S;
A1 is O; S; NR15; or a direct bond; A2 is O; NR15; or a direct bond; A3 is -C(=O)-; -S(O)2-; or a direct bond; each R6 is independently H; 1-2 CH3; C2-C3 alkyl; CrC3 alkoxy; C3-C6 cycloalkyl; formylamino; C2-C4 alkylcarbonylamino; C -C4 alkoxycarbonylamino; NH2C(O)NH; (CrC3 alkyl)NHC(O)NH;
(Cι-C3 alkyl)2NC(O)NH; N(CrC3 alkyl)2; piperidinyl; moφholinyl;
1-2 halogen; cyano; or nitro; each R7 is independently H; CrC6 alkyl; CrC6 haloalkyl; CrC6 alkoxy; CrC6 haloalkoxy; Cι-C6 alkylthio; CrC6 alkylsulfinyl; CrC6 alkylsulfonyl; CrC6 haloalkylthio; Cj-Cg haloalkylsulfinyl; CrC6 haloalkylsulfonyl; C2-C6 alkenyl; C2-Cg haloalkenyl; C2-C6 alkynyl; C -C6 haloalkynyl; C3~C6 cycloalkyl; C -C alkylcarbonyl; C2-C4 alkoxycarbonyl; halogen; cyano; nitro; hydroxy; amino; NH(Cι-Cg alkyl); N(Cj-C6 alkyl)2; or moφholinyl; each Z is independently selected from: i) C Cjo alkyl, C2-C*o alkenyl, or C2-C10 alkynyl each substituted with R9 and optionally substituted with one or more R10; ii) C3-C8 cycloalkyl, C3-C8 cycloalkenyl or phenyl each substituted with R9 and optionally substituted with one or more R10; iii) a ring system selected from 3 to 14-membered monocyclic, fused bicyclic and fused tricyclic nonaromatic heterocyclic ring systems and 5 to 14-membered monocyclic, fused bicyclic and fused tricyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each nonaromatic or aromatic heterocyclic ring system substituted with R9 and optionally substituted with one or more R10; iv) a multicyclic ring system selected from 8 to 14-membered fused-bicyclic and fused-tricyclic ring systems which are an aromatic carbocyclic ring system, a nonaromatic carbocyclic ring system, or a ring system containing one or two nonaromatic rings that each include one or two Q as ring members and one or two ring members independently selected from C(=O) and S(O)2, and any remaining rings as aromatic carbocyclic rings, each multicyclic ring system substituted with R9 and optionally substituted with one or more R10; and v) adamantyl substituted with R9 and optionally substituted with one or more
RlO; each Q is independently selected from the group -CHR13-, -NR13-, -O-, and
-S(O)p-; R8 is H; 1-2 halogen; CrC6 alkyl; CrC6 haloalkyl; CrC6 alkoxy; CrC6 haloalkoxy; C2-Cg alkenyl; C2-C6 haloalkenyl; C2- alkynyl; Ci-Cg alkylthio; Ci-Cg haloalkylthio; Ci-Cg alkylsulfinyl; Ci-Cg alkylsulfonyl; C3-C6 cycloalkyl; C3-C6 alkenyloxy; CO2(CrC6 alkyl); NH(CrC6 alkyl);
N(CrC6 alkyl)2; cyano; nitro; SiR19R20R21; or GeR19R 0R21; R9 is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy each substituted with R1 1 and optionally substituted with R12; each R10 is independently halogen; Cj-C alkyl; C1-C4 haloalkyl; C1-C4 alkoxy; nitro; or cyano; or when R9 and an R10 are attached to adjacent atoms on Z, R9 and said adjacently attached R10 can be taken together as -OCH2O- or -OCH2CH2O-; each CH2 group of said taken together R9 and R10 optionally substituted with 1-2 halogen; or when Y and an R10 are attached to adjacent atoms on Z and Y is
-CHR15O-N=C(R7)-, -O-N=C(R7)-, -O-CH2CH2O-N=C(R7)-, -CHR15O-C(R15)=C(R7)-, -CH=N-N=C(R7)-, -CHR15N(R15)-N=C(R7)- or -CHR15N(COCH3)-N=C(R7)-, R7 and said adjacently attached R10 can be taken together as -(CH2)r-J- such that J is attached to Z; J is -CH2-; -CH2CH2-; -OCH2-; -CH2O-; -SCH2-; -CH2S-; -N(R16)CH2-; or
-CH2N(R16)-; each CH2 group of said J optionally substituted with 1 to 2 CH3; R11 is C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C2-C6 alkoxyalkyl; C2-C6 alkyl thioalkyl; C3-C6 alkoxy alkynyl; C7-C10 tetrahydropyranyloxyalkynyl; benzyloxymethyl; C3-C6 alkenyloxy; C3-C6 haloalkenyloxy; C3-C6 alkynyloxy; C3-C6 haloalkynyloxy; C2-C6 alkoxyalkoxy; C5-C9 trialkylsilylalkoxyalkoxy; C2-Cg alkylthioalkoxy; C1-C4 alkylthio; C1-C4 haloalkylthio; C1-C4 alkylsulfinyl; C1-C4 haloalkylsulfinyl; C1-C4 alkylsulfonyl; CrC4 haloalkylsulfonyl; C3-C6 alkenylthio; C3-C6 haloalkenylthio; C2-C6 alkylthioalkylthio; thiocyanato; hydroxy; N(R26)2;
SF5; (R25)3Si-C≡C-; OSi(R25)3; OGe(R25)3; C(=O)R26; C(=S)R26; C(=O)OR26; C(=S)OR26; C(=O)SR26; C(=S)SR26; C(=O)N(R26)2; C(=S)N(R26)2; OC(=O)R26; OC(=S)R26; SC(=O)R26; SC(=S)R26; N(R26)C(=O)R26; N(R26)C(=S)R26; OC(=O)OR27; OC(=O)SR27; OC(=O)N(R26)2; SC(=O)OR27; SC(=O)SR27; S(O)2OR26; S(O)2N(R26)2;
OS(O)2R27; N(R26)S(O)2R27; or phenyl, phenoxy, benzyl, benzyloxy, phenylsulfonyl, phenylethynyl or pyridinylethynyl, each optionally substituted with halogen, C1-C4 alkyl, Cj-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano; R12 is 1-2 halogen; CrC4 alkyl; CrC4 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-Cg alkynyl; C2-C6 haloalkynyl; C2-C6 alkoxyalkyl; C2-C6 alkylthioalkyl; C3-C<5 alkoxy alkynyl; C7-C10 tetrahydropyranyloxyalkynyl; benzyloxymethyl; -C4 alkoxy; CrC4 haloalkoxy; C3-C6 alkenyloxy; C3-C6 haloalkenyloxy; C3-C6 alkynyloxy; C3-C6 haloalkynyloxy; C2-Cg alkoxyalkoxy; C5-C9 trialkylsilylalkoxyalkoxy; C2-Cg alkylthioalkoxy; C*-C4 alkylthio; C1-C4 haloalkylthio; Cj-C4 alkylsulfinyl; Cj-C4 haloalkylsulfinyl; CrC4 alkylsulfonyl; CrC4 haloalkylsulfonyl; C3-C6 alkenylthio; C3-C6 haloalkenylthio; C -C6 alkylthioalkylthio; nitro; cyano; thiocyanato; hydroxy;
N(R26)2; SF5; Si(R2 )3; Ge(R25)3; (R25)3Si-C≡C-; OSi(R 5)3; OGe(R25)3;
C(=O)R26; C(=S)R26; C(=O)OR26; C(=S)OR26; C(=O)SR26; C(=S)SR26; C(=O)N(R26)2; C(=S)N(R26)2; OC(=O)R26; OC(=S)R26; SC(=O)R26;
SC(=S)R26; N(R26)C(=O)R26; N(R26)C(=S)R26; OC(=O)OR27;
OC(=O)SR27; OC(=O)N(R26)2; SC(=O)OR27; SC(=O)SR27; S(O)2OR26;
S(O)2N(R26)2; OS(O)2R27; N(R26)S(O)2R27; or phenyl, phenoxy, benzyl, benzyloxy, phenylsulfonyl, phenylethynyl or pyridinylethynyl, each optionally substituted with halogen, C * -C4 alkyl, C } -C4 haloalkyl, C j -C4 alkoxy, C j -C4 haloalkoxy, nitro or cyano; each R13 is independently H; Cι-C6 alkyl; CrC6 haloalkyl; or phenyl optionally substituted with halogen, CrC4 alkyl, CrC4 haloalkyl, CrC4 alkoxy, CrC4 haloalkoxy, nitro or cyano; R14 is H; halogen; CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl;
C2-C6 alkynyl; C2-C6 haloalkynyl; or C3-C6 cycloalkyl; each R15 is independently H; -C3 alkyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, CrC4 alkyl,
C]-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano; or when Y is -CHR15N(R15)C(=O)N(R15)-, the two R15 attached to nitrogen atoms on said group can be taken together as -(CH2)S-; or when Y is -CHR15O-N=C(R7)NR15-, R7 and the adjacently attached R15 can be taken together as -CH2-(CH2)S-; -O-(CH2)s-; -S-(CH2)S-; or
-N(CrC3 alkyl)-(CH )s-; with the directionality of said linkage defined such that the moiety depicted on the left side of the linkage is bonded to the carbon and the moiety on the right side of the linkage is bonded to the nitrogen; R16 is H; Cj-C3 alkyl; C3-C6 cycloalkyl; or phenyl optionally substituted with halogen, CrC4 alkyl, CrC haloalkyl, C1-C4 alkoxy, C|-C4 haloalkoxy, nitro or cyano;
R19, R20, and R21 are each independently CrC6 alkyl; C2-C6 alkenyl; CrC4 alkoxy; or phenyl; each R25 is independently CrC4 alkyl; CrC4 haloalkyl; C2-C4 alkenyl; CrC4 alkoxy; or phenyl; each R26 is independently H; CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C--C4 alkyl, C1-C4 haloalkyl, CpC4 alkoxy, CrC4 haloalkoxy, nitro or cyano; each R27 is independently CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C C4 alkyl, Cι-C haloalkyl, Cι-C4 alkoxy, Cι-C4 haloalkoxy, nitro or cyano; m, n and p are each independently 0, 1 or 2; r is 0 or 1 ; and s is 2 or 3. This invention also provides compounds of Formula II including all geometric and stereoisomers which are useful as intermediates for the preparation of the fungicides and arthropodicides of Formula I where Y is oxygen:
π wherein
E is 1,2-phenylene optionally substituted with one of R3, R4, or both R3 and R4; A is O; S; N; NR5; or CR14;
G is C or N; provided that when G is C, then A is O, S or NR5 and the floating double bond is attached to G; and when G is N, then A is N or CR14 and the floating double bond is attached to A;
W is O; S; NH; N(CrC6 alkyl); or NO(CrC6 alkyl);
X is OR1; SCO^R1; or halogen;
R1 is CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; or C2-C4 alkoxycarbonyl;
R2 is H; CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; 2-C^ haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; C2-C4 alkoxycarbonyl; hydroxy; C*-C2 alkoxy; or acetyloxy; R3 and R4 are each independently halogen; cyano; nitro; hydroxy; C*-C6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; Cj-Cg alkoxy; CrC6 haloalkoxy; C2-C6 alkenyloxy; C2-C6 18 alkynyloxy; C.-Cg alkylthio; CpC6 alkylsulfinyl; Cj-Cg alkylsulfonyl; formyl; C2-C6 alkylcarbonyl; C2-C6 alkoxycarbonyl; NH2C(O); (CrC4 alkyl)NHC(O); (CrC4 alkyl)2NC(O); Si(R25)3; Ge(R25)3; (R25)3Si-C≡C-; or phenyl, phenylethynyl, benzoyl, or phenylsulfonyl each substituted with R8 and optionally substituted with one or more R10; or when R3 and R4 are attached to adjacent atoms, R3 and R4 can be taken together as C3-C5 alkylene, C3-C5 haloalkylene, C3-C5 alkenylene or C3-C5 haloalkenylene each optionally substituted with 1-2 C1-C3 alkyl; R5 is H; CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C -C6 haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; or C2-C4 alkoxycarbonyl; R8 is H; 1-2 halogen; CrC6 alkyl; CrC6 haloalkyl; ^-Cg alkoxy; CrC6 haloalkoxy; C2-C6 alkenyl; C -Cg haloalkenyl; C2-Cg alkynyl; C1-C6 alkylthio; C Cg haloalkylthio; Cj-Cg alkylsulfinyl; CrC6 alkylsulfonyl; C3-C6 cycloalkyl; C3-C6 alkenyloxy; CO2(C1-C6 alkyl); NH(CrC6 alkyl);
N(CrC6 alkyl)2; cyano; nitro; SiR19R θR21; or GeR19R2θR2l ; each R10 is independently halogen; C C alkyl; C1-C4 haloalkyl; CrC4 alkoxy; nitro; or cyano; R14 is H; halogen; CrC6 alkyl; CrC6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; or C3-C6 cycloalkyl;
R19, R20 and R21 are each independently CrC6 alkyl; C2-C6 alkenyl; CrC4 alkoxy; or phenyl; each R25 is independently C1-C4 alkyl; C1-C4 haloalkyl; C2-C4 alkenyl; C1-C4 alkoxy; or phenyl; and m is 0, 1 or 2.
DETAILS OF THE INVENTION In the above recitations, the term "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. The term "1-2 CH3" indicates that the substituent can be methyl or, when there is a hydrogen attached to the same atom, the substituent and said hydrogen can both be methyl. "Alkenyl" includes straight-chain or branched alkenes such as vinyl, 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 alkanediyl. Examples of "alkylene" include CH2CH2CH2, CH2CH2CH2CH2, CH2CH2CH2CH2CH2. "Alkenylene" denotes a straight-chain alkenediyl containing one olefinic bond. Examples of "alkenylene" include CH2CH=CH, CH2CH2CH=CH, CH2CH=CHCH2 and CH2CH=CHCH2CH2. "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2. "Alkoxyalkoxy" denotes alkoxy substitution on alkoxy. "Alkenyloxy" includes straight-chain or branched alkenyloxy moieties. Examples of "alkenyloxy" include H2C=CHCH2O, (CH3)2C=CHCH2O, (CH3)CH=CHCH2O, (CH3)CH=C(CH3)CH2O and CH2=CHCH2CH2O. "Alkynyloxy" includes straight-chain or branched alkynyloxy moieties. Examples of "alkynyloxy" include HC≡CCH2O, CH3OCCH2O and CH3C≡CCH2CH2O. "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylfhio, butylthio, pentylthio and hexylthio isomers. "Alkylthioalkyl" denotes alkylthio substitution on alkyl. Examples of "alkylthioalkyl" include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. "Alkylthioalkylthio" denotes alkylthio substitution on alkylthio. Analogously, "alkylthioalkoxy" denotes alkylthio substitution on alkoxy. "Alkylsulfinyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH3S(O), CH3CH2S(O), CH3CH2CH2S(O), (CH3)2CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH3S(O)2, CH3CH2S(O)2, CH3CH2CH2S(O)2, (CH3)2CHS(O)2 and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. "Alkenylthio" is defined analogously to the above examples. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. "Cycloalkenyl" includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- and 1,4-cyclohexadienyl. "Trialkylsilylalkoxyalkoxy" denotes trialkylsilylalkoxy substitution on alkoxy. Examples of "trialkylsilylalkoxyalkoxy" includes, for example,
(CH3)3SiCH2CH2OCH2O. The term "aromatic carbocyclic ring system" includes fully aromatic carbocycles and carbocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the Hϋckel rule is satisfied). The term "nonaromatic carbocyclic ring system" denotes fully saturated carbocycles as well as partially or fully unsaturated carbocycles where the Hϋckel rule is not satisfied by any of the rings in the ring system. The term "aromatic heterocyclic ring system" includes fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the Hϋckel rule is satisfied . The term "nonaromatic heterocyclic ring system" denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles where the Hϋckel rule is not satisfied by any of the rings in the ring system. The heterocyclic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen. One skilled in the art will appreciate that not all nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides .
The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. The term "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 F3C, C1CH2, CF3CH2 and CF3CC12. The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include (C1)2C=CHCH2 and CF3CH2CH=CHCH2. Examples of "haloalkynyl" include HC≡CCHCl, CF3C≡C, CC13C≡C and FCH2C≡CCH2. Examples of "haloalkoxy" include CF3O, CCl3CH2O, HCF2CH2CH2O and CF3CH2O. Examples of "haloalkylthio" include CC13S, CF3S, CC13CH2S and C1CH2CH2CH2S. Examples of "haloalkylsulfinyl" include CF3S(O), CCl3S(O), CF3CH2S(O) and CF3CF2S(O). Examples of "haloalkylsulfonyl" include CF3S(O)2, CCl3S(O)2, CF3CH2S(O)2 and CF3CF2S(O)2. The total number of carbon atoms in a substituent group is indicated by the "C--Cj" prefix where i and j are numbers from 1 to 10. For example, C1-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl. Examples of "alkylcarbonyl" include C(O)CH3, C(O)CH2CH2CH3 and C(O)CH(CH3)2. Examples of "alkoxycarbonyl" include CH3OC(=O), CH3CH2OC(=O), CH3CH2CH2OC(=O), (CH3)2CHOC(=O) and the different butoxy- or pentoxycarbonyl isomers. In the above recitations, when a compound of Formula I 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.
When a group contains a substituent which can be hydrogen, for example R9 or R13, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that 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. Accordingly, the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form. The salts of the compounds of the invention include acid- addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a phenol.
Preferred methods for reasons of better activity and/or ease of synthesis are: Preferred 1. Methods for controlling arthropods using compounds of Formula I above, and N-oxides and agriculturally suitable salts thereof, wherein:
E is selected from the group 1,2-phenylene; 1,5-, 1,6-, 1,7-, 1,8-, 2,6-, 2,7-, 1,2-, and 2,3-naphthalenediyl; lH-pyrrole-1,2-, 2,3- and 3,4-diyl; 2,3- and 3,4-furandiyl; 2,3- and 3,4-thiophenediyl; lH-pyrazole-1,5-, 3,4- and 4,5-diyl; lH-imidazole-1,2-, 4,5- and 1,5-diyl; 3,4- and 4,5-isoxazolediyl; 4,5-oxazolediyl; 3,4- and
4,5-isothiazolediyl; 4,5-thiazolediyl; lH-l,2,3-triazole-l,5- and 4,5-diyl; 2H-l,2,3-triazole-4,5-diyl; lH-l,2,4-triazole- 1,5-diyl; 4H-l,2,4-triazole-3,4-diyl; l,2,3-oxadiazole-4,5-diyl; l,2,5-oxadiazole-3,4-diyl; l,2,3-thiadiazole-4,5-diyl; l,2,5-thiadiazole-3,4-diyl; lH-tetrazole- 1,5-diyl; 2,3- and
3,4-pyridinediyl; 3,4- and 4,5-pyridazinediyl; 4,5-pyrimidinediyl; 2,3-pyrazinediyl; l,2,3-triazine-4,5-diyl; l,2,4-triazine-5,6-diyl; lH-indole-1,4-, 1,5-, 1,6-, 1,7-, 2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 1,2-, 2,3-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 2,3-, 4,5-, 5,6- and 6,7-benzofurandiyl; benzo[fe]thiophene-2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 2,3-, 4,5-, 5,6- and 6,7-diyl; lH-indazole-1,4-, 1,5-, 1,6-, 1,7-, 3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; lH-benzimidazole-1,4-, 1,5-, 1,6-, 1,7-, 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-diyl; l,2-benzisoxazole-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 5 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-benzoxazolediyl; l,2-benzisothiazole-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-benzothiazolediyl; 2,5-, 2,6-, 2,7-, 2,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 2,3-, 3,4-, 5,6-, 6,7- and 7,8-quinolinediyl; 1,5-, 1,6-, 1,7-, 1,8-, 3,5-, 3,6-,
10 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 3,4-, 5,6-, 6,7- and
7,8-isoquinolinediyl; 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 3,4-, 5,6-, 6,7- and 7,8-cinnolinediyl; 1,5-, 1,6-, 1,7-, 1,8-, 5,6-, 6,7- and 7,8-phthalazinediyl; 2,5-, 2,6-, 2,7-, 2,8-, 4,5-, 4,6-, 4,7-, 4,8-, 5,6-, 6,7- and 7,8-quinazolinediyl; 2,5-, 2,6-, 2,7-, 2,8-, 2,3-, 5,6-, 6,7-
15 and 7,8-quinoxalinediyl; l,8,-naphthyridine-2,5-, 2,6-, 2,7-, 3,5-,
3,6-, 4,5-, 2,3- and 3,4-diyl; 2,6-, 2,7-, 4,6-, 4,7-, 6,7-ρteridinediyl; pyrazolo[5,l-b]thiazole-2,6-, 2,7-, 3,6-, 3,7-, 2,3- and 6,7-diyl; thiazolo[2,3-c]-l,2,4-triazole-2,5-, 2,6-, 5,6-diyl; 2-oxo-l,3-benzodioxole-4,5- and 5,6-diyl;
20 l,3-dioxo-lH-isoindole-2,4-, 2,5-, 4,5- and 5,6-diyl;
2-oxo-2H-l-benzopyran-3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 5,6-, 6,7- and 7,8-diyl; [l,2,4]triazolo[l,5-a]pyridine-2,5-, 2,6-, 2,7-, 2,8-, 5,6-, 6,7- and 7,8-diyl; 3,4-dihydro-2,4-dioxo-2H-l,3-benzoxazine-3,5-, 3,6-, 3,7-, 3,8-,
25 5,6-, 6,7- and 7,8-diyl; 2,3-dihydro-2-oxo-3,4-, 3,5-, 3,6-, 3,7-,
4,5-, 5,6- and 6,7-benzofurandiyl; thieno[3,2-cf]thiazole-2,5-, 2,6-, and 5,6-diyl; 5,6,7,8-tetrahydro-2,5-, 2,6-, 2,7-, 2,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 2,3- and 3,4-quinolinediyl; 2,3-dihydro-l,l,3-trioxo-l,2-benzisothiazole-2,4-, 2,5-, 2,6-, 2,7-,
30 4,5-, 5,6- and 6,7-diyl; l,3-benzodioxole-2,4-, 2,5-, 4,5- and
5,6-diyl; 2,3-dihydro-2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-benzofurandiyl;
2,3-dihydro-l,4-benzodioxin-2,5-, 2,6-, 2,7-, 2,8-, 5,6- and 6,7-diyl; and 5,6,7, 8-tetrahydro-4H-cyclohepta[6]thiophene-2,4-, 2,5-, 2,6-,
35 2,7-, 2,8-, 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, and 2,3-diyl; each aromatic ring system optionally substituted with one of R3, R4, or both R3 and R4; W is O;
R1 is C1-C3 alkyl or CrC3 haloalkyl; 5 R2 is H; CrC6 alkyl; CrC6 haloalkyl; or C3-C6 cycloalkyl;
R3 and R4 are each independently halogen; cyano; nitro; Ci-Cg alkyl;
C C6 haloalkyl; Cι-C6 alkoxy; CrC6 haloalkoxy; CrC6 alkylthio;
Cj-Cg alkylsulfonyl; C2-Cg alkylcarbonyl; C2-Cg alkoxycarbonyl;
(CrC4 alkyl)NHC(O); (CrC4 alkyl)2NC(O); benzoyl; or 10 phenylsulfonyl;
Y is -O-; -S(O)n-; -NR15-; -C(=O)-; -CH(OR15)-; -CH2-; -CH2CH2-;
-CH=CH-; -C≡C-; -CH2O-; -OCH2-; -CH2S(O)n-; -S(O)nCH2-;
-CH2O-N=C(R7)-; -(R7)C=N-OCH(R15)-; -C(R7)=N-O-; or a direct bond; 15 R7 is H; CrC6 alkyl; CrC6 haloalkyl; CrC6 alkoxy; CrC6 alkylthio;
C2-Cg alkenyl; C2-Cg alkynyl; C3-C6 cycloalkyl; halogen; or cyano; or when Y and an R10 are attached to adjacent atoms on Z and Y is
-CH2O-N=C(R7)-, R7 and said adjacently attached R10 can be taken 20 together as -(CH2)r-J- such that J is attached to Z;
Z is selected from the group Cι-C10 alkyl; C3-Cg cycloalkyl; phenyl; naphthalenyl; anthracenyl; phenanthrenyl; lH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; lH-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; lH-l,2,3-triazolyl; 2H-l,2,3-triazolyl; 25 1H- 1 ,2,4-triazolyl; 4H- 1 ,2,4-triazolyl; 1 ,2,3-oxadiazolyl;
1,2,4-oxadiazolyl; 1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl;
1,2,3-thiadiazolyl; 1,2,4-thiadiazolyl; 1,2,5-thiadiazolyl;
1,3,4-thiadiazolyl; lH-tetrazolyl; 2H-tetrazolyl; pyridinyl; pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4-triazinyl; 30 1,2,4,5-tetrazinyl; lH-indolyl; benzofuranyl; benzo[ ?]thiophenyl; lH-indazolyl; lH-benzimidazolyl; benzoxazolyl; benzothiazolyl; quinolinyl; isoquinolinyl; cinnolinyl; phthalazinyl; quinazolinyl; quinoxalinyl; 1,8-naphthyridinyl; pteridinyl; 2,3-dihydro-lH-indenyl;
1 ,2,3,4-tetrahydronaphthalenyl; 35 6,7,8,9-tetrahydro-5H-benzocycloheptenyl;
5,6,7,8,9, 10-hexahydrobenzocyclooctenyl; 2,3-dihydro-3-oxobenzofuranyl; 1 ,3-dihydro- 1 -oxoisobenzofuranyl;
2,3-dihydro-2-oxobenzofuranyl;
3,4-dihydro-4-oxo-2H-l-benzopyranyl;
3,4-dihydro- 1 -oxo- lH-2-benzopyranyl; 3,4-dihydro-3-oxo- lH-2-benzopyranyl;
3 ,4-dihydro-2-oxo-2H- 1 -benzopyranyl; 4-oxo-4H- 1 -benzopyranyl;
2-oxo-2H- 1 -benzopyranyl;
2,3,4,5-tetrahydro-5-oxo-l-benzoxepinyl;
2,3,4,5-tetrahydro-2-oxo-l-benzoxepinyl; 2,3-dihydro- 1 ,3-dioxo- lH-isoindolyl;
1 ,2,3,4-tetrahydro- 1 ,3-dioxoisoquinoUnyl;
3,4-dihydro-2,4-dioxo-2H- 1 ,3-benzoxazinyl;
2-oxo- 1 ,3-benzodioxyl;
2,3-dihydro- 1 , 1 ,3-trioxo- 1 ,2-benzisothiazolyl; 9H-fluorenyl; azulenyl; and thiazolo[2,3-c]-l,2,4-triazolyl; each group substituted with R9 and optionally substituted with one or more R10; and R15 is Η; Cι-C3 alkyl; or C3-C6 cycloalkyl. Preferred 2. Methods of Preferred 1 wherein:
E is selected from the group 1,2-phenylene; 1,6-, 1,7-, 1,2-, and 2,3-naphfhalenediyl; 2,3- and 3,4-furandiyl; 2,3- and
3,4-thiophenediyl; 2,3- and 3,4-pyridinediyl; 4,5-pyrimidinediyl;
2,4-, 2,7-, 3,5-, 2,3-, 4,5-, 5,6- and 6,7-benzofurandiyl; and benzo[b]thiophene-2,4-, 2,7-, 3,5-, 2,3-, 4,5-, 5,6- and 6,7-diyl; each aromatic ring system optionally substituted with one of R3, R4, or both R3 and R4;
Z is selected from the group phenyl; naphthalenyl; 2-thiazolyl;
1,2,4-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,4-thiadiazolyl;
1,3,4-thiadiazolyl; pyridinyl; and pyrimidinyl; each group substituted with R9 and optionally substituted with one or more R10; R7 is Η; CrC6 alkyl; CrC6 haloalkyl; CrC6 alkoxy; CrC6 alkylthio;
C2-Cg alkenyl; C2-Cg alkynyl; cyclopropyl; halogen; or cyano; or when Y and an R10 are attached to adjacent atoms on Z and Y is
-CΗ2O-N=C(R7)-, R7 and said adjacently attached R10 can be taken together as -(CH2)r-J- such that J is attached to Z; J is -CH2- or -CH2CH2-; and r is 1. Preferred 3. Methods of Preferred 2 wherein:
E is 1 ,2-phenylene optionally substituted with one of R3, R4, or both R3 and R4; A is O or N; X is OR1;
R1 is Cι-C3 alkyl; R2 is H or CrC2 alkyl;
Y is -O-; -S(O)n-; -NR15-; -C(=O)-; -CH(OR15)-; -CH2-; -CH2CH2-;
-CH=CH-; -C≡C-; -CH2O-; -OCH2-; -CH2S(O)n-; -S(O)nCH2-; or a direct bond;
Z is selected from the group 2-thiazolyl; 1,2,4-oxadiazolyl;
1,3,4-oxadiazolyl; 1,2,4-thiadiazolyl; and 1,3,4-thiadiazolyl; each group substituted with R9 and optionally substituted with R10; and R15 is H; C1-C3 alkyl; or cyclopropyl. Preferred 4. Methods of Preferred 3 wherein:
R1 is methyl; R2 is methyl;
Y is -O-; -S(O)n-; -NR15-; -C(=O)-; -CH(OR15)-; -CH2-; or a direct bond; and R9 is H; halogen; CrC6 alkyl; CrC6 haloalkyl; CrC6 alkoxy; CrC6 haloalkoxy; C C alkylthio; C^Cg haloalkylthio; Cι-C6 alkylsulfinyl; CrCg alkylsulfonyl; C3-Cg cycloalkyl;
CO2(CrC6 alkyl); -C(R18)=NOR17; cyano; nitro; SF5;
S1R22R23R24. or GeR22R23R24; or R9 is phenyl, benzyl, phenoxy, pyridinyl, thienyl, furanyl, or pyrimidinyl each optionally substituted with one of R11, R12, or both R11 and R12. Preferred 5. Methods of Preferred 4 wherein:
Z is selected from the group 2-thiazolyl; 1,2,4-oxadiazolyl; and
1,2,4-thiadiazolyl; each group substituted with R9 and optionally substituted with R10; and
Y is -O-; and
R9 is phenyl optionally substituted with one of R11, R12, or both R1 1 and R12. Most preferred are methods of Preferred 5 where the compound is selected from the group:
4-[2-[[3-[3,5-bis(trifluoromethyl)phenyl]-l,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4- dihydro-5-methoxy-2-methyl-3H- 1 ,2,4-triazol-3-one; and 4-[2-[[3-[3,5-bis(trifluoromethyl)phenyl]-l,2,4-thiadiazol-5-yl]oxy]-6- methylphenyl]-2,4-dihydro-5-methoxy-2-methyl-3H-l,2,4-triazol-3-one. Preferred compounds of Formula IA for reasons of better arthropodicidal or fungicidal activity and/or ease of synthesis are:
Preferred IA. Compounds of Formula IA above, and N-oxides and agriculturally suitable salts thereof, wherein:
R1 is methyl; R2 is methyl;
Y is -O-; -S(O)n-; -ΝR15-; -C(=O)-; -CΗ(OR15)-; -CH2-; or a direct bond; and R9 is H; halogen; CrC6 alkyl; CrC6 haloalkyl; CrC6 alkoxy; CrC6 haloalkoxy; CrC6 alkylthio; CrC6 haloalkylthio; CrC6 alkylsulfinyl; Cι-C6 alkylsulfonyl; C3-C6 cycloalkyl;
CO2(C1-C6 alkyl); -C(R18)=ΝOR17; cyano; nitro; SF5;
SiR22R23R24; or GeR22R23R24; or R9 is phenyl, benzyl, phenoxy, pyridinyl, thienyl, furanyl, or pyrimidinyl each optionally substituted with one of R11, R12, or both R11 and R12. Preferred 2A. Compounds of Preferred IA wherein:
Z is selected from the group 2-thiazolyl; 1,2,4-oxadiazolyl;
1,2,4-thiadiazolyl; and pyrazinyl; each group substituted with R9 and optionally substituted with R10; and
Y is -O-; and
R9 is phenyl optionally substituted with one of R11, R12, or both R11 and R12. Most preferred are compounds of Preferred IA selected from the group: 4-[2-[[3-[3,5-bis(trifluoromethyl)phenyl]-l,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4- dihydro-5-methoxy-2-methyl-3H- 1 ,2,4-triazol-3-one; 4-[2-[[3-[3,5-bis(trifluoromethyl)phenyl]-l,2,4-thiadiazol-5-yl]oxy]-6- methylphenyl]-2,4-dihydro-5-methoxy-2-methyl-3H-l,2,4-triazol-3-one; 4-[2-[[3-( 1 , 1 -dimethylethyl)- 1 ,2,4-thiadiazol-5-yl]oxy]-6-methylphenyl]-2,4- dihydro-5-methoxy-2-methyl-3H- 1 ,2,4-triazol-3-one; 4-[2-[[3-(l,l-dimethylethyl)-l,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4-dihydro-5- methoxy-2-methyl-3H- 1 ,2,4-triazol-3-one;
4-[2-[[3-(3,4-dichlorophenyl)-l,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4-dihydro-5- methoxy-2-methyl-3H- 1 ,2,4-triazol-3-one; 2,4-dihydro-5-methoxy-2-methyl-4-[2-[[3-[3-(trifluoromethoxy)phenyl]- 1,2,4- thiadiazol-5-yl]oxy]phenyl]-3H- 1 ,2,4-triazol-3-one;
4-[2-[[3-(4-bromophenyl)-l,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4-dihydro-5- methoxy-2-methyl-3H- 1 ,2,4-triazol-3-one;
2,4-dihydro-5-methoxy-2-methyl-4-[2-[[5-methyl-4-[3-(trifluoromethyl)phenyl]- 2-thiazolyl]oxy]phenyl]-3H-l,2,4-triazol-3-one; and
2,4-dihydro-5-methoxy-2-methyl-4-[2-[[6-[4-(trifluoromethyl)phenyl]-2- pyrazinyl]oxy]phenyl]-3H- 1 ,2,4-triazol-3-one. This invention also relates to fungicidal compositions comprising fungicidally effective amounts of the compounds of Formula IA and at least one of a surfactant, a solid diluent or a liquid diluent. The preferred compositions of the present invention are those which comprise the above preferred compounds of Formula IA.
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 seedling, a fungicidally effective amount of the compounds of Formula IA and the compositions described herein. The preferred methods of use are those involving the above preferred compounds of Formula IA.
This invention also relates to arthropodicidal compositions comprising arthropodicidally effective amounts of the compounds of Formula IA and at least one of a surfactant, a solid diluent or a liquid diluent. The preferred compositions of the present invention are those which comprise the above preferred compounds of Formula IA. This invention also relates to a method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of the compounds of Formula IA and the compositions described herein. The preferred methods of use are those involving the above preferred compounds of Formula IA.
Preferred compounds of Formula IB for reasons of better fungicidal or arthropodicidal activity and/or ease of synthesis are:
Preferred IB. Compounds of Formula IB above, and N-oxides and agriculturally suitable salts thereof, wherein: E is selected from the group 1,2-phenylene; 1,5-, 1,6-, 1,7-, 1,8-, 2,6-,
2,7-, 1,2-, and 2,3-naphthalenediyl; lH-ρyrrole-1,2-, 2,3- and 3,4-diyl; 2,3- and 3,4-furandiyl; 2,3- and 3,4-thiophenediyl; lH-pyrazole-1,5-, 3,4- and 4,5-diyl; lH-imidazole-1,2-, 4,5- and 1,5-diyl; 3,4- and 4,5-isoxazolediyl; 4,5-oxazolediyl; 3,4- and 4,5-isothiazolediyl; 4,5-thiazolediyl; lH-l,2,3-triazole-l,5- and 5 4,5-diyl; 2H-l,2,3-triazole-4,5-diyl; lH-l,2,4-triazole- 1,5-diyl;
4H-l,2,4-triazole-3,4-diyl; l,2,3-oxadiazole-4,5-diyl; l,2,5-oxadiazole-3,4-diyl; l,2,3-thiadiazole-4,5-diyl; l,2,5-thiadiazole-3,4-diyl; lH-tetrazole- 1,5-diyl; 2,3- and 3,4-pyridinediyl; 3,4- and 4,5-pyridazinediyl; 4,5-pyrimidinediyl;
10 2,3-pyrazinediyl; l,2,3-triazine-4,5-diyl; l,2,4-triazine-5,6-diyl; lH-indole-1,4-, 1,5-, 1,6-, 1,7-, 2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 1,2-, 2,3-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 2,3-, 4,5-, 5,6- and 6,7-benzofurandiyl; benzo[b]thiophene-2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 2,3-,
15 4,5-, 5,6- and 6,7-diyl; lH-indazole-1,4-, 1,5-, 1,6-, 1,7-, 3,4-, 3,5-,
3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; lH-benzimidazole-1,4-, 1,5-, 1,6-, 1,7-, 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-diyl; l,2-benzisoxazole-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-benzoxazolediyl;
20 l,2-benzisothiazole-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl;
2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-benzothiazolediyl; 2,5-, 2,6-, 2,7-, 2,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 2,3-, 3,4-, 5,6-, 6,7- and 7,8-quinolinediyl; 1,5-, 1,6-, 1,7-, 1,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 3,4-, 5,6-, 6,7- and
25 7,8-isoquinolinediyl; 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 3,4-,
5,6-, 6,7- and 7,8-cinnolinediyl; 1,5-, 1,6-, 1,7-, 1,8-, 5,6-, 6,7- and 7,8-phthalazinediyl; 2,5-, 2,6-, 2,7-, 2,8-, 4,5-, 4,6-, 4,7-, 4,8-, 5,6-, 6,7- and 7,8-quinazolinediyl; 2,5-, 2,6-, 2,7-, 2,8-, 2,3-, 5,6-, 6,7- and 7,8-quinoxalinediyl; l,8,-naphthyridine-2,5-, 2,6-, 2,7-, 3,5-,
30 3,6-, 4,5-, 2,3- and 3,4-diyl; 2,6-, 2,7-, 4,6-, 4,7-, 6,7-pteridinediyl; pyrazolo[5,l-b]thiazole-2,6-, 2,7-, 3,6-, 3,7-, 2,3- and 6,7-diyl; thiazolo[2,3-c]-l,2,4-triazole-2,5-, 2,6-, 5,6-diyl; 2-oxo-l,3-benzodioxole-4,5- and 5,6-diyl; l,3-dioxo-lH-isoindole-2,4-, 2,5-, 4,5- and 5,6-diyl;
35 2-oxo-2H-l-benzopyran-3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-,
5,6-, 6,7- and 7,8-diyl; [l,2,4]triazolo[l,5-α]pyridine-2,5-, 2,6-, 2,7-, 2,8-, 5,6-, 6,7- and 7,8-diyl;
3,4-dihydro-2,4-dioxo-2H-l,3-benzoxazine-3,5-, 3,6-, 3,7-, 3,8-, 5,6-, 6,7- and 7,8-diyl; 2,3-dihydro-2-oxo-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-benzofurandiyl; thieno[3,2-'i]thiazole-2,5-) 2,6-, 5 and 5,6-diyl; 5,6,7,8-tetrahydro-2,5-, 2,6-, 2,7-, 2,8-, 3,5-, 3,6-,
3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 2,3- and 3,4-quinolinediyl; 2,3-dihydro-l,l,3-trioxo-l,2-benzisothiazole-2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-diyl; l,3-benzodioxole-2,4-, 2,5-, 4,5- and 5,6-diyl; 2,3-dihydro-2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 10 4,5-, 5,6- and 6,7-benzofurandiyl;
2,3-dihydro-l,4-benzodioxin-2,5-, 2,6-, 2,7-, 2,8-, 5,6- and 6,7-diyl; and 5,6,7,8-tetrahydro-4H-cyclohepta[b]thiophene-2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, and 2,3-diyl; each aromatic ring system optionally substituted with one of R3, R4, or both R3 15 and R4;
W is O;
R1 is Cι-C3 alkyl or CrC3 haloalkyl;
R2 is Η; CrCg alkyl; CrC6 haloalkyl; or C3-C6 cycloalkyl;
R3 and R4 are each independently halogen; cyano; nitro; Cj-C alkyl; 20 CrC6 haloalkyl; CrC6 alkoxy; CrC6 haloalkoxy; CrC6 alkylthio;
Ci-Cg alkylsulfonyl; C2-Cg alkylcarbonyl; C2-C alkoxycarbonyl; (CrC4 alkyl)NΗC(O); (CrC4 alkyl)2NC(O); benzoyl; or phenylsulfonyl;
Y is -O-; -S(O)n-; -NR15-; -C(=O)-; -CH(OR15)-; -CH2-; -CH2CH2-; 25 -CH=CH-; -C≡C-; -CH2O-; -OCH2-; -CH2S(O)n-; -S(O)nCH2-;
-CH2O-N=C(R7)-; -(R7)C=N-OCH(R15)-; -C(R7)=N-O-; or a direct bond;
R7 is H; CrC6 alkyl; CrC6 haloalkyl; CrC6 alkoxy; CrC6 alkylthio; C2-Cg alkenyl; C2-Cg alkynyl; C3-Cg cycloalkyl; halogen; or cyano; 30 or when Y and an R10 are attached to adjacent atoms on Z and Y is
-CH2O-N=C(R7)-, R7 and said adjacently attached R10 can be taken together as -(CH2)r-J- such that J is attached to Z;
Z is selected from the group CrC10 alkyl; C3-C8 cycloalkyl; phenyl; 35 naphthalenyl; anthracenyl; phenanthrenyl; lH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; lH-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; lH-l,2,3-triazolyl; 2H-l,2,3-triazolyl; lH-l,2,4-triazolyl; 4H-l,2,4-triazolyl; 1,2,3-oxadiazolyl;
1,2,4-oxadiazolyl; 1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl;
1,2,3-thiadiazolyl; 1,2,4-thiadiazolyl; 1,2,5-thiadiazolyl; 1,3,4-thiadiazolyl; lH-tetrazolyl; 2H-tetrazolyl; pyridinyl; pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4-triazinyl;
1,2,4,5-tetrazinyl; lH-indolyl; benzofuranyl; benzo[b]thiophenyl; lH-indazolyl; lH-benzimidazolyl; benzoxazolyl; benzothiazolyl; quinolinyl; isoquinolinyl; cinnolinyl; phthalazinyl; quinazolinyl; quinoxalinyl; 1,8-naphthyridinyl; pteridinyl; 2,3-dihydro-lH-indenyl;
1 ,2,3,4-tetrahydronaphthalenyl;
6,7,8,9-tetrahydro-5H-benzocycloheptenyl;
5,6,7,8,9,10-hexahydrobenzocyclooctenyl ;
2,3-dihydro-3-oxobenzofuranyl; 1 ,3-dihydro- 1 -oxoisobenzofuranyl; 2,3-dihydro-2-oxobenzofuranyl;
3 ,4-dihydro-4-oxo-2H- 1 -benzopyranyl ;
3,4-dihydro- 1 -oxo- lH-2-benzopyranyl;
3,4-dihydro-3-oxo-lH-2-benzopyranyl;
3 ,4-dihydro-2-oxo-2H- 1 -benzopyranyl ; 4-oxo-4H- 1 -benzopyranyl ; 2-oxo-2H-l -benzopyranyl;
2,3,4,5-tetrahydro-5-oxo- 1 -benzoxepinyl;
2,3 ,4,5-tetrahydro-2-oxo- 1 -benzoxepinyl;
2,3-dihydro- 1 ,3-dioxo- lH-isoindolyl;
1 ,2,3 ,4-tetrahydro- 1 ,3-dioxoisoquinolinyl; 3,4-dihydro-2,4-dioxo-2H- 1 ,3-benzoxazinyl;
2-oxo- 1 ,3-benzodioxyl;
2,3-dihydro- 1 , 1 ,3-trioxo- 1 ,2-benzisothiazolyl; 9H-fluorenyl; azulenyl; and thiazolo[2,3-c]-l,2,4-triazolyl; each group substituted with R9 and optionally substituted with one or more R10; and R15 is Η; CrC3 alkyl; or C3-C6 cycloalkyl.
Preferred 2B. Compounds of Preferred IB wherein:
E is selected from the group 1,2-phenylene; 1,6-, 1,7-, 1,2-, and
2,3-naphthalenediyl; 2,3- and 3,4-furandiyl; 2,3- and
3,4-thiophenediyl; 2,3- and 3,4-pyridinediyl; 4,5-pyrimidinediyl; 2,4-, 2,7-, 3,5-, 2,3-, 4,5-, 5,6- and 6,7-benzofurandiyl; and benzo[&]thiophene-2,4-, 2,7-, 3,5-, 2,3-, 4,5-, 5,6- and 6,7-diyl; each aromatic ring system optionally substituted with one of R3, R4, or both R3 and R4; Z is selected from the group phenyl; naphthalenyl; 2-thiazolyl; 1,2,4-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,4-thiadiazolyl; 1 ,3,4-thiadiazolyl; pyridinyl; and pyrimidinyl; each group substituted with R9 and optionally substituted with one or more R10; R7 is H; Cι-C6 alkyl; CrC6 haloalkyl; CrC6 alkoxy; CrC6 alkylthio; C2-Cg alkenyl; C2-Cg alkynyl; cyclopropyl; halogen; or cyano; or when Y and an R10 are attached to adjacent atoms on Z and Y is -CH2O-N=C(R7)-, R7 and said adjacently attached R10 can be taken together as -(CH2)r-J- such that J is attached to Z; J is -CH2- or -CH2CH2-; and r is 1. Preferred 3B. Compounds of Preferred 2B wherein: E is 1,2-phenylene optionally substituted with one of R3, R4, or both R3 and R4; A is O or N; X is OR1; R1 is C1-C3 alkyl; R2 is H or CrC2 alkyl;
Y is -O-; -S(O)n-; -NR15-; -C(=O)-; -CH(OR15)-; -CH2-; -CH2CH2-;
-CH=CH-; -C≡C-; -CH2O-; -OCH2-; -CH2S(O)n-; -S(O)nCH2-; or a direct bond; Z is selected from the group 2-thiazolyl; 1,2,4-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,4-thiadiazolyl; and 1,3,4-thiadiazolyl; each group substituted with R9 and optionally substituted with R10; and R15 is H; C!-C3 alkyl; or cyclopropyl. Preferred 4B. Compounds of Preferred 3B wherein: R1 is methyl; R2 is methyl;
Y is -O-; -S(O)n-; -NR15-; -C(=O)-; -CH(OR15)-; -CH2-; or a direct bond; and R9 is phenyl, benzyl, phenoxy, pyridinyl, thienyl, furanyl, or pyrimidinyl each substituted with R1 1 and optionally substituted with R12. Preferred 5B. Compounds of Preferred 4B wherein:
Z is selected from the group 2-thiazolyl; 1,2,4-oxadiazolyl; and
1,2,4-thiadiazolyl; each group substituted with R9 and optionally substituted with R10; and Y is -O-; and
R9 is phenyl substituted with R1 1 and optionally substituted with R12. Most preferred are compounds of Preferred 5B selected from the group: 4-[2-[[3-(3-ethynylphenyl)-l,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4-dihydro-5- methoxy-2-methyl-3H- 1 ,2,4-triazol-3-one; and [3-[5-[2-(l ,5-dihydro-3-methoxy- l-methyl-5-oxo-4H- 1 ,2,4-triazol-4- yl)phenoxy]- 1 ,2,4-thiadiazol-3-yl]phenyl] trifluoromethanesulfonate. This invention also relates to fungicidal compositions comprising fungicidally effective amounts of the compounds of Formula IB and at least one of a surfactant, a solid diluent or a liquid diluent. The preferred compositions of the present invention are those which comprise the above preferred compounds of Formula IB .
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 seedling, a fungicidally effective amount of the compounds of Formula IB and the compositions described herein. The preferred methods of use are those involving the above preferred compounds of Formula IB.
This invention also relates to arthropodicidal compositions comprising arthropodicidally effective amounts of the compounds of Formula IB and at least one of a surfactant, a solid diluent or a liquid diluent. The preferred compositions of the present invention are those which comprise the above preferred compounds of Formula IB. This invention also relates to a method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of the compounds of Formula IB and the compositions described herein. The preferred methods of use are those involving the above preferred compounds of Formula IB. Preferred intermediates for the preparation of the fungicides and arthropodicides of
Formula I where Y is oxygen are:
Preferred lC. Compounds of Formula II above wherein: W is O;
R1 is CrC3 alkyl or CrC3 haloalkyl; R2 is Η; CrC6 alkyl; CrC6 haloalkyl; or C3-C6 cycloalkyl; and R3 and R4 are each independently halogen; cyano; nitro; C--Cg alkyl;
Cj-Cg haloalkyl; C--Cg alkoxy; Cj-Cg haloalkoxy; Ci-Cg alkylthio; C Cg alkylsulfonyl; C2-Cg alkylcarbonyl; C2-Cg alkoxycarbonyl; (CrC4 alkyl)NHC(O); (CrC4 alkyl)2NC(O); benzoyl; or phenylsulfonyl.
Preferred 2C. Compounds of Preferred 1C wherein: A is O or N; X is OR1 or halogen; R1 is Cι-C3 alkyl; R2 is H or C1-C2 alkyl; and
R3 and R4 are each independently halogen; C1-C3 alkyl; Cj-C3 alkoxy; or C1 -C3 alkylthio. Preferred 3C. Compounds of Preferred 2C wherein: A is N; R1 is methyl;
R2 is methyl; and
R3 and R4 are each independently halogen or methyl. Most preferred are compounds of Preferred 3C selected from the group: 2,4-dihydro-4-(2-hydroxyphenyl)-5-methoxy-2-methyl-3H-l,2,4-triazol-3-one; 2,4-dihydro-4-(2-hydroxy-6-methylphenyl)-5-methoxy-2-methyl-3H- 1 ,2,4- triazol-3-one;
5-chloro-2,4-dihydro-4-(2-hydroxy-6-methylphenyl)-2-methyl-3H-l,2,4-triazol- 3-one; and
5-chloro-2,4-dihydro-4-(2-hydroxyphenyl)-2-methyl-3H-l,2,4-triazol-3-one. Of note are embodiments where X is other than Η; embodiments where R2 is Η,
CrCg alkyl, CrC6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C cycloalkyl, C2-C alkylcarbonyl or C2-C alkoxycarbonyl; embodiments where Y is -O-, -S(O)n-, -NR15-, -C(=O)-, -CΗ(OR15)-, -CHR6-, -CHR6CHR6-, -CR6=CR6-, -C≡C-, -CHR15O-, -OCHR15-, -CHR15S(0)n-, -S(O)nCHR15-, -CHR15O-N=C(R7)-, -(R7)C=N-OCH(R15)-, -C(R7)=N-O-, -O-N=C(R7)-, -CHR15OC(=O)N(R15)-, -CHR15OC(=S)N(R15)-, -CHR15O-N(R15)C(=O)N(R15)-, -CHR15O-N(R 5)C(=S)N(R15)-, -CHR15O-N=C(R7)NR15-, -CHR15O-N=C(R7)OCH2-, -CHR15O-N=C(R7)-N=N-, -CHR15O-N=C(R7)-C(=O)-, -CHR15S-C(R7)=N-, -C(R7)=N-NR15-, -CH=N-N=C(R7)-, -CHR15N(COCH3)-N=C(R7)-, -OC(=S)NR15C(=O)-, -CHR6-C(=W1)-A1-, -CHR6CHR6-C(=W1)-A1-, -CR6=CR6-C(=W1)-A1-, -C≡C-C(=W1)-A1-, -N=CR6-C(=W1)-A1- or a direct bond; embodiments where R7 is H, CrCg alkyl, CrC6 haloalkyl, CrC6 alkoxy, CrC6 haloalkoxy, CrC6 alkylthio, Cj-Cg alkylsulfinyl, CrC6 alkylsulfonyl, CrC6 haloalkylthio, C C6 haloalkylsulfinyl, CrC6 haloalkylsulfonyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-Cg cycloalkyl, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, halogen, cyano or moφholinyl; embodiments where Z is other than C3-C8 cycloalkenyl and adamantyl each substituted with R9 and optionally substituted with one or more R10; embodiments where, when Y and an R10 are attached to adjacent atoms on Z and Y is -CHR15O-N=C(R7)-, -O-N=C(R7)-, -CH=N-N=C(R7)- or -CHR15N(COCH3)-N=C(R7)-, R7 and said adjacently attached R10 are taken together as -(CH2)r-J- such that J is attached to Z; embodiments where R11 and R12 are each independently halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C6 alkenyl, C2-Cg haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 alkoxy, CrC haloalkoxy, C3-C6 alkenyloxy, C3-Cg haloalkenyloxy, C1-C4 alkylthio, Cj-C4 haloalkylthio, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C| -C4 alkylsulfonyl, Cj -C haloalkylsulfonyl, C3-C6 alkenylthio, C3-C6 haloalkenylthio, nitro, cyano, SF5, Si(R25)3 or Ge(R25)3; embodiments where R19, R20, R21, R22, R23, and R24 are each independently Cj-Cg alkyl, CrC4 alkoxy or phenyl; embodiments where each R25 is independently C1-C4 alkyl or phenyl; embodiments where R3 and R4 are each independently halogen, cyano, nitro, Ci-Cg alkyl, Cj-Cg haloalkyl, Cj-Cg alkoxy, Cj-Cg haloalkoxy, Cj-Cg alkylsulfonyl, C2-Cg alkylcarbonyl, C2-C6 alkoxycarbonyl, (CrC4 alkyl)NHC(O), (Cj^ alkyl)2NC(O), benzoyl or phenylsulfonyl; embodiments where Z is selected from the group 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-thiadiazolyl and 1,3,4-thiadiazolyl, each group substituted with R9; embodiments where R11 is C2-Cg alkenyl, C2-Cg haloalkenyl, C2-Cg alkynyl, C2-Cg haloalkynyl, C3-Cg alkenyloxy, C3-C6 haloalkenyloxy, C } -C4 alkylthio, C 1 -C4 haloalkylthio, C1-C4 alkylsulfinyl, CrC haloalkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C3-Cg alkenylthio, C3-Cg haloalkenylthio or SF5; embodiments where R12 is halogen, CrC4 alkyl, CrC4 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-Cg haloalkynyl, C1-C4 alkoxy, CrC4 haloalkoxy, C3-C6 alkenyloxy, C3-C6 haloalkenyloxy, C 1 -C alkylthio, C j -C4 haloalkylthio, C 1 -C4 alkylsulfinyl, C 1 -C haloalkylsulfinyl, Cι-C4 alkylsulfonyl, CrC haloalkylsulfonyl, C3-Cg alkenylthio, C3-C6 haloalkenylthio, nitro, cyano, SF5, Si(R25)3 or Ge(R 5)3; embodiments where Z is selected from the group phenyl, naphthalenyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, pyridinyl and pyrimidinyl, each group substituted with R9 and optionally substituted with one or more R10; and embodiments where Z is selected from the group 1,2,4-oxadiazolyl and 1,2,4-thiadiazolyl, each group substituted with R9.
The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-33. One skilled in the art will recognize that compounds of Formula IA and IB are encompassed by Formula I and, therefore, can be prepared by these procedures. The definitions of E, A, G, W, X, R!-R27, Y, Z1, W1, A^A3, Z, Q, J, m, n, p, r and s in the compounds of Formulae 1-58 below are as defined above in the Summary of the Invention. Compounds of Formulae Ia-Im are various subsets of the compounds of Formula I, and all substituents for Formulae Ia-Im are as defined above for Formula I.
One skilled in the art will recognize that some compounds of Formula I can exist in one or more tautomeric forms. For example, a compound of Formula I wherein R2 is H may exist as tautomer la or lb, or both la and lb. The present invention comprises all tautomeric forms of compounds of Formula I.
& lb
The compounds of Formula I can be prepared as described below in Procedures 1) to 5). Procedures 1) to 4) describe syntheses involving construction of the amide ring after the formation of the aryl moiety (E-Y-Z). Procedure 5) describes syntheses of the aryl moiety (E-Y-Z) with the amide ring already in place. 1) Alkylation Procedures
The compounds of Formula I are prepared by treating compounds of Formula 1 with an appropriate alkyl transfer reagent in an inert solvent with or without additional acidic or basic reagents or other reagents (Scheme 1). Suitable solvents are selected from the group consisting of polar aprotic solvents such as acetonitrile, dimethylformamide or dimethyl sulfoxide; ethers such as tetrahydrofuran, dimethoxyethane, or diethyl ether; ketones such as acetone or 2-butanone; hydrocarbons such as toluene or benzene; and halocarbons such as dichloromethane or chloroform.
For example, compounds of Formula I can be prepared by the action of diazoalkane reagents of Formula 2 such as diazomethane (U = H) or trimethylsilyldiazomethane (U = (C^^Si) on dicarbonyl compounds of Formula 1 (Method 1). Use of trimethylsilyldiazomethane requires a protic cosolvent such as methanol. For examples of these procedures, see Chem. Pharm. Bull, (1984), 32, 3759.
As indicated in Method 2, compounds of Formula I can also be prepared by contacting carbonyl compounds of Formula 1 with alkyl trichloroacetimidates of Formula 3 and a Lewis acid catalyst. Suitable Lewis acids include trimethylsilyl triflate and tetrafluoroboric acid. The alkyl trichloroacetimidates can be prepared from the appropriate alcohol and trichloroacetonitrile as described in the literature (J. Danklmaier and H. Honig, Synth. Commun., (1990), 20, 203).
Compounds of Formula I can also be prepared from compounds of Formula 1 by treatment with a trialkyloxonium tetrafluoroborate (i.e., Meerwein's salt) of Formula 4 (Method 3). The use of trialkyloxonium salts as powerful alkylating agents is well known in the art (see U. Schollkopf, U. Groth, C. Deng, Angew. Chem., Int. Ed. Engl, (1981), 20, 798). Other alkylating agents which can convert carbonyl compounds of Formula 1 to compounds of Formula I are dialkyl sulfates such as dimethyl sulfate, haloalkyl sulfonates such as methyl trifluoromethanesulfonate, and alkyl halides such as iodomethane and propargyl bromide (Method 4). These alkylations can be conducted with or without additional base. Appropriate bases include alkali metal alkoxides such as potassium tert-butoxide, inorganic bases such as sodium hydride and potassium carbonate, or tertiary amines such as triethylamine, pyridine, l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and triethylenediamine. See R. E. Benson, T. L. Cairns, J. Am. Chem. Soc, (1948), 70, 2115 for alkylation examples using agents of this type. Compounds of Formula la (compounds of Formula 1 wherein G = C, W = O and
X = OH) can be prepared by condensation of malonates or malonate derivatives of Formula 5 with an ambident nucleophile of Formula 6 (Scheme 2). The nucleophiles of Formula 6 are N-substituted hydroxylamines (HO-ΝHR2) and substituted hydrazines (HΝ(R5)-ΝHR2). Examples of such nucleophiles are N-methylhydroxylamine and methylhydrazine. The malonate esters of Formula 5 can be prepared by methods described hereinafter. The esters of Formula 5 can also be activated by first hydrolyzing the ester to form the corresponding carboxylic acid, and then converting the acid into the acid chloride (T = Cl) using thionyl chloride or oxalyl chloride, or into the acyl imidazole (T = 1-imidazolyl) by treating with 1,1 '-carbonyldiimidazole.
Scheme 2
T = 0(C!-C4 alkyl), Cl, 1-imidazDlyl
Esters of Formula 5a can be prepared from copper (I)-catalyzed reaction of malonate esters of Formula 7 with substituted aryl halides of Formula 8 according to methods adapted from A. Osuka, T. Kobayashi and H. Suzuki, Synthesis, (1983), 67 and M. S. Malamas, T. C. Hohman, and J. Millen, J. Med. Chem., 1994, 37, 2043-2058, and illustrated in Scheme 3. Procedures to prepare compounds of Formula 8 are described below (see Scheme 32).
Malonate esters of Formula 5a can also be prepared from diester carboxylic acids of Formula 5b after modification of the carboxylic acid functional group to the appropriate Y and Z group. A copper (I)-catalyzed coupling of malonates of Formula 7 with orthobromocarboxylic acids of Formula 8a (see A. Bruggink, A. McKillop, Tetrahedron, (1975), 31, 2607) can be used to prepare compounds of Formula 5b as shown in Scheme 3. Methods to prepare compounds of Formula 8a are common in the art (see P. Beak, V. Snieckus, Ace. Chem. Res., (1982), 15, 306 and Org. React., (1979), 26, 1 and references therein).
Scheme 3
5a R = Cι-C4 alkyl
Additionally, the malonate esters of Formula 5a can be prepared by treating aryl acetic acid esters of Formula 9 with a dialkyl carbonate or alkyl chloroformate in the presence of a suitable base such as, but not limited to, sodium metal or sodium hydride (Scheme 4). For example, see J. Am. Chem. Soc, (1928), 50, 2758. Scheme 4
9 5a
R=C1-C alkyl
Esters of Formula 9 can be prepared from acid-catalyzed alcoholysis of aryl acetonitriles of Formula 10 or esterification of aryl acetic acids of Formula 11 as illustrated in Scheme 5 (see Org. Synth., Coll. Vol. I, (1941), 270).
Additionally, esters of formula 9 can be prepared by palladium (O)-catalyzed cross coupling reaction of aryl iodides of Formula 8 with a Reformatsky reagent or an alkoxy(trialkylstannyl)acetylene followed by hydration (Scheme 5). For example, .see T. Sakamoto, A. Yasuhara, Y. Kondo, H. Yamanaka, Synlett, (1992), 502, and J. F. Fauvarque, A. Jutard, J. Organometal. Chem., (1977), 132, C17.
Scheme 5
R = C1-C4 alkyl Aryl acetic acid esters of Formula 9a can also be prepared by copper (I)-catalyzed condensation of aryl halides of Formula 12 with compounds of Formula 13 as described in EP-A-307,103 and illustrated below in Scheme 6.
Scheme 6
12 9a
R = C1-C4 alkyl Y O. S. OCHR15, SCHR15 0-N=C(R7), NR15
Some esters of Formula 9 (Formula 9b) can also be prepared by forming the Y2 bridge using conventional nucleophilic substitution chemistry (Scheme 7). Displacement of an appropriate leaving group (Lg) in electrophiles of Formula 15 or 16 with a nucleophilic ester of Formula 14 affords compounds of Formula 9b. A base, for example sodium hydride, is used to generate the corresponding alkoxide or thioalkoxide of the compound of Formula 14.
Scheme 7
R = C!-C4 alkyl
R26 _ OH, SH, CHR15OH, CHR15SH, NHR15
Y2 = O, S, OCHR15 SCHR15, CHR150, CHR15S, NR15
Lg = Br, Cl, I, OSO2CH3, 0S02(4-Me-Ph)
Some esters of Formula 9 (Formula 9e) can also be prepared by forming the Y3 bridge from substituted hydroxylamine 9d and carbonyl compounds 14a. The hydroxylamine 9d is in turn prepared from esters 9c. This method has been described in EP-A-600,835 and illustrated in Scheme 8.
Scheme 8
9c B = CHR Br =
9d B = CHR15ONH2«HCI Y3 = CHR15ON=C(R7)
2) Displacement and Conjugate Addition/Elimination Procedures
Compounds of Formula I can also be prepared by reaction of Formula 17 compounds with alkali metal alkoxides (R^M+ alkali metal thioalkoxides (R^'M "), or an amine derivative in a suitable solvent (Scheme 9). The leaving group Lg1 in the amides of Formula 17 are any group known in the art to undergo a displacement reaction of this type. Examples of suitable leaving groups include chlorine, bromine, and sulfonyl and sulfonate groups. Examples of suitable inert solvents are dimethylformamide or dimethyl sulf oxide, dimethoxyethane methanol.
Scheme 9
17 I
X- ORi. SR^ NH^ HR1,
NC -Cg alkyOR1, NH(Cι-Cg alkoxy), or
N(CrCg alkoxy^1
Lg l = Br, -SC^V, or -OSO2V
V= CrCg alkyl, -C haloalkyl, or4-CH3-CgH4
M = KorNa
Compounds of Formula 17a can be prepared from compounds of Formula lb
(compounds of Formula 1 wherein X is OH) by reaction with halogenating agents such as thionyl chloride or phosphorus oxybromide to form the corresponding β-halo-substituted derivatives (Scheme 10). Alternatively, compounds of Formula lb can be treated with an alkylsulfonyl halide or haloalkylsulfonyl anhydride, such as methanesulfonyl chloride, -toluenesulfonyl chloride, and trifluoromethanesulfonyl anhydride, to form the corresponding β-alkylsulfonate of Formula 17a. The reaction with the sulfonyl halides may be performed in the presence of a suitable base (e.g., triethylamine).
Scheme 10
lb 17a
Lg2 = α, Br, or-OS02V
V= CrCg alkyl, Ci-Cg haloalkyl, or 4-CH3-CgH4 hal = Br, α orF As illustrated in Scheme 1 1, sulfonyl compounds of Formula 17b can be prepared by oxidation of the corresponding thio compound of Formula 18 using well-known methods for the oxidation of sulfur (see Schrenk, K. In The Chemistry of Sulphones and Sulphoxides; Patai, S. et al., Eds.; Wiley: New York, 1988). Suitable oxidizing reagents include meta-chloro-peroxybenzoic acid, hydrogen peroxide and Oxone® (KHSO5).
Scheme 11
18 17b
V = Cj-Cg alkyl, Cj-Cg haloalkyl, or 4-CH3-CgH4
Alternatively, halo-compounds of Formula 17c (compounds of Formula 17a wherein A = N, G = N, and W = O) can be prepared from hydrazides of Formula 19 as illustrated in Scheme 12. When R27 = C(=S)S(CrC4 alkyl), the diacyl compound of Formula 19 is treated with excess thionyl halide, for example excess thionyl chloride. The product formed first is the ring-closed compound of Formula 20 which can be isolated or converted in situ to the compound of Formula 17c; see P. Molina, A. Tarraga, A. Espinosa, Synthesis, (1989), 923 for a description of this process.
Alternatively, when R27 = R2 as defined above, the hydrazide of Formula 19 is cyclized with phosgene to form the cyclic urea of Formula 17c wherein hal = CL This procedure is described in detail in J. Org. Chem., (1989), 54, 1048.
Scheme 12
17c hal =α. Br. I
The hydrazides of Formula 19 can be prepared as illustrated in Scheme 13. Condensation of the isocyanate of Formula 21 with the hydrazine of Formula H NNR2R27 in an inert solvent such as tetrahydrofuran affords the hydrazide.
Scheme 13
R27 = alkyl) or R2
3) Conjugate Addition/Cyclization Procedures In addition to the methods disclosed above, compounds of Formula I wherein
X = SR1 and G = C (Formula Ic) can be prepared by treating a ketenedithioacetal of Formula 22 with an ambident nucleophile of Formula 6 (Scheme 14). The nucleophiles of Formula 6 are described above.
Scheme 14
22 Ic
R = C1-C4 alkyl
Ketene dithioacetals of Formula 22a can be prepared by condensing arylacetic acid esters of Formula 9 with carbon disulfide in the presence of a suitable base, followed by reaction with two equivalents of an Rϊ-halide, such as iodomethane or propargyl bromide (Scheme 15).
Scheme 15
hal = α, BrorI 9 R = Cι-C4 alkyl 22a
Compounds of Formula Id (compounds of Formula 1 wherein A = N, G = N) can be prepared by condensation of N-amino-ureas of Formula 23 with a carbonylating agent of Formula 24 (Scheme 16). The carbonylating agents of Formula 24 are carbonyl or thiocarbonyl transfer reagents such as phosgene, thiophosgene, diphosgene
(ClC(=O)OCCl3), triphosgene (Cl3COC(=O)OCCl3), NN'-carbonyldiimidazole, N,N'-thiocarbonyldiimidazole, and l, -carbonyldi(l,2,4-triazole). Alternatively, the compounds of Formula 24 can be alkyl chloroformates or dialkyl carbonates. Some of these carbonylating reactions may require the addition of a base to effect reaction. Appropriate bases include alkali metal alkoxides such as potassium t -butoxide, inorganic bases such as sodium hydride and potassium carbonate, tertiary amines such as triethylamine and triethylenediamine, pyridine, or l,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Suitable solvents include polar aprotic solvents such as acetonitrile, dimethylformamide, or dimethyl sulfoxide; ethers such as tetrahydrofuran, dimethoxyethane, or diethyl ether; ketones such as acetone or 2-butanone; hydrocarbons such as toluene or benzene; or halocarbons such as dichloromethane or chloroform. The reaction temperature can vary between 0°C and 150°C and the reaction time can be from 1 to 72 hours depending on the choice of base, solvent, temperature, and substrates.
23 Id
T1 and T2 are independently Cl, OCCI3, C C1-C alkyl), 1-imidazolyl, 1,2,4-triazolyl X = OH or SH x Oor S
N-Amino-ureas of Formula 23 can be prepared as illustrated in Scheme 17. Treatment of an arylamine of Formula 25 with phosgene, thiophosgene,
N,N'-carbonyldiimidazole, or N,N'-thiocarbonyldiimidazole produces the isocyanate or isothiocyanate of Formula 26. A base can be added for reactions with phosgene or thiophosgene. Subsequent treatment of the iso(thio)cyanate with an R2-substituted hydrazine produces the N-amino-urea of Formula 23.
23
Compounds of Formula le (compounds of Formula 1 wherein A = CR5, G = N, and X = O) can be prepared by either method illustrated in Scheme 18. Ureas of Formula 27 are reacted with activated 2-halocarboxylic acid derivatives such as
2-halocarboxylic acid chlorides, 2-halocarboxylic acid esters or 2-haloacyl imidazoles. The initial acylation on the arylamino nitrogen is followed by an intramolecular displacement of the 2-halo group to effect cyclization. Base may be added to accelerate the acylation and/or the subsequent cyclization. Suitable bases include triethylamine and sodium hydride. Alternatively, Formula le compounds can be prepared by reaction of Formula 26 isocyanates with Formula 28a esters. As described above, base may be added to accelerate the reaction and subsequent cyclization to Formula le compounds.
Scheme 18
The ureas of Formula 27 can be prepared by either of the methods illustrated in Scheme 19. The arylamine of Formula 25 can be contacted with an isocyanate or isothiocyanate of Formula R2N=C=W as described above. Alternatively, an isocyanate or isothiocyanate of Formula 26 can be condensed with an amine of Formula R2-NH2 to form the urea. The arylamine and iso(thio)cyanates of Formulae 25 and 26, respectively, are commercially available or prepared by well-known methods. For example, isothiocyanates can be prepared by methods described in J. Heterocycl. Chem., (1990), 27, 407. Isocyanates can be prepared as described in March, j. Advanced Organic
Chemistry; 3rd ed., John Wiley: New York, (1985), pp 944, 1166 and also in Synthetic Communications, (1993), 23(3), 335 and references therein. For methods describing the preparation of arylamines of Formula 25 that are not commercially available, see M. S. Gibson In The Chemistry ofthe Amino Group; Patai, S., Ed.; Interscience Publishers, 1968; p 37 and Tetrahedron Lett. (1982), 23(7), 699 and references therein. Scheme 19
4) Thionation Procedures
Compounds of Formula le, compounds of Formula I wherein W = S, can be prepared by treating compounds of Formula Id (I wherein W = O) with thionating reagents such as P2S5 or Lawesson's reagent (2,4-bis(4-methoxyphenyl)-l,3-dithia-2,4- diphosphetane-2,4-disulfide) as illustrated in Scheme 20 (see Bull. Soc. Chim. Belg., (1978), 87, 229; and Tetrahedron Lett, (1983), 24, 3815).
Scheme 20
le w
5) Aryl Moiety (E-Y-Z) Synthesis Procedures
Compounds of Formula If (compounds of Formula I wherein Y is CHR15O, CHR15S, or CHR15O-N=CR7) can be prepared by contacting halides of Formula 29 with various nucleophiles (Scheme 21). The appropriate alcohol or thiol is treated with a base, for example sodium hydride, to form the corresponding alkoxide or thioalkoxide which acts as the nucleophile. Scheme 21
30
Some aryl halides of Formula 29 can be prepared by radical halogenation of the corresponding alkyl compound (i.e., H instead of halogen in Formula 29), or by acidic cleavage of the corresponding methylether (i.e., OMe instead of halogen in Formula 29). Other aryl halides of Formula 29 can be prepared from the appropriate alcohols of Formula 30 by well known halogenation methods in the art (see Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry; 3rd ed., Part B, Plenum: New York, (1990), p 122). Compounds of Formula I wherein Y is CR°=CR6 or CHR6-CHR6 (Formula lg and Ih, respectively) can be prepared as illustrated in Scheme 22. Treatment of the halides of Formula 29 with triphenylphosphine or a trialkylphosphite produces the corresponding phosphonium salt (Formula 31) or phosphonate (Formula 32), respectively. Condensation of the phosphorus compound with a base and a carbonyl compound of Formula Z(R6)C=O affords the olefin of Formula lg.
29 31: P1 = P+(CgH5)3 haUde- O
R = Cι-C alkyl 32: P P OR^
1) Halogenation
2) Dehalogenation
Ih li
The olefins of Formula lg can be converted to the saturated compounds of Formula Ih by hydrogenation over a metal catalyst such as palladium on carbon as is well-known in the art (Rylander, Catalytic Hydrogenation in Organic Synthesis; Academic: New York, 1979).
Formula li alkynes can be prepared by halogenation/dehalogenation of Formula lg olefins using procedures well-known in the art (March, J. Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985), p 924). Additionally, Formula li alkynes can be prepared by well-known reaction of aryl halides with alkyne derivatives in the presence of catalysts such as nickel or palladium (see J. Organomet. Chem., (1975), 93 253-257).
The olefin of Formula lg can also be prepared by reversing the reactivity of the reactants in the Wittig or Horner-Emmons condensation. For example, 2-alkylaryl derivatives of Formula 33 can be converted into the corresponding dibromo-compound of Formula 34 as illustrated in Scheme 23 (see Synthesis, (1988), 330). The dibromo- compound can be hydrolyzed to the carbonyl compound of Formula 35, which in turn can be condensed with a phosphorus-containing nucleophile of Formula 36 or 37 to afford the olefin of Formula lg. Additionally, compounds of Formula 35 can be prepared by oxidation of the corresponding alcohols of Formula 30.
Vinylhalides of Formula Ij can be prepared by reacting phosphorus reagents of Formulae 37a or 37b with carbonyl compounds of Formula 35 (Scheme 23). The preparations of halides of Formula 37a from the appropriate diethylphosphonoacetate are described by McKenna and Khawli in J. Org. Chem., (1986), 51, 5467. The thiono esters of Formula 37b can be prepared from esters of Formula 37a by converting the carbonyl oxygen of the ester to a thiocarbonyl (see Chem. Rev., (1984), 84, 17 and Tetrahedron Lett., (1984), 25, 2639).
Scheme 23
OZ
Ij Oximes of Formula Ik (Formula I wherein Y is C(R7)=N-O) can be prepared from carbonyl compounds of Formula 38 by condensation with hydroxylamine, followed by O-alkylation with electrophiles of Formula Z-(C1, Br, or I) (Scheme 24). Alternatively, the O-substituted hydroxylamine can be condensed with the carbonyl compound of Formula 38 to yield oximes of Formula Ik directly.
Scheme 24
38 hal = α, BrorI ■*
Carbamates of Formula II can be prepared by reacting aryl alcohols of Formula 30 with isocyanates of Formula 39 (Scheme 25). A base such as triethylamine can be added to catalyze the reaction. As shown, carbamates of Formula II can be further alkylated to provide the carbamates of Formula Im.
Compounds of Formula I wherein Y is -CHR15O-N=C(R7)-C(=N-A2-Z1)-A1-, -CHR15O-N=C(R7)-C(R7)=N-A2-A3- or -CHR15O-N=C(-C(R7)=N-A2-Z1)- can be prepared by methods known in the art or obvious modifications (see, for example, WO 95/18789, WO 95/21153, and references therein) together with the methods disclosed herein.
Compounds of Formula I wherein Y is -CHRl5OC(=O)O-, -CHR15OC(=S)O-, -CHR15OC(=O)S-, -CHR15OC(=S)S-, -CHR15SC(=O)N(R15)-, -CHR15SC(=S)N(R15)-, -CHR15SC(=O)O-, -CHR15SC(=S)O-, -CHR15SC(=O)S-, -CHR15SC(=S)S-, -CHR15SC(=NRl5)S- or -CHR15N(R15)C(=O)N(R15)- can be prepared by methods known in the art or obvious modifications (see, for example, U.S. 5,416,110, EP 656,351 and references therein) together with the methods disclosed herein. The compounds of the present invention are prepared by combinations of reactions as illustrated in the Schemes 1-25 in which Z is a moiety as described in the summary. Preparation of the compounds containing the radical Z as described in the summary, substituted with L (defined as any group attached to Z as depicted in each of the individual schemes) can be accomplished by one skilled in the art by the appropriate combination of reagents and reaction sequences for a particular Z-L. Such reaction sequences can be developed based on known reactions available in the chemical art. For a general reference, see March, J. Advanced Organic Chemistry; 3rd ed., John Wiley:
New York, (1985) and references therein. See the following paragraphs for some examples of how L is defined in individual schemes, and the preparation of representative
Z-L examples. Compounds of Formula 41 in Scheme 26 can be prepared from compounds of
Formula 40 by reaction with hydroxylamine or hydroxylamine salts. See Sandier and
Karo, "Organic Functional Group Preparations," Vol. 3 Academic Press, New York,
(1972) 372-381 for a review of methods. Compounds of Formula 41 correspond to compounds of Formula 13 in Scheme 6 when Y1 = 0-N=C(R7) and in Scheme 21, reagent HO-N=CR7.
Scheme 26
H2NOHor 0=C 7-Z H2NOH.HO base* HO-N=CR7-Z
40 41
Compounds of Formula 40 can be prepared from compounds of Formula 39a (Scheme 27) by Friedel-Crafts acylation with compounds of Formula 42. (See Olah, G. "Friedel-Crafts and Related Reactions," Interscience, New York (1963-1964) for a general review). Compounds of Formula 40 may also be prepared by reaction of acyl halides, anhydrides, esters, or amides of Formula 45 with organometallic reagents of Formula 44. (See March, J. Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985), pp 433-435 and references therein.) The organometallic compounds of Formula 44 may be prepared by reductive metallation or halogen-metal exchange of a halogen-containing compound of Formula 43 using, for example, magnesium or an organolithium reagent, or by deprotonation of compounds of Formula 39a using a strong base such as a lithioamide or an organolithium reagent, followed by transmetallation. Compound 40 corresponds to Compound 14a in Scheme 8, while compound 40a corresponds to O=C(R6)Z in Scheme 22. Scheme 27
R = C!-C4 alkyl R^ -z RO orR7
Compounds of Formula 43 may be prepared by reaction of compounds of Formula 39a (Scheme 28) with, for example, bromine or chlorine, with or without additional catalysts, under free-radical or aromatic electrophilic halogenation conditions, depending on the nature of Z. Alternative sources of halogen, such as N- halosuccinimides, tert-butyl hypohalites or SO2Cl2, may also be used. (See March, J. Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985), pp 476-479, 620-626, and references therein.) For a review of free-radical halogenation, see Huyser, in Patai," The Chemistry of the Carbon-Halogen Bond," Part 1, Wiley, New York (1973) pp 549-607. For electrophilic substitutions, see de la Mare, "Electrophilic Halogenation," Cambridge University Press, London (1976). Compounds of Formula 43 correspond to compounds of Formula 15 in Scheme 7 where Lg = Br, Cl, or I and reagent Z-hal in Scheme 24. Compounds of Formula 47 can be prepared from compounds of Formula 46 by similar procedures. Compounds of Formula 47 correspond to compounds of Formula 16 in Scheme 7 where Lg = Br, Cl, or I. Compounds of Formula 36 or 37 in Scheme 23 can be prepared by reaction of compounds of Formula 47 with triphenylphosphine or trialkyl phosphites, respectively, followed by deprotonation with base. See Cadogen, "Organophosphorus Reagents in Organic Synthesis," Academic Press, New York (1979) for a general treatise on these reagents. or Sθ2α2 optional catalyst hal = Cl, Br, I
H-CHR6-Z hal-CHR6-Z 46
47 l) (CgH5)3P or
(RO)3P
2) base
R= Cj-C4 alkyl 36 or 37 in Scheme 23
Compounds of Formula 48 can be prepared from compounds of Formula 40b by treatment with peracids such as perbenzoic or peracetic acid, or with other peroxy compounds in the presence of an acid catalysts, followed by hydrolysis of the resultant ester. For a review, see Plesnicar, in Trahanovsky, "Oxidation in Organic Chemistry, pt. C, Academic Press, New York (1978) pp 254-267. Formula 48 corresponds to Formula 13 in Scheme 6 when Y1 = O and reagent HO-Z in Scheme 21. Compounds of Formula 52 can be prepared from compounds of Formula 48 by conversion to the dialkylthiocarbamates of Formula 50 followed by rearrangement to Formula 51 and subsequent hydrolysis. See M. S. Newman and H. A. Karnes, J. Org. Chem. (1966), 31, 3980-4. Formula 52 corresponds to Formula 13 in Scheme 6 when Y1 = S and reagent HS-Z in Scheme 21.
Scheme 29
0=C(CH3)-Z 1) [0]
HO-Z 40b 2) hydrolysis 48
αCSN(R)2 HO-Z ► Z-0-CSN(R)2 heat
Z-S-CON(R)2 HS-Z
49 50 51 52
R = Cι-C4 alkyl
Compounds of Formula 53 can be converted to compounds of Formulae 43, 48 or 52 via the diazonium compounds 54, by treatment with nitrous acid followed by subsequent reaction (Scheme 30). See reviews by Hegarty , pt. 2, pp 511-91 and Schank, pt. 2, pp 645-657, in Patai, "The Chemistry of Diazonium and Diazo Groups," Wiley, New York (1978). Treatment of Formula 54 compounds with cuprous halides or iodide ions yield compounds of Formula 43. Treatment of Formula 54 compounds with cuprous oxide in the presence of excess cupric nitrate provides compounds of Formula 48. (Cohen, Dietz, and Miser, J. Org. Chem., (1977), 42, 2053). Treatment of Formula 54 compounds with (S2)"2 yields compounds of Formula 52.
Compounds of Formula 53 can be prepared from compounds of Formula 39a by nitration, followed by reduction (Scheme 31). A wide variety of nitrating agents is available (see Schofield, " Aromatic Nitration," Cambridge University Press, Cambridge (1980)). Reduction of nitro compounds can be accomplished in a number of ways (see March, J. Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985), pp 1 103-4 and references therein). Formula 53 corresponds to Formula 13 in Scheme 6 when Y1 = NR15 and R15 = H.
Scheme 31
Z-H Z-NO2 Z-NH2
39a 55 53
Iodides of Formula 8 can be prepared from compounds of Formula 58 by the methods described above in Schemes 21-25 for various Y-Z combinations. Compounds of Formula 58 can in turn be prepared from compounds of Formula 57 by functional group interconversions which are well known to one skilled in the art. The compounds of Formula 57 can be prepared by treating compounds of Formula 56 with an organolithium reagent such as rc-BuLi or LDA followed by trapping the intermediate with iodine (Beak, P., Snieckus, V. Ace. Chem. Res., (1982), 15, 306). Additionally, lithiation via halogen metal exchange of compounds of Formula 56, where H is replaced by Br, will produce an intermediate which can be trapped with iodine to prepare compounds of Formula 57 (Parham, W. E., Bradsher, C. K. Ace. Chem. Res., (1982), 15, 300 (Scheme 32).
Scheme 32
,-r Organolithium -/ T4 ,T5
I reagent, Functional r
H I Group I
56 „7 Interconversion 58
Y-Z construction
T4 = CO2H, CONR2, CONHR,
CH2OH, OMe, OCH2OMe t = 1 or 2 Compounds of Formula In (Formula IA where Y is (CH2)xO, where x = 0 or 1) can be prepared by contacting hydroxy compounds of Formula 59 with appropriate heterocycles or activated aromatic hydrocarbons Lg-Z (where Lg is an appropriate leaving group, for example, halogen or alkylsulfonyl) in the presence of suitable bases (for example, K2CO3, KO-t-Bu or NaH) in suitable solvents (for example, acetone, dimethylformamide, dimethyl sulfoxide or tetrahydrofuran) (see Scheme 33).
Scheme 33
where x = 0 or 1 In
Compounds of Formula Lg-Z may be prepared according to literature procedures, for example, Comprehensive Heterocyclic Chemistry, Pergamon Press, vol. 6, 1984, pp 463-511 or J. Org. Chem. (1973), 38, 469 or J. Het. Chem. (1979), 961 for the preparation of 1,2,4-thiadiazoles, U.S. 5,166,165 or J. Chem. Soc, Perkin Trans. 1 (1983), 967 for the preparation of 1,3,4-oxadiazoles and 1,3,4-thiadiazoles, EP 446,010 or J. Med. Chem. (1992), 35, 3691 for the preparation of 1,2,4-oxadiazoles.
Additionally, when Z is substituted with iodine or Lg2 from Scheme 10, R9 may be introduced via a palladium(0)-catalyzed cross coupling reaction with the appropriate nucleophile containing R9, such as arylboronic acids, aryl or alkyl zinc reagents, and substituted acetylenes. It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula I.
One skilled in the art will also recognize that compounds of Formula I and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. lR NMR spectra are reported in ppm downfield from tetramethylsilane; s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = doublet of doublets, br = broad, br s = broad singlet.
EXAMPLE 1 Step A: Preparation of N-(2-methoxyphenyl)-2.2-dimethylhydrazinecarboxamide
To a stirred solution of 15.0 g of 2-methoxyphenyl isocyanate in 100 mL of toluene at 5 °C under nitrogen was slowly added 7.65 mL of 1,1-dimethylhydrazine in 10 mL toluene. The cooling bath was then removed and the reaction was allowed to stir for an additional 10 min, and was then concentrated under reduced pressure. The resulting material was dissolved in diethyl ether and concentrated again. A solid was obtained which was triturated with hexanes to afford 21 g of the title compound of Step A as a white solid. lR ΝMR (CDC13) δ 8.6 (br s.lH), 8.24 (m,lH), 6.95 (m,2H), 6.85 (m,lH), 5.35 (br s,lH), 3.89 (s,3H), 2.60 (s,6H). Step B: Preparation of 5-chloro-2.4-dihydro-4-(2-methoxyphenyl)-2-methyI-3H- 1.2.4-triazol-3-one
To a stirred solution of 21 g of the title compound of Step A in 800 mL of dichloromethane under nitrogen was added 29.85 g of triphosgene. The reaction was heated to reflux and allowed to reflux overnight, cooled, and then concentrated under reduced pressure. The resulting residue was dissolved in ethyl acetate, washed with distilled water, and then with saturated aqueous sodium chloride solution. The organic layer was dried (MgSO4), filtered, and concentrated under reduced pressure. The solid was recrystallized from dichloromethane and the resulting solid was triturated with diethyl ether to afford 10 g of the title compound of Step B as a white solid melting at 152-154 °C. -H NMR (CDC13) 57.45 (t,lH),7.25 (d,lH), 7.05 (m,2H), 3.84 (s,3H), 3.53 (s,3H). Step C: Preparation of 5-chloro-2.4-dihydro-4-C2-hydroxypheny -2-methyl-
3H- 1.2.4-triazol-3-one The title compound of Step B (7.7 g) was dissolved in 65 mL of dichloromethane under nitrogen, cooled to -78 °C, and 34 mL of a 1.0 M boron tribromide solution in dichloromethane was then added over 0.5 h with stirring. After the addition, the cooling bath (dry ice/acetone) was kept in place for an additional 0.5 h and then the reaction was allowed to warm to room temperature. Ice was added to the reaction mixture which was then diluted with diethyl ether and the product was extracted using IN aqueous sodium hydroxide solution. The aqueous layer was acidified with 6N aqueous hydrochloric acid solution and extracted with dichloromethane and then with ethyl acetate. The organic layers were combined, dried (MgSO4), filtered and concentrated under reduced pressure. The resulting residue was triturated with diethyl ether to afford 5.54 g of the title . compound of Step C as a white solid. !Η NMR (CDC13) δ 8.18 (s,lΗ), 7.11 (t,2H), 6.91 (t,lH), 6.76 (d,lH), 3.56 (s,3H). Step D: Preparation of 2.4-dihydro-4-f 2-hyclroxyphenyl)-5-methoxy-2-methyl- 3H- 1.2.4-triazol-3-one
To a stirred solution of 5.54 g of the title compound of Step C in 50 mL of methanol and 25 mL of 1,2-dimethoxyethane under nitrogen was added 18.6 mL of 30% sodium methoxide solution in methanol. The reaction was heated at reflux for 5.5 h and then cooled to room temperature. The mixture was diluted with diethyl ether and the product was extracted using IN aqueous sodium hydroxide solution. The aqueous layer was acidified with 6N aqueous hydrochloric acid solution and extracted with dichloromethane. The organic layer was dried (MgSO4), filtered, and then concentrated under reduced pressure. The resulting residue was triturated with diethyl ether to afford 3.85 g of the title compound of Step D as a white solid (85% pure). !Η NMR (CDC13) δ 8.40 (br s,lH), 7.20 (m,2H), 7.03 (d,lH), 6.94 (t,lH), 4.00 (s,3H), 3.48 (s,3H).
Step E: Preparation of 4-r2-rr3-f3.5-bis('trifluoromethyl)phenyll-1.2.4-thiadiazol-
5-ynoxylphenyl]-2.4-dihydro-5-methoxy-2-methyl-3H- 2,4-triazol-3-one To a solution of 5-chloro-3-[3,5-bis(trifluoromethyl)phenyl]-l,2,4-thiadiazole (0.8 g, 2.4 mmol, available from Maybridge, Catalog No. RDR03892) in DMF (8 mL) was added the title compound of Step D (0.44 g, 2.4 mmol) at room temperature. The solution was cooled to 5 °C and potassium carbonate (0.33 g, 2.4 mmol) was added followed by a catalytic amount of cuprous chloride (about 3-5 mg). The reaction mixture was stirred at room temperature for 4 h. The reaction was partitioned between water (30 mL) and ether (30 mL), and the aqueous layer was extracted twice with ether (25 mL). The combined ether layers were washed with water (30 mL), dried over anhydrous magnesium sulfate, and then concentrated to give 1.14 g of crude product. Flash column chromatography (gradient elution with 30-50% ethyl acetate in hexane) gave the title compound of Step E, a compound of the invention, as a white solid (0.62 g) melting at 139.5-141.5 °C. IH NMR (CDC13) δ 8.36 (s,2H), 7.94 (s,lH), 7.60 (m,2H), 7.50 (d,2H), 3.81 (s,3H), 3.37 (s,3H). EXAMPLE 2
Step A: Preparation of ethyl 3-(trifluoromethoxy)benzenecarboximidate hydrochloride To a solution of 3-(trifluoromethoxy)benzonitrile (10 g. 53.4 mmol) in ethyl ether (55 mL) is added absolute ethanol (3.3 mL). The solution is cooled to 0 °C and saturated with dry HC1 gas. The reaction mixture is then left to stand at ambient temperature for 7 days after which time it is filtered under a stream of dry nitrogen to give the title compound of Step A (10.99 g) as a white solid. lR NMR (Me2SO-d6) δ 8.2 (m,lH), 7.95 (d,lH), 7.83 (s,lH), 7.59 (m,lH), 4.66 (q,2H), 1.52 (t,3H). Step B: Preparation of 3-(trifluoromethoxy benzenecarboximidamide hydrochloride
To a solution of the title compound of Step A (10.99 grams, 40.76 mmol) in methanol (15 mL) is added ammonia (8.2 mL, 7N solution in methanol). This mixture was stirred for 5 days before being concentrated to give the title compound of Step B (10.36 g). l NMR (Me2SO-d6) δ 9.4-8.8 (br,4H), 8.01 (m,lH), 7.97 (m,lH), 7.81 (m,2H).
Step C: Preparation of 5-cMoro-3-r3-(tτifluoromethoxy)phenyl~l- 1.2.4-thiadiazole
To a solution of the title compound of Step B (10.36 g, 43.06 mmol) in water (100 mL) is added methylene chloride (200 mL), benzyltriethylammonium chloride (0.8 g) and perchloromethyl mercaptan (4.7 mL, 32.6 mmol) and the mixture is cooled in an ice bath. With efficient stirring, sodium hydroxide (6.89 g) in water (100 mL) is then added drop wise such that the internal temperature does not exceed 10 °C. After the addition is complete, the cooling bath is removed and the reaction mixture stirred for a further 1.5 h. The organic layer is then separated, dried over magnesium sulfate and concentrated. The yellow/brown tar is extracted with boiling hexane and the hot solution is filtered through a pad of silica gel. The silica gel is washed with hexane and the solution is then concentrated to a give the title compound of Step C as a yellow oil which is used without further purification. >H NMR (CDC13) δ 8.18 (d,lH), 8.11 (s,lH), 7.49
(t,lH), 7.34 (m,lH).
Step D: Preparation of 2.4-dihydro-5-methoxy-2-methyl-4-[2-l 3-r3-
(trifluoromethoxy)phenyl"l- 1.2.4-thiadiazol-5-ylloxylphenyll-3H- 1.2.4- triazol-3-one
To a solution of the title compound of Step D in Example 1 (71.44 g, 323.3 mmol) in DMF (680 mL) is added freshly ground potassium carbonate (93.9 g) and the title compound of Step C (95.5 g, 340 mmol). The mixture was stirred at ambient temperature for 3 days before being diluted with water and extracted with ethyl acetate. The aqueous phase was re-extracted with ethyl acetate and the combined organic layers were washed with water. The organic layer was dried over magnesium sulfate and concentrated. The material was purified by column chromatography (silica gel, 40%, then 60%, and then 80% ethyl ether in petroleum ether) followed by crystallization of the material from the concentrated fractions to yield 65g of the title compound of Step D, a compound of the invention, as an off white solid melting at 112-113 °C. lR NMR (CDC13) δ 8.10 (d,lΗ), 8.05 (s,lH), 7.6-7.4 (m,5H), 7.27 (m,lH), 3.79 (s,3H), 3.37 (s,3H).
EXAMPLE 3 Step A: Preparation of 2-(4-chlorophenyl)-5-(methylthioV 1.3.4-oxadiazole To a solution of 4-chlorobenzoic hydrazide (15.0 g, 87.92 mmol) in ethanol
(133 mL) and water (10 mL) is added potassium hydroxide (5.18 g, 92.3 mmol) and carbon disulfide (5.82 mL) in a dropwise fashion. The mixture was further diluted with ethanol (88 mL) and the mixture is heated at reflux overnight. Methyl iodide (6.02 mL) is then added and the mixture is cooled in an ice bath and stirred for a further 0.5 h. The solution is concentrated and redissolved in methylene chloride. The solution is filtered through a pad of silica gel and concentrated to give the title compound of Step A (17.69 g) as a white solid.
Step B: Preparation of 2-(4-chlorophenyl)-5-(mefhylsulfonyl)- 1.3.4-oxadiazole
To a solution of the title compound from Step A (17.69 g, 78.1 mmol) in acetic acid (156 mL) was added a solution of potassium permanganate (25.92 g, 164.01 mmol) in water (547 mL) in a dropwise fashion. A slight exotherm was controlled with an ice bath. On complete addition, sodium hydrosulfite (80 mL, 40% aqueous solution) was added and the resultant precipitate was filtered to give the title compound of Step B. ]H NMR (CDCI3) δ 8.70 (m,2H), 7.57 (m,2H), 3.53 (s,3H). Step C: Preparation of 4-r2-IT5-f4-chlorophenyπ- 1.3.4-oxadiazol-2- yl1oxy1phenvn-2.4-dihydro-5-methoxy-2-methyl-3H-1.2.4-triazol-3-one To a solution of the title compound of Step D in Example 1 (0.5 g, 2.26 mmol) in acetone (5 mL) was added potassium carbonate (406 mg) and the title compound of Step B (585 mg). The mixture was stirred overnight before being diluted with methylene chloride and washed with water. The aqueous phase was re-extracted with methylene chloride and the combined organic phases were dried over magnesium sulfate and the solution was concentrated under reduced pressure. The resulting solid was triturated with ethyl ether to give the title compound of Step C (719 mg, 80 %), a compound of the invention, as a solid melting at 130-132 °C. JΗ NMR (CDC13) δ 7.92 (d,2H), 7.85 (d,lH), 7.6-7.4 (m,5H), 3.88 (s,3H), 3.43 (s,3H).
EXAMPLE 4 Preparation of 2.4-dihydro-4-|"2-|Y3-iodo- 1.2.4-thiadiazol-5-y oxy]phenvn-5-methoxy-
2-methyl-3H- 1 ,2.4-triazol-3-one To a solution of the title compound of Step D in Example 1 (3.0 g, 13.6 mmol) in acetone (27 mL) was added potassium carbonate (2.44 g) and 3-iodo-5-(methylsulfonyl)- 1,2,4-thiadiazole (J Org Chem. (1973), 38, 469) (4.33 g). The mixture was stirred at ambient temperature for 36 h before being diluted with water. The resulting mixture was extracted twice with methylene chloride and the combined extracts were dried over magnesium sulfate. The solution was concentrated to a solid which was triturated with hot ethanol to give the title compound of Example 4 (2.8 g, 48%), a compound of the invention. *Η NMR (CDC13) δ 7.55 (m,2Η), 7.46 (m,2H), 3.86 (s,3H), 3.40 (s,3H).
EXAMPLE 5 Preparation of 4-[2-rf3-(3.3-dimethyl-l-butynyl)-1.2.4-thiadiazol-5-ylloxylphenyl1-2.4- dihydro-5-methoxy-2-methyl-3H- 1.2.4-triazol-3-one
To a solution of the title compound of Example 4 (307 mg, 0.71 mmol) in DMF (4 mL) was added copper(I) iodide (14 mg), triethylamine (0.347 mL), 3,3-dimethyl-l- butyne (0.219 mL) and bis(triphenylphosphine)palladium(II) chloride (25 mg). The mixture was stirred for 40 h at ambient temperature before being diluted with ethyl acetate, washed with IN ΗC1 and dried over magnesium sulfate. The solution was concentrated and purified by column chromatography (silica gel, 80 % ethyl ether in petroleum ether) to give the title compound of Example 5, a compound of the invention. lU NMR (CDC13) δ 7.55 (m,2Η), 7.45 (m,2H), 3.83 (s,3H), 3.39 (s,3H), 1.32 (s,9H). EXAMPLE 6 Preparation of 2.4-dihydro-5-methoxy-2-methyl-4-r2-[T3-["3- (trimethylsilyl)ethynyllphenyll- 1.2.4-thiadiazol-5-ylloxylphenyll-3H- 1.2.4-triazol-3-one To a solution of 2,4-dihydro-4-[2-[[3-(3-iodophenyl)-l,2,4-thiadiazol-5- yl]oxy]phenyl]-5-methoxy-2-methyl-3H-l,2,4-triazol-3-one (prepared from 3-iodobenzonitrile according to the procedure described in Example 2) (1.0 g, 1.97 mmol) in DMF (4 mL) was added copper(I) iodide (38 mg), triethylamine (0.96 mL), (trimethylsilyl)acetylene (0.70 mL) and bis(triphenylphosphine)palladium(II) chloride (35 mg). The mixture was stirred overnight at ambient temperature before being diluted with ethyl ether. The resulting mixture was washed with a saturated aqueous solution of ethylenediaminetetraacetic acid, a saturated aqueous solution of NaΗCU3, and a saturated aqueous solution of NaCl and then was dried over magnesium sulfate. The solution was concentrated and the material was crystallized from ethanol to give the title compound of Example 6 (315 mg), a compound of the invention, as a solid melting at 133-134 °C. lR NMR (CDC13) δ 8.27 (s,lH), 8.05 (d,lH), 7.65-7.5 (m,5H), 7.4 (t,lH), 3.77 (s,3H), 3.37 (s,3H), 0.26 (s,9H).
EXAMPLE 7 Preparation of 4-f2-rr3-(3-ethynylphenyl)-l .2.4-thiadiazol-5-yl1oxylphenyll-2.4-dihydro- 5-methoxy-2-methyl-3H- 1.2.4-triazol-3-one To a solution of the title compound of Example 6 (300 mg, 0.629 mmol) in methanol (3 mL) was added potassium carbonate (87 mg). The mixture was stirred at ambient temperature for 10 min before being diluted with water and extracted three times with methylene chloride. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure. Recrystallization from ethanol afforded the title compound of Example 7 (153 mg), a compound of the invention, as a white solid melting at 177-178 °C. lR NMR (CDC13) δ 8.29 (s,lΗ), 8.15 (d,lH), 7.62 (m,lH), 7.57 (m,2H), 7.49 (m,2H), 7.4 (t,lH), 3.78 (s,3H), 3.37 (s,3H).
EXAMPLE 8 Step A: Preparation of 3-(5-chloro-1.2,4-thiadiazol-3-yl)phenol To a solution of 3-chloro-5-(3-methoxyphenyl)- 1 ,2,4-thiadiazole (prepared from
3-methoxybenzonitrile according to the procedure described in Step C in Example 2) (11.4 g, 50.4 mmol) in methylene chloride (150 mL) was added boron tribromide (5.25 mL) with ice bath cooling. The reaction was allowed to warm slowly to ambient temperature. After 20 h, a saturated aqueous solution of NaHCO3 was added and the mixture was extracted with ethyl ether and the extract was dried over magnesium sulfate. Purification by column chromatography (silica gel, 20% and then 40% ethyl ether in petroleum ether) gives the title compound of Step A. -H NMR (CDC13) δ 7.85 (d,lH), 7.73 (s,lH), 7.36 (t,lH), 6.95 (d,lH), 5.42 (s,lH).
Step B: Preparation of r3-[5-r2-d.5-dihydro-3-methoxy-l-methyl-5-oxo-4H- l.Σ^-triazol^-yDphenoxyl-l.Σ^-thiadiazol-S-yllphenyll benzoate To a solution of the title compound of Step A (7.15 g, 33.6 mmol) in methylene chloride (112 mL) was added triethylamine (6.1 mL), 4-(dimethylamino)pyridine (206 mg) and benzoyl chloride (4.5 mL) with ice bath cooling. The ice bath was removed and the mixture was stirred at ambient temperature for 15 min. ΗC1 ( 1 N aqueous solution) was then added and the mixture was extracted with ethyl ether then with methylene chloride. The combined organic layers were dried over magnesium sulfate and concentrated to give a solid. To this solid was added the title compound of Step D in Example 1 (7.44 g), potassium carbonate (6.04 g) and acetone (150 mL). The mixture was stirred for 5 days before being diluted with water. The resulting mixture was extracted with methylene chloride and the extract was dried over magnesium sulfate. Purification by column chromatography (silica gel, 1% and then 2% methanol in methylene chloride) gave the title compound of Step B (10. lg), a compound of the invention. lR NMR (CDC13) δ 8.21 (d,2Η), 8.1 (d,2H), 7.7-7.4 (m,9H), 3.77 (s,3H), 3.37 (s,3H).
EXAMPLE 9 Preparation of 2.4-dihvdro-4-r2-rr3-G-hvdroxyphenylV 1.2.4-thiadiazol-5- ylloxy1phenyl1-5-methoxy-2-methyl-3H- 1.2.4-triazol-3-one To a solution of the title compound of Step B in Example 8 (10.1 g, 20 mmol) in methanol (50 mL) was added sodium methoxide (1.306g). Ethanol (50 mL) and methylene chloride (25 mL) were then added and the mixture was stirred overnight. The mixture was acidified with ΗC1 (I N aqueous solution) and was extracted twice with methylene chloride. The combined extracts were dried over magnesium sulfate. Purification by column chromatography (silica gel, 30% and then 40% ethyl acetate in benzene) gave the title compound of Example 9 (4.8 g), a compound of the invention. ]Η NMR (CDCI3) δ 7.7 (d,lH), 7.6-7.4 (m,5H), 7.25 (m,lH), 6.9 (dd,lH), 6.75 (s,lH), 3.80 (s,3H), 3.34 (s,3H).
EXAMPLE 10 Preparation of T3-r5-r2-( 1.5-dihydro-3-methoxy- l-methyl-5-oxo-4H- 1.2.4-triazol-4- y phenoxyl- 1.2.4-thiadiazol-3-yl]phenyll trifluoromethanesulfonate To a solution of the title compound of Example 9 (0.2 g, 0.5 mmol) in methylene chloride (2.5 mL) was added pyridine (0.061 mL), trifluoromethanesulfonic anhydride (0.102 mL) and a catalytic amount of 4-(dimethylamino)pyridine. The reaction mixture was stirred for 3 days before being diluted with methylene chloride and washed with HC1 (1 N aqueous solution). The organic layer was dried over magnesium sulfate. Concentration yielded the title compound of Example 10, a compound of the invention, as an off white solid. *H NMR (CDC13) δ 8.2 (d, IH), 8.1 (s,lH), 7.65-7.45 (m,5H), 7.35 (dd.lH), 3.80 (s,3H), 3.37 (s,3H).
EXAMPLE 11 Step A: Preparation of 2-furancarboximidamide
(See Tetr. Lett. (1990), 31, 1969). To a solution of trimethylaluminum (18 mL, 2 M in hexanes) in toluene (40 mL) at 0 °C was added ammonium chloride (1.926 g) in small portions. Upon complete addition, the cooling bath was removed and the mixture was stirred for a further 1.5 h. 2-furonitrile (3.15 mL, 36.0 mmol) was added and the mixture was heated at 85 °C overnight. The mixture was then cooled and poured onto a slurry of silica gel (600 g) in chloroform (300 mL). The mixture was stirred for 5 min, filtered and washed with methanol (800 mL). Concentration yielded the title compound of Step A (4.01 g). !H NMR (Me2SO- 6) δ 9.6 (br s, 2H), 9.3 (br s, 2H), 8.2 (m,lH), 7.98 (m,lH), 6.88 (m,lH). Step B: Preparation of 5-chloro-3-(2-furanyl)-L2.4-thiadiazole
To a solution of the title compound of Step A (4.01 g, 36 mmol) in water (89 mL) and methylene chloride (177 mL) was added benzyltriethylammonium chloride (675 mg) and perchloromethyl mercaptan (4.0 mL) and the mixture was cooled in an ice bath. A solution of sodium hydroxide (4.36 g) in water (89 mL) was then added such that the internal temperature did not exceed 10 °C. Upon complete addition, the cooling bath was removed and the mixture was stirred for 3 h. The layers were separated and the organic layer was dried over magnesium sulfate. Purification by column chromatography (petroleum ether and then 1-chlorobutane) gave the title compound of Step B. IH NMR (CDC13) δ 7.6 (m,lH), 7.19 (m,lH), 6.57 (m,lH). Step C: Preparation of 4-r2-rr3-(2-furanyl -1.2.4-thiadiazol-5-vnoxy1phenyll-2.4- dihydro-5-methoxy-2-methyl-3H- 1.2.4-triazol-3-one To a solution of the title compound of Step D in Example 1 (355 mg, 1.61 mmol) in acetone (3 mL) was added potassium carbonate (289 mg) and the title compound of Step B. The mixture was stirred overnight at ambient temperature before being diluted with water. The resulting mixture was extracted with methylene chloride three times and the combined extracts were dried over magnesium sulfate. The solution was concentrated to a solid which was recrystallized from ethanol to give the title compound of Step C (213 mg), a compound of the invention, as a solid melting at 107-108 °C. IH NMR (CDC13) δ 7.55 (m,3H), 7.49 (m,2H), 7.07 (m,lH), 6.5 (m,lH), 3.79 (s,3H), 3.38 (s,3H).
EXAMPLE 12 Preparation of 4-f2-IT3-('5-bromo-2-thienyl)- 1.2.4-thiadiazol-5-ynoxy1phenyll-2.4- dihydro-5-methoxy-2-methyl-3H- 1.2.4-triazol-3-one
To a solution of 5-chloro-3-(2-thienyl)-l,2,4-thiadiazole (prepared from 2-thiophenecarbonitrile according to the procedure described in Step C in Example 2) (1.0 g, 4.94 mmol) in methylene chloride was added bromine (0.253 mL). After 1 h, the mixture was concentrated and redissolved in acetone (8 mL). The title compound of Step D in Example 1 (850 mg) and potassium carbonate (1.33 g) were added and the mixture was stirred overnight before being diluted with water and twice extracted with methylene chloride. The organic phases were combined, dried over magnesium sulfate, and concentrated. The residue was purified by column chromatography (silica gel, ethyl ether) to give the title compound of Example 12, a compound of the invention. !Η NMR (CDCI3) δ 7.65-7.55 (m,2H), 7.5-7.45 (m,3H), 7.04 (d,lH), 3.80 (s,3H), 3.38 (s,3H).
EXAMPLE 13 Step A: Preparation of 5-cMoro-3-(2.5-dichloro-3-tnienyl)-1.2.4-thiadiazole
A solution of 5-chloro-3-(3-thienyl)-l,2,4-thiadiazole (prepared from 3- thiophenecarbonitrile according to the procedure described in Step C in Example 2) (2.0 g, 9.88 mmol) in sulfuryl chloride (10 mL) was stirred at ambient temperature for 1.5 h before being poured into water and extracted with ethyl ether. The ether layer was washed with a saturated aqueous solution of NaHCO3 and dried over magnesium sulfate. Concentration yielded the title compound of Step A ( 1.87 g). lR NMR (CDC13) δ 7.45 (s,lH).
Step B: Preparation of 4-r2- r3-('2.5-dichloro-3-thienylV1.2.4-thiadiazol-5- ylloxy]phenyl1-2,4-dihydro-5-methoxy-2-methyI-3H-1.2.4-triazol-3-one To a solution of the title compound of Step D in Example 1 (1.83 g, 6.74 mmol) in acetone (13 mL) was added potassium carbonate (1.21 g) and the title compound of Step A. The mixture was stirred at ambient temperature for 30 h at which point extra potassium carbonate (0.6 g) was added. When the reaction was judged to be complete by TLC analysis, it was diluted with ethyl acetate, washed twice with water, with saturated aqueous NaCl and the combined aqueous layers were re-extracted with ethyl acetate. The combined organic phases were dried over magnesium sulfate, concentrated and the residue was purified by crystallization from ethanol. The mother liquor was concentrated and purified by column chromatography (silica gel, 60% and then 80% ethyl ether in petroleum ether) to give the title compound of Step B (2.5 g), a compound of the invention, as a solid melting at 144-147 °C. !H NMR (CDC13) δ 7.65 (d,lH), 7.6-7.5 (m,lH), 7.5-7.4 (m,2H), 7.37 (s,lH), 3.81 (s,3H), 3.39 (s,3H).
EXAMPLE 14 Step A: Preparation of 2.2-dimethylpropanimidic acid hydrochloride
To a solution of trimethylacetonitrile (100 g, 1.203 mol) in ethyl ether (600 mL) is added absolute ethanol (74.1 mL). The solution is cooled to 0 °C and then is saturated with dry HC1 gas. The reaction mixture is then left to stand at ambient temperature for 6 days after which time it is concentrated to give the title compound of Step A (54.37 g) as a white solid. *H NMR (Me2SO-< ) δ 11.4 (br s, 2H), 4.4 (q,2H), 1.22 (s,9H), 1.05 (t,3H). Step B: Preparation of 2.2-dimethylpropanimidamide hydrochloride
To a solution of the title compound of Step A (54.37 g, 328.2 mmol) in methanol (20 mL) is added ammonia (65.7 mL, 7N solution in methanol). This mixture was stirred for 3 days before being concentrated to give the title compound of Step B (33.15 g) as an off white solid. *H NMR (Me2SO-rf6) δ 1.25 (s,9H). Step C: Preparation of 5-chloro-3-f 1.1 -dimefhylethylV 1.2.4-thiadiazole
To a solution of the title compound of Step B (5.0 g, 36.61 mmol) in water (23 mL) and methylene chloride (45 mL) is added perchloromethyl mercaptan (4.0 mL, 36.61 mmol) and the mixture is cooled in an ice bath. With efficient stirring, a solution of sodium hydroxide (5.86 g ) in water (23 mL ) is then added dropwise such that the internal temperature does not exceed 10 °C. After the addition is complete, the cooling bath is removed and the reaction mixture is stirred for a further 1.5 h. The organic layer is then separated, dried over magnesium sulfate and concentrated. The yellow/brown tar is extracted with boiling hexane and the hot solution is filtered through a pad of silica gel. The silica gel is washed with hexane and the solution is concentrated to a give the title compound of Step C (5.88 g) as a yellow oil which is used without further purification. !H NMR (CDC13) δ 1.42 (s,9H). Step D: Preparation of 4-r2-fr3-f 1.1 -dimethylethylV 1 ,2.4-thiadiazol-5- ylloxy1phenyl1-2.4-dihydro-5-methoxy-2-methyl-3H-1.2.4-triazol-3-one
To a solution of the title compound of Step D in Example 1 (500 mg, 2.26 mmol) in DMF (4.5 mL) is added freshly ground potassium carbonate (406 mg) and the title compound of Step C (399 mg). The mixture was stirred at ambient temperature for 2 days before being diluted with ethyl acetate and washed with water. The organic layer was dried over magnesium sulfate and concentrated. Purification by column chromatography (silica gel, 40%, then 60%, and then 80% ethyl ether in petroleum ether) yields the title compound of Step D (0.19 g), a compound of invention, as an off white solid melting at 110-1 1 1 °C. -H NMR (CDC13) δ 7.58 (d,lH), 7.50 (m,lH), 7.47 (m,lH), 7.44 (m,lH), 3.78 (s,3H), 3.40 (s,3H), 1.36 (s,9H).
EXAMPLE 15 Preparation of 4-[2-r(6-chloro-2-pyrazinyl)oxylphenyl1-2.4-dihydro-5-methoxy-2- methyl-3H- 1 ,2.4-triazol-3-one To a solution of the title compound of Step D in Example 1 (2.2 g, 10.0 mmol) in DMF (10 mL) was added sodium hydride (0.47g, 60% oil dispersion) in small portions. The resulting slurry was stirred for 5 min and then 2,6-dichloropyrazine (1.5 g, 10.1 mmol) was added all at once. The reaction mixture was stirred for 16 h at
70-75 °C, and then the DMF was removed by vacuum distillation. The residue was partitioned between 125 mL of ethyl acetate and 50 mL of water. The organic layer was dried over anhydrous magnesium sulfate and concentrated to give a brown solid which was triturated with diethyl ether to afford 1.65 g of the title compound of Example 15, a compound of invention, as a white solid melting at 135-137 °C. lR NMR (CDC13) δ 8.30 (m,2Η), 7.50 (m,lH), 7.40 (m,3H), 3.81 (s,3H), 3.33 (s,3H).
EXAMPLE 16
Preparation of 2.4-dihydro-5-methoxy-2-methyl-4-r2-rr6-|"4-(trifluoromethyl phenyn-2- pyrazinyl"loxy1phenyll-3H- 1.2.4-triazol-3-one A slurry made up of the title compound of Example 15 (3.0g, 9.12 mmol) and palladium acetate (76 mg) in dimethoxyethane (18.5 mL) was stirred for 0.5 h. To this mixture was added a solution of 4-trifluoromethylbenzene boronic acid (2.5 g, 13.1 mmol, available from Lancaster Synthesis Inc.) and sodium carbonate (3.1 g) in 46 mL of water. The reaction mixture was stirred at 100 °C for 5 h. The dimethoxyethane was removed under reduced pressure and the resulting mixture was partitioned between 150 mL of ethyl acetate and 50 mL of water. The aqueous layer was extracted with 50 mL of ethyl acetate and the combined organic layers were filtered through Celite®, dried over anhydrous potassium carbonate, and concentrated under reduced pressure to give a crude product. Flash column chromatography (gradient elution with 60-75% ethyl acetate in hexane) gave the title compound of Example 16, a compound of the invention, as a white solid (3.3 g) melting at 145-148 °C. lΗ NMR (CDC13) δ 8.79 (s,lΗ), 8.39 (s,lH), 7.98 (d,2H), 7.67 (d,2H), 7.51 (m,lH), 7.41 (m,3H), 3.65 (s,3H), 3.31 (s,3H). EXAMPLE 17 Preparation of 4~r6-r2-( 1.5-dihydro-3-methoxy- 1 -methyl-5-oxo-4H- 1.2.4-triazol-4- yl)phenoxy1-2-pyrazinyllbenzonitrile To a solution of the title compound of Example 15 (333 mg, 1.0 mmol) and tetrakis(triphenylphosphine)palladium (60 mg) in nitrogen-purged tetrahydrofuran (2.8 mL) was added a solution of bromo(4-cyanophenyl)zinc (2.8 mL, 0.5M in tetrahydrofuran, available from Rieke Metals, Inc.). The resulting dark solution was stirred for 22 h at room temperature and an additional 1.5 mL of the organozinc reagent was then added to complete the reaction. After stirring for another 6 h, the reaction mixture was partitioned between 100 mL of ethyl acetate and 50 mL of diluted aqueous hydrochloric acid. The aqueous layer was extracted with 50 mL of ethyl acetate and the combined organic layers were dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give a crude product. Flash column chromatography (gradient elution with 50-70% ethyl acetate in hexane) gave the title compound of Example 17, a compound of invention, as a white solid (230 mg) melting at 195-199 °C. JΗ NMR (CDC13) δ 8.79 (s,lH), 8.40 (s,lH), 8.00 (d,2H), 7.72 (d,2H), 7.53 (m,lH), 7.41 (m,3H), 3.68 (s,3H), 3.30 (s,3H).
EXAMPLE 18 Step A: Preparation of 5-(4-chlorophenyl)-1.3.4-tMadiazol-2-arnine The title compound was prepared according to Zubets, I. V.; Boikov, Yu. A.;
Niktorovskii, I. V.; Nyunov, K. A.; Chem. Het. Comp. 1148 (1986). Starting from 4-chlorobenzaldehyde thiosemicarbazone (8.6g, 50.1 mmol), the reaction afforded 6.3 g of the title compound of Step A as an off white solid. JH ΝMR (Me2SO- 6) δ 7.82-7.54 (AA'BB", 4H), 7.48 (s, 2H). Elemental analysis: (Calculated) C: 44.97, H: 3.77, Ν: 19.66, S: 15.00. (Found) C: 45.10, H: 3.92, Ν: 19.67, S: 14.65.
Step B: Preparation of 2-chloro-5-(4-chlorophenyl)- 1 ,3,4-thiadiazole
The title compound was prepared according to Zubets, I. V.; Boikov, Yu. A.; Viktorovskii, I. V.; V'yunov, K. A.; Chem. Het. Comp. 1148 (1986). Starting from the title compound of Step A (0.6g, 3 mmol), the reaction afforded 0.4 g of a yellow oil which was used without further purification. !H ΝMR (Me2SO- 6) δ 8.02-7.67 (AA'BB', 4H). Step C: Preparation of 4-r2-[T5-f4-chlorophenyl)- 3,4-thiadiazol-2- yl1oxylphenyl1-2,4-dihydro-5-methoxy-2 methyl-3H- 1 ,2,4-triazol-3-one The title compound of Step B (0.46 g, 2 mmol), the title compound of Step D in Example 1 (0.44 g, 2 mmol) and potassium carbonate (0.8 g, 5.8 mmol) were combined in 30 mL of 4-methyl-pentane-2-one. The mixture was heated at reflux temperature for 5 h and was then allowed to cool to ambient temperature. The solvent was removed under reduced pressure and the residue was partitioned between 50 mL of ethyl acetate and 50 mL of water. The aqueous layer was extracted with ethyl acetate (2x30 mL). The combined organic layers were extracted with IN sodium hydroxide (2x20 mL) and saturated aqueous NaCl (2x20 mL), respectively. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. Preparative TLC (eluent: ethyl acetate/hexane=2/l) afforded the title compound of Step C, a compound of invention, as a white solid. lU NMR (Me2SO-d6) δ 7.92-7.45 (m,8H), 3.79 (s,3H), 3.25 (s,3H). EXAMPLE 19
Step A: Preparation of 4-f3-Ctrifluoromethyl)phenyl]-2-thiazolamine
To a stirring solution of 10 g of 3'-(trifluoromethyl)acetophenone in 100 mL of dichloromethane was added dropwise 8.5 g of bromine. The bromine color dissipated immediately during the dropwise addition. The reaction mixture was then concentrated under reduced pressure and the resulting oil was dissolved in 80 mL of ethanol. To this oil was added 4.0 g of thiourea and the resulting mixture was heated at reflux for 8 h. Upon cooling, a solid precipitated. Approximately 100 mL of diethyl ether was added to enhance precipitation. The solid was collected and washed with diethyl ether followed by neutralization with excess aqueous sodium bicarbonate. The free base was extracted into ethyl acetate. The ethyl acetate solution was washed with water and saturated aqueous NaCl. The ethyl acetate solution was then dried over MgSO4 and concentrated under reduced pressure to give 11.5 g of the title compound of Step A as a white (yellow tinted) solid melting at 87-88 °C. lR NMR (CDC13) δ 8.05 (s.lH), 7.95 (d,lH), 7.5 (m,2H), 6.8 (s,lH), 5.15 (br s,2H). Step B: Preparation of 5-bromo-4-r3-(trifluoromethyl)phenyl1-2-thiazolamine
To a stirring solution of 8.5 g of the title compound of Step A in 100 mL of dichloromethane was added dropwise 6 g of bromine. The bromine color dissipated immediately during the dropwise addition. The reaction mixture was stirred for 10 minutes after the addition and then was concentrated under reduced pressure. The resulting residue was partitioned between 150 mL of ethyl acetate and 100 mL of saturated aqueous NaHCO3 and the mixture was stirred for 0.5 h. The organic layer was separated, washed with saturated aqueous NaCl, dried over MgSO4 and concentrated under reduced pressure to give an oil which soon crystallized. The solid was suspended in hexanes, then collected by filtration to give 10.5 g of the title compound of Step B as a white solid melting at 96-98 °C. lH NMR (CDC13) δ 8.15 (s,lH), 8.05 (d.lH), 7.65 (d,lH), 7.55 (t,lH), 5.75 (br s,2H). Step C: Preparation of 5-bromo-2-chloro-4-r3-ftrifluoromethvL)phenyl1thiazole
The title compound of Step B (3 g) was dissolved in 50 mL of acetonitrile and to this solution was added with stirring 2.5 g of copper(II) chloride followed by 2 mL of tert-butylnitrite (dropwise). Nitrogen evolution was evident and the reaction exothermically warmed to approximately 30 °C. The dark reaction mixture was stirred for 45 min and was then partitioned between 200 mL of ethyl acetate and 200 mL of distilled water. The organic layer was separated, washed with IN aqueous HC1, water, and then saturated aqueous NaCl. The organic layer was dried over MgSO4 and then was concentrated under reduced pressure to give a dark oil/solid residue. The main component was isolated by flash chromatography on silica gel using 5-10% ethyl acetate in hexanes as eluant to give 2.4 g of the title compound of Step C as a red tinted solid melting at 52-55 °C. JH NMR (CDC13) δ 8.2 (s,lH), 8.15 (d,lH), 7.65 (d,lH), 7.6 (t,lH). Step D: Preparation of 4-f2-[r5-bromo-4-13-ftrifluoromethyl)phenyl"l-2- thiazolyl1oxylphenyll-2.4-dihydro-5-methoxy-2-methyl-3H-1.2.4-triazol-
3-one To a stirring solution of 2.2 g of the title compound of Step C in 50 mL of acetonitrile was added 1.4 g of the title compound of Step D in Example 1 and 1.8 g of potassium carbonate. The reaction mixture was heated at reflux for 14 h and then was allowed to cool. The reaction mixture was partitioned between 100 mL of ethyl acetate and 100 mL of distilled water. The organic layer was separated, washed with distilled water, dried over MgSO4, and then concentrated under reduced pressure to give a dark oil. The main component was isolated by flash chromatography on silica gel using 50% ethyl acetate in hexanes as eluant to give 2.1 g of the title compound of Step D, a compound of the invention, as a gum. lR NMR (CDC13) δ 8.2 (s,lΗ), 8.1 (d,lH), 7.6 (d,lH), 7.35-7.55 (m,5H), 3.84 (s,3H), 3.40 (s,3H).
EXAMPLE 20
Preparation of 2.4-dihydro-5-methoxy-2-methyl-4-|"2-rf4-r3-("trifluoromethyl)phenyl"|-2- thiazolynoxy1phenyl1-3H- 1.2.4-triazol-3-one A mixture of 0.8 g of the title compound of Step D in Example 19, 2.0 g of ammonium formate and 0.3 g of 10% palladium on carbon in 20 mL methanol was stirred at room temperature for 2 days. The reaction mixture was then filtered through Celite® rinsing thoroughly with ethyl acetate. The filtrate was partitioned between 100 mL of ethyl acetate and 50 mL of distilled water. The organic layer was separated, washed with distilled water and then with saturated aqueous NaCl. The organic layer was dried over MgSO4 and then was concentrated under reduced pressure to give an oil. The main component was isolated by flash chromatography on silica gel using 50% ethyl acetate in hexanes as eluant to give a white foam which crystallized to a white solid upon the addition of a small amount of diethyl ether. The solid was filtered to give 0.52 g of the title compound of Example 20, a compound of the invention, as a white solid melting at 116-118 °C. lR NMR (CDC13) δ 8.05 (s,lH), 7.95 (d,lH), 7.35-7.6 (m,6H), 7.1 (s,lH), 3.81 (s,3H), 3.37 (s,3H).
EXAMPLE 21
Preparation of 2.4-dihydro-5-methoxy-2-methyl-4-f2-rr5-methyl-4-r3-
(trifluoromethyDphenyll-Σ-thiazolynoxylphenyn-SH-l.Σ -triazol-S-one To a stirring solution of 0.75 g of the title compound of Example 19 in Step D in
7 mL of tetrahydrofuran at -78 °C under N2 was added dropwise 0.70 mL of n-butyllithium (2.5 M in hexanes). The reaction was allowed to stir at -78 °C for 0.5 h, and then 0.12 mL of iodomethane was slowly added. After stirring at -78 °C for another 2 min, the cooling bath was removed and the reaction mixture was stirred an additional 2 h at ambient temperature. The reaction mixture was diluted with diethyl ether and washed with distilled water and saturated aqueous NaCl. The organic layer was dried over MgSθ4 and then was concentrated under reduced pressure. Purification by flash chromatography on silica gel using 50-60% ethyl acetate in hexanes as eluant gave 0.40 g of the title compound of Example 21, a compound of the invention, as an oil. lR NMR (CDCI3) δ 7.85 (s,lΗ), 7.8 (d,lH), 7.3-7.6 (m,6H), 3.85 (s,3H), 3.40 (s,3H), 2.49 (s,3H).
EXAMPLE 22 Step A: Preparation of N-(2-methoxy-6-methylphenyl)-2.2- dimethylhydrazinecarboxamide To a stirred solution of phosgene (108 g, 1.09 moles) in ethyl acetate (750 mL) at 0 °C was added dropwise 2-methoxy-6-methylaniline (125.0 g, 911 mmol) dissolved in ethyl acetate (250 mL) over 20 min. The reaction mixture was slowly warmed to room temperature and was then heated at reflux for 1 h. The solution was cooled to room temperature and was concentrated under reduced pressure to provide the crude isocyanate as a dark red liquid which was redissolved in ethyl acetate (1 L) and cooled to 0 °C. 1,1-Dimethylhydrazine (55.0 g, 911 mmol) was added dropwise over 30 min and then the mixture was allowed to warm to room temperature and stir overnight. The mixture was cooled, filtered, and the solid was washed with ethyl acetate and dried to provide 200.0 g of the title compound of Step A as a white solid melting at 151-153 °C. lH ΝMR (CDCI3) δ 7.58 (br s,lH), 7.10 (t,lH), 6.84 (d,lH), 6.74 (d,lH), 5.22 (br s,lH), 3.80 (s,3H), 2.63 (s,6H), 2.31 (s,3H). Step B: Preparation of 5-chloro-2.4-dihydro-4-(2-methoxy-6-methylphenyl')-2- methyl-3H- 1 ,2.4-triazol-3-one The title compound of Step A (100.0 g, 447.9 mmol) was suspended in ethyl acetate (1 L) and added dropwise, via mechanical pump, over 3.5 h to a stirring solution of phosgene ( 177 g, 1.79 moles) in ethyl acetate (1.5 L) which was heated at reflux. After the addition was complete, the mixture was heated at reflux for a further 3 h, cooled to room temperature and stirred overnight. The solution was concentrated under reduced pressure and the residue was dissolved in ethyl acetate and water and extracted four times with ethyl acetate. The combined organic phases were washed with saturated aqueous NaCl, dried (MgSO4), filtered and concentrated to afford 111.4 g of the title compound of Step B as a pale yellow solid melting at 132-134 °C. lH NMR (CDC13) δ 7.34 (t,lΗ), 6.93 (d,lH), 6.85 (d,lH), 3.79 (s,3H), 3.54 (s,3H), 2.20 (s,3H). Step C: Preparation of 5-chloro-2.4-dihydro-4-(2-hydroxy-6-methylphenyl)-2- methyl-3H- 1 ,2.4-triazol-3-one To a stirring solution of the title compound of Step B (15.0 g, 59.3 mmol) in benzene (200 mL) at 0 °C was added aluminum chloride (23.7 g, 178 mmol) in small portions. The mixture was warmed to room temperature and stirred for 2 days. The mixture was poured over ice and water and then extracted four times with ethyl acetate. The combined organic phases were washed with saturated aqueous NaCl, dried (MgSO4), filtered and concentrated to an oil that was purified by flash column chromatography on silica gel to provide 13.6 g of the title compound of Step C as a pale orange solid melting at 175-178 °C. !Η NMR (CDC13) δ 8.11 (s,lΗ), 6.92 (t,lH), 6.71 (d,lH), 6.41 (d,lH), 3.56 (s,3H), 2.12 (s,3H). Step D: Preparation of 2.4-dihydro-4-("2-hydroxy-6-methylphenylV5-methoxy-2- methyl-3H- 1.2.4-triazol-3-one
To a stirred solution of the title compound of Step C (133.5 g, 557.0 mmol) in tetrahydrofuran (1.5 L) was added dropwise sodium methoxide (25% by weight in methanol, 382 mL, 1.67 moles). The mixture was heated at reflux for 3 h, cooled to room temperature and then diluted with aqueous ammonium chloride and ethyl acetate. The aqueous layer was acidified (pΗ 4-5) with IN ΗC1 and extracted three times with ethyl acetate. The combined organic phases were washed with saturated aqueous NaCl, dried (MgSO4), filtered and concentrated to a dark brown solid which was triturated with ethyl acetate to afford 75.0 g of the title compound of Step D as a white solid melting at 194-196 °C. lR NMR (Me2SO-d6) δ 9.91 (s,lΗ), 7.17 (t,lH), 6.78 (m,2H), 3.84 (s,3H), 3.30 (s,3H), 2.03 (s,3H). Step E: Preparation of 4-r2-rF3-r3,5-bis(trifluoromethyl)phenyll-1.2.4-thiadiazol-
5-ylloxy1-6-methylphenyll-2.4-dihydro-5-methoxy-2-methyl-3H- 1.2,4- triazol-3-one To a solution of 5-chloro-3-[3,5-bis(trifluoromethyl)phenyl]-l,2,4-thiadiazole ( 1.50 g, 4.51 mmol, available from Maybridge, Catalog No. RDR03892) in DMF (10 mL) was added the title compound of Step D (1.06 g, 4.51 mmol) at room temperature. Potassium carbonate (1.25 g, 9.02 mmol) was added and the mixture was stirred for 18 h. The mixture was diluted with water and extracted three times with ethyl acetate. The combined organic phases were washed with saturated aqueous NaCl, dried (MgSO ), filtered and concentrated. The residue was purified by flash column chromatography on silica gel to provide 2.20 g of the title compound of Step E, a compound of the invention, as a white solid melting at 95-98 °C. lK NMR (CDC13) δ 8.64 (s,2Η), 7.95(s,lH), 7.50 (t,lH), 7.42 (d,lH), 7.37 (d,lH), 3.80 (s,3H), 3.39 (s,3H), 2.33 (s,3H). EXAMPLE 23
Step A: Preparation of 2.4-dihydro-5-methoxy-2-methyl-4-[2-[rtris(l- methylethyl silylloxylphenyll-3H- 1.2.4-triazol-3-one To a solution of the title compound of Step D in Example 1 (10.54 g, 47.65 mmol) and imidazole (6.50 g, 95.3 mmol) in DMF (100 mL) was added dropwise triisopropylsilyl chloride (13.3 mL, 61.9 mmol) at 0 °C. The mixture was allowed to warm to room temperature and was stirred for 3 h. Then mixture was then diluted with aqueous sodium bicarbonate and water and was extracted three times with ethyl acetate. The combined organic phases were washed with saturated aqueous NaCl, dried (MgSO4), filtered and concentrated to an oil which was purified by flash column chromatography on silica gel to give 16.8 g of the title compound of Step A as a light tan solid melting at 107-109 °C. ]Η NMR (CDC13) δ 7.27 (m,2H), 6.98 (m,2H), 3.89 (s,3H), 3.42 (s,3H), 1.25 (m,3H), 1.04 (m,18H).
Step B: Preparation of 4-|'2-ethyl-6-l|"tris('l-methylethyl)silylloxylphenyll-2.4- dihydro-5-methoxy-2-methyl-3H-l,2.4-triazol-3-one A solution of the title compound of Step A (2.16 g, 5.72 mmol) in anhydrous tetrahydrofuran was cooled to -78 °C and terr-butyllithium (4.0 mL, 1.7 M solution in pentane, 6.8 mmol) was added dropwise. The resulting dark yellow solution was stirred for 1 h at -78 °C and ethyl iodide (4.6 mL, 57.2 mmol) was then added dropwise and the mixture was slowly warmed to 0 °C and stirred for 20 min. The mixture was diluted with aqueous ammonium chloride and extracted three times with ethyl acetate. The combined organic phases were washed with saturated aqueous NaCl, dried (MgSO4), filtered and concentrated. The crude product was purified by flash column chromatography on silica gel to afford 1.64 g of the title compound of Step B as a white solid melting at 90-92 °C. *H NMR (CDC13) δ 7.23 (t,lH), 6.90 (d,lH), 6.77 (d,lH), 3.89 (s,3H), 3.43 (s,3H), 2.53 (q,2H), 1.24 (m, 3H), 1.15 (t,3H), 1.04 (m,18H). Step C: Preparation of 4-r2-rr3-r3.5-bisCtrifluoromethyl)phenyll-1.2.4-thiadiazol-
5-ylloxyl-6-ethylphenyl1-2.4-dihydro-5-methoxy-2-methyl-3H-1.2.4- triazol-3-one The title compound of Step B (0.244 g, 0.60 mmol) and 5-chloro-3-[3,5- bis(trifluoromethyl)phenyl]-l,2,4-thiadiazole (0.200 g, 0.60 mmol) was dissolved in anhydrous tetrahydrofuran (10 mL). A solution of tetrabutylammonium fluoride
(0.70 mL, 1.0M solution in tetrahydrofuran, 0.70 mmol) was added dropwise and the solution was stirred for 1 h at room temperature. The mixture was diluted with water and extracted three times with ethyl acetate. The combined organic phases were washed with saturated aqueous NaCl, dried (MgSO4), filtered and concentrated. The residue was purified by flash column chromatography on silica gel to afford 0.32 g of the title compound of Step C, a compound of the invention, as a white solid melting at 136-138 °C. IΗ NMR (CDC13) δ 8.64 (s,2Η), 7.94 (s,lH), 7.56 (t, IH), 7.42 (m, 2H), 3.80 (s,3H), 3.40 (s,3H), 2.63 (m,2H), 1.23 (t,3H).
By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 14 can be prepared. The following abbreviations are used in the Tables which follow: t = tertiary, Me = methyl, Et = ethyl, Bu = butyl, Ph = phenyl, MeO = methoxy, EtO = ethoxy, CN = cyano, and NO2 = nitro.
TABLE 1 Compounds of Formula IA defined as:
TABLE Compounds of Formula IA defined as:
E9 E9 E9
3,4-diF-Ph 4-Ph-Ph 6-CF3>2-pyridinyl
3,5-diBr-4-MeO-Ph 4-Br-3-Me-Ph 2-pyrimidinyl
3-Cl-4-Me-Ph 3-Br-4-MeO-Ph 4-pyrimidinyl
3,5-diF-Ph 5-F-2-thienyl 4-MeO-2-pyrimidinyl
3-F-4-Cl-Ph 5-Br-2-thienyl 4-Me-2-pyrimidinyl
3-MeO-Ph 5-Cl-2-thienyl 6-MeO-4-pyrimidinyl
3-Cl-Ph 2,5-diF-3-thienyl 5-Me-2-furanyl
C(CH3)3 2,5-diCl-3-thienyl 2,5-diMe-3-thienyl
3-Br-Ph 2,5-diBr-3-thienyl 3-OCF2H-Ph -Br-Ph 4-SCF2H-Ph 4-OCF2H-Ph -CN-Ph 2-Me-Ph 3-Me3Si-Ph ,4-diCI-Ph 2-F-Ph 4-Me3Si-Ph -CF3-Ph 2-Me-4-Cl-Ph 3-Me3Ge-Ph -I-Ph 3,5-diCl-Ph 4-Me3Ge-Ph -N02-Ph 3,5-diCF3-Ph Ph -CF30-Ph 2-MeO-Ph 3-CN-Ph -Me-Ph 2,6-diMeO-Ph 4-C02Me-Ph -Cl-Ph 3-CF30-Ph 4-C02-r-Bu-Ph -Me-Ph 4-Br-Ph 4-C02Et-Ph -CF3-Ph 3-Et-Ph 6-CF3-4-pyrimidinyl -Cl-2-Me-Ph 4-MeO-Ph 4-CF3-2-pyridinyl -r-Bu-Ph 4-/-Bu-Ph 4-CF3-2-pyrimidinyl -F-Ph 4-CN-Ph 5-CF3-3-pyridinyl -CF3-Ph 4-N02-Ph 3-MeO-2-pyridinyl ,4-diCl-Ph 3,4-diMe-Ph 5-CN-2-pyridinyl ,4-diCF3-Ph 3,5-diMe-Ph 6-Me-2-pyridinyl -F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph -I-Ph 5-F-3-CF3-Ph 4-r-Bu-2-pyridinyl -Br-5-pyridinyl 3-Cl-benzyl 4-Me3Si-2-pyridinyl ,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-pyridinyl ,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl ,5-diF-2-thienyl 3-(Me3Si-C≡C)-Ph 5-CF3-2-furanyl ,4,5-triCl-2-thienyl 4-(Me3Si-CsC)-Ph 5-CF3-2-thienyl -(C≡CH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph -(C≡CH)-Ph 3-OS02CF3-Ph 4-I-Ph -CF3CH20-5-pyridinyl 4-OS02CF3-Ph 3-C02Me-Ph -Cl-benzyl 4-EtO-2-pyrimidinyl 3-C02-r-Bu-Ph -Et-Ph 4,6-diMeO-2-pyrimidinyl 3-C02Et-Ph -Cl-Ph 4,6-diMe-2-pyrimidinyl TABLE 3
Compounds of Formula IA defined as:
4-F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph
3-I-Ph 5-F-3-CF3-Ph 4-f-Bu-2-pyridinyl
2-Br-5-pyridinyl 3-Cl-benzyl 4-Me3Si-2-pyridinyl
4,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-pyridinyl
4,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl
4,5-diF-2-thienyl 3-(Me3Si-C≡C)-Ph 5-CF3-2-furanyl
3,4,5-triCl-2-thienyl 4-(Me3Si-C≡C)-Ph 5-CF3-2-thienyl
3-(C≡CH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph
4-(C≡CH)-Ph 3-OS02CF3-Ph 4-I-Ph
2-CF3CH2θ-5-pyridinyl 4-OS02CF3-Ph 3-C02Me-Ph
4-Cl-benzyl 4-EtO-2-pyrimidinyl 3-C02-r-Bu-Ph
2-Et-Ph 4,6-diMeO-2-pyrimidinyl 3-C02Et-Ph
2-Cl-Ph 4,6-diMe-2-pyrimidinyl
TABLE 4 Compounds of Formula I A defined as:
TABLE 6
Compounds of Formula IA defined as:
E9
6-CF3-2-pyridinyl
2-pyrimidinyl
4-pyrimidinyl
4-MeO-2-pyrimidinyl
4-Me-2-pyrimidinyl
6-MeO-4-pyrimidinyl
5-Me-2-furanyl
2,5-diMe-3-thienyl
3-OCF2H-Ph
4-OCF2H-Ph
3-Me3Si-Ph
4-Me3Si-Ph
3-Me3Ge-Ph
4-Me3Ge-Ph
Ph
3-CN-Ph
4-C02Me-Ph
4-C02-r-Bu-Ph
4-C02Et-Ph
6-CF3-4-pyrimidinyl
4-CF3-2-pyridinyl 4-CF3-2-pyrimidinyl
TABLE 8
3-r-Bu-Ph 4-CN-Ph 3-Me3Si-Ph 4-Me3Si-2-pyridinyl
3-F-Ph 4-N02-Ph 4-Me3Si-Ph 4-Me3Ge-2-pyridinyl
4-CF3-Ph 3,4-diMe-Ph 3-Me3Ge-Ph 4,6-diCF3-2-pyrimidinyl
3,4-diCl-Ph 3,5-diMe-Ph 4-Me3Ge-Ph 5-CF3-2-furanyl
3,4-diCF3-Ph 4-F-3-CF3-Ph 3-EtO-Ph 5-CF3-2-thienyl
4-F-Ph 5-F-3-CF3-Ph Ph (2-CN-Ph)CH2
3-Cl-Ph 3-Br-Ph 3-I-Ph 4-I-Ph r-Bu
TABLE 9
-Me-Ph 2,6-diMeO-Ph 4-C02Me-Ph -Cl-Ph 3-CF30-Ph 4-C02-f-Bu-Ph -Me-Ph 4-Br-Ph 4-C02Et-Ph -CF3-Ph 3-Et-Ph 6-CF3-4-pyrimidinyl -Cl-2-Me-Ph 4-MeO-Ph 4-CF3-2-pyridinyl -r-Bu-Ph 4-r-Bu-Ph 4-CF3-2-pyrimidinyl -F-Ph 4-CN-Ph 5-CF3-3-pyridinyl -CF3-Ph 4-N02-Ph 3-MeO-2-pyridinyl ,4-diCl-Ph 3,4-diMe-Ph 5-CN-2-pyridinyl ,4-diCF3-Ph 3,5-diMe-Ph 6-Me-2-pyridinyl -F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph -I-Ph 5-F-3-CF3-Ph 4-f-Bu-2-pyridinyl -Br-5-pyridinyl 3-Cl-benzyl 4-Me3Si-2-pyridinyl ,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-pyridinyl ,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl ,5-diF-2-thienyl 3-(Me3Si-C≡C)-Ph 5-CF3-2-furanyl ,4,5-triCl-2-thienyl 4-(Me3Si-OC)-Ph 5-CF3-2-thienyl -(C≡CH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph -(C≡CH)-Ph 3-OS02CF3-Ph 4-I-Ph -CF3CH20-5-pyridinyl 4-OS02CF3-Ph 3-C02Me-Ph -Cl-benzyl 4-Et0-2-pyrimidinyl 3-C02-r-Bu-Ph -Et-Ph 4,6-diMe0-2-pyrimidinyl 3-C02Et-Ph -Cl-Ph 4,6-diMe-2-pyrimidinyl
TABLE 10 Compounds of Formula IA defined as:
4-CF3-Ph 4-N02-Ph 3-MeO-2-pyridinyl
3,4-diCl-Ph 3,4-diMe-Ph 5-CN-2-pyridinyl
3,4-diCF3-Ph 3,5-diMe-Ph 6-Me-2-pyridinyI
4-F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph
3-I-Ph 5-F-3-CF3-Ph 4-r-Bu-2-pyridinyl
2-Br-5-pyridinyl 3-Cl-benzyl 4-Mβ3 Si-2-pyridinyl
4,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-ρyridinyl
4,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl
4,5-diF-2-thienyl 3-(Me3Si-C≡C)-Ph 5-CF3-2-furanyl
3,4,5-triCl-2-thienyl 4-(Me3Si-C≡C)-Ph 5-CF3-2-thienyl
3-(C≡CH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph
4-(C≡CH)-Ph 3-OS02CF3-Ph 4-I-Ph
2-CF3CH20-5-pyridinyl 4-OS02CF3-Ph 3-C02Me-Ph
4-Cl-benzyl 4-EtO-2-pyrimidinyl 3-C02-r-Bu-Ph
2-Et-Ph 4,6-diMeO-2-pyrimidinyl 3-CQ2Et-Ph
2-Cl-Ph 4,6-diMe-2-ρyrimidinyl
R10a = Me and
E9 E9 E9
3,4-diF-Ph 4-Ph-Ph 6-CF3-2-pyridinyl
3,5-diBr-4-MeO-Ph 4-Br-3-Me-Ph 2-pyrimidinyl
3-Cl-4-Me-Ph 3-Br-4-MeO-Ph 4-pyrimidinyl
3,5-diF-Ph 5-F-2-thienyl 4-MeO-2-pyrimidinyl
3-F-4-Cl-Ph 5-Br-2-thienyl 4-Me-2-pyrimidinyl
3-MeO-Ph 5-Cl-2-thienyl 6-MeO-4-pyrimidinyl
3-Cl-Ph 2,5-diF-3-thienyl 5-Me-2-furanyl
C(CH3)3 2,5-diCl-3-thienyl 2,5-diMe-3-thienyl
3-Br-Ph 2,5-diBr-3-thienyl 3-OCF2H-Ph
2-Br-Ph 4-SCF2H-Ph 4-OCF2H-Ph
2-CN-Ph 2-Me-Ph 3-Me3Si-Ph
2,4-diCl-Ph 2-F-Ph 4-Me3Si-Ph
2-CF3-Ph 2-Me-4-Cl-Ph 3-Me3Ge-Ph
2-I-Ph 3,5-diCl-Ph 4-Me3Ge-Ph
4-N02-Ph 3,5-diCF3-Ph Ph
4-CF30-Ph 2-MeO-Ph 3-CN-Ph
4-Me-Ph 2,6-diMeO-Ph 4-C02Me-Ph 4-Cl-Ph 3-CF30-Ph 4-C02-f-Bu-Ph
3-Me-Ph 4-Br-Ph 4-C02Et-Ph
3-CF3-Ph 3-Et-Ph 6-CF3-4-pyrimidinyl
3-Cl-2-Me-Ph 4-MeO-Ph 4-CF3-2-pyridinyl
3-f-Bu-Ph 4-r-Bu-Ph 4-CF3-2-pyrimidinyl
3-F-Ph 4-CN-Ph 5-CF3-3-pyridinyl
4-CF3-Ph 4-N02-Ph 3-Me0-2-pyridinyl
3,4-diCl-Ph 3,4-diMe-Ph 5-CN-2-pyridinyl
3,4-diCF3-Ph 3,5-diMe-Ph 6-Me-2-pyridinyl
4-F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph
3-I-Ph 5-F-3-CF3-Ph 4-f-Bu-2-pyridinyl
2-Br-5-pyridinyl 3-Cl-benzyl 4-Me3Si-2-pyridinyl
4,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-pyridinyl
4,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl
4,5-diF-2-thienyl 3-(Me3Si-C=C)-Ph 5-CF3-2-furanyl
3,4,5-triCl-2-thienyl 4-(Me3Si-C≡C)-Ph 5-CF3-2-thienyl
3-(G≡CH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph
4-(C≡CH)-Ph 3-OS02CF3-Ph 4-I-Ph
2-CF3CH20-5-pyridinyl 4-OS02CF3-Ph 3-C02Me-Ph
4-Cl-benzyl 4-EtO-2-pyrimidinyl 3-C02-r-Bu-Ph
2-Et-Ph 4,6-diMeO-2-pyrimidinyl 3-C02Et-Ph
2-Cl-Ph 4,6-diMe-2-pyrimidinyl
R10a = Br and
E9 E9 E9
3,4-diF-Ph 4-Ph-Ph 6-CF3-2-pyridinyl
3,5-diBr-4-Me0-Ph 4-Br-3-Me-Ph 2-pyrimidinyl
3-Cl-4-Me-Ph 3-Br-4-Me0-Ph 4-pyrimidinyI
3,5-diF-Ph 5-F-2-thienyl 4-MeO-2-pyrimidinyl
3-F-4-Cl-Ph 5-Br-2-thienyl 4-Me-2-pyrimidinyl
3-MeO-Ph 5-Cl-2-thienyl 6-MeO-4-pyrimidinyl
3-Cl-Ph 2,5-diF-3-thienyl 5-Me-2-furanyl
C(CH3)3 2,5-diCl-3-thienyl 2,5-diMe-3-thienyl
3-Br-Ph 2,5-diBr-3-thienyl 3-OCF2H-Ph
2-Br-Ph 4-SCF2H-Ph 4-OCF2H-Ph
2-CN-Ph 2-Me-Ph 3-Me3Si-Ph 2,4-diCl-Ph 2-F-Ph 4-Me3Si-Ph
2-CF3-Ph 2-Me-4-Cl-Ph 3-Me3Ge-Ph
2-I-Ph 3,5-diCl-Ph 4-Me3Ge-Ph
4-N02-Ph 3,5-diCF3-Ph Ph
4-CF30-Ph 2-MeO-Ph 3-CN-Ph
4-Me-Ph 2,6-diMeO-Ph 4-C02Me-Ph
4-Cl-Ph 3-CF30-Ph 4-C02-r-Bu-Ph
3-Me-Ph 4-Br-Ph 4-C02Et-Ph
3-CF3-Ph 3-Et-Ph 6-CF3-4-pyrimidinyl
3-Cl-2-Me-Ph 4-MeO-Ph 4-CF3-2-pyridinyl
3-r-Bu-Ph 4-f-Bu-Ph 4-CF3-2-pyrimidinyl
3-F-Ph 4-CN-Ph 5-CF3-3-pyridinyl
4-CF3-Ph 4-N02-Ph 3-MeO-2-pyridinyl
3,4-diCl-Ph 3,4-diMe-Ph 5-CN-2-pyridinyl
3,4-diCF3-Ph 3,5-diMe-Ph 6-Me-2-pyridinyl
4-F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph
3-I-Ph 5-F-3-CF3-Ph 4-r-Bu-2-pyridinyl
2-Br-5-pyridinyl 3-Cl-benzyl 4-Me3Si-2-pyridinyl
4,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-pyridinyl
4,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl
4,5-diF-2-thienyl 3-(Me3Si-C≡C)-Ph 5-CF3-2-furanyl
3,4,5-triCl-2-thienyl 4-(Me3Si-C≡C)-Ph 5-CF3-2-thienyl
3-(C=CH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph
4-(C≡CH)-Ph 3-OS02CF3-Ph 4-I-Ph
2-CF3CH20-5-pyridinyl 4-OS02CF3-Ph 3-C02Me-Ph
4-Cl-benzyl 4-EtO-2-pyrimidinyl 3-C02-f-Bu-Ph
2-Et-Ph 4,6-diMeO-2-pyrimidinyl 3-C02Et-Ph
2-Cl-Ph 4,6-diMe-2-pyrimidinyl
R10a = Cl and
B9 E9 E9 3,4-diF-Ph 4-Ph-Ph 6-CF3-2-pyridinyl 3,5-diBr-4-MeO-Ph 4-Br-3-Me-Ph 2-pyrimidinyl 3-Cl-4-Me-Ph 3-Br-4-MeO-Ph 4-pyrimidinyl 3,5-diF-Ph 5-F-2-thienyl 4-MeO-2-pyrimidinyl 3-F-4-CI-Ph 5-Br-2-thienyl 4-Me-2-pyrimidinyl 3-MeO-Ph 5-Cl-2-thienyl 6-MeO-4-pyrimidinyl
3-Cl-Ph 2,5-diF-3-thienyl 5-Me-2-furanyl
C(CH3)3 2,5-diCl-3-thienyl 2,5-diMe-3-thienyl
3-Br-Ph 2,5-diBr-3-thienyl 3-OCF2H-Ph
2-Br-Ph 4-SCF2H-Ph 4-OCF2H-Ph
2-CN-Ph 2-Me-Ph 3-Me3Si-Ph
2,4-diCl-Ph 2-F-Ph 4-Me3Si-Ph
2-CF3-Ph 2-Me-4-Cl-Ph 3-Me3Ge-Ph
2-I-Ph 3,5-diCl-Ph 4-Me3Ge-Ph
4-N02-Ph 3,5-diCF3-Ph Ph
4-CF30-Ph 2-MeO-Ph 3-CN-Ph
4-Me-Ph 2,6-diMeO-Ph 4-C02Me-Ph
4-Cl-Ph 3-CF30-Ph 4-C02-r-Bu-Ph
3-Me-Ph 4-Br-Ph 4-C02Et-Ph
3-CF3-Ph 3-Et-Ph 6-CF3-4-pyrimidinyl
3-Cl-2-Me-Ph 4-MeO-Ph 4-CF3-2-pyridinyl
3-r-Bu-Ph 4-r-Bu-Ph 4-CF3-2-pyrimidinyl
3-F-Ph 4-CN-Ph 5-CF3-3-pyridinyl
4-CF3-Ph 4-N02-Ph 3-MeO-2-pyridinyl
3,4-diCl-Ph 3,4-diMe-Ph 5-CN-2-pyridinyl
3,4-diCF3-Ph 3,5-diMe-Ph 6-Me-2-pyridinyl
4-F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph
3-I-Ph 5-F-3-CF3-Ph 4-r-Bu-2-pyridinyl
2-Br-5-pyridinyl 3-Cl-benzyl 4-Me3Si-2-pyridinyl
4,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-pyridinyl
4,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl
4,5-diF-2-thienyl 3-(Me3Si-CsC)-Ph 5-CF -2-furanyl
3,4,5-triCl-2-thienyl 4-(Me3Si-C=C)-Ph 5-CF3-2-thienyl
3-(C≡CH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph
4-(CsCH)-Ph 3-OS02CF3-Ph 4-I-Ph
2-CF3CH20-5-pyridinyl 4-OS02CF3-Ph 3-C02Me-Ph -Cl-benzyl 4-EtO-2-pyrimidinyl 3-C02-f-Bu-Ph
2-Et-Ph 4,6-diMe0-2-pyrimidinyl 3-CO-7Et-Ph
2-Cl-Ph 4,6-diMe-2-pyrimidinyl R10a = CN and
B9 E9 E9 3,4-diF-Ph 4-Ph-Ph 6-CF3-2-pyridinyl 3,5-diBr-4-MeO-Ph 4-Br-3-Me-Ph 2-pyrimidinyl 3-Cl-4-Me-Ph 3-Br-4-MeO-Ph 4-pyrimidinyl 3,5-diF-Ph 5-F-2-thienyl 4-MeO-2-ρyrimidinyl 3-F-4-Cl-Ph 5-Br-2-thienyl 4-Me-2-pyrimidinyl 3-MeO-Ph 5-Cl-2-thienyl 6-MeO-4-pyrimidinyl 3-Cl-Ph 2,5-diF-3-thienyl 5-Me-2-furanyl C(CH3)3 2,5-diCl-3-thienyl 2,5-diMe-3-thienyl 3-Br-Ph 2,5-diBr-3-thienyl 3-OCF2H-Ph 2-Br-Ph 4-SCF2H-Ph 4-OCF2H-Ph 2-CN-Ph 2-Me-Ph 3-Me3Si-Ph 2,4-diCl-Ph 2-F-Ph 4-Me3Si-Ph 2-CF3-Ph 2-Me-4-Cl-Ph 3-Me3Ge-Ph 2-I-Ph 3,5-diCl-Ph 4-Me3Ge-Ph 4-N02-Ph 3,5-diCF3-Ph Ph -CF30-Ph 2-MeO-Ph 3-CN-Ph -Me-Ph 2,6-diMeO-Ph 4-C02Me-Ph -Cl-Ph 3-CF30-Ph 4-C02-f-Bu-Ph -Me-Ph 4-Br-Ph 4-C02Et-Ph -CF3-Ph 3-Et-Ph 6-CF3-4-pyrimidinyl -Cl-2-Me-Ph 4-MeO-Ph 4-CF3-2-pyridinyl -r-Bu-Ph 4-f-Bu-Ph 4-CF3-2-pyrimidinyl -F-Ph 4-CN-Ph 5-CF3-3-pyridinyl -CF3-Ph 4-N02-Ph 3-Me0-2-pyridinyl ,4-diCl-Ph 3,4-diMe-Ph 5-CN-2-pyridinyl ,4-diCF3-Ph 3,5-diMe-Ph 6-Me-2-pyridinyI -F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph -I-Ph 5-F-3-CF3-Ph 4-?-Bu-2-pyridinyl -Br-5-pyridinyl 3-Cl-benzyI 4-Me3Si-2-pyridinyl ,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-pyridinyl ,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl ,5-diF-2-thienyl 3-(Me3Si-C≡C)-Ph 5-CF3-2-furanyl ,4,5-triCl-2-thienyl 4-(Me3Si-C≡C)-Ph 5-CF3-2-thienyl 3-(C≡CH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph
4-(C=CH)-Ph 3-OS02CF3-Ph 4-I-Ph
2-CF3CH20-5-pyridinyl 4-0S02CF3-Ph 3-C02Me-Ph
4-Cl-benzyl 4-EtO-2-pyrimidinyl 3-C02-f-Bu-Ph
2-Et-Ph 4,6-diMeO-2-pyrimidinyl 3-C02Et-Ph
2-Cl-Ph 4,6-diMe-2-pyrimidinyl
R10a = F and R10a = I and RlOa = ri-propyl and R!0a = isopropyl and
E? s2 E? E? 3-CF3-Ph 3-CF3-Ph 3-CF3-Ph 3-CF3-Ph 3-CF30-Ph 3-CF30-Ph 3-CF30-Ph 3-CF30-Ph 3-OCF2H-Ph 3-OCF2H-Ph 3-OCF2H-Ph 3-OCF2H-Ph 3,5-diF-Ph 3,5-diF-Ph 3,5-diF-Ph 3,5-diF-Ph 3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph C(CH3)3 C(CH3)3 C(CH3)3 C(CH3)3
R10a = n-butyl and R10a = ferf-butyl and R10a = CF3 and R10a = MeO and
E? E? E9. E? 3-CF3-Ph 3-CF3-Ph 3-CF3-Ph 3-CF3-Ph 3-CF30-Ph 3-CF30-Ph 3-CF30-Ph 3-CF30-Ph 3-0CF2H-Ph 3-0CF2H-Ph 3-OCF2H-Ph 3-OCF2H-Ph 3,5-diF-Ph 3,5-diF-Ph 3,5-diF-Ph 3,5-diF-Ph 3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph C(CH3)3 C(CH3)3 C(CH3)3 C(CH3)3
TABLE 11
Compounds of Formula I A defined as:
4-F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph
3-I-Ph 5-F-3-CF3-Ph 4-f-Bu-2-pyridinyl
2-Br-5-pyridinyl 3-Cl-benzyl 4-Me3Si-2-pyridinyl
4,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-pyridinyl
4,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl
4,5-diF-2-thienyl 3-(Me3Si-C≡C)-Ph 5-CF3-2-furanyl
3,4,5-triCl-2-thienyl 4-(Me3Si-C-iC)-Ph 5-CF3-2-thienyl
3-(C≡CH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph
4-(C≡CH)-Ph 3-OS02CF3-Ph 4-I-Ph
2-CF3CH20-5-pyridinyl 4-OS02CF3-Ph 3-C02Me-Ph
4-Cl-benzyl 4-EtO-2-pyrimidinyl 3-C02-'-Bu-Ph
2-Et-Ph 4,6-diMeO-2-pyrimidinyl 3-C02Et-Ph
2-Cl-Ph 4,6-diMe-2-pyrimidinyl
TABLE 12 Compounds of Formula IA defined as:
E9 E9 E9 3,4-diF-Ph 4-Ph-Ph 6-CF3-2-pyridinyl 3,5-diBr-4-Me0-Ph 4-Br-3-Me-Ph 2-pyrimidinyl 3-Cl-4-Me-Ph 3-Br-4-MeO-Ph 4-pyrimidinyl 3,5-diF-Ph 5-F-2-thienyl 4-MeO-2-pyrimidinyl 3-F-4-Cl-Ph 5-Br-2-thienyl 4-Me-2-pyrimidinyl 3-MeO-Ph 5-Cl-2-thienyl 6-MeO-4-pyrimidinyl 3-Cl-Ph 2,5-diF-3-thienyl 5-Me-2-furanyl C(CH3)3 2,5-diCl-3-thienyl 2,5-diMe-3-thienyl 3-Br-Ph 2,5-diBr-3-thienyl 3-OCF2H-Ph 2-Br-Ph 4-SCF2H-Ph 4-OCF2H-Ph 2-CN-Ph 2-Me-Ph 3-Me3Si-Ph 2,4-diCl-Ph 2-F-Ph 4-Me3Si-Ph -CF3-Ph 2-Me-4-Cl-Ph 3-Me3Ge-Ph -I-Ph 3,5-diCl-Ph 4-Me3Ge-Ph -N02-Ph 3,5-diCF3-Ph Ph -CF30-Ph 2-MeO-Ph 3-CN-Ph -Me-Ph 2,6-diMeO-Ph 4-C0 Me-Ph -Cl-Ph 3-CF30-Ph 4-C02-f-Bu-Ph -Me-Ph 4-Br-Ph 4-C02Et-Ph -CF3-Ph 3-Et-Ph 6-CF3-4-pyrimidinyl -Cl-2-Me-Ph 4-MeO-Ph 4-CF3-2-pyridinyl -t-Bu-Ph 4-r-Bu-Ph 4-CF3-2-pyrimidinyl -F-Ph 4-CN-Ph 5-CF3-3-pyridinyl -CF3-Ph 4-N02-Ph 3-MeO-2-pyridinyl ,4-diCl-Ph 3,4-diMe-Ph 5-CN-2-pyridinyl ,4-diCF -Ph 3,5-diMe-Ph 6-Me-2-pyridinyl -F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph -I-Ph 5-F-3-CF3-Ph 4-r-Bu-2-pyridinyl -Br-5-pyridinyl 3-Cl-benzyl 4-Me3Si-2-pyridinyl ,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-pyridinyl ,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl ,5-diF-2-thienyl 3-(Me3Si-C≡C)-Ph 5-CF3-2-furanyl ,4,5-triCl-2-thienyl 4-(Me3Si-C≡C)-Ph 5-CF3-2-thienyl -(C≡CH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph -(C≡CH)-Ph 3-OS02CF3-Ph 4-I-Ph -CF3CH20-5-pyridinyl 4-0S02CF3-Ph 3-C02Me-Ph -Cl-benzyl 4-EtO-2-pyrimidinyl 3-C02-/-Bu-Ph -Et-Ph 4,6-diMeO-2-pyrimidinyl 3-C02Et-Ph -Cl-Ph 4,6-diMe-2-pyrimidinyl
TABLE 13 Compounds of Formula IA defined as:
4-Me-Ph 2,6-diMeO-Ph 4-Cθ2Me-Ph
4-Cl-Ph 3-CF30-Ph 4-C02-r-Bu-Ph
3-Me-Ph 4-Br-Ph 4-C02Et-Ph
3-CF3-Ph 3-Et-Ph 6-CF3-4-pyrimidinyl
3-Cl-2-Me-Ph 4-MeO-Ph 4-CF3-2-pyridinyl
3-f-Bu-Ph 4-r-Bu-Ph 4-CF3-2-pyrimidinyl
3-F-Ph 4-CN-Ph 5-CF3-3-pyridinyl
4-CF3-Ph 4-N02-Ph 3-MeO-2-pyridinyl
3,4-diCl-Ph 3,4-diMe-Ph 5-CN-2-pyridinyl
3,4-diCF3-Ph 3,5-diMe-Ph 6-Me-2-pyridinyl
4-F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph
3-I-Ph 5-F-3-CF3-Ph 4-r-Bu-2-pyridinyl
2-Br-5-pyridinyl 3-Cl-benzyl 4-Me3Si-2-pyridinyl
4,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-pyridinyl
4,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl
4,5-diF-2-thienyl 3-(Me3Si-C=C)-Ph 5-CF3-2-furanyl
3,4,5-triCl-2-thienyl 4-(Me3Si-OC)-Ph 5-CF3-2-thienyl
3-(CsCH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph
4-(C≡CH)-Ph 3-OS02CF3-Ph 4-I-Ph
2-CF3CH20-5-pyridinyl 4-OS02CF3-Ph 3-C02Me-Ph
4-Cl-benzyl 4-EtO-2-pyrimidinyl 3-C02-r-Bu-Ph
2-Et-Ph 4,6-diMeO-2-pyrimidinyl 3-C02Et-Ph
2-Cl-Ph 4,6-diMe-2-pyrimidinyl
R10a = Br and
E9 B9 B9
3,4-diF-Ph 4-Ph-Ph 6-CF3-2-pyridinyl
3,5-diBr-4-MeO-Ph 4-Br-3-Me-Ph 2-pyrimidinyl
3-Cl-4-Me-Ph 3-Br-4-MeO-Ph 4-pyrimidinyl
3,5-diF-Ph 5-F-2-thienyl 4-MeO-2-pyrimidinyl
3-F-4-Cl-Ph 5-Br-2-thienyl 4-Me-2-pyrimidinyl
3-MeO-Ph 5-Cl-2-thienyl 6-MeO-4-pyrimidinyl
3-Cl-Ph 2,5-diF-3-thienyl 5-Me-2-furanyI
C(CH3)3 2,5-diCl-3-thienyl 2,5-diMe-3-thienyl
3-Br-Ph 2,5-diBr-3-thienyl 3-OCF2H-Ph
2-Br-Ph 4-SCF2H-Ph 4-OCF2H-Ph 3-Me3Si-Ph
4-Me3Si-Ph
3-Me3Ge-Ph
4-Me3Ge-Ph
Ph
3-CN-Ph
4-C02Me-Ph
4-C02-f-Bu-Ph
4-C02Et-Ph
6-CF3-4-pyrimidinyl
4-CF3-2-pyridinyl
4-CF3-2-pyrimidinyl
5-CF3-3-pyridinyl
3-MeO-2-pyridinyl
5-CN-2-pyridinyl
6-Me-2-pyridinyl
3,5-diBr-Ph
4-r-Bu-2-ρyridinyl
4-Me3Si-2-pyridinyl
4-Me3Ge-2-pyridinyl
4,6-diCF3-2-pyrimidinyl
5-CF3-2-furanyl
5-CF3-2-thienyl
3-EtO-Ph
4-I-Ph
3-C02Me-Ph
3-C02-r-Bu-Ph
3-C02Et-Ph
E9 6-CF3-2-pyridinyl 2-pyrimidinyl 4-ρyrimidinyl 4-Me0-2-pyrimidinyl 3-F-4-Cl-Ph 5-Br-2-thienyl 4-Me-2-pyrimidinyl
3-MeO-Ph 5-Cl-2-thienyl 6-MeO-4-pyrimidinyl
3-Cl-Ph 2,5-diF-3-thienyl 5-Me-2-furanyl
C(CH3)3 2,5-diCl-3-thienyl 2,5-diMe-3-thienyl
3-Br-Ph 2,5-diBr-3-thienyl 3-OCF2H-Ph
2-Br-Ph 4-SCF2H-Ph 4-OCF2H-Ph
2-CN-Ph 2-Me-Ph 3-Me3Si-Ph
2,4-diCl-Ph 2-F-Ph 4-Me3Si-Ph
2-CF3-Ph 2-Me-4-Cl-Ph 3-Me3Ge-Ph
2-I-Ph 3,5-diCl-Ph 4-Me3Ge-Ph
4-N02-Ph 3,5-diCF3-Ph Ph
4-CF30-Ph 2-MeO-Ph 3-CN-Ph
4-Me-Ph 2,6-diMeO-Ph 4-C02Me-Ph
4-Cl-Ph 3-CF30-Ph 4-C02-f-Bu-Ph
3-Me-Ph 4-Br-Ph 4-C02Et-Ph
3-CF3-Ph 3-Et-Ph 6-CF3-4-pyrimidinyl
3-Cl-2-Me-Ph 4-MeO-Ph 4-CF3-2-pyridinyl
3-r-Bu-Ph 4-r-Bu-Ph 4-CF3-2-pyrimidinyl
3-F-Ph 4-CN-Ph 5-CF3-3-pyridinyl
4-CF3-Ph 4-N02-Ph 3-MeO-2-pyridinyl
3,4-diCl-Ph 3,4-diMe-Ph 5-CN-2-pyridinyl
3,4-diCF3-Ph 3,5-diMe-Ph 6-Me-2-pyridinyl -F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph
3-I-Ph 5-F-3-CF3-Ph 4-r-B u-2-pyridi ny 1
2-Br-5-pyridinyl 3-Cl-benzyl 4-Me3Si-2-pyridinyl ,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-pyridinyl ,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl ,5-diF-2-thienyl 3-(Me3Si-C≡C)-Ph 5-CF3-2-furanyl ,4,5-triCl-2-thienyl 4-(Me3Si-C≡C)-Ph 5-CF3-2-thienyl -(C=CH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph -(G≡CH)-Ph 3-OS02CF3-Ph 4-I-Ph -CF3CH2θ-5-pyridinyl 4-OS02CF3-Ph 3-C02Me-Ph -Cl-benzyl 4-EtO-2-pyrimidinyl 3-C02-r-Bu-Ph -Et-Ph 4,6-diMeO-2-pyrimidinyI 3-C02Et-Ph -Cl-Ph 4,6-diMe-2-pyrimidinyl R1 Qa = CN and
E9 E9 E9
3,4-diF-Ph 4-Ph-Ph 6-CF3-2-pyridinyl
3,5-diBr-4-MeO-Ph 4-Br-3-Me-Ph 2-pyrimidinyl
3-CI-4-Me-Ph 3-Br-4-MeO-Ph 4-pyrimidinyl
3,5-diF-Ph 5-F-2-thienyl 4-MeO-2-pyrimidinyl
3-F-4-Cl-Ph 5-Br-2-thienyl 4-Me-2-pyrimidinyl
3-MeO-Ph 5-Cl-2-thienyl 6-MeO-4-pyrimidinyl
3-Cl-Ph 2,5-diF-3-thienyl 5-Me-2-furanyl
C(CH3)3 2,5-diCl-3-thienyl 2,5-diMe-3-thienyl
3-Br-Ph 2,5-diBr-3-thienyl 3-OCF2H-Ph
2-Br-Ph 4-SCF2H-Ph 4-OCF2H-Ph
2-CN-Ph 2-Me-Ph 3-Me3Si-Ph
2,4-diCl-Ph 2-F-Ph 4-Me3Si-Ph
2-CF3-Ph 2-Me-4-Cl-Ph 3-Me Ge-Ph
2-I-Ph 3,5-diCl-Ph 4-Me3Ge-Ph
4-N02-Ph 3,5-diCF3-Ph Ph
4-CF3O-PI1 2-MeO-Ph 3-CN-Ph
4-Me-Ph 2,6-diMeO-Ph 4-C02Me-Ph
4-Cl-Ph 3-CF30-Ph 4-C02-r-Bu-Ph
3-Me-Ph 4-Br-Ph 4-C02Et-Ph
3-CF3-Ph 3-Et-Ph 6-CF3-4-pyrimidinyl
3-Cl-2-Me-Ph 4-MeO-Ph 4-CF3-2-pyridinyl
3-/-Bu-Ph 4-r-Bu-Ph 4-CF3-2-pyrimidinyl -F-Ph 4-CN-Ph 5-CF3-3-pyridinyl -CF3-Ph 4-N02-Ph 3-Me0-2-pyridinyl ,4-diCl-Ph 3,4-diMe-Ph 5-CN-2-pyridinyl ,4-diCF3-Ph 3,5-diMe-Ph 6-Me-2-pyridinyl -F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph -I-Ph 5-F-3-CF3-Ph 4-f-Bu-2-pyridinyl -Br-5-pyridinyl 3-Cl-benzyl 4-Me3Si-2-pyridinyl ,5-diBr-2-thienyl 2-Cl-benzyI 4-Me3 Ge-2-pyridiny] ,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl ,5-diF-2-thienyl 3-(Me3Si-C≡C)-Ph 5-CF3-2-furanyl ,4,5-triCl-2-thienyI 4-(Me3Si-C--C)-Ph 5-CF3-2-thienyl -(C=CH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph 4-(C≡CH)-Ph 3-OS02CF3-Ph 4-I-Ph
2-CF3CH20-5-pyridinyl 4-OS02CF3-Ph 3-C0 Me-Ph
4-Cl-benzyl 4-EtO-2-pyrimidinyl 3-C02- -Bu-Ph
2-Et-Ph 4,6-diMeO-2-pyrimidinyl 3-C02Et-Ph
2-Cl-Ph 4,6-diMe-2-pyrimidinyl
R10a = F and R10a = I and RlOa _ w.pr0pyi and RlOa _ iSOpro yl and
E£ E?
3-CF3-Ph 3-CF3-Ph 3-CF3-Ph 3-CF3-Ph
3-CF30-Ph 3-CF30-Ph 3-CF30-Ph 3-CF30-Ph
3-OCF2H-Ph 3-OCF2H-Ph 3-OCF2H-Ph 3-OCF2H-Ph
3,5-diF-Ph 3,5-diF-Ph 3,5-diF-Ph 3,5-diF-Ph
3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCl-Ph
3,5-diCF3-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph
C(CH3)3 C(CH3)3 C(CH3)3 C(CH3)3
R10a = «-butyl and RlOa _ tert_ butyl and R10a = CF3 and RlOa - MeQ and
B? B? E? 3-CF3-Ph 3-CF3-Ph 3-CF3-Ph 3-CF3-Ph 3-CF30-Ph 3-CF30-Ph 3-CF30-Ph 3-CF30-Ph 3-OCF2H-Ph 3-OCF2H-Ph 3-OCF2H-Ph 3-OCF2H-Ph 3,5-diF-Ph 3,5-diF-Ph 3,5-diF-Ph 3,5-diF-Ph 3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph C(CH3)3 C(CH3)3 C(CH3)3 C(CH3)3
TABLE 14 Compounds of Formula IA defined as:
4-Me-Ph 2,6-diMeO-Ph 4-C02Me-Ph
4-Cl-Ph 3-CF30-Ph 4-C02-f-Bu-Ph
3-Me-Ph 4-Br-Ph 4-C02Et-Ph
3-CF3-Ph 3-Et-Ph 6-CF3-4-pyrimidinyl
3-Cl-2-Me-Ph 4-MeO-Ph 4-CF3-2-pyridinyl
3-i-Bu-Ph 4-/-Bu-Ph 4-CF3-2-pyrimidinyl
3-F-Ph 4-CN-Ph 5-CF3-3-pyridinyl
4-CF3-Ph 4-N02-Ph 3-MeO-2-ρyridinyl
3,4-diCI-Ph 3,4-diMe-Ph 5-CN-2-pyridinyl
3,4-diCF3-Ph 3,5-diMe-Ph 6-Me-2-pyridinyl
4-F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph
3-I-Ph 5-F-3-CF3-Ph 4-r-Bu-2-pyridinyl
2-Br-5-pyridinyl 3-Cl-benzyl 4-Me3 Si-2-pyridinyl
4,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-pyridinyl
4,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl
4,5-diF-2-thienyl 3-(Me3Si-CsC)-Ph 5-CF3-2-furanyl
3,4,5-triCl-2-thienyl 4-(Me3Si-C≡C)-Ph 5-CF3-2-thienyl
3-(C≡CH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph
4-(C≡CH)-Ph 3-0S02CF3-Ph 4-I-Ph
2-CF3CH20-5-pyridinyl 4-OS02CF3-Ph 3-C02Me-Ph
4-Cl-benzyl 4-EtO-2-pyrimidinyl 3-C02-f-Bu-Ph
2-Et-Ph 4,6-diMeO-2-pyrimidinyl 3-C02Et-Ph
2-Cl-Ph 4,6-diMe-2-pyrimidinyl
R10a = Br and
B9 B9 B9
3,4-diF-Ph 4-Ph-Ph 6-CF3-2-pyridinyl
3,5-diBr-4-MeO-Ph 4-Br-3-Me-Ph 2-pyrimidinyl
3-Cl-4-Me-Ph 3-Br-4-MeO-Ph 4-pyrimidinyl
3,5-diF-Ph 5-F-2-thienyl 4-MeO-2-pyrimidinyl
3-F-4-Cl-Ph 5-Br-2-thienyl 4-Me-2-pyrimidinyI
3-MeO-Ph 5-Cl-2-thienyl 6-MeO-4-pyrimidinyl
3-Cl-Ph 2,5-diF-3-thienyI 5-Me-2-furanyl
C(CH3)3 2,5-diCl-3-thienyl 2,5-diMe-3-thienyl
3-Br-Ph 2,5-diBr-3-thienyl 3-OCF2H-Ph
2-Br-Ph 4-SCF2H-Ph 4-OCF2H-Ph 2-CN-Ph 2-Me-Ph 3-Me3Si-Ph
2,4-diCl-Ph 2-F-Ph 4-Me3Si-Ph
2-CF3-Ph 2-Me-4-Cl-Ph 3-Me3Ge-Ph
2-I-Ph 3,5-diCl-Ph 4-Me3Ge-Ph
4-N02-Ph 3,5-diCF3-Ph Ph
4-CF30-Ph 2-MeO-Ph 3-CN-Ph
4-Me-Ph 2,6-diMeO-Ph 4-C02Me-Ph
4-Cl-Ph 3-CF30-Ph 4-C02-f-Bu-Ph
3-Me-Ph 4-Br-Ph 4-C02Et-Ph
3-CF3-Ph 3-Et-Ph 6-CF3-4-pyrimidinyl
3-Cl-2-Me-Ph 4-MeO-Ph 4-CF3-2-pyridinyl
3-f-Bu-Ph 4-r-Bu-Ph 4-CF3-2-pyrimidinyl
3-F-Ph 4-CN-Ph 5-CF3-3-pyridinyl
4-CF3-Ph 4-N02-Ph 3-MeO-2-pyridinyl
3,4-diCl-Ph 3,4-diMe-Ph 5-CN-2-pyridinyl
3,4-diCF3-Ph 3,5-diMe-Ph 6-Me-2-pyridinyl
4-F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph
3-I-Ph 5-F-3-CF3-Ph 4-r-Bu-2-pyridinyl
2-Br-5-pyridinyl 3-Cl-benzyl 4-Me3Si-2-pyridinyl
4,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-pyridinyl
4,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl
4,5-diF-2-thienyl 3-(Me3Si-OC)-Ph 5-CF3-2-furanyl
3,4,5-triCl-2-thienyl 4-(Me3Si-C≡C)-Ph 5-CF3-2-thienyl
3-(CsCH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph
4-(C==CH)-Ph 3-OS02CF3-Ph 4-I-Ph
2-CF3CH 0-5-pyridinyl 4-OS02CF3-Ph 3-C02Me-Ph
4-Cl-benzyl 4-Et0-2-pyrimidinyl 3-C02-r-Bu-Ph
2-Et-Ph 4,6-diMeO-2-pyrimidinyl 3-C02Et-Ph
2-Cl-Ph 4,6-diMe-2-pyrimidinyl
R10a = Cl and
B9 B9 E9
3,4-diF-Ph 4-Ph-Ph 6-CF3-2-pyridinyI 3,5-diBr-4-MeO-Ph 4-Br-3-Me-Ph 2-pyrimidinyl 3-Cl-4-Me-Ph 3-Br-4-MeO-Ph 4-pyrimidinyl 3,5-diF-Ph 5-F-2-thienyl 4-MeO-2-pyrimidinyl 3-F-4-Cl-Ph 5-Br-2-thienyl 4-Me-2-pyrimidinyl
3-MeO-Ph 5-Cl-2-thienyl 6-MeO-4-pyrimidinyl
3-Cl-Ph 2,5-diF-3-thienyl 5-Me-2-furanyl
C(CH3)3 2,5-diCl-3-thienyl 2,5-diMe-3-thienyl
3-Br-Ph 2,5-diBr-3-thienyl 3-OCF2H-Ph
2-Br-Ph 4-SCF2H-Ph 4-OCF2H-Ph
2-CN-Ph 2-Me-Ph 3-Me3Si-Ph
2,4-diCl-Ph 2-F-Ph 4-Me3Si-Ph
2-CF3-Ph 2-Me-4-Cl-Ph 3-Me3Ge-Ph
2-I-Ph 3,5-diCl-Ph 4-Me3Ge-Ph
4-N02-Ph 3,5-diCF3-Ph Ph
4-CF30-Ph 2-MeO-Ph 3-CN-Ph
4-Me-Ph 2,6-diMeO-Ph 4-C02Me-Ph
4-Cl-Ph 3-CF30-Ph 4-C02-r-Bu-Ph
3-Me-Ph 4-Br-Ph 4-C02Et-Ph
3-CF3-Ph 3-Et-Ph 6-CF3-4-pyrimidinyl -Cl-2-Me-Ph 4-MeO-Ph 4-CF3-2-pyridinyl
3-/-Bu-Ph 4-r-Bu-Ph 4-CF3-2-pyrimidinyl -F-Ph 4-CN-Ph 5-CF3-3-pyridinyl -CF3-Ph 4-N02-Ph 3-MeO-2-pyridinyl ,4-diCl-Ph 3,4-diMe-Ph 5-CN-2-pyridinyl ,4-diCF3-Ph 3,5-diMe-Ph 6-Me-2-pyridinyl -F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph -I-Ph 5-F-3-CF3-Ph 4-r-Bu-2-pyridinyl -Br-5-pyridinyl 3-Cl-benzyl 4-Me3Si-2-pyridinyl ,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-pyridinyl ,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl ,5-diF-2-thienyl 3-(Me3Si-C≡C)-Ph 5-CF3-2-furanyl ,4,5-triCl-2-thienyl 4-(Me3Si-C≡C)-Ph 5-CF3-2-thienyl -(C=CH)-Ph 3,5-diCF3-benzyl 3-EtO-Ph -(C≡CH)-Ph 3-OS02CF3-Ph 4-I-Ph -CF3CH20-5-pyridinyl 4-OS02CF3-Ph 3-C02Me-Ph -Cl-benzyl 4-EtO-2-pyrimidinyl 3-C02-f-Bu-Ph -Et-Ph 4,6-diMeO-2-pyrimidinyl 3-C02Et-Ph -Cl-Ph 4,6-diMe-2-pyrimidinyl R10 = CN and
E9 E9 B9 3,4-diF-Ph 4-Ph-Ph 6-CF3-2-pyridinyl 3,5-diBr-4-MeO-Ph 4-Br-3-Me-Ph 2-pyrimidinyl 3-Cl-4-Me-Ph 3-Br-4-MeO-Ph 4-pyrimidinyl 3,5-diF-Ph 5-F-2-thienyl 4-MeO-2-pyrimidinyl 3-F-4-Cl-Ph 5-Br-2-thienyl 4-Me-2-pyrimidinyl 3-MeO-Ph 5-Cl-2-thienyl 6-MeO-4-pyrimidinyl 3-Cl-Ph 2,5-diF-3-thienyl 5-Me-2-furanyl C(CH3)3 2,5-diCl-3-thienyl 2,5-diMe-3-thienyl 3-Br-Ph 2,5-diBr-3-thienyl 3-OCF2H-Ph 2-Br-Ph 4-SCF2H-Ph 4-OCF2H-Ph 2-CN-Ph 2-Me-Ph 3-Me3Si-Ph 2,4-diCl-Ph 2-F-Ph 4-Me3Si-Ph 2-CF3-Ph 2-Me-4-Cl-Ph 3-Me3Ge-Ph 2-I-Ph 3,5-diCl-Ph 4-Me3Ge-Ph 4-N02-Ph 3,5-diCF3-Ph Ph -CF30-Ph 2-MeO-Ph 3-CN-Ph 4-Me-Ph 2,6-diMeO-Ph 4-C02Me-Ph 4-Cl-Ph 3-CF30-Ph 4-C02-f-Bu-Ph 3-Me-Ph 4-Br-Ph 4-C02Et-Ph 3-CF3-PI1 3-Et-Ph 6-CF3-4-pyrimidinyl -Cl-2-Me-Ph 4-MeO-Ph 4-CF3-2-pyridinyl -r-Bu-Ph 4-r-Bu-Ph 4-CF3 -2-pyrimidi ny 1 -F-Ph 4-CN-Ph 5-CF3-3-pyridinyl -CF3-Ph 4-N02-Ph 3-MeO-2-pyridinyl ,4-diCl-Ph 3,4-diMe-Ph 5-CN-2-pyridinyl ,4-diCF3-Ph 3,5-diMe-Ph 6-Me-2-pyridinyl -F-Ph 4-F-3-CF3-Ph 3,5-diBr-Ph -I-Ph 5-F-3-CF3-Ph 4-/-Bu-2-pyridinyl -Br-5-pyridinyl 3-Cl-benzyl 4-Me3Si-2-pyridinyl ,5-diBr-2-thienyl 2-Cl-benzyl 4-Me3Ge-2-pyridinyl ,5-diCl-2-thienyl 2-CN-benzyl 4,6-diCF3-2-pyrimidinyl ,5-diF-2-thienyl 3-(Me3Si-C≡C)-Ph 5-CF3-2-furanyl ,4,5-triCl-2-thienyl 4-(Me3Si-C≡C)-Ph 5-CF3-2-thienyl 3-(CsCH)-Ph 3,5-diCF3-benzyI 3-EtO-Ph
4-(C CH)-Ph 3-OS02CF3-Ph 4-I-Ph
2-CF3CH20-5-pyridinyl 4-OS02CF3-Ph 3-C02Me-Ph
4-Cl-benzyl 4-EtO-2-pyrimidinyl 3-C02-f-Bu-Ph
2-Et-Ph 4,6-diMeO-2-pyrimidinyl 3-C02Et-Ph
2-CI-Ph 4,6-diMe-2-pyrimidinyl
RlOa = F and R 1 Oa k¬ l and RlOa - w.pr0py* and lOa _ iSOpro yi and
E9. E? E? E9. 3-CF3-Ph 3-CF3-Ph 3-CF3-Ph 3-CF3-Ph 3-CF30-Ph 3-CF30-Ph 3-CF30-Ph 3-CF30-Ph 3-0CF2H-Ph 3-OCF2H-Ph 3-OCF2H-Ph 3-OCF2H-Ph 3,5-diF-Ph 3,5-diF-Ph 3,5-diF-Ph 3,5-diF-Ph 3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph C(CH3)3 C(CH3)3 C(CH3)3 C(CH3)3
R10a = w-butyl and R10a _ grr.butyl and > 10a _ •= CF*ι and >10a _ = MeO and
E R£ E9. E9.
3-CF3-Ph 3-CF3-Ph 3-CF3-Ph 3-CF3-Ph
3-CF30-Ph 3-CF30-Ph 3-CF30-Ph 3-CF30-Ph
3-0CF2H-Ph 3-OCF H-Ph 3-OCF2H-Ph 3-OCF2H-Ph
3,5-diF-Ph 3,5-diF-Ph 3,5-diF-Ph 3,5-diF-Ph
3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCl-Ph 3,5-diCl-Ph
3,5-diCF3-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph 3,5-diCF3-Ph
C(CH3)3 C(CH3)3 C(CH3)3 C(CH3)3
Formulation/Utility
Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifϊable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.
The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
Weight Percent
High Strength Compositions 90-99 0-10 0-2
Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity. Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, N,N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4- methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.
Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in
U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566. For further information regarding the art of formulation, see U.S. 3,235,361 ,
Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.
In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A-M. Example A
Wettable Powder
Compound 345 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%. Example B Granule
Compound 515 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
Example C Extruded Pellet
Compound 680 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
Example D Emulsifiable Concentrate Compound 699 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%.
The compounds of this invention are useful as plant disease control agents. The present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed or seedling to be protected, an effective amount of a compound of the invention or a fungicidal composition containing said compound. The compounds and compositions of this invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septoria nodorum, Septoria tritici, Cercosporidium personatum, Cercospora arachidicola, Pseudocercosporella herpotrichoides, Cercospora beticola, Botrytis cinerea, Monilinia fructicola, Pyricularia oryzae, Podosphaera leucotricha, Venturia inaequalis, Erysiphe graminis, Uncinula necatur, Puccinia recondita, Puccinia graminis, Hemileia vastatrix, Puccinia striiformis, Puccinia arachidis, Rhizoctonia solani, Sphaerotheca fuliginea, Fusarium oxysporum, Verticillium dahliae, Pythium aphanidermatum, Phytophthora megasperma, Sclerotinia sclerotiorum, Sclerotium rolfsii, Erysiphe polygoni, Pyrenophora teres, Gaeumannomyces graminis, Rynchosporium secalis, Fusarium roseum, Bremia lactucae and other generea and species closely related to these pathogens.
The compounds of this invention also exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, stem or root feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term "arthropods" includes insects, mites and nematodes) which are pests of growing and stored agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skilled in the art will appreciate that not all compounds are equally effective against all growth stages of all pests. Nevertheless, all of the compounds of this invention display activity against pests that include: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs, immatures and adults of the Orders Hemiptera and Homoptera; eggs, larvae, nymphs and adults of the Order Acari; eggs, immatures and adults of the Orders Thysanoptera, Orthoptera and
Dermaptera; eggs, immatures and adults of the Order Diptera; and eggs, juveniles and adults of the Phylum Nematoda. The compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanura and Psocoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes. Specifically, the compounds are active against southern corn rootworm (Diabrotica undecimpunctata howardi), aster leafhopper (Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spotted spider mite (Tetranychus urticae), fall armyworm (Spodopterafrugiperda), black bean aphid (Aphis fabae), green peach aphid (Myzus persica), cotton aphid (Aphis gossypii), Russian wheat aphid (Diuraphis noxia), English grain aphid (Sitobion avenae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus oryzophilus), rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatellafurcifera), green leafhopper (Nephotettix cincticeps), brown planthopper (Nilaparvata lugens), small brown planthopper (Laodelphax striatellus), rice stem borer (Chilo suppressalis), rice leafroller (Cnaphalocrocis medinalis), black rice stink bug (Scotinophara lurida), rice stink bug (Oebalus pugnax), rice bug (Leptocorisa chinensis), slender rice bug (Cletus puntiger), and southern green stink bug (Nezara viridula). The compounds are active on mites, demonstrating ovicidal, larvicidal and chemosterilant activity against such families as Tetranychidae including Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus pacificus, Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi, Panonychus citri,
Eotetranychus carpini borealis, Eotetranychus, hicoriae, Eotetranychus sexmaculatus, Eotetranychus yumensis, Eotetranychus banksi and Oligonychus pratensis; Tenuipalpidae including Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpus californicus and Brevipalpus obovatus; Eriophyidae including Phyllocoptruta oleivora, Eriophyes sheldoni, Aculus cornutus, Epitrimerus pyri and Eriophyes mangiferae. See WO 90/10623 and WO 92/00673 for more detailed pest descriptions.
Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Examples of such agricultural protectants with which compounds of this invention can be formulated are: insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorpyrifos, chlorpyrifos-methyl, cyfluthrin, beta-cyfluthrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenpropathrin, fenvalerate, fipronil, flucythrinate, tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, monocrotophos, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, rotenone, sulprofos, tebufenozide, tefluthrin, terbufos, tetrachlorvinphos, thiodicarb, tralomethrin, trichlorfon and triflumuron; fungicides such as azoxystrobin (ICIA5504), benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), bromuconazole, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, cymoxanil, cyproconazole, cyprodinil (CGA 219417), diclomezine, dicloran, difenoconazole, dimethomorph, diniconazole, diniconazole-M, dodine, edifenphos, epoxyconazole (BAS 480F), fenarimol, fenbuconazole, fenpiclonil, fenpropidin, fenpropimorph, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fosetyl-aluminum, furalaxyl, hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, kresoxim-methyl (BAS 490F), mancozeb, maneb, mepronil, metalaxyl, metconazole, myclobutanil, neo-asozin (ferric methanearsonate), oxadixyl, penconazole, pencycuron, probenazole, prochloraz, propiconazole, pyrifenox, pyroquilon, sulfur, tebuconazole, tetraconazole, thiabendazole, thiophanate-methyl, thiram, triadimefon, triadimenol, tricyclazole, triticonazole, uniconazole, validamycin and vinclozolin; nematocides such as aldoxycarb and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.
In certain instances, combinations with other fungicides or arthropodicides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management.
Preferred for better control of plant diseases caused by fungal plant pathogens (e.g., lower use rate or broader spectrum of plant pathogens controlled) or resistance management are mixtures of a compound of this invention with a fungicide selected from the group cyproconazole, cyprodinil (CGA 219417), epoxyconazole (BAS 480F), fenpropidin, fenpropimorph, flusilazole and tebuconazole. Specifically preferred mixtures (compound numbers refer to compounds in Index Tables A-M) are selected from the group: compound 290 and cyproconazole; compound 290 and cyprodinil (CGA 219417); compound 290 and epoxyconazole (BAS 480F); compound 290 and fenpropidin; compound 290 and fenpropimorph; compound 290 and flusilazole; compound 290 and tebuconazole; compound 295 and cyproconazole; compound 295 and cyprodinil (CGA 219417); compound 295 and epoxyconazole (BAS 480F); compound 295 and fenpropidin; compound 295 and fenpropimorph; compound 295 and flusilazole; compound 295 and tebuconazole; compound 343 and cyproconazole; compound 343 and cyprodinil (CGA 219417); compound 343 and epoxyconazole (BAS 480F); compound 343 and fenpropidin; compound 343 and fenpropimorph; compound 343 and flusilazole; compound 343 and tebuconazole; compound 345 and cyproconazole; compound 345 and cyprodinil (CGA 219417); compound 345 and epoxyconazole (BAS 480F); compound 345 and fenpropidin; compound 345 and fenpropimorph; compound 345 and flusilazole; compound 345 and tebuconazole; compound 358 and cyproconazole; compound 358 and cyprodinil (CGA 219417); compound 358 and epoxyconazole (BAS 480F); compound 358 and fenpropidin; compound 358 and fenpropimorph; compound 358 and flusilazole; compound 358 and tebuconazole; compound 507 and cyproconazole; compound 507 and cyprodinil (CGA 219417); compound 507 and epoxyconazole (BAS 480F); compound 507 and fenpropidin; compound 507 and fenpropimorph; compound 507 and flusilazole; compound 507 and tebuconazole; compound 515 and cyproconazole; compound 515 and cyprodinil (CGA 219417); compound 515 and epoxyconazole (BAS 480F); compound 515 and fenpropidin; compound 515 and fenpropimorph; compound 515 and flusilazole; compound 515 and tebuconazole; compound 538 and cyproconazole; compound 538 and cyprodinil (CGA 219417); compound 538 and epoxyconazole (BAS 480F); compound 538 and fenpropidin; compound 538 and fenpropimorph; compound 538 and flusilazole; compound 538 and tebuconazole; compound 699 and cyproconazole; compound 699 and cyprodinil (CGA 219417); compound 699 and epoxyconazole (BAS 480F); compound 699 and fenpropidin; compound 699 and fenpropimorph; compound 699 and flusilazole; and compound 699 and tebuconazole. Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compounds can also be applied to the seed to protect the seed and seedling. For plant disease control, rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g/ha to 5,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed. Arthropod pests are controlled and protection of agronomic, horticultural and specialty crops, animal and human health is achieved by applying one or more of the compounds of this invention, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Thus, the present invention further comprises a method for the control of foliar and soil inhabiting arthropods and nematode pests and protection of agronomic and/or nonagronomic crops, comprising applying one or more of the compounds of the invention, or compositions containing at least one such compound, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. A preferred method of application is by spraying. Alternatively, granular formulations of these compounds can be applied to the plant foliage or the soil. Other methods of application include direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others. The compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like.
For the control arthropod pests, the compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance compound efficacy.
The rate of application required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.001 kg/hectare may be sufficient or as much as 8 kg hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required.
The following TESTS demonstrate the control efficacy of compounds of this invention on specific pathogens and arthropod pests. For the tests on arthropod pests, "control efficacy" represents inhibition of arthropod development (including mortality) that causes significantly reduced feeding. The pathogen and arthropod pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-M for compound descriptions. The following abbreviations are used in the Index Tables which follow: t = tertiary, n = normal, i - iso, c = cyclo, Me = methyl, Et = ethyl, Pr = propyl, -Pr = isopropyl, Bu = butyl, Ph = phenyl,
MeO and OMe = methoxy, EtO = ethoxy, PhO = phenoxy, MeS = methylthio, CHO = formyl, CN = cyano, CO2Me = methoxycarbonyl, CO2Et = ethoxycarbonyl, NO2 = nitro, Me3Si = trimethylsilyl, Et3Si = triethylsilyl, MeNH = methylamino, Me N = dimethylamino, MeS(O) = methylsulfϊnyl, and MeSO2 and SO2Me = methylsulfonyl. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared.
INDEX TABLE A
*See Index Table M for lR NMR data. INDEX TABLE B
m.p. (°C) oil* oil* oil* oil* 59-61 oil* 71-73 oil* oil* oil* oil* oil* oil* oil* oil* oil* oil* oil* oil* oil* oil* oil* oil* oil*
6-MeO-2-pyrimidinyl oil*
2-naphthalenyl oil*
6-Me-2-naphthalenyl oil*
6-MeO-2-naphthalenyl oil*
6-Br-2-naphthalenyl oil*
5,6,7,8-tetrahydro-2-naphthalenyl oil* 3-[3,5-bis(trifluoromethyl)- 94-97 phenyl]- 1 ,2,4-thiadiazol-5-yl
240 OCH2 4-MeO-Ph solid*
*See Index Table M for *H NMR data.
INDEX TABLE C
m.p. f°C) 129-130 123-126 95-97 95-97 99-100 88-91 88-96 110-113 oil* 80-88 122-130 oil*
116-118 oil* S MeS O Ph oil*
O Cl CH2ON=C(H) Ph oil *
3-CF3-4-F-Ph oil*
5-Ph- 1 ,3,4-oxadiazol-2-yl 130-132
5-(4-Me-Ph)- 1 ,3,4-oxadiazol-2- 150- 151 y]
5-(4-Br-Ph)-l,3,4-oxadiazol-2- solid* yi
5-(4-Cl-Ph)-l,3,4-oxadiazol-2- 130-132 yi
5-(3-MeO-Ph)-l,3,4-oxadiazol- 108-111
2-yl
5-(3-Me-Ph)-l,3,4-oxadiazol-2- 119-121 yi
5-(4-f-Bu-Ph)- 1 ,3,4-oxadiazol- 159- 161
2-yl
5-(3-F-Ph)- 1 ,3,4-oxadiazol-2-yl 105- 108
5-(4-F-Ph)-l,3,4-oxadiazol-2-yl 124-125 5-(3-Cl-Ph)-l,3,4-oxadiazol-2- 130-135 yi
273 O MeO O 5-(4-CF3-Ph)-l ,3,4-oxadiazol- solid* 2-yl
275 O MeO O 3-(2-CN-PhO)-Ph oil*
276 O MeO O 3-(2-N02-PhO)-Ph oil*
277 O MeO O 3-(3-N02-2-pyridinyl-0)-Ph oil*
278 O Cl CH20-N=C(CH3) 4-CF3-2-pyridinyl 85-86
279 O MeO O 5-(3-Br-Ph)-l,3,4-oxadiazol-2- 147-157 yi
280 O MeO O 3-(3-N02-Ph)-l,2,4-thiadiazol- 169-170
5-yl
281 O MeO CH20-N=C(OCH3) 3,5-diCF3-Ph oil ι**
282 O MeO CH20-N=C(CH3)CH2S 3,5-diCF3-Ph oil 1**
283 O MeO CH20-N=C(CH3)CH20 3,5-diCF3-Ph oil* 284e O MeO CH20-N=C(CH3) 2,8-diCF3-quinolin-4-yl 149-151 285f O MeO CH20-N=C(CH3)
286 O MeO CH20-N=C(CH3)
287 O MeO O
288 O MeO O
O
O
O
O
O
O
O
O
O oil* oil* oil* oil* oil*
118-120
123-126 oil*
48-51
oil* oil* 309 O MeO O
310 O MeO O
31 1 O MeO O 312 o MeO O
313 O MeO O
2S 5,7-diMe-6-Ph- 121-124
[ 1 ,2,4] triazolof 1 ,5-α]pyrimidin-
2-yl
319 O MeO CH2S 5,7-diMe-6-Ph- 155-160
[ 1 ,2,4]triazolo[ 1 ,5-α]pyrimidin-
2-yl
320 O MeO 3-(4-Ph-Ph)-l,2,4-thiadiazol-5- 159-161 yi 21 O MeO O 3-(3-CF3-Ph)-l,2,4-thiadiazol- 122-123
5-yl 22 O MeO O 3-(4-r-Bu-Ph)-l,2,4-thiadiazol- 174-175
5-yl 23 O MeO O 3-(3-Br-Ph)- 1 ,2,4-thiadiazol-5- 137-139 yi 24 O MeO O 3-(3-Br-4-MeO-Ph)- 1,2,4- 161-162 thiadiazol-5-yl 25 O MeO O 3-(4-F-3-CF3-Ph)- 1,2,4- 164-165 thiadiazol-5-yl 26 O MeO O 3-(4-Br-3-Me-Ph)- 1,2,4- 160-162 thiadiazol-5-yl 27 O MeO O 5-(4-MeO-Ph)-l ,3,4-oxadiazol- 180-181
2-yl 328 O MeO O 5-(4-Ph-Ph)- 1 ,3,4-oxadiazol-2- 179- 180 yi
329 O MeO O 3-(3,5-diCl-Ph)- 1,2,4- 159-160 thiadiazol-5-yl
330 O MeO O 5-(3,5-diCF3-Ph)-l,3,4- 175-176 oxadiazol-2-yl
5-(2-F-Ph)- 1 ,3,4-oxadiazol-2-yl 139- 140
5-(2-Cl-Ph)- 1 ,3 ,4-oxadiazol-2- 139- 140 yi
5-(2,4-diCl-Ph)- 1,3,4- 181-182 oxadiazol-2-yl
3-(4-MeS-Ph)- 1 ,2,4-thiadiazol- solid*
5-yl
3-(3-F-Ph)-l,2,4-thiadiazol-5-yl 116-118
3-CF3-Ph solid*
5-(4-Cl-Ph)-l ,3,4-thiadiazol-2- solid* yi
6-F-pyridin-2-yl 175-178
6-(3-Me-PhO)-pyrimidin-4-yl oil*
3-(4-Cl-Ph)- ltf-pyrazol- 1 -yl 159- 163
3-(4-Cl-Ph)- 1 ,2,4-thiadiazol-5- 126- 127 yi
3-(4-CF30-Ph)- 1,2,4- solid* thiadiazol-5-yl
3-(3-CF30-Ph)- 1,2,4- 112-113 thiadiazol-5-yl
3-(4-HCF20-Ph)- 1,2,4- solid* thiadiazol-5-yl
3-f-Bu-l,2,4-thiadiazol-5-yl 110-111
4-(CF3CH20)-3-CF3-Ph oil*
3-Br-Ph oil*
6-(4-CF3-Ph)-pyrimidin-4-yl 163-165
3-(2-CHO-PhO)-Ph 106-108
3-(2-Me-PhO)-2-N02-Ph 131-133 5-N02-6-PhO-pyridin-2-yl 127-130 3-(2-Me-PhO)-Ph oil* 3-c-Pr-l,2,4-thiadiazol-5-yl * 3-c-penty 1- 1 ,2,4-thiadiazol-5-yl * 3-(4-Cl-Ph)- 1 tf-pyrazol- 1 -y 1 * 4-(4-Cl-Ph)- 1 ,2,5-thiadiazol-3- yi
2-Cl-5-thiazolyl 6-(4-CF3-Ph)-2-pyrazinyl 145-148
5-CF3-2-pyridinyl 128-130
3-[r-BuOC(=0)]-Ph gum*
6-(3,5-diCF3-Ph)-2-pyrazinyl 173-174
6-(2,4-diCl-Ph)-4-pyrimidinyl 170-175 3-(3-CF30-Ph)- 1,2,4- thiadiazol-5-yl
364 O Cl O 3-(3,4-diCl-Ph)- 1,2,4- thiadiazol-5-yl
365 O Cl 3-(3,5-diCl-Ph)- 1,2,4- 149-150 thiadiazol-5-yl
366 O Cl O 3-(4-Br-Ph)- 1 ,2,4-thiadiazol-5- 158-159 yi
367 O Cl O 3_(4-CF3-Ph)- 1 ,2,4-thiadiazol-
5-yl
368 O Cl O 3-(4-/-Bu-Ph)-l ,2,4-thiadiazol-
5-yl
3-t-Bu- 1 ,2,4-thiadiazol-5-yl
6-Ph0-2-pyridinyl oil*
3-(4-Me-PhO)-2-N02-Ph 150-152
3-(2-C02Me-6-N02-PhO)-Ph oil*
3,5-diCF3-Ph solid*
4-Me3Si-benzyl oil*
4-Me3 Si-benzyl oil*
3-(3-CN-2-pyridinyl-0)-Ph 132-134
6-Cl-3-N0 -2-pyridinyl 146-151
3-(3,5-diCF3-Ph)-Ph 52-57 4-(C02-«-Bu)-2-pyridinyl 106-108 487 O MeO CH2S 3-(3-CF3-Ph)- 1 ,2,4-thiadiazol- 139-140 5-yl
488 O MeO O 3-(3,4,5-triCI-2-thienyl)- 1 ,2,4- 175-177 thiadiazol-5-yl
489 O MeO O 3-(5-Cl-2-thienyl)- 1,2,4- 130-131 thiadiazol-5-yl
490 O MeO O 3-[3-(PhC=C)-Ph]- 1,2,4- thiadiazol-5-yl
491 O MeO O 3-[3-(Me3SiG- )-Ph]-l ,2,4- 133-134 Ex. 6 thiadiazol-5-yl 492 O MeO O 3-[3-(EtOG=C)-Ph]-l,2,4- solid* thiadiazol-5-yl
493 O MeO O 3-[3-(4-F-PhCsC)-Ph]- 1 ,2,4- solid* thiadiazoI-5-yl
494 O MeO O 3-[3-(2-pyridinyl-C≡C)-Ph]- solid* l,2,4-thiadiazol-5-yl
495 O MeO O 3- [3-(tetrahydropyran-2-yl- solid*
OCH2-C=C)-Ph]- 1,2,4- thiadiazol-5-yl
496 O MeO O 3-[3-(r-Bu-C≡C)-Ph]- 1,2,4- 130-131 thiadiazol-5-yl
3-(3-CHO-Ph)- 1 ,2,4-thiadiazol-
5-yl
3-(2,5-diCl-PhO)-Ph 110-112
3-(3,5-diCl-PhO)-Ph oil*
3-(4-CF3-Ph)-l ,2,4-thiadiazol- 107-111
5-yl
3-(3,5-diCF3-Ph)-l,2,4- 132-136 thiadiazol-5-yl
2-(3-Cl-4-MeO-Ph)-5-Me-4- 172-175 thiazolyl
3-(3-CF3-PhO)-Ph oil*
3-(3-F-PhO)-Ph oil*
3-(2,3-diF-PhO)-Ph oil* 3-(2,4-diF-PhO)-Ph oil* 3-(3-HC≡C-Ph)- 1,2,4- 177-178 thiadiazol-5-yl 3-(6-CF3CH20-3-pyridinyl)- solid* l,2,4-thiadiazol-5-yl
3-CF3-Ph 125-130
523 O MeO 2-thiazolyl 166-170
141
3-CF3-Ph 130-135
l,6-diBr-2-naphthalenyl 189-191
3-(5-Br-2-furanyI)- 1,2,4- solid* thiadiazol-5-yl
3-[3-PhC(=0)0-Ph]- 1,2,4- * thiadiazol-5-yl
3-(3-HO-Ph)- 1 ,2,4-thiadiazol-5- solid* yi
6-Ph-4-pyrimidinyl 123-125
3-(f-Bu-C≡C)-l,2,4-thiadiazol- *
5-yl 3-(3-Et3SiO-Ph)-l,2,4- * thiadiazol-5-yl
532 O MeO O 3-[3-(f-BuMe2SiO)-Ph]-l,2,4- * thiadiazol-5-yl
533 O MeO O 3-[3-Cl3CCH2OC(=0)0-Ph]- * l,2,4-thiadiazol-5-yl
534 O MeO O 3-[3-MeCHC10C(=0)0-Ph]- * l,2,4-thiadiazol-5-yl
535 O MeO O 3-[3-[CH2=CHOC(=0)0]-Ph]- * l,2,4-thiadiazol-5-yl
536 O MeO O 3-[3-[r-BuC(=0)0]-Ph]- 1,2,4- * thiadiazol-5-yI
537 O MeO O 3-[3-[Me3Si(CH2)2θCH20]- *
Ph]- 1 ,2,4-thiadiazol-5-yl
538 O MeO O 3-[3-CF3S(0)20-PhJ- 1,2,4- solid* Ex. 10 thiadiazol-5-yl
539 O MeO O 3-(2,5-diBr-3-thienyl)- 1,2,4- solid* thiadiazol-5-yl
540 O MeO O 3-(3-Cl-benzyI)- 1,2,4- solid* thiadiazol-5-yl
541 O MeO O 3-(4-Cl-benzyl)- 1,2,4- solid* thiadiazol-5-yl 142
567 O MeO O 3-[4-(HC≡C)-Ph]- 1,2,4- thiadiazol-5-yl
568 O MeO O 3-[4-(Me3SiG=C)-Ph]- 1 ,2.4- thiadiazol-5-yl
144 oil* solid* oil* a Compound contains 15% by weight of 4-[2-(bromomethyl)phenyl]-5-
(difluoromethoxy)-2,4-dihydro- 1 -methyl-3H- 1 ,2,4,-triazol-3-one. b Compound isolated in a 1:1 ratio of Z and E isomers. c Compound isolated in a 2: 1 ratio of Z and E isomers. d Compound isolated in a 2:3 ratio of Z and E isomers. e Compound isolated as the Z isomer. f Compound isolated as the E isomer. S Compound isolated in a 1:2 ratio of geometric isomers. n Compound isolated as the Z isomer. *See Index Table M for lR NMR data.
INDEX TABLE D
145
588 O MeO CH20-N=C(CH3) 2-naphthalenyl 124-125
589c O MeO CH20-N=C(CH2CH3) 3-CF3-Ph oil*
590 O MeO CH20 3-(4-Cl-Ph)- 1 ,2,4-thiadiazol-5-yl 184-185
591 O MeO CH20 3-(3,5-diCl-Ph)- 1 ,2,4-thiadiazol-5-yl 185-186
592 O MeO CH20 3-(4-CF3-Ph)-l,2,4-thiadiazol-5-yl 138-139
*See Index Table M for lH NMR data. a Compound isolated in a 7:3 ratio of Z and E isomers, respectively. b Compound isolated in a 5: 1 ratio of Z and E isomers, respectively. cCompound contains 28% by weight of 2,4-dihydro-5-methoxy-2-methyl-4-[5-methyl-2- [[[[ 1 -[3-(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]-3-thienyl]-3H- 1 ,2,4- triazol-3-one which is also a compound of this invention.
*See Index Table M for !H NMR data.
INDEX TABLE G
*See Index Table M for *H NMR data.
INDEX TABLE H
Me
3-(4-CF3-Ph)- 1 ,2,4-thiadiazol-5-yl
3-(3,5-diCI-Ph)-l,2,4-thiadiazol-5-yl 3-(4-Cl-Ph)- 1 ,2,4-thiadiazol-5-yl 621 MeO O Me 180-181
Cmpd No. X m.p. (°C) 622 MeO CH20-N=C(CH3) 3-CF3-Ph 153-155
INDEX TABLE J
R10
Cmpd No. R9 R10a m.p. (°C)
159-162 204-209 175-181 187-197 207-210 205-209 205-208 210-214 210-216 191-192 225-229 R10
Cmpd No. X Rl R9 R10a γ m.p. (°C)
641 MeO n-Bu 6-1 8-1 CH20 166-169 642 MeO n-Pr 6-Br 8-Br CH20 160-163 643 MeO Me 6-1 H CH20 200-204 644 MeO ,ι-Bu 6-1 8-1 O 165-167
INDEX TABLE L
l Rfa Y Z m.p. CO
H O 3-(3-CF30-Ph)-l,2,4-thiadiazol-5-yl * H O 3-(3,4-diCl-Ph)-l,2,4-thiadiazol-5-yl 154-155 3-(3,5-diCl-Ph)- 1 ,2,4-thiadiazol-5-yl 3-(3,5-diCF3-Ph)- 1 ,2,4-thiadiazol-5-yl 3-(4-Br-Ph)- 1 ,2,4-thiadiazol-5-yl 166-168 3-(4-CF3-Ph)- 1 ,2,4-thiadiazoI-5-yl * 3-(4-r-Bu-Ph)- 1 ,2,4-thiadiazol-5-yl 159-160 3-r-Bu- 1 ,2,4-thiadiazol-5-yl 3-(4-Br-Ph)- 1 ,2,4-thiadiazol-5-yl 3-(3,4-diCl-Ph)-l,2,4-thiadiazol-5-yl 3-(4-CF3-Ph)- 1 ,2,4-thiadiazol-5-yl 3-(3-CF30-Ph)- 1 ,2,4-thiadiazol-5-yl 3-f-Bu- 1 ,2,4-thiadiazol-5-yI 3-(3,5-diCl-Ph)-l,2,4-thiadiazol-5-yl 3-(3,5-diCF3-Ph)-l,2,4-thiadiazol-5-yl 3-(4-r-Bu-Ph)- 1 ,2,4-thiadiazol-5-yl 3-(3,5-diCl-Ph)-l,2,4-thiadiazol-5-yl 3-(3,4-diCl-Ph)- 1 ,2,4-thiadiazol-5-yl 3-(3-CF3-Ph)-l,2,4-thiadiazol-5-yl 3-(3,5-diF-Ph)-l,2,4-thiadiazol-5-yl 3-(3-CH3-Ph)-l,2,4-thiadiazol-5-yl 3-(3-CF30-Ph)- 1 ,2,4-thiadiazol-5-yl 3-(4-CH3-Ph)- 1 ,2,4-thiadiazol-5-yl 3-(4-CF3-Ph)- 1 ,2,4-thiadiazol-5-yl 3-(3,5-diCF3-Ph)-l,2,4-thiadiazol-5-yl 95-98
3-(2-CH3-PhO)-Ph oil*
3-PhO-Ph oil*
3-(2-Cl-PhO)-Ph oil*
3-(2-F-PhO)-Ph oil*
3-(4-CF3-Ph)- 1 ,2,4-thiadiazol-5-yl 130-132
CH2Br 120-121
6-(2-CH3-PhO)-4-pyrimidinyl 135-136
3-(4-F-PhO)-Ph oil*
3-(2,6-diF-PhO)-Ph oil*
3.(4-CF3-Ph)- 1 ,2,4-thiadiazol-5-yl 1 10-112 3-(3,5-diCF3-Ph)-l,2,4-thiadiazol-5-yl 107-1 10 3-(2,6-diCl-4-pyridinyl)-l,2,4- oil/solid* thiadiazol-5-yI
3-(2,6-diCl-benzyl)- 1 ,2,4-thiadiazol-5 128-129 yi
3-(2,6-diCl-4-pyridinyl)- 1 ,2,4- 150- 156 thiadiazol-5-yl
3-(2,6-diCl-benzyl)- 1 ,2,4-thiadiazol-5- 113-119 yi
CH3 132-134 CH3 144-146
6-Cl-4-pyrimidinyl 108-110
3-r-Bu- 1 ,2,4-thiadiazol-5-yl 146-147
3-r-Bu- 1 ,2,4-thiadiazol-5-yl oil*
6-(3,5-diCF3-Ph)-4-pyrimidinyl 195-198
3-CF3-l#-pyrazoI-l-yl 368**
6-(4-CF3-Ph)-4-pyrimidinyl 148-150
6-(4-CF3-Ph)-2-pyrazinyl 128-131
3-(3,5-diCl-Ph)-l,2,4-thiadiazol-5-yl 173-176
6-(3-CF3-Ph)-2-pyrazinyl 118-120
3-F-2-N02-Ph oil*
6-(3,5-diCF3-Ph)-2-pyrazinyl 185-187
6-Cl-2-pyrazinyl 122-124
CH2Br 168-170
CHBr2 129-131
3-(3,5-diF-Ph)- 1 ,2,4-thiadiazol-5-yl 149-153
6-(4-C02Et-Ph)-4-pyrimidinyl 97-103
6-(4-C02Et-Ph)-2-pyrazinyl 158-161
6-(3-CF3-Ph)-4-pyrimidinyl 125-127
6-Ph-2-pyrazinyl 137-139
6-(4-Cl-Ph)-2-pyrazinyl 166-171
6-(2-Br-PhO)-4-pyrimidinyl 127-129
3-(3,5-diCF3-Ph)-l,2,4-thiadiazol-5-yl 136-138
3-(3,5-diCF3-Ph)-l,2,4-thiadiazol-5-yl 154-156
3-(3,5-diCl-Ph)-l,2,4-thiadiazol-5-yl 204-208 3-(3,5-diF-Ph)-1,2,4-thiadiazol-5-yl 164-166 3-(3,5-diCl-Ph)- 1 ,2,4-thiadiazol-5-yl 139- 142 3-(3,5-diF-Ph)-l,2,4-thiadiazol-5-yl 115-119
3-(3,5-diF-Ph)- 1 ,2,4-thiadiazol-5-y 1 125- 128
3-(2-Br-PhO)-Ph oil*
3-(4-CH3-Ph)- 1 ,2,4-thiadiazol-5-yl 43-55
3-(4-CH3-Ph)-l,2,4-thiadiazol-5-yl 138-140
3-(3,5-diCl-Ph)-l ,2,4-thiadiazol-5-yl 180-185 3-(3,5-diCF3-Ph)-l,2,4-thiadiazol-5-yl 144-146 3-(4-CH3-Ph)- 1 ,2,4-thiadiazol-5-yl 118- 123
*See Index Table M for lR NMR data. ** Protonated parent molecular ion (m/e) measured by mass spectrometry using atmospheric pressure chemical ionization in the positive ion mode (APCI+). The ion shown corresponds to the M+H+ ion calculated from the integral values of the atomic weights of the most abundant isotope of each element present.
INDEX TABLE M
Cmpd No. *H NMR Data (CDCI3 solution unless indicated otherwise)3
67.51(dd,lH), 7.27(dt,lH), 7.17(m,2H), 6.97(dd,lH), 6.6(m,3H),
3.92(s,3H), 3.74 (s,3H), 3.33 (s,3H).
3 67.32(m,7H), 6.99(m,2H), 5.08(s,2H), 3.84(s,3H), 3.42(s,3H). 4 δ 7.25(m,4H), 3.98(s,3H), 3.45(s,3H), 2.30(s,3H). 5 δ 7.61(d,lH), 7.35(m,3H), 7.1 l(m,2H), 6.84(t,2H), 5.12(s,2H),
3.96(s,3H), 3.415(s,3H), 2.24(s,3H).
14 δ 7.65(d,lH), 7.45(m,2H), 7.23(m,lH), 7.10(m,2H), 6.82(t,lH),
6.78(d,lH), 5.08(s,2H), 4.29(m,2H), 3.41(s,3H), 2.24(s,3H), 1.31(t,3H).
17 δ 7.6-7.45(m,5H), 7.20(m,lH), 7.14(d,2H), 5.27(d,lH), 5.16(d,lH),
3.46(s,3H), 2.34(s,3H), 2.16(s,3H).
19 δ 7.6(d,lH), 7.5(m,3H), 7.4(t,lH), 7.25(m,lH), 7.15(d,2H), 5.26(d,lH),
5.20(d,lH), 3.48(s,3H), 2.41(s,3H), 2.43(s,3H), 2.18(s,3H).
20 δ 7.62(m,2H), 7.5(m,2H), 7.35-7.2(m,4H), 5.25(d,lH), 5.15(d,lH),
3.48(s,3H), 3.02(m,2H), 2.85(m,2H).
21 δ 7.42(m,2H), 7.10(m,lH), 7.06(m,3H), 6.99(t,lH), 6.68(d,2H),
3.37(s,3H), 2.51(s,3H).
23 δ 8.01(s,lH), 7.61(d,lH), 7.52(m,4H), 7.35(m,3H), 7.25(d,lH),
5.23(d,lH), 5.15(d,lH), 3.49(s,3H).
24 δ 7.6(m,2H), 7.5-7.4(m,3H), 7.3-7.2(m,3H), 5.24(d,lH), 5.20(d,lH), 3.48(s,3H), 2.40(s,3H).
25 δ 7.6-7.4(m,4H), 7.35(m,2H), 7.2(m,2H), 7.0(d,2H), 6.6(m,3H), 5.04(d,lH), 5.00(d,lH), 3.45(s,3H).
26 δ 7.6(d,lH), 7.45(m,2H), 7.33(t,2H), 7.19(m,2H), 7.10(t, lH), 7.01(d,2H), 6.6(m,3H), 5.03(m,2H), 3.87(s,3H), 3.39(s,3H).
35 δ 7.6-7.4(m,7H), 7.23(d,lH), 5.28(d,lH), 5.17(d,lH), 3.46(s,3H), 2.14(s,3H).
36 δ 7.80(d,2H), 7.65-7.45(m,6H), 7.36(d,2H), 7.30(m,lH), 7.25(m,lH), 7.10(t,lH), 5.15(d,lH), 5.10(d,lH), 3.45(s,2H).
38 δ 7.77(d,2H), 7.6(m,2H), 7.47(m,4H), 7.35(m,3H), 7.25(m,lH), 7.10 (m.lH), 5.13(d,lH), 5.12(d,lH), 3.89(s,3H), 3.38(s,3H).
39 δ 8.03(s,lH), 7.70(d,lH), 7.53(m,2H), 7.35-7.25(m,5H), 5.06(s,2H), 3.46(s,3H).
40 δ 7.6-7.5(m,3H), 7.24(m,lH), 7.13(s,lH), 7.02(d,lH), 6.78(d,lH), 5.96(s,2H), 5.26(d,lH), 5.14(d,lH), 3.48(s,3H), 2.13(s,3H).
41 δ 8.04(s,lH), 7.8(m,lH), 7.45(m,2H)7.35-7.25(m,5H), 5.10(s,2H), 3.86(s,3H), 3.41(s,3H).
42 δ 7.58(m,lH), 7.43(m,2H), 7.25(m,lH), 7.15(m,lH), 7.02(d,lH), 6.76(d,lH), 5.96(s,2H), 5.22(d,lH), 5.18(d,lH)3.89(s,3H), 3.42(s,3H), 2.15(s,3H).
43 δ 8.40(s,lH), 7.6(m,lH), 7.5-7.4(m,5H), 7.3(d,lH), 7.18(m,2H), 6.38(s,lH), 3.45(s,3H).
45 δ 7.55(d,lH), 7.40(m,3H), 7.20(m,4H), 5.21(d,lH), 3.87(s,3H),
3.42(s,3H), 2.24(s,3H).
47 δ 7.6-7.2(m,9H), 5.4-5.2(m,2H), 3.87,3.83(s,3H), 3.41,3.40(s,3H).
48 δ 7.6(m,3H), 7.44(m,2H), 7.35(m,3H), 7.25(m,lH), 5.26(d,lH), 5.22(d,lH), 3.88(s,3H), 3.49(s,3H), 2.20(s,3H).
49 δ 7.5(d,lH), 7.40(m,4H), 7.23(m,2H), 7.18(d,lH), 5.26(d,lH), 5.21(d,lH), 3.88(s,3H)3.41(s,3H), 2.36(s,3H), 2.19(s,3H).
50 δ 7.56(m,3H), 7.45(m,2H), 7.25(m,lH), 6.86(d,2H), 5.24(d,lH), 5.19(d,lH), 3.88(s,3H), 3.81(s,3H), 3,41(s,3H), 2.17(s,3H).
51 δ 7.5(m,2H), 7.45(m,3H), 7.3(m,3H), 5.27(d,lH), 5.22(d,lH), 3.89(s,3H).
52 δ 8.02,8.01(s,lH), 7.8,7.7(m,lH), 7.45(m,2H), 7.35(m,4H), 7.25(m,2H), 5.25(m,lH), 3.88,3.74(s,3H), 3.45,3.39(s,3H), 1.62-1.56(m,3H).
53 δ 8.04(s,lH), 7.81(m,lH), 7.45(m,2H), 7.38-7.18(m,5H), 5.18(s,2H), 3.86(s,3H), 3.42(s,3H), 2.38(s,3H). 54 δ 7.35(m,4H), 7.20(m,2H), 7.05(d,2H), 6.95(d, 1 H), 3.46(s,3H).
55 δ 7.6-7.45(m,3H), 7.2(m, 1 H), 4.67(d, 1 H), 4.48(d, 1 H), 3.56(s,3H).
56 δ 7.5(m, lH), 7.44(m,2H), 7.22(m,lH), 4.60(d,lH), 4.36(d,lH), 3.96(s,3H), 3.47(s,3H).
60 δ 7.72(d,2H), 7.58(d,3H), 7.50(m,2H), 7.26(m,lH), 5.30(d,lH), 5.24(d,lH), 3.48(s,3H), 2.42(s,3H), 2.21(s,3H).
61 δ 7.70(m,2H), 7.60(m,2H), 7.43(m,3H), 7.23(m, 1 H), 5.30(d, 1 H), 5.25(d,lH), 3.85(s,3H), 3.41(s,3H).
62 δ 8.40(s,lH), 7.70(m,2H), 7.6-7.3(m,6H), 6.59(s,lH), 3.80(s,3H), 339(s,3H).
64 δ 8.40(s,lH), 7.5-7.2(m,7H), 7.02(,1H), 6.33(s,lH)3.78(s,3H), 3.36(s,3H), 2.18(s,3H).
65 δ 8.42(s,lH), 7.55-7.26(m,7H), 7.16(d,2H), 6.36(s,lH), 3.79(s,3H)3.36(s,3H).
69 δ 7.6-7.3(m,7H), 7.25(m,lH), 5.24(d,lH), 5.21(d,lH)3.89(s,3H), 3.41(s,3H), 2.18(s,3H), 1.31(s,9H).
70 δ 7.60(d,lH), 7.45-7.38(m,3H), 7.35-7.20(m,2H), 7.1 l(d,lH), 5.74(d,lH), 5.21(d,lH), 3.88(s,3H), 3.41(s,3H), 2.27(s,3H), 2.26(s,3H), 2.18(s,3H).
75 δ 8.56(s,lH), 7.58(m,lH), 7.40(m,3H), 6.99(s,lH), 3.43(s,3H).
76 δ 7.66(d,2H), 7.58(m,5H), 7.5-7.3(m,5H), 7.25(m,lH), 5.28(d,lH), 5.24(d,lH), 3.90(s,3H), 3.47(s,3H), 2.23(s,3H).
77 δ 7.68(d,lH), 7.6-7.5(m,2H), 7.25(m,lH), 7.00(d,lH), 6.68(d,lH), 6.61(s,lH), 5.05(d,lH), 5.00(d,lH), 3.49(s,3H), 2.29(s,3H), 2.16(s,3H).
82 δ 8.02(s,2H), 7.82(s,lH), 7.6-7.45(m,3H), 7.25(m,lH), 5.33(d,lH),
5.21(d,lH), 3.50(s,3H), 2.23(s,3H). 84 δ 7.6(d,lH), 7.5-7.4(m,2H), 7.4-7.2(m,5H) ,5.20(d,2H), 3.89(s,3H),
3.40(s,3H), 2.18(m,lH), 0.90(m,2H), 0.60(m,2H). 86 Two isomers: δ 7.75-7.40(m,8H), [5.29(s) and 5.22(m)](2H), [3.58(s) and 3.55(s)](3H), [2.88(s) and 2.83(s)l(3H), [2.23(s) and 2.17(s)](3H).
88 δ 7.60(m,2H), 7.40(m,4H), 7.26(m,2H), 5.25(d,lH), 5.22(d,lH), 3.88(s,3H), 3.40(s,3H), 2.20(s,3H), 1.33(s,9H).
89 δ 7.80(s,lH), 7.58(m,5H), 7.40(m,6H), 7.25(m,lH), 5.25(m,2H), 3.87(s,3H), 3.39(s,3H), 2.25(s,3H).
90 δ 7.58(d,lH), 7.42(m,2H), 7.24(m,2H), 7.17(m,2H), 6.85(d,lH), 5.22(m,2H), 4.58(m,lH), 3.89(s,3H), 3.41(s,3H), 2.17(s,3H), 1.33(d,6H).
94 δ 7.67(s,lH), 7.60-7.45(m,3H), 7.41(s,2H), 7.22(m,lH), 5.30(d,lH), 5.16(d, lH), 3.49(s,3H), 2.14(s,3H). 96 δ 7.80(m,2H), 7.58(m,2H), 7.50(m,3H), 7.25(m, lH), 5.28(d,lH),
5.25(d,lH), 3.89(s,3H), 3.40(s,3H), 2.22(s,3H).
99 δ 7.82(s,lH), 7.79(d,lH), 7.58(m,2H), 7.45(m,3H), 7.25(m,lH), 5.22(m,2H), 3.89(s,3H), 3.41(s,3H), 2.77(q,2H), 1.10(t,3H).
100 δ 8.45(s,lH), 8.20(m,lH), 7.95(d,lH), 7.6-7.4(m,4H), 7.25(m,lH), 5.30(d,lH), 5.26(d,lH), 3.90(s,3H), 3.41(s,3H), 2.24(s,3H).
110 δ 7.60(d,lH), 7.45(m,2H), 7.25(m,lH), 7.20(s,2H), 7.00(s,lH), 5.25(d,lH), 5.21(d,lH), 3.88(s,3H), 3.41(s,3H), 2.32(s,6H), 2.18(s,3H).
111 δ 7.8(m,lH), 7.75(m,lH), 7.6-7.4(m,5H), 7.2(m,lH), 5.33(d,lH), 5.17(d,lH), 3.45(s,3H), 2.18(s,3H).
112 Major Isomer: δ 7.6-7.4(m,3H), 7.34-7.20(m,5H), 5.24(d,lH), 5.14(d,lH), 3.46(s,3H), 2.10(m,lH), 0.90(m,2H), 0.55(m,2H).
113 δ 7.89(s,lH), 7.80(d,lH), 7.60(m,2H), 7.43(m,3H), 7.25(m,lH), 5.28(d,lH), 5.24(d,lH), 3.90(s,3H), 3.42(s,3H), 2.19(s,3H).
114 δ 8.6(d,lH), 8.0(d,lH), 7.6(m,2H), 7.5(m,3H), 7.2(m,lH), 5.48(d,lH), 4.6(d,lH), 3.56(s,3H), 3.4(s,3H).
115 δ 7.64(s,lH), 7.58-7.42(m,4H), 7.30(m,lH), 7.25(m,lH), 5.29(d,lH), 5.24(d,lH), 3.90(s,3H), 3.41(s,3H), 2.19(s,3H).
121 δ 7.6-7.4(m,5H), 7.36(t,lH), 7.20(m,2H), 5.30(d,lH), 5.18(d,lH),
3.47(s,3H), 2.17(s,3H). 123 δ 7.72(d,2H), 7.58(d,2H), 7.51(m,lH), 7.34(m,3H), 5.31(s,2H),
3.94(s,3H), 3.43(s,3H), 2.24(s,3H).
125 δ 7.62(m,lH), 7.49(m,2H), 7.32(m,5H), 5.28(s,2H), 3.95(s,3H), 3.44(s,3H), 2.21(s,3H).
126 δ 7.77(t,lH), 7.49(m,3H), 7.34(m,3H), 7.22(m,lH), 5.28(s,2H), 3.94(s,3H), 3.44(s,3H), 2.2(s,3H).
127 δ 7.53(m,3H), 7.32(m,5H), 5.27(s,2H), 3.93(s,3H), 3.43(s,3H), 2.20(s,3H).
128 δ 7.48(m,5H), 7.33(m,3H), 5.27(s,2H), 3.93(s,3H), 3.42(s,3H), 2.2(s,3H).
129 δ 7.59(m,2H), 7.52(m, 1 H), 7.34(m,3H), 7.02(m,2H), 5.27(s,2H), 3.94(s,3H), 3.43(s,3H), 2.22(s,3H).
130 δ 7.56(m,3H), 7.33(m,3H), 6.86(m,2H), 5.25(s,2H), 3.93(s,3H), 3.81(s,3H), 2.43(s,3H), 2.21 (s,3H).
131 δ 7.92(m,lH), 7.84(d,lH), 7.6(m,lH), 7.47(m,2H), 7.33(m,3H), 5.30(s,2H), 3.98(S,3H), 3.45(s,3H), 2.23(s,3H). 132 δ7.73(d,2H), 7.62(d,2H), 7.50(m,1H), 7.35(m,3H),5.31(s,2H), 3.96(s,3H),3.44(s,3H),2.23(s,3H).
133 δ7.5(m,3H), 7.33(m,3H), 7.14(d,2H), 5.26(s,2H), 3.92(s,3H), 3.43(s,3H), 2.34(s,3H), 2.21(s,3H).
134 δ7.51(m,2H),7.34(m,5H), 5.27(s,2H), 3.94(s,3H), 3.43(s,3H), 2.37(s,3H),2.2(s,3H).
135 δ7.51(m,lH), 7.33(m,3H), 7.18(d,lH),7.06(m,lH), 6.76(d,lH), 5.95(s,2H), 5.24(s,2H), 3.94(s,3H), 3.43(s,3H), 2.18(s,3H).
136 δ7.53(m,lH),7.40(s,lH), 7.34(m,4H), 7.1(d,lH),5.26(s,2H), 3.93(s,3H), 3.43(s,3H),2.26(s,3H),2.25(s,3H),2.21(s,3H).
137 δ7.72(d,IH), 7.44(m,3H), 7.33(m,3H), 5.28(s,2H), 3.96(s,3H), 3.44(s,3H), 2.19(s,3H).
138 δ7.71(m,2H),7.58(m,5H), 7.44(m,2H), 7.34(m,4H),5.3(s,2H), 3.93(s,3H),3.43(s,3H),2.26(s,3H).
139 7.63(m,lH),7.54(m,lH),7.37(m,3H), 7.3(m,3H),5.28(s,2H), 3.92(s,3H), 3.43(s,3H), 2.24(s,3H), 1.33(s,9H).
140 δ8.07(s,2H),7.83(s,lH),7.51(m,lH),7.35(m,3H),5.35(s,2H), 3.96(s,3H),3.44(s,3H),2.27(s,3H).
141 δ7.53(d,lH),7.34(m,3H),7.24(m,lH),7.18(m,2H), 6.89(m,lH), 5.28(s,2H), 3.94(s,3H), 3.82(s,3H), 3.44(s,3H),2.22(s,3H).
142 δ7.83(t,lH),7.58(m,5H),7.43(m,3H),7.34(m,4H),5.3(s,2H),3.91(s,3H), 3.42(s,3H),2.28(s,3H).
143 δ7.56(m,3H), 7.33(m,5H), 7.13(m,lH), 6.99(m,4H),5.26(s,2H), 3.94(s,3H),3.43(s,3H),2.22(s,3H).
144 δ8.57(d,lH),7.85(d,lH),7.65(t,lH),7.53(d,lH),7.3-7.4(m,3H), 7.22(t,lH),5.32(s,2H), 3.95(s,3H), 3.44(s,3H),2.3(s,3H).
145 δ7.54(m,lH), 7.32(m,3H), 7.2(t,lH), 6.95(m,2H), 6.73(m,lH), 5.27(s,2H), 3.91(s,3H),3.43(s,3H), 2.95(s,6H), 2.22(s,3H).
146 δ7.52(m,3H),7.34(m,4H),7.18(m,lH),5.29(s,2H),3.94(s,3H), 3.43(s,3H), 2.22(s,3H).
147 δ7.54(m,3H), 7.33(m,3H), 6.96(m,2H),6.88(m,4H),5.25(s,2H), 3.93(s,3H), 3.8(s,3H), 3.43(s,3H), 2.21(s,3H).
153 δ7.5(m,lH),7.34(m,7H),7.26(m,lH),7.11(m,lH),6.97(m,2H), 5.25(s,2H), 3.92(s,3H), 3.42(s,3H), 2.2(s,3H).
154 δ7.53(m,lH), 7.33(m,3H), 7.24(m,lH), 7.15(m,2H), 6.86(m,lH), 5.27(s,2H),4,57(m,lH),3.92(s,3H), 3.43(s,3H),2.21(s,3H), 1.33(d,6H). 155 δ 7.49(m,3H), 7.34(m,4H), 5.29(s,2H), 3.95(s,3H), 3.44(s,3H), 2.18(s,3H).
156 δ 7.87(d, lH), 7.78(d, lH), 7.6(m, lH), 7.5(m,2H), 7.33(m,3H), 5.3(s,2H), 3.95(s,3H), 3.44(s,3H), 2.77(q,2H), 1.12(t,3H).
157 δ 7.47-7.45(m,lH), 7.39-7.27(m,3H), 5.09(s,2H), 3.95(s,3H), 3.43(s,3H), 1.79- 1.68(m,9H), 1.31-1.20(m,5H).
158 δ 7.48-7.28(m,4H), 5.10 and 5.08(2s,2H total), 3.95 and 3.81(2s,2H total), 3.44 and 3.35(2s,3H total), 1.85-1.79(m,8H), 1.26-0.84(m,14H).
159 δ 7.82(d,2H), 7.77(d,lH), 7.58(m,5H), 7.45(t,lH), 7.34(m,3H), 5.31(s,2H), 3.92(s,3H), 3.42(s,3H)2.29(s,3H).
160 δ 7.48(m,3H), 7.33(m,6H), 7.23(m,lH), 7.14(d,lH), 7.00(d,lH), 5.26(s,2H), 3.93(s,3H), 3.42(s,3H), 2.2(s,3H).
161 δ 7.66(s,lH), 7.51(m,2H), 7.33(m,4H), 5.32(s,2H), 3.96(s,3H), 3.44(s,3H), 2.22(s,3H).
162 δ 7.53(d,lH), 7.35(m,3H), 7.24(m,2H), 6.98(s,lH), 5.27(s,2H), 3.92(s,3H), 3.43(s,3H), 2.31(s,6H), 2.21(s,3H).
164 δ 7.45-7.55(d,lH), 7.30-7.35(m,3H), 6.45(d,lH), 6.05(d,lH), 5.26(s,2H), 3.96(s,3H), 3.43(s,3H), 2.33(s,3H), 2.13(s,3H).
165 δ 7.52(d,lH), 7.45(s,lH), 7.37-7.3 l(m,3H), 6.92(s,lH), 5.30(s,2H), 3.95(s,3H), 3.44(s,3H), 2.50(s,3H), 2.32(s,3H), 2.30(s,3H).
166 δ 7.53(m,3H), 7.34(m,3H), 7.18(d,2H), 5.26(s,2H), 3.93(s,3H), 3.43(s,3H), 2.5(br,lH), 2.22(s,3H), 1.78(m,6H), 1.41(m,4H).
168 δ 8.57(s,lH), 8.40-8.50(m,2H), 7.43-7.50(m,4H), 7.35-7.40(m,3H), 5.30(s,2H), 3.96(s,3H), 3.44(m,3H), 2.55(s,3H), 2.24(s,3H).
169 δ 8.45(t,lH), 7.80(t,lH), 7.57(s,lH), 7.33-7.50(m,6H), 5.35(s,2H), 3.89(s,3H), 3.43(s,3H), 2.33(s,3H).
171 δ 7.69(d,2H), 7.62(m,lH), 7.49(m,lH), 7.34(m,3H), 5.29(s,2H), 3.96(s,3H), 3.45(s,3H), 2.17(s,3H).
172 δ 7.86(m,2H), 7.5(m,lH), 7.33(m,3H), 7.18(m,lH), 5.29(s,2H), 3.96(s,3H), 3.44(s,3H), 2.23(s,3H).
173 δ 7.47(d,lH), 7.30-7.39(m,3H), 7.19(s,lH), 6.79(s,lH), 5.30(s,2H), 3.97(s,3H), 3.91(s,3H), 3.45(s,3H), 2.15(s,3H).
176 Major isomer: δ 7.69(t,lH), 7.57(d,2H), 7.35(m,4H), 5.17(s,2H),
4.03(s,3H), 3.97(s,3H), 3,45(s,3H). Minor isomer: δ 7.7(t,lH), 7.6(d,2H), 7.50(m,4H), 5.1 l(s,2H), 3.88(s,3H), 3.73(s,3H), 3.43(s,3H). 177 δ7.53(m,lH), 7.45(mlH), 7.42(m,lH), 7.34(m,3H), 7.24(m,lH), 7.17(mlH),5.28(s,2H), 3.91(s,3H), 3.42(s,3H), 2.65(q,2H), 2.23(s,3H), 1.23(t,3H).
178 δ7.60-7.30(m,7H), 5.29(s,2H), 3.95(s,3H), 3.94(s,3H), 3.44(s,3H), 2.30(s,3H).
179 δ2.34(s,3H), 3.43(s,3H), 3.93(s,3H),5.33(s,2H), 7.35(m,3H), 7.47(m,2H),7.56(t,lH),7.83(m,4H), 7.97(d,lH).
180 δ2.34(s,3H), 2.51(s,3H), 3.44(d,3H), 3.94(d,3H), 5.32(s,2H),7.35(m,4H), 7.565(m,2H),7.71(m,2H), 7.83(m,lH),7.93(s,lH).
181 δ2.33(s,3H), 3.43(s,3H), 3.91(s,3H), 3.93(s,3H),5.32(s,2H),7.13(m,2H), 7.35(m,3H), 7.56(m,lH),7.70(m,lH),7.75(m,lH), 7.83(m,lH), 7.905(s,lH).
182 δ2.33(s,3H), 3.44(s,3H), 3.95(s,3H),5.33(s,2H), 7.35(m,3H), 7.55(m,2H),7.70(t,2H),7.925(m,3H).
183 δ 1.78(m,4H), 2.21(s,3H), 2.75(d,4H), 3.43(s,3H), 3.92(s,3H), 5.26(s,2H), 7.01(m,lH),7.20(m,lH),7.32(m,5H),7.52(m,lH).
189 δ7.63(m,3H),7.40(m,5H),7.20(m,lH),5.12(AB q, 2H), 3.94(d,3H), 3.875(s,3H),3.41(s,3H).
190 δ7.75(m,1H),7.48(m,5H),7.22(m,2H), 5.24(q,2H),3.89(s,3H), 3.41(s,3H),2.16(s,3H).
192 δ8.05(d,lH),7.6-7.9(m,lH), 7.6(s,lH), 7.4-7.6(m,5H),7.2-7.3(lH), 5.3(m,lH), 3.7-3.9(d,3H), 3.45(m,3H), 1.6(m,3H).
193 δ3.47(s,3H),6.7-6.8(m,3H),7.0(m,3H),7.12(t,3H),7.2-7.3(m,2H), 7.3-7.5(m,4H).
194 δ3.38(s,3H),3.83(s,3H),6.7-6.8(m,3H),7.0-7.l(m,3H),7.1-7.2(m,3H), 7.3-7.4(m,4H).
198 δ7.94(t,lH), 7.66(m,lH), 7.54(m,2H), 7.43(m,2H), 7.23(d,lH), 7.06(t,lH), 5.24(q,2H), 3.88(s,3H), 3.41(s,3H), 2.14(s,3H).
199 δ7.55(m,lH), 7.51(m,2H), 7.46(m,2H), 7.25(m,lH), 5.14(q,2H), 4.08(s,3H), 3.915(s,3H),3.435(s,3H).
200 δ7.92(s,lH),7.85(d,lH), 7.60(m,2H), 7.45(m,3H), 7.24(m,lH), 5.14(q,2H),4.03(s,3H),3.88(s,3H),3.41(s,3H).
201 δ7.2-7.5(m,4H), 6.9-7.3(1,1H), 3.42(s,3H), 2.22(s,3H).
203 δ7.55(m,5H), 7.25(d,lH),5.12(q,2H),4.07(s,3H),3.53(s,3H).
204 δ7.85(s,lH), 7.75(d,lH), 7.4-7.7(m,5H), 7.3(d,lH), 7.05(t,lH), 5.23(m,2H), 3.34(s,3H), 2.19(s,3H). 205 δ 7.45-7.65(m,5H), 7.33(s,lH), 7.26(d,lH), 5.1-5.4(m,2H), 3.5(s,3H),
2.13(s,3H). 207 δ 7.60(d,l H), 7.50-7.30(m,4H), 7.25(m,2H), 5.23(d,lH), 5.20(d,lH),
3.89(s,3H), 3.41 (s,3H), 2.18(s,3H), 1.68(s,4H), 1.26(m,12H).
209 δ 7.58(m,lH), 7.37(m,2H), 7.23(m,3H), 6.60(d,2H), 4.23(s,2H), 3.86(s,3H), 3.41(s,3H).
210 (for the EIZ mixture) δ 7.66 and 7.21 (2s, IH total), 7.25-7.54 (m,4H total), 3.93 and 3.91 (2s,3H total), 3.44 (s,3H), 1.54 and 1.25 (2s,9H total).
211 δ 8.18(s,lH), 7.98(m,lH), 7.82(m,lH), 7.50(m,4H), 7.30(d,lH), 5.59(d,lH), 5.46(d,lH), 3.39(s,3H), 3.41(s,3H).
212 δ 7.56(m,2H), 7.44(m,3H), 7.25(m,2H), 5.26(AB q, 2H), 3.9(s,3H), 3.41(s,3H), 2.1(s,3H).
214 δ 7.68(d,lH), 7.6(m,lH), 7.48(m,4H), 7.28(m,lH), 5.41(AB q,2H), 3.91(s,3H), 3.38(s,3H), 3.20(s,3H).
215 δ 7.6(d,lH), 7.3-7.5(m,4H), 7.2(d,lH), 6.95(s,lH), 6.9(d,lH), 4.27(s,2H), 3.86(s,3H), 3.41(s,3H), 1.95(s,3H).
217 δ 7.65(d,lH), 7.6-7. l(m,6H), 5.15(m,2H), 3.95(m,lH), 3.45(s,3H),
2.6(d,3H), 2.2(s,3H), 1.65(s,4H), 1.25(s,12H).
220 δ 3.6(s,3H), 6.8(m,3H), 7.0-7. l(m,3H), 7.1-7.2(m,2H), 7.3(m,lH), 7.35(m,3H), 7.45(m,lH).
221 [in Me2SO-rf6]: δ 1.95(s,3H), 2.0(s,3H), 3.75(d,2H), 3.85(s,3H), 6.55(m,2H), 7.05(m,lH), 7.4-7.5(m,3H), 9.05(s,lH).
222 δ 7.76(s,lH), 7.60(m,lH), 7.54(m,lH), 7.36(d,lH), 7.32(d,lH), 6.94(d,lH), 5.29(s,2H), 3.89(s,3H), 3.41(s,3H), 2.21(s,3H), 0.28(s,9H).
231 δ 7.67(m,lH), 7.52(m,3H), 7.36(m,4H), 5.35(s,2H), 3.77(s,3H),
3.44(s,3H), 2.20(s,3H), 0.27(s,9H).
236 δ 8.68(d,lH), 7.80(s,lH), 7.75(d,lH), 7.60(m,2H), 7.43(m,2H), 5.54(d,lH), 5.40(d,lH), 3.82(s,3H), 3.35(s,3H), 2.17(s,3H).
237 δ 7.84(s,lH), 7.77(d,J=8Hz, IH), 7.58(m,2H), 7.45(m,3H), 7.26(m,lH), 5.31(d,J=13Hz, IH), 5.22(d,J=13Hz, IH), 3.89(s,3H), 3.81(m,2H), 2.21 (s,3H), 1.33(t,J=7Hz, 3H).
238 δ 1.6-1.8 (m,13H), 2.0-2.1 (m,5H), 3.44 (s,3H), 3.94 (s,3H), 5.09 (s,2H), 7.32 (m,3H), 7.48 (m,lH).
240 δ 7.39 (m,lH), 7.33 (d,2H), 7.26 (m,lH), 6.99 (m,2H), 6.88 (m,2H), 5.01
(s,2H), 3.84 (s,3H), 3.81 (s,3H), 3.41 (s,3H). 243 δ7.43 (m,3H), 7.28 (m,1H), 7.22(m,2H), 7.15 (m,1H),7.04(m,1H), 5.12 (q,2H)4.51 (s,2H),3.89(s,3H),3.43 (s,3H), 1.91 (s,3H).
244 δ7.45 (m,3H), 7.23 (m,1H), 5.06(q,2H),4.05 (s,2H), 3.93 (s,3H), 3.895 (s,3H),3.44(s,3H), 1.94(s,3H).
246 δ7.58 (m,lH), 7.41 (m,4H), 7.26(m,3H), 5.12(q,2H),4.08 (d,2H), 3.92 (s,3H), 3.44(s,3H), 1.96(s,3H).
247 δ7.57 (m,lH), 7.44(m,3H),7.32(d,2H), 7.24 (m,lH), 5.27 (q,2H), 3.9 (s,3H), 3.415 (s,3H),2.12(s,3H).
249 δ7.44 (m,3H),7.23 (m,lH),6.96(m,lH), 6.81 (m,2H), 5.12(q,2H),4.44 (s,2H),3.9 (s,3H), 3.43 (s,3H), 1.89 (s,3H).
250 δ7.6(d,lH),7.15-7.5 (m,5H), 6.95 (s.lH), 6.85 (d,lH),4.24 (s,2H), 3.85 (s,3H),3.41 (s,3H),2.3 (m,2H), 1.05 (t,3H).
252 δ7.45 (m,4H),7.25 (m,2H),5.30and5.10(2m,2Htotal), 3.91 and3.88 (2s,3Htotal), 3.42and3.41 (2s,3Htotal), 2.14and2.11 (2s,3Htotal).
254 δ7.56(m,3H),7.45 (m,2H), 7.35 (t,lH),7.25 (m,lH),5.12(q,2H),4.01 (s,3H), 3.89(s,3H), 3.43 (s,3H).
255 δ3.47(s,3H), 3.77(s,3H),6.61 (m,2H), 6.70(m,lH),7.01 (dd,lH,J=1.2,8.2),7.2-7.3 (m,2H), 7.34-7.42(m,2H).
259 δ 1.80(d,6H),3.52(s,3H),5.01 (q,2H), 7.26(m,lH),7.52(m,3H). 262 δ7.85 (d,lH),7.8 (m,lH),7.55 (d,lH),7.45 (m,2H),7.25 (IH),7.2
(t,lH),5.25 (m,2H), 3.9(s,3H),3.4 (s,3H),2.19 (s,3H). 265 δ7.84(m,3H),7.64 (d,2H), 7.6-7.55 (m,lH),7.5-7.4 (m,2H), 3.88 (s,3H),
3.43 (s,3H). 273 δ8.11 (d,2H),7.85 (d,1H),7.77(d,2H),7.6-7.5 (m,1H),7.5-7.4 (m,2H),
3.89(s,3H),3.43 (s,3H).
275 δ3.38 (s,3H), 3.85 (s,3H), 6.7-6.9 (m,3H), 6.95 (m,lH), 7.1 (m,lH), 7.2-7.4(m,5H),7.5(m,lH),7.6(m,lH).
276 δ3.38 (s,3H), 3.84(s,3H),6.71-6.78 (m,3H),7.0-7.1 (m,2H),7.2-7.4 (m,5H),7.54(m,lH),7.95(dd,lH,J=1.7,8.0).
277 δ3.39 (s,3H), 3.85 (s,3H),6.87 (t,lH),J=2.2), 6.92-6.96(m,2H),7.08 (d,lH,J=8.2),7.17-7.26(m,2H),7.3-7.4(m,3H), 8.3-8.4 (m,2H).
281 δ8.13 (s,2H), 7.86(s,lH),7.58 (m,lH), 7.46 (m,2H), 7.24(m,lH),5.15 (q,2H),4.11 (s,3H), 3.9(s,3H), 3.41 (s,3H).
282 δ7.78 (s,2H), 7.625 (s,lH), 7.42(m,3H), 7.23 (m,lH), 5.03 (q,2H), 3.92 (d,3H), 3.67 (s,2H), 3.42(s,3H), 1.905 (s,3H).
283 δ7.45 (m,4H), 7.33 (s,2H),7.24 (m,lH), 5.12(q,2H),4.57 (s,2H), 3.91 (s,3H), 3.43 (s,3H), 1.925 (s,3H).
298 δ 8.0 (m, 1 H), 7.88 (m, 1 H), 7.625 (m, 1 H), 7.48 (m,4H), 7.25 (m, 1 H), 5.09 (m,2H), 4.046 (s,3H), 3.75 (s,3H), 3.49 (s,3H), 2.41 (s,3H), 2.32 (s,3H). Compound is a 1 :2 mixture of geometric isomers.
299 δ 7.85 (m,lH), 7.75 (m,lH), 7.38 (m,6H), 5.10 (q,2H), 4.10 (s,2H), 3.91 (s,3H), 3.44 (s,3H), 1.95 (s,3H).
300 δ 3.41 (s,3H), 3.88 (s,3H), 4.02 (s,3H), 5.17 (AB q,2H), 7.25 (m,lH), 7.46 (m,4H), 7.64 (m,lH), 7.8 (m,4H), 8.12 (s,lH).
301 δ 3.37 (s,3H), 3.86 (s,3H), 6.7-6.9 (m,3H), 7.0-7.1 (m,3H), 7.2-7.5 (m,4H), 7.61 (d,2H,J=9.0).
302 3.37 (s,3H), 3.86 (s,3H), 6.8-6.9 (m,3H), 7.03 (dd,2H,J=2.3,7.1), 7.1 (m,lH), 7.25 (m,lH), 7.3-7.5 (m,3H), 8.21 (dd,lH,J=2.3,7.1).
305 δ 7.37 (m,2H), 7.26 (m,3H), 7.02 (m,3H), 3.86 (s,3H), 3.37 (s,3H).
307 δ 8.30 (d,lH), 7.85 (dd,lH), 7.60-7.40 (m,3H), 7.20 (d.lH), 6.70 (d,lH), 5.21 (AB q,2H), 3.94 (s,3H), 3.89 (s,3H), 3.41(s,3H), 2.17 (s,3H).
308 δ 7.41 (m,3H), 7.21 (m,3H), 7.14 (m.lH), 5.06 (q,2H), 3.9 (s,3H), 3.58 (s,2H), 3.43 (s,3H), 1.89 (s,3H).
311 δ 8.18 (m,2H), 7.65 (m,lH), 7.55 (t,lH), 7.49 (s,2H), 7.13 (t,2H), 3.78
(s,3H), 3.36 (s,3H).
314 δ 3.39 (s,3H), 3.85 (s,3H), 6.8-7.0 (m,4H), 7.0-7.1 (m,2H), 7.2 (m,lH), 7.3-7.4 (m,3H), 7.69 (m,lH), 8.19 (dd,lH,J=l.8,5.0).
315 δ 3.40 (s,3H), 3.84 (s,3H), 6.9-7.0 (m,3H), 7.0-7.1 (m,2H), 7.2-7.3 (m,lH), 7.35-7.40 (m,3H), 8.55 (d,2H,J=4.7).
316 δ 2.38 (s,3H), 3.36 (s,3H), 3.79 (s,3H), 6.35 (d,lH,J=0.7), 7.0 (m,2H), 7.2-7.25 (m,2H), 7.3-7.6 (m,4H), 8.41 (d,lH,J=0.7).
334 δ 8.08 (d,2H), 7.65 (d,lH), 7.55 (m,lH), 7.49 (m,2H), 7.28 (d,2H), 3.77
(s,3H), 3.37 (s,3H), 2.52 (s,3H).
336 δ 7.41 (m,4H), 7.26 (m,2H), 7.21 (m,lH), 7.02 (d,lH), 3.81 (s,3H), 3.357 (s,3H).
337 fin Me2SO- 6]: δ 7.92-7.45 (m,8H), 3.79 (s,3H), 3.25 (s,3H).
339 δ 2.88 (s,3H), 3.37 (s,3H), 3.79 (s,3H), 6.35 (d,lH,J=0.7), 6.9 (m,2H),
7.10 (d,lH,J=7.5), 7.3-7.5 (m,5H), 8.43 (d,lH,J=0.7).
342 δ 8.22 (d,2H), 7.61-7.48 (m,4H), 7.28 (m,2H), 3.78 (s,3H), 3.36 (s,3H).
344 δ 8.19 (d,2H), 7.65-7.50 (m,2H), 7.49 (s,2H), 7.17 (d,2H), 6.57 (t,lH),
3.78 (s,3H), 3.36 (s,3H).
346 δ 7.86 (d,lH), 7.77 (m,lH), 7.55 (m,lH), 7.44 (m,2H), 7.23 (d,lH), 6.95 (d,lH), 5.24 (q,2H), 4.44 (q,2H), 3.9 (s,3H), 3.4 (s,3H), 2.18 (s,3H). 347 δ 7.79 (t,lH), 7.57 (d,2H), 7.5 (m,3H), 7.23 (m,2H), 5.12 (AB q,2H), 3.98
(s,3H), 3.88 (s,3H), 3.42 (s,3H).
352 δ 2.22 (s,3H), 3.38 (s,3H), 3.82 (s,3H), 6.60-6.66 (m,3H), 6.97 (m,lH), 7.0-7.1 (m,2H), 7.1-7.3 (m,4H), 7.4-7.5 (m,2H).
353 δ 7.53 (m,2H), 7.45 (m,2H), 3.81 (s,3H), 3.40 (s,3H), 2.15 (m,lH), 1.0 (m,4H).
354 δ 7.56 (m,lH), 7.50 (m,lH), 7.46 (m,2H), 3.79 (s,3H), 3.40 (s,3H), 3.23 (t,lH), 2.05 (br m,2H), 1.90 (br m,2H), 1.80 (br m,2H), 1.70 (br m,2H).
355 [in C6D6]: δ 7.7 (d,2H), 7.2 (d,2H), 6.85 (m,4H), 6.6 (d,lH), 6.2 (d,lH), 5.35 (d,lH), 4.75 (d,lH), 3.10 (s, 3H).
356 δ 8.09 (d,2H), 7.65 (d, 1 H), 7.55 (m, 1 H), 7.5-7.35 (m,4H), 3.70 (s,3H),
3.24 (s,3H).
357 δ 7.49 (s,lH), 7.4 (m,lH), 7.3 (d,lH), 7.1 (m,2H), 5.19 (dd,2H), 3.90 (s,3H), 3.44 (s,3H).
360 δ 8.2 (s,lH), 7.95 (d,lH), 7.8 (d.lH), 7.6 (d,lH), 7.45 (m,3H), 7.25 (IH),
5.25 (m,2H), 3.89 (s,3H), 3.41 (s,3H), 2.22 (s,3H), 1.6 (s,9H).
363 δ 8.1 (d,lH), 8.0 (s,lH), 7.75-7.6 (m,2H), 7.55-7.4 (m,3H), 7.3 (m,lH), 3.45 (s,3H).
364 δ 8.24 (s,lH), 8.0 (d,lH), 7.65 (m,2H), 7.5 (m,3H), 3.45 (s,3H).
367 δ 8.26 (d,2H), 7.75-7.6 (m,4H), 7.55-7.45 (m,2H), 3.45 (s,3H).
368 δ 8.06 (d,2H), 7.75 (d,lH), 7.7-7.6 (m,lH), 7.5-7.4 (m, 4H), 3.46 (s,3H), 1.34 (s,9H).
369 δ 7.71 (d,lH), 7.65-7.55 (m,lH), 7.5-7.4 (m,2H), 3.49 (s,3H), 1.35 (s,9H).
370 δ 3.34 (s,3H), 3.76 (s,3H), 6.49 (d,lH,J=7.9), 6.53 (d,lH,J=7.9), 7.1-7.2 (m,3H), 7.2-7.4 (m,6H), 7.64 (t,lH,J=8.0).
372 δ 3.40 (s,3H), 3.74 (s,3H), 3.84 (s,3H), 6.5-6.6 (m,2H), 6.7 (m,lH), 6.95 (m,lH), 7.2-7.3 (m,2H), 7.3-7.4 (m,2H), 7.6-7.7 (m,lH), 8.07 (dd,lH,J=1.8, 8.1), 8.15 (dd,lH,J=1.7,7.8).
373 δ 7.93 (m,3H), 7.56 (m,lH), 7.43 (m,2H), 7.25 (m,lH), 5.3 (q,2H), 3.89 (s,3H), 3.4 (s,3H), 2.15 (s,3H).
374 δ 7.5 (d,lH), 7.4 (m,4H), 7.2 (d.lH), 7.1 (d,2H), 5.1 (q,2H), 3.888 (s,3H), 3.4 (m,5H), 1.715 (s,3H), 0.252 (s,10H).
375 δ 7.4-7.6 (m,5H), 7.2 (d,2H), 7.1 (d,2H), 5.0-5.2 (q,2H), 3.5 (s, 4H), 3.382 (s,2H), 1.695 (s,3H), 0.250 (s,10H).
381 δ 3.4 (s,3H), 3.8 (s,3H), 7.2-7.6 (m,6H), 7.8 (d,lH), 8.0 (s,lH). 384 δ3.34(s,3H), 3.82(s,3H), 7.05 (m,lH),7.21 (m,2H), 7.36-7.50(m,5H), 7.71 (d,lH),7.81(d,2H).
386 δ2.33 (s,3H), 3.38 (s,3H), 3.83 (s,3H), 6.65-6.75 (m,3H), 6.95 (d,2H,J=8.5),7.01 (dd,lH,J=1.3,8.3),7.14(d,2H,J=8.2), 7.2-7.3(m,2H), 7.3-7.4 (m,2H).
387 δ3.39 (s,3H),3.82(s,3H), 3.83 (s,3H), 6.65-6.72 (m,3H), 6.99-7.04 (m,2H), 7.2-7.3 (m,3H),7.3-7.4 (m,2H),7.5 (m,lH), 7.91 (dd,lH,J=1.8,7.8)
389 δ2.05 (s,3H), 3.39 (s,3H), 3.83 (s,3H), 6.7-6.8 (m,3H), 6.8-6.9 (m,2H), 6.95 (m,lH),7.0(m,lH), 7.2-7.3 (m,3H),7.3-7.4 (m,2H).
390 δ8.15 (s,lH), 8.05 (m,lH),7.65 (d,lH),7.55 (t,lH),7.46(m,4H), 3.70 (s,3H), 3.24(s,3H).
391 δ7.80(s,lH),7.65 (d.lH), 7.45 (m,2H),7.35 (m,2H),7.30-7.20(m,3H), 6.53 (s.lH), 5.50(d.lH),5.35 (d,lH), 3.80(s,3H), 3.43 (s,3H).
392 δ7.67(d,2H), 7.62(d,lH), 7.60-7.35 (m,4H), 3.77 (s,3H), 3.35 (s,3H).
393 δ7.55 (m,2H),7.45 (m,2H),3.89 (s,3H), 3.42(s,3H), 3.40(s,3H).
394 δ7.63 (d,2H),7.5 (m,lH),7.43 (m,lH),3.5 (s,3H), 3.42(s,3H).
395 δ8.18 (d,2H), 7.75-7.6(m,2H), 7.55-7.45 (m,2H), 7.25 (m,2H), 3.45 (s,3H).
396 δ3.4(s,3H), 3.9(s,3H),7.3-7.6(m,8H), 8.1 (d,lH).
397 δ3.4 (s,3H),3.9 (s,3H),7.38-7.5 (m,7H), 8.2(IH), 7.61 (d,lH).
400 δ7.93 (t,lH),7.845 (t,lH),7.77 (t,lH),7.57 (m,lH), 7.45 (m,2H),7.25 (m,lH), 5.12(q,2H), .40(s,3H), 3.9 (s,3H), 3.43 (s,3H).
401 δ7.74(s,lH),7.6(m,2H),7.45 (m,2H), 7.31 (d,lH), 7.2(m,lH), 5.13 (AB q,2H),4.06(s,3H),3.90(s,3H), 3.42(s,3H).
402 δ7.85 (IH),7.65 (m,2H),7.4(m,2H),7.25 (m,2H),4.6(m,2H), 3.94 (s,3H), 3.39 (s,3H).
406 δ7.87 (d,2H),7.45-7.35 (m,3H), 7.3 (m,2H), 7.07 (t,2H),5.33 (s,2H), 3.92(s,3H), 3.46(s,3H).
410 δ3.4(s,3H), 3.89 (s,3H),7.4-7.73 (m,8H).
411 δ3.4(s,3H), 3.87 (s,3H),7.3-7.6(m,12H).
412 δ2.3 (s,9H), 3.4 (s,3H), 3.87 (s,3H), 7.5 (m,6H), 7.7 (d,2H).
415 δ3.40(s,3H), 3.80 (s,3H), 6.6-6.8 (m,3H), 6.9-7.1 (m,4H), 7.2(m,2H),
7.4 (m,3H). 417 δ2.14 (s,3H), 3.35 (s,3H),3.75 (s,3H), 6.40(d,lH,J=8.0), 6.48
(d,lH,J=8.0),7.03 (m,lH), 7.1-7.3 (m,5H), 7.3-7.4 (m,2H), 7.59 (m,lH). 418 δ3.38 (s,3H), 3.82(s,3H), 6.65-6.75 (m,3H), 7.0-7.3 (m,7H), 7.3-7.4 (m,2H).
419 δ3.38 (s,3H), 3.86(s,3H), 6.8-6.9 (m,2H), 7.0-7.1 (m,2H), 7.15 (m.lH), 7.2-7.3 (m,lH), 7.4-7.5 (m,3H), 8.35 (m,lH), 8.6(m,lH).
420 δ3.39 (s,3H),3.82(s,3H),3.83 (s,3H),6.6-6.7 (m,3H),6.9-7.0(m,lH), 7.0(m,3H), 7.1-7.2(m,3H), 7.3-7.4 (m,2H).
421 δ3.39(s,3H),3.82(s,3H),3.93 (s,3H),6.46(d,lH,J=7.8),6.66 (d,lH,J=7.7),6.9-7.0(m,3H),7.1-7.3 (m,4H), 7.4 (m,2H).
422 δ3.39(s,3H), 3.85 (s,3H), 6.68 (d,1H,J=6.5), 6.85-6.95 (m,3H),7.04 (dd,lH,J=1.2,8.3), 7.25 (m,lH), 7.30-7.45 (m,4H).
423 δ3.38(s,3H), 3.83 (s,3H), 6.7-6.8 (m,3H), 7.0-7.1 (m,2H),7.2-7.3 (m,3H),7.4(m,2H), 7.5 (m,lH),7.66(m,lH).
424 δ2.13 (s,6H), 3.38 (s,3H), 3.81 (s,3H), 6.5 (m,2H), 6.6(m.lH),7.0-7.2 (m,6H),7.35 (m,2H).
425 δ3.4 (s,3H), 3.89 (s,3H),7.4(m,5H),7.7 (s,2H).
427 δ8.18 (s,lH), 8.05 (d,lH),7.75 (m,2H),7.55 (m,2H),7.4(m,2H),3.45 (s,3H).
428 δ3.4(s,3H),3.89(s,3H),7.3-7.6(m,6H),7.65 (d,lH),7.8(3.1H). 430 δ7.65 (d,lH),7.05-7.6(m,lIH),6.9(d,lH),5.15 (m,2H),3.89(s,3H),
3.38 (s,3H). 442 δ7.82(t.lH), 7.64(m,3H), 7.44(m,3H), 7.25 (m,lH), 6.71 (s,lH),5.13 (q,2H),4.0(s,3H),3.88(s,3H), 3.41 (s,3H).
447 δ3.39(s,3H),3.83(s,3H),6.60-6.75(m,3H),7.00-7.10(m,3H),7.2-7.4 (m,5H),7.62(dd,lH,J=l.6,7.8).
448 δ 1.19(t,3H), 2.62(q,2H,J=7.5), 3.39(s,3H), 3.82(s,3H),6.60-6.70 (m,3H), 6.95 (m,lH),7.05 (m.lH), 7.1-7.3 (m,5H),7.38 (m,2H).
449 δ7.55 (m,2H),7.47(m,2H), 3.86(s,3H), 3.39 (s,3H).
452 δ8.05 (s,lH), 7.65 (d,lH), 7.60(m,lH),7.55 (m,lH),7.45 (m,2H), 7.35 (m,lH), 3.78 (s,3H),3.36(s,3H).
453 δ7.75(s,lH),7.60(d.lH),7.55(m,lH),7.45(m,2H),7.40(d,lH),7.10 (m,lH), 3.79 (s,3H),3.38 (s,3H).
454 δ3.4(s,3H),3.87(s,3H),7.3-7.6(m,13H).
455 δ3.4 (s,3H), 3.9(s,3H), 7.4-7.6 (m,4H), 8.0(s,lH), 8.3 (s,2H). 462 δ7.65-7.55 (m,2H),7.5-7.45 (m,3H), 7.04 (d,lH), 3.80(s,3H), 3.38
(s,3H). 466 δ3.408 (s,3H), 3.89 (s,3H), 7.4-7.6 (m,3H), 7.7 (d,lH), 7.9 (d,lH). 467 δ8.2 (s,lH), 8.1 (d,lH), 7.6(d,lH), 7.35-7.55 (m,5H), 3.84 (s,3H), 3.40 (s,3H).
468 δ3.35 (s,3H), 3.84 (s,3H), 3.88 (s,3H), 7.0(m,4H),7.2 (m,2H),7.4 (m,2H), 7.71 (dd,2H), 8.03 (s,lH).
469 δ3.38 (s,3H), 3.86(s,3H), 6.68 (d,lH,J=8.5), 6.80 (m,lH), 6.82-6.91 (m,3H), 7.07 (dd,lH,J=l.0,8.2), 7.2(m,lH),7.3-7.5 (m,4H).
470 δ3.40(s,3H), 3.83 (s,3H), 6.66(m,2H), 6.76(m,lH), 7.04 (d,lH,J=8.2), 7.2-7.5 (m,7H).
471 δ3.40(s,3H), 3.83 (s,3H), 6.6(m.lH), 6.65 (m,lH), 6.80(m,lH), 7.00 (m,lH),7.2-7.3 (m,2H),7.35-7.40(m,2H),7.55-7.60(m.lH), 8.19 (d,2H,J=8.2).
472 δ3.38 (s,3H), 3.84(s,3H), 6.7-6.9(m,5H),7.0-7.5 (m,6H).
473 δ2.16 (s,3H),2.29 (s,3H), 3.38 (s,3H), 3.83 (s,3H), 6.6-6.7 (m,3H), 6.76 (m,lH), 6.89 (d,lH,J=7.8), 7.02(m,lH, 7.1 (m,lH), 7.2-7.3 (m,2H), 7.3-7.4 (m,2H).
479 δ7.57 (m,2H), 7.44(m,2H), 7.24(m,2H), 7.05 (d,lH),5.21 (q,2H), 3.89 (s,3H), 3.4 (s,3H),3.02(m,2H),2.15 (s,3H), 1.95 (m,2H), 1.33 (s,6H).
480 δ7.48 (m,4H), 7.27(m,3H), 5.23 (q,2H),3.89(s,3H),3.66(t,2H),3.4 , (s,3H), 3.09(t,2H),2.17 (s,3H),2.06(m,2H).
481 δ7.5 (m,4H),7.2(m,2H),7.03(d,lH),5.26(ABq,2H), 3.46(s,3H),3.01 (m,2H), 2.14 (s,3H), 1.9 (m,2H), 1.32(s,6H).
482 δ7.51 (m,4H), 7.26 (m,3H), 5.22 (dd,2H), 3.65 (t,2H), 3.46(s,3H), 3.08 (t,2H), 2.15 (s,3H), 2.08 (m,2H).
483 δ7.55 (d,lH), 7.45 (m,2H),7.2-7.35 (m,4H), 6.95 (d,lH), 5.25 (m,2H), 4.4(m,2H),3.88 (s,3H), 3.40(s,3H), 2.18 (s,3H).
485 δ7.6-7.45 (m,5H), 3.82(s,3H), 3.38 (s,3H).
490 δ8.35 (s,lH), 8.15(d,lH),7.7-7.4(m,8H),7.36(m,3H),3.78(s,3H),3.37 (s,3H).
492 δ8.15 (s,lH), 8.00(d,lH),7.65-7.30 (m,6H),4.24 (q,2H), 3.76 (s,3H),
3.37 (s,3H), 1.48 (t,3H).
493 δ8.35 (s,lH), 8.15 (d,lH), 7.7-7.4 (m,7H), 7.09 (m,3H), 3.79 (s,3H), 3.38 (s,3H).
494 δ8.65 (d,lH), 8.40(s,lH), 8.20(d,lH), 7.75-7.4 (m,9H), 3.78 (s,3H),
3.38 (s,3H).
495 δ8.25 (s,lH), 8.10 (d,lH), 7.65-7.45 (m,5H), 7.40 (t,lH), 4.9 (m,lH), 4.51 (m,2H), 3.90(m,lH), 3.77 (s,3H), 3.60(m,lH), 3.37 (s,3H), 1.90-1.55 (m,6H). 497 δ 10.09 (s,lH), 8.66 (s.lH), 8.45 (d,lH), 8.0(d,lH), 7.7-7.55 (m,3H) 7.5
(m,2H), 3.80(s,3H), 3.36(s,3H). 499 δ3.38 (s,3H), 3.86(s,3H), 6.75 (s,lH), 6.75-6.83 (m,2H), 6.88
(d,2H,J=1.7), 7.05 (m,2H), 7.09 (t,lH,J=1.7),7.2-7.4 (m,3H).
503 δ3.38 (s,3H), 3.84 (s,3H), 6.7-6.8 (m,3H), 7.04(dd,lH,J=l.l, 8.2), 7.19-7.45 (m,9H).
504 δ3.38(s,3H),3.84(s,3H), 6.70(m,2H),6.75-6.83 (m,4H),7.04 (dd,lH,J=1.0,8.2), 7.2-7.3 (m,3H), 7.35-7.40(m,2H).
505 δ3.38 (s,3H),3.84(s,3H),6.7-6.8(m,3H),6.8-6.9(m,lH),6.9-7.1 (m,3H),7.2-7.3 (m,2H), 7.35-7.40(m,2H).
506 δ3.38(s,3H), 3.83 (s,3H),6.6-6.7 (m,3H), 6.80-7.00(m,4H), 7.20-7.25 (m,2H), 7.30-7.40(m,2H).
508 δ8.9 (s.lH), 8.4 (d,lH),7.65 (d.lH),7.55 (m.lH), 7.49 (m,2H), 6.9
(d,lH),4.82(q,2H), 3.80(s,3H), 3.37 (s,3H). 515 δ7.85 (s,lH),7.8 (d.lH), 7.3-7.6(m,6H), 3.85(s,3H), 3.40(s,3H), 2.49
(s,3H).
526 δ7.57 (m,2H),7.49(m,2H),7.02(d.lH), 6.45 (d,lH),3.80(s,3H), 3.37 (s,3H)
527 δ8.21 (d,2H), 8.1 (d,2H),7.7-7.4(m,9H), 3.77(s,3H),3.37 (s,3H)
528 δ7.7(d,lH),7.6-7.4(m,5H),7.25(m,lH),6.9(dd.lH),6.75 (s,lH),3.80 (s,3H), 3.34(s,3H).
530 δ7.55 (m,2H),7.45 (m,2H), 3.83 (s,3H),3.39 (s,3H), 1.32(s,9H).
531 δ7.75 (d,lH),7.7-7.4 (m,5H),7.3 (m.lH),6.95(dd,lH), 3.77(s,3H), 3.38 (s,3H), 1.00(t,9H),0.76(q,6H).
532 δ7.75 (d,lH),7.65(m,2H),7.6-7.45 (m,3H),7.3 (m,lH),6.9(m,lH), 3.77(s,3H), 3.38 (s,3H), 1.00(s,9H),0.22(s,6H).
533 δ8.1 (d,lH), 8.05(s.lH),7.65-7.55(m,2H),7.5-7.45(m,3H),7.3 (dd.lH),4.88 (s,2H),3.78 (s,3H),3.37(s,3H).
534 δ8.1 (d,lH), 8.0(s,lH),7.65-7.45 (m,5H),7.3(m,lH),6.5 (q,lH),3.78 (s,3H), 3.37 (s,3H), 1.92(d,3H).
535 δ8.1 (d,lH), 8.0(s,lH), 7.65-7.55 (m,2H), 7.5-7.45 (m,3H), 7.3 (m,lH), 7.15 (dd.lH), 5.05 (dd.lH),4.7 (dd.lH), 3.78 (s,3H), 3.37 (s,3H).
536 δ8.05 (d,lH), 7.95 (s,lH), 7.65-7.4(m,5H), 7.15 (dd,lH), 3.77 (s,3H), 3.37(s,3H), 1.37 (s,9H).
537 δ7.95 (d,lH), 7.7-7.3 (m,6H),7.15 (dd,lH),5.28 (s,2H), 3.8 (s,2H), 3.77 (s,3H), 3.38 (s,3H), 0.95 (m,2H), 0.0 (s,9H).
538 δ 8.2 (d.lH), 8.1 (s, lH), 7.65-7.45 (m,5H), 7.35 (dd.lH), 3.80 (s,3H), 3.37 (s,3H).
539 δ 7.64 (d.lH), 7.55 (m,lH), 7.47 (m,3H), 3.80 (s,3H), 3.39 (s,3H).
540 δ 7.54 (m,2H), 7.46 (m,2H), 7.33 (s,lH), 7.24 (m,3H), 4.09 (s,2H), 3.73 (s,3H), 3.39 (s,3H).
541 δ 7.53 (m,2H), 7.46 (m,2H), 7.27 (s,4H), 4.08 (s,2H), 3.73 (s,3H), 3.38 (s,3H).
547 [in C6D6]: δ 8.15 (s,lH), 8.1 (d,lH), 7.15 (m,lH), 7.1 (t,lH), 7.05 (m,lH), 6.9 (dd,lH), 6.8 (m,2H), 3.25 (s,3H), 3.0 (s,3H), 0.15 (s,9H).
548 δ 7.75 (d,lH), 7.7 (s.lH), 7.65 (s.lH), 7.55 (m,lH), 7.5 (m,2H), 7.35 (t,lH), 7.0 (d.lH), 6.15-6.0 (m,lH), 5. 45 (d,lH), 5.3 (d,lH), 4.6 (d,2H), 3.77 (s,3H), 3.37 (s,3H).
549 δ 7.8 (d,lH), 7.75 (s.lH), 7.65 (s,lH), 7.55 (m,lH), 7.5 (m,2H), 7.35 (t,lH), 7.05 (dd,lH), 6.05 (s,lH), 5. 7 (s,lH), 4.7 (s,2H), 3.78 (s,3H), 3.37 (s,3H).
553 δ 7.3-7.5 (m,3H), 7.2 (s,lH), 4.4-4.7 (q,2H), 3.861 (s,3H), 3.6 (q,2H), 3.384 (s,3H).
554 δ 7.65 (s,2H), 7.35-7.6 (m,4H), 7.3 (IH), 7.1 (IH), 3.8 (s,3H), 3.4 (s,3H). 556 δ 8.21 (s.lH), 8.05 (d.lH), 7.65 (d,lH), 7.55 (m,lH), 7.5 (m,3H), 7.4
(m,lH), 6.8 (dd,lH), 5. 85 (d,lH), 5.3 (d.lH), 3.77 (s,3H), 3.37 (s,3H).
562 δ 8.2 (s,lH), 8.1 (d,lH), 7.35-7.65 (m,6H), 3.84 (s,3H), 3.40 (s,3H).
563 [in Me2SO-rf6]: δ 7.75 (d,lH), 7.65 (m,2H), 7.55 (t,lH), 3.80 (s,3H), 3.5 (m,4H), 3.27 (s,3H), 1.15 (m,6H).
564 δ 7.85 (s.lH), 7.75 (d,lH), 7.3-7.6 (m,6H), 3.84 (s,3H), 3.40 (s,3H), 2.9 (m,2H), 1.3 (t,3H).
566 δ 8.82 (d,J=5Hz,lH), 7.95 (s,lH), 7.61 (m,lH), 7.47 (m,3H), 7.25 (m,lH), 5.19 (m,2H), 4.11 (s,3H), 3.90 (s,3H), 3.42 (s,3H).
567 δ 8.14 (d,2H), 7.6 (d,2H), 7.56 (m,2H), 7.49 (m,2H), 3.78 (s,3H), 3.36 (s,3H), 3.19 (s,lH).
568 δ 8.1 1 (d,2H), 7.6 (m,2H), 7.53 (d,2H), 7.48 (m,2H), 3.77 (s,3H), 3.36 (s,3H), 0.26 (s,9H).
569 δ 7.55 (m,2H), 7.46 (m,2H), 3.86 (s,3H), 3.40 (s,3H).
570 δ 7.51 (m,5H), 7.26 (m,3H), 5.23 (q,2H), 3.89 (s,3H), 3.41 (s,3H), 2.48 (s,3H), 2.17 (s,3H).
571 δ 7.55 (d,lH), 7.39 (m,4H), 7.2 (m,lH), 7.08 (IH), 6.99 (d,lH), 4.34 (m,2H), 3.84 (s,3H), 3.42 (s,3H), 2.46 (s,3H).
572 δ 8.25 (m.lH), 8.15 (d.lH), 7.65-7.45 (m,6H), 7.39 (t,lH), 3.78 (s,3H), 3.37 (s,3H).
573 δ 7.65 (d, lH), 7.55 (m,lH), 7.49 (m,4H), 6.85 (m,lH), 5.26 (s,4H), 3.77 (m,7H), 3.39 (s,3H), 1.0 (m,4H), 0.00 (s,18H).
575 δ 7.78 (distorted d.lH), 7.57-7.50 (m,2H), 7.45-7.40 (m,2H), 7.30-7.28 (m,lH), 7.04 (s,lH), 6.83-6.80 (m,lH), 3.95 (apparent d, 3H), 1.28 (s,9H).
576 δ 7.6 (d.lH), 7.45 (m,4H), 7.4 (s,lH), 7.25 (m,2H), 5.0 (m,2H), 3.91 (s,3H), 3.41 (s,3H), 2.24 (s,3H).
577 δ 7.55 (m,2H), 7.5 (m,2H), 7.45 (d,2H), 6.67 (t.lH), 4.43 (q,4H), 3.81 (s,3H), 3.33 (s,3H).
580 δ 7.55 (s,lH), 7.4 (m,4H), 7.2 ( .lH), 6.7 (m,2H), 4.33 (m,2H), 3.86 (s,3H), 3.43 (s,3H), 2.44 (s,3H).
581 δ 7.53 (d,lH), 7.4 (m,2H), 7.2 (m.lH), 7.06 (m,lH), 6.71 (d,2H), 4.32 (q,2H), 3.875 (s,3H), 3.44 (s,3H), 2.46 (s,3H).
589 major component: δ 7.33 (d,lH), 6.95 (d,lH), 5.31 (d,2H), 3.904 (s,3H),
3.42 (s,3H), 2.74 (q,2H), 1.11 (t,3H) plus peaks overlapping with minor component at 7.88 (d), 7.79 (m), 7.61 (d), 7.49 (t); minor component: δ 6.62 (s,lH), 5.22 (d,2H), 3.899 (s,3H), 3.41 (s,3H), 2.45 (s,3H), 2.22 (d,3H) plus peaks overlapping with major component at 7.88 (d), 7.79 (m), 7.61 (d), 7.49 (t).
604 δ 8.69 (m,lH), 7.94 (s.lH), 7.85-7.73 (m,4H), 7.61 (d,lH), 7.59-7.45
(m,2H), 7.38 (dd,lH), 5.50 (AB pattern, 2H), 3.78 (s,3H), 3.35 (s,3H), 2.25 (s,3H).
613 δ 7.70 (s,lH), 7.54 (m,4H), 7.34 (t,lH), 5.11 (s,2H), 3.86 (s,3H), 3.32 (s,3H), 2.14 (s,3H), 0.28 (s,9H).
614 δ 7.86 (s,lH), 7.76 (d,lH), 7.64 (d,lH), 7.59 (d,lH), 7.54 (d,lH), 7.53-7.47 (m,lH), 5.01 (br s,2H), 4.96 (s,2H), 3.89 (s,3H), 3.33 (s,3H).
645 δ 7.65 (d,lH), 7.6 (s,lH), 7.4-7.55 (m,4H), 7.35 (t,lH), 7.25 (d,lH), 5.2
(m,2H), 4.0 (m,lH), 3.43 (s,3H), 2.6 (d,3H), 2.23 (s,3H), 0.24 (s,9H).
649 δ 7.6 (d.lH), 7.4-7.55 (m,5H), 7.35 (m,2H), 5.24 (s,2H), 3.54 (s,3H), 2.15 (s,3H).
650 δ 7.65 (m,2H), 7.55 (s,2H), 7.5 (m,2H), 7.25 ( 1 H), 5.2 (m,2H), 4.1 (m,lH), 3.43 (s,3H), 2.55 (d,3H), 2.24. (s,3H), 0.25 (s,18H).
652 δ 7.2-7.7 (m,8H), 5.3 (d,2H), 3.4 (s,3H), 2.6 (s,6H), 2.2 (s,3H), 0.3 (s,9H).
653 δ7.85 (s,lH),7.75 (d,lH), 7.6(m,2H), 7.45 (m,3H), 7.2(d,lH), 5.2 (m,2H), 3.5 (s,3H), 2.2 (s,3H), 2.0(s,3H).
654 δ7.45 (s,lH), 7.25-7.4 (m,3H), 7.2(d.lH), 3.55 (s,3H), 2.28 (s,3H).
655 δ7.25-7.4 (m,3H), 7.15 (d,lH), 3.5 (s,3H), 2.3 (m,2H), 2.2(s,3H), 1.1 (t,3H).
656 δ8.1 (d,lH), 8.0(s.lH),7.65-7.4 (m,4H),7.3 (m,lH), 3.79 (s,3H),3.36 (s,3H).
658 δ8.03 (s,2H),7.55 (s,2H), 7.5 (s.lH), 7.45 (s,lH), 3.81 (s,3H), 3.35 (s,3H).
659 δ8.61 (s,2H), 7.95 (s,lH),7.56(m,2H),7.5 (m.lH), 3.82(s,3H), 3.35 (s,3H).
661 δ8.25 (d,2H),7.69(d,2H), 7.59 (d,lH), 7.55-7.5 (m,2H), 3.79 (s,3H), 3.35 (s,3H).
663 δ7.55 (d,lH), 7.5 (m,2H), 3.79 (s,3H), 3.40(s,3H), 1.35 (s,9H).
664 δ7.98 (d,2H),7.65 (d,lH),7.53 (d,2H),7.5-7.35 (m,2H), 3.77 (s,3H), 3.30(s,3H).
665 δ8.2(s.lH),7.95 (d.lH),7.65 (d,lH),7.5-7.35 (m,3H), 3.79(s,3H), 3.31 (s,3H).
667 δ8.05 (d,lH),7.95 (s,lH), 7.65 (d.lH),7.5-7.35(m,3H),7.3 (d.lH), 3.77 (s,3H),3.45 (s,3H).
668 δ7.6(dd.lH), 7.5 (m,2H), 3.81 (s,3H), 3.36(s,3H), 1.30(s,9H).
670 δ8.58 (s,2H), 7.95 (s,lH),7.65 (d,lH), 7.5-7.35 (m,2H), 3.80(s,3H), 3.31 (s,3H).
671 δ8.04(d,2H),7.6(dd.lH),7.43 (d,4H),3.75 (s,3H), 3.31 (s,3H), 1.32 (s,9H).
681 δ2.22(s,3H),2.25 (s,3H), 3.39(s,3H), 3.82(s,3H), 6.80-6.90 (m,3H), 6.82 (d,lH,J=8.2), 6.93 (d,lH,J=7.7),7.05-7.10(m,2H), 7.15-7.30 (m,4H).
682 δ2.26(s,3H), 3.39 (s,3H), 3.82(s,3H), 6.65 (m.lH), 6.70(m,2H), 6.84 (d,lH,J=7.5), 7.0-7.1 (m,4H),7.2-7.4 (m,4H).
683 δ2.26(s,3H), 3.39 (s,3H), 3.83 (s,3H),6.6-6.7 (m,3H), 6.84 (d,lH,J=7.4), 7.0-7.15 (m,3H), 7.2-7.3 (m,3H), 7.49 (dd,lH,J=l.7,7.9).
684 δ2.26(s,3H), 3.39 (s,3H), 3.82(s,3H), 6.6-6.7 (m,3H), 6.84 (d,1H,J=7.7), 7.0-7.2(m,5H), 7.25 (m,lH), 7.28 (m,lH).
688 δ2.26 (s,3H), 3.38 (s,3H), 3.84 (s,3H), 6.63 (t,lH,J=2.2), 6.68 (m,2H), 6.83 (d,lH,J=8.0), 6.95-7.10 (m,5H), 7.2 (m,lH), 7.26 (m. lH). 689 δ 2.26 (s,3H), 3.39 (s,3H), 3.81 (s,3H), 6.6-6.7 (m,3H), 6.82 (m, 1 H),
6.95-7.05 (m,3H), 7.1-7.2 (m,2H), 7.28 (m,lH). 692 δ 7.99 (s,2H), 7.50 (m,lH), 7.38 (m,2H), 3.82 (s,3H), 3.38 (s,3H), 2.32
(s,3H). 700 δ 7.35 (d,J=9.0Hz, 1 H), 7.15 (d,J=2.7Hz, 1 H), 6.93 (dd, J=9.0, 2.7 Hz, 1 H),
3.85 (s,3H), 3.78 (s,3H), 3.39 (s,3H), 1.37 s,9H). 707 δ 2.28 (s,3H), 3.36 (s,3H), 3.91 (s,3H), 6.85 (m,lH), 6.9-7.0 (m,2H), 7.25
(m,lH), 7.3-7.4 (m,2H). 726 δ 2.26 (s,3H), 3.39 (s,3H), 3.83 (s,3H), 6.6-6.7 (m,3H), 6.80-6.85 (m,lH),
7.0-7.1 (m,3H), 7.2-7.4 (m,3H), 7.61 (dd,lH,J=l.4,7.8). a lR NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (q)-quartet, ( )-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets, (br)-broad, (br s)-broad singlet, (br m)-broad multiplet, (AB q)-AB pattern quartet. Coupling constants (indicated by J) are in Hertz.
BIOLOGICAL EXAMPLES OF THE INVENTION Test compounds were first dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem® 014 (polyhydric alcohol esters). The resulting test suspensions were then used in Tests A-F. Spraying these 200 ppm test suspensions to the point of run-off on the test plants is the equivalent of a rate of 500 g/ha.
TEST A The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore dust of Erysiphe graminis f. sp. tritici, (the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20°C for 7 days, after which disease ratings were made.
TEST B The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made. TEST C The test suspension was sprayed to the point of run-off on rice seedlings. The following day the seedlings were inoculated with a spore suspension of Pyricularia oryzae (the causal agent of rice blast) and incubated in a saturated atmosphere at 27°C for 24 h, and then moved to a growth chamber at 30°C for 5 days, after which disease ratings were made.
TEST D The test suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.
TEST E The test suspension was sprayed to the point of run-off on grape seedlings. The following day the seedlings were inoculated with a spore suspension of Plasmopara viticola (the causal agent of grape downy mildew) and incubated in a saturated atmosphere at 20°C for 24 h, moved to a growth chamber at 20°C for 6 days, and then incubated in a saturated atmosphere at 20°C for 24 h, after which disease ratings were made. TEST F
The test suspension was sprayed to the point of run-off on cucumber seedlings. The following day the seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of gray mold on many crops) and incubated in a saturated atmosphere at 20°C for 48 h, and moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.
Results for fungicide Tests A-F are given in Table A for compounds of Formulae IA and IB. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls). A dash (-) indicates no test results. ND indicates disease control not determined due to phytotoxicity.
Table A
Cmpd No. Test A 187 100 239 99 263 35
a Compound was tested at 10 ppm (equivalent to 25 g/ha). b Compound was tested at 40 ppm (equivalent to 100 g/ha). c Compound was tested at 2 ppm (equivalent to 5 g/ha). d Compound was tested at 100 ppm (equivalent to 250 g/ha).
Results for arthropodicide Tests G-L are given below for compounds of Formulae I, IA and IB.
TEST G Fall Armyworm Test units, each consisting of a H.I.S. (high impact styrene) tray with 16 cells were prepared. Wet filter paper and approximately 8 cm2 of lima bean leaf was placed into twelve of the cells. A 0.5-cm layer of wheat germ diet was placed into the four remaining cells. Fifteen to twenty third-instar larvae of fall armyworm (Spodoptera frugiperda) were placed into a 230-mL (8-ounce) plastic cup. Solutions of each of the test compounds in 75:25 acetone-distilled water solvent were sprayed into the tray and cup. Spraying was accomplished by passing the tray and cup on a conveyer belt directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.138 kilograms of active ingredient per hectare (about 0.13 pounds per acre) at 207 kPa (30 p.s.i.). The insects were transferred from the 230-mL cup to the H.I.S. tray (one insect per cell). The trays were covered and held at 27°C and 50% relative humidity for 48 hours, after which time readings were taken on the twelve cells with lima bean leaves. The four remaining cells were read at 6-8 days for delayed toxicity. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 313, 329, 404, 493, 538, 543, 546, 672, 673, 674, 677, 678, 679, 680, 688, 699, 701, and 703. TEST H
Southern Corn Rootworm
Test units, each consisting of a 230-mL (8-ounce) plastic cup containing a 6.5-cm2 (1 -square-inch) plug of a wheatgerm diet, were prepared. The test units were sprayed as described in TEST G with individual solutions of the test compounds. After the spray on the cups had dried, five second-instar larvae of the southern corn rootworm (Diabrotica undecimpunctata howardi) were placed into each cup. The cups were held at 27 °C and 50% relative humidity for 48 hours, after which time mortality readings were taken. The same units were read again at 6-8 days for delayed toxicity. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 11*, 207, 304, 313, 341, 345, 403, 404, 413, 442, 443, 445, 451, 479, 500, 506, 514, 515, 537, 542, 546, 550, 179
675, 677, 679, 680, 682, 683, 684, 687, 688, 689, 699, 700, 701, 703, 704, 705, 706,
715, and 717.
* Tested at 0.55 kg/ha.
TEST I Aster Leafhopper
Test units were prepared from a series of 350-mL (12-ounce) cups, each containing oat (Avena sativa) seedlings in a 2.5-cm (1-inch) layer of sterilized soil. The test units were sprayed as described in TEST G with individual solutions of the test compounds. After the oats had dried from the spraying, 10 to 15 adult aster leafhoppers (Mascrosteles fascifrons) were aspirated into each of the cups. The cups were covered with vented lids and held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 345, 672, 679, and 715.
TEST J Contact Test Against Black Bean Aphid
Individual nasturtium leaves were infested with 10 to 15 aphids (all morphs and growth stages of Aphis fabae) and sprayed with their undersides facing up as described in TEST G. The leaves were then set in 0.94-cm (3/8-inch) diameter vials containing 4 mL of sugar solution (approximately 1.4 g per liter) and covered with a clear plastic 29-mL (1 -ounce) cup to prevent escape of the aphids that drop from the leaves. The test units were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 187, 272, 288, 304, 321, 325, 329, 342, 343, 348, 400, 413, 515, 538, 550, 554, 674, 679, and 688. TEST K
Two-Spotted Spider Mite
Pieces of kidney bean leaves, each approximately 6.5 cm2 (1 square inch) in area, that had been infested on the undersides with 25 to 30 adult mites (Tetranychus urticae), were sprayed with their undersides facing up on a hydraulic sprayer with a solution of the test compound in 75:25 acetone-distilled water solvent. Spraying was accomplished by passing the leaves, on a conveyor belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.138 kilograms of active ingredient per hectare (about 0.13 pounds per acre) at 207 kPa (30 p.s.i.). The leaf squares were then placed underside-up on a square of wet cotton in a petri dish and the perimeter of the leaf square was tamped down onto the cotton with forceps so that the mites could not escape onto the untreated leaf surface. The test units were held at 27°C and 50% relative 180 humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 146, 162, 187, 239, 247, 296, 306, 321, 325, 329, 343, 345, 373, 378, 467, 490, 493, 500, 515, 531, 532, 537, 538, 550, 670, 672, 673, 674, 675, 676, 677, 679, 680, 681, 683, 690, 693, 699, 701, 715, and 717.
The same units were held an additional 5 days and read for larvicide/ovicide mortality and/or developmental effects. Of the compounds tested, the following gave activity levels of 80% or higher: 15*, 187, 343, 420, 466, 520, 534, 535, 536, 540, 541, 548, 550, 554, 682, 689, and 693. * Tested at 0.55 kg/ha.
TEST L Larval two-Spotted Spider Mites (Tetranychus urticae)
Solutions of the test compounds were prepared by dissolving in a minimum of acetone and then adding water containing a wetting agent until the concentration of the compound was 50 ppm. Two-week old red kidney bean plants infested with two-spotted spider mites eggs were sprayed to run-off (equivalent to 28 g/ha) with the test solution using a turntable sprayer. Plants were held in a chamber at 25 °C and 50% relative humidity. Of the compounds tested, the following gave larvicide/ovicide activity of 80% or higher seven days after spraying: 187, 466, 670, 674, 675, and 677.
Specific compounds of Formula II which are useful as intermediates for the preparation of the fungicides and arthropodicides of Formula I where Y is oxygen are described in Index Tables N and O. The abbreviation "Ex." stands for "Example" and is followed by a number and step indicating in which example step the intermediate is prepared.
181 INDEX TABLE N
is H or P
.p. (°C) solid* solid*
194-196
175-178
163-165
192-194
*See Index Table O for lR NMR data.
INDEX TABLE O
Cmpd No. *H NMR Data (CDC13 solution unless indicated otherwise)3
733 δ 8.18 (s.lH), 7.11 (t,2H), 6.91 (t,lH), 6.76 (d,lH), 3.56 (s,3H).
734 δ 8.40 (br s.lH), 7.20 (m,2H), 7.03 (d,lH), 6.94 (t,lH), 4.00 (s,3H), 3.48 (s,3H). a *H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (m)-multiplet, (br s)-broad singlet.

Claims

CLAIMS What is claimed is:
1. A method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound selected from Formula I, N-oxides and agriculturally suitable salts thereof,
wherein
E is selected from:
i) 1,2-phenylene optionally substituted with one of R3, R4, or both R3 and
R4;
ii) a naphthalene ring, provided that when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, the naphthalene ring optionally substituted with one of R3, R4, or both R3 and R4; and iii) a ring system selected from 5 to 12-membered monocyclic and fused bicyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each fused bicyclic ring system optionally containing one nonaromatic ring that optionally includes one or two Q as ring members and optionally includes one or two ring members independently selected from C(=O) and S(O)2, provided that G is attached to an aromatic ring, and when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, each aromatic heterocyclic ring system optionally substituted with one of R3, R4, or both R3 and R4;
A is O; S; Ν; ΝR5; or CR14;
G is C or N; provided that when G is C, then A is O, S or NR5 and the floating double bond is attached to G; and when G is N, then A is N or CR14 and the floating double bond is attached to A;
W is O; S; NH; N(C1-C6 alkyl); or NO(C1-C6 alkyl); X is H; OR1; S(O)mR1; halogen; C1-C6 alkyl; C1-C6 haloalkyl; C3-C6 cycloalkyl; cyano; NH2; NHR1; N(C1-C6 alkyl) R1; NH(C1-C6 alkoxy); or
N(C1-C6 alkoxy)R1;
R1 is C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6
alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; or C2-C4 alkoxycarbonyl;
R2 is H; C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-CG haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; C2-C4 alkoxycarbonyl; hydroxy; C1-C2 alkoxy; or acetyloxy;
R3 and R4 are each independently halogen; cyano; nitro; hydroxy; C1-C6 alkyl;
C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C1-C6 alkoxy; C1-C6 haloalkoxy; C2-C6 alkenyloxy; C2-C6 alkynyloxy; C1-C6 alkylthio; C1-C6 alkylsulfinyl; C1-C6 alkylsulfonyl; formyl;
C2-C6 alkylcarbonyl; C2-C6 alkoxycarbonyl; NH2C(O);
(C1-C4 alkyl)NHC(O); (C1-C4 alkyl)2NC(O); Si(R25)3; Ge(R25)3;
(R25)3Si-C≡C-; or phenyl, phenylethynyl, benzoyl, or phenylsulfonyl each substituted with R8 and optionally substituted with one or more R10; or when E is 1,2-phenylene and R3 and R4 are attached to adjacent atoms, R3 and R4 can be taken together as C3-C5 alkylene, C3-C5 haloalkylene, C3-C5 alkenylene or C3-C5 haloalkenylene each optionally substituted with 1-2
C1-C3 alkyl;
R5 is H; C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; or C2-C4 alkoxycarbonyl;
Y is -O-; -S(O)n-; -NR15-; -C(=O)-; -CH(OR15)-; -CHR6-; -CHR6CHR6-;
-CR6=CR6-; -C≡C-; -CHR15O-; -OCHR15-; -CHR15S(O)n-; -S(O)nCHR15-;
-CHR15O-N=C(R7)-; -(R7)C=N-OCH(R15)-; -C(R7)=N-O-; -O-N=C(R7)-;
-CHR15OC(=O)N(R15)-; -CHR15OC(=S)N(R15)-; -CHR15OC(=O)O-;
-CHR15OC(=S)O-; -CHR15OC(=O)S-; -CHR15OC(=S)S-;
-CHR15SC(=O)N(R15)-; -CHR15SC(=S)N(R15)-; -CHR15SC(=O)O-;
-CHR15SC(=S)O-; -CHR15SC(=O)S-; -CHR15SC(=S)S-;
-CHR15SC(=NR15)S-; -CHR15N(R15)C(=O)N(R15)-;
-CHR15O-N(R15)C(=O)N(R15)-; -CHR15O-N(R15)C(=S)N(R15)-;
-CHR15O-N=C(R7)NR15-; -CHR15O-N=C(R7)OCH2-;
-CHR15O-N=C(R7)-N=N-; -CHR15O-N=C(R7)-C(=O)-;
-CHR15O-N=C(R7)-C(=N-A2-Z1)-A1-; -CHR15O-N=C(R7)-C(R7)=N-A2-A3-; -CHR15O-N=C(-C(R7)=N-A2-Z1)-;
-CHR15O-N=C(R7)-CH2O-; -CHR15O-N=C(R7)-CH2S-;
-O-CH2CH2O-N=C(R7)-; -CHR15O-C(R15)=C(R7)-; -CHR15O-C(R7)=N-;
-CHR15S-C(R7)=N-; -C(R7)=N-NR15-; -CH=N-N=C(R7)-;
-CHR15N(R15)-N=C(R7)-; -CHR15N(COCH3)-N=C(R7)-;
-OC(=S)NR15C(=O)-; -CHR6-C(=W1)-A1-; -CHR6CHR6-C(=W1)-A1-;
-CR6=CR6-C(=W1)-A1-; -C≡C-C(=W1)-A1-; -N=CR6-C(=W1)-A1-; or a direct bond; and the directionality of the Y linkage is defined such that the moiety depicted on the left side of the linkage is bonded to E and the moiety on the right side of the linkage is bonded to Z;
Z1 is H or -A3-Z;
W1 is O or S;
A1 is O; S; NR15; or a direct bond;
A2 is O; NR15; or a direct bond;
A3 is -C(=O)-; -S(O)2-; or a direct bond;
each R6 is independently H; 1-2 CH3; C2-C3 alkyl; C1-C3 alkoxy; C3-C6
cycloalkyl; formylamino; C2-C4 alkylcarbonylamino; C2-C4
alkoxycarbonylamino; NH2C(O)NH; (C1-C3 alkyl)NHC(O)NH;
(C1-C3 alkyl)2NC(O)NH; N(C1-C3 alkyl)2; piperidinyl; morpholinyl;
1-2 halogen; cyano; or nitro;
each R7 is independently H; C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy; C1-C6 haloalkoxy; C1-C6 alkylthio; C1-C6 alkylsulfinyl; C1-C6 alkylsulfonyl; C1-C6 haloalkylthio; C1-C6 haloalkylsulfinyl; C1-C6 haloalkylsulfonyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; C2-C4 alkoxycarbonyl; halogen; cyano; nitro; hydroxy; arnino; NH(Cι-C6 alkyl); N(C1-C6 alkyl)2; or morp holinyl; each Z is independently selected from:
i) C1-C10 alkyl, C2-C10 alkenyl, and C2-C10 alkynyl each substituted with R9 and optionally substituted with one or more R10;
ii) C3-C8 cycloalkyl, C3-C6 cycloalkenyl and phenyl each substituted with R9 and optionally substituted with one or more R10;
iii) a ring system selected from 3 to 14-membered monocyclic, fused bicyclic and fused tricyclic nonaromatic heterocyclic ring systems and 5 to
14-membered monocyclic, fused bicyclic and fused tricyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each nonaromatic or aromatic heterocyclic ring system substituted with R9 and optionally substituted with one or more R10;
iv) a multicyclic ring system selected from 8 to 14-membered fused-bicyclic and fused-tricyclic ring systems which are an aromatic carbocyclic ring system, a nonaromatic carbocyclic ring system, or a ring system containing one or two nonaromatic rings that each include one or two Q as ring members and one or two ring members independently selected from C(=O) and S(O)2, and any remaining rings as aromatic carbocyclic rings, each multicyclic ring system substituted with R9 and optionally substituted with one or more R10; and
v) adamantyl substituted with R9 and optionally substituted with one or more
R10;
each Q is independently selected from the group -CHR13-, -NR13-, -O-, and
-S(O)p-;
R8 is H; 1-2 halogen; C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy; C1-C6
haloalkoxy; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C1-C6 alkylthio; C1-C6 haloalkylthio; C1-C6 alkylsulfinyl; C1-C6 alkylsulfonyl; C3-C6 cycloalkyl; C3-C6 alkenyloxy; CO2(C1-C6 alkyl); NH(C1-C6 alkyl);
N(C1-C6 alkyl)2; cyano; nitro; SiR19R20R21; or GeR19R20R21;
R9 is H; 1-2 halogen; C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy; C1-C6
haloalkoxy; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C1-C6 alkylthio; C1-C6 haloalkylthio; C1-C6 alkylsulfinyl; C1-C6 alkylsulfonyl; C3-C6 cycloalkyl; C3-C6 alkenyloxy; CO2(C1-C6 alkyl); NH(C1-C6 alkyl);
N(C1-C6 alkyl)2; -C(R18)=NOR17; cyano; nitro; SF5; SiR22R23R24; or GeR22R23R24; or R9 is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R1 1, R12, or both R11 and R12;
each R10 is independently halogen; C1-C4 alkyl; C1-C4 haloalkyl; C1-C4 alkoxy; nitro; or cyano; or
when R9 and an R10 are attached to adjacent atoms on Z, R9 and said adjacently attached R10 can be taken together as -OCH2O- or -OCH2CH2O-; each CH2 group of said taken together R9 and R10 optionally substituted with 1-2 halogen; or when Y and an R10 are attached to adjacent atoms on Z and Y is
-CHR15O-N=C(R7)-, -O-N=C(R7)-, -O-CH2CH2O-N=C(R7)-,
-CHR15O-C(R15)=C(R7)-, -CH=N-N=C(R7)-, -CHR15N(R15)-N=C(R7)- or
-CHR15N(COCH3)-N=C(R7)-, R7 and said adjacently attached R10 can be taken together as -(CH2)r-J- such that J is attached to Z;
J is -CH2-; -CH2CH2-; -OCH2-; -CH2O-; -SCH2-; -CH2S-; -N(R16)CH2-; or
-CH2N(R16)-; each CH2 group of said J optionally substituted with 1 to 2
CH3;
R11 and R12 are each independently 1-2 halogen; C1-C4 alkyl; C1-C4 haloalkyl;
C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C2-C6 alkoxyalkyl; C2-C6 alkylthioalkyl; C3-C6 alkoxy alkynyl; C7-C 10
tetrahydropyranyloxyalkynyl; benzyloxymethyl; C1-C4 alkoxy; C1-C4 haloalkoxy; C3-C6 alkenyloxy; C3-C6 haloalkenyloxy; C3-C6 alkynyloxy; C3-C6 haloalkynyloxy; C2-C6 alkoxyalkoxy; C5-C9 trialkylsilylalkoxyalkoxy; C2-C6 alkylthioalkoxy; C1-C4 alkylthio; C1-C4 haloalkylthio; C1-C4 alkylsulfinyl; C1-C4 haloalkylsulfinyl; C1-C4 alkylsulfonyl; C1-C4
haloalkylsulfonyl; C3-C6 alkenylthio; C3-C6 haloalkenylthio; C2-C6 alkylthioalkylthio; nitro; cyano; thiocyanato; hydroxy; N(R26)2; SF5;
Si(R25)3; Ge(R25)3; (R25)3Si-C≡C-; OSi(R25)3; OGe(R25)3; C(=O)R26; C(=S)R26; C(=O)OR26 ; C(=S)OR26 ; C(=O)SR26; C(=S)SR26;
C(=O)N(R26)2; C(=S)N(R26)2; OC(=O)R26; OC(=S)R26; SC(=O)R26;
SC(=S)R26; N(R26)C(=O)R26; N(R26)C(=S)R26; OC(=O)OR27;
OC(=O)SR27; OC(=O)N(R26)2; SC(=O)OR27; SC(=O)SR27; S(O)2OR26;
S(O)2N(R26)2; OS(O)2R27; N(R26)S(O)2R27; or phenyl, phenoxy, benzyl, benzyloxy, phenylsulfonyl, phenylethynyl or pyridinylethynyl, each optionally substituted with halogen, C1- C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano;
each R13 is independently H; C1-C6 alkyl; C1-C6 haloalkyl; or phenyl optionally substituted with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano;
R14 is H; halogen; C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl;
C2-C6 alkynyl; C2-C6 haloalkynyl; or C3-C6 cycloalkyl;
each R15 is independently H; C1-C3 alkyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C1-C4 alkyl, C1- C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano; or when Y is -CHR15N(R15)C(=O)N(R15)-, the two R15 attached to nitrogen atoms on said group can be taken together as -(CH2)s-; or
when Y is -CHR15O-N=C(R7)NR15-, R7 and the adjacently attached R15 can be taken together as -CH2-(CH2)s-; -O-(CH2)s-; -S-(CH2)s-; or
-N(C1-C3 alkyl)-(CH2)s-; with the directionality of said linkage defined such that the moiety depicted on the left side of the linkage is bonded to the carbon and the moiety on the right side of the linkage is bonded to the nitrogen;
R16, R17, and R18 are each independently H; C1-C3 alkyl; C3-C6 cycloalkyl; or phenyl optionally substituted with halogen, C1-C4 alkyl, C1-C4 haloalkyl,
C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano;
R19, R20, R21, R22, R23, and R24 are each independently C1-C6 alkyl; C2-C6 alkenyl; Cι-C4 alkoxy; or phenyl;
each R25 is independently C1-C4 alkyl; C1-C4 haloalkyl; C2-C4 alkenyl; C1-C4 alkoxy; or phenyl;
each R26 is independently H; C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano; each R27 is independently C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3~C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C1-C4 alkyl, C1- C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano; m, n and p are each independently 0, 1 or 2;
r is 0 or 1 ; and
s is 2 or 3;
provided that
(i) when E is 1 ,2-phenylene optionally substituted with one of R3, R4, or both R3 and R4; X is OR1, S(O)mR1 or halogen; Y is -O-, -S(O)n-, -NR15-, -C(=O)-,-CH(OR15)-, -CHR6-, -CHR6CHR6-, -CR6=CR6-, -C≡C-,
-CHR15O-, -OCHR15-, -CHR15S(O)n-, -S(O)nCHR15-,
-CHR15O-N=C(R7)-, -(R7)C=N-OCH(R15)-, -C(R7)=N-O-, -O-N=C(R7)-, -CHR15OC(=O)N(R15)- or a direct bond; and R9 is SiR22R23R24 or GeR22R23R24; then Z is other than phenyl or a 5 to 14-membered aromatic heterocyclic ring system each substituted with R9 and optionally substituted with one or more R10; (ii) when E is a naphthalene ring optionally substituted with one of R3, R4, or both R3 and R4; R3 or R4 is Si(R25)3 or Ge(R25)3; and Y is -O-, -S(O)n-, -C(=O)-, -CHR6-, -CHR6CHR6-, -CR6=CR6-, -C≡C-, -OCHR15-, -S(O)nCHR15- or a direct bond; then Z is other than C1-C10 alkyl, C2-C10 alkenyl or C2-C10 alkynyl each substituted with R9 and optionally substituted with one or more R10; and
(iii) when E is a naphthalene ring optionally substituted with one of R3, R4, or both R3 and R4; R3 or R4 is Si(R25)3 or Ge(R25)3; and Y is -S(O)n-, -C(=O)-, -C≡C- or a direct bond; then Z is other than phenyl substituted with R9 and optionally substituted with one or more R10.
2. A compound selected from Formula IA, N-oxides and agriculturally suitable salts thereof,
wherein
E is 1,2-phenylene optionally substituted with one of R3, R4, or both R3 and R4; A is O or Ν;
G is C or Ν; provided that when G is C, then A is O and the floating double bond is attached to G; and when G is Ν, then A is Ν and the floating double bond is attached to A;
W is O;
X is OR1;
R1 is C1-C3 alkyl;
R2 is H or C1-C2 alkyl;
R3 and R4 are each independently halogen; cyano; nitro; C1-C6 alkyl; C1-C6
haloalkyl; C1-C6 alkoxy; or C1-C6 haloalkoxy; C1-C6 alkylsulfonyl; C2-C6 alkylcarbonyl; C2-C6 alkoxycarbonyl; (C1-C4 alkyl)ΝHC(O);
(C1-C4 alkyl)2NC(O); benzoyl; or phenylsulfonyl;
Y is -O-; -S(O)n-; -NR15-; -C(=O)-; -CH(OR15)-; -CH2-; -CH2CH2-; -CH=CH-;
-C≡C-; -CH2O-; -OCH2-; -CH2S(O)n-; -S(O)nCH2-; or a direct bond; and the directionality of the Y linkage is defined such that the moiety depicted on the left side of the linkage is bonded to E and the moiety on the right side of the linkage is bonded to Z;
Z is selected from the group 2-thiazolyl; 1,2,4-oxadiazolyl; 1,3,4-oxadiazolyl;
1,2,4-thiadiazolyl; 1,3,4-thiadiazolyl; and pyrazinyl; each group substituted with R9 and optionally substituted with one or more R10;
R9 is H; halogen; C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy; C1-C6 haloalkoxy;
C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C1-C6 alkylthio; C1-C6 haloalkylthio; C1-C6 alkylsulfinyl; C1-C6 alkylsulfonyl; C3-C6 cycloalkyl;
C3-C6 alkenyloxy; CO2(C1-C6 alkyl); NH(C1-C6 alkyl); N(C1-C6 alkyl)2; -C(R18)=NOR17; cyano; nitro; SF5; SiR22R23R24; or GeR22R23R24; or R9 is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R11, R12, or both R11 and R12; provided that when Z is pyrazinyl, then R9 is other than H or C1-C6 haloalkyl;
each R10 is independently halogen; C1-C4 alkyl; C1-C4 haloalkyl; C1-C4 alkoxy; nitro; or cyano; or
when R9 and an R10 are attached to adjacent atoms on Z, R9 and said adjacently attached R10 can be taken together as -OCH2O- or -OCH2CH2O-; each CH2 group of said taken together R9 and R10 optionally substituted with 1-2 halogen;
R11 and R12 are each independently 1-2 halogen; C1-C4 alkyl; C1-C4 haloalkyl;
C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C2-C6 alkoxyalkyl; C2-C6 alkylthioalkyl; C3-C6 alkoxyalkynyl; C7-C10
tetrahydropyranyloxyalkynyl; benzyloxymethyl; C1-C4 alkoxy; C1-C4 haloalkoxy; C3-C6 alkenyloxy; C3-C6 haloalkenyloxy; C3-C6 alkynyloxy;
C3-C6 haloalkynyloxy; C2-C6 alkoxyalkoxy; C5-C9 trialkylsilylalkoxyalkoxy;
C2-C6 alkylthioalkoxy; C1-C4 alkylthio; C1-C4 haloalkylthio; C1-C4 alkylsulfinyl; C1-C4 haloalkylsulfinyl; C1-C4 alkylsulfonyl; C1-C4
haloalkylsulfonyl; C3-C6 alkenylthio; C3-C6 haloalkenylthio; C2-C6 alkylthioalkylthio; nitro; cyano; thiocyanato; hydroxy; N(R26)2; SF5;
Si(R25)3; Ge(R25)3; (R25)3Si-C≡C-; OSi(R25)3; OGe(R25)3; C(=O)R26;
C(=S)R26; C(=O)OR26; C(=S)OR26; C(=O)SR26; C(=S)SR26;
C(=O)N(R26)2; C(=S)N(R26)2; OC(=O)R26; OC(=S)R26; SC(=O)R26;
SC(=S)R26; N(R26)C(=O)R26; N(R26)C(=S)R26; OC(=O)OR27;
OC(=O)SR27; OC(=O)N(R26)2; SC(=O)OR27; SC(=O)SR27; S(O)2OR26;
S(O)2N(R26)2; OS(O)2R27; N(R26)S(O)2R27; or phenyl, phenoxy, benzyl, benzyloxy, phenylsulfonyl, phenylethynyl or pyridinylethynyl, each optionally substituted with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano;
R15 is H; C1-C3 alkyl; or cyclopropyl;
R17 and R18 are each independently H; C1-C3 alkyl; C3-C6 cycloalkyl; or phenyl optionally substituted with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano;
R22, R23, and R24 are each independently C1-C6 alkyl; C2-C6 alkenyl; C1-C4
alkoxy; or phenyl;
each R25 is independently C1-C4 alkyl; C1-C4 haloalkyl; C2-C4 alkenyl; C1-C4 alkoxy; or phenyl;
each R26 is independently H; C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano; each R27 is independendy C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano; and n is 0, 1 or 2.
3. A compound of Claim 2 wherein:
R1 is methyl;
R2 is methyl;
Y is -O-; -S(O)n-; -NR15-; -C(=O)-; -CH(OR15)-; -CH2-; or a direct bond; and R9 is H; halogen; C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy; C1-C6 haloalkoxy;
C1-C6 alkylthio; C1-C6 haloalkylthio; C1-C6 alkylsulfinyl; C1-C6
alkylsulfonyl; C3-C6 cycloalkyl; CO2(C1-C6 alkyl); -C(R18)=NOR17; cyano; nitro; SF5; SiR22R23R24; or GeR22R23R24; or R9 is phenyl, benzyl, phenoxy, pyridinyl, thienyl, furanyl, or pyrimidinyl each optionally substituted with one of R11, R 12, or both R11 and R12.
4. A compound of Claim 3 wherein:
Z is selected from the group 2-thiazolyl; 1,2,4-oxadiazolyl; 1,2,4-thiadiazolyl; and pyrazinyl; each group substituted with R9 and optionally substituted with R10; and
Y is -O-; and
R9 is phenyl optionally substituted with one of R11, R12, or both R1 - and R12.
5. The compound of Claim 3 which is selected from the group:
4-[2-[[3-[3,5-bis(trifluoromethyl)phenyl]-1,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4- dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one;
4-[2-[[3-[3,5-bis(trifluoromethyl)phenyl]-1,2,4-thiadiazol-5-yl]oxy]-6- methylphenyl]-2,4-dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one;
4-[2-[[3-(1,1-dimethylethyl)-1,2,4-thiadiazol-5-yl]oxy]-6-methylρhenyl]-2,4- dihydro-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one;
4-[2-[[3-(1,1-dimethylethyl)-1,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4-dihydro-5- methoxy-2-methyl-3H-1,2,4-triazol-3-one;
4-[2-[[3-(3,4-dichlorophenyl)-1,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4-dihydro-5- methoxy-2-methyl-3H-1,2,4-triazol-3-one;
2,4-dihydro-5-methoxy-2-methyl-4-[2-[[3-[3-(trifluoromethoxy)phenyl]-1,2,4- thiadiazol-5-yl]oxy]phenyl]-3H-1,2,4-triazol-3-one;
4-[2-[[3-(4-bromophenyl)-1,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4-dihydro-5- methoxy-2-methyl-3H-1,2,4-triazol-3-one;
2,4-dihydro-5-methoxy-2-methyl-4-[2-[[5-methyl-4-[3-(trifluoromethyl)phenyl]-
2-thiazolyl]oxy]phenyl]-3H-1,2,4-triazol-3-one; and
2,4-dihydro-5-methoxy-2-methyl-4-[2-[[6-[4-(trifluoromethyl)phenyl]-2- pyrazinyl]oxy]phenyl]-3H-1,2,4-triazol-3-one.
6. A compound selected from Formula IB, N-oxides and agriculturally suitable salts thereof,
wherein
E is selected from:
i) 1,2-phenylene optionally substituted with one of R3, R4, or both R3 and
R4;
ii) a naphthalene ring, provided that when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, the naphthalene ring optionally substituted with one of R3, R4, or both R3 and R4; and iii) a ring system selected from 5 to 12-membered monocyclic and fused bicyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each fused bicyclic ring system optionally containing one nonaromatic ring that optionally includes one or two Q as ring members and optionally includes one or two ring members independently selected from C(=O) and S(O)2, provided that G is attached to an aromatic ring, and when G and Y are attached to the same ring, then G and Y are attached to adjacent ring members, each aromatic heterocyclic ring system optionally substituted with one of R3, R4, or both R3 and R4;
A is O; S; N; NR5; or CR14;
G is C or N; provided that when G is C, then A is O, S or NR5 and the floating double bond is attached to G; and when G is N, then A is N or CR14 and the floating double bond is attached to A;
W is O; S; NH; N(C1-C6 alkyl); or NO(C1-C6 alkyl);
X is H; OR1; StO^R1; halogen; C1-C6 alkyl; C1-C6 haloalkyl; C3-C6 cycloalkyl; cyano; NH2; NHR1; N(C1-C6 alkyl)R1; NH(C1-C6 alkoxy); or
N(C1-C6 alkoxy)R1;
R1 is C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6
alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; or C2-C4 alkoxycarbonyl;
R2 is H; C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; C2-C4 alkoxycarbonyl; hydroxy; C1 -C2 alkoxy; or acetyloxy;
R3 and R4 are each independently halogen; cyano; nitro; hydroxy; C1-C6 alkyl;
C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C1-C6 alkoxy; C1-C6 haloalkoxy; C2-C6 alkenyloxy; C2-C6 alkynyloxy; C1-C6 alkylthio; C1-C6 alkylsulfinyl; C1-C6 alkylsulfonyl; formyl; C2-C6 alkylcarbonyl; C2-C6 alkoxycarbonyl; NH2C(O);
(C1-C4 alkyl)NHC(O); (C1-C4 alkyl)2NC(O); Si(R25)3; Ge(R25)3;
(R25)3Si-C≡C-; or phenyl, phenylethynyl, benzoyl, or phenylsulfonyl each substituted with R8 and optionally substituted with one or more R10; or when E is 1,2-phenylene and R3 and R4 are attached to adjacent atoms, R3 and R4 can be taken together as C3-C5 alkylene, C3-C5 haloalkylene, C3-C5 alkenylene or C3-C5 haloalkenylene each optionally substituted with 1-2
C1-C3 alkyl;
R5 is H; C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; or C2-C4 alkoxycarbonyl;
Y is -O-; -S(O)n-; -NR15-; -C(=O)-; -CH(OR15)-; -CHR6-; -CHR6CHR6-;
-CR6=CR6-; -C≡C-; -CHR15O-; -OCHR15-; -CHR15S(O)n-; -S(O)nCHR15-;
-CHR15O-N=C(R7)-; -(R7)C=N-OCH(R15)-; -C(R7)=N-O-; -O-N=C(R7)-;
-CHR15OC(=O)N(R15)-; -CHR15OC(=S)N(R15)-; -CHR15OC(=O)O-; -CHR15OC(=S)O-; -CHR15OC(=O)S-; -CHR15OC(=S)S-;
-CHR15SC(=O)N(R15)-; -CHR15SC(=S)N(R15)-; -CHR15SC(=O)O-;
-CHR15SC(=S)O-; -CHR15SC(=O)S-; -CHR15SC(=S)S-;
-CHR15SC(=NR15)S-; -CHR15N(R15)C(=O)N(R15)-;
-CHR15O-N(R15)C(=O)N(R15)-; -CHR15O-N(R15)C(=S)N(R15)-;
-CHR15O-N=C(R7)NR15-; -CHR15O-N=C(R7)OCH2-;
-CHR15O-N=C(R7)-N=N-; -CHR15O-N=C(R7)-C(=O)-;
-CHR15O-N=C(R7)-C(=N-A2-Z1)-A1-;
-CHR15O-N=C(R7)-C(R7)=N-A2-A3-; -CHR15O-N=C(-C(R7)=N-A2-Z1)-;
-CHR15O-N=C(R7)-CH2O-; -CHR15O-N=C(R7)-CH2S-;
-O-CH2CH2O-N=C(R7)-; -CHR15O-C(R15)=C(R7)-; -CHR15O-C(R7)=N-;
-CHR15S-C(R7)=N-; -C(R7)=N-NR15-; -CH=N-N=C(R7)-;
-CHR15N(R15)-N=C(R7)-; -CHR15N(COCH3)-N=C(R7)-;
-OC(=S)NR15C(=O)-; -CHR6-C(=W1)-A1-; -CHR6CHR6-C(=W1)-A1-;
-CR6=CR6-C(=W1)-A1-; -C≡C-C(=W1)-A1-; -N=CR6-C(=W1)-A1-; or a direct bond; and the directionality of the Y linkage is defined such that the moiety depicted on the left side of the linkage is bonded to E and the moiety on the right side of the linkage is bonded to Z;
Z1 is H or -A3-Z;
WMs O or S;
A1 is O; S; NR15; or a direct bond;
A2 is O; NR15; or a direct bond;
A3 is -C(=O)-; -S(O)2-; or a direct bond;
each R6 is independently H; 1-2 CH3; C2-C3 alkyl; C1-C3 alkoxy; C3-C6
cycloalkyl; formylamino; C2-C4 alkylcarbonylamino; C2-C4
alkoxycarbonylamino; NH2C(O)NH; (C1-C3 alkyl)NHC(O)NH; (C1-C3 alkyl)2NC(O)NH; N(C1-C3 alkyl)2; piperidinyl; morp holinyl;
1-2 halogen; cyano; or nitro;
each R7 is independently H; C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy; C1-C6 haloalkoxy; C1-C6 alkylthio; C1-C6 alkylsulfinyl; C1-C6 alkylsulfonyl; C1-C6 haloalkylthio; C1-C6 haloalkylsulfinyl; C1-C6 haloalkylsulfonyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; C2-C4 alkoxycarbonyl; halogen; cyano; nitro; hydroxy; amino; NH(C1-C6 alkyl); N(C1-C6 alkyl)2; or morp holinyl; each Z is independently selected from:
i) C1-C10 alkyl, C2-C10 alkenyl, or C2-C10 alkynyl each substituted with R9 and optionally substituted with one or more R10;
ii) C3-C8 cycloalkyl, C3-C8 cycloalkenyl or phenyl each substituted with R9 and optionally substituted with one or more R10;
iii) a ring system selected from 3 to 14-membered monocyclic, fused bicyclic and fused tricyclic nonaromatic heterocyclic ring systems and 5 to
14-membered monocyclic, fused bicyclic and fused tricyclic aromatic heterocyclic ring systems, each heterocyclic ring system containing 1 to 6 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 4 nitrogens, no more than 2 oxygens, and no more than 2 sulfurs, each nonaromatic or aromatic heterocyclic ring system substituted with R9 and optionally substituted with one or more R10;
iv) a multicyclic ring system selected from 8 to 14-membered fused-bicyclic and fused-tricyclic ring systems which are an aromatic carbocyclic ring system, a nonaromatic carbocyclic ring system, or a ring system containing one or two nonaromatic rings that each include one or two Q as ring members and one or two ring members independently selected from C(=O) and S(O)2, and any remaining rings as aromatic carbocyclic rings, each multicyclic ring system substituted with R9 and optionally substituted with one or more R10; and
v) adamantyl substituted with R9 and optionally substituted with one or more
R10;
each Q is independently selected from the group -CHR13-, -NR13-, -O-, and
-S(O)p-;
R8 is H; 1-2 halogen; C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy; C1-C6
haloalkoxy; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C1-C6 alkylthio; C1-C6 haloalkylthio; C1-C6 alkylsulfinyl; C1-C6 alkylsulfonyl;
C3-C6 cycloalkyl; C3-C6 alkenyloxy; CO2(C1-C6 alkyl); NH(C1-C6 alkyl);
N(C1-C6 alkyl)2; cyano; nitro; SiR19R20R21; or GeR19R20R21;
R9 is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy each substituted with R1 1 and optionally substituted with R12;
each R10 is independently halogen; C1-C4 alkyl; C1-C4 haloalkyl; C1-C4 alkoxy; nitro; or cyano; or
when R9 and an R10 are attached to adjacent atoms on Z, R9 and said adjacently attached R10 can be taken together as -OCH2O- or -OCH2CH2O-; each CH2 group of said taken together R9 and R10 optionally substituted with 1-2 halogen; or
when Y and an R10 are attached to adjacent atoms on Z and Y is
-CHR15O-N=C(R7)-, -O-N=C(R7)-, -O-CH2CH2O-N=C(R7)-,
-CHR15O-C(R15)=C(R7)-, -CH=N-N=C(R7)-, -CHR15N(R15)-N=C(R7)- or
-CHR15N(COCH3)-N=C(R7)-, R7 and said adjacently attached R10 can be taken together as -(CH2)r-J- such that J is attached to Z;
J is -CH2-; -CH2CH2-; -OCH2-; -CH2O-; -SCH2-; -CH2S-; -N(R16)CH2-; or
-CH2N(R16)-; each CH2 group of said J optionally substituted with 1 to 2 CH3;
R11 is C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C2-C6 alkoxyalkyl; C2-C6 alkylthioalkyl; C3-C6 alkoxy alkynyl; C7-C10
tetrahydropyranyloxyalkynyl; benzyloxymethyl; C3-C6 alkenyloxy; C3-C6 haloalkenyloxy; C3-C6 alkynyloxy; C3-C6 haloalkynyloxy; C2-C6
alkoxyalkoxy; C5-C9 trialkylsilylalkoxyalkoxy; C2-C6 alkylthioalkoxy; C1-C4 alkylthio; C1-C4 haloalkylthio; C1-C4 alkylsulfinyl; C1-C4 haloalkylsulfinyl;
C1-C4 alkylsulfonyl; C1-C4 haloalkylsulfonyl; C3-C6 alkenylthio; C3-C6 haloalkenylthio; C2-C6 alkylthioalkylthio; thiocyanato; hydroxy; N(R26)2;
SF5; (R25)3Si-C≡C-; OSi(R25)3; OGe(R25)3; C(=O)R26; C(=S)R26;
C(=O)OR26; C(=S)OR26; C(=O)SR26; C(=S)SR26; C(=O)N(R26)2;
C(=S)N(R26)2; OC(=O)R26; OC(=S)R26; SC(=O)R26; SC(=S)R26;
N(R26)C(=O)R26; N(R26)C(=S)R26; OC(=O)OR27; OC(=O)SR27;
OC(=O)N(R26)2; SC(=O)OR27; SC(=O)SR27; S(O)2OR26; S(O)2N(R26)2;
OS(O)2R27; N(R26)S(O)2R27; or phenyl, phenoxy, benzyl, benzyloxy, phenylsulfonyl, phenylethynyl or pyridinylethynyl, each optionally substituted with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano;
R12 is 1-2 halogen; C1-C4 alkyl; C1-C4 haloalkyl; C2-C6 alkenyl; C2-C6
haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C2-C6 alkoxyalkyl; C2-C6 alkylthioalkyl; C3-C6 alkoxy alkynyl; C7-C10 tetrahydropyranyloxyalkynyl; benzyloxymethyl; C1-C4 alkoxy; C1-C4 haloalkoxy; C3-C6 alkenyloxy;
C3-C6 haloalkenyloxy; C3-C6 alkynyloxy; C3-C6 haloalkynyloxy; C2-C6 alkoxyalkoxy; C5-C9 trialkylsilylalkoxyalkoxy; C2-C6 alkylthioalkoxy; C1-C4 alkylthio; C1-C4 haloalkylthio; C1-C4 alkylsulfinyl; C1-C4 haloalkylsulfinyl; C1-C4 alkylsulfonyl; C1-C4 haloalkylsulfonyl; C3-C6 alkenylthio; C3-C6 haloalkenylthio; C2-C6 alkylthioalkylthio; nitro; cyano; thiocyanato; hydroxy;
N(R26)2; SF5; Si(R25)3; Ge(R25)3; (R25)3Si-C≡C-; OSi(R25)3; OGe(R25)3;
C(=O)R26; C(=S)R26; C(=O)OR26; C(=S)OR26; C(=O)SR26; C(=S)SR26;
C(=O)N(R26)2; C(=S)N(R26)2; OC(=O)R26; OC(=S)R26; SC(=O)R26; SC(=S)R26; N(R26)C(=O)R26; N(R26)C(=S)R26; OC(=O)OR27;
OC(=O)SR27; OC(=O)N(R26)2; SC(=O)OR27; SC(=O)SR27; S(O)2OR26;
S(O)2N(R26)2; OS(O)2R27; N(R26)S(O)2R27; or phenyl, phenoxy, benzyl, benzyloxy, phenylsulfonyl, phenylethynyl or pyridinylethynyl, each optionally substituted with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano;
each R13 is independently H; C1-C6 alkyl; C1-C6 haloalkyl; or phenyl optionally substituted with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano;
R14 is H; halogen; C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl;
C2-C6 alkynyl; C2-C6 haloalkynyl; or C3-C6 cycloalkyl;
each R15 is independently H; C1-C3 alkyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C1-C4 alkyl,
C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano; or when Y is -CHR15N(R15)C(=O)N(R15)-, the two R15 attached to nitrogen atoms on said group can be taken together as -(CH2)s-; or
when Y is -CHR15O-N=C(R7)NR15-, R7 and the adjacently attached R15 can be taken together as -CH2-(CH2)s-; -O-(CH2)s-; -S-(CH2)s-; or
-N(C1-C3 alkyl)-(CH2)s-; with the directionality of said linkage defined such that the moiety depicted on the left side of the linkage is bonded to the carbon and the moiety on the right side of the linkage is bonded to the nitrogen; R16 is H; C1-C3 alkyl; C3-C6 cycloalkyl; or phenyl optionally substituted with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano;
R19, R20, and R21 are each independently C1-C6 alkyl; C2-C6 alkenyl; C1-C4 alkoxy; or phenyl;
each R25 is independently C1-C4 alkyl; C1-C4 haloalkyl; C2-C4 alkenyl; C1-C4 alkoxy; or phenyl;
each R26 is independently H; C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano; each R27 is independently C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; or phenyl or benzyl, each optionally substituted on the phenyl ring with halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, nitro or cyano; m, n and p are each independently 0, 1 or 2;
r is 0 or 1 ; and
s is 2 or 3.
7. A compound of Claim 6 wherein:
E is selected from the group 1,2-phenylene; 1,5-, 1,6-, 1,7-, 1,8-, 2,6-, 2,7-, 1,2-, and 2,3-naphthalenediyl; 1H-pyrrole-1,2-, 2,3- and 3,4-diyl; 2,3- and 3,4-furandiyl; 2,3- and 3,4-thiophenediyl; 1H-pyrazole-1,5-, 3,4- and 4,5-diyl; 1H-imidazole-1,2-, 4,5- and 1,5-diyl; 3,4- and 4,5-isoxazolediyl; 4,5-oxazolediyl; 3,4- and 4,5-isothiazolediyl; 4,5-thiazolediyl;
1H-1,2,3-triazole-1,5- and 4,5-diyl; 2H-1,2,3-triazole-4,5-diyl;
1H-1,2,4-triazole-1,5-diyl; 4H-1,2,4-triazole-3,4-diyl;
1,2,3-oxadiazole-4,5-diyl; 1,2,5-oxadiazole-3,4-diyl;
1,2,3-thiadiazole-4,5-diyl; 1,2,5-thiadiazole-3,4-diyl; 1H-tetrazole-1,5-diyl; 2,3- and 3,4-pyridinediyl; 3,4- and 4,5-pyridazinediyl; 4,5-pyrimidinediyl; 2,3-pyrazinediyl; 1,2,3-triazine-4,5-diyl; 1,2,4-triazine-5,6-diyl;
1H-indole-1,4-, 1,5-, 1,6-, 1,7-, 2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 1,2-, 2,3-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 2,3-, 4,5-, 5,6- and 6,7-benzofurandiyl; benzo[b]thiophene-2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 2,3-, 4,5-, 5,6- and 6,7-diyl; 1H-indazole-1,4-, 1,5-, 1,6-, 1,7-, 3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl;
1H-benzimidazole-1,4-, 1,5-, 1,6-, 1,7-, 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-diyl; 1,2-benzisoxazole-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-benzoxazolediyl; 1,2-benzisothiazole-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-diyl; 2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-benzothiazolediyl; 2,5-, 2,6-, 2,7-, 2,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 2,3-, 3,4-, 5,6-, 6,7- and 7,8-quinolinediyl; 1,5-, 1,6-, 1,7-, 1,8-,
3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 3,4-, 5,6-, 6,7- and
7,8-isoquinolinediyl; 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 3,4-, 5,6-, 6,7- and 7,8-cinnolinediyl; 1,5-, 1,6-, 1,7-, 1,8-, 5,6-, 6,7- and
7,8-phthalazinediyl; 2,5-, 2,6-, 2,7-, 2,8-, 4,5-, 4,6-, 4,7-, 4,8-, 5,6-, 6,7- and 7,8-quinazolinediyl; 2,5-, 2,6-, 2,7-, 2,8-, 2,3-, 5,6-, 6,7- and
7,8-quinoxalinediyl; 1,8,-naphthyridine-2,5-, 2,6-, 2,7-, 3,5-, 3,6-, 4,5-, 2,3- and 3,4-diyl; 2,6-, 2,7-, 4,6-, 4,7-, 6,7-pteridinediyl;
pyrazolo[5,1- b]thiazole-2,6-, 2,7-, 3,6-, 3,7-, 2,3- and 6,7-diyl;
thiazolo[2,3-c]-1,2,4-triazole-2,5-, 2,6-, 5,6-diyl;
2-oxo-1,3-benzodioxole-4,5- and 5,6-diyl; 1,3-dioxo-1H-isoindole-2,4-, 2,5-,
4,5- and 5,6-diyl; 2-oxo-2H-1-benzopyran-3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 5,6-, 6,7- and 7,8-diyl; [1,2,4]triazolo[1,5-α]pyridine-2,5-, 2,6-, 2,7-, 2,8-, 5,6-, 6,7- and 7,8-diyl;
3,4-dihydro-2,4-dioxo-2H-1,3-benzoxazine-3,5-, 3,6-, 3,7-, 3,8-, 5,6-, 6,7- and 7,8-diyl; 2,3-dihydro-2-oxo-3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and
6,7-benzofurandiyl; thieno[3,2- d]thiazole-2,5-, 2,6-, and 5,6-diyl;
5,6,7,8-tetrahydro-2,5-, 2,6-, 2,7-, 2,8-, 3,5-, 3,6-, 3,7-, 3,8-, 4,5-, 4,6-, 4,7-, 4,8-, 2,3- and 3,4-quinolinediyl;
2,3-dihydro-1,1,3-trioxo-1,2-benzisothiazole-2,4-, 2,5-, 2,6-, 2,7-, 4,5-, 5,6- and 6,7-diyl; 1,3-benzodioxole-2,4-, 2,5-, 4,5- and 5,6-diyl; 2,3-dihydro-2,4-,
2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6-, 3,7-, 4,5-, 5,6- and 6,7-benzofurandiyl;
2,3-dihydro-1,4-benzodioxin-2,5-, 2,6-, 2,7-, 2,8-, 5,6- and 6,7-diyl; and 5,6,7,8-tetrahydro-4H-cyclohepta[6]thiophene-2,4-, 2,5-, 2,6-, 2,7-, 2,8-, 3,4-, 3,5-, 3,6-, 3,7-, 3,8-, and 2,3-diyl; each aromatic ring system optionally substituted with one of R3, R4, or both R3 and R4;
W is O;
R1 is C1-C3 alkyl or C1-C3 haloalkyl;
R2 is Η; C1-C6 alkyl; C1-C6 haloalkyl; or C3-C6 cycloalkyl;
R3 and R4 are each independently halogen; cyano; nitro; C1-C6 alkyl; C1-C6
haloalkyl; C1-C6 alkoxy; C1-C6 haloalkoxy; C1-C6 alkylthio; C1-C6 alkylsulfonyl; C2-C6 alkylcarbonyl; C2-C6 alkoxycarbonyl;
(C1-C4 alkyl)NHC(O); (C1-C4 alkyl)2NC(O); benzoyl; or phenylsulfonyl; Y is -O-; -S(O)n-; -NR15-; -C(=O)-; -CH(OR15)-; -CH2-; -CH2CH2-; -CH=CH-;
-C≡C-; -CH2O-; -OCH2-; -CH2S(O)n-; -S(O)nCH2-; -CH2O-N=C(R7)-; -(R7)C=N-OCH(R15)-; -C(R7)=N-O-; or a direct bond;
R7 is H; C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy; C1-C6 alkylthio; C2-C6 alkenyl; C2-C6 alkynyl; C3-C6 cycloalkyl; halogen; or cyano; or
when Y and an R10 are attached to adjacent atoms on Z and Y is
-CH2O-N=C(R7)-, R7 and said adjacently attached R10 can be taken together as -(CH2)r-J- such that J is attached to Z;
Z is selected from the group C1-C10 alkyl; C3-C6 cycloalkyl; phenyl; naphthalenyl; anthracenyl; phenanthrenyl; 1H-pyrrolyl; furanyl; thienyl; lH-pyrazolyl;
1H-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl;
1H-1,2,3-triazolyl; 2H-1,2,3-triazolyl; 1H-1,2,4-triazolyl; 4H-1,2,4-triazolyl; 1,2,3-oxadiazolyl; 1,2,4-oxadiazolyl; 1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl;
1,2,3-thiadiazolyl; 1,2,4-thiadiazolyl; 1,2,5-fhiadiazolyl; 1,3,4-thiadiazolyl;
1H-tetrazolyl; 2H-tetrazolyl; pyridinyl; pyridazinyl; pyrimidinyl; pyrazinyl;
1,3,5-triazinyl; 1,2,4-triazinyl; 1,2,4,5-tetrazinyl; 1H-indolyl; benzofuranyl; benzo[b]thiophenyl; 1H-indazolyl; 1H-benzimidazolyl; benzoxazolyl;
benzothiazolyl; quinolinyl; isoquinolinyl; cinnolinyl; phthalazinyl;
quinazolinyl; quinoxalinyl; 1,8-naphthyridinyl; pteridinyl;
2,3-dihydro- 1H-indenyl; 1,2,3,4-tetrahydronaphthalenyl;
6,7,8,9-tetrahydro-5H-benzocycloheptenyl;
5,6,7,8,9, 10-hexahydrobenzocyclooctenyl; 2,3-dihydro-3-oxobenzofuranyl; 1 ,3-dihydro-1-oxoisobenzofuranyl; 2,3-dihydro-2-oxobenzofuranyl;
3 ,4-dihydro-4-oxo-2H-1-benzopyranyl;
3,4-dihydro-1-oxo-1H-2-benzopyranyl;
3,4-dihydro-3-oxo-1H-2-benzopyranyl;
3,4-dihydro-2-oxo-2H-1-benzopyranyl; 4-oxo-4H-1-benzopyranyl;
2-oxo-2H-1-benzopyranyl; 2,3,4,5-tetrahydro-5-oxo-1-benzoxepinyl;
2,3,4,5-tetrahydro-2-oxo-1-benzoxepinyl ;
2,3-dihydro-1,3-dioxo-1H-isoindolyl;
1,2,3,4-tetrahydro-1,3-dioxoisoquinolinyl;
3,4-dihydro-2,4-dioxo-2H-1,3-benzoxazinyl; 2-oxo-1,3-benzodioxyl;
2,3-dihydro-1,1,3-trioxo-1,2-benzisothiazolyl; 9H-fluorenyl; azulenyl; and thiazolo[2,3-c]-1,2,4-triazolyl; each group substituted with R9 and optionally substituted with one or more R10; and
R15 is H; C1-C3 alkyl; or C3-C6 cycloalkyl.
8. A compound of Claim 7 wherein:
E is selected from the group 1,2-phenylene; 1,6-, 1,7-, 1,2-, and
2,3-naphthalenediyl; 2,3- and 3,4-furandiyl; 2,3- and 3,4-thiophenediyl; 2,3- and 3,4-pyridinediyl; 4,5-pyrimidinediyl; 2,4-, 2,7-, 3,5-, 2,3-, 4,5-, 5,6- and 6,7-benzofurandiyl; and benzo[ b]thiophene-2,4-, 2,7-, 3,5-, 2,3-, 4,5-, 5,6- and 6,7-diyl; each aromatic ring system optionally substituted with one of R3, R4, or both R3 and R4;
Z is selected from the group phenyl; naphthalenyl; 2-thiazolyl; 1,2,4-oxadiazolyl;
1,3,4-oxadiazolyl; 1,2,4-thiadiazolyl; 1,3,4-thiadiazolyl; pyridinyl; and pyrimidinyl; each group substituted with R9 and optionally substituted with one or more R10;
R7 is H; C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy; C1-C6 alkylthio; C2-C6
alkenyl; C2-C6 alkynyl; cyclopropyl; halogen; or cyano; or
when Y and an R10 are attached to adjacent atoms on Z and Y is
-CH2O-N=C(R7)-, R7 and said adjacently attached R10 can be taken together as -(CH2)r-J- such that J is attached to Z;
J is -CH2- or -CH2CH2-; and
r is 1.
9. The compound of Claim 8 which is selected from the group:
4-[2-[[3-(3-ethynylphenyl)-1,2,4-thiadiazol-5-yl]oxy]phenyl]-2,4-dihydro-5- methoxy-2-methyl-3H-1,2,4-triazol-3-one; and
[3-[5-[2-(1,5-dihydro-3-methoxy-1-methyl-5-oxo-4H-1,2,4-triazol-4- yl)phenoxy]-1,2,4-thiadiazol-3-yl]phenyl] trifluoromethanesulfonate.
10. A fungicidal composition comprising a fungicidally effective amount of a compound of any of Claims 2-9 and at least one of a surfactant, a solid diluent or a liquid diluent.
11. An arthropodicidal composition comprising an arthropodicidally effective amount of a compound of any of Claims 2-9 and at least one of a surfactant, a solid diluent or a liquid diluent.
12. 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 seedling, a fungicidally effective amount of a compound of any of Claims 2-9.
13. A compound selected from Formula II,
wherein
E is 1,2-phenylene optionally substituted with one of R3, R4, or both R3 and R4;
A is O; S; N; NR5; or CR14;
G is C or N; provided that when G is C, then A is O, S or NR5 and the floating double bond is attached to G; and when G is N, then A is N or CR14 and the floating double bond is attached to A;
W is O; S; NH; N(C1-C6 alkyl); or NO(C1-C6 alkyl);
X is OR1; S(O)m R1; or halogen;
R1 is C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6
alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; or C2-C4 alkoxycarbonyl;
R2 is H; C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; C2-C4 alkoxycarbonyl; hydroxy; C1-C2 alkoxy; or acetyloxy;
R3 and R4 are each independently halogen; cyano; nitro; hydroxy; C1-C6 alkyl;
C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C1-C6 alkoxy; C1-C6 haloalkoxy; C2-C6 alkenyloxy; C2-C6 alkynyloxy; C1-C6 alkylthio; C1-C6 alkylsulfinyl; C1-C6 alkylsulfonyl; formyl; C2-C6 alkylcarbonyl; C2-C6 alkoxycarbonyl; NH2C(O);
(C1-C4 alkyl)NHC(O); (C1-C4 alkyl)2NC(O); Si(R25)3; Ge(R25)3; (R25)3Si-C≡C-; or phenyl, phenylethynyl, benzoyl, or phenylsulfonyl each substituted with R8 and optionally substituted with one or more R10; or when R3 and R4 are attached to adjacent atoms, R3 and R4 can be taken together as C3-C5 alkylene, C3-C5 haloalkylene, C3-C5 alkenylene or C3-C5 haloalkenylene each optionally substituted with 1-2 C1-C3 alkyl; R5 is H; C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C6 cycloalkyl; C2-C4 alkylcarbonyl; or C2-C4 alkoxycarbonyl; R8 is H; 1-2 halogen; C1-C6 alkyl; C1-C6 haloalkyl; C1-C6 alkoxy; C1-C6 haloalkoxy; C2-C6 alkenyl; C2-C6 haloalkenyl; C2-C6 alkynyl; C1-C6 alkylthio; C1-C6 haloalkylthio; C1-C6 alkylsulfinyl; C1-C6 alkylsulfonyl; C3-C6 cycloalkyl; C3-C6 alkenyloxy; CO2(C1-C6 alkyl); NH(C1-C6 alkyl); N(C1-C6 alkyl)2; cyano; nitro; SiR19R20R21; or GeR19R20R21;
each R10 is independently halogen; C1-C4 alkyl; C1-C4 haloalkyl; C1-C4 alkoxy; nitro; or cyano;
R14 is H; halogen; C1-C6 alkyl; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 haloalkenyl;
C2-C6 alkynyl; C2-C6 haloalkynyl; or C3-C6 cycloalkyl;
R19, R20 and R21 are each independently C1-C6 alkyl; C2-C6 alkenyl; C1-C4
alkoxy; or phenyl;
each R25 is independentiy C1-C4 alkyl; C1-C4 haloalkyl; C2-C4 alkenyl; C1-C4 alkoxy; or phenyl; and
m is 0, 1 or 2.
14. The compound of Claim 13 which is selected from the group:
2,4-dihydro-4-(2-hydroxyphenyl)-5-methoxy-2-methyl-3H-1,2,4-triazol-3-one; 2,4-dihydro-4-(2-hydroxy-6-methylphenyl)-5-methoxy-2-methyl-3H-1,2,4- triazol-3-one;
5-chloro-2,4-dihydro-4-(2-hydroxy-6-methylphenyl)-2-methyl-3H-1,2,4-triazol- 3-one; and
5-chloro-2,4-dihydro-4-(2-hydroxyphenyl)-2-methyl-3H-1,2,4-triazol-3-one.
EP96919422A 1995-06-20 1996-06-13 Arthropodicidal and fungicidal cyclic amides Withdrawn EP0836384A1 (en)

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