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WO1996033180A1 - Oxazoline and thiazoline arthropodicides - Google Patents

Oxazoline and thiazoline arthropodicides Download PDF

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Publication number
WO1996033180A1
WO1996033180A1 PCT/US1996/004478 US9604478W WO9633180A1 WO 1996033180 A1 WO1996033180 A1 WO 1996033180A1 US 9604478 W US9604478 W US 9604478W WO 9633180 A1 WO9633180 A1 WO 9633180A1
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Prior art keywords
group
alkyl
independently selected
haloalkyl
optionally substituted
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PCT/US1996/004478
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French (fr)
Inventor
Victor Ekow Amoo
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to JP8531760A priority Critical patent/JPH11505213A/en
Priority to EP96911528A priority patent/EP0821677A1/en
Priority to BR9608107A priority patent/BR9608107A/en
Priority to AU54391/96A priority patent/AU5439196A/en
Publication of WO1996033180A1 publication Critical patent/WO1996033180A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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.
  • arthropod pests The control of arthropod pests is extremely important in achieving high crop efficiency. Arthropod damage to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of arthropod pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.
  • U.S. 5,141,948 discloses insecticidal oxazolines and thiazolines of Formula i:
  • R 1 and R 2 are independently H, halogen, lower alkyl, lower alkoxy, nitro, lower haloalkyl or lower haloalkoxy, provided that R 1 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 alkylene, lower alkyleneoxy, lower alkylenedioxy or a di(lower alkyl)silyl;
  • 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
  • Z is O or S.
  • U.S. 4,977,171 discloses insecticidal and acaricidal oxazoline or thiazoline derivatives of Formula ii:
  • X 1 and X 2 are independently H, lower alkyl, lower alkoxy, halogen,
  • Y 1 and Y 2 are independently H, lower alkyl, lower alkoxy, lower alkylthio, cyano, nitro, halogen or trifluoromethyl;
  • Z is O or S
  • n 0 or 1.
  • WO 95/04726 discloses insecticidal and acaricidal oxazoline and thiazoline derivatives of Formula iii:
  • A is selected from the group a direct bond and C 1 -C 3 straight or branched chain alkylene
  • R 3 is selected from the group C 3 -C 7 halocycloalkyl; C 2 -C 10 haloalkenyl optionally substituted with at least one member independently selected from the group cyano and C 2 -C 6 alkoxycarbonyl; C 1 -C 10 alkyl substituted with at least one member independently selected from the group Si(R 6 )(R 7 )R 8 , cyano, C 2 -C 6 alkylcarbonyl, C 2 -C 6 haloalkylcarbonyl, C 2 -C 6 haloalkoxycarbonyl, and C 2 -C 6 alkoxycarbonyl; C 2 -C 6 alkylcarbonyl; C 2 -C 10 alkenyl optionally substituted with at least one member independently selected from R 9 ; C 2 -C 10 alkynyl optionally substituted with at least one member independently selected from R 9 ; C 2 -C 6 haloalkylcarbonyl; C 2 -C 6 al
  • R 9 is selected from the group phenyl and pyridyl, each optionally substituted with at least one member independently selected from W;
  • W is selected from the group halogen, cyano, formyl, nitro, SF 5 , C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkylthio, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 2 -C 4 alkylcarbonyl and C 2 -C 4 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 1 -C 4 alkyl and C 1 -C 4 haloalkyl;
  • X is selected from the group C 1 -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 C 1 -C 16
  • alkyl C 1 -C 16 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 7 cycloalkyl, C 3 -C 7 halocycloalkyl and C 4 -C 7 cycloalkylalkyl, each group optionally substituted with W;
  • J is selected from the group phenyl, naphthalenyl, anthracenyl, phenanthrenyl, 1H-pyrrolyl, furanyl, thienyl, 1H-pyrazolyl, 1H-imidazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, 1H-1,2,3-triazolyl, 2H-1,2,3-triazolyl, 1H-1,2,4-triazolyl, 4H-1,2,4-triazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1H-tetrazolyl, 2H-tetrazolyl, pyridinyl,
  • 1,3-dihydro-1-oxoisobenzofu ranyl 2,3-dihydro-2-oxobenzofuranyl, 3,4-dihydro-4-oxo-2H-1-benzopyranyl and 9H-fluorenyl, wherein J is optionally substituted with 1-4 R 3 ;
  • R 1 is selected from the group 1 -2 halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, S(O) t R 11 , cyano and nitro;
  • R 2 is selected from the group ⁇ , 1-2 halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl. C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, S(O) t R 1 1 , cyano and nitro;
  • each R 3 is independently selected from the group halogen, C 1 -C 16 alkyl, C 1 -C 16 , haloalkyl, C 2 -C 16 alkenyl, C 2 -C 16 haloalkenyl, C 2 -C 16 alkynyl, C 2 -C 16 haloalkynyl, C 2 -C 16 alkoxyalkyl, C 2 -C 16 alkylthioalkyl, C 2 -C 16 cyanoalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, cyano, nitro, S(O) t R 11 , OR 9 , C 1 -C 5 alkyldithio, C 1 -C 5 haloalkyldithio, formyl, C(O)R 21 , C(O)OR 21 ,
  • each R 4 is independently selected from the group C 1 -C 4 alkyl, C 1 -C 4 haloalkyl,
  • R 5 is selected from the group ⁇ , halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylthio, C 1 -C 6 haloalkylsulfinyl and C 1 -C 6 haloalkylsulfonyl;
  • each R 6 and R 7 is independently C 1 -C 12 alkyl
  • each R 8 is independently selected from the group C 1 -C 12 alkyl and phenyl
  • each R 9 is independently selected from the group H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 4 -C 7 cyanocycloalkyl, C 4 -C 7
  • alkylcycloalkyl C 4 -C 7 cycloalkylalkyl, C 4 -C 7 halocycloalkylalkyl, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylthioalkyl, C 2 -C 4 cyanoalkyl, C(O)R 18 , C(O)OR 18 ,
  • R 10 is selected from the group H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, formyl, C 2 -C 4 alkylcarbonyl, C 2 -C 4 alkoxycarbonyl, NH 2 C(O), (C 1 -C 4 alkyl)NHC(O) and (C 1 - C 4 alkyl) 2 NC(O);
  • each R 11 is independently selected from the group C 1 -C 6 alkyl, C 1 -C 6 haloalkyl,
  • each R 12 , R 14 and R 16 is independently selected from the group H, C 1 -C 6 alkyl, C 1 -C 6 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, C 3 -C 6 cycloalkyl, C 3 -C 6 hal
  • each R 13 , R 15 and R 17 is independently selected from the group H, C 1 -C 4 alkyl and C 1 -C 4 alkoxy; or
  • 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 20 is independently selected from the group H, C 1 -C 6 alkyl, C 1 -C 6
  • haloalkyl C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C(O)R 18 , C(O)OR 18 , C(O)NR 12 R 13 , S(O) 2 NR 14 R 15 , S(O) 2 R 1 1 , phenyl optionally substituted with 1-3 W 1 and benzyl optionally substituted with 1-3 W 1 ;
  • each R 21 is independently selected from the group C 1 -C 6 alkyl, C 1 -C 6 haloalkyl,
  • each M is independently selected from the group direct bond, S, O, C(O), C 1 -C 4 alkylene, C 2 -C 4 alkenylene and C 2 -C 4 alkynylene;
  • each J 1 is independently selected from the group Si(R 22 )(R 23 )(R 24 );
  • each R 22 and R 23 is independently selected from the group C 1 -C 12 alkyl and
  • each R 24 is independently selected from the group C 1 -C 12 alkyl; C 1 -C 12 alkoxy; and phenyl optionally substituted with 1-3 W 1 ;
  • W is selected from the group J, C 1 -C 6 alkoxy and C 1 -C 6 haloalkoxy;
  • each W 1 is independently selected from the group halogen, cyano, nitro, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy, C 1 -C 2 alkylthio, C 1 -C 2 haloalkylthio, C 1 -C 2 alkylsulfinyl, C 1 -C 2 haloalkylsulfinyl, C 1 -C 2 alkylsulfonyl and C 1 -C 2 haloalkylsulfonyl;
  • n 1 or 2;
  • n 1, 2 or 3;
  • p 1 or 2;
  • q 0, 1 or 2;
  • each t is independently 0, 1 or 2.
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, 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
  • 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.
  • Alkynylene denotes a straight-chain or branched alkynediyl containing one triple bond.
  • alkynylene include C ⁇ C, CH 2 C ⁇ C, C ⁇ CCH 2 and the different butynylene isomers.
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • the term "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.
  • 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 ,
  • 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
  • alkyldithio straight-chain alkyldithio moieties.
  • alkyldithio straight-chain alkyldithio moieties.
  • alkyldithio straight-chain alkyldithio moieties.
  • alkyldithio straight-chain alkyldithio moieties.
  • alkyldithio straight-chain alkyldithio moieties.
  • alkyldithio include CH 3 SS,
  • 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.
  • 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.
  • 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, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 .
  • haloalkenyl “haloalkynyl", “haloalkoxy", and the like, are defined analogously to the term “haloalkyl”.
  • CF 3 CH 2 CH CHCH 2 .
  • haloalkynyl include HC ⁇ CCHCl, CF 3 OC, CCl 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio include CC1 3 S, CF 3 S, CCl 3 CH 2 S and ClCH 2 CH 2 CH 2 S.
  • haloalkylsulfonyl 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 i -C j The total number of carbon atoms in a substituent group is indicated by the "C i -C j " prefix where i and j are numbers from 1 to 16.
  • C 1 -C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or
  • 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 .
  • 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.
  • 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 C 1 -C 16 alkyl
  • J is selected from the group phenyl, thienyl and pyridinyl, each optionally substituted with 1-3 R 3 ;
  • n 1 ;
  • Z is O
  • J is selected from the group phenyl and pyridinyl, each optionally
  • 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, C 1 -C 6 alkyl,
  • each R 9 is independently selected from the group C 1 -C 4 alkyl and C 1 -C 4 haloalkyl;
  • each R 11 is independently selected from the group C 1 -C 6 alkyl and C 1 -C 6 haloalkyl;
  • each J 1 is independently selected from the group phenyl, thienyl, pyridinyl and furanyl.
  • This invention also relates to arthropodicidal compositions comprising
  • 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 1 -R 24 , M, J 1 , W, W 1 , m, n, p, q and t in the compounds of Formulae I-XIX 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.
  • 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 dehydrobromination 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.
  • Aldehydes of Formula VII and phosphonium salts of Formula VIII are commercially available or can be prepared by known methods.
  • a typical reaction involves mixing a Formula VIII 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 of
  • 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
  • DABCO 1,4-diazabicyclo[2.2.2]octane
  • 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.
  • 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-Bu 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 XVI can be prepared by the reaction of serine derivatives (Formula XVII) with an imidate of Formula XVIII 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
  • Step E 3-(4-Chlorophenyl)- N-[2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolyl]-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-[(4-Chlorophenynmethylenel-3-[2-[2,6-difluorophenyn-4,5- dihydro-4-oxazolyl]-4-oxazolidinone
  • Step C N-[2-(2,6-Difluorophenyl)-4,5-dihydro-4-oxazolyl]-3-(4-iodophenyl)-2- propynamide
  • Step D (Z)3-[2-(2,6-Difluorophenyl)-4,5-dihydro-4-oxazolyl]-5-[(4- iodophenyl)methylene]-4-oxazolidinone
  • c-C 5 H 9 cyclopentyl
  • c-C 6 H 1 1 cyclohexyl
  • Ph phenyl
  • OMe methoxy
  • OEt ethoxy
  • OPh phenoxy
  • SMe methylthio
  • SEt ethylthio
  • SPh phenylthio
  • N(Me) 2 dimethylamino
  • CN cyano
  • NO 2 nitro
  • COOMe methoxycarbonyl
  • CHO formyl
  • COMe methylcarbonyl
  • COPh phenylcarbonyl
  • compositions 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
  • 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 any suitable ingredient such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible (“wettable”) or water-soluble.
  • Active ingredient can be any suitable ingredient such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible (“wettable”) or water-soluble.
  • Active ingredient can be
  • the entire formulation of active ingredient can be encapsulated (or
  • 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, N,N-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,
  • 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
  • the compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, stem or root feeding, seed-feeding, aquatic and
  • 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
  • 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 (
  • 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 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.
  • 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,
  • insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlo ⁇ yrifos, chlo ⁇ yrifos-methyl
  • metaldehyde methamidophos, methidathion, methomyl, methoprene, methoxychlor, monocrotophos, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, rotenone, sulprofos, tebufenozide, tefluthrin, terbufos, tetrachlorvinphos, thiodicarb, tralomethrin, trichlorfon and triflumuron; fungicides such as azoxystrobin (ICIA5504), benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), bromuconazole, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper
  • 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 15 and propargite; compound 15 and pyridaben; compound 15 and tebufenozide; compound 15 and tebufenpyrad; compound 19 and abamectin;
  • compound 19 and fenpropathrin compound 19 and fipronil; compound 19 and imidacloprid; compound 19 and methomyl; compound 19 and propargite; compound 19 and pyridaben; compound 19 and tebufenozide; compound 19 and tebufenpyrad;
  • 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.
  • 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.
  • 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.
  • 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 0.55 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 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:
  • 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.

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Abstract

Compounds of Formula (I), and their N-oxides and agriculturally-suitable salts, are disclosed which are useful as arthropodicides, wherein X is selected from the group C1-C4 alkylene, -(CH2)n-A-, -(CH2)p-A-CH2-, each group optionally substituted with one to four R4; Y and Z are independently selected from the group O and S; A is selected from the group O, S and NR10; R1 is selected from the group 1-2 halogen, C¿1?-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, S(O)tR?11¿, cyano and nitro; R2 is selected from the group H, 1-2 halogen, C¿1?-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, S(O)tR?11¿, cyano and nitro; m is 1 or 2; n is 1, 2 or 3; p is 1 or 2; and E, Q, R?4, R5, R10, R11¿, q and t are as defined in the text. Also disclosed are compositions containing the compounds of Formula (I) and a method for controlling arthropods which involves contacting the arthropods or their environment with an effective amount of a compound of Formula (I).

Description

TITLE
OXAZOLINE AND THIAZOLINE ARTHROPODICIDES
BACKGROUND OF THE INVENTION
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.
The control of arthropod pests is extremely important in achieving high crop efficiency. Arthropod damage to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of arthropod pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.
U.S. 5,141,948 discloses insecticidal oxazolines and thiazolines of Formula i:
wherein:
Figure imgf000003_0001
R1 and R2 are independently H, halogen, lower alkyl, lower alkoxy, nitro, lower haloalkyl or lower haloalkoxy, provided that R1 and R2 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 Ν; 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 oxazoline or thiazoline derivatives of Formula ii:
Figure imgf000004_0001
wherein:
X1 and X2 are independently H, lower alkyl, lower alkoxy, halogen,
trifluoromethyl or trifluoromethoxy;
Y1 and Y2 are independently H, lower alkyl, lower alkoxy, lower alkylthio, cyano, nitro, halogen or trifluoromethyl;
Z is O or S; and
n is 0 or 1.
WO 95/04726 discloses insecticidal and acaricidal oxazoline and thiazoline derivatives of Formula iii:
Figure imgf000004_0002
wherein, inter alia,
A is selected from the group a direct bond and C1-C3 straight or branched chain alkylene;
R3 is selected from the group C3-C7 halocycloalkyl; C2-C10 haloalkenyl optionally substituted with at least one member independently selected from the group cyano and C2-C6 alkoxycarbonyl; C1 -C10 alkyl substituted with at least one member independently selected from the group Si(R6)(R7)R8, cyano, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 haloalkoxycarbonyl, and C2-C6 alkoxycarbonyl; C2-C6 alkylcarbonyl; C2-C10 alkenyl optionally substituted with at least one member independently selected from R9; C2-C10 alkynyl optionally substituted with at least one member independently selected from R9; C2-C6 haloalkylcarbonyl; C2-C6 alkoxycarbonyl; C2-C6 haloalkoxycarbonyl; C(O)R9; C(O)OR9; C(O)N(R10)R1 1; OR12; tetrahydropyranyl; phenyl substituted with at least one member independently selected from W1; and an 8- to 12-membered fused bicyclic ring system containing 0-4 heteroatoms independently selected from 0-4 nitrogen, 0-2 oxygen and 0-2 sulfur, the ring system optionally substituted with at least one member independently selected from W;
R9 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, SF5, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkylthio, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C4 alkylcarbonyl and C2-C4 alkoxycarbonyl.
The oxazoline and thiazoline compounds of the present invention are not disclosed in any of these publications.
SUMMARY OF THE INVENTION
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:
Figure imgf000005_0001
wherein:
each E is independently selected from the group C1-C4 alkyl and C1-C4 haloalkyl;
X is selected from the group C1-C4 alkylene, -(CH2)n-A-, -(CH2)p-A-CH2-, each group optionally substituted with one to four R4;
Y and Z are independently selected from the group O and S;
A is selected from the group O, S and ΝR10;
Q is selected from the group H and J; or Q is selected from the group C1-C16
alkyl, C1-C16 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C7 cycloalkyl, C3-C7 halocycloalkyl and C4-C7 cycloalkylalkyl, each group optionally substituted with W;
J is selected from the group phenyl, naphthalenyl, anthracenyl, phenanthrenyl, 1H-pyrrolyl, furanyl, thienyl, 1H-pyrazolyl, 1H-imidazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, 1H-1,2,3-triazolyl, 2H-1,2,3-triazolyl, 1H-1,2,4-triazolyl, 4H-1,2,4-triazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1H-tetrazolyl, 2H-tetrazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-triazinyl, 1,2,4-triazinyl,
1,2,4,5-tetrazinyl, 1H-indolyl, benzofuranyl, benzo[b]thiophenyl,
1H-indazolyl, 1H-benzimidazolyl, benzoxazolyl, benzothiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl,
1,8-naphthyridinyl, pteridinyl, 2,3-dihydro-1H-indenyl,
1,2,3,4-tetrahydronaphthalenyl, 6,7,8,9-tetrahydro-5H-benzocycloheptenyl, 2,3-dihydrobenzofuranyl, 3,4-dihydro-2H-1-benzopyranyl,
2,3,4,5-tetrahydro-1-benzoxepinyl, 1,3-benzodioxolyl,
1,3-dihydro-1-oxoisobenzofu ranyl ; 2,3-dihydro-2-oxobenzofuranyl, 3,4-dihydro-4-oxo-2H-1-benzopyranyl and 9H-fluorenyl, wherein J is optionally substituted with 1-4 R3;
R1 is selected from the group 1 -2 halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, S(O)tR11 , cyano and nitro;
R2 is selected from the group Η, 1-2 halogen, C1-C6 alkyl, C1-C6 haloalkyl. C1-C6 alkoxy, C1-C6 haloalkoxy, S(O)tR1 1, cyano and nitro;
each R3 is independently selected from the group halogen, C1-C16 alkyl, C1-C16, haloalkyl, C2-C16 alkenyl, C2-C16 haloalkenyl, C2-C16 alkynyl, C2-C16 haloalkynyl, C2-C16 alkoxyalkyl, C2-C16 alkylthioalkyl, C2-C16 cyanoalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, cyano, nitro, S(O)tR11 , OR9, C1-C5 alkyldithio, C1-C5 haloalkyldithio, formyl, C(O)R21, C(O)OR21,
C(O)NR12R13, S(O)2NR14R15, NR16R17, Si(R6)(R7)(R8), SF5 and M-J1; each R4 is independently selected from the group C1-C4 alkyl, C1-C4 haloalkyl,
C2-C4 cyanoalkyl, C2-C4 alkoxyalkyl, and phenyl optionally substituted with 1-3 W1; or two R4 bonded to the same carbon atom can be taken together with the carbon to which they are attached to form C(=O) or C(=S);
R5 is selected from the group Η, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylthio, C1-C6 haloalkylsulfinyl and C1-C6 haloalkylsulfonyl;
each R6 and R7 is independently C1-C12 alkyl;
each R8 is independently selected from the group C1-C12 alkyl and phenyl
optionally substituted with 1-3 W1;
each R9 is independently selected from the group H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 cyanocycloalkyl, C4-C7
alkylcycloalkyl, C4-C7 cycloalkylalkyl, C4-C7 halocycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C2-C4 cyanoalkyl, C(O)R18, C(O)OR18,
C(O)NR12R13, S(O)2NR14R15 and S(O)2R11 ;
R10 is selected from the group H, C1-C4 alkyl, C1-C4 haloalkyl, formyl, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, NH2C(O), (C1-C4 alkyl)NHC(O) and (C1- C4 alkyl)2NC(O);
each R11 is independently selected from the group C1-C6 alkyl, C1-C6 haloalkyl,
C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 cyanocycloalkyl, C4-C7
alkylcycloalkyl, C4-C7 cycloalkylalkyl, C4-C7 halocycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C2-C4 cyanoalkyl, phenyl optionally substituted with 1-3 W1 and benzyl optionally substituted with 1-3 W1 ; each R12, R14 and R16 is independently selected from the group H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 cycloalkylalkyl, phenyl optionally substituted with 1-3 W1 and benzyl optionally substituted with 1-3 W1 ;
each R13, R15 and R17 is independently selected from the group H, C1-C4 alkyl and C1-C4 alkoxy; or
R12 and R13, R14 and R15, or R16 and R17, when attached to the same atom, can be taken together as (CH2)4, (CH2)5 or CH2CH2OCH2CH2, each group optionally substituted with 1-3 CH3;
each R18 is independently selected from the group C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C3- C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 cycloalkylalkyl, phenyl optionally substituted with 1-3 W1 and benzyl optionally substituted with 1-3 W1; each R19 is independently selected from the group halogen, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C4 cyanoalkyl, S(O)tR11 , OR20, C1-C5 alkyldithio, C1-C5
haloalkyldithio, SF5, formyl, C(O)R18, C(O)OR18 and Si(R6)(R7)(R8); each R20 is independently selected from the group H, C1-C6 alkyl, C1-C6
haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C(O)R18, C(O)OR18, C(O)NR12R13, S(O)2NR14R15, S(O)2R1 1, phenyl optionally substituted with 1-3 W1 and benzyl optionally substituted with 1-3 W1;
each R21 is independently selected from the group C1 -C6 alkyl, C1 -C6 haloalkyl,
C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl and C4-C7 cycloalkylalkyl;
each M is independently selected from the group direct bond, S, O, C(O), C1-C4 alkylene, C2-C4 alkenylene and C2-C4 alkynylene;
each J1 is independently selected from the group Si(R22)(R23)(R24);
Ge(R22)(R23)(R24); 2,8,9-trioxa-5-aza-1-silabicyclo[3.3.3]undecan-1-yl optionally substituted with 1-6 C1-C3 alkyl; C1-C6 alkyl substituted with 1-3 C1-C4 alkoxy; and phenyl, naphthalenyl and pyridyl, each optionally substituted with 1-4 R19;
each R22 and R23 is independently selected from the group C1-C12 alkyl and
C1-C12 alkoxy;
each R24 is independently selected from the group C1-C12 alkyl; C1-C12 alkoxy; and phenyl optionally substituted with 1-3 W1;
W is selected from the group J, C1-C6 alkoxy and C1-C6 haloalkoxy;
each W1 is independently selected from the group halogen, cyano, nitro, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio, C1-C2 alkylsulfinyl, C1-C2 haloalkylsulfinyl, C1-C2 alkylsulfonyl and C1-C2 haloalkylsulfonyl;
m is 1 or 2;
n is 1, 2 or 3;
p is 1 or 2;
q is 0, 1 or 2; and
each t is independently 0, 1 or 2.
In the above recitations, the term "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. The term "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 CH2, CH2CH2, CH(CH3), CH2CH2CH2, CH2CH(CH3) and the different butylene isomers. "Alkenylene" denotes a straight-chain or branched alkenediyl containing one olefinic bond. Examples of "alkenylene" include CH=CH, CH2CH=CH, CH=C(CH3) and the different butenylene isomers. "Alkynylene" denotes a straight-chain or branched alkynediyl containing one triple bond. Examples of "alkynylene" include C≡C, CH2C≡C, C≡CCH2 and the different butynylene isomers. "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. The term "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 CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and
CH3CH2OCH2CH2. "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 CH3SCH2, CH3SCH2CH2, CH3CH2SCH2,
CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. "Alkylsulfinyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH3S(O), CH3CH2S(O), CH3CH2CH2S(O), (CH3)2CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH3S(O)2, CH3CH2S(O)2, CH3CH2CH2S(O)2, (CH3)2CHS(O)2 and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. "Alkyldithio" denotes branched or
straight-chain alkyldithio moieties. Examples of "alkyldithio" include CH3SS,
CH3CH2SS, CH3CH2CH2SS, (CH3)2CHSS and the different butyldithio and
pentyldithio isomers. "Cyanoalkyl" denotes an alkyl group substituted with one cyano group. Examples of "cyanoalkyl" include NCCH2, NCCH2CH2 and CH3CH(CN)CH2. "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. "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. One skilled in the art will appreciate that not all 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.
The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. The term "1-2 halogen" indicates that one or two of the available positions for that substituent may be halogen which are independently selected. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include F3C, ClCH2, CF3CH2 and CF3CCl2. The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include (Cl)2C=CHCH2 and
CF3CH2CH=CHCH2. Examples of "haloalkynyl" include HC≡CCHCl, CF3OC, CCl3C≡C and FCH2C≡CCH2. Examples of "haloalkoxy" include CF3O, CCl3CH2O, HCF2CH2CH2O and CF3CH2O. Examples of "haloalkylthio" include CC13S, CF3S, CCl3CH2S and ClCH2CH2CH2S. Examples of "haloalkylsulfonyl" include CF3S(O)2, CCl3S(O)2, CF3CH2S(O)2 and CF3CF2S(O)2.
The total number of carbon atoms in a substituent group is indicated by the "Ci-Cj" prefix where i and j are numbers from 1 to 16. For example, C1-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C2 alkoxyalkyl designates CH3OCH2: C3 alkoxyalkyl designates, for example, CH3CH(OCH3), CH3OCH2CH2 or
CH3CH2OCH2; 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 CH3CH2CH2OCH2 and CH3CH2OCH2CH2. Examples of "alkylcarbonyl" include C(O)CH3, C(O)CH2CH2CH3 and C(O)CH(CH3)2. Examples of
"alkoxycarbonyl" include CH3OC(=O), CH3CH2OC(=O), CH3CH2CH2OC(=O),
(CH3)2CHOC(=O) and the different butoxycarbonyl isomers. In the above recitations, 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-1-silabicyclo[3.3.3]undecan-1-yl" designates the silyl radical:
Figure imgf000011_0001
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.
When a group contains a substituent which can be hydrogen, for example R2 or
R10, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, 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.
Preferred compounds for reasons of better activity and/or ease of synthesis are:
Preferred 1. Compounds of Formula I above, and N-oxides and
agriculturally-suitable salts thereof, wherein:
X is -(CH2)n-A- optionally substituted with one to four R4; Y is O;
A is O;
Q is selected from the group J and C1-C16 alkyl;
J is selected from the group phenyl, thienyl and pyridinyl, each optionally substituted with 1-3 R3;
m is 1 ; and n is 1.
Preferred 2. Compounds of Preferred 1 wherein:
Z is O;
Q is J;
J is selected from the group phenyl and pyridinyl, each optionally
substituted with 1-3 R3; and
q is O.
Preferred 3. Compounds of Preferred 2 wherein:
R1 is selected from the group F and Cl in the 2-position;
R2 is selected from the group H, F and Cl in the 6-position; each R3 is independently selected from the group halogen, C1-C6 alkyl,
C1-C6 haloalkyl, S(O)tR1 1, OR9 and M-J1;
each R9 is independently selected from the group C1-C4 alkyl and C1-C4 haloalkyl;
each R11 is independently selected from the group C1 -C6 alkyl and C1-C6 haloalkyl; and
each J1 is independently selected from the group phenyl, thienyl, pyridinyl and furanyl.
Most preferred are compounds of Preferred 3 selected from the group:
(Z)-5-[(4-chlorophenyl)methylene]-3-[2-(2,6-difluorophenyl)-4,5-dihydro-4- oxazolyl]-4-oxazolidinone;
(Z)-3-[2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolyl]-5-[[4- (trifluoromethyl)phenyl]methylene]-4-oxazolidinone;
(Z)-5-[(4,-chloro[1,1'-biphenyl]-4-yl)methylene]-3-[2-(2,6-difluorophenyl)-4,5- dihydro-4-oxazolyl]-4-oxazolidinone;
(Z)-3-[2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolyl]-5-[(4'-fluoro[1,1'- biphenyl]-4-yl)methylene]-4-oxazolidinone; and
(Z)-5-[(2',4,-dichloro[1,1'-biphenyl]-4-yl)methylene]-3-[2-(2,6-difluorophenyl)- 4,5-dihydro-4-oxazolyl]-4-oxazolidinone.
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. 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.
DETAILS OF THE INVENTION
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, R1-R24, M, J1, W, W1, m, n, p, q and t in the compounds of Formulae I-XIX below are as defined above in the Summary of the Invention.
Compounds of Formula I (R5 = H, X = -C(R4a)2A-) can be prepared by the reaction of a Formula II compound with a Formula HI compound in the presence of a base such as sodium hydride or lithium diisopropylamide (Scheme 1). The reaction may be run in the presence or absence of a solvent such as tetrahydrofuran (THF), dimethylformamide (DMF), 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.
Figure imgf000013_0001
Compounds of Formula II (Y = S) may be prepared by thionation of a Formula II compound (Y = O) with 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4- disulfide (Lawesson's Reagent). Thionation reactions have been thoroughly reviewed by
M. Cava and M. Levinson in Tetrahedron (1987), 41, 5061-5087. This transformation is shown in Scheme 2.
Figure imgf000013_0002
Formula II compounds (Y = O) can be prepared by a condensation reaction between a propiolic acid of Formula IV (V = OH) and an amine of Formula V in the presence of a coupling agent such as dicyclohexylcarbodiimide (DCC). Typically, the reaction involves mixing a Formula IV compound (V = OH) with an equimolar amount of a Formula V compound in a suitable solvent such as methylene chloride, ethyl acetate or DMF and adding a slight excess of DCC. The reaction temperature can vary from 0-150°C. (A review of DCC coupling reactions can be found in Tetrahedron (1981), 37, 233). Alternatively, the condensation reaction can be performed with an acid chloride of Formula IV (V = Cl) and a Formula V compound in the presence of an acid scavenger (usually a tertiary amine base such as triethylamine) at room temperature or below. 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.
Figure imgf000014_0001
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 dehydrobromination 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. An example of this transformation can be found in Organic Synthesis, Coll. Vol. II, p 270. Alternative methods of making compounds of Formula IV (V = OH) have been described by Chenault and Dupin in Synthesis (1987), 498, by Yamanaka et al. in Synthesis (1992), 746 and by Hendrickson and Hussoin in Synthesis (1989), 217. A Formula IV compound (V = OH) can further be transformed into a Formula IV compound (V = Cl) using conventional methods of converting a carboxylic acid into an acid chloride. (See Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York).
Figure imgf000015_0001
Compounds of Formula VI (L = Me, Et) can be prepared by the reaction of aldehydes of Formula VII with phosphonium salts of Formula VIII (L = Me, Et) in the presence of a strong base. Aldehydes of Formula VII and phosphonium salts of Formula VIII are commercially available or can be prepared by known methods. A typical reaction involves mixing a Formula VIII 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. The temperature of the reaction can vary from
-70-200°C with a preferred temperature range of 0-100°C. The Wittig reaction has been reviewed by Maercker in Organic Reactions (1965), 14, 270-490. The transformation is illustrated in Scheme 5.
Figure imgf000015_0002
, .
Alternatively, 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
1,4-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.
Figure imgf000016_0001
Scheme 7 shows the preparation of compounds of Formula IX (where
X = -A(CH2)n-). The reaction involves the cyclization of a Formula X compound with a compound of Formula XI in the presence of a base. Compounds of Formula XI are commercially available or can be prepared by known methods. Examples of bases that can be used include sodium hydride or potassium t-Bu 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.
Figure imgf000016_0002
Compounds of Formula X (Y = O) can be prepared by reaction of a carboxylic acid of Formula XII with an amine of Formula V. Compounds of Formula XII are commercially available or can be prepared by known methods. The reaction conditions are as described for Scheme 3.
Figure imgf000016_0003
Compounds of Formula IX (where X is -CH2(CH2)n-) can be prepared by cyclization of a bromide of Formula XIII in the presence of a base as shown in Scheme 9. Reaction conditions are similar to those of Scheme 7.
Figure imgf000017_0001
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.
Figure imgf000017_0002
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
[hydroxy(tosyloxy)iodo]benzene in refluxing acetonitrile. (See J. Org. Chem. (1986), 51, 2669-2671).
Figure imgf000018_0001
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.
Figure imgf000018_0002
Compounds of Formula XVI can be prepared by the reaction of serine derivatives (Formula XVII) with an imidate of Formula XVIII 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.
Figure imgf000019_0001
As depicted in Scheme 14, 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.
Figure imgf000019_0002
It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of
protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in Schemes 1-? in an order other than that implied by the particular sequence presented to prepare the compounds of Formula I. One skilled in the art will also recognize that compounds of Formula I and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.
Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except for
chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated.
1H NMR spectra are reported in ppm downfield from tetramethylsilane; s = singlet, d = doublet, t = triplet, q = quartet, ABq = "AB" quartet, m = multiplet, dd = doublet of doublets, br s = broad singlet.
EXAMPLE 1
Step A: Methyl 2,6-difluorobenzenecarboximidate
An amount of 10.62 g (0.068 mol) of 2,6-difluorobenzamide was added to a suspension of 10.0 g (0.068 mol) of trimethyloxonium tetrafluoroborate in 70 mL of methylene chloride. The reaction was stirred under nitrogen overnight. Saturated aqueous sodium bicarbonate was slowly added and the mixture was extracted with methylene chloride. The combined extracts were washed with brine, dried over MgSO4 and evaporated. The residue was passed through a silica gel column eluting with EtOAc:hexane (1:6) to give 9.13 g of the title compound of Step A as a pale yellow oil. 1H NMR (CDCl3): δ 7.70 (br s.1H), 7.73 (m,1H). 6.94 (t,2H). 3.94 (s,3H).
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 H2O. The mixture was stirred at reflux for 1.5 h. Volatiles were evaporated under reduced pressure and the residue was partitioned between ethyl acetate (EtOAc) and H2O. The EtOAc layer was washed with brine, dried over MgSO4 and evaporated. The residue was passed through a silica gel column eluting with
EtOAc:hexane (1:4) to give 6.0 g of the title compound of Step B as a colorless oil.
1H NMR (CDCl3): δ 7.43 (m,1H), 6.98 (t,2H) 5.00 (t,1H), 4.63-4.72 (2t,2H), 3.84
(s,3H).
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
2M solution of ammonia in MeOH was stirred at room temperature overnight. Evaporation of the solvent afforded 9.04 g of the title compound of Step C as a white powder melting at 148-149°C. 1H NMR (Me2SO-d6): δ 7.67 (m,1H), 7.49 (br s,1H), 7.39 (br s,1H), 7.27 (t,2H), 4.85 (t,1H), 4.56 (2t,2H).
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 H2O. 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. Et2O and H2O were added and the mixture was extracted with EtOAc. The combined extracts were washed with brine, dried over MgSO4 and evaporated to give 0.350 g of the title compound of Step D as a white solid melting at 81-85°C. 1H NMR (Me2SO-d 6): δ 7.62 (m,1H), 7.24 (t,2H), 5.15 (t,1H), 4.70 (t.1H), 3.83 (t,1H).
Step E: 3-(4-Chlorophenyl)- N-[2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolyl]-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),
4-dimethylaminopyridine (0.061 g, 0.0005 mol) and 3-(4-chlorophenyl)propiolic acid (0.963 g, 0.005 mol) in 18 mL of methylene chloride. The mixture was stirred at room temperature for 0.5 h and then the solids were filtered off. The filtrate was evaporated and the residue was passed through a silica gel column eluting with EtOAc :hexanes (1:3) to give 1.66 g of the title compound of Step E as a yellow solid melting at 134- 135°C. 1H ΝMR (CDCl3): δ 4.35 (dd,1H), 4.70 (t,1H), 6.20 (m.1H), 6.51 (d.1H), 7.00 (t,2H), 7.35 (m,2H), 7.45 (m,3H).
Step F: (Z)-5-[(4-Chlorophenynmethylenel-3-[2-[2,6-difluorophenyn-4,5- dihydro-4-oxazolyl]-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. The organic layer was dried (MgSO4) and evaporated to give a yellow solid which, upon trituration with ether/hexanes, afforded 0.432 g of the title compound of Step F, a compound of the invention, as a white solid melting at 131 - 134°C. 1H ΝMR (CDCl3): δ 4.25 (dd.1H), 4.70 (t,1H), 5.48 (ABq,2H), 6.28 (s,1H), 6.50 (dd.1H), 7.00 (t,2H), 7.35 (d,2H), 7.50 (m,1H), 7.60 (d,2H). EXAMPLE 2
Step A: Methyl 3-(4-iodophenyl)-2-propenoate
An amount of 5.0 g (0.0215 mol) of 4-iodobenzaldehyde was dissolved in 22 mL of acetonitrile. Methyl(triphenylphosphoranylidene) acetate (14.41 g, 0.043 mol) was added and the mixture was refluxed overnight. The reaction was quenched with 1N HCl and extracted three times with EtOAc. The combined extracts were washed with water, dried (MgSO4) and evaporated. The residue was passed through a silica gel column eluting with EtOAc:hexanes (1: 10) to give 5.60 g of the title compound of Step A as an oil. 1H-NMR (CDCl3): δ 3.805 (s,3H), 6.439 (d,1H), 7.228 (d,2H), 7.629 (d,1H), 7.712 (d,2H).
Step B: 3-(4-Iodophenyl)-2-propynoic acid
5.60 g (0.019 mol) of the title compound of Step A was dissolved in 19 mL of methylene chloride. The mixture was cooled to 0°C and bromine (0.97 mL) was added dropwise. The reaction was stirred at room temperature for 1 h and the solvents were evaporated. The residue was added to a solution of 4.78 g of KOH in 23 mL of EtOH at 50°C. This mixture was refluxed for 18 h. The solvents were evaporated and the solid was dissolved in water. Insoluble material was filtered and the pH of the solution was adjusted to 2 using HCl. The resulting precipitate was filtered to give 4.7 g of the title compound of Step B as an off-white solid melting at 180-184°C. 1H-NMR (DMSO-d6): δ 7.390 (d,2H), 7.50 (d,2H).
Step C: N-[2-(2,6-Difluorophenyl)-4,5-dihydro-4-oxazolyl]-3-(4-iodophenyl)-2- propynamide
To a cooled (0°C) solution of 0.680 g (0.0025 mol) of the title compound of Step B in 7 mL CH2Cl2 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. Evaporation of the solvents from the filtrate produced a residue which was passed through a silica gel column eluting with EtOAc:hexanes ( 1 : 1 ) to give 0.960 g of the title compound of Step C as a solid melting at 150-152°C. 1H-ΝMR (CDCl3): δ 4.340 (m,1H), 4.691 (t,1H), 6.204 (m.1H), 7.200 (m,3H), 7.205 (d,2H), 7.449 (m,1H), 7.684 (d,2H).
Step D: (Z)3-[2-(2,6-Difluorophenyl)-4,5-dihydro-4-oxazolyl]-5-[(4- iodophenyl)methylene]-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 the cold. The resulting mixture was extracted with EtOAc and the combined extracts were washed with water. The organic layer was dried (MgSO4) and evaporated. The residue was passed through a silica gel column eluting with EtOAc:h exane (1:2) to give 0.170 g of the title compound of Step D, a compound of the invention, as an oil which solidified on standing to a solid melting at 165-167°C. 1H-NMR (CDCl3): δ 4.471 (q.1H), 4.679 (t,1H), 5.439 (d,1H), 5.516 (d,1H), 6.237 (s,1H), 6.507 (m,1H), 7.026 (t,2H), 7.381 (m,2H), 7.505 (m,1H), 7.683 (m,2H).
EXAMPLE 3
(Z)-5-[(2',4'-Dichloro[1,1'-biphenyl]-4-yl)methylenel-3-[2-(2,6-difluorophenyl)-4,5- dihydro-4-oxazolyl]-4-oxazolidinone
An amount of the title compound of Step D in Example 2 (0.482 g, 0.001 mol) was dissolved in 2 mL of dimethoxyethane. To this solution was added 1.04 mL of 2M Na2CO3, 0.036 g (0.00003 mol) of tetrakis(triphenylphosphine)palladium(0) and 0.191 g (0.001 mol) of 2,4-dichlorobenzeneboronic acid in 0.53 mL of MeOH. The reaction was stirred at 80°C overnight and then was quenched with 9.75 mL of a 2M Na2CO3 solution containing 0.78 mL of 30% NH4OH. The mixture was extracted with methylene chloride and the organic extracts were washed with aqueous saturated NaHCO3. The organic extracts were dried, filtered and evaporated to give a residue which was passed through a silica gel column eluting with EtOAc:hexanes ( 1 :2) to give 0.300 g of the title compound of Example 3, a compound of the invention, as a solid melting at 151-153°C. 1H-NMR (CDCl3): δ 4.488 (m, 1H), 4.688 (m, 1H), 5.532 (m,1H), 5.463 (d.1H), 6.370 (s.1H), 6.522 (m.1H). 7.026 (m.2H), 7.285 (m.2H), 7.424 (m,2H), 7.486 (m,2H), 7.719 (m,2H).
EXAMPLE 4
(Z)-3-[2-[2,6-Difluorophenyl)-4,5-dihydro-4-oxazolyl]-5-[[4- [(trimethylsilyl)ethynynphenyllmethylene-4-oxazolidinone An amount of the title compound of Step D in Example 2 (0.482 g, 0.001 mol) was added to 2.3 mL of CH3CN and 2.3 mL of Et3N. To this mixture was added (trimethylsilyl)acetylene (0.28 mL, 0.002 mol), bis(triphenylphosphine)palladium(II) chloride (0.035 g, 0.00005 mol) and copper(I) iodide (0.0095 g, 0.00005 mol). The reaction mixture was stirred at room temperature overnight. The solvents were evaporated, water was added to the residue and the resulting mixture was extracted with EtOAc. The EtOAc extract was washed with brine, dried (MgSO4), filtered and evaporated. The residue was passed through a silica gel column eluting with
EtOAc:hexanes (1:2) to give 0.380 g of a solid melting at 123-124°C. 1H-NMR (CDCI3): 0.253 (s,9H), 4.449 (m,1H), 4.674 (m.1H), 5.445 (d,1H), 5.525 (d,1H), 6.288 (s,1H), 6.512 (m,1H), 7.023 (m,2H), 7.445 (m,3H), 7.581 (d,2H).
By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 7 can be prepared. The following abbreviations are used in the Tables which follow: t = tertiary, s = secondary, n = normal, i = iso, c = cyclo, Me = methyl, Et = ethyl, Pr = propyl, n-Pr = n-propyl, i-Pr = isopropyl, Bu = butyl, n-Bu = n-butyl, i-Bu = i-butyl, s-Bu = s-butyl, t-Bu = t-butyl,
c-C5H9 = cyclopentyl, c-C6H1 1 = cyclohexyl, Ph = phenyl, OMe = methoxy,
OEt = ethoxy, OPh = phenoxy, SMe = methylthio, SEt = ethylthio, SPh = phenylthio, N(Me)2 = dimethylamino, CN = cyano, NO2 = nitro, COOMe = methoxycarbonyl, CHO = formyl, COMe = methylcarbonyl, COPh = phenylcarbonyl,
SiMe3 = trimethylsilyl, and SO2Me = methylsulfonyl.
Figure imgf000024_0001
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Formulation / Utility
Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable
concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble. Active ingredient can be
(micro)encapsulated and further formed into a suspension or solid formulation;
alternatively the entire formulation of active ingredient can be encapsulated (or
"overcoated"). Encapsulation can control or delay release of the active ingredient.
Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.
The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
Figure imgf000072_0001
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, N,N-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, including emulsifiable concentrates, 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. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4, 144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2.095,558 and U.S. 3,299,566.
For further information regarding the art of formulation, see U.S. 3,235,361 , Col. 6, line 16 through Col. 7, line 19 and Examples 10-41 ; U.S. 3,309,192. Col. 5. line 43 through Col. 7, line 62 and Examples 8, 12. 15, 39, 41, 52, 53, 58. 132. 138- 140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.
In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A-C.
Figure imgf000074_0001
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. Nevertheless, 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.
Specifically, 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 frugiperdα), 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 (Nilaparvata lugens), small brown planthopper (Laodelphax striatellus), rice stem borer (Chilo suppressalis), rice leafroller (Cnaphalocrocis medinalis), black rice stink bug (Scotinophara lurida), rice stink bug (Oebalus pugnax), rice bug (Leptocorisa chinensis), slender rice bug (Cletus puntiger), and southern green stink bug (Nezara viridula). 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. 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. Examples of such agricultural protectants with which compounds of this invention can be formulated are: insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chloφyrifos, chloφyrifos-methyl, cyfluthrin, beta-cyfluthrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenpropathrin, fenvalerate, fipronil, flucythrinate, tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion,
metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, monocrotophos, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, rotenone, sulprofos, tebufenozide, tefluthrin, terbufos, tetrachlorvinphos, thiodicarb, tralomethrin, trichlorfon and triflumuron; fungicides such as azoxystrobin (ICIA5504), benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), bromuconazole, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, cymoxanil, cyproconazole, cyprodinil (CGA 219417), diclomezine, dicloran, difenoconazole, dimethomorph, diniconazole, diniconazole-M, dodine, edifenphos, epoxyconazole (BAS 480F), fenarimol, fenbuconazole, fenpiclonil, fenpropidin, fenpropimorph, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fosetyl-aluminum, furalaxyl, hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, kresoxim-methyl (BAS 490F), mancozeb, maneb, mepronil, metalaxyl, metconazole, myclobutanil, neo-asozin (ferric methanearsonate), oxadixyl, penconazole, pencycuron, probenazole, prochloraz, propiconazole, pyrifenox, pyroquilon, sulfur, tebuconazole, tetraconazole, thiabendazole, thiophanate-methyl, thiram, triadimefon, triadimenol, tricyclazole, triticonazole, uniconazole, validamycin and vinclozolin; nematocides such as aldoxycarb and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and biological agents such as Bacillus thuringiensis. Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi.
In certain instances, combinations with other arthropodicides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management.
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. Specifically preferred mixtures (compound numbers refer to compounds in Index Tables A-C) 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 15 and propargite; compound 15 and pyridaben; compound 15 and tebufenozide; compound 15 and tebufenpyrad; compound 19 and abamectin;
compound 19 and fenpropathrin; compound 19 and fipronil; compound 19 and imidacloprid; compound 19 and methomyl; compound 19 and propargite; compound 19 and pyridaben; compound 19 and tebufenozide; compound 19 and tebufenpyrad;
compound 23 and abamectin; compound 23 and fenpropathrin; compound 23 and fipronil; compound 23 and imidacloprid; compound 23 and methomyl; compound 23 and propargite; compound 23 and pyridaben; compound 23 and tebufenozide; and compound 23 and tebufenpyrad.
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. Thus, 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. Alternatively, 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. 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.
The following 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. The following abbreviations are used in the Index Tables which follow: t = tertiary, Me = methyl, Et = ethyl, Bu = butyl, Ph = phenyl, OMe = methoxy, OEt = ethoxy, CHO = formyl, CN = cyano, and
TMS = trimethylsilyl.
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
INDEX TABLE C
Cmpd No. 1H NMR Data (CDCl3 solution unless indicated otherwise)a
2 δ4.48 (m,1H), 4.68 (t,1H), 5.20 (dd,2H), 6.33 (s,1H), 6.55 (dd,1H), 7.02
(t,2H), 7.26 (t,1H), 7.35 (t,2H), 7.50 (m,1H), 7.68 (d,2H).
13 δ4.47 (dd,1H), 4.68 (t,1H), 5.45 (d,1H), 5.53 (d,1H), 6.24 (s,1H), 6.51
(dd,1H).7.03 (t,2H), 7.21 (m,1H), 7.37 (d,1H), 7.49 (m,2H), 7.87 (s,1H)
17 δ4.47 (m,1H), 4.68 (m,1H), 5.46 (d,1H), 5.53 (d,1H), 6.38 (s,1H).6.53
(m,1H), 7.02 (t,2H), 7.42 (m,5H), 7.51 (m,2H), 7.62 (m,1H), 7.86 (s,1H)
27 δ4.40 (m,1H), 4.69 (m,1H), 5.49 (d,1H), 5.56 (d,1H), 6.39 (s,1H), 6.55
(m,1H), 7.03 (t,2H), 7.36 (d,2H), 7.49 (m,3H), 7.64 (m,1H), 7.76 (d,2H).
8.01 (d,1H), 10.01 (s,1H)
30 δ4.400 (m,1H), 4.687 (m,1H), 5.530 (d,1H), 5.572 (d,1H), 6.391 (s,1H),
6.700 (m,1H), 7.026 (t,2H), 7.281 (m,5H), 7.488 (m,2H), 7.698 (m,2H)
31 δ4.477 (m,1H), 4.683 (m,1H), 5.459 (d,1H), 5.537 (d,1H), 6.381 (s,1H),
6.537 (m.1H), 7.022 (t,2H), 7.340 (m,3H), 7.482 (m,2H), 7.536 (m,1H),
7.695 (m,3H)
34 δ 3.80 (s,3H), 4.51 (m,1H), 4.70 (m,1H), 5.45 (d,1H), 5.53 (d,1H), 6.36
(s,1H), 6.52 (m,1H), 6.72 (m,2H), 7.02 (m,2H), 7.27 (m,1H), 7.49
(m,3H), 7.69 (d,2H).
35 δ 3.73 (s,3H), 4.48 (m,1H), 4.68 (m,1H), 5.45 (d,1H), 5.53 (d,1H), 6.39
(s.1H), 6.53 (m,1H), 6.88 (d,1H), 7.03 (m,2H), 7.25 (m,3H), 7.49 (m,1H),
7.75 (d,1H) 36 δ4.66 (m,1H), 4.69 (m,1H), 5.50 (m,1H), 5.25 (m,1H), 6.48 (s,1H), 6.53 (m,1H), 7.03 (t,2H), 7.05 (m,1H), 7.47 (m,2H), 7.80 (m,4H), 8.12 (m,1H)
37 δ 4.66 (m,1H), 4.69 (t,1H), 5.44 (d,1H), 5.54 (d,1H), 6.55 (m,1H), 7.01
(t,2H) 7.09 (s,1H), 7.49 (m,4H), 7.80 (m,2H), 8.17 (m.2H) a 1H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by
(s)-singlet, (d)-doublet, (t)-triplet, (m)-multiplet, (dd)-doublet of doublets.
BIOLOGICAL EXAMPLES OF THE INVENTION TEST A
Fall Armyworm
Test units, each consisting of a H.I.S. (high impact styrene) tray with 16 cells were prepared. Wet filter paper and approximately 8 cm2 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. 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.
TEST B
Two-Spotted Spider Mite
Pieces of kidney bean leaves, each approximately 6.5 cm2 (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 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:
The same units were held an additional 5 days and read for larvicide/ovicide mortality and/or developmental effects. Of the compounds tested, the following gave activity levels of 80% or higher: 20.
TEST C
Larval two-Spotted Spider Mites (Tetranychus urticae)
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. Of the compounds tested, 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*.
*Compound was tested at 5 ppm (equivalent to 2.8 g/ha).
TEST D
Fall Armyworm Whole Plant Test
Solutions of the 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).

Claims

CLAIMS What is claimed is:
1. A compound selected from Formula I, N-oxides and agriculturally-suitable salts thereof,
Figure imgf000083_0001
wherein:
each E is independently selected from the group C1-C4 alkyl and C1-C4 haloalkyl; X is selected from the group C1-C4 alkylene, -(CH2)n-A-, -(CH2)p-A-CH2-, each group optionally substituted with one to four R4;
Y and Z are independently selected from the group O and S;
A is selected from the group O, S and ΝR10;
Q is selected from the group H and J; or Q is selected from the group C1-C16 alkyl, C1-C16 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C7 cycloalkyl, C3-C7 halocycloalkyl and C4-C7 cycloalkylalkyl, each group optionally substituted with W;
J is selected from the group phenyl, naphthalenyl, anthracenyl, phenanthrenyl, 1H-pyrrolyl, furanyl, thienyl, 1H-pyrazolyl, 1H-imidazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, 1H-1,2,3-triazolyl, 2H-1,2,3-triazolyl, 1H-1,2,4-triazolyl, 4H-1,2,4-triazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl,
1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1H-tetrazolyl, 2H-tetrazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,4,5-tetrazinyl, 1H-indolyl, benzofuranyl, benzo[b]thiophenyl, 1H-indazolyl, 1H-benzimidazolyl, benzoxazolyl, benzothiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 1,8-naphthyridinyl, pteridinyl, 2,3-dihydro-1H-indenyl,
1,2,3,4-tetrahydronaphthalenyl, 6,7,8,9-tetrahydro-5H-benzocycloheptenyl, 2,3-dihydrobenzofuranyl, 3,4-dihy dro-2H-1-benzopyranyl,
2,3,4,5-tetrahydro-1-benzoxepinyl, 1,3-benzodioxolyl, 1,3-dihydro-1-oxoisobenzofuranyl; 2,3-dihydro-2-oxobenzofuranyl, 3,4-dihydro-4-oxo-2H-1-benzopyranyl and 9H-fluorenyl, wherein J is optionally substituted with 1-4 R3;
R1 is selected from the group 1-2 halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, S(O)R11, cyano and nitro;
R2 is selected from the group H, 1-2 halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, S(O)tR1 1, cyano and nitro;
each R3 is independently selected from the group halogen, C1-C16 alkyl, C1-C16 haloalkyl, C2-C16 alkenyl, C2-C16 haloalkenyl, C2-C16 alkynyl, C2-C16 haloalkynyl, C2-C16 alkoxyalkyl, C2-C16 alkylthioalkyl, C2-C16 cyanoalkyl,
C3-C6 cycloalkyl, C3-C6 halocycloalkyl, cyano, nitro, S(O)tR11 , OR9, C1-C5 alkyldithio, C1-C5 haloalkyldithio, formyl, C(O)R21, C(O)OR21,
C(O)NR12R13, S(O)2NR14R15, NR16R17 , Si(R6)(R7)(R8), SF5 and M-J1; each R4 is independently selected from the group C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 cyanoalkyl, C2-C4 alkoxyalkyl, and phenyl optionally substituted with
1-3 W1; or two R4 bonded to the same carbon atom can be taken together with the carbon to which they are attached to form C(=O) or C(=S);
R5 is selected from the group H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalky lthio, C1-C6 haloalky lsulfiny l and C1-C6 haloalkylsulfonyI;
each R6 and R7 is independently C1-C12 alkyl;
each R8 is independently selected from the group C1-C12 alkyl and phenyl
optionally substituted with 1-3 W1;
each R9 is independently selected from the group H, C1-C6 alkyl, C1-C6 haloalkyl.
C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 cyanocycloalkyl, C4-C7
alkylcycloalkyl, C4-C7 cycloalkylalkyl, C4-C7 halocycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C2-C4 cyanoalkyl, C(O)R18, C(O)OR18, C(O)NR12R13, S(O)2NR14R15 and S(O)2R11 ;
R10 is selected from the group H, C1-C4 alkyl, C1-C4 haloalkyl, formyl, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, NH2C(O), (C1-C4 alkyl)NHC(O) and (C1-C4 alkyl)2NC(O);
each R1 1 is independently selected from the group C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 cyanocycloalkyl, C4-C7 alkylcycloalkyl, C4-C7 cycloalkylalkyl, C4-C7 halocycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C2-C4 cyanoalkyl, phenyl optionally substituted with 1-3 W1 and benzyl optionally substituted with 1-3 W1; each R12, R14 and R16 is independently selected from the group H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C3-C6 cycloalkyl,
C3-C6 halocycloalkyl, C4-C7 cycloalkylalkyl, phenyl optionally substituted with 1-3 W1 and benzyl optionally substituted with 1-3 W1;
each R13, R15 and R17 is independently selected from the group H, C1-C4 alkyl and C1-C4 alkoxy; or
R12 and R13, R14 and R15, or R16 and R17, when attached to the same atom, can be taken together as (CH2)4, (CH2)5 or CH2CH2OCH2CH2, each group optionally substituted with 1-3 CH3;
each R18 is independently selected from the group C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl,
C4-C7 cycloalkylalkyl, phenyl optionally substituted with 1-3 W1 and benzyl optionally substituted with 1-3 W1;
each R19 is independently selected from the group halogen, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl,
C2-C4 cyanoalkyl, S(O)tR11 , OR20, C1-C5 alkyldithio, C1-C5
haloalkyldithio, SF5, formyl, C(O)R18, C(O)OR-8 and Si(R6)(R7)(R8); each R20 is independently selected from the group H, C1-C6 alkyl, C1-C6
haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl. C2-C6 alkynyl, C2-C6 haloalkynyl, C(O)R18, C(O)OR18, C(O)NR12R13, S(O)2NR14R15,
S(O)2R11 , phenyl optionally substituted with 1-3 W1 and benzyl optionally substituted with 1-3 W1;
each R21 is independently selected from the group C1-C6 alkyl, C1-C6 haloalkyl,
C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl and C4-C7 cycloalkylalkyl;
each M is independently selected from the group direct bond, S, O, C(O), C1-C4 alkylene, C2-C4 alkenylene and C2-C4 alkynylene;
each J1 is independently selected from the group Si(R22)(R23)(R24);
Ge(R22)(R23)(R24); 2,8,9-trioxa-5-aza-1-silabicyclo[3.3.3]undecan-1-yl optionally substituted with 1-6 C1-C3 alkyl; C1-C6 alkyl substituted with 1-3 C1-C4 alkoxy; and phenyl, naphthalenyl and pyridyl, each optionally substituted with 1-4 R19;
each R22 and R23 is independently selected from the group C1-C12 alkyl and
C1-C12 alkoxy;
each R24 is independently selected from the group C1-C12 alkyl; C1-C12 alkoxy; and phenyl optionally substituted with 1-3 W1;
W is selected from the group J, C1-C6 alkoxy and C1-C6 haloalkoxy;
each W1 is independently selected from the group halogen, cyano, nitro, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio, C1 -C2 alkylsulfinyl, C1-C2 haloalkylsulfiny 1, C1 -C2 alkylsulfonyl and C1-C2 haloalkylsulfonyl;
m is 1 or 2;
n is 1, 2 or 3;
p is 1 or 2;
q is 0, 1 or 2; and
each t is independently 0, 1 or 2.
2. A compound of Claim 1 wherein:
X is -(CH2)n-A- optionally substituted with one to four R4;
Y is O;
A is O;
Q is selected from the group J and C1-C16 alkyl;
J is selected from the group phenyl, thienyl and pyridinyl, each optionally
substituted with 1-3 R3;
m is 1 ; and
n is 1.
3. A compound of Claim 2 wherein:
Z is O;
Q is J;
J is selected from the group phenyl and pyridinyl, each optionally substituted with 1-3 R3; and
q is 0.
4. A compound of Claim 3 wherein:
R1 is selected from the group F and Cl in the 2-position;
R2 is selected from the group H, F and Cl in the 6-position;
each R3 is independently selected from the group halogen, C1-C6 alkyl, C1-C6 haloalkyl, S(O)tR11 , OR9 and M-J1; each R9 is independently selected from the group C1-C4 alkyl and C1-C4 haloalkyl; each R11 is independently selected from the group C1-C6 alkyl and C1-C6
haloalkyl; and
each J1 is independently selected from the group phenyl, thienyl, pyridinyl and furanyl.
5. The compound of Claim 4 which is selected from the group:
(Z)-5-[(4-chlorophenyl)methylene]-3-[2-(2,6-difluorophenyl)-4,5-dihydro-4- oxazolyl]-4-oxazolidinone;
(Z)-3-[2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolyl]-5-[[4- (trifluoromethyl)phenyl]methylene]-4-oxazolidinone;
(Z)-5-[(4'-chloro[1,1'-biphenyl]-4-yl)methylene]-3-[2-(2,6-difluorophenyl)-4,5- dihydro-4-oxazolyl]-4-oxazolidinone ;
(Z)-3-[2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolyl]-5-[(4'-fluoro[1,1'- biphenyl]-4-yl)methylene]-4-oxazolidinone; and
(Z)-5-[(2',4'-dichloro[1,1'-biphenyl]-4-yl)methylene]-3-[2-(2,6-difluorophenyl)-
4,5-dihydro-4-oxazolyl]-4-oxazolidinone.
6. An arthropodicidal composition comprising an arthropodicidally effective amount of a compound of Claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent.
7. A method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound of Claim 1.
PCT/US1996/004478 1995-04-18 1996-04-01 Oxazoline and thiazoline arthropodicides Ceased WO1996033180A1 (en)

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BR9608107A BR9608107A (en) 1995-04-18 1996-04-01 Arthropodicidal composition compounds and method for controlling arthropods
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6251892B1 (en) 1997-02-28 2001-06-26 Gpi Nil Holdings, Inc. N-oxides of heterocyclic esters, amides, thioesters, and ketones
US9732051B2 (en) 2011-12-23 2017-08-15 Basf Se Isothiazoline compounds for combating invertebrate pests

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0345775A1 (en) * 1988-06-09 1989-12-13 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
WO1993024470A1 (en) * 1992-05-26 1993-12-09 E.I. Du Pont De Nemours And Company Arthropodicidal oxazolines and thiazolines
WO1995004726A1 (en) * 1993-08-04 1995-02-16 E.I. Du Pont De Nemours And Company Arthropodicidal oxazolines and thiazolines

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0345775A1 (en) * 1988-06-09 1989-12-13 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
WO1993024470A1 (en) * 1992-05-26 1993-12-09 E.I. Du Pont De Nemours And Company Arthropodicidal oxazolines and thiazolines
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
US6251892B1 (en) 1997-02-28 2001-06-26 Gpi Nil Holdings, Inc. N-oxides of heterocyclic esters, amides, thioesters, and ketones
US9732051B2 (en) 2011-12-23 2017-08-15 Basf Se Isothiazoline compounds for combating invertebrate pests

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AU5439196A (en) 1996-11-07

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