+

WO2002048137A2 - Arthropodicides de diamide d'acide phthalique heterocycliques substitutes - Google Patents

Arthropodicides de diamide d'acide phthalique heterocycliques substitutes Download PDF

Info

Publication number
WO2002048137A2
WO2002048137A2 PCT/US2001/047572 US0147572W WO0248137A2 WO 2002048137 A2 WO2002048137 A2 WO 2002048137A2 US 0147572 W US0147572 W US 0147572W WO 0248137 A2 WO0248137 A2 WO 0248137A2
Authority
WO
WIPO (PCT)
Prior art keywords
ffl
ffi
ffi ffi
hcj
chf
Prior art date
Application number
PCT/US2001/047572
Other languages
English (en)
Other versions
WO2002048137A3 (fr
Inventor
George Philip Lahm
Thomas Paul Selby
Original Assignee
E. I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Priority to JP2002549668A priority Critical patent/JP2004515547A/ja
Priority to AU2002228938A priority patent/AU2002228938A1/en
Priority to US10/415,566 priority patent/US20040063738A1/en
Priority to EP01990065A priority patent/EP1341780A2/fr
Publication of WO2002048137A2 publication Critical patent/WO2002048137A2/fr
Publication of WO2002048137A3 publication Critical patent/WO2002048137A3/fr

Links

Classifications

    • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pyridine Compounds (AREA)

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).
PCT/US2001/047572 2000-12-11 2001-12-05 Arthropodicides de diamide d'acide phthalique heterocycliques substitutes WO2002048137A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2002549668A JP2004515547A (ja) 2000-12-11 2001-12-05 置換複素環式フタル酸ジアミド殺節足動物剤
AU2002228938A AU2002228938A1 (en) 2000-12-11 2001-12-05 Substituted heterocyclic phthalic acid diamide arthropodicides
US10/415,566 US20040063738A1 (en) 2001-12-05 2001-12-05 Substituted heterocyclic phthalic acid diamide arthropodicides
EP01990065A EP1341780A2 (fr) 2000-12-11 2001-12-05 Arthropodicides de diamide d'acide phthalique heterocycliques substitutes

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US25463600P 2000-12-11 2000-12-11
US60/254,636 2000-12-11
US32401201P 2001-09-21 2001-09-21
US60/324,012 2001-09-21

Publications (2)

Publication Number Publication Date
WO2002048137A2 true WO2002048137A2 (fr) 2002-06-20
WO2002048137A3 WO2002048137A3 (fr) 2003-06-05

Family

ID=26944169

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2001/047572 WO2002048137A2 (fr) 2000-12-11 2001-12-05 Arthropodicides de diamide d'acide phthalique heterocycliques substitutes

Country Status (4)

Country Link
EP (1) EP1341780A2 (fr)
JP (1) JP2004515547A (fr)
AU (1) AU2002228938A1 (fr)
WO (1) WO2002048137A2 (fr)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003011028A1 (fr) * 2001-08-01 2003-02-13 Nissan Chemical Industries, Ltd. Amides substitues et pesticides
WO2006053643A1 (fr) * 2004-11-18 2006-05-26 Bayer Cropscience Ag Diamides d'acide n-heterocyclylphtalique utilises comme insecticide
WO2006040113A3 (fr) * 2004-10-11 2006-09-14 Syngenta Participations Ag Nouveaux insecticides
WO2006055922A3 (fr) * 2004-11-18 2006-12-21 Du Pont Insecticides a base d'anthranilamides
WO2007147888A1 (fr) 2006-06-22 2007-12-27 Basf Se Derives de malononitrile
WO2008055883A1 (fr) 2006-11-10 2008-05-15 Basf Se Modification cristalline de fipronil
WO2008055884A1 (fr) 2006-11-10 2008-05-15 Basf Se Modification cristalline de fipronil
WO2008055881A1 (fr) 2006-11-10 2008-05-15 Basf Se Modification cristalline de fipronil
WO2008055882A1 (fr) 2006-11-10 2008-05-15 Basf Se Modification cristalline de fipronil
WO2008064891A1 (fr) * 2006-12-01 2008-06-05 Syngenta Participations Ag N-cyanoalkylanthranilamides à usage insecticide
EP1944304A1 (fr) * 2001-08-13 2008-07-16 E.I.Du pont de nemours and company Nouveaux 1H-dihydropyrazoles substitués, leur préparation et utilisation
US7622595B2 (en) 2001-08-13 2009-11-24 E.I. Du Pont De Nemours And Company Substituted 1H-dihydropyrazoles, their preparation and use
CN101019548B (zh) * 2007-03-23 2010-05-19 陈美英 驱防虫液的配制及其使用方法
EP2258177A2 (fr) 2006-12-15 2010-12-08 Rohm and Haas Company Mélanges contenant du methylcyclopropène
EP2392662A2 (fr) 2007-04-23 2011-12-07 Basf Se Amélioration de la productivité des plantes en combinant les agents chimiques avec des modifications transgéniques
US8097562B2 (en) 2006-11-30 2012-01-17 Basf Se Agrochemical formulations comprising N-vinylamid co-polymers
EP2500340A1 (fr) 2008-01-25 2012-09-19 Syngenta Participations AG. Dérives de 2-cyanophenyl sulfonamide en tant que pesticides
EP2514316A1 (fr) 2006-09-14 2012-10-24 Basf Se Composition de pesticide
US8916613B2 (en) 2003-12-12 2014-12-23 Bayer Cropscience Ag Synergistic insecticidal mixtures
US9006142B2 (en) 2006-11-30 2015-04-14 Basf Se Agrochemical formulations comprising 1-vinyl-2-pyrrolidinone co-polymers
US9149034B2 (en) 2006-11-30 2015-10-06 Basf Se Agrochemical formulations comprising co-polymers based on diisocyanates
EP3150068A1 (fr) 2007-08-16 2017-04-05 Basf Se Composition et procédé de traitement de semences
EP3199026A1 (fr) 2007-04-12 2017-08-02 Basf Se Mélanges pesticides comprenant des composés de cyanosulfoximine
CN107864983A (zh) * 2017-11-29 2018-04-03 孙铭岐 一种防治水稻病虫害的生物农药
CN108432817A (zh) * 2018-04-22 2018-08-24 陈太师 一种杀螨剂及其制备方法
CN116376504A (zh) * 2023-03-17 2023-07-04 西安工程大学 利用废弃pet瓶制备功能性材料的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9815792B2 (en) * 2014-04-02 2017-11-14 Bayer Cropscience Aktiengesellschaft Method for producing carboxamides

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3305569A1 (de) * 1983-02-18 1984-08-23 Bayer Ag, 5090 Leverkusen Biscarboxamide zur bekaempfung von erkrankungen sowie verfahren zu ihrer herstellung
TW515786B (en) * 1997-11-25 2003-01-01 Nihon Nohyaku Co Ltd Phthalic acid diamide derivatives, agricultural and horticultural insecticides, and a method for application of the insecticides
AR030154A1 (es) * 1999-07-05 2003-08-13 Nihon Nohyaku Co Ltd Derivado de ftalamida, derivado de amina heterociclico util como intermediario para la produccion del mismo, insecticida agrohorticola y metodo para utilizar dicho insecticida
AU768851B2 (en) * 1999-09-24 2004-01-08 Nihon Nohyaku Co., Ltd. Aromatic diamide derivatives or salts thereof, agricultural/horticultural chemicals and method of using the same
EP1241159A4 (fr) * 1999-12-22 2006-03-01 Nihon Nohyaku Co Ltd Derives de diamide aromatique, produits chimiques utilises en agriculture ou en horticulture et utilisations de ces derniers
KR100551925B1 (ko) * 2000-04-28 2006-02-16 니혼노야쿠가부시키가이샤 2-할로벤조산의 제조 방법

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003011028A1 (fr) * 2001-08-01 2003-02-13 Nissan Chemical Industries, Ltd. Amides substitues et pesticides
EP1944304A1 (fr) * 2001-08-13 2008-07-16 E.I.Du pont de nemours and company Nouveaux 1H-dihydropyrazoles substitués, leur préparation et utilisation
US7932395B2 (en) 2001-08-13 2011-04-26 E. I. Du Pont De Nemours And Company Substituted 1H-dihydropyrazoles, their preparation and use
US7622595B2 (en) 2001-08-13 2009-11-24 E.I. Du Pont De Nemours And Company Substituted 1H-dihydropyrazoles, their preparation and use
US8916613B2 (en) 2003-12-12 2014-12-23 Bayer Cropscience Ag Synergistic insecticidal mixtures
WO2006040113A3 (fr) * 2004-10-11 2006-09-14 Syngenta Participations Ag Nouveaux insecticides
US8106075B2 (en) 2004-10-11 2012-01-31 Syngenta Crop Protection, Inc. Insecticides
CN101061110B (zh) * 2004-10-11 2010-09-29 辛根塔参与股份公司 杂环二酰胺杀虫剂
US7884242B2 (en) 2004-11-18 2011-02-08 Bayer Cropscience Ag N-heterocyclylphthaldiamides as insecticides
WO2006053643A1 (fr) * 2004-11-18 2006-05-26 Bayer Cropscience Ag Diamides d'acide n-heterocyclylphtalique utilises comme insecticide
EA012929B1 (ru) * 2004-11-18 2010-02-26 Е.И. Дюпон Де Немур Энд Компани Антраниламидные инсектициды
WO2006055922A3 (fr) * 2004-11-18 2006-12-21 Du Pont Insecticides a base d'anthranilamides
WO2007147888A1 (fr) 2006-06-22 2007-12-27 Basf Se Derives de malononitrile
EP2514316A1 (fr) 2006-09-14 2012-10-24 Basf Se Composition de pesticide
WO2008055884A1 (fr) 2006-11-10 2008-05-15 Basf Se Modification cristalline de fipronil
WO2008055881A1 (fr) 2006-11-10 2008-05-15 Basf Se Modification cristalline de fipronil
WO2008055883A1 (fr) 2006-11-10 2008-05-15 Basf Se Modification cristalline de fipronil
WO2008055882A1 (fr) 2006-11-10 2008-05-15 Basf Se Modification cristalline de fipronil
US9149034B2 (en) 2006-11-30 2015-10-06 Basf Se Agrochemical formulations comprising co-polymers based on diisocyanates
US9006142B2 (en) 2006-11-30 2015-04-14 Basf Se Agrochemical formulations comprising 1-vinyl-2-pyrrolidinone co-polymers
US8097562B2 (en) 2006-11-30 2012-01-17 Basf Se Agrochemical formulations comprising N-vinylamid co-polymers
US8501950B2 (en) 2006-12-01 2013-08-06 Syngenta Crop Protection Llc N-cyanoalkylanthranilamides as insecticides
WO2008064891A1 (fr) * 2006-12-01 2008-06-05 Syngenta Participations Ag N-cyanoalkylanthranilamides à usage insecticide
EP2258177A2 (fr) 2006-12-15 2010-12-08 Rohm and Haas Company Mélanges contenant du methylcyclopropène
CN101019548B (zh) * 2007-03-23 2010-05-19 陈美英 驱防虫液的配制及其使用方法
EP3199026A1 (fr) 2007-04-12 2017-08-02 Basf Se Mélanges pesticides comprenant des composés de cyanosulfoximine
EP2392662A2 (fr) 2007-04-23 2011-12-07 Basf Se Amélioration de la productivité des plantes en combinant les agents chimiques avec des modifications transgéniques
EP3150068A1 (fr) 2007-08-16 2017-04-05 Basf Se Composition et procédé de traitement de semences
EP2500340A1 (fr) 2008-01-25 2012-09-19 Syngenta Participations AG. Dérives de 2-cyanophenyl sulfonamide en tant que pesticides
CN107864983A (zh) * 2017-11-29 2018-04-03 孙铭岐 一种防治水稻病虫害的生物农药
CN108432817A (zh) * 2018-04-22 2018-08-24 陈太师 一种杀螨剂及其制备方法
CN116376504A (zh) * 2023-03-17 2023-07-04 西安工程大学 利用废弃pet瓶制备功能性材料的方法

Also Published As

Publication number Publication date
JP2004515547A (ja) 2004-05-27
AU2002228938A1 (en) 2002-06-24
EP1341780A2 (fr) 2003-09-10
WO2002048137A3 (fr) 2003-06-05

Similar Documents

Publication Publication Date Title
EP1417204B1 (fr) Amides d'aryle ortho-substitue par un heterocycle permettant de lutter contre les depredateurs invertebres
AU2003212811B2 (en) Quinazoline(di) ones for invertebrate pest control
EP1423379B1 (fr) Amides d'aryle a substitution ortho utilises dans le controle des depredateurs invertebres
US7541377B2 (en) Substituted anthranilamides for controlling invertebrate pests
EP1373210B1 (fr) Agents heterocycliques diamide de lutte contre des parasites invertebres
WO2002048137A2 (fr) Arthropodicides de diamide d'acide phthalique heterocycliques substitutes
AU2003212811A1 (en) Quinazoline(di) ones for invertebrate pest control
AU2002331706A1 (en) Ortho-substituted aryl amides for controlling invertebrate pests
WO2003106427A2 (fr) Insecticides de pyrazolecarboxamide
AU2002326748A1 (en) Substituted anthranilamides for controlling invertebrate pests
US20040110777A1 (en) Quinazolinones and pyridinylpyrimidinones for controlling invertebrate pests
AU2002343512A1 (en) Iminobenzoxazines, iminobenzthiazines and iminoquinazolines for controlling invertebrate pests
EP1435785A1 (fr) Iminobenzoxazines, iminobenzthiazines et iminoquinazolines servant a lutter contre les parasites invertebres
US20040259913A1 (en) Diamide invertebrate pest control agents
EP1511385B1 (fr) Amides insecticides comprenant des systemes a noyau bicyclique condenses avec un noyau benzenique et contenant de l'azote
WO2002032856A9 (fr) 1,8-naphthalenedicarboxamides insecticides
US20040063738A1 (en) Substituted heterocyclic phthalic acid diamide arthropodicides
US20040053786A1 (en) Insecticidal 1,8-naphthalenedicarboxamides
AU2003202966A1 (en) Diamide invertebrate pest control agents

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PH PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 10415566

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2001990065

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2002549668

Country of ref document: JP

WWP Wipo information: published in national office

Ref document number: 2001990065

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWW Wipo information: withdrawn in national office

Ref document number: 2001990065

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载