WO2002006252A1 - Dihydrotriazines asymetriques utilisees comme pesticides - Google Patents

Dihydrotriazines asymetriques utilisees comme pesticides Download PDF

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Publication number
WO2002006252A1
WO2002006252A1 PCT/EP2001/008193 EP0108193W WO0206252A1 WO 2002006252 A1 WO2002006252 A1 WO 2002006252A1 EP 0108193 W EP0108193 W EP 0108193W WO 0206252 A1 WO0206252 A1 WO 0206252A1
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Prior art keywords
alkyl
spp
cycloalkyl
alkoxy
compounds
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PCT/EP2001/008193
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English (en)
Inventor
Saleem Farooq
André Jeanguenat
Stephan Trah
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Syngenta Participations Ag
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Priority to AU2001289663A priority Critical patent/AU2001289663A1/en
Publication of WO2002006252A1 publication Critical patent/WO2002006252A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • C07D253/06—1,2,4-Triazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • 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
    • C07D401/10—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 carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the invention relates to a compound of formula
  • X ⁇ is R 8 ;
  • X 2 and X 3 are each independently of the other H or R 8 ;
  • R 1 is unsubstituted or mono- to penta-substituted aryl or heteroaryl, the substituents of the aryl and heteroaryl groups being selected from the group consisting of OH, halogen, CN, NO 2 , C C 12 alkyl, C 3 -C 8 cycloalkyl, d-Cealkyl-Cg-CsCycloalkyl, C 3 -C 8 -cycloalkyl-C ⁇ -C 6 alkyl, CrC ⁇ 2 haloalkyl, C 3 -C 8 halocycloalkyl, CrC ⁇ alkoxy, C 3 -C 8 cyclo-alkoxy, CrC 12 haloalkoxy, C 3 -C 8 halocycloalkoxy, CrC 12 alkylthio, C 3 -C 8 cycloalkylthio, CrC 2 haloalkylthio, C 3 -C 8 halocycloalkylthio
  • R 3a and R 3b are R 3 ;
  • R 3a is R 3 ; and R 3b and R together form a bond; or
  • R 3 is R 3 ; and R 3a and R together form a bond;
  • R 4 is C ⁇ -C 4 alkyl or C 3 -C 6 cycloalkyl; each R 5 independently of the other is H, d-C 12 alkyl, C 3 -C 8 cycloalkyl, C ⁇ -C 12 haloalkyl,
  • R 6 is H, C- ⁇ -C 12 alkyl, C 3 -C 8 cycloalkyl, C C ⁇ 2 haloalkyl, d-C ⁇ 2 alkoxy, N(R 7 ) 2 or d-C 6 alkoxy- C 2 -C 6 alkyl; each R 7 independently of the other is H, d-C ⁇ 2 alkyl, C 3 -C 8 cycloalkyl, d-C 12 haloalkyl or aryl- C C 6 alkyl;
  • R 8 is halogen, CN, NO 2 , C C 12 alkyl, C C 12 haloalkyl, C C 12 alkoxy, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkoxy, C C ⁇ 2 haloalkoxy, C 3 -C 8 halocycloalkoxy, C C 12 alkylthio, C 3 -C 8 -cycloalkylthio, d-C 12 haloalkylthio or C 3 -C 8 halocycloalkylthio;
  • R 9 is H, OH, halogen, CN, d-C ⁇ alkyl, d-dsalkoxy-d-C ⁇ alkyl, d-C 12 alkylthio- C Ci 2 -alkyl, C 3 -C 8 cycloalkyl, CrC 12 haloalkyl, C C 12 cyanoalkyl, C 3 -C 12 alkenyl, C 3 -C ⁇ 2 alkinyl, C 3 -C 8 ha!ocycloalkyi, phenyl, phenyl-C C 6 alkyl, or phenyl or phenyl- d-C 6 alkyl, wherein the phenyl groups are each mono- to tri-substituted by halogen, C C ⁇ 2 alkyl, d-C 12 alkoxy, C C 12 alkylthio, C 3 -C 8 cycloalkyl, d-C ⁇ 2 haloalkyl, d-C 12 halo
  • Rn and R 12 are each independently of the other H or d-C ⁇ alkyl; the group -A- is a direct bond, C C 12 alkylene, -O-, -O(C 1 -C ⁇ 2 alkylene), -S(O) q -,
  • W is a direct bond, -O-, -S-, -SO-, -SO 2 -, -SO 2 -NH-, -NH- or -N(d-C 4 alkyl);
  • Y is O or S;
  • Z is O or S;
  • m is 1 , 2, 3 or 4;
  • n is O, 1 or 2;
  • p is 0, 1 , 2, 3, 4, 5 or 6; and
  • q is 0, 1 or 2; where appropriate to E/Z isomers, to mixtures of E/Z isomers and/or tautomers, in each case in free form or in salt form; to a process for the preparation of those compounds and their salts, isomers and tautomers and to the use thereof; to pesticidal compositions, the active ingredient of which is selected from those compounds and their tautomers; and to processes for the preparation of those compositions and to the use thereof, and to intermediates, in free form or in salt form, in the preparation of those compounds, and,
  • the literature proposes certain tetrahydropyrimidine derivatives in pesticidal compositions.
  • the biological properties of those known compounds are not, however, fully satisfactory in the area of pest control and there is accordingly a need to provide further compounds having pesticidal properties, especially for the control of insects, that problem being solved according to the invention by the provision of the present compounds of formula (I).
  • any reference to the compounds of formula (I) should be understood as including also corresponding isomers, tautomeric forms of the isomers and, where appropriate, the salts of the isomers and tautomers, even when the latter are not specifically mentioned in each case.
  • the compounds of formula (I) and, where appropriate, the tautomers thereof can form salts, e.g. acid addition salts.
  • Those salts are formed, for example, with strong inorganic acids, such as mineral acids, e.g. sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted or substituted, for example halo-substituted, d-C 4 alkanecarboxylic acids, e.g. acetic acid, or saturated or unsaturated dicarboxylic acids, e.g. oxalic, malonic, maleic, fumaric or phthalic acid, or hydroxycarboxylic acids, e.g.
  • strong inorganic acids such as mineral acids, e.g. sulfuric acid, a phosphoric acid or a hydrohalic acid
  • strong organic carboxylic acids such as unsubstituted or substituted, for example halo-substituted
  • compounds of formula (I) having at least one acidic group are capable of forming salts with bases.
  • Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, e.g.
  • sodium, potassium or magnesium salts or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethylamine, diethylamine, triethylamine or dimethylpropylamine, or a mono-, di- or tri- hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine.
  • corresponding internal salts may also be formed. Preference is given to the free form.
  • preference is given to agrochemically advantageous salts.
  • Carbon-containing groups and compounds each contain from 1 up to and including 6 carbon atoms, preferably from 1 up to and including 4 carbon atoms, especially 1 or 2 carbon atoms.
  • Aryl is phenyl or naphthyl.
  • Heteroaryl is especially pyridyl, pyrimidyl, s-triazinyl, 1 ,2,4-triazinyl, thienyl, furanyl, pyrryl, pyrazolyl, imidazolyl, thiazolyl, triazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, benzothienyl, benzofuranyl, benzothiazolyl, indolyl or indazolyl, which are preferably bonded via a carbon atom; preference is given to thienyl, thiazolyl, benzofuranyl, benzothiazolyl or indolyl, especially thienyl, thiazolyl or indolyl, more especially thienyl.
  • Halogen - as a group perse and as a structural element of other groups and compounds, such as of haloalkyl, haloalkoxy and haloalkylthio - is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine.
  • Alkyl - as a group perse and as a structural element of other groups and compounds, such as of haloalkyl, alkoxy and alkylthio, - is, in each case giving due consideration to the number of carbon atoms present in the group or compound in question, either straight-chain, e.g. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, or branched, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
  • straight-chain e.g. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, or branched, e.g. isopropyl, isobutyl, sec-
  • Cycloalkyl - as a group perse and as a structural element of other groups and compounds, such as of halocycloalkyl, cycloalkoxy and cycloalkylthio, - is, in each case giving due consideration to the number of carbon atoms present in the group or compound in question, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • Alkenyl - as a group perse and as a structural element of other groups and compounds - is, in each case giving due consideration to the number of carbon atoms and conjugated or isolated double bonds present in the group or compound in question, either straight-chain, e.g. allyl, 2-butenyl, 3-pentenyl, 1 -hexenyl, 1 -heptenyl, 1 ,3-hexadienyl or 1 ,3-octadienyl, or branched, e.g.
  • Alkynyl - as a group perse and as a structural element of other groups and compounds - is, in each case giving due consideration to the number of carbon atoms and conjugated or isolated double bonds present in the group or compound in question, either straight-chain, e.g.
  • Halo-substituted carbon-containing groups and compounds such as haloalkyl, haloalkoxy or haloalkylthio, may be partially halogenated or per-halogenated, the halogen substituents in the case of poly-halogenation being the same or different.
  • haloalkyl - as a group perse and as a structural element of other groups and compounds, such as of haloalkoxy or haloalkylthio - are methyl substituted from one to three times by fluorine, chlorine and/or by bromine, such as CHF 2 or CF 3 ; ethyl substituted from one to five times by fluorine, chlorine and/or by bromine, such as CH 2 CF 3 , CF 2 CF 3 , CF 2 CCI 3 , CF 2 CHCI 2 , CF 2 CHF 2 , CF 2 CFCI 2 , CF 2 CHBr 2 , CF 2 CHCIF, CF 2 CHBrF or CCIFCHCIF; propyl or isopropyl each substituted from one to seven times by fluorine, chlorine and/or by bromine, such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 , CH 2 CF 2 CF 3 or CH(CF 3 ) 2
  • halogen CN, NO 2 , C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, CH 2 -C 3 -C 6 cycloalkyl, C . -C 4 haloalkyl- C 3 -C 6 halocycloalkyl, C C 4 alkoxy, d-C 4 haloalkoxy, C C 4 alkylthio, C C 4 haloalkylthio, C C 4 alkylsulfinyl, d-C haloalkylsulfinyl, C ⁇ -C 4 alkylsulfonyl, C ⁇ -C haloalkylsulfonyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl; unsubstituted or mono- or di-substituted phenyl, the substituents being selected from the group consisting of halogen, CN, NO 2 , d
  • R is especially unsubstituted or mono- or di-substituted phenyl, the substituents being selected from the group consisting of halogen, CN, NO 2 , C C 2 alkyl, C 3 -C 6 cycloalkyl, C C 2 haloalkyl, d-C 2 alkoxy, C C 2 halo- alkoxy, C C 2 alkylthio, d-C 2 haloalkylthio, d-C 2 alkylsulfinyl, d-C 2 haloalkylsulfinyl, d-C 2 alkylsulfonyl, d-C 2 haloalkylsulfonyl, C 3 -C 4 alkenyl and C 3 -C 4 alkynyl; unsubstituted or mono- or di-substituted phenyl, the substituents being selected from the group consisting of fluorine, chlorine, CN, NO
  • Ri is very especially mono-substituted phenyl substituted by a mono- or di-substituted phenyl, the substituents on the mono- or di-substituted phenyl being selected from the group consisting of fluorine, chlorine, methyl, cyclopropyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio and trifluoromethylthio; more especially wherein R ⁇ is phenyl substituted in the p-position by an unsubstituted or mono- or di-substituted phenyl;
  • each R 5 independently of the other is H or d-C 4 alkyl; especially H, methyl or ethyl;
  • the invention relates also to a process for the preparation of compounds of formula (I) and, where appropriate, their tautomers, in each case in free form or in salt form, wherein
  • reaction medium in a temperature range of from about -80°C to the boiling temperature of the reaction medium, preferably from about 0°C to about +150°C, and, if necessary, in a sealed container, under pressure, in an inert gas atmosphere and/or under anhydrous conditions.
  • a temperature range of from about -80°C to the boiling temperature of the reaction medium preferably from about 0°C to about +150°C
  • a sealed container under pressure, in an inert gas atmosphere and/or under anhydrous conditions.
  • reaction time is not critical; preference is given to a reaction time of from about 0.1 to about 24 hours, especially from about 0.5 to about 10 hours.
  • the product is isolated according to customary methods, e.g. by filtration, crystallisation, distillation or chromatography or any suitable combination of those procedures.
  • solvents or diluents examples include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene and tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran
  • Alcohols such as methanol, ethanol and isopropanol, and amides, such as dimethylformamide and dimethylacetamide, are especially suitable.
  • the reactions are carried out advantageously in a temperature range of from about room temperature to the boiling point of the solvent used, preferably from room temperature to about +150°C.
  • the reaction is carried out at from 25°C to 100°C, in an alcohol, preferably at from 80°C to 100°C, in n-propanol.
  • Example P1 Especially preferred conditions for the reaction are described in Example P1.
  • the reactants can be reacted with one another as such, that is to say without the addition of a solvent or diluent, e.g. in the molten state. It is generally advantageous, however, to add an inert solvent or diluent or a mixture thereof.
  • solvents or diluents examples include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene and tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofur
  • reaction time Preference is given to a reaction time of from about 1 hour to about 24 hours, especially from about 12 to about 24 hours.
  • Preferred hydrogenation catalysts are, for example, Raney nickel or palladium on carbon.
  • a compound of formula (IV) is reacted with a complex hydride, such as, for example, sodium borohydride, at approximately 30°C in an ether, such as tetrahydrofuran.
  • a complex hydride such as, for example, sodium borohydride
  • ethers for example dimethoxyethane, dioxane and tetrahydrofuran, especially tetrahydrofuran.
  • the reaction is advantageously carried out in a temperature range of from about 0°C to about 100°C, preferably at from 50 to 80°C.
  • a base is added.
  • bases are amines, such as trialkylamines, especially triethylamine, alcoholates, such as sodium methanolate, sodium ethanolate and potassium tert-butanolate, salts of amines, such as lithium diethylamide and lithium diisopropylamide, and hydrides, such as sodium hydride.
  • Advantageous leaving groups G in the compounds of formula (V) are, for example, hydroxy, d-C 8 alkoxy, halo-CrC ⁇ alkoxy, d-dsalkanoyloxy, mercapto, d-C 8 alkylthio, haIo-C C 8 alkyl- thio, d-C 8 alkanesulfonyloxy, halo-d-C 8 alkanesulfonyloxy, benzenesulfonyloxy, toluene- sulfonyloxy and halogen, preferably toluenesulfonyloxy, t fluoromethanesulfonyloxy and halogen, especially halogen.
  • alkanes such as hexane, or cyclohexane
  • ethers such as tetrahydrofuran, dioxane, diethyl ether or dimethoxyethane
  • sulfoxides such as dimethyl sulfoxide
  • alcohols such as methanol, ethanol, propanol, isopropanol or tert- butanol.
  • nucleophiles are, for example, organometal compounds of formula R 2 -M, wherein M is, for example, Mg, Li, Na, Al or Zn; M enolates, wherein M is, for example, Li, Na, K, Zn, Ti or B; enamines and anions of compounds having an acidic methylene or methyl group, such as, for example, nitroalkanes, such as nitromethane or nitroethane; nitriles, such as acetonitrile; diketones, such as acetylacetone or trifluoroacetylacetone; beta-keto esters, such as acetoacetic ester; malonic acid or malonic acid derivatives, such as malonic dinitrile or malonic dialdehyde.
  • M is, for example, Mg, Li, Na, Al or Zn
  • M enolates wherein M is, for example, Li, Na, K, Zn, Ti or B
  • the reaction temperature is from -30 to +150 ° C, preferably from room temperature to the boiling point of the reaction mixture.
  • the reaction is advantageously carried out in a temperature range of from about room temperature to about 0°C to +150°C, especially from 20°C to +100°C, in an ether and in the presence of a palladium catalyst.
  • a compound of formula (la) is reacted with a compound of formula (VI) at from 40 to 90°C, especially at 60°C, in dimethoxyethane, in the presence of a palladium catalyst, for example Pd(PPh 3 ) 2 CI 2 , and in the presence of aqueous NaHCO 3 .
  • a palladium catalyst for example Pd(PPh 3 ) 2 CI 2
  • aqueous NaHCO 3 aqueous NaHCO 3
  • Salts of compounds of formula (I) can be prepared in a manner known perse. For example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion-exchange reagent, and salts with bases are obtained by treatment with a suitable base or a suitable ion-exchange reagent.
  • Salts of compounds of formula (I) can be converted into the free compounds of formula (I) in customary manner: acid addition salts, for example, by treatment with a suitable basic agent or a suitable ion-exchange reagent, and salts with bases, for example, by treatment with a suitable acid or a suitable ion-exchange reagent.
  • Salts of compounds of formula (I) can be converted into different salts of compounds of formula (I) in a manner known perse: acid addition salts, for example, can be converted into different acid addition salts, e.g. by treatment of a salt of an inorganic acid, such as a hydro- chloride, with a suitable metal salt, such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt being formed, e.g. silver chloride, is insoluble and therefore separates out from the reaction mixture.
  • a salt of an inorganic acid such as a hydro- chloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula (I) having salt-forming properties can be obtained in free form or in the form of salts.
  • the compounds of formula (I) may be in the form of one of the possible isomers or in the form of a mixture thereof, in the form of pure isomers or in the form of mixtures of isomers, that is to say in the form of a racemic mixture; the invention relates both to the pure isomers and to the racemic mixtures, and this is to be understood hereinbefore and hereinafter, even if stereochemical details are not specifically mentioned in each case.
  • racemates can be separated into the optical antipodes according to known methods, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, e.g. high-pressure liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific immobilised enzymes, via the formation of inclusion compounds, e.g. using chiral crown ethers, in which case only one isomer is complexed.
  • HPLC high-pressure liquid chromatography
  • the compounds of formula (I) can also be obtained in the form of their hydrates and/or may include other solvents, for example solvents which may have been used for the crystallisation of compounds in solid form.
  • the invention relates to all those forms of the process according to which a compound obtainable as starting material or intermediate at any stage of the process is used as starting material and all or some of the remaining steps are carried out, or a starting material is used in the form of a derivative or a salt and/or its racemates or antipodes or, especially, is formed under the reaction conditions.
  • the invention relates especially to the preparation processes described in Examples P1 to P8.
  • the compounds of formula (I) according to the invention are valuable preventive and/or curative active ingredients having a very advantageous very broad biocidal spectrum even at low rates of concentration, while being well tolerated by warm-blooded animals, fish and plants. They are surprisingly equally suitable for controlling plant pests as for controlling ecto- and endo-parasites in humans and especially in productive livestock, domestic animals and pets. They are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and representatives of the order Acarina, nematodes, cestodes and trematodes, whilst simultaneosuly sparing useful organisms.
  • the insecticidal or acaricidal action of the compounds according to the invention may manifest itself directly, i.e. in the death of the pests, which occurs immediately or only after some time, for example during moulting, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %.
  • the action of the compounds according to the invention and of compositions comprising them against animal pests can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticides and/or acaricides.
  • additives there come into consideration, for example, representatives of the following classes of compound: organophosphorus compounds, nitrophenols and derivatives, formamidines, ureas, especially benzoylureas, nitroguanidines, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.
  • Examples of especially suitable mixing partners include: azamethiphos; chlorfenvinphos; cypermeth n, cypermethrin high-cis; cyromazine; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; iodofenphos; kinoprene; lufenuron; methacrifos; methidathion; monocrotophos; phosphamidon; profe- nofos; diofenolan; a substance obtainable from Bacillus thuringiensis strain GC91 or from NCTC11821 ; pymetrozine; bromopropylate; methoprene; disulfoton; quinalphos; tau-fluva- linate; thiocyclam; thiometon; aldiearb; azinpho
  • the mentioned animal pests include, for example, representatives of the classes Insecta, Arachnida, Nematoda and Gastropoda.
  • the class insecta they are preferably representatives of the order Lepidoptera, for example
  • Blatta spp. Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp.; of the order Psocoptera, for example Liposcelis spp.; of the order Anoplura, for example
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. und Phylloxera spp.; of the order Mallophaga, for example Damalinea spp. and Trichodectes spp.; of the order Thysanoptera, for example Frankliniella spp., Hercinothrips spp., Taeniothhps spp., Thrips palmi, Thrips tabaci and Scirtoth ps aurantii; of the order Heteroptera, for example Cimex spp., Distantiella theobroma, Dysdercus spp.,
  • Aonidiella spp. Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp.,
  • Paratoria spp. Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp.,
  • Saissetia spp. Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri; of the order Hymenoptera, for example Acromyrmex, Atta spp., Cephus spp., Diprion spp.,
  • Neodiprion spp. Solenopsis spp. and Vespa spp.; of the order Diptera, for example Aedes spp., Antherigona soccata, Bibio hortulanus,
  • Dacus spp. Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp.,
  • Musca spp. Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp.,
  • Rhagoletis pomonella Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.
  • Siphonaptera for example Ceratophyllus spp. and Xenopsylla cheopis
  • Thysanura for example Lepisma saccharina
  • Isoptera insectitidae
  • Allondothermes ssp. e.g. A. giffardi and A. tenax; ; Ancistrotermes ssp:, e.g. A. cavithorax, A. guineensis, A. latinotus and A. periphrasis; Amitermes ssp., e.g. A. evuncifer; Heterotermes ssp., e.g. H. indicola uhd H. tenuis; Hodotermes ssp., e.g. H.
  • Macrotermes ssp. e.g. M. michaelseni, M. falcifager, M. bellicosus, M. subhyalinus and M. natalensis
  • Microtermes ssp. e.g. M. albopartitus, M. redenianus, M. lepidus, M-. traghardi and M. thoracalis
  • Nasutitermes ssp. e.g. N. costalis
  • Neotermes ssp. e.g. N. gestroi
  • Odontotermes ssp. e.g. O. bruneus, O. classicus, O. smeathmani, O.
  • wood-boring insects such as representatives of the family Lyctidae, the family Apidae, for example Xylocopa virginica, and of the family Anobiidae, such as Anobium punctatum.
  • the said pests are preferably representatives of the order Acarina, for example
  • a further preferred subject according to the invention is the control of representatives of the class Nematoda, such as root knot nematodes, stem eelworms and foliar nematodes; especially Heterodera spp., for example Heterodera schachtii, Heterodora avenae and Heterodora trifolii; Globodera spp., for example Globodera rostochiensis; Meloidogyne spp., for example Meloidogyne incognita and Meloidogyne javanica; Radopholus spp., for example Radopholus similis; Pratylenchus, for example Pratylenchus neglectans and Pratylenchus penetrans; Tylenchulus, for example Tylenchulus semipenetrans; Longidorus, T chodorus, Xiphinema, Ditylenchus, Aphelenchoides and Anguina, in particular Melo
  • a further preferred subject according to the invention is the control of representatives of the class of the Gastropoda.
  • These molluscs include, for example, Ampullariidae; Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); Bradybaenidae (Bradybaena fruticum); Cepaea (C. hortensis, C. nemoralis); Cochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (G. trunculata); Helicella (H.
  • H. obvia Helicidae (Helicigona arbustorum); Helicodiscus; Helix (H. aperta); Umax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.
  • the present invention places special emphasis on the use of the compounds of formula (I) according to the invention in the protection of plants against parasitic feeding pests.
  • Target crops are especially cereals, such as wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, such as pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries, or berries, for example strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans and groundnuts; cucurbitaceae, such as marrows, cucumbers and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruit, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocados, cinnamon and camphor; and tobacco, nuts,
  • the invention accordingly relates also to pesticides, such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising - at least - one of the compounds of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances.
  • pesticides such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising - at least - one of the compounds of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances.
  • the active ingredient is used in those compositions in pure form, a solid active ingredient, for example, in a specific particle size, or preferably together with - at least - one of the adjuvants customary in formulation technology, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).
  • extenders for example solvents or solid carriers, or surface-active compounds (surfactants).
  • surfactants surface-active compounds
  • formulation adjuvants for example, solid carriers, solvents, stabilisers, "slow release” adjuvants, colorants and, where appropriate, surface-active substances (surfactants).
  • carriers and adjuvants there come into consideration all the substances customarily used, such as solvents, solid carriers, surface-active compounds, nonionic surfactants, cationic surfactants, anionic surfactants and further adjuvants known in the art.
  • solvents which are suitable are: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions C 8 to C 12 of alkylbenzenes, such as xylene mixtures, alkylated naphthalene or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols, such as ethanol, propanol or butanol, glycols and their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as unepoxidized or
  • Solid carriers which are used for example for dusts and dispersable powders are, as a rule, ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly- disperse silicas or highly-disperse absorptive polymers may also be used to improve the physical properties.
  • Suitable particulate, adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, and suitable non-absorptive carrier materials are calcite or sand.
  • a large number of granulated materials of inorganic or organic nature, in particular dolomite or comminuted plant residues may be used.
  • Suitable surface-active compounds are, depending on the nature of the active ingredient to be formulated, non-ionic, cationic and/or anionic surfactants or surfactant mixtures have good emulsifying, dispersing and wetting properties.
  • the surfactants listed below are only given by way of example; a large number of other surfactants conventionally used in the art of formulation and suitable according to the invention are described in the relevant literature.
  • Suitable non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or cyclo- liphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can have 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols. Also suitable are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylene diaminoolypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain and comprising 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups.
  • the abovementioned compounds conventionally have 1 to 5 ethylene glycol units per propylene glycol unit.
  • examples which may be mentioned are nonylphenol polyethoxyethanols, castor oil polyglycol ether, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxy- ethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • fatty acid esters or polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate.
  • the cationic surfactants are mainly quaternary ammonium salts which have, as substituents, at least one alkyl radical having 8 to 22 carbon atoms and as further substituents lower, halogenated or unhalogenated alkyl, benzyl or lower hydroxyalkyl radicals.
  • the salts are preferably in the form of halides, methylsulfates or ethylsulfates. Examples are stearyl-- trimethyl-ammonium chloride and benzyl di-(2-chloroethyl)ethylammonium bromide.
  • Suitable anionic surfactants can be water-soluble soaps and also water-soluble synthetic surface-active compounds.
  • Soaps which are suitable are the alkali metal salts, alkaline earth metal salts and substituted or unsubstituted ammonium salts of higher fatty acids (C 10 -C 22 ), such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut or tall oil; fatty acid methyl- tauhnates should furthermore be mentioned.
  • fatty sulfonates are, as a rule, in the form of alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts and have, as a rule, an alkyl radical of 8 to 22 carbon atoms, alkyl also including the alkyl moiety of acyl radicals, for example the sodium salt or calcium salt of lignosulfonic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids.
  • This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives comprise preferably 2 sulfonyl groups and a fatty acid radical having approximately 8-22 carbon atoms.
  • Alkylarylsulfonates are, for example, the sodium salts, calcium salts or triethanolammonium salts of dodecylbenzenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensate.
  • Suitable phosphates for example salts of the phosphoric ester of a p-nonylphenol/(4-14)-ethylene oxide adduct, or phospholipids, are also suitable.
  • compositions for use in crop protection and in humans, domestic animals, productive livestock and pets generally contain from 0.1 to 99 %, especially from 0.1 to 95 %, of active ingredient and from 1 to 99.9 %, especially from 5 to 99.9 %, of - at least - one solid or liquid adjuvant, it generally being possible for the compositions to contain from 0 to 25 %, especially from 0.1 to 20 %, surfactants (in each case percentages are by weight). Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations which have considerably lower active ingredient concentrations.
  • Preferred crop protection compositions have especially the following composition (throughout, percentages are by weight):
  • Emulsifiable concentrates active ingredient: from 1 to 90 %, preferably from 5 to 20 % surfactant: from 1 to 30 %, preferably from 10 to 20 % solvent: from 5 to 98 %, preferably from 70 to 85 %
  • Dusts active ingredient: from 0.1 to 10 %, preferably from 0.1 to 1 % solid carrier: from 99.9 to 90 %, preferably from 99.9 to 99 %
  • Suspension concentrates active ingredient: from 5 to 75 %, preferably from 10 to 50 % water: from 94 to 24 %, preferably from 88 to 30 % surfactant: from 1 to 40 %, preferably from 2 to 30 %
  • Wettable powders active ingredient: from 0.5 to 90 %, preferably from 1 to 80 % surfactant: from 0.5 to 20 %, preferably from 1 to 15 % solid carrier: from 5 to 99 %, preferably from 15 to 98 %
  • Granules active ingredient: from 0.5 to 30 %, preferably from 3 to 15 % solid carrier: from 99.5 to 70 %, preferably from 97 to 85 %
  • compositions according to the invention may also comprise further solid or liquid adjuvants, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilisers or other active ingredients for obtaining special effects, for example acaricides, bactericides, fungicides, nematicides, molluscicides or selective herbicides.
  • stabilisers e.g. vegetable oils or epoxidised vegetable oils (e.g. epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilisers or other active ingredients for obtaining special effects, for example acaricides, bactericide
  • the crop protection compositions according to the invention are prepared in known manner, in the absence of adjuvants, for example by grinding, sieving and/or compressing a solid active ingredient or mixture of active ingredients, for example to a specific particle size, and in the presence of at least one adjuvant, for example by intimately mixing and/or grinding the active ingredient or mixture of active ingredients with the adjuvant(s).
  • the invention relates also to those processes for the preparation of the compositions according to the invention and to the use of the compounds of formula (I) in the preparation of those compositions.
  • the invention relates also to the methods of application of the crop protection compositions, i.e. the methods of controlling pests of the mentioned type, such as spraying, atomising, dusting, coating, dressing, scattering and pouring, which are selected in accordance with the intended objectives and prevailing circumstances, and to the use of the compositions for controlling pests of the mentioned type.
  • Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient.
  • the rates of application per hectare are generally from 1 to 2000 g of active ingredient per hectare, especially from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.
  • a preferred method of application in the area of crop protection is application to the foliage of the plants (foliar application), the number of applications and the rate of application depending on the risk of infestation by the pest in question.
  • the active ingredient can also penetrate the plants through the roots (systemic action) if the locus of the plants is impregnated with a liquid formulation or if the active ingredient is incorporated in solid form, e.g. in granular form, into the locus of the plants, for example into the soil (soil application).
  • granules may be applied in metered amounts to the flooded rice field.
  • the crop protection compositions according to the invention are also suitable for protecting plant propagation material, e.g. seed material, such as fruit, tubers or grains, or plant cuttings, against animal pests.
  • the propagation material can be treated with the formulation before planting: seed, for example, can be dressed before being sown.
  • the compounds of the invention can also be applied to grains (coating), either by impregnating the grains with a liquid formulation or by coating them with a solid formulation.
  • the formulation can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing.
  • the invention relates also to those methods of treating plant propagation material and to the plant propagation material thus treated.
  • Variant 1 5 g of 3-(2,6-difluorophenyl)-6-(4'-trifluoromethoxybiphenyl-4-yl)- ⁇ 1 ,2,4 ⁇ triazine are mixed into 100 ml of tetrahydrofuran and 1 g of Pd/C (5 % by weight of Pd). 300 ml of hydrogen are introduced over a period of 90 minutes with stirring at room temperature. The catalyst is removed by filtration, the filtrate is concentrated by evaporation and the residue is purified with ethyl acetate : hexane (volumetric ratio 1 : 1) on silica gel. The title compound having a melting point of 208-209°C is obtained.
  • Variant 2 85.6 g of 3-(2,6-difluorophenyl)-6-(4'-trifluoromethoxybiphenyl-4-yl)- ⁇ 1 ,2,4 ⁇ triazine are introduced into 3 litres of absolute tetrahydrofuran. 4 g of sodium borohydride are then added. 300 ml of absolute methanol are added dropwise within a period of 30 minutes, the temperature of the reaction mixture rising to 31 °C. Stirring is carried out at room temperature for 90 minutes and then the reaction mixture is concentrated by evaporation.
  • 0.14 g of pyridine is added to 0.7 g of 3-(2,6-difluorophenyl)-6-(4'-trifluoromethoxybiphenyl-4- yl)-5H- ⁇ 1 ,2,4 ⁇ triazine in 15 ml of toluene, and 0.13 g of acetyl chloride is added dropwise with stirring at room temperature. Stirring is carried out for 2 hours, and then a further 0.14 g of pyridine and 0.13 g of acetyl chloride are added and the mixture is stirred for a further 14 hours.
  • Example P5 Preparation of 1-r3-(2.6-difluorophenyl)-6-(4'-trifluoromethoxybiphenyl-4-yl)-5H- (1 ,2.4)triazin-4-yll-2- ethyl-1hexanone
  • Example P6 Preparation of H3-(2-chloro-4-fluorophenvO-6-(4 rifluoromethoxybiphenyl-4- yl)-5H-(1.2.4)triazin-2-vn-ethanone
  • Example P8 The other compounds of formula (I) can also be prepared in a manner analogous to Examples P1 to P7.
  • Table 1 Compounds of the general formula (lb) wherein R 3 is H and the combination of the substituents X ⁇ X 2 , X 3 , R 2 and R b for each compound corresponds to a line A.1 to A.322 of Table A.
  • Table 2 Compounds of the general formula (lb) wherein R 3 is -CH 3 and the combination of the substituents X ⁇ X 2 , X 3 , R 2 and R b for each compound corresponds to a line A.1 to A.322 of Table A.
  • Table 3 Compounds of the general formula (lb) wherein R 3 is -C 2 H 5 and the combination of the substituents X 1 ; X 2 , X 3 , R 2 and R b for each compound corresponds to a line A.1 to A.322 of Table A.
  • Table 4 Compounds of the general formula (lb) wherein R 3 is -CH 2 OCH 3 and the combination of the substituents X ⁇ X 2 , X 3 , R 2 and R for each compound corresponds to a line A.1 to A.322 of Table A.
  • Table 5 Compounds of the general formula (lb) wherein R 3 is -CH 2 OCH 2 CH 3 and the combination of the substituents X-,, X 2 , X 3 , R 2 and R b for each compound corresponds to a line A.1 to A.322 of Table A.
  • Table 13 Compounds of the general formula (lb) wherein R 3 is -CH 2 C ⁇ CH and the combination of the substituents X 1 ; X 2 , X 3 , R 2 and R for each compound corresponds to a line A.1 to A.322 of Table A.
  • Table 16 Compounds of the general formula (lb) wherein R 3 is -CH 2 -C 6 H 4 -4-CF 3 and the combination of the substituents X ⁇ X 2 , X 3 , R 2 and R b for each compound corresponds to a line A.1 to A.322 of Table A.
  • Table 21 Compounds of the general formula (Ic) wherein R 3 is H and the combination of the substituents Xi, X 2 , X 3 , R 2 and R b for each compound corresponds to a line A.1 to A.322 of Table A.
  • Table 22 Compounds of the general formula (Ic) wherein R 3 is -CH 3 and the combination of the substituents Xi, X 2 , X 3 , R 2 and R b for each compound corresponds to a line A.1 to A.322 of Table A.
  • Table 23 Compounds of the general formula (Ic) wherein R 3 is -C 2 H 5 and the combination of the substituents Xi, X 2 , X 3 , R 2 and R b for each compound corresponds to a line A.1 to A.322 of Table A.
  • Table 24 Compounds of the general formula (Ic) wherein R 3 is -CH 2 OCH 3 and the combination of the substituents Xi, X 2 , X 3 , R 2 and R for each compound corresponds to a line A.1 to A.322 of Table A.
  • Table 25 Compounds of the general formula (Ic) wherein R 3 is -CH 2 OCH 2 CH 3 and the combination of the substituents Xi, X 2 , X3, R 2 and R b for each compound corresponds to a line A.1 to A.322 of Table A.
  • Table 33 Compounds of the general formula (Ic) wherein R 3 is -CH 2 C ⁇ CH and the combination of the substituents Xi, X 2 , X 3 , R 2 and R b for each compound corresponds to a line A.1 to A.322 of Table A.
  • Table 36 Compounds of the general formula (Ic) wherein R 3 is -CH 2 -C 6 H 4 -4-CF 3 and the combination of the substituents Xi, X 2 , X 3 , R 2 and R b for each compound corresponds to a line A.1 to A.322 of Table A.
  • Example F1 Emulsifiable concentrates a) b) c) active ingredient 25% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol ether (36 mol EO) 5% - - tributylphenol polyethylene glycol ether (30 mol EO) - 12% 4% cyclohexanone - 15% 20% xylene mixture 65% 25% 20%
  • the finely ground active ingredient and adjuvants are mixed to give an emulsifiable concentrate which yields emulsions of any desired concentration when diluted with water.
  • Example F2 Solutions a) b) c) d) active ingredient 80% 10% 5% 95% ethylene glycol monomethyl ether 20% - - - polyethylene glycol (MW 400) - 70% - -
  • N-methylpyrrolid-2-one 20% - - epoxidised coconut oil - - 1 % 5% petrol ether (boiling range: 160-190°) - - 94% -
  • the finely ground active ingredient and adjuvants are mixed to yield a solution suitable for use in the form of microdrops.
  • Example F3 Granules a) b) c) d) active ingredient 5% 10% 8% 21% kaolin 94% - 79% 54% highly dispersed silicic acid 1 % - 13% 7% attapulgite - 90% - 18%
  • the active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier mixture and the solvent is removed by evaporation in vacuo.
  • Example F4 Wettable powders a) b) c) active ingredient 25% 50% 75% sodium lignosulfonate 5% 5% - sodium lauryl sulfate 3% - 5% sodium diisobutylnaphthalenesulfonate - 6% 10% octylphenol polyethylene glycol ether (7-8 mol EO) - 2% - highly dispersed silicic acid 5% 10% 10% kaolin 62% 27% -
  • the active ingredient and adjuvants are mixed and the mixture is ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.
  • Example F5 Emulsifiable concentrate active ingredient 10% octylphenol polyethylene glycol ether (4-5 mol EO) 3% calcium dodecylbenzenesulfonate 3% castor oil polyethylene glycol ether (36 mol EO) 4% cyclohexanone 30% xylene mixture 50%
  • the finely ground active ingredient and the adjuvants are mixed to yield an emulsifiable concentrate which gives emulsions of any desired concentration when diluted with water.
  • Example F6 Extruder granules active ingredient 10% sodium lignosulfonate 2% carboxymethylcellulose 1 % kaolin 87%
  • Example F7 Coated granules active ingredient 3% polyethylene glycol (MW 200) 3% kaolin 94%
  • the finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol to yield non-dusty coated granules.
  • Example F8 Suspension concentrate active ingredient 40% ethylene glycol 10% nonylphenol polyethylene glycol ether (15 mol EO) 6% sodium lignosulfonate 10% carboxymethylcellulose 1 % aqueous formaldehyde solution (37 %) 0.2% aqueous silicone oil emulsion (75 %) 0.8% water 32%
  • the finely ground active ingredient and adjuvants are mixed, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
  • Example B1 Action against Aphis craccivora
  • Pea seedlings are infested with Aphis craccivora, subsequently sprayed with a spray mixture comprising 100 ppm of active ingredient and then incubated at 20°C. 3 and 6 days later the percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants.
  • Maize seedlings are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of active ingredient. After the spray-coating has dried, the maize seedlings are populated with 10 Diabrotica balteata larvae in the second stage and then placed in a plastics container. 6 days later, the percentage reduction in population (% activity) is determined by comparing the number of dead larvae on the treated plants with that on untreated plants.
  • Example B3 Action against Heliothis virescens
  • Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of active ingredient. After the spray-coating has dried, the plants are populated with 10 caterpillars of Heliothis virescens in the first stage and then placed in a plastics container. 6 days later, the percentage reduction in population and in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
  • Example B4 Action against Spodoptera littoralis
  • Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of active ingredient. After the spray-coating has dried, the plants are populated with 10 caterpillars of Spodoptera littoralis in the third stage and then placed in a plastics container. 3 days later, the percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
  • Example B5 Action against Nilaparvata lugens
  • Rice plants are treated with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After the spray-coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stages. The evaluation is carried out 21 days later. The percentage reduction in population (% activity) is determined by comparing the number of surviving cicadas on the treated plants with that on untreated plants. Compounds of the Tables exhibit good activity in this test. For example, compounds B.12 and B.18, in particular, exhibit a reduction in the pest population of more than 80 %.
  • Example B6 Action against Tetranychus urticae
  • Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed one day later with an aqueous emulsion spray mixture comprising 100 ppm of active ingredient. The plants are then incubated for 6 days at 25°C and subsequently evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on untreated plants.
  • the compounds of the Tables exhibit good activity in this test.
  • compounds B.11 , B.12, B.13 and B.18 in particular, exhibit a reduction in the pest population of more than 80 %.

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Abstract

L'invention concerne un composé de formule (I) dans laquelle x1 désigne R8 ; X2 et X3 désignent indépendamment l'un de l'autre H ou R8 ; R1 est aryle ou hétéroaryle non substitué ou substitué, les substituants ayant été sélectionnés par exemple dans le groupe comprenant : OH, halogène, CN, NO2, alkyle C1-C12, cycloalkyle C3-C8, alkyle C1-C6-cycloalkyle C3-C8, cycloalkyle C3-C8-alkyle C1-C6 et alkyle halogéné C1-C12 ; R2 désigne par exemple H, OH, halogène, CN, NO2, alkyle C1-C12 ou alcoxy C1-C12 ; R3a et R3b désignent R3 ;R3 désigne (C=Y)n-W-R9 ; et soit R3a désigne R3 ; et R3b et R forment conjointement une liaison ; soit R3b désigne R3 ; et R3a et R forment conjointement une liaison ; R4 désigne alkyle C1-C4 ou cycloalkyle C3-C6 ;R5 désigne par exemple H, alkyle C1-C12 ou cycloalkyle C3-C8 ; R6 désigne par exemple H,alkyle C1-C12 ou cycloalkyle C3-C8 ; R7 désigne par exemple H ou alkyle C1-C12 ; R8 désigne par exemple halogène, CN, NO2 ou alkyle C1-C12 ; R9 désigne par exemple H, OH, halogène ou CN ; Le groupe A- désigne par exemple une liaison directe ou alkylène C1-C12 ; W désigne une liaison directe, -O-, -S-, -SO-, -SO2-, -SO2-NH-, -NH- ou N(alkyle C1-C4) ; Y désigne O ou S ; Z désigne O ou S ; n vaut 0,1, ou 2 ; p vaut 0,1,2,3,4,5 ou 6 ; et q vaut 0,1 ou 2 ; et, quand c'est approprié, ses tautomères potentiels, dans chaque cas sous forme libre ou sous forme de sel. L'invention concerne un procédé pour préparer ces composés et leurs tautomères et leur utilisation ; des compositions pesticides, dont le principe actif est sélectionné dans ces composés et leurs tautomères. L'invention concerne également un procédé de préparation de compositions de ce type et leur utilisation, et des intermédiaires, sous forme libre ou sous forme de sel, dans la préparation de ces composés et, quand c'est approprié, leurs tautomères, sous forme libre ou sous forme de sel.
PCT/EP2001/008193 2000-07-18 2001-07-16 Dihydrotriazines asymetriques utilisees comme pesticides WO2002006252A1 (fr)

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WO2006132015A1 (fr) * 2005-06-09 2006-12-14 Adeka Corporation Nouveau composé et composition à cristaux liquides

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Publication number Priority date Publication date Assignee Title
DE4011740A1 (de) * 1989-04-14 1990-10-18 Ciba Geigy Ag 1,2,4-triazinonderivate

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
DE4011740A1 (de) * 1989-04-14 1990-10-18 Ciba Geigy Ag 1,2,4-triazinonderivate

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006132015A1 (fr) * 2005-06-09 2006-12-14 Adeka Corporation Nouveau composé et composition à cristaux liquides
GB2441918A (en) * 2005-06-09 2008-03-19 Adeka Corp Novel compound and liquid-crystal composition
GB2441918B (en) * 2005-06-09 2010-06-16 Adeka Corp Chemical compounds and liquid-crystal compositions comprising the compounds
US7785675B2 (en) 2005-06-09 2010-08-31 Adeka Corporation Compound and liquid crystal composition
CN101193846B (zh) * 2005-06-09 2012-05-30 株式会社艾迪科 新型化合物和液晶组合物

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