WO1993018038A1 - Arthropodicidal amides - Google Patents

Arthropodicidal amides Download PDF

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Publication number
WO1993018038A1
WO1993018038A1 PCT/US1993/001532 US9301532W WO9318038A1 WO 1993018038 A1 WO1993018038 A1 WO 1993018038A1 US 9301532 W US9301532 W US 9301532W WO 9318038 A1 WO9318038 A1 WO 9318038A1
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Prior art keywords
alkyl
group
optionally substituted
independently selected
haloalkyl
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PCT/US1993/001532
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French (fr)
Inventor
Patrick Doyle Lowder
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E.I. Du Pont De Nemours And Company
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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 EP93906122A priority Critical patent/EP0629201A1/en
Priority to JP5515715A priority patent/JPH07504658A/en
Publication of WO1993018038A1 publication Critical patent/WO1993018038A1/en

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Classifications

    • 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
    • C07D401/12—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 linked by a chain containing hetero atoms as chain links
    • 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
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
    • C07D273/02—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and only one oxygen atom
    • C07D273/04—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems

Definitions

  • EP-A-443, 162 discloses insecticidal pyrazoline cyclohexyl amides but neither describes nor suggests the particular compounds of this invention.
  • This invention pertains to amides of Formula I including all geometric and stereoisomers, suitable salt thereof, useful compositions containing them and use of these compounds to control arthropods in both agronomic and nonagronomic environments.
  • the term "compounds” will be understood to include all such isomers and salts thereof.
  • the compounds are:
  • A is H
  • E is selected from the group H and C 1 -C 3 alkyl; or A and E can be taken together to form -CH 2 -, -CH 2 CH 2 -, -O-, -S-, -S(O)-, -S(O) 2 -, -NR 7 -, -OCH 2 -, -SCH 2 -, -N(R 7 )CH 2 -, substituted -CH 2 -, and substituted -CH 2 CH 2 - the substituents independently selected from 1-2 halogen and 1-2 methyl;
  • M is selected from the group H and C 1 -C 3 alkyl; or E and M can be taken together as -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 2 CH 2 CH 2 CH 2 - each group optionally
  • G is selected from the group
  • G being G-2 or G-3 when Q is Q-1 , A and E are not taken together and R 3 is J;
  • X is selected from the group 0 and S;
  • Y is selected from the group H; C 1 -C 6 alkyl; benzyl;
  • cycloalkylalkyl CHO; C 2 -C 6 alkylcarbonyl; C 2 -C 6 alkoxycarbonyl; C 2 -C 6 haloalkylcarbonyl; C(O)R 33 ; C(O) 2 R 33 ; C 1 -C 6 alkylthio; C 1 -C 6 haloalkylthio; phenylthio; R 11 OC(O)N(R 12 ) S-; R 13 (R 14 )NS-;
  • N CR 9 R 10 ; OR 8 and NR 8 R 9 ;
  • Z is selected from the group CH 2 , O, S and NR 29 ;
  • R 1 and R 2 are independently 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 3 -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, halogen, CN, N 3 , SCN, NO 2 , OR 16 , SR 17 , S(O)R 16 , S(O) 2 R 16 , OC(O)R 16 , OS(O) 2 R 16 , C(O) 2 R 16 ,
  • NR 17 S (O) 2 R 16 phenyl optionally substituted with to 3 substituents independently selected from W, and benzyl optionally substituted with 1 to 3 substituents independently selected from W; or when m or n is 2, (R 1 ) 2 can be taken together, or (R 2 ) 2 can be taken together as -OCH 2 O-, -OCF 2 O-, -OCH 2 CH 2 O-, -CH 2 C(CH 3 ) 2 O-, -CF 2 CF 2 O- or -OCF 2 CF 2 O- to form a cyclic bridge; provided that when R 1 or R 2 is S(O)R 16 , S(O) 2 R 16 , OC(O) R 16 or OS (O) 2 R 16 then R 16 is other than H; and R 1 being other than haloalkyl and haloalkoxy when G is G-l, Q is Q-1, A and E are not taken together and R 3 is
  • R 3 is C 2 -C 6 epoxyalkyl optionally substituted with one or more members independently selected from the group C 1 -C 3 alkyl, CN, C(O)R 23 , C(O) 2 R 23 and phenyl optionally substituted with W; or R 3 is C 1 -C 6 alkyl substituted with one or more members independently selected from the group
  • J is selected from the group saturated, partially
  • heterocyclic ring bonded through carbon or nitrogen, containing 1-4 heteroatoms
  • R 4 and R 5 are independently selected from the group C 2 -C 4 alkyl, C(O)R 19 and C 2 -C 4 alkoxycarbonyl;
  • R 6 is selected from the group H, C 1 -C 4 alkyl, C(O)R 19 and C(O) 2 R 19 ;
  • R 7 is selected from the group H, C 2 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, SR 16 S(O)R 16 , S(O) 2 R 16 , C(O)R 16 , C(O) 2 R 16 , C(O)NR 16 R 20 , C(S)NR 16 R 20 , C(S)R 16 , C(S)OR 16 , -P(O)(OR 16 ) 2 , -P(S)(OR 16 ) 2 , -P(O)(R 16 )OR 16 , -P(O)(R 16 )SR 20 , optionally substituted phenyl, and optionally substituted benzyl wherein the optional phenyl and benzyl substituent (s) are independently selected from F, Cl, Br, CH 3 , CF 3 or OCF 3 ;
  • R 7 is other than C(O)R 16 , C(O)NR 16 R 20 or C(S)NR 16 R 20 then R 16 is other than
  • R 8 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 alkynyl,
  • R 9 is selected from the group H, C 1 -C 4 alkyl and
  • R 10 is selected from the group H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, and phenyl optionally substituted with one or more members independently selected from the group halogen, CN, NO 2 , CF 3 and OCF 3 ; or R 9 and R 10 can be taken together as -CH 2 CH 2 CH 2 -,
  • R 11 is C 1 -C 6 alkyl
  • R 12 is C 1 -C 4 alkyl
  • R 13 and R 14 are independently C 1 -C 4 alkyl; or R 13 and R 14 can be taken together as -CH 2 CH 2 CH 2 CH 2 CH 2 - or -CH 2 CH 2 OCH 2 CH 2 -;
  • R 15 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 3 -C 6 haloalkynyl, C 2 -C 6 alkoxyalkyl,
  • R 15 ) 2 can be taken together as -OCH 2 O-, -OCF 2 O-, -OCH 2 CH 2 O-, -CH 2 C(CH 3 ) 2 O-, -CF 2 CF 2 O- or -OCF 2 CF 2 O- to form a cyclic bridge; provided that when R 15 is S(O)R 16 , S(O) 2 R 16 , OC(O)R 16 or OS (O) 2 R 16 then R 16 is other than H;
  • R 16 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 haloalkenyl, C 2 -C 6 alkynyl, C 3 -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, optionally substituted phenyl, and optionally substituted benzyl wherein the optional phenyl and benzyl substituents are 1 to 3 substituents
  • R 17 is selected from the group H and C 1 -C 4 alkyl; or R 15 and R 17 , when attached to the same atom, can be taken together as -(CH 2 ) 4 -, -(CH 2 ) 5 -, or
  • R 18 is selected from the group H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 2 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl and C 1 -C 4 alkylsulfonyl;
  • R 19 is C 1 -C 3 alkyl
  • R 20 is selected from the group H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl;
  • R 21 is selected from the group H, C 2 -C 7 alkylcarbonyl C 2 -C 7 alkoxycarbonyl, optionally substituted C 1 -C 4 alkyl, optionally substituted C 2 -C 4 alkenyl, and optionally substituted C 2 -C 4 alkynyl, all of thes optional substituents being independently
  • R 22 is selected from the group H, C 1 -C 3 alkyl, phenyl optionally substituted with at least one member independently selected from W, and benzyl
  • R 23 is selected from the group H, C 1 -C 4 alkyl, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl;
  • R 24 is selected from the group H and C 1 -C 2 alkyl
  • R 25 is selected from the group C 1 -C 3 alkyl and phenyl optionally substituted with at least one member independently selected from W;
  • R 26 is C 1 -C 3 alkyl
  • R 27 is C 1 -C 3 alkyl
  • R 28 is selected from the group H, C 1 -C 3 alkyl and
  • phenyl optionally substituted with at least one member independently selected from W;
  • R 29 is selected from the group H, C 1 -C 4 alkyl, C 2 -C 4 alkylcarbonyl and C 2 -C 4 alkoxycarbonyl;
  • R 30 is C 1 -C 3 alkyl;
  • R 31 is selected from the group H, Cl, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 2 alkylthio and CN;
  • R 32 is selected from the group H, C 1 -C 4 alkyl, C 2 -C 3 alkylcarbonyl and C 2 -C 3 alkoxycarbonyl;
  • R 33 is phenyl, optionally substituted with at least one member independently selected from W;
  • R 34 is selected from the group H and C 1 -C 2 alkyl;
  • W 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,
  • n 1 to 3;
  • p 1 to 3;
  • r 0, 1 or 2.
  • Exemplary values of J include:
  • Preferred Compounds A are those wherein:
  • R 1 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 haloalkenyl, C 2 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 2 -C 6 alkoxyalkyl,
  • R 2 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 haloalkenyl, C 2 -C 6 alkynyl, C 3 -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, halogen, CN, SCN, NO 2 , OR 16 , SR 16 , S(O) 2 R 16 , OC(O)R 16 ,
  • R 3 is selected from the group H, C 1 -C 4 alkyl, C 3 -C 4 alkoxycarbonylalkyl, C(O) 2 R 16 , C(O)R 16 , and phenyl optionally substituted by one or more
  • R 15 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 3 -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, halogen, CN, SCN, NO 2 , OR 16 , SR 16 , S(O) 2 R 16 , OC(O)R 16 , OS (O) 2 R 16 , C(O) 2 R 16 , C(O)R 16 , C(O)NR 16 R 17 , S(O) 2 NR 16 R 17 ,
  • R 16 is selected from the group C 1 -C 4 alkyl, C 1 -C 2
  • haloalkyl C 3 -C 4 alkenyl and propargyl
  • R 17 is selected from the group H and CH 3 ;
  • n 1 or 2.
  • Preferred Compounds B are those of Preferred A wherein G is G-1, R 4 is H and R 5 is H. Preferred
  • Compounds C are those of Preferred A wherein G is G-2, R 4 is H and R 5 is H.
  • Preferred Compounds D are those of Preferred B wherein Q is Q-1.
  • Preferred Compounds E are those of Preferred B wherein Q is Q-2. Preferred
  • Compounds F are those of Preferred B wherein Q is Q-5.
  • Preferred Compounds G are those of Preferred C wherein Q is Q-1 .
  • Preferred Compounds H are those of Preferred C wherein Q is Q-2.
  • Preferred Compounds I are those of Preferred C wherein Q is Q-5.
  • 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, isopropyl or the
  • Alkoxy denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy or pentoxy isomers.
  • Alkenyl denotes straight chain or branched alkenes, such as vinyl,
  • Alkynyl denotes straight chain or branched alkynes, such as ethynyl, 1-propynyl, 3-propynyl and the different butynyl,
  • alkylthio denotes methylthio, ethylthio and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylsulfinyl As alkylsulfinyl, “alkylsulfonyl”, “alkylamino”, and the like, are defined analogously to the above examples.
  • Cycloalkyl denotes cyclopropyl, cyclobutyl, cyclopentyl and ⁇ yclohexyl.
  • 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 can be partially or fully
  • haloalkyl examples include CH 2 CH 2 F, CF 2 CF 2 and CH 2 CHFCl.
  • halocycloalkyl haloalkenyl
  • haloalkynyl are defined analogously to the term “haloalkyl”.
  • C i -C j The total number of carbon atoms in a substituent group is indicated by the "C i -C j " prefix where i and j are numbers from 1 to 8.
  • C 1 -C 3 alkylsulfonyl includes methylsulfonyl through propylsulfonyl;
  • C 2 alkoxyalkoxy designates OCH 2 OCH 3 ;
  • C 2 cyanoalkyl designates CH 2 CN and C 3 cyanoalkyl includes CH 2 CH 2 CN and CH(CN)CH 3 ;
  • alkylcarbonyl designates C(O)CH 3 and C 4 alkylcarbonyl includes C(O) CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 ;
  • C 2 alkoxycarbonyl designates C(O)0CH 3 and C 4 alkoxycarbonyl includes
  • C 3 alkoxycarbonylalkyl designates CH 2 CO 2 CH 3 and C 4
  • alkoxycarbonylalkyl includes CH 2 CH 2 CO 2 CH 3 , CH 2 CO 2 CH 2 CH 3 and CH(CH 3 )CO 2 CH 3 .
  • Compounds of Formula I may exist as one or more stereoisomers.
  • the various stereoisomers include
  • the present invention comprises racemic mixtures, individual stereoisomers, and optically active mixtures, as well as agriculturally suitable salts of the compounds of Formula I.
  • acyl derivatives of Formula II can be prepared according to Scheme 2 by reaction of the appropriate amine with acylating agents such as phosgene, carbonyldiimidazole, substituted phenylchloroformates and the like (Helv. Chem. Acta, 1972, 55, 388; Ann. Chem., 1961, 648, 72; and J. Am. Chem. Soc., 1948, 70, 3439).
  • acylating agents such as phosgene, carbonyldiimidazole, substituted phenylchloroformates and the like
  • Typical reactions involve the combination of equimolar amounts of Formula V compounds and Formula IV compounds 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-dimethoxyethane, methylene chloride and chloroform.
  • a base such as an alkali metal, tertiary amine, metal hydride and the like
  • organic solvents including ether, tetrahydrofuran, 1,2-dimethoxyethane, methylene chloride and chloroform.
  • compounds of Formula I can be prepared by the reaction of Formula V compounds with isocyanates of Formula VI.
  • Typical reactions involve the combination of equimolar amounts of V and VI in a conventional organic solvent such as but not limited to ethyl acetate, methylene chloride,
  • Formula VIII compounds are hydrazones whose syntheses are well-known to those skilled in the art.
  • Typical acid catalysts include alkyl or aryl sulfonic acids (such as methyl, camphor or p-toluene) and mineral acids (such as hydrochloric or sulfuric).
  • alkyl or aryl sulfonic acids such as methyl, camphor or p-toluene
  • mineral acids such as hydrochloric or sulfuric.
  • Conventional, polar organic solvents such as acetonitrile,
  • reaction temperature can vary from 0°C to the reflux temperature of the particular solvent being used and the reaction is usually complete in less than 24 hours.
  • Scheme 5 illustrates this transformation.
  • Formula IX compounds can be prepared by the reaction of compounds of Formula XI with semicarbazides of Formula XII.
  • An acid catalyst such as hydrochloric, sulfuric or p-toluene sulfonic acid may be used in this reaction.
  • Reaction temperatures can range from 0 to 150°C with the reflux temperature of the particular solvent generally being preferred.
  • Suitable solvents include, but are not limited to, methanol, ethanol, isopropanol, tetra hydrofuran and dioxane. Scheme 6 illustrates this transformation.
  • ⁇ -Keto sulfides of Formula XI where Z is S can be prepared from ketones of Formula XIII using procedures known in the art (J. Am. Chem. Soc., 1985, 107, 4175;
  • ⁇ -Amino ketones of Formula XI where Z is NR 29 can be prepared from ketones of Formula XIII using procedures known in the art (J. Chem. Soc., 1959, 1479; Synthesis, 1972, 191).
  • indanones indanones, tetralones, chromanones, thiochromanones, benzofuran-3-ones, isochromanones and others.
  • Formula XIII compounds into Formula XI compounds may require the use of protecting groups to prevent unwanted side reactions of functionalities that may be sensitive to the reaction conditions (for example an amino group attached to an indanone may require a protecting group to render it unreactive in an
  • Compounds of Formula VI are treated with an excess of a molar amount of hydrazine or hydrazine hydrate in an anhydrous aprotic solvent at a temperature between -100°C and 100°C.
  • Typical solvents include but are not limited to ether, methylene chloride, chloroform, toluene and tetrahydrofuran.
  • Formula XV compound in the presence of an acid catalyst (with 0.05 to 0.2 molar equivalents preferred).
  • the reaction can be carried out in a variety of polar organic solvents, including, but not limited to, tetrahydrofuran, acetonitrile, methanol or ethanol at a temperature between 0 and 90°C with the preferred temperature being the reflux temperature of the solvent. This reaction is illustrated by Scheme 10.
  • Compounds of Formula XIV where Z is O can be prepared by treatment. of Formula XVI compounds with a carboxylic acid such as formic, acetic or benzoic acid in the presence of 0 to 2.0 equivalents of a base including, but not limited to, potassium carbonate, sodium carbonate or sodium hydroxide. Suitable solvents for the reaction include, but are not limited to, ethanol, tetrahydrofuran or dimethylformamide.
  • the ester formed in the initial reaction is subsequently hydrolyzed to the alcohol XIV (Z is O) using a base such as sodium ethoxide in a solvent such as ethanol.
  • Z is O or S
  • L 2 is H, alkyl or aryl.
  • Formula XIX compounds can be prepared from Formula XXI derivatives by a diazotization/reduction reaction well documented in the literature (see Organic Functional Group Preparation, 1983, 452-453 and references cited therein). Scheme 13 illustrates this transformation.
  • Formula XXI compounds are known in the art or can be obtained by methods analogous to known procedures. Those skilled in the art will recognize Formula XXI compounds to be substituted anilines.
  • reaction of Formula XXIII hydrazines with esters of the Formula XXIV can be conducted in the presence or the absence of an acid or base in an
  • unreactive solvent such as methanol, ethanol, methylene chloride, chloroform, tetrahydrofuran and dioxane, but not limited to these.
  • the temperature of the reaction can be varied from 0°C to the reflux temperature of the particular solvent.
  • the reaction is usually complete in 24 h. Scheme 15 illustrates this transformation.
  • Compounds of the Formula XXIII can be prepared by the reaction of Formula XXV derivatives with a reagent such as O-(2,4-dinitrophenyl)hydroxylamine (XXVI) in the presence of a base such as sodium carbonate, sodium bicarbonate or potassium carbonate in a nonreactive solvent such as, but not limited to, dimethylformamide, dimethylsulfoxide, tetrahydrofuran and dioxane.
  • a base such as sodium carbonate, sodium bicarbonate or potassium carbonate
  • a nonreactive solvent such as, but not limited to, dimethylformamide, dimethylsulfoxide, tetrahydrofuran and dioxane.
  • the reaction temperature can vary from 0 to 100°C with 25°C being preferred.
  • the reaction is usually complete in 24 hours. This procedure is analogous to that described in J. Med. Chem., 1984, 27, 1103. Scheme 16 illustrates these transformations.
  • Compounds of the Formula XXV can be prepared by a two-step procedure whereby Formula XXVII compounds are reacted with appropriately substituted amines of Formula XXVIII in the presence of a base such as sodium or potassium carbonate in a solvent such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran and the like.
  • a base such as sodium or potassium carbonate
  • a solvent such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran and the like.
  • the temperature of the reaction can vary from about 25 to 150°C and the reaction is usually complete in 48 h.
  • the amine can be protected and the ortho-nitro substituent can be removed by
  • Amines of Formula XXX are known to those skilled in the art as piperidines and tetrahydropyridines. The syntheses of these derivatives are found throughout the literature (see Fieser and Fieser, Reagents for Organic Synthesis, vol. 1, 1967, 981; Liebigs Ann . Chem . , 1972 , 1M, 21-27 ) .
  • Formula I compounds, where Y is other than H, can be prepared by standard alkylation, acylation or
  • protecting groups to prevent unwanted side reactions or use reagents that do not affect functional groups other than those desired to be changed.
  • One skilled in the art will be able to select appropriate protecting groups and reagents to this end.
  • Step A methyl 2,3-dihydro-2-(1H-imidazo-1-ylcarbonyl )7-(trifluoromethyl)-[1]-benzopyrano[4,3-c]pyrazole- 3a(4H)-carboxylate
  • Lithium aluminum hydride (4.0 g, 0.105 mol) was suspended in diethylether (150 mL).
  • i-Pr -CH(CH 3 ) 2 ;
  • each line of Tables 1-3 defines four separate compounds.
  • Table 1, line 1, column 1 describes a compound wherein Y is H, column 2 describes one compound where Y is Me, column 3 describes one compound where Y is COOMe and column 4 describes one compound where Y is COMe.
  • each line of each page of Tables 1-3 describes four separate compounds.
  • Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent or an organic solvent.
  • Use formulations include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry
  • 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.
  • surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc.
  • 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 be agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations,.
  • Suspensions are prepared by wet-milling; see, for example, U.S.
  • Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning,
  • Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can also be prepared as taught in DE 3,246,493.
  • Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%
  • Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%
  • the compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding seed-feeding, aquatic and soil-inhabiting arthropods (term 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 pests.
  • all of the compounds of this invention display activity against pests that include: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs,
  • Thysanoptera Orthoptera and Dermaptera
  • eggs immatures and adults of the Order Diptera
  • eggs junveniles and adults of the Phylum Nemata.
  • the compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Phthiraptera, Siphonoptera,
  • Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, 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.
  • other agricultural protectants with which compounds of this invention can be formulated are: insecticides such as monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl,
  • chlorpyrifos dimethoate, fipronil, flufenprox, fonophos, isofenphos, methidathion, methamidophos, phosmet,
  • fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanil, fenpropidine, fenpropimorph,
  • nematocides such as aldoxycarb, fenamiphos and
  • 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 Bacillus thuringiensis,
  • arthropodicides having a similiar spectrum of control but a different mode of action will be particularly
  • Arthropod pests are controlled and protection of agronomic 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.
  • 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, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, and many others.
  • the compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like.
  • the compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with
  • suitable carriers diluents, and surfactants and possibly in combination with a food depending on the contemplated end use.
  • a preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, 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.
  • Test units each consisting of an 8-ounce (230 mL) plastic cup containing a layer of wheat germ diet, approximately 0.5 cm thick, were prepared. Ten third-instar larvae of fall armyworm (Spodoptera frugiperda) were placed into a cup. Solutions of each of the test compounds (acetone/distilled water 75/25 solvent) were sprayed into the cups, a single solution per set of three cups. Spraying was accomplished by passing the cups, on a conveyer belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.5 pounds of active ingredient per acre (about 0.55 kg/ha) at
  • Test A The test procedure of Test A was repeated for
  • Test units each consisting of an 8-ounce (230 mL) plastic cup containing 1 sprouted corn seed, were
  • Test units were prepared from a series of 12-ounce (350 mL) cups, each containing oat (Avena sativa)
  • test units were sprayed as described in Test A with individual solutions of the below-listed compounds.
  • Aft the oats had dried from the spraying, between 10 and 15 adult aster leafhoppers (Mascrosteles fascifrons) were aspirated into each of the covered cups.
  • the cups were held at 27°C and 50% relative humidity for 48 hours, aft which time mortality readings were taken.

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Abstract

Insecticidal compounds of the formula (I) wherein G, X, Y and Q are as defined in the text, agricultural compositions containing them and a method for using the compounds to control arthropods in agronomic and nonagronomic environments.

Description

TITLE
ARTHROPODICIDAL AMIDES EP-A-443, 162 discloses insecticidal pyrazoline cyclohexyl amides but neither describes nor suggests the particular compounds of this invention.
SUMMARY OF THE INVENTION
This invention pertains to amides of Formula I including all geometric and stereoisomers, suitable salt thereof, useful compositions containing them and use of these compounds to control arthropods in both agronomic and nonagronomic environments. The term "compounds" will be understood to include all such isomers and salts thereof. The compounds are:
Figure imgf000003_0003
wherein:
Q is selected from the group
Figure imgf000003_0001
Figure imgf000003_0002
Figure imgf000004_0001
A is H;
E is selected from the group H and C1-C3 alkyl; or A and E can be taken together to form -CH2-, -CH2CH2-, -O-, -S-, -S(O)-, -S(O)2-, -NR7-, -OCH2-, -SCH2-, -N(R7)CH2-, substituted -CH2-, and substituted -CH2CH2- the substituents independently selected from 1-2 halogen and 1-2 methyl;
M is selected from the group H and C1-C3 alkyl; or E and M can be taken together as -CH2CH2-, -CH2CH2CH2- or -CH2CH2CH2CH2- each group optionally
substituted with one or more members
independently selected from the group halogen, NO2, CN, C1-C3 alkyl, C1-C3 haloalkyl, OH, OR6 and CO2R19;
G is selected from the group
Figure imgf000004_0002
G being G-2 or G-3 when Q is Q-1 , A and E are not taken together and R3 is J;
X is selected from the group 0 and S;
Y is selected from the group H; C1-C6 alkyl; benzyl;
C2-C6 alkenyl; C2-C6 alkynyl; C1-C6 alkyl
substituted by halogen, C1-C3 alkoxy, C1-C3 haloalkoxy, CN, NO2, S(O)rR30, C(O)R30, C(O)2R30, and phenyl optionally substituted by halogen, CN C1-C2 haloalkyl and C1-C2 haloalkoxy; C3-C6 cycloalkyl; C3-C6 halocycloalkyl; C4-C6
cycloalkylalkyl; CHO; C2-C6 alkylcarbonyl; C2-C6 alkoxycarbonyl; C2-C6 haloalkylcarbonyl; C(O)R33; C(O)2R33; C1-C6 alkylthio; C1-C6 haloalkylthio; phenylthio; R11OC(O)N(R12) S-; R13(R14)NS-;
N=CR9R10; OR8 and NR8R9;
Z is selected from the group CH2, O, S and NR29;
R1 and R2 are independently selected from the group C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, halogen, CN, N3, SCN, NO2, OR16, SR17, S(O)R16, S(O)2R16, OC(O)R16, OS(O)2R16, C(O)2R16, C(O)R16, C(O)NR16R17, S (O) 2NR16R17, NR16R17,
NR17C(O)R16, OC(O)NHR16, NR17C (O) NHR16,
NR17S (O)2R16, phenyl optionally substituted with to 3 substituents independently selected from W, and benzyl optionally substituted with 1 to 3 substituents independently selected from W; or when m or n is 2, (R1)2 can be taken together, or (R2)2 can be taken together as -OCH2O-, -OCF2O-, -OCH2CH2O-, -CH2C(CH3)2O-, -CF2CF2O- or -OCF2CF2O- to form a cyclic bridge; provided that when R1 or R2 is S(O)R16, S(O)2R16, OC(O) R16 or OS (O) 2R16 then R16 is other than H; and R1 being other than haloalkyl and haloalkoxy when G is G-l, Q is Q-1, A and E are not taken together and R3 is
optionally substituted phenyl, optionally
substituted alkyl, or C(O)2(C1-C6 alkyl);
R3 is selected from the group H, J, N3, NO2, halogen, N(R21)R22, C(R31)=N-O-R32, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 alkoxyalkyl, C3-C8 alkoxycarbonylalkyl, C(O)R16, C(O)2R16, OR18, C(O)NR16R17,
C(S)NR16R17, C(S)R16, C(S)SR16, CN, Si(R26)(R27)R25, SR25, S(O)R25, S(O)2R25, -P(O)(OR25)2, phenyl optionally substituted with (R15)p, and benzyl optionally substituted with 1 to 3 substituents independently selected from W; or R3 is C2-C6 epoxyalkyl optionally substituted with one or more members independently selected from the group C1-C3 alkyl, CN, C(O)R23, C(O)2R23 and phenyl optionally substituted with W; or R3 is C1-C6 alkyl substituted with one or more members independently selected from the group
C(O)N(R24)R34, C(O)R24, SR25, S(O)R25, S(O)2R25, SCN, CN, C1-C2 haloalkoxy. Si (R26) (R27)R28,
N(R21)R22, NO2, OC(O)R24, -P(O)(OR25)2 and J;
J is selected from the group saturated, partially
unsaturated or aromatic 5- or 6-membered
heterocyclic ring, bonded through carbon or nitrogen, containing 1-4 heteroatoms
independently selected from the group consisting of 0-2 oxygen, 0-2 sulfur and 0-4 nitrogen, this substituent optionally containing one carbonyl and optionally substituted with one or more members independently selected from W; R4 and R5 are independently selected from the group C2-C4 alkyl, C(O)R19 and C2-C4 alkoxycarbonyl;
R6 is selected from the group H, C1-C4 alkyl, C(O)R19 and C(O)2R19;
R7 is selected from the group H, C2-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, SR16 S(O)R16, S(O)2R16, C(O)R16, C(O)2R16, C(O)NR16R20, C(S)NR16R20, C(S)R16, C(S)OR16, -P(O)(OR16)2, -P(S)(OR16)2, -P(O)(R16)OR16, -P(O)(R16)SR20, optionally substituted phenyl, and optionally substituted benzyl wherein the optional phenyl and benzyl substituent (s) are independently selected from F, Cl, Br, CH3, CF3 or OCF3;
provided that when R7 is other than C(O)R16, C(O)NR16R20 or C(S)NR16R20 then R16 is other than
H;
R8 is selected from the group H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl,
SO2NR17R18, S(O)2R16, C(O)R16, C(O)NR16R20,
C(O)2R16, phenyl optionally substituted with halogen or C1-C4 alkoxy, and benzyl optionally substituted with halogen; provided that when R8 S(O)2R16, R16 is other than H;
R9 is selected from the group H, C1-C4 alkyl and
C(O)R16;
R10 is selected from the group H, C1-C4 alkyl, C1-C4 haloalkyl, and phenyl optionally substituted with one or more members independently selected from the group halogen, CN, NO2, CF3 and OCF3; or R9 and R10 can be taken together as -CH2CH2CH2-,
-CH2CH2CH2CH2- or -CH2CH2CH2CH2CH2-;
R11 is C1-C6 alkyl;
R12 is C1-C4 alkyl;
R13 and R14 are independently C1-C4 alkyl; or R13 and R14 can be taken together as -CH2CH2CH2CH2CH2- or -CH2CH2OCH2CH2-;
R15 is selected from the group C1-C6 alkyl, C1-C6
haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-C6 haloalkynyl, C2-C6 alkoxyalkyl,
C2-C6 alkylthioalkyl , C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxy carbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, halogen, CN, N3, SCN, N02, OR16, SR16, S (O) R16, S (O) 2R16, OC (O) R16, OS (O) 2R16, C (O) 2R16, C (O) R16, C (O) NR16R17,
S(O)2NR16R17, NR16R17, NR17C(O)R16, OC(O)NHR16, NR17C(O)NHR16, NR17S(O)2R16, phenyl optionally substituted with 1 to 3 substituents
independently selected from W, and benzyl
optionally substituted with 1 to 3 substituents independently selected from W; or when p is 2, (R15)2 can be taken together as -OCH2O-, -OCF2O-, -OCH2CH2O-, -CH2C(CH3)2O-, -CF2CF2O- or -OCF2CF2O- to form a cyclic bridge; provided that when R15 is S(O)R16, S(O)2R16, OC(O)R16 or OS (O) 2R16 then R16 is other than H;
R16 is selected from the group H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, optionally substituted phenyl, and optionally substituted benzyl wherein the optional phenyl and benzyl substituents are 1 to 3 substituents
independently selected from W;
R17 is selected from the group H and C1-C4 alkyl; or R15 and R17, when attached to the same atom, can be taken together as -(CH2)4-, -(CH2)5-, or
-CH2CH2OCH2CH2-;
R18 is selected from the group H, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C2-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl and C1-C4 alkylsulfonyl;
R19 is C1-C3 alkyl;
R20 is selected from the group H, C1-C4 alkyl, C2-C4 alkenyl and C2-C4 alkynyl;
R21 is selected from the group H, C2-C7 alkylcarbonyl C2-C7 alkoxycarbonyl, optionally substituted C1-C4 alkyl, optionally substituted C2-C4 alkenyl, and optionally substituted C2-C4 alkynyl, all of thes optional substituents being independently
selected from C1-C2 alkoxy, CN, C(O)R28 and
C(O)2R25;
R22 is selected from the group H, C1-C3 alkyl, phenyl optionally substituted with at least one member independently selected from W, and benzyl
optionally substituted with at least one member independently selected from W;
R23 is selected from the group H, C1-C4 alkyl, C2-C4 alkenyl and C2-C4 alkynyl;
R24 is selected from the group H and C1-C2 alkyl;
R25 is selected from the group C1-C3 alkyl and phenyl optionally substituted with at least one member independently selected from W;
R26 is C1-C3 alkyl;
R27 is C1-C3 alkyl;
R28 is selected from the group H, C1-C3 alkyl and
phenyl optionally substituted with at least one member independently selected from W;
R29 is selected from the group H, C1-C4 alkyl, C2-C4 alkylcarbonyl and C2-C4 alkoxycarbonyl; R30 is C1-C3 alkyl;
R31 is selected from the group H, Cl, C1-C4 alkyl, C1-C4 alkoxy, C1-C2 alkylthio and CN;
R32 is selected from the group H, C1-C4 alkyl, C2-C3 alkylcarbonyl and C2-C3 alkoxycarbonyl;
R33 is phenyl, optionally substituted with at least one member independently selected from W;
R34 is selected from the group H and C1-C2 alkyl; W 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; m is 1 to 3;
n is 1 to 3;
p is 1 to 3; and
r is 0, 1 or 2.
Exemplary values of J include:
Figure imgf000010_0001
Figure imgf000011_0001
Preferred for reasons including ease of synthesis and/or greater arthropodicidal efficacy are the followin compounds.
Preferred Compounds A are those wherein:
R1 is selected from the group H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-C6 haloalkynyl, C2-C6 alkoxyalkyl,
C2-C6 alkylthioalkyl, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-Cg halocycloalkyl, halogen, CN, SCN, NO2, OR16, SR16, S(O)2R16, C(O)2R16, C(O)R16, phenyl optionally substituted with 1 to 3
substituents independently selected from W, and benzyl optionally substituted with 1 to 3
substituents independently selected from W; with one R1 substituent in the 4-position, or when m is 2 then (R1) 2 can be taken together as
-CH2C(CH3)2O-, -OCH2CH2O-, -OCF2CF2O-, or
-CF2CF2O- to form a 5- or 6-membered fused ring; R2 is selected from the group H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, halogen, CN, SCN, NO2, OR16, SR16, S(O)2R16, OC(O)R16,
OS(O)2R16, C(O)2R16, C(O)R16, C(O)NR16R17,
S(O)2NR16R17, NR16R17, phenyl optionally
substituted with 1 to 3 substituents
independently selected from W, and benzyl
optionally substituted with 1 to 3 substituents independently selected from W;
R3 is selected from the group H, C1-C4 alkyl, C3-C4 alkoxycarbonylalkyl, C(O)2R16, C(O)R16, and phenyl optionally substituted by one or more
substituents independently selected from (R15)p;
R15 is selected from the group C1-C6 alkyl, C1-C6
haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, halogen, CN, SCN, NO2, OR16, SR16, S(O)2R16, OC(O)R16, OS (O) 2R16, C(O)2R16, C(O)R16, C(O)NR16R17, S(O)2NR16R17,
NR16R17, phenyl optionally substituted with 1 to 3 substituents independently selected from W, and benzyl optionally substituted with 1 to 3 substituents independently selected from W;
R16 is selected from the group C1-C4 alkyl, C1-C2
haloalkyl, C3-C4 alkenyl and propargyl;
R17 is selected from the group H and CH3; and
m is 1 or 2.
Preferred Compounds B are those of Preferred A wherein G is G-1, R4 is H and R5 is H. Preferred
Compounds C are those of Preferred A wherein G is G-2, R4 is H and R5 is H. Preferred Compounds D are those of Preferred B wherein Q is Q-1. Preferred Compounds E are those of Preferred B wherein Q is Q-2. Preferred
Compounds F are those of Preferred B wherein Q is Q-5. Preferred Compounds G are those of Preferred C wherein Q is Q-1 . Preferred Compounds H are those of Preferred C wherein Q is Q-2. Preferred Compounds I are those of Preferred C wherein Q is Q-5.
Specifically preferred are the compounds of Preferred C which are:
(J) methyl 2,3-dihydro-7-(trifluoromethyl)-2-[[4- (trifluoromethyl)-1-piperidinylamino]carbonyl][1]benzopyrano[4,3-c]-pyrazole-3a(4H)- carboxylate;
(K) 3,4-bis(4-chlorophenyl)-4,5-dihydro-N-[4- (trifluoromethyl)-1-piperidinyl]-1H-pyrazole-1- carboxamide;
(L) methyl 7-chloro-2,5-dihydro-2-[[[4-(trifluoromethyl)-1-piperidinyl]amino]carbonyl]-indeno[1,2- e][1,3,4]oxadiazine-4a(3H)-carboxylate; and
(M) 2-(5-fluoro-2,3-dihydro-2-methyl-1H-inden-1- ylidene)-N-[4-(trifluoromethyl)-1-piperidinyl]hydrazinecarboxamide. In the above definitions, 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, isopropyl or the
different butyl, pentyl, hexyl isomers . "Alkoxy" denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy or pentoxy isomers. "Alkenyl" denotes straight chain or branched alkenes, such as vinyl,
1-propenyl, 2-propenyl, 3-propenyl and the different butenyl, pentenyl and hexenyl isomers. "Alkynyl" denotes straight chain or branched alkynes, such as ethynyl, 1-propynyl, 3-propynyl and the different butynyl,
pentynyl and hexynyl isomers. "Alkylthio" denotes methylthio, ethylthio and the different propylthio, butylthio, pentylthio and hexylthio isomers.
"Alkylsulfinyl", "alkylsulfonyl", "alkylamino", and the like, are defined analogously to the above examples.
"Cycloalkyl" denotes cyclopropyl, cyclobutyl, cyclopentyl and σyclohexyl.
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 can be partially or fully
substituted with halogen atoms, which can be the same or different. Examples of haloalkyl include CH2CH2F, CF2CF2 and CH2CHFCl. The terms "halocycloalkyl", "haloalkenyl" and "haloalkynyl" are defined analogously to the term "haloalkyl".
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 8. For example, C1-C3 alkylsulfonyl includes methylsulfonyl through propylsulfonyl; C2 alkoxyalkoxy designates OCH2OCH3; C4 alkoxyalkoxy
designates the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms, examples including OCH2OCH2CH2CH3 and OCH2CH2OCH2CH3; C2 cyanoalkyl designates CH2CN and C3 cyanoalkyl includes CH2CH2CN and CH(CN)CH3; C2
alkylcarbonyl designates C(O)CH3 and C4 alkylcarbonyl includes C(O) CH2CH2CH3 and C(O)CH(CH3)2; C2 alkoxycarbonyl designates C(O)0CH3 and C4 alkoxycarbonyl includes
C(O)OCH2CH2CH3 and C(O)OCH(CH3)2; and as a final example, C3 alkoxycarbonylalkyl designates CH2CO2CH3 and C4
alkoxycarbonylalkyl includes CH2CH2CO2CH3, CH2CO2CH2CH3 and CH(CH3)CO2CH3.
Compounds of Formula I may 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 the more active. One skilled in the art knows how to separate said enantiomers, diastereomers and geometric isomers. Accordingly, the present invention comprises racemic mixtures, individual stereoisomers, and optically active mixtures, as well as agriculturally suitable salts of the compounds of Formula I.
DETAILS OF THE INVENTION
Compounds of Formula I are prepared according to Schemes 1 through 18 with substituents as previously defined, unless otherwise noted.
Compounds of Formula I are prepared by the reaction of acyl derivatives of Formula II (Q-1, Q-2, Q-3, Q-4, Q-5 (Z=CH2) and Q-6) with compounds of Formula III as illustrated in Scheme 1. Typical reactions involve the combination of equimolar amounts of II and III 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-dimethoxyethane, methylene chloride, chloroform, N,N-dimethyl formamide and dimethylsulfoxide. The reaction can be conducted at temperatures in the range of -100°C to 100°C.
SCHEME 1
Figure imgf000016_0001
The acyl derivatives of Formula II (Q-1, Q-2 and Q-5 (Z=CH2) ) can be prepared according to Scheme 2 by reaction of the appropriate amine with acylating agents such as phosgene, carbonyldiimidazole, substituted phenylchloroformates and the like (Helv. Chem. Acta, 1972, 55, 388; Ann. Chem., 1961, 648, 72; and J. Am. Chem. Soc., 1948, 70, 3439). Typical reactions involve the combination of equimolar amounts of Formula V compounds and Formula IV compounds 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-dimethoxyethane, methylene chloride and chloroform. The reaction can be conducted at temperatures in the range of -100°C to 100°C. SCHEME 2
Figure imgf000017_0002
Alternatively, compounds of Formula I (Q-1, Q-2, Q-5 (Z=CH2)) can be prepared by the reaction of Formula V compounds with isocyanates of Formula VI. Typical reactions involve the combination of equimolar amounts of V and VI in a conventional organic solvent such as but not limited to ethyl acetate, methylene chloride,
chloroform, benzene or toluene. A base such as an alkali metal, tertiary amine, alkali metal alkoxide or metal hydride can be used. Scheme 3 illustrates this
transformation.
SCHEME 3
Figure imgf000017_0001
The synthesis of compounds of Formula VI is well known to those skilled in the art. Reaction of compound of Formula III (Y=H) with compounds of Formula IV as illustrated in Scheme 4 readily provides compounds of Formula VI (Fieser & Fieser, Reagents for Organic
Synthesis. Vol. 1, 1967). SCHEME 4
Figure imgf000018_0001
Syntheses of Formula V (Q-1) compounds are described in U.S. 4,070,365 and WO 88/01004. In those documents, amines of Formula V are reacted with phenyl isocyanates to afford the desired amides. The syntheses of compounds of Formula VII (Q-2, Z=CH2) and Formula VIII (Q-5) are described in WO 91/17983 and WO 90/07495, respectively.
Figure imgf000018_0002
Formula VII (Z=CH2) compounds are formed by reduction of pyridazinones (R4=R5=O). Formula VIII compounds are hydrazones whose syntheses are well-known to those skilled in the art.
Compounds of Formula II (Q-3) are prepared according to methods described in WO 88/05046. These materials are formed by 1,3-dipolar cycloadditions of a nitrile ylides; a reaction well-known to those skilled in the art.
Compounds of Formula I (Q-2, Z = O, S and NR29) can be prepared by the reaction of semicarbazones of Formula IX with compounds of Formula X. Typical reactions involve the combination of an excess in molar amounts of a Formula X compound (1 . 1 molar equivalents to 40 molar equivalents) with 1 equivalent of a Formula IX compound in the presence of less than one molar equivalent of an acid catalyst (0 equivalents to 0.9 equivalents).
Typical acid catalysts include alkyl or aryl sulfonic acids (such as methyl, camphor or p-toluene) and mineral acids (such as hydrochloric or sulfuric). Conventional, polar organic solvents such as acetonitrile,
dimethylformamide, tetrahydrofuran, methanol or ethanol can be used. The reaction temperature can vary from 0°C to the reflux temperature of the particular solvent being used and the reaction is usually complete in less than 24 hours. Scheme 5 illustrates this transformation.
SCHEME 5
Figure imgf000019_0001
Formula IX compounds can be prepared by the reaction of compounds of Formula XI with semicarbazides of Formula XII. An acid catalyst such as hydrochloric, sulfuric or p-toluene sulfonic acid may be used in this reaction. Reaction temperatures can range from 0 to 150°C with the reflux temperature of the particular solvent generally being preferred. Suitable solvents include, but are not limited to, methanol, ethanol, isopropanol, tetra hydrofuran and dioxane. Scheme 6 illustrates this transformation.
SCHEME 6
Figure imgf000020_0001
Compounds of Formula XI where Z is O ccn be prepared by the α-hydroxylation of ketones of Formula XIII using procedures that are well-known to one skilled in the art (see J. Am. Chem. Soc., 1974, 96, 5944; Tetrahedron
Lett., 1988, 29, 2835; and J. Org. Chem., 1986, 51, 2402). Scheme 7 illustrates this transformation.
SCHEME 7
Figure imgf000020_0002
Numerous alternative procedures exist for the
preparation of α-hydroxyketones of Formula XI. Such procedures are well-known to one skilled in the art
(March, Advanced Organic Chemistry, 3rd Edition, 1985,
1164). Compounds of Formula XI where Z is 0, R3 is aryl and E is H are benzoins whose preparations are well-known to one skilled in the art.
α-Keto sulfides of Formula XI where Z is S can be prepared from ketones of Formula XIII using procedures known in the art (J. Am. Chem. Soc., 1985, 107, 4175;
J. Org. Chem., 1988, 53, 3125).
α-Amino ketones of Formula XI where Z is NR29 can be prepared from ketones of Formula XIII using procedures known in the art (J. Chem. Soc., 1959, 1479; Synthesis, 1972, 191).
The starting ketones of Formula XIII are known in the art or can be obtained by methods analogous to known procedures. Those skilled in the art will recognize the Formula XIII compounds to include deoxybenzoins,
indanones, tetralones, chromanones, thiochromanones, benzofuran-3-ones, isochromanones and others.
One skilled in the art will recognize that the transformation of Formula XIII compounds into Formula XI compounds may require the use of protecting groups to prevent unwanted side reactions of functionalities that may be sensitive to the reaction conditions (for example an amino group attached to an indanone may require a protecting group to render it unreactive in an
α-hydroxylation of the carbonyl group).
Semicarbazides of Formula XII where X is O or S can be prepared by using the procedure shown in Scheme 8.
Compounds of Formula VI are treated with an excess of a molar amount of hydrazine or hydrazine hydrate in an anhydrous aprotic solvent at a temperature between -100°C and 100°C. Typical solvents include but are not limited to ether, methylene chloride, chloroform, toluene and tetrahydrofuran. SCHEME 8
Figure imgf000022_0002
Compounds of the Formula II (Q-4, Z = O, S and NR29) can be prepared from compounds of the Formula XIII through conventional methodology generally used for the conversion of esters to their corresponding acid
chlorides as illustrated in Scheme 9.
SCHEME 9
Figure imgf000022_0001
The preparation of compounds of Formula XIII, where Q is Q-4 and Z is CH2, is disclosed in WO 91/17983.
Formula XIII derivatives (where A is equal to H, Z = O, S, or NR29) can be prepared by the reaction of Formula XIV compounds with an equimolar or greater amount of a
Formula XV compound in the presence of an acid catalyst (with 0.05 to 0.2 molar equivalents preferred). The reaction can be carried out in a variety of polar organic solvents, including, but not limited to, tetrahydrofuran, acetonitrile, methanol or ethanol at a temperature between 0 and 90°C with the preferred temperature being the reflux temperature of the solvent. This reaction is illustrated by Scheme 10.
SCHEME 10
Figure imgf000023_0001
Compounds of Formula XIV where Z is O can be prepared by treatment. of Formula XVI compounds with a carboxylic acid such as formic, acetic or benzoic acid in the presence of 0 to 2.0 equivalents of a base including, but not limited to, potassium carbonate, sodium carbonate or sodium hydroxide. Suitable solvents for the reaction include, but are not limited to, ethanol, tetrahydrofuran or dimethylformamide. The ester formed in the initial reaction is subsequently hydrolyzed to the alcohol XIV (Z is O) using a base such as sodium ethoxide in a solvent such as ethanol. Thiols of the Formula XIV
(where Z is S) can be prepared using analogous procedures starting with a thiocarboxylic acid (such as thiolacetic acid). The preparation of Formula XIV compounds (Z is O or S) is illustrated by Scheme 11.
SCHEME 11
Figure imgf000024_0001
wherein
Z is O or S; and
L2 is H, alkyl or aryl.
Compounds of Formula XIV where Z is NR29 can be prepared using procedures analogous to those shown in Scheme 11 using either ammonia or a primary amine (R29NH2) in place of the carboxylic or thiocarboxylic acid.
Compounds of Formula XVI can be prepared from
compounds of the Formula XIX by the reaction with an equimolar amount of compounds of Formula XX in
conventional organic solvents such as, but not limited to, ether, tetrahydrofuran, methanol, ethanol, methylene chloride, benzene and toluene. Typical reaction
temperatures can range from room temperature to the reflux temperature of the particular solvent utilized and the reaction is usually complete in 24 hours. Scheme 12 illustrates this reaction.
SCHEME 12
Figure imgf000025_0002
Formula XIX compounds can be prepared from Formula XXI derivatives by a diazotization/reduction reaction well documented in the literature (see Organic Functional Group Preparation, 1983, 452-453 and references cited therein). Scheme 13 illustrates this transformation.
SCHEME 13
Figure imgf000025_0001
Formula XXI compounds are known in the art or can be obtained by methods analogous to known procedures. Those skilled in the art will recognize Formula XXI compounds to be substituted anilines.
Compounds of the Formula I where Q is Q-6 and A is H can be prepared in a conventional three-step process whereby Formula XXII esters are saponified, converted to the acid chloride and reacted with an appropriately substituted amine. Scheme 14 illustrates this method. SCHEME 14
Figure imgf000026_0001
Formula XXII compounds can be prepared by the
reaction of Formula XXIII hydrazines with esters of the Formula XXIV. The reaction can be conducted in the presence or the absence of an acid or base in an
unreactive solvent such as methanol, ethanol, methylene chloride, chloroform, tetrahydrofuran and dioxane, but not limited to these. The temperature of the reaction can be varied from 0°C to the reflux temperature of the particular solvent. The reaction is usually complete in 24 h. Scheme 15 illustrates this transformation.
SCHEME 15
Figure imgf000026_0002
Compounds of the Formula XXIII can be prepared by the reaction of Formula XXV derivatives with a reagent such as O-(2,4-dinitrophenyl)hydroxylamine (XXVI) in the presence of a base such as sodium carbonate, sodium bicarbonate or potassium carbonate in a nonreactive solvent such as, but not limited to, dimethylformamide, dimethylsulfoxide, tetrahydrofuran and dioxane. The reaction temperature can vary from 0 to 100°C with 25°C being preferred. The reaction is usually complete in 24 hours. This procedure is analogous to that described in J. Med. Chem., 1984, 27, 1103. Scheme 16 illustrates these transformations.
SCHEME 16
Figure imgf000027_0001
Compounds of the Formula XXV can be prepared by a two-step procedure whereby Formula XXVII compounds are reacted with appropriately substituted amines of Formula XXVIII in the presence of a base such as sodium or potassium carbonate in a solvent such as dimethylformamide, dimethylsulfoxide, tetrahydrofuran and the like. The temperature of the reaction can vary from about 25 to 150°C and the reaction is usually complete in 48 h. In the subsequent step the amine can be protected and the ortho-nitro substituent can be removed by
hydrogenation and reductive diazotization (Tetrahedron Lett. 1989, 929). Scheme 17 illustrates these
transformations. SCHEME 17
Figure imgf000028_0001
One skilled in the art will recognize Formula XXVIII compounds as substituted amines, the preparations of which are in the literature (J. Chem. Soc, Chem.
Commun., 1987, 897; Synth. Commun., 1980, 10, 107).
Compounds of the Formula I (where Q is Q-6 and A and E are taken together) are easily recognized by those skilled in the art as dihydroindoles and tetrahydroquinolines, preparations of which are well documented in the literature (J. Med. Chem., 1984 1439).
The preparation of compounds of Formula III (where G is G-2 and G-3 and Y is H) is shown in Scheme 18. The preparation of nitrosoamines of Formula XXXI from
compounds of Formula XXX is readily accomplished by known literature methods (Sandier and Karo, "Organic Functional Group Preparations," 1968, vol. 2, 424-450). Reduction of nitrosoamines of Formula XXXI is readily accomplished by known literature methods (Sandier and Karo, Organic Functional Group Preparations, 1968, vol. 1, 374-376). SCHEME 18
Figure imgf000029_0001
Amines of Formula XXX are known to those skilled in the art as piperidines and tetrahydropyridines. The syntheses of these derivatives are found throughout the literature (see Fieser and Fieser, Reagents for Organic Synthesis, vol. 1, 1967, 981; Liebigs Ann . Chem . , 1972 , 1M, 21-27 ) .
Formula I compounds, where Y is other than H, can be prepared by standard alkylation, acylation or
sulferiylation methods well documented in the literature.
It is recognized that in many of the transformations described it is necessary to utilize appropriate
protecting groups to prevent unwanted side reactions or use reagents that do not affect functional groups other than those desired to be changed. One skilled in the art will be able to select appropriate protecting groups and reagents to this end.
EXAMPLE 1
Step A: methyl 2,3-dihydro-2-(1H-imidazo-1-ylcarbonyl )7-(trifluoromethyl)-[1]-benzopyrano[4,3-c]pyrazole- 3a(4H)-carboxylate
To a suspension of methyl 2,3,3a,4-tetrahydro-7- (trifluoromethyl)-[1]-benzopyrano[4,3-c]pyrazole-3a-carboxylate hydrochloride (2.0 g, 0.006 mol) in
dichloromethane (40 mL) was added triethylamine (0.66 g, 0.0065 mol). The suspension became a clear solution. After 5 minutes, N,N'-carbonyldiimidazole (1.5 g,
0.009 mol) was added in one portion. After 1 h., a white precipitate had formed. The reaction was partitioned between water and methylene chloride. The organic phase was washed with concentrated aqueous sodium bicarbonate solution then dried over anhydrous sodium sulfate.
Filtration and concentration under reduced pressure gave an oil that was triturated with ether to give 1.82 g of the title compound as a white solid, mp. 208-209°C.
1H NMR (CDCl3) δ 3.8(s, 3H), 4.3 (ABq, 2H), 4.6 (ABq, 2H), 7.1(s, 1H), 7.3 (s, 1H), 7.8(s, 1H), 8.0(d, 1H), 8.6(s, 1H).
Step B: 1-nitroso-4-(trifluoromethyl)piperidine
To a solution (100 mL) of 10% sulfuric acid in water was added 4- (trifluoromethyl)piperidine (10 g, 0.072 mol) and the resulting solution was cooled to 0°C. An aqueous solution of sodium nitrite (6.5 g, 0.094 mol) was added and the reaction was stirred for 48 hours. The reaction mixture was then continuously extracted with ether for 4 hours. The organic phase was dried with anhydrous magnesium sulfate, filtered and concentrated under reduced pressure to leave the title compound as a yellow oil (5.2 g). 1H NMR δ 1.6(m, 1H), 1.8 (m, 1H), 2.0 (m, 1H), 2.2 (m, 1H), 2.4 (m, 1H), 2.6(dt, 1H), 3.7 (dt, 1H), 4.9(d, 1H), 5.1 (d, 1H).
Step C: 4-(trifluoromethyl)-1-piperidinamine
hydrochloride
Lithium aluminum hydride (4.0 g, 0.105 mol) was suspended in diethylether (150 mL). A solution of the product of Step B (5.2 g, 0.031 mol) in diethyl ether (15 mL) was added at room temperature over 10 min. The reaction was heated at reflux for 2 hours. After cooling to 0°C the mixture was diluted with 100 mL wet ether and then quenched slowly with 25% aqueous sodium hydroxide solution. The aqueous phase was washed three times with ether, dried over anhydrous potassium carbonate and filtered. A 1M solution of anhydrous hydrogen chloride in ether (100 mL) was added which provided a white precipitate that was filtered and dried to give the title compound (4.2 g) 1H NMR (DMSO-d6) δ 1.6 (m, 2H), 1.9 (m, 2H), 2.5 (m, 1H), 2.7 (t, 2H), 3.4 (d, 2H), 7.0 (brs, 2H). Step D: methyl 2.3-dihydro-7-(trifluoromethyl)-2-[[4-(trifluoromethyl)-1-piperidinylaminolcarbonyl]-[1]-benzopyrano[4,3-c]-pyrazole-3a(4H)-carboxyate
To a solution of the product from Step C (1.0 g, 0.0049 mol) in 1, 2-dichloroethane (10 mL) was added triethylamine (1.0 g, 0.0098 mol). To this solution was added the product of Step A (1.5 g, 0.0039 mol) in one portion and the resulting mixture was heated to reflux for 18 hours. The mixture was partioned between
dichloromethane and water and the organic phase dried over sodium sulfate. After filtration, the organic phase was concentrated under reduced pressure and subjected to silica gel chromatography using 13:9 hexanes : ethyl acetate to give 0.32 g of the title compound as a white solid, mp 219-220°C. 1H NMR (CDCl3) δ 2.0 (m, 5H), 2.7 (m, 2H), 3.3 (m, 2H), 3.8 (s, 3H), 4.1 (ABq, 2H), 4.7 (ABq, 2H), 7.0 (s, 1H), 7.2 (s, 1H), 7.3 (d, 1H), 7.7 (d, 1H) IR (cm-1) 3188, 1739, 1672.
By the general procedures described herein, or obvious modification thereof, the compounds of Tables 1 through 3 can be prepared.
Figure imgf000032_0001
Figure imgf000033_0002
The abbreviations Me, Et, i-Pr, and Ph have the following meaning:
Me = -CH3;
Et = -CH2CH3;
i-Pr = -CH(CH3)2; and
Figure imgf000033_0001
Each line of Tables 1-3 defines four separate compounds. For example. Table 1, line 1, column 1 describes a compound wherein Y is H, column 2 describes one compound where Y is Me, column 3 describes one compound where Y is COOMe and column 4 describes one compound where Y is COMe. Thus, each line of each page of Tables 1-3 describes four separate compounds.
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Formulation/Utility
Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent or an organic solvent. Use 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 25-90 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, etc.
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 be 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. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can also be prepared as taught in DE 3,246,493.
For further information regarding the art of
form'ulation, 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 worked up in conventiona ways. Compound numbers refer to compounds in Index Tabl A.
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 volative
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 seed-feeding, aquatic and soil-inhabiting arthropods (term 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 pests. Nevertheless, all of the compounds of this invention display activity against pests that include: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs,
immatures and adults of the Orders Hemiptera and
Homoptera; eggs, larvae, nymphs and adults of the Order Acari; eggs, immatures and adults of the Orders
Thysanoptera, Orthoptera and Dermaptera; eggs, immatures and adults of the Order Diptera; and eggs, junveniles and adults of the Phylum Nemata. The compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Phthiraptera, Siphonoptera,
Blattaria, Thysanaura and Pscoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes. 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, 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 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, methamidophos, phosmet,
phosphamidon, phosalone, pirimicarb, phorate, terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate,
cyfluthrin, fenpropathrin, fluvalinate, fluσythrinate, tralomethrin, 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 Bacillus thuringiensis,
baculovirus and avermectin B.
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 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. 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, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, and many others.. The compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like.
The compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with
suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, 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. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Table A for compound descriptions.
Figure imgf000079_0001
TEST A
Fall Armyworm
Test units, each consisting of an 8-ounce (230 mL) plastic cup containing a layer of wheat germ diet, approximately 0.5 cm thick, were prepared. Ten third-instar larvae of fall armyworm (Spodoptera frugiperda) were placed into a cup. Solutions of each of the test compounds (acetone/distilled water 75/25 solvent) were sprayed into the cups, a single solution per set of three cups. Spraying was accomplished by passing the cups, on a conveyer belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.5 pounds of active ingredient per acre (about 0.55 kg/ha) at
30 p.s.i. (207 kPa). The cups were then covered and held at 27°C and 50% relative humidity for 72 hours, after which time readings were taken. Of the compounds tested, the following resulted in greater than or equal to 80% mortality: 1 and 3*.
TEST B
Tobacco Budworm
The test procedure of Test A was repeated for
efficacy against third-instar larvae of the tobacco budworm (Heliothis virescens) except that mortality was assessed at 48 hours. Of the compounds tested, the following resulted in greater than or equal to 80% mortality: 3*.
TEST C
Southern Corn Rootworm
Test units, each consisting of an 8-ounce (230 mL) plastic cup containing 1 sprouted corn seed, were
prepared. Sets of three test units were sprayed as described in Test A with individual solutions of the test compounds. After the spray on the cups had dried, five third-instar larvae of the southern corn rootworm
(Diabrotica undecimpunctata howardi) were placed into ea cup. A moistened dental wick was inserted into each cup to prevent drying and the cups were then covered. The cups were then held at 27°C and 50% relative humidity fo 48 hours, after which time mortality readings were taken. Of the compounds tested, the following resulted in great than or equal to 80% mortality: 3*.
TEST D
Aster Leafhopper
Test units were prepared from a series of 12-ounce (350 mL) cups, each containing oat (Avena sativa)
seedlings in a 1-inch (2.54 cm) layer of sterilized soil The test units were sprayed as described in Test A with individual solutions of the below-listed compounds.• Aft the oats had dried from the spraying, between 10 and 15 adult aster leafhoppers (Mascrosteles fascifrons) were aspirated into each of the covered cups. The cups were held at 27°C and 50% relative humidity for 48 hours, aft which time mortality readings were taken. Of the
compounds tested, the following resulted in greater than or equal to 80% mortality: 3*.
TEST E
Boll Weevil
Five adult boll weevils (Anthonomus grandis) were placed into each of a series of 9 ounce (260 mL) cups. The test procedure employed was then otherwise the same in Test A with three cups per treatment. Mortality readings were taken 48 hours after treatment. Of the compounds tested, no mortality levels greater than or equal to 80% were observed.
*Tested at 0.125 lbs.

Claims

1. A compound of the formula
Figure imgf000082_0001
wherein :
Q is selected from the group
Figure imgf000082_0002
A is H;
E is selected from the group H and C1-C3 alkyl; or
A and E can be taken together to form -CH2-, -CH2CH2-, -O-, -S- S(O)-, -S(O)2-, -NR7-, -OCH2-, -SCH2-,
-N(R7)CH2CH2substituted -CH2-, and substituted -CH2CH2- the substitutedis independently selected from 1-2 halogen and 2 methyl;
M is selected from the group H and C1-C3 alkyl; cr
and M can be taken together as -CH2CH2-, -CH2CH2- or -CH2CH2CH2CH2- each group optionally
substitutec with one or more members
independently selected from the group halogen, NO2, CN, C1-C3 alkyl, C1-C3 haloalkyl, OH, OR6 and CO2R19;
G is selected from the group
;
Figure imgf000083_0001
G being G-2 or G-3 when Q is Q-1, A and E are not
taken together and R3 is J;
7 is selected from the group O and S;
Y is selected from the group H; C1-C6 alkyl; benzyl;
C2-C6 alkenyl; C2-C6 alkynyl; C1-C6 alkyl
substituted by halogen, C1-C3 alkoxy, C1-C3 haloalkoxy, CN, NO2, S(O)rR30, C(O)R30, C(O)2R30, and phenyl optionally substituted by halogen, CN, C1-C2 haloalkyl and C1-C2 haloalkoxy; C3-C6 cycloalkyl; C3-C6 halocycloalkyl; C4-C6
cycloalkylalkyl; CHO; C2-C6 alkylcarbonyl; C2-C6 alkoxycarbonyl; C2-C6 haloalkylcarbonyl; C(O)R33; C(O)2R33; C1-C6 alkylthio; C1-C6 haloalkylthio; phenylthio; R11OC(O)N(R12)S-; R13(R14)NS-;
N=CR9R10; OR8 and NR8R9;
Z is selected from the group CH2, O, S and NR29;
R1 and R2 are independently selected from the group H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C1-C6 nitroalkyl, C2-Cg cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, halogen, CN, N3, SCN, NO2, OR16, SR17,
S(O)R16, S(O)2R16, OC(O)R16, OS(O)2R16, C(O)2R16,
C(O)R16, C(O)NR16R17, S(O)2NR16R17, NR16R17,
NR17C(O)R16, OC(O)NHR16, NR17C(O)NHR16,
NR17S(O)2R16, phenyl optionally substituted with 1 to 3 substituents independently selected from W, and benzyl optionally substituted with 1 to 3 substituents independently selected from W; or when m or n is 2, (R1)2 can be taken together, or (R2)2 can be taken together as -OCH2O-, -OCF2O-, -OCH2CH2O-, -CH2C(CH3)2O-, -CF2CF2O- or -OCF2CF2O- to form a cyclic bridge; provided that when R1 or R2 is S(O)R16, S(O)2R16, OC(O)R16 or OS(O)2R16 then R16 is other than H; and R1 being other than haloalkyl and haloalkoxy when G is G-1, Q is Q-1, A and E are not taken together and R3 is
optionally substituted phenyl, optionally
substituted alkyl, or C(O)2(C1-C6 alkyl);
R3 is selected from the group H, J, N3, NO2, halogen, N(R21)R22, C(R31)=N-O-R32, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 alkoxyalkyl, C3-C8 alkoxycarbonylalkyl, C(O)R16, C(O)2R16, OR18, C(O)NR16R17,
C(S)NR16R17, C(S)R16, C(S)SR16, CN, Si(R26)(R27)R25, SR25, S(O)R25, S(O)2R25, -P(O)(OR25)2, phenyl optionally substituted with (R15)p, and benzyl optionally substituted with 1 to 3 substituents independently selected from W; or R3 is C2-C6 epoxyalkyl optionally substituted with one or more members independently selected from the group C1-C3 alkyl, CN, C(O)R23, C(O)2R23 and phenyl optionally substituted with- W; or R3 is C1-C6 alkyl substituted with one or more members independently selected from the group
C(O)N(R24)R34, C(O)R24, SR25, S(O)R25, S(O)2R25,
SCN, CN, C1-C2 haloalkoxy, Si(R26)(R27)R28,
N(R21)R22, NO2, OC(O)R24, -P(O)(OR25)2 and J;
J is selected from the group saturated, partially
unsaturated or aromatic 5- or 6-membered
heterocyclic ring, bonded through carbon or nitrogen, containing 1-4 heteroatoms
independently selected from the group consisting of 0-2 oxygen, 0-2 sulfur and 0-4 nitrogen, this substituent optionally containing one carbonyl and optionally substituted with one or more members independently selected from W;
R4 and R5 are independently selected from the group H, C1-C4 alkyl, C(O)R19 and C2-C4 alkoxycarbonyl;
R6 is selected from the group H, C1-C4 alkyl, C(O)R19 and C(O)2R19;
R7 is selected from the group H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, SR16, S(O)R16, S(O)2R16, C(O)R16, C(O)2R16, C(O)NR16R20, C(S)NR16R20, C(S)R16, C(S)0R16, -P (O) (OR16) 2,
-P(S)(OR16)2, -P(O)(R16)OR16, -P(O)(R16)SR20, optionally substituted phenyl, and optionally substituted benzyl wherein the optional phenyl and benzyl substituent (s) are independently selected from F, Cl, Br, CH3, CF3 or OCF3; provided that when R7 is other than C(O)R16,
C(O)NR16R20 or C(S)NR16R20 then R16 is other than H;
R8 is selected from the group H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl,
SO2NR17R18, S(O)2R16, C(O)R16, C (O)NR16R20,
C(O)2R16, phenyl optionally substituted with halogen or C1-C4 alkoxy, and benzyl optionally substituted with halogen; provided that when R8 is S(O)2R16, R16 is other than H;
R9 is selected from the group H, C1-C4 alkyl and
C(O)R16;
R10 is selected from the group H, C1-C4 alkyl, C1-C4 haloalkyl, and phenyl optionally substituted with one or more members independently selected from the group halogen, CN, NO2, CF3 and OCF3; or
R9 and R10 can be taken together as -CH2CH2CH2-,
-CH2CH2CH2CH2- or -CH2CH2CH2CH2CH2-;
R11 is C1-C6 alkyl;
R12 is C1-C4 alkyl;
R13 and R14 are independently C1-C4 alkyl; or
R13 and R14 can be taken together as -CH2CH2CH2CH2CH2- or -CH2CH2OCH2CH2-;
R15 is selected from the group C1-C6 alkyl, C1-C6
haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-Cg haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, halogen, CN, N3, SCN, NO2, OR16, SR16, S(O)R16, S (O)2R16, OC(O)R16,
OS(O)2R16, C(O)2R16, C(O)R16, C(O)NR16R17,
S(O)2NR16R17, NR16R17, NR17C (O) R16, OC(O)NHR16, NR17C(O)NHR16, NR17S(O)2R16, phenyl optionally substituted with 1 to 3 substituents independently selected from W, and benzyl
optionally substituted with 1 to 3 substituents independently selected from W; or when p is 2, (R15)2 can be taken together as -OCH2O-, -OCF2O-, -OCH2CH2O-, -CH2C(CH3)2O-, -CF2CF2O- or -OCF2CF2O- to form a cyclic bridge; provided that when R15 is S(O)R16, S(O)2R16, OC(O)R16 or OS(O)2R16 then R16 is other than H;
R16 is selected from the group H, Ci-Cg alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, optionally substituted phenyl, and optionally substituted benzyl wherein the optional phenyl and benzyl substituents are 1 to 3 substituents
independently selected from W;
R17 is selected from the group H and C1-C4 alkyl; or R16 and R17, when attached to the same atom, can be taken together as -(CH2)4-, -(CH2)5-, or
-CH2CH2OCH2CH2-;
R18 is selected from the group H, C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl and C1-C4 alkylsulfonyl;
R19 is C1-C3 alkyl;
R20 is selected from the group H, C1-C4 alkyl, C2-C4 alkenyl and C2-C4 alkynyl;
R21 is selected from the group H, C2-C7 alkylcarbonyl, C2-C7 alkoxycarbonyl, optionally substituted C1-C4 alkyl, optionally substituted C2-C4 alkenyl, and optionally substituted C2-C4 alkynyl, all of these optional substituents being independently selected from C1-C2 alkoxy, CN, C(O)R28 and
C(O)2R25;
R22 is selected from the group H, C1-C3 alkyl, phenyl optionally substituted with at least one member independently selected from W, and benzyl optionally substituted with at least one member independently selected from W;
R23 is selected from the group H, C1-C4 alkyl, C2-C4 alkenyl and C2-C4 alkynyl;
R24 is selected from the group H and C1-C2 alkyl;
R25 is selected from the group C1-C3 alkyl and phenyl optionally substituted with at least one member independently selected from W;
R26 is C1-C3 alkyl;
R27 is C1-C3 alkyl;
R28 is selected from the group H, C1-C3 alkyl and
phenyl optionally substituted with at least one member independently selected from W;
R29 is selected from the group H, C1-C4 alkyl, C2-C4 alkylcarbonyl and C2-C4 alkoxycarbonyl;
R30 is C1-C3 alkyl;
R31 is selected from the group H, Cl, C1-C4 alkyl, C1-C4 alkoxy, C1-C2 alkylthio and CN;
R32 is selected from the group H, C1-C4 alkyl, C2-C3 alkylcarbonyl and C2-C3 alkoxycarbonyl;
R33 is phenyl, optionally substituted with at least one member independently selected from W;
R34 is selected from the group H and C1-C2 alkyl;
W 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; m is 1 to 3;
n is 1 to 3; p is 1 to 3; and
r is 0, 1 or 2.
2. A compound according to Claim 1 wherein:
R1 is selected from the group H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, halogen, CN, SCN, NO2, OR16, SR16, S(O)2R16, C(O)2R16, C(O)R16, phenyl optionally substituted with 1 to 3
substituents independently selected from W, and benzyl optionally substituted with 1 to 3
substituents independently selected from W; with one R1 substituent in the 4-position, or when m is
2 then (R1)2 can be taken together as
-CH2C(CH3)2O-, -OCH2CH2O-, -OCF2CF2O-, or -CF2CF2O- to form a 5- or 6-membered fused ring;
R2 is selected from the group H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, halogen, CN, SCN, NO2, OR16, SR16, S(O)2R16, OC(O)R16, OS(O)2R16,
C(O)2R16, C(O)R16, C(O)NR16R17, S (O) 2NR16R17,
NR16R17, phenyl optionally substituted with 1 to 3 substituents independently selected from W, and benzyl optionally substituted with 1 to 3
substituents independently selected from W;
R3 is selected from the group H, C1-C4 alkyl, C3-C4 alkoxycarbonylalkyl, C(O)2R16, C(O)R16, and phenyl optionally substituted by one or more
substituents independently selected from (R15)p; R15 is selected from the group C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C3-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C1-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, halogen, CN, SCN, NO2, OR16, SR16, S(O)2R16, OC(O)R16, OS(O)2R16, C(O)2R16, C(O)R16, C(O)NR16R17, S(O)2NR16R17, NR16R17, phenyl optionally substituted with 1 to 3 substituents independently selected from W, and benzyl optionally substituted with 1 to 3 substituents independently selected from W;
R16 is selected from the group C1-C3 alkyl, C1-C2
haloalkyl, C3-C4 alkenyl and propargyl;
R17 is selected from the group H and CH3; and
m is 1 or 2.
3. A compound according to Claim 2 wherein G is G-1 and R4 and R5 are each H.
4. A compound according to Claim 2 wherein G is G-2 and R4 and R5 are each H.
5. A compound according to Claim 3 wherein Q is selected from the group Q-1, Q-2 and Q-5.
6. A compound according to Claim 4 wherein Q is selected from Q-1, Q-2 and Q-5.
7. A compound according to Claim 4 selected from the group consisting of: methyl 2,3-dihydro-7-(trifluoromethyl)-2-[[4-(trifluoromethyl)-1-piperidinylamino]carbonyl][1]benzopyrano[4,3-c]-pyrazole-3a(4H)-carboxylate; 3,4-bis(4-chlorophenyl)-4,5-dihydro-N-[4-(trifluoromethyl)-1-piperidinyl]-1H-pyrazole-1-carboxamide; methyl 7-chloro-2,5-dihydro-2-[[[4-(trifluoromethyl)-1-piperidinyl]amino]carbonyl]indeno-[1,2-e][1,3,4]oxadiazine-4a(3H)-carboxylate; and 2-(5-fluoro- 2,3-dihydro-2-methyl-1H-inden-1-ylidene)-N-[4-(trifluoromethyl)-1-piperidinyl]hydrazinecarboxamide.
8. An arthropodicidal composition comprising an arthropodically effective amount of a compound according to any one of Claims 1 to 7 and a carrier therefor.
9. A method for controlling arthropods comprising contacting them or their environment with an arthropodically effective amount of a compound according to any one of Claims 1 to 7.
PCT/US1993/001532 1992-03-02 1993-02-26 Arthropodicidal amides WO1993018038A1 (en)

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GB1570635A (en) * 1976-01-09 1980-07-02 Philips Nv 1,3,4 substituted pyrazoline derivatives
EP0333131A1 (en) * 1988-03-17 1989-09-20 Hoechst Aktiengesellschaft Plant protective agent based on pyrazolecarboxylic acid derivatives
EP0386892A2 (en) * 1989-03-09 1990-09-12 E.I. Du Pont De Nemours And Company Arthropodicidal tetrahydrobenzopyranopyrazoles
EP0438690A2 (en) * 1990-01-24 1991-07-31 Bayer Ag Substituted pyrazolin derivatives
EP0443162A1 (en) * 1990-02-17 1991-08-28 Bayer Ag Substituted pyrazoline derivatives

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Publication number Priority date Publication date Assignee Title
GB1570635A (en) * 1976-01-09 1980-07-02 Philips Nv 1,3,4 substituted pyrazoline derivatives
EP0333131A1 (en) * 1988-03-17 1989-09-20 Hoechst Aktiengesellschaft Plant protective agent based on pyrazolecarboxylic acid derivatives
EP0386892A2 (en) * 1989-03-09 1990-09-12 E.I. Du Pont De Nemours And Company Arthropodicidal tetrahydrobenzopyranopyrazoles
EP0438690A2 (en) * 1990-01-24 1991-07-31 Bayer Ag Substituted pyrazolin derivatives
EP0443162A1 (en) * 1990-02-17 1991-08-28 Bayer Ag Substituted pyrazoline derivatives

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Title
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY vol. 25, no. 5, 1977, WASHINGTON US pages 987 - 992 K. WELLINGA ET AL '1-Phenylcarbamoyl-2-pyrazolines: A new class of insecticides. 1. Synthesis and insecticidal properties of 3-phenyl-1-phenylcarbamoyl-2-pyrazolines' *

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