WO2001014373A1 - Derivatives of trifluoromethylpyri(mi)dine - Google Patents

Derivatives of trifluoromethylpyri(mi)dine Download PDF

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Publication number
WO2001014373A1
WO2001014373A1 PCT/EP2000/008082 EP0008082W WO0114373A1 WO 2001014373 A1 WO2001014373 A1 WO 2001014373A1 EP 0008082 W EP0008082 W EP 0008082W WO 0114373 A1 WO0114373 A1 WO 0114373A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
halogen
cycloalkyl
alkoxy
formula
Prior art date
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PCT/EP2000/008082
Other languages
French (fr)
Inventor
Saleem Farooq
Peter Maienfisch
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Syngenta Participations Ag
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Filing date
Publication date
Application filed by Syngenta Participations Ag filed Critical Syngenta Participations Ag
Priority to JP2001518704A priority Critical patent/JP2003507477A/en
Priority to EP00960488A priority patent/EP1204661A1/en
Priority to KR1020027002158A priority patent/KR20020022817A/en
Priority to BR0013438-4A priority patent/BR0013438A/en
Priority to AU72777/00A priority patent/AU767519B2/en
Publication of WO2001014373A1 publication Critical patent/WO2001014373A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/88—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the object of the present invention is a compound of formula
  • Z signifies six- or seven-membered, optionally substituted, aromatic or non- aromatic heterocyclyl
  • X is CH or N
  • Y is halogen
  • n is 1 , 2 or 3
  • m is O or l
  • the E/Z isomers, E/Z isomeric mixtures and/or tautomers thereof, each in free form or in salt form a method of producing and the use of these compounds, pesticides whose active ingredient is selected from these compounds or from an agrochemically acceptable salt thereof, a method of producing and the use of these compositions, plant propagating material that has been treated with these compositions and a method of controlling pests.
  • the compounds of formula (I) and where appropriate their tautomers can form salts, for example acid addition salts. These are formed for example with strong inorganic acids, typically mineral acids, e.g. sulphuric acid, a phosphoric acid or a hydrohalic acid, or with strong organic carboxylic acids, typically acids substituted where appropriate for example by halogen, e.g. acetic acid, such as optionally unsaturated dicarboxylic acids, e.g. oxalic, malonic, maleic, fumaric or phthalic acid, such as hydroxycarboxylic acids, e.g.
  • strong inorganic acids typically mineral acids, e.g. sulphuric acid, a phosphoric acid or a hydrohalic acid
  • strong organic carboxylic acids typically acids substituted where appropriate for example by halogen, e.g. acetic acid, such as optionally unsaturated dicarboxylic acids, e.g. oxalic, malonic, maleic,
  • compounds of formula (I) with at least one acid group can form salts with bases.
  • Suitable salts with bases are for example metal salts, such as alkali 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. ethyl, diethyl, triethyl or dimethylpropylamine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. mono-, di- or triethanolamine.
  • Corresponding internal salts where appropriate may also be formed. The free form is preferred. Of the salts of compounds of formula (I), the agrochemically beneficial salts are preferred.
  • Halogen - as a group perse or as structural element of other groups and compounds such as haloalkyl, halocycloalkyl, haloalkenyl, haloalkinyl and haloalkoxy - is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, mainly fluorine or chlorine, especially chlorine.
  • carbon-containing groups and compounds each contain 1 to 20, inclusively, preferably 1 to 18, in particular 1 to 10, especially 1 to 6, in particular 1 to 4, especially 1 to 3, particularly 1 or 2, carbon atoms, with methyl being preferred in particular.
  • Alkyl - as a group per se and as structural element of other groups and compounds such as haloalkyl, alkoxy, alkoxyalkyl, haloalkoxy, alkoxycarbonyl, alkylthio, haloalkylthio, alkylsulphonyl and alkylsulphonyloxy is, in each case with due consideration of the specific number of carbon atoms in the group or compound in question, either straight-chained, e.g.
  • Alkenyl and alkinyl - as groups per se and as structural elements of other groups and compounds, such as of haloalkenyl, haloalkinyl, alkenyloxy, haloalkenyloxy, alkinyloxy or haloalkinyloxy - are straight-chained or branched and respectively contain two or preferably one unsaturated carbon-carbon bond(s).
  • Vinyl, prop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2- en-1-yl, but-3-en-1-yl, prop-2-in-1-yl, but-2-in-1-yl and but-3-in-1-yl may be mentioned by way of example.
  • Cycloalkyl - as a group per se and as a structural element of other groups and compounds, for example of alkyl - is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Cyclopentyl and cyclohexyl are preferred, in particular cyclopropyl.
  • Halogen-substituted carbon-containing groups and compounds can be partially halogenated or perhalogenated, in the case of polyhalogenation it being possible for the halogen substituents to be identical or different.
  • haloalkyl - as a group perse and as structural element of other groups and compounds such as haloalkoxy, - are methyl which is mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHF , CF 3 or CH 2 CI; ethyl which is mono- to pentasubstituted by fluorine, chlorine and/or 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 , CH 2 CH 2 CI, CF 2 CHBr 2 , CF 2 CHCIF, CF 2 CHBrF oder CCIFCHCIF; propyl or isopropyl, mono- to heptasubstituted by fluorine, chlorine and/or bromine, such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 , CH 2 CF 2 CF
  • di-(C 1 -C -alkyl)amine the two alkyl groups are independent of each other.
  • Aryl signifies especially phenyl or naphthyl, preferably phenyl.
  • Heterocyclyl signifies a 6- or 7-membered, saturated or unsaturated ring which is bonded to the basic structure by a carbon atom, the ring having preferably two to four hetero atoms selected from the group comprising N, O and S. Preference is given to 6-rings having a nitrogen atom as the hetero atom and two further hetero atoms, preferably nitrogen or oxygen, especially one oxygen and one nitrogen.
  • the heterocyclyl radicals may bear one to three, preferably one, substituent selected from the group comprising C ⁇ -C 6 -alkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -alkinyl; halogen, nitro, cyano, -OH, -SH, C 3 -C 8 -cycloalkyl, halogen-C 3 -C 8 -cycloalkyl, C C 6 -alkoxy, halogen-d-C 6 -alkoxy, C 3 -C 6 - alkenyloxy, C ⁇ -C 4 -alkylthio and di-(C 1 -C -alkyl)amine.
  • substituent selected from the group comprising C ⁇ -C 6 -alkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -alkinyl; halogen, nitro, cyano, -OH, -SH, C 3 -C 8 -cycl
  • Preferred embodiments in terms of the invention are compounds of formula (I) a) wherein Z signifies a ring of formula
  • bonds U-A, A-M, M-D, D-E, E-G and G-U are single or double bonds, with the provision that no accumulated double bonds occur
  • Ri, R 2 , R 7 and R 10 independently of one another, signify hydrogen, d-C 20 -alkyl, C 3 -C 8 - cycloalkyl, C 2 -C 20 -alkenyl or C 3 -C 20 -alkinyl; or mono- or poly-substituted d-C 2 o-alkyl,
  • C 2 -C 20 -alkenyl or C 3 -C 20 -alkinyl aryl which is optionally substituted by one or more substituents selected from the group comprising d-C- 6 -alkyl, halogen-d-C 6 -alkyl, C 2 -C 6 -alkenyI, C 3 -C 6 -alkinyl, halogen, C C 6 - alkoxy, halogen-d-Ce-alkoxy, nitro, cyano, C 3 -C 8 -cycloaIkyl, halogen-C 3 -C 8 -cycloalkyl,
  • Rn signifies hydrogen, OH, SH, d-C 6 -alkyl, C 3 -C 8 -cycloalkyl, d-C 6 -alkoxy, d-C 6 -alkylthio,
  • C 3 -C 6 -alkinyl or C 3 -C 6 -alkinyloxy which are substituted by one or more substituents selected from the group comprising halogen, nitro, cyano, -OH, -SH, C 3 -C 8 -cycloalkyl, halogen-C 3 -C 8 -cycloalkyl and di-(d-C 4 -alkyl)amine; or aryl, heterocyclyl, aryloxy, benzyloxy or heterocyclyloxy, which are substituted by one to three substituents selected from the group comprising halogen, nitro, cyano, -OH, -SH,
  • Z preferably has the following definitions, whereby Ri, R 2 , R 22 and R 7 are defined as described above:
  • a further object of the invention is a process for the production of the compounds of formula (la), or a salt thereof, wherein a) a compound of formula
  • a compound of formula (la), in which m is 1 , a compound of formula (I) in which m is 0 is reacted with an oxidation agent, for example inorganic peroxides, such as sodium perborate, potassium permanganate or hydrogen peroxide; or with mCPBA or organic per acids, such as perbenzoic acid or peracetic acid, or mixtures of organic acids and hydrogen peroxide, e.g. acetic acid/hydrogen peroxide;
  • an oxidation agent for example inorganic peroxides, such as sodium perborate, potassium permanganate or hydrogen peroxide; or with mCPBA or organic per acids, such as perbenzoic acid or peracetic acid, or mixtures of organic acids and hydrogen peroxide, e.g. acetic acid/hydrogen peroxide;
  • a compound of formula (I) obtainable according to the method or by other means, present in free form or in the form of a salt, is converted into a different compound of formula (I)
  • a mixture of isomers obtainable according to the method is separated and the desired isomer is isolated and/or a free compound of formula (I) obtainable according to the method or by other means is converted into a salt, or a salt of a compound of formula (I) obtainable according to the method or by other means is converted into the free compound of formula (I) or into a different salt.
  • the starting materials of formulae (II) and (III), listed hereinbefore and hereinafter, which are used to produce the compounds of formula (I), in free form or in salt form, are known or may be produced by methods known per se.
  • the starting materials of formula (IV) are novel and therefore similarly form an object of the invention.
  • the reactions described hereinbefore and hereinafter are carried out in a known manner, e.g. in the absence or, where appropriate, in the presence of a suitable solvent or diluent or a mixture thereof, proceeding as required under conditions of cooling, of ambient temperature, or of heating, e.g.
  • reaction medium in a temperature range of about -80°C to the boiling temperature of the reaction medium, preferably about -20°C to about +150°C, and where appropriate in a closed vessel, under pressure, in an inert gas atmosphere, and/or under non-aqueous conditions.
  • a temperature range of about -80°C to the boiling temperature of the reaction medium preferably about -20°C to about +150°C
  • a closed vessel under pressure, in an inert gas atmosphere, and/or under non-aqueous conditions.
  • non-aqueous conditions are described in the Examples.
  • reaction of process a) is effected in the presence of an acid, for example HCI, sulphuric acid or phosphoric acid.
  • an acid for example HCI, sulphuric acid or phosphoric acid.
  • the reaction is generally carried out at temperatures of -30°C to +70°C, preferably from -10°C to +50°C.
  • the process is conveniently carried out in the presence of an inert solvent or solvent mixture.
  • suitable solvents for this purpose are for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, ethylene tetrachloride; ethers and ether-like compounds, such as dialkyl ether (diethyl ether, diisopropyl ether, tert.-butylmethyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile; esters such as ethyl acetate (acetic
  • the reaction is carried out at atmospheric pressure, although it may also be carried out at elevated or reduced pressure.
  • the reaction is advantageously carried out in the presence of an inert solvent or solvent mixture at temperatures of -30°C to +70°C, preferably -10°C to +50°C. It is preferably carried out in the presence of a base, for example in the presence of an organic amine such as a trialkylamine (trimethylamine, triethylamine, triisopropylamine or diisopropylethylamine), a pyridine (pyridine itself, 4-dimethylaminopyridine or 4-pyrrolidino- pyridine), a morpholine (N-methylmorpholine) or a N,N-dialkylaniline (N,N-dimethylaniline or N-methyl-N-ethylaniline).
  • an organic amine such as a trialkylamine (trimethylamine, triethylamine, triisopropylamine or diisopropylethylamine), a pyridine (pyridine itself, 4-dimethylaminopyridine or 4-
  • Suitable solvents for this purpose are for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, ethylene tetrachloride; ethers such as dialkyl ether (diethyl ether, diisopropyl ether, tert.-butylmethyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile; esters such as ethyl acetate (acetic acid ethyl ester), propyl acetate or butyl acetate; and mixtures of such solvents with one another.
  • aliphatic and aromatic hydrocarbons such as benzene, toluene, xy
  • the reactions are expediently carried out in the presence of an inert solvent or solvent mixture at temperatures of -40°C to +120°C, preferably -20°C to +80°C.
  • the solvents in question may be the same as those mentioned for variant b).
  • a base for example alkali or alkaline earth metal hydroxides or for example alkali or alkaline earth metal carbonates or hydrogen carbonates, pyridine, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, lutidine, collidine, trialkylamine, N,N- dialkylaniline, or a bicyclic, non-nucleophilic base such as 1 ,4-diazabicyclo[2.2.2]octane (DABCO), 1 ,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1 ,8-diazabicyclo[5.4.0]undec-7-ene (1 ,5-5) (DBU).
  • DABCO 1 ,4-diazabicyclo[2.2.2]octane
  • DBN 1 ,5-diazabicyclo[4.3.0]non-5-ene
  • DBU 1 ,8-diazabicyclo[5.4.0]und
  • Salts of compounds of formula (I) may be prepared in a known manner. For example, it is possible to obtain salts of compounds of formula (I) with bases, by treating the free compounds with an appropriate base or with an appropriate ion exchanger reagent.
  • Salts of compounds of formula (I) may be converted in conventional manner into the free compounds of formula (I), e.g. by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) may be transformed in known manner into other salts of a compound of formula (I).
  • the compounds of formula (I) in free form or in salt form may exist in the form of one of the possible isomers or as a mixture thereof, e.g. depending on the number, the absolute and relative configuration of asymmetric carbon atoms appearing in the molecule and/or depending on the configuration of non-aromatic double bonds appearing in the molecule, as pure isomers such as antipodes and/or diastereoisomers, or as isomer mixtures such as enantiomer mixtures, e.g. racemates, diastereoisomer mixtures or racemate mixtures.
  • the invention relates both to the pure isomers and to all the possible mixtures of isomers, and hereinbefore and hereinafter is to be understood as such accordingly, even if the stereo- chemical details are not specifically mentioned in each case.
  • diastereoisomer mixtures, racemate mixtures and mixtures of double bond isomers of compounds of formula (I) in free form or in salt form which are obtainable by the process or in another way, may be separated in known manner, on the basis of the physical-chemical differences in their components, into the pure diastereoisomers or racemates, for example by fractiional crystallisation, distillation and/or chromatography.
  • Enantiomer mixtures that are obtainable correspondingly, such as racemates may be broken down by known methods into the optical antipodes, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, e.g. high pressure liquid chromatography on acetyl cellulose, with the assistance of suitable microorganisms, by cleavage with specific, immobilised enzymes, through the formation of inclusion compounds, e.g. using chiral crown ethers, whereby only one enantiomer is complexed, or by converting into diastereoisomeric salts and separating the diastereoisomer mixture obtained in this way, e.g. on the basis of their different solubilities, by fractional crystallisation, into the diastereoisomers, from which the desired enantiomer can be released upon the action of suitable agents.
  • chiral adsorbents e.g. high pressure liquid chromatography on acetyl
  • the invention relates to all those forms of the method, according to which one starts from a compound obtainable as a primary material or an intermediate at any stage of the method and carries out all or some of the missing steps, or uses, or - especially under the reaction conditions - produces a starting material in the form of a derivative or a salt and/or its racemate or antipodes.
  • the starting materials and intermediates used are preferably those that lead to the compounds of formula (I) or salts thereof described at the beginning as being especially useful.
  • the invention relates especially to the method of preparation described in Example P1.
  • the compounds of formula (I) according to the invention are active ingredients of preventive and/or curative merit for use in pest control and offer a very favourable spectrum of biocidal activity with favourable tolerability in warm-blooded animals, fish, and plants even at low concentrations.
  • the active ingredients according to the invention are active against all or individual development stages of animal pests showing normal sensitivity, as well as those showing resistance, such as insects or members of the order Acarina.
  • the insecticidal or acaricidal effect of the active substances of the invention can manifest itself directly, i.e. killing the pests either immediately or after some time has elapsed, for example when moulting occurs, or indirectly, e.g. reducing the number of eggs laid and/or the hatching rate, good efficacy corresponding to a pesticidal rate (mortality) of at least 50 to 60%.
  • the said animal pests include, for example, those which are mentioned in the European Patent application EP-A-736'252, page 2, line 55 to page 6, line 55.
  • the pests mentioned therein are thus included by reference in the object of the present invention.
  • the compounds according to the invention are also active against pests from the class of the nematodes, for example, of the families Filariidae and Setariidae and the genera Haemonchus, Tricho- strongylus, Ostertagia, Nematodirus, Cooperia, Ascaris, Bunostumum, Oesophagostonum, Chabertia, Trichuris, especially Trichuris vulpis, Strongylus, Trichonema, Dictyocaulus, Capillaria, Strongyloides, Heterakis, Toxocara, especially Toxocara canis, Ascaridia, Oxyuris, Ancylostoma, especially Ancylostoma caninum, Uncinaria, Toxascar
  • the active ingredients according to the invention are especially suitable for controlling sucking insects, especially of the order Homoptera, preferably for controlling these pests in vegetable, fruit, rice and cotton crops.
  • sucking insects especially of the order Homoptera
  • One particular advantage of the compounds according to the invention is their systemic action.
  • Pests of said type which occur on plants, especially on crops and ornamentals in agriculture, horticulture and forestry, or on parts of such plants, such as fruits, blooms, leaves, stems, tubers or roots, can be controlled, i.e. kept in check or eradicated, using the active ingredients of the invention, this protection remaining for parts of some plants whose growth does not occur until later.
  • Target crops include especially cereals, such as wheat, barley, rye, oats, rice, corn or sorghum; beet, such as sugar beet or fodder beet; fruit, e.g. pomes, drupes and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, e.g.
  • strawberries, raspberries or blackberries leguminous plants, such as beans, lentils, peas or soybean; oleaginous fruits, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants, such as squashes, cucumbers or melons; fibrous plants, such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruit or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or paprika; lauraceae, such as avocado, cinnamon or camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, banana plants, natural rubber plants and ornamentals.
  • oleaginous fruits such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts
  • cucumber plants such as squashes, cucumbers or melons
  • fibrous plants such as cotton
  • the invention therefore relates also to pesticides, such as emulsifiable concentrates, suspension concentrates, ready-to-spray or ready-to-dilute solutions, coatable pastes, dilute emulsions, spray powders, soluble powders, dispersible powders, wettable powders, dusts, granulates or encapsulations in polymeric substances, chosen in accordance with the intended objectives and prevailing circumstances, and comprising at least one active ingredient of the invention.
  • pesticides such as emulsifiable concentrates, suspension concentrates, ready-to-spray or ready-to-dilute solutions, coatable pastes, dilute emulsions, spray powders, soluble powders, dispersible powders, wettable powders, dusts, granulates or encapsulations in polymeric substances, chosen in accordance with the intended objectives and prevailing circumstances, and comprising at least one active ingredient of the invention.
  • the active ingredient is used in these compositions in pure form, a solid active ingredient e.g. in a specific particle size, or preferably together with at least one of the adjuvants conventionally employed in the art of formulation, such as extenders, e.g. solvents or solid carriers, or surface-active compounds (surfactants).
  • adjuvants conventionally employed in the art of formulation, such as extenders, e.g. solvents or solid carriers, or surface-active compounds (surfactants).
  • the adjuvants which can be used for formulation are, for example, solid carriers, solvents, stabilisers, "slow-release” agents, dyes, and where appropriate surfactants.
  • Carriers and adjuvants can be any substance conventionally used in crop protection agents, especially agents for slug and snail control.
  • Adjuvants such as solvents, solid carriers, surface-active agents, non-ionic surfactants, cationic surfactants, anionic surfactants, and other adjuvants in the compositions of the invention can, for example, be the same as those described in EP- A-736'252 , and are included by reference in the object of the present invention.
  • the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of active ingredient and 1 to 99.9%, especially 5 to 99.9%, of at least one solid or liquid adjuvant, it being possible as a rule for 0 to 25%, especially 0.1 to 20%, of the composition to be surfactants (% in each case meaning percent by weight).
  • surfactants % in each case meaning percent by weight.
  • Emulsifiable concentrates active ingredient: 1 to 95%, preferably 5 to 20% surfactant: 1 to 30%, preferably 10 to 20 % solvent: 5 to 98%, preferably 70 to 85%
  • Dusts active ingredient: 0.1 to 10%, preferably 0.1 to 1% solid carrier: 99.9 to 90%, preferably 99.9 to 99%
  • Suspension concentrates active ingredient: 5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30%
  • Wettable powders active ingredient: 0.5 to 90%, preferably 1 to 80% surfactant: 0.5 to 20%, preferably 1 to 15% solid carrier: 5 to 99%, preferably 15 to 98%
  • Granulates active ingredient: 0.5 to 30%, preferably 3 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%
  • compositions of the invention can be substantially broadened and adapted to prevailing circumstances by adding other insecticidal substances.
  • Additional active ingredients are, for example, substances from the following classes: organic phosphorus compounds, nitrophenols and their derivatives, formamidines, acylureas, carbamates, pyre- throids, neonicotinoides and their derivatives, pyrroles, thioureas and their derivatives, chlorinated hydrocarbons and Bacillus thuringiensis preparations.
  • azamethiphos chlorfenvinphos; cypermethrin, cypermethrin high- cis; cyromazin; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; iodofenphos; kinoprene; lufenuron; methacriphos; methi- dathion; monocrotophos; phosphamidon; profenofos; diofenolan; a substance obtainable from the Bacillus thuringiensis strain GC91 or from NCTC11821; pymetrozine; bromo- propylate; methoprene; disulfuton; quinalphos; tau-fluvalinate; thiocyclam; thiometon; aldicarb; azinphos-methyl
  • compositions of the invention can also contain further solid or liquid adjuvants, such as stabilisers, e.g. vegetable oils, epoxidized where appropriate (e.g. epoxidized coconut oil, rapeseed oil or soya oil), antifoaming agents, e.g. silicone oil, preservatives, viscosity modulators, binders and/or tackifiers, as well as fertilisers or other active ingredients to achieve specific effects, e.g. acaricides, bactericides, fungicides, nematocides, molluscicides or selective herbicides.
  • stabilisers e.g. vegetable oils, epoxidized where appropriate (e.g. epoxidized coconut oil, rapeseed oil or soya oil), antifoaming agents, e.g. silicone oil, preservatives, viscosity modulators, binders and/or tackifiers, as well as fertilisers or other active ingredients to achieve specific
  • compositions of the invention are prepared in a known manner, in the absence of adjuvants, for example, by grinding, sieving, and/or compressing a solid active ingredient or active ingredient mixture, e.g. 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 the mixture of active ingredients with the adjuvant(s).
  • adjuvants for example, by grinding, sieving, and/or compressing a solid active ingredient or active ingredient mixture, e.g. to a specific particle size
  • at least one adjuvant for example, by intimately mixing and/or grinding the active ingredient or the mixture of active ingredients with the adjuvant(s).
  • Typical concentrations of active ingredient are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm.
  • the rates of application are generally 1 to 2000 g of active ingredient per hectare, especially 10 to 1000 g/ha, and preferably 20 to 600 g/ha.
  • a preferred method of application for crop protection is to apply the active ingredient to the foliage of the plants (leaf application), the number of applications and the rate of application depending on the intensity of infestation by the pest in question.
  • the active ingredients can also penetrate the plant through the roots (systemic action) by impregnating the locus of the plant with a liquid composition, or by applying the active ingredient in solid form to the locus of the plants, e.g. the soil, for example in granular form (soil application). With paddy rice cultures, granules may be metered into the flooded paddy field.
  • compositions of the invention are also suitable for protecting plant propagation material, including genetically modified propagation material, e.g. seeds, such as fruits, tubers or grains, or plant seedlings, from animal pests.
  • the propagation material can be treated with the composition before the start of cultivation, seeds for example being dressed before they are sown.
  • the active ingredients of the invention can also be applied to seeds (coating) by either soaking the seeds in a liquid composition or coating them with a solid composition.
  • the composition can also be applied when the propagation material is introduced to the place of cultivation, e.g. when the seeds are sown in the seed furrow.
  • the treatment procedures for plant propagation material and the propagation material thus treated are further objects of the invention.
  • Example P2 The remaining compounds of Table 1 may be produced analogously to the manner described above.
  • Example F1 Emulsion concentrates a) b) c) active ingredient 25% 40% 50% calcium dodecylbenzenesulphonate 5% 8% 6% castor oil polyethylene glycol ether(36 mols EO) 5% - - tributyl phenol polyethylene glycol ether (30 mols EO) - 12% 4% cyclohexanone - 15% 20% xylene mixture 65% 25% 20%
  • 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 (boiling limits: 160-190°) - - 94% -
  • Example F3 Granulates 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 sprayed onto the carrier mixture, and the solvent evaporated off under vacuum.
  • Example B1 Effect on Diabrotica balteata larvae
  • Corn seedlings are sprayed with an aqueous emulsion spray mixture containing 400 ppm of active ingredient. After drying of the spray deposit, the corn seedlings are colonised with 10 second instar larvae of Diabrotica balteata and placed in a plastic container. Six days later they are evaluated. The percentage reduction of the population (% response) is determined by comparing the number of dead larvae on the treated plants with those on the untreated plants.
  • Especially compound 1.2 has an effect of over 80%.
  • Example B2 Systemic effect against Myzus persicae
  • Pea seedlings are infected with Myzus persicae, then the roots are placed in a spray mixture containing 400 ppm of active ingredient, and incubated at 20°C. 3 and 6 days later, they are evaluated.
  • the percentage reduction of the population is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants.
  • Especially compound 1.2 has an effect of over 80%.

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Abstract

Compounds of formula (I) are described, wherein Z signifies six- or seven-membered, optionally substituted, aromatic or non-aromatic heterocyclyl; X is CH or N; Y is halogen; n is 1, 2 or 3; and m is 0 or 1; and, if appropriate, the E/Z isomers, E/Z isomeric mixtures and/or tautomers thereof, each in free form or in salt form; a method of producing and the use of these compounds, pesticides whose active ingredient is selected from these compounds or from an agrochemically acceptable salt thereof, a method of producing and the use of these compositions, plant propagating material that has been treated with these compositions and a method of controlling pests.

Description

Derivatives of trifluoromethylpyri,mi)dine
The object of the present invention is a compound of formula
Figure imgf000002_0001
wherein Z signifies six- or seven-membered, optionally substituted, aromatic or non- aromatic heterocyclyl; X is CH or N; Y is halogen; n is 1 , 2 or 3; and m is O or l ; and, if appropriate, the E/Z isomers, E/Z isomeric mixtures and/or tautomers thereof, each in free form or in salt form; a method of producing and the use of these compounds, pesticides whose active ingredient is selected from these compounds or from an agrochemically acceptable salt thereof, a method of producing and the use of these compositions, plant propagating material that has been treated with these compositions and a method of controlling pests.
In literature, certain pyridine derivatives have been proposed as active ingredients in pesticides. The biological properties of these known compounds, however, are not fully satisfactory in the field of pest control, which is why there is a need to produce further compounds with pesticidal properties, especially for the control of insects and members of the order Acarina; this problem is solved according to the invention with the development of the present compounds of formula (I).
The compounds of formula (I) and where appropriate their tautomers can form salts, for example acid addition salts. These are formed for example with strong inorganic acids, typically mineral acids, e.g. sulphuric acid, a phosphoric acid or a hydrohalic acid, or with strong organic carboxylic acids, typically
Figure imgf000002_0002
acids substituted where appropriate for example by halogen, e.g. acetic acid, such as optionally unsaturated dicarboxylic acids, e.g. oxalic, malonic, maleic, fumaric or phthalic acid, such as hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulphonic acids, typically C C4alkane or arylsulphonic acids substituted where appropriate for example by halogen, e.g. methane- or p-toluene-sulphonic acid. In a broader sense, compounds of formula (I) with at least one acid group can form salts with bases. Suitable salts with bases are for example metal salts, such as alkali 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. ethyl, diethyl, triethyl or dimethylpropylamine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. mono-, di- or triethanolamine. Corresponding internal salts where appropriate may also be formed. The free form is preferred. Of the salts of compounds of formula (I), the agrochemically beneficial salts are preferred. Hereinbefore and hereinafter, the free compounds of formula (I) or their salts are understood where appropriate to include also the corresponding salts, or the salts are understood to include also the free compounds of formula (I). The same applies to tautomers of compounds of formula (I) and salts thereof.
Unless otherwise defined, the general terms used hereinabove and hereinbelow have the meanings given hereinbelow.
Halogen - as a group perse or as structural element of other groups and compounds such as haloalkyl, halocycloalkyl, haloalkenyl, haloalkinyl and haloalkoxy - is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, mainly fluorine or chlorine, especially chlorine.
If not otherwise defined, carbon-containing groups and compounds each contain 1 to 20, inclusively, preferably 1 to 18, in particular 1 to 10, especially 1 to 6, in particular 1 to 4, especially 1 to 3, particularly 1 or 2, carbon atoms, with methyl being preferred in particular.
Alkyl - as a group per se and as structural element of other groups and compounds such as haloalkyl, alkoxy, alkoxyalkyl, haloalkoxy, alkoxycarbonyl, alkylthio, haloalkylthio, alkylsulphonyl and alkylsulphonyloxy is, in each case with due consideration of the specific number of carbon atoms in the group or compound in question, either straight-chained, e.g. methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-hexadecyl or n-octa- decyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl. Alkenyl and alkinyl - as groups per se and as structural elements of other groups and compounds, such as of haloalkenyl, haloalkinyl, alkenyloxy, haloalkenyloxy, alkinyloxy or haloalkinyloxy - are straight-chained or branched and respectively contain two or preferably one unsaturated carbon-carbon bond(s). Vinyl, prop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2- en-1-yl, but-3-en-1-yl, prop-2-in-1-yl, but-2-in-1-yl and but-3-in-1-yl may be mentioned by way of example.
Cycloalkyl - as a group per se and as a structural element of other groups and compounds, for example of alkyl - is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Cyclopentyl and cyclohexyl are preferred, in particular cyclopropyl.
Halogen-substituted carbon-containing groups and compounds, such as haloalkyl and haloalkoxy , can be partially halogenated or perhalogenated, in the case of polyhalogenation it being possible for the halogen substituents to be identical or different. Examples of haloalkyl - as a group perse and as structural element of other groups and compounds such as haloalkoxy, - are methyl which is mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHF , CF3 or CH2CI; ethyl which is mono- to pentasubstituted by fluorine, chlorine and/or bromine, such as CH2CF3, CF2CF3, CF2CCI3, CF2CHCI2, CF2CHF2, CF2CFCI2, CH2CH2CI, CF2CHBr2, CF2CHCIF, CF2CHBrF oder CCIFCHCIF; propyl or isopropyl, mono- to heptasubstituted by fluorine, chlorine and/or bromine, such as CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3, CF2CF2CF3, CH(CF3)2 or CH2CH2CH2CI; and butyl or one of its isomers, mono- to nonasubstituted by fluorine, chlorine and/or bromine, such as CF(CF3)CHFCF3, CF2(CF2)2CF3 oder CH2(CF2)2CF3.
In di-(C1-C -alkyl)amine, the two alkyl groups are independent of each other.
Aryl signifies especially phenyl or naphthyl, preferably phenyl.
Heterocyclyl signifies a 6- or 7-membered, saturated or unsaturated ring which is bonded to the basic structure by a carbon atom, the ring having preferably two to four hetero atoms selected from the group comprising N, O and S. Preference is given to 6-rings having a nitrogen atom as the hetero atom and two further hetero atoms, preferably nitrogen or oxygen, especially one oxygen and one nitrogen.
Depending on the substitution possibilities on the heterocyclyl radical, the heterocyclyl radicals may bear one to three, preferably one, substituent selected from the group comprising Cι-C6-alkyl, C2-C6-alkenyl, C3-C6-alkinyl; halogen, nitro, cyano, -OH, -SH, C3-C8-cycloalkyl, halogen-C3-C8-cycloalkyl, C C6-alkoxy, halogen-d-C6-alkoxy, C3-C6- alkenyloxy, Cι-C4-alkylthio and di-(C1-C -alkyl)amine.
Preferred embodiments in terms of the invention are compounds of formula (I) a) wherein Z signifies a ring of formula
A D
I I (ii),
whereby bonds U-A, A-M, M-D, D-E, E-G and G-U are single or double bonds, with the provision that no accumulated double bonds occur,
A is -O-, -NRr, -S-, or -N=;
M is -NR2-, -O-, -S-, -CR3P -, -N= or -CR3=;
D is -CR5R6-, -NR7-, -O-, -S-, -N= or -CR5=;
E is -NR2-; -O-, -S- or -CR8R9-; -N= or -CR8=; and
G is -O-, -NR10-, -S-, or -N=;
U is carbon;
Ri, R2, R7 and R10, independently of one another, signify hydrogen, d-C20-alkyl, C3-C8- cycloalkyl, C2-C20-alkenyl or C3-C20-alkinyl; or mono- or poly-substituted d-C2o-alkyl,
C2-C20-alkenyl or C3-C20-alkinyl; aryl which is optionally substituted by one or more substituents selected from the group comprising d-C-6-alkyl, halogen-d-C6-alkyl, C2-C6-alkenyI, C3-C6-alkinyl, halogen, C C6- alkoxy, halogen-d-Ce-alkoxy, nitro, cyano, C3-C8-cycloaIkyl, halogen-C3-C8-cycloalkyl,
C3-C6-alkenyloxy, d-C -alkylthio and di-(Cι-C -alkyl)amine; or -C(=O)-Rn;
R3, R > R5, Re, Rs and R9, independently of one another, signify hydrogen, d-C6-alkyl,
C3-C8-cycloalkyl, d-C6-alkoxy, Cι-C6-alkylthio, C2-C6-alkenyl, C3-C6-alkenyloxy, C3-C6-alkinyl,
C3-C6-alkinyloxy, aryl, heterocyclyl, aryloxy, benzyloxy or heterocyclyloxy;
Cι-C6-alkyl, C3-C8-cycloalkyl, d-C6-alkoxy, d-Cβ-alkylthio, C3-C6-alkenyl, C3-C6-alkenyloxy,
C3-C6-alkinyl or C3-Cβ-alkinyloxy, which are substituted by one or more substituents selected from the group comprising halogen, nitro, cyano, -OH, -SH, C3-C8-cycloalkyl, halogen-
C3-C8-cycloalkyl, phenyl and di-(C C4-alkyl)amine; or aryl, which is substituted by one to three substituents selected from the group comprising halogen, nitro, cyano, -OH, -SH, COOH, COH, d-Ce-alkyl, d-C6-alkoxy, C C6-alkylthio, halogen-d-Ce-alkyl, halogen-d-C6-alkoxy, halogen-C C6-alkylthio, C3-C8-cycloalkyl, halogen-C3-C8-cycloalkyl and di-(d-C4-alkyl)amine; or together are =O or =S;
Rn signifies hydrogen, OH, SH, d-C6-alkyl, C3-C8-cycloalkyl, d-C6-alkoxy, d-C6-alkylthio,
C -C6-alkenyl, C3-C6-alkenyloxy, C3-C6-alkinyl, C3-C6-alkinyloxy, di-(Cι-C4-alkyl)amine, aryl, heterocyclyl, aryloxy, benzyloxy or heterocyclyloxy; d-Cs-alkyl, C3-C8-cycloalkyl, C C6-alkoxy, d-C6-alkylthio, C3-C6-alkenyl, C3-C6-alkenyloxy,
C3-C6-alkinyl or C3-C6-alkinyloxy, which are substituted by one or more substituents selected from the group comprising halogen, nitro, cyano, -OH, -SH, C3-C8-cycloalkyl, halogen-C3-C8-cycloalkyl and di-(d-C4-alkyl)amine; or aryl, heterocyclyl, aryloxy, benzyloxy or heterocyclyloxy, which are substituted by one to three substituents selected from the group comprising halogen, nitro, cyano, -OH, -SH,
COOH, COH, d-Ce-alkyl, CrC6-alkoxy, d-C6-alkylthio, halogen-C C6-alkyl, halogen-d-C6- alkoxy, halogen-d-C6-alkylthio, C3-C8-cycloalkyl, halogen-C3-C8-cycloalkyl and di-
(d-C -alkyl)amine; with the provision that D signifies -CR5R6- or -CR5= if either M or E, or M and E simultaneously independently of one another are -NR2, -N=, -O- or -S-; b) wherein A signifies -O-, -NR or -N=; and
RT is hydrogen, d-C6-alkyl, C3-C8-cycIoalkyl, C2-C6-alkenyl; or C C6-alkyl, C2-C6-alkenyl or C3-C8-cycloalkyl, which are substituted by one or more substituents selected from the group comprising halogen, nitro, cyano, -OH, -SH, C3-C8-cycloalkyl, halogen-C3-C8-cycloalkyl, d-C6-alkoxy, halogen-d-C6-alkoxy, C3-C6-alkenyloxy, d-d-alkylthio, di-(d-C4-alkyl)amine, -C(=O)-R12, aryl, aryloxy, arylthio, heterocyclyl or heterocyclyloxy; and R12 is hydrogen, OH, Ci-Ce-alkyl, d-C6-alkoxy, di-(d-C4-alkyl)amine, aryl, aryloxy or benzyloxy; especially wherein Ri is hydrogen or d-C2-alkyl; in particular wherein A is -O- or -N=, most preferably -O-; c) wherein M is -NR2-, -O-, -CRaR.,-, -N= or -CR3=;
R2 is hydrogen, d-C6-alkyl, C3-C8-cycloalkyl, C2-C6-alkenyl; or d-d-alkyl, C2-C6-alkenyl or C3-C8-cycloalkyl, which are substituted by one or more substituents selected from the group comprising halogen, nitro, cyano, -OH, -SH, C3-C8-cycloalkyl, halogen-C3-C8-cycloalkyl, d-Ce-alkoxy, halogen-d-Ce-alkoxy, di-(d-C_.-alkyl)amine, -C(=O)-Rι2, aryl, aryloxy, arylthio, heterocyclyl or heterocyclyloxy; and R12 is Cι-C6-alkyl or d-C6-alkoxy; R3 and R.j independently of one another, are hydrogen, d-C6-alkyl, C3-C8-cycloalkyl, d-C6- alkoxy, C3-C6-alkenyl or aryl; or d-C6-alkyl or C3-C8-cycloalkyl, which are substituted by one or more substituents selected from the group comprising halogen, nitro, cyano, C3-C8-cycloalkyl, phenyl and di-
(C-i-C -alkyl)amine; or aryl, which is substituted by one to three substituents selected from the group comprising halogen, nitro, cyano, Cι-C6-alkyl, d-C6-alkoxy, d-C6-alkylthio, halogen-d-C6-alkyl, halogen-d-Ce-alkoxy and di-(d-C4-alkyl)amine; or together are =O or =S; especially wherein M is -CR3R4- or -CR3=; and
R3 and R independently of one another, are hydrogen, Cι-C6-alkyl, C3-C8-cycloalkyl, C C6- alkoxy, C3-C6-alkenyl or aryl; or together signify =O or =S; in particular wherein M is -CR3R4- or -CR3=; and R3 is hydrogen or d-Ce-alkyl, and R4 is hydrogen, especially R3 and R4 are hydrogen, or R3 and R4 together signify =O or =S; in particular wherein M is C=O; d) wherein D is -CR5R6-, -NR7- or -O-, -N= or -CR5=;
R5 and R6 independently of one another, are hydrogen, Ci-Ce-alkyl, C3-C8-cycloalkyl, d-C6- alkoxy, aryl or aryloxy; or together signify =O or =S;
R7 is hydrogen, d-C6-alkyl, C3-C8-cycloalkyl, C3-C12-alkenyl or C3-C20-alkinyl; or d-C6-alkyl mono- or poly-substituted by halogen, d-C -alkoxy or phenyl ; aryl; or -C(=O)-Rn;
Rn is hydrogen, OH, d-C6-alkyl, d-C6-alkoxy, di-(d-C4-alkyl)amine, aryl, aryloxy or benzyloxy; especially wherein D is -CR5R6- or -NR7-; R5 and R6 independently of one another, are hydrogen or d-C2-alkyl, and R7 is hydrogen, d-C6-alkyl, C3-C8-cycloalkyl, phenyl or benzyl; in particular wherein D is CH2- or -NR7-; and R7 is hydrogen or d-C6-alkyl; especially wherein D is -NCH3-; e) E is -NR22-; -O-, -CR8R9-; -N= or -CR8=;
R8 and R9 independently of one another, are hydrogen or d-C6-alkyl, which is optionally substituted by one or more substituents selected from the group comprising halogen, nitro, cyano, -OH, -SH, C3-C8-cycloalkyl, halogen-C3-C8-cycloalkyl, phenyl and di-(d-C4-alkyl)- amine; or together are =O or =S; and
R22 is hydrogen or d-C6-alkyl, which is optionally substituted by one or more substituents selected from the group comprising halogen, nitro, cyano, -OH, -SH, C3-C8-cycloalkyl, halogen-C3-C8-cycloalkyl, Cι-C6-alkoxy, halogen-d-Ce-alkoxy, C3-C6-alkenyloxy, C1-C4- alkylthio, di-(C1-C4-alkyl)amine and aryl; especially wherein E signifies -CR8R9-, and R8 and R9 independently of one another, signify hydrogen or d-C6-alkyl, or together signify =O, especially hydrogen; f) wherein G signifies -O-, -NR10- or -N=; and R10 is hydrogen or d-C2o-alkyl; especially wherein G signifies -N=; g) wherein X is CH; h) wherein n is 3; i) wherein Y is fluorine; j) wherein m is 0.
Z preferably has the following definitions, whereby Ri, R2, R22 and R7 are defined as described above:
Figure imgf000008_0001
Figure imgf000009_0001
Figure imgf000010_0001
Particularly preferred in terms of the invention are the compounds of formula (I) listed in Table 1.
The methods for producing the compounds of formula (I) are known to the person skilled in the art from analogous processes. This relates in particular to a process for the preparation of a compound of formula
Figure imgf000010_0002
wherein X, R7 and m are defined as indicated above, A is O or S and R3 and R together are O or S. Therefore, a further object of the invention is a process for the production of the compounds of formula (la), or a salt thereof, wherein a) a compound of formula
Figure imgf000011_0001
which is known or may be produced by processes known per se, and wherein X is defined as indicated for formula (I), is reacted where appropriate in an inert solvent with a compound of formula
R 7\ N' N'
(III)
R which is known or may be produced by processes known per se, to form a compound of formula
Figure imgf000011_0002
or a salt thereof, and wherein X, R7 and m are defined as indicated for formula (I), and
b) this compound of formula (III) is reacted with phosgene or thiophosgene;
c) in order to produce a compound of formula (la), in which m is 1 , a compound of formula (I) in which m is 0 is reacted with an oxidation agent, for example inorganic peroxides, such as sodium perborate, potassium permanganate or hydrogen peroxide; or with mCPBA or organic per acids, such as perbenzoic acid or peracetic acid, or mixtures of organic acids and hydrogen peroxide, e.g. acetic acid/hydrogen peroxide;
and/or, if so desired, a compound of formula (I) obtainable according to the method or by other means, present in free form or in the form of a salt, is converted into a different compound of formula (I), a mixture of isomers obtainable according to the method is separated and the desired isomer is isolated and/or a free compound of formula (I) obtainable according to the method or by other means is converted into a salt, or a salt of a compound of formula (I) obtainable according to the method or by other means is converted into the free compound of formula (I) or into a different salt.
Further compounds of formula (I) can also be produced analogously to known processes. For example, a compound of formula (I), wherein Z is
Figure imgf000012_0001
can be produced by reacting a compound of formula
Figure imgf000012_0002
or a salt thereof, and wherein X is defined as mentioned above, by reacting with formaldehyde in the presence of a compound NH2R7 and the compound of formula
Figure imgf000012_0003
thus obtained is optionally reacted with a compound of formula Q-R1, wherein Q is a leaving group and Ri is defined as above except for H, and the compound of formula (I) thus obtained, wherein m is 0, is optionally oxidised in accordance with the above process c).
The starting materials of formulae (II) and (III), listed hereinbefore and hereinafter, which are used to produce the compounds of formula (I), in free form or in salt form, are known or may be produced by methods known per se. The starting materials of formula (IV) are novel and therefore similarly form an object of the invention. The reactions described hereinbefore and hereinafter are carried out in a known manner, e.g. in the absence or, where appropriate, in the presence of a suitable solvent or diluent or a mixture thereof, proceeding as required under conditions of cooling, of ambient temperature, or of heating, e.g. in a temperature range of about -80°C to the boiling temperature of the reaction medium, preferably about -20°C to about +150°C, and where appropriate in a closed vessel, under pressure, in an inert gas atmosphere, and/or under non-aqueous conditions. Especially advantageous reaction conditions are described in the Examples.
The reaction of process a) is effected in the presence of an acid, for example HCI, sulphuric acid or phosphoric acid.
The reaction is generally carried out at temperatures of -30°C to +70°C, preferably from -10°C to +50°C. The process is conveniently carried out in the presence of an inert solvent or solvent mixture. Suitable solvents for this purpose are for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, ethylene tetrachloride; ethers and ether-like compounds, such as dialkyl ether (diethyl ether, diisopropyl ether, tert.-butylmethyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile; esters such as ethyl acetate (acetic acid ethyl ester), propyl acetate or butyl acetate; ketones such as acetone, diethyl ketone, methyl ethyl ketone or methyl isobutyl ketone; and mixtures of such solvents with one another.
The reaction is carried out at atmospheric pressure, although it may also be carried out at elevated or reduced pressure.
In process variant b), the reaction is advantageously carried out in the presence of an inert solvent or solvent mixture at temperatures of -30°C to +70°C, preferably -10°C to +50°C. It is preferably carried out in the presence of a base, for example in the presence of an organic amine such as a trialkylamine (trimethylamine, triethylamine, triisopropylamine or diisopropylethylamine), a pyridine (pyridine itself, 4-dimethylaminopyridine or 4-pyrrolidino- pyridine), a morpholine (N-methylmorpholine) or a N,N-dialkylaniline (N,N-dimethylaniline or N-methyl-N-ethylaniline). Suitable solvents for this purpose are for example aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, ethylene tetrachloride; ethers such as dialkyl ether (diethyl ether, diisopropyl ether, tert.-butylmethyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile; esters such as ethyl acetate (acetic acid ethyl ester), propyl acetate or butyl acetate; and mixtures of such solvents with one another.
In process variant c), the reactions are expediently carried out in the presence of an inert solvent or solvent mixture at temperatures of -40°C to +120°C, preferably -20°C to +80°C. The solvents in question may be the same as those mentioned for variant b). The process is optionally carried out in the presence of a base, for example alkali or alkaline earth metal hydroxides or for example alkali or alkaline earth metal carbonates or hydrogen carbonates, pyridine, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, lutidine, collidine, trialkylamine, N,N- dialkylaniline, or a bicyclic, non-nucleophilic base such as 1 ,4-diazabicyclo[2.2.2]octane (DABCO), 1 ,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1 ,8-diazabicyclo[5.4.0]undec-7-ene (1 ,5-5) (DBU).
Compounds of formula (I) obtainable according to the method or by other means may be converted in a manner known perse into other compounds of formula (I), by replacing one or more substituents of the starting compound of formula (I) in conventional manner with (an)other substituent(s) according to the invention.
Depending on the choice of appropriate reaction conditions and starting materials, it is possible to replace only one substituent with another substituent according to the invention in one reaction step, or several substituents may be replaced with other substituents according to the invention in the same reaction step.
Salts of compounds of formula (I) may be prepared in a known manner. For example, it is possible to obtain salts of compounds of formula (I) with bases, by treating the free compounds with an appropriate base or with an appropriate ion exchanger reagent.
Salts of compounds of formula (I) may be converted in conventional manner into the free compounds of formula (I), e.g. by treatment with a suitable acid or with a suitable ion exchanger reagent.
Salts of compounds of formula (I) may be transformed in known manner into other salts of a compound of formula (I).
The compounds of formula (I) in free form or in salt form may exist in the form of one of the possible isomers or as a mixture thereof, e.g. depending on the number, the absolute and relative configuration of asymmetric carbon atoms appearing in the molecule and/or depending on the configuration of non-aromatic double bonds appearing in the molecule, as pure isomers such as antipodes and/or diastereoisomers, or as isomer mixtures such as enantiomer mixtures, e.g. racemates, diastereoisomer mixtures or racemate mixtures. The invention relates both to the pure isomers and to all the possible mixtures of isomers, and hereinbefore and hereinafter is to be understood as such accordingly, even if the stereo- chemical details are not specifically mentioned in each case.
Depending on the choice of starting materials and methods, diastereoisomer mixtures, racemate mixtures and mixtures of double bond isomers of compounds of formula (I) in free form or in salt form, which are obtainable by the process or in another way, may be separated in known manner, on the basis of the physical-chemical differences in their components, into the pure diastereoisomers or racemates, for example by fractiional crystallisation, distillation and/or chromatography.
Enantiomer mixtures that are obtainable correspondingly, such as racemates, may be broken down by known methods into the optical antipodes, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, e.g. high pressure liquid chromatography on acetyl cellulose, with the assistance of suitable microorganisms, by cleavage with specific, immobilised enzymes, through the formation of inclusion compounds, e.g. using chiral crown ethers, whereby only one enantiomer is complexed, or by converting into diastereoisomeric salts and separating the diastereoisomer mixture obtained in this way, e.g. on the basis of their different solubilities, by fractional crystallisation, into the diastereoisomers, from which the desired enantiomer can be released upon the action of suitable agents.
According to the invention, apart from isolation of corresponding isomer mixtures, generally known methods of diastereoselective or enantioselective synthesis can also be applied to obtain pure diastereoisomers or enantiomers, e.g. by carrying out the method of the invention using educts with correspondingly suitable stereochemistry.
It is advantageous to isolate or synthesise the biologically more active isomer, e.g. enantiomer or diastereoisomer, or isomer mixture, e.g. enantiomer mixture or diastereoisomer mixture, provided that the individual components have differing biological efficacy. Compounds of formula (I) in free form or in salt form can also be obtained in the form of their hydrates and/or also can include other solvents, used for example where necessary for the crystallisation of compounds present in solid form.
The invention relates to all those forms of the method, according to which one starts from a compound obtainable as a primary material or an intermediate at any stage of the method and carries out all or some of the missing steps, or uses, or - especially under the reaction conditions - produces a starting material in the form of a derivative or a salt and/or its racemate or antipodes.
In the method of the present invention, the starting materials and intermediates used, each in free form or in salt form, are preferably those that lead to the compounds of formula (I) or salts thereof described at the beginning as being especially useful.
The invention relates especially to the method of preparation described in Example P1.
The compounds of formula (I) according to the invention are active ingredients of preventive and/or curative merit for use in pest control and offer a very favourable spectrum of biocidal activity with favourable tolerability in warm-blooded animals, fish, and plants even at low concentrations. The active ingredients according to the invention are active against all or individual development stages of animal pests showing normal sensitivity, as well as those showing resistance, such as insects or members of the order Acarina. The insecticidal or acaricidal effect of the active substances of the invention can manifest itself directly, i.e. killing the pests either immediately or after some time has elapsed, for example when moulting occurs, or indirectly, e.g. reducing the number of eggs laid and/or the hatching rate, good efficacy corresponding to a pesticidal rate (mortality) of at least 50 to 60%.
The said animal pests include, for example, those which are mentioned in the European Patent application EP-A-736'252, page 2, line 55 to page 6, line 55. The pests mentioned therein are thus included by reference in the object of the present invention. The compounds according to the invention are also active against pests from the class of the nematodes, for example, of the families Filariidae and Setariidae and the genera Haemonchus, Tricho- strongylus, Ostertagia, Nematodirus, Cooperia, Ascaris, Bunostumum, Oesophagostonum, Chabertia, Trichuris, especially Trichuris vulpis, Strongylus, Trichonema, Dictyocaulus, Capillaria, Strongyloides, Heterakis, Toxocara, especially Toxocara canis, Ascaridia, Oxyuris, Ancylostoma, especially Ancylostoma caninum, Uncinaria, Toxascaris and Parascaris; Dirofilaria, especially Dirofilaria immitis (heartworm); also especially against representatives of the genera Heterodora spp., for example Heterodera schachtii, Heterodora avenae and Heterodora trifolii; Globodera spp., for example Globodera rostochiensis; Meloidogyne spp., for example Meloidogyne incoginita and Meloidogyne javanica; Radopholus spp., for example Radopholus similis; Pratylenchus, for example Pratylenchus neglectans and Pratylenchus penetrans; Tylenchulus, for example Tylenchulus semipenetrans; Longidorus, Trichodorus, Xiphinema, Ditylenchus, Aphelenchoides and Anguina.
The active ingredients according to the invention are especially suitable for controlling sucking insects, especially of the order Homoptera, preferably for controlling these pests in vegetable, fruit, rice and cotton crops. One particular advantage of the compounds according to the invention is their systemic action.
Pests of said type which occur on plants, especially on crops and ornamentals in agriculture, horticulture and forestry, or on parts of such plants, such as fruits, blooms, leaves, stems, tubers or roots, can be controlled, i.e. kept in check or eradicated, using the active ingredients of the invention, this protection remaining for parts of some plants whose growth does not occur until later.
Target crops include especially cereals, such as wheat, barley, rye, oats, rice, corn or sorghum; beet, such as sugar beet or fodder beet; fruit, e.g. pomes, drupes and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, e.g. strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soybean; oleaginous fruits, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants, such as squashes, cucumbers or melons; fibrous plants, such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruit or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or paprika; lauraceae, such as avocado, cinnamon or camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, banana plants, natural rubber plants and ornamentals.
Other indication areas for the active ingredients of the invention are the protection of stored products and stores and of material and, in the hygiene sector, especially the protection of domestic animals and livestock against pests of said type. The invention therefore relates also to pesticides, such as emulsifiable concentrates, suspension concentrates, ready-to-spray or ready-to-dilute solutions, coatable pastes, dilute emulsions, spray powders, soluble powders, dispersible powders, wettable powders, dusts, granulates or encapsulations in polymeric substances, chosen in accordance with the intended objectives and prevailing circumstances, and comprising at least one active ingredient of the invention.
The active ingredient is used in these compositions in pure form, a solid active ingredient e.g. in a specific particle size, or preferably together with at least one of the adjuvants conventionally employed in the art of formulation, such as extenders, e.g. solvents or solid carriers, or surface-active compounds (surfactants).
The adjuvants which can be used for formulation are, for example, solid carriers, solvents, stabilisers, "slow-release" agents, dyes, and where appropriate surfactants. Carriers and adjuvants can be any substance conventionally used in crop protection agents, especially agents for slug and snail control. Adjuvants such as solvents, solid carriers, surface-active agents, non-ionic surfactants, cationic surfactants, anionic surfactants, and other adjuvants in the compositions of the invention can, for example, be the same as those described in EP- A-736'252 , and are included by reference in the object of the present invention.
As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of active ingredient and 1 to 99.9%, especially 5 to 99.9%, of at least one solid or liquid adjuvant, it being possible as a rule for 0 to 25%, especially 0.1 to 20%, of the composition to be surfactants (% in each case meaning percent by weight). Whereas concentrated compositions tend to be preferred for commercial goods, the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient. Preferred compositions are composed in particular as follows (% = percent by weight):
Emulsifiable concentrates: active ingredient: 1 to 95%, preferably 5 to 20% surfactant: 1 to 30%, preferably 10 to 20 % solvent: 5 to 98%, preferably 70 to 85%
Dusts: active ingredient: 0.1 to 10%, preferably 0.1 to 1% solid carrier: 99.9 to 90%, preferably 99.9 to 99% Suspension concentrates: active ingredient: 5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30%
Wettable powders: active ingredient: 0.5 to 90%, preferably 1 to 80% surfactant: 0.5 to 20%, preferably 1 to 15% solid carrier: 5 to 99%, preferably 15 to 98%
Granulates: active ingredient: 0.5 to 30%, preferably 3 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%
The activity of the compositions of the invention can be substantially broadened and adapted to prevailing circumstances by adding other insecticidal substances. Additional active ingredients are, for example, substances from the following classes: organic phosphorus compounds, nitrophenols and their derivatives, formamidines, acylureas, carbamates, pyre- throids, neonicotinoides and their derivatives, pyrroles, thioureas and their derivatives, chlorinated hydrocarbons and Bacillus thuringiensis preparations. Especially suitable components in the mixture are azamethiphos; chlorfenvinphos; cypermethrin, cypermethrin high- cis; cyromazin; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; iodofenphos; kinoprene; lufenuron; methacriphos; methi- dathion; monocrotophos; phosphamidon; profenofos; diofenolan; a substance obtainable from the Bacillus thuringiensis strain GC91 or from NCTC11821; pymetrozine; bromo- propylate; methoprene; disulfuton; quinalphos; tau-fluvalinate; thiocyclam; thiometon; aldicarb; azinphos-methyl; benfuracarb; bifenthrin; buprofezin; carbofuran; dibutylaminothio; cartap; chlorfluazuron; chlorpyrifos; cyfluthrin; lambda-cy-halothrin; alpha-cypermethrin; zeta- cypermethrin; deltamethrin; diflubenzuron; endosulfan; ethiofencarb; fenitrothion; feno- bucarb; fenvalerate; formothion; methiocarb; heptenophos; imidacloprid; isoprocarb; metha- midophos; methomyl; mevinphos; parathion; parathion-methyl; phosalone; pirimicarb; propoxur; teflubenzuron; terbufos; triazamate; abamectin; fenobucarb; tebufenozide; fipronil; beta-cyfluthrin; silafluofen; fenpyroximate; pyridaben; fenazaquin; pyriproxyfen; pyrimidifen; nitenpyram; NI-25, acetamiprid; avermectin B1 (Abamectin); an insect-active extract from a plant; a preparation containing insect-active nematodes ; a preparation obtainable from Bacillus subtilis; a preparation containing insect-active fungi; a preparation containing insect- active viruses; AC 303 630; acephat; acrinathrin; alanycarb; alphamethrin; amitraz; AZ 60541 ; azinphos A; azinphos M; azocyclotin; bendiocarb; bensultap; betacyfluthrin; BPMC; brofenprox; bromophos A; bufencarb; butocarboxin; butylpyridaben; cadusafos; carbaryl; carbopheno-thion; chloethocarb; chlorethoxyfos; chlormephos; cis-res-methrin; clocythrin; clofentezin; cyanophos; cycloprothrin; cyhexatin; demeton M; demeton S; demeton-S- methyl; dichlofenthion; dicliphos; diethion; dimethoat; dimethylvinphos; dioxathion; edifenphos; emamectin; esfenvalerat; ethion; ethofenprox; ethoprophos; etrimphos; fenamiphos; fenbutatinoxid; fenothiocarb; fenpropathrin; fenpyrad; fenthion; fiuazinam; flucycloxuron; flucythrinat; flufenoxuron; flufenprox; fonophos; fosthiazat; fubfenprox; HCH; hexaflumuron; hexythiazox; iprobenfos; isofenphos; isoxathion; ivermectin; lambda-cy- halothrin; malathion; mecarbam; mesulfenphos; metaldehyd; metolcarb; milbemectin; moxidectin; naled; NC 184; omethoat; oxamyl; oxydemethon m; oxydeprofos; permethrin; phenthoat; phorat; phosmet; phoxim; pirimiphos M; pirimiphos A; promecarb; propaphos; prothiofos; prothoate; pyrachlophos; pyrada-phenthion; pyresmethrin; pyrethrum; RH 5992; salithion; sebufos; sulfotep; sulprofos; tebufenpyrad; tebupirimphos; tefluthrin; temephos; terbam; tetrachlor- vinphos; thiacloprid; thiamethoxam; thiafenox; thiodicarb; thiofanox; thionazin; thuringiensin; tralomethrin; triarthen; triazophos; triazuron; trichlorfon; triflumuron; trimethacarb; vamidothion; xylylcarb; Yl 5301/5302; zetamethrin; DPX-MP062; RH-2485; D 2341 and XMC (3,5,-xylyl methyl carbamate).
The compositions of the invention can also contain further solid or liquid adjuvants, such as stabilisers, e.g. vegetable oils, epoxidized where appropriate (e.g. epoxidized coconut oil, rapeseed oil or soya oil), antifoaming agents, e.g. silicone oil, preservatives, viscosity modulators, binders and/or tackifiers, as well as fertilisers or other active ingredients to achieve specific effects, e.g. acaricides, bactericides, fungicides, nematocides, molluscicides or selective herbicides.
The compositions of the invention are prepared in a known manner, in the absence of adjuvants, for example, by grinding, sieving, and/or compressing a solid active ingredient or active ingredient mixture, e.g. 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 the mixture of active ingredients with the adjuvant(s). These methods for preparing compositions of the invention and the use of compounds I for preparing these compositions likewise form an object of the invention. The methods of application for the compositions, i.e. the methods of controlling pests of said type, such as spraying, atomising, dusting, coating, dressing, scattering or pouring, which are chosen in accordance with the intended objectives and prevailing circumstances, and the use of the compositions for controlling pests of said type are further objects of the invention. Typical concentrations of active ingredient are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The rates of application are generally 1 to 2000 g of active ingredient per hectare, especially 10 to 1000 g/ha, and preferably 20 to 600 g/ha.
A preferred method of application for crop protection is to apply the active ingredient to the foliage of the plants (leaf application), the number of applications and the rate of application depending on the intensity of infestation by the pest in question. However, the active ingredients can also penetrate the plant through the roots (systemic action) by impregnating the locus of the plant with a liquid composition, or by applying the active ingredient in solid form to the locus of the plants, e.g. the soil, for example in granular form (soil application). With paddy rice cultures, granules may be metered into the flooded paddy field.
The compositions of the invention are also suitable for protecting plant propagation material, including genetically modified propagation material, e.g. seeds, such as fruits, tubers or grains, or plant seedlings, from animal pests. The propagation material can be treated with the composition before the start of cultivation, seeds for example being dressed before they are sown. The active ingredients of the invention can also be applied to seeds (coating) by either soaking the seeds in a liquid composition or coating them with a solid composition. The composition can also be applied when the propagation material is introduced to the place of cultivation, e.g. when the seeds are sown in the seed furrow. The treatment procedures for plant propagation material and the propagation material thus treated are further objects of the invention.
The invention is illustrated by the following examples. They do not impose any limitation on the invention. The temperatures are given in degrees Celsius, and the proportions of solvents in the mixture are given as parts by volume. Preparation examples
Example P1: Preparation of the compound of formula
Figure imgf000022_0001
P1a): Preparation of the compound of formula
Figure imgf000022_0002
20 ml of acetonitrile are placed in a flask and 1.06 g of hydrogen chloride gas passed in. Cooling is then effected to -40°C and 0.58 g of 1 ,3,5-trimethylhexahydro-1 ,3,5-triazine are added dropwise. Stirring is continued for 10 minutes at -40°C and then 2.5 g of 4-tri- fluoromethyl-nicotinic acid amide are added in portions. The temperature is allowed to rise to room temperature and stirring continues over night. 40 ml of tert.butylmethyl ether are added, the mixture is stirred for a further 15 minutes and filtered. The residue of filtration is washed twice with 20 ml of tert.-butylmethyl ether. Compound (B) is obtained as a solid.
P1b): Preparation of the title compound (A)
3.4 g of the compound of the above formula (B) and 40 ml of ethyl acetate are prepared. They are cooled to 0 to 5°C and 5 ml of 30% sodium hydroxide solution is added dropwise. The reaction mixture is extracted twice with 20 ml of ethyl acetate, and the combined organic phases are dried over sodium sulphate and concentrated on a rotary evaporator. The residue is admixed with 20 ml of dimethoxyethane and added dropwise over the course of one hour at 0°C to a mixture of 6.5 g of phosgene in 20 ml of dimethoxyethane. The temperature of the mixture is allowed to rise to room temperature and then 2.61 g of pyridine, dissolved in 20 ml of dimethoxyethane, are added dropwise. The reaction mass is stirred over night with slight refluxing.
The mixture is then concentrated on a rotary evaporator, the residue is taken up in 20 ml of ethyl acetate, washed twice with 10 ml of water, the organic phase is dried over sodium sulphate and the residue purified on silica gel with hexane/ethyl acetate (volume ratio 3/7). Compound (A) is obtained as a viscous oil (compound 1.2).
Example P2: The remaining compounds of Table 1 may be produced analogously to the manner described above.
Table 1 : Compounds of formula
Figure imgf000023_0001
Ex. No. R7 m phys. data
1.1 H CH O 0
1.2 methyl CH O 0 oil
1.3 ethyl CH O 0
1.4 n-propyl CH O 0
1.5 i-propyl CH O 0 oil
1.6 n-butyl CH O 0
1.7 phenyl CH O 0
1.8 4-CI-phenyl CH O 0
1.9 4-CF3-O-phenyl CH O 0
1.10 4-CF3-phenyl CH O 0
1.11 4-F-phenyl CH O 0
1.12 benzyl CH O 0
1.13 cyclopropyl CH O 0
1.14 cyclohexyl CH O 0
1.15 methyl CH O 1
1.16 ethyl CH O 1
1.17 n-propyl CH O 1
1.18 i-propyl CH O 1
Figure imgf000024_0001
Formulation examples (% = percent by weight)
Example F1 : Emulsion concentrates a) b) c) active ingredient 25% 40% 50% calcium dodecylbenzenesulphonate 5% 8% 6% castor oil polyethylene glycol ether(36 mols EO) 5% - - tributyl phenol polyethylene glycol ether (30 mols EO) - 12% 4% cyclohexanone - 15% 20% xylene mixture 65% 25% 20%
Mixing of finely ground active ingredient and adjuvants results in an emulsion concentrate which is diluted with water to yield emulsions of the desired concentration.
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 (boiling limits: 160-190°) - - 94% -
Mixing of finely ground active ingredient and adjuvants results in a solution which is suitable for application in the form of fine droplets.
Example F3: Granulates 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 sprayed onto the carrier mixture, and the solvent evaporated off under vacuum.
Biological Examples
Example B1 : Effect on Diabrotica balteata larvae
Corn seedlings are sprayed with an aqueous emulsion spray mixture containing 400 ppm of active ingredient. After drying of the spray deposit, the corn seedlings are colonised with 10 second instar larvae of Diabrotica balteata and placed in a plastic container. Six days later they are evaluated. The percentage reduction of the population (% response) is determined by comparing the number of dead larvae on the treated plants with those on the untreated plants.
The compounds of table 1 show good efficacy against Diabrotica balteata in this test.
Especially compound 1.2 has an effect of over 80%.
Example B2: Systemic effect against Myzus persicae
Pea seedlings are infected with Myzus persicae, then the roots are placed in a spray mixture containing 400 ppm of active ingredient, and incubated at 20°C. 3 and 6 days later, they are evaluated. The percentage reduction of the population (% response) is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants.
The compounds of the tables show good efficacy against Myzus persicae in this test.
Especially compound 1.2 has an effect of over 80%.

Claims

What we claim is:
1. A compound of formula
Figure imgf000027_0001
wherein Z signifies six- or seven-membered, optionally substituted, aromatic or non- aromatic heterocyclyl; X is CH or N; Y is halogen; n is 1 , 2 or 3; and m is 0 or 1 ; and, if appropriate, the E/Z isomers, E/Z isomeric mixtures and/or tautomers thereof, each in free form or in salt form;
2. A compound of formula (I) according to claim 1 , in free form.
3. A compound according to one of claims 1 or 2 of formula (I), wherein Z is a ring of formula
A D
I I (ii),
whereby bonds U-A, A-M, M-D, D-E, E-G and G-U are single or double bonds, with the provision that no accumulated double bonds occur,
A is -O-, -NR , -S-, or -N=;
M is -NR2-, -O-, -S-, -CR3R4-, -N= or -CR3=;
D is -CR5R6-, -NR7-, -O-, -S-, -N= or -CR5=;
E is -NR2-; -O-, -S- or -CR8R9-; -N= or -CR8=; and
G is -O-, -NR10-, -S-, or -N=;
U is carbon; Rι, R2, R7 and Rι0, independently of one another, signify hydrogen, C C20-alkyl, C3-C8- cycloalkyl, C2-C20-alkenyl or C3-C20-alkinyl; or mono- or poly-substituted d-do-alkyl, C2-C20-alkenyl or C3-C20-alkinyl; aryl which is optionally substituted by one or more substituents selected from the group comprising Ci-Ce-alkyl, halogen-d-C6-alkyl, C2-C6-alkenyl, C3-C6-alkinyl, halogen, d-C6- alkoxy, halogen-Cι-C6-alkoxy, nitro, cyano, C3-C8-cycIoalkyl, halogen-C3-C8-cycloalkyl, C3-C6-alkenyloxy, Cι-C -alkylthio and di-(Cι-C -alkyl)amine; or -C(=O)-Rn;
R3, R4, R5, Re, Rs and R9, independently of one another, signify hydrogen, d-C6-alkyl, C3-C8-cycloalkyl, d-Ce-alkoxy, d-Ce-alkylthio, C2-C6-alkenyl, C3-C6-alkenyloxy, C3-C6-alkinyl, C3-C6-alkinyloxy, aryl, heterocyclyl, aryloxy, benzyloxy or heterocyclyloxy; d-Ce-alkyl, C3-C8-cycloalkyl, Cι-C6-alkoxy, Cι-C6-alkylthio, C3-C6-alkenyl, C3-C6-alkenyloxy, C3-C6-alkinyl or C3-C6-alkinyloxy, which are substituted by one or more substituents selected from the group comprising halogen, nitro, cyano, -OH, -SH, C3-C8-cycloalkyl, halogen- C3-C8-cycloalkyl, phenyl and di-(C1-C4-alkyl)amine; or aryl, which is substituted by one to three substituents selected from the group comprising halogen, nitro, cyano, -OH, -SH, COOH, COH, d-C6-alkyl, d-C6-alkoxy, d-Ce-aikylthio, halogen-d-Ce-alkyl, halogen-d-Ce-alkoxy, halogen-Cι-C6-alkylthio, C3-C8-cycloalkyl, halogen-C3-C8-cycloalkyl and dKd-d-alky amine; or together are =O or =S;
Rn signifies hydrogen, OH, SH, d-Ce-alkyl, C3-C8-cycloalkyl, CrC6-alkoxy, d-C6-alkylthio, C2-C6-alkenyl, C3-C6-alkenyloxy, C3-C6-alkinyl, C3-C6-alkinyloxy, di-(C C4-alkyl)amine, aryl, heterocyclyl, aryloxy, benzyloxy or heterocyclyloxy; d-Ce-alkyl, C3-C8-cycloalkyl, d-C6-alkoxy, d-C-e-alkylthio, C3-C6-alkenyl, C3-C6-alkenyloxy, C3-C6-alkinyl or C3-C6-alkinyloxy, which are substituted by one or more substituents selected from the group comprising halogen, nitro, cyano, -OH, -SH, C3-C8-cycloalkyl, halogen-C3-C8-cycloalkyl and di-(C1-C -alkyl)amine; or aryl, heterocyclyl, aryloxy, benzyloxy or heterocyclyloxy, which are substituted by one to three substituents selected from the group comprising halogen, nitro, cyano, -OH, -SH, COOH, COH, Ci-Ce-alkyl, d-C6-alkoxy, d-Ce-alkylthio, halogen-d-Ce-alkyl, halogen-d-Ce- alkoxy, halogen-d-Ce-alkylthio, C3-C8-cycloalkyl, halogen-C3-C8-cycloalkyl and di- (d-C4-alkyl)amine; with the provision that D signifies -CR5R6- or -CR5= if either M or E, or M and E simultaneously independently of one another are -NR2, -N=, -O- or -S-.
4. A compound according to one of claims 1 or 3 of formula (I), whereby A is -O-, -NR or -N=; and
Ri is hydrogen, d-C6-alkyl, C3-C8-cycloalkyl, C2-C6-alkenyl; or C C6-alkyl, C2-C6-alkenyl or C3-C8-cycloalkyl, which are substituted by one or more substituents selected from the group comprising halogen, nitro, cyano, -OH, -SH, C3-C8-cycloalkyl, halogen-C3-C8-cycloalkyl, Cι-C6-alkoxy, halogen-d-C6-alkoxy, C3-C6-alkenyloxy, C C4-alkylthio, di-(C1-C4-alkyl)amine, -C(=O)-Rι2, aryl, aryloxy, arylthio, heterocyclyl or heterocyclyloxy; and R12 is hydrogen, OH, Ci-Ce-alkyl, Ci-Ce-alkoxy, di-(d-C -alkyl)amine, aryl, aryloxy or benzyloxy.
5. A pesticidal composition comprising at least one compound of formula (I) according to claim 1 as active ingredient, either in free form or in the form of an agrochemically acceptable salt, and at least one adjuvant.
6. Method of producing a composition as described in claim 5, in which the active ingredient is intimately mixed with the adjuvant(s).
7. A method for the control of pests in which a compound of formula (I) according to one of claims 1 to 4 as the active ingredient is applied, in free form or optionally in the form of an agrochemically acceptable salt, to pests or their habitat.
8. Use of a compound of formula (I) according to one of claims 1 to 4, in free form or optionally in the form of an agrochemically acceptable salt, in the preparation of a composition as described in claim 5.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005113553A2 (en) * 2004-05-10 2005-12-01 Bayer Cropscience Ag Azinyl imidazoazine and azinyl carboxamide
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Publication number Priority date Publication date Assignee Title
WO2005113553A2 (en) * 2004-05-10 2005-12-01 Bayer Cropscience Ag Azinyl imidazoazine and azinyl carboxamide
WO2005113553A3 (en) * 2004-05-10 2006-01-05 Bayer Cropscience Ag Azinyl imidazoazine and azinyl carboxamide
US8017632B2 (en) 2004-07-20 2011-09-13 Bayer Cropscience Ag Selective insecticides based on haloalkylnicotinic acid derivatives, anthranilic acid diamides, or phthalic acid diamides and safeners
US8685985B2 (en) 2004-07-20 2014-04-01 Bayer Cropscience Ag Selective insecticides based on anthranilic acid diamides and safeners
US8841328B2 (en) 2004-07-20 2014-09-23 Bayer Cropscience Ag Selective insecticides based on anthranilic acid diamides and safeners
DE102008041214A1 (en) 2008-08-13 2010-02-18 Bayer Cropscience Ag New N-substituted azinylalkyl-azincarboxamide compounds useful e.g. in plant protection, for combating animal pests, arthropods, nematodes and plant diseases, and for protecting industrial materials against attack and destruction by insect
WO2017060389A1 (en) 2015-10-06 2017-04-13 Syngenta Participations Ag Compounds and compositions having knock-down or blood feed inhibition activity against insect pests
EP3659438A1 (en) 2015-10-06 2020-06-03 Syngenta Participations Ag Compounds and compositions having knock-down or blood feed inhibition activity against insect pests

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