EP1341780A2 - Arthropodicides de diamide d'acide phthalique heterocycliques substitutes - Google Patents

Arthropodicides de diamide d'acide phthalique heterocycliques substitutes

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Publication number
EP1341780A2
EP1341780A2 EP01990065A EP01990065A EP1341780A2 EP 1341780 A2 EP1341780 A2 EP 1341780A2 EP 01990065 A EP01990065 A EP 01990065A EP 01990065 A EP01990065 A EP 01990065A EP 1341780 A2 EP1341780 A2 EP 1341780A2
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EP
European Patent Office
Prior art keywords
ffl
ffi
ffi ffi
hcj
chf
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EP01990065A
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German (de)
English (en)
Inventor
George Philip Lahm
Thomas Paul Selby
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/38—Nitrogen atoms
    • C07D231/40—Acylated on said nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • This invention relates to certain heterocyclic phthalic acid diamides, their N-oxides, agriculturally suitable salts and compositions, and methods of their use as arthropodicides in both agronomic and nonagronomic environments.
  • invetebrate pests The control of invetebrate pests is extremely important in achieving high crop efficiency. Damage by invertebrate pests to growing and stored agronomic crops can cause significant reduction in productivity and thereby result in increased costs to the consumer.
  • the control of invertebrate pests in forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different modes of action.
  • EP919542 discloses phthalic acid diamides of Formula i as insecticides
  • Z 1 and Z 2 are O or S;
  • R 1 , R 2 and R 3 are, among others, H, alkyl or substituted alkyl.
  • WOO 1/02354 discloses phthalic acid diamides of Formula ii as insecticides
  • Q is an optionally substituted hetero cycle containing O, S or ;
  • Z 1 and Z 2 are O or S; and
  • R 1 , R 2 and R 3 are, among others, H, alkyl or substituted alkyl.
  • This invention pertains to compounds of Formula I and N-oxides and agriculturally suitable salts thereof
  • J is selected from the group consisting of J-l, J-2, J-3, J-4, J-5, J-6, J-7 and J-8
  • R 1 is H, Ci-C 6 alkyl, C 2 -C6 alkoxycarbonyl or C2-C6 alkylcarbonyl;
  • R 2 is H or C ⁇ -C 6 alkyl
  • R 3 is H; C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, or C 4 -C 8 cycloalkylalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO 2 , hydroxy, C1-C4 alkyl, C !
  • R 4 group is attached to the phenyl ring at the 3-position or 6-position, and said R 4 is C r C4 alkyl, C r C 4 haloalkyl, halogen, CN, NO 2 , C !
  • R 5 is H, Ci-C 4 alkyl, C r C 4 haloalkyl, or
  • Y is N, CH, CF, CC1, CBr or Cl; each R 6 and R 7 is independently H, C ⁇ -Cg alkyl, C3-C6 cycloalkyl, Cj-Cg haloalkyl, halogen, CN, C 1 -C4 alkoxy, C1-C 4 haloalkoxy or C1-C 4 haloalkylthio;
  • R 9 is H, C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl or C 3 -C6 haloalkynyl; provided R 7 and R 9 are not both H; R 10 is H or Cr-C- alkyl or C1-C haloalkyl; R 1 1 is H or -C4 alkyl; and n is 1 or 2.
  • This invention also pertains to a composition for controlling an invertebrate pest comprising a biologically effective amount of a compound of Formula I and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • This invention also pertains to a composition comprising a biologically effective amount of a compound of Formula I and an effective amount of at least one additional biologically active compound or agent.
  • This invention also pertains to a method for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound of Formula I (e.g., as a composition described herein).
  • a biologically effective amount of a compound of Formula I e.g., as a composition described herein.
  • This invention also relates to such method wherein the invertebrate pest or its environment is contacted with a biologically effective amount of a compound of Formula I or a composition comprising a compound of Formula I and a biologically effective amount of at least one additional compound or agent for controlling invertebrate pests.
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as methyl, ethyl, /.-propyl, t ' -propyl, or the different butyl, pentyl or hexyl isomers.
  • Alkenyl can include straight-chain or branched alkenes such as 1 -propenyl, 2-propenyl, and the different butenyl, pentenyl andhexenyl isomers.
  • Alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain or branched alkynes such as 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkoxy includes, for example, methoxy, ethoxy, «-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyi denotes alkoxy substitution on alkyl.
  • alkoxyalkyi include CH 3 OCH2, CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Cycloalkylalkyi indicates an alkyl group substituted with a cycloalky group and includes, for example, cyclopropylmethyl, cyclobutylethyl, cyclopentylpropyl and cyclohexylmethyl.
  • heteroaromatic ring denotes fully aromatic rings in which at least one ring atom is not carbon and can contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each heteroaromatic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs (where aromatic indicates that the H ⁇ ckel rule is satisfied).
  • the heteroaromatic ring can be attached through any available carbon or nitrogen by replacement of hydrogen on said carbon or nitrogen.
  • halogen either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine.
  • haloalkyl 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 include F 3 C, CICH2, CF3CH2 and CF 3 CC1 2 .
  • haloalkenyl “haloalkynyl”, “haloalkoxy”, and the like, are defined analogously to the term “haloalkyl”.
  • haloalkynyl examples include HC ⁇ CCHCl, CF 3 C ⁇ C, CC1 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • C1-C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 2 alkoxyalkyi designates CH 3 OCH 2
  • C 3 alkoxyalkyi designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C4 alkoxyalkyi designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH 2 CH 2 OCH 2 and CH3CH2OCH2CH2.
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s).
  • the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the compounds ofthe invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • the present invention comprises of compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof.
  • nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides.
  • tertiary amines can form N-oxides.
  • the salts ofthe compounds ofthe invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, saHcylic, tartaric, 4-toluenesulfonic or valeric acids.
  • inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, saHcylic, tartaric, 4-toluenesulfonic or valeric acids.
  • the wavy line represents the rema ⁇ inder of the J group to which said R 5 moiety is attached.
  • Preferred compounds for reasons of better activity, cost and/or ease of synthesis are: Preferred 1. Compounds of Formula I wherein V is N. Preferred 2. Compounds of Formula I wherein V is CH, CF, CC1 or CBr. Preferred 3. Compounds of Preferred 1 or Preferred 2 wherein
  • R 1 and R 2 are both H
  • R 3 is C r C 4 alkyl optionally substituted with halogen, CN, OCH 3 , S(O) p CH ; one R 4 group is attached to the phenyl ring at the 3-position and said R 4 is CH 3 , CF 3 , OCF 3 , OCHF 2 , S(O) p CF 3 , S(O) p CHF 2 , CN or halogen; a second R 4 is H, F, Cl, Br, I or CF 3 ;
  • R 6 is C r C 4 alkyl, C 1 -C 4 haloalkyl, halogen or CN; R 7 is H, CH 3 , CF 3 , OCHF 2 or halogen; and p is 0, 1 or 2.
  • Preferred 4 Compounds of Preferred 3 wherein J is J-l;
  • R 3 is C1-C 4 alkyl; one R 4 group is attached to the phenyl ring at the 3-position and said R 4 is
  • R 4 is H, F, Cl, Br, I or CF 3 ;
  • R6 is Cl or Br;
  • R 7 is halogen or CF3.
  • Preferred 5 Compounds of Preferred 4 wherein V is N;
  • R 3 is methyl, ethyl, isopropyl or tertiary butyl; one R 4 group is attached to the phenyl ring at the 3-position and said R 4 is
  • R 3 is C r C 4 alkyl; one R 4 group is attached to the phenyl ring at the 3-position and said R 4 is CH 3 , CL Br or l; a second R 4 is H, F, Cl, Br, I or CF 3 ;
  • R 6 is Cl or Br
  • R 9 is CF 3 , CHF 2 , CH 2 CF 3 , CF 2 CHF 2 .
  • Preferred 7 Compounds of Preferred 3 wherein J is J-3; R 3 is C r C 4 alkyl; one R 4 group is attached to the phenyl ring at the 3-position and said R 4 is
  • R 4 is H, F, Cl, Br, I or CF 3 ;
  • R 6 is Cl or Br; and
  • R 7 is halogen or CF 3 .
  • R 3 is C ! -C 4 alkyl; one R 4 group is attached to the phenyl ring at the 3-position and said R 4 is CH 3 , CL Br orl; a second R 4 is H, F, Cl, Br, I or CF ; R 6 is Cl or Br; and R 7 is CF 3 .
  • Preferred 9. Compounds of Preferred 3 wherein J is J-5;
  • R 3 is C r C 4 alkyl; one R 4 group is attached to the phenyl ring at the 3-position and said R 4 is
  • R 4 is H, F, Cl, Br, I or CF 3 ;
  • R 6 is Cl or Br;
  • R9 is CF 3 , CHF 2 , CH 2 CF 3 , CF 2 CHF 2 .
  • Preferred 10 Compounds of Preferred 3 wherein J is J-6;
  • R 3 is C r C 4 alkyl; one R 4 group is attached to the phenyl ring at the 3-position and said R 4 is
  • R 3 is C r C 4 alkyl; one R 4 group is attached to the K-ring at the 2-position and said R 4 is CH3, Cl or Br; a second R 4 is H, F, Cl, Br, I or CF 3 ; R 6 is Cl or Br; R 7 is H, halogen or CF 3 .and R9 is H, CF 3 , CHF 2 , CH 2 CF 3 , CF 2 CHF 2 .
  • R 3 is C r C 4 alkyl; one R 4 group is attached to the phenyl ring at the 3-position and said R 4 is CH 3 , CL Brorl; a second R 4 is H, F, Cl, Br, I or CF 3 ; R 6 is Cl or Br; R 7 is H, halogen or CF3.and R9 is H, CF 3 , CHF 2 , CH 2 CF 3 , CF 2 CHF 2 . Specifically preferred are compounds selected from the group consisting of:
  • compositions ofthe present invention are those that comprise the above preferred compounds.
  • J is selected from the group consisting of
  • R 1 is H, C ⁇ -Cg alkyl, C 2 -C6 alkoxycarbonyl or C 2 -Cg alkylcarbonyl;
  • R 2 is H or C r C 6 alkyl
  • R 3 is H; Cj-Cg alkyl, C -C6 alkenyl, C 2 -Cg alkynyl, or C3-C 6 cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO 2 , hydroxy, C 1 -C4 alkyl, -C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, -C 4 alkylsulfmyl, C 1 -C4 alkylsulfonyl, C 2 -C6 alkoxycarbonyl, C 2 -Cg alkylcarbonyl, C3-C6 trialkylsilyl, or a phenyl, phenoxy or 5- or 6-membered heteroaromatic ring, each ring optionally substituted with one to three substituents independently selected from the group consisting of Cj -C alkyl, C 2 -C4 alken
  • each R 6 is independently Cj-Cg alkyl, C j -Cg haloalkyl, halogen, CN, C1-C4 alkoxy,
  • R 7 is C1-C4 alkyl, C 2 -C alkenyl, C 2 -C4 alkynyl, C 3 -C6 cycloalkyl, -C4 haloalkyl, C 2 -C4 haloalkenyl, C 2 -C4 haloalkynyl, C3-C6 halocycloalkyl, halogen, CN, NO 2 , C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C4 alkylthio, C1-C4 alkylsulfinyl, Cy C 4 alkylsulfonyl, C1-C4 alkylamino, C 2 -Cg dialkylamino, C 3 -C6 cycloalkylamino, C3-C6 (alkyl)cycloalkyla
  • X is , CH, CF, CCl or CBr.
  • Selection A Compounds of Formulal d wherein X is N.
  • Selection B Compounds of Formulald wherein X is CH, CF, CC1 or CBr.
  • Selection C The compounds of Selection A or Selection B wherein
  • J is J-59;
  • R 1 , R 2 andR 8 are all H;
  • R 3 is C ⁇ -C 4 alkyl optionally substituted with halogen, CN, OCH 3 , S(O) p CH 3 ; one R 4 is CH 3 , CF 3 , OCF 3 , OCHF 2 , S(O) p CF 3 , S(O) p CHF 2 , CN or halogen; a second R 4 is H, F, Cl, Br, I or CF 3 ;
  • R 6 is CH3, CF 3 or halogen; and ' p is 0, 1 or 2.
  • Selection D Compounds of Selection C wherein R 3 is C r C 4 alkyl; one R 4 is CH 3 , Cl orBr; a second R 4 is H, F, Cl, Br, I or CF ; R 6 is CF 3 ; and R 7 is Cl or Br.
  • Selection E The compounds of Selection A or Selection B wherein
  • R 1 and R 2 are both H
  • R 3 is C r C 4 alkyl optionally substituted with halogen, CN, OCH 3 , S(O) p CH 3 ; one R 4 is CH 3 , CF 3 , OCF 3 , OCHF 2 , S(O) p CF 3 , S(O) p CHF 2 , CN or halogen; a second R 4 is H, F, Cl, Br, I or CF 3 ;
  • R 9 is C 2 -Cg alkyl or Cj-Cg haloalkyl; and p is 0, lor 2.
  • Selection F Compounds of Selection E wherein R 3 is C r C 4 alkyl; one R 4 is CH 3 , Cl orBr; a second R 4 is H, F, Cl, Br, I or CF 3 ;
  • R 9 is CF 3 , CHF 2 , CH 2 CF 3 , CF 2 CHF 2 ;
  • R 7 is Cl or Br.
  • Selection G The compounds of Selection A or Selection B wherein
  • J is J-61;
  • R 1 , R andR 8 are all H
  • R 3 is C r C 4 alkyl optionally substituted with halogen, CN, OCH 3 , S(O) p CH 3 ; one R 4 is CH 3 , CF 3 , OCF 3 , OCHF 2 , S(O) p CF 3 , S(O) p CHF 2 , CN or halogen; a second R 4 is H, F, Cl, Br, I or CF 3 ;
  • R 6 is CH 3 , CF 3 or halogen; and p is 0, 1 or 2.
  • Selection H Compounds of Selection G wherein
  • R 3 is C r C 4 alkyl; one R 4 is CH 3 , Cl orBr; a second R 4 is H, F, Cl, Br, I or CF 3 ;
  • R 6 is CF 3 ;
  • R 7 is Cl or Br.
  • Selection I The compounds of Selection A or Selection B wherein J is J-62;
  • R 1 , R 2 and R 8 are all H;
  • R 3 is C r C 4 alkyl optionally substituted with halogen, CN, OCH 3 , S(O) p CH ; one R 4 is CH 3 , CF 3 , OCF 3 , OCHF 2 , S(O) p CF 3 , S(O) p CHF 2 , CN or halogen; a second R 4 is H, F, Cl, Br, I or CF 3 ; R 6 is CH 3 , CF 3 or halogen; and p is 0, 1 or 2.
  • R 3 is C r C 4 alkyl; one R 4 is CH 3 , Cl or Br; a second R 4 is H, F, Cl, Br, I or CF 3 ; R 6 is CF 3 ; and R 7 is Cl or Br.
  • compositions comprising a biologically effective amount of a compound of Formula Id and at least one additional component selected from the group consisting of surfactants, solid diluents and Hquid diluents. Also of note are said compositions further comprising at least one additional biologically active compound or agent. Selected compositions are those comprising the selected compounds above.
  • Also of note is a method for controlling lepidopteran, homopteran and coleopteran insects comprising contacting the insects or their environment with a biologically effective amount of a compound of Formula Id, its N-oxide or an agriculturally suitable salt thereof.
  • Selected methods are those comprising the selected compounds above.
  • the compounds of Formula I can be prepared by one or more of the following methods and variations described in Schemes 1 and 2.
  • the definitions of J, R 1 , R 2 , R 3 , R 4 and n in the compounds of Formulae 1-9 are as defined above in the Summary ofthe Invention.
  • Phthalic acid diamides of formula lb and Ic can be made by the method described in Scheme 1. Heating a phthalic anhydride of formula 2 with an aminoheterocycle of Formula H 2 ⁇ -J in an inert solvent such as glacial acetic acid affords a phthalimide of Formula 3. Ring-opening of phthalimide 3 with an amine ofthe Formula HNR 2 R 3 in an inert solvent such as dioxane or tetrahydrofuran at room temperture or heating at reflux gives a phthalic acid diamide of formula lb. Alkylation of a compound of formula lb with a suitable alkylating agent (e.g.
  • alkyl halide or an alkyl methane- or 4-toluene-sulfonate or acylating agent (e.g. an alkylchloroformate or acid chloride) in the presence of a base such as sodium hydride or H-butyl lithium in an inert solvent such as tefrahydrofuran or
  • N,N-dimethylformamide affords a phthaHc acid diamide of formula Ic wherein R 1 is a substituent other than hydrogen.
  • PhthaHc anhydrides of Formula 2 can be made by methods taught in/. Org. Chem., 1987, 52, 129, J. Am. Chem. Soc, 1929, 51, 1865, and/. Am. Chem. Soc, 1941, 63, 1542.
  • Aminoheterocycles of formula H 2 ⁇ -J can be made by methods as described in Rodd's Chemistry of Organic Compounds: HeterocycHc Compounds, volume IN, parts C, F and IJ (1989), Comprehensive Heterocyclic Chemistry, volumes 2, 3,4,5 and 6 (1984) and Comprehensive Heterocyclic Chemistry II, volumes 3, 4, 5 and 6 (1996).
  • Scheme 1
  • Hthiation of a benzamide of Formula 7 with w-butyl lithium in an inert solvent such as tefrahydrofuran foUowed by reaction with a carbamoyl chloride chloride of Formula 8 provides a phthalic acid diamide of Formula I wherein R 2 is other than hydrogen.
  • Reaction of a benzamide of Formula 7 with n-butyl lithium in an inert solvent such as tefrahydrofuran followed by reaction with an isocyanate of Formula 9 provides a phthalic acid diamide of Formula 1 wherein R 2 is hydrogen.
  • Benzamides of Formulae 4 and 7 are readily made from the corresponding benzoic acids via a benzoyl chloride intermediate or by direct coupling of a benzoic acid and amine in the presence of a suitable acid/amine coupling agent such as 1,3- cHcyclohexylcarbodiimide or 1,1 '-carbonyldiimidazole in an inert solvent such as dichloromethane or N,N-&methylformamide.
  • Benzoic acids are readily converted to the acid chlorides on treatment with thionyl chloride or oxalyl chloride in an inert solvent such as dichloromethane or toluene.
  • the benzoyl chloride is subsequently coupled with an amine of formula H ⁇ R 2 R 3 or H ⁇ R 1 J in an inert solvent such as tefrahydrofuran or dichloromethane.
  • An additional base such as tertiary amines, pyridine or polymer-bound bases may be used to neutralize the hydrochloric acid produced in the reaction.
  • Step C Preparation of 3-iodo-N-(2.2.2-trifluoroethoxy)pyridin-5-yl phmalimide
  • Step D Preparation of 3-Iodo-N - ⁇ -methyletfaylVN -[6-r2.2.2-trifluoroethoxyV3- pyrid yl]-!.2-benzenedicarboxamide and ⁇ -Iodo-N ⁇ -fl-me ylethylVN - ⁇ - (2.2.2-trifluoroethoxy)-3-pyridinyl]- 1.2-benzenedicarboxamide
  • 3-iodo-N-(2,2,2-trifluoroethoxy)pyridin-5-yl phthalimide 0.5 g, 1.1 mmol
  • isopropylamine 1.5 g, 25 mmol
  • Step C Preparation of l-(2-chlorophenylV3-ftrifluoromethylVlH-pyra7:n1-5-arr ⁇ ine
  • thionyl chloride (1.26 mL, 17.2 mmol, 5.0 equivalents)
  • N,N-dimethylformamide 2 drops
  • Step D Preparation of 2- [ 1 -( 2-ChlorophenylV 3 -ftrifluoromethyl)- lH-pyrazol-5-y 1] -4- iodo- lH-isoindole- 1.3(2H)-dione
  • Step E Preparation of N 2 -[ 1 -(2-Chlorophenyl)-3- trifluoromethyl)- lH-pyrazol-5-yl]-
  • the foUowing compounds of Tables 1 to 25 can be prepared.
  • the foUowing abbreviations are used in the Tables: t is tertiary, s is secondary, n is normal, is iso, c is cyclo, Me is methyl, Et is ethyl, Pr is propyl, / ' -Pr is isopropyl, t-Bu is tertiary butyl, Ph is phenyl and C ⁇ is cyano.

Abstract

L'invention concerne des composés de formule (I), leurs N-oxydes et des sels appropriés au domaine agricole, qu'on utilise pour réguler les déprédateurs invertébrés. Dans ladite formule, J est sélectionné à partir du groupe comprenant J-1, J-2, J-3, J-4, J-5, J-6, J-7 et J-8, et R1, R2, R3, R4, R5, R7, R9 et n sont définis tels que dans la divulgation. Cette invention a également trait à des compositions permettant de réguler les déprédateurs invertébrés et contenant une quantité efficace d'un composé de la formule (I) agissant sur le plan biologique, ainsi qu'à des méthodes de régulation de déprédateurs invertébrés consistant à mettre en contact ces déprédateurs ou leur environnement avec une quantité du composé de la formule (I) efficace sur le plan biologique (par ex. une composition susmentionnée).
EP01990065A 2000-12-11 2001-12-05 Arthropodicides de diamide d'acide phthalique heterocycliques substitutes Withdrawn EP1341780A2 (fr)

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UA110598C2 (uk) 2006-11-10 2016-01-25 Басф Се Спосіб одержання кристалічної модифікації фіпронілу
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CN101778561B (zh) 2007-08-16 2013-12-25 巴斯夫欧洲公司 种子处理组合物和方法
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