EP0869963A1 - Arthropodizide und fungizide organosilane und organogermane - Google Patents

Arthropodizide und fungizide organosilane und organogermane

Info

Publication number
EP0869963A1
EP0869963A1 EP95940809A EP95940809A EP0869963A1 EP 0869963 A1 EP0869963 A1 EP 0869963A1 EP 95940809 A EP95940809 A EP 95940809A EP 95940809 A EP95940809 A EP 95940809A EP 0869963 A1 EP0869963 A1 EP 0869963A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
formula
compounds
compound
haloalkyl
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.)
Ceased
Application number
EP95940809A
Other languages
English (en)
French (fr)
Inventor
Richard James Brown
John Powell Daub
Joseph Eugene Drumm, Iii
Deborah Ann Frasier
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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0869963A1 publication Critical patent/EP0869963A1/de
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/30—Germanium compounds
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring

Definitions

  • This invention relates to certain (hetero)arylsilanes and (hetero)arylgermanes, their N-oxides, agriculturally-suitable salts and compositions, and methods of their use as fungicides and arthropodicides.
  • EP-A-398,692 discloses amides of Formula i as fungicides for crop protection.
  • Compounds of Formula i are:
  • R 1 and R 2 are each hydrogen, lower alkyl, or lower cycloalkyl;
  • R 3 is lower alkyl, or lower cycloalkyl;
  • A is, inter alia, a phenyl group or a heterocyclic group optionally substituted with not more than three substituents chosen from, among others, lower alkyl- substituted silyl; and
  • CA 2,032,045 discloses compounds of Formula ii as fungicides for crop protection.
  • Compounds of Formula ii are:
  • R 1 is aryl or heteroaryl; and
  • R 4 and R 5 are, inter alia, aryl or heteroaryl; and each aryl and heteroaryl group can have one or more substituents selected from, among others, WO 93/08183 discloses compounds of Formula iii as fungicides for crop protection.
  • Compounds of Formula iii are:
  • X is N or CH
  • Rj is C ] -C 4 alkyl
  • R 2 and R 3 are, among others, independently C 1 -C 4 alkyl, halo-C ] -C 4 alkyl, C] -C 4 alkoxy, unsubstituted or substituted aryl or heteroaryl group; and each substituted aryl and heteroaryl group is substituted by one, two or three substituents selected from, among others, trimethylsilyl.
  • EP-A-596,692 discloses processes to compounds of Formula iv useful as fungicides for crop protection.
  • Compounds of Formula iv are:
  • A is, inter alia, a phenyl group or a heterocyclic group optionally substituted with substituents chosen from, among others, lower alkylsilyl;
  • R 1 and R 2 are independently H or lower alkyl.
  • the (hetero)arylsilanes and (hetero)arylgermanes of this invention are not disclosed in these documents.
  • 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:
  • A is O; S; N; NR 5 ; or CR 14 ;
  • 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 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 ; S O ⁇ - j R 1 ; or halogen; R 1 and R 5 are each independently H; C j -C 6 alkyl; C j -C 6 haloalkyl; C 2 -C 6 alkenyl;
  • 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 -C,5 haloalkynyl; C 3 -Cg cycloalkyl; C -C 4 alkylcarbonyl; C 2 -C 4 alkoxycarbonyl; hydroxy; Cj-C 2 alkoxy; or acetyloxy; R 3 and R 4 are each independently H; halogen; cyano; nitro; hydroxy; Cj-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 j -Cg alkoxy; C ] -Cg haloalkoxy; C 2 -C 6 alkenyloxy; C 2 -C 6 alkynyloxy; C Cg alkylthio; C j -Cg alkylsulfinyl; Ci-C alkylsulfonyl; fo ⁇ nyl;
  • R 13 3 Si-CsC-; or phenyl, phenylethynyl, benzoyl, or phenylsulfonyl each substituted with R 9 and R 10 ;
  • R 6 is independently H or C1-C 3 alkyl
  • R 7 is H
  • R 3 , Y, and Z are taken together with the phenyl ring to form a naphthalene moiety substituted on either ring with R 8 and on either ring with R 4 ;
  • 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 8 is SiR 19 R 20 R 21 or GeR 19 R2°R 21 ;
  • R 9 is H; 1-2 halogen; C r C 6 alkyl; C C 6 haloalkyl; C r C 6 alkoxy; C r C 6 haloalkoxy; C -Cg alkenyl; C 2 -Cg haloalkenyl; C 2 -C 6 alkynyl; C j -Cg alkylthio; C r C 6 haloalkylthio; C C 6 alkylsulfinyl; C r C 6 alkylsulfonyl;
  • R 10 is H; halogen; C C alkyl; C r C 4 haloalkyl; C j -C 4 alkoxy; nitro; or cyano; or R 1 J and R 12 are each independently H; halogen; C r C 4 alkyl; C j -C 4 haloalkyl;
  • R 13 is independently C]-C 4 alkyl;
  • R 14 is H; halogen; C r C 6 alkyl; C,-C 6 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 haloalkenyl;
  • R 15 , R 16 , R 17 , and R 18 are each independently H; C r C 3 alkyl; or phenyl optionally substituted with halogen, C r C 4 alkyl, C r C haloalkyl, C r C 4 alkoxy, C]-C 4 haloalkoxy, nitro or cyano;
  • R 8 is GeRl 9 R ⁇ R I.
  • 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, i-propyl, or the different butyl, pentyl or hexyl isomers.
  • 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 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, ⁇ -propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • alkenyloxy includes HOCCH 2 O, CH 3 CECCH 2 O and CH 3 CeCCH 2 CH 2 O.
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group. For example, 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 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.
  • aromatic heterocyclic ring system includes fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic.
  • 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.
  • 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 .
  • haloalkynyl examples include HOCCHC1, CF 3 OC, CCl 3 C ⁇ C and FCH 2 OCCH 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 include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
  • C C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl.
  • alkylcarbonyl include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • 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 fo ⁇ n.
  • 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.
  • R 1 , R 2 , and R 5 are each independently H; C j -Cg alkyl; C 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 2 -C alkoxycarbonyl.
  • preferred alkyl groups include C j -C 3 alkyl; preferred haloalkyl groups include C j -C haloalkyl; preferred alkenyl groups include allyl; preferred haloalkenyl groups include haloallyl; preferred alkynyl groups include propargyl; preferred haloalkynyl groups include halopropargyl; and preferred cycloalkyl groups include cyclopropyl.
  • W is O or S
  • R 3 and R 4 are each independently H, halogen, cyano, nitro, C Cg alkyl, C r Cg haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C r C 6 alkoxy, C r C 6 haloalkoxy, C 2 -Cg alkenyloxy, C -Cg alkynyloxy, or phenyl substituted with R 9 and R 10 ; embodiments where R 9 is other than SF 5 ; and embodiments where R 19 , R 20 , R 21 , R 22 , R 23 , and R 24 are each independently Cj-Cg alkyl, Cj-C 4 alkoxy, or phenyl.
  • Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1.
  • R 7 is H; Cj-Cg alkyl; C j -Cg haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 alkynyl; C 3 -Cg cycloalkyl; or cyano;
  • Z is phenyl substituted with R 8 , R 9 , and R 10 ; or Z is
  • R 3 , Y, and Z are taken together with the phenyl ring to form a naphthalene moiety substituted on either ring with R 8 and with a floating R 4 ;
  • R 9 is H; 1-2 halogen; C j -Cg alkyl; C j -C 6 haloalkyl; Cj-C 6 alkoxy; Cj-C 6 haloalkoxy; C j -C 6 alkylthio; C 3 -C 6 cycloalkyl; CO 2 (Cj-C 6 alkyl);
  • R 9 is phenyl, phenoxy, pyridinyl, pyridinyloxy, pyrimidinyl, or pyrimidinyloxy each optionally substituted with R 1 i and R 12 ; and R 25 is H; C j -Cg alkyl; C j -Cg haloalkyl; or phenyl optionally substituted with halogen, C j -C 4 alkyl, C j -C 4 haloalkyl, C ] -C 4 alkoxy, Cj-C 4 haloalkoxy, nitro or cyano.
  • Preferred 2 Compounds of Preferred 1 wherein:
  • Z is phenyl substituted with R 8 , R 9 , and R 10 ; or Z is Z-l to Z-21, each substituted with R 8 and optionally substituted with one of R 9 , R 10 , or both R 9 , and R 10 ; or Y and Z are taken together to fonn
  • J is -CH 2 - or -CH 2 CH 2 -; p is 0; and r is 1.
  • R 7 is H; C j -C 3 alkyl; or Cj-C 3 haloalkyl;
  • Z is phenyl substituted with R 8 , R 9 , and R 10 ; or Z is Z-16, Z-18, or Z-l, each substituted with R 8 and optionally substituted with one of R 9 .
  • G is N
  • Preferred 7 Compounds of Preferreds 2 through 6 wherein: R 1 is methyl; R 2 is methyl; and
  • Z is phenyl substituted with R 8 , R 9 , and R 10 .
  • Most preferred are compounds of Preferred 3 selected from the group:
  • This invention also relates to fungicidal compositions comprising fungicidally effective amounts of the compounds of Formula I 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 I 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.
  • 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 I (e.g., as a composition described herein).
  • a fungicidally effective amount of the compounds of Formula I e.g., as a composition described herein.
  • the preferred methods of use are those involving the above preferred compounds.
  • This invention also relates to arthropodicidal compositions comprising arthropodicidally effective amounts of the compounds of Formula I and at least one of a surfactant, a solid diluent or a liquid diluent.
  • a surfactant e.g., a surfactant for removing arthropodicidally effective amounts of the compounds of Formula I.
  • the preferred compositions of the present invention are those which comprise the above preferred compounds.
  • 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 I (e.g., as a composition described herein).
  • the preferred methods of use are those involving the above preferred compounds.
  • the compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-30.
  • the definitions of E, A, G, W, X, Y, Z, J, Ri-R 24 , m, n, p, r, s and q in the compounds of Formulae l-44d below are as defined above in the Summary of the Invention.
  • a compound of Formula I wherein E is E 1 and R 2 is H may exist as tautomer la or lb, or both la and lb.
  • 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-butan
  • a protic cosolvent such as methanol.
  • 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. H ⁇ nig, Synth. Commun., (1990), 20, 203).
  • a trialkyloxonium tetrafluoroborate e.g., Meerwein's salt
  • the use of trialkyloxonium salts as powerful alkylating agents is well known in the art (see U. Sch ⁇ llkopf, U. Groth, C. Deng, Angew. Chem., Int. Ed. Engl., (1981), 20, 798).
  • Appropriate bases include alkali metal alkoxides such as potassium t -butoxide, inorganic bases such as sodium hydride and potassium carbonate, pyridine, or tertiary amines such as triethylamine, l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and triethylenediamine.
  • alkali metal alkoxides such as potassium t -butoxide
  • inorganic bases such as sodium hydride and potassium carbonate
  • pyridine or tertiary amines such as triethylamine, l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and triethylenediamine.
  • Formula 5 with an ambident nucleophile of Formula 6 (Scheme 2).
  • the nucleophiles of Formula 6 are N-substituted hydroxylamines (HO- ⁇ HR 2 ) and substituted hydrazines (H ⁇ (R 5 )- ⁇ HR 2 ). Examples of such nucleophiles arc N-methylhydroxylamine and methylhydrazine.
  • the preparation of the malonate esters of Formula 5 can be prepared by methods described hereinafter.
  • Compounds of Formula laa can be prepared by reaction of nitrile esters of Formula 5b with ambident nucleophiles of Formula 6. See M. Scobie and G. Tennant, J. Chem. Soc, Chem. Comm., (1994), 2451. Alkylation of laa with alkyl halides in the presence of base provides compounds of Formula lab. Alternatively, treatment of laa with alkylamines or alkoxyamines provides compounds of Formula lab. la
  • T 0(C,-C 4 alkyl), Q, 1-i ⁇ idazolyl
  • W N(C j -Cg alkyl) or NO(C j -C alkyl)
  • Esters of Formula 5a can be prepared from copper (I)-catalyzed reaction of malonate esters of Formula 7 with substituted iodobenzenes of Formula 8 according to methods adapted from A. Osuka, T. Kobayashi and H. Suzuki, Synthesis , (1983), 67, and illustrated in Scheme 3.
  • Scheme 3
  • R C j -C alkyl
  • malonate esters of Formula 5a can be prepared by treating phenyl 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 and sodium hydride (Scheme 4).
  • a suitable base such as, but not limited to, sodium metal and sodium hydride (Scheme 4).
  • Nitrile esters of Formula 5b can be prepared similarly from compounds of Formula 10.
  • R Cj-C4 alkyl base
  • R C j -C 4 alkyl
  • Esters of Formula 9 can be prepared from acid-catalyzed alcoholysis of phenyl acetonitriles of Formula 10 or by estenfication of phenyl acetic acids of Formula 1 1 as illustrated in Scheme 5 (see Org. Synth., Coll. Vol. I, (1941), 270).
  • R C j -C 4 alkyl
  • Phenyl acetic acid esters of Formula 9a can also be prepared by copper (I)-catalyzed condensation of phenyl halides of Formula 12 with compounds of Fo ⁇ nula 13 as described in EP-A-307,103 and illustrated below in Scheme 6.
  • Scheme s
  • 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 Cj-C4 alkyl
  • 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 is illustrated in Scheme 8. Esters of Formula 9e can be used to O 96/17851
  • the leaving group Lg 1 in the amides of Formula 17 is 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 dimethylfor amide or dimethyl sulfoxide.
  • Lg 1 ⁇ Br, -SO2Q, or-OSO-jC;
  • Q Cj-Cg alkyl or Cj-Cg haloalkyl
  • compounds of Formula lb can be treated with an alkylsulfonyl halide or haloalkylsulfonyl anhydride, such as methane sulfonyl chloride, /Moluenesulfonyl 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 77 ⁇ e Chemistry ofSulphones and Sulphoxides; Patai, S. et al., Eds.; Wiley: New York, 1988).
  • Suitable oxidizing reagents include mer ⁇ -chloro-peroxybenzoic acid, hydrogen peroxide and Oxone® (KHSO 5 ).
  • R 27 alkyl
  • the diacyl compound of Formula 19 is treated with excess of a thionyl halide such as 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. Ta ⁇ aga, 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 Fo ⁇ nula H 2 NNR 2 R 27 in an inert solvent such as tetrahydrofuran affords the hydrazide.
  • Ketene dithioacetals of Formula 22a or 22b can be prepared by condensing phenyl acetic acid esters of Formula 9 or amides of Formula 9a, respectively, with carbon disulfide in the presence of a suitable base, followed by reaction with two equivalents of an R -halide, such as iodomethane orpropargyl bromide (Scheme 15). Conversion of 22b to 22c can be accomplished by reaction with trialkyl tetrafluoroborates.
  • 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 te rt-butoxide, inorganic bases such as sodium hydride and potassium carbonate, pyridine, or tertiary amines such as triethylamine, l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or triethylenediamine.
  • 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 aniline of Formula 25 with phosgene, thiophosgene, NN'-carbonyldiimidazole, or N.N'-thiocarbonyld ⁇ midazole 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.
  • Fo ⁇ nula lb compounds can be prepared by reaction of Formula 26 iso(thio)cyanates or Formula 26a carbodiimides with Formula 28a esters. As described above, base may be added to accelerate the reaction and subsequent cyclization to Formula lb compounds. Carbodiimides 26a can be prepared as shown in Scheme 18, starting with compounds of Formula 26.
  • the (thio)ureas or amidines of Formula 27 can be prepared by either of the methods illustrated in Scheme 19.
  • an iso(thio)cyanate of Formula 26 or carbodiimide of Formula 26a can be condensed with an amine of Formula R 2 -NH 2 to form the urea or amidine.
  • the anilines 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 Chemistry; 3rd ed., John Wiley: New York, (1985), pp 944, 1166.
  • Scheme 20 see Bull. Soc. Chim. Belg., (1978), 87, 229; and Tetrahedron Lett., (1983), 24, 3815).
  • Reaction of compounds of Formula lea with an alkyl halide in the presence of base provides compounds of Formula Ieb, which can be reacted with compounds of Formula Q 5 NH 2 and then alkylated with R 2 -(Br, Cl, or I) to provide compounds of Formula Iec.
  • the appropriate alcohol or thiol is treated with a base, for example sodium hydride, to form the corresponding alkoxide or thioalkoxide which acts as the nucleophile.
  • Benzyl halides of Formula 29 can be prepared by radical halogenation of the co ⁇ esponding alkyl compound (i.e., H instead of halogen in Fo ⁇ nula 29), or by acidic cleavage of the corresponding methyl ether (i.e., OMe instead of halogen in Formula 29).
  • the olefins of Formula Ig can be converted to the saturated compounds of Formula Hi by hydrogenation over a metal catalyst such palladium on carbon as is well-known in the art (Rylander, Catalytic Hydrogenation in Organic Synthesis; Academic: New York, 1979).
  • Formula Ii alkynes can be prepared by halogenation/dehalogenation of Formula Ig olefins using procedures well-known in the art (March, J.
  • Formula Ii alkynes can b prepared by well-known reaction of aromatic 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 Fo ⁇ nula Ig can also be prepared by reversing the reactivity of the reactants in the Wittig or Horner-Emmons condensation.
  • 2-alkylphenyl derivatives of Formula 31 can be converted into the corresponding dibromo-compounds of Formula 33 as illustrated in Scheme 23 (see Synthesis, (1988), 330).
  • the dibromo- compounds can be hydrolyzed to the carbonyl compounds of Formula 34, which in tum can be condensed with a phosphorus-containing nucleophile of Formula 35 or 36 to afford the olefins of Formula Ig.
  • Carbamates of Formula Ik can be prepared by reacting benzyl alcohols of Formula 38 with isocyanates of Formula 39 (Scheme 25). A base such as triethylamine can be added to catalyze the reaction.
  • Silicon- or germanium-containing compounds can be prepared using methods well- known in the art. (For leading references on the art of preparing silyl- and germyl- substituted compounds, see The Organic Compounds of Germanium, Michel Lesabre, Pierre Mazerolles, and Jacques Satg ⁇ , Dietmar Seyferth, ed., John Wiley & Sons, NY; C. Eaborn and K. C. Pande, J. Chem. Soc. (I960) 3200-3203; M. Wieber and
  • a second method is deprotonation of compounds of Formula 40b using a strong base such as a lithioamide or an organolithium reagent, followed by treatment with a silyl- or germyl-halide of Formula 42.
  • a strong base such as a lithioamide or an organolithium reagent
  • these methods may require protection and deprotection sequences for certain V moieties which may be incompatible with the reagents. See the preparation of Intermediate 1 in the Examples for an example of a protection-deprotection strategy.
  • One skilled in the art would also recognize that, in some cases, additional synthetic steps after the introduction of R 8 would be necessary to prepare a particular V group as it is depicted in any individual scheme. See the preparation of Intermediate 2 in the Examples for an example of this strategy.
  • R 28 Cj- alkyl or Si (Cj- alkyl) 3
  • Formula 41 which would be coupled to another moiety to provide a third molecule which could be elaborated further to provide compounds of Formula I.
  • R 8 can be introduced as a substituent on a reagent of Formula 41 which can be elaborated further to provide the compounds of this invention or their precursors.
  • Scheme 29 A more specific illustration of the strategy for introduction of R 8 into compounds of Formula I is shown in Scheme 29 (see below). This Scheme illustrates an example of preparation of Z-OH in Scheme 21 followed by coupling to give compounds of the invention. Finally, R 8 can be introduced as the final step in which compounds of Formula I are prepared from compounds of Formula 42a or b (see Scheme 28).
  • R 2 ' OH, 0(C j -C2 alkyl) or 00(0) R 3
  • Step B The title compound of Step B (31.5 g) was added to a solution of HCl in methanol (prepared by adding 20 mL of acetyl chloride slowly to 200 rnL of methanol). The mixture was heated to 60°C for 1.5 h. The solvent was removed in vacuo. The residue was taken up in 100 mL of diethyl ether and sti ⁇ ed at room temperature for 30 min. The ether was decanted off and the solid was taken up in 100 mL of tetrahydrofuran and heated to ⁇ 50°C.
  • Step D Methvl 2-rrrri-f3- ftrimethylsilynphenvnethvlidenelaminoloxylmethvnbenzeneacetate l-[3-(Trimethylsilyl)phenyl]ethanone (Intermediate 1, 1.15 g) and the title compound of Step C (1.39 g) were dissolved in 40 mL of pyridine. The solution was heated to 90°C for 6 h, then cooled to room temperature overnight.
  • Step F 5-Methoxy-2-methyl-4-r2-rrr ⁇ -r3- ftrimethvlsilvnphenvnethvlidene1amino1oxy1methvnphenvn-3(2H -isoxazolone N-methylhydroxylamine hydrochloride (1.43 g) was dissolved in 25 mL of methanol. A solution of 1.92 g of potassium hydroxide dissolved in 25 mL of methanol was added while cooling the reaction mixture with an ice bath. After 15 minutes, the precipitated potassium chloride was removed by filtration. To the filtrate was added a solution of 2.8 g of the title compound of Step E in 10 mL of methanol. The resulting mixture was stirred at room temperature overnight.
  • Step B 5-Chloro 2.4-dihvdro-2-methyl- -(2-methylphenvn-3H-1.2.4-triazol-3-one
  • Step C 2.4-Dihvdro-5-methoxy-2-methyl- -f2-methylphenvn-3H- 1.2.4-triazol-3-one 8.25 g of the title compound of Step B was dissolved in 80 mL of 1: 1 dimethoxyethane/methanol under nitrogen. 14.0 mL of sodium methoxide (30% solution in methanol) was added and the solution was heated at reflux for 3 h.
  • Step D 4-r2-(Bromomethyl ) phenvn-2.4-dihvdro-5-methoxy-2-methyl-3H- 1.2.4-triazol-
  • N-bromosuccinimide (6.53 g) followed by a catalytic amount of benzoyl peroxide.
  • the solution was heated at reflux for 2 h.
  • Another 1.63 g of N-bromosuccinimide and a catalytic amount of benzoyl peroxide were added and the solution was heated at reflux for an hour.
  • methylene chloride was added and the organic layer was washed successively with water, 0.1 ⁇ sodium thiosulfate solution, and then saturated aqueous NaCl.
  • Step E 2.4-Dihvdro-5-methoxv-2-methvl-4-r2-rrrri-r3- ftrimethvlsilvl)ohenvnethvlidene1aminoloxvlmethvnphenvn-3H-1.2.4-triazol-3- one To a suspension of 5.22 g of l-[3-(trimethylsilyl)phenyl]ethanone oxime
  • Step B 2- ⁇ ( Aminooxy ) methyl1- ⁇ -fmethoxyiminoVN-methyl-benzeneacetamide
  • Step A The title compound of Step A (5.0 g) was dissolved in 33 mL of 40% aqueous methylamine solution and heated to reflux for 4 hours. The solution was cooled and extracted with methylene chloride (3x30 mL) and the organic phase was washed with 30 mL of water. The organic phase was dried (MgSO 4 ), filtered and concentrated in vacuo to yield 5 g of a dark amber oil. Trituration in methyl tert-butyl ether/hexane provided 1.1 g (34% yield) of the title compound of Step B as an off-white soljd melting at 91-93°C.
  • Step C ⁇ -fMethoxyimino)-N-methvl-2-rrr ⁇ -r3- rtrimemvlsilynphenvnethvlidenelaminoloxvlmethvnbenzeneacetamide A mixture of 430 mg of the title compound of Step B, 350 mg of l-[3-
  • Step A l-r ⁇ -mimethvlpermvttphenvllethanone
  • Step C l-f4-rTrimethvlgermvl)Dhenvnethanone oxime
  • Step D Methvl ⁇ -fmethoxvmethvlene -2-rrrri-r4- ftrimethvlge ⁇ nvnphenvnethvlidenelaminoloxvlmethvnbenzeneacetate
  • DMF dimethyl methyl sulfoxide
  • Step A t4-Bromo-2-methvlphenoxv)(l.l-dimethvlethvl)dimethvlsilane
  • Step B f 1.1 -Dimethvlethvl)dimethvir2-methvl-4-(trimethylgermyl)phenoxv1silane
  • Step C Methvl ⁇ -(methoxvimino)-2-rr2-methvl-4- (trimethylgermyl)phenoxylmethyllbenzeneacetate
  • Step C The title compound of Step C was dissolved in 30 mL of 2-butano ⁇ e. 0.5 g of finely ground (mortar and pestle) potassium carbonate was added followed by 0.5 g of methyl 2-(bromomethyl)- -(methoxyimino)benzeneacetate and the resulting mixture was heated to reflux overnight. Evaporation of the solvent in vacuo was followed by partitioning between water and ethyl acetate. The resulting aqueous phase was extracted with ethyl acetate and diethyl ether.
  • finely ground (mortar and pestle) potassium carbonate was added followed by 0.5 g of methyl 2-(bromomethyl)- -(methoxyimino)benzeneacetate and the resulting mixture was heated to reflux overnight. Evaporation of the solvent in vacuo was followed by partitioning between water and ethyl acetate. The resulting aqueous phase was extracted with ethyl acetate and diethyl ether
  • Step A 2-f3-Bromophenvn-2-methvl-1.3-dioxolane
  • Step B l-r3-frrimethvlsilvl)phenvnethanone fInter ⁇ nediate 11
  • Step C l-r3-(Trimethvlsilvl)phenvllethanone oxime (Intermediate 2)
  • H 2 C CHCH 2 0 N
  • H 2 C CHCH 2 S N
  • H 2 C CHCH 2 0 N
  • H 2 C CHCH 2 S N
  • H 2 O HCH 2 0 CH
  • H 2 C CHCH 2 S CH
  • H 2 C CHCH 2 S N
  • H 2 C CHCH S CH
  • H 2 C CHCH 2 0
  • CEt H 2 C CHCH 2 S
  • CEt H 2 C CHCH 2 0 CMe
  • H 2 C CHCH 2 S CMe
  • G C.
  • A O
  • the floating double G N
  • A N.
  • the floating double bond is bond is attached to G and attached to A and W W W W W W W
  • Y CH 2 0.
  • Z 3-Me 3 Si-Ph and
  • 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 which add up to 100 percent by weight.
  • Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, CaldweU, 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-diinethylfo ⁇ namide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4- methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetiahydrofurfuryl alcohol.
  • Dusts and powders can be prepared by blending and, usually, grinding a in a hammer mill or fluid-energy mill.
  • Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084.
  • Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry 's Chemical Engineer 's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546.
  • Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
  • Compound 15 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium sihcoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • Example B Granule Compound 15 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%. 92
  • Compound 15 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium magnesium bentonite 59.0%.
  • Example P Ernulsifiable Concentrate Compound 15 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
  • the compounds of this invention also exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, stem or root feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term “arthropods” includes insects, mites and nematodes) which are pests of growing and stored agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skilled in the an will appreciate that not all compounds are equally effective against all growth stages of all pests.
  • all of the compounds of this invention display activity against pests that include: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs, immatures and adults of the Orders Hemiptera and Homoptera; eggs, larvae, nymphs and adults of the Order Acari; eggs, immatures and adults of the Orders Thysanoptera, Orthoptera and Dermaptera; eggs, immatures and adults of the Order Diptera; and eggs, juveniles and adults of the Phylum Nematoda.
  • the compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanura and Psocoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes.
  • the compounds are active against southern corn rootworm (Diabrotica undecimpunctata howard ⁇ ), aster leafhopper (Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spotted spider mite (Tetranychus urticae), fall army worm (Spodopterafrugiperda), black bean aphid (Aphis fabae), green peach aphid (Myzus persica), cotton aphid (Aphis gossypif), Russian wheat aphid (Diuraphis noxia), English grain aphid (Sitobion avenae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus oryzophilus), rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatellafurcifer ⁇ ), green leafhopper (Nephotettix cincticeps), brown plant
  • Tetranychidae including Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus pacificus, Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi, Panonychus citri, Eotetranychus carpini borealis, Eotetranychus, hicoriae, Eotetranychus sexmaculatus, Eotetranychus yumensis, Eotetranychus banksi and Oligonychus pratensis;
  • Tenuipalpidae including Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpus calif ornicus and Brevipalpus obovatus; Eriophyidae including Phyllocoptruta oleivora, E ⁇ ophyes sheldoni, Aculus cornutus, Epitrimerus pyri and Eriophyes mangiferae. See WO 90/10623 and WO 92/00673 for more detailed pest descriptions.
  • Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorpyrifos, chlo yrifos-methyl, cyfluthrin, beta-cyfluthrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenpropathrin, fenvalerate, fipronil, flucythrinate, tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, monocrotophos, oxamyl, parathion, parathion-methyl,
  • a fungicide selected from the group cyproconazole, cyprodinil (CGA 219417), epoxyconazole (BAS 480F), fenpropidin, fenpropimorph, flusilazole and tebuconazole.
  • Specifically preferred mixtures are selected from the group: compound 2 and cyproconazole; compound 2 and cyprodinil (CGA 219417); compound 2 and epoxyconazole (BAS 480F); compound 2 and fenpropidin; compound 2 and fenpropimorph; compound 2 and flusilazole; compound 2 and tebuconazole; compound 15 and cyproconazole; compound 15 and cyprodinil (CGA 219417); compound 15 and epoxyconazole (BAS 480F); compound 15 and fenpropidin; compound 15 and fenpropimorph; compound 15 and flusilazole; compound 15 and tebuconazole; compound 16 and cyproconazole; compound 16 and cyprodinil (CGA 219417); compound 16 and epoxyconazole (BAS 480F); compound 16 and fenpropidin; compound 16 and fenpropimorph; compound 16 and flusilazole and tebuconazole; compound 16 and
  • 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.
  • Arthropod pests are controlled and protection of agronomic, horticultural and specialty crops, animal and human health is achieved by applying one or more of the compounds of this invention, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • the present invention further comprises a method for the control of foliar and soil inhabiting arthropods and nematode pests and protection of agronomic and/or nonagronomic crops, comprising applying one or more of the compounds of the invention, or compositions containing at least one such compound, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • a preferred method of application is by spraying.
  • granular formulations of these compounds can be applied to the plant foliage or the soil.
  • Other methods of application include direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others.
  • the compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like.
  • the compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use.
  • a preferred method o application involves spraying a water dispersion or refined oil solution of the compound Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance compound efficacy.
  • the rate of application required for effective control will depend on such factors a the species of arthropod to be controlled, the pest's life cycle, life stage, its size, locationo time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.001 kg/hectare may be sufficient or as much as 8 kg hectar may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient o as much as 150 mg/square meter may be required.
  • control efficacy represents inhibition of arthropod development (including mortality) that causes significantly reduced feeding.
  • pathogen and arthropod pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-E for compound descriptions.
  • a 'H 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.
  • Test compounds were first dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem® 014 (polyhydric alcohol esters). The resulting test suspensions were then used in Tests A-F. Spraying these 200 ppm test suspensions to the point of run-off on the test plants is the equivalent of a rate of 500 g/ha.
  • test suspension was sprayed to the point of run-off on wheat seedlings.
  • seedlings were inoculated with a spore dust of Erysiphe graminis f sp. tritici, (the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20°C for 7 days, after which disease ratings were made.
  • TESTB The test suspension was sprayed to the point of run-off on wheat seedlings.
  • TEST C The test suspension was sprayed to the point of run-off on rice seedlings. The following day the seedlings were inoculated with a spore suspension of Pyricularia oryzae (the causal agent of rice blast) and incubated in a saturated atmosphere at 27 °C for 24 h, and then moved to a growth chamber at 30°C for 5 days, after which disease ratings were made.
  • Pyricularia oryzae the causal agent of rice blast
  • 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. lES ⁇ E. The test suspension was sprayed to the point of run-off on grape seedlings.
  • 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 of Botrytis cinerea (the causal agent of gray mold on many crops) and incubated in a saturated atmosphere at 20°C for 48 h, and moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.
  • Botrytis 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.
  • Test units each consisting of a H.I.S. (high impact styrene) tray with 16 cells were prepared. Wet filter paper and approximately 8 cm 2 of lima bean leaf was placed into twelve of the cells. A 0.5-cm layer of wheat germ diet was placed into the four remaining cells. Fifteen to twenty third-instar larvae of fall armyworm (Spodoptera frugiperda) were placed into a 230-mL (8-ounce) plastic cup. Solutions of each of the test compounds in 75:25 acetone-distilled water solvent were sprayed into the tray and cup.
  • H.I.S. high impact styrene
  • Spraying was accomplished by passing the tray and cup on a conveyer belt directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.14 kilograms of active ingredient per hectare (about 0.14 pounds per acre) at 207 kPa (30 p.s.i.).
  • the insects were transferred from the 230-mL cup to the H.I.S. tray (one insect per cell).
  • the trays were covered and held at 27°C and 50% relative humidity for 48 hours, after which time readings were taken on the twelve cells with lima bean leaves. The four remaining cells were read at 6-8 days for delayed toxicity. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 13, 21, and 22.
  • Test units each consisting of a 230-mL (8-ounce) plastic cup containing a 6.5-cm 2 (1 -square-inch) plug of a wheatgerm diet, were prepared. The test units were sprayed as described in TEST G with individual solutions of the test compounds. After the spray on the cups had dried, five second-instar larvae of the southern corn rootworm (Diabrotica undecimpunctata howardi) were placed into each cup. The cups were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. The same units were read again. at 6-8 days for delayed toxicity. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 11, 19, and 22. TES I
  • Pieces of kidney bean leaves each approximately 6.5 cm 2 (1 square inch) in area, that had been infested on the undersides with 25 to 30 adult mites (Tetranychus urticae), were sprayed with their undersides facing up on a hydraulic sprayer with a solution of the test compound in 75:25 acetone-distilled water solvent. Spraying was accomplished by passing the leaves, on a conveyor belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.14 kilograms of active ingredient per hectare (about 0.14 pounds per acre) at 207 kPa (30 p.s.i.).
  • the leaf squares were then placed underside-up on a square of wet cotton in a petri dish and the perimeter of the leaf square was tamped down onto the cotton with forceps so that the mites could not escap onto the untreated leaf surface.
  • the test units were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 7, 10, 11, 13, 19, 21, 22, 24, and 25.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
EP95940809A 1994-12-08 1995-11-28 Arthropodizide und fungizide organosilane und organogermane Ceased EP0869963A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US352002 1982-02-24
US35200294A 1994-12-08 1994-12-08
PCT/US1995/015236 WO1996017851A1 (en) 1994-12-08 1995-11-28 Arthropodicidal and fungicidal organosilanes and organogermanes

Publications (1)

Publication Number Publication Date
EP0869963A1 true EP0869963A1 (de) 1998-10-14

Family

ID=23383379

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95940809A Ceased EP0869963A1 (de) 1994-12-08 1995-11-28 Arthropodizide und fungizide organosilane und organogermane

Country Status (5)

Country Link
EP (1) EP0869963A1 (de)
AU (1) AU4243896A (de)
IL (1) IL115894A0 (de)
WO (1) WO1996017851A1 (de)
ZA (1) ZA959560B (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL323498A1 (en) * 1995-05-17 1998-03-30 Du Pont Cyclic amides acting as fungicides
MX9708802A (es) * 1995-05-17 1998-02-28 Du Pont Amidas ciclicas fungicidas.
MX9710259A (es) * 1995-06-20 1998-03-29 Du Pont Amidas ciclicas fungicidas y artropodicidas.
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
KR100311846B1 (ko) 1999-07-05 2001-10-18 우종일 신규 아크릴레이트계 살균제
WO2017024971A1 (zh) * 2015-08-12 2017-02-16 沈阳中化农药化工研发有限公司 一种不饱和肟醚类化合物及其用途
WO2022008303A1 (en) * 2020-07-08 2022-01-13 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors vi
CN112661732B (zh) * 2020-12-23 2023-08-04 湖南化研院检测技术有限公司 呋喃酚衍生物及其制备方法与应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5185342A (en) * 1989-05-17 1993-02-09 Shionogi Seiyaku Kabushiki Kaisha Alkoxyiminoacetamide derivatives and their use as fungicides
EP0433233B1 (de) * 1989-12-14 1995-01-25 Ciba-Geigy Ag Heterocyclische Verbindungen
CA2102078A1 (en) * 1992-11-02 1994-05-03 Akira Takase A process for producing (e)-alkoxyimino or hydroxyiminoacetamide compounds and intermediates therefor
TW299310B (de) * 1993-05-18 1997-03-01 Ciba Geigy Ag

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9617851A1 *

Also Published As

Publication number Publication date
AU4243896A (en) 1996-06-26
ZA959560B (en) 1997-05-12
WO1996017851A1 (en) 1996-06-13
IL115894A0 (en) 1996-01-31

Similar Documents

Publication Publication Date Title
EP0944314A1 (de) Methyl substituierte fungizide und arthropodizide
AU677448B2 (en) Fungicidal cyclic amides
WO1997000612A1 (en) Arthropodicidal and fungicidal cyclic amides
WO1996036229A1 (en) Fungicidal cyclic amides
US6057352A (en) Fungicidal cyclic amides
WO1995007278A1 (en) Fungicidal, miticidal and arthropodicidal aminopyrimidines
WO1998023155A1 (en) Arthropodicidal and fungicidal cyclic amides
WO1998005652A2 (en) Arthropodicidal and fungicidal cyclic amides
EP0642502B1 (de) Fungizide imidazolinone
WO1995003306A1 (en) Arthropodicidal azacyclic heterocycles
WO1999031072A1 (en) Cyclohexylamine arthropodicides and fungicides
US5962436A (en) Fungicidal cyclic amides
EP0737188B1 (de) Oxadiazincarboxanilide arthropodizide
WO1999028305A1 (en) Fungicidal cyclic amides
EP0869963A1 (de) Arthropodizide und fungizide organosilane und organogermane
WO1999011129A1 (en) Enantiomerically enriched compositions and their pesticidal use
WO1997011057A1 (en) Arthropodicidal 1,4-dihydropyridines and 1,4-dihydropyrimidines
WO1995019972A1 (en) Arthropodicidal 2-oxa and thia-zolines
US5538967A (en) Arthropodicidal oxazines and thiazines
WO1994008976A1 (en) Fungicidal and miticidal aminopyrimidines
EP0871634A1 (de) Arthropodizide oxazoline und thiazoline
WO1996033180A1 (en) Oxazoline and thiazoline arthropodicides
WO1995016676A1 (en) Arthropodicidal pentafluorothio substituted anilides
EP0637302A1 (de) Arthropodizide oxa- und thia-zoline
WO1995000491A1 (en) Arthropodicidal sulfonates

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19970505

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES FR GB IT

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19991028

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20000409