WO1997013773A1 - Arthropodicidal oxazolines and thiazolines - Google Patents

Arthropodicidal oxazolines and thiazolines Download PDF

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Publication number
WO1997013773A1
WO1997013773A1 PCT/US1996/015876 US9615876W WO9713773A1 WO 1997013773 A1 WO1997013773 A1 WO 1997013773A1 US 9615876 W US9615876 W US 9615876W WO 9713773 A1 WO9713773 A1 WO 9713773A1
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group
alkyl
optionally substituted
compound
independently selected
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PCT/US1996/015876
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English (en)
French (fr)
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George Chihshu Chiang
Thomas Martin Stevenson
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E.I. Du Pont De Nemours And Company
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Priority to AU73879/96A priority Critical patent/AU7387996A/en
Priority to KR1019980702683A priority patent/KR19990064197A/ko
Priority to BR9610961A priority patent/BR9610961A/pt
Priority to EP96936165A priority patent/EP0871634A1/en
Priority to JP9515101A priority patent/JPH11513663A/ja
Publication of WO1997013773A1 publication Critical patent/WO1997013773A1/en

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    • 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
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • 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
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D263/14—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals substituted by oxygen 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
    • 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
    • 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

Definitions

  • This invention relates to certain oxazolines and thiazolines, their N-oxides, agriculturally suitable salts and compositions, and methods of their use as arthropodicides in both agronomic and nonagronomic environments.
  • R j 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;
  • R 3 is H, halogen, lower alkyl or lower alkoxy;
  • R 4 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 a y ene, lower alkyleneoxy, lower alkylenedioxy or a di(lower alkyl)silyl;
  • Q is CH or N;
  • n is 0-5; each R5 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 oxa- or thia-zoline derivatives of Formula ii:
  • 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 oxa- or thia-zoline derivatives of Formula iii:
  • A is selected from the group a direct bond and C1-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, CN, CHO, NO 2 , SF 5 , C r C 3 alkyl, C r 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 -C4 alkoxycarbonyl.
  • 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:
  • A is selected from the group a direct bond, C C 4 alkylene, C 2 -C 4 alkenylene, C 2 -C 4 alkynylene, O and ⁇ R 10 ; each E is independently selected from the group C j -C alkyl and C j -C 4 haloalkyl;
  • Y is selected from the group C 2 -Cg alkenylene, Cp Cg haloalkenylene, -C ⁇ alkynylene and yC ⁇ haloalkynylene;
  • Z is selected from the group O and S;
  • R 1 is selected from the group 1-2 halogen, C r C 6 alkyl, C r C 6 haloalkyl, C r C 6 alkoxy, Ci -C 6 haloalkoxy, SCO ⁇ R 1 ] , cyano and nitro;
  • R 2 is selected from the group H, 1-2 halogen, Ci-Cg alkyl, C r C 6 haloalkyl, C r C 6 alkoxy, C1-C6 haloalkoxy, SCO ⁇ R 11 , cyano and nitro;
  • R 3 is selected from the group Si(R 6 )(R 7 )(R 8 ); Ge(R 6 )(R 7 )(R 8 );
  • R 4 and R 5 are independently selected from the group H, halogen, C j -Cig alkyl, C j -Cj 6 haloalkyl, C 2 -C j 6 alkenyl, C 2 -C]6 haloalkenyl, C 2 -Cj6 alkynyl, C 2 -C ⁇ 6 haloalkynyl, C 2 -C 16 alkoxyalkyl, C 2 -C 16 alkylthioalkyl, C 2 -C ] 6 cyanoalkyl, C ⁇ -Cg cycloalkyl, C 3 -C 6 halocycloalkyl, cyano, nitro, SCO ⁇ R 1 * ,
  • 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.
  • 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. Examples of “alkylene” 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.
  • Alkynylene denotes a straight-chain or branched alkynediyl containing one triple bond.
  • alkynylene include C ⁇ C, CH 2 C ⁇ C, G_CCH 2 and the different butynylene isomers.
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl.
  • alkoxyalkyl examples include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio and butylthio isomers.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl.
  • alkylthioalkyl examples 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. Examples of “alkylsulfinyl” include CH 3 S(O), CH 3 CH 2 S(O), CH 3 CH 2 CH 2 S(O), (CH 3 ) 2 CHS(O) and the different butylsulfinyl 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 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.
  • Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.
  • nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides.
  • nitrogen containing heterocycles which can form N-oxides.
  • tertiary amines can form N-oxides.
  • N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as t-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethydioxirane
  • 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 HOCCHC1, CF 3 C ⁇ C, CCl 3 OC 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 .
  • haloalkylsulfonyloxy examples include CF 3 S(O) 2 O, CCl 3 S(O) 2 O, CF 3 CH 2 S(O) 2 O and CF 3 CF 2 S(O) 2 O.
  • C C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 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 .
  • a compound of Formula I when a compound of Formula I is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • the term "2,8,9-trioxa-5-aza-l-silabicyclo[3.3.3]undecan-l-yl" designates the silyl radical:
  • 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
  • R 3 is selected from the group Si(R 6 )(R 7 )(R 8 ); Ge(R 6 )(R 7 )(R 8 ); 2,8,9-trioxa-5-aza- 1 -silabicyclo[3.3.3]undecan- 1 -yl optionally substituted with 1-6 C r C 3 alkyl; C r C 3 alkylthio; C r C 3 haloalkylthio; C r C 3 alkylsulfinyl; C r C 3 haloalkylsulfinyl; C r C 3 alkylsulfonyl; C1-C3 haloalkylsulfonyl; phenyl substituted with C r C 3 haloalkylthio, C r C 3 haloalkylsulfinyl or C r C 3 haloalkylsulfonyl and optionally substituted with 1-2 W; and C j -C ⁇ al
  • Y is selected from the group C 2 -Cg alkenylene and C 2 -C6 alkynylene;
  • R 1 is halogen;
  • R 2 is selected from the group H and halogen
  • R 3 is selected from the group Si(R 6 )(R 7 )(R 8 ); and C r C 2 alkyl substituted with 1-2 independently selected C j -C 4 alkoxy
  • R 4 and R 5 are independently selected from the group H, halogen, C j -C j g alkyl, cyano, S(O) t R ⁇ and OR 9
  • each R 6 and R 7 is independently selected from the group C ⁇ -C 4 alkyl and C j -C 4 alkoxy
  • each R 8 is independently selected from the group C r C 4 alkyl; C r C 4 alkoxy; and phenyl optionally substituted with 1-3 W
  • each R 9 is independently selected from the group C r C 4 alkyl and C r C haloalkyl
  • each R 11 is independently selected from the group C r C alkyl and C j -C haloalkyl
  • q is O
  • R 1 is selected from the group F and Cl in the 2-position; and R 2 is selected from the group H, F and Cl in the 6- ⁇ osition.
  • Preferred 4. Compounds of Preferred 3 wherein: Y is 1,2-ethynediyl.
  • Preferred 5. Compounds of Formula I above, and N-oxides and agriculturally-suitable salts thereof, wherein:
  • R 3 is selected from the group phenyl substituted with C j -C 3 haloalkylsulfonyloxy and optionally substituted with 1-2 W; and hydroxymethyl substituted on the carbon atom with 1-2 J.
  • Most preferred are compounds of Formula I selected from the group:
  • This invention also relates to 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.
  • 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 compound 2-(2,6-difluorophenyl)-4,5-dihydro-4-[4- [(trimethylsilyl)ethynyl]phenyl]oxazole can be desilylated with base and thus used as an intermediate for the preparation of other arthropodicides (see WO 95/04726).
  • the compound 2-(2,6-difluorophenyl)-4,5- dihydro-4-[4-[(trimethylsilyl)ethynyl]phenyl]oxazole itself is of particular note for its arthropodicidal activity.
  • the present invention also includes compounds of Formula I other than 2-(2,6-difluorophenyl)-4,5-dihydro-4-[4- [(trimethylsilyl)ethynyl]phenyl]oxazole.
  • Y is selected from the group C 2 -Cg alkenylene, C 2 -Cg haloalkenylene, C 3 -Cg alkynylene and C 3 -C 6 haloalkynylene.
  • R 1 is selected from the group halogen, C j -C alkyl, C r C 6 haloalkyl, C r C 6 alkoxy, C r C 6 haloalkoxy, SCO ⁇ R 1 ! , CN and NO 2 ; embodiments where R 2 is selected from the group H, halogen, alkyl, Ci-Cg haloalkyl, C r C 6 alkoxy, C r C 6 haloalkoxy, S(O) t R !
  • R 3 is selected from the group Si(R 6 )(R 7 )(R 8 ), Ge(R 6 )(R 7 )(R 8 ), and 2,8,9-trioxa-5-aza-l-silabicyclo[3.3.3]undecan-l-yl optionally substituted with 1-6 C ] -C 3 alkyl; embodiments where R 3 is other than C r C 3 alkylthio, C j -C 3 haloalkylthio, C r C 3 alkylsulfinyl, C r C 3 haloalkylsulfinyl, C r C 3 alkylsulfonyl, C C 3 haloalkylsulfonyl, and phenyl substituted with C j -C 3 haloalkylthio, C j -C 3 haloalkylsulfinyl or C ⁇ -C 3 haloalkyl;
  • the compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-9.
  • the definitions of A, E, Y, Z, R!-R 21 , M, J, W, q and t in the compounds of Formulae El-XIV below are as defined above in the Summary of the Invention.
  • Compounds of Formula I can be made from compounds of Formula II and silicon-containing alkynes or alkenes of Formula III. This sequence is known as the Heck reaction which has been discussed in great detail by Heck in Palladium Reagents in Organic Synthesis, Academic Press, London, (1985). Other more recent modifications of this reaction are summarized in Larock and Baker, Tetrahedron Lett. (1988) 29, 905-908 and in Cabri et al., J. Org. Chem. (1992) 57, 3558-3563.
  • a base such as triethylamine, sodium acetate, sodium carbonate or potassium carbonate is required.
  • Alkynes of Formula HI with R 3 equal to Cj-C 2 alkyl substituted with two alkoxy groups can be synthesized from either acrolein (Le Coq and Gorgues, Org. Synth., Coll. Vol. VI ( 1988) p 954) or alkyl vinyl ethers (Skattelbol, J. Org. Chem. (1966), 31, 1554).
  • Compounds of Formula II can be made from amino alcohols (or thiols) of
  • This transformation generally consists of two steps.
  • a generally useful way to do this is to treat the compound of Formula IV with an aroyl chloride in the presence of an acid acceptor (usually a tertiary amine base such as triethylamine) at room temperature or below.
  • This reaction can be carried out in an inert solvent such as dichloromethane, tetrahydrofuran, toluene and other solvents which will not react with acid chlorides or bases.
  • an inert solvent such as dichloromethane, tetrahydrofuran, toluene and other solvents which will not react with acid chlorides or bases.
  • the second step carried out is the ring closure.
  • Some useful reagent systems for this transformation include but are not limited to triphenylphosphine/carbon tetrachloride, diethyl azodicarboxylate/triphenylphosphine and thionyl chloride.
  • An especially useful method for ring closure involves treatment of the amide with thionyl chloride in benzene or another inert solvent at reflux until the starting material is consumed (usually 30 min to 3 h). The residue of this reaction is treated with an inorganic base such as sodium or potassium hydroxide in an alcoholic or aqueous medium (usually heating to reflux for 30 min to 2 h is required).
  • Many methods for ring closure to oxazolines have been compiled by Frump (Chem. Rev. (1971) 71, 483-505).
  • compounds of Formula V (where A is a direct bond) can be prepared in two steps as shown in Scheme 3.
  • compounds of Formula VI are amidoalkylated with a compound of Formula VII to form Formula VIII compounds.
  • a typical reaction involves the combination of compounds of Formula VI and VII in an acid such as sulfuric acid, methanesulfonic acid, trifluoroacetic acid, polyphosphoric acid or perchloric acid.
  • the reaction can be run in a cosolvent such as acetic acid.
  • the reaction temperature can range from -10° to 200 °C with 0°-100 °C being preferred.
  • the reaction can be carried out in an inert solvent such as chloroform, methylene chloride, benzene, toluene or ether in the presence of a Lewis acid such as aluminum chloride or boron trifluoride.
  • a Lewis acid such as aluminum chloride or boron trifluoride.
  • the acid, temperature, and time of the reaction vary according to the relative reactivity of Formula VI compound towards electrophilic substitution reactions. Amidoalkylation reactions have been extensively reviewed in the literature (see Zaugg, Synthesis (1984), 85-1 10).
  • the second step is the reduction of a Formula VHI compound to form a Formula V compound. Reductions of this type are well-known in the art (see Hudlicky, Reductions in Organic Chemistry ( 1984), 136-163).
  • Typical reducing agents include the alkali metal borohydrides and diborane.
  • U is a lower alkyl group
  • Formula VII compounds can be accomplished by refluxing glyoxylic acid derivatives (Formula IX) and commercially available benzamides (Formula X) in an inert solvent such as acetone, benzene and chloroform (Scheme 4). This procedure is known in the art (see Ben-Ishai, Tetrahedron (1975), 31, 863-866 and Tetrahedron (1977), 33, 881-883).
  • amino alcohols of Formula IV can be produced by the treatment of an amino acid derivative of Formula XI with a reducing agent.
  • amino esters are preferred, but amino acids themselves can also be used.
  • alkali metal hydrides and boranes are particularly useful.
  • treatment of a compound of Formula XI with lithium aluminum hydride at 0-50 °C in ether solvents such as tetrahydrofuran, diethyl ether, or dimethoxyethane gives an alcohol of Formula IV.
  • amino alcohols of Formula IV can be produced by the direct reaction of oximino acids and esters of Formula XII with boranes or alkali metal hydrides.
  • the reaction conditions with lithium aluminum hydride are as described for Scheme 5.
  • Aryl-substituted amino acids and esters of Formula XI are known in the art as are methods for their preparation. Useful compendia of methods for their synthesis are contained in Kukolja, J. Med. Chem. ( 1958), 28, 1886- 1896, Bohme J. Med. Chem. (1980), 23, 405-412 and O'Donnell Tetrahedron Lett. (1989), 30, 3909-3912 and references cited therein.
  • Oxime esters of Formula XII are especially suitable intermediates for the synthesis of compounds of Formula II. They can be made from aryl acetic esters of Formula XIII by reaction, in the presence of base, with nitrosating agents such as inorganic and organic nitrites as shown in Scheme 7. Typically, the compound of Formula XIII is treated with an alkyl nitrite such as butyl nitrite in an alcoholic solvent such as ethanol in the presence of a strong base such as a sodium ethoxide at the reflux temperature of the solvent.
  • an alkyl nitrite such as butyl nitrite in an alcoholic solvent such as ethanol
  • a strong base such as a sodium ethoxide at the reflux temperature of the solvent.
  • compounds of Formula XII can be produced from aryl glyoxalates of Formula XTV by treatment with hydroxylamine.
  • Aryl glyoxalates can also be made by the reaction of an organometallic species with a derivative of oxalic acid.
  • diethyl oxalate can be treated with an aryl Grignard or lithium reagent at low temperature in ether/tetrahydrofuran mixtures (Rambaud, et al., Synthesis (1988), 564-567.
  • the Grignard or lithium reagent can be generated from an optionally substituted haloaromatic compound by conventional methods.
  • Step B 2-(2.6-Difluorophenyl)-4.5-dihydro-4-(4-iodophenyl)oxazole
  • the title compound of Step A (31.0 g, 0.13 mol) and iodobenzene (40.2 g,
  • Step C 2-(2.6-Difluorophenyl)-4.5-dihydro-4-f4-r(trimethylsilyDethvnyll- phenylloxazole
  • the title compound of Step B (10 g, 25.9 mmol), (trimethylsilyl )acety lene (5.1 g, 52 mmol), bis(triphenylphosphine)palladium dichloride (910 mg, 1.29 mmol), and copper(I) iodide (250 mg, 1.31 mmol) were mixed together in a mixed solvent of triethylamine (60 mL) and acetonitrile (60 mL). The reactants were stirred at 23 °C for 18 h and the solvent evaporated.
  • the reaction mixture was concentrated under reduced pressure and then partitioned between water (100 mL) and dichloromethane (100 mL).
  • the dichloromethane was dried over magnesium sulfate and evaporated under reduced pressure to a crude oil which was chromatographed on silica gel using diethyl ether and hexane ( 1 :4) as the eluent to produce 2.0 g of the title compound of Step B as a solid melting at 74-77°C.
  • EXAMPLE 8 4-f4-(3.3-Diethoxy-l-propynyl)-2-ethoxyphenyll-2-(2.6-difluorophenyI)-4.5- dihydrooxazole
  • the title compound of Step B in Example 6 (0.50 g, 1.16 mmol), 3,3-diethoxy-l- propyne (0.20 g, 1.56 mmol), bis(rriphenylphosphine)palladium dichloride (50 mg, 0.08 mmol) and copper (I) iodide (20 mg, 0.10 mmol) were mixed together in a mixed solvent of triethylamine (15 mL) and acetonitrile (15 mL).
  • Step B f4-rr4-r2-(2.6-Difluorophenvn-4.5-dihvdro-4- oxazolyllphenyllethynyllphenyll trifluoromethanesulfonate
  • the title compound of Step A (0.43 g, 2.1 mmol), 4-iodophenyl trifluoromethanesulfonate (0.60 g, 1.7 mmol), bis(triphenylphosphine)palladium dichloride (30 mg, 0.04 mmol), and copper(I) iodide (30 mg, 0.15 mmol) were mixed together in a mixture of triethylamine (15 mL) and acetonitrile (15 mL) under nitrogen at 23 °C for
  • OEt ethoxy
  • SMe methylthio
  • CN cyano
  • G_C-Si( ⁇ -Pr) 3 CH CH-SiMe 2 (r-Bu) C ⁇ C-SiMe 2 (4-SF 5 -Ph)
  • OC-SiMe 2 ( ⁇ -Pr) CH CH-SiMe 2 (4-CI-Ph) C ⁇ C-SiMe 2 (2,4-diCl-Ph)
  • C C-Si(CH 2 CCl 3 ) 3
  • C C-CH 2 SiMe 2 (4-SF 5 -Ph)
  • 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-dime ⁇ ylfo ⁇ r ⁇ amide, 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 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • Example B Granule Compound 11 10.0% attapulgite granules (low volatile matter
  • Example C Extruded Pellet Compound 36 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 36 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 36 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • 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 frugiperda), 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 (
  • 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 califomicus and Brevipalpus obovatus; Eriophyid
  • 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, chlorpyrifos-methyl, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flucythrinate, ' tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxy
  • 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 4 and abamectin; compound 4 and fenpropathrin; compound 4 and fipronil; compound 4 and imidacloprid; compound 4 and methomyl; compound 4 and propargite; compound 4 and pyridaben; compound 4 and tebufenozide; compound 4 and tebufenpyrad; compound 5 and abamectin; compound 5 and fenpropathrin; compound 5 and fipronil; compound 5 and imidacloprid; compound 5 and methomyl; compound 4 and propargite; compound 4 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 inco ⁇ orated 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. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required.
  • 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-B for compound descriptions.
  • a ⁇ 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, (br s)-broad singlet.
  • 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 0.138 kilograms of active ingredient per hectare (about 0.13 pounds per acre) at 207 kPa (30 p.s.i.).
  • the insects were transferred from the 230-mL cup to the H.I.S. tray (one insect per cell).
  • the trays were covered and held at 27°C and 50% relative humidity for 48 hours, after which time readings were taken on the twelve cells with lima bean leaves. The four remaining cells were read at 6-8 days for delayed toxicity.
  • the following gave control efficacy levels of 80% or greater: 1 , 4, 5, 6, 11, 14, 16, 18, 22, 26, 29, 30, 34, 35, 36, 38, 39, 40 and 42.
  • TEST A The test procedure of TEST A was repeated for determining efficacy against third-instar larvae of the tobacco budworm (Heliothis virescens) except that three 230-mL (8-ounce) plastic cups with wheat germ diet were used in place of the H.I.S. tray, with each cup pre-infested with five third-instar larvae. Of the compounds tested, the following gave mortality levels of 80% or higher: 1, 4, 5 and 33.
  • 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 A 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 507c 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: 16 and 28.
  • Test units consisting of 260-mL (9-ounce) cups containing five adult boll weevils (Anthonomus grandis) were prepared. The test units were sprayed as described in TEST A with individual solutions of the test compounds. Each cup was covered with a vented lid and held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 14*. * Compound was sprayed at a concentration of 50 ppm (equivalent to 28 g ha).
  • TEST E Contact Test Against Black Bean Aphid Individual nasturtium leaves were infested with 10 to 15 aphids (all mo ⁇ hs and growth stages of Aphis fabae) and sprayed with their undersides facing up as described in TEST A. The leaves were then set in 0.94-cm (3/8-inch) diameter vials containing 4 mL of sugar solution (approximately 1.4 g per liter) and covered with a clear plastic 29-mL (1 -ounce) cup to prevent escape of the aphids that drop from the leaves. The test units were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 7 and 17.
  • 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 0.138 kilograms of active ingredient per hectare (about 0.13 pounds per acre) at 207 kPa (30 p.s.i.).
  • the leaf squares were then placed underside-up on a square of wet cotton in a petri dish and the perimeter of the leaf square was tamped down onto the cotton with forceps so that the mites could not escape onto the untreated leaf surface.
  • the test units were held at 27°C and 50% relative humidity for 48 hours, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher:
  • 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.
  • larvicide/ovicide activity of 80% or higher seven days after spraying: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12*, 13*, 14*, 15*, 16*, 17*, 18*, 19, 22*, 23*, 24*, 25*, 26*, 27*, 28*, 29*, 30*, 32*, 33*, 34*, 35*, 36*, 37*, 38*, 39*, 40* and 42*.
  • 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, 2, 4*, 5, 6, 11, 16, 18, 24, 25, 26, 29, 30, 32, 33, 34, 35, 36, 38, 39, 40 and 42. * Compound was sprayed at a concentration of 3 ppm (equivalent to 1.6 g/ha).

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PCT/US1996/015876 1995-10-12 1996-10-03 Arthropodicidal oxazolines and thiazolines WO1997013773A1 (en)

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AU73879/96A AU7387996A (en) 1995-10-12 1996-10-03 Arthropodicidal oxazolines and thiazolines
KR1019980702683A KR19990064197A (ko) 1995-10-12 1996-10-03 살절지동물성 옥사졸린 및 티아졸린
BR9610961A BR9610961A (pt) 1995-10-12 1996-10-03 Composto composição artropodicida e método para controlar artrópodes
EP96936165A EP0871634A1 (en) 1995-10-12 1996-10-03 Arthropodicidal oxazolines and thiazolines
JP9515101A JPH11513663A (ja) 1995-10-12 1996-10-03 殺節足動物性オキサゾリン類およびチアゾリン類

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6413912B2 (en) 1997-11-04 2002-07-02 Syngenta Crop Protection, Inc. Azoline derivatives
WO2008150393A1 (en) * 2007-05-31 2008-12-11 E. I. Du Pont De Nemours And Company 3-cyano-4-triazolyl phenylisoxazoline invertebrate pest control agents

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* Cited by examiner, † Cited by third party
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JP6555144B2 (ja) * 2016-02-01 2019-08-07 Jnc株式会社 液晶性化合物、液晶組成物および液晶表示素子
CN112624996B (zh) * 2019-09-24 2022-11-11 南开大学 含磺酸酯结构的噁唑啉类衍生物及其制备和在防治植食性螨中的应用

Citations (3)

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US4977171A (en) * 1988-06-09 1990-12-11 Yashima Chemical Industrial Co., Ltd. Oxa- or thia-zoline derivative
EP0432661A2 (en) * 1989-12-09 1991-06-19 Yashima Chemical Industrial Co., Ltd. 2-Substituted phenyl-2-oxazoline or thiazoline derivatives, process for producing the same and insecticides and acaricides containing the same
WO1995004726A1 (en) * 1993-08-04 1995-02-16 E.I. Du Pont De Nemours And Company Arthropodicidal oxazolines and thiazolines

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
US4977171A (en) * 1988-06-09 1990-12-11 Yashima Chemical Industrial Co., Ltd. Oxa- or thia-zoline derivative
EP0432661A2 (en) * 1989-12-09 1991-06-19 Yashima Chemical Industrial Co., Ltd. 2-Substituted phenyl-2-oxazoline or thiazoline derivatives, process for producing the same and insecticides and acaricides containing the same
US5141948A (en) * 1989-12-09 1992-08-25 Yashima Chemical Industrial Co., Ltd. 2-substituted phenyl-2-oxazoline or thiazoline derivatives, process for producing the same and insecticides and acaricides containing the same
WO1995004726A1 (en) * 1993-08-04 1995-02-16 E.I. Du Pont De Nemours And Company Arthropodicidal oxazolines and thiazolines

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6413912B2 (en) 1997-11-04 2002-07-02 Syngenta Crop Protection, Inc. Azoline derivatives
WO2008150393A1 (en) * 2007-05-31 2008-12-11 E. I. Du Pont De Nemours And Company 3-cyano-4-triazolyl phenylisoxazoline invertebrate pest control agents

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AU7387996A (en) 1997-04-30
JPH11513663A (ja) 1999-11-24
CN1199401A (zh) 1998-11-18

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