EP0821677A1 - Arthropodicides d'oxazoline et de thiazoline - Google Patents

Arthropodicides d'oxazoline et de thiazoline

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Publication number
EP0821677A1
EP0821677A1 EP96911528A EP96911528A EP0821677A1 EP 0821677 A1 EP0821677 A1 EP 0821677A1 EP 96911528 A EP96911528 A EP 96911528A EP 96911528 A EP96911528 A EP 96911528A EP 0821677 A1 EP0821677 A1 EP 0821677A1
Authority
EP
European Patent Office
Prior art keywords
group
alkyl
independently selected
haloalkyl
optionally substituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP96911528A
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German (de)
English (en)
Inventor
Victor Ekow Amoo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
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Publication of EP0821677A1 publication Critical patent/EP0821677A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D263/36—One oxygen atom
    • C07D263/40—One oxygen atom attached in position 4
    • 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 oxazoline and thiazoline compounds, their N-oxides, agriculturally-suitable salts and compositions, and methods of their use as arthropodicides in both agronomic and nonagronomic environments.
  • R ] and R 2 are independently H, halogen, lower alkyl, lower alkoxy, nitro, lower haloalkyl or lower haloalkoxy, provided that R* and R 2 are not simultaneously H;
  • R3 is H, halogen, lower alkyl or lower alkoxy;
  • R4 is alkyl having 7 or more carbon atoms, alkoxy having 7 or more carbon atoms, alkylthio, lower alkoxy-lower alkyl, lower alkoxy-lower alkoxy, alkenyloxy having 3 or more carbon atoms, lower alkynyloxy, tri(lower alkyl)silyl, cycloalkyl which may be substituted by a lower alkyl, or
  • B is a direct bond, O, lower alkylene, lower alkyleneoxy, lower alkylenedioxy or a di(lower alkyl)silyl;
  • Q is CH or ⁇ ;
  • n is 0-5; each R 5 is independently halogen, alkyl, alkoxy, lower haloalkyl, lower haloalkoxy or tri(lower alkyl)silyl;
  • A is a direct bond or lower alkylene; and Z is O or S.
  • U.S. 4,977,171 discloses insecticidal and acaricidal oxazoline or thiazoline derivatives of Formula ⁇ :
  • X 1 and X 2 are independently H, lower alkyl, lower alkoxy, halogen, trifluoromethyl or trifluoromethoxy; Y 1 and Y 2 are independently H, lower alkyl, lower alkoxy, lower alkylthio, cyano, nitro, halogen or trifluoromethyl; Z is O or S; and n is O or l.
  • WO 95/04726 discloses insecticidal and acaricidal oxazoline and thiazoline derivatives of Formula iii:
  • A is selected from the group a direct bond and CJ-C3 straight or branched chain alkylene;
  • R 3 is selected from the group C3-C7 halocycloalkyl;
  • R 9 is selected from the group phenyl and pyridyl, each optionally substituted with at least one member independently selected from W; and W is selected from the group halogen, cyano, formyl, nitro, SF 5 , C ⁇ -C ⁇ alkyl, C1-C 3 haloalkyl, C r C 3 alkylthio, C r C 3 alkoxy, C r C 3 haloalkoxy, C 2 -C 4 alkylcarbonyl and C 2 -C-j alkoxycarbonyl.
  • oxazoline and thiazoline compounds of the present invention are not disclosed in any of these publications.
  • 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 arthropodicides:
  • each E is independently selected from the group C]-C 4 alkyl and C 1 -C 4 haloalkyl;
  • X is selected from the group C1-C 4 alkylene, -(CH 2 ) n -A-, -(CH 2 ) p -A-CH 2 -, each group optionally substituted with one to four R 4 ;
  • Y and Z are independently selected from the group O and S;
  • A is selected from the group O, S and ⁇ R 10 ;
  • Q is selected from the group H and J; or
  • Q is selected from the group Ci-C j g alkyl, C r C 16 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 7 cycloalkyl, C3-C7 halocycloalkyl and C4-C7 cycloalkylalkyl, each group optionally substituted with W;
  • J is selected from the group phenyl, naphthalenyl, anthracenyl, phenanthrenyl, lH-pyr
  • R 1 is selected from the group 1 -2 halogen, C • -C 6 alkyl, C , -C 6 haloalkyl, C • -C 6 alkoxy, C j -C 6 haloalkoxy, S(O) t R- -, cyano and nitro;
  • R 2 is selected from the group ⁇ , 1-2 halogen, C j -C 6 alkyl, C
  • each R 3 is independently selected from the group halogen, C*-C*6 alkyl, C*-C*(, haloalkyl, C 2 -C ⁇ 6 alkenyl, C 2 -C 16 haloalkenyl, C 2 -C 16 alkynyl, C 2 -C )6 haloalkynyl, C -Cj 6 alkoxyalkyl, C -Ci6 alkylthioalkyl, C -C ⁇ 6 cyanoalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, cyano, nitro, S(0) t R ** •* , OR 9 , C,-C 5 alkyldithio, C r C 5 haloalkyldithio, formy
  • R 5 is selected from the group ⁇ , halogen, C C 6 alkyl, C r C 6 haloalkyl, C r C 6 alkoxy, C r C 6 haloalkoxy, C r C 6 alkylthio, C r C 6 alkylsulfinyl, C r C 6 alkylsulfonyl, C ⁇ -C 6 haloalkylthio, C ⁇ -C 6 haloalkylsulfinyl and C j -C 6 haloalkylsulfonyl; each R 6 and R 7 is independently C ⁇ -C ⁇ 2 alkyl; each R 8 is independently selected from the group C ⁇
  • R 10 is selected from the group H, C1-C 4 alkyl, C1-C 4 haloalkyl, formyl, C 2 -C alkylcarbonyl, C 2 -C 4 alkoxycarbonyl, NH 2 C(O), (C r C 4 alkyl)NHC(O) and (C r C 4 alkyl) 2 NC(0); each R 1 J is independently selected from the group C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl,
  • each R 12 , R 14 and R 16 is independently selected from the group H, C r C 6 alkyl, C r C 6 haloalkyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 4 -C 7 cyanocycloalkyl, C 4 -C 7 alkylcycloalkyl, C 4 -C7 cycloalkylalkyl, C 4 -C 7 halocycloalkylalkyl, C-j-Cg alkoxyalkyl, C -C6 alkylthioalkyl, C 2 -C 4 cyanoalkyl, phenyl optionally substituted with 1-3 W 1 and benzyl optionally substituted with 1-3 W 1 ; each R 12 , R 14 and R 16 is independently selected from the group H, C r C 6 alkyl,
  • R 12 and R 13 , R 14 and R 15 , or R 16 and R 17 when attached to the same atom, can be taken together as (CH 2 ) 4 , (CH 2 ) 5 or CH 2 CH 2 OCH 2 CH 2 , each group optionally substituted with 1-3 CH 3 ; each R 18 is independently selected from the group Cj-Cg alkyl, C j -Cg haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylthioalkyl, CyC 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 4 -C7 cycloalkylalkyl, phenyl optionally substituted with 1-3 W 1 and benzyl optionally substituted with 1-3 W 1
  • each R 24 is independently selected from the group C j -Ct alkyl; C j -C- 2 alkoxy; and phenyl optionally substituted with 1-3 W 1 ;
  • W is selected from the group J, Ci-Cg alkoxy and C j -Cg haloalkoxy;
  • each W 1 is independently selected from the group halogen, cyano, nitro, C ⁇ -C 2 alkyl, C ⁇ -C 2 haloalkyl, C ] -C 2 alkoxy, C j -C 2 haloalkoxy, C ⁇ -C alkylthio, C r C 2 haloalkylthio, C r C 2 alkylsulfinyl, C r C 2 haloalkylsulfinyl, C r C 2 alkylsulfonyl and C C 2 haloalkylsulfonyl;
  • m is 1 or 2;
  • n is 1, 2 or 3
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers.
  • 1-6 alkyl indicates that one to six of the available positions for that substituent may be alkyl which are independently selected.
  • Alkenyl includes straight-chain or branched alkenes such as vinyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkylene denotes a straight-chain or branched alkanediyl.
  • alkylene examples include CH 2 , CH 2 CH 2 , CH(CH 3 ), CH 2 CH 2 CH 2 , CH 2 CH(CH 3 ) and the different butylene isomers.
  • alkenylene denotes a straight-chain or branched alkenediyl containing one olefinic bond.
  • Alkynylene denotes a straight-chain or branched alkynediyl containing one triple bond.
  • alkynylene examples include C ⁇ C, CH 2 G ⁇ C, C ⁇ CCH 2 and the different butynylene isomers.
  • Alkoxy includes, for example, methoxy, ethoxy, ⁇ -propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • 1-3 alkoxy indicates that one to three of the available positions for that substituent may be alkoxy which are independently selected.
  • 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
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 .
  • Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group.
  • alkylsulfinyl include CH 3 S(O), CH 3 CH 2 S(O), CH 3 CH 2 CH 2 S(O), (CH 3 ) 2 CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers.
  • alkylsulfonyl examples include 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.
  • Alkyldithio denotes branched or straight-chain alkyldithio moieties.
  • alkyldithio examples include CH 3 SS, CH 3 CH 2 SS, CH 3 CH 2 CH 2 SS, (CH 3 ) 2 CHSS and the different butyldithio and pentyldithio isomers.
  • Cyanoalkyl denotes an alkyl group substituted with one cyano group.
  • Examples of “cyanoalkyl” include NCCH 2 , NCCH 2 CH 2 and CH 3 CH(CN)CH 2 .
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • cycloalkylalkyl examples include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.
  • Alkylcycloalkyl denotes alkyl substitution on a cycloalkyl moiety. Examples include 4-methylcyclohexyl and 3-ethylcyclopentyl.
  • Cyanocycloalkyl denotes a cycloalkyl group substituted with one cyano group. Examples of “cyanocycloalkyl” include 4-cyanocyclohexyl and 3-cyanocyclopentyl.
  • nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides.
  • halogen either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine.
  • 1-2 halogen indicates that one or two of the available positions for that substituent may be halogen which are independently selected.
  • alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • haloalkenyl “haloalkynyl", “haloalkoxy”, and the like, are defined analogously to the term “haloalkyl”.
  • haloalkynyl examples include HC ⁇ CCHCl, CF 3 OC, 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.
  • haloalkylsulfonyl examples include CF 3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 and CF 3 CF 2 S(O) 2 .
  • C--C The total number of carbon atoms in a substituent group is indicated by the "C--C.” prefix where i and j are numbers from 1 to 16.
  • C*-C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 2 alkoxyalkyl designates CH3OCH2
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or
  • CH 3 CH 2 OCH 2 ; and C4 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 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • alkylcarbonyl include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • 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.
  • substituents When a group contains a substituent which can be hydrogen, for example R 2 or
  • 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, 4-toluenesulfonic or valeric acids.
  • the salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a phenol.
  • organic bases e.g., pyridine, ammonia, or triethylamine
  • inorganic bases e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium
  • X is -(CH 2 ) n -A- optionally substituted with one to four R 4 ;
  • Y is O;
  • A is O;
  • Q is selected from the group J and Ci-C j g alkyl
  • J is selected from the group phenyl, thienyl and pyridinyl, each optionally substituted with 1-3 R 3 ; m is 1 ; and n is 1.
  • Z is O; Q is J; J is selected from the group phenyl and pyridinyl, each optionally substituted with 1-3 R 3 ; and q is O.
  • Preferred 3. Compounds of Preferred 2 wherein:
  • R 1 is selected from the group F and Cl in the 2-position
  • R 2 is selected from the group H, F and Cl in the 6-position
  • each R 3 is independently selected from the group halogen, Ci-Cg alkyl,
  • each R 9 is independently selected from the group CJ-C 4 alkyl and C*-C 4 haloalkyl; each R 11 is independently selected from the group C j -Cg alkyl and C j -Cg haloalkyl; and each J 1 is independently selected from the group phenyl, thienyl, pyridinyl and furanyl.
  • arthropodicidal compositions comprising arthropodicidally effective amounts of the compounds of the invention 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 arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of the compounds of the invention (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 1-14.
  • the definitions of E, X, Y, Z, A, Q, J, R ! -R 24 , M, J 1 , W, W 1 , m, n, p, q and t in the compounds of Formulae I-XD below are as defined above in the Summary of the Invention.
  • the reaction may be run in the presence or absence of a solvent such as tetrahydrofuran (THF), dimethylformamide (DMF), ether, benzene or toluene.
  • THF tetrahydrofuran
  • DMF dimethylformamide
  • ether benzene or toluene
  • the reaction temperature can vary from 0°C to the boiling point of the solvent being used and is usually completed in less than 24 h.
  • R a is independently H or R 4 )
  • a coupling agent such as dicyclohexylcarbodiimide (DCC).
  • the reaction temperature can vary from 0-150°C.
  • an acid scavenger usually a tertiary amine base such as triethylamine
  • the reaction can be carried out in an inert solvent as methylene chloride, chloroform, benzene, tetrahydrofuran, toluene or other solvents that will not react with acid chlorides or bases.
  • the reaction is normally completed in less than 24 h. (See Scheme 3).
  • Other useful methods for the formation of amides are discussed in Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York.
  • Scheme 4 illustrates the preparation of Formula IV compounds.
  • An acrylate of Formula VI is brominated with bromine in an inert solvent such as methylene chloride, carbon tetrachloride, chloroform or ether followed by dehydrobromi ation of the dibromo intermediate with a base such as sodium hydroxide or potassium hydroxide.
  • the reaction may be run in a solvent such as methanol, ethanol, water or DMF.
  • a solvent such as methanol, ethanol, water or DMF.
  • An example of this transformation can be found in Organic Synthesis, Coll. Vol. II, p 270.
  • Aldehydes of Formula VII and phosphonium salts of Formula VIE are commercially available or can be prepared by known methods.
  • a typical reaction involves mixing a Formula VHI compound with a strong base such as an alkyllithium (e.g., butyllithium), a metal alkoxide (e.g., sodium methoxide), sodium amide or sodium hydride in a suitable solvent such as tetrahydrofuran, ether, benzene, methanol, toluene, acetonitrile, dimethoxyethane and dimethyl sulfoxide, followed by addition of an aldehyde of Formula VII.
  • a strong base such as an alkyllithium (e.g., butyllithium), a metal alkoxide (e.g., sodium methoxide), sodium amide or sodium hydride in a suitable solvent such as tetrahydrofuran, ether, benzene, methanol, toluene, acetonitrile, dimethoxyethane and dimethyl sulfoxide, followed by addition of an aldehyde
  • compounds of Formula I can be prepared by an aldol-type condensation of a Formula IX compound with an aldehyde of Formula VII.
  • Scheme 6 illustrates this transformation.
  • the reaction can be run in the presence of a base such as a metal alkoxide, e.g., sodium methoxide, or an amine base as piperidine or l,4-diazabicyclo[2.2.2]octane (DABCO).
  • a suitable solvent for this transformation can be chosen from, but not limited to, methanol, ethanol, water, xylene, DMF, dioxane or THF.
  • the reaction temperature can vary from 0-200°C and the reaction is done in less than 48 h. An example of this reaction can be found in Organic Synthesis, Coll. Vol. 5, (1973), p 627.
  • Scheme 6 illustrates this transformation.
  • the reaction can be run in the presence of a base such as a metal alkoxide, e.g., sodium methoxide,
  • the reaction involves the cyclization of a Formula X compound with a compound of Formula XI in the presence of a base.
  • a base examples include sodium hydride or potassium t-i5 «toxide.
  • the reaction may be run in a solvent such as benzene, THF, ether, toluene, DMF, dimethyl sulfoxide (DMSO) or dioxane.
  • the reaction temperature may vary from 0-200°C and the reaction is usually done within 24 h.
  • Compounds of Formula XII are commercially available or can be prepared by known methods. The reaction conditions are as described for Scheme 3.
  • Scheme 10 illustrates the synthesis of compounds of Formula XIII.
  • the reaction involves the coupling of an acid of Formula XIV with an amine of Formula V as described for Scheme 3.
  • Compounds of Formula V can be prepared by the reaction of compounds of Formula XV with sodium hypobromite (or sodium hydroxide and bromine). This transformation is shown in Scheme 11. A review of the Hofmann rearrangement can be found in Organic Reactions (1946), 3, 267-306. A typical reaction involves the addition of a compound of Formula XIII to an aqueous solution of sodium hypobromite. The temperature of the reaction can range from 0-200°C with the preferred temperature range between 30-100°C. The reaction is usually complete in 24 h. Alternatively, the transformation can be accomplished by treating a Formula XV compound with sodium hypobromite (or sodium hydroxide and bromine). This transformation is shown in Scheme 11. A review of the Hofmann rearrangement can be found in Organic Reactions (1946), 3, 267-306. A typical reaction involves the addition of a compound of Formula XIII to an aqueous solution of sodium hypobromite. The temperature of the reaction can range from 0-200°C with the preferred temperature range between 30-100°C. The reaction is usually complete in
  • Compounds of Formula XV can be prepared by reacting compounds of Formula XVI with ammonia. This transformation is shown in Scheme 12. The reaction can be run in solvents such as methanol, ethanol, ether, benzene and toluene. Typical reactions are carried out at ambient temperature, and reactions are usually completed in 24 h. For reference, see D. W. Jones, J. Chem. Soc. (1969), 1729.
  • Compounds of Formula XVI can be prepared by the reaction of serine derivatives (Formula XVII) with an imidate of Formula XVIJI as shown in Scheme 13.
  • Serine derivatives of Formula XVIII are commercially available or can be prepared by known methods.
  • the reaction can be carried out in solvents such as methanol, methylene chloride, chloroform, benzene, dioxane and tetrahydrofuran. Water can be added as a cosolvent.
  • the reaction can be carried out at temperatures varying from 0°C to the reflux temperature of the particular solvent being used, and the reaction is usually complete in 24 h. For reference, see Agric. Biol. Chem. (1986), 50, 615-623.
  • imidates of Formula XVI can be prepared from amides of Formula XVII by reaction with a trialkyloxonium tetrafluoroborate in an inert solvent such as methylene chloride, benzene or toluene.
  • Amides of Formula XVII are commercially available or can be prepared by known methods. The syntheses of imidates has been extensively reviewed by D. A. Neilson in The Chemistry of Amidines and Imidates, Patai and Rappoport, Eds., Vol. 2, (1991), pp 425-483.
  • Step B Methyl 2-(2.6-difluorophenyl)-4.5-dihydro-4-oxazolecarboxylate An amount of 9.09 g (0.058 mol) of serine methyl ester hydrochloride was added portionwise to a 10.0 g (0.058 mol) solution of the title compound of Step A in 15 mL EtOH and 5 mL H 2 O. The mixture was stirred at reflux for 1.5 h.
  • Step C 2-(2.6-Difluorophenyl)-4.5-dihydro-4-oxazolecarboxamide A solution of 10.0 g (0.041 mol) of the title compound of Step B in 100 mL of a
  • Step D 2-(2.6-Difluorophenyl)-4.5-dihydro-4-oxazolamine An amount of 0.386 g (0.0044 mol) of bromine was added dropwise to a cooled solution of 0.440 g (0.011 mol) of NaOH in 3.7 mL of H 2 O. 0.500 g (0.002 mol) of the title compound of Step C was added portionwise. The reaction was stirred at 80°C for 0.5 h. Et 2 O and H 2 O were added and the mixture was extracted with EtOAc. The combined extracts were washed with brine, dried over MgSO 4 and evaporated to give 0.350 g of the title compound of Step D as a white solid melting at 81-85°C. !
  • Step E 3-(4-ChlorophenylVN-r2-(2.6-difluorophenvn-4.5-dihvdro-4-oxazolvn-2- propynamide 1 ,3-Dicyclohexylcarbodiimide (1.03 g, 0.005 mol) was added portionwise to a cooled (ice-bath) mixture of the title compound of Step D (0.991 g, 0.005 mol),
  • Step F (Z)-5-f(4-Chlorophenynmethylenel-3-r2-f2.6-difluorophenvn-4.5- dihydro-4-oxazolyll-4-oxazolidinone Sodium hydride (60% dispersion in oil, 0.088 g, 0.0022 mol) was added to a cooled (ice-bath) mixture of the title compound of Step E (0.731 g, 0.002 mol) and paraformaldehyde (0.300 g, 0.01 mol) in 2 mL of dry DMF. The mixture was stirred in the cold for 0.5 h and then was carefully quenched with water while cooling. The resulting mixture was extracted with EtOAc and the combined extracts were washed with water.
  • Step C N-r2-(2.6-Difluorophenvn-4.5-dihydro-4-oxazolyll-3-f4-iodophenyl)-2- propynamide
  • a cooled (0°C) solution of 0.680 g (0.0025 mol) of the title compound of Step B in 7 mL CH 2 C1 2 was added 0.533 g (0.0025 mol) of 1 ,3-dicyclohexylcarbodiimide, 0.032 g of 4-dimethylaminopyridine and 0.500 g of the title compound of Step D in Example 1.
  • the reaction mixture was stirred at room temperature for 30 minutes and the solids were filtered off.
  • Step D (Z 3-r2-(2.6-Difluoro ⁇ henyl)-4.5-dihvdro-4-oxazolyll-5-r(4- iodophenyl)methylene1-4-oxazolidinone
  • Sodium hydride (60% dispersion in oil, 0.044 g, 0.0011 mol) was added to a cooled (ice-bath) mixture of the title compound of Step C (0.452 g, 0.001 mol) and paraformaldehyde (0.148 g, 0.005 mol) in 1 mL of dry DMF. The mixture was stirred in the cold for 1 hour and was then carefully quenched with water in die cold.
  • A O
  • Y O
  • Rl F
  • R 2 H
  • P H
  • n l
  • R 19
  • Rl F
  • R 2 F
  • P 4-F
  • A O
  • Y O
  • Z O
  • R 1 F
  • R 2 F
  • A O
  • Y O
  • Z O
  • Q Q
  • R 1 F
  • R 2 F
  • A O
  • Y S
  • Z O
  • R 1 F
  • R 2 F
  • R 1 F
  • R 2 F
  • X CH 2 .
  • Y O.
  • R 1 Cl
  • R 2 F
  • X CH 2
  • Y O
  • Z O
  • R 3
  • R 4 H.
  • 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, 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, N,N-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4- methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.
  • Solutions 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 23 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • Example B Granule Compound 23 10.0% attapulgite granules (low volatile matter
  • Example C Extruded Pellet Compound 23 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • Example D Extruded Pellet Compound 23 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • Example D Extruded Pellet Compound 23 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • Compound 23 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%.
  • the compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, stem or root feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term “arthropods” includes insects, mites and nematodes) which are pests of growing and stored agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skilled in the art will appreciate that not all compounds are equally effective against all growth stages of all pests.
  • 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 howardi), aster leafhopper (Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spotted spider mite (Tetranychus urticae), fall armyworm (Spodoptera frugiperd ⁇ ), black bean aphid (Aphis fabae), green peach aphid (Myzus persica), cotton aphid (Aphis gossypii), Russian wheat aphid (Diuraphis noxia), English grain aphid (Sitobion avenae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus oryzophilus), rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatellafurcifera), green leafhopper (Nephotettix cincticeps), brown planthopper (
  • the compounds are active on mites, demonstrating ovicidal, larvicidal and chemosterilant activity against such families as Tetranychidae including Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus pacificus, Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi, Panonychus citri, Eotetranychus carpini borealis, Eotetranychus, hicoriae, Eotetranychus sexmaculatus.
  • Tetranychidae including Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus pacificus, Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi, Panonych
  • Eotetranychus yumensis Eotetranychus banksi and Oligonychus pratensis
  • Tenuipalpidae including Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpus californicus and Brevipalpus obovatus
  • Eriophyidae including Phyllocoptruta oleivora. Eriophyes sheldoni, Aculus cornutus, Epitrimerus pyri and Eriophyes mangiferae. See WO 90/10623 and WO 92/00673 for more detailed pest descriptions.
  • Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlo ⁇ yrifos, 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, para
  • Preferred for better control of pests (use rate or spectrum) or resistance management are mixtures of a compound of this invention with an arthropodicide selected from the group abamectin, fenpropathrin, fipronil, imidacloprid, methomyl, propargite, pyridaben, tebufenozide and tebufenpyrad.
  • an arthropodicide selected from the group abamectin, fenpropathrin, fipronil, imidacloprid, methomyl, propargite, pyridaben, tebufenozide and tebufenpyrad.
  • Specifically preferred mixtures are selected from the group: compound 1 and abamectin; compound 1 and fenpropathrin; compound 1 and fipronil; compound 1 and imidacloprid; compound 1 and methomyl; compound 1 and propargite; compound 1 and pyridaben; compound 1 and tebufenozide; compound 1 and tebufenpyrad; compound 7 and abamectin; compound 7 and fenpropathrin; compound 7 and fipronil; compound 7 and imidacloprid; compound 7 and methomyl; compound 7 and propargite; compound 7 and pyridaben; compound 7 and tebufenozide; compound 7 and tebufenpyrad; compound 15 and abamectin; compound 15 and fenpropathrin; compound 15 and fipronil; compound 15 and imidacloprid; compound 15 and methomyl; compound 7 and propargite; compound 7 and
  • 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 of application involves spraying a water dispersion or refined oil solution of the compounds.
  • Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, other solvents, and synergists such as piperonyl butoxide often enhance compound efficacy.
  • the rate of application required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.001 kg/hectare may be sufficient or as much as 8 kg hectare may be required.
  • TESTS demonstrate the control efficacy of compounds of this invention on specific pests. "Control efficacy” represents inhibition of arthropod development (including mortality) that causes significantly reduced feeding. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-C for compound descriptions.
  • 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 0.55 kilograms of active ingredient per hectare (about 0.5 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: 20.
  • 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 0.55 kilograms of active ingredient per hectare (about 0.5 pounds per acre) at 207 kPa (30 p.s.i.).
  • the leaf squares were then placed undersiderup on a square of wet cotton in a petri dish and the perimeter of the leaf square was tamped down onto the cotton with forceps so that the mites could not escape onto the untreated leaf surface.
  • the test units were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher:
  • Solutions of the test compounds were prepared by dissolving in a minimum of acetone and then adding water containing a wetting agent until the concentration of the compound was 50 ppm.
  • Two- week old red kidney bean plants infested with two-spotted spider mites eggs were sprayed to run-off (equivalent to 28 g/ha) with the test solution using a turntable sprayer. Plants were held in a chamber at 25°C and 50% relative humidity.
  • the following gave larvicide/ovicide activity of 80% or higher seven days after spraying: 1, 2, 3, 4, 5, 6, 7, 9, 10, 11, 15, 17, 18*, 19*, 20*, 21*, 22*, 23*, 29*. 31*, and 32*.
  • Test compounds were prepared by dissolving in a minimum of acetone and adding water containing a wetting agent until the concentration of the compounds was 10 ppm. Test compounds were then sprayed to run-off (equivalent to 5.5 g/ha) onto soybean plants utilizing a rotating platform and an atomizing sprayer. Treated plants were dried, and fall armyworm (Spodoptera frugiperda) larvae were exposed to excised, treated leaves. Test units were held at 27°C and 50% relative humidity, and evaluated for larval mortality 120 h post-infestation. Of the compounds tested, the following gave mortality levels of 80% or higher: 1, 3, 7*, 15, 18, 19, 21, 22, 23, 24, 26, 28, and 31. ⁇ Compound was tested at 3 ppm (equivalent to 1.7 g/ha).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

La présente invention décrit des composés de formule (I), leurs N oxydes ainsi que leurs sels à usage agricole, utilisés comme arthropodicides, dans laquelle X est choisi parmi le group alkylène C1-C4, -(CH2)n-A, -(CH2)p-A-CH2-, chaque groupe étant facultativement substitué par un à quatre R4; Y et Z sont indépendamment choisis parmi le groupe O et S; A est choisi parmi le groupe O, S et NR10; R1 est sélectionné parmi le groupe 1-2 halogène, alkyle C¿1?-C6, haloalkyle C1-C6, alcoxy C1-C6, haloalcoxy C1-C6, S(O)tR?11¿, cyano et nitro; R2 est sélectionné parmi le groupe H, 1-2 halogène, alkyle C¿1?-C6, haloalkyle C1-C6, alcoxy C1-C6, haloalcoxy C1-C6, S(O)tR?11¿, cyano et nitro; m vaut 1 ou 2; n vaut 1, 2 ou 3; p vaut 1 ou 2; et E, Q, R?4, R5, R10, R11¿, q et t sont tels que définis dans la description. L'invention décrit également des compositions contenant des composés de formule (I) ainsi qu'un procédé de régulation des arthropodes qui consiste à mettre en contact les arthropodes ou leur environnement avec une quantité suffisante d'un composé de formule (I).
EP96911528A 1995-04-18 1996-04-01 Arthropodicides d'oxazoline et de thiazoline Withdrawn EP0821677A1 (fr)

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US5846979A (en) 1997-02-28 1998-12-08 Gpi Nil Holdings, Inc. N-oxides of heterocyclic esters, amides, thioesters, and ketones
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US4977171A (en) * 1988-06-09 1990-12-11 Yashima Chemical Industrial Co., Ltd. Oxa- or thia-zoline derivative
AU634608B2 (en) * 1989-12-09 1993-02-25 Kyoyu Agri Co., Ltd. 2-substituted phenyl-2-oxazoline or thiazoline derivatives, process for producing the same and insectides and acaricides containing the same
WO1993024470A1 (fr) * 1992-05-26 1993-12-09 E.I. Du Pont De Nemours And Company Oxazolines et thiazolines pour la destruction des arthropodes
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