WO2000053585A1 - Fongicides amide et ester et arthropodicides - Google Patents

Fongicides amide et ester et arthropodicides Download PDF

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Publication number
WO2000053585A1
WO2000053585A1 PCT/US2000/005241 US0005241W WO0053585A1 WO 2000053585 A1 WO2000053585 A1 WO 2000053585A1 US 0005241 W US0005241 W US 0005241W WO 0053585 A1 WO0053585 A1 WO 0053585A1
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compounds
formula
alkyl
optionally substituted
haloalkyl
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PCT/US2000/005241
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English (en)
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King-Mo Sun
Michael Paul Walker
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E.I. Du Pont De Nemours And Company
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Priority to AU32479/00A priority Critical patent/AU3247900A/en
Publication of WO2000053585A1 publication Critical patent/WO2000053585A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/50—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
    • 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
    • A01N43/82—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
    • C07C251/58—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms

Definitions

  • This invention relates to certain fungicides and arthropodicides, 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 consumer.
  • 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 that are more effective, less costly, less toxic, environmentally safer or have different modes of action.
  • strobilurins The evolution of a class of active substances known as strobilurins is reviewed in Sauter, et al. Angew. Chem. Int. Ed. 1999, 38, pp. 1328-1349. Compounds related to these strobilurins, at least with respect to the attachment of two key substituents on adjacent carbon atoms of a phenyl group, are disclosed in PCT International Publication ⁇ os.
  • This invention is directed to compounds of Formula I, including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use as fungicides and arthropodicides:
  • E together with two contiguous carbon atoms, forms a 5- or 6-membered aromatic ring containing carbon atoms and from 0-3 atoms selected from oxygen, nitrogen and sulfur which is substituted with T on one of the contiguous carbon atoms and with Y 1 -Y -Z on the second contiguous carbon atom, and is optionally substituted on E;
  • X is OR 1 , SCO ⁇ R 1 or halogen
  • A is O, S, N, NR 5 or CR 7 ;
  • G is C or N; provided that when G is C, A is O, S or NR 5 and the floating double bond is attached to G; and when G is N, A is N or CR 7 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);
  • the directionality of the Y 1 - Y 2 -Z linkage is defined such that the moiety depicted on the left side of the Y 1 linkage is bonded to the ring having the T substituent and the moiety on the right side of the linkage is bonded to Y 2 ;and the moiety depicted on the left side of the Y 2 linkage is bonded to Y 1 and the moiety on the right side of the linkage is bonded to Z;
  • Z is CpCio alkyl; C-pCjo alkenyl; C ⁇ -C 10 alkynyl; haloalkyl; a phenyl ring; a 5- or 6-membered aromatic heterocyclic ring, each heterocyclic ring containing 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 3 nitrogens, no more than 1 oxygen, and no more than 1 sulfur; a naphthalene ring system or tetrahydronaphthalene ring system; wherein each group is optionally substituted; each R 1 is independently C ⁇ -Cg alkyl, C1-C6 haloalkyl, C2-Cg alkenyl, C 2 -C 6 haloalkenyl, C2-Cg alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl,
  • R 2 and R 6 are each independently H, Cj-Cg alkyl, C j -Cg haloalkyl, C2-Cg alkenyl, C2-C 6 haloalkenyl, C 2 -C 6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, hydroxy, C1-C2 alkoxy or acetyloxy; each R 5 is independently H, C Cg alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl,
  • R 7 is H, halogen or C1-C6 alkyl
  • R 8 , R 18 and R 23 are each independently H or C1-C4 alkyl;
  • R 14 , RI 5 , R 24 and R 25 are each independently H, halogen, C r C 4 alkyl, C r C 4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl or cyano;
  • R 16 , R 17 and R 22 are each independently H, C r C 4 alkyl, C r C 4 haloalkyl, C 2 -C 4 alkenyl, C2-C4 haloalkenyl or C2-C4 alkynyl;
  • R 19 is C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 3 -C 6 alkoxyalkyl, optionally substituted phenyl or optionally substituted phenylmethyl;
  • R 20 is H, C r C 4 alkyl, C C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, or C3-C6 haloalkynyl;
  • R 21 is H, C r C 4 alkyl or C r C 4 alkylthio;
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, «-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers.
  • Alkenyl includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkoxy includes, for example, methoxy, ethoxy, w-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 .
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylsulf ⁇ nyl includes both enantiomers of an alkylsulfinyl group.
  • alkylsulfmyl 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. Examples of
  • alkylsulfonyl include CH 3 S(O) 2 , CH 3 CH 2 S(O) 2 , CH 3 CH 2 CH 2 S(O) 2 , (CH 3 ) 2 CHS(O) 2 and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • alkylcarbonyl include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • aromatic ring denotes fully unsaturated carbocycles and heterocycles in which the ring is aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied for the ring).
  • 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 halogens that are independently selected. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • haloalkynyl examples include HC ⁇ CCHCl, CF 3 C ⁇ C, CC1 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
  • nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides.
  • nitrogen containing heterocycles which can form N-oxides.
  • tertiary amines can form N-oxides.
  • E is a sequence of three or four carbon atoms in an aromatic ring system.
  • the term "optionally substituted” in reference to E refers to an E group that is unsubstituted, or is substituted with at least one non-hydrogen group that does not extinguish the fungicidal or arthropodicidal activity possessed by the analog in which the E sequence is unsubstituted.
  • 1 ,2-phenylene i.e.
  • the optional non-hydrogen group is attached to the sequence of four carbon atoms in the phenylene ring that are not substituted with either T or Y- -Y ⁇ -Z.
  • the optional non-hydrogen group is attached to the three- atom sequence containing the two carbon atoms in the ring that are not substituted with either T or Y- ⁇ Y ⁇ Z.
  • pyridine e.g.
  • the optional non-hydrogen group is attached to the 4-atom sequence containing the three carbon atoms in the ring that are not substituted with either T or Y- ⁇ Y- ⁇ Z.
  • T is T 1 ; compounds where T is T 2 ; compounds where T is T 3 or T 4 ; compounds where T is T 5 or T 6 ; and compounds where T is
  • optionally substituted aromatic rings are those wherein said rings are optionally substituted with R 3 and optionally substituted with R 4 , wherein R 3 and R 4 are each independently halogen or CH 3 .
  • optionally substituted 1,2-phenylene rings optionally substituted with R 3 and optionally substituted with R 4 are illustrated as Formula la in Exhibit 1 A. It is noted that compounds of Formula la are a subset of compounds of
  • R 3 and R 4 groups are shown in Exhibit 1 A and Exhibit IB, it is noted that R 3 and/or R 4 do not need to be present since they are optional substituents.
  • Z is C-J-CJQ alkyl, C Cjo alkenyl, CJ-CJ Q alkynyl, CJ-CJO haloalkyl, a phenyl ring; one of certain 5- or 6-membered aromatic heterocyclic rings, a naphthalene ring system or a tetrahydronaphthalene ring system, wherein each group is optionally substituted.
  • the term "optionally substituted” in connection with these Z groups refers to Z groups that are unsubstituted or have at least one non-hydrogen substituent attached that does not extinguish the fungicidal or arthropodicidal activity possessed by the unsubstituted analog.
  • optionally substituted Z groups are C Cio alkyl, C-pCio alkenyl, CpCio alkynyl, C ⁇ -Cio haloalkyl, phenyl ring, certain 5 or 6-membered aromatic heterocyclic rings, naphthalene ring systems or tetrahydronaphthalene ring systems, each of which is optionally substituted with R 9 and R 10 , wherein
  • R 9 is independently 1-2 halogen, C- ( -C 6 alkyl, C Cg haloalkyl, Cj-Cg alkoxy, Cj-Cg haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl,
  • optionally substituted Z rings wherein said rings are optionally substituted with R 9 and/or R 10 include the rings illustrated in Exhibit 2 as a phenyl ring (Z-30), 5- or 6-membered aromatic heterocyclic rings (Z-l to Z-29), naphthalene rings (Z-31 and Z-32) and tetrahydronaphthalene rings (Z-33 and Z-34).
  • the nitrogen atoms that require substitution to fill their valence are substituted with hydrogen or with R 9 and/or R 10 .
  • R 9 and/or R 10 groups are shown in the structures Z-l to Z-34, it is noted that R 9 and/or R 10 do not need to be present since they are optional substituents. It is also noted that the optional substituents R 9 and/or R 10 may be attached independently to either ring in Z-31 through Z-34.
  • optionally substituted phenyl or optionally substituted phenoxy means a phenyl or phenoxy, each of which is unsubstituted or has at least one non- hydrogen substituent attached that does not extinguish the fungicidal or arthropodicidal activity possessed by the unsubstituted analog.
  • optionally substituted phenyl or optionally substituted phenylmethyl means a phenyl or phenylmethyl, each of which is unsubstituted or has at least one non-hydrogen substituent attached that does not extinguish the fungicidal or arthropodicidal activity possessed by the unsubstituted analog.
  • optionally substituted phenyl, optionally substituted phenoxy and optionally substituted phenylmethyl are phenyl, phenoxy or phenylmethyl, each of which are optionally substituted with R 12 and optionally substituted with one or more R 13 , wherein R 12 is 1-2 halogen, C r C 6 alkyl, C r C 6 haloalkyl, C r C 6 alkoxy, C r C 6 haloalkoxy,
  • R 13 is halogen, C Cg alkyl, Cj-Cg haloalkyl, C j -Cg alkoxy, C J -C 6 haloalkoxy or cyano.
  • R 12 and/or R 13 do not need to be present since they are optional substituents.
  • Cj-C j The total number of carbon atoms in a substituent group is indicated by the "Cj-C j " prefix where i and j are numbers from 1 to 10.
  • C ! -C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH2 and CH 3 CH 2 OCH 2 CH 2 .
  • all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen
  • substituents When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)i_ j , then the number of substituents may be selected from the integers between i and j inclusive.
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s).
  • 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,
  • 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 carboxylic acid or 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 compounds for reasons of better activity and/or ease of synthesis are: Preferred 1.
  • R 3 and R 4 are each independently halogen or CH 3 ; Z is optionally substituted with R 9 and optionally substituted with one or more R 10 ; each R 9 is independently 1-2 halogen, C r C 6 alkyl, C haloalkyl, C j -Cg alkoxy, C Cg haloalkoxy, C 2 -C6 alkenyl, C2-Cg haloalkenyl, C 2 -C6 alkynyl, Cj-Cg alkylthio, Cj-Cg haloalkylthio, C Cg alkylsulfinyl, C Cg alkylsulfonyl, C 3 -C 6 cycloalkyl, phenyl or phenoxy, each phenyl or phenoxy optionally substituted with R 12 and optionally substituted with one or more R 13 ; each R 10 is independently halogen, C Cg alkyl, C j -Cg haloalkyl,
  • X is OR 1 ; A is O or N;
  • G is C or N; provided that when G is C, A is O and the floating double bond is attached to G; and when G is N, A is N and the floating double bond is attached to A;
  • W is O
  • This invention also relates to fungicidal compositions comprising fungicidally effective amounts of the compounds of the invention and at least one other component selected from surfactants, solid diluents and liquid diluents.
  • This invention also relates to arthropodicidal compositions comprising an arthropodicidally effective amount of a compound of this invention and at least one other component selected from surfactants, solid diluents and liquid diluents.
  • the preferred compositions of the present invention are those which comprise the preferred compounds above.
  • 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 the invention (e.g., as a composition described herein).
  • 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 this invention.
  • the preferred methods of use are those involving the preferred compounds above.
  • the compounds of Formula I may be prepared by one or more of the following methods and variations as described in Schemes 1-28.
  • the definitions of E, R 8 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 23 , R 24 , R 25 , T and Z in the compounds of Formulae 1-53 below are as defined above in the Summary of the Invention.
  • Compounds of Formulae Ib-Im are various classes of the compounds of Formula I. Unless otherwise specified, Q 1 to Q 14 are defined as in Exhibit 3.
  • Q 1 is -C(R 16 R 17 )-C(R 14 R 15 )- or -C(R 16 R 17 )-;
  • Q 3 is direct bond, -O-, -S-, -NR 23 - or - C(R 24 R 25 )-;
  • Q 4 is -O- or -NR 18 -;
  • Q ⁇ is •C(R 16 R 17 )-C(R 14 R 15 )- or -C(R 16 R 17 )-
  • Q 3 is direct bond, -O-, -S-, -NR 23 -, or -C(R 24 R 25 )- Q 4 is -0-, or -NR 18 -
  • Hydrazones and oximes of Formula 1 can be prepared by condensing the carbonyl compounds of Formula 3 or 5 with hydrazine or hydroxylamine or its salt respectively in an inert organic solvent (Scheme 2).
  • Scheme 2 See WO95/14009 and EP 596,254 for leading references for the preparation of compounds of Formula 3.
  • the hydroxylamine hydrochloride salt is commonly used with the presence of a base such as pyridine.
  • Ketones of Formula 5 can be prepared from the aldehydes of Formula 3 with the reaction of an alkyl anion to give the corresponding alcohols of Formula 4 followed by an oxidation (for the conversion of compounds of Formula 3 to compounds of Formula 4, see Wardell, J.L.
  • compounds of Formula 5 can be converted to the corresponding irnines of Formula 6 with the use of ammonia or its derivatives and then converted to compounds of Formula 1.
  • Formula 6 For the conversion of compounds of Formula 5 to compounds of Formula 6, see Sollenberger, P.Y., Martin, R.B. in The Chemistry of the Amino Group, Patai, S. Ed., Interscience: New York, 1968; Chapter 7, Reeves, R.L. in The Chemistry of the Carbonyl Group; Patai, S. Ed., Interscience: New York, 1966, Chapter 12.
  • Q 1 is -C(R 16 R 17 )-C(R 14 R 15 )- or -C(R 16 R 17 )-
  • Q 3 is direct bond, -0-, -S-, -NR 23 -, or -C(R 24 R 25 )-
  • Q 7 is -0-, -S-, or -N(R 23 )-
  • Q 8 is direct bond or -C(R 24 R 25 )-
  • Compounds of Formula 8 can then be converted to imidoyl chloride-type compounds of Formula 9 with the use of reagents such as phosphorous pentachloride, oxayl chloride or thionyl chloride, according to standard literature procedures.
  • reagents such as phosphorous pentachloride, oxayl chloride or thionyl chloride
  • Compounds of Formula 10 can be prepared by reacting the imidoyl chloride-type compounds of Formula 9 with nucleophilic species such as compounds of Formula Z-Q 7 -H or carbanions of Formula Z-Q 8( - ) or under Freidel-Craft Reaction conditions with compounds of Formula Z-H.
  • nucleophilic species such as compounds of Formula Z-Q 7 -H or carbanions of Formula Z-Q 8( - ) or under Freidel-Craft Reaction conditions with compounds of Formula Z-H.
  • the hydroxyl group in compounds of Formula 10 can then be deprotected and converted to a leaving group, such as a bromide with the use of PBr 3 or a sulfonate, such as methanesulfonate with the use of methanesulfonyl chloride, in an inert solvent.
  • a leaving group such as a bromide with the use of PBr 3 or a sulfonate, such as methanesulfonate with the use of methanesulfonyl chloride
  • Ketones of Formula 12 with the hydroxyl group protected, can be condensed with compounds of Formula H-Q 5 -H in an inert solvent to provide the compounds of Formula 13, following the chemistry described for the conversion of compounds of Formula 5 to compounds of Formula 1 in Scheme 2.
  • the ketones of Formula 12 can be treated with reagents such as Wittig reagents or alpha-silyl lithium anions to provide compounds of Formula 14 (see Crowell, T.I. in The Chemistry of Alkenes; Patai, S. Ed., Interscience: New York, 1964, Chapter 4; Maercker, A. In Organic Reactions, Cope, A., et, al. Ed., John Wiley and Sons, 1965, Vol.
  • Q 1 is -C(R 16 R 17 )-C(R 14 R 15 )- or -C(R 16 R 17 )-
  • Q 7 is -0-, -S-, or -N(R 23 )-
  • Q 8 is direct bond or -C(R 24 R 25 )-
  • Compounds of Formula lb can also be prepared by condensing the carbonyl compounds of Formula 5 or the corresponding imino compounds of Formula 6 with substituted hydrazines or hydroxylamines (or their salts) of Formula 16 (Scheme 5). The reactions can be conducted with or without the presence of base or acid, in an inert solvent, following the chemistry described for the conversion of the compounds of Formula 5 or 6 to the compounds of Formula 1 in Scheme 2.
  • Q 1 is -C(R 16 R 17 )-C(R 14 R 15 )- or -C(R 16 R 17 )-
  • Q 3 is direct bond, -0-, -S-, -NR 23 -, or -C(R 24 R 25 )-
  • Q 4 is -0-, or -NR 18 -
  • Compounds of Formula 16 can be prepared from compounds of Formula 2 (Scheme 6) by first replacing the leaving group (Lg) of compounds of Formula 2 with a hydroxylamine or its salt or a mono-substituted hydrazine with the NH 2 group protected (compounds of Formula 17) to give compounds of Formula 18.
  • Scheme 6 Scheme 6
  • Compounds of Formula 18 can be converted to compounds of Formula 16 by removing the protective group (Pg) on the nitrogen (see Daudel R. In The Chemistry of the Amino Group; Patai, S. Ed.; Interscience: New York, 1968, Chapter 11).
  • Q 1 is -C(R 16 R 17 )-C(R 14 R 15 )- or -C(R 16 R 17 )-
  • Q 3 is direct bond, -O-, -S-, -NR 23 -, or -C(R 24 R 25 )-
  • Q 4 is -0-, or -NR 18 -
  • Q 1 is -C(R 16 R I7 )-C(R
  • Compounds of Formula 19 can be prepared by coupling substituted oximes or hydrazones of Formula 1 with compounds of Formula 20 (Scheme 8) following the chemistry described in Scheme 1 for the combination of compounds of Formula 1 and 2 to compounds of Formula lb.
  • Q 1 is -C(R 16 R 17 )-C(R 14 R 15 )- or -C(R 16 R 17 )-
  • Q 4 is -0-, or -NR 18 -
  • Q 8 is direct bond or -C(R 24 R 25 )-
  • Q 1 is -C(R 16 R 17 )-C(R 14 R 15 )- or -C(R 16 R 17 )-
  • Q 3 is direct bond, -0-, -S-, -NR 23 -, or -C(R 24 R 25 )-
  • Q 4 is -0-, or-NR 18 -
  • Q 1 is -C(R 16 R 17 )-C(R 14 R 15 )- or -C(R 16 R 17 )-
  • Q 4 is -0-, or -NR 18 -
  • Compounds of Formula 21 can be prepared by combining compounds of Formula 23 and 1 (Scheme 10 above), following the methods described for the preparation of compounds of Formula lb from 1 and 2 in Scheme 1.
  • Compounds of Formula 23 can be prepared from the compounds of Formula 8 by first de-protecting the hydroxyl group and then converting it to a leaving group, such as an alkyl- or aryl-sulfonate or a halide such as a bromide. The reactions can be conducted following the chemistry for the conversion of compounds of Formula 10 to compounds of Formula 11 described in Scheme 3.
  • Q * is -C(R 1W R X ')-C(R"R iJ )- or -C(R'"R")-
  • Compounds of Formula If can also be prepared by condensing compounds of Formula 5 with compounds of Formula 24 or their salts (Scheme 12).
  • the condensations can be conducted with or without the presence of a small amount of acid or base, with or without heating, or with or without the continuous removal of water formed as the byproduct.
  • Q 1 is -C(R 16 R 17 )-C(R 14 R 15 )- or -C(R 16 R 17 )-
  • Q 3 is direct bond, -0-, -S-, -NR 23 -, or -C(R 24 R 25 )-
  • Amines of Formula 24 can be prepared by treating compounds of Formula 2 with ammonia.
  • amines of Formula 24 can be prepared by treating compounds of Formula 2 with a protected form of ammonia to provide compounds of Formula 25 followed by removing the protective group on the nitrogen (Scheme 13).
  • Scheme 13 See Buehler, C.A., Pearson, D.E. Survey of Organic Syntheses, John Wiley and Sons: New York, 1977, Vol 2, Chapter 8; Sandier, S.R.; Karo, W. Organic Functional Group Preparations Academic: New York, 1983; Vol. 1 Chapter 13).
  • Q 1 is -C(R 16 R 17 )-C(R 14 R 15 )- or -C(R 16 R 17 )-
  • Q 3 is direct bond, -0-, -S-, -NR 23 -, or -C(R 24 R 25 )-
  • Q 1 is -C(R 16 R 17 )-C(R 14 R 15 )- or -C(R 16 R 17 )-
  • Q 8 is direct bond or -C(R 24 R 25 )-
  • Forma lg (Scheme 14) can be prepared by first reacting compounds of Formula 6 with compounds of Formula 20, to provide compounds of Formula 26, similar to the conditions described for the reaction between compounds of Formula 6 and compounds of Formula 2 to provide compounds of Formula If in Scheme 11. Compounds of Formula 26 can then be converted to compounds of Formula lg according to the procedure for the conversion of Formula 19 to Formula Ic or Formula Id described in Scheme 7.
  • Q 1 is -C(R 16 R 17 )-C(R 14 R 15 )- or -C(R 16 R 17 )-
  • Compounds of Formula 27 can be prepared from compounds of Formula 6 and Formula 23 according to the procedure described to prepare compounds of Formula If from compounds of Formula 6 and Formula 2 described in Scheme 11. Another method to prepare compounds of Formula 27 is to react compounds of Formula 6 or Formula 5 with compounds of Formula 31 according to the procedure described to prepare compounds of Formula If from compounds of Formula 5 and Formula 24 in Scheme 12.
  • Compounds of Formula 31 can be prepared from carboxylic acids of Formula 29 by first reaction with H-Q 5 -H, following the procedure described for the preparation of compounds of Formula 8 from compounds of Formula 7 in Scheme 3, followed by deprotecting the amino group. (See Wolman, Y. The Chemistry of the Amino Group, Patai, S. Ed., Interscience: New York, 1968, Chapter 11).
  • Compounds ofFormula 32 then can be condensed with carbonyl compounds ofFormula 33 to provide compounds of Formula Ii according to literature procedures (see Hunig, S., Herrmann, H. Liebigs Ann. Chem. 1960, 636; Overberger, C.G., Gainer, H. J., Am. Chem. Soc, 1958, 80, 6703).
  • Q3 is direct bond, -0-, -S-, -NR23-, or -C(R24R25)-
  • Carbonyl compounds ofFormula 33 can be obtained by oxidizing alcohols ofFormula 38 (Scheme 18) following chemistry described for the oxidation of compounds of Formula 4 to compounds ofFormula 5 in Scheme 2.
  • Alcohols of Formula 38 can in turn be obtained by de-protecting the hydroxyl group of compounds ofFormula 35 and Formula 37 (see Green, T.W. Protective Groups in Organic Chemistry, 2 nd ed.; Wiley: New York, 1991).
  • Compounds ofFormula 35 can be obtained from compounds ofFormula 34, following the chemistry described for the preparation of compounds ofFormula 10 from compounds of Formula 7 via compounds ofFormula 8 and Formula 9 in Scheme 3.
  • compounds ofFormula 37 can be prepared from compounds ofFormula 36 following the chemistry described for the preparation of compounds ofFormula 14 from compounds ofFormula 12 in Scheme 4.
  • Q 3 is direct bond, -0-, -S-, -NR 23 -, or -C(R 24 R 25 )-
  • Q 8 is direct bond or -C(R 24 R 25 )-
  • Q 10 is direct bond or -C(R 14 R 15 )-
  • compounds ofFormula Ii can be prepared by first condensing carbonyl compounds ofFormula 33 with hydrazine to give hydrazones ofFormula 39 (Scheme 19). Hydrazones ofFormula 39 can then be further condensed with compounds ofFormula 5 to provide compounds ofFormula Ii, following the chemistry described to prepare compounds ofFormula Ii from compounds ofFormula 32 and Formula 33 in Scheme 17.
  • Q 3 is direct bond, -0-, -S-, -NR 23 -, or -C(R 24 R 25 )-
  • Q 10 is direct bond or -C(R 14 R 15 )-
  • Compounds ofFormula 40 can be prepared from compounds ofFormula 42 according to the chemistry described for the preparation of compounds ofFormula 9 from compounds ofFormula 8 in Scheme 3.
  • Compounds ofFormula 42 in turn can be prepared by condensing compounds ofFormula 32 with compounds ofFormula 41, following the procedure described for the conversion of compounds ofFormula 32 and Formula 33 to compounds ofFormula I in Scheme 16.
  • Q 10 is direct bond or -C(R 14 R 15 )-
  • Compounds ofFormula 41 can be prepared as described in Scheme 22, starting from carboxylic acids with a protected hydroxyl group of Formula 43.
  • Compounds of Formula 43 first can be converted to compounds ofFormula 44, following the chemistry described for the conversion of compounds ofFormula 7 to Formula 8 in Scheme 3. Then the hydroxyl group in compounds ofFormula 44 can be de-protected to provide alcohols ofFormula 45 which can be oxidized to compounds ofFormula 41 following the chemistry described for the conversion of compounds ofFormula 38 to compounds ofFormula 33 in Scheme 18.
  • Scheme 22
  • Q 10 is direct bond or -C(R 14 R 15 )-
  • Q 1 is -C(R 16 R 17 )-C(R 14 R 15 )- or -C(R 16 R 17 )-
  • Q 3 is direct bond, -O-, -S-, -NR 23 -, or -C(R 24 R 25 )-
  • Compounds ofFormula 46 can be prepared by first acylating anilines ofFormula 47 (Scheme 24), using an acylating reagent such as an acyl chloride in the presence of a base such as pyridine in an inert solvent to provide anilides ofFormula 48 (Beckwith, A.L.J. in The Chemistry of Amides; Zabicky, J. Ed. Interscience: New York, 1970 Chapter 2).
  • Anilides ofFormula 48 then can be converted to compounds ofFormula 46 with the use of a reagent such as phosphorous pentachloride, oxayl chloride, or thionyl chloride (Sandier, S.R. Karo, W. Organic Functional Group Preparations Academic: New York, 1983 Chapter 11).
  • Q 1 is -C(R 16 R 17 )-C(R 14 R 15 )- or -C(R 16 R 17 )-
  • Q 3 is direct bond, -0-, -S-, -NR 23 -, or -C(R 24 R 25 )-
  • Compounds ofFormula 49 can be obtained by reacting substituted hydroxylamines of Formula 50 (Scheme 27) with compounds ofFormula 2 wherein Q 1 is Q 12 (Formula 2a) to provide compounds ofFormula 51 followed by the deprotection of the hydroxyl group.
  • Scheme 27 See Sandier, S.R., Karo, W. Organic Functional Group Preparations, Academic: New York, 1972; Vol. 3, Chapter 10).
  • Q 3 is direct bond, -0-, -S-, -NR 23 -, or -C(R 24 R 25 )-
  • Q 12 is -C(R 16 R 17 )-
  • Compounds ofFormula 47 can be prepared as described in Scheme 28 above.
  • Compounds ofFormula 5 or Formula 6, described in Scheme 2 can be converted to compounds ofFormula 47 by following general literature procedures (McCarty, C.G. in The Chemistry of the Caron-Nitrogen Double Bond, Patai, S. Ed., Interscience: New York, 1970; Chapter 9; Hauser, C.R.; Hoffenberg, D.S. J. Am. Chem. Soc, 1955, 77, 5742; Huntress, E.H.; Walter, CH. J. Am. Chem. Soc, 1948, 70, 3523; Elango, V. U.S. Patent 5,235,090).
  • compounds ofFormula 47 could be prepared from compounds ofFormula 3 via carboxylic acids ofFormula 53.
  • For the conversion of compounds ofFormula 53 to compounds of 47 see Pearson, D.E.; Carter, K.N.; Greer, CM. J. Am. Chem. Soc, 1953, 75, 5905. Neville, C.F.; et. al. J. Chem. Soc, Perkin Trans 1, 1991, 259).
  • Example 1 Step A Preparation of 2-[2-(4-fluorophenylV 1 -methyl-2-oxoethoxyl- lH-isoindole- 13(2H)- dione
  • l-(4-fluoro-phenyl)-propan-l-one 10.0 g, 66.2 mmol
  • carbon tetrachloride 300 mL
  • bromine 10.6 g, 66.2 mmol
  • the reaction went from deep orange to colorless over 3 h.
  • the carbon tetrachloride was removed under reduced pressure to provide the crude 2-bromo-l-(4-fluoro-phenyl)-propan-l-one.
  • Step B Preparation of 2-aminoxy-l-(4-fluorophenyl)-propan-l-one O-methyloxime
  • pyridine 5 mL
  • methanol 70 mL
  • 2-[2-(4- fluorophenyl)-l-methyl-2-oxoethoxy]-lH-isoindole-l,3(2H)-dione 3.0 g, 9.6 mmol.
  • the reaction was stirred for 36 h, followed by removal of the methanol under reduced pressure.
  • Step C Preparation of 2-(l,5-dihvdro-3-metho ⁇ y-l-methyl-5-oxo-4H-1.2,4-triazol-4-yl)-3- methylbenzaldehvde 1 -rO-r2-(4-fluo henylV2-(methoxyimino)- 1 - methylethyll oximel
  • 2-aminooxy-l-(4-fluoro-phenyl)-propan-l-one O-methyl-oxime (0.4 g, 1.9 mmol) in pyridine (5 mL) at room temperature was added 2- (1 ,5-dihydro-3-methoxy- 1 -methyl-5-oxo-4H- 1 ,2,4-triazol-4-yl)-3-methylbenzaldehyde (0.5 g, 2.0 mmol).
  • the reaction was stirred for 18 h, then partitioned between water and diethyl ether.
  • the combined organic extracts were further washed with water, then dried over anhydrous magnesium sulfate and the diethyl ether was removed under reduced pressure to give a crude oil.
  • the crude oil was purified by column chromatography (silica gel, ethyl acetate/hexanes mixture) to provide 0.7 g of the title compound as a white solid melting at 128-130 °C NMR showed that the title compound thus obtained was a mixture of four compounds (2 pairs of diastereomeric enatiomers) in about equal amount.
  • Step B Preparation of l-(4-fluorophenyl)-1.2-propanedione l-CO-methyloxime)
  • Step C Preparation of l-(4-fluorophenyl-l,2-propanedione 2-hvdrazone 1-CO-methyloxime
  • l-(4-fluorophenyl)-l,2-propanedione l-(O-methyloxime) 3.4 g, 17.4 mmol
  • hydrazine 0.7 g, 21.8 mmol
  • the reaction was partitioned between brine and ethyl acetate.
  • the combined organic extracts were dried over anhydrous magnesium sulfate and the ethyl acetate was removed under reduced pressure to provide a crude solid.
  • Step D Preparation of 1 -( ⁇ -fluorophenyl)- 1 ,2-propanedione 2-IT2-( 1.5-dihvdrvo-3- methoxy- 1 -methyl-5-oxo-4H- 1.2.4-triazol-4-yl)-3- methylphenyllmethylenelhvdrazone 1 -CO-methyloxime)
  • 1 -(4-fluorophenyl- 1 ,2-propanedione 2-hydrazone 1 -(O- methyloxime) 0.8 g, 3.6 mmol
  • 2-(l,5- dihydro-3-methoxy-l-methyl-5-oxo-4H-l,2,4-triazol-4-yl)-3-methylbenzaldehyde 0.9 g, 3.6 mmol).
  • the reaction was heated to 78 °C for 10 min, then cooled to room temperature and allowed to stir for an additional 18 h.
  • the ethanol was removed under reduced pressure, the residue was partitioned between water and ethyl acetate.
  • the combined organic extracts were dried over anhydrous magnesium sulfate and the ethyl acetate was removed under reduced pressure to give a crude oil.
  • CH 3 T is T 2 ;
  • R 1 is CH 3 ;
  • s is 1;
  • R 5 is CH 3 ;
  • T is T 4 ;
  • R 1 is CH3;
  • R 3 is 6-Me;
  • R 5 is CH3;
  • R 6 is
  • T is T 6 ;
  • R 1 is CH 3 ;
  • s is 1;
  • R 5 is CH 3 ;
  • R 6 is H;
  • T is T 8 ;
  • T is T 3 ;
  • R 1 is CH3;
  • R3 is 6-Me;
  • R 5 is CH3;
  • T is T 4 ;
  • R 1 is CH3;
  • R3 is 6-Me;
  • R 5 is CH3;
  • R 6 is H;
  • T is T 6 ;
  • R 1 is CH3;
  • R 5 is CH3;
  • T is T 8 ;
  • R 1 is CH 3 ;
  • s is 1;
  • T is T 2 ;
  • R 1 is CH3; s is 1;
  • R 5 is CH3;
  • PhO(CH 2 ) 3 PhCH CHCH 2 PhC ⁇ CCH 2 (c- ⁇ ropyl)CH 2
  • T is T 3 ;
  • R 1 is CH3;
  • R3 is 6-Me;
  • R 5 is CH3;
  • T is T 6 ;
  • R 1 is CH3; s is 1;
  • R 6 is H;
  • R 5 is CH 3 ;
  • T is T 7 ;
  • R 1 is CH3;
  • s is 1;
  • T is T 8 ;
  • R 1 is CH 3 ;
  • s is 1;
  • T is T 2 ;
  • R 1 is CH3; s is 1;
  • R 5 is CH3;
  • T is T 5 ;
  • R 5 is CH3;
  • PhO(CH 2 ) 3 PhCH CHCH 2 PhC ⁇ CCH 2 (c- ⁇ ropyl)CH
  • T is T 6 ;
  • R 1 is CH3; s is 1;
  • R 6 is H;
  • R 5 is CH3;
  • T is T 7 ;
  • R 1 is CH 3 ;
  • s is 1;
  • T T 8 ;
  • R 1 is CH3; s is 1;
  • PhCH CHCH 2 PhC ⁇ CCH 2 (c-propyl)CH 2
  • Tables 6 through 10 are the same as Tables 1 through 5, respectively, except that the structure at the head of Tables 6 through 10 is E-2 (see Exhibit IB) and the three-atom E sequence is unsubstituted.
  • 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 emulsifiable 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 that add up to 100 percent by weight. Weight Percent
  • Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Borland 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, NN-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, NN-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, rung, 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 tettahydrofurfuryl alcohol.
  • Solutions 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.
  • Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
  • Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • Compound 1 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 1 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.
  • 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 fuligine
  • 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.
  • insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorfenapyr, chlorpyrifos, chlorpyrifos-methyl, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flucythrinate, tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene
  • insecticides such as abamectin, acep
  • 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.
  • 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.
  • the following TESTS demonstrate the control efficacy of compounds of this invention on specific pathogens. The pathogen control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-B for compound descriptions.
  • the oxime is in the E configuration unless otherwise specified. See Index Table C for l U NMR data.
  • - ⁇ NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (q)-quartet, (m)-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets, (br s)-broad singlet.
  • bThe oximes in Y and Y ⁇ of these samples are of E configuration unless otherwise specified. *The sample was a mixture of two pairs of diastereomeric enantiomers in approximately equal amounts and the J H NMR spectrum consisted of two sets of signals, one set for each of the enantiomeric pairs. **The sample was a mixture of two pairs of diastereomeric enantiomers. fThe sample was a pair of enantiomers.
  • 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 the following tests. 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 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.
  • 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.
  • Phytophthora infestans the causal agent of potato and tomato late blight
  • 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.
  • Plasmopara viticola the causal agent of grape downy mildew
  • 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 oiBotrytis 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.
  • a spore suspension oiBotrytis cinerea the causal agent of gray mold on many crops
  • Results for Tests A-F are given in Table A.
  • 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.
  • a # indicates significant activity.
  • a * indicates tested at 10 ppm.
  • a ** indicates tested at 2 ppm.

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  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne des composés de formule T-E-Y1-Y2-Z et leurs N-oxydes et sels agricolement acceptables utiles comme fongicides et acaricides dans laquelle E, pris ensemble avec deux atomes de carbone adjacents, forme certains cycles aromatiques substitués par T sur un des atomes de carbone adjacents et par Y1-Y2-Z sur le second atome de carbone adjacent, et est éventuellement substitué sur E; Y1 désigne -C(R8)=NO-C(R?16R17), -C(R8¿)=NO-C(R?16R17)-C(R14R15¿)-, -C(R?8)=N-C(R16R17¿)-, -C(R?8)=N-C(R16R17)-C(R14R15¿)-, -C(R?8)=N-N(R18)-C(R16R17¿)-, -C(R?8)=N-N(R18)-C(R16R17)-C(R14R15¿)-, -C(R8)=N-N=C(R21)-, -C(R8)=N-N=C(R?21)-C(R14R15¿)-, -N=C(R?21)-O-C(R16R17¿)-, -N=C(R?21)-O-C(R16R17)-C(R14R15¿)-, -N=C(R?21)-N(R18)-C(R16R17¿)-, -N=C(R?21)-N(R18)-C(R16R17) -C(R14R15¿)-, or -N=C(R?21)-ON(R18)-C(R16R17)-; Y2¿ is -C(=N-O-R19)-, -C(=N-R19)-, -C(=N-N(R19R20))-, -C(=N-N=C(R19R20))-, -C(=C(R?22)-O-R19¿)-, -C(=C(R23R19))-, -C(=N-O-R19)-O-, -C(=N-R19)-O-, -C(=N-N(R19R20))-O-, -C(=N-N=C(R19R20))-O-, -C(=N-O-R?19)-C(R24R25¿)-, -C(=N-R?19)-C(R24R25¿)-, -C(=N-N(R?19R20))-C(R24R25¿)-, -C(=N-N=C(R?19R20))-C(R24R25¿)-, -C(=C(R?22)-O-R19)-C(R24R25¿)-, -C(=C(R?23R19))-C(R24R25¿)-, -C(=N-O-R?19)-N(R23¿)-, -C(=N-R?19)-N(R23¿)-, -C(=N-N(R?19R20))-N(R23¿)-, -C(=N-N=C(R?19R20))-N(R23¿)-, -C(=N-O-R19)-S-, -C(=N-R19)-S-, -C(=N-N(R19R20))-S-, ou -C(=N-N=C(R19R20))-S-, et la directionalité de Y1-Y2-Z est définie de telle sorte que le fragment représenté sur le côté gauche de la liaison Y1 soit lié au cycle ayant le substituant T et que le fragment représenté sur le côté droit de la liaison soit lié à Y2; et que le fragment représenté sur le côté gauche de la liaison Y2 soit lié à Y1 et que le fragment sur le côté droit de la liaison soit lié à Z; et T, R?8, R16, R17, R14, R15, R18, R21, R19, R20, R22, R23, R24, R25¿ et Z sont tels que définis dans le descriptif. L'invention concerne aussi des compositions contenant ces composés, un procédé de contrôle des arthropodes nécessitant la mise en contact des arthropodes ou de leur environnement avec une quantité efficace de ces composés et un procédé permettant de lutter contre les maladies chez les plantes causées par des pathogènes de plantes fongiques nécessitant l'application d'une quantité efficace de ces composés.
PCT/US2000/005241 1999-03-06 2000-03-01 Fongicides amide et ester et arthropodicides WO2000053585A1 (fr)

Priority Applications (1)

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AU32479/00A AU3247900A (en) 1999-03-06 2000-03-01 Amide and ester fungicides and arthropodicides

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US12312099P 1999-03-06 1999-03-06
US60/123,120 1999-03-06

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AU (1) AU3247900A (fr)
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US6372787B1 (en) * 1998-03-27 2002-04-16 Bayer Aktiengesellschaft Phenyl-methoxyimino-glyoxylic acid derivatives as pesticides
US6436981B1 (en) * 1998-07-23 2002-08-20 Bayer Aktiengesellschaft Dihydrotriazolone derivatives as pesticides
CN103734139A (zh) * 2013-12-28 2014-04-23 上海艳紫化工科技有限公司 井冈霉素和己唑醇复配的农药悬浮剂
WO2018055133A1 (fr) * 2016-09-23 2018-03-29 Syngenta Participations Ag Dérivés de tétrazolone microbiocides
CN110037063A (zh) * 2019-04-12 2019-07-23 浙江禾本科技有限公司 一种用于花生褐斑病的药物组合物及其制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6372787B1 (en) * 1998-03-27 2002-04-16 Bayer Aktiengesellschaft Phenyl-methoxyimino-glyoxylic acid derivatives as pesticides
US6436981B1 (en) * 1998-07-23 2002-08-20 Bayer Aktiengesellschaft Dihydrotriazolone derivatives as pesticides
CN103734139A (zh) * 2013-12-28 2014-04-23 上海艳紫化工科技有限公司 井冈霉素和己唑醇复配的农药悬浮剂
CN103734139B (zh) * 2013-12-28 2016-02-17 上海艳紫化工科技有限公司 井冈霉素和己唑醇复配的农药悬浮剂
WO2018055133A1 (fr) * 2016-09-23 2018-03-29 Syngenta Participations Ag Dérivés de tétrazolone microbiocides
CN110037063A (zh) * 2019-04-12 2019-07-23 浙江禾本科技有限公司 一种用于花生褐斑病的药物组合物及其制备方法

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