WO2001017965A2 - Cyanopiperidines - Google Patents

Cyanopiperidines Download PDF

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Publication number
WO2001017965A2
WO2001017965A2 PCT/EP2000/008660 EP0008660W WO0117965A2 WO 2001017965 A2 WO2001017965 A2 WO 2001017965A2 EP 0008660 W EP0008660 W EP 0008660W WO 0117965 A2 WO0117965 A2 WO 0117965A2
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Prior art keywords
optionally substituted
chloropyrid
alkyl
formula
compound
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PCT/EP2000/008660
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English (en)
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WO2001017965A3 (fr
Inventor
Ottmar Franz HÜTER
William Lutz
Peter Renold
Arthur Steiger
Werner Zambach
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Syngenta Participations Ag
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Priority to AU75147/00A priority Critical patent/AU7514700A/en
Publication of WO2001017965A2 publication Critical patent/WO2001017965A2/fr
Publication of WO2001017965A3 publication Critical patent/WO2001017965A3/fr

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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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • 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
    • C07D401/06—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 only aliphatic carbon atoms
    • 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
    • C07D401/14—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 three or more hetero 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
    • C07D405/14—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 three or more hetero 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
    • 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
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • 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
    • 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
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • the invention relates to organic compounds of formula (1), their preparation and their usage in the control of pests, as well as compositions containing such compounds.
  • Ri is an optionally substituted 5-, 6- or 7-membered, saturated or unsaturated ring with one, two or three hetero atoms, which are selected from the group comprising N, O and S;
  • R 2 is hydrogen, CN, OH, formyl, optionally substituted CrC 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl. optionally substituted C 3 -C 6 -cycloalkyl, optionally substituted C 3 -C 6 -cycloalkenyl, optionally substituted C 2 -C 6 -alkinyl, optionally substituted C C 6 -alkoxy, optionally substituted C r C 6 -alkylsulfinyl, optionally substituted d-C 6 -aikylsulfonyl, optionally substituted d-C- ⁇ -alkoxy-C-i-C ⁇ -alkyl, optionally substituted d-C ⁇ -alkylthio-d-Ce-alkyl, optionally substituted C ⁇ -C 6 - alkylsulfinyl-d-Ce-alkyl, optionally substituted d-Ce-alkylsulfony
  • G is a direct bond, O, NH, N-(d-C 6 -alkyl), N-formyl, S, SO, S0 2 , optionslly substituted d-d-alkylene, optionally substituted C 2 -C 6 -alkenyiene, optionally substituted C 2 -C 6 -alkinylene, d-C 6 -alkylenoxy, C 2 -C 6 -alkenylenoxy, C ⁇ -C 6 -alkylenecarbonyl, C 2 -C 6 -alkenylenecarbonyl, C 2 -C 6 -alkinylenecarbonyl, aminocarbonyl, carbonyl, carbonyloxy, oxycarbonyl, thiocarbonyl, thiocarbonyloxy, oxythiocarbonyl; and
  • L is an optionally substituted aryl or heterocyclyl
  • R 3 is halogen, hydroxy, carboxyl, nitrile, d-d-alkyl, halogen-d-d-alkyl, C 3 -C 6 - cycloalkyl, CrC 4 -alkoxymethyl, C ⁇ -C 4 -alkoxy, halogen-C C 4 -alkoxy, C1-C4- alkylthio or halogen-d-C 4 -alkylthio;
  • A is optionally substituted d-C 2 -alkylene; n is 0 or 1 ; and m is 0, 1 , 2, 3 or 4; whereby the radicals R ⁇ L and E, independently of each other, may be substituted by one or more radicals from the group halogen, hydroxy, N0 2 , NH 2 , CN, SF 5 , hydrazinyl, formyl, thioamido, thiocyanatomethyl, trimethylsilyl, optionally substituted d-C 6 -alkyl, optionally substituted C 2 -C 6 -alkenyl, optionally substituted C 2 -C 6 -alkinyl, optionally substituted C 3 -C 6 -cycloalkyl, optionally substituted C 3 -C 6 -cycloalkenyl.
  • optionally substituted d-C 6 -alkoxy optionally substituted ( d-d-alkylthio, optionally substituted d-C 6 -alkylsulfinyl, optionally substituted d-C ⁇ -alkylsulfonyl, optionally substituted CrC 6 -alkylsulfonyloxy, optionally substituted d-Ce-alkoxy-d-Ce-alkyl, optionally substituted C-rC 6 - alkylthio-C ⁇ -C 6 -alkyl, optionally substituted d-d-alkylsulfinyl-d-Ce-alkyl.
  • Ci-C 6 -alkylsulfonyl-Ci-C 6 -alkyl optionally substituted d- Ce-alkylcarbonyl, optionally substituted C C 6 -alkoxycarbonyl, optionally substituted C ⁇ -C 6 -alkylaminocarbonyl, optionally substituted Ci-d-alkoxyimino- methyl, optionally substituted di-(C ⁇ -C 6 -alkyl)-aminocarbonyl, whereby the alkyl groups may be identical or different, optionally substituted C ⁇ -C 6 -alkylaminothio- carbonyl, optionally substituted di-(C ⁇ -C 6 -alkyl)-aminothiocarbonyl, whereby the alkyl groups may be identical or different, optionally substituted Ci-C 6 -alkylamino and optionally substituted di-(CrC 6 -alkyl)-amino, whereby the alkyl groups may be identical or different,
  • D is a direct bond, O, NH, N-(d-C 6 -alkyl), N-formyl, S, SO, S0 2 , optionally substituted d-C 6 -alkylene, optionally substituted C 2 -C 6 -alkenylene, optionally substituted C 2 -C 6 -alkinylene, C ⁇ -C 6 -alkylenoxy, C 2 -C 6 -alkenylenoxy.
  • E is an optionally substituted aryl or heterocyclyl; and the aforementioned alkyl, alkenyl and alkinyl groups may be substituted perse or as a structural element, for example in alkoxy or cycloalkyl, independently of each other, by one or more radicals from the group halogen, amino, nitro, hydroxy, cyano and carboxy; or a salt thereof.
  • Further aspects of the present invention are a method for the preparation of the compounds and their usage, including their possible enantiomers, enantiomer mixtures and/or tautomers, in free form or in the form of a salt, and also, as intermediates, possible N-oxides of these compounds, where appropriate tautomers, in free form or in the form of a salt, of these intermediates, and a method for the preparation and the usage of these intermediates and their tautomers.
  • Some of the compounds of formula (I) contain asymmetric carbon atoms, whereupon the compounds may occur in optically active form.
  • the corresponding formulae are to include all these possible isomeric forms, as well as mixtures thereof, for example racemates, as well as where appropriate their salts or their N-oxides, even if this is not specifically mentioned in each case.
  • Carbon-containing groups and compounds contain, unless otherwise defined, in each case 1 up to and including 6, preferably 1 up to and including 4, in particular 1 or 2, carbon atoms.
  • Alkyl - as a group perse and as structural element of other groups and compounds, for example of alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, alkoxy- carbonyl, alkylamino, alkoxyiminomethyl, alkylaminocarbonyl and alkylaminothio- carbonyl, - is, in each case with due consideration of the specific number of carbon atoms in the group or compound in question, either straight-chained, i.e. methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, i.e.
  • Alkyl may be optionally substituted by one or more radicals, such as halogen, amino, nitro, hydroxy, cyano and carboxy.
  • Alkenyl - as a group perse and as structural element of other groups and compounds such as alkenyloxy - is, in each case with due consideration of the specific number of carbon atoms in the group or compound in question, either straight-chained, for example vinyl, 1 -methylvinyl, allyl, 1-butenyl or 2-hexenyl, or branched, for example isopropenyl.
  • Alkenyl may be optionally substituted by one or more radicals, such as halogen, amino, nitro, hydroxy, cyano and carboxy.
  • Alkinyl - as a group perse and as structural element of other groups and compounds such as alkinyloxy - is, in each case with due consideration of the specific number of carbon atoms in the group or compound in question, either straight-chained, for example propargyl, 2-butinyl or 5-hexinyl, or branched, for example 2-ethinylpropyl or 2-propargylisopropyl.
  • Alkinyl may be optionally substituted by one or more radicals, such as halogen, amino, nitro, hydroxy, cyano and carboxy.
  • C 3 -C 6 -cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • Cycloalkyl may be optionally substituted by one or more radicals, such as halogen, amino, nitro, hydroxy, cyano and carboxy.
  • Alkylene - as a group perse and as structural element of other groups and compounds such as of halogenalkyiene - is, in each case with due consideration of the specific number of carbon atoms in the group or compound in question, either straight-chained, for example -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - or -CH 2 CH 2 CH 2 CH 2 -, or branched, for example -CH(CH 3 )-, -CH(C 2 H 5 )-, -C(CH 3 ) 2 -. - CH(CH 3 )CH 2 - or -CH(CH 3 )CH(CH 3 )-.
  • Alkylene may be optionally substituted by one or more radicals, such as halogen, amino, nitro, hydroxy, alkoxy, cyano and carboxy.
  • Aryl is phenyl or naphthyl, especially phenyl.
  • Heterocyclyl signifies a 5-, 6- or 7-membered, saturated or unsaturated ring with one, two or three hetero atoms selected from the group comprising N, O and S. Preference is given to unsaturated 5- and 6-rings that have one nitrogen atom as a hetero atom and optionally one further hetero atom, preferably nitrogen or sulphur, especially nitrogen.
  • Preferred unsaturated heterocyclyl radicals are: pyrazinyl, pyridyl(3'), pyridyl(2'), py ⁇ ' dyl(4'), pyrimidinyl(2'), pyrimidinyl(4'), pyrimidinyl(5'), pyridazinyl(3').
  • pyridazinyl(4') ( thiazolyl(2'), thiazolyl(4'), thiazolyl(5'), pyrrolyl(2'), pyrrolyl(3'), pyrazolyl(3'), pyrazolyl(4'), pyrazolyl(5'), oxazolyl(2'), oxazolyl(4*), oxazolyl(5'), furanyl(2'), furanyl(3'), thienyl(2'), thi ⁇ nyl(3'), isothiazolyl(3'), isothiazolyl(4'), isothiazolyl(5'), isothiazolyl(3'), isothiazolyl(4'), isothiazolyl(5'), triazolyl(3'), triazolyl(4'), triazolyl(5') .
  • Halogen - as a group perse and as structural element of other groups and compounds such as halogenalkyl, halogenalkenyl and halogenalkinyl - is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, mainly fluorine or chlorine, particularly fluorine.
  • Halogen-substituted carbon-containing groups and compounds such as halogenalkyl, halogenalkenyl or halogenalkinyl, can be partially halogenated or perhalogenated, in the case of polyhalogenation it being possible for the halogen substituents to be identical or different.
  • halogenalkyl - as a group perse and as structural element of other groups and compounds such as halogenalkoxy - are methyl which is mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHF 2 or CF 3 ; ethyl which is mono- to pentasubstituted by fluorine, chlorine and/or bromine, such as CH2CF3, CF2CF3, CF2CCI3, 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, 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 3 or CH(CF 3 ) 2 ; and butyl or one of its iso
  • Halogenalkinyl is e.g. CH 2 C ⁇ CF, CH 2 C ⁇ CCH 2 CI or CF 2 CF 2 CsCCH 2 F.
  • Compounds of formula (I) having at least one basic centre may form e.g. acid addition salts. These are formed for example with strong inorganic acids, such as mineral acids, e.g. perchloric acid, sulphuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohaiic acid, with strong organic carboxylic acids, typically d-C 4 alkanecarboxylic acids substituted where appropriate for example by halogen, e.g. acetic acid, such as optionally unsaturated dicarboxylic acids, e.g.
  • mineral acids e.g. perchloric acid, sulphuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohaiic acid
  • strong organic carboxylic acids typically d-C 4 alkanecarboxylic acids substituted where appropriate for example by halogen, e.g. acetic acid, such as optionally unsaturated dicarboxylic acids,
  • oxalic, malonic, succinic, maleic, fumaric or phthaiic acid such as hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic acids, such as C 1 - dalkanesulfonic or arylsulfonic acids substituted where appropriate for example by halogen, e.g. methanesulfonic or p-toluenesulfonic acid.
  • 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 morphoiine, 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.
  • Preferred compounds within the scope of this invention are agrochemically advantageous salts.
  • Ri is an unsaturated 5- or 6-membered heterocycle, whereby the heterocycle is joined via a carbon atom.
  • Ri is a substituted unsaturated 5- or 6-membered heterocycle, whereby the heterocycle is joined via a carbon atom.
  • R 1 is a halogen-substituted unsaturated 5- or 6- membered heterocycle, whereby the heterocycle is joined via a carbon atom.
  • R 2 is CrC ⁇ -alkyl or CrC ⁇ -haioalkyl, especially
  • compounds of formula (I), in which R 1 f R 2) R 3 and A are defined as given for formula (I), can be prepared by reacting piperidine-4-carbonitriles of the general formula (VIII), wherein R 2 , R 3 and A are defined as above, with compounds of formula (VI), wherein Ri and A are defined as above and U 2 is a leaving group.
  • the compounds of formula (I) according to the invention are active substances of preventive and/or curative merit for use in pest control even at low concentrations and offer a very favourable spectrum of biocidal activity with favourable tolerability in warm-blooded animals, fish, and plants.
  • 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.
  • the said animal pests include, for example, those that are mentioned in the European Patent application EP-A-736'252.
  • the pests mentioned therein are thus included by reference in the object of the present invention.
  • 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 in some instances for parts of plants whose growth does not occur until later.
  • Target crops include especially cereals, such as wheat, barley, rye, oats, rice, com 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 pesticidal compositions, 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), comprising at least one active ingredient of the invention.
  • pesticidal compositions 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), comprising at least one active ingredient of the invention.
  • the active ingredient is used in these compositions in pure form and 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.
  • 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.
  • Active ingredient 0,1 to 10%, preferably 0,1 to 1%
  • Solid carrier 99.9 bis 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 also contain further solid or liquid adjuvants, such as stabilisers, e.g. vegetable oils, epoxidised where appropriate (e.g. epoxidised 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, epoxidised where appropriate (e.g. epoxidised 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).
  • 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.
  • T e 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.
  • the index n signifies the number 0 if there is no entry in the column (A) n -
  • Compound nos. 2.1 to 2.284 of formula (IB) are those which have a combination of substituents R ⁇ R 2 and (A) n each corresponding to one line of Table 1.
  • Compound nos. 3.1 to 3.284 of formula (IC) are those which have a combination of substituents R,, R 2 and (A) n each corresponding to one line of Table 1.
  • Example B1 Effect on Aphis craccivora
  • Pea seedlings are infected with Aphis craccivora, subsequently sprayed with a spray mixture containing 400 ppm of active ingredient, and then 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.
  • the compounds of table 1 especially compounds 1.5 and 1.6, show good efficacy against Aphis craccivora in this test.
  • Example B2 Systemic effect on Mvzus 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.
  • the compounds of table 1 especially compounds 1.5 and 1.64, show good efficacy against Myzus persicae in this test.
  • 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 1 o 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.
  • Young bean plants are colonised with a mixed population of Tetranychus urticae and, one day later, are sprayed with an aqueous emulsion spray mixture containing 400 ppm of active ingredient. The plants are subsequently incubated for 6 days at 25°C and then evaluated. The percentage reduction of the population (% response) is determined by comparing the total number of dead eggs, larvae, and adults on the treated plants with those on the untreated plants.
  • the compounds of table 1 especially compounds 1.7, 1.60 and 1.64, show good efficacy against Tetranychus urticae in this test.
  • Example B5 Effect on Trichostron ⁇ ylus colubriformis and Haemonchus contortus in Mongolian qerbils (Meriones un ⁇ uiculatus) using subcutaneous injection
  • the compounds of Table 1 especially compounds 1.13, 1.73, 1.87, 1.92, 1 .147, show good efficacy against Trichostrongylus colubriformis and Haemonchus contortus in this test.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Hydrogenated Pyridines (AREA)

Abstract

L'invention concerne des composés représentés par la formule (I), dans laquelle les substituants sont tels que définis dans les revendications. L'invention concerne la préparation de ces composés, leur utilisation pour lutter contre les parasites, et des produits intermédiaires servant à préparer ces composés.
PCT/EP2000/008660 1999-09-07 2000-09-05 Cyanopiperidines WO2001017965A2 (fr)

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CH163999 1999-09-07
CH1639/99 1999-09-07

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US6953801B2 (en) 2001-05-22 2005-10-11 Neurogen Corporation Melanin concentrating hormone receptor ligands: substituted 1-benzyl-4-aryl piperazine analogues
US7115632B1 (en) * 1999-05-12 2006-10-03 G. D. Searle & Co. Sulfonyl aryl or heteroaryl hydroxamic acid compounds
JP2006528642A (ja) * 2003-07-24 2006-12-21 ユーロ−セルティーク エス．エイ． 疼痛を治療するのに有用な治療薬
US7253168B2 (en) 2004-04-07 2007-08-07 Neurogen Corporation Substituted 1-benzyl-4-substituted piperazine analogues
US7776861B2 (en) * 2003-07-24 2010-08-17 Purdue Pharma L.P. Therapeutic agents useful for treating pain
US8476277B2 (en) 2007-04-27 2013-07-02 Purdue Pharma L.P. TRPV1 antagonists including dihydroxy substituent and uses thereof
WO2013164954A1 (fr) * 2012-05-01 2013-11-07 住友化学株式会社 Composé de pipéridine et son utilisation pour la lutte contre des organismes nuisibles
US9273043B2 (en) 2011-06-22 2016-03-01 Purdue Pharma L.P. TRPV1 antagonists including dihydroxy substituent and uses thereof
WO2023102022A1 (fr) * 2021-11-30 2023-06-08 Vertex Pharmaceuticals Incorporated Dérivés de 4-phényl-2-(1h-1,2,3-triazol-4-yl)pipéridin-4-ole utiles en tant qu'inhibiteurs d'apol1 et leurs procédés d'utilisation
US11801234B2 (en) 2020-03-06 2023-10-31 Vertex Pharmaceuticals Incorporated Methods of treating APOL-1 dependent focal segmental glomerulosclerosis
US11866446B2 (en) 2020-08-26 2024-01-09 Vertex Pharmaceuticals Incorporated Inhibitors of APOL1 and methods of using same

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7115632B1 (en) * 1999-05-12 2006-10-03 G. D. Searle & Co. Sulfonyl aryl or heteroaryl hydroxamic acid compounds
JP2004507607A (ja) * 2000-08-30 2004-03-11 クラリアント　インターナショナル　リミテッド 液晶混合物
US6953801B2 (en) 2001-05-22 2005-10-11 Neurogen Corporation Melanin concentrating hormone receptor ligands: substituted 1-benzyl-4-aryl piperazine analogues
US7081458B2 (en) 2001-05-22 2006-07-25 Neurogen Corp. Melanin concentrating hormone receptor ligands: substituted 1-benzyl-4-aryl piperazine analogues
US8637548B2 (en) 2003-07-24 2014-01-28 Purdue Pharma L.P. Therapeutic agents useful for treating pain
JP2006528642A (ja) * 2003-07-24 2006-12-21 ユーロ−セルティーク エス．エイ． 疼痛を治療するのに有用な治療薬
US7572812B2 (en) 2003-07-24 2009-08-11 Purdue Pharma, L.P., Usa Therapeutic agents useful for treating pain
US7776861B2 (en) * 2003-07-24 2010-08-17 Purdue Pharma L.P. Therapeutic agents useful for treating pain
US8178560B2 (en) 2003-07-24 2012-05-15 Purdue Pharma L.P. Therapeutic agents useful for treating pain
US8349842B2 (en) 2003-07-24 2013-01-08 Purdue Pharma, L.P. Therapeutic agents useful for treating pain
US9301953B2 (en) 2003-07-24 2016-04-05 Purdue Pharma L.P. Therapeutic agents useful for treating pain
US7253168B2 (en) 2004-04-07 2007-08-07 Neurogen Corporation Substituted 1-benzyl-4-substituted piperazine analogues
US8575199B2 (en) 2007-04-27 2013-11-05 Purdue Pharma L.P. Formula (IA″) compounds comprising (piperidin-4-yl)pyridine or (1,2,3,6-tetrahydropyridin-4-4yl) as TRPV1 antagonists
US8476277B2 (en) 2007-04-27 2013-07-02 Purdue Pharma L.P. TRPV1 antagonists including dihydroxy substituent and uses thereof
US9878991B2 (en) 2007-04-27 2018-01-30 Purdue Pharma L.P. TRPV1 antagonists including dihydroxy substituent and uses thereof
US10584110B2 (en) 2007-04-27 2020-03-10 Purdue Pharma L.P. TRPV1 antagonists including dihydroxy substituent and uses thereof
US9273043B2 (en) 2011-06-22 2016-03-01 Purdue Pharma L.P. TRPV1 antagonists including dihydroxy substituent and uses thereof
US9630959B2 (en) 2011-06-22 2017-04-25 Purdue Pharma L.P. TRPV1 antagonists including dihydroxy substituent and uses thereof
US10450308B2 (en) 2011-06-22 2019-10-22 Purdue Pharma L.P. TRPV1 antagonists including dihydroxy substituent and uses thereof
WO2013164954A1 (fr) * 2012-05-01 2013-11-07 住友化学株式会社 Composé de pipéridine et son utilisation pour la lutte contre des organismes nuisibles
US11801234B2 (en) 2020-03-06 2023-10-31 Vertex Pharmaceuticals Incorporated Methods of treating APOL-1 dependent focal segmental glomerulosclerosis
US11866446B2 (en) 2020-08-26 2024-01-09 Vertex Pharmaceuticals Incorporated Inhibitors of APOL1 and methods of using same
WO2023102022A1 (fr) * 2021-11-30 2023-06-08 Vertex Pharmaceuticals Incorporated Dérivés de 4-phényl-2-(1h-1,2,3-triazol-4-yl)pipéridin-4-ole utiles en tant qu'inhibiteurs d'apol1 et leurs procédés d'utilisation

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AU7514700A (en) 2001-04-10

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