WO1998000408A1 - N-phenylimino heterocyclic derivatives and their use as herbicides - Google Patents

N-phenylimino heterocyclic derivatives and their use as herbicides Download PDF

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Publication number
WO1998000408A1
WO1998000408A1 PCT/EP1997/003420 EP9703420W WO9800408A1 WO 1998000408 A1 WO1998000408 A1 WO 1998000408A1 EP 9703420 W EP9703420 W EP 9703420W WO 9800408 A1 WO9800408 A1 WO 9800408A1
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formula
compound
group
alkyl
hydrogen
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PCT/EP1997/003420
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French (fr)
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Haukur Kristinsson
Hermann Rempfler
Hans Nussbaumer
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Novartis Ag
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Priority to AU34405/97A priority Critical patent/AU3440597A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
    • C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
    • C07D253/06—1,2,4-Triazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • 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
    • A01N43/74—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 five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters 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
    • 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<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C261/00—Derivatives of cyanic acid
    • C07C261/04—Cyanamides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07—ORGANIC CHEMISTRY
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    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/28—Nitrogen atoms not forming part of a nitro radical
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    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/48—Nitrogen atoms not forming part of a nitro radical
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    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
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    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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    • 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
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    • 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
    • C07D413/12—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 linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to novel N-phenylimino heterocycles with herbicidal activity, processes for their preparation, compositions which comprise these compounds, and their use for controlling weeds, especially in growing crops or for inhibiting plant growth.
  • Iminothiazolines with a herbicidal action are described, for example, in EP-A-0 529 482, EP-A-0 446 802 and US-A-5 244 863.
  • the present invention thus relates to compounds of the formula I
  • R 3 is CrC 4 alkyl, it being possible for this radical to be substituted by halogen, cyano, d-
  • R 5 and R 6 are, independently of one another, hydrogen or CrC 4 alkyl
  • R T is halogen, C 1 -C 4 alkyl, C ⁇ -C 4 haloalkyl, C C 4 alkoxy, d-C haloalkoxy, CrC 4 alkylthio, d-dhaloalkylthio, cyano or nitro;
  • R 2 is hydrogen, halogen, C ⁇ -C 4 alkyl or C ⁇ -C 4 haloalkyl
  • R 4 is Ci-C ⁇ alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or C 3 -C ⁇ cycloalkyl, it being possible for these alkyl, alkenyl and alkynyl radicals to be substituted by halogen, C ⁇ -C 3 alkyl, d-C 3 alkoxy,
  • R 4 is CrC 7 alkylaminosulfonyl, di-d-CTalkylaminosulfonyl, C ⁇ -C 7 alkylsulfonyl or
  • alkylsul.inyl it being possible for these alkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl and alkylsulfinyl radicals to be substituted by halogen, C C 3 alkoxy, d-daikylthio, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkoxy, cyano, aryl, aryloxy or a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or
  • R 4 is cyano, arylsulfonyl, sulfamoyl or a -C(X)R 7 or -C(X)NHR group;
  • X is oxygen or sulfur
  • R 7 is C ⁇ -C ⁇ alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, d-C 6 alkoxy, C 2 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy,
  • R 7 is hydrogen, C 3 -C 6 -cycloalkyl, C 3 -C 6 cycloalkoxy, C 3 -C 6 cycloalkylthio, aryl, aryloxy, hetaryl, a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or a saturated heterocyclyloxy radical which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms
  • R 9 is hydrogen, CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl, it being possible for these alkyl, alkenyl and alkynyl radicals to be substituted by halogen, d-C 3 alkyl, d-C 3 alkoxy, d-C 3 alkylthio, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkoxy, hydroxyl, cyano, aryl,
  • alkyl groups occurring in the definitions of substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the various isomeric pentyl, h ⁇ xyl and heptyl radicals.
  • Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl are preferred.
  • Halogen means iodine and preferably fluorine, chlorine and bromine.
  • Alkoxy radicals preferably have a chain length of from 1 to 6 carbon atoms.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert- butoxy and one of the various isomeric pentoxy and hexyloxy radicals; preferably methoxy, ethoxy and propoxy.
  • Alkylthio radicals preferably have a chain length of from 1 to 4 carbon atoms.
  • Alkylthio is, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio.
  • Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino and the isomeric butylamino radicals.
  • Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylarnino, dibutylamino and diisopropylamino.
  • Alkylamino radicals with a chain length of from 1 to 6 carbon atoms are preferred.
  • the cycioalkyl radicals preferably have 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • the cycloalkyl radicals may, unless otherwise indicated, be substituted by halogen, C ⁇ -C 3 alkyl, d-C 3 alkoxy or C ⁇ -C 3 alkylthio.
  • Aryl in the definition of the radicals R 3 , FU, R and R 9 is ⁇ - or ⁇ -naphthyl and, in particular, phenyl, it being possible for these aromatic rings to carry one or more, identical or different substituents, for example halogen, nitro, cyano, d-C alkoxy, d-C 4 haloalkoxy, d-dalkylthio, d-dhaloalkylthio, C ⁇ -C 4 alkyl and d-C haloalkyl.
  • substituents for example halogen, nitro, cyano, d-C alkoxy, d-C 4 haloalkoxy, d-dalkylthio, d-dhaloalkylthio, C ⁇ -C 4 alkyl and d-C haloalkyl.
  • Heteroaryl in the definition of R 7 means, in particular, five- or six-membered aromatic heterocyclic rings, for example 2-, 3- or 4-pyridyl, pyrimidyl, pyrazolyl, pyrazinyl, pyridazinyl, imidazolyl, triazolyl, pyrrolyl, furyl, thienyl, oxazolyl, thiazolyl or isoxazolyl; preferably 2- and 3-pyridyl, 2- and 3-furyl and 2-thienyl.
  • heterocycles can in turn be substituted; examples of substituents are d-C 3 alkyl, halogen, d-C 3 haloalkyl, cyano, nitro, hydroxyl, d- C 3 alkoxy, C ⁇ -C 3 haloalkoxy, amino, C ⁇ -C 3 alkylamino, di-d-C 3 alkylamino or carboxyl.
  • Saturated heterocyclic rings mean ring systems which, besides carbon atoms, contain at least one hetero atom such as nitrogen, oxygen or sulfur atom. Ring systems of these types preferably contain 3 to 6 ring atoms, for example oxiranyl, aziridinyl, azetidinyl, oxetanyl, thietanyl, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, tetrahydropyranyl, dioxanyl, 1 ,3- dioxanyl, piperidinyl, morpholinyl, thiomorpholinyl or piperazinyl.
  • nitrogen atom as hetero atom
  • the bonding to the ring system can take place both via the ring carbon atom and via the ring nitrogen atom.
  • haloalkyl are alkyl groups substituted one or more times, in particular once to three times by halogen, where halogen means specifically iodine and, in particular, fluorine, chlorine and bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, fluorochloromethyl, 2-fluoroethyl, 2,2,2- trifluoroethyl, 1 ,1 ,2,2,2-pentafluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyi and 2-chloro-2- propyl.
  • halogen means specifically iodine and, in particular, fluorine, chlorine and bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, fluorochloromethyl, 2-fluoroethyl, 2,2,2- trifluoroeth
  • Haloalkoxy radicals preferably have a chain length of from 1 to 6 carbon atoms.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2-fluoroethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 1 ,1 ,2,2,2-pentafiuoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
  • Haloalkylthio radicals preferably have a chain length of from 1 to 4 carbon atoms.
  • Haloalkylthio is, for example, trifluoromethylthio or 2,2,2-trifluoroethylthio.
  • alkenyl and alkynyl groups can be straight-chain or branched, and this also applies to the alkenyl and alkynyl moiety in alkenylthio, alkynylthio, alkenylamino and alkynylamino groups.
  • Alkenyl means, for example, vinyl, 1 -methylvinyl, allyl, methallyl or 2-butenyl. Alkenyl radicals with a chain length of from 2 to 6 carbon atoms are preferred. The alkenyl radicals are preferably linked via a saturated carbon atom to a hetero atom.
  • alkynyl examples include propargyl, 2-butynyl, 2-methyl-3-butyn-2- yl, 3-butyn-2-yl and 4-pentynyl.
  • Alkynyl radicals with a chain length of from 3 to 6 carbon atoms are preferred.
  • the alkynyl radicals are preferably linked via a saturated carbon atom to a hetero atom.
  • Alkenylthio means, for example, allylthio, methallylthio, 3-butenylthio, 4-pentenylthio or 2-hexenylthio.
  • Alkynylthio means, for example, propargylthio, 1-methylpropargylthio, 3-butynylthio, 4-pentynylthio or 2-hexynylthio.
  • Alkenylamino is, for example, allylamino, methallylamino and 2-butenylamino.
  • Alkynylamino is, for example, propargylamino, 1 -methylpropargylamino and 4-pentynylamino.
  • Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfony, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl and one of the isomeric pentyl-, hexyl- and heptylsulfonyl radicals; preferably methylsulfonyl and ethylsulfonyl.
  • the invention likewise embraces the salts which the compounds of the formula I are able to form with acids.
  • Acids suitable for forming the acid addition salts are both organic and inorganic acids. Examples of such acids are, inter alia, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, various phosphorus acids, sulfuric acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, fumaric acid, organic sulfonic acids, lactic acid, tartaric acid, citric acid and salicylic acid.
  • the present invention also embraces these isomers.
  • Preferred compounds of the formula I are those in which R, is halogen, d-C 4 haloalkyl, cyano, nitro, d-C 4 haloalkoxy or d-C 4 haloalkylthio; and R 7 has the same meaning as indicated under formula I with the exception of C 7 and C 8 alkyl.
  • Preferred compounds of the formula I are those in which Ri is trifluoromethyl or trifluoromethoxy.
  • R 3 is methyl, ethyl or cyclopropyl.
  • R 4 is a -C(X)R 7 group; X is oxygen; and R 7 is C C 6 alkyl, d-C 6 alkoxy or d-C ⁇ alkylamino, it being possible for these radicals to be substituted by halogen, d-C 3 alkyl, C ⁇ -C 3 alkoxy, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkoxy.
  • particularly preferred compounds are those in which R 7 is d-C 6 alkyl, d-C 6 haloalkyl or d-C 6 -alkoxy.
  • Important compounds of the formula I are those in which -A- is a group
  • Ri is trifluoromethyl or trifluoromethoxy
  • R 4 is a -C(X)R 7 group
  • X is oxygen
  • R 7 is C ⁇ -C 3 haloalkyl or d-C 4 alkoxy.
  • R 3 is methyl or ethyl; Ri is trifluoromethyl or trifluoromethoxy; R 2 is hydrogen; R 4 is a -C(X)R 7 group; X is oxygen; and R 7 is d-C 4 alkoxy.
  • a group of preferred compounds of the formula I is that in which -A- is a group
  • R 3 is d-C 4 alkyl, cyclopropyl, phenyl or benzyloxymethyl; Ri is
  • R 4 is cyano, methyl, methyl • HI salt, propargyl, cyclopentyl, benzyl, methylsulfonyl, dimethylaminosulfonyl, trifluoromethylsulfonyl, 2-chlorophenylsulfonyl or 2-chloro-2-propylsulfinyl; or R 4 is a -C(X)R 7 group; X is oxygen or sulfur; R 7 is hydrogen, C ⁇ -C 3 alkyl, cyanomethyl, methoxymethyl, methoxyethyl
  • Another group of preferred compounds of the formula I is that in which -A- is a group ft (A3); R 3 is C ⁇ -C 4 alkyl, hydroxymethyl, chloromethyl,
  • R 6 is hydrogen or methyl
  • R t is fluorine, C ⁇ - or C 2 alkyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy or trifluoromethylthio
  • R 2 is hydrogen, 4-fluoro, 4- or 6-chloro or 5-trifluoromethyl; or R 2 in position 2 of the phenyl ring and Ri together form a -OCF 2 O- group
  • R 4 is methyl, propargyl, cyclopentyl, benzyl, cyano, methylsulfonyl, isopropylsulfonyl, trifluoromethylsulfonyl, 2- chloro-2-propylsulfinyl, phenylsulfonyl or 2-chlorophenylsulfonyl; or R 4 is a -C(X)R 7 group; X is oxygen or sulfur
  • R 3 I — CH C-N— (A!);
  • R 3 is C or C 2 alkyl, cyclopropyl or phenyl;
  • R 5 is hydrogen, methyl or
  • R 5 cyclopropyl; R 5 is hydrogen, methyl or cyclopropyl; Ri is cyano, trifluoromethyl, pentafluoroethyl, trifluoromethoxy or trifluoromethylthio; R 2 is hydrogen; or R 2 in position 2 of the phenyl ring and R together form a -OCF 2 O- group; R 4 is cyano or a -C(X)R 7 group; X is oxygen; and R 7 is methyl, difluoromethyl, trifluoromethyl, d-C 3 alkoxy or pentafluoroethyl.
  • the process according to the invention for preparing the compounds of the formula I comprises alkylating a compound of the formula II
  • R 3 has the meanings stated under formula I, and L, is a leaving group, for example halogen, preferably chlorine, bromine or iodine, alkylsulfonyl or arylsulfonyl, preferably
  • R 4 is d-C 6 alkyl, C 3 -C e alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C ⁇ -C 7 alkylaminosulfonyl, di-C -C 7 alkylaminosulfonyl, C C 7 alkylsulfonyl or d-dalkylsulfinyl, it being possible for these radicals to be substituted as stated under formula I, cyano, arylsulfonyl or sulfamoyl, with a compound of the formula XIa
  • L 2 is a leaving group, for example halogen, preferably
  • R 3 which -A- is a grouprage, . ' . , composer,_ (A3) and R 3 and R e are defined as under
  • formula I comprises c) cyclizing a compound of the formula
  • R 4 is d-C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C ⁇ -C 7 alkylaminosulfonyl, di-d-C 7 alkylaminosulfonyl, C ⁇ -C 7 alkylsulfonyl or d-C 7 alkylsulfinyl, it being possible for all of these radicals to be substituted as indicated under formula I, cyano, arylsulfonyl or sulfamoyl, with a compound of the formula XIa
  • R has the stated meaning
  • L 2 is a leaving group, for example halogen, preferably chlorine, bromine or iodine, hydroxyl, R OSO 2 O-, CH 3 SO 2 O- or
  • R 7 and X have the stated meaning, and is a leaving group, for example halogen, preferably fluorine, chlorine or bromine, or imidazolide, triazolide, N-hydroxyphthalimide or R 7 C(X)O-, or
  • L 3 is a leaving group, for example halogen, preferably chlorine or bromine, and R ⁇
  • reaction scheme 1 The processes according to the invention for preparing compounds of the formulae I and la, lb and Ic are explained in detail in the following reaction schemes 1 , 2 and 3.
  • Reaction scheme 1 Reaction scheme 1 :
  • the starting compounds of the formula II are known. They are prepared in analogy to known processes as described, for example, in DE-A-3 538 128.
  • ⁇ -halo ketones of the formula X can be bought or can be prepared in analogy to known processes as described, for example, in Organic Synthesis, Vol. 55, page 24 (1973).
  • the ⁇ -cyanamido ketones of the formula III are expediently prepared by alkylation of the arylcyanamides of the formula II with ⁇ -halo ketones, ⁇ -alkylsulfonyl ketones or ⁇ -arylsulfonyl ketones of the formula X in the presence of a base in an organic solvent at temperatures of 0-200'C, preferably at 0-60°C.
  • the alkylation is as a rule complete within 1-30 hours depending on the solvent used and the reaction temperature.
  • base inorganic and organic bases for example, hydroxides, for example sodium or potassium hydroxide, carbonates such as sodium or potassium carbonate or bicarbonates such as sodium or potassium bicarbonate, hydrides, for example sodium or calcium hydride, alcoholates, for example sodium or potassium methoxide, sodium or potassium ethoxide or sodium or potassium tert-butoxide, alkyl- and arylamines, for example triethylamine, N,N-diethylaniline and pyridine. It is moreover advantageous to add the base used in a ratio of amounts of 1 -100 equivalents based on the starting compound of the formula II.
  • hydroxides for example sodium or potassium hydroxide
  • carbonates such as sodium or potassium carbonate or bicarbonates such as sodium or potassium bicarbonate
  • hydrides for example sodium or calcium hydride
  • alcoholates for example sodium or potassium methoxide, sodium or potassium ethoxide or sodium or potassium tert-butoxide
  • alkyl- and arylamines
  • Suitable solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitro compounds, for example nitroethane or
  • Suitable as base are inorganic and organic bases, for example hydrides, for example sodium hydride, alcoholates, for example sodium or potassium methoxide, sodium or potassium ethoxide or sodium or potassium tert-butoxide, amidine bases, for example 1 ,8-diazabicyclo[5.4.0]u ⁇ dec-7-ene (DBU) or 1 ,5-diazabicyclo[4.3.0]non-5-ene (DBN), alkyl- or arylamines for example triethylamine or N,N-diethylaniline, and pyridine.
  • hydrides for example sodium hydride
  • alcoholates for example sodium or potassium methoxide, sodium or potassium ethoxide or sodium or potassium tert-butoxide
  • amidine bases for example 1 ,8-diazabicyclo[5.4.0]u ⁇ dec-7-ene (DBU) or 1 ,5-diazabicyclo[4.3.0]non-5-ene
  • suitable organic solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acet
  • the substituent R is introduced on the imino nitrogen atom of compounds of the formula IV expediently by standard methods via 1) alkylation or sulfonylation, 2) (thio)acylation (formylation), (thio)carboxylation or (thio)amidation, or 3) by reaction with iso(thio)cyanates using appropriate reagents of the formula XIa (for example alkyl halides, hydroxyalkanes, dialkyl sulfates or alkylsulfonyl chlorides), Xlb (for example chloroformic esters, carbonyl halides, anhydrides or carboxylic acids) or Xlc (for example iso(thio)cyanates) in an organic solvent in the presence or absence of a base.
  • XIa for example alkyl halides, hydroxyalkanes, dialkyl sulfates or alkylsulfonyl chlorides
  • Xlb for example chloroformic esters, carbony
  • N-(thio)acrylations, N-(thio)carboxylations and N-(thio)amidations can be carried out in analogy to Houben-Weyl, "Methoden der Organischen Chemie", Volume VIII, page 138 et seq., ibid. Volume VIII, page 154 et seq., Volume IX, page 833 et seq., Volume IX, page 885 et seq., Volume XI, pages 69-72 and Volume XI/2, page 3 et seq., and N-sulfonylations in analogy to Houben-Weyl, "Methoden der Organischen Chemie", Volume IX, page 398 et seq.
  • the acylation reaction is advantageously carried out in the presence of 1-10 equivalents of a carboxylic acid activating reagent, for example carbodiimide, for example N,N'-dicyclohexy!carbodiimide (DCC) or 1 ,1 '-carbonyldiimidazole (lm 2 CO).
  • a carboxylic acid activating reagent for example carbodiimide, for example N,N'-dicyclohexy!carbodiimide (DCC) or 1 ,1 '-carbonyldiimidazole (lm 2 CO).
  • the alkylation, acylation, carboxylation, amidation and sulfonylation reactions with reagents XIa and Xlb are generally carried out in an organic solvent, in the presence or absence of a base, at temperatures of 0-100°C.
  • the reactions are as a rule complete within 1/2-30 hours depending on the solvent used and base used.
  • Bases which can be used are both inorganic and organic bases, for example hydroxides, for example sodium or potassium hydroxide, carbonates such as sodium or potassium carbonate or bicarbonates such as sodium or potassium bicarbonate, hydrides, for example sodium hydride, alcoholates, for example sodium or potassium methoxide, sodium or potassium ethoxide, sodium or potassium tert-butoxide, alkyl- and arylamines, for example triethylamine or N,N-diethylaniline, and pyridine, 4-N,N-dimethylaminopyridine (DMAP) and DBU.
  • the base is preferably used in a ratio of amounts of 1-100 equivalents relative to the compound of the formula IV employed.
  • suitable organic solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acet
  • the addition reactions with the reagent Xlc can expediently be carried out by allowing the compound of the formula IV and the iso(thio)cyanate of the formula Xlc to react together in an inert aprotic organic solvent such as an aliphatic or cyclic ether, for example diethyl ether, 1 ,2-dimethoxyethane, tetrahydrofuran or dioxane, a chlorinated aliphatic hydrocarbon, for example methylene chloride, an aromatic compound, for example toluene or xylenes, an aliphatic ester, for example ethyl acetate, or a nitrile, for example acetonitrile, in the presence of a catalyst, for example 4-N,N-dimethylaminopyridine or triethylamine, preferably at temperatures from 0°C to the reflux temperature of the reaction solution.
  • a catalyst for example 4-N,N-dimethylaminopyridine or tri
  • the ring expansion reaction by route a) in reaction scheme 1 to give the 4,5-dihydro-2H- [1 ,2,4]triazin-3-ylideneamines of the formula Ic takes place starting from the 3H-oxazol-2- ylideneamines of the formula la, expediently with hydrazines of the formula XII in an organic solvent at temperatures of 0-150°C.
  • the ring expansion reaction is as a rule complete after 1 -100 hours.
  • solvents suitable for this are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, nitrites, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamin, N,N-diethylaniline or N-methylmorpholine, or amides, for example N,N-dimethylform
  • the ring rearrangement reaction is as a rule complete after 1-30 hours.
  • suitable solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N- diethylaniline or N-methylmorpholine, or amides, for example N,N-dimethylformamide.
  • the subsequent dehydration of the compounds of the formula V takes place, for example, thermally in the presence of catalytic amounts of acid, for example p-toluenesulfonic acid, or in the presence or equimolar amounts of anhydrides, for example acetic anhydride or trifluoroacetic anhydride, or by reaction with alkyl- or arylsulfonyl halides, for example methylsulfonyl chloride, in the presence or absence of bases, for example triethylamine.
  • the dehydration reaction advantageously takes place in an organic solvent at temperatures of 0-200°C and is as a rule complete after 1/2-30 hours.
  • anhydride is also possible where appropriate to employ the anhydride as solvent.
  • suitable solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or die
  • Reaction scheme 2 depicts two processes according to the invention for preparing
  • the process by route c) starts from ⁇ -cyanamido ketones of the formula III which can expediently be cyclized with the aid of hydrazine hydrate in a solvent at temperatures of 0-100°C to the 3-amino-2-imino-4-imidazolidinol derivatives of the formula VI within 1/2-10 hours.
  • solvents suitable for this are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine, or amides, for example N,N-dimethylform
  • the compound of the formula Vi is subsequently subjected to a ring expansion which affords the 4,5-dihydro-2H-[1 ,2,4]triazin-3-ylidenamines of the formula VII.
  • the ring expansion reaction expediently takes place thermally in an organic solvent. The reaction can take place in a time of 1/2-30 hours at temperatures of 0-200°C, depending on the solvent used.
  • suitable solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example aceton
  • reaction scheme 2 starts from compounds of the formula IV.
  • the imino group is then expediently converted with chloroformic ester of the formula XIV in the presence of a base in an inert organic solvent into the corresponding 3H-oxazol-2- ylidenecarbamic esters of the formula VIII.
  • the reaction is advantageously carried out at 0-200°C and is as a rule complete after 1 -100 hours.
  • Suitable bases are both inorganic and organic bases, for example carbonates and bicarbonates, for example sodium or potassium carbonate or sodium or potassium bicarbonate, hydrides, for example sodium hydride, alcoholates, for example sodium or potassium tert-butoxide, or tertiary bases, for example pyridine, triethylamine or N,N-diethylaniline.
  • the bases can advantageously be employed in a ratio of amounts of 1-100 equivalents based on the starting compound of the formula IV.
  • suitable solvents are aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or
  • suitable solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine, or amides, for example N,N- dimethylformamide.
  • the final products of the formula I can be isolated in a conventional way by concentration and/or evaporation of the solvent and be purified by recrystallization or trituration of the solid residue in solvents in which they are not very soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, or by means of column chromatography or flash column chromatography with a suitable eluent.
  • solvents in which they are not very soluble such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, or by means of column chromatography or flash column chromatography with a suitable eluent.
  • the product may result as a mixture of two or more isomers.
  • the isomers can be fractionated by methods known per se.
  • the compounds of the formula I can be employed in unchanged form, i.e. as they result in the synthesis, but are preferably processed in a conventional way with the auxiliaries employed in formulation technology, for example to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powder, soluble powders, dusts, granules or microcapsules.
  • the application methods such as spraying, atomizing, dusting, wetting, scattering or pouring are, just like the type of compositions, chosen appropriate for the intended aims and the given conditions.
  • compositions comprising the active ingredient of the formula I or at least one active ingredient of the formula I and, as a rule, one or more soiid or liquid formulation auxiliaries, are produced in a known manner, for example by intimately mixing and/or grinding the active ingredients with the formulation auxiliaries, for example solvents or solid carriers. It is furthermore possible additionally to use surface-active compounds (surfactants) for producing the formulations.
  • surfactants surface-active compounds
  • Suitable solvents may be: aromatic hydrocarbons, preferably C 8 to d 2 fractions, for example xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or N,N-dimethylformamide, and vegetable oils which may be epoxidized, such as epoxidized coconut oil or soya oil; or water.
  • aromatic hydrocarbons preferably C 8 to d 2 fractions, for example xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl or dioc
  • the solid carriers used as a rule are natural rock powders such as calcite, talc, kaolin, montmorillonite or attapulgite. It is also possible to add highly disperse silica or highly disperse absorbent polymers to improve the physical properties of the formulation.
  • Suitable particulate, adsorptive granule carriers are porous types, for example pumice, crushed bricks, sepiolite or bentonite, and nonsorptive carrier materials are, for example, calcite or sand. It is also possible to use a large number of pregranulated materials of an inorganic or organic nature such as, in particular, dolomite or comminuted plant residues.
  • Suitable surface-active compounds are, depending on the type of the active ingredient of the formula I to be formulated, nonionic, cationic and/or anionic surfactants and surfactant mixtures with good emulsifiying, dispersing and wetting properties.
  • Suitable anionic surfactants may be both so-called water-soluble salts and water-soluble synthetic surface-active compounds.
  • Soaps which may be mentioned are the alkali metal, alkaline earth metal or unsubstituted or substituted ammonium salts of higher fatty acids ( o-da), for example the Na or K salts of oleic acid or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut or tallow oil. Mention should also be made of the fatty acid methyltaurine salts.
  • fatty alcohol sulfonates are, as a rule, in the form of alkali metal, alkaline earth metal or unsubstituted or substituted ammonium salts and have an alkyl radical having 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals, for example the Na or Ca salt of ligninsulfonic acid, of dodecyl sulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids.
  • the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts include the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulfo groups and one fatty acid residue having 8-22 C atoms.
  • alkylarylsulfonates are the Na, Ca or triethanolamine salts of dodecyl benzenesulfonic acid, of dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensate.
  • corresponding phosphates for example salts of the phosphoric ester of a p-nonylphenol (4-14) ethylene oxide adduct or phospholipids.
  • Suitable nonionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaiiphatic alcohols, saturated or unsaturated fatty acids and alkylphenols which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
  • nonionic surfactants are the water-soluble adducts, containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, of polyethylene oxide onto polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain.
  • the said compounds normally contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • nonionic surfactants examples include nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate.
  • the cationic surfactants are, in particular, quaternary ammonium salts which contain as N-substituents at least one alkyl radical having 8 to 22 C atoms and have as further substituents lower, u ⁇ halogenated or halogenated alkyl, benzyl or lower hydroxyalkyl radicals.
  • the salts are preferably halides, methyl sulfates or ethyl sulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
  • the herbicidal formulations comprise as a rule 0.1 to 99 % by weight, in particular 0.1 to 95 % by weight, of herbicide, 1 to 99.9 % by weight, in particular 5 to 99.8 % by weight, of a solid or liquid formulation aid and 0 to 25 % by weight, in particular 0.1 to 25 % by weight, of a surfactant.
  • compositions may also comprise other additives such as stabilizers, for example unepoxidized or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilizers or other active ingredients.
  • stabilizers for example unepoxidized or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil)
  • antifoams for example silicone oil
  • preservatives for example silicone oil
  • viscosity regulators binders
  • tackifiers tackifiers
  • fertilizers or other active ingredients.
  • Emulsifiable concentrates are:
  • Active ingredient 1 to 90 %, preferably 5 to 50 %
  • Surface-active agent 5 to 30 %, preferably 10 to 20 %
  • Active ingredient 0.1 to 50 %, 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 % Surface-active agent: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders Active ingredient: 0.5 to 90 %, preferably 1 to 80 %
  • Surface-active agent 0.5 to 20 %, preferably 1 to 15 %
  • Solid carrier material 5 to 95 %, preferably 15 to 90 %
  • Granules Active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %
  • Solid carrier 99.5 bis 70 %, vorzugêt 97 bis 85 %
  • the active ingredients of the formula I are, as a rule, successfully employed on the plant or its habitat with application rates of 0.001 to 4 kg/ha, in particular 0.005 to 2 kg/ha.
  • the dose necessary for the required effect can be found by tests. It depends on the mode of action, the stage of development of the crop plant and of the weed, and on the application (site, time, method) and may vary within wide ranges determined by these parameters.
  • the compounds of the formula I are distinguished by herbicidal and growth-inhibiting properties which mean that they can be used in crops of useful plants, in particular in cereals, cotton, soya, sugarbeet, sugarcane, sunflowers, vegetables, plantations, for example fruit and citrus plantations, oilseed rape, maize, sorghum, rice and fodder crops, and for nonselective weed control.
  • Crops are also to be understood to mean those which have been made tolerant to herbicides or classes of herbicides by conventional breeding or genetic engineering methods.
  • the weeds to be controlled may be both mono- and dicotyledonous weeds, for example stellaria, nasturtium, agrostis, digitaria, avena, setaria, sinapis, lolium, solanum, phaseoius, echinochloa, scirpus, monochoria, sagittaria, bromus, alopecurus, sorghum halepense, rottboellia, cyperus, abutilon, sida, xanthium, amaranthus, chenopodium, ipomoea, chrysanthemum, galium, viola and veronica.
  • Example H7 6-Methyl-4-(3-trifluoromethylphenyl.-4.5-dihvdro-2H-f1.2.41triazin-3- ylidenamine
  • Example H14 1 -r6-Ethyl-4-(3-trifluoromethylphenyl.-4.5-dihvdro-2H-f1.2.4.triazin-3-ylidenel- 3-ethylurea
  • reaction mixture is then evaporated, ice-water is added, and the mixture is acidified with 2N hydrochloric acid and extracted with ethyl acetate.
  • the combined organic phases are washed with water and brine, dried and evaporated.
  • the resulting oil crystallizes from an ether/hexane mixture.
  • the required product is obtained in a yield of 2.7 g (82% of theory) with melting point 90-91 °C.
  • Example H18 1 - ⁇ 6-Ethyl-4-(3-trifluoromethylphenyl.-4.5-dihvdro-2H-ri ,2.41triazin-3- ylidenelurea
  • Emulsion concentrates a) b) c) d)
  • Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
  • the active ingredient is thoroughly mixed with the additives and thoroughly ground in a suitable mill.
  • the resulting wettable powders can be diluted with water to give suspensions of any desired concentration.
  • the active ingredient is dissolved in methylene chloride and sprayed onto the carrier, and the solvent is thoroughly evaporated off in vacuo.
  • the finely ground active ingredient is applied uniformly to the carrier material which is moistened with polyethylene glycol in a mixer. This results in dust-free coated granules.
  • the active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and subsequently dried in a stream of air.
  • Dusts ready for application are obtained by mixing the active ingredient with the carriers and grinding in a suitable mill.
  • F8. Suspension concentrates a) b) c) d)
  • the finely ground active ingredient is intimately mixed with the additives. This results in a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
  • Example B1 Herbicidal action before emergence of the plants (preemergence action.
  • Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastic pots.
  • the test substances are sprayed on as aqueous suspension (prepared from a 25% wettable powder (Example F3, b)) or as emulsion (prepared from a 25% emulsion concentrate (Example F1 , c)) corresponding to a dose of 2 kg AS/ha (5001 water/ha).
  • Table B1 Preemeroence action:
  • Test plant Setaria Sinapis Stellaria n r + No.
  • Monocotyledonous and dicotyledonous test plants are grown in plastic pots containing standard soil in a glasshouse and sprayed at the 4- to 6-leaf stage with an aqueous suspension of the test substances of the formula I prepared from a 25% wettable powder (Example F3, b)) or with an emulsion of the test substances of the formula I prepared from a 25% emulsion concentrate (Example F1 , c)), corresponding to a dose of 2 kg AS/ha (500 I water/ha).
  • the compounds of the formula I show a strong herbicidal action in this experiment.
  • Table B2 Postemer ence action:

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Abstract

Compounds of the formula (I), in which -A- is a group (A1), (A2) or (A3) where the bonding of -A- to the nitrogen atom takes place via the carbon atom; R1 is halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4haloalkoxy, C1-C4alkylthio, C1-C4haloalkylthio, cyano or nitro; R2 is hydrogen, halogen, C1-C4alkyl or C1-C4haloalkyl; or R2 in position 2 of the phenyl ring and R1 together form a -OCF2O-group; R4 is C1-C6alkyl, C3-C6alkenyl, C3-C6alkynyl or C3-C6cycloalkyl, it being possible for these alkyl, alkenyl and alkynyl radicals to be substituted by halogen, C1-C3alkyl, C1-C3alkoxy, C1-C3alkylthio, C3-C6cycloalkyl, C3-C6cycloalkoxy, cyano, aryl, aryloxy or a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or R4 is C1-C7alkylaminosulfonyl, di-C1-C7alkylaminosulfonyl, C1-C7alkylsufonyl or C1-C7alkylsulfinyl, it being possible for these alkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl and alkylsulfinyl radicals to be substituted by halogen, C1-C3alkoxy, C1-C3alkylthio, C3-C6cycloalkyl, C3-C6cycloalkoxy, cyano, aryl, aryloxy or a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or R4 is cyano, arylsulfonyl, sulfamoyl or a -C(X)R7 or -C(X)NHR9 group; and agronomically suitable salts of compounds of the formula (I), are suitable as herbicides.

Description

N-PHENYLIMINO HETEROCYCLIC DERIVATIVES AND THEIR USE AS HERBICIDES
The present invention relates to novel N-phenylimino heterocycles with herbicidal activity, processes for their preparation, compositions which comprise these compounds, and their use for controlling weeds, especially in growing crops or for inhibiting plant growth.
Iminothiazolines with a herbicidal action are described, for example, in EP-A-0 529 482, EP-A-0 446 802 and US-A-5 244 863.
Novel N-phenylimino heterocyclic compounds with herbicidal and growth-inhibiting properties have now been found.
The present invention thus relates to compounds of the formula I
Figure imgf000003_0001
in which
R3
-A- is a group — CH=C-N- (A.), I 3 (Aa) or
— CH=C-0-
F
I (A3) where the bonding of -A- to the nitrogen atom takes place via
— CH— C=N-NR—
the carbon atom; R3 is CrC4alkyl, it being possible for this radical to be substituted by halogen, cyano, d-
C4alkoxy, benzyloxy, hydroxyl, C1-C4alkylthio, Cι-C4alkylamino or di-d-C4alkylamino, or is
C3-Cβcycloalkyl, aryl or substituted aryl;
R5 and R6 are, independently of one another, hydrogen or CrC4alkyl;
RT is halogen, C1-C4alkyl, Cι-C4haloalkyl, C C4alkoxy, d-C haloalkoxy, CrC4alkylthio, d-dhaloalkylthio, cyano or nitro;
R2 is hydrogen, halogen, Cι-C4alkyl or Cι-C4haloalkyl; or
R2 in position 2 of the phenyl ring and Ri together form a -OCF2O- group;
R4 is Ci-Cβalkyl, C3-C6alkenyl, C3-C6alkynyl or C3-Cβcycloalkyl, it being possible for these alkyl, alkenyl and alkynyl radicals to be substituted by halogen, Cι-C3alkyl, d-C3alkoxy,
C C3alkylthio, C3-Cecycloalkyl, C3-Cecycloalkoxy, cyano, aryl, aryloxy or a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or
R4 is CrC7alkylaminosulfonyl, di-d-CTalkylaminosulfonyl, Cι-C7alkylsulfonyl or
C C7alkylsul.inyl, it being possible for these alkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl and alkylsulfinyl radicals to be substituted by halogen, C C3alkoxy, d-daikylthio, C3-C6-cycloalkyl, C3-C6-cycloalkoxy, cyano, aryl, aryloxy or a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or
R4 is cyano, arylsulfonyl, sulfamoyl or a -C(X)R7or -C(X)NHR group;
X is oxygen or sulfur;
R7 is Cι-Cβalkyl, C2-C6alkenyl, C3-C6alkynyl, d-C6alkoxy, C2-C6alkenyloxy, C3-C6alkynyloxy,
CrCβalkylthio, C2-C6alkenylthio, C3-Cβalkynylthio or di-d-C6alkylamino, it being possible for these alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio, alkynylthio and dialkylamino radicals to be substituted by halogen, d-C3alkyl, d-C3alkoxy, d-C3haloalkoxy, CrC6alkylcarbonyl, Cι-C6alkylcarbonyloxy, C C3alkoxycarbonyl,
Cι-C3alkylthio, C3-Cecycloalkyl, C3-C6cycloalkoxy, hydroxyl, cyano, aryl, aryloxy, benzyloxy or a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or
R7 is hydrogen, C3-C6-cycloalkyl, C3-C6cycloalkoxy, C3-C6cycloalkylthio, aryl, aryloxy, hetaryl, a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or a saturated heterocyclyloxy radical which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, and R9 is hydrogen, CrC6alkyl, C3-C6alkenyl or C3-C6alkynyl, it being possible for these alkyl, alkenyl and alkynyl radicals to be substituted by halogen, d-C3alkyl, d-C3alkoxy, d-C3alkylthio, C3-C6cycloalkyl, C3-C6cycloalkoxy, hydroxyl, cyano, aryl, aryloxy or a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or is C3-C6cycloalkyl or aryl, and agronomically suitable salts of compounds of the formula I.
These alkyl groups occurring in the definitions of substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the various isomeric pentyl, hβxyl and heptyl radicals. Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl are preferred.
Halogen means iodine and preferably fluorine, chlorine and bromine.
Alkoxy radicals preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert- butoxy and one of the various isomeric pentoxy and hexyloxy radicals; preferably methoxy, ethoxy and propoxy.
Alkylthio radicals preferably have a chain length of from 1 to 4 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio.
Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino and the isomeric butylamino radicals.
Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n-propylmethylarnino, dibutylamino and diisopropylamino. Alkylamino radicals with a chain length of from 1 to 6 carbon atoms are preferred.
The cycioalkyl radicals preferably have 3 to 6 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. The cycloalkyl radicals may, unless otherwise indicated, be substituted by halogen, Cι-C3alkyl, d-C3alkoxy or Cι-C3alkylthio.
Aryl in the definition of the radicals R3, FU, R and R9 is α- or β-naphthyl and, in particular, phenyl, it being possible for these aromatic rings to carry one or more, identical or different substituents, for example halogen, nitro, cyano, d-C alkoxy, d-C4haloalkoxy, d-dalkylthio, d-dhaloalkylthio, Cι-C4alkyl and d-C haloalkyl. Corresponding statements also apply to aryloxy and arylsulfonyl in the definition of R , R7and R9.
Heteroaryl in the definition of R7 means, in particular, five- or six-membered aromatic heterocyclic rings, for example 2-, 3- or 4-pyridyl, pyrimidyl, pyrazolyl, pyrazinyl, pyridazinyl, imidazolyl, triazolyl, pyrrolyl, furyl, thienyl, oxazolyl, thiazolyl or isoxazolyl; preferably 2- and 3-pyridyl, 2- and 3-furyl and 2-thienyl. These heterocycles can in turn be substituted; examples of substituents are d-C3alkyl, halogen, d-C3haloalkyl, cyano, nitro, hydroxyl, d- C3alkoxy, Cι-C3haloalkoxy, amino, Cι-C3alkylamino, di-d-C3alkylamino or carboxyl.
Saturated heterocyclic rings mean ring systems which, besides carbon atoms, contain at least one hetero atom such as nitrogen, oxygen or sulfur atom. Ring systems of these types preferably contain 3 to 6 ring atoms, for example oxiranyl, aziridinyl, azetidinyl, oxetanyl, thietanyl, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, tetrahydropyranyl, dioxanyl, 1 ,3- dioxanyl, piperidinyl, morpholinyl, thiomorpholinyl or piperazinyl. In the case of nitrogen atom as hetero atom, the bonding to the ring system can take place both via the ring carbon atom and via the ring nitrogen atom.
These saturated heterocycles can in turn be substituted; examples of substituents are Cι-C3alkyl.
Suitable as haloalkyl are alkyl groups substituted one or more times, in particular once to three times by halogen, where halogen means specifically iodine and, in particular, fluorine, chlorine and bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, fluorochloromethyl, 2-fluoroethyl, 2,2,2- trifluoroethyl, 1 ,1 ,2,2,2-pentafluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyi and 2-chloro-2- propyl. Haloalkoxy radicals preferably have a chain length of from 1 to 6 carbon atoms. Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2-fluoroethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 1 ,1 ,2,2,2-pentafiuoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
Haloalkylthio radicals preferably have a chain length of from 1 to 4 carbon atoms. Haloalkylthio is, for example, trifluoromethylthio or 2,2,2-trifluoroethylthio.
The alkenyl and alkynyl groups can be straight-chain or branched, and this also applies to the alkenyl and alkynyl moiety in alkenylthio, alkynylthio, alkenylamino and alkynylamino groups.
Alkenyl means, for example, vinyl, 1 -methylvinyl, allyl, methallyl or 2-butenyl. Alkenyl radicals with a chain length of from 2 to 6 carbon atoms are preferred. The alkenyl radicals are preferably linked via a saturated carbon atom to a hetero atom.
Examples of alkynyl which may be mentioned are propargyl, 2-butynyl, 2-methyl-3-butyn-2- yl, 3-butyn-2-yl and 4-pentynyl. Alkynyl radicals with a chain length of from 3 to 6 carbon atoms are preferred. The alkynyl radicals are preferably linked via a saturated carbon atom to a hetero atom.
Alkenylthio means, for example, allylthio, methallylthio, 3-butenylthio, 4-pentenylthio or 2-hexenylthio.
Alkynylthio means, for example, propargylthio, 1-methylpropargylthio, 3-butynylthio, 4-pentynylthio or 2-hexynylthio.
Alkenylamino is, for example, allylamino, methallylamino and 2-butenylamino.
Alkynylamino is, for example, propargylamino, 1 -methylpropargylamino and 4-pentynylamino. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfony, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl and one of the isomeric pentyl-, hexyl- and heptylsulfonyl radicals; preferably methylsulfonyl and ethylsulfonyl.
Corresponding meanings can also be assigned to the substituents in composite definitions, for example alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, cycloalkoxy, cycloalkylamino, cycloalkylthio, (di-)alkylaminosulfonyl, alkylsulfinyl, alkenyloxy, alkynyloxy, benzyloxy and heterocyclyloxy.
The invention likewise embraces the salts which the compounds of the formula I are able to form with acids. Acids suitable for forming the acid addition salts are both organic and inorganic acids. Examples of such acids are, inter alia, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, various phosphorus acids, sulfuric acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, fumaric acid, organic sulfonic acids, lactic acid, tartaric acid, citric acid and salicylic acid.
The compounds of the formula I contain an aliphatic C=N-R4 double bond, and thus geometric isomerism (syn/anti) may occur. Geometric isomerism (Z E) may likewise occur if an aliphatic C=C double bond is present. The present invention also embraces these isomers.
Preferred compounds of the formula I are those in which R, is halogen, d-C4haloalkyl, cyano, nitro, d-C4haloalkoxy or d-C4haloalkylthio; and R7 has the same meaning as indicated under formula I with the exception of C7 and C8alkyl.
Preferred compounds of the formula I are those in which Ri is trifluoromethyl or trifluoromethoxy.
Likewise preferred compounds of the formula I are those in which R is hydrogen.
Likewise among the preferred compounds of the formula I are those in which R3 is methyl, ethyl or cyclopropyl. Further preferred compounds of the formula I are those in which R4 is a -C(X)R7 group; X is oxygen; and R7 is C C6alkyl, d-C6alkoxy or d-Cβalkylamino, it being possible for these radicals to be substituted by halogen, d-C3alkyl, Cι-C3alkoxy, C3-C6cycloalkyl or C3-C6cycloalkoxy. Of these, particularly preferred compounds are those in which R7 is d-C6alkyl, d-C6haloalkyl or d-C6-alkoxy.
Important compounds of the formula I are those in which -A- is a group
R3 has the meaning stated under formula I; and Rε is hydrogen or
Figure imgf000009_0001
methyl. Particularly important among these are those in which R5 is hydrogen.
Likewise important compounds of the formula I are those in which -A- is a group ft (As); R3 is methyl or ethyl; R2 is hydrogen or halogen; R6 is
— CH— C = N-NR—
hydrogen; Ri is trifluoromethyl or trifluoromethoxy; R4 is a -C(X)R7 group; X is oxygen; and R7 is Cι-C3haloalkyl or d-C4alkoxy.
Further important compounds are those in which -A- is a group
(A2); R3 is methyl or ethyl; Ri is trifluoromethyl or trifluoromethoxy; R2 is
Figure imgf000009_0002
hydrogen; R4 is a -C(X)R7 group; X is oxygen; and R7 is d-C4alkoxy.
A group of preferred compounds of the formula I is that in which -A- is a group
R3
| (A2); R3 is d-C4alkyl, cyclopropyl, phenyl or benzyloxymethyl; Ri is
— CH=C-0- fiuorine, C or C2alkyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, trifluoromethylthio or cyano; R2 is hydrogen, 4-fluoro, 4- or 6-chloro or 5-trifluoromethyl; or R2 in position 2 of the phenyl ring and R, together form a -OCF2O- group; R4 is cyano, methyl, methyl • HI salt, propargyl, cyclopentyl, benzyl, methylsulfonyl, dimethylaminosulfonyl, trifluoromethylsulfonyl, 2-chlorophenylsulfonyl or 2-chloro-2-propylsulfinyl; or R4 is a -C(X)R7 group; X is oxygen or sulfur; R7 is hydrogen, Cι-C3alkyl, cyanomethyl, methoxymethyl, methoxyethyl, methylthiomethyl, methoxycarbonylmethyl, trifluoromethoxymethyl, phenoxymethyl, d-C4alkoxy, methoxyethoxy, vinyloxy, allyloxy, propargyloxy, d- C3alky.tl.i0, dimethylamino, difluoromethyl, trifluoromethyl, pentafluoroethyl, chloromethoxy, 2,2,2-trichloroethoxy, C3-C6cycloalkoxy, cyclopropylmethoxy, cyclobutylmethoxy, 2,6- difluorophenyl, 2-furyl, phenoxy, benzyloxy, N-morpholino, N-piperidino or N-pyrrolidino; or R4 is a -C(X)NHR9 group; X is oxygen or sulfur; and R9 is d- or C2alkyl, cyanomethyl or phenyl.
Another group of preferred compounds of the formula I is that in which -A- is a group ft (A3); R3 is Cι-C4alkyl, hydroxymethyl, chloromethyl,
— CH— C=N-NR6—
dimethylaminomethyl, cyclopropyl, phenyl or benzyloxymethyl; R6 is hydrogen or methyl; Rt is fluorine, Cι- or C2alkyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy or trifluoromethylthio; R2 is hydrogen, 4-fluoro, 4- or 6-chloro or 5-trifluoromethyl; or R2 in position 2 of the phenyl ring and Ri together form a -OCF2O- group; R4 is methyl, propargyl, cyclopentyl, benzyl, cyano, methylsulfonyl, isopropylsulfonyl, trifluoromethylsulfonyl, 2- chloro-2-propylsulfinyl, phenylsulfonyl or 2-chlorophenylsulfonyl; or R4 is a -C(X)R7 group; X is oxygen or sulfur; R7 is hydrogen, Cι-C4alkyl, cyanomethyl, hydroxymethyl, methoxymethyl, methoxyethyl, methoxycarbonylmethyl, trifluoromethoxymethyl, methylthiomethyl, benzyloxymethyl, phenoxymethyl, cyclopropyl, cyclopentyl, dimethylaminomethyl, d-C4alkoxy, methoxyethoxy, vinyloxy, 1 -methylvinyloxy, allyloxy, propargyloxy, C C3alkylthio, dimethylamino, cyanomethyl-methylamino, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, fluorochloro methyl, pentafluoroethyl, 2-chloroethoxy, 2,2,2-trichloroethoxy, C3-Cβcycloalkoxy, cyclopropylmethoxy, cyclobutylmethoxy, 2-furyl, phenyl, 2,6-difluorophenyl, 2,6- difluorobenzyl, phenoxy, benzyloxy, 3-oxetanyloxy, N-morpholino, N-piperidino or N- pyrrolidino; or R7 is a -C(X)NHRβ group; X is oxygen or sulfur; and R9 is hydrogen, C C3alkyl, cyanomethyl, cyclopropyl, phenyl or 2-, 3- or 4-chlorophenyl. Another group of preferred compounds of the formula I is that in which -A- is a group
R 3 I — CH=C-N— (A!); R3 is C or C2alkyl, cyclopropyl or phenyl; R5 is hydrogen, methyl or
R5 cyclopropyl; R5 is hydrogen, methyl or cyclopropyl; Ri is cyano, trifluoromethyl, pentafluoroethyl, trifluoromethoxy or trifluoromethylthio; R2 is hydrogen; or R2 in position 2 of the phenyl ring and R together form a -OCF2O- group; R4 is cyano or a -C(X)R7 group; X is oxygen; and R7 is methyl, difluoromethyl, trifluoromethyl, d-C3alkoxy or pentafluoroethyl.
The process according to the invention for preparing the compounds of the formula I comprises alkylating a compound of the formula II
Figure imgf000011_0001
in which Ri and R2 have the meanings stated under formula I, with a compound of the formula X
(X),
L CH-C-R3
in which R3 has the meanings stated under formula I, and L, is a leaving group, for example halogen, preferably chlorine, bromine or iodine, alkylsulfonyl or arylsulfonyl, preferably
CH3SO2O- or in the presence of a base and of a solvent to give a
Figure imgf000011_0002
compound of the formula
Figure imgf000012_0001
cyclizing the latter in the presence of a base to give the compound of the formula IV
Figure imgf000012_0002
subsequently reacting the latter
1) to prepare compounds of the formula I in which R4 is d-C6alkyl, C3-Cealkenyl, C3-C6alkynyl, C3-C6cycloalkyl, Cι-C7alkylaminosulfonyl, di-C -C7alkylaminosulfonyl, C C7alkylsulfonyl or d-dalkylsulfinyl, it being possible for these radicals to be substituted as stated under formula I, cyano, arylsulfonyl or sulfamoyl, with a compound of the formula XIa
L2-R4 (XIa),
in which R has the stated meaning, L2 is a leaving group, for example halogen, preferably
chlorine, bromine or iodine, hydroxyl, R4OSO2O-, CH3SO2O- or >
Figure imgf000012_0003
or
2) to prepare compounds of the formula I in which R4 is a -C(X)R7 group; and R7 and X have the meanings stated under formula I, with a compound of the formula Xlb
X
II (Xlb),
R7-C-L4 in which R7and X have the stated meaning, and U is a leaving group, for example halogen, preferably fluorine, chlorine or bromine, imidazolide, triazolide, N-hydroxyphthalimide or R7C(X)O-, or
3) to prepare compounds of the formula I in which R is a -C(X)NHR9 group; and R9, with the exception of hydrogen, and X have the meaning stated under formula I, with a compound of the formula Xlc
R9-N=C=X (Xlc),
in which R9 and X have the stated meaning, to give a compound of the formula la
Figure imgf000013_0001
in which R1 t R2, R3 and R4 have the stated meaning, and the latter subsequently either a) being converted with a compound of the formula XII
R6-NH-NH2 (XII),
in which R6 has the meaning stated under formula I, into the compound of the formula Ic
Figure imgf000013_0002
or b) being rearranged with a compound of the formula XIII R5-NH2 (XIII),
in which R5 has the meaning stated under formula I, to give the compound of the formula V
Figure imgf000014_0001
and the latter subsequently being converted with elimination of water into the compound of the formula lb
Figure imgf000014_0002
Another process according to the invention for preparing compounds of the formula I in
R3 which -A- is a group „, . ' . , „,_ (A3) and R3 and Re are defined as under
— Cπ^-C— N — NF.g — formula I, comprises c) cyclizing a compound of the formula
Figure imgf000014_0003
in which R1t R2 and R3 have the meaning stated under formula I, with hydrazine to give the compound of the formula VI
Figure imgf000015_0004
Figure imgf000015_0001
obtaining, by ring expansion, the compound of the formula VII
Figure imgf000015_0002
and subsequently reacting the latter
1) to prepare compounds of the formula I in which R4 is d-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C3-C6cycloalkyl, Cι-C7alkylaminosulfonyl, di-d-C7alkylaminosulfonyl, Cι-C7alkylsulfonyl or d-C7alkylsulfinyl, it being possible for all of these radicals to be substituted as indicated under formula I, cyano, arylsulfonyl or sulfamoyl, with a compound of the formula XIa
L2-R4 (XIa),
in which R has the stated meaning, and L2 is a leaving group, for example halogen, preferably chlorine, bromine or iodine, hydroxyl, R OSO2O-, CH3SO2O- or
Figure imgf000015_0003
2) to prepare compounds of the formula I in which R is a -C(X)R7 group; and R7 and X have the meaning stated under formula I, with a compound of the formula Xlb (Xlb),
R7-C-L4
in which R7and X have the stated meaning, and is a leaving group, for example halogen, preferably fluorine, chlorine or bromine, or imidazolide, triazolide, N-hydroxyphthalimide or R7C(X)O-, or
3) to prepare compounds of the formula I in which R4 is a -C(X)NHR9 group; and R9, with the exception of hydrogen, and X have the meaning stated under formula I, with a compound of the formula Xlc
R9-N=C=X (Xlc),
in which R9 and X have the stated meaning, to give the compound of the formula I, or d) reacting a compound of the formula IV
Figure imgf000016_0001
in which Ri, R2 and R3 have the meaning stated under formula I, with the compound of the formula XIV
Figure imgf000016_0002
in which L3 is a leaving group, for example halogen, preferably chlorine or bromine, and Rβ
is — CHf-( ) or -C(CH3)3 to give a compound of the formula VIII
Figure imgf000017_0001
in which Ri, R2, R3 and R8 have the stated meaning, and subsequently converting with the compound of the formula XII
R6-NH-NH2 (XII),
in which R6 has the meaning stated under formula I, into the compound of the formula IX
Figure imgf000017_0002
reductively cleaving the latter in the presence of a catalyst to the compound of the formula VII
Figure imgf000017_0003
and subsequently converting with a compound of the formula XIa, Xlb or Xlc, as described above under c), into the compound of the formula I.
The processes according to the invention for preparing compounds of the formulae I and la, lb and Ic are explained in detail in the following reaction schemes 1 , 2 and 3. Reaction scheme 1 :
Figure imgf000018_0001
or -C(X)NHR9)
Figure imgf000018_0002
Figure imgf000018_0003
Reaction scheme 2: Route c):
Figure imgf000019_0001
VI
Figure imgf000019_0002
-C(X)NHR9)
VII lc(R6 = H)
Route d):
Figure imgf000020_0001
Figure imgf000020_0004
Figure imgf000020_0002
Figure imgf000020_0003
R7 or -C(X)NHRΘ)
Ic
The starting compounds of the formula II are known. They are prepared in analogy to known processes as described, for example, in DE-A-3 538 128.
The α-halo ketones of the formula X can be bought or can be prepared in analogy to known processes as described, for example, in Organic Synthesis, Vol. 55, page 24 (1973).
The α-alkyl- and α-arylsulfonyl ketones of the formula X (Li = alkylSO2O- and arylSO2O-) can be obtained, for example, in analogy to Chem. Ber. 119, 524 (1986) and Houben-Weyl, "Methoden der Organischen Chemie", Volume IX, page 388 et seq. As shown in reaction scheme 1 , the α-cyanamido ketones of the formula III are expediently prepared by alkylation of the arylcyanamides of the formula II with α-halo ketones, α-alkylsulfonyl ketones or α-arylsulfonyl ketones of the formula X in the presence of a base in an organic solvent at temperatures of 0-200'C, preferably at 0-60°C. The alkylation is as a rule complete within 1-30 hours depending on the solvent used and the reaction temperature.
It is possible to use as base inorganic and organic bases , for example, hydroxides, for example sodium or potassium hydroxide, carbonates such as sodium or potassium carbonate or bicarbonates such as sodium or potassium bicarbonate, hydrides, for example sodium or calcium hydride, alcoholates, for example sodium or potassium methoxide, sodium or potassium ethoxide or sodium or potassium tert-butoxide, alkyl- and arylamines, for example triethylamine, N,N-diethylaniline and pyridine. It is moreover advantageous to add the base used in a ratio of amounts of 1 -100 equivalents based on the starting compound of the formula II. Suitable solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitro compounds, for example nitroethane or nitrobenzene, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine, amides, for example N,N- dimethylformamide or sulfur oxide compounds, for example dimethyl sulfoxide or sulfolane. These solvents can be used alone or in combination.
Reactions of this type are generally known from the literature and described with diverse variations in respect of the leaving group Li, for example in in Houben-Weyl, "Methoden der Organischen Chemie", Volume XI/1 , pages 96 and 97. Cyclization of the compound of the formula II to the 3H-oxazol-2-ylideneamines of the formula IV is expediently carried out in the presence of a base in a suitable organic solvent at temperatures of 0-100°C and is generally complete after a few minutes up to 10 hours. Suitable as base are inorganic and organic bases, for example hydrides, for example sodium hydride, alcoholates, for example sodium or potassium methoxide, sodium or potassium ethoxide or sodium or potassium tert-butoxide, amidine bases, for example 1 ,8-diazabicyclo[5.4.0]uπdec-7-ene (DBU) or 1 ,5-diazabicyclo[4.3.0]non-5-ene (DBN), alkyl- or arylamines for example triethylamine or N,N-diethylaniline, and pyridine. Examples of suitable organic solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine, amides, for example N,N-dimethylformamide or sulfur oxides, for example dimethyl sulfoxide or sulfolane. These solvents can be used alone or in combination.
The substituent R is introduced on the imino nitrogen atom of compounds of the formula IV expediently by standard methods via 1) alkylation or sulfonylation, 2) (thio)acylation (formylation), (thio)carboxylation or (thio)amidation, or 3) by reaction with iso(thio)cyanates using appropriate reagents of the formula XIa (for example alkyl halides, hydroxyalkanes, dialkyl sulfates or alkylsulfonyl chlorides), Xlb (for example chloroformic esters, carbonyl halides, anhydrides or carboxylic acids) or Xlc (for example iso(thio)cyanates) in an organic solvent in the presence or absence of a base.
For example, N-(thio)acrylations, N-(thio)carboxylations and N-(thio)amidations can be carried out in analogy to Houben-Weyl, "Methoden der Organischen Chemie", Volume VIII, page 138 et seq., ibid. Volume VIII, page 154 et seq., Volume IX, page 833 et seq., Volume IX, page 885 et seq., Volume XI, pages 69-72 and Volume XI/2, page 3 et seq., and N-sulfonylations in analogy to Houben-Weyl, "Methoden der Organischen Chemie", Volume IX, page 398 et seq. and page 609 et seq. In the case of compounds of the formula Xlb as carboxylic acids, the acylation reaction is advantageously carried out in the presence of 1-10 equivalents of a carboxylic acid activating reagent, for example carbodiimide, for example N,N'-dicyclohexy!carbodiimide (DCC) or 1 ,1 '-carbonyldiimidazole (lm2CO).
The alkylation, acylation, carboxylation, amidation and sulfonylation reactions with reagents XIa and Xlb are generally carried out in an organic solvent, in the presence or absence of a base, at temperatures of 0-100°C. The reactions are as a rule complete within 1/2-30 hours depending on the solvent used and base used.
Bases which can be used are both inorganic and organic bases, for example hydroxides, for example sodium or potassium hydroxide, carbonates such as sodium or potassium carbonate or bicarbonates such as sodium or potassium bicarbonate, hydrides, for example sodium hydride, alcoholates, for example sodium or potassium methoxide, sodium or potassium ethoxide, sodium or potassium tert-butoxide, alkyl- and arylamines, for example triethylamine or N,N-diethylaniline, and pyridine, 4-N,N-dimethylaminopyridine (DMAP) and DBU. The base is preferably used in a ratio of amounts of 1-100 equivalents relative to the compound of the formula IV employed.
Examples of suitable organic solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine, amides, for example N,N-dimethylformamide or sulfur oxide compounds, for example dimethyl sulfoxide or sulfolane. These solvents can be used alone or in combination with one another.
The addition reactions with the reagent Xlc can expediently be carried out by allowing the compound of the formula IV and the iso(thio)cyanate of the formula Xlc to react together in an inert aprotic organic solvent such as an aliphatic or cyclic ether, for example diethyl ether, 1 ,2-dimethoxyethane, tetrahydrofuran or dioxane, a chlorinated aliphatic hydrocarbon, for example methylene chloride, an aromatic compound, for example toluene or xylenes, an aliphatic ester, for example ethyl acetate, or a nitrile, for example acetonitrile, in the presence of a catalyst, for example 4-N,N-dimethylaminopyridine or triethylamine, preferably at temperatures from 0°C to the reflux temperature of the reaction solution. The addition reaction is as a rule complete after a few minutes up to 15 hours. Addition reactions of this type are known and are described with diverse variations in respect of X and R9, for example in Houben-Weyl, "Methoden der Organischen Chemie", Volume VIII, page 154 et seq. and ibid., Volume IX, page 885 et seq.
The ring expansion reaction by route a) in reaction scheme 1 to give the 4,5-dihydro-2H- [1 ,2,4]triazin-3-ylideneamines of the formula Ic takes place starting from the 3H-oxazol-2- ylideneamines of the formula la, expediently with hydrazines of the formula XII in an organic solvent at temperatures of 0-150°C. The ring expansion reaction is as a rule complete after 1 -100 hours.
Examples of solvents suitable for this are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, nitrites, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamin, N,N-diethylaniline or N-methylmorpholine, or amides, for example N,N-dimethylformamide. These solvents can be used alone or in combination.
The ring rearrangement reaction by route b) in reaction scheme 1 to give the imidazolidin-2- ylideneamines of the formula V takes place starting from 3H-oxazol-2-ylideneamine derivatives of the formula la expediently with ammonia (R5 = hydrogen) or primary amines of the formula XIII in an organic solvent at temperatures of 0-100°C. The ring rearrangement reaction is as a rule complete after 1-30 hours. Examples of suitable solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N- diethylaniline or N-methylmorpholine, or amides, for example N,N-dimethylformamide. These solvents can be used alone or in combination. The subsequent dehydration of the compounds of the formula V takes place, for example, thermally in the presence of catalytic amounts of acid, for example p-toluenesulfonic acid, or in the presence or equimolar amounts of anhydrides, for example acetic anhydride or trifluoroacetic anhydride, or by reaction with alkyl- or arylsulfonyl halides, for example methylsulfonyl chloride, in the presence or absence of bases, for example triethylamine. The dehydration reaction advantageously takes place in an organic solvent at temperatures of 0-200°C and is as a rule complete after 1/2-30 hours. It is also possible where appropriate to employ the anhydride as solvent. Examples of suitable solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acetonitrile or isobutyronitrile, or amides, for example N,N-dimethylformamide. These solvents can be used alone or in combination.
Reaction scheme 2 depicts two processes according to the invention for preparing
compounds of the formula I in which -A- is a group _u ft ' . , κιn (A3).
— CH^C — N~NR —
The process by route c) starts from α-cyanamido ketones of the formula III which can expediently be cyclized with the aid of hydrazine hydrate in a solvent at temperatures of 0-100°C to the 3-amino-2-imino-4-imidazolidinol derivatives of the formula VI within 1/2-10 hours. Examples of solvents suitable for this are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine, or amides, for example N,N-dimethylformamide. These solvents can be used alone or in combination.
In route c), the compound of the formula Vi is subsequently subjected to a ring expansion which affords the 4,5-dihydro-2H-[1 ,2,4]triazin-3-ylidenamines of the formula VII. The ring expansion reaction expediently takes place thermally in an organic solvent. The reaction can take place in a time of 1/2-30 hours at temperatures of 0-200°C, depending on the solvent used. Examples of suitable solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine or amides, for example dimethyiformamide. These solvents can be used alone or in combination.
Conversion of the compounds of the formula VII into the 4,5-dihydro-2H-[1 ,2,4]triazin-3- ylideneamines of the formula Ic takes places in analogy to the description under reaction scheme 1 via 1) alkylation or sulfonylation, 2) (thio)acylation (formylation), (thio)carboxylation or (thio)amidation or 3) reaction with iso(thio)cyanates using the appropriate reagents of the formulae XIa, Xlb or Xlc depending on the required substituents R in the compounds of the formula Ic.
The process in route d) in reaction scheme 2 starts from compounds of the formula IV. The imino group is then expediently converted with chloroformic ester of the formula XIV in the presence of a base in an inert organic solvent into the corresponding 3H-oxazol-2- ylidenecarbamic esters of the formula VIII. The reaction is advantageously carried out at 0-200°C and is as a rule complete after 1 -100 hours.
Suitable bases are both inorganic and organic bases, for example carbonates and bicarbonates, for example sodium or potassium carbonate or sodium or potassium bicarbonate, hydrides, for example sodium hydride, alcoholates, for example sodium or potassium tert-butoxide, or tertiary bases, for example pyridine, triethylamine or N,N-diethylaniline. The bases can advantageously be employed in a ratio of amounts of 1-100 equivalents based on the starting compound of the formula IV. Examples of suitable solvents are aromatic hydrocarbons, for example benzene, toluene or xylenes, halogenated hydrocarbons, for example chloroform, tetrachloromethane, chlorobenzene or dichlorobenzenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine, or amides, for example N,N-dimethylformamide. These solvents can be used alone or in combination.
The ring expansion of the resulting compounds of the formula VIII with hydrazines of the formula XII in an organic solvent at temperatures of 0-150°C is carried out in analogy to the description under reaction scheme 1 , route a), and affords the 4,5-dihydro-2H-[1 ,2,4]triazin- 3-ylidenecarbamic esters of the formula IX.
The subsequent elimination of the carboxylate group in the compound of the formula IX is expediently carried out by reduction (hydrogenolysis) in analogy to known processes, for example with 5 % palladium on carbon as catalyst in an inert organic solvent at temperatures of 0-100°C. Elimination of the carboxylate group is as a rule complete after 1 -30 hours. Examples of suitable solvents are alcohols, for example methanol, ethanol, isopropanol, tert-butanol, octanol, cyclohexanol or 2-methoxyethanol, aromatic hydrocarbons, for example benzene, toluene or xylenes, ethers, for example diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or 1 ,2-dimethoxyethane, esters, for example ethyl formate, ethyl acetate, butyl acetate or diethyl carbonate, nitriles, for example acetonitrile or isobutyronitrile, tertiary amines, for example pyridine, triethylamine, tributylamine, N,N-diethylaniline or N-methylmorpholine, or amides, for example N,N- dimethylformamide. These solvents can be used alone or in combination.
Conversion of the compounds of the formula VII into the compounds of the formula Ic takes place in analogy to the description under route c). Reaction scheme 3:
Figure imgf000028_0001
Id I (R4 = -C(X)NH2)
As shown in reaction scheme 3, compounds of the formula I in which R4 is a -C(X)NHR9 group; X has the meaning stated under formula I; and R9 is hydrogen, are expediently prepared via aminolysis of the appropriate aryloxy carbamic ester derivatives of the formula Id, for example using ammonia dissolved in ethanol. This variant of the preparation is illustrated by Example H18.
Compounds of the formulae XIa, Xlb and Xlc can either be bought or be prepared in analogy to known processes as described, for example, in Houben-Weyl, "Methoden der Organischen Chemie", Volume VIII, page 120 et seq. and page 463 et seq., and ibid., Volume IX, page 867 et seq.
Compounds of the formulae XII and XIII can be bought.
Compounds of the formula XIV are known or can be prepared in analogy to known processes as described, for example, in Houben-Weyl, "Methoden der Organischen Chemie", Volume VIII, page 101 et seq.
The final products of the formula I can be isolated in a conventional way by concentration and/or evaporation of the solvent and be purified by recrystallization or trituration of the solid residue in solvents in which they are not very soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, or by means of column chromatography or flash column chromatography with a suitable eluent. The preferences applying to the intermediates of the formulae II, III, IV, V, VI and VII are the same as for the compounds of the formula I.
Where no specific synthesis for isolating pure isomers is carried out, the product may result as a mixture of two or more isomers. The isomers can be fractionated by methods known per se.
Applications which are suitable for the use according to the invention of the compounds of the formula I or compositions containing them are all those customary in agriculture, for example preemergence application, postemergence application and seed dressing, and various methods and techniques, for example controlled release of active ingredient. For this purpose, the active ingredient in solution is adsorbed onto granular mineral carriers or polymerized granules (urea/formaldehyde) and dried. It is possible where appropriate additionally to apply a coating (coated granules) which permits dosed release of the active ingredient over a defined period.
The compounds of the formula I can be employed in unchanged form, i.e. as they result in the synthesis, but are preferably processed in a conventional way with the auxiliaries employed in formulation technology, for example to emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powder, soluble powders, dusts, granules or microcapsules. The application methods such as spraying, atomizing, dusting, wetting, scattering or pouring are, just like the type of compositions, chosen appropriate for the intended aims and the given conditions.
The formulations, i.e. the compositions comprising the active ingredient of the formula I or at least one active ingredient of the formula I and, as a rule, one or more soiid or liquid formulation auxiliaries, are produced in a known manner, for example by intimately mixing and/or grinding the active ingredients with the formulation auxiliaries, for example solvents or solid carriers. It is furthermore possible additionally to use surface-active compounds (surfactants) for producing the formulations.
Suitable solvents may be: aromatic hydrocarbons, preferably C8 to d2 fractions, for example xylene mixtures or substituted naphthalenes, phthalic esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or N,N-dimethylformamide, and vegetable oils which may be epoxidized, such as epoxidized coconut oil or soya oil; or water.
The solid carriers used as a rule, for example for dusts and dispersible powders, are natural rock powders such as calcite, talc, kaolin, montmorillonite or attapulgite. It is also possible to add highly disperse silica or highly disperse absorbent polymers to improve the physical properties of the formulation. Suitable particulate, adsorptive granule carriers are porous types, for example pumice, crushed bricks, sepiolite or bentonite, and nonsorptive carrier materials are, for example, calcite or sand. It is also possible to use a large number of pregranulated materials of an inorganic or organic nature such as, in particular, dolomite or comminuted plant residues.
Suitable surface-active compounds are, depending on the type of the active ingredient of the formula I to be formulated, nonionic, cationic and/or anionic surfactants and surfactant mixtures with good emulsifiying, dispersing and wetting properties.
Suitable anionic surfactants may be both so-called water-soluble salts and water-soluble synthetic surface-active compounds.
Soaps which may be mentioned are the alkali metal, alkaline earth metal or unsubstituted or substituted ammonium salts of higher fatty acids ( o-da), for example the Na or K salts of oleic acid or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut or tallow oil. Mention should also be made of the fatty acid methyltaurine salts.
However, so-called synthetic surfactants will be used more often, especially fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfona.es. The fatty alcohol sulfonates or sulfates are, as a rule, in the form of alkali metal, alkaline earth metal or unsubstituted or substituted ammonium salts and have an alkyl radical having 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals, for example the Na or Ca salt of ligninsulfonic acid, of dodecyl sulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. These also include the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfo groups and one fatty acid residue having 8-22 C atoms. Examples of alkylarylsulfonates are the Na, Ca or triethanolamine salts of dodecyl benzenesulfonic acid, of dibutylnaphthalenesulfonic acid, or of a naphthalenesulfonic acid/formaldehyde condensate.
Also suitable are corresponding phosphates, for example salts of the phosphoric ester of a p-nonylphenol (4-14) ethylene oxide adduct or phospholipids.
Suitable nonionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaiiphatic alcohols, saturated or unsaturated fatty acids and alkylphenols which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
Other suitable nonionic surfactants are the water-soluble adducts, containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, of polyethylene oxide onto polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The said compounds normally contain 1 to 5 ethylene glycol units per propylene glycol unit.
Examples of nonionic surfactants which may be mentioned are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Also suitable are fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate.
The cationic surfactants are, in particular, quaternary ammonium salts which contain as N-substituents at least one alkyl radical having 8 to 22 C atoms and have as further substituents lower, uπhalogenated or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably halides, methyl sulfates or ethyl sulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
The surfactants which are customary in formulation technology and can also be used in the compositions according to the invention are described inter alia in "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol Mil, Chemical Publishing Co., New York, 1980-81.
The herbicidal formulations comprise as a rule 0.1 to 99 % by weight, in particular 0.1 to 95 % by weight, of herbicide, 1 to 99.9 % by weight, in particular 5 to 99.8 % by weight, of a solid or liquid formulation aid and 0 to 25 % by weight, in particular 0.1 to 25 % by weight, of a surfactant.
Whereas more concentrated compositions are preferred as commercial products, the final user as a rule employs dilute compositions.
The compositions may also comprise other additives such as stabilizers, for example unepoxidized or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilizers or other active ingredients.
Preferred formulations have, in particular, the following compositions: (% = per cent by weight)
Emulsifiable concentrates:
Active ingredient: 1 to 90 %, preferably 5 to 50 %
Surface-active agent: 5 to 30 %, preferably 10 to 20 %
Solvent: 15 to 94 % , preferably 70 to 85 % Dusts:
Active ingredient: 0.1 to 50 %, 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 % Surface-active agent: 1 to 40 %, preferably 2 to 30 %
Wettable powders: Active ingredient: 0.5 to 90 %, preferably 1 to 80 % Surface-active agent: 0.5 to 20 %, preferably 1 to 15 % Solid carrier material: 5 to 95 %, preferably 15 to 90 %
Granules: Active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % Solid carrier: 99.5 bis 70 %, vorzugsweise 97 bis 85 %
The active ingredients of the formula I are, as a rule, successfully employed on the plant or its habitat with application rates of 0.001 to 4 kg/ha, in particular 0.005 to 2 kg/ha. The dose necessary for the required effect can be found by tests. It depends on the mode of action, the stage of development of the crop plant and of the weed, and on the application (site, time, method) and may vary within wide ranges determined by these parameters.
The compounds of the formula I are distinguished by herbicidal and growth-inhibiting properties which mean that they can be used in crops of useful plants, in particular in cereals, cotton, soya, sugarbeet, sugarcane, sunflowers, vegetables, plantations, for example fruit and citrus plantations, oilseed rape, maize, sorghum, rice and fodder crops, and for nonselective weed control.
Crops are also to be understood to mean those which have been made tolerant to herbicides or classes of herbicides by conventional breeding or genetic engineering methods. The weeds to be controlled may be both mono- and dicotyledonous weeds, for example stellaria, nasturtium, agrostis, digitaria, avena, setaria, sinapis, lolium, solanum, phaseoius, echinochloa, scirpus, monochoria, sagittaria, bromus, alopecurus, sorghum halepense, rottboellia, cyperus, abutilon, sida, xanthium, amaranthus, chenopodium, ipomoea, chrysanthemum, galium, viola and veronica.
The following examples illustrate the invention further without restricting it.
Preparation examples;
Example H1 : (2-QxobutvD (3-trifluoromethylphenyl)cvanamide
Figure imgf000034_0001
37.8 g of potassium carbonate are introduced into a solution of 52 g (0.275 mol) of 3-trifluoromethylphenylcyanamide in 300 ml of N.N-dimethylformamide (DMF) at 10°C. After 10 minutes, 41 .4 g (0.275 mol) of 1 -bromo-2-butanone are added dropwise at 10-15CC. After the reaction mixture has been stirred at 25°C for 2 hours, it is poured into ice-water and stirred thoroughly, and the precipitated solid is filtered off. After washing with water, the required product is dried under high vacuum. Yield 67.6 g (96 % of theory). Melting point 81-83 °C.
Analysis: Cι2HnF3N2O (256.23)
Calculated [%] : C: 56.25 H: 4.33 N: 10.93 F: 22.24
Found [%] : C: 55.8 H: 4.2 N: 11.1 F: 22.8 Example H2: (2-Oxobutyl) (3-trifluorophenylmethyl)cvanamide
Figure imgf000035_0001
6.9 g of potassium carbonate are introduced into a solution of 9.3 g (0.05 mol) of 3-trifluoromethylphenylcyanamide in 75 ml of DMF at 5°C. After 10 minutes, 8.3 g (0.05 mol) of 2-oxobutyl methanesulfonate are introduced in portions at 10-15CC. After the reaction mixture has been stirred at 25°C for 2.5 hours, it is poured into ice-water and thoroughly stirred, and the precipitated solid is filtered off. After washing with water, the required product is dried under high vacuum. Yield 10.3 g (80 % of theory). Melting point 78-82 °C.
Example H3: (2-Oxopropyl) (3-trifluoromethylphenyl)cvanamide
Figure imgf000035_0002
69 g of potassium carbonate are introduced into a solution of 93 g (0.5 mol) of 3-trifluoromethylphenyl cyanamide in 625 ml of DMF at 5°C. After a few minutes, 42 ml (0.5 mol) of chloroacetone are added dropwise at 10-15°C, and the mixture is stirred at 25°C for 2 hours. The reaction mixture is then poured into 3 I of ice-water and thoroughly stirred, and the precipitated solid is filtered off. After washing with water, the required product is dried under high vacuum. Yield 99.2 g (82 % of theory). Melting point 93-95 °C.
Analysis: CnH9F3N2O (242.20)
Calculated [%] : C: 54.55 H: 3.75 N: 11.57 F: 23.53
Found [%] : C: 54.3 H: 3.6 N: 11.6 F: 23.9 The compounds listed in following Table 1 can be prepared in analogy to the Preparation Examples H1 to H3.
Table 1 : Compounds of the formula HI
Figure imgf000036_0001
Figure imgf000036_0002
Figure imgf000037_0001
Figure imgf000038_0002
Example H4: 5-Cvclopropyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidenamine
Figure imgf000038_0001
10 drops of 1 ,8-diazabicyclo[5.4.0]undec-7-ene (DBU) are added dropwise to a solution of 5.36 g (0.02 mol) of (2-cyclopropyl-2-oxoethyl) (3-trifluoromethylphenyi)cyanamide in 50 ml of tetrahydrofuran at 25°C. After half an hour, the mixture is evaporated, the oily residue is taken up in diethyl ether, and the ethereal solution is washed thoroughly with water, dried and evaporated. The required product is obtained as an oil in a yield of 5.1 g (95 % of theory).
Analysis: Cι3HnF3N2O (268)
Calculated [%] : C: 58.20 H: 4.10 N: 10.44 F: 21.26
Found f%l : C: 58.2 H: 4.2 N: 10.2 F: 21.2 Example Hδ: 5-Ethyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidenamine
Figure imgf000039_0001
1 ml of DBU is added dropwise to a solution of 60.3 g (0.235 mol) of (2-oxo-butyl) (3-trifluoromethylphenyl)cyanamide (Examples H1 and H2) in 250 ml of tetrahydrofuran at 25°C. After 1 hour, the mixture is evaporated, the oily residue is taken up in diethyl ether, and the ethereal solution is washed thoroughly with water, dried and evaporated. The required product is obtained as an oil in a yield of 61.7 g (95 % of theory). Addition of a little diethyl ether at low temperature is followed by crystallization of the compound. Melting point 50-52°C.
Analysis: C12HnF3N2O (256.23)
Calculated [%] : C: 56.25 H: 4.33 N: 10.93 F: 22.24
Found [%] : C: 56.3 H: 4.3 N: 11.0 F: 22.3
The compounds listed in following Table 2 can be prepared in analogy to Preparation Examples H4 and H5.
Table 2: Compounds of the formula IV
Figure imgf000040_0001
Figure imgf000040_0002
Figure imgf000041_0001
Figure imgf000042_0002
Example H6: 3-Amino-4-ethyl-2-imino-1 -(3-trifluoromethylphenyl)-4-imidazolidinol
Figure imgf000042_0001
12.8 ml (0.263 mol) of hydrazine hydrate are added dropwise to a solution of 67.5 g (0.263 mol) of (2-oxobutyl) (3-trifluoromethylphenyl)cyanamide (Examples H1 and H2) in 675 ml of acetonitrile while cooling with an ice/salt mixture at 0-5°C. The resulting suspension is stirred while cooling in ice-water for 1 hour, and then the precipitated solid is filtered off, washed with acetonitrile and diethyl ether and dried under high vacuum. Yield of required product 66 g (87 % of theory). Melting point > 135°C (decomposition)
Analysis: C12Hι5F3N4O (288.27)
Calculated [%] : C: 50.00 H: 5.24 N: 19.44 F: 19.77
Found [%] : C: 50.1 H: 5.2 N: 19.5 F: 19.8 The compounds listed in following Table 3 can be prepared in analogy to Preparation Example H6.
Table 3: Compounds of the formula VI
Figure imgf000043_0001
Figure imgf000043_0002
Figure imgf000044_0001
Figure imgf000045_0001
Example H7: 6-Methyl-4-(3-trifluoromethylphenyl.-4.5-dihvdro-2H-f1.2.41triazin-3- ylidenamine
Figure imgf000046_0001
36.3 g (0.93 mol) of benzyl [6-methyl-4-(3-trifluoromethylphenyl)-4,5-dihydro-2H- [1 ,2,4]triazin-3-ylidene]carbamate is hydrogenated using 5 g of 5% palladium on carbon as catalyst in 720 ml of tetrahydrofuran at 25°C under atmospheric pressure. After the hydrogenation has ceased, the reaction solution is filtered off from the catalyst and evaporated to half the volume, and the resulting solution is treated with active carbon. It is again filtered and evaporated completely. The resulting residue is stirred with cold diethyl ether, filtered off and dried under high vacuum. The required product is obtained in a yield of 22.4 g (94% of theory) with melting point 145-148°C.
Analysis: CnHnF3N4 (256.23)
Calculated [%] : C: 51.56 H: 4.33 N: 21.87 F: 22.24
Found [%]: C: 51.4 H: 4.3 N: 21.8 F: 22.2
Example H8: 6-Ethyl-4-(3-trifluoromethylphenyl)-4.5-dihydro-2H-f1.2.41triazin-3-ylidenamine
Figure imgf000046_0002
71.3 g (0.248 mol) of 3-amino-4-ethyl-2-imino-1-(3-trifluoromethylphenyl)-4-imidazoiidinol (Example H6) are suspended in 500 ml of ethanol and heated to the reflux temperature and kept there for half an hour. The clear solution is then evaporated, and 500 ml of diethyl ether are added to the oily residue while cooling. The precipitated crystalline product is filtered off, washed with hexane and dried under high vacuum. The required product is obtained in a yield of 52 g (78% of theory) with melting point 124-126°C.
Analysis: Cι2Hι3F3N4 (270.26)
Calculated [%] : C: 53.33 H: 4.85 N: 20.73 F: 21.09
Found [%] : C: 53.2 H: 4.9 N: 20.5 R 21.1
The compounds listed in following Table 4 can be prepared in analogy to Preparation Examples H7 and H8.
Table 4: Compounds of the formula VII
Figure imgf000047_0001
Figure imgf000047_0002
Figure imgf000048_0001
Figure imgf000049_0001
Example H9: Ethyl f5-methyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidenelcarbamate
Figure imgf000050_0001
10.5 g (0.1 mol) of ethyl chloroformate are added dropwise to a solution of 0.1 mol of 5-methyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidenamine (crude product; see Example H5) in 200 ml of acetonitrile at 5°C. Subsequently, 16.7 ml (0.12 mol) of triethylamine are added dropwise at 5-15°C, and the mixture is stirred for 3/4 hour. The reaction mixture is evaporated, stirred with ice-water and filtered. The crystalline product is dried under high vacuum. Yield of required product 25.8 g (82% of theory). Melting point 96-98°C.
Analysis: Cι4Hι3F3N203 (314.26)
Calculated [%] : C: 53.51 H. 4.17 N: 8.91 F: 18.14 found [%] : C: 53.4 H: 4.2 N: 9.0 F: 18.2
Example H10: 1 -|5-Ethyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidene]-3-methylurea
Figure imgf000050_0002
A solution of 3.84 g (0.015 mol) of 5-ethyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2- ylidenamine (Example H5), 1.25 ml (0.0165 mol) of methyl isocyanate and 3 drops of triethylamine in 25 ml of acetonitrile is stirred at 25°C for 6 hours. After evaporation of the solution, the reaction mixture is stirred with 25 ml of cold diethyl ether and filtered. Yield of required product 2.8 g (60% of theory). Melting point 102-103°C.
Analysis: d4Hι4F3N302 (313.28)
Calculated [%] : C: 53.68 H: 4.50 N: 13.41 F: 18.19
Found [%]: C: 53.5 H: 4.5 N: 13.5 F: 18.3
Example H11 : Benzyl r5-methyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidenelcarbamate
Figure imgf000051_0001
36.3 g (0.15 mol) of 5-methyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidenamine (see Example H5) are introduced into 280 ml of pyridine, and 19.5 g (0.18 mol) of benzyl chloroformate are added dropwise at 10-15°C. After the reaction mixture has been stirred at 25°C for 1.5 hours it is poured into ice-water and extracted with ethyl acetate. The combined organic phases are washed with water and brine, dried and evaporated. The crude oily product crystallizes on stirring with a mixture of 100 ml of diethyl ether and 150 ml of hexane and is filtered off. The required product is obtained in a yield of 45.4 g (80.5% of theory) with melting point 68-70°C.
Analysis: d Hi5F3N203 (376.33)
Calculated [%] : C: 60.64 H: 4.02 N: 7.44 F: 15.14
Found [%] : C: 60.6 H: 4.0 N: 7.5 F: 15.2 Example H12: sec-Butyl [5-ethyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidenelcarbamate
Figure imgf000052_0001
7.68 g (0.03 mol) of (2-oxobutyl)(3-trifluoromethylphenyl)cyanamide (Examples H1 and H2) are introduced into 60 ml of pyridine at 25°C, and 0.3 ml of DBU is added. The reaction is slightly exothermic. After cooling to 5°C, 4.3 g (0.0315 mol) of sec-butyl chloroformate are added dropwise at 5-10°C, and the reaction mixture is stirred at 25°C for 1 hour. Evaporation is followed by addition of ice-water to the residue and extraction with ethyl acetate. The organic phases are washed with water, dried and evaporated, and the resulting oil is chromatographed on silica gel with ethyl acetate/hexane 2/3 as eluent. Yield of required product 9.3 g (87% of theory) as oil which crystallizes on standing. Melting point 40-44°C.
Analysis: Cι7Hι9F3N203 (356.34)
Calculated [%] : C: 57.30 H: 5.37 N: 7.86 F: 15.99
Found [%] : C: 57.7 H: 5.4 N: 8.0 F: 16.1
The compounds listed in following Table 5 can be prepared in analogy to Preparation Examples H9 to H12. Table 5: Compounds of the formula la
Figure imgf000053_0001
Figure imgf000053_0002
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Examole H13: Ethyl f6-methyl-4-(3-trifluoromethylphenyll-4.5-dihvdro-2H-f1.2.4ltriazin-3- ylidenelcarbamate
Figure imgf000060_0001
25.8 g (0.0822 mol) of ethyl [5-methyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2-ylidene]- carbamate (Example H9) are suspended in 150 ml of ethanol at 5°C, and 4.8 ml (0.0986 mol) of hydrazine hydrate are added dropwise. The reaction mixture is left to stir overnight and is then evaporated, ice-water is added, and the mixture is extracted with methylene chloride. The combined organic phases are washed with water, dried and evaporated, and the resulting oily product is chromatographed on silica gel with ethyl acetate/hexane 1/1 as eluant. The oil resulting after evaporation crystallizes by stirring with a little diethyl ether/hexane mixture. Yield of required product 22 g (81% of theory). Melting point 89-90°C.
Analysis: Cι4Hι5F3N402 (328.29)
Calculated [%] : C: 51.22 H: 4.61 N: 17.07 F: 17.36
Found [%] : C: 51.4 H: 4.6 N: 16.9 F: 17.4
Example H14: 1 -r6-Ethyl-4-(3-trifluoromethylphenyl.-4.5-dihvdro-2H-f1.2.4.triazin-3-ylidenel- 3-ethylurea
Figure imgf000061_0001
A mixture of 1.31 g (0.004 mol) of 1-[5-ethyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2- ylidene]-3-ethylurea (see Example H10) and 0.25 ml of hydrazine hydrate in 15 ml of ethanol is boiled under reflux for 7 hours. The crude product after evaporation of the reaction mixture is chromatographed on silica gel with ethyl acetate/hexane 2/1 as eluent. The resulting oil crystallizes from a diethyl ether/hexane mixture. The required product is obtained in a yield of 0.95 g (70% of theory) with melting point 126-127°C.
Analysis: C15Hι8F3N50 (341.34)
Calculated [%] : C: 52.78 H: 5.32 N: 20.52 F: 16.70
Found [%] : C: 52.7 H: 5.2 N: 20.5 F: 16.9
Example H15: N-f6-Methyl-4-.3-trifluoromethylphenyl .5-dihvdro-2H-f1.2.41triazin-3- ylidene]-2.2.2-trifluoracetamide
Figure imgf000062_0001
39 ml of trifluoroacetic anhydride are added dropwise to a suspension of 34.3 g (0.134 mol) of 6-methyl-4-(3-trifluoromethylphenyl)-4,5-dihydro-2H-[1 ,2,4]triazin-3-ylideneamine (Example H7) in 350 ml of methylene chloride at 10-20°C. Then 75 ml of triethylamine are added dropwise at 10-20CC, and the mixture is then stirred at 25°C for 1 hour. The reaction mixture is subsequently stirred vigorously with ice-water for 10 minutes, the organic phase is separated off, and the aqueous phase is washed with methylene chloride. The methylene chloride phase is dried and evaporated. The resulting oil is chromatographed on silica gel with ethyl acetate/hexane 2/3 as eluant. After evaporation of the collected fractions, the required product crystallizes from a diethyl ether/hexane mixture (1/10). The product is filtered off and dried under high vacuum. Yield 38.2 g (81% of theory). Melting point. 118- 119°C.
Analysis: d3H10FeN40 (352.24)
Calculated [%] : C: 44.33 H: 2.86 N: 15.91 F: 32.36
Found [%] : C: 44.5 H: 2.9 N: 15.9 F: 32.4 Example H16: N-f6-Ethyl-4-(3-trifluoromethylPhenyl)-4.5-dihvdro-2H-f1.2.41triazin-3-ylidene1- 2-fluoroacetamide
Figure imgf000063_0002
Figure imgf000063_0001
0.78 g (0.01 mol) of fluoroacetic acid is dissolved in 30 ml of tetrahydrofuran at 25°C, and 1.62 g (0.01 mol) of carbonyldiimidazole are added in portions. After stirring for 1 hour, 2.7 g (0.01 mol) of 6-ethyl-4-(3-trrfluoromethylphenyl)-4,5-dihydro-2H-[1 ,2,4]triazin-3- ylideneamine (Example H8) are added to this clear solution, which is then stirred for a further 1 hour. The reaction mixture is then evaporated, ice-water is added, and the mixture is acidified with 2N hydrochloric acid and extracted with ethyl acetate. The combined organic phases are washed with water and brine, dried and evaporated. The resulting oil crystallizes from an ether/hexane mixture. The required product is obtained in a yield of 2.7 g (82% of theory) with melting point 90-91 °C.
Analysis: Cι4Hι4F4N40 (330.29)
Calculated [%] : C: 50.91 H: 4.27 N: 16.96 F: 23.01
Found [%] : C: 51.3 H: 4.4 N: 16.9 23.1
Example H17: 2-Methoxy-N-f6-ethyl-4-(3-trifluoromethylphenyl)-4,5-dihvdro-2H- f1.2.4|triazin-3-ylidene]acetamide
Figure imgf000064_0001
0.61 ml (0.005 mol) of 4-N,N-dimethylaminopyridine (DMAP) is introduced into 6 ml of methylene chloride at 0-5°C, and 0.45 ml (0.005 mol) of methoxyacetyl chloride is added dropwise. This clear solution is added dropwise to a prepared solution of 1.35 g (0.005 mol) of 6-ethyl-4-(3-trifluoromethylphenyl)-4,5-dihydro-2H-[1 ,2,4]triazin-3-ylideneamine (Example H8) in 14 ml of methylene chloride at 5°C. The reaction solution is then stirred overnight, washed with water, dried and evaporated. The resulting oil is chromatographed on silica gel with ethyl acetate as eluent. After evaporation of the collected fractions, the required product crystallizes from diethyl ether/hexane. Yield 0.8 g (47% of theory). Melting point 105-106°C.
Analysis: d5Hi7F3N402 (342.32)
Calculated [%] : C: 52.63 H: 5.01 N: 16.37 F: 16.65
Found [%] : C: 52.5 H: 5.0 N: 16.2 F: 16.8
Example H18: 1 -■6-Ethyl-4-(3-trifluoromethylphenyl.-4.5-dihvdro-2H-ri ,2.41triazin-3- ylidenelurea
Figure imgf000065_0001
A suspension of 7 g (0.018 mol) of phenyl [6-ethyl-4-(3-trifluoromethylphenyl)-4,5-dihydro- 2H-[1 ,2,4]triazin-3-ylidene]carbamate (see Example H13) in 20 ml of a saturated ammonia/ethanol solution is stirred at 25°C overnight. This results in crystal transformation and suspension of the required product. The latter is filtered off and washed with alcohol, and the product is dried. Yield 4.8 g (85% of theory). Melting point 179-180°C.
Analysis: Cι3Hι4F3N50 (342.32)
Calculated [%] : C: 49.84 H: 4.50 N: 22.35 F: 18.19
Found [%1 : C: 49.5 H: 4.6 N: 22.3 F: 18.3
The compounds listed in following Table 6 can be prepared in analogy to Preparation Examples H13 to H 18.
Table 6: Compounds of the formula Ic
Figure imgf000066_0001
Figure imgf000066_0002
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Example H19: Isopropyl f4-Ethyl-4-hvdroxy-1-(3-trifluoromethylphenyl)-2- imidazolidinylidenej-carbamate
Figure imgf000085_0001
2.7 g (0.008 mol) of isopropyl [5-ethyl-3-(3-trifluoromethylphenyl)-3H-oxazol-2- ylidene]carbamate (see Example H12) are introduced into 20 ml of a saturated ammonia/ethanol solution diluted with 5 ml of ethanol at 25°C. After stirring for 2 hours, the clear solution is evaporated, and the resulting residue is thoroughly stirred with cold diethyl ether, filtered off and dried. The required product is obtained in a yield of 2.3 g (75% of theory) with melting point 132-134°C.
Analysis: Cι6H2OF3N303 (359.75)
Calculated [%] : C: 53.48 H: 5.60 N: 11.70 F: 15.86
Found [%] : C: 52.9 H: 5.5 N: 11.7 F: 16.0
The compounds listed in following Table 7 can be prepared in analogy to Preparation Example H19.
-84-
Table 7: Compounds of the formula V
Figure imgf000086_0001
Figure imgf000086_0002
85-
Figure imgf000087_0001
Example H20: Isopropyl [4-ethyl-1-(3-trifluoromethylphenyl)-1.3-dihydro-2-imidazolylidenel- carbamate
Figure imgf000088_0001
1.25 g (0.00336 mol) of isopropyl [4-ethyl-4-hydroxy-1-(3-trifluoromethylphenyl)-2- imidazolidinylidene]carbamate (Example H19) are introduced into 15 ml of trifluoroacetic anhydride at 25°C. After stirring for half an hour, the clear solution is concentrated, and the resulting residue is taken up in ethyl acetate. The ethyl acetate solution is washed with • dilute sodium bicarbonate solution and then with water and brine. Evaporation results in a solid residue which is stirred with diethyl ether/hexane 2/3 and then filtered off. The required product is obtained in a yield of 1.05 g (88% of theory) with melting point 116-118°C.
Analysis: Cι6Hι8F3N302 (359.75)
Calculated [%] : C: 56.30 H: 5.31 N: 12.31 F: 16.69
Found [%) : C: 56.2 H: 5.3 N: 12.3 F: 16.7
The compounds listed in following Table 8 can also be prepared in an analogous manner.
87-
Table 8: Compounds of the formula lb
Figure imgf000089_0001
Figure imgf000089_0002
88
Figure imgf000090_0001
Examples of formulations of active ingredients of the formula I (% = per cent bv weight)
F1. Emulsion concentrates a) b) c) d)
Active ingredient in Tables 5, 6 and 8 5% 10% 25% 50%
Ca dodecylbenzenesulfonate 6 % 8 % 6 % 8 %
Castor oil polyglycol ether 4 % - 4 % 4 %
(36 mol EO)
Octylphenol polyglycol ether - 4 % - 2 %
(7-8 mol EO)
Cyclohexanone - - 10% 20%
Arom. Cg-Cι2 85% 78% 55% 16% hydrocarbon mixture
Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
F2. Solutions a) b) c) d)
Active ingredient in Tables 5, 6 and 8 5% 10% 50% 90%
1 -Methoxy-3-(3-methoxy- propoxy)propane - 20% 20%
Polyethylene glycol MW 400 20% 10%
N-Methyl-2-pyrrolidone - - 30% 10%
Arom. C9-Cι2 75 % 60 % hydrocarbon mixture
The solutions are suitable for use in the form of very fine drops. F3. Wettable powders a) b) c) d)
Active ingredient in Tables 5, 6 and 8 5% 25% 50% 80%
Na ligninsulfonate 4 % - 3 %
Na lauryl sulfate 2% 3% - 4%
Nadiisobutylnaphthalenesulfonate - 6% 5% 6%
Octylphenol polyglycol ether - 1 % 2 %
(7-8 mol EO)
Highly disperse silica 1 % 3% 5% 10%
Kaolin 88% 62% 35%
The active ingredient is thoroughly mixed with the additives and thoroughly ground in a suitable mill. The resulting wettable powders can be diluted with water to give suspensions of any desired concentration.
F4. Coated granules a) b) c)
Active ingredient in Tables 5, 6 and 8 0.1 %
Highly disperse silica 0.9 %
Inorg. carrier material 99.0 %
Figure imgf000092_0001
(00.1 - 1 mm) for example CaCO3 or SiO2
The active ingredient is dissolved in methylene chloride and sprayed onto the carrier, and the solvent is thoroughly evaporated off in vacuo.
F5. Coated granules a) b) c)
Active ingredient in Tables 5, 6 and 8 0.1 % 5% 15% Polyethylene glycol MW 200 1.0 %
High disperse silica 0.9 %
Inorg. carrier material 98.0 %
Figure imgf000093_0001
(0 0.1 - 1 mm) for example CaCO3 or SiO2
The finely ground active ingredient is applied uniformly to the carrier material which is moistened with polyethylene glycol in a mixer. This results in dust-free coated granules.
F6. Pellets a) b) c) d)
Active ingredient in Tables 5, 6
Figure imgf000093_0002
The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and subsequently dried in a stream of air.
Figure imgf000093_0003
Dusts ready for application are obtained by mixing the active ingredient with the carriers and grinding in a suitable mill. F8. Suspension concentrates a) b) c) d)
Active ingredient in Tables 5, 6 and 8 3 % 10 % 25 % 50 %
Ethylene glycol 5 % 5 % 5 % 5 %
0.2
0.8
Figure imgf000094_0001
The finely ground active ingredient is intimately mixed with the additives. This results in a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
Biological examples
Example B1 : Herbicidal action before emergence of the plants (preemergence action.
Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastic pots. Immediately after sowing, the test substances are sprayed on as aqueous suspension (prepared from a 25% wettable powder (Example F3, b)) or as emulsion (prepared from a 25% emulsion concentrate (Example F1 , c)) corresponding to a dose of 2 kg AS/ha (5001 water/ha). The test plants are then grown in a glasshouse under optimal conditions. After the test has lasted 3 weeks, the experiment is evaluated using a nine-point scoring scale (1 = complete damage, 9 = no action). Rating scores from 1 to 4 (in particular 1 to 3) mean that the herbicidal action is good to very good. Table B1 : Preemeroence action:
Test plant: Setaria Sinapis Stellaria n r dient No.
Figure imgf000095_0001
6.73 1 2
6.84 2 2
6.87 2
6.88 2
6.89
6.93
6.166
6.206
6.208
6.250
7.16
8.3 3 3
8.11 2 1
8.17 1 2
The same results are obtained when the compounds of the formula I are formulated as in Examples F2 and F4 to F8.
Example B2: Postemergence herbicidal action
Monocotyledonous and dicotyledonous test plants are grown in plastic pots containing standard soil in a glasshouse and sprayed at the 4- to 6-leaf stage with an aqueous suspension of the test substances of the formula I prepared from a 25% wettable powder (Example F3, b)) or with an emulsion of the test substances of the formula I prepared from a 25% emulsion concentrate (Example F1 , c)), corresponding to a dose of 2 kg AS/ha (500 I water/ha). The test plants are then grown further in a glasshouse under optimal conditions. After the test has lasted about 18 days, the experiment is evaluated using a nine-point scoring scale (1 = complete damage, 9 = no action). Rating scores from 1 to 4 (in particular 1 to 3) mean that the herbicidal action is good to very good. The compounds of the formula I show a strong herbicidal action in this experiment. Table B2: Postemer ence action:
inapis
Figure imgf000097_0001
The same results are obtained when the compounds of the formula I are formulated as in Examples F2 and F4 to F8.

Claims

What is claimed is:
1. A compound of the formula
Figure imgf000098_0001
in which
-A- is a group — CH=C-N- (A,), (A2) or
-CH=C-0- R_=
I (A3) where the bonding of -A- to the nitrogen atom takes place via
— CH— C = :N-NRK-
the carbon atom;
R3 is Cι-C4alkyl, it being possible for this radical to be substituted by halogen, cyano,
Cι-C alkoxy, benzyloxy, hydroxyl, C C4alkylthio, Cι-C4alkylamino or di-CrC4alkylamino, or is C3-C6cycloalkyl, aryl or substituted aryl;
R5 and R6 are, independently of one another, hydrogen or d-C4alkyl;
Ri is halogen, Cι-C4alkyl, Cι-C4haloalkyl, C C alkoxy, C C4haloalkoxy, CrC4alkylthio,
Cι-C haloalkylthio, cyano or nitro;
R2 is hydrogen, halogen, Cι-C4alkyl or Cι-C4haloalkyl; or
R2 in position 2 of the phenyl ring and Ri together form an -OCF2O- group;
R is C C6alkyl, C3-C6alkenyl, C3-C6alkynyl or C3-C6cycloalkyl, it being possible for these alkyl, alkenyl and alkynyl radicals to be substituted by halogen, C -C3alkyl, Cι-C3alkoxy,
CrOsalkylthio, C3-C6cycloalkyl, C3-C6cycloalkoxy, cyano, aryl, aryloxy or a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or
R4 is Cι-C7alkylaminosulfonyl, di-Cι-C7alkylaminosulfonyl, Cι-C7alkylsulfonyl or
C C7alkylsulfinyl, it being possible for these alkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl and alkylsulfinyl radicals to be substituted by halogen, CrC3alkoxy,
CrC3alkylthio, C3-C6cycloalkyl, C3-C6cycloalkoxy, cyano, aryl, aryloxy or a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or
R4 is cyano, arylsulfonyl, sulfamoyl or a -C(X)R7or -C(X)NHR9 group;
X is oxygen or sulfur;
R7 is C C8alkyl, C2-C6alkenyl, C3-C6alkynyl, CrC6alkoxy, C2-C6alkenyloxy, C3-C6alkynyloxy,
Cι-C6alkylthio, C2-C6alkenylthio, C3-C6alkynylthio or di-Cι-C6alkylamino, it being possible for these alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio, alkynylthio and dialkylamino radicals to be substituted by halogen, d-C3alkyl, C C3alkoxy,
Cι-C3haloalkoxy, Cι-C6alkylcarbonyl, Cι-Cealkylcarbonyloxy, Cι-C3alkoxycarbonyl,
C -C3alkylthio, C3-C6cycloalkyl, C3-C6cycloalkoxy, hydroxyl, cyano, aryl, aryloxy, benzyloxy or a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or
R7 is hydrogen, C3-C6cycloalkyl, C3-C6cycloalkoxy, C3-C6cycloalkylthio, aryl, aryloxy, hetaryl, a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or a saturated heterocyclyloxy radical which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms; and
R9 is hydrogen, Cι-C6alkyl, C3-Cealkenyl or C3-C6alkynyl, it being possible for these alkyl, alkenyl and alkynyl radicals to be substituted by halogen, Cι-C3alkyl, Cι-C3alkoxy,
C C3alkylthio, C3-C6cycloalkyl, C3-Cecycloalkoxy, hydroxyl, cyano, aryl, aryloxy or a saturated heterocyclic ring which contains 2-6 carbon atoms and nitrogen, oxygen and/or sulfur atoms, or is C3-Cβcycloalkyl or aryl, and agronomically suitable salts of compounds of the formula I.
2. A compound according to claim 1 , in which Ri is halogen, CrC haloalkyl, cyano, nitro, d-C haloalkoxy or C C4haloalkylthio; and R7 has the same meaning as defined in Claim 1 with the exception of C7- and Cθalkyl.
3. A compound according to claim 1 , in which Ri is trifluoromethyl or trifluoromethoxy.
4. A compound according to claim 1 , in which R2 is hydrogen.
5. A compound according to claim 1 , in which R3 is methyl, ethyl or cyclopropyl.
6. A compound according to claim 1 , in which R4 is a -C(X)R7 group; X is oxygen; and R7 is C C6alkyl, Cι-C6alkoxy or CrC6alkylamino, it being possible for these radicals to be substituted by halogen, CrC3alkyl, Cι-C3alkoxy, C3-C6cycloalkyl or C3-C6cycloalkoxy.
7. A compound according to claim 5, in which R7 is CrC6alkyl, C C6haloalkyl or Ci- C6alkoxy.
8. A compound according to claim 1 , in which -A- is a group (Ai); R3 has
Figure imgf000100_0001
the meaning stated in claim 1 ; and Rs is hydrogen or methyl.
9. A compound according to claim 8, in which R5 is hydrogen.
?a
10. A compound according to claim 1 , in which -A- is a group I (As);
— CH— C=N-NR—
R3 is methyl or ethyl; R2 is hydrogen or halogen; R6 is hydrogen; Ri is trifluoromethyl or trifluoromethoxy; R4 is a -C(X)R7 group; X is oxygen; and R is C C3haloalkyl or d- C alkoxy.
R 3
11. A compound according to claim 1 , in which -A- is a group | (A2); R3 is
— CH=C-0- methyl or ethyl; Ri is trifluoromethyl or trifluoromethoxy; R2 is hydrogen; R4is a -C(X)R7 group, X is oxygen; and R is C -C4alkoxy. R3
12. A compound according to claim 1 , in which -A- is a group | (A2); R3 is
— CH=C-o-
C C4alkyl, cyclopropyl, phenyl or benzyloxymethyl; Ri is fluorine, Ci- or C2alkyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, trifluoromethylthio or cyano; R2 is hydrogen, 4-fluoro, 4- or 6-chloro or 5-trifluoromethyl; or R2 in position 2 of the phenyl ring and Ri together form a -OCF2O- group; R4 is cyano, methyl, methyl • HI salt, propargyl, cyclopentyl, benzyl, methylsulfonyl, dimethylaminosulfonyl, trifluoromethylsulfonyl, 2-chlorophenylsulfonyl or 2-chloro-2-propylsulfinyl; or R4 is a -C(X)R7 group; X is oxygen or sulfur; R is hydrogen, d-Qjalkyl, cyanomethyl, methoxymethyl, methoxyethyl, methylthiomethyl, methoxycarbonylmethyl, trifluoromethoxymethyl, phenoxymethyl, CrC4alkoxy, methoxyethoxy, vinyloxy, allyloxy, propargyloxy, Cι-C3alkylthio, dimethylamino, difluoromethyl, trifluoromethyl, pentafluoroethyl, chloromethoxy, 2,2,2-trichloroethoxy, C3-C6cycloalkoxy, cyclopropylmethoxy, cyclobutylmethoxy, 2,6-difluorophenyl, 2-furyl, phenoxy, benzyloxy, N-morpholino, N-piperidino or N-pyrrolidino; or R4 is a -C(X)NHR9 group; X is oxygen or sulfur; and R9 is Ci- or C2alkyl, cyanomethyl or phenyl.
13. A compound according to claim 1 , in which -A- is a group I (Aa);
— CH— C=N-NR—
R3 is Cι-C4alkyl, hydroxymethyl, chloromethyl, dimethylaminomethyl, cyclopropyl, phenyl or benzyloxymethyl; R6 is hydrogen or methyl; Ri is fluorine, C or C2alkyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy or trifluoromethylthio; R2 is hydrogen, 4-fluoro, 4- or 6-chloro or 5-trifluoromethyl; or R2 in position 2 of the phenyl ring and Ri together form a -OCF2O- group; R4 is methyl, propargyl, cyclopentyl, benzyl, cyano, methylsulfonyl, isopropylsulfonyl, trifluoromethylsulfonyl, 2-chloro-2-propylsulfinyl, phenylsulfonyl or 2-chlorophenylsulfonyl; or R4 is a -C(X)R7 group; X is oxygen or sulfur; R7 is hydrogen, C C4alkyl, cyanomethyl, hydroxymethyl, methoxymethyl, methoxyethyl, methoxycarbonylmethyl, trifluoromethoxymethyl, methylthiomethyl, benzyloxymethyl, phenoxymethyl, cyclopropyl, cyclopentyl, dimethylaminomethyl, CrC4alkoxy, methoxyethoxy, vinyloxy, 1 -methylvinyloxy, allyloxy, propargyloxy, Cι-C3alkylthio, dimethylamino, cyanomethyl-methylamino, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, fluorochloromethyl, pentafluoroethyl, 2-chloroethoxy, 2,2,2- trichloroethoxy, C3-C6cycloalkoxy, cyclopropylmethoxy, cyclobutylmethoxy, 2-furyl, phenyl, 2,6-difluorophenyl, 2,6-difluorobenzyl, phenoxy, benzyloxy, 3-oxetanyloxy, N-morpholino, N-piperidino or N-pyrrolidino; or R7 is a -C(X)NHR9 group; X is oxygen or sulfur; and R9 is hydrogen, Cι-C3alkyl, cyanomethyl, cyclopropyl, phenyl or 2-, 3- or 4-chlorophenyl.
14. A compound according to claim 1 , in which -A- is a group (Ai); R3 is
Figure imgf000102_0001
Ci- or C2alkyl, cyclopropyl or phenyl; R5 is hydrogen, methyl or cyclopropyl, R, is cyano, trifluoromethyl, pentafluoroethyl, trifluoromethoxy or trifluoromethylthio; R2 is hydrogen; or R2 in position 2 of the phenyl ring and Ri together form a -OCF2O- group; R4 is cyano or a -C(X)R7 group; X is oxygen; and R7 is methyl, difluoromethyl, trifluoromethyl, C C3alkoxy or pentafluoroethyl.
15. A process for preparing compounds of the formula I according to claim 1 , which comprises reacting a compound of the formula II
Figure imgf000102_0002
in which Ri and R2 have the meaning stated in claim I, with a compound of the formula X
Figure imgf000102_0003
in which R3 has the meaning stated in claim I, and L, is a leaving group, in the presence of a base and of a solvent to give a compound of the formula III
Figure imgf000103_0001
cyclizing the latter in the presence of a base to give the compound of the formula IV
Figure imgf000103_0002
subsequently reacting the latter
1 ) to prepare compounds of the formula I in which R4 is Cι-C6alkyl, C3-C6alkenyl, C3-C6alkynyl, C3-C6cycloalkyl, Cι-C7alkylaminosulfonyl, di-Cι-C alkylaminosulfonyl, Cι-C7alkylsulfonyl or C -C7alkylsulfinyl, it being possible for all of these radicals to be substituted as stated in claim I, cyano, arylsulfonyl or sulfamoyl, with a compound of the formula XIa
L2-R4 (XIa),
in which R4 has the stated meaning and L2 is a leaving group, or
2) to prepare compounds of the formula I in which R4 is a -C(X)R group; and R7 and X have the meaning stated in claim I, with a compound of the formula Xlb
X
II (Xlb),
RΓC-L4
in which R7and X have the stated meaning, and L» is a leaving group, or 3) to prepare compounds of the formula I in which R4 is a -C(X)NHR9 group; and R9, with the exception of hydrogen, and X have the meaning stated in claim I, with a compound of the formula Xlc
R9-N=C=X (Xlc),
in which R9 and X have the stated meaning, to give a compound of the formula la
Figure imgf000104_0001
in which Ri, R2, R3 and R have the stated meaning, and the latter subsequently either a) being converted with a compound of the formula XII
R6-NH-NH2 (XII),
in which R6 has the meaning stated in claim I, into the compound of the formula Ic
Figure imgf000104_0002
or b) being rearranged with a compound of the formula XIII
R5-NH2 (XIII),
in which R5 has the meaning stated in claim I, to give the compound of the formula V
Figure imgf000105_0001
and the latter subsequently being converted with elimination of water into the compound of the formula lb
Figure imgf000105_0002
16. A process for preparing compounds of the formula I in which -A- is a group
(Aa), and R3 and R6 are as defined in claim 1 , which comprises
— CH— C=N-NR6— c) cyclizing a compound of the formula
Figure imgf000106_0001
in which Ri, R2 and R3 have the meaning stated in claim I, with hydrazine to give the compound of the formula VI
Figure imgf000106_0002
obtaining, by ring expansion, the compound of the formula VII
Figure imgf000106_0003
and subsequently reacting the latter
1) to prepare compounds of the formula I in which R4 is Cι-Cβalkyl, d-Cealkenyl, C3-C6alkynyl, C3-C6cycloalkyl, Cι-Cτalkylaminosulfonyl, di-d-C^lkylaminosulfonyl, Cι-C7alkylsulfonyl or d-C7alkylsulfinyl, it being possible for all of these radicals to be substituted as indicated in claim I, cyano, arylsulfonyl or sulfamoyl, with a compound of the formula XIa
Figure imgf000107_0001
in which R., has the stated meaning and L2 is a leaving group, or
2) to prepare compounds of the formula I in which R4 is a -C(X)R7 group; and R7 and X have the meaning stated in claim I, with a compound of the formula Xlb
X
II (Xlb),
R7-C-L4
in which R7and X have the stated meaning and U is a leaving group, or 3) to prepare compounds of the formula I in which R4 is a -C(X)NHR9 group; and R9, with the exception of hydrogen, and X have the meaning stated in claim I, with a compound of the formula Xlc
R9-N=C=X (Xlc),
in which R9 and X have the stated meaning, to give the compound of the formula I, or d) reacting a compound of the formula IV
Figure imgf000107_0002
in which Ri, R2 and R3 have the meaning stated in claim I, with the compound of the formula XIV
RβOC(O)-U (XIV), in which U is a leaving group and Rθ is or -C(CH3)3 to give a compound
Figure imgf000108_0001
of the formula VIII
Figure imgf000108_0002
in which Ri, R2, R3 and R8 have the stated meaning, and subsequently converting with the compound of the formula XII
R6-NH-NH2 (XII),
in which R6 has the meaning stated in claim I, into the compound of the formula IX
Figure imgf000108_0003
reductively cleaving the latter in the presence of a catalyst to the compound of the formula VII
(VII),
Figure imgf000108_0004
and subsequently converting with a compound of the formula XIa, Xlb or Xlc, as described above under c), into the compound of the formula I.
17. A compound of the formula II
Figure imgf000109_0001
in which Ri is cyano, d-C3haloalkoxy or Cι-C4haloalkylthio; R2 has the meaning stated in claim 1 ; or R2 in position 2 of the phenyl ring and Ri together form a -OCF2O- group.
18. A compound of the formula III
Figure imgf000109_0002
in which Ri, R2 and R3 are as defined in claim 1.
19. A compound of the formula IV
Figure imgf000109_0003
in which R1 t R2 and R3 are as defined in claim 1.
20. A compound of the formula V
Figure imgf000110_0001
in which R1 f R2, R3, R and R5 are as defined in claim 1.
21. A compound of the formula VI
Figure imgf000110_0002
in which Ri, R2 and R3 are as defined in claim 1.
22. A compound of the formula VII
Figure imgf000110_0003
in which Ri, R2 and R3 are as defined in claim 1.
23. A herbicidal and plant growth-inhibiting composition which comprises a herbicidally effective content of compound of the formula I, and an inert carrier.
24. A composition according to claim 23 which comprises between 0.1% and 95% of active ingredient of the formula I.
25. A method for controlling unwanted plant growth, which comprises applying an active ingredient of the formula I, or a composition containing this active ingredient, in a herbicidally effective amount to the plants or their habitat.
26. A method according to claim 25, wherein an amount of between 0.001 and 4 kg of active ingredient is applied per hectare.
27. A method for inhibiting plant growth, which comprises applying an active ingredient of the formula I, or a composition containing this active ingredient, in a herbicidally effective amount to the plants or their habitat.
28. The use of a composition according to claim 23 for controlling unwanted plant growth.
29. A method according to claim 25, characterized in that the useful plants are cereals, cotton, soya, sugar beet, sugar cane, sunflowers, vegetables, plantations, oilseed rape, maize, sorghum, rice and fodder crops.
PCT/EP1997/003420 1996-07-02 1997-07-01 N-phenylimino heterocyclic derivatives and their use as herbicides WO1998000408A1 (en)

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000034257A1 (en) * 1998-12-10 2000-06-15 Bayer Aktiengesellschaft Substituted 2-imino-thiazolines and their use as herbicides
EP1391456A1 (en) * 2001-04-19 2004-02-25 Eisai Co., Ltd. 2-iminoimidazole derivative (2)
US7186834B2 (en) * 2000-05-19 2007-03-06 Bayer Aktiengesellschaft Substituted iminoazines
US7375236B2 (en) 2003-02-19 2008-05-20 Eisai Co., Ltd. Methods for producing cyclic benzamidine derivatives
JP2015508407A (en) * 2012-01-06 2015-03-19 アビデ セラピューティクス，インク． Carbamate compounds and their manufacture and use
WO2017093409A1 (en) * 2015-12-03 2017-06-08 Syngenta Participations Ag Pesticidal compounds and their uses
US9771341B2 (en) 2015-03-18 2017-09-26 Abide Therapeutics, Inc. Piperazine carbamates and methods of making and using same
US9981930B1 (en) 2016-11-16 2018-05-29 Abide Therapeutics, Inc. MAGL inhibitors
US10093635B2 (en) 2016-11-16 2018-10-09 Abide Therapeutics, Inc. MAGL inhibitors
US10450302B2 (en) 2015-05-11 2019-10-22 Lundbeck La Jolla Research Center, Inc. Methods of treating inflammation or neuropathic pain
US10463753B2 (en) 2016-02-19 2019-11-05 Lundbeck La Jolla Research Center, Inc. Radiolabeled monoacylglycerol lipase occupancy probe
US10570106B2 (en) 2018-05-15 2020-02-25 Lundbeck La Jolla Research Center, Inc. MAGL inhibitors
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1458914A (en) * 1974-09-11 1976-12-15 Monsanto Co Imidazoles
EP0265162A1 (en) * 1986-10-17 1988-04-27 Stauffer Chemical Company Iminooxazolidines, process of preparation and method of use
EP0446802A1 (en) * 1990-03-12 1991-09-18 Sumitomo Chemical Company, Limited Iminothiazolines, their production and use as herbicides, and intermediates for their production
EP0529482A1 (en) * 1991-08-23 1993-03-03 Sumitomo Chemical Company, Limited Iminothiazolines, their production and use as herbicides, and intermediates for their production
US5244863A (en) * 1990-03-12 1993-09-14 Sumitomo Chemical Company, Limited Iminothiazolines, their production and use as herbicides, and intermediates for their production

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1458914A (en) * 1974-09-11 1976-12-15 Monsanto Co Imidazoles
EP0265162A1 (en) * 1986-10-17 1988-04-27 Stauffer Chemical Company Iminooxazolidines, process of preparation and method of use
EP0446802A1 (en) * 1990-03-12 1991-09-18 Sumitomo Chemical Company, Limited Iminothiazolines, their production and use as herbicides, and intermediates for their production
US5244863A (en) * 1990-03-12 1993-09-14 Sumitomo Chemical Company, Limited Iminothiazolines, their production and use as herbicides, and intermediates for their production
EP0529482A1 (en) * 1991-08-23 1993-03-03 Sumitomo Chemical Company, Limited Iminothiazolines, their production and use as herbicides, and intermediates for their production

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US7186834B2 (en) * 2000-05-19 2007-03-06 Bayer Aktiengesellschaft Substituted iminoazines
US7476688B2 (en) 2001-04-19 2009-01-13 Eisai R&D Management Co., Ltd. Cyclic amidine derivatives
EP1391456A1 (en) * 2001-04-19 2004-02-25 Eisai Co., Ltd. 2-iminoimidazole derivative (2)
EP1391456A4 (en) * 2001-04-19 2006-02-01 Eisai Co Ltd 2-iminoimidazole derivative (2)
US7244730B2 (en) 2001-04-19 2007-07-17 Eisai Co., Ltd 2-iminopyrrolidine derivatives
US7304083B2 (en) 2001-04-19 2007-12-04 Eisai R&D Management Co., Ltd. 2-iminoimidazole derivatives (2)
US7375236B2 (en) 2003-02-19 2008-05-20 Eisai Co., Ltd. Methods for producing cyclic benzamidine derivatives
JP2015508407A (en) * 2012-01-06 2015-03-19 アビデ セラピューティクス，インク． Carbamate compounds and their manufacture and use
US9487495B2 (en) 2012-01-06 2016-11-08 The Scripts Research Institute Carbamate compounds and of making and using same
US11530189B2 (en) 2012-01-06 2022-12-20 H. Lundbecka/S Carbamate compounds and methods of making and using same
JP2017125039A (en) * 2012-01-06 2017-07-20 アビデ セラピューティクス，インク． Carbamate compounds and of making and using same
US11021453B2 (en) 2012-01-06 2021-06-01 Lundbeck La Jolla Research Center, Inc. Carbamate compounds and methods of making and using same
US9957242B2 (en) 2012-01-06 2018-05-01 The Scripps Research Institute Carbamate compounds and methods of making and using same
US9771341B2 (en) 2015-03-18 2017-09-26 Abide Therapeutics, Inc. Piperazine carbamates and methods of making and using same
US9994537B2 (en) 2015-03-18 2018-06-12 Abide Therapeutics, Inc. Piperazine carbamates and methods of making and using same
US10450302B2 (en) 2015-05-11 2019-10-22 Lundbeck La Jolla Research Center, Inc. Methods of treating inflammation or neuropathic pain
US11034674B2 (en) 2015-05-11 2021-06-15 H. Lundbeck A/S Methods of treating inflammation or neuropathic pain
WO2017093409A1 (en) * 2015-12-03 2017-06-08 Syngenta Participations Ag Pesticidal compounds and their uses
US10463753B2 (en) 2016-02-19 2019-11-05 Lundbeck La Jolla Research Center, Inc. Radiolabeled monoacylglycerol lipase occupancy probe
US10899737B2 (en) 2016-09-19 2021-01-26 Lundbeck La Jolla Research Center, Inc. Piperazine carbamates and methods of making and using same
US10093635B2 (en) 2016-11-16 2018-10-09 Abide Therapeutics, Inc. MAGL inhibitors
US9981930B1 (en) 2016-11-16 2018-05-29 Abide Therapeutics, Inc. MAGL inhibitors
US10570106B2 (en) 2018-05-15 2020-02-25 Lundbeck La Jolla Research Center, Inc. MAGL inhibitors
US11214557B2 (en) 2018-05-15 2022-01-04 H. Lundbeck A/S MAGL inhibitors
US11332453B2 (en) 2018-05-15 2022-05-17 H. Lundbeck A/S MAGL inhibitors
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