WO1995019972A1 - Arthropodicidal 2-oxa and thia-zolines - Google Patents

Arthropodicidal 2-oxa and thia-zolines Download PDF

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Publication number
WO1995019972A1
WO1995019972A1 PCT/US1995/000208 US9500208W WO9519972A1 WO 1995019972 A1 WO1995019972 A1 WO 1995019972A1 US 9500208 W US9500208 W US 9500208W WO 9519972 A1 WO9519972 A1 WO 9519972A1
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group
alkyl
haloalkyl
optionally substituted
independently selected
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PCT/US1995/000208
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French (fr)
Inventor
Victor Ekow Amoo
Renee Marie Lett
George Chihshu Chiang
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E.I. Du Pont De Nemours And Company
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Priority to BR9506625A priority Critical patent/BR9506625A/en
Priority to AU16765/95A priority patent/AU1676595A/en
Priority to EP95908447A priority patent/EP0741714A1/en
Priority to JP7519575A priority patent/JPH09508366A/en
Priority to MX9602949A priority patent/MX9602949A/en
Publication of WO1995019972A1 publication Critical patent/WO1995019972A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with 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
    • C07D263/28—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention comprises compounds useful for the control of arthropods.
  • JP 05001060 discloses 4-thienyl-2-oxa(thia)zoline derivatives wherein the thienyl moiety is bonded directly to the oxa- or thia-zoline ring.
  • U.S. 5,141,948 discloses oxa- and thia-zoline derivatives wherein the left hand phenyl ring is appended to the oxa- or thia-zoline ring either directly or through a lower alkylene bridge. Neither of these references suggests the compounds of the instant invention.
  • This invention pertains to compounds of Formula I, including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use to control arthropods in both agronomic and nonagronomic environments.
  • the compounds are:
  • A is selected from the group
  • B is selected from the group O and N-Y;
  • E is selected from the group C 1 -C 4 alkyl and C 1 -C 4 haloalkyl;
  • X 1 and Z are independently selected from the group O and S;
  • X 2 is selected from the group H, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C(O)OR 13 and CN;
  • Y is selected from the group H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6
  • halocycloalkyl C 4 -C 7 cycloalkylalkyl, CHO, C(O)R 16 , C(O)OR 16 , C(S)R 16 ,
  • X is selected from the group O and S;
  • G 2 is selected from the group single bond, O, S and N-Y;
  • G 3 is selected from the group single bond, O and N-Y;
  • G 4 is selected from the group single bond, O and N-Y;
  • G 5 is selected from the group single bond, O, S and N-Y;
  • G 6 is selected from the group C 2 -C 4 alkenylene, C 2 -C 4 alkynylene, O-C 2 -C 4 alkenylene and O-C 2 -C 4 alkynylene;
  • 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 16 alkenyl, C 2 -C 16 haloalkenyl, C 2 -C 16 alkynyl, C 2 -C ] 6 haloalkynyl, C 3 -C 7 cycloalkyl, C 3 -C 7 halocycloalkyl and C 4 -C 7 cycloalkylalkyl, each group optionally substituted with 1-4 substituents independently selected from W; J is a 5- or 6-membered aromatic ring containing 0 to 4 heteroatoms independently
  • J is a 9- to 14-membered aromatic ring system selected from the group fused bicylic ring and fused tricylic ring, each ring system containing 0 to 6 heteroatoms independently selected from the group 0-4 nitrogen, 0-2 oxygen, and 0-2 sulfur; wherein J is optionally substituted with 1-4 substituents independently selected from the group
  • R 1 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, S(O) t R 16 , CN and NO 2 ;
  • R 2 is selected from the group H, 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 16 , CN and NO 2 ;
  • R 3 is 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 1 -C 16 nitroalkyl, C 2 -C 16 cyanoalkyl, C 3 -C 18 alkoxycarbonylalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, CN, N 3 , SCN, NO 2 , SH, S(O) t R 16 , OCHO, OR 20 , CHO, C(O)R 21 , C(O)OR 21 , C(O)NR 16 R 17 ,
  • R 4 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 and phenyl optionally substituted with R 5 ;
  • R 5 is selected from the group halogen, CN, NO 2 , C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C(O)R 16 , C(O)OR 16 and Si(R 6 )(R 7 )(R 8 );
  • R 6 and R 7 are independently C 1 -C 12 alkyl
  • R 8 is selected from the group C 1 -C 12 alkyl and phenyl optionally substituted with 1-3 substituents independently selected from W 1 ;
  • R 9 is selected from the group H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, C(O)R 16 , C(O)OR- 6 ,
  • R 10 is selected from the group H, C 1 -C 4 alkyl, C(O)R 16 and C(O)OR 16 ;
  • R 1 1 is selected from the group H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl and phenyl optionally substituted with 1-3 substituents independently selected from W 1 ; or
  • R 10 and R 1 1 are taken together as (CH 2 ) 4 or (CH 2 ) 5 ;
  • R 12 is C 1 -C 18 alkyl
  • R 13 is C 1 -C 4 alkyl
  • R 14 and R 15 are independently C 1 -C 4 alkyl; or
  • R 14 and R 15 are taken together as (CH 2 ) 4 , (CH 2 ) 5 or CH 2 CH 2 OCH 2 CH 2 ;
  • R 16 is selected from the group 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 1 -C 6 nitroalkyl, C 2 -C 6 cyanoalkyl, C 3 -C 8 alkoxycarbonylalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 4 -C 7 cycloalkylalkyl, optionally substituted phenyl and optionally substituted benzyl wherein the phenyl and benzyl substituents are 1-3 substituents independently selected from W 1 ;
  • R 17 is selected from the group H and C 1 -C 4 alkyl
  • R 16 and R 17 when attached to the same atom, are taken together as (CH 2 ) 4 , (CH 2 ) 5 or
  • R 18 is selected from the group C 1 -C 3 alkyl and phenyl optionally substituted with 1-3 substituents independently selected from W- ;
  • R 19 is selected from the group halogen, CN, NO 2 , C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, OR 9 , C(O)R 16 , C(O)OR 16 and Si(R 6 )(R 7 )(R 8 );
  • R 20 is selected from the group H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, C(O)R 16 , C(O)OR 16 ,
  • R 21 is selected from the group 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 1 -C 6 nitroalkyl, C 2 -C 6 cyanoalkyl, C 3 -C 8 alkoxycarbonylalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl and C 4 -C 7 cycloalkylalkyl;
  • M is selected from the group direct bond, S, O, C(O), C(O)-C 1 -C 2 alkylene,
  • J 1 is selected from the group phenyl and naphthyl, each optionally substituted with 1-4 substituents independently selected from R 19 ; or J 1 is a 5-or 6-membered aromatic ring, attached through carbon or nitrogen, containing 1 to 4 heteroatoms independently selected from the group 1-4 nitrogen, 0-1 oxygen, and 0-1 sulfur, the ring optionally substituted with 1-4 substituents independently selected from R 19 ;
  • W is selected from the group J, NO 2 , CN, OH, C 1 -C 6 alkoxy and C 1 -C 6 haloalkoxy;
  • W 1 is selected from the group, halogen, CN, NO 2 , 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 -C 2
  • alkylsulfonyl and C 1 -C 2 haloalkylsulfonyl
  • q 0, 1 or 2;
  • t 0, 1 or 2.
  • Preferred compounds A are compounds of Formula I wherein:
  • A is A-1;
  • Q is selected from the group J, C 1 -C 16 alkyl and C 2 -C 16 alkenyl;
  • J is selected from the group phenyl and thienyl, each optionally substituted with 1-3 substituents independently selected from the group R 3 .
  • Preferred Compounds B are Compounds of Preferred A wherein:
  • J is phenyl optionally substituted with 1-3 substituents independently selected from the group R 3 .
  • Preferred Compounds C are Compounds B wherein:
  • G 1 is C(O);
  • 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
  • R 3 is independently selected from the group, halogen, C 1 -C 6 alkyl, C 1 -C 6
  • R 20 is selected from the group C 1 -C 4 alkyl and C 1 -C 4 haloalkyl;
  • J 1 is selected from the group phenyl, thienyl, pyridyl and furyl.
  • Compound D of Preferred C which is: N-[2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolyl]-2-fluoro-4-(trifluoromethyl)benzamide.
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when anriched relative to the other stereoisomer(s) or when seperated from the other stereoisomer(s).
  • the skilled artisan knows how to separate said stereoisomers. Accordingly, the present invention comprises racemic mixtures, individual stereoisomers, and optically active mixtures of compounds of Formula I as well as agriculturally suitable salts thereof.
  • aromatic ring and “aromatic ring system” are defined as those rings or ring systems which satisfy the H ⁇ ckel rule. Examples include: a 5- or 6- membered monocyclic aromatic ring containing 0 to 4 heteroatoms such as phenyl, furyl, furazanyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, oxadiazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl isothiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl with said ring attached through any available carbon or nitrogen.
  • the aromatic ring system is furyl, it can be 2-furyl or 3-furyl, for pyrrolyl, the aromatic ring system is 1-pyrrolyl, 2-pyrrolyl or
  • 3-pyrrolyl for pyridyl, the aromatic ring system is 2-pyridyl, 3-pyridyl or 4-pyridyl and similarly for other monocyclic aromatic rings; fused carbobicyclic rings containing at least one phenyl ring, examples include naphthyl and tetralinyl; fused carbotricyclic ring containing at least one phenyl ring, examples include fluorenyl and phenanthrenyl; fused bicyclic rings containing 1 to 4 heteroatoms and 1 or 2 aromatic rings, examples include quinolyl, isoquinolyl, quinoxalinyl, benzofuryl, isobenzofuranyl, benzothienyl, benzodioxolyl, chromanyl, indolinyl, isoindolyl, thienofuranyl, and purinyl; and fused tricyclic rings containing 1 to 6 heteroatoms and at least 1 aromatic ring, examples include acri
  • the bicyclic and tricyclic aromatic ring systems can be attached through any available carbon or nitrogen, for example, for naphthyl, the carbobicyclic aromatic ring system is 1-naphthyl or 2-naphthyl, for benzofuryl, the aromatic ring system can be 2-, 3-, 4-, 5-, 6-, or 7-benzofuryl, for fluorenyl, the aromatic ring system can be 1-, 2-, 3-, 4-, or 9-fluorenyl and similarly for the other bicyclic and tricyclic aromatic ring systems.
  • alkyl used either alone or in compound words such as
  • alkylthio or haloalkyl denotes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different isomers through C 16 .
  • alkylene examples include CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 and the different butylene isomers.
  • Alkenyl denotes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different isomers through C 16 .
  • Alkenyl also denotes polyenes such as 1,3-hexadiene.
  • Alkynyl denotes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 3-propynyl and the different isomers through C 16 .
  • alkynylene examples include C ⁇ C, CH 2 C ⁇ C, G ⁇ CCH 2 and the different butynylene isomers.
  • Alkoxy denotes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl.
  • alkoxyalkyl examples include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 and the different isomers through C 16 .
  • Alkylthio denotes straight-chain or branched alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl.
  • Alkylthioalkyl examples include CH 3 SCH 2 .
  • Alkylsulfonyl denotes CH 3 S(O) 2 and CH 3 CH 2 S(O) 2 .
  • Cycloalkyl denotes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • cycloalkylalkyl examples include cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl and the different Cg and C7 isomers bonded to straight-chain or branched alkyl groups.
  • Alkoxycarbonylalkyl denotes straight-chain or branched esters substituted on straight-chain or branched alkyl groups.
  • alkoxycarbonylalkyl include CH 2 C(O)OCH 3 ,
  • halogen either alone or in compound words such as “haloalkyl”, denotes fluorine, chlorine, bromine or iodine. 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.
  • haloalkyl examples include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 .
  • haloalkynyl include HC ⁇ CCHCl, CF 3 C ⁇ C, CCl 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy include CF 3 O, CCl 3 CH 2 O, CF 2 HCH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio include CCl 3 S, CF 3 S, and CCl 3 CH 2 S.
  • haloalkylsulfonyl examples include CF 3 SO 2 , CCl 3 SO 2 , CF 3 CH 2 SO 2 and CF 3 CF 2 SO 2 .
  • 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 18.
  • C 1 -C 6 alkyl designates methyl, ethyl, and propyl through hexyl isomers
  • C 2 alkoxy designates CH 3 CH 2 O-
  • C 3 alkoxy designates CH 3 CH 2 CH 2 O- or (CH 3 ) 2 CHO-.
  • Nitroalkyl designates a straight or branched-chain alkyl group substituted with NO 2 .
  • Cyanoalkyl designates a straight or branched-chain alkyl group substituted with CN.
  • a generally useful method is the reaction of the Formula II compound with the Formula III 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 such as methylene chloride, tetrahydrofuran, chloroform, toluene and other solvents that will not react with acid chlorides or bases.
  • the reaction is normally completed in less than 24 h.
  • Other useful methods for the formation of amides, sulfonamides and carbamates are discussed in Larock, Comprehensive Organic
  • Typical reactions involve the combination of equimolar amounts of II and IV in an organic solvent such as ethyl acetate, methylene chloride, tetrahydrofuran, chloroform, benzene or toluene.
  • a base such as an alkali metal, tertiary amine, alkali metal hydroxide or metal hydride can be used.
  • the reaction can be run at temperatures ranging from about -20-100 °C with temperatures in the range of -10-30 °C being preferred. The reaction is completed within
  • Compounds of Formula I (where A is A-1 and Y is H) can be prepared by reaction of a compound of Formula II with an aldehyde of Formula V as shown in Scheme 3. This reaction can be carried out in a solvent such as methanol or ethanol in the presence of a reducing agent such as sodium borohydride or sodium cyanoborohydride (Borch et al., J. Am. Chem. Soc. (1971), 93, 2897). The reaction temperature can vary from -30-200 °C and the reaction is completed in about 2-72 h.
  • a solvent such as methanol or ethanol
  • a reducing agent such as sodium borohydride or sodium cyanoborohydride
  • Formula I compounds (where A is A-1, A-1 is QCH 2 N(Y) and Y is H) can be prepared by the reduction of compounds of Formula I (where A is A-1, A-1 is QC(O)N(Y) and Y is H) as shown in Scheme 4.
  • Useful reducing agents are alkali metal hydrides.
  • treatment of a compound of Formula I (A is A-1, G 1 is C(O) and Y is H) with lithium aluminum hydride at 0-50 °C in ethereal solvents such as tetrahydrofuran, ether or dimethoxyethane yields compounds of Formula I (A is A-1 and Y is H).
  • the reduction is usually completed in 24 h.
  • Compounds of Formula II can be prepared by the reaction of compounds of Formula VI with sodium hypobromite (or sodium hydroxide and bromine). This transformation is shown in Scheme 5. A review of the Hofmann rearrangement can be found in Org. Rxns. (1946), 3, pp. 267-306.
  • a typical reaction involves the addition of a compound of Formula VI 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.
  • the transformation can be accomplished by treating a
  • Compounds of Formula VII can be prepared by the reaction of commercially available serine derivatives (Formula VIII) with an imidate of Formula IX as shown in Scheme 7.
  • 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.
  • imidates of Formula IX can be prepared from commercially available amides of Formula X by reaction with a trialkyloxonium tetrafluoroborate in an inert solvent such as methylene chloride, benzene or toluene.
  • an inert solvent such as methylene chloride, benzene or toluene.
  • an appropriate halogenating agent such as phosphorous trichloride, phosphorous tribromide, phosphorous pentachloride, phosphorous pentabromide, thionyl chloride, thionyl bromide, sulfuryl chloride, triphenylphosphorous and carbon tetrachloride or carbon te
  • Typical reactions involve combination of the reactant with an excess of halogenating agent in the presence or absence of an organic solvent such as benzene, toluene, xylene, chloroform, methylene chloride and hexane.
  • an organic solvent such as benzene, toluene, xylene, chloroform, methylene chloride and hexane.
  • the preferred reaction temperature ranges from 35-100 °C and the reaction is generally complete within 24 h.
  • Compounds of Formula I can be prepared by reaction of Formula II compounds with Formula V compounds.
  • Typical reactions include the combination of equimolar amounts of Formula II compounds with Formula V compound in a suitable solvent such as acetonitrile, methanol, ethanol or benzene.
  • the reaction can be run in the presence or absence of an acid catalyst.
  • Typical acid catalysts include alkyl or arylsulfonic acids and mineral acids such as hydrochloric acid.
  • the reaction temperature can vary from 0 °C to the reflux temperature of the particular solvent being used. Scheme 11 illustrates this transformation. The reaction is normally completed within 24 h.
  • Compounds of Formula I (where A is A-2, G 2 is O, S or NH and X 1 is O) can be prepared by condensation of Formula XI compounds with Formula XII compounds.
  • a generally useful method is treatment of an acid chloride of Formula XI with an amine, alcohol or thiol of Formula XII in the presence of an acid scavenger such as triethylamine at room temperature or below.
  • the reaction can be carried out in an inert solvent such as methylene chloride, tetrahydrofuran, toluene, benzene and chloroform.
  • An alternative method is treatment of an acid of Formula XI with a Formula XII compound in the presence of a condensation reagent such as dicyclohexylcarbodiimide in a suitable solvent such as methylene chloride, chloroform, tetrahydrofuran, toluene, dimethylformamide and ethyl acetate.
  • a condensation reagent such as dicyclohexylcarbodiimide
  • a suitable solvent such as methylene chloride, chloroform, tetrahydrofuran, toluene, dimethylformamide and ethyl acetate.
  • the temperature can range from 0-200 °C with the preferred temperature range from 20-100 °C.
  • the reaction can be run in the presence of a catalyst such as dimethylaminopyridine (see Synthesis (1972), 453) and is completed in 30 min to 48 h.
  • Formula VII compound as shown in Scheme 13.
  • Typical reactions involve treating Formula VII compounds with a base such as sodium hydroxide or potassium hydroxide in a suitable solvent such as water, methanol or ethanol.
  • the reaction temperature can vary from 0 °C to the reflux temperature of the particular solvent being used.
  • Hydrolysis of esters have been thoroughly discussed in March, Advanced Organic Chemistry, 3rd Ed., (1985), pp 334-338. Typical reactions are completed in less than 24 h.
  • Compounds of Formula I can be prepared by reaction of compounds of Formula XIII with an aldehyde of Formula V in the presence of a strong base. This transformation is shown in Scheme 14.
  • a typical reaction involves mixing a compound of Formula XIII 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, ethanol, toluene, dimethoxyethane and dimethylsulfoxide, followed by the addition of an aldehyde of Formula V.
  • the temperature of the reaction can vary from -70-200 °C.
  • the Wittig reaction has been reviewed by Maercker in Org. Rxns. (1965), 14, pp 270-490. The reaction is complete in 1-48 h.
  • Formula XIII compounds can be prepared by reaction of equimolar amounts of a
  • halogenating agent such as triphenylphosphine and carbon tetrachloride or carbon tetrabromide, triphenylphosphine, imidazole and iodine in a suitable solvent such as acetonitrile or methylene chloride.
  • a suitable solvent such as acetonitrile or methylene chloride.
  • Compounds of Formula I (where A is A-6, G 6 is C 2 alkylene, and Q is aryl) can be prepared by reaction of a compound of Formula XVI, first with thionyl chloride and then with sodium hydroxide in methanol as shown in Scheme 18.
  • a typical reaction involves mixing a compound of Formula XVI with thionyl chloride neat or with a suitable solvent such as toluene or carbon tetrachloride. The mixture is heated from 30-100°C for 0.25-4 h. The solvent and excess thionyl chloride are concentrated under vacuum and the resultant crude chloride is dissolved in methanol and treated with aqueous sodium hydroxide. This second reaction is then heated for 0.25-4 h at 30-65°C. Extraction of the cooled reaction mixture with an organic solvent enables the isolation of the product of Formula I where A is A-6 and G 6 is C 2 alkylene.
  • Compounds of Formula XVI can be prepared from compounds of Formula XVII as shown in Scheme 19.
  • Amino alcohols of Formula XVII are first converted to silyl ethers by reaction with trimethylsilyl cyanide at 0-30°C in a suitable solvent such as methylene chloride, chloroform, or tetrahydrofuran.
  • a suitable solvent such as methylene chloride, chloroform, or tetrahydrofuran.
  • the alcohol group in compounds of Formula XVII is protected as the silyl ether so it does not react with the benzoyl chloride in the next step.
  • the solution of silyl ether is treated with an organic base like triethylamine and then with an appropriate benzoyl chloride at 0-30°C for 0.5-4 h.
  • the crude intermediate amide can be isolated by addition of water and extraction with an appropriate organic solvent.
  • the silyl ether protecting group is removed by treatment of the crude intermediate (dissolved in an appropriate solvent like tetrahydrofuran) with a solution of tetrabutylammonium fluoride at 0-30°C for 5-60 min.
  • Compounds of Formula XVI are then isolated by addition of water and extraction with an organic solvent like ethyl acetate.
  • Compounds of Formula XVII can be prepared from compounds of Formula XVIII as shown in Scheme 20.
  • a typical reaction involves treatment of a phthalimide of Formula XVIII, dissolved in an appropriate solvent like methanol or ethanol, with an excess of hydrazine at 40-80°C for 0.5-8 h.
  • Compounds of Formula I (where A is A-1, Y is H, Q is J) can also be prepared by reaction of a compound of Formula II with a triarylbismuth of Formula XXI in the presence of cupric acetate as shown in Scheme 23. This reaction can be carried out in a solvent such as methylene chloride at room temperature in less than 24 h (see Barton et al. Tetrahedron Letts. (1987), 28, pp 887-890).
  • Formula XXII are prepared by reacting substituted benzamide with 2-haloacetaldehyde dialkylacetal (see EP-A-594,129). The conversion of XXII to I takes place at room temperature over a period of several hours. Scheme 24 discloses this transformation.
  • Step B Methyl 2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolecarboxylate
  • Step D 2-(2,6-Difluorophenyl)-4,5-dihydro-N-(4-methoxyphenyl)-4- oxazolecarboxamide
  • Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent.
  • Useful formulations include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • 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
  • formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 weight percent.
  • Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill.
  • Water-dispersible granules can be produced by agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., (1988), pp 251-259.
  • Suspensions are prepared by wet-milling; see, for example, U.S. 3,060,084.
  • Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques.
  • 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.
  • compounds of this invention display activity against one or more of the following pests: 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, junveniles and adults of the Phylum Nematoda.
  • the compounds of this invention are also active against pests of the Orders
  • Hymenoptera Isoptera, Siphonaptera, Blattaria, Thysanura and Psocoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes.
  • the compounds are active against southern corn rootworm (Diabrotica undecimpunctata howardi), aster leafhopper
  • Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellants, 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 avermectin B, monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fipronil, flufenprox, fonophos, isofenphos, methidathion, metha-midophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, t
  • bactericides such as oxytetracyline, streptomycin and tribasic copper sulfate; acaricides such as binapacryl, oxythioquinox, chlorobenzilate, dicofol, dienochlor, cyhexatin, hexythiazox, amitraz, propargite, tebufenpyrad and fenbutatin oxide; and biological agents such as entomopathogenic bacteria, virus and fungi.
  • 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 Formula I, or compositions containing at least one such compound, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • a preferred method of application is by spraying.
  • granular formulations of these compounds can be applied to the plant foliage or the soil.
  • Other methods of application include direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others.
  • the compounds can be inco ⁇ orated into baits that are consumed by the arthropods or in devices such as traps and the like.
  • the compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use.
  • a preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, and synergists and other solvents 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.
  • Control efficacy represents inhibition of arthropod development (including mortality) that causes significantly reduced feeding.
  • Test units each consisting of a 230 mL (8 ounce) plastic cup containing a 2.54 cm 2 plug (1 square inch) of a wheatgerm diet, were prepared. 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 kg of active ingredient per hectare (about 0.5 pounds per acre) at 207 kPa (30 p.s.i.). After the spray on the cups had dried, five secondinstar larvae of the southern corn rootworm (Diabrotica undecimpunctata howardi) were placed into each cup. The cups were held at 27°C and 50% relative humidity for 6-8 days. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 54.
  • Pieces of kidney bean leaves each approximately 2.54 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 207kPa (30 p.s.i.).
  • the leaf squares were then placed underside-up on 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 7 days and read for larvacide/ovacide mortality Of the
  • test compound was prepared by dissolving it in a minimum of acetone and then adding water containing a wetting agent until the concentration of the compound was 100 ppm.
  • Two- week old red kidney bean plants infested with two-spotted spider mite eggs (Tetranychus urticae) were. sprayed to run-off with the test solution using a turntable sprayer. Plants were held in a chamber at 25°C and 50% relative humidity and scored for activity seven days after spray.

Abstract

Arthropodicidal compounds, compositions and use of compounds having formula (I), wherein A, E, Z, R1, R2 and q are as defined in the text.

Description

TITLE
ARTHROPODICIDAL 2-OXA AND THIA-ZOLINES
The present invention comprises compounds useful for the control of arthropods.
JP 05001060 discloses 4-thienyl-2-oxa(thia)zoline derivatives wherein the thienyl moiety is bonded directly to the oxa- or thia-zoline ring. U.S. 5,141,948 discloses oxa- and thia-zoline derivatives wherein the left hand phenyl ring is appended to the oxa- or thia-zoline ring either directly or through a lower alkylene bridge. Neither of these references suggests the compounds of the instant invention.
SUMMARY OF THE INVENTION
This invention pertains to compounds of Formula I, including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use to control arthropods in both agronomic and nonagronomic environments. The compounds are:
Figure imgf000003_0007
wherein:
A is selected from the group
, , ,
Figure imgf000003_0001
Figure imgf000003_0002
Figure imgf000003_0003
, and ;
Figure imgf000003_0006
Figure imgf000003_0005
Figure imgf000003_0004
B is selected from the group O and N-Y;
E is selected from the group C1-C4 alkyl and C1-C4 haloalkyl;
X1 and Z are independently selected from the group O and S; X2 is selected from the group H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C(O)OR13 and CN;
Y is 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 cycloalkylalkyl, CHO, C(O)R16, C(O)OR16, C(S)R16,
C(S)OR16, C(S)SR16, C(O)C(O)OR16, C(O)CH2C(O)OR16, S(O)tR16,
S(O)2CH2C(O)OR16, P(X)(OR18)2, S(O)tN(R13)C(O)OR12, S(O)tN(R14)R15, N=CR10R11, OR9, NR9R10; phenyl optionally substituted with 1-3 substituents independently selected from W1; and C1-C6 alkyl substituted with 1-3 substituents independently selected from the group C1-C3 alkoxy, C1-C3 haloalkoxy, CN, NO2,
S(O)tR16, P(X)(OR18)2, C(O)R16, C(O)OR16 and phenyl optionally substituted with 1-3 substituents independently selected from W1 ;
X is selected from the group O and S;
G1 is selected from the group single bond, C(=X1), C(=X1)N(Y), C(=XJ)O and S(O)2; G2 is selected from the group single bond, O, S and N-Y;
G3 is selected from the group single bond, O and N-Y;
G4 is selected from the group single bond, O and N-Y;
G5 is selected from the group single bond, O, S and N-Y;
G6 is selected from the group C2-C4 alkenylene, C2-C4 alkynylene, O-C2-C4 alkenylene and O-C2-C4 alkynylene;
Q is selected from the group H and J; or Q is selected from the group C1-C16 alkyl,
C1-C16 haloalkyl, C2-C16 alkenyl, C2-C16 haloalkenyl, C2-C16 alkynyl, C2-C] 6 haloalkynyl, C3-C7 cycloalkyl, C3-C7 halocycloalkyl and C4-C7 cycloalkylalkyl, each group optionally substituted with 1-4 substituents independently selected from W; J is a 5- or 6-membered aromatic ring containing 0 to 4 heteroatoms independently
selected from the group 0-4 nitrogen, 0-1 oxygen, and 0-1 sulfur; or J is a 9- to 14-membered aromatic ring system selected from the group fused bicylic ring and fused tricylic ring, each ring system containing 0 to 6 heteroatoms independently selected from the group 0-4 nitrogen, 0-2 oxygen, and 0-2 sulfur; wherein J is optionally substituted with 1-4 substituents independently selected from the group
R3;
R1 is selected from the group halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, S(O)tR16, CN and NO2;
R2 is selected from the group H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, S(O)tR16, CN and NO2;
R3 is 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, C1-C16 nitroalkyl, C2-C16 cyanoalkyl, C3-C18 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, CN, N3, SCN, NO2, SH, S(O)tR16, OCHO, OR20, CHO, C(O)R21, C(O)OR21 , C(O)NR16R17,
S(O)2NR16R17, C(R4)=NR9, N=CR4R9, NR16R17, NR17C(O)R16,
NR17C(O)NHR16, NR17S(O)2R16, Si(R6)(R7)(R8), SF5 and M-J1 ;
R4 is selected from the group halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy and phenyl optionally substituted with R5;
R5 is selected from the group halogen, CN, NO2, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C(O)R16, C(O)OR16 and Si(R6)(R7)(R8);
R6 and R7 are independently C1-C12 alkyl;
R8 is selected from the group C1-C12 alkyl and phenyl optionally substituted with 1-3 substituents independently selected from W1 ;
R9 is selected from the group H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C(O)R16, C(O)OR-6,
C(O)NR16R17, S(O)2NR16R17, S(O)2R16, optionally substituted phenyl, and optionally substituted benzyl wherein the phenyl and benzyl substituents are 1-3 substituents independently selected from W1 ;
R10 is selected from the group H, C1-C4 alkyl, C(O)R16 and C(O)OR16;
R1 1 is selected from the group H, C1-C4 alkyl, C1-C4 haloalkyl and phenyl optionally substituted with 1-3 substituents independently selected from W1 ; or
R10 and R1 1 are taken together as (CH2)4 or (CH2)5;
R12 is C1-C18 alkyl;
R13 is C1-C4 alkyl;
R14 and R15 are independently C1-C4 alkyl; or
R14 and R15 are taken together as (CH2)4, (CH2)5 or CH2CH2OCH2CH2;
R16 is 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, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 cycloalkylalkyl, optionally substituted phenyl and optionally substituted benzyl wherein the phenyl and benzyl substituents are 1-3 substituents independently selected from W1;
R17 is selected from the group H and C1-C4 alkyl; or
R16 and R17, when attached to the same atom, are taken together as (CH2)4, (CH2)5 or
CH2CH2OCH2CH2, each group optionally substituted with 1-3 CH3;
R18 is selected from the group C1-C3 alkyl and phenyl optionally substituted with 1-3 substituents independently selected from W- ;
R19 is selected from the group halogen, CN, NO2, C1-C6 alkyl, C1-C6 haloalkyl, OR9, C(O)R16, C(O)OR16 and Si(R6)(R7)(R8); R20 is selected from the group H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C(O)R16, C(O)OR16,
C(O)NR16R17, S(O)2NR-6R17 and S(O)2R16;
R21 is 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, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl and C4-C7 cycloalkylalkyl;
M is selected from the group direct bond, S, O, C(O), C(O)-C1-C2 alkylene,
C(O)O-C,-C2 alkylene, C1-C4 alkylene, O- C1-C4 alkylene, O-C2-C4 alkenylene and O-C2-C4 alkynylene; provided that when M is O-C1-C4 alkylene, O-C2-C4 alkenylene or O-C2-C4 alkynylene, the oxygen atom is attached to the J ring; and when M is C(O)O-C1-C2 alkylene, the C(O) is attached to the J ring;
J1 is selected from the group phenyl and naphthyl, each optionally substituted with 1-4 substituents independently selected from R19; or J1 is a 5-or 6-membered aromatic ring, attached through carbon or nitrogen, containing 1 to 4 heteroatoms independently selected from the group 1-4 nitrogen, 0-1 oxygen, and 0-1 sulfur, the ring optionally substituted with 1-4 substituents independently selected from R19; W is selected from the group J, NO2, CN, OH, C1-C6 alkoxy and C1-C6 haloalkoxy; W1 is selected from the group, halogen, CN, NO2, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio, C1-C2
alkylsulfonyl, and C1-C2 haloalkylsulfonyl;
q is 0, 1 or 2; and
t is 0, 1 or 2.
Preferred compounds A are compounds of Formula I wherein:
A is A-1;
Q is selected from the group J, C1-C16 alkyl and C2-C16 alkenyl; and
J is selected from the group phenyl and thienyl, each optionally substituted with 1-3 substituents independently selected from the group R3.
Preferred Compounds B are Compounds of Preferred A wherein:
Q is J; and
J is phenyl optionally substituted with 1-3 substituents independently selected from the group R3.
Preferred Compounds C are Compounds B wherein:
G1 is C(O);
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;
R3 is independently selected from the group, halogen, C1-C6 alkyl, C1-C6
haloalkyl, OR20 and M-J1 ; R20 is selected from the group C1-C4 alkyl and C1-C4 haloalkyl; and
J1 is selected from the group phenyl, thienyl, pyridyl and furyl.
Specifically preferred for biological activity is Compound D of Preferred C which is: N-[2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolyl]-2-fluoro-4-(trifluoromethyl)benzamide.
Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when anriched relative to the other stereoisomer(s) or when seperated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate said stereoisomers. Accordingly, the present invention comprises racemic mixtures, individual stereoisomers, and optically active mixtures of compounds of Formula I as well as agriculturally suitable salts thereof.
The terms "aromatic ring" and "aromatic ring system" are defined as those rings or ring systems which satisfy the Hϋckel rule. Examples include: a 5- or 6- membered monocyclic aromatic ring containing 0 to 4 heteroatoms such as phenyl, furyl, furazanyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, oxadiazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl isothiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl and triazinyl with said ring attached through any available carbon or nitrogen. For example, when the aromatic ring system is furyl, it can be 2-furyl or 3-furyl, for pyrrolyl, the aromatic ring system is 1-pyrrolyl, 2-pyrrolyl or
3-pyrrolyl, for pyridyl, the aromatic ring system is 2-pyridyl, 3-pyridyl or 4-pyridyl and similarly for other monocyclic aromatic rings; fused carbobicyclic rings containing at least one phenyl ring, examples include naphthyl and tetralinyl; fused carbotricyclic ring containing at least one phenyl ring, examples include fluorenyl and phenanthrenyl; fused bicyclic rings containing 1 to 4 heteroatoms and 1 or 2 aromatic rings, examples include quinolyl, isoquinolyl, quinoxalinyl, benzofuryl, isobenzofuranyl, benzothienyl, benzodioxolyl, chromanyl, indolinyl, isoindolyl, thienofuranyl, and purinyl; and fused tricyclic rings containing 1 to 6 heteroatoms and at least 1 aromatic ring, examples include acridinyl, phenanthridinyl, phenanthrolinyl, phenoxazinyl, and dibenzofuranyl. As with the monocyclic aromatic rings, the bicyclic and tricyclic aromatic ring systems can be attached through any available carbon or nitrogen, for example, for naphthyl, the carbobicyclic aromatic ring system is 1-naphthyl or 2-naphthyl, for benzofuryl, the aromatic ring system can be 2-, 3-, 4-, 5-, 6-, or 7-benzofuryl, for fluorenyl, the aromatic ring system can be 1-, 2-, 3-, 4-, or 9-fluorenyl and similarly for the other bicyclic and tricyclic aromatic ring systems.
In the above recitations, the term "alkyl", used either alone or in compound words such as
"alkylthio" or "haloalkyl" denotes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different isomers through C16. Examples of "alkylene" include CH2, CH2CH2, CH2CH2CH2 and the different butylene isomers. "Alkenyl" denotes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different isomers through C16. "Alkenyl" also denotes polyenes such as 1,3-hexadiene. Examples of "alkenylene" include CH=CH, CH2CH=CH, CH=CHCH2 and the different butenylene isomers. "Alkynyl" denotes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 3-propynyl and the different isomers through C16. Examples of "alkynylene" include C≡C, CH2C≡C, G≡CCH2 and the different butynylene isomers. "Alkoxy" denotes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2 and the different isomers through C16. "Alkylthio" denotes straight-chain or branched 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. CH3CH2SCH2, CH3SCH2CH2, CH3CH2CH2SCH2, CH3CH2SCH2CH2 and the different isomers through C16. "Alkylsulfonyl" denotes CH3S(O)2 and CH3CH2S(O)2.
"Cycloalkyl" denotes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl and the different Cg and C7 isomers bonded to straight-chain or branched alkyl groups.
"Alkoxycarbonylalkyl" denotes straight-chain or branched esters substituted on straight-chain or branched alkyl groups. Examples of "alkoxycarbonylalkyl" include CH2C(O)OCH3,
CH2C(O)OCH2CH3, CH2CH2C(O)OCH3 and the different isomers through C18. The term "halogen", either alone or in compound words such as "haloalkyl", denotes fluorine, chlorine, bromine or iodine. 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. Examples of
"haloalkenyl" include (Cl)2C=CHCH2 and CF3CH2CH=CHCH2. Examples of "haloalkynyl" include HC≡CCHCl, CF3C≡C, CCl3C≡C and FCH2C≡CCH2. Examples of "haloalkoxy" include CF3O, CCl3CH2O, CF2HCH2CH2O and CF3CH2O. Examples of "haloalkylthio" include CCl3S, CF3S, and CCl3CH2S. Examples of "haloalkylsulfonyl" include CF3SO2, CCl3SO2, CF3CH2SO2 and CF3CF2SO2. 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 18. For example, C1-C6 alkyl designates methyl, ethyl, and propyl through hexyl isomers; C2 alkoxy designates CH3CH2O-; and C3 alkoxy designates CH3CH2CH2O- or (CH3)2CHO-. Nitroalkyl designates a straight or branched-chain alkyl group substituted with NO2. Cyanoalkyl designates a straight or branched-chain alkyl group substituted with CN.
DETAILS OF THE INVENTION
Compounds of Formula I (where A is A-l, G1 is C(O), S(O)2 or C(O)O, and Y is H) can be prepared by condensation of a compound of Formula II and a compound of Formula III. This transformation is illustrated in Scheme 1. A generally useful method is the reaction of the Formula II compound with the Formula III 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 such as methylene chloride, tetrahydrofuran, chloroform, toluene and other solvents that will not react with acid chlorides or bases. The reaction is normally completed in less than 24 h. Other useful methods for the formation of amides, sulfonamides and carbamates are discussed in Larock, Comprehensive Organic
Transformations, VCH Publishers, Inc., New York.
Figure imgf000009_0001
As illustrated in Scheme 2, compounds of Formula I (where A is A-l, G1 is C(X1)N(Y) and Y is H) can be prepared by reaction of Formula II compounds with isocyanates of
Formula IV. Typical reactions involve the combination of equimolar amounts of II and IV in an organic solvent such as ethyl acetate, methylene chloride, tetrahydrofuran, chloroform, benzene or toluene. A base such as an alkali metal, tertiary amine, alkali metal hydroxide or metal hydride can be used. The reaction can be run at temperatures ranging from about -20-100 °C with temperatures in the range of -10-30 °C being preferred. The reaction is completed within
24 h.
Figure imgf000009_0002
Compounds of Formula I (where A is A-1 and Y is H) can be prepared by reaction of a compound of Formula II with an aldehyde of Formula V as shown in Scheme 3. This reaction can be carried out in a solvent such as methanol or ethanol in the presence of a reducing agent such as sodium borohydride or sodium cyanoborohydride (Borch et al., J. Am. Chem. Soc. (1971), 93, 2897). The reaction temperature can vary from -30-200 °C and the reaction is completed in about 2-72 h.
Figure imgf000010_0002
Alternatively, Formula I compounds (where A is A-1, A-1 is QCH2N(Y) and Y is H) can be prepared by the reduction of compounds of Formula I (where A is A-1, A-1 is QC(O)N(Y) and Y is H) as shown in Scheme 4. Useful reducing agents are alkali metal hydrides. For example, treatment of a compound of Formula I (A is A-1, G1 is C(O) and Y is H) with lithium aluminum hydride at 0-50 °C in ethereal solvents such as tetrahydrofuran, ether or dimethoxyethane yields compounds of Formula I (A is A-1 and Y is H). The reduction is usually completed in 24 h. For alternative methods of reduction of amides to amines, see March, Advanced Organic Chemistry 3rd Ed., (1985), pp 1099-1100.
Figure imgf000010_0001
Compounds of Formula II can be prepared by the reaction of compounds of Formula VI with sodium hypobromite (or sodium hydroxide and bromine). This transformation is shown in Scheme 5. A review of the Hofmann rearrangement can be found in Org. Rxns. (1946), 3, pp. 267-306. A typical reaction involves the addition of a compound of Formula VI 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 VI compound with [hydroxy(tosyloxy)iodo]benzene in refluxing acetonitrile. (See J. Org. Chem. (1986), 51, pp 2669-2671).
Figure imgf000010_0004
Figure imgf000010_0003
Compounds of Formula VI can be prepared by reacting compounds of Formula VII with ammonia. This transformation is shown in Scheme 6. 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 imgf000011_0002
Compounds of Formula VII can be prepared by the reaction of commercially available serine derivatives (Formula VIII) with an imidate of Formula IX as shown in Scheme 7. 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, pp 615-623. One skilled in the art would recognize that this transformation can be extended to the preparation of compounds where A=A-3.
Figure imgf000011_0001
As depicted in Scheme 8, imidates of Formula IX can be prepared from commercially available amides of Formula X by reaction with a trialkyloxonium tetrafluoroborate in an inert solvent such as methylene chloride, benzene or toluene. The syntheses of imidates has been extensively reviewed by D. A. Neilson in The Chemistry ofAmidines and Imidates, Patai and Rappoport, Eds., Vol. 2, (1991), pp 425-483.
Figure imgf000012_0002
Compounds of Formula I (where A is A-4 or A-5 and X2 is alkoxy or thioalkyl) can be prepared by the reaction of Formula I compounds (where A is A-4 or A-5 and X2 is Cl or Br) with sulfur or oxygen nucleophiles as illustrated in Scheme 9. Typical reactions involve the combination of equimolar amounts of the reactants in the presence of a base such as an alkali metal, tertiary amine, metal hydride and the like in conventional organic solvents including ether, tetrahydrofuran, 1,2-dimethoxyether, methylene chloride, chloroform, N,N-dimethylformamide and dimethylsulfoxide. The reaction can be conducted at temperatures ranging from -20-100 °C with temperatures in the range of -10-30 °C preferred. One skilled in the art will recognize that the reactions of this general type can be extended to other nucleophilic reagents.
Figure imgf000012_0001
As illustrated in Scheme 10, compounds of Formula I (where A is A-4 or A-5 and X2 is Cl or Br) can be prepared by the reaction of Formula I compounds (where A is A-1 or A-2, G1 is C(O) or G2 = ΝH, X1 is O, and Y is H, ) with an appropriate halogenating agent such as phosphorous trichloride, phosphorous tribromide, phosphorous pentachloride, phosphorous pentabromide, thionyl chloride, thionyl bromide, sulfuryl chloride, triphenylphosphorous and carbon tetrachloride or carbon tetrabromide (Wolkoff, Can. J. Chem. (1975), 53, 1333).
Typical reactions involve combination of the reactant with an excess of halogenating agent in the presence or absence of an organic solvent such as benzene, toluene, xylene, chloroform, methylene chloride and hexane. The preferred reaction temperature ranges from 35-100 °C and the reaction is generally complete within 24 h.
Figure imgf000013_0002
Compounds of Formula I (where A is A-5 and X2 is H ) can be prepared by reaction of Formula II compounds with Formula V compounds. Typical reactions include the combination of equimolar amounts of Formula II compounds with Formula V compound in a suitable solvent such as acetonitrile, methanol, ethanol or benzene. The reaction can be run in the presence or absence of an acid catalyst. Typical acid catalysts include alkyl or arylsulfonic acids and mineral acids such as hydrochloric acid. The reaction temperature can vary from 0 °C to the reflux temperature of the particular solvent being used. Scheme 11 illustrates this transformation. The reaction is normally completed within 24 h.
Figure imgf000013_0001
Compounds of Formula I (where A is A-2, G2 is O, S or NH and X1 is O) can be prepared by condensation of Formula XI compounds with Formula XII compounds. A generally useful method is treatment of an acid chloride of Formula XI with an amine, alcohol or thiol of Formula XII in the presence of an acid scavenger such as triethylamine at room temperature or below. The reaction can be carried out in an inert solvent such as methylene chloride, tetrahydrofuran, toluene, benzene and chloroform. An alternative method is treatment of an acid of Formula XI with a Formula XII compound in the presence of a condensation reagent such as dicyclohexylcarbodiimide in a suitable solvent such as methylene chloride, chloroform, tetrahydrofuran, toluene, dimethylformamide and ethyl acetate. The temperature can range from 0-200 °C with the preferred temperature range from 20-100 °C. The reaction can be run in the presence of a catalyst such as dimethylaminopyridine (see Synthesis (1972), 453) and is completed in 30 min to 48 h.
Figure imgf000014_0003
Compounds of Formula XI (where L1 is OH) can be prepared by hydrolysis of a
Formula VII compound as shown in Scheme 13. Typical reactions involve treating Formula VII compounds with a base such as sodium hydroxide or potassium hydroxide in a suitable solvent such as water, methanol or ethanol. The reaction temperature can vary from 0 °C to the reflux temperature of the particular solvent being used. Hydrolysis of esters have been thoroughly discussed in March, Advanced Organic Chemistry, 3rd Ed., (1985), pp 334-338. Typical reactions are completed in less than 24 h.
Figure imgf000014_0002
Compounds of Formula I (where A is A-6 and G6 is alkenylene) can be prepared by reaction of compounds of Formula XIII with an aldehyde of Formula V in the presence of a strong base. This transformation is shown in Scheme 14. A typical reaction involves mixing a compound of Formula XIII 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, ethanol, toluene, dimethoxyethane and dimethylsulfoxide, followed by the addition of an aldehyde of Formula V. The temperature of the reaction can vary from -70-200 °C. The Wittig reaction has been reviewed by Maercker in Org. Rxns. (1965), 14, pp 270-490. The reaction is complete in 1-48 h.
Figure imgf000014_0001
Formula XIII compounds can be prepared by reaction of equimolar amounts of a
Formula XIV compound and triphenylphosphine. The transformation is shown in Scheme 15. The reaction can be run in a solvent such as benzene, toluene, xylene, ether, tetrahydrofuran, nitromethane, nitrobenzene, acetonitrile, ethyl acetate and dimethylformamide. The reaction temperature can vary from 0-200°C. For details see Maercker, Org. Rxn. (1965), 14, pp 270-490. The reaction is completed in 24 h.
Figure imgf000015_0001
Compounds of Formula XIV can be prepared from compounds of XV as shown in
Scheme 16. The reaction involves combination of an alcohol of Formula XV with a
halogenating agent such as triphenylphosphine and carbon tetrachloride or carbon tetrabromide, triphenylphosphine, imidazole and iodine in a suitable solvent such as acetonitrile or methylene chloride. (Hooz et al., Can. J. Chem. (1968), 46, 86; Lange et al., Syn. Commun. (1990), 20, 1473). The reaction temperature may vary from 0-100 °C and is usually completed in 24 h.
Figure imgf000015_0002
Compounds of Formula XV can be prepared by reduction of esters of Formula VII with alkali metal hydrides (Scheme 17). The reaction conditions are as described for Scheme 4.
Figure imgf000015_0003
Compounds of Formula I (where A is A-6, G6 is C2 alkylene, and Q is aryl) can be prepared by reaction of a compound of Formula XVI, first with thionyl chloride and then with sodium hydroxide in methanol as shown in Scheme 18. A typical reaction involves mixing a compound of Formula XVI with thionyl chloride neat or with a suitable solvent such as toluene or carbon tetrachloride. The mixture is heated from 30-100°C for 0.25-4 h. The solvent and excess thionyl chloride are concentrated under vacuum and the resultant crude chloride is dissolved in methanol and treated with aqueous sodium hydroxide. This second reaction is then heated for 0.25-4 h at 30-65°C. Extraction of the cooled reaction mixture with an organic solvent enables the isolation of the product of Formula I where A is A-6 and G6 is C2 alkylene.
Figure imgf000016_0002
Compounds of Formula XVI can be prepared from compounds of Formula XVII as shown in Scheme 19. Amino alcohols of Formula XVII are first converted to silyl ethers by reaction with trimethylsilyl cyanide at 0-30°C in a suitable solvent such as methylene chloride, chloroform, or tetrahydrofuran. (The alcohol group in compounds of Formula XVII is protected as the silyl ether so it does not react with the benzoyl chloride in the next step.) After
15-60 min, the solution of silyl ether is treated with an organic base like triethylamine and then with an appropriate benzoyl chloride at 0-30°C for 0.5-4 h. The crude intermediate amide can be isolated by addition of water and extraction with an appropriate organic solvent. The silyl ether protecting group is removed by treatment of the crude intermediate (dissolved in an appropriate solvent like tetrahydrofuran) with a solution of tetrabutylammonium fluoride at 0-30°C for 5-60 min. Compounds of Formula XVI are then isolated by addition of water and extraction with an organic solvent like ethyl acetate.
Figure imgf000016_0001
Compounds of Formula XVII can be prepared from compounds of Formula XVIII as shown in Scheme 20. A typical reaction involves treatment of a phthalimide of Formula XVIII, dissolved in an appropriate solvent like methanol or ethanol, with an excess of hydrazine at 40-80°C for 0.5-8 h.
Figure imgf000017_0003
Compounds of Formula XVIII can in turn be prepared from compounds of Formula XIX as shown in Scheme 21. An epoxide of Formula XIX is dissolved in an appropriate solvent like tetrahydrofuran and treated with one equivalent of phthalimide and a catalytic amount
(10 mol %) of an appropriate palladium catalyst like tetrakis-(triphenylphosphine) palladium (0) at 15-35°C for 0.5-4 h.
Figure imgf000017_0002
Compounds of Formula XIX can be prepared as shown in Scheme 22. Compounds of Formula XX are treated with trimethylsulfonium iodide under phase transfer conditions to give epoxides of Formula XIX (Syn. Commun. (1987), 17, 503-513). Compounds of Formula XX are available commercially or can be easily prepared by those skilled in the art. A useful preparation can be found in J. Chem. Soc. Chem. Commun. (1984), 1287.
Figure imgf000017_0001
Compounds of Formula I (where A is A-1, Y is H, Q is J) can also be prepared by reaction of a compound of Formula II with a triarylbismuth of Formula XXI in the presence of cupric acetate as shown in Scheme 23. This reaction can be carried out in a solvent such as methylene chloride at room temperature in less than 24 h (see Barton et al. Tetrahedron Letts. (1987), 28, pp 887-890).
Figure imgf000018_0002
Compounds of Formula I (where R1 and R2 are halogens and R3 is alkyl or aryl) can be obtained by reaction of a compound of Formula XXII with a base. Compounds of
Formula XXII are prepared by reacting substituted benzamide with 2-haloacetaldehyde dialkylacetal (see EP-A-594,129). The conversion of XXII to I takes place at room temperature over a period of several hours. Scheme 24 discloses this transformation.
Figure imgf000018_0001
One skilled in the art would recognized that the transformations described in Schemes 7 and 12 can be extended to the preparation of compounds of Formula I where A is A-3 by using appropriate commercially available serine derivatives.
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 into the synthesis will aid in obtaining the desired products. The use and choice of the protecting group will be apparent to one skilled in chemical synthesis.
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 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 9J 3 g of a pale yellow oil: 1H NMR (CDCl3) 6 7.70 (br,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 product 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 partitioned between EtOAc and H2O. The EtOAc layer was washed with brine, dried over MgSU4 and evaporated. The residue was passed through a silica gel column eluting with EtOAc:hexane (1:4) to give 6.0 g of a colorless oil: 1H NMR (CDCl3) δ 7.43 (mJH), 6.98 (t,2 H) 5.00 (t,1H), 4.63-4.72 (2t,2H), 3.84 (s,3H).
Step C: 2-(2,6-Difluorophenyl)-4,5-dihydro-4-oxazolecarboxylic acid
A solution of 24.37 g (0.101 mol) of the product of Step 6 and 6.17 g (0.109 mol) of KOH in 100 mL of MeOH was stirred at room temperature for 5 h. The MeOH was evaporated under reduced pressure and the residue dissolved in H2O. Hydrochloric acid was added to the solution resulting in precipitation of a white solid. The solid was filtered and air dried to give 19.6 g of product: m.p. 149-150 °C; 1H NMR (DMSO-d6) δ 13.10 (br,1H), 7.68 (m,1H), 7.28 (t,2H), 4.95 (t,1H), 4.59 (2 t,2H).
Step D: 2-(2,6-Difluorophenyl)-4,5-dihydro-N-(4-methoxyphenyl)-4- oxazolecarboxamide
The compound, 1,3-dicyclohexylcarbodiimide (0.433 g, 0.0021 mol), was added to a mixture of the product of Step C (0.500 g, 0.0021 mol), 4-dimethylaminopyridine (0.044 g, 0.00036 mol) and p-anisidine (0.259 g, 0.0021 mol) in 3.5 mL of methylene chloride. The mixture was stirred at reflux for 1.5 h. The solvent was evaporated and the residue passed through a silica gel column eluting with EtOAc:hexane (1:4) to give 0.881 g of a solid: m.p. 144-146.5 °C; 1H ΝMR (DMSO-d6) δ 10.17 (s,1H), 7.65 (m,1H), 7.58 (d,2H), 7.28 (t,2H), 6.90 (d,2H), 5.05 (t,1H), 4.69 (2t,2H), 3.73 (s,3H).
EXAMPLE 2
Step A: 2-(2,6-DifluorophenyI)-4,5-dihydro-4-oxazolecarboxamide
A solution of 10.0 g (0.041 mol) of methyl 2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolecarboxylate in 100 mL of a 2M solution of ammonia in MeOH was stirred at room temperature overnight. Evaporation of solvent afforded 9.04 g of a white powder: m.p.
148-149 °C; 1H ΝMR (DMSO-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 (2 t,2H).
Step B: 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 ΝaOH in 3.7 mL of H2O. 0.500 g (0.002 mol) of the product of Step A was added portionwise. The reaction was stirred at 80 °C for 0.5 h. Et2O and H2O was added and the mixture extracted with EtOAc. The combined extracts were washed with brine, dried MgSO4 and evaporated to give 0.350 g of a white solid: m.p. 81-85 °C; 1H ΝMR (DMSO-d6) δ 7.62 (m,1H), 7.24 (t,2H), 5.15 (t,1H), 4.70 (t,1H), 3.83 (t,1H).
Step C: N-[2-(2,6-Difluorophenyl)-4,5-dihydro-4-oxazolyl]nonanamide
The compound, 1,3-dicyclohexylcarbodiimide (1.03 g, 0.005 mol) was added to a mixture of the product of Step B (1.00 g, 0.005 mol), 4-dimethylaminopyridine (0.106 g, 0.00087 mol). and nonanoic acid (0.756 g, 0.005 mol) in 9 mL of methylene chloride. The reaction was stirred at room temperature overnight. The solvent was evaporated and the residue passed through a silica gel column eluting with EtOAc:hexane (1:2) to give 1.28 g of a white solid: m.p.
55-58 °C; 1H NMR CDCl3 δ 7.45 (m,1H), 7.10 (br,1H), 6.98 (t,2H), 6.09 (m,1H), 4.67 (t,1H), 4.20 (dd,1H), 2.20 (t,2H), 1.61 (m,2H), 1.26 (br,10H), 0.87 (t,3H).
EXAMPLE 3
N-[2-(2,6-Difluorophenyl)-4, 5-dihydro-4-oxazolyl]-2-fluoro-4- (trifluoromethyl)benzamide
Thionyl chloride (2.008 g, 0.017 mol) was added to a cooled solution of 1.10 g
(0.005 mol) of 2-fluoro-4-trifluoromethylbenzoic acid in 5 mL of benzene. The mixture was refluxed for 1 h. The benzene was evaporated and fresh benzene added to azeotrope off excess thionyl chloride. The residue was dissolved in 2 mL of dry THF and added dropwise to a cooled solution of 0.952 g (0.0048 mol) of 2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolamine and 0.81 mL of Et3Ν in 3 mL of dry THF. The reaction was allowed to warm to room temperature and stirred overnight. Et2O was added and the salts filtered. The filtrate was washed successively with 1N HCl, brine, 1N NaOH and brine. It was dried over MgSO4, filtered, and evaporated to give a light brown solid. This solid was triturated with hexanes to give 0.825 g of product: m.p. 146-147 °C; 1H NMR (DMSO-d6) δ 9.39 (dJH), 7.83 (t,2H), 7.69 (m,2H), 7.30 (t,2H), 6.26 (m,1H), 4.68 (t,1H), 4.30 (t,1H).
EXAMPLE 4
2-(2,6-Difluorophenyl)-4,5-dihydro-N-[4-(trifluoromethyl)-phenylmethylenel-4- oxazolamine
A mixture of 1.00 g (0.005 mol) of 2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolamine, 0.870 g (0.005 mol) of 4-trifluoromethylbenzaldehyde and 0.530 g (0.005 mol) of Νa2CO3 in 6 mL of MeOH was stirred at room temperature overnight. Solvents were evaporated and the residue passed through a silica gel column eluting with EtOAc:hexane (1:4) affording 0.560 g of a yellow solid: m.p. 85-87 °C; 1H NMR (CDCl3) δ 8.70 (s,1H), 7.91 (d,2H), 7.68 (d,2H), 7.45 (m,1H), 7.02 (t,1H), 6.18 (t,1H); 4.78 (t,1H), 4.39 (dd,1H).
EXAMPLE 5
2-(2,6-Difluorophenyl)-4,5-dihydro-N-phenyl-4-oxazolamine
A mixture of 2.98 g (0.015 mol) of 2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolamine, 7.79 g (0.018 mol) of triphenylbismuth (Alfa Research Chemicals) and 2.57 g (0.014 mol) of anhydrous cupric acetate (Aldrich Chemical Co.) in 48 mL of methylene chloride was stirred at room temperature for 2 h. Solvent was evaporated and the residue passed through a silica gel column eluting with 30% EtOAc/hexane affording 1.76 g of the title compound as a light yellow solid, which was further purified by recrystallization from CHCl3-hexane: m.p. 109.5-110.5°C; 1H NMR (CDCl3) δ 7.45 (m, 1H), 7.22 (m,2H), 7.00 (m,2H), 6.80 (m,3H), 5.90 (dd,1H), 4.69 (t,1H), 4.20 (dd,1H), 4.15 (bs,1H). EXAMPLE 6
2-(2,6-Difluorophenyl)-4,5-dihydro-4-methoxyoxazoline
A mixture of 2.5 g (0.01 mol) of N-(1-methoxy-2-chloroethyl)-2,6-diflurobenzamide and 0.7 g (0.01 1 mol) of KOH pelletes (85%) in 30 mL methanol were stirred at room temperature overnight. The white slurry that formed was filtered, and the filtrate evaporated to remove residual solvent. The residue was extracted with water/methylene chloride. Upon evaporation of the methylene chloride, 1.5g (70% yield) of the title compound was obtained as an oil: 1H NMR (CDCl3) δ 7.42 (m,1H), 6.98 (m,2H), 5.59 (t,1H), 4.42 (d,1H), 4.27 (d,1H), 3.55 (s,3H).
By the procedures described herein the following compounds of Tables 1-12 can be prepared. The compounds in Table 1, line 1 can be referred to as 1-1, 1-2, 1-3, 1-4 , 1-5, 1-6 and 1-7 (as designated by line and column). All the other specific compounds covered in these Tables can be designated in an analogous fashion. The following abbreviations have been used in Tables 1-12: Me = methyl, Ph = phenyl, and pyr = pyridyl.
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000022_0002
Figure imgf000023_0001
Figure imgf000023_0002
Figure imgf000023_0003
Figure imgf000024_0001
Figure imgf000024_0002
Figure imgf000025_0001
Figure imgf000025_0002
Figure imgf000025_0003
Figure imgf000026_0001
Figure imgf000026_0002
Figure imgf000026_0003
Figure imgf000027_0001
Figure imgf000027_0002
Figure imgf000027_0003
Figure imgf000028_0001
Formulation/Utility
Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent. Useful formulations include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. 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 weight percent.
Weight Percent
Active
Ingredient Diluent Surfactant
Wettable Powders 5-90 0-74 1-10
Oil Suspensions, Emulsions, 5-50 40-95 0-15
Solutions, (including Emulsifiable
Concentrates)
Dusts 1-25 70-99 0-5
Granules, Baits and Pellets 0.01-99 5-99.99 0-15
High Strength Compositions 90-99 0-10 0-2 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 and solvents 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. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced by agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., (1988), pp 251-259. Suspensions are prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-148, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, (1963), pages 8-57 and following, and WO 91/13546.
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-E.
Example A
Wettable Powder
Compound 1 65.0%
dodecylphenol polyethylene glycol ether 2.0%
sodium ligninsulfonate 4.0%
sodium silicoaluminate 6.0%
montmorillonite (calcined) 23.0%.
Example B
Granule
Compound 1 10.0%
attapulgite granules (low volatile
matter, 0.71/0.30 mm; U.S.S. No.
25-50 sieves) 90.0%.
Example C
Extruded Pellet
Compound 1 25.0%
anhydrous sodium sulfate 10.0%
crude calcium ligninsulfonate 5.0%
sodium alkylnaphthalenesulfonate 1.0%
calcium/magnesium bentonite 59.0%. Example D
Emulsifiable Concentrate
Compound 1 20.0%
blend of oil soluble sulfonates
and polyoxyethylene ethers 10.0%
isophorone 70.0%.
The compounds of this invention 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, compounds of this invention display activity against one or more of the following pests: 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, junveniles 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 frugiperda), black bean aphid(Aphis fabae), green peach aphid (Myzus persica), cotton aphid (Aphis gossypii), Russian wheat aphid
(Diuraphis noxia), English grain aphid (Sitobion avenae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus oryzophilus), rice leaf beetle (Oulema oryzae), whitebacked planthopper( Sogatella furcifera), 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, repellants, 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 other agricultural protectants with which compounds of this invention can be formulated are: insecticides such as avermectin B, monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fipronil, flufenprox, fonophos, isofenphos, methidathion, metha-midophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, tefluthrin, fenpropathrin, fluvalinate, flucythrinate, tralomethrin, imidacloprid, metaldehyde and rotenone; fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanil, fenpropidine, fenpropimorph, triadimefon, captan, thiophanate-methyl, thiabendazole, phosethyl-Al, chlorothalonil, dichloran, metalaxyl, captafol, iprodione, oxadixyl, vinclozolin, kasugamycin, myclobutanil, tebuconazole, difenoconazole, diniconazole, fluquinconazole, ipconazole, metconazole, penconazole, propiconazole, uniconzole, flutriafol, prochloraz, pyrifenox, fenarimol, triadimenol, diclobutrazol, copper oxychloride, furalaxyl, folpet, flusilazol, blasticidin S, diclomezine, edifenphos, isoprothiolane, iprobenfos, mepronil, neo-asozin, pencycuron, probenazole, pyroquilon, tricyclazole, validamycin, and flutolanil; nematocides such as aldoxycarb, fenamiphos and fosthietan;
bactericides such as oxytetracyline, streptomycin and tribasic copper sulfate; acaricides such as binapacryl, oxythioquinox, chlorobenzilate, dicofol, dienochlor, cyhexatin, hexythiazox, amitraz, propargite, tebufenpyrad and fenbutatin oxide; and biological agents such as entomopathogenic bacteria, virus and fungi.
In certain instances, combinations with other arthropodicides having a similiar spectrum of control but a different mode of action will be particularly advantageous for resistance
management.
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 Formula I, 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 incoφorated 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, and synergists and other solvents 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-G for compound descriptions. The following abbreviations have been used in Index Tables A-G: Me = methyl, Bu = butyl and Ph = phenyl.
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000034_0002
Figure imgf000034_0003
Figure imgf000035_0001
Figure imgf000035_0002
Figure imgf000036_0001
Figure imgf000036_0002
Compound O m.p. (°C)
68 Ph 109.5-1 10.5
69 4-F-Ph 101.5-102
70 4-Cl-Ph 11 1-113
71 4-Br-Ph 125
72 4-Me-Ph 81.5-82
73 4-F-3-Me-Ph 101-102
74 3-F-Ph 108
75 3,5-diF-Ph 128-129
76 4-tBu-Ph oil*
77 4-OCF3-Ph oil*
78 4-(4-Me-Ph)-Ph 131-139
79 CH2(2-F-4-CF3-Ph) 61-63
* see Index Table G for spectral data.
INDEX TABLE G
Spectral Data
CMPD
1 1H NMR (CDCl3): δ 7.43 (m,1H); 6.98 (t,2H); 5.00 (ABq,1H);4.63-4.72(m,2H);
3.84 (s,3H).
4 1H NMR (CDCl3): δ 8.24 (d,2H), 7.30-7.70 (m,4H), 6.93 (t,2H), 5.79 (t,1H), 5.14
(t,1H), 4.60 (t,1H).
9 1H NMR (CDCl3): δ 7.42 (m,1H), 6.98 (m,2H), 5.59 (t,1H), 4.42 (d,1H),
4.27 (d,1H), 3.55 (s, 3H).
10 1H NMR (CDCl3): δ 7.35 (m,1H), 7.25 (m,1H), 7.05 (m,1H), 5.60 (m,1H),
4.42 (m,1H), 4.30 (m, 1H), 3.55 (s,3H).
11 1H NMR (CDCl3): δ 4.10 (ABq,2H), 4.13 (t,1H), 4.52 (t,1H), 5.35 (t,1H),
6.92-7.45 (m,7H).
12 1H NMR (CDCl3): δ 7.50-7.20 (m,6H), 6.98 (t,2H), 6.71 (d,1H), 6.28 (dd,1H),
5.08 (q,1H), 4.67 (t, 1H), 4.24 (t,1H).
13 1H NMR (CDCl3): δ 7.43 (m,1H), 7.37 (m,2H), 7.00 (m,4H), 6.65 (d,1H),
6,18 (dd,1H), 5.06 (q,1H), 4.66 (t,1H), 4.23 (t,1H).
16 1H NMR (CDCl3): δ 3.71 (s,3H), 4.67 (m,2H), 6.99 (m,3H), 7.30-7.70 (m,4H).
18 1H NMR (CDCl3): δ 4.05 (ABq,2H), 4J0 (t,1H), 4.55 (t,1H), 5.36 (t,1H),
6.95 (t,2H), 7.35-7.55 (m,9H).
19 1H NMR (CDCl3) δ 7.55-7.35 (m,9H), 6.99 (t,2H), 6.73 (d,1H), 6.33 (dd,1H),
5,10 (q,1H), 4.68 (t,1H), 4.26 (t,1H). 33 1H NMR (Me2SO-d6): δ 10.20 (s,1H), 7.70 (m,1H), 7.30 (s,1H), 7.45 (d,1H), 7.20-7.32
(m,3H), 6.94 (d,1H), 5.06 (t,1H), 4.63-4.69 (m,2H), 2.29 (s,3H).
53 1H NMR (CDCl3): δ 8.58 (s,1H), 7.72 (d,2H), 7.39 (m,3H), 7.01 (t,2H), 6J2 (t,1H),
4.75 (t,1H), 4.39 (t,1H).
55 1H NMR (CDCl3): δ 8.59 (s,1H), 7.72 (d,2H), 7.44 (m,3H), 6.99 (t,2H), 6J0 (t,1H),
4.72 (t,1H), 4.36 (t,1H), 1.33 (s,9H).
76 1H NMR (Me2SO): δ 7.62 (m,1H), 7.24 (t,2H), 7.16 (d,2H), 6.69 (d,2H), 6.2 (d,1H),
5.80 (q,1H), 4.65 (t,1H), 4.18 (t,1H), 1.22 (s,9H).
77 1H NMR (Me2SO): δ 7.62 (m,1H), 7.25 (t,2H), 7.14 (d,2H), 6.84 (d,2H), 6.75 (d,1H),
5.85 (q,1H), 4.70 (t,1H), 4.20 (t,1H).
TEST A
Southern Corn Rootworm
Test units, each consisting of a 230 mL (8 ounce) plastic cup containing a 2.54 cm2 plug (1 square inch) of a wheatgerm diet, were prepared. 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 kg of active ingredient per hectare (about 0.5 pounds per acre) at 207 kPa (30 p.s.i.). After the spray on the cups had dried, five secondinstar larvae of the southern corn rootworm (Diabrotica undecimpunctata howardi) were placed into each cup. The cups were held at 27°C and 50% relative humidity for 6-8 days. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 54.
TEST B
Two-Spotted Spider Mite
Pieces of kidney bean leaves, each approximately 2.54 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 207kPa (30 p.s.i.). The leaf squares were then placed underside-up on 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 7 days and read for larvacide/ovacide mortality Of the
compounds tested, the following gave activity levels of 80% or higher: 5, 7, 12, 13, 19, 20 and 27. TEST C
Two-Spotted Spider Mite
A solution of the test compound was prepared by dissolving it in a minimum of acetone and then adding water containing a wetting agent until the concentration of the compound was 100 ppm. Two- week old red kidney bean plants infested with two-spotted spider mite eggs (Tetranychus urticae) were. sprayed to run-off with the test solution using a turntable sprayer. Plants were held in a chamber at 25°C and 50% relative humidity and scored for activity seven days after spray. Of the compounds tested, 80% or greater control was achieved using the following compounds: 7, 11*, 12, 13, 16*, 18*, 19, 35, 40*, 41*, 44*, 48*, 49*, 51*, 53, 56, 57, 58, 68*, 70*, 71*, 72*, 74*, 76*, 77* and 79*.
* - tested at 50 ppm.

Claims

1. A compound of the formula
Figure imgf000040_0007
wherein:
A is selected from the group
, , ,
Figure imgf000040_0001
Figure imgf000040_0004
Figure imgf000040_0005
, and ;
Figure imgf000040_0002
Figure imgf000040_0003
Figure imgf000040_0006
B is selected from the group O and N-Y;
E is selected from the group C1-C4 alkyl and C1-C4 haloalkyl;
X1 and Z are independently selected from the group O and S;
X2 is selected from the group H, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C(O)OR13 and CN;
Y is 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 cycloalkylalkyl, CHO, C(O)R16, C(O)OR16, C(S)R16, C(S)OR16, C(S)SR16, C(O)C(O)OR16, C(O)CH2C(O)OR16, S(O)tR16, S(O)2CH2C(O)OR16, P(X)(OR18)2, S(O)tN(R13)C(O)OR12, S(O)tN(R14)R15, NsCR-OR1 1, OR9, NR9R10 ; phenyl optionally substituted with 1-3 substituents independently selected from W1; and C1-C6 alkyl substituted with 1-3 substituents independently selected from the group C1-C3 alkoxy, C1-C3 haloalkoxy, CN, NO2, S(O)tR16, P(X)(OR18)2, C(O)R16, C(O)OR16 and phenyl optionally substituted with 1-3 substituents independently selected from W1 ;
X is selected from the group O and S; G1 is selected from the group single bond, C(=X1), C(=X1)N(Y), C(=X1)O and S(O)2;
G2 is selected from the group single bond, O, S and N-Y;
G3 is selected from the group single bond, O and N-Y;
G4 is selected from the group single bond, O and N-Y;
G5 is selected from the group single bond, O, S and N-Y;
G6 is selected from the group C2-C4 alkenylene, C2-C4 alkynylene, O-C2-C4
alkenylene and O-C2-C4 alkynylene;
Q is selected from the group H and J; or Q is selected from the group C1-C16 alkyl, C1-C16 haloalkyl, C2-C16 alkenyl, C2-C16 haloalkenyl, C2-C16 alkynyl,
C2-C16 haloalkynyl, C3-C7 cycloalkyl, C3-C7 halocycloalkyl and C4-C7 cycloalkylalkyl, each group optionally substituted with 1-4 substituents independently selected from W;
J is a 5- or 6-membered aromatic ring containing 0 to 4 heteroatoms independently selected from the group 0-4 nitrogen, 0-1 oxygen, and 0-1 sulfur; or J is a 9- to 14-membered aromatic ring system selected from the group fused bicylic ring and fused tricylic ring, each ring system containing 0 to 6 heteroatoms independently selected from the group 0-4 nitrogen, 0-2 oxygen, and 0-2 sulfur; wherein J is optionally substituted with 1-4 substituents independently selected from the group R3;
R1 is selected from the group halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6
alkoxy, C1-C6 haloalkoxy, S(O)tR16, CN and NO2;
R2 is selected from the group H, halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, S(O)tR16, CN and NO2;
R3 is 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, C1-C16 nitroalkyl, C2-C16 cyanoalkyl, C3-C18 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, CN, N3, SCN, NO2, SH, S(O)tR16, OCHO, OR20, CHO, C(O)R21, C(O)OR21, C(O)NR16R17, S(O)2NR16R17, C(R4)=NR9, N=CR4R9, NRW7,
NR17C(O)R16, NRl7C(O)NHR16, NR17S(O)2R16, Si(R6)(R7)(R8), SF5 and M-J1 ;
R4 is selected from the group halogen, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6
alkoxy, C1-C6 haloalkoxy and phenyl optionally substituted with R5;
R5 is selected from the group halogen, CN, NO2, C1-C6 alkyl, C1-C6 haloalkyl,
C1-C6 alkoxy, C1-C6 haloalkoxy, C(O)R16, C(O)OR16 and Si(R6)(R7)(R8);
R6 and R7 are independently C1-C12 alkyl; R8 is selected from the group C1-C12 alkyl and phenyl optionally substituted with
1 -3 substituents independently selected from W 1;
R9 is selected from the group H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl,
C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C(O)R16, C(O)OR16, C(O)NR16R17, S(O)2NR16R17, S(O)2R16, optionally substituted phenyl, and optionally substituted benzyl wherein the phenyl and benzyl substituents are
1-3 substituents independently selected from W1 ;
R10 is selected from the group H, C1-C4 alkyl, C(O)R16 and C(O)OR16;
R1 1 is selected from the group H, C1-C4 alkyl, C1-C4 haloalkyl and phenyl
optionally substituted with 1-3 substituents independently selected from W1 ; or
R10 and R1 1 are taken together as (CH2)4 or (CH2)5;
R12 is C1-C18 alkyl;
R13 is C1-C4 alkyl;
R14 and R15 are independently C1-C4 alkyl; or
R14 and R15 are taken together as (CH2)4, (CH2)5 or CH2CH2OCH2CH2;
R16 is 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, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 cycloalkylalkyl, optionally substituted phenyl and optionally substituted benzyl wherein the phenyl and benzyl substituents are 1-3 substituents independently selected from W1;
R17 is selected from the group H and C1-C4 alkyl; or
R16 and R17, when attached to the same atom, are taken together as (CH2)4,
(CH2)5 or CH2CH2OCH2CH2, each group optionally substituted with 1-3
CH3;
R18 is selected from the group C1-C3 alkyl and phenyl optionally substituted with
1-3 substituents independently selected from W1 ;
R19 is selected from the group halogen, CN, NO2, C1-C6 alkyl, C1-C6 haloalkyl,
OR9, C(O)R16, C(O)OR16 and Si(R6)(R7)(R8);
R20 is selected from the group H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl,
C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C(O)R16, C(O)OR16,
C(O)NR16R17, S(O)2NR16R17 and S(O)2R16;
R21 is 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, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl and C4-C7 cycloalkylalkyl; M is selected from the group direct bond, S, O, C(O), C(O)-C1-C2 alkylene, C(O)O-C1-C2 alkylene, C1-C4 alkylene, O-C1-C4 alkylene, O-C2-C4 alkenylene and O-C2-C4 alkynylene; provided that when M is O-C1-C4 alkylene, O-C2-C4 alkenylene or O-C2-C4 alkynylene, the oxygen atom is attached to the J ring; and when M is C(O)O-C1-C2 alkylene, the C(O) is attached to the J ring;
J1 is selected from the group phenyl and naphthyl, each optionally substituted with 1-4 substituents independently selected from R19; or J1 is a 5-or 6-membered aromatic ring, attached through carbon or nitrogen, containing 1 to 4 heteroatoms independently selected from the group 1-4 nitrogen, 0-1 oxygen, and 0-1 sulfur, the ring optionally substituted with 1-4 substituents independently selected from R19;
W is selected from the group J, NO2, CN, OH, C1-C6 alkoxy and C1-C6
haloalkoxy;
W1 is selected from the group, halogen, CN, NO2, C1-C2 alkyl, C1-C2 haloalkyl,
C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio, C1-C2 haloalkylthio, C1-C2 alkylsulfonyl, and C1-C2 haloalkylsulfonyl;
q is 0, 1 or 2; and
t is 0, 1 or 2.
2. A compound according to Claim 1 wherein:
A is A-l;
Q is selected from the group J, C1-C16 alkyl and C2-C16 alkenyl; and J is selected from the group phenyl and thienyl, each optionally substituted with 1-3 substituents independently selected from the group R3.
3. A compound according to Claim 2 wherein:
Q is J; and
J is phenyl optionally substituted with 1-3 substituents independently selected from the group R3.
4. A compound according to Claim 3 wherein:
G1 is C(O);
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;
R3 is independently selected from the group, halogen, Cj-Cg alkyl, Cj-C6 haloalkyl, OR20 and M-J1 ;
R20 is selected from the group C1-C4 alkyl and C1-C4 haloalkyl; and
J1 is selected from the group phenyl, thienyl, pyridyl and furyl.
5. A compound according to Claim 4 which is: N-[2-(2,6-difluorophenyl)-4,5-dihydro-4-oxazolyl]-2-fluoro-4-(trifluoromethyl)benzamide.
6. An arthropodicidal composition comprising an arthropodicidally effective amount of a compound according to Claim 1 and a carrier therefor.
7. A method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound according to Claim 1.
PCT/US1995/000208 1994-01-24 1995-01-17 Arthropodicidal 2-oxa and thia-zolines WO1995019972A1 (en)

Priority Applications (5)

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BR9506625A BR9506625A (en) 1994-01-24 1995-01-17 Composite arthropodicidal composition and method for controlling arthropods
AU16765/95A AU1676595A (en) 1994-01-24 1995-01-17 Arthropodicidal 2-oxa and thia-zolines
EP95908447A EP0741714A1 (en) 1994-01-24 1995-01-17 Arthropodicidal 2-oxa and thia-zolines
JP7519575A JPH09508366A (en) 1994-01-24 1995-01-17 2-Oxa and thia-zolines of arthropodicides
MX9602949A MX9602949A (en) 1994-01-24 1995-01-17 Arthropodicidal 2-oxa and thia-zolines.

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US08/185,550 1994-01-24

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US6933308B2 (en) 2002-12-20 2005-08-23 Bristol-Myers Squibb Company Aminoalkyl thiazole derivatives as KCNQ modulators
US7273866B2 (en) 2002-12-20 2007-09-25 Bristol-Myers Squibb Company 2-aryl thiazole derivatives as KCNQ modulators
AU2002305669B2 (en) * 2001-05-21 2008-09-11 E.I. Du Pont De Nemours And Company Diamide invertebrate pest control agents containing a non-aromatic heterocyclic ring

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DE602004008300T2 (en) * 2003-06-13 2008-05-08 Janssen Pharmaceutica N.V. THIAZOLINE DERIVATIVES AS SELECTIVE ANDROGEN RECEPTOR MODULATORS (SARMS)
JP2023007504A (en) * 2019-09-30 2023-01-19 日本農薬株式会社 Imine compound or salt thereof, pest control agent containing that compound as active ingredient, and pest control method
CN115894398B (en) * 2022-12-02 2024-03-12 青岛科技大学 Fluothiazole amide-containing insecticidal acaricide

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
AU2002305669B2 (en) * 2001-05-21 2008-09-11 E.I. Du Pont De Nemours And Company Diamide invertebrate pest control agents containing a non-aromatic heterocyclic ring
US6933308B2 (en) 2002-12-20 2005-08-23 Bristol-Myers Squibb Company Aminoalkyl thiazole derivatives as KCNQ modulators
US7273866B2 (en) 2002-12-20 2007-09-25 Bristol-Myers Squibb Company 2-aryl thiazole derivatives as KCNQ modulators

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NZ279591A (en) 1997-04-24
AU1676595A (en) 1995-08-08
MX9602949A (en) 1997-06-28
CN1143957A (en) 1997-02-26
BR9506625A (en) 1997-09-30
JPH09508366A (en) 1997-08-26

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