EP0629201A1 - Amides utilises pour la lutte contre les arthropodes - Google Patents

Amides utilises pour la lutte contre les arthropodes

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Publication number
EP0629201A1
EP0629201A1 EP93906122A EP93906122A EP0629201A1 EP 0629201 A1 EP0629201 A1 EP 0629201A1 EP 93906122 A EP93906122 A EP 93906122A EP 93906122 A EP93906122 A EP 93906122A EP 0629201 A1 EP0629201 A1 EP 0629201A1
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EP
European Patent Office
Prior art keywords
alkyl
group
optionally substituted
independently selected
haloalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP93906122A
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German (de)
English (en)
Inventor
Patrick Doyle Lowder
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EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Publication date
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Publication of EP0629201A1 publication Critical patent/EP0629201A1/fr
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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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Furan Compounds (AREA)
  • Hydrogenated Pyridines (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Composés insecticides de la formule (I) dans laquelle G, X, Y et Q sont tels que définis dans le descriptif de l'invention, compositions à usage agricole les contenant et procédé d'utilisation de ces composés pour lutter contre les arthropodes dans des environnements agricoles et non agricoles.
EP93906122A 1992-03-02 1993-02-26 Amides utilises pour la lutte contre les arthropodes Withdrawn EP0629201A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US843378 1977-10-19
US84337892A 1992-03-02 1992-03-02
PCT/US1993/001532 WO1993018038A1 (fr) 1992-03-02 1993-02-26 Amides utilises pour la lutte contre les arthropodes

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EP0629201A1 true EP0629201A1 (fr) 1994-12-21

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EP (1) EP0629201A1 (fr)
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WO (1) WO1993018038A1 (fr)

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HRP20080549T3 (en) * 2004-01-30 2008-11-30 Solvay Pharmaceuticals B.V. 1,3,5-trisubstituted 4,5-dihydro-1h-pyrazole derivatives having cb1-antagonistic activity

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Publication number Priority date Publication date Assignee Title
NL183400C (nl) * 1976-01-09 1988-10-17 Duphar Int Res Werkwijze ter bereiding van een insecticide preparaat dat een pyrazoline-verbinding bevat en werkwijze ter bereiding van een pyrazoline-verbinding met insecticide werking.
DE3808896A1 (de) * 1988-03-17 1989-09-28 Hoechst Ag Pflanzenschuetzende mittel auf basis von pyrazolcarbonsaeurederivaten
EP0463090A1 (fr) * 1989-03-09 1992-01-02 E.I. Du Pont De Nemours And Company Tetrahydrobenzopyranopyrazoles arthropodicides
DE4032089A1 (de) * 1990-01-24 1991-07-25 Bayer Ag Substituierte pyrazolinderivate
DE4005114A1 (de) * 1990-02-17 1991-08-22 Bayer Ag Substituierte pyrazolinderivate

Non-Patent Citations (1)

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Title
See references of WO9318038A1 *

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JPH07504658A (ja) 1995-05-25
WO1993018038A1 (fr) 1993-09-16

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