EP0836384A1 - Amides cycliques arthropodicides et fongicides - Google Patents

Amides cycliques arthropodicides et fongicides

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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
Authority
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Withdrawn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)
English (en)
Inventor
Richard James Brown
Dominic Ming-Tak Chan
Michael Henry Howard, Jr.
Dilon Jancey Daniel
David Alan Clark
Thomas Paul Selby
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0836384A1 publication Critical patent/EP0836384A1/fr
Withdrawn legal-status Critical Current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.

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Abstract

Cette invention concerne l'utilisation en tant qu'arthropodicides de composés de Formule (I), ainsi que de leurs N-oxides et de leurs sels adaptés à agriculture. Dans cette formule: R est un 1,2-phénylène éventuellement substitué; un cycle de naphtalène éventuellement substitué, ou un système cyclique choisi parmi certains systèmes cycliques hétérocycliques aromatiques monocycliques à 5 à 12 éléments et bicycliques fusionnés, tels que définis par l'invention; A est O; S; N; NR5; G est C ou N; à condition que quand G est C, alors A est O, S ou NR5 et la double liaison flottante est attachée à G; et quand G est N, alors A est N ou CR14 et la double liaison flottante est attachée à A; W est O; S; NH; N(alkyle C¿1?-C6); ou NO(alkyle C1-C6); X est H; OR?1¿; S(O)¿mR?1; halogène; alkyle C¿1?-C6; haloalkyle C1-C6; cycloalkyle C3-C6; cyano; NH2; NHR?1¿; N(alkyle C¿1-C6)R?1; NH(alcoxy C¿1?-C6); ou N(alcoxy C1-C6)R?1; R2¿ est H; alkyle C¿1?-C6; haloalkyle C1-C6; alcényle C2-C6; haloalcényle C2-C6; alcynyle C2-C6; haloalcynyle C2-C6; cycloalkyle C3-C6; alkylcarbonyl C2-C4; alcoxycarbonyle C2-C4; hydroxy; alcoxy C1-C2; or acétyloxy; R?1, R5¿, Y, Z, R14 et m sont tels que définis dans l'invention. L'invention concerne également des composés et des compositions de Formule (IA) tels que définis dans l'invention et leur utilisation comme arthropodicides et fongicides, et des composés et des compositions de Formule (IB) tels que définis dans l'invention et leur emploi comme arthropodicides et fongicides. Elle concerne enfin des composés de Formule (II) tels que définis dans l'invention qui sont utiles comme intermédiaires pour la préparation des arthropodicides et des fongicides de cette invention, où Y représente oxygène et E représente 1,2-phénylène.
EP96919422A 1995-06-20 1996-06-13 Amides cycliques arthropodicides et fongicides Withdrawn EP0836384A1 (fr)

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GB9615831D0 (en) * 1996-07-27 1996-09-11 Agrevo Uk Ltd Fungicides
CN1231663A (zh) * 1996-08-01 1999-10-13 纳幕尔杜邦公司 杀节肢动物剂和杀真菌剂环酰胺
JP2001503424A (ja) * 1996-11-01 2001-03-13 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー 殺菌・殺カビ性の環状アミド類
CZ184599A3 (cs) * 1996-11-26 1999-09-15 E. I. Du Pont De Nemours And Company Methylem substituované fungicidy a artropodicidy
EP1310169A3 (fr) * 1997-01-30 2003-08-27 E.I. Du Pont De Nemours And Company Mélange fongicide
WO1998033382A1 (fr) * 1997-01-30 1998-08-06 E.I. Du Pont De Nemours And Company Melanges fongicides
ZA9711323B (en) * 1997-01-30 1999-06-17 I E Du Pont De Nemours And Com Fungicidal mixtures
AU9206598A (en) * 1997-09-04 1999-03-22 E.I. Du Pont De Nemours And Company Enantiomerically enriched compositions and their pesticidal use
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ZA965196B (en) 1997-12-19
AU6177096A (en) 1997-01-22
HUP9901228A2 (hu) 1999-07-28
JPH11508257A (ja) 1999-07-21
PL324291A1 (en) 1998-05-11
NZ310884A (en) 1999-04-29
BR9609001A (pt) 1999-06-29
CZ394097A3 (cs) 1998-09-16
IL122670A0 (en) 1998-08-16
WO1997000612A1 (fr) 1997-01-09
HUP9901228A3 (en) 2001-11-28
MX9710259A (es) 1998-03-29

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