Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
  • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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
  • C07D207/36—Oxygen or sulfur atoms
  • C07D207/38—2-Pyrrolones
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
  • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
  • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
  • C07C255/29—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton containing cyano groups and acylated amino groups bound to the carbon skeleton
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
  • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
  • C07C255/31—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing rings other than six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
  • C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with 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
  • C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/56—Ring systems containing three or more rings
  • C07D209/80—[b, c]- or [b, d]-condensed
  • C07D209/94—[b, c]- or [b, d]-condensed containing carbocyclic rings other than six-membered
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/56—Ring systems containing three or more rings
  • C07D209/96—Spiro-condensed ring systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
  • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
  • C07D279/12—1,4-Thiazines; Hydrogenated 1,4-thiazines not condensed with other rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
  • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no 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
  • C07D309/14—Nitrogen atoms not forming part of a nitro radical
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/04—Ortho-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
  • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
  • C07D491/10—Spiro-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
  • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
  • C07D513/04—Ortho-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

• the invention relates to new 2,4-dihalogen-6- (C2-C3-alkyl) -phenyl-substituted tetramic acid derivatives, several processes and intermediates for their preparation and their use as pesticides and / or herbicides.
• the invention also relates to selective herbicidal compositions which contain 2,4-dihalogen-6- (C2-C3-alkyl) -phenyl-substituted tetramic acid derivatives on the one hand and at least one compound which improves the tolerance of crop plants on the other hand.
• EP-A-0 262 399 and GB-A-2 266 888 disclose similarly structured compounds (3-arylpyrrolidine-2,4-diones), of which no herbicidal, insecticidal or acaricidal activity has been disclosed.
• Unsubstituted, bicyclic 3-aryl-pyrrolidine-2,4-dione derivatives EP-A-355 599 and EP-A-415 211) and substituted monocyclic 3-aryl-pyrrolidin-2 are known to have herbicidal, insecticidal or acaricidal activity , 4-dione derivatives (EP-A-377 893 and EP-A-442 077).
• Z represents ethyl or n-propyl
• a for hydrogen for in each case optionally substituted alkyl, cycloalkyl or alkoxyalkyl,
• a and B together with the carbon atom to which they are attached for a saturated or unsaturated C -Cg ring which is optionally substituted by alkyl or haloalkyl,
• D represents hydrogen or an optionally substituted radical from the series
• Alkyl alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl or optionally substituted cycloalkyl, or
• a and D together with the atoms to which they are attached for a saturated or unsaturated and optionally at least one heteroatom contained in the A, D part of the unsubstituted or substituted cycle,
• E represents a metal ion equivalent or an ammonium ion
• L represents oxygen or sulfur
• M oxygen or sulfur
• R 1 for each optionally substituted by halogen, alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl or for each cycloalkyl or heterocyclyl optionally substituted by halogen, alkyl or alkoxy or for each optionally substituted phenyl or hetaryl,
• R 2 for alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl optionally substituted by halogen or for cycloalkyl, phenyl or benzyl optionally substituted in each case,
• R 3 , R 4 and R 5 independently of one another each for alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or optionally substituted by halogen
• R ⁇ and R 7 independently of one another represent hydrogen for each optionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, for optionally substituted phenyl or benzyl, or together with the
• a and B together with the carbon atom to the. they are bound for a saturated or unsaturated, unsubstituted or substituted cycle optionally containing at least one heteroatom,
• a and D together with the atoms to which they are attached, for a saturated or unsaturated and optionally containing at least one heteroatom, in the A, D part unsubstituted or substituted cycle.
• the compounds of the formula (I) can be present in different compositions as geometric and / or optical isomers or isomer mixtures, which, if appropriate, can be separated in a customary manner. Both the pure isomers and the isomer mixtures, their preparation and use, and these 'compositions comprising' are the subject of the present invention. However, for the sake of simplicity, the following always refers to compounds of the formula (I), although both the pure compounds and, if appropriate, mixtures with different proportions of isomeric compounds are meant.
• A, B, D, X, Y and Z have the meanings given above,
• A, B, D, X, Y and Z have the meanings given above,
• R 8 represents alkyl (preferably d-Ce-alkyl)
• R 1 has the meaning given above and
• R 1 has the meaning given above
• R 2 has the meaning given above and
• R 3 has the meaning given above
• R 4 and R 5 have the meanings given above and
• Shark represents halogen (especially chlorine or bromine), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
• Me for a mono- or divalent metal preferably an alkali or alkaline earth metal such as lithium, sodium, potassium, magnesium or calcium
• an alkali or alkaline earth metal such as lithium, sodium, potassium, magnesium or calcium
• R 10 , R 11 , R 12 independently of one another represent hydrogen or alkyl (preferably C 1 -C 4 -alkyl),
• R 6 and L have the meanings given above,
• the invention also relates to selective herbicidal compositions comprising an active ingredient in a combination of active ingredients comprising as components
• EP-A-582198 4-carboxy-chroman-4-yl-acetic acid (AC-304415, cf. EP-A-613618), 4-chlorophenoxy-acetic acid, 3,3'-dimethyl -4-methoxy-benzophenone, l-bromo-4-chloromethylsulfonyl-benzene, l- [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3-methyl-urea (aka N- (2-methoxy-benzoyl) - 4- [(methylamino-carbonyl) amino] benzenesulfonamide), 1 - [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3,3-dimethyl-urea, l- [4- (N-4.5 -Dimethylbenzoyl-sulfamoyl) -phenyl] -3 -methyl
• A represents one of the divalent heteroeyclic groups outlined below,
• n stands for a number between 0 and 5
• a 2 represents alkanediyl having 1 or 2 carbon atoms which is optionally substituted by C 1 -C 4 -alkyl and or -C-C 4 -alkoxy-carbonyl,
• R 14 stands for hydroxy, mercapto, amino, -C 6 -alkoxy, -Ce-alkylthio, Ci-C ⁇ -alkylamino or di- (-C 4 -alkyl) amino,
• R 15 represents hydroxyl, mercapto, amino, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylthio, C 1 -C 8 -alkylamino or di- (C 1 -C 8 -alkyl) amino,
• R 16 represents C 1 -C 4 -alkyl which is optionally substituted by fluorine, chlorine and / or bromine,
• R 17 for hydrogen, each optionally substituted by fluorine, chlorine and or bromine - C ⁇ -alkyl, C 2 -C 6 -alkenyl or C 2 -C 6 -alkynyl, -C-C 4 -alkoxy-C 1 -C 4 -alkyl , Dioxolanyl-Cr ' C 4 -alkyl, furyl, furyl-C C 4 -alkyl, thienyl, thiazolyl, piperidinyl, or phenyl optionally substituted by fluorine, chlorine and / or bromine or dC-alkyl,
• Fluorine, chlorine and / or bromine, or C ⁇ -C 4 -A-alkyl substituted phenyl, or together with R 17 represents in each case optionally substituted by -C 4 - alkyl, phenyl, furyl, a benzene ring anneli faced or C 3 -C 6 alkanediyl or C 2 -C 5 oxaalkanediyl which is substituted by two substituents which, together with the carbon atom to which they are attached, form a 5- or 6-membered carboxy cycle,
• R : 19 represents hydrogen, cyano, halogen, or CC 4 -alkyl, C 3 -C 6 -cycloalkyl or phenyl which are each optionally substituted by fluorine, chlorine and or bromine,
• R 20 represents hydrogen, in each case optionally substituted by hydroxy, cyano, halogen or -C 4 -alkoxy-substituted CC 6 -alkyl, C 3 -C 6 -cycloalkyl or tri- (CrC4-alkyl) -silyl,
• R 2 represents hydrogen, cyano, halogen, or GC 4 alkyl, C 3 -C 6 cycloalkyl or phenyl, which are each optionally substituted by fluorine, chlorine and or bromine,
• X 1 represents nitro, cyano, halogen, CC 4 -alkyl, CC 4 -haloalkyl, -Q-alkoxy or dC 4 - haloalkoxy,
• X 2 represents hydrogen, cyano, nitro, halogen, CC 4 alkyl, CC 4 haloalkyl, C 1 -C 4 alkoxy or -Q-haloalkoxy,
• X 3 represents hydrogen, cyano, nitro, halogen, C r C 4 - alkyl, CC 4 haloalkyl, C, -C 4 alkoxy or CC is 4 haloalkoxy,
• n stands for a number between 0 and 5
• R 22 represents hydrogen or C r C 4 alkyl
• R 23 represents hydrogen or C r C 4 alkyl, •
• R 24 for hydrogen, in each case optionally substituted by cyano, halogen or QC 4 - alkoxy -CC 6 alkyl, CC 6 -alkoxy, -C-C 6 -alkylthio, -C-C 6 -alkylamino or di- (-C-C 4 - alkyl) amino, or in each case optionally substituted by cyano, halogen or C 1 -C 4 alkyl substituted C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyloxy, C 3 -C 6 cycloalkylthio or C 3 -C 6 -cycloalkylamino,
• R 25 for hydrogen, optionally substituted by cyano, hydroxy, halogen or CC 4 - alkoxy Ci-C ö alkyl, each optionally substituted by cyano or halogen C 3 - Q-alkenyl or C 3 -C 6 alkynyl, or optionally by Cyano, halogen or C r C 4 alkyl substituted C 3 -C 6 cycloalkyl,
• R 26 for hydrogen, CC 6 - alkyl which is optionally substituted by cyano, hydroxy, halogen or Ci-Gralkoxy, in each case optionally C 3 - substituted by cyano or halogen
• C 6 - alkenyl or C 3 -C 6 alkynyl optionally substituted by cyano, halogen or C 1 -C 4 alkyl substituted C 3 -C a cycloalkyl, or optionally by nitro, cyano, halogen, CC 4 alkyl, C r C 4 haloalkyl, CC 4 -alkoxy or C ⁇ -C is 4 -haloalkoxy-substituted phenyl, or together with R 25 represents in each case optionally substituted by CC alkyl C 2 -C 6 - alkanediyl or Cj-Cs-oxaalkanediyl group,
• X 4 represents nitro, cyano, carboxy, carbamoyl, formyl, sulfamoyl, hydroxy, amino, halo, C 'C 4 -alkyl, C 4 haloalkyl, C GrAlko y or C r C is 4 haloalkoxy, and
• X 1 is nitro, cyano, carboxy, carbamoyl, formyl, sulfamoyl, hydroxy, amino, halogen, GC 4 -alkyl, C 4 -haloalkyl 5 CC 4 -alkoxy or C r C 4 haloalkoxy.
• X preferably represents chlorine or bromine
• Y preferably represents chlorine or bromine
• Z preferably represents ethyl or n-propyl
• G preferably represents hydrogen (a)
• A is preferred for hydrogen, or for Ci-Cg-alkyl which is optionally monosubstituted to trisubstituted by halogen, or for C3-Cg-cycloalkyl or Ci- which is optionally monosubstituted to trisubstituted by halogen, Ci-Cg-alkyl or Ci-Cg-alkoxy Cg-alkoxy-C ⁇ -C j -alkyl,
• Ci-Cg-alkyl or Ci -Cg-AJkoxy-Ci ⁇ alkyl is preferred for hydrogen, Ci-Cg-alkyl or Ci -Cg-AJkoxy-Ci ⁇ alkyl or
• a and B preferably together with the carbon atom to which they are attached, for saturated C3-Cg-cycloalkyl, which is optionally substituted by Ci-Cg-alkyl or -CC4-haloalkyl,
• Ci-Cg-alkyl for each optionally mono- to trisubstituted by halogen-substituted Ci-Cg-alkyl, d-Cg-alkenyl, Crd-alkoxy-d-gralkyl or CC 6 -alkylthio- C 2 -C -alkyl, for optionally single up to three times by halogen, CC 4 - alkyl, C ⁇ -C -
• a and D together are preferred for a C 3 -C 6 -alkanediyl or C 3 -C6 -alkenediyl group, uv which in each case a methylene group is optionally replaced by oxygen or sulfur and which in each case are optionally mono- to disubstituted by halogen, hydroxy, _C 1 -C 4 - alkyl or -CC4 alkoxy, or by another, ⁇ a condensed.
• E represents a metal ion equivalent or an ammonium ion
• L represents oxygen or sulfur
• M oxygen or sulfur
• R 1 preferably represents in each case optionally monosubstituted to pentasubstituted by halogen C r
• halogen for optionally single to triple by halogen, cyano, nitro, dC 6 -alkyl, -C-C 6 -alkoxy, C r C 6 -haloalkyl, -C-C 6 -haloalkoxy, d-Ce-alkylthio or -C-C 6 -alkylsulfo nyl substituted phenyl,
• R 2 preferably represents in each case optionally mono- to trisubstituted by halogen-substituted C r
• C 20 alkyl C 2 -C 20 alkenyl, C r C 6 alkoxy-C 2 -C 6 alkyl or poly-Ci-Ce-alkoxy-d-Cg-alkyl,
• phenyl or benzyl which is optionally monosubstituted to trisubstituted by halogen, cyano, nitro, C 1 -C 6 -alkyl, C 1 -C 6 alkoxy, Ci-Q-haloalkyl or CC 6 -haloalkoxy. , - •
• R 3 preferably for C 1 -C 8 -alkyl which is optionally mono- to polysubstituted by halogen or for in each case optionally monosubstituted to double by halogen, -C-C 6 -alkyl, dC 6 -
• R 6 and R 7 independently of one another are preferably hydrogen, for each optionally mono- to trisubstituted by halogen -CC 8 alkyl, C 3 -C 8 -cycloalkyl, Ci-Cg-alkoxy, C 3 -C 8 - alkenyl or C ⁇ -C 8 alkoxy-C 2 -C 8 alkyl, for each optionally optionally up to three times by halogen, dC 8 alkyl, -C-C 8 haloalkyl or CC 8 alkoxy substituted phenyl or benzyl or together for an optionally simple to C 3 -C 6 alkylene radical which is substituted twice by C 1 - alkyl and in which a methylene group is optionally replaced by oxygen or sulfur,
• A preferably represents hydrogen, in each case optionally mono- to trisubstituted by halogen, C r C 8 alkyl, C 2 -C 8 alkenyl, or dQ-alkylthio-dC 4 -alkyl, for C 3 -C 8 -cycloalkyl which is optionally mono- to trisubstituted by halogen, d- -alkyl or CC 6 -alkoxy,
• B is preferably hydrogen, Ci-Cs-alkyl or C r C 4 -alkoxy-C 1 -C 2 -alkyl or
• A, B and the carbon atom to which they are attached preferably for saturated C 3 -C 8 cycloalkyl, in which a methylene group is optionally replaced by oxygen or sulfur and which is optionally replaced by CC 6 alkyl, dC 4 haloalkyl or CC 6 Alkoxy is substituted,
• D preferably for hydrogen, for in each case optionally mono- to trisubstituted by halogen C, -C 8 -alkyl, C, -C 8 -alkenyl, C 1 -C 6 -alkoxy-C 2 -C 4 -alkyl or dC 6 -alkylthio -.
• a and D together preferably for a dd-alkanediyl or C 3 -C 6 -alkenediyl group, in which in each case one methylene group is optionally replaced by oxygen or sulfur and which in each case are optionally mono- to disubstituted by halogen, hydroxy, -C-C - Alkyl or C r C4-alkoxy, or by another, a condensed
• halogen represents fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine.
• X particularly preferably represents chlorine or bromine
• Y particularly preferably represents chlorine or bromine
• Z particularly preferably represents ethyl or n-propyl
• G particularly preferably represents hydrogen (a), then stands
• A is particularly preferred for hydrogen, for Ci -Q ⁇ alkyl which is optionally monosubstituted to trisubstituted by fluorine or chlorine, or for in each case optionally monosubstituted or disubstituted by fluorine, chlorine, -C-C2-alkyl or Ci -C2-alkoxy-C ⁇ -Cg- Cycloalkyl or
• B particularly preferably for hydrogen, C -C4-alkyl or C 1 -Q4-alkoxy-C j -C2-alk l or
• a and B particularly preferably together with the carbon atom to which they are attached, for saturated C3-C7-cycloalkyl which is optionally substituted by Ci-C4-alkyl or C oder-C2-halogeno-alkyl,
• Alkylthio-C 2 -C 3 alkyl optionally monosubstituted or disubstituted by fluorine, chlorine, C r C 2 - alkyl, CC 2 alkoxy or trifluoromethyl-substituted C 3 -C 3 cycloalkyl, with the proviso that
• A only represents hydrogen or C ⁇ -C3 alkyl
• a and D together are particularly preferred for a C 3 -C 5 -alkanediyl group, in which a methylene group is optionally replaced by oxygen or sulfur and which is optionally monosubstituted or disubstituted by dd-alkyl or CC 2 -alkoxy,
• E represents a metal ion equivalent or an ammonium ion
• L represents oxygen or sulfur
• M oxygen or sulfur
• R 1 particularly preferably for each optionally monosubstituted to trisubstituted by fluorine or chlorine, CC 10 alkyl, C 2 -C 0 -alkenyl, C 1 -C 4 -alkoxy-C 1 -C 2 -alkyl or dC 4 -alkyl-tiiio-Ci -d-alkyl or represents optionally mono- to disubstituted by fluorine, chlorine, C ⁇ -C 2 - alkyl or C r C 2 -alkoxy-substituted C 3 -C 6 -cycloalkyl in which optionally substituted one or two not directly adjacent methylene groups by oxygen are,
• phenyl which is optionally monosubstituted or disubstituted by fluorine, chlorine, bromine, cyano, nitro, CC 4 -alkyl, Ci-d-alkoxy, C 1 -C 2 -haloalkyl or CC 2 -haloalkoxy,
• pyrazolyl for pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl, each of which is optionally mono- to disubstituted by fluorine, chlorine, bromine or C 1 -C 2 -alkyl,
• R 2 particularly preferably represents in each case optionally mono- to trisubstituted by fluorine or chlorine-substituted C ⁇ -C ⁇ o-alkyl, C 2 -C ⁇ 0 alkenyl, C 1 -C 4 -alkoxy-C 2 -C 4 -alkyl or poly-C 4 C alkoxy-C 2 -C 4 -alkyl,
• C 3 -C 7 cycloalkyl which is optionally substituted by CC 2 alkyl or CC 2 alkoxy or
• phenyl or benzyl which is optionally mono- to disubstituted by fluorine, chlorine, bromine, cyano, nitro, Q- C 4 -alkyl, methoxy, trifluoromethyl or trifluoromethoxy,
• R 3 particularly preferably for C 1 -C 4 -alkyl which is optionally monosubstituted to trisubstituted by fluorine or chlorine or for in each case optionally monosubstituted by fluorine, chlorine, bromine, C r C 4 alkyl, CC 4 alkoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro substituted phenyl or benzyl,
• R and R 5 independently of one another are particularly preferred for Q-C ⁇ -alkyl which is optionally mono- to trisubstituted by fluorine or chlorine, C) -C 6 -alkoxy, -C-C 5 -alkylamino, di- (dC 6 -all-y- ) to -_- no, -C-C 6 alkylthio or C 3 -C 4 alkenylthio or for each optionally optionally up to twice by fluorine, chlorine, bromine, nitro, cyano, C 1 -C 3 alkoxy, trifluoromethoxy, CC 3- alkylthio, dC 3 -alkyl or trifluoromethyl-substituted phenyl, phenoxy or phenylthio,
• R 6 and R 7 independently of one another particularly preferably for hydrogen, for each optionally mono- to trisubstituted by fluorine or chlorine -CC 6 alkyl, C 3 -C 6 cycloalkyl, C
• C -alkoxy, C 3 -C 6 -alkenyl or -CC 6 -alkoxy-C 2 -C 6 -alkyl for optionally monosubstituted or disubstituted by fluorine, chlorine, bromine, trifluoromethyl, Crd-alkyl or CC 4 -alkoxy phenyl, or together represent an optionally mono- or disubstituted by methyl-substituted C 5 -C 6 -alkylene radical in which optionally one methylene group is replaced by oxygen,
• A is particularly preferred for hydrogen, for in each case optionally up to three times
• B particularly preferably represents hydrogen, C r C 4 - alkyl or C 1 -C 4 -alkoxy-C 1 -C 2 alkyl, or
• A, B and the carbon atom to which they are attached particularly preferably for saturated C 3 -d-cycloalkyl, in which a methylene group may be replaced by oxygen and which may be simply by dC 4 -alkyl, dC 2 -haloalkyl or C r C 4 Alkoxy is substituted,
• Alkylthio-dd-alkyl for optionally single to double by fluorine, chlorine, CC 2 -
• halogen represents fluorine, chlorine and bromine, in particular fluorine and chlorine.
• X very particularly preferably represents chlorine or bromine,
• Y very particularly preferably represents chlorine or bromine
• Z very particularly preferably represents ethyl
• Z also very particularly preferably represents n-propyl
• G very particularly preferably represents hydrogen (a), then stands
• B very particularly preferably for hydrogen, methyl or ethyl or
• a and B very particularly preferably together with the carbon atom to which they are attached for saturated C0-cycloalkyl which is optionally substituted by methyl, ethyl or trifluoromethyl,
• D also very particularly preferably for methyl, ethyl, n-propyl, isopropyl, n-butyl ; sec-butyl, iso-butyl, cyclopropyl, cyclopentyl or cyclohexyl, with the proviso that then
• a and D together very particularly preferably for a C 3 -C 4 -alkanediyl group, in which in each case one methylene group is optionally replaced by oxygen or sulfur and which is optionally mono- or disubstituted by methyl or
• E represents a metal ion equivalent or an ammonium ion
• M oxygen or sulfur
• R 1 very particularly preferably for in each case optionally up to three times by fluorine or
• phenyl optionally substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,
• furanyl, thienyl or pyridyl each optionally substituted by chlorine, bromine or methyl
• R 2 very particularly preferably for dC 8 alkyl, C 2 -C 6 alkenyl or CC 3 alkoxy-C 2 -C 3 alkyl,
• R 6 very particularly preferably for hydrogen, for C r C 4 alkyl, C 3 -C 3 cycloalkyl or allyi; for phenyl optionally substituted by fluorine, chlorine, bromine, methyl, methoxy or trifluoromethyl,
• R 7 very particularly preferably for methyl, ethyl, n-propyl, isopropyl or allyl
• R 6 and R 7 together are very particularly preferably for a dQ-alkylene radical in which a methylene group is optionally replaced by oxygen,
• B very particularly preferably for hydrogen, methyl or ethyl, or
• A, B and the carbon atom to which they are attached very particularly preferably for saturated d-cycloalkyl, in which a methylene group is optionally replaced by oxygen and which is optionally simply replaced by methyl, ethyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, iso- Propoxy, n-butoxy or iso-butoxy is substituted or
• D also very particularly preferably for methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, cyclopropyl, cyclopentyl or cyclohexyl, with the proviso that then
• a and D together very particularly preferably for a C 3 -C 4 -alkanediyl group, in which in each case one methylene group is optionally replaced by oxygen or sulfur and which is optionally mono- or disubstituted by methyl or
• AD-1 X stands for chlorine or bromine
• Y stands for chlorine or bromine
• Z also stands for n-propyl
• R 1 is Ci-Cg-alkyl or dd-alkoxy-dd-alkyl
• R 2 for CC 6 alkyl, C 2 -C 6 alkenyl or benzyl
• B for hydrogen, methyl or ethyl, or A, B and the carbon atom to which they are attached are emphasized for saturated C 6 -cycloalkyl, in which a methylene group is optionally replaced by oxygen and which is optionally simply substituted by methyl or methoxy,
• D also emphasizes methyl, ethyl, i-propyl, cyclopropyl or cyclohexyl, with the proviso that A then only represents hydrogen, methyl or ethyl,
• Saturated or unsaturated hydrocarbon radicals such as alkyl, alkanediyl or alkenyl can also be used in connection with heteroatoms, e.g. in alkoxy, where possible, be straight-chain or branched.
• Optionally substituted radicals can be mono- or polysubstituted, and in the case of multiple substitutions the substituents can be the same or different.
• the following compounds of the formula (Ia) may be mentioned in detail:
• n preferably represents the numbers 0, 1, 2, 3 or 4.
• a 1 preferably represents one of the divalent heterocyclic groups outlined below
• a 2 preferably represents methylene or ethylene which is optionally substituted by methyl, ethyl, methoxycarbonyl or ethoxycarbonyl.
• R 14 preferably represents hydroxy, mercapto, amino, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylfhio, ethylthio, n- or i-propylthio, n-, i -, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino.
• R 15 preferably represents hydroxy, mercapto, amino, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i -, s- or t-butylthio,
• R 16 preferably represents methyl, ethyl, n- or i-propyl, each optionally substituted by fluorine, chlorine and / or bromine.
• R 17 preferably represents hydrogen, in each case optionally substituted by fluorine and / or chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, propenyl, butenyl, propynyl or butynyl, methoxymethyl, Ethoxymethyl, methoxyethyl, ethoxyethyl, dioxolanylmethyl, furyl, furylmethyl, thienyl, thiazolyl, piperidinyl, or phenyl substituted by fluorine, chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl , R 18 preferably represents hydrogen, in each case optionally substituted by fluorine and / or chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s
• R 19 preferably represents hydrogen, cyano, fluorine, chlorine, bromine, or methyl, ethyl, n- or i-propyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl, each optionally substituted by fluorine, chlorine and / or bromine.
• R 20 preferably represents hydrogen, in each case optionally methyl, ethyl, n- or i-propyl, n-, i-, s- or t-substituted by hydroxy, cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy butyl.
• R 21 preferably represents hydrogen, cyano, fluorine, chlorine, bromine, or methyl, ethyl, n- or i-propyl, n-, i-, s- or t- which is optionally substituted by fluorine, chlorine and / or bromine. Butyl, cyclopropyl, cyclobutyl, cyclopentyl; Cyclohexyl or phenyl.
• X 1 preferably represents nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl , Fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
• X 2 preferably represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl , Fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
• X 3 preferably represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl , Fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
• R 22 preferably represents hydrogen, methyl, ethyl, n- or i-propyl.
• R 23 preferably represents hydrogen, methyl, ethyl, n- or i-propyl.
• R 24 preferably represents hydrogen, in each case optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl , Methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino , Ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino, or in each case optionally substituted by cyano, fluorine, chlorine, bro
• R 25 preferably represents hydrogen, in each case optionally methyl, ethyl, n- or i-propyl, n-, i- or s-butyl substituted by cyano, hydroxyl, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, propenyl, butenyl, propynyl or butynyl, optionally substituted by cyano, fluorine, chlorine or bromine, or cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl optionally substituted by cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl.
• R 26 preferably represents hydrogen, in each case optionally methyl, ethyl, n- or i-propyl, n-, i- or s-butyl substituted by cyano, hydroxy, fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, propenyl, butenyl, propynyl or butynyl, optionally substituted by cyano, fluorine, chlorine or bromine, each optionally substituted by cyano, fluorine, chlorine,
• Bromine methyl, ethyl, n- or i-propyl substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or optionally by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i- , s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy substituted phenyl, or together with R 25 for butane-1,4-diyl (tri- optionally substituted by methyl or ethyl) methylene), pentane-l, 5-diyl, 1-oxa-butane-1,4-diyl or 3-oxa-pentane-l, 5-diyl.
• X 4 preferably represents nitro, cyano, carboxy, carbamoyl, formyl, sulfamoyl, hydroxy, amino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl , Trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
• X 5 preferably represents nitro, cyano, carboxy, carbamoyl, formyl, sulfamoyl, hydroxy, amino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl , Trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
• Table 2 examples of the compounds of the formula (Ha) which are particularly preferred as herbicide safeners according to the invention are listed in Table 2 below.
• Croquintocet-mexyl Cloquintocet-mexyl, Fenchlorazol-ethyl, Isoxadifen-ethyl, Mefenpyr-diethyl, Furilazole, Fenclorim, Cumyluron, Dymron, Dimepiperate and the compounds He-5 and Ee-11 most preferred, with Cloquintocet-exyl and Mefenpyr-diethyl being particularly emphasized.
• the compounds of the general formula (Hc) to be used as safeners according to the invention are known and / or can be prepared by processes known per se (cf. DE-A-2218 097 5 DE-A-2 350 547).
• component (c ') in particular with regard to the protection of cereal plants, such as, for example, Wheat, barley and rye, but also maize and rice, as crops.
• A, B, D, X, Y, Z and R 8 have the meanings given above,
• acylamino acid esters of the formula (II) are obtained, for example, if amino acid derivatives of the formula (XIV)
• a ; B, D, X, Y and Z have the meanings given above,
• A, B, D ; X, Y and Z have the meanings given above,
• halogenating agents eg thionyl chloride, thionyl bromide, oxalyl chloride, phosgene, phosphorus trichloride, phosphorus tribromide or phosphorus pentachloride
• a compound fertilizer for example, optionally chlorinated aliphatic or aromatic hydrocarbons such as toluene or methylene chloride
• temperatures from -20 ° C to 150 ° C, preferably from -10 ° C to 100 ° C, implemented.
• an acid e.g. an inorganic acid such as hydrochloric acid
• a base e.g. an alkali hydroxide such as sodium or potassium hydroxide
• a diluent e.g. an aqueous alcohol such as methanol or ethanol
• X, Y and Z have the meaning given above, first with alcoholates (e.g. alkali metal alcoholates such as sodium methylate or sodium ethylate) in the presence of a diluent (e.g. alcohol derived from the alcoholate) at temperatures between 0 ° C and 150 ° C, preferably between 20 ° C and 120 ° C, and then with an acid (preferably an inorganic acid such as sulfuric acid) at temperatures between -20 ° C and 150 ° C, preferably 0 ° C and 100 ° C.
• alcoholates e.g. alkali metal alcoholates such as sodium methylate or sodium ethylate
• a diluent e.g. alcohol derived from the alcoholate
• an acid preferably an inorganic acid such as sulfuric acid
• R 13 represents alkyl, preferably C r C 6 alkyl
• the compounds of formula (XXI) are new and can be prepared by processes which are generally known in principle.
• the compounds of formula (XXH) are known compounds of organic chemistry. Copper QOQ chloride and vinylidene chloride have long been known and can be bought.
• A, B, D, X, Y, Z and R s have the meanings given above,
• A, B, D, X, Y and Z have the meanings given above,
• the acid halides of the formula (IH), carboxylic anhydrides of the formula (III) which are also required as starting materials for carrying out processes (B), (C), (D), (E), (F), (G) and - - (H) IV), chloroformic acid ester or chloroformic acid thioester of the formula (V), chloromonothioformic acid ester or chlorodithioformic acid ester of the formula (VI), alkyl halides of the formula (VH), sulfonic acid chlorides of the formula (VÜI), phosphorus compounds of the formula (IX) and metal hydroxides, metal alkoxides or amines of the formula (X) and (XI) and isocyanates of the formula (Xu) and carbamic acid chlorides of the formula (XHI) are generally known compounds of organic or inorganic chemistry.
• the compounds of the formulas (XTV) and (XVH) are also known from the patent applications cited at the outset and
• Process (A) is characterized in that compounds of the formula (R), in which A, B, D, X, Y, Z and R 8 have the meanings given above, in the presence of a diluent and in the presence of a base subject to intramolecular condensation.
• Diluents which can be used in process (A) according to the invention are all organic solvents which are inert to the reactants.
• Hydrocarbons such as toluene and xylene, preferably ethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, and also polar solvents, such as dimethyl sulfoxide, sulfolane, dimethylformamide and N-methylpyrrolidone, and alcohols, such as methanol, ethanol, are preferably usable.
• All the usual proton acceptors can be used as the base (deprotonating agent) when carrying out process (A) according to the invention.
• Alkali metals such as sodium or potassium can also be used.
• alkali metal and alkaline earth metal amides and hydrides such as sodium amide, sodium hydride and calcium hydride, and also alkali metal alcoholates, such as sodium methylate, sodium ethylate and potassium tert-butoxide, can also be used.
• reaction temperature can be varied within a substantial range when carrying out process (A) according to the invention. In general, temperatures between 0 ° C and 250 ° C, preferably between 50 ° C and 150 ° C.
• Process (A) according to the invention is generally carried out under normal pressure.
• reaction component of the formula (R) and the deprotonating base are generally employed in equimolar to approximately double-equimolar amounts. However, it is also possible to use one or the other component in a larger excess (up to 3 moles).
• Process (B ⁇ ) is characterized in that compounds of the formula (Ia) are each reacted with carboxylic acid halides of the formula (IH), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
• All solvents which are inert towards the acid halides can be used as diluents in the process (B ⁇ ) according to the invention.
• Hydrocarbons such as gasoline, benzene, toluene, xylene and tetralin are preferably usable, furthermore halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, also ketones such as acetone and methylisopropyl ketone, furthermore ethers such as diethyl ether, tetrahydrofuran and dioxane, in addition carboxylic acid esters, such as ethyl acetate, and also strongly polar solvents, such as dimethyl sulfoxide and sulfolane. If the hydrolysis stability of the acid halide permits, the reaction can also be carried out in the presence of water.
• Suitable acid binders for the reaction according to the process (B ⁇ ) according to the invention are all customary acid acceptors.
• Tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclonones (DBN), Hünig base and N, N-dimethyl-aniline, and also alkaline earth metal oxides, such as magnesium and calcium oxide, can preferably be used.
• the reaction temperature can be varied within a substantial range in the process (B ⁇ ) according to the invention. In general, temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.
• the starting materials of the formula (I-a) and the carboxylic acid halide of the formula (ELI) are generally in each case used in approximately equivalent amounts. However, it is also possible to use the carboxylic acid halide in a larger excess (up to 5 mol). The processing takes place according to usual methods.
• Process (Bß) is characterized in that compounds of the formula (I-a) are each reacted with carboxylic anhydrides of the formula (TV), if appropriate in the presence of a diluent and, if appropriate, in the presence of an acid binder.
• Diluents which can preferably be used in the process (Bß) according to the invention are those diluents which are also preferred when using acid halides.
• an excess of carboxylic acid anhydride can also act as a diluent.
• Suitable acid binders which may be added in process (Bß) are preferably those acid binders which are also preferred when using acid halides.
• the reaction temperature can be varied within a substantial range in the process (Bß) according to the invention. In general, temperatures between -20 ° C and + 150 ° C, preferably between 0 ° C and 100 ° C.
• the starting materials of the formula (I-a) and the carboxylic anhydride of the formula (IV) are generally used in approximately equivalent amounts in each case. However, it is also possible to use the carboxylic anhydride in a larger excess (up to 5 mol). The processing takes place according to usual methods.
• the general procedure is to remove diluent and excess carboxylic acid anhydride and the carboxylic acid formed by distillation or by washing with an organic solvent or with water.
• Process (C) is characterized in that compounds of the formula (I-a) are each reacted with chloroformate or chloroformate thiol ester of formula (V), if appropriate in the presence of a diluent and, if appropriate, in the presence of an acid binder.
• Suitable acid binders in process (C) according to the invention are all customary acid acceptors.
• Tertiary amines such as triethylamine, pyridine, DABCO, DBU, DBA, Hunig base and N, N-dimethylaniline, furthermore alkaline earth metal oxides such as magnesium and calcium oxide, and also alkali and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate are preferably usable and alkali hydroxides such as sodium hydroxide and potassium hydroxide.
• Diluents which can be used in process (C) according to the invention are all solvents which are inert to chloroformic acid esters or chloroformic acid thiol esters.
• Hydrocarbons such as gasoline, benzene, toluene, xylene and tetralin, preferably furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, and also ketones, such as acetone and methylisopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxane in addition carboxylic acid esters, such as ethyl acetate, and also strongly polar solvents, such as dimethyl sulfoxide and sulfolane.
• the reaction temperature can be varied within a relatively wide range when carrying out process (C) according to the invention.
• Process (C) according to the invention is generally carried out under normal pressure.
• the starting materials of the formula (I-a) and the corresponding chloroformate or chloroformate thiol ester of the formula (V) are generally in each case used in approximately equivalent amounts. However, it is also possible to use one or the other component in a larger excess (up to 2 mol).
• the processing takes place according to usual methods. The general procedure is to remove precipitated salts and to concentrate the remaining reaction mixture by stripping off the diluent.
• the process (D) according to the invention is characterized in that compounds of the formula (Ia) are each reacted with (Da) compounds of the formula (VI) in the presence of a diluent and, if appropriate, in the presence of an acid binder or (Dß) carbon disulfide and then with alkyl halides of the formula (VH) if appropriate in the presence of a diluent and if appropriate in the presence of a base.
• inert polar organic solvents such as Erher, esters, amides, sulfones, sulfoxides, but also haloalkanes, are suitable as diluents which may be added.
• Dimethyl sulfoxide, ethyl acetate, tetrahydrofuran, dimethylformamide or methylene chloride are preferably used.
• acid binders customary inorganic or organic bases are possible, examples being sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.
• the reaction can be carried out under normal pressure or under elevated pressure, preferably under normal pressure.
• the processing takes place according to usual methods.
• the equimolar amount or an excess of carbon disulfide is added per mole of starting compounds of the formula (I-a).
• the process is preferably carried out at temperatures from 0 to 50 ° C. and in particular at 20 to 30 ° C.
• Alkali metal hydrides, alkali metal alcoholates, alkali metal or alkaline earth metal carbonates or hydrogen carbonates or nitrogen bases are preferably usable.
• Examples include sodium hydride, sodium methoxide, sodium hydroxide, calcium hydroxide, potassium carbonate, sodium hydrogen carbonate, triethylamine, dibenzylamine, diisopropylethylamine, pyridine, quinoline, diazabicyclooctane (DABCO), diazabicyclonones (DBN) and diazabicycloundecene (DBU).
• Aromatic hydrocarbons such as benzene or toluene, alcohols such as methanol, ethanol, isopropanol or ethylene glycol, nitriles such as acetonitrile, ethers such as tetrahydrofuran or dioxane, amides such as dimethylformamide or other polar solvents such as dimethyl sulfoxide or sulfolane can preferably be used.
• the further reaction with the alkyl halide of the formula ( ⁇ TJ) is preferably carried out at 0 to 70 ° C. and in particular at 20 to 50 ° C.
• at least the equimolar amount of alkyl halide is used.
• the processing is again carried out using customary methods.
• Process (E) according to the invention is characterized in that compounds of the formula (I-a) are each reacted with sulfonyl chlorides of the formula (V ⁇ i), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
• Suitable diluents are all inert polar organic solvents such as ethers, esters, amides, nitriles, sulfones, sulfoxides or halogenated hydrocarbons such as methylene chloride.
• Dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, dimethylformamide and methylene chloride are preferably used.
• the enolate salt of the compound (I-a) is prepared by adding strong deprotonating agents (such as sodium hydride or potassium tertiary butoxide), the further addition of acid binders can be dispensed with.
• strong deprotonating agents such as sodium hydride or potassium tertiary butoxide
• customary inorganic or organic bases "question, for example sodium hydroxide, sodium carbonate, Kahumcarbonat, pyridine and triethylamine.
• the reaction can be carried out at atmospheric pressure or under elevated pressure, preferably at atmospheric pressure.
• the processing takes place according to usual methods.
• Process (F) according to the invention is characterized in that compounds of the formula (I-a) are each reacted with phosphorus compounds of the formula (IX), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
• Process (F) is preferably carried out in the presence of a diluent.
• Suitable diluents are all inert, polar organic solvents, such as ethers, esters, amides, nitriles, sulfides, sulfones, sulfoxides, etc.
• Acetonitrile, ethyl acetate, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide, methylene chloride are preferably used.
• Possible inorganic binders which may be added are conventional inorganic or organic bases, such as hydroxides, carbonates or amines. Examples include sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.
• the reaction can be carried out under normal pressure or under elevated pressure, preferably under normal pressure.
• the processing takes place according to the usual methods of organic chemistry.
• the end products are preferably purified by crystallization, chromatographic purification or by so-called "distillation", ie removal of the volatile constituents in vacuo.
• Process (G) is characterized in that compounds of the formula (I-a) are each reacted with metal hydroxides or metal alkoxides of the formula (X) or amines of the formula (XL), if appropriate in the presence of a diluent.
• Diluents which can be used in process (G) according to the invention are preferably ethers such as tetrahydrofuran, dioxane, diethyl ether or alcohols such as methanol, ethanol, isopropanol, but also water.
• Process (G) according to the invention is generally carried out under normal pressure.
• the reaction temperature is generally between -20 ° C and 100 ° C, preferably between 0 ° C and 50 ° C.
• the process (ET) according to the invention is characterized in that compounds of the formula "(La) are each treated with (H ⁇ ) compounds of the formula (XH) optionally in the presence of a diluent and optionally in the presence of a catalyst or (Hß) with compounds of the formula ( XTTT) if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
• Process (H ⁇ ) is preferably carried out in the presence of a diluent.
• Suitable diluents are all inert organic solvents, such as ethers, esters, amides, nitriles, sulfones or sulfoxides. ,
• catalysts can be added to accelerate the reaction.
• Organic tin compounds such as e.g. Dibutyltin dilaurate can be used.
• Dimethyl sulfoxide, ethyl acetate, tetrahydrofuran, dimethylformamide or methylene chloride are preferably used.
• the enolate salt of the compound (Ia) is represented by the addition of strong deprotonating agents (such as sodium hydride or potassium tertiary butylate), the further addition of acid binders can be dispensed with.
• strong deprotonating agents such as sodium hydride or potassium tertiary butylate
• customary inorganic or organic bases are suitable, examples being sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine.
• the reaction can be carried out under normal pressure or under elevated pressure, preferably under normal pressure.
• the processing takes place according to usual methods.
• the active substances are suitable for combating animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored products and materials, and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
• the pests mentioned above include:
• Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
• Thysanura e.g. Lepisma saccharina.
• Phthiraptera e.g. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.
• Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis.
• Homoptera e.g
• Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
• Plant parasitic nematodes include e.g. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaph.
• the compounds of the invention can also be used as herbicides, at certain concentrations or application rates.
• the compounds can optionally also be used as intermediates or precursors for the synthesis of other active compounds.
• plants and parts of plants can be treated.
• Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
• Cultivated plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by plant breeders' rights.
• Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, Flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes are listed.
• the plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.
• the treatment of the plants and plant parts according to the invention with the active substances or combinations of active substances takes place directly or by acting on their surroundings, living space or storage space according to the usual treatment methods, e.g. by dipping, spraying, spraying, vaporizing, atomizing, scattering, spreading and, in the case of propagation material, in particular in the case of seeds, furthermore by coating in one or more layers.
• the active ingredients or combinations of active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations polymeric fabrics.
• formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
• organic solvents can also be used as auxiliary solvents: the following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g.
• Petroleum fractions mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
• ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, as solid carriers for granulates are possible: e.g.
• emulsifying and / or foam-generating agents are possible: for example non- ionogenic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene ' fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; as dispersants are: Lignin sulfite liquor and methyl cellulose.
• Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
• Other additives can be mineral and vegetable oils.
• Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
• the formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
• the active compounds according to the invention can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to to broaden the spectrum of activities or to prevent the development of resistance.
• fungicides bactericides
• acaricides nematicides or insecticides
• synergistic effects are obtained, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components ..
• Debacarb dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithorphoxin, dithorphononodine, Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,
• Imazalil Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaledione,
• Mancopper Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
• Oxadixyl Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
• Paclobutrazole pefurazoate, penconazole, pencycuron, phosdiphen, picoxystrobin, pimaricin, piperalin,
• Tebuconazole Tebuconazole, tecloftalam, tecnazene, Tetcyclacis, tetraconazole, thiabendazole, Thicyofen, Thifluzamide, thiophanate-methyl, thiram, Tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, Triazbutil, triazoxide, Trichlamid, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole,
• Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlo ⁇ yrifos,
• Chlo ⁇ yrifos M Chlovaporthrin, Chromafenozide, Cis-Resmethrin, Cispermethrin, Clocythrin,
• Fenamiphos Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flubrocythrinate, Flucycloxuron, Fluthrinoxin, Fluutinoxin, Fluutinoxin , Fubfenprox, Furathiocarb,
• Halofenozide HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene, Imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion, ivermectin,
• Mecarbam Metaldehyde, Methamidophos, Metharhizin anisopliae, Metharhizin flavoviride, Methidathion, Methiocarb, Methoprene, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Milbemycin, Monocrotophos,
• Paecilpmyces fumosoroseus Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propargite, Propoxur, Prothiofos, Pyrothhrinosine, Prothrohrinos, Prothofhrinos , Pyridaben, pyridathione, pyrimidifen, pyriproxyfen,
• the active compounds according to the invention can also be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
• Synergists are compounds that increase the effectiveness of the active ingredients without the added synergist itself having to be active.
• the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
• the active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.
• the application takes place in a customary manner adapted to the application forms.
• the active ingredient or combination of active ingredients When used against hygiene pests and pests of stored products, the active ingredient or combination of active ingredients is distinguished by an excellent residual action on wood and clay and by a good stability to alkali on limed substrates.
• Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention.
• Plant cultivars are understood to mean plants with new properties (“traits”) which have been grown by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be varieties, bio and genotypes. Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, growing season, nutrition), the treatment according to the invention can also cause superadditive (“synergistic”) effects.
• the preferred transgenic (genetically engineered) plants or plant cultivars to be treated according to the invention include all plants which, by virtue of the genetic engineering modification, have received genetic material which gives these plants particularly advantageous properties (“traits”). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated ripening, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or workability of the harvested products.
• plants such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed, beets,
• Sugar cane and fruit plants (with the fruits apples, pears, citrus fruits and grapes) are mentioned, with corn, soybeans, potatoes, cotton and rapeseed being particularly emphasized.
• the traits are particularly emphasized as the increased defense of the plants against insects by toxins which arise in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (for example by the genes Cry ⁇ A (a), CryIA (b), CryIA (c), Cryl ⁇ A, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and their combinations) are generated in the plants (hereinafter "Bt plants”).
• the properties (“traits”) also particularly emphasize the increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins.
• the properties (“traits”) which are particularly emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulfonylureas, glycerin phosate or phosphinotricin (eg "PAT" gene).
• the genes conferring the desired properties (“traits”) can also occur in combinations with one another in the transgenic plants.
• Bt plants are corn varieties, cotton varieties, soy varieties and potato varieties which are sold under the trade names YIELD GARD® (e.g. corn, cotton, soy), KnockOut® (e.g. corn), StarLink® (e.g. corn), Bollgard® (Cotton), Nucotn® (cotton) and NewLeaf® (potato).
• YIELD GARD® e.g. corn, cotton, soy
• KnockOut® e.g. corn
• StarLink® e.g. corn
• Bollgard® Cotton
• Nucotn® cotton
• NewLeaf® potato
• herbicide-tolerant plants are maize varieties, cotton varieties and soy varieties that are marketed under the trade names Roundup Ready® (tolerance to glyphosate e.g. corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, e.g.
• rapeseed rapeseed
• IMI® tolerance to Imidazolinone
• STS® tolerance to sulfonylureas such as maize
• the herbicide-resistant plants include the varieties sold under the name Clearfield® (eg maize). Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").
• the plants listed can be treated particularly advantageously with the compounds according to the invention or the active compound mixtures according to the invention.
• the preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants.
• the treatment of plants should be emphasized 'the specifically mentioned in the present text, compounds or mixtures.
• the active substances or combinations of active substances according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, space mites, running mites, flies (stinging and licking), parasitic fly larvae and lice , Hair lice, featherlings and fleas.
• animal parasites ectoparasites
• tick ticks such as tick ticks, leather ticks, space mites, running mites, flies (stinging and licking), parasitic fly larvae and lice , Hair lice, featherlings and fleas.
• parasites include:
• Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp ..
• Nematocerina and Brachycerina for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp.
• Atylotus spp. Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp ⁇ - Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp ..
• Siphonaptrida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp ..
• Actinedida Prostigmata
• Acaridida e.g. Acarapis spp., Cheyletiella. spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes , Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp ..
• the active compounds according to the invention or combinations of active compounds are also suitable for combating arthropods which are used for agricultural purposes, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, Other pets such as dogs, cats, house birds, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and mice are attacked by fighting these arthropods to prevent deaths and reduced performance (in meat, milk, wool, skins, eggs, honey, etc. ) are reduced, so that more economical and simple animal husbandry is possible through the use of the active compounds according to the invention.
• arthropods which are used for agricultural purposes, such as cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, Other pets such as dogs, cats, house birds, aquarium fish and so-called experimental animals such as ham
• the active substances or combinations of active substances according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, • suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasal application, by dermal application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), washing, pumping in, and with the aid of shaped articles containing active ingredients, such as necklaces, ear tags, tail marks, limb bands, Halters, marking devices etc.
• enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, • suppositories
• parenteral administration
• the active ingredients or combinations of active ingredients can be used as formulations (for example powders, emulsions, flowable agents) which contain the active ingredients in an amount of 1 to 80% by weight, directly or after 100 Apply up to 10,000-fold dilution or use it as a chemical bath.
• formulations for example powders, emulsions, flowable agents
• insects may be mentioned by way of example and preferably, but without limitation:
• Kalotermes flavicollis Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
• Bristle tails such as Lepisma saccharina.
• non-living materials such as preferably plastics, adhesives, glues, papers and cartons, leather, wood, wood processing products and paints.
• the material to be protected from insect infestation is very particularly preferably wood and wood processing products.
• Wood and wood processing products that can be protected by the agent according to the invention or mixtures containing it are to be understood as examples:
• the active substances or combinations of active substances can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.
• the formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellant, optionally siccatives and UV stabilizers and optionally dyes and pigments and further processing aids.
• the insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
• the amount of the agents or concentrates used depends on the type and occurrence of the insects and on the medium. The optimum amount of use can be determined in each case by test series. In general, however, it is sufficient 0.0001 to 20% by weight, preferably 0.001 to 10% by weight ; of the active ingredient, based on the material to be protected.
• the organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above half 45 ° C, used.
• Corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such poorly volatile, water-insoluble, oily and oily solvents.
• Mineral oils with a boiling range of 170 to 220 ° C, white spirit with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C, Te ⁇ entinöl and Like. Used.
• liquid aliphatic hydrocarbons with a boiling range from 180 to 210 ° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 to 220 ° C. and / or locker oil and / or monochloronaphthalene, preferably ⁇ -monochlomaphthalene, are used.
• the organic semi-volatile oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can partially. be replaced by volatile or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble in this solvent mixture or is emulsifiable.
• part of the organic chemical solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture is replaced.
• the known organic-chemical binders are the water-dilutable synthetic resins and / or soluble or dispersible or emulsifiable synthetic resins and / or binding drying oils, in particular binders consisting of or containing an acrylic resin, which are soluble or dispersible or emulsifiable in the organic-chemical solvents used , a vinyl resin,. z_B.
• the synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances can also be used as binders 10% by weight can be used. In addition, known dyes, pigments, water-repellants, odor correctors and inhibitors or anticorrosive agents and the like can be used.
• At least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder.
• Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.
• binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).
• the plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, higher glycerol glycol or glycerol ether and p-toluenesulfonic acid ester.
• phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate
• phosphoric acid esters such as tributyl phosphate
• adipic acid esters such as di- (2-ethylhexyl) adipate
• stearates such as butyl stearate or amyl
• Fixing agents are chemically based on polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.
• Water is also particularly suitable as a solvent or diluent, optionally in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.
• a particularly effective wood protection is achieved through industrial impregnation processes, e.g. Vacuum, double vacuum or pressure process.
• the ready compositions may also optionally contain "other insecticides and optionally one or more fungicides.
• insecticides and fungicides mentioned in WO 94/29 268 are preferably suitable as additional mixing partners.
• the compounds mentioned in this document are an integral part of the present application.
• Insecticides such as Chlo ⁇ yriphos, Phoxim, Silafluofin, Alphamethrin, Cyfluthrin, Cypermethrin, Deltamethrin, Permethrin, Imidacloprid, NI-25, Flufenoxuron, Hexaflumuron, Transfluthrin, Methoxyphenuroprid, Thiacloxiduron as well as fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorofluoride, tolylfluanid, 3-iodo-2-propynyl butyl carbamate, N-octyl-isothiazolin-3-one and 4,5 -N-octylisothiazolin-3-one.
• the compounds or combinations of active substances according to the invention can be used to protect objects, in particular ship hulls, sieves, nets, structures, quay systems and signaling systems which come into contact with sea or brackish water.
• Ledamo ⁇ ha barnacles
• Balanomo ⁇ ha barnacles
• Baianus or Pollicipes species increases the frictional resistance of Ships and subsequently leads to a significant increase in operating costs due to increased energy consumption and, moreover, frequent dry dock stays.
• heavy metals such as e.g. in bis (trialkylzi ⁇ m) sulfides, tri-H-butyltin laurate, tri-butyltin chloride, copper (T) oxide, triethyltin chloride, tri -? .- butyl (2. phenyl-4-chlorophenoxy) tin, tributyltin oxide,.
• the ready-to-use antifouling paints may also contain other active ingredients, preferably algicides, fungicides, herbicides, molluscicides or other antifouling active ingredients.
• inventive antifouling compositions are preferably ':
• the antifouling agents used contain the active compound according to the invention of the compounds according to the invention in a concentration of 0.001 to 50% by weight, in particular 0.01 to 20% by weight.
• the antifouling agents according to the invention further contain the usual ingredients such as in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.
• antifouling paints contain in particular binders.
• Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system especially in an aqueous system, vinyl chloride / vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene / styrene / acrylonitrile rubbers, drying oils, such as linseed oil, resin esters or modified hard resins in combination with tar or bitumen, asphalt as well as epoxy compounds, small amounts of chlorinated rubber, chlorinated polypropylene and vinyl resins.
• Paints may also contain inorganic pigments, organic pigments or dyes, which are preferably insoluble in seawater. Paints may also contain materials such as rosin to enable controlled release of the active ingredients. The paints may also contain plasticizers, theological properties modifiers and other conventional ingredients. The compounds according to the invention or the abovementioned mixtures can also be incorporated into self-polishing antifouling systems.
• insects in particular insects, arachnids and mites, which live in closed rooms, such as, for example, apartments, factory halls, offices, vehicle cabins and the like. occurrence.
• closed rooms such as, for example, apartments, factory halls, offices, vehicle cabins and the like.
• insects in particular insects, arachnids and mites
• closed rooms such as, for example, apartments, factory halls, offices, vehicle cabins and the like. occurrence.
• active ingredients and auxiliaries in household insecticide products. They are effective against sensitive and resistant species and against all stages of development.
• These pests include:
• Sco ⁇ ionidea e.g. Buthus occitanus.
• Acarina e.g. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.
• Opiliones e.g. Pseudosco ⁇ iones chelifer, Pseudosco ⁇ iones cheiridiüm, Opiliones phalangium.
• Diplopoda e.g. Blaniulus guttulatus, Polydesmus spp ..
• Anthrenus spp. From the order of the Coleptera, for example Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum. '
• Lepidoptera e.g. Achroia grisella, Galleria mellonella, Plodia inte ⁇ unctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
• Ctenocephalides canis Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
• Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginösus, Lasius niger, Lasius umbratus, -Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
• the active substances or combinations of active substances according to the invention can also be used as defoliants, desiccants , herbicides and in particular as weed killers. Weeds in the broadest sense are understood to mean all plants that grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
• the active substances or combinations of active substances according to the invention can e.g. can be used in the following plants:
• the active compounds or combinations of active compounds according to the invention are suitable for combating total weeds, e.g. on industrial and track systems and on paths and squares with and without tree cover.
• the active compounds for weed control in permanent crops e.g. Forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants, on ornamental and sports turf and pasture land and for selective purposes Weed control can be used in annual crops.
• the compounds or active ingredient combinations according to the invention show strong herbicidal activity and a broad spectrum of activity when used on the soil and on above-ground parts of plants. To a certain extent, they are also suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops, both in the pre-emergence and in the post-emergence method.
• the active substances or combinations of active substances according to the invention can also be used in certain concentrations or application rates for controlling animal pests and fungal or bacterial plant diseases. If appropriate, they can also be used as intermediates or products for the synthesis of further active ingredients.
• the active ingredients or combinations of active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations polymeric fabrics.
• formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, that is liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.
• extenders that is liquid solvents and / or solid carriers
• surface-active agents ie emulsifiers and / or dispersants and / or foam-generating agents.
• organic solvents can, for example, also be used as auxiliary solvents.
• auxiliary solvents include aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
• aromatics such as xylene, toluene, or alkylnaphthalenes
• chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzene
• Possible solid carriers are: e.g. Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g.
• nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
• Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
• adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex-like polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, 'such as cephalins and lecithins and synthetic phospholipids.
• Other additives can be mineral and vegetable oils.
• Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc are used.
• inorganic pigments e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc are used.
• the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
• the active compounds according to the invention can also be used in a mixture with known herbicides and / or with substances which improve crop tolerance ("safeners") for weed control, ready-to-use formulations or tank mixes being possible mixtures with weed control compositions which contain one or more known herbicides and a safener are also possible.
• safeners substances which improve crop tolerance
• a mixture with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and soil conditioners, is also possible.
• the active ingredients or combinations of active ingredients can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.
• the active ingredients or active ingredient combinations according to the invention can be applied both before ⁇ after emergence of the plants. They can also be worked into the soil before sowing.
• the amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha.
• 1 part by weight of active compound of the formula (I) salts comprises 0.001 to 1000 parts by weight, preferably 0.01 to 100 parts by weight, particularly preferably 0.05 to 20 parts by weight of one of the compounds mentioned above under (c ') which improve the tolerance of the crop plants ( antidotes / safeners).
• the active compound combinations according to the invention are generally used in the form of finished formulations.
• the active ingredients contained in the active ingredient combinations can also be mixed in individual formulations during use, i.e. be used in the form of tank mixes.
• mineral-based or vegetable-compatible oils for example the commercial preparation "Rako Binol”
• ammonium salts such as ammonium sulfate or ammonium rhodanide
• the new active substance combinations can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions; Suspensions, emulsions, powders, pastes and granules can be used. They are used in the customary manner, for example by watering, spraying, spraying, dusting or scattering.
• the application rates of the active compound combinations according to the invention can be varied within a certain range; they hang among other things depending on the weather and soil factors.
• the application rates are between 0.001 and 5 kg per ha, preferably between 0.005 and 2 kg per ha, particularly preferably between 0.01 and 0.5 kg per ha.
• the active compound combinations according to the invention can be applied before and after emergence of the plants, that is to say in the pre-emergence and post-emergence process.
• the safeners to be used according to the invention can be used for pretreating the seed of the cultivated plant (dressing the seeds) or introduced into the seed furrows prior to sowing or used separately before the herbicide or together with the herbicide before or after the plants have run off become.
• reaction solution is poured into 80 ml of ice water, the solution is adjusted to pH 1 at 0-20 ° C. with concentrated hydrochloric acid, the precipitate is filtered off with suction and dried. The mixture is then stirred with MTB ether / n-hexane.
• reaction solution is poured onto 0.17 kg of ice, the precipitate is filtered off with suction and extracted with dichloromethane, and the organic phase is dissolved in NaHC03 solution washed, dried, the solvent was spun in, and the residue was recrystallized from MTB ether / n-hexane.
• reaction solution is poured into a mixture of 200 ml ice water / 100 ml IN hydrochloric acid solution.
• the precipitate is filtered off and taken up in dichloromethane.
• the organic phase is dried, evaporated and the residue is recrystallized from MTB ether / n-hexane.
• thionyl chloride 67.6 ml (0.93 mol) of thionyl chloride are added dropwise to 100 g (0.310 mol) of 2,4-dibromo-6-ethylphenylacetic acid at room temperature and then heated to 70 ° C. until the evolution of gas has ended. Excess thionyl chloride is distilled off in vacuo and the residue is distilled in a high vacuum.
• reaction solution is carefully added to 80 ml of 20% hydrochloric acid solution and extracted with 85 ml of MTB ether.
• the organic phase is washed with 40 ml of 20% hydrochloric acid solution, then dried and filtered. The solvent is distilled off.
• reaction mixture with conc. Made alkaline NaOH; After the salt has been suctioned off, the crude product is extracted with CH2C12 and dried. It takes place
• Emulsifier 1 part by weight of ' alkylaryl polyglycol ether
• active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted to the desired concentration with water containing emulsifier.
• Cotton leaves which are heavily infested with the cotton aphid (Aphis gossypii), are treated by dipping into the active ingredient preparation of the desired concentration.

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• 2003
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