US20110190493A1 - Spiroketal-Substituted Cyclic Ketoenols - Google Patents

Spiroketal-Substituted Cyclic Ketoenols Download PDF

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US20110190493A1
US20110190493A1 US13/035,293 US201113035293A US2011190493A1 US 20110190493 A1 US20110190493 A1 US 20110190493A1 US 201113035293 A US201113035293 A US 201113035293A US 2011190493 A1 US2011190493 A1 US 2011190493A1
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alkyl
alkoxy
spp
haloalkyl
formula
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Thomas Bretschneider
Reiner Fischer
Oliver Gaertzen
Stefan Lehr
Mark Wilhelm Drewes
Dieter Feucht
Olga Malsam
Udo Reckmann
Christian Arnold
Thomas Auler
Waltraud Hempel
Martin Jeffrey Hills
Heinz Kehne
Christopher Hugh Rosinger
Erich Sanwald
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Bayer CropScience AG
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Bayer CropScience AG
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    • 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
    • C07D491/113—Spiro-condensed systems with two or more oxygen atoms as ring hetero atoms in the oxygen-containing ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N43/38—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 condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/32—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
    • 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
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/10—Spiro-condensed systems

Definitions

  • the present invention relates to novel spiroketal-substituted cyclic ketoenols, to a plurality of processes for their preparation and to their use as pesticides and/or herbicides and/or microbicides.
  • the invention also provides selective herbicidal compositions comprising, firstly, spiroketal-substituted cyclic ketoenols and, secondly, a crop plant compatibility-improving compound.
  • EP-A-0 262 399 and GB-A-2 266 888 disclose compounds of a similar structure (3-arylpyrrolidine-2,4-diones); however, a herbicidal, insecticidal or acaricidal action of these compounds is not known.
  • Known to have a herbicidal, insecticidal or acaricidal action are unsubstituted bicyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-355 599, EP-A-415 211 and JP-A-12-053 670), and also substituted monocyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-377 893 and EP-A-442 077).
  • EP-A-442 073 polycyclic 3-arylpyrrolidine-2,4-dione derivatives
  • 1H-arylpyrrolidine dione derivatives EP-A-456 063, EP-A-521 334, EP-A-596 298, EP-A-613 884, EP-A-613 885, WO 94/01 997, WO 95/26 954, WO 95/20 572, EP-A-0 668 267, WO 96/25 395, WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO 97/43275, WO 98/05638, WO 98/06721, WO 98/25928, WO 99/24437, WO 99/43649, WO 99/48869 and WO 99/55673, WO 01/17972, WO 01/23354, WO 01/74770, WO 03/013249, WO 03/06
  • ketal-substituted 1H-arylpyrrolidine-2,4-diones from WO 99/16748 and (spiro)-ketal-substituted N-alkoxyalkoxy-substituted arylpyrrolidinediones from JP-A-14 205 984 and Ito M. et al., Bioscience, Biotechnology and Biochemistry 67, 1230-1238, (2003).
  • 3-aryl- ⁇ 3 -dihydrofuranone derivatives having herbicidal, acaricidal and insecticidal properties are known from EP-A-528 156, EP-A-0 647 637, WO 95/26 345, WO 96/20 196, WO 96/25 395, WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO 98/05638, WO 98/25928, WO 99/16748, WO 99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/23354 and WO 01/74770, WO 03/013 249, WO 2004/024 688, WO 04/080962, WO 04/111042, WO 05/092897 and DE-A-04 030 753.
  • the compounds of the formula (I) can be present as optical isomers or isomer mixtures of varying composition which, if appropriate, may be separated in a customary manner.
  • the present invention provides both the pure isomers and the isomer mixtures, their preparation and use, and compositions comprising them.
  • compounds of the formula (I) are referred to, although what is meant are both the pure compounds and, if appropriate, also mixtures having varying proportions of isomeric compounds.
  • novel compounds of the formula (I) have good activity as pesticides, preferably as insecticides and/or acaricides and/or fungicides and/or herbicides, and are additionally frequently highly compatible with plants, in particular with crop plants.
  • the invention also provides selective herbicidal compositions comprising an effective amount of an active compound combination comprising, as components,
  • EP-A-86750 also related compounds in EP-A-86750, EP-A-94349, EP-A-191736, EP-A-492366
  • 3-(2-chlorobenzyl)-1-(1-methyl-1-phenyl ethyl)urea cumyluron
  • ⁇ -(cyanomethoximino)phenylacetonitrile cyometrinil
  • 1-(1-methyl-1-phenylethyl)-3-(4-methylphenyl)urea (daimuron, dymron), 3,6-dichloro-2-methoxybenzoic acid (dicamba), S-1-methyl-1-phenylethyl piperidine-1-thiocarboxylate (dimepiperate), 2,2-dichloro-N-(2-oxo-2-(2-propeny
  • EP-A-174562 and EP-A-346620 also related compounds in EP-A-174562 and EP-A-346620
  • phenylmethyl 2-chloro-4-trifluoromethylthiazole-5-carboxylate flurazole
  • 4-chloro-N-(1,3-dioxolan-2-ylmethoxy)- ⁇ -trifluoroacetophenone oxime fluluxofenim
  • 3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyloxazolidine furilazole, MON-13900
  • ethyl 4,5-dihydro-5,5-diphenyl-3-isoxazolecarboxylate isoxadifen-ethyl—cf.
  • EP-A-269806 and EP-A-333131 also related compounds in EP-A-269806 and EP-A-333131, ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate, ethyl 5-phenyl-2-isoxazoline-3-carboxylate, ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (cf.
  • EP-A-582198 4-carboxychroman-4-ylacetic acid (AC-304415, cf. EP-A-613618), 4-chlorophenoxyacetic acid, 3,3′-dimethyl-4-methoxy-benzophenone, 1-bromo-4-chloromethylsulphonylbenzene, 1-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3-methylurea (also known as N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulphonamide), 1-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3,3-dimethylurea, 1-[4-(N-4,5-dimethylbenzoyl sulphamoyl)phenyl]-3-methylurea, 1-[4-(N-naphthyl sulphamoyl)phenyl]-3
  • radicals is optionally mono- to tetrasubstituted by C 1 -C 6 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 6 -alkoxy or C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl,
  • halogen represents fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine.
  • halogen represents fluorine, chlorine and bromine, in particular fluorine and chlorine.
  • the phenyl ring is, with emphasis, substituted 3 times, resulting in the following substitution patterns: 2,4,6-, 2,4,5- or 2,5,6-substitution.
  • the phenyl ring is, with emphasis, substituted 4 times, resulting in the following substitution pattern: 2,4,5,6-substitution.
  • the phenyl ring is, with emphasis, also substituted 2 times (2,5-position).
  • the phenyl ring is, with emphasis, also monosubstituted (ortho position).
  • the other substituents W, X, Y, Z, G, A, B, Q 1 and Q 2 are as defined in the text.
  • the substituent G represents, with emphasis, the group (b), but also the group (c) or (d) or (e) or (f) or (g). In this case, G represents especially the groups (a), (b) or (c).
  • the other substituents W, X, Y, Z, A, B, Q 1 and Q 2 are as defined in the text.
  • the substituents A and B are, with emphasis, in the 3′-position on the spirocycle.
  • the substituents A and B are, with emphasis, in the 4′-position on the spirocycle.
  • Saturated or unsaturated hydrocarbon radicals such as alkyl, alkanediyl or alkenyl, may in each case be straight-chain or branched as far as this is possible, including in combination with heteroatoms, such as, for example, in alkoxy.
  • optionally substituted radicals may be mono- or polysubstituted, where in the case of polysubstitution the substituents may be identical or different.
  • Table 2 W, X, Y and Z as stated in Table 1
  • A-B 4′-O—CH 2 —CHCH 3 —O—
  • A-B 4′-O—CHCH 3 —CHCH 3 —O—
  • A-B 4′-O—(CH 2 ) 3 —O—
  • A-B 4′-O—CHCH 3 —(CH 2 ) 2 —O—
  • A-B 4′-O—CHCH 3 —CH 2 —CHCH 3 —O—
  • A-B ⁇ 4′O—CH 2 —C(CH 3 ) 2 —CH 2 —O—
  • Table 8 W, X, Y and Z as stated in Table 1
  • A-B 3′-O—(CH 2 ) 2 —O—
  • A-B 3′-O—CH 2 —CHCH 3 —O—
  • Table 11 W, X, Y and Z as stated in Table 1
  • A-B 3′-O—CHCH 3 —CHCH 3 —O—
  • Table 12 W, X, Y and Z as stated in Table 1
  • A-B 3′-O—(CH 2 ) 3 —O—
  • A-B 3′-O—CHCH 3 —(CH 2 ) 2 —O—
  • A-B 3′-O—CHCH 3 —CH 2 —CHCH 3 —O—
  • A-B 3′-O—CH 2 —C(CH 3 ) 2 —CH 2 —O—
  • Table 16 W, X, Y and Z as stated in Table 1
  • A-B 4′-O—CH 2 —CHCH 3 —O—
  • A-B 4′-O—CHCH 3 —CHCH 3 —O—
  • A-B 4′-O—(CH 2 ) 3 —O—
  • A-B 4′-O—CHCH 3 —(CH 2 ) 2 —O—
  • A-B 4′-O—CHCH 3 —CH 2 —CHCH 3 —O—
  • A-B 4′-O—CH 2 —C(CH 3 ) 2 —CH 2 —O—
  • A-B 3′-O—(CH 2 ) 2 —O—
  • A-B 3′-O—CH 2 —CHCH 3 —O—
  • A-B 3′-O—CHCH 3 —CHCH 3 —O—
  • A-B 3′-O—(CH 2 ) 3 —O—
  • A-B 3′-O—CHCH 3 —(CH 2 ) 2 —O—
  • A-B 3′-O—CHCH 3 —CH 2 —CHCH 3 —O—
  • A-B 3′-O—CH 2 —C(CH 3 ) 2 —CH 2 —O—
  • herbicide safeners of the formulae (IIa), (IIb), (IIc), (IId) and (IIe) are defined below.
  • crop plant compatibility-improving compound [component (b′)] are cloquintocetmexyl, fenchlorazole-ethyl, isoxadifen-ethyl, mefenpyr-diethyl, furilazole, fenclorim, cumyluron, dymron, dimepiperate and the compounds IIe-5 and IIe-11, and particular emphasis is given to cloquintocet-mexyl and mefenpyr-diethyl.
  • the compounds of the general formula (IIa) to be used as safeners according to the invention are known and/or can be prepared by processes known per se (cf. WO-A-91/07874, WO-A-95/07897).
  • the compounds of the general formula (IIb) to be used as safeners according to the invention are known and/or can be prepared by processes known per se (cf. EP-A-191736).
  • the compounds of the general formula (IIc) to be used as safeners according to the invention are known and/or can be prepared by processes known per se (cf. DE-A-2218097, DE-A-2350547).
  • the compounds of the general formula (IId) to be used as safeners according to the invention are known and/or can be prepared by processes known per se (cf. DE-A-19621522/U.S. Pat. No. 6,235,680).
  • the compounds of the general formula (IIe) to be used as safeners according to the invention are known and can be prepared by processes known per se (cf. WO-A-99/66795/U.S. Pat. No. 6,251,827).
  • acylamino acid esters of the formula (II) are obtained, for example, when amino acid derivatives of the formula (XVI)
  • the compounds of the formula (XXI) are likewise novel. Some of the compounds of the formula (XX) are novel and can be prepared, for example, as described in EP-A-595 130.
  • the 1-hydroxy-3-alkoxycyclohexylcarboxylic esters of the formula (XXII) are novel. They are obtained, for example, when substituted 1-hydroxy-4,4′-alkylidenyldioxycyclohexanecarbonitriles are reacted with alcohols in the presence of acids, for example according to Pinner, and the 1-hydroxy-4-oxocyclohexanecarboxylic esters formed, which are known from WO 99/16748 (Ex. XXI-1), are re-ketalized with diols.
  • the cyanohydrin is obtained, for example, by reacting 4,4′-alkylidenyldioxycyclohexan-1-ones with hydrocyanic acid (see WO 99/16748).
  • the acid halides of the formula (IV), carboxylic anhydrides of the formula (V), chloroformic esters or chloroformic thioesters of the formula (VI), chloromonothioformic esters or chlorodithioformic esters of the formula (VII), sulphonyl chlorides of the formula (VIII), phosphorus compounds of the formula (IX) and metal hydroxides, metal alkoxides or amines of the formulae (X) and (XI) and isocyanates of the formula (XII) and carbamoyl chlorides of the formula (XIII) and diols of the formula (XV) furthermore required as starting materials for carrying out the processes (C), (D), (E), (F), (G), (H), (I) and (J) according to the invention are generally known compounds of organic or inorganic chemistry. Some of the compounds of the formula (XIV) are known from WO 99/16748.
  • the process (A) is characterized in that compounds of the formula (II) in which A, B, Q 1 , Q 2 , W, X, Y, Z and R 8 are as defined above are subjected to an intramolecular condensation in the presence of a diluent and in the presence of a base.
  • Suitable diluents for use in the process (A) according to the invention are all organic solvents which are inert towards the reaction participants. Preference is given to using hydrocarbons, such as toluene and xylene, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, moreover polar solvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide and N-methylpyrrolidone, and also alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.
  • hydrocarbons such as toluene and xylene
  • ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether
  • polar solvents such as
  • alkali metals such as sodium or potassium.
  • Alkali metal or alkaline earth metal amides and hydrides such as sodium amide, sodium hydride and calcium hydride, and additionally also alkali metal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, can be employed, too.
  • the reaction temperature can be varied within a relatively wide range.
  • the process is carried out at temperatures between ⁇ 75° C. and 200° C., preferably between ⁇ 50° C. and 150° C.
  • the process (A) according to the invention is generally carried out under atmospheric pressure.
  • reaction component of the formula (II) and the deprotonating base are generally employed in equimolar to about doubly equimolar amounts.
  • the process (B) is characterized in that compounds of the formula (III) in which A, B, Q 1 , Q 2 , W, X, Y, Z and R 8 are as defined above are condensed intramolecularly in the presence of a diluent and in the presence of a base.
  • Suitable diluents for use in the process (B) according to the invention are all organic solvents which are inert towards the reaction participants.
  • hydrocarbons such as toluene and xylene
  • ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether
  • polar solvents such as dimethyl sulphoxide, sulpholane, dimethylformamide and N-methylpyrrolidone.
  • alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.
  • alkali metals such as sodium or potassium.
  • Alkali metal or alkaline earth metal amides and hydrides such as sodium amide, sodium hydride and calcium hydride, and additionally also alkali metal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, can be employed, too.
  • the reaction temperature can be varied within a relatively wide range.
  • the process is carried out at temperatures between ⁇ 75° C. and 200° C., preferably between ⁇ 50° C. and 150° C.
  • the process (B) according to the invention is generally carried out under atmospheric pressure.
  • reaction component of the formula (II) and the deprotonating base are generally employed in equimolar to about doubly equimolar amounts.
  • the process (C ⁇ ) is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case reacted with carbonyl halides of the formula (IV), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • Suitable diluents for the process (C ⁇ ) according to the invention are all solvents which are inert towards the acid halides.
  • hydrocarbons such as benzine, benzene, toluene, xylene and tetralin; furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketones, such as acetone and methylisopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxane, additionally carboxylic esters, such as ethyl acetate, and also strongly polar solvents, such as dimethylformamide, dimethyl sulphoxide and sulpholane.
  • the hydrolytic stability of the acid halide permitting, the reaction may also be carried out in the presence of water.
  • Suitable acid binders for the reaction according to the process (C ⁇ ) according to the invention are all customary acid acceptors. Preference is given to using tertiary amines, such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hünig base and N,N-dimethylaniline, furthermore alkaline earth metal oxides, such as magnesium oxide and calcium oxide, moreover alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide.
  • tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hünig
  • reaction temperature in the process (C ⁇ ) according to the invention can be varied within a relatively wide range.
  • the process is carried out at temperatures between ⁇ 20° C. and +150° C., preferably between 0° C. and 100° C.
  • the starting materials of the formulae (I-1-a) to (I-2-a) and the carbonyl halide of the formula (IV) are generally each used in approximately equivalent amounts. However, it is also possible to employ a relatively large excess (up to 5 mol) of the carbonyl halide. Work-up is carried out by customary methods.
  • the process (C ⁇ ) is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case reacted with carboxylic anhydrides of the formula (V), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • Suitable diluents for use in the process (C ⁇ ) according to the invention are preferably those diluents which are also preferred when using acid halides. Besides, it is also possible for excess carboxylic anhydride to act simultaneously as diluent.
  • Suitable acid binders for the process (C ⁇ ), which are added, if appropriate, are preferably those acid binders which are also preferred when using acid halides.
  • reaction temperature in the process (C ⁇ ) according to the invention can be varied within a relatively wide range.
  • the process is carried out at temperatures between ⁇ 20° C. and +150° C., preferably between 0° C. and 100° C.
  • the starting materials of the formulae (I-1-a) to (I-2-a) and the carboxylic anhydride of the formula (V) are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess (up to 5 mol) of the carboxylic anhydride. Work-up is carried out by customary methods.
  • diluent and excess carboxylic anhydride and the carboxylic acid formed are removed by distillation or by washing with an organic solvent or with water.
  • the process (D) is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case reacted with chloroformic esters or chloroformic thioesters of the formula (VI), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • Suitable acid binders for the process (D) according to the invention are all customary acid acceptors. Preference is given to using tertiary amines, such as triethylamine, pyridine, DABCO, DBU, DBN, Hünig base and N,N-dimethylaniline, furthermore alkaline earth metal oxides, such as magnesium oxide and calcium oxide, moreover alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide.
  • tertiary amines such as triethylamine, pyridine, DABCO, DBU, DBN, Hünig base and N,N-dimethylaniline
  • alkaline earth metal oxides such as magnesium oxide and calcium oxide
  • alkali metal and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate
  • alkali metal hydroxides such as sodium hydroxide and potassium
  • Suitable diluents for use in the process (D) according to the invention are all solvents which are inert towards the chloroformic esters or chloroformic thioesters.
  • hydrocarbons such as benzine, benzene, toluene, xylene and tetralin; furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketones, such as acetone and methyl isopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxane, additionally carboxylic esters, such as ethyl acetate, moreover nitriles, such as acetonitrile, and also strongly polar solvents, such as dimethylformamide, dimethyl sulphoxide and sulpholane.
  • the reaction temperature can be varied within a relatively wide range.
  • the reaction temperature is between ⁇ 20° C. and +100° C., preferably between 0° C. and 50° C.
  • Process (D) according to the invention is generally carried out under atmospheric pressure.
  • the starting materials of the formulae (I-1-a) to (I-2-a) and the appropriate chloroformic ester or chloroformic thioester of the formula (VI) are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess (up to 2 mol) of one component or the other. Work-up is carried out by customary methods. In general, precipitated salts are removed and the reaction mixture that remains is concentrated by removing the diluent under reduced pressure.
  • the process (E) according to the invention is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case reacted with compounds of the formula (VII) in the presence of a diluent and, if appropriate, in the presence of an acid binder.
  • Suitable diluents which are added, if appropriate, are all inert polar organic solvents, such as ethers, amides, sulphones, sulphoxides, and also halogenated alkanes.
  • the enolate salt of the compounds (I-1-a) to (I-2-a) is prepared by adding strong deprotonating agents, such as, for example, sodium hydride or potassium tert-butoxide, the further addition of acid binders may be dispensed with.
  • strong deprotonating agents such as, for example, sodium hydride or potassium tert-butoxide
  • Suitable bases for use in the process (E) are all customary proton acceptors. Preference is given to using alkali metal hydrides, alkali metal alkoxides, alkali metal or alkaline earth metal carbonates or bicarbonates or nitrogen bases.
  • Sodium hydride, sodium methoxide, sodium hydroxide, calcium hydroxide, potassium carbonate, sodium bicarbonate, triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoline diazabicyclooctane (DABCO), diazabicyclononene (DBN) and diazabicycloundecene (DBU) may be mentioned by way of example.
  • the reaction can be carried out at atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods.
  • the process (F) according to the invention is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case reacted with sulphonyl chlorides of the formula (VIII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • the process (F) is preferably carried out in the presence of a diluent.
  • Suitable diluents are all inert polar organic solvents, such as ethers, amides, ketones, carboxylic esters, nitriles, sulphones, sulphoxides or halogenated hydrocarbons, such as methylene chloride.
  • the enolate salt of the compounds (I-1-a) to (I-2-a) is prepared by adding strong deprotonating agents (such as, for example, sodium hydride or potassium tert-butoxide), the further addition of acid binders may be dispensed with.
  • strong deprotonating agents such as, for example, sodium hydride or potassium tert-butoxide
  • acid binders may be customary inorganic or organic bases, for example sodium hydride, sodium carbonate, potassium carbonate, pyridine and triethylamine.
  • the reaction can be carried out at atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods.
  • the process (G) according to the invention is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case 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.
  • the process (G) is preferably carried out in the presence of a diluent.
  • Suitable diluents are all inert polar organic solvents, such as ethers, carboxylic esters, halogenated hydrocarbons, ketones, amides, nitriles, sulphones, sulphoxides, etc.
  • Suitable acid binders which are added, if appropriate, are customary inorganic or organic bases, such as hydroxides, carbonates or amines.
  • hydroxides such as sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine may be mentioned by way of example.
  • the reaction can be carried out at atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods of organic chemistry.
  • the end products are preferably purified by crystallization, chromatographic purification or “incipient distillation”, i.e. removal of the volatile components under reduced pressure.
  • the process (H) is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case reacted with metal hydroxides or metal alkoxides of the formula (X) or amines of the formula (XI), if appropriate in the presence of a diluent.
  • Suitable diluents for use in the process (H) according to the invention are, preferably, ethers, such as tetrahydrofuran, dioxane, diethyl ether, or else alcohols, such as methanol, ethanol, isopropanol, and also water.
  • the process (H) according to the invention is generally carried out under atmospheric pressure.
  • the reaction temperature is generally between ⁇ 20° C. and 100° C., preferably between 0° C. and 50° C.
  • the process (I) according to the invention is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case reacted with (I ⁇ ) compounds of the formula (XII), if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst, or (I ⁇ ) with compounds of the formula (XIII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • the process (I ⁇ ) is preferably carried out in the presence of a diluent.
  • Suitable diluents are all inert organic solvents, such as aromatic hydrocarbons, halogenated hydrocarbons, ethers, amides, nitriles, sulphones or sulphoxides.
  • catalysts may be added to promote the reaction.
  • Suitable for use as catalysts are, very advantageously, organotin compounds, such as, for example, dibutyltin dilaurate.
  • the reaction is preferably carried out at atmospheric pressure.
  • Suitable diluents which are added, if appropriate, are all inert polar organic solvents, such as ethers, carboxylic esters, nitriles, ketones, amides, sulphones, sulphoxides or halogenated hydrocarbons.
  • the enolate salt of the compound (I-1-a) to (I-2-a) is prepared by adding strong deprotonating agents (such as, for example, sodium hydride or potassium tert-butoxide), the further addition of acid binders may be dispensed with.
  • strong deprotonating agents such as, for example, sodium hydride or potassium tert-butoxide
  • acid binders may be customary inorganic or organic bases, for example sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine.
  • the reaction can be carried out at atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods.
  • Suitable diluents are all inert organic solvents, such as aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters, amides, nitriles, sulphones or sulphoxides.
  • catalysts may be added to promote the reaction.
  • acids such as, for example, p-toluenesulphonic acid, concentrated sulphuric acid, and also Lewis acids, such as, for example, boron trifluoride etherate.
  • the reaction is preferably carried out at atmospheric pressure.
  • the dehydrating conditions can be achieved both by azeotropic removal of the water and by adding suitable dehydrating agents, such as, for example, orthoformates, dimethoxypropane and also molecular sieves.
  • the active compounds/active compound combinations in combination with good plant tolerance and favourable toxicity to warm-blooded animals and being tolerated well by the environment, are suitable for protecting plants and plant organs, for increasing the harvest yields, for improving the quality of the harvested material and for controlling animal pests, in particular insects, arachnids, helminths, nematodes and molluscs, which are encountered in agriculture, in horticulture, in animal husbandry, in forests, in gardens and leisure facilities, in the protection of stored products and of materials, and in the hygiene sector. They may be preferably employed as plant protection agents. They are active against normally sensitive and resistant species and against all or some stages of development.
  • the abovementioned pests include:
  • Anoplura for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.
  • Acarus siro Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Demianyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus lat
  • Gastropoda From the class of the Gastropoda, for example, Anion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
  • helminths from the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius veiinicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp.,
  • Hymenoptera From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonic, Vespa spp.
  • Isopoda for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber.
  • Orthoptera for example, Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
  • Siphonaptera for example, Ceratophyllus spp., Xenopsylla cheopis.
  • Symphyla for example, Scutigerella immaculata.
  • Thysanoptera From the order of the Thysanoptera, for example, Basothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
  • Thysanura for example, Lepisma saccharina.
  • the phytoparasitic nematodes include, for example, Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Trichodorus spp., Tylenchulus semipenetrans, Xiphinema spp.
  • the compounds/active compound combinations according to the invention can, at certain concentrations or application rates, also be used as herbicides, safeners, growth regulators or agents to improve plant properties, or as microbicides, for example as fungicides, antimycotics, bactericides, viricides (including agents against viroids) or as agents against MLO (Mycoplasma-like organisms) and RLO (Rickettsia-like organisms). If appropriate, they can also be employed as intermediates or precursors for the synthesis of other active compounds.
  • Plants are to be understood as meaning in the present context all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants can be plants which can be obtained by conventional plant breeding and optimization methods or by biotechnological and genetic engineering methods or by combinations of these methods, including the transgenic plants and including the plant cultivars protectable or not protectable by plant breeders' rights.
  • Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes.
  • the plant parts also include harvested material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.
  • Treatment according to the invention of the plants and plant parts with the active compounds/active compound combinations is carried out directly or by allowing the compounds to act on the surroundings, habitat or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on, injection and, in the case of propagation material, in particular in the case of seeds, also by applying one or more coats.
  • the active compounds/active compound combinations can be converted to the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspension-emulsion concentrates, natural materials impregnated with active compound, synthetic materials impregnated with active compound, fertilizers and microencapsulations in polymeric substances.
  • customary formulations such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspension-emulsion concentrates, natural materials impregnated with active compound, synthetic materials impregnated with active compound, fertilizers and microencapsulations in polymeric substances.
  • formulations are produced in a known manner, for example by mixing the active compounds/active compound combinations with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
  • Suitable liquid solvents are substantially aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example 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 sulphoxide, and also water.
  • aromatics such as xylene, toluene or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride
  • Suitable solid carriers are:
  • suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks;
  • suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates;
  • suitable dispers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydroly
  • Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic colorants such as alizarin colorants, azo colorants and metal phthalocyanine colorants, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • the formulations generally comprise between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
  • the active compound/active compound combinations according to the invention can be present in their commercially available formulations, as well as in the use forms prepared from these formulations, in a mixture with other active compounds such as insecticides, attractants, sterilizers, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners, fertilizers or semiochemicals.
  • active compounds such as insecticides, attractants, sterilizers, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners, fertilizers or semiochemicals.
  • bronopol dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
  • Oxidative Phosphorylation Decouplers Acting by Interrupting the H-Proton Gradient
  • a mixture with other known active compounds, such as herbicides, fertilizers, growth regulators, safeners, semiochemicals, or else with agents which improve plant properties is also possible.
  • the active compounds/active compound combinations according to the invention can furthermore be present in the form of a mixture with synergists.
  • Synergists are compounds by which the activity of the active compounds is increased without it being necessary for the synergist added to be active itself.
  • the active compounds/active compound combinations according to the invention can furthermore be present in the form of a mixture with inhibitors which reduce the degradation of the active compound after application in the habitat of the plant, on the surface of parts of plants or in plant tissues.
  • the active compound content of the use foams prepared from the commercially available formulations can vary within broad ranges.
  • the active compound concentration of the use forms can be from 0.00000001 up to 95% by weight of active compound and is preferably between 0.00001 and 1% by weight.
  • Plants which are treated particularly preferably in accordance with the invention are those of the plant cultivars which are in each case commercially available or in use. Plant cultivars are understood as meaning plants with new traits which have been bred either by conventional breeding, by mutagenesis or by recombinant DNA techniques. They may take the form of cultivars, biotypes and genotypes.
  • the treatment according to the invention may also result in superadditive (“synergistic”) effects.
  • superadditive for example, reduced application rates and/or a widened activity spectrum and/or an increase in the activity of the substances and compositions which can be used in accordance with the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to salinity in the water or soil, increased flowering performance, facilitated harvesting, accelerated maturation, higher yields, higher quality and/or better nutritional value of the harvested products, better storage characteristics and/or processability of the harvested products are possible which exceed the effects which were actually to be expected.
  • the preferred transgenic plants or plant cultivars to be treated in accordance with the invention include all those plants which, owing to the process of recombinant modification, were given genetic material which confers particular, advantageous, valuable traits to these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to salinity in the water or soil, increased flowering performance, facilitated harvesting, accelerated maturation, higher yields, higher quality and/or higher nutritional value of the harvested products, better storage characteristics and/or better processability of the harvested products.
  • transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soybeans, potato, sugar beet, tomatoes, peas and other vegetable varieties, cotton, tobacco, oilseed rape and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with particular emphasis on maize, soybeans, potatoes, cotton, tobacco, and oilseed rape.
  • Traits which are especially emphasized are the increased defence of the plants against insects, arachnids, nematodes and slugs and snails, owing to toxins being formed in the plants, in particular toxins which are generated in the plants by the genetic material of Bacillus thuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and their combinations; hereinbelow “Bt plants”).
  • SAR systemic acquired resistance
  • PAT phosphinotricin
  • Bt plants are maize cultivars, cotton cultivars, soybean cultivars and potato cultivars which are commercially available under the trade names YIELD GARD® (for example maize, cotton, soybeans), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato).
  • YIELD GARD® for example maize, cotton, soybeans
  • KnockOut® for example maize
  • StarLink® for example maize
  • Bollgard® cotton
  • Nucotn® cotton
  • NewLeaf® potato
  • herbicide-tolerant plants examples include maize cultivars, cotton cultivars and soybean cultivars which are commercially available under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soybean), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize).
  • Herbicide-resistant plants plants bred in a conventional manner for herbicide tolerance
  • Clearfield® for example maize.
  • the plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula I or the active compound mixtures according to the invention.
  • the preferred ranges stated above for the active compounds and mixtures also apply to the treatment of these plants. Particular emphasis may be given to the treatment of plants with the compounds or mixtures specifically mentioned in the present text.
  • the active compounds/active compound combinations according to the invention are not only active against plant, hygiene and stored-product pests, but also, in the veterinary medicine sector, against animal parasites (ectoparasites and endoparasites), such as ixodid ticks, argasid ticks, scab mites, trombi-culid mites, flies (stinging and sucking), parasitic fly larvae, lice, hair lice, bird lice and fleas.
  • animal parasites ectoparasites and endoparasites
  • ixodid ticks argasid ticks
  • scab mites scab mites
  • trombi-culid mites flies (stinging and sucking)
  • parasitic fly larvae lice, hair lice, bird lice and fleas.
  • Anoplurida for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
  • Nematocerina and Brachycerina From the order of the Diptera and the sub-orders 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., Glossina spp
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • 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 spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
  • the active compounds/active compound combinations of the formula (I) according to the invention are also suitable for controlling arthropods which attack agricultural livestock, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, honeybees, other domestic animals, such as, for example, dogs, cats, cage birds, aquarium fish, and so-called experimental animals, such as, for example, hamsters, guinea-pigs, rats and mice.
  • arthropods By combating these arthropods, it is intended to reduce deaths and decreased performances (in meat, milk, wool, hides, eggs, honey and the like), so that more economical and simpler animal keeping is made possible by using the active compounds according to the invention.
  • the active compounds/active compound combinations according to the invention are used in a known manner by enteral administration, for example in the form of tablets, capsules, drinks, drenches, granules, pastes, boli, the feed-through method, suppositories, by parenteral administration, such as, for example, by means of injections (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal application, by dermal administration, for example in the form of dipping or bathing, spraying, pouring-on and spotting-on, washing, dusting, and with the aid of shaped articles which comprise active compound, such as collars, ear tags, tail marks, limb bands, halters, marking devices and the like.
  • enteral administration for example in the form of tablets, capsules, drinks, drenches, granules, pastes, boli, the feed-through method, suppositories
  • parenteral administration such as, for example, by means of injections (intramuscular, sub
  • the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowables) which comprise the active compounds in an amount of 1 to 80% by weight, either directly or after dilution by a factor of 100 to 10 000, or they may be used in the form of a chemical bath.
  • formulations for example powders, emulsions, flowables
  • the compounds/active compound combinations according to the invention have a potent insecticidal action against insects which destroy industrial materials.
  • insects may be mentioned by way of example and as being preferred, but without any limitation:
  • Dermapterans such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.
  • Termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitelines santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
  • Bristletails such as Lepisma saccharina.
  • Industrial materials are to be understood as meaning, in the present context, non-live materials, such as, preferably, synthetic materials, glues, sizes, paper and board, leather, wood and timber products, and paint.
  • the materials to be very particularly preferably protected against attack by insects are wood and timber products.
  • Wood and timber products which can be protected by the composition according to the invention or mixtures comprising such a composition are to be understood as meaning, for example:
  • the active compounds 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, for example by mixing the active compounds with at least one solvent or diluent, emulsifier, dispersant and/or binder or fixative, water repellent, if appropriate desiccants and UV stabilizers and, if appropriate, colorants and pigments and other processing auxiliaries.
  • the insecticidal compositions or concentrates used for the protection of wood and wooden materials comprise 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.
  • compositions or concentrates employed depends on the species and the occurrence of the insects and on the medium. The optimum rate of application can be determined upon use in each case by a test series. However, in general, it suffices to employ 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
  • the solvent and/or diluent used is an organochemical solvent or solvent mixture and/or an oily or oil-type organochemical solvent or solvent mixture of low volatility and/or a polar organochemical solvent or solvent mixture and/or water and, if appropriate, an emulsifier and/or wetting agent.
  • Organochemical solvents which are preferably employed are oily or oil-type solvents having an evaporation number of above 35 and a flashpoint of above 30° C., preferably above 45° C.
  • Substances which are used as such oily and oil-type solvents which have low volatility and are insoluble in water are suitable mineral oils or their aromatic fractions, or mineral-oil-containing solvent mixtures, preferably white spirit, petroleum and/or alkylbenzene.
  • Substances which are advantageously used are 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 of boiling range 160 to 280° C., essence of terpentine and the like.
  • liquid aliphatic hydrocarbons with a boiling range of 180 to 210° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180 to 220° C. and/or spindle oil and/or monochloronaphthalene, preferably ⁇ -monochloronaphthalene, are used.
  • organic oily or oil-type solvents of low volatility having an evaporation number of above 35 and a flashpoint of above 30° C., preferably above 45° C. can be partially replaced by organochemical solvents of high or medium volatility, with the proviso that the solvent mixture also has an evaporation number of above 35 and a flashpoint of above 30° C., preferably above 45° C., and that the insecticide/fungicide mixture is soluble or emulsifiable in this solvent mixture.
  • organochemical solvent or solvent mixture part of the organochemical solvent or solvent mixture or an aliphatic polar organochemical solvent or solvent mixture is replaced.
  • Substances which are preferably used are aliphatic organochemical solvents having hydroxyl and/or ester and/or ether groups, such as, for example, glycol ethers, esters and the like.
  • the organochemical binders used within the scope of the present invention are the synthetic resins and/or binding drying oils which are known per se and can be diluted with water and/or are soluble or dispersible or emulsifiable in the organochemical solvents employed, in particular binders composed of, or comprising, an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenol resin, hydrocarbon resin, such as indene/cumarone resin, silicone resin, drying vegetable and/or drying oils and/or physically drying binders based on a natural and/or synthetic resin.
  • binders composed of, or comprising, an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenol resin, hydrocarbon resin, such as
  • the synthetic resin used as the binder can be employed in the form of an emulsion, dispersion or solution. Up to 10% by weight of bitumen or bituminous substances can also be used as binders. In addition, colorants, pigments, water repellents, odour-masking substances and inhibitors or anticorrosives known per se and the like can also be employed.
  • composition or the concentrate preferably comprises, in accordance with the invention, at least one alkyd resin or modified alkyd resin and/or a drying vegetable oil as the organochemical binder.
  • alkyd resins with an oil content of over 45% by weight, preferably 50 to 68% by weight.
  • binder can be replaced by a fixative (mixture) or a plasticizer (mixture).
  • fixative mixture
  • plasticizer mixture
  • additives are intended to prevent volatilization of the active compounds and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of binder employed).
  • the plasticizers are from the chemical classes of the phthalic esters, such as dibutyl phthalate, dioctyl phthalate or benzyl butyl phthalate, the phosphoric esters, such as tributyl phosphate, the adipic esters, such as di(2-ethylhexyl) adipate, the stearates, such as butyl stearate or amyl stearate, the oleates, such as butyl oleate, the glycerol ethers or relatively high-molecular-weight glycol ethers, glycerol esters and p-toluenesulphonic esters.
  • the phthalic esters such as dibutyl phthalate, dioctyl phthalate or benzyl butyl phthalate
  • the phosphoric esters such as tributyl phosphate
  • the adipic esters such as di(2-ethyl
  • Fixatives are chemically based on polyvinyl alkyl ethers, such as, for example, polyvinyl methyl ether, or ketones, such as benzophenone or ethylenebenzophenone.
  • Particularly suitable as a solvent or diluent is also water, if appropriate as a mixture with one or more of the abovementioned organochemical solvents or diluents, emulsifiers and dispersants.
  • the ready-to-use compositions can additionally comprise other insecticides and, if appropriate, additionally one or more fungicides.
  • Suitable additional components which may be admixed are, preferably, the insecticides and fungicides mentioned in WO 94/29 268.
  • the compounds mentioned in that document are expressly part of the present application.
  • Very particularly preferred components which may be admixed are insecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin, thiacloprid, methoxyphenoxid, triflumuron, chlothianidin, spinosad, tefluthrin,
  • insecticides such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin, thiacloprid, methoxyphenoxid, triflumuron, chlot
  • fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid, 3-iodo-2-propynylbutyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.
  • the compounds according to the invention can at the same time be employed for protecting objects which come into contact with saltwater or brackish water, in particular hulls, screens, nets, buildings, moorings and signalling systems, against fouling.
  • Ledamorpha group such as various Lepas and Scalpellum species
  • Balanomorpha group acorn barnacles
  • Balanus or Pollicipes species increases the frictional drag of ships and, as a consequence, leads to a marked increase in operation costs owing to higher energy consumption and additionally frequent residence in the dry dock.
  • the ready-to-use antifouling paints can additionally comprise other active compounds, preferably algicides, fungicides, herbicides, molluscicides, or other antifouling active compounds.
  • suitable components in combination with the antifouling compositions according to the invention are:
  • algicides such as
  • the antifouling compositions used comprise 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.
  • antifouling compositions according to the invention comprise the customary components such as, for example, those described in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.
  • antifouling paints comprise, 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, in particular 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 hardened resins in combination with tar or bitumens, asphalt and epoxy compounds, small amounts of chlorine rubber, chlorinated polypropylene and vinyl resins.
  • paints also comprise inorganic pigments, organic pigments or colorants which are preferably insoluble in saltwater. Paints may furthermore comprise materials such as rosin to allow controlled release of the active compounds. Furthermore, the paints may comprise plasticizers, modifiers which affect the rheological properties and other conventional constituents.
  • the compounds according to the invention or the abovementioned mixtures may also be incorporated into self-polishing antifouling systems.
  • the active compounds are also suitable for controlling animal pests, in particular insects, arachnids and mites, which are found in enclosed spaces such as, for example, dwellings, factory halls, offices, vehicle cabins and the like. They can be employed in domestic insecticide products for controlling these pests alone or in combination with other active compounds and auxiliaries. They are active against sensitive and resistant species and against all development stages. These pests include:
  • Acarina for example, Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.
  • Opiliones From the order of the Opiliones, for example, Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.
  • Saltatoria for example, Acheta domesticus.
  • 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.
  • Aedes aegypti Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.
  • Lepidoptera From the order of the Lepidoptera, for example, Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
  • Ctenocephalides canis Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
  • Hymenoptera From the order of the Hymenoptera, for example, Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
  • the active compounds/active compound combinations according to the invention can also be used as defoliants, desiccants, haulm killers and, in particular, as weed killers. Weeds in the broadest sense are understood as meaning all plants which grow at locations where they are undesired. Whether the substances according to the invention act as nonselective or selective herbicides depends essentially on the application rate.
  • the active compounds/active compound combinations according to the invention can be used, for example, in the following plants:
  • Monocotyledonous crops of the genera Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea.
  • the active compounds/active compound combinations according to the invention are suitable for the nonselective weed control on, for example, industrial terrains and railway tracks and on paths and locations with and without trees.
  • the active compounds according to the invention can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantations and hop fields, on lawns, turf and pastureland, and for the selective control of weeds in annual crops.
  • the compounds of the formula (I)/active compound combinations according to the invention have strong herbicidal activity and a broad activity spectrum when used on the soil and on aerial plant parts. To a certain extent, they are also suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both pre- and post-emergence.
  • the active compounds/active compound combinations according to the invention can also be employed for controlling animal pests and fungal or bacterial plant diseases. If appropriate, they can also be used as intermediates or precursors for the synthesis of other active compounds.
  • the active compounds/active compound combinations can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspoemulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
  • formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
  • Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes 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 also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water.
  • aromatics such as xylene, toluene or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chlor
  • Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates
  • suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks
  • suitable emulsifiers and/or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates
  • Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations.
  • Other possible additives are mineral and vegetable oils.
  • colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic colorants, such as alizarin colorants, azo colorants and metal phthalocyanine colorants, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • the formulations generally comprise between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds/active compound combinations according to the invention can also be used for weed control purposes as a mixture with known herbicides and/or with substances which improve crop plant tolerance (“safeners”), ready mixes or tank mixes being possible. Mixtures with herbicide products which contain one or more known herbicides and a safener are hence also possible.
  • safeners substances which improve crop plant tolerance
  • Herbicides which are suitable for the mixtures are known herbicides, for example
  • acetochlor acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), ametryne, amicarbazone, amidochlor, amidosulfuron, aminopyralid, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin (-ethyl), benfuresate, bensulfuron (-methyl), bentazone, bencarbazone, benzfendizone, benzobicyclon, benzolenap, benzoylprop (-ethyl), bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil (-allyl), butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfen
  • a mixture with other known active compounds such as fungicides, insectides, acaricides, nematicides, bird repellents, plant nutrients and soil conditioners, is also possible.
  • the active compounds/active compound combinations can be applied 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. They are applied in the customary manner, for example by pouring, spraying, atomizing, spreading.
  • the active compounds/active compound combinations according to the invention can be applied both before and after plant emergence. They can also be incorporated into the soil prior to planting.
  • the application rate of active compound can vary within a substantial range. Essentially, it depends on the nature of the desired effect. In general, the application rates are between 1 g and 10 kg of active compound per hectare of soil area, preferably between 5 g and 5 kg per ha.
  • the substances/active compound combinations according to the invention have potent microbicidal activity and can be employed for controlling unwanted microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.
  • Fungicides can be employed in crop protection for controlling Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
  • Bactericides can be employed in crop protection for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
  • Xanthomonas species such as, for example, Xanthomonas campestris pv. oryzae;
  • Pseudomonas species such as, for example, Pseudomonas syringae pv. lachrymans;
  • Erwinia species such as, for example, Erwinia amylovora;
  • Pythium species such as, for example, Pythium ultimum
  • Phytophthora species such as, for example, Phytophthora infestans
  • Pseudoperonospora species such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;
  • Plasmopara species such as, for example, Plasmopara viticola
  • Bremia species such as, for example, Bremia lactucae
  • Peronospora species such as, for example, Peronospora pisi or P. brassicae;
  • Erysiphe species such as, for example, Erysiphe graminis
  • Sphaerotheca species such as, for example, Sphaerotheca fuliginea
  • Podosphaera species such as, for example, Podosphaera leucotricha
  • Venturia species such as, for example, Venturia inaequalis
  • Pyrenophora species such as, for example, Pyrenophora teres or P. graminea
  • Cochliobolus species such as, for example, Cochliobolus sativus
  • Uromyces species such as, for example, Uromyces appendiculatus
  • Puccinia species such as, for example, Puccinia recondita
  • Sclerotinia species such as, for example, Sclerotinia sclerotiorum
  • Tilletia species such as, for example, Tilletia caries
  • Ustilago species such as, for example, Ustilago nuda or Ustilago avenae;
  • Pellicularia species such as, for example, Pellicularia sasakii;
  • Pyricularia species such as, for example, Pyricularia oryzae
  • Fusarium species such as, for example, Fusarium culmorum
  • Botrytis species such as, for example, Botrytis cinerea
  • Septoria species such as, for example, Septoria nodorum
  • Leptosphaeria species such as, for example, Leptosphaeria nodorum;
  • Cercospora species such as, for example, Cercospora canescens
  • Alternaria species such as, for example, Alternaria brassicae ;
  • Pseudocercosporella species such as, for example, Pseudocercosporella herpotrichoides.
  • the active compounds/active compound combinations according to the invention also have very good fortifying action in plants. Accordingly, they can be used for mobilizing the defences of the plant against attack by unwanted microorganisms.
  • plant-fortifying (resistance-inducing) substances are to be understood as meaning those substances which are capable of stimulating the defence system of plants such that, when the treated plants are subsequently inoculated with unwanted microorganisms, they show substantial resistance against these microorganisms.
  • the substances according to the invention can be used to protect plants for a certain period after the treatment against attack by the pathogens mentioned.
  • the period for which protection is provided generally extends over 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.
  • the active compounds/active compound combinations according to the invention are also suitable for increasing the yield of crops. In addition, they show reduced toxicity and are well tolerated by plants.
  • the active compounds/active compound combinations according to the invention can if appropriate also be used as herbicides, for influencing plant growth and for controlling animal pests. If appropriate, they can also be used as intermediates and precursors for the synthesis of further active compounds.
  • the compounds according to the invention can be employed for protecting industrial materials against infection with, and destruction by, unwanted microorganisms.
  • Industrial materials in the present context are understood as meaning non-living materials which have been prepared for use in industry.
  • industrial materials which are intended to be protected by active compounds according to the invention from microbial change or destruction can be adhesives, sizes, paper and board, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which can be infected with, or destroyed by, microorganisms.
  • Parts of production plants, for example cooling-water circuits, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected.
  • Industrial materials which may be mentioned within the scope of the present invention are preferably adhesives, sizes, paper and board, leather, wood, paints, cooling lubricants and heat-transfer liquids, particularly preferably wood.
  • Microorganisms capable of degrading or changing the industrial materials are, for example, bacteria, fungi, yeasts, algae and slime organisms.
  • the active compounds according to the invention preferably act against fungi, in particular moulds, wood-discolouring and wood-destroying fungi (Basidiomycetes), and against slime organisms and algae.
  • Alternaria such as Alternaria tenuis
  • Aspergillus such as Aspergillus niger
  • Chaetomium such as Chaetomium globosum
  • Coniophora such as Coniophora puetana
  • Lentinus such as Lentinus tigrinus
  • Penicillium such as Penicillium glaucum
  • Polyporus such as Polyporus versicolor
  • Aureobasidium such as Aureobasidium pullulans
  • Sclerophoma such as Sclerophoma pityophila
  • Trichoderma such as Trichoderma viride
  • Escherichia such as Escherichia coli
  • Pseudomonas such as Pseudomonas aeruginosa
  • Pseudomonas aeruginosa Pseudomonas
  • Staphylococcus such as Staphylococcus aureus.
  • the active compounds/active compound combinations can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and microencapsulations in polymeric substances and in coating compositions for seeds, and ULV cool and warm fogging formulations.
  • formulations are produced in a known manner, for example by mixing the active compounds/active compound combinations with extenders, that is liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers. If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents.
  • suitable liquid solvents are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, 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 sulphoxide, or else water.
  • aromatics such as xylene, toluene or alkylnaphthalenes
  • chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohe
  • Liquefied gaseous extenders or carriers are to be understood as meaning liquids which are gaseous at standard temperature and under atmospheric pressure, for example aerosol propellants such as halogenated hydrocarbons, or else butane, propane, nitrogen and carbon dioxide.
  • Suitable solid carriers are: for example ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as finely divided silica, alumina and silicates.
  • Suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
  • Suitable emulsifiers and/or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates.
  • Suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.
  • Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
  • Other possible additives are mineral and vegetable oils.
  • colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic colorants such as alizarin colorants, azo colorants and metal phthalocyanine colorants, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • the formulations generally comprise between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can be used as such or in their formulations, also in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, to broaden, for example, the activity spectrum or to prevent development of resistance. In many cases, synergistic effects are obtained, i.e. the activity of the mixture is greater than the activity of the individual components.
  • copper salts and preparations such as Bordeaux mixture; copper hydroxide; copper naphthenate; copper oxychloride; copper sulphate; cufraneb; cuprous oxide; mancopper; oxine-copper.
  • bronopol dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
  • abamectin ABG-9008, acephate, acequinocyl, acetamiprid, acetoprole, acrinathrin, AKD-1022, AKD-3059, AKD-3088, alanycarb, aldicarb, aldoxycarb, allethrin 1R-isomers, alpha-cypermethrin (alphamethrin), amidoflumet, aminocarb, amitraz, avermectin, AZ-60541, azadirachtin, azamethiphos, azinphos-methyl, azinphos-ethyl, azocyclotin,
  • cadusafos camphechlor, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, CGA-50439, quinomethionate, chlordane, chlordimeform, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorobenzilate, chloropicrin, chlorproxyfen, chlorpyrifos-methyl, chlorpyrifos (-ethyl), chlovaporthrin, chromafenozide, cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrin, cloethocarb, clofentezine, clothianidin, clothiazoben, codlemone, coumaphos, cyanofenphos, cyanophos, cycloprene,
  • DDT deltamethrin, demeton-S-methyl, demeton-S-methylsulphone, diafenthiuron, dialifos, diazinon, dichlofenthion, dichlorvos, dicofol, dicrotophos, dicyclanil, diflubenzuron, dimethoate, dimethylvinphos, dinobuton, dinocap, dinotefuran, diofenolan, disulfoton, docusate-sodium, dofenapyn, DOWCO-439,
  • gamma-HCH gossyplure, grandlure, granulosis viruses
  • IKA-2002 imidacloprid, imiprothrin, indoxacarb, iodofenphos, iprobenfos, isazofos, isofenphos, isoprocarb, isoxathion, ivermectin, japonilure,
  • NC-104 NC-170, NC-184, NC-194, NC-196, niclosamide, nicotine, nitenpyram, nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI-9768, novaluron, noviflumuron,
  • Paecilomyces fumosoroseus parathion-methyl, parathion (-ethyl), permethrin (cis-, trans-), petroleum, PH-6045, phenothrin (1R-trans isomer), phenthoate, phorate, phosalone, phosmet, phosphamidon, phosphocarb, phoxim, piperonyl butoxide, pirimicarb, pirimiphos-methyl, pirimiphos-ethyl, prallethrin, profenofos, promecarb, propaphos, propargite, propetamphos, propoxur, prothiofos, prothoate, protrifenbute, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridalyl, pyridaphenthion, pyridathion, pyr
  • tau-fluvalinate tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, temivinphos, terbam, terbufos, tetrachlorvinphos, tetradifon, tetramethrin, tetramethrin (1R isomer), tetrasul, theta-cypermethrin, thiacloprid, thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thiometon, thiosultap-sodium, thuringiensin, tolfenpyrad, tralocythrin, tralomethrin, transfluthrin, triarathene, triaza
  • vamidothion vaniliprole, verbutin, Verticillium lecanii
  • the compounds of the formula (I)/active compound combinations according to the invention also have very good antimycotic activity. They have a very broad antimycotic activity spectrum in particular against dermatophytes and yeasts, moulds and diphasic fungi (for example against Candida species, such as Candida albicans, Candida glabrata ), and Epidermophyton floccosum, Aspergillus species, such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species, such as Trichophyton mentagrophytes,
  • Microsporon species such as Microsporon canis and audouinii .
  • the listing of these fungi by no means limits the mycotic spectrum that can be covered, but is only for illustration.
  • the active compounds/active compound combinations can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules.
  • Application is carried out in a customary manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming, spreading, etc. It is further possible to apply the active compounds by the ultra-low-volume method, or to inject the active compound preparation or the active compound itself into the soil. It is also possible to treat the seeds of the plants.
  • the application rates can be varied within a relatively wide range, depending on the kind of application.
  • the active compound application rates are generally between 0.1 and 10 000 g/ha, preferably between 10 and 1000 g/ha.
  • the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed.
  • the active compound application rates are generally between 0.1 and 10 000 g/ha, preferably between 1 and 5000 g/ha.
  • Example XIV-1-1 Under argon protective gas, 0.644 g (2 mmol) of the compound of Example XIV-1-1 is initially charged in 30 ml of xylene, 2.083 g (20 mmol) of 1,2-pentanediol and 0.059 g (0.29 mmol) of p-toluenesulphonic acid are added at room temperature, 0.5 g of molecular sieve 4 ⁇ (powder) is added and the mixture is stirred under reflux for three days and monitored by thin-layer chromatography.
  • Example I-1-a-44 0.159 g of the compound of Example I-1-a-44 is initially charged in 10 ml of trichloromethane, 0.098 ml of diisopropylethylamine and 1.5 mg of DMAP are added at room temperature, 0.037 ml of methanesulphonyl chloride is added and the mixture is stirred for 20 hours, 5 ml of NaCl solution are added, the mixture is stirred at room temperature for about 0.5 hours and the organic phase is separated off, dried with sodium sulphate and concentrated using a rotary evaporator. The resulting crude product is purified by column chromatography on silica gel using an n-heptane/ethyl acetate gradient of from 4:1 to 0:100.
  • Example I-1-a-72 0.233 g of the compound of Example I-1-a-72 is initially charged in 8 ml of chloroform, 0.098 ml of diisopropylethylamine and 1.5 mg of DMAP are added, 0.056 ml of morpholinecarbonyl chloride is then added, the mixture is stirred at room temperature for 20 hours, 5 ml of 5% strength sodium bicarbonate solution are added, the mixture is stirred for another 0.5 hours and the organic phase is separated off, dried with sodium sulphate and concentrated using a rotary evaporator. The crude product is purified by column chromatography on silica gel using an n-heptane/ethyl acetate gradient from 4:1 to 0:100.
  • the mixture is stirred at room temperature for 3 h.
  • reaction solution is poured into 250 ml of ice-water, and the precipitate is filtered off with suction.
  • the precipitate is washed with water and taken up in dichloromethane, the mixture is dried and the solvent is distilled off.
  • the mixture is stirred at an external temperature of 40 to 70° C. for a further 6 h.
  • reaction solution is poured onto 1.5 kg of ice, extracted with dichloromethane and washed with NaHCO 3 solution. The mixture is dried and the solvent is distilled off.
  • the determination is carried out at pH 2.3 using 0.1% aqueous phosphoric acid and acetonitrile as mobile phases; linear gradient from 10% acetonitrile to 95% acetonitrile.
  • the determination by LC-MS in the acidic range is carried out at pH 2.7 using 0.1% aqueous formic acid and acetonitrile (comprises 0.1% formic acid) as mobile phases; linear gradient from 10% acetonitrile to 95% acetonitrile.
  • LC-MS determination by LC-MS in the neutral range is carried out at pH 7.8 using 0.001 molar aqueous ammonium bicarbonate solution and acetonitrile as mobile phases; linear gradient from 10% acetonitrile to 95% acetonitrile.
  • Calibration is carried out using unbranched alkan-2-ones (having 3 to 16 carbon atoms) with known logP values (determination of the logP values by the retention times using linear interpolation between two successive alkanones).
  • the lambda-max values were determined in the maxima of the chromatographic signals using the UV spectra from 200 nm to 400 nm.
  • the mixture is stirred at room temperature.
  • reaction solution is added with stirring to 1.2 l of ice-water, 200 ml of 1N HCl are added and the precipitate is filtered off with suction. The latter is taken up in dichloromethane, and the aqueous phase is removed. The organic phase is dried, the solvent is distilled off and the residue is recrystallized from 320 ml of toluene/640 ml of n-hexane.
  • Example I-1-c-2 At room temperature, 20.6 g of the compound of Example I-1-c-2 in 24 g of semiconcentrated aqueous sodium hydroxide solution and about 100 ml of ethanol are stirred under argon protective gas for one hour, and the ethanol is then evaporated off. The solution is then acidified using hydrochloric acid, the entire mixture is dissolved in methylene chloride and the organic phase is separated off and concentrated by evaporation. The residue is stirred at 60° C. in 4 N hydrochloric acid for two hours.
  • the precipitate is separated off and stirred in ethyl acetate.
  • the mixture is acidified with concentrated HCl to a pH of from 5.2 to 5.3 and filtered off with suction, the filtrate is subjected to an azeotropic distillation with methanol until a volume of about 0.5 l is obtained, the potassium chloride is filtered off with suction and the filtrate is concentrated using a rotary evaporator and dehydrated azeotropically with methanol.
  • the mixture is stirred at from 55 to 60° C. for about 12 to 15 hours.
  • the mixture is cooled to 0° C., the solid is filtered off with suction and resuspended in water, the suspension is filtered off with suction and the product is washed with hexane and dried.
  • reaction is quenched with 500 ml of water and the mixture is stirred for another 15 minutes.
  • ketones of the formula (XXIV) are commercially available, some are known (JACS 108, 2691-2699; 1986; JACS 109, 1363-1370, 1987) and some are novel.
  • the mixture is cooled and the solid is filtered off with suction and dried.
  • the mixture is extracted with 10% strength citric acid solution and saturated sodium bicarbonate solution and the organic phase is dried with sodium sulphate and concentrated using a rotary evaporator.
  • the mixture is extracted with 10% strength citric acid solution and saturated sodium bicarbonate solution and the organic phase is dried with sodium sulphate and concentrated using a rotary evaporator.
  • 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 with emulsifier-containing water to the desired concentration.
  • Cabbage leaves Brassica oleracea
  • green peach aphid Myzus persicae
  • the kill in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
  • Emulsifier 1 parts 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 with emulsifier-containing water to the desired concentration.
  • Cotton leaves which are heavily infested by the cotton aphid ( Aphis gossypii ) are treated by being dipped into the preparation of active compound of the desired concentration.
  • the kill in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
  • 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 with emulsifier-containing water to the desired concentration.
  • Cabbage leaves Brassica oleracea
  • Cabbage leaves Brassica oleracea
  • active compound of the desired concentration are treated by being dipped into the preparation of active compound of the desired concentration and are populated with larvae of the mustard beetle ( Phaedon cochleariae ) while the leaves are still moist.
  • the kill in % is determined. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.
  • 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 with emulsifier-containing water to the desired concentration.
  • Cabbage leaves Brassica oleracea
  • Cabbage leaves Brassica oleracea
  • the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.
  • 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 with emulsifier-containing water to the desired concentration.
  • Cabbage leaves Brassica oleracea
  • Cabbage leaves Brassica oleracea
  • active compound of the desired concentration are treated by being dipped into the preparation of active compound of the desired concentration and are populated with caterpillars of the army worm ( Spodoptera frugiperda ) while the leaves are still moist.
  • the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.
  • 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 with emulsifier-containing water to the desired concentration.
  • Rice seedlings ( Oryza sativa ) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with the green rice leaf hopper ( Nephotettix cincticeps ) while the leaves are still moist.
  • the kill in % is determined. 100% means that all leaf hoppers have been killed; 0% means that none of the leaf hoppers have been killed.
  • 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 with emulsifier-containing water to the desired concentration.
  • Bean plants Phaseolus vulgaris ) which are heavily infested by all stages of the greenhouse red spider mite ( Tetranychus urticae ) are treated by being dipped into a preparation of active compound of the desired concentration.
  • the activity in % is determined. 100% means that all spider mites have been killed; 0% means that none of the spider mites have been killed.
  • 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 with water to the desired concentration.
  • Vessels are filled with sand, solution of active compound, Meloidogyne incognita egg/larvae suspension and lettuce seeds.
  • the lettuce seeds germinate and the plants develop. On the roots, galls are formed.
  • the nematicidal activity is determined in % by the formation of galls. 100% means that no galls have been found; 0% means that the number of galls on the treated plants corresponds to that of the untreated control.
  • Emulsifier 2 parts 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 with emulsifier-containing water to the desired concentration.
  • Cabbage leaves Brassica oleracea
  • green peach aphid Myzus persicae
  • the kill in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
  • Emulsifier 2 parts 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 with emulsifier-containing water to the desired concentration.
  • Bean plants Phaseolus vulgaris ) which are heavily infested by all stages of the greenhouse red spider mite ( Tetranychus urticae ) are treated by being dipped into a preparation of active compound of the desired concentration.
  • the activity in % is determined. 100% means that all spider mites have been killed; 0% means that none of the spider mites have been killed.
  • Emulsifier 2 parts 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 with water to the desired concentration.
  • Vessels are filled with sand, solution of active compound, Meloidogyne incognita egg/larvae suspension and lettuce seeds.
  • the lettuce seeds germinate and the plants develop. On the roots, galls are formed.
  • the nematicidal activity is determined in % by the formation of galls. 100% means that no galls have been found; 0% means that the number of galls on the treated plants corresponds to that of the untreated control.
  • Emulsifier 2 parts 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 with emulsifier-containing water to the desired concentration.
  • Cotton leaves which are heavily infested by the cotton aphid ( Aphis gossypii ) are treated by being dipped into the preparation of active compound of the desired concentration.
  • the kill in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
  • Emulsifier 2 parts 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 with emulsifier-containing water to the desired concentration.
  • Cabbage leaves Brassica oleracea
  • Cabbage leaves Brassica oleracea
  • active compound of the desired concentration are treated by being dipped into the preparation of active compound of the desired concentration and are populated with larvae of the mustard beetle ( Phaedon cochleariae ) while the leaves are still moist.
  • the kill in % is determined. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Discs of Chinese cabbage ( Brassica pekinensis ) are sprayed with a preparation of active compound of the desired concentration and, after drying, populated with larvae of the mustard beetle ( Phaedon cochleariae ).
  • the activity in % is determined. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Bean plants Phaseolus vulgaris ) which are heavily infested by all stages of the greenhouse red spider mite ( Tetranychus urticae ) are treated by being dipped into a preparation of active compound of the desired concentration.
  • the activity in % is determined. 100% means that all spider mites have been killed; 0% means that none of the spider mites have been killed.
  • Vessels are filled with sand, solution of active compound, Meloidogyne incognita egg/larvae suspension and lettuce seeds.
  • the lettuce seeds germinate and the plants develop. On the roots, galls are formed.
  • the nematicidal activity is determined in % by the formation of galls. 100% means that no galls have been found; 0% means that the number of galls on the treated plants corresponds to that of the untreated control.
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with emulsifying-containing water to the desired concentration.
  • Discs of Chinese cabbage Brassica pekinensis ) which are infested by all stages of the green peach aphid ( Myzus persicae ) are sprayed with a preparation of active compound of the desired concentration.
  • the activity in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
  • I-1-a-45 Ex. I-1-a-46, Ex. I-1-a-47, Ex. I-1-a-48, Ex. I-1-a-49, Ex. I-1-a-50, Ex. I-1-a-51, Ex. I-1-a-52, Ex. I-1-a-53, Ex. I-1-a-54, Ex. I-1-a-56, Ex. I-1-a-57, Ex. I-1-a-58, Ex. I-1-a-59, Ex. I-1-a-60, Ex. I-1-a-61, Ex. I-1-a-62, Ex. I-1-a-63, Ex. I-1-a-64, Ex. I-1-a-65, Ex. I-1-a-66, Ex.
  • I-1-c-30 Ex. I-1-c-31, Ex. I-1-c-32, Ex. I-1-c-33, Ex. I-1-c-34, Ex. I-1-c-35, Ex. I-1-c-36, Ex. I-1-c-40, Ex. I-1-c-41, Ex. I-1-c-42, Ex. I-1-c-43.
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Discs of maize leaves ( Zea mays ) are sprayed with a preparation of active compound of the desired concentration and, after drying, populated with caterpillars of the army worm ( Spodoptera frugiperda ).
  • the activity in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.
  • Emulsifier 2 parts 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 with water to the desired concentration.
  • the preparation of active compound is mixed with water.
  • the treated water is filled into vessels containing a pea plant ( Pisum sativum ). After the desired period of time, the plant is infected with the green peach aphid ( Myzus persicae ).
  • the kill in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • Test plants of a height of 5-15 cm are sprayed with the preparation of active compounds such that the particular amounts of active compound desired are applied per unit area.
  • the concentration of the spray liquor is chosen such that the particular amounts of active compound desired are applied in 1000 l of water/ha.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area.
  • the concentration of the spray liquor is chosen such that the particular amounts of active compound desired are applied in 1000 l of water/ha.
  • Test compounds formulated in the form of wettable powders (WP) are then, as an aqueous suspension with a water application rate of 600 l/ha (converted), with 0.2% of wetting agent added, applied to the surface of the covering soil in various dosages.
  • WP wettable powders
  • test plants Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed into sandy loam in wood fibre pots, covered with soil and cultivated in a greenhouse under good growth conditions. 2-3 weeks after sowing, the test plants are treated at the one-leaf stage.
  • the test compounds formulated as wettable powders (WP) are then, in various dosages with a water application rate of 600 l/ha (converted), with 0.2% of wetting agent added, sprayed onto the green parts of the plants.
  • WP wettable powders
  • test plants are placed into sandy loam in wood fibre pots or in plastic pots, covered with soil and cultivated in a greenhouse, during the vegetation period also outdoors outside of the greenhouse, under good growth conditions. 2-3 weeks after sowing, the test plants are treated at the one- to three-leaf stage.
  • the test compounds formulated as wettable powders (WP) or emulsifiable concentrates (EC) are, in various dosages with a water application rate of 300 l/ha (converted), with wetting agent (0.2 to 0.3%) added, sprayed onto the plants and the surface of the soil.
  • WP wettable powders
  • EC emulsifiable concentrates
  • Test insect Diabrotica balteata - larvae in the soil
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • the preparation of active compound is poured onto the soil.
  • concentration of active compound in the preparation is virtually immaterial; only the amount by weight of active compound per volume unit of soil, which is stated in ppm (mg/l), matters.
  • the soil is filled into 0.25 l pots, and these are allowed to stand at 20° C.
  • 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 the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Soybean shoots ( Glycine max ) of the cultivar Roundup Ready (trademark of Monsanto Comp. USA) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with the tobacco bud worm Heliothis virescens while the leaves are still moist.
  • the kill of the insects is determined.

Abstract

The invention relates to novel spiroketal-substituted cyclic ketoenols of the formula (I)
Figure US20110190493A1-20110804-C00001
in which
  • A, B, Q1, Q2, D, G, W, X, Y, and Z are as defined above,
    to processes and intermediates for their preparation and to their use as pesticides and/or microbicides and/or herbicides.
Moreover, the invention relates to selective herbicidal compositions comprising, firstly, spiroketal-substituted cyclic ketoenols and, secondly, a crop plant compatibility-improving compound.

Description

  • The present invention relates to novel spiroketal-substituted cyclic ketoenols, to a plurality of processes for their preparation and to their use as pesticides and/or herbicides and/or microbicides. The invention also provides selective herbicidal compositions comprising, firstly, spiroketal-substituted cyclic ketoenols and, secondly, a crop plant compatibility-improving compound.
  • Pharmaceutical properties of 3-acylpyrrolidine-2,4-diones are described in the prior art (S. Suzuki et al. Chem. Pharm. Bull. 15 1120 (1967)). Furthermore, R. Schmierer and H. Mildenberger (Liebigs Ann. Chem. 1985, 1095) synthesized N-phenylpyrrolidine-2,4-diones. A biological activity of these compounds has not been described.
  • EP-A-0 262 399 and GB-A-2 266 888 disclose compounds of a similar structure (3-arylpyrrolidine-2,4-diones); however, a herbicidal, insecticidal or acaricidal action of these compounds is not known. Known to have a herbicidal, insecticidal or acaricidal action are unsubstituted bicyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-355 599, EP-A-415 211 and JP-A-12-053 670), and also substituted monocyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-377 893 and EP-A-442 077).
  • Also known are polycyclic 3-arylpyrrolidine-2,4-dione derivatives (EP-A-442 073), and also 1H-arylpyrrolidine dione derivatives (EP-A-456 063, EP-A-521 334, EP-A-596 298, EP-A-613 884, EP-A-613 885, WO 94/01 997, WO 95/26 954, WO 95/20 572, EP-A-0 668 267, WO 96/25 395, WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO 97/43275, WO 98/05638, WO 98/06721, WO 98/25928, WO 99/24437, WO 99/43649, WO 99/48869 and WO 99/55673, WO 01/17972, WO 01/23354, WO 01/74770, WO 03/013249, WO 03/062244, WO 2004/007448, WO 2004/024688, WO 04/065366, WO 04/080962, WO 04/111042, WO 05/044791, WO 05/044796, WO 05/048710, WO 05/049596, WO 05/066125, WO 05/092897 and DE-A-04 030 753). Further well known are ketal-substituted 1H-arylpyrrolidine-2,4-diones from WO 99/16748 and (spiro)-ketal-substituted N-alkoxyalkoxy-substituted arylpyrrolidinediones from JP-A-14 205 984 and Ito M. et al., Bioscience, Biotechnology and Biochemistry 67, 1230-1238, (2003).
  • It is known that certain substituted Δ3-dihydrofuran-2-one derivatives have herbicidal properties (cf. DE-A-4 014 420). The synthesis of the tetronic acid derivatives (such as, for example, 3-(2-methylphenyl)-4-hydroxy-5-(4-fluorophenyl)-Δ3-dihydrofuran-2-one) used as starting materials is also described in DE-A-4 014 420. Compounds of a similar structure with no stated insecticidal and/or acaricidal activity are known from the publication Campbell et al., J. Chem. Soc., Perkin Trans. 1, 1985, (8) 1567-76. Furthermore, 3-aryl-Δ3-dihydrofuranone derivatives having herbicidal, acaricidal and insecticidal properties are known from EP-A-528 156, EP-A-0 647 637, WO 95/26 345, WO 96/20 196, WO 96/25 395, WO 96/35 664, WO 97/01 535, WO 97/02 243, WO 97/36 868, WO 98/05638, WO 98/25928, WO 99/16748, WO 99/43649, WO 99/48869, WO 99/55673, WO 01/17972, WO 01/23354 and WO 01/74770, WO 03/013 249, WO 2004/024 688, WO 04/080962, WO 04/111042, WO 05/092897 and DE-A-04 030 753.
  • However, the herbicidal and/or acaricidal and/or insecticidal activity and/or activity spectrum and/or the plant compatibility of the known compounds, in particular with respect to crop plants, is/are not always satisfactory.
  • This invention now provides novel compounds of the formula (I)
  • Figure US20110190493A1-20110804-C00002
  • in which
    • W represents hydrogen, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkenyloxy, haloalkyl, haloalkoxy or cyano,
    • X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy, haloalkenyloxy, nitro or cyano,
    • Y and Z independently of one another represent hydrogen, alkyl, alkenyl, alkynyl, alkoxy, halogen, haloalkyl, haloalkoxy, cyano, nitro or in each case optionally substituted aryl or hetaryl,
      • with the proviso that at least one of the radicals W or Z has to be different from hydrogen if X and Y represent methyl,
    • A and B and the carbon atom to which they are attached represent five- to seven-membered ketal, thioketal or dithioketal which may optionally be interrupted by a further heteroatom, each of which radicals is optionally substituted by alkyl, haloalkyl, alkoxy, alkoxyalkyl or optionally substituted phenyl,
    • D represents NH and oxygen,
    • Q1, Q2 independently of one another represent hydrogen, alkyl, haloalkyl or alkoxy,
    • G represents hydrogen (a) or represents one of the groups
  • Figure US20110190493A1-20110804-C00003
      • in which
      • E represents a metal ion or an ammonium ion,
      • L represents oxygen or sulphur,
      • M represents oxygen or sulphur,
    • R1 represents in each case optionally halogen- or cyano-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl or represents in each case optionally halogen-, alkyl- or alkoxy-substituted cycloalkyl or heterocyclyl or represents in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
    • R2 represents in each case optionally halogen- or cyano-substituted alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl or represents in each case optionally substituted cycloalkyl, phenyl or benzyl,
    • R3, R4 and R5 independently of one another represent in each case optionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio or represent in each case optionally substituted phenyl, benzyl, phenoxy or phenylthio,
    • R6 and R7 independently of one another represent hydrogen, represent in each case optionally halogen- or cyano-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represent in each case optionally substituted phenyl or benzyl, or together with the N atom to which they are attached form an optionally substituted cycle which optionally contains oxygen or sulphur.
  • Depending inter alia on the nature of the substituents, the compounds of the formula (I) can be present as optical isomers or isomer mixtures of varying composition which, if appropriate, may be separated in a customary manner. The present invention provides both the pure isomers and the isomer mixtures, their preparation and use, and compositions comprising them. However, for the sake of simplicity, hereinbelow only compounds of the formula (I) are referred to, although what is meant are both the pure compounds and, if appropriate, also mixtures having varying proportions of isomeric compounds.
  • Including D for NH (1) and D for O (2), the following principal structures (I-1) and (I-2) result:
  • Figure US20110190493A1-20110804-C00004
  • in which
    A, B, G, Q1, Q2, W, X, Y and Z are as defined above.
  • Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following principal structures (I-1-a) to (I-1-g) result if D represents NH (1)
  • Figure US20110190493A1-20110804-C00005
    Figure US20110190493A1-20110804-C00006
  • in which
    A, B, E, L, M, Q1, Q2, W, X, Y, Z, R1, R2, R3, R4, R5, R6 and R7 are as defined above.
  • Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of the group G, the following principal structures (I-2-a) to (I-2-g) result if D represents O (2)
  • Figure US20110190493A1-20110804-C00007
    Figure US20110190493A1-20110804-C00008
  • in which
    A, B, E, L, M, Q1, Q2, W, X, Y, Z, R1, R2, R3, R4, R5, R6 and R7 are as defined above.
  • Furthermore, it has been found that the novel compounds of the formula (I) are obtained by the processes described below:
    • (A) compounds of the formula (I-1-a)
  • Figure US20110190493A1-20110804-C00009
      • in which
      • A, B, Q1, Q2, W, X, Y and Z are as defined above
      • are obtained when
      • compounds of the formula (II)
  • Figure US20110190493A1-20110804-C00010
      • in which
      • A, B, Q1, Q2, W, X, Y and Z are as defined above
      • and
      • R8 represents alkyl (preferably C1-C6-alkyl),
      • are condensed intramolecularly in the presence of a diluent and in the presence of a base.
    • (B) Moreover, it has been found that compounds of the formula (I-2-a)
  • Figure US20110190493A1-20110804-C00011
      • in which
      • A, B, Q1, Q2, W, X, Y and Z are as defined above, are obtained when compounds of the formula (III)
  • Figure US20110190493A1-20110804-C00012
      • in which
      • A, B, Q1, Q2, W, X, Y, Z and R8 are as defined above,
      • are condensed intramolecularly in the presence of a diluent and in the presence of a base.
  • Moreover, it has been found
    • (C) that the compounds of the formulae (I-1-b) to (I-2-b) shown above in which R1, A, B, Q1, Q2, W, X, Y and Z are as defined above are obtained when compounds of the formulae (I-1-a) to (I-2-a) shown above in which A, B, Q1, Q2, W, X, Y and Z are as defined above are in each case reacted
      • α) with compounds of the formula (IV)
  • Figure US20110190493A1-20110804-C00013
      • in which
        • R1 is as defined above and
        • Hal represents halogen (in particular chlorine or bromine)
      • or
      • β) with carboxylic anhydrides of the formula (V)

  • R1—CO—O—CO—R1  (V)
      • in which
        • R1 is as defined above,
      • if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
    • (D) that the compounds of the formulae (I-1-c) to (I-2-c) shown above in which R2, A, B, Q1, Q2, W, M, X, Y and Z are as defined above and L represents oxygen are obtained when compounds of the formulae (I-1-a) to (I-2-a) shown above in which A, B, Q1, Q2, W, X, Y and Z are as defined above are in each case reacted
      • with chloroformic esters or chloroformic thioesters of the formula (VI)

  • R2-M-CO—Cl  (VI)
      • in which
      • R2 and M are as defined above,
      • if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
    • (E) that compounds of the formulae (I-1-c) to (I-2-c) shown above in which R2, A, B, Q1, Q2, W, M, X, Y and Z are as defined above and L represents sulphur are obtained when compounds of the formulae (I-1-a) to (I-2-a) shown above in which A, B, Q1, Q2, W, X, Y and Z are as defined above are in each case reacted
      • with chloromonothioformic esters or chlorodithioformic esters of the formula (VII)
  • Figure US20110190493A1-20110804-C00014
      • in which
      • M and R2 are as defined above,
      • if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
    • (F) that compounds of the formulae (I-1-d) to (I-2-d) shown above in which R3, A, B, W, Q1, Q2, X, Y and Z are as defined above are obtained when compounds of the formulae (I-1-a) to (I-2-a) shown above in which A, B, Q1, Q2, W, X, Y and Z are as defined above are in each case reacted
      • with sulphonyl chlorides of the formula (VIII)

  • R3—SO2—Cl  (VIII)
      • in which
      • R3 is as defined above,
      • if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
    • (G) that compounds of the formulae (I-1-e) to (I-2-e) shown above in which L, R4, R5, A, B, Q1, Q2, W, X, Y and Z are as defined above are obtained when compounds of the formulae (I-1-a) to (I-2-a) shown above in which A, B, Q1, Q2, W, X, Y and Z are as defined above are in each case reacted
      • with phosphorus compounds of the formula (IX)
  • Figure US20110190493A1-20110804-C00015
      • in which
      • L, R4 and R5 are as defined above and
      • Hal represents halogen (in particular chlorine or bromine),
      • if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
    • (II) that compounds of the formulae (I-1-0 to (I-2-0 shown above in which E, A, B, Q1, Q2, W, X, Y and Z are as defined above are obtained when compounds of the formulae (I-1-a) to (I-2-a) in which A, B, Q1, Q2, W, X, Y and Z are as defined above are in each case reacted
      • with metal compounds or amines of the formula (X) or (X1)
  • Figure US20110190493A1-20110804-C00016
      • in which
      • Me represents a mono- or divalent metal (preferably an alkali metal or alkaline earth metal, such as lithium, sodium, potassium, magnesium or calcium),
      • t represents the number 1 or 2 and
      • R10, R11, R12 independently of one another represent hydrogen or alkyl (preferably C1-C8-alkyl),
      • if appropriate in the presence of a diluent,
    • (I) that compounds of the formulae (I-1-g) to (I-2-g) shown above in which L, R6, R7, A, B, Q1, Q2, W, X, Y and Z are as defined above are obtained when compounds of the formulae (I-1-a) to (I-2-a) shown above in which A, B, Q1, Q2, W, X, Y and Z are as defined above are in each case
      • α) reacted with isocyanates or isothiocyanates of the formula (XII)

  • R6—N═C=L  (XII)
      • in which
      • R6 and L are as defined above,
      • if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst, or
      • β) reacted with carbamoyl chlorides or thiocarbamoyl chlorides of the formula (XIII)
  • Figure US20110190493A1-20110804-C00017
        • in which
        • L, R6 and R7 are as defined above,
        • if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
    • (J) that compounds of the formulae (I-1-a) to (I-1-g) and (I-2-a) to (I-2-g) shown above in which A, B, D, G, Q1, Q2, W, X, Y and Z are as defined above are obtained when compounds of the formula (XIV)
  • Figure US20110190493A1-20110804-C00018
      • in which
      • D, G, Q1, Q2, W, X, Y and Z are as defined above,
      • and A, B and the carbon atom to which they are attached represent a
  • Figure US20110190493A1-20110804-C00019
      • are reacted, for example, with diols of the formula (XV)

  • HO-A-B—OH  (XV)
      • in which
      • A and B are as defined above,
      • if appropriate in the presence of a diluent, in the presence of an acidic catalyst and under dehydrating conditions.
  • The following compound of the formula (I-a) has been disclosed in 1994 in the context of the European Patent Examination of EP 596 298.
  • Figure US20110190493A1-20110804-C00020
  • Furthermore, it has been found that the novel compounds of the formula (I) have good activity as pesticides, preferably as insecticides and/or acaricides and/or fungicides and/or herbicides, and are additionally frequently highly compatible with plants, in particular with crop plants.
  • Surprisingly, it has now also been found that certain substituted cyclic ketoenols, when employed together with the crop plant compatibility-improving compounds (safeners/antidotes) described later on, are extremely good at preventing damage to the crop plants and can be used with particular advantage as broad-spectrum combination products for the selective control of unwanted plants in crops of useful plants, such as, for example, in cereals, but also in maize, soy and rice.
  • The invention also provides selective herbicidal compositions comprising an effective amount of an active compound combination comprising, as components,
    • (a′) at least one compound of the formula (I) in which A, B, D, G, Q1, Q2, W, X, Y and Z are as defined above and
    • (b′) at least one crop plant compatibility-improving compound from the following group of compounds:
  • 4-dichloroacetyl-1-oxa-4-azaspiro[4.5]decane (AD-67, MON-4660), 1-dichloroacetylhexahydro-3,3,8a-trimethylpyrrolo pyrimidin-6(2H)-one (dicyclonon, BAS-145138), 4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine (benoxacor), 1-methylhexyl 5-chloroquinoline-8-oxyacetate (cloquintocet-mexyl—cf. also related compounds in EP-A-86750, EP-A-94349, EP-A-191736, EP-A-492366), 3-(2-chlorobenzyl)-1-(1-methyl-1-phenyl ethyl)urea (cumyluron), α-(cyanomethoximino)phenylacetonitrile (cyometrinil), 2,4-dichlorophenoxyacetic acid (2,4-D), 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB), 1-(1-methyl-1-phenylethyl)-3-(4-methylphenyl)urea (daimuron, dymron), 3,6-dichloro-2-methoxybenzoic acid (dicamba), S-1-methyl-1-phenylethyl piperidine-1-thiocarboxylate (dimepiperate), 2,2-dichloro-N-(2-oxo-2-(2-propenyl amino)ethyl)-N-(2-propenyl)acetamide (DKA-24), 2,2-dichloro-N,N-di-2-propenylacetamide (dichlormid), 4,6-dichloro-2-phenylpyrimidine (fenclorim), ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl-1H-1,2,4-triazole-3-carboxylate (fenchlorazole-ethyl—cf. also related compounds in EP-A-174562 and EP-A-346620), phenylmethyl 2-chloro-4-trifluoromethylthiazole-5-carboxylate (flurazole), 4-chloro-N-(1,3-dioxolan-2-ylmethoxy)-α-trifluoroacetophenone oxime (fluxofenim), 3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyloxazolidine (furilazole, MON-13900), ethyl 4,5-dihydro-5,5-diphenyl-3-isoxazolecarboxylate (isoxadifen-ethyl—cf. also related compounds in WO-A-95/07897), 1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate (lactidichlor), (4-chloro-o-tolyloxy)acetic acid (MCPA), 2-(4-chloro-o-tolyloxy)propionic acid (mecoprop), diethyl 1-(2,4-dichorophenyl)-4,5-dihydro-5-methyl-1H-pyrazole-3,5-dicarboxylate (mefenpyr-diethyl—cf. also related compounds in WO-A-91/07874), 2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191), 2-propenyl-1-oxa-4-azaspiro[4.5]decane-4-carbodithioate (MG-838), 1,8-naphthalic anhydride, α-(1,3-dioxolan-2-ylmethoximino)phenylacetonitrile (oxabetrinil), 2,2-dichloro-N-(1,3-dioxolan-2-ylmethyl)-N-(2-propenyl)acetamide (PPG-1292), 3-dichloroacetyl-2,2-dimethyloxazolidine (R-28725), 3-dichloroacetyl-2,2,5-trimethyloxazolidine (R-29148), 4-(4-chloro-o-tolyl)butyric acid, 4-(4-chlorophenoxy)butyric acid, diphenylmethoxyacetic acid, methyl diphenylmethoxyacetate, ethyl diphenylmethoxyacetate, methyl 1-(2-chlorophenyl)-5-phenyl-1H-pyrazole-3-carboxylate, ethyl 1-(2,4-dichlorophenyl)-5-methyl-1H-pyrazole-3-carboxylate, ethyl 1-(2,4-dichlorophenyl)-5-isopropyl-1H-pyrazole-3-carboxylate, ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)-1H-pyrazole-3-carboxylate, ethyl 1-(2,4-dichlorophenyl)-5-phenyl-1H-pyrazole-3-carboxylate (cf. also related compounds in EP-A-269806 and EP-A-333131), ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate, ethyl 5-phenyl-2-isoxazoline-3-carboxylate, ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (cf. also related compounds in WO-A-91/08202), 1,3-dimethylbut-1-yl 5-chloroquinoline-8-oxyacetate, 4-allyloxybutyl 5-chloroquinoline-8-oxyacetate, 1-allyloxyprop-2-yl 5-chloroquinoline-8-oxyacetate, methyl 5-chloroquinoxaline-8-oxyacetate, ethyl 5-chloroquinoline-8-oxyacetate, allyl 5-chloroquin-oxaline-8-oxyacetate, 2-oxoprop-1-yl 5-chloroquinoline-8-oxyacetate, diethyl 5-chloroquinoline-8-oxymalonate, diallyl 5-chloroquinoxaline-8-oxymalonate, diethyl 5-chloroquinoline-8-oxymalonate (cf. also related compounds in EP-A-582198), 4-carboxychroman-4-ylacetic acid (AC-304415, cf. EP-A-613618), 4-chlorophenoxyacetic acid, 3,3′-dimethyl-4-methoxy-benzophenone, 1-bromo-4-chloromethylsulphonylbenzene, 1-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3-methylurea (also known as N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulphonamide), 1-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3,3-dimethylurea, 1-[4-(N-4,5-dimethylbenzoyl sulphamoyl)phenyl]-3-methylurea, 1-[4-(N-naphthyl sulphamoyl)phenyl]-3,3-dimethylurea, N-(2-methoxy-5-methylbenzoyl)-4-(cyclopropylaminocarbonyl)benzenesulphonamide,
  • and/or one of the following compounds, defined by general formulae,
    of the general formula (IIa)
  • Figure US20110190493A1-20110804-C00021
  • or of the general formula (IIb)
  • Figure US20110190493A1-20110804-C00022
  • or of the formula (IIc)
  • Figure US20110190493A1-20110804-C00023
  • where
    • m represents a number 0, 1, 2, 3, 4 or 5,
    • A1 represents one of the divalent heterocyclic groupings shown below
  • Figure US20110190493A1-20110804-C00024
    • n represents a number 0, 1, 2, 3, 4 or 5,
    • A2 represents optionally C1-C4-alkyl- and/or C1-C4-alkoxy-carbonyl- and/or C1-C4-alkenyloxycarbonyl-substituted alkanediyl having 1 or 2 carbon atoms,
    • R14 represents hydroxyl, mercapto, amino, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylamino or di(C1-C4-alkyl)-amino,
    • R15 represents hydroxyl, mercapto, amino, C1-C7-alkoxy, C1-C6-alkylthio, C1-C6-alkenyloxy, C1-C6-alkenyloxy-C1-C6-alkoxy, C1-C6-alkylamino or di(C1-C4-alkyl)-amino,
    • R16 represents optionally fluorine-, chlorine- and/or bromine-substituted C1-C4-alkyl,
    • R17 represents hydrogen, in each case optionally fluorine-, chlorine- and/or bromine-substituted C1-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, C1-C4-alkoxy-C1-C4-alkyl, dioxolanyl-C1-C4-alkyl, furyl, furyl-C1-C4-alkyl, thienyl, thiazolyl, piperidinyl, or optionally fluorine-, chlorine- and/or bromine- or C1-C4-alkyl-substituted phenyl,
    • R18 represents hydrogen, in each case optionally fluorine-, chlorine- and/or bromine-substituted C1-C6-alkyl, C2-C6-alkenyl or C2-C6-alkynyl, C1-C4-alkoxy-C1-C4-alkyl, dioxolanyl-C1-C4-alkyl, furyl, furyl-C1-C4-alkyl, thienyl, thiazolyl, piperidinyl, or optionally fluorine-, chlorine- and/or bromine- or C1-C4-alkyl-substituted phenyl, R17 and R18 also together represent C3-C6-alkanediyl or C2-C5-oxaalkanediyl, each of which is optionally substituted by C1-C4-alkyl, phenyl, furyl, a fused benzene ring or by two substituents which, together with the C atom to which they are attached, form a 5- or 6-membered carboxycle,
    • R19 represents hydrogen, cyano, halogen, or represents in each case optionally fluorine-, chlorine- and/or bromine-substituted C1-C4-alkyl, C3-C6-cycloalkyl or phenyl,
    • R20 represents hydrogen, in each case optionally hydroxyl-, cyano-, halogen- or C1-C4-alkoxy-substituted C1-C6-alkyl, C3-C6-cycloalkyl or tri-(C1-C4-alkyl)-silyl,
    • R21 represents hydrogen, cyano, halogen, or represents in each case optionally fluorine-, chlorine- and/or bromine-substituted C1-C4-alkyl, C3-C6-cycloalkyl or phenyl,
    • X1 represents nitro, cyano, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy,
    • X2 represents hydrogen, cyano, nitro, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy,
    • X3 represents hydrogen, cyano, nitro, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy,
      and/or the following compounds, defined by general formulae,
      of the general formula (IId)
  • Figure US20110190493A1-20110804-C00025
  • or of the general formula (IIe)
  • Figure US20110190493A1-20110804-C00026
  • where
    • t represents a number between 0 and 5,
    • v represents a number between 0 and 5,
    • R22 represents hydrogen or C1-C4-alkyl,
    • R23 represents hydrogen or C1-C4-alkyl,
    • R24 represents hydrogen, in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylamino or di(C1-C4-alkyl)-amino, or in each case optionally cyano-, halogen- or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkylthio or C3-C6-cycloalkylamino,
    • R25 represents hydrogen, optionally cyano-, hydroxyl-, halogen- or C1-C4-alkoxy-substituted C1-C6-alkyl, in each case optionally cyano- or halogen-substituted C3-C6-alkenyl or C3-C6-alkynyl, or optionally cyano-, halogen- or C1-C4-alkyl-substituted C3-C6-cycloalkyl,
    • R26 represents hydrogen, optionally cyano-, hydroxyl-, halogen- or C1-C4-alkoxy-substituted C1-C6-alkyl, in each case optionally cyano- or halogen-substituted C3-C6-alkenyl or C3-C6-alkynyl, optionally cyano-, halogen- or C1-C4-alkyl-substituted C3-C6-cycloalkyl, or optionally nitro-, cyano-, halogen-, C1-C4-alkyl-, C1-C4-haloalkyl-, C1-C4-alkoxy- or C1-C4-haloalkoxy-substituted phenyl, or together with R25 represents in each case optionally C1-C4-alkyl-substituted C2-C6-alkanediyl or C2-C5-oxaalkanediyl,
    • X4 represents nitro, cyano, carboxyl, carbamoyl, formyl, sulphamoyl, hydroxyl, amino, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy, and
    • X5 represents nitro, cyano, carboxyl, carbamoyl, formyl, sulphamoyl, hydroxyl, amino, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy.
  • The formula (I) provides a general definition of the compounds according to the invention. Preferred substituents or ranges of the radicals listed in the formulae given above and below are illustrated below:
    • W preferably represents hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, halogen, C1-C6-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy or cyano,
    • X preferably represents halogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C1-C6-alkoxy, C3-C6-alkenyloxy, C1-C6-alkylthio, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, C1-C6-haloalkoxy, C3-C6-haloalkenyloxy, nitro or cyano,
    • Y and Z independently of one another preferably represent hydrogen, halogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C1-C6-haloalkyl, C1-C6-haloalkoxy, cyano, C2-C6-alkenyl, C2-C6-alkynyl or one of the (het)aryl radicals
  • Figure US20110190493A1-20110804-C00027
  • where in the case of (het)aryl only one of the radicals Y or Z may represent (het)aryl,
    • V1 preferably represents hydrogen, halogen, C1-C12-alkyl, C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylsulphinyl, C1-C6-alkylsulphonyl, C1-C4-haloalkyl, C1-C4-haloalkoxy, nitro, cyano or represents phenyl, phenoxy, phenoxy-C1-C4-alkyl, phenyl-C1-C4-alkoxy, phenylthio-C1-C4-alkyl or phenyl-C1-C4-alkylthio, each of which is optionally mono- or polysubstituted by halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, nitro or cyano,
    • V2 and V3 independently of one another preferably represent hydrogen, halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C4-haloalkyl or C1-C4-haloalkoxy,
      • with the proviso that at least one of the radicals W or Z has to be different from hydrogen if X and Y represent methyl,
    • A and B and the carbon atom to which they are attached preferably represent five- to seven-membered ketal, thioketal, or dithioketal which may optionally be interrupted by a further oxygen atom, sulphur atom or by the group
  • Figure US20110190493A1-20110804-C00028
  • reach of which radicals is optionally mono- to tetrasubstituted by C1-C6-alkyl, C1-C4-haloalkyl, C1-C6-alkoxy or C1-C4-alkoxy-C1-C4-alkyl,
    • V4 preferably represents hydrogen, C1-C6-alkyl, C3-C6-alkenyl, or represents the groups —CO2V5, CO—NH—V5 or CO—NH—O—V5,
    • V5 preferably represents C1-C6-alkyl,
    • D preferably represents NH (1) or oxygen (2),
    • Q1 and Q2 independently of one another preferably represent hydrogen, C1-C6-alkyl, C1-C2-haloalkyl or C1-C4-alkoxy,
    • G preferably represents hydrogen (a) or represents one of the groups
  • Figure US20110190493A1-20110804-C00029
  • in which
    • E represents a metal ion or an ammonium ion,
    • L represents oxygen or sulphur and
    • M represents oxygen or sulphur,
    • R1 preferably represents in each case optionally halogen- or cyano-substituted C1-C20-alkyl, C2-C20-alkenyl, C1-C8-alkoxy-C1-C8-alkyl, C1-C8-alkylthio-C1-C8-alkyl or poly-C1-C8-alkoxy-C1-C8-alkyl or represents optionally halogen-, C1-C6-alkyl- or C1-C6-alkoxy-substituted C3-C8-cycloalkyl in which optionally one or two not directly adjacent methylene groups are replaced by oxygen and/or sulphur,
      • represents optionally halogen-, cyano-, nitro-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C6-haloalkyl-, C1-C6-haloalkoxy-, C1-C6-alkylthio- or C1-C6-alkylsulphonyl-substituted phenyl,
      • represents optionally halogen-, nitro-, cyano-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C6-haloalkyl- or C1-C6-haloalkoxy-substituted phenyl-C1-C6-alkyl,
      • represents optionally halogen- or C1-C6-alkyl-substituted 5- or 6-membered hetaryl having one or two heteroatoms from the group consisting of oxygen, sulphur and nitrogen,
      • represents optionally halogen- or C1-C6-alkyl-substituted phenoxy-C1-C6-alkyl or
      • represents optionally halogen-, amino- or C1-C6-alkyl-substituted 5- or 6-membered hetaryloxy-C1-C6-alkyl having one or two heteroatoms from the group consisting of oxygen, sulphur and nitrogen,
    • R2 preferably represents in each case optionally halogen- or cyano-substituted C1-C20-alkyl, C2-C20-alkenyl, C1-C8-alkoxy-C2-C8-alkyl or poly-C1-C8-alkoxy-C2-C8-alkyl,
      • represents optionally halogen-, C1-C6-alkyl- or C1-C6-alkoxy-substituted C3-C8-cycloalkyl or
      • represents in each case optionally halogen-, cyano-, nitro-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C6-haloalkyl- or C1-C6-haloalkoxy-substituted phenyl or benzyl,
    • R3 preferably represents optionally halogen-substituted C1-C8-alkyl or in each case optionally halogen-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C4-haloalkyl-, C1-C4-haloalkoxy-, cyano- or nitro-substituted phenyl or benzyl,
    • R4 and R5 independently of one another preferably represent in each case optionally halogen-substituted C1-C8-alkyl, C1-C8-alkoxy, C1-C8-alkylamino, di(C1-C8-alkyl)amino, C1-C8-alkylthio or C3-C8-alkenylthio or represent in each case optionally halogen-, nitro-, cyano-, C1-C4-alkoxy-, C1-C4-haloalkoxy-, C1-C4-alkylthio-, C1-C4-haloalkylthio-, C1-C4-alkyl- or C1-C4-haloalkyl-substituted phenyl, phenoxy or phenylthio,
    • R6 and R7 independently of one another preferably represent hydrogen, represent in each case optionally halogen- or cyano-substituted C1-C8-alkyl, C3-C8-cycloalkyl, C1-C8-alkoxy, C3-C8-alkenyl or C1-C8-alkoxy-C2-C8-alkyl, represent in each case optionally halogen-, C1-C8-alkyl-, C1-C8-haloalkyl- or C1-C8-alkoxy-substituted phenyl or benzyl or together represent an optionally C1-C6-alkyl-substituted C3-C6-alkylene radical in which optionally one methylene group is replaced by oxygen or sulphur.
  • In the radical definitions mentioned as being preferred, halogen represents fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine.
    • W particularly preferably represents hydrogen, chlorine, bromine, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, C1-C2-haloalkyl or C1-C2-haloalkoxy,
    • X particularly preferably represents chlorine, bromine, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy or cyano,
    • Y and Z independently of one another particularly preferably represent hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C6-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, cyano, C2-C4-alkenyl, C2-C4-alkynyl or represent one of the (het)aryl radicals
  • Figure US20110190493A1-20110804-C00030
      • where in the case of (het)aryl only one of the radicals Y or Z may represent (het)aryl,
    • V1 particularly preferably represents hydrogen, fluorine, chlorine, bromine, C1-C6-alkyl, C1-C4-alkoxy, C1-C2-haloalkyl, C1-C2-haloalkoxy, nitro, cyano or represents phenyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-haloalkyl, C1-C2-haloalkoxy, nitro or cyano,
    • V2 and V3 independently of one another particularly preferably represent hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-haloalkyl or C1-C2-haloalkoxy,
      • with the proviso that at least one of the radicals W or Z has to be different from hydrogen if X and Y represent methyl,
    • A and B and the carbon atom to which they are attached particularly preferably represent a five-, six- or seven-membered ketal which may optionally be interrupted by a further oxygen atom and which is optionally mono- to trisubstituted by C1-C4-alkyl, C1-C3-haloalkyl, C1-C4-alkoxy or C1-C4-alkoxy-C1-C2-alkyl,
    • D particularly preferably represents NH (1) or oxygen (2),
    • Q1 and Q2 independently of one another particularly preferably represent hydrogen, methyl, ethyl, trifluoromethyl, methoxy or ethoxy,
    • G particularly preferably represents hydrogen (a) or represents one of the groups
  • Figure US20110190493A1-20110804-C00031
      • in which
      • E represents a metal ion or an ammonium ion,
      • L represents oxygen or sulphur and
      • M represents oxygen or sulphur,
    • R1 particularly preferably represents C1-C16-alkyl, C2-C16-alkenyl, C1-C6-alkoxy-C1-C4-alkyl, C1-C6-alkylthio-C1-C4-alkyl or poly-C1-C6-alkoxy-C1-C4-alkyl, each of which is optionally mono- to trisubstituted by fluorine or chlorine, or represents C3-C7-cycloalkyl which is optionally mono- or disubstituted by fluorine, chlorine, C1-C5-alkyl or C1-C5-alkoxy and in which optionally one or two not directly adjacent methylene groups are replaced by oxygen and/or sulphur,
      • represents phenyl which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C3-haloalkyl, C1-C3-haloalkoxy, C1-C4-alkylthio or C1-C4-alkylsulphonyl,
      • represents phenyl-C1-C4-alkyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C3-haloalkyl or C1-C3-haloalkoxy,
      • represents pyrazolyl, thiazolyl, pyridyl, pyrimidyl, furanyl or thienyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine or C1-C4-alkyl,
      • represents phenoxy-C1-C5-alkyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine or C1-C4-alkyl or
      • represents pyridyloxy-C1-C5 -alkyl, pyrimidyloxy-C1-C5-alkyl or thiazolyloxy-C1-C5-alkyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, amino or C1-C4-alkyl,
    • R2 particularly preferably represents C1-C16-alkyl, C2-C16-alkenyl, C1-C6-alkoxy-C2-C6-alkyl or poly-C1-C6-alkoxy-C2-C6-alkyl, each of which is optionally mono- to trisubstituted by fluorine or chlorine,
      • represents C3-C7-cycloalkyl which is optionally mono- or disubstituted by fluorine, chlorine, C1-C4-alkyl or C1-C4-alkoxy or
      • represents phenyl or benzyl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl or C1-C3-haloalkoxy,
    • R3 particularly preferably represents C1-C6-alkyl which is optionally mono- to trisubstituted by fluorine or chlorine or represents phenyl or benzyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-haloalkoxy, C1-C2-haloalkyl, cyano or nitro,
    • R4 and R5 independently of one another particularly preferably represent C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylamino, di(C1-C6-alkyl)amino, C1-C6-alkylthio or C3-C4-alkenylthio, each of which is optionally mono- to trisubstituted by fluorine or chlorine, or represent phenyl, phenoxy or phenylthio, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, nitro, cyano, C1-C3-alkoxy, C1-C3-haloalkoxy, C1-C3-alkylthio, C1-C3-haloalkylthio, C1-C3-alkyl or C1-C3-haloalkyl,
    • R6 and R7 independently of one another particularly preferably represent hydrogen, represent C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C3-C6-alkenyl or C1-C6-alkoxy-C2-C6-alkyl, each of which is optionally mono- to trisubstituted by fluorine or chlorine, represent phenyl or benzyl, each of which is optionally mono- to trisubstituted by fluorine, chlorine, bromine, C1-C5-haloalkyl, C1-C5-alkyl or C1-C5-alkoxy, or together represent an optionally C1-C4-alkyl-substituted C3-C6-alkylene radical in which optionally one methylene group is replaced by oxygen or sulphur.
  • In the radical definitions mentioned as being particularly preferred, halogen represents fluorine, chlorine and bromine, in particular fluorine and chlorine.
    • W very particularly preferably represents hydrogen, chlorine, bromine, methyl, ethyl, vinyl, ethynyl, propynyl, methoxy, ethoxy or trifluoromethyl,
    • X very particularly preferably represents chlorine, bromine, methyl, ethyl, propyl, isopropyl, vinyl, ethynyl, propynyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy or cyano,
    • Y and Z independently of one another very particularly preferably represent hydrogen, fluorine, chlorine, bromine, methyl, ethyl, vinyl, ethynyl, propynyl, methoxy, trifluoromethyl, trifluoromethoxy, cyano or a phenyl radical
  • Figure US20110190493A1-20110804-C00032
      • where in the case of phenyl only one of the radicals Y or Z may represent phenyl,
    • V1 very particularly preferably represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, trifluoromethyl or trifluoromethoxy,
    • V2 very particularly preferably represents hydrogen, fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy or trifluoromethyl,
      • with the proviso that at least one of the radicals W or Z has to be different from hydrogen if X and Y represent methyl,
    • A and B and the carbon atom to which they are attached very particularly preferably represent a five-, six- or seven-membered ketal which may optionally be interrupted by a further oxygen atom and which is optionally mono- or disubstituted by methyl, ethyl, propyl, trifluoromethyl, monochloromethyl, methoxy, ethoxy, methoxymethyl or ethoxymethyl,
    • D very particularly preferably represents NH (1) or oxygen (2),
    • Q1 and Q2 very particularly preferably represent hydrogen,
    • G very particularly preferably represents hydrogen (a) or represents one of the groups
  • Figure US20110190493A1-20110804-C00033
      • in which
      • E represents a metal ion or an ammonium ion,
      • L represents oxygen or sulphur and
      • M represents oxygen or sulphur,
    • R1 very particularly preferably represents C1-C10-alkyl, C2-C10-alkenyl, C1-C4-alkoxy-C1-C2-alkyl, C1-C4-alkylthio-C1-C2-alkyl, each of which is optionally mono- to trisubstituted by fluorine or chlorine, or represents C3-C6-cycloalkyl which is optionally monosubstituted by fluorine, chlorine, methyl, ethyl or methoxy,
      • represents phenyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, trifluoromethyl or trifluoromethoxy,
      • represents (uranyl, thienyl or pyridyl, each of which is optionally monosubstituted by chlorine, bromine or methyl,
    • R2 very particularly preferably represents C1-C10-alkyl, C2-C10-alkenyl or C1-C4-alkoxy-C2-C4-alkyl, each of which is optionally mono- to trisubstituted by fluorine or chlorine,
      • represents cyclopentyl or cyclohexyl,
      • or represents phenyl or benzyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, cyano, nitro, methyl, ethyl, methoxy, trifluoromethyl or trifluoromethoxy,
    • R3 very particularly preferably represents methyl, ethyl, propyl or isopropyl, each of which is optionally mono- to trisubstituted by fluorine or chlorine, or represents phenyl which is optionally monosubstituted by fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro,
    • R4 and R5 independently of one another very particularly preferably represent C1-C4-alkoxy or C1-C4-alkylthio or represent phenyl, phenoxy or phenylthio, each of which is optionally monosubstituted by fluorine, chlorine, bromine, nitro, cyano, methyl, methoxy, trifluoromethyl or trifluoromethoxy,
    • R6 and R7 independently of one another very particularly preferably represent hydrogen, represent C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C3-C4-alkenyl or C1-C4-alkoxy-C2-C4-alkyl, represent phenyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, methyl, methoxy or trifluoromethyl, or together represent a C5-C6-alkylene radical in which optionally one methylene group is replaced by oxygen or sulphur.
    • W especially preferably represents hydrogen, chlorine, bromine, methyl, ethyl or methoxy,
    • X especially preferably represents chlorine, bromine, methyl, ethyl or methoxy,
    • Y and Z independently of one another especially preferably represent hydrogen, chlorine, bromine, methyl or represent the radical
  • Figure US20110190493A1-20110804-C00034
      • where in this case only one of the radicals Y or Z may represent
  • Figure US20110190493A1-20110804-C00035
      • with the proviso that at least one of the radicals W or Z has to be different from hydrogen if X and Y represent methyl,
    • A and B and the carbon atom to which they are attached especially preferably represent a five- or six-membered ketal which is optionally mono- or disubstituted by methyl, ethyl, propyl, monochloromethyl or methoxymethyl,
    • D especially preferably represents NH (1) or oxygen (2),
    • Q1 and Q2 especially preferably represent hydrogen,
    • G especially preferably represents hydrogen (a) or represents one of the groups
  • Figure US20110190493A1-20110804-C00036
    • R1 especially preferably represents C1-C10-alkyl, C1-C4-alkoxy-C1-C2-alkyl, C3-C6-cycloalkyl,
      • represents phenyl which is optionally monosubstituted by chlorine, or represents thienyl,
    • R2 especially preferably represents C1-C10-alkyl, C2-C10-alkenyl or benzyl,
    • R3 especially preferably represents methyl,
    • R6 and R7 together especially preferably represent a C5-C6-alkylene radical in which optionally one methylene group is replaced by oxygen or sulphur.
    • General or preferred radical definitions or illustrations given above can be combined with one another as desired, i.e. including combinations between the respective ranges and preferred ranges. They apply both to the end products and, correspondingly, to precursors and intermediates.
  • Preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings given above as being preferred (preferable).
  • Particular preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings given above as being particularly preferred.
  • Very particular preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings given above as being very particularly preferred.
  • Special preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings given above as being especially preferred.
  • Emphasis is given to compounds of the formula (I) in which G represents hydrogen.
  • In the case of the compounds of the formula (I-1), the phenyl ring is, with emphasis, substituted 3 times, resulting in the following substitution patterns: 2,4,6-, 2,4,5- or 2,5,6-substitution. Moreover, in the case of the compounds of the formula (I-1), the phenyl ring is, with emphasis, substituted 4 times, resulting in the following substitution pattern: 2,4,5,6-substitution. In the case of the compounds of the formula (I-1), the phenyl ring is, with emphasis, also substituted 2 times (2,5-position). In the case of the compounds of the formula (I-1), the phenyl ring is, with emphasis, also monosubstituted (ortho position). The other substituents W, X, Y, Z, G, A, B, Q1 and Q2 are as defined in the text.
  • Moreover, in the case of the compounds of the formula (I-1) in which the phenyl ring is substituted in the 2,4-position, the substituent G represents, with emphasis, the group (b), but also the group (c) or (d) or (e) or (f) or (g). In this case, G represents especially the groups (a), (b) or (c). The other substituents W, X, Y, Z, A, B, Q1 and Q2 are as defined in the text. Furthermore, in the case of the compounds of the formula (I-1) in which the phenyl ring is substituted in the 2,4-position, the substituents A and B are, with emphasis, in the 3′-position on the spirocycle. Furthermore, in the case of the compounds of the formula (I-1) in which the phenyl ring is substituted in the 2,4-position, the substituents A and B are, with emphasis, in the 4′-position on the spirocycle.
  • Saturated or unsaturated hydrocarbon radicals, such as alkyl, alkanediyl or alkenyl, may in each case be straight-chain or branched as far as this is possible, including in combination with heteroatoms, such as, for example, in alkoxy.
  • Unless indicated otherwise, optionally substituted radicals may be mono- or polysubstituted, where in the case of polysubstitution the substituents may be identical or different.
  • In addition to the compounds mentioned in the Preparation Examples, the following compounds of the formula (I-1-a) may be specifically mentioned:
  • TABLE 1
    (I-1-a)
    Figure US20110190493A1-20110804-C00037
    A-B X W Y Z
    —O—(CH2)2—O— CH3 H H H
    —O—(CH2)2—O— Br H H H
    —O—(CH2)2—O— Cl H H H
    —O—(CH2)2—O— CF3 H H H
    —O—(CH2)2—O— OCH3 H H H
    —O—(CH2)2—O— Br H Cl H
    —O—(CH2)2—O— Cl H Br H
    —O—(CH2)2—O— Cl H Cl H
    —O—(CH2)2—O— Cl H CH3 H
    —O—(CH2)2—O— CH3 H Cl H
    —O—(CH2)2—O— Cl Cl H H
    —O—(CH2)2—O— Cl OCH3 H H
    —O—(CH2)2—O— Cl CH3 H H
    —O—(CH2)2—O— Cl OC2H5 H H
    —O—(CH2)2—O— OCH3 OCH3 H H
    —O—(CH2)2—O— CH3 CH3 H H
    —O—(CH2)2—O— C2H5 CH3 H H
    —O—(CH2)2—O— C2H5 C2H5 H H
    —O—(CH2)2—O— Br CH3 Br H
    —O—(CH2)2—O— Cl CH3 Cl H
    —O—(CH2)2—O— CH3 Br CH3 H
    —O—(CH2)2—O— CH3 Cl CH3 H
    —O—(CH2)2—O— OCH3 CH3 CH3 H
    —O—(CH2)2—O— OC2H5 CH3 CH3 H
    —O—(CH2)2—O— OC3H7 CH3 CH3 H
    —O—(CH2)2—O— CH3 CH3 CH3 H
    —O—(CH2)2—O— Br Br CH3 H
    —O—(CH2)2—O— Cl Cl CH3 H
    —O—(CH2)2—O— CH3 CH3 Br H
    —O—(CH2)2—O— OCH3 C2H5 CH3 H
    —O—(CH2)2—O— OC2H5 C2H5 CH3 H
    —O—(CH2)2—O— CH3 CH3 OCH3 H
    —O—(CH2)2—O— Br Cl CH3 H
    —O—(CH2)2—O— Br CH3 Cl H
    —O—(CH2)2—O— Cl CH3 Br H
    —O—(CH2)2—O— CH3 CH3 Cl H
    —O—(CH2)2—O— C2H5 CH3 CH3 H
    —O—(CH2)2—O— C2H5 C2H5 CH3 H
    —O—(CH2)2—O— C2H5 CH3 C2H5 H
    —O—(CH2)2—O— C2H5 C2H5 C2H5 H
    —O—(CH2)2—O— C2H5 CH3 Cl H
    —O—(CH2)2—O— C2H5 C2H5 Cl H
    —O—(CH2)2—O— C2H5 CH3 Br H
    —O—(CH2)2—O— C2H5 C2H5 Br H
    —O—(CH2)2—O— C2H5 Cl CH3 H
    —O—(CH2)2—O— C2H5 Br CH3 H
    —O—(CH2)2—O— C2H5 Cl Cl H
    —O—(CH2)2—O— C2H5 Br Br H
    —O—(CH2)2—O— C2H5 Cl Br H
    —O—(CH2)2—O— C2H5 Br Cl H
    —O—(CH2)2—O— OCH3 CH3 Cl H
    —O—(CH2)2—O— OCH3 C2H5 Cl H
    —O—(CH2)2—O— OC2H5 CH3 Cl H
    —O—(CH2)2—O— OC2H5 C2H5 Cl H
    —O—(CH2)2—O— Cl OCH3 CH3 H
    —O—(CH2)2—O— Cl OC2H5 CH3 H
    —O—(CH2)2—O— CH3 CH3 Cl H
    —O—(CH2)2—O— Cl H Cl Cl
    —O—(CH2)2—O— CH3 H CH3 CH3
    —O—(CH2)2—O— CH3 H Cl CH3
    —O—(CH2)2—O— Br H Cl CH3
    —O—(CH2)2—O— Br H CH3 CH3
    —O—(CH2)2—O— Cl H Br CH3
    —O—(CH2)2—O— Cl H Cl CH3
    —O—(CH2)2—O— CH3 H Br CH3
    —O—(CH2)2—O— Cl H CH3 Cl
    —O—(CH2)2—O— CH3 H H CH3
    —O—(CH2)2—O— Cl H H CH3
    —O—(CH2)2—O— Br H H CH3
    —O—(CH2)2—O— CH3 H H Cl
    —O—(CH2)2—O— CH3 H H Br
    —O—(CH2)2—O— CH3 CH3 CH3 CH3
    —O—(CH2)2—O— CH3 CH3 CH3 F
    —O—(CH2)2—O— CH3 CH3 CH3 Cl
    —O—(CH2)2—O— CH3 CH3 CH3 Br
    —O—(CH2)2—O— CH3 CH3 H Cl
    —O—(CH2)2—O— CH3 CH3 H Br
    —O—(CH2)2—O— Cl Cl H Br
    —O—(CH2)2—O— CH3 CH3 4-Cl—C6H4 H
    —O—(CH2)2—O— C2H5 CH3 4-Cl—C6H4 H
    —O—(CH2)2—O— C2H5 C2H5 4-Cl—C6H4 H
    —O—(CH2)2—O— Cl CH3 4-Cl—C6H4 H
    —O—(CH2)2—O— Cl C2H5 4-Cl—C6H4 H
    —O—(CH2)2—O— CH3 H H 4-Cl—C6H4
    —O—(CH2)2—O— CH3 CH3 H 4-Cl—C6H4
    —O—(CH2)2—O— CH3 H CH3 4-Cl—C6H4
    —O—(CH2)2—O— CH3 CH3 CH3 4-Cl—C6H4
    —O—(CH2)2—O— Cl H H 4-Cl—C6H4
    —O—(CH2)2—O— I H H H
    —O—(CH2)2—O— I H CH3 H
    —O—(CH2)2—O— I CH3 H H
    —O—(CH2)2—O— I C2H5 H H
    —O—(CH2)2—O— CH3 H H I
    —O—(CH2)2—O— CH3 H CH3 I
    —O—(CH2)2—O— I CH3 CH3 H
    —O—(CH2)2—O— I C2H5 CH3 H
    —O—(CH2)2—O— I CH3 Cl H
    —O—(CH2)2—O— I C2H5 Cl H
    —O—(CH2)2—O— I Cl CH3 H
    —O—(CH2)2—O— I H CH3 CH3
    —O—(CH2)2—O— CH3 H I H
    —O—(CH2)2—O— C2H5 H I H
    —O—(CH2)2—O— CH3 CH3 I H
    —O—(CH2)2—O— C2H5 CH3 I H
    —O—(CH2)2—O— C2H5 C2H5 I H
    —O—(CH2)2—O— Cl CH3 I H
    —O—(CH2)2—O— Cl C2H5 I H
    —O—(CH2)2—O— CH3 H I CH3
    —O—(CH2)2—O— CH3 CH3 H I
    —O—(CH2)2—O— I H H CH3
    —O—(CH2)2—O— C2H5 H H H
  • Table 2: W, X, Y and Z as stated in Table 1

  • A-B=4′-O—CH2—CHCH3—O—
  • Table 3: W, X, Y and Z as stated in Table 1

  • A-B=4′-O—CHCH3—CHCH3—O—
  • Table 4: W, X, Y and Z as stated in Table 1

  • A-B=4′-O—(CH2)3—O—
  • Table 5: W, X, Y and Z as stated in Table 1

  • A-B=4′-O—CHCH3—(CH2)2—O—
  • Table 6: W, X, Y and Z as stated in Table 1

  • A-B=4′-O—CHCH3—CH2—CHCH3—O—
  • Table 7: W, X, Y and Z as stated in Table 1

  • A-B=−4′O—CH2—C(CH3)2—CH2—O—
  • Table 8: W, X, Y and Z as stated in Table 1
  • Figure US20110190493A1-20110804-C00038
  • Table 9: W, X, Y and Z as stated in Table 1

  • A-B=3′-O—(CH2)2—O—
  • Table 10: W, X, Y and Z as stated in Table 1

  • A-B=3′-O—CH2—CHCH3—O—
  • Table 11: W, X, Y and Z as stated in Table 1

  • A-B=3′-O—CHCH3—CHCH3—O—
  • Table 12: W, X, Y and Z as stated in Table 1

  • A-B=3′-O—(CH2)3—O—
  • Table 13: W, X, Y and Z as stated in Table 1

  • A-B=3′-O—CHCH3—(CH2)2—O—
  • Table 14: W, X, Y and Z as stated in Table 1

  • A-B=3′-O—CHCH3—CH2—CHCH3—O—
  • Table 15: W, X, Y and Z as stated in Table 1

  • A-B=3′-O—CH2—C(CH3)2—CH2—O—
  • Table 16: W, X, Y and Z as stated in Table 1
  • Figure US20110190493A1-20110804-C00039
  • In addition to the compounds mentioned in the Preparation Examples, the following compounds of the formula (I-2-a) may be specifically mentioned:
  • TABLE 17
    (I-2-a)
    Figure US20110190493A1-20110804-C00040
    A-B X W Y Z
    —O—(CH2)2—O— CH3 H H H
    —O—(CH2)2—O— Br H H H
    —O—(CH2)2—O— Cl H H H
    —O—(CH2)2—O— CF3 H H H
    —O—(CH2)2—O— OCH3 H H H
    —O—(CH2)2—O— Br H Cl H
    —O—(CH2)2—O— Cl H Br H
    —O—(CH2)2—O— Cl H Cl H
    —O—(CH2)2—O— Cl H CH3 H
    —O—(CH2)2—O— CH3 H Cl H
    —O—(CH2)2—O— Cl Cl H H
    —O—(CH2)2—O— Cl OCH3 H H
    —O—(CH2)2—O— Cl CH3 H H
    —O—(CH2)2—O— Cl OC2H5 H H
    —O—(CH2)2—O— OCH3 OCH3 H H
    —O—(CH2)2—O— CH3 CH3 H H
    —O—(CH2)2—O— C2H5 CH3 H H
    —O—(CH2)2—O— C2H5 C2H5 H H
    —O—(CH2)2—O— Br CH3 Br H
    —O—(CH2)2—O— Cl CH3 Cl H
    —O—(CH2)2—O— CH3 Br CH3 H
    —O—(CH2)2—O— CH3 Cl CH3 H
    —O—(CH2)2—O— OCH3 CH3 CH3 H
    —O—(CH2)2—O— OC2H5 CH3 CH3 H
    —O—(CH2)2—O— OC3H7 CH3 CH3 H
    —O—(CH2)2—O— CH3 CH3 CH3 H
    —O—(CH2)2—O— Br Br CH3 H
    —O—(CH2)2—O— Cl Cl CH3 H
    —O—(CH2)2—O— CH3 CH3 Br H
    —O—(CH2)2—O— OCH3 C2H5 CH3 H
    —O—(CH2)2—O— OC2H5 C2H5 CH3 H
    —O—(CH2)2—O— CH3 CH3 OCH3 H
    —O—(CH2)2—O— Br Cl CH3 H
    —O—(CH2)2—O— Br CH3 Cl H
    —O—(CH2)2—O— Cl CH3 Br H
    —O—(CH2)2—O— CH3 CH3 Cl H
    —O—(CH2)2—O— C2H5 CH3 CH3 H
    —O—(CH2)2—O— C2H5 C2H5 CH3 H
    —O—(CH2)2—O— C2H5 CH3 C2H5 H
    —O—(CH2)2—O— C2H5 C2H5 C2H5 H
    —O—(CH2)2—O— C2H5 CH3 Cl H
    —O—(CH2)2—O— C2H5 C2H5 Cl H
    —O—(CH2)2—O— C2H5 CH3 Br H
    —O—(CH2)2—O— C2H5 C2H5 Br H
    —O—(CH2)2—O— C2H5 Cl CH3 H
    —O—(CH2)2—O— C2H5 Br CH3 H
    —O—(CH2)2—O— C2H5 Cl Cl H
    —O—(CH2)2—O— C2H5 Br Br H
    —O—(CH2)2—O— C2H5 Cl Br H
    —O—(CH2)2—O— C2H5 Br Cl H
    —O—(CH2)2—O— OCH3 CH3 Cl H
    —O—(CH2)2—O— OCH3 C2H5 Cl H
    —O—(CH2)2—O— OC2H5 CH3 Cl H
    —O—(CH2)2—O— OC2H5 C2H5 Cl H
    —O—(CH2)2—O— Cl OCH3 CH3 H
    —O—(CH2)2—O— Cl OC2H5 CH3 H
    —O—(CH2)2—O— CH3 CH3 Cl H
    —O—(CH2)2—O— Cl H Cl Cl
    —O—(CH2)2—O— CH3 H CH3 CH3
    —O—(CH2)2—O— CH3 H Cl CH3
    —O—(CH2)2—O— Br H Cl CH3
    —O—(CH2)2—O— Br H CH3 CH3
    —O—(CH2)2—O— Cl H Br CH3
    —O—(CH2)2—O— Cl H Cl CH3
    —O—(CH2)2—O— CH3 H Br CH3
    —O—(CH2)2—O— Cl H CH3 Cl
    —O—(CH2)2—O— CH3 H H CH3
    —O—(CH2)2—O— Cl H H CH3
    —O—(CH2)2—O— Br H H CH3
    —O—(CH2)2—O— CH3 H H Cl
    —O—(CH2)2—O— CH3 H H Br
    —O—(CH2)2—O— CH3 CH3 CH3 CH3
    —O—(CH2)2—O— CH3 CH3 CH3 F
    —O—(CH2)2—O— CH3 CH3 CH3 Cl
    —O—(CH2)2—O— CH3 CH3 CH3 Br
    —O—(CH2)2—O— CH3 CH3 H Cl
    —O—(CH2)2—O— CH3 CH3 H Br
    —O—(CH2)2—O— Cl Cl H Br
    —O—(CH2)2—O— CH3 CH3 4-Cl—C6H4 H
    —O—(CH2)2—O— C2H5 CH3 4-Cl—C6H4 H
    —O—(CH2)2—O— C2H5 C2H5 4-Cl—C6H4 H
    —O—(CH2)2—O— Cl CH3 4-Cl—C6H4 H
    —O—(CH2)2—O— Cl C2H5 4-Cl—C6H4 H
    —O—(CH2)2—O— CH3 H H 4-Cl—C6H4
    —O—(CH2)2—O— CH3 CH3 H 4-Cl—C6H4
    —O—(CH2)2—O— CH3 H CH3 4-Cl—C6H4
    —O—(CH2)2—O— CH3 CH3 CH3 4-Cl—C6H4
    —O—(CH2)2—O— Cl H H 4-Cl—C6H4
    —O—(CH2)2—O— I H H H
    —O—(CH2)2—O— I H CH3 H
    —O—(CH2)2—O— I CH3 H H
    —O—(CH2)2—O— I C2H5 H H
    —O—(CH2)2—O— CH3 H H I
    —O—(CH2)2—O— CH3 H CH3 I
    —O—(CH2)2—O— I CH3 CH3 H
    —O—(CH2)2—O— I C2H5 CH3 H
    —O—(CH2)2—O— I CH3 Cl H
    —O—(CH2)2—O— I C2H5 Cl H
    —O—(CH2)2—O— I Cl CH3 H
    —O—(CH2)2—O— I H CH3 CH3
    —O—(CH2)2—O— CH3 H I H
    —O—(CH2)2—O— C2H5 H I H
    —O—(CH2)2—O— CH3 CH3 I H
    —O—(CH2)2—O— C2H5 CH3 I H
    —O—(CH2)2—O— C2H5 C2H5 I H
    —O—(CH2)2—O— Cl CH3 I H
    —O—(CH2)2—O— Cl C2H5 I H
    —O—(CH2)2—O— CH3 H I CH3
    —O—(CH2)2—O— CH3 CH3 H I
    —O—(CH2)2—O— I H H CH3
  • Table 18: W, X, Y and Z as stated in Table 17

  • A-B=4′-O—CH2—CHCH3—O—
  • Table 19: W, X, Y and Z as stated in Table 17

  • A-B=4′-O—CHCH3—CHCH3—O—
  • Table 20: W, X, Y and Z as stated in Table 17

  • A-B=4′-O—(CH2)3—O—
  • Table 21: W, X, Y and Z as stated in Table 17

  • A-B=4′-O—CHCH3—(CH2)2—O—
  • Table 22: W, X, Y and Z as stated in Table 17

  • A-B=4′-O—CHCH3—CH2—CHCH3—O—
  • Table 23: W, X, Y and Z as stated in Table 17

  • A-B=4′-O—CH2—C(CH3)2—CH2—O—
  • Table 24: W, X, Y and Z as stated in Table 17
  • Figure US20110190493A1-20110804-C00041
  • Table 25: W, X, Y and Z as stated in Table 17

  • A-B=3′-O—(CH2)2—O—
  • Table 26: W, X, Y and Z as stated in Table 17

  • A-B=3′-O—CH2—CHCH3—O—
  • Table 27: W, X, Y and Z as stated in Table 17

  • A-B=3′-O—CHCH3—CHCH3—O—
  • Table 28: W, X, Y and Z as stated in Table 17

  • A-B=3′-O—(CH2)3—O—
  • Table 29: W, X, Y and Z as stated in Table 17

  • A-B=3′-O—CHCH3—(CH2)2—O—
  • Table 30: W, X, Y and Z as stated in Table 17

  • A-B=3′-O—CHCH3—CH2—CHCH3—O—
  • Table 31: W, X, Y and Z as stated in Table 17

  • A-B=3′-O—CH2—C(CH3)2—CH2—O—
  • Table 32: W, X, Y and Z as stated in Table 17
  • Figure US20110190493A1-20110804-C00042
  • Preferred definitions of the groups listed above in connection with the crop plant compatibility-improving compounds (“herbicide safeners”) of the formulae (IIa), (IIb), (IIc), (IId) and (IIe) are defined below.
    • m preferably represents the numbers 0, 1, 2, 3 or 4.
    • A1 preferably represents one of the divalent heterocyclic groupings shown below
  • Figure US20110190493A1-20110804-C00043
    • n preferably represents the numbers 0, 1, 2, 3 or 4.
    • A2 preferably represents in each case optionally methyl-, ethyl-, methoxycarbonyl- or ethoxycarbonyl- or allyloxycarbonyl-substituted methylene or ethylene.
    • R14 preferably represents hydroxyl, mercapto, amino, methoxy, ethoxy, n- or i-propoxy, n-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, s- or t-butylamino, dimethylamino or diethylamino.
    • R15 preferably represents hydroxyl, mercapto, amino, methoxy, ethoxy, n- or i-propoxy, n-, s- or t-butoxy, 1-methylhexyloxy, allyloxy, 1-allyloxymethylethoxy, methylthio, ethylthio, n- or i-propylthio, n-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, s- or t-butylamino, dimethylamino or diethylamino.
    • R16 preferably represents in each case optionally fluorine-, chlorine-, and/or bromine-substituted methyl, ethyl, n- or i-propyl.
    • R17 preferably represents hydrogen, in each case optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, propenyl, butenyl, propynyl or butynyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, dioxolanylmethyl, furyl, furylmethyl, thienyl, thiazolyl, piperidinyl, or optionally fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, s- or t-butyl-substituted phenyl.
    • R18 preferably represents hydrogen, in each case optionally fluorine- and/or chlorine-substituted methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, propenyl, butenyl, propynyl or butynyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, dioxolanylmethyl, furyl, furylmethyl, thienyl, thiazolyl, piperidinyl, or optionally fluorine-, chlorine-, methyl-, ethyl-, n- or i-propyl-, n-, s- or t-butyl-substituted phenyl, or together with R17 represents one of the radicals —CH2—O—CH2—CH2— and —CH2—CH2—O—CH2—CH2— which are optionally substituted by methyl, ethyl, furyl, phenyl, a fused benzene ring or by two substituents which, together with the C atom to which they are attached, form a 5- or 6-membered carbocycle.
    • R19 preferably represents hydrogen, cyano, fluorine, chlorine, bromine, or represents in each case optionally fluorine-, chlorine- and/or bromine-substituted methyl, ethyl, n- or i-propyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl.
    • R20 preferably represents hydrogen, optionally hydroxyl-, cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methyl, ethyl, n- or i-propyl, n-, s- or t-butyl.
    • R21 preferably represents hydrogen, cyano, fluorine, chlorine, bromine, or represents in each case optionally fluorine-, chlorine- and/or bromine-substituted methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl.
    • X1 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.
    • X2 preferably represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
    • X3 preferably represents hydrogen, nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
    • t preferably represents the numbers 0, 1, 2, 3 or 4.
    • v preferably represents the numbers 0, 1, 2, or 3.
    • R22 preferably represents hydrogen, methyl, ethyl, n- or i-propyl.
    • R23 preferably represents hydrogen, methyl, ethyl, n- or i-propyl.
    • R24 preferably represents hydrogen, in each case optionally cyano-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, dimethylamino or diethylamino, or in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino or cyclohexylamino.
    • R25 preferably represents hydrogen, in each case optionally cyano-, hydroxyl-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, in each case optionally cyano-, fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propynyl or butynyl, or in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
    • R26 preferably represents hydrogen, in each case optionally cyano-, hydroxyl-, fluorine-, chlorine-, methoxy-, ethoxy-, n- or i-propoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, in each case optionally cyano-, fluorine-, chlorine- or bromine-substituted propenyl, butenyl, propynyl or butynyl, in each case optionally cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-substituted cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or optionally nitro-, cyano-, fluorine-, chlorine-, bromine-, methyl-, ethyl-, n- or i-propyl-, n-, s- or t-butyl-, trifluoromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy- or trifluoromethoxy-substituted phenyl, or together with R25 represents in each case optionally methyl- or ethyl-substituted butane-1,4-diyl (trimethylene), pentane-1,5-diyl, 1-oxabutane-1,4-diyl or 3-oxapentane-1,5-diyl.
    • X4 preferably represents nitro, cyano, carboxyl, carbamoyl, formyl, sulphamoyl, hydroxyl, amino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
    • X5 preferably represents nitro, cyano, carboxyl, carbamoyl, formyl, sulphamoyl, hydroxyl, amino, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy or trifluoromethoxy.
  • Examples of the compounds of the formula (IIa) which are very particularly preferred as herbicide safeners according to the invention are listed in the table below.
  • TABLE
    Examples of the compounds of the formula (IIa)
    (IIa)
    Figure US20110190493A1-20110804-C00044
    Example (Positions)
    No. (X1)m A1 R14
    IIa-1 (2) Cl, (4) Cl
    Figure US20110190493A1-20110804-C00045
         		OCH3
    IIa-2 (2) Cl, (4) Cl
    Figure US20110190493A1-20110804-C00046
         		OCH3
    IIa-3 (2) Cl, (4) Cl
    Figure US20110190493A1-20110804-C00047
         		OC2H5
    IIa-4 (2) Cl, (4) Cl
    Figure US20110190493A1-20110804-C00048
         		OC2H5
    IIa-5 (2) Cl
    Figure US20110190493A1-20110804-C00049
         		OCH3
    IIa-6 (2) Cl, (4) Cl
    Figure US20110190493A1-20110804-C00050
         		OCH3
    IIa-7 (2) F
    Figure US20110190493A1-20110804-C00051
         		OCH3
    IIa-8 (2) F
    Figure US20110190493A1-20110804-C00052
         		OCH3
    IIa-9 (2) Cl, (4) Cl
    Figure US20110190493A1-20110804-C00053
         		OC2H5
    IIa-10 (2) Cl, (4) CF3
    Figure US20110190493A1-20110804-C00054
         		OCH3
    IIa-11 (2) Cl
    Figure US20110190493A1-20110804-C00055
         		OCH3
    IIa-12 —
    Figure US20110190493A1-20110804-C00056
         		OC2H5
    IIa-13 (2) Cl, (4) Cl
    Figure US20110190493A1-20110804-C00057
         		OC2H5
    IIa-14 (2) Cl, (4) Cl
    Figure US20110190493A1-20110804-C00058
         		OC2H5
    IIa-15 (2) Cl, (4) Cl
    Figure US20110190493A1-20110804-C00059
         		OC2H5
    IIa-16 (2) Cl, (4) Cl
    Figure US20110190493A1-20110804-C00060
         		OC2H5
    IIa-17 (2) Cl, (4) Cl
    Figure US20110190493A1-20110804-C00061
         		OC2H5
    IIa-18 —
    Figure US20110190493A1-20110804-C00062
         		OH
  • Examples of the compounds of the formula (IIb) which are very particularly preferred as herbicide safeners according to the invention are listed in the table below.
  • Figure US20110190493A1-20110804-C00063
  • TABLE
    Examples of the compounds of the formula (IIb)
    Example (Position) (Position)
    No. X2 X3 A2 R15
    IIb-1 (5) Cl — CH2 OH
    IIb-2 (5) Cl — CH2 OCH3
    IIb-3 (5) Cl — CH2 OC2H5
    IIb-4 (5) Cl — CH2 OC3H7-n
    IIb-5 (5) Cl — CH2 OC3H7-i
    IIb-6 (5) Cl — CH2 OC4H9-n
    IIb-7 (5) Cl — CH2 OCH(CH3)C5H11-n
    IIb-8 (5) Cl (2) F CH2 OH
    IIb-9 (5) Cl (2) Cl CH2 OH
    IIb-10 (5) Cl — CH2 OCH2CH═CH2
    IIb-11 (5) Cl — CH2 OC4H9-i
    IIb-12 (5) Cl — CH2
    Figure US20110190493A1-20110804-C00064
    IIb-13 (5) Cl —
    Figure US20110190493A1-20110804-C00065
         		OCH2CH═CH2
    IIb-14 (5) Cl —
    Figure US20110190493A1-20110804-C00066
         		OC2H5
    IIb-15 (5) Cl —
    Figure US20110190493A1-20110804-C00067
         		OCH3
  • Examples of the compounds of the formula (IIc) which are very particularly preferred as herbicide safeners according to the invention are listed in the table below.
  • Figure US20110190493A1-20110804-C00068
  • TABLE
    Examples of the compounds of the formula (IIc)
    Example
    No. R16 N(R17, R18)
    IIc-1 CHCl2 N(CH2CH═CH2)2
    IIc-2 CHCl2
    Figure US20110190493A1-20110804-C00069
    IIc-3 CHCl2
    Figure US20110190493A1-20110804-C00070
    IIc-4 CHCl2
    Figure US20110190493A1-20110804-C00071
    IIc-5 CHCl2
    Figure US20110190493A1-20110804-C00072
    IIc-6 CHCl2
    Figure US20110190493A1-20110804-C00073
    IIc-7 CHCl2
    Figure US20110190493A1-20110804-C00074
  • Examples of the compounds of the formula (IId) which are very particularly preferred as herbicide safeners according to the invention are listed in the table below.
  • Figure US20110190493A1-20110804-C00075
  • TABLE
    Examples of the compounds of the formula (IId)
    Example (Positions) (Positions)
    No. R22 R23 R24 (X4)t (X5)v
    IId-1 H H CH3 (2) OCH3 —
    IId-2 H H C2H5 (2) OCH3 —
    IId-3 H H C3H7-n (2) OCH3 —
    IId-4 H H C3H7-i (2) OCH3 —
    IId-5 H H
    Figure US20110190493A1-20110804-C00076
         		(2) OCH3 —
    IId-6 H H CH3 (2) OCH3 —
    (5) CH3
    IId-7 H H C2H5 (2) OCH3 —
    (5) CH3
    IId-8 H H C3H7-n (2) OCH3 —
    (5) CH3
    IId-9 H H C3H7-i (2) OCH3 —
    (5) CH3
    IId-10 H H
    Figure US20110190493A1-20110804-C00077
         		(2) OCH3 (5) CH3 —
    IId-11 H H OCH3 (2) OCH3 —
    (5) CH3
    IId-12 H H OC2H5 (2) OCH3 —
    (5) CH3
    IId-13 H H OC3H7-i (2) OCH3 —
    (5) CH3
    IId-14 H H SCH3 (2) OCH3 —
    (5) CH3
    IId-15 H H SC2H5 (2) OCH3 —
    (5) CH3
    IId-16 H H SC3H7-i (2) OCH3 —
    (5) CH3
    IId-17 H H NHCH3 (2) OCH3 —
    (5) CH3
    IId-18 H H NHC2H5 (2) OCH3 —
    (5) CH3
    IId-19 H H NHC3H7-i (2) OCH3 —
    (5) CH3
    IId-20 H H
    Figure US20110190493A1-20110804-C00078
         		(2) OCH3 (5) CH3 —
    IId-21 H H NHCH3 (2) OCH3 —
    IId-22 H H NHC3H7-i (2) OCH3 —
    IId-23 H H N(CH3)2 (2) OCH3 —
    IId-24 H H N(CH3)2 (3) CH3 —
    (4) CH3
    IId-25 H H CH2—O—CH3 (2) OCH3 —
  • Examples of the compounds of the formula (Ile) which are very particularly preferred as herbicide safeners according to the invention are listed in the table below.
  • Figure US20110190493A1-20110804-C00079
  • TABLE
    Examples of the compounds of the formula (IIe)
    Example (Positions) (Positions)
    No. R22 R25 R26 (X4)t (X5)v
    IIe-1 H H CH3 (2) OCH3 —
    IIe-2 H H C2H5 (2) OCH3 —
    IIe-3 H H C3H7-n (2) OCH3 —
    IIe-4 H H C3H7-i (2) OCH3
    IIe-5 H H
    Figure US20110190493A1-20110804-C00080
         		(2) OCH3 —
    IIe-6 H CH3 CH3 (2) OCH3 —
    IIe-7 H H CH3 (2) OCH3 —
    (5) CH3
    IIe-8 H H C2H5 (2) OCH3 —
    (5) CH3
    IIe-9 H H C3H7-n (2) OCH3 —
    (5) CH3
    IIe-10 H H C3H7-i (2) OCH3 —
    (5) CH3
    IIe-11 H H
    Figure US20110190493A1-20110804-C00081
         		(2) OCH3 (5) CH3 —
    IIe-12 H CH3 CH3 (2) OCH3 —
    (5) CH3
  • Most preferred as crop plant compatibility-improving compound [component (b′)] are cloquintocetmexyl, fenchlorazole-ethyl, isoxadifen-ethyl, mefenpyr-diethyl, furilazole, fenclorim, cumyluron, dymron, dimepiperate and the compounds IIe-5 and IIe-11, and particular emphasis is given to cloquintocet-mexyl and mefenpyr-diethyl.
  • The compounds of the general formula (IIa) to be used as safeners according to the invention are known and/or can be prepared by processes known per se (cf. WO-A-91/07874, WO-A-95/07897).
  • The compounds of the general formula (IIb) to be used as safeners according to the invention are known and/or can be prepared by processes known per se (cf. EP-A-191736).
  • The compounds of the general formula (IIc) to be used as safeners according to the invention are known and/or can be prepared by processes known per se (cf. DE-A-2218097, DE-A-2350547).
  • The compounds of the general formula (IId) to be used as safeners according to the invention are known and/or can be prepared by processes known per se (cf. DE-A-19621522/U.S. Pat. No. 6,235,680).
  • The compounds of the general formula (IIe) to be used as safeners according to the invention are known and can be prepared by processes known per se (cf. WO-A-99/66795/U.S. Pat. No. 6,251,827).
  • Examples of the selective herbicidal combinations according to the invention comprising in each case one active compound of the formula (I) and one of the safeners defined above are listed in the table below.
  • TABLE
    Examples of the combinations according to the invention
    Active compounds of the formula (I) Safeners
    I-1-a cloquintocet-mexyl
    I-1-a fenchlorazole-ethyl
    I-1-a isoxadifen-ethyl
    I-1-a mefenpyr-diethyl
    I-1-a furilazole
    I-1-a fenclorim
    I-1-a cumyluron
    I-1-a daimuron/dymron
    I-1-a dimepiperate
    I-1-a IIe-11
    I-1-a IIe-5
    I-1-b cloquintocet-mexyl
    I-1-b fenchlorazole-ethyl
    I-1-b isoxadifen-ethyl
    I-1-b mefenpyr-diethyl
    I-1-b furilazole
    I-1-b fenclorim
    I-1-b cumyluron
    I-1-b daimuron/dymron
    I-1-b dimepiperate
    I-1-b IIe-11
    I-1-b IIe-5
    I-1-c cloquintocet-mexyl
    I-1-c fenchlorazole-ethyl
    I-1-c isoxadifen-ethyl
    I-1-c mefenpyr-diethyl
    I-1-c furilazole
    I-1-c fenclorim
    I-1-c cumyluron
    I-1-c daimuron/dymron
    I-1-c dimepiperate
    I-1-c IIe-5
    I-1-c IIe-11
    I-1-d cloquintocet-mexyl
    I-1-d fenchlorazole-ethyl
    I-1-d isoxadifen-ethyl
    I-1-d mefenpyr-diethyl
    I-1-d furilazole
    I-1-d fenclorim
    I-1-d cumyluron
    I-1-d daimuron/dymron
    I-1-d dimepiperate
    I-1-d IIe-11
    I-1-d IIe-5
    I-1-e cloquintocet-mexyl
    I-1-e fenchlorazole-ethyl
    I-1-e isoxadifen-ethyl
    I-1-e mefenpyr-diethyl
    I-1-e furilazole
    I-1-e fenclorim
    I-1-e cumyluron
    I-1-e daimuron/dymron
    I-1-e dimepiperate
    I-1-e IIe-5
    I-1-e IIe-11
    I-1-f cloquintocet-mexyl
    I-1-f fenchlorazole-ethyl
    I-1-f isoxadifen-ethyl
    I-1-f mefenpyr-diethyl
    I-1-f furilazole
    I-1-f fenclorim
    I-1-f cumyluron
    I-1-f daimuron/dymron
    I-1-f dimepiperate
    I-1-f IIe-5
    I-1-f IIe-11
    I-1-g cloquintocet-mexyl
    I-1-g fenchlorazole-ethyl
    I-1-g isoxadifen-ethyl
    I-1-g mefenpyr-diethyl
    I-1-g furilazole
    I-1-g fenclorim
    I-1-g cumyluron
    I-1-g daimuron/dymron
    I-1-g dimepiperate
    I-1-g IIe-5
    I-1-g IIe-11
    I-2-a cloquintocet-mexyl
    I-2-a fenchlorazole-ethyl
    I-2-a isoxadifen-ethyl
    I-2-a mefenpyr-diethyl
    I-2-a furilazole
    I-2-a fenclorim
    I-2-a cumyluron
    I-2-a daimuron/dymron
    I-2-a dimepiperate
    I-2-a IIe-5
    I-2-a IIe-11
    I-2-b cloquintocet-mexyl
    I-2-b fenchlorazole-ethyl
    I-2-b isoxadifen-ethyl
    I-2-b mefenpyr-diethyl
    I-2-b furilazole
    I-2-b fenclorim
    I-2-b cumyluron
    I-2-b daimuron/dymron
    I-2-b dimepiperate
    I-2-b IIe-5
    I-2-b IIe-11
    I-2-c cloquintocet-mexyl
    I-2-c fenchlorazole-ethyl
    I-2-c isoxadifen-ethyl
    I-2-c mefenpyr-diethyl
    I-2-c furilazole
    I-2-c fenclorim
    I-2-c cumyluron
    I-2-c daimuron/dymron
    I-2-c dimepiperate
    I-2-c IIe-5
    I-2-c IIe-11
    I-2-d cloquintocet-mexyl
    I-2-d fenchlorazole-ethyl
    I-2-d isoxadifen-ethyl
    I-2-d mefenpyr-diethyl
    I-2-d furilazole
    I-2-d fenclorim
    I-2-d cumyluron
    I-2-d daimuron/dymron
    I-2-d dimepiperate
    I-2-d IIe-5
    I-2-d IIe-11
    I-2-e cloquintocet-mexyl
    I-2-e fenchlorazole-ethyl
    I-2-e isoxadifen-ethyl
    I-2-e mefenpyr-diethyl
    I-2-e furilazole
    I-2-e fenclorim
    I-2-e cumyluron
    I-2-e daimuron/dymron
    I-2-e dimepiperate
    I-2-e IIe-5
    I-2-e IIe-11
    I-2-f cloquintocet-mexyl
    I-2-f fenchlorazole-ethyl
    I-2-f isoxadifen-ethyl
    I-2-f mefenpyr-diethyl
    I-2-f furilazole
    I-2-f fenclorim
    I-2-f cumyluron
    I-2-f daimuron/dymron
    I-2-f dimepiperate
    I-2-f IIe-5
    I-2-f IIe-11
    I-2-g cloquintocet-mexyl
    I-2-g fenchlorazole-ethyl
    I-2-g isoxadifen-ethyl
    I-2-g mefenpyr-diethyl
    I-2-g furilazole
    I-2-g fenclorim
    I-2-g cumyluron
    I-2-g daimuron/dymron
    I-2-g dimepiperate
    I-2-g IIe-5
    I-2-g IIe-11
  • It has now surprisingly been found that the above-defined active-compound combinations of compounds of the general formula (I) and safeners (antidotes) from the group (b′) set out above combine very good useful plant tolerance with a high herbicidal activity and can be used in various crops, in particular in cereals (especially wheat), but also in soya, potatoes, maize and rice, for selective weed control.
  • In this context it is considered surprising that, from a multiplicity of known safeners or antidotes capable of antagonizing the damaging effect of a herbicide on the crop plants, it is specifically the compounds of group (b′) set out above which are suitable for compensating—almost completely—the damaging effect of substituted cyclic ketoenols on the crop plants, without at the same time having any critical adverse effect on the herbicidal activity against the weeds.
  • Emphasis may be given here to the particularly advantageous effect of the particularly preferred and most preferred combination partners from group (b′), particularly with regard to the gentle treatment of cereal plants, such as wheat, barley and rye, for example, but also maize and rice, as crop plants.
  • Using, for example, according to process (A) ethyl N-[(4-chloro-2,6-dimethyl)phenylacetyl]-1-amino-4,4′-propylenedioxycyclohexanecarboxylate as starting material, the course of the process according to the invention can be represented by the reaction scheme below:
  • Figure US20110190493A1-20110804-C00082
  • Using, for example, according to process (B) ethyl O-[(2-chloro-6-methyl)phenylacetyl]-1-hydroxy-4,4′-ethylenedioxycyclohexanecarboxylate, the course of the process according to the invention can be represented by the reaction scheme below:
  • Figure US20110190493A1-20110804-C00083
  • Using, for example, according to process (Cα) 8,8′-ethylenedioxy-3-[(4-chloro-2,6-dimethyl)phenyl]-1-azaspiro[4,5]decane-2,4-dione and pivaloyl chloride as starting materials, the course of the process according to the invention can be represented by the reaction scheme below:
  • Figure US20110190493A1-20110804-C00084
  • Using, for example, according to process (C) (variant β) 8,8′-propylenedioxy-3-[(2,4-dichloro)phenyl]-1-oxaspiro-[4,5]-decane-2,4-dione and acetic anhydride as starting materials, the course of the process according to the invention can be represented by the reaction scheme below:
  • Figure US20110190493A1-20110804-C00085
  • Using, for example, according to process (D) 8,8′-propylenedioxy-3-[2,4-dichloro-6-methyl)phenyl]-1-azaspiro[4,5]decane-2,4-dione and ethyl chloroformate as starting materials, the course of the process according to the invention can be represented by the reaction scheme below:
  • Figure US20110190493A1-20110804-C00086
  • Using, for example, according to process (E) 8,8′-ethylenedioxy-3-[(2,4,6-trimethyl)phenyl]-1-oxaspiro[4,5]decane-2,4-dione and methyl chloromonothioformate as starting materials, the course of the reaction can be represented as follows:
  • Figure US20110190493A1-20110804-C00087
  • Using, for example, according to process (F) 8,8′-propylenedioxy-3-[(2,4,6-trimethyl)phenyl]-1-azaspiro[4,5]decane-2,4-dione and methanesulphonyl chloride as starting materials, the course of the reaction can be represented by the reaction scheme below:
  • Figure US20110190493A1-20110804-C00088
  • Using, for example, according to process (G) 8,8′-propylenedioxy-3-[(2,4-dichloro-6-methyl)phenyl]-1-oxaspiro[4,5]decane-2,4-dione and 2,2,2-trifluoroethyl methanethiophosphonyl chloride as starting materials, the course of the reaction can be represented by the reaction scheme below:
  • Figure US20110190493A1-20110804-C00089
  • Using, for example, according to process (H) 8,8′-ethylenedioxy-3-[(2,3,4,6-tetramethyl)phenyl]-1-azaspiro[4,5]decane-2,4-dione and NaOH as components, the course of the process according to the invention can be represented by the reaction scheme below:
  • Figure US20110190493A1-20110804-C00090
  • Using, for example, according to process (I) (variant α) 8,8′-ethylenedioxy-3-[(2,4,5-trimethyl)phenyl]-1-oxaspiro[4,5]decane-2,4-dione and ethyl isocyanate as starting materials, the course of the reaction can be represented by the reaction scheme below:
  • Figure US20110190493A1-20110804-C00091
  • Using, for example, according to process (I) (variant β) 8,8′-ethylenedioxy-3-[(2,4,6-trimethyl)phenyl]-1-azaspiro[4,5]decane-2,4-dione and dimethylcarbamoyl chloride as starting materials, the course of the reaction can be represented by the scheme below:
  • Figure US20110190493A1-20110804-C00092
  • The compounds, required as starting materials in the process (A) according to the invention, of the formula (II)
  • Figure US20110190493A1-20110804-C00093
  • in which
    • A, B, Q1, Q2, W, X, Y, Z and R8 are as defined above
      are novel.
  • The acylamino acid esters of the formula (II) are obtained, for example, when amino acid derivatives of the formula (XVI)
  • Figure US20110190493A1-20110804-C00094
  • in which
    • A, B, Q1 and Q2 and R8 are as defined above
      are acylated with substituted phenylacetic acid derivatives of the formula (XVII)
  • Figure US20110190493A1-20110804-C00095
  • in which
    • W, X, Y and Z are as defined above and
    • U represents a leaving group introduced by reagents for activating carboxylic acids, such as carbonyldiimidazole, carbodiimides (such as, for example, dicyclohexylcarbodiimide), phosphorylating agents (such as, for example, POCl3, BOP-Cl), halogenating agents, such as, for example, thionyl chloride, oxalyl chloride, phosgene or chloroformic esters
      (Chem. Reviews 52, 237-416 (1953); Bhattacharya, Indian J. Chem. 6, 341-5, 1968)
      or when acylamino acids of the formula (XVIII)
  • Figure US20110190493A1-20110804-C00096
  • in which
    • A, B, Q1, Q2, W, X, Y and Z are as defined above,
      are esterified (Chem. Ind. (London) 1568 (1968)).
  • The compounds of the formula (XVIII)
  • Figure US20110190493A1-20110804-C00097
  • in which
    • A, B, Q1, Q2, W, X, Y and Z are as defined above,
      are novel.
  • The compounds of the formula (XVIII) are obtained, for example, when 1-aminocyclohexane-carboxylic acids of the formula (XIX)
  • Figure US20110190493A1-20110804-C00098
  • in which
    • A, B, Q1 and Q2 are as defined above
      are acylated with substituted phenylacetic acid derivatives of the formula (XVII)
  • Figure US20110190493A1-20110804-C00099
  • in which
    • U, W, X, Y and Z are as defined above,
      for example according to Schotten-Baumann (Organikum, VEB Deutscher Verlag der Wissen-schaften, Berlin 1977, p. 505).
  • Some of the compounds of the formula (XVII) are known, and/or they can be prepared by the known processes described in the laid-open publications cited at the outset.
  • Some of the compounds of the formulae (XVI) and (XIX) are novel, and they can be prepared by known processes (see, for example, Compagnon, Ann. Chim. (Paris) [14] 5, pp. 11-22, 23-27 (1970), L. Munday, J. Chem. Soc. 4372 (1961); J. T. Eward, C. Jitrangeri, Can. J. Chem. 53, 3339 (1975)).
  • Furthermore, the starting materials, used in the above process (A), of the formula (II)
  • Figure US20110190493A1-20110804-C00100
  • in which
    • A, B, Q1, Q2, W, X, Y, Z and R8 are as defined above,
      can be prepared by reacting 1-aminocyclohexanecarbonitriles of the formula (XX)
  • Figure US20110190493A1-20110804-C00101
  • in which
    • A, B, Q1 and Q2 are as defined above,
      with substituted phenylacetic acid derivatives of the formula (XVII)
  • Figure US20110190493A1-20110804-C00102
  • in which
    • U, W, X, Y and Z are as defined above,
      to give compounds of the formula (XXI)
  • Figure US20110190493A1-20110804-C00103
  • in which
    • A, B, Q1, Q2, W, X, Y and Z are as defined above,
      and then subjecting these to an acidic alcoholysis.
  • The compounds of the formula (XXI) are likewise novel. Some of the compounds of the formula (XX) are novel and can be prepared, for example, as described in EP-A-595 130.
  • The compounds, required as starting materials in the process (B) according to the invention, of the formula (III)
  • Figure US20110190493A1-20110804-C00104
  • in which
    • A, B, Q1, Q2, W, X, Y, Z and R8 are as defined above,
      are novel.
  • They can be prepared in a simple manner by methods known in principle.
  • The compounds of the formula (III) obtained, for example, when 1-hydroxycyclohexanecarboxylic esters of the formula (XXII)
  • Figure US20110190493A1-20110804-C00105
  • in which
    • A, B, Q1, Q2 and R8 are as defined above,
      are acylated with substituted phenylacetic acid derivatives of the formula (XVII)
  • Figure US20110190493A1-20110804-C00106
  • in which
    • U, W, X, Y and Z are as defined above,
      (Chem. Reviews 52, 237-416 (1953)).
  • The 1-hydroxy-3-alkoxycyclohexylcarboxylic esters of the formula (XXII) are novel. They are obtained, for example, when substituted 1-hydroxy-4,4′-alkylidenyldioxycyclohexanecarbonitriles are reacted with alcohols in the presence of acids, for example according to Pinner, and the 1-hydroxy-4-oxocyclohexanecarboxylic esters formed, which are known from WO 99/16748 (Ex. XXI-1), are re-ketalized with diols. The cyanohydrin is obtained, for example, by reacting 4,4′-alkylidenyldioxycyclohexan-1-ones with hydrocyanic acid (see WO 99/16748).
  • The acid halides of the formula (IV), carboxylic anhydrides of the formula (V), chloroformic esters or chloroformic thioesters of the formula (VI), chloromonothioformic esters or chlorodithioformic esters of the formula (VII), sulphonyl chlorides of the formula (VIII), phosphorus compounds of the formula (IX) and metal hydroxides, metal alkoxides or amines of the formulae (X) and (XI) and isocyanates of the formula (XII) and carbamoyl chlorides of the formula (XIII) and diols of the formula (XV) furthermore required as starting materials for carrying out the processes (C), (D), (E), (F), (G), (H), (I) and (J) according to the invention are generally known compounds of organic or inorganic chemistry. Some of the compounds of the formula (XIV) are known from WO 99/16748.
  • Additionally, the compounds of the formula (XVII) are known from the patent applications cited at the outset, and/or they can be prepared by the methods given therein.
  • The process (A) is characterized in that compounds of the formula (II) in which A, B, Q1, Q2, W, X, Y, Z and R8 are as defined above are subjected to an intramolecular condensation in the presence of a diluent and in the presence of a base.
  • Suitable diluents for use in the process (A) according to the invention are all organic solvents which are inert towards the reaction participants. Preference is given to using hydrocarbons, such as toluene and xylene, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, moreover polar solvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide and N-methylpyrrolidone, and also alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.
  • Suitable bases (deprotonating agents) for carrying out the process (A) according to the invention are all customary proton acceptors. Preference is given to using alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which can also be used in the presence of phase-transfer catalysts, such as, for example, triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464 (=methyltrialkyl(C8-C10)ammonium chloride) or TDA 1 (=tris(methoxyethoxyethyl)amine). It is furthermore possible to use alkali metals, such as sodium or potassium. Alkali metal or alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride and calcium hydride, and additionally also alkali metal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, can be employed, too.
  • When carrying out the process (A) according to the invention, the reaction temperature can be varied within a relatively wide range. In general, the process is carried out at temperatures between −75° C. and 200° C., preferably between −50° C. and 150° C.
  • The process (A) according to the invention is generally carried out under atmospheric pressure.
  • When carrying out the process (A) according to the invention, the reaction component of the formula (II) and the deprotonating base are generally employed in equimolar to about doubly equimolar amounts. However, it is also possible to use a relatively large excess (up to 3 mol) of one component or the other.
  • The process (B) is characterized in that compounds of the formula (III) in which A, B, Q1, Q2, W, X, Y, Z and R8 are as defined above are condensed intramolecularly in the presence of a diluent and in the presence of a base.
  • Suitable diluents for use in the process (B) according to the invention are all organic solvents which are inert towards the reaction participants. Preference is given to using hydrocarbons, such as toluene and xylene, furthermore ethers, such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, moreover polar solvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide and N-methylpyrrolidone. It is furthermore possible to use alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tert-butanol.
  • Suitable bases (deprotonating agents) for carrying out the process (B) according to the invention are all customary proton acceptors. Preference is given to using alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which can also be used in the presence of phase-transfer catalysts, such as, for example, triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464 (=methyltrialkyl(C8-C10)ammonium chloride) or TDA 1 (=tris(methoxyethoxyethyl)amine). It is furthermore possible to use alkali metals, such as sodium or potassium. Alkali metal or alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride and calcium hydride, and additionally also alkali metal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, can be employed, too.
  • When carrying out the process (B) according to the invention, the reaction temperature can be varied within a relatively wide range. In general, the process is carried out at temperatures between −75° C. and 200° C., preferably between −50° C. and 150° C.
  • The process (B) according to the invention is generally carried out under atmospheric pressure.
  • When carrying out the process (B) according to the invention, the reaction component of the formula (II) and the deprotonating base are generally employed in equimolar to about doubly equimolar amounts. However, it is also possible to use a relatively large excess (up to 3 mol) of one component or the other.
  • The process (Cα) is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case reacted with carbonyl halides of the formula (IV), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • Suitable diluents for the process (Cα) according to the invention are all solvents which are inert towards the acid halides. Preference is given to using hydrocarbons, such as benzine, benzene, toluene, xylene and tetralin; furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketones, such as acetone and methylisopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxane, additionally carboxylic esters, such as ethyl acetate, and also strongly polar solvents, such as dimethylformamide, dimethyl sulphoxide and sulpholane. The hydrolytic stability of the acid halide permitting, the reaction may also be carried out in the presence of water.
  • Suitable acid binders for the reaction according to the process (Cα) according to the invention are all customary acid acceptors. Preference is given to using tertiary amines, such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hünig base and N,N-dimethylaniline, furthermore alkaline earth metal oxides, such as magnesium oxide and calcium oxide, moreover alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide.
  • The reaction temperature in the process (Cα) according to the invention can be varied within a relatively wide range. In general, the process is carried out at temperatures between −20° C. and +150° C., preferably between 0° C. and 100° C.
  • When carrying out the process (Cα) according to the invention, the starting materials of the formulae (I-1-a) to (I-2-a) and the carbonyl halide of the formula (IV) are generally each used in approximately equivalent amounts. However, it is also possible to employ a relatively large excess (up to 5 mol) of the carbonyl halide. Work-up is carried out by customary methods.
  • The process (Cβ) is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case reacted with carboxylic anhydrides of the formula (V), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • Suitable diluents for use in the process (Cβ) according to the invention are preferably those diluents which are also preferred when using acid halides. Besides, it is also possible for excess carboxylic anhydride to act simultaneously as diluent.
  • Suitable acid binders for the process (Cβ), which are added, if appropriate, are preferably those acid binders which are also preferred when using acid halides.
  • The reaction temperature in the process (Cβ) according to the invention can be varied within a relatively wide range. In general, the process is carried out at temperatures between −20° C. and +150° C., preferably between 0° C. and 100° C.
  • When carrying out the process (Cβ) according to the invention, the starting materials of the formulae (I-1-a) to (I-2-a) and the carboxylic anhydride of the formula (V) are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess (up to 5 mol) of the carboxylic anhydride. Work-up is carried out by customary methods.
  • In general, diluent and excess carboxylic anhydride and the carboxylic acid formed are removed by distillation or by washing with an organic solvent or with water.
  • The process (D) is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case reacted with chloroformic esters or chloroformic thioesters of the formula (VI), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • Suitable acid binders for the process (D) according to the invention are all customary acid acceptors. Preference is given to using tertiary amines, such as triethylamine, pyridine, DABCO, DBU, DBN, Hünig base and N,N-dimethylaniline, furthermore alkaline earth metal oxides, such as magnesium oxide and calcium oxide, moreover alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide.
  • Suitable diluents for use in the process (D) according to the invention are all solvents which are inert towards the chloroformic esters or chloroformic thioesters. Preference is given to using hydrocarbons, such as benzine, benzene, toluene, xylene and tetralin; furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketones, such as acetone and methyl isopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxane, additionally carboxylic esters, such as ethyl acetate, moreover nitriles, such as acetonitrile, and also strongly polar solvents, such as dimethylformamide, dimethyl sulphoxide and sulpholane.
  • When carrying out the process (D) according to the invention, the reaction temperature can be varied within a relatively wide range. In general, the reaction temperature is between −20° C. and +100° C., preferably between 0° C. and 50° C.
  • Process (D) according to the invention is generally carried out under atmospheric pressure.
  • When carrying out the process (D) according to the invention, the starting materials of the formulae (I-1-a) to (I-2-a) and the appropriate chloroformic ester or chloroformic thioester of the formula (VI) are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess (up to 2 mol) of one component or the other. Work-up is carried out by customary methods. In general, precipitated salts are removed and the reaction mixture that remains is concentrated by removing the diluent under reduced pressure.
  • The process (E) according to the invention is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case reacted with compounds of the formula (VII) in the presence of a diluent and, if appropriate, in the presence of an acid binder.
  • In the preparation process (E), about 1 mol of chloromonothioformic ester or chlorodithioformic ester of the formula (VII) is employed per mole of starting material of the formulae (I-1-a) to (I-2-a), at from 0 to 120° C., preferably from 20 to 60° C.
  • Suitable diluents which are added, if appropriate, are all inert polar organic solvents, such as ethers, amides, sulphones, sulphoxides, and also halogenated alkanes.
  • Preference is given to using dimethyl sulphoxide, tetrahydrofuran, dimethylformamide, ethyl acetate or methylene chloride.
  • If, in a preferred embodiment, the enolate salt of the compounds (I-1-a) to (I-2-a) is prepared by adding strong deprotonating agents, such as, for example, sodium hydride or potassium tert-butoxide, the further addition of acid binders may be dispensed with.
  • Suitable bases for use in the process (E) are all customary proton acceptors. Preference is given to using alkali metal hydrides, alkali metal alkoxides, alkali metal or alkaline earth metal carbonates or bicarbonates or nitrogen bases. Sodium hydride, sodium methoxide, sodium hydroxide, calcium hydroxide, potassium carbonate, sodium bicarbonate, triethylamine, dibenzylamine, diisopropylamine, pyridine, quinoline diazabicyclooctane (DABCO), diazabicyclononene (DBN) and diazabicycloundecene (DBU) may be mentioned by way of example.
  • The reaction can be carried out at atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods.
  • The process (F) according to the invention is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case reacted with sulphonyl chlorides of the formula (VIII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • In the preparation process (F), about 1 mol of sulphonyl chloride of the formula (VIII) is reacted per mole of starting material of the formulae (I-1-a) to (I-2-a), at from −20 to 150° C., preferably from 0 to 70° C.
  • The process (F) is preferably carried out in the presence of a diluent.
  • Suitable diluents are all inert polar organic solvents, such as ethers, amides, ketones, carboxylic esters, nitriles, sulphones, sulphoxides or halogenated hydrocarbons, such as methylene chloride.
  • Preference is given to using dimethyl sulphoxide, tetrahydrofuran, dimethylformamide, ethyl acetate, methylene chloride.
  • If, in a preferred embodiment, the enolate salt of the compounds (I-1-a) to (I-2-a) is prepared by adding strong deprotonating agents (such as, for example, sodium hydride or potassium tert-butoxide), the further addition of acid binders may be dispensed with.
  • If acid binders are used, these may be customary inorganic or organic bases, for example sodium hydride, sodium carbonate, potassium carbonate, pyridine and triethylamine.
  • The reaction can be carried out at atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods.
  • The process (G) according to the invention is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case 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.
  • In the preparation process (G), to obtain compounds of the formulae (I-1-e) to (I-2-e), from 1 to 2, preferably from 1 to 1.3, mol of the phosphorus compound of the formula (IX) are employed per mole of the compounds (I-1-a) to (I-2-a), at temperatures between −40° C. and 150° C., preferably between −10 and 110° C.
  • The process (G) is preferably carried out in the presence of a diluent.
  • Suitable diluents are all inert polar organic solvents, such as ethers, carboxylic esters, halogenated hydrocarbons, ketones, amides, nitriles, sulphones, sulphoxides, etc.
  • Preference is given to using acetonitrile, dimethyl sulphoxide, tetrahydrofuran, dimethylformamide, methylene chloride.
  • Suitable acid binders, which are added, if appropriate, are customary inorganic or organic bases, such as hydroxides, carbonates or amines. Sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine may be mentioned by way of example.
  • The reaction can be carried out at atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods of organic chemistry. The end products are preferably purified by crystallization, chromatographic purification or “incipient distillation”, i.e. removal of the volatile components under reduced pressure.
  • The process (H) is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case reacted with metal hydroxides or metal alkoxides of the formula (X) or amines of the formula (XI), if appropriate in the presence of a diluent.
  • Suitable diluents for use in the process (H) according to the invention are, preferably, ethers, such as tetrahydrofuran, dioxane, diethyl ether, or else alcohols, such as methanol, ethanol, isopropanol, and also water. The process (H) according to the invention is generally carried out under atmospheric pressure. The reaction temperature is generally between −20° C. and 100° C., preferably between 0° C. and 50° C.
  • The process (I) according to the invention is characterized in that compounds of the formulae (I-1-a) to (I-2-a) are in each case reacted with (Iα) compounds of the formula (XII), if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst, or (Iβ) with compounds of the formula (XIII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
  • In the preparation process (Iα), about 1 mol of isocyanate of the formula (XII) is employed per mole of starting material of the formulae (I-1-a) to (I-2-a) at from 0 to 100° C., preferably from 20 to 50° C.
  • The process (Iα) is preferably carried out in the presence of a diluent.
  • Suitable diluents are all inert organic solvents, such as aromatic hydrocarbons, halogenated hydrocarbons, ethers, amides, nitriles, sulphones or sulphoxides.
  • If appropriate, catalysts may be added to promote the reaction. Suitable for use as catalysts are, very advantageously, organotin compounds, such as, for example, dibutyltin dilaurate.
  • The reaction is preferably carried out at atmospheric pressure.
  • In the preparation process (Iβ), about 1 mol of carbamoyl chloride of the formula (XIII) is employed per mole of starting material of the formulae (I-1-a) to (I-2-a), at from 0 to 150° C., preferably from 20 to 70° C.
  • Suitable diluents which are added, if appropriate, are all inert polar organic solvents, such as ethers, carboxylic esters, nitriles, ketones, amides, sulphones, sulphoxides or halogenated hydrocarbons.
  • Preference is given to using dimethyl sulphoxide, tetrahydrofuran, dimethylfoiniamide or methylene chloride.
  • If, in a preferred embodiment, the enolate salt of the compound (I-1-a) to (I-2-a) is prepared by adding strong deprotonating agents (such as, for example, sodium hydride or potassium tert-butoxide), the further addition of acid binders may be dispensed with.
  • If acid binders are used, these may be customary inorganic or organic bases, for example sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine.
  • The reaction can be carried out at atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods.
  • In the preparation process (J), up to 50 mol of diol of the formula (XVI), preferably from 1 to 10 mol, are employed per mole of the starting materials (I-1-a) to (I-1-g) or (I-2-a) to (I-2-g), at from −50 to 250° C., preferably from 0 to 150° C.
  • Suitable diluents are all inert organic solvents, such as aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters, amides, nitriles, sulphones or sulphoxides.
  • If appropriate, catalysts may be added to promote the reaction. Suitable for use as catalysts are, very advantageously, acids, such as, for example, p-toluenesulphonic acid, concentrated sulphuric acid, and also Lewis acids, such as, for example, boron trifluoride etherate.
  • The reaction is preferably carried out at atmospheric pressure.
  • The dehydrating conditions can be achieved both by azeotropic removal of the water and by adding suitable dehydrating agents, such as, for example, orthoformates, dimethoxypropane and also molecular sieves.
  • Work-up is carried out by customary methods.
  • The active compounds/active compound combinations, in combination with good plant tolerance and favourable toxicity to warm-blooded animals and being tolerated well by the environment, are suitable for protecting plants and plant organs, for increasing the harvest yields, for improving the quality of the harvested material and for controlling animal pests, in particular insects, arachnids, helminths, nematodes and molluscs, which are encountered in agriculture, in horticulture, in animal husbandry, in forests, in gardens and leisure facilities, in the protection of stored products and of materials, and in the hygiene sector. They may be preferably employed as plant protection agents. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:
  • From the order of the Anoplura (Phthiraptera), for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.
  • From the class of the Arachnida, for example, Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Demianyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici.
  • From the class of the Bivalva, for example, Dreissena spp.
  • From the order of the Chilopoda, for example, Geophilus spp., Scutigera spp.
  • From the order of the Coleoptera, for example, Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica spp., Epilachna spp., Faustinus cubae, Gibbium psylloides, Heteronychus arator, Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosterna consanguinea, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp., Meligethes aeneus, Melolontha melolontha, Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorrhynchus sulcatus, Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Sternechus spp., Symphyletes spp., Tenebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.
  • From the order of the Collembola, for example, Onychiurus armatus.
  • From the order of the Dermaptera, for example, Forficula auricularia.
  • From the order of the Diplopoda, for example, Blaniulus guttulatus.
  • From the order of the Diptera, for example, Aedes spp., Anopheles spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia spp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp., Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Stomoxys spp., Tabanus spp., Tannia spp., Tipula paludosa.
  • From the class of the Gastropoda, for example, Anion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
  • From the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius veiinicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp, Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.
  • It is furthermore possible to control Protozoa, such as Eimeria.
  • From the order of the Heteroptera, for example, Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus seriatus, Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.
  • From the order of the Homoptera, for example, Acyrthosipon spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Cameocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Geococcus coffeae, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii.
  • From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonic, Vespa spp.
  • From the order of the Isopoda, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber.
  • From the order of the Isoptera, for example, Reticulitermes spp.
  • From the order of the Lepidoptera, for example, Acronicta major, Aedia leucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Chematobia brumata, Chilo spp., Choristoneura fumiferana, Clysia ambiguella, Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella, Helicoverpa spp., Heliothis spp., Hofmannophila pseudospretella, Homona magnanima, Hyponomeuta padella, Laphygma spp., Lithocolletis blancardella, Lithophane antennata, Loxagrotis albicosta, Lymantria spp., Malacosoma neustria, Mamestra brassicae, Mocis repanda, Mythimna separata, Oria spp., Oulema oryzae, Panolis flammea, Pectinophora gossypiella, Phyllocnistis citrella, Pieris spp., Plutella xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp.
  • From the order of the Orthoptera, for example, Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
  • From the order of the Siphonaptera, for example, Ceratophyllus spp., Xenopsylla cheopis.
  • From the order of the Symphyla, for example, Scutigerella immaculata.
  • From the order of the Thysanoptera, for example, Baliothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
  • From the order of the Thysanura, for example, Lepisma saccharina.
  • The phytoparasitic nematodes include, for example, Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Trichodorus spp., Tylenchulus semipenetrans, Xiphinema spp.
  • If appropriate, the compounds/active compound combinations according to the invention can, at certain concentrations or application rates, also be used as herbicides, safeners, growth regulators or agents to improve plant properties, or as microbicides, for example as fungicides, antimycotics, bactericides, viricides (including agents against viroids) or as agents against MLO (Mycoplasma-like organisms) and RLO (Rickettsia-like organisms). If appropriate, they can also be employed as intermediates or precursors for the synthesis of other active compounds.
  • All plants and plant parts can be treated in accordance with the invention. Plants are to be understood as meaning in the present context all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional plant breeding and optimization methods or by biotechnological and genetic engineering methods or by combinations of these methods, including the transgenic plants and including the plant cultivars protectable or not protectable by plant breeders' rights. Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.
  • Treatment according to the invention of the plants and plant parts with the active compounds/active compound combinations is carried out directly or by allowing the compounds to act on the surroundings, habitat or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on, injection and, in the case of propagation material, in particular in the case of seeds, also by applying one or more coats.
  • The active compounds/active compound combinations can be converted to the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspension-emulsion concentrates, natural materials impregnated with active compound, synthetic materials impregnated with active compound, fertilizers and microencapsulations in polymeric substances.
  • These formulations are produced in a known manner, for example by mixing the active compounds/active compound combinations with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
  • If the extender used is water, it is also possible to use organic solvents, for example, as auxiliary solvents. Suitable liquid solvents are esentially aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example 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 sulphoxide, and also water.
  • Suitable solid carriers are:
  • for example ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly disperse silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates; suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.
  • Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.
  • It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic colorants such as alizarin colorants, azo colorants and metal phthalocyanine colorants, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • The formulations generally comprise between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
  • The active compound/active compound combinations according to the invention can be present in their commercially available formulations, as well as in the use forms prepared from these formulations, in a mixture with other active compounds such as insecticides, attractants, sterilizers, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners, fertilizers or semiochemicals.
  • Compounds which are suitable as mixing partners are, for example, the following:
    • Fungicides:
  • 2-phenylphenol; 8-hydroxyquinoline sulphate; acibenzolar-5-methyl; aldimorph; amidoflumet; ampropylfos; ampropylfos-potassium; andoprim; anilazine; azaconazole; azoxystrobin; benalaxyl; benodanil; benomyl; benthiavalicarb-isopropyl; benzamacril; benzamacril-isobutyl; bilanafos; binapacryl; biphenyl; bitertanol; blasticidin-S; bromuconazole; bupirimate; buthiobate; butylamine; calcium polysulphide; capsimycin; captafol; captan; carbendazim; carboxin; carpropamid; carvone; chinomethionat; chlobenthiazone; chlorfenazole; chloroneb; chlorothalonil; chlozolinate; clozylacon; cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram; Dagger G; debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; diclomezine; dicloran; diethofencarb; difenoconazole; diflumetorim; dimethirimol; dimethomorph; dimoxystrobin; diniconazole; diniconazole-M; dinocap; diphenylamine; dipyrithione; ditalimfos; dithianon; dodine; drazoxolon; edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole; famoxadone; fenamidone; fenapanil; fenarimol; fenbuconazole; fenfuram; fenhexamid; fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam; flubenzimine; fludioxonil; flumetover; flumorph; fluoromide; fluoxastrobin; fluquinconazole; flurprimidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; fosetyl-A1; fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil; furmecyclox; guazatine; hexachlorobenzene; hexaconazole; hymexazole; imazalil; imibenconazole; iminoctadine triacetate; iminoctadine tris(albesilate); iodocarb; ipconazole; iprobenfos; iprodione; iprovalicarb; irumamycin; isoprothiolane; isovaledione; kasugamycin; kresoxim-methyl; mancozeb; maneb; meferimzone; mepanipyrim; mepronil; metalaxyl; metalaxyl-M; metconazole; methasulfocarb; methfuroxam; metiram; metominostrobin; metsulfovax; mildiomycin; myclobutanil; myclozolin; natamycin; nicobifen; nitrothal-isopropyl; noviflumuron; nuarimol; ofurace; orysastrobin; oxadixyl; oxolinic acid; oxpoconazole; oxycarboxin; oxyfenthiin; paclobutrazole; pefurazoate; penconazole; pencycuron; phosdiphen; phthalide; picoxystrobin; piperalin; polyoxins; polyoxorim; probenazole; prochloraz; procymidone; propamocarb; propanosine-sodium; propiconazole; propineb; proquinazid; prothioconazole; pyraclostrobin; pyrazophos; pyrifenox; pyrimethanil; pyroquilon; pyroxyfur; pyrrolenitrine; quinconazole; quinoxyfen; quintozene; simeconazole; spiroxamine; sulphur; tebuconazole; tecloftalam; tecnazene; tetcyclacis; tetraconazole; thiabendazole; thicyofen; thifluzamide; thiophanate-methyl; thiram; tioxymid; tolclofos-methyl; tolylfluanid; triadimefon; triadimenol; triazbutil; triazoxide; tricyclamide; tricyclazole; tridemorph; trifloxystrobin; triflumizole; triforine; triticonazole; uniconazole; validamycin A; vinclozolin; zineb; ziram; zoxamide; (2S)—N-[2-[4-[[3-(4-chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulphonyl)amino]butanamide; 1-(1-naphthalenyl)-1H-pyrrole-2,5-dione; 2,3,5,6-tetrachloro-4-(methylsulphonyl)pyridine; 2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide; 2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide; 3,4,5-tri chloro-2,6-pyridinedicarbonitrile; actinovate; cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol; methyl 1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate; monopotassium carbonate; N-(6-methoxy-3-pyridinyl)cyclopropanecarboxamide; N-butyl-8-(1,1-dimethylethyl)-1-oxaspiro[4.5]decane-3-amine; sodium tetrathiocarbonate; and copper salts and preparations, such as Bordeaux mixture; copper hydroxide; copper naphthenate; copper oxychloride; copper sulphate; cufraneb; cuprous oxide; mancopper; oxine-copper.
    • Bactericides:
  • bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
    • Insecticides/Acaricides/Nematicides:
  • 1. Acetylcholine esterase (AChE) inhibitors
  • 1.1 Carbamates,
      • for example alanycarb, aldicarb, aldoxycarb, allyxycarb, aminocarb, bendiocarb, benfuracarb, bufencarb, butacarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb, dimetilan, ethiofencarb, fenobucarb, fenothiocarb, formetanate, furathiocarb, isoprocarb, metam-sodium, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, promecarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate
  • 1.2 Organophosphates,
      • for example acephate, azamethiphos, azinphos (-methyl, -ethyl), bromophos-ethyl, bromfenvinfos (-methyl), butathiofos, cadusafos, carbophenothion, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos (-methyl/-ethyl), coumaphos, cyanofenphos, cyanophos, chlorfenvinphos, demeton-S-methyl, demeton-S-methylsulphon, dialifos, diazinon, dichlofenthion, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos, dioxabenzofos, disulfoton, EPN, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, fensulfothion, fenthion, flupyrazofos, fonofos, formothion, fosmethilan, fosthiazate, heptenophos, iodofenphos, iprobenfos, isazofos, isofenphos, isopropyl O-salicylate, isoxathion, malathion, mecarbam, methacrifos, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion (-methyl/-ethyl), phenthoate, phorate, phosalone, phosmet, phosphamidon, phosphocarb, phoxim, pirimiphos (-methyl/-ethyl), profenofos, propaphos, propetamphos, prothiofos, prothoate, pyraclofos, pyridaphenthion, pyridathion, quinalphos, sebufos, sulfotep, sulprofos, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, triclorfon, vamidothion
  • 2. Sodium channel modulators/voltage-gated sodium channel blockers
  • 2.1 Pyrethroids,
      • for example acrinathrin, allethrin (d-cis-trans, d-trans), beta-cyfluthrin, bifenthrin, bioallethrin, bioallethrin-S cyclopentyl isomer, bioethanomethrin, biopermethrin, bioresmethrin, chlovaporthrin, cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin (alpha-, beta-, theta-, zeta-), cyphenothrin, deltamethrin, empenthrin (1R isomer), esfenvalerate, etofenprox, fenfluthrin, fenpropathrin, fenpyrithrin, fenvalerate, flubrocythrinate, flucythrinate, flufenprox, flumethrin, fluvalinate, fubfenprox, gamma-cyhalothrin, imiprothrin, kadethrin, lambda-cyhalothrin, metofluthrin, permethrin (cis-, trans-), phenothrin (1R trans-isomer), prallethrin, profluthrin, protrifenbute, pyresmethrin, resmethrin, RU15525, silafluofen, tau-fluvalinate, tefluthrin, terallethrin, tetramethrin (1R isomer), tralomethrin, transfluthrin, ZXI 8901, pyrethrins (pyrethrum)
      • DDT
  • 2.2 Oxadiazines,
      • for example indoxacarb
  • 2.3 Semicarbazones,
      • for example metaflumizone (BAS 3201)
    Acetylcholine Receptor Agonists-Antagonists
  • 3.1 Chloronicotinyls,
      • for example acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid, thiamethoxam
  • 3.2 Nicotine, bensultap, cartap
    • Acetylcholine Receptor Modulators
  • 4.1 Spinosyns,
      • for example spinosad
      • GABA-gated chloride channel antagonists
  • 5.1 Cyclodiene organochlorines,
      • for example camphechlor, chlordane, endosulfan, gamma-HCH, HCH, heptachlor, lindane, methoxychlor
  • 5.2 Fiproles,
      • for example acetoprole, ethiprole, fipronil, pyrafluprole, pyripole, van liprole
    Chloride Channel Activators
  • 6.1 Mectins,
      • for example avermectin, emamectin, emamectin-benzoate, ivermectin, milbemycin
    Juvenile Bon Lone Mimetics,
      • for example diofenolan, epofenonane, fenoxycarb, hydroprene, kinoprene, methoprene, pyriproxifen, triprene
    Ecdyson Agonists/Disruptors
  • 8.1 Diacylhydrazines,
      • for example chromafenozide, halofenozide, methoxyfenozide, tebufenozide
    Chitin Biosynthesis Inhibitors
  • 9.1 Benzoylureas,
      • for example bistrifluoron, chlofluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluoron, teflubenzuron, triflumuron
  • 9.2 Buprofezin
  • 9.3 Cyromazine
    • Oxidative Phosphorylation Inhibitors, ATP Disruptors
  • 10.1 Diafenthiuron
  • 10.2 Organotins,
      • for example azocyclotin, cyhexatin, fenbutatin-oxide
  • Oxidative Phosphorylation Decouplers Acting by Interrupting the H-Proton Gradient
  • 11.1 Pyrroles,
      • for example chlorfenapyr
  • 11.2 Dinitrophenols,
      • for example binapacyrl, dinobuton, dinocap, DNOC
    Electron Transport Inhibitors
  • 12.1 Site-I electron transport inhibitors
      • from the group of the
      • METIs,
      • for example fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad and also
      • Hydramethylnon
      • Dicofol
  • 12.2 Site-II electron transport inhibitors
      • Rotenone
  • 12.3 Site-III electron transport inhibitors
      • Acequinocyl, fluacrypyrim
    Microbial Disruptors of the Insect Gut Membrane
      • Bacillus thuringiensis strains
    Fat Biosynthesis Inhibitors
  • 14.1 Tetronic acids,
      • for example spirodiclofen, spiromesifen
  • 14.2 Tetramic acids,
      • for example spirotetramat
    Carboxamides,
      • for example flonicamid
  • Octopaminergic agonists,
      • for example amitraz
  • Inhibitors of magnesium-stimulated ATPase,
      • propargite
  • Ryanodine receptor effectors
      • 18.1 Benzoic acid dicarboxamides,
        • for example flubendiamide
      • 18.2 Anthranilamides, for example DPX E2 Y45
  • Nereistoxin analogues,
      • for example thiocyclam hydrogen oxalate, thiosultap-sodium
  • Biologicals, hormones or pheromones,
      • azadirachtin, Bacillus spec., Beauveria spec., codlemone, Metarrhizium spec., Paecilomyces spec., thuringiensin, Verticillium spec.
  • Active compounds with unknown or unspecific mechanisms of action
  • 21.1 Fumigants,
      • for example aluminium phosphide, methyl bromide, sulphuryl fluoride
  • 21.2 Antifeedants,
      • for example cryolite, flonicamid, pymetrozine
  • 21.3 Mite growth inhibitors,
      • for example clofentezine, etoxazole, hexythiazox
  • 21.4 Amidoflumet, benclothiaz, benzoximate, bifenazate, bromopropylate, buprofezin, chinomethionat, chlordimeform, chlorobenzilate, chloropicrin, clothiazoben, cycloprene, cyflumetofen, dicyclanil, fenoxacrim, fentrifanil, flubenzimine, flufenerim, flutenzin, gossyplure, hydramethylnone, japonilure, metoxadiazone, petroleum, piperonyl butoxide, potassium oleate, pyridalyl, sulfluramid, tetradifon, tetrasul, triarathene, verbutin
  • A mixture with other known active compounds, such as herbicides, fertilizers, growth regulators, safeners, semiochemicals, or else with agents which improve plant properties is also possible.
  • When used as insecticides in their commercially available formulations and in the use forms prepared with these formulations, the active compounds/active compound combinations according to the invention can furthermore be present in the form of a mixture with synergists. Synergists are compounds by which the activity of the active compounds is increased without it being necessary for the synergist added to be active itself.
  • When used as insecticides in their commercially available formulations and in the use forms prepared with these formulations, the active compounds/active compound combinations according to the invention can furthermore be present in the form of a mixture with inhibitors which reduce the degradation of the active compound after application in the habitat of the plant, on the surface of parts of plants or in plant tissues.
  • The active compound content of the use foams prepared from the commercially available formulations can vary within broad ranges. The active compound concentration of the use forms can be from 0.00000001 up to 95% by weight of active compound and is preferably between 0.00001 and 1% by weight.
  • Application is in a customary manner adapted to suit the use forms.
  • As already mentioned above, it is possible to treat all plants and their parts in accordance with the invention. In a preferred embodiment, wild plant species or plant varieties and plant cultivars which have been obtained by traditional biological breeding methods, such as hybridization or protoplast fusion, and the parts of these varieties and cultivars are treated. In a further preferred embodiment, transgenic plants and plant cultivars which have been obtained by recombinant methods, if appropriate in combination with conventional methods (genetically modified organisms), and their parts are treated. The term “parts” or “parts of plants” or “plant parts” has been explained above.
  • Plants which are treated particularly preferably in accordance with the invention are those of the plant cultivars which are in each case commercially available or in use. Plant cultivars are understood as meaning plants with new traits which have been bred either by conventional breeding, by mutagenesis or by recombinant DNA techniques. They may take the form of cultivars, biotypes and genotypes.
  • Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, nutrition), the treatment according to the invention may also result in superadditive (“synergistic”) effects. Thus, for example, reduced application rates and/or a widened activity spectrum and/or an increase in the activity of the substances and compositions which can be used in accordance with the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to salinity in the water or soil, increased flowering performance, facilitated harvesting, accelerated maturation, higher yields, higher quality and/or better nutritional value of the harvested products, better storage characteristics and/or processability of the harvested products are possible which exceed the effects which were actually to be expected.
  • The preferred transgenic plants or plant cultivars (those obtained by recombinant methods) to be treated in accordance with the invention include all those plants which, owing to the process of recombinant modification, were given genetic material which confers particular, advantageous, valuable traits to these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to salinity in the water or soil, increased flowering performance, facilitated harvesting, accelerated maturation, higher yields, higher quality and/or higher nutritional value of the harvested products, better storage characteristics and/or better processability of the harvested products. Further examples of such traits, examples which must be mentioned especially, are better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses and an increased tolerance of the plants to certain herbicidal active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soybeans, potato, sugar beet, tomatoes, peas and other vegetable varieties, cotton, tobacco, oilseed rape and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with particular emphasis on maize, soybeans, potatoes, cotton, tobacco, and oilseed rape. Traits which are especially emphasized are the increased defence of the plants against insects, arachnids, nematodes and slugs and snails, owing to toxins being formed in the plants, in particular toxins which are generated in the plants by the genetic material of Bacillus thuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and their combinations; hereinbelow “Bt plants”). Other traits which are particularly emphasized are the increased defence of plants against fungi, bacteria and viruses by the systemic acquired resistance (SAR), systemins, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Other traits which are especially emphasized are the increased tolerance of the plants to certain herbicidal active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example “PAT” gene). The genes which confer the desired traits in each case may also be present in the transgenic plants in combination with one another. Examples of “Bt plants” which may be mentioned are maize cultivars, cotton cultivars, soybean cultivars and potato cultivars which are commercially available under the trade names YIELD GARD® (for example maize, cotton, soybeans), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize cultivars, cotton cultivars and soybean cultivars which are commercially available under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soybean), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned also include the varieties commercially available under the name Clearfield® (for example maize). Naturally, these statements also apply to plant cultivars having these genetic traits or genetic traits still to be developed, which plant cultivars will be developed and/or marketed in the future.
  • The plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula I or the active compound mixtures according to the invention. The preferred ranges stated above for the active compounds and mixtures also apply to the treatment of these plants. Particular emphasis may be given to the treatment of plants with the compounds or mixtures specifically mentioned in the present text.
  • The active compounds/active compound combinations according to the invention are not only active against plant, hygiene and stored-product pests, but also, in the veterinary medicine sector, against animal parasites (ectoparasites and endoparasites), such as ixodid ticks, argasid ticks, scab mites, trombi-culid mites, flies (stinging and sucking), parasitic fly larvae, lice, hair lice, bird lice and fleas. These parasites include:
  • From the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
  • From the order of the Mallophagida and the sub-orders Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
  • From the order of the Diptera and the sub-orders 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. and Melophagus spp.
  • From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopyslla spp. and Ceratophyllus spp.
  • From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
  • From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp.
  • From the sub-class of the Acaria (Acarina) and the orders of the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.
  • From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.
  • The active compounds/active compound combinations of the formula (I) according to the invention are also suitable for controlling arthropods which attack agricultural livestock, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, honeybees, other domestic animals, such as, for example, dogs, cats, cage birds, aquarium fish, and so-called experimental animals, such as, for example, hamsters, guinea-pigs, rats and mice. By combating these arthropods, it is intended to reduce deaths and decreased performances (in meat, milk, wool, hides, eggs, honey and the like), so that more economical and simpler animal keeping is made possible by using the active compounds according to the invention.
  • In the veterinary sector, the active compounds/active compound combinations according to the invention are used in a known manner by enteral administration, for example in the form of tablets, capsules, drinks, drenches, granules, pastes, boli, the feed-through method, suppositories, by parenteral administration, such as, for example, by means of injections (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal application, by dermal administration, for example in the form of dipping or bathing, spraying, pouring-on and spotting-on, washing, dusting, and with the aid of shaped articles which comprise active compound, such as collars, ear tags, tail marks, limb bands, halters, marking devices and the like.
  • When administered to livestock, poultry, domestic animals and the like, the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowables) which comprise the active compounds in an amount of 1 to 80% by weight, either directly or after dilution by a factor of 100 to 10 000, or they may be used in the form of a chemical bath.
  • Furthermore, it has been found that the compounds/active compound combinations according to the invention have a potent insecticidal action against insects which destroy industrial materials.
  • The following insects may be mentioned by way of example and as being preferred, but without any limitation:
  • Beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec., Dinoderus minutus.
  • Dermapterans, such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.
  • Termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitelines santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
  • Bristletails, such as Lepisma saccharina.
  • Industrial materials are to be understood as meaning, in the present context, non-live materials, such as, preferably, synthetic materials, glues, sizes, paper and board, leather, wood and timber products, and paint.
  • The materials to be very particularly preferably protected against attack by insects are wood and timber products.
  • Wood and timber products which can be protected by the composition according to the invention or mixtures comprising such a composition are to be understood as meaning, for example:
  • construction timber, wooden beams, railway sleepers, bridge components, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wood cladding, windows and doors made of wood, plywood, particle board, joiner's articles, or wood products which, quite generally, are used in the construction of houses or in joinery.
  • The active compounds 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, for example by mixing the active compounds with at least one solvent or diluent, emulsifier, dispersant and/or binder or fixative, water repellent, if appropriate desiccants and UV stabilizers and, if appropriate, colorants and pigments and other processing auxiliaries.
  • The insecticidal compositions or concentrates used for the protection of wood and wooden materials comprise 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 compositions or concentrates employed depends on the species and the occurrence of the insects and on the medium. The optimum rate of application can be determined upon use in each case by a test series. However, in general, it suffices to employ 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
  • The solvent and/or diluent used is an organochemical solvent or solvent mixture and/or an oily or oil-type organochemical solvent or solvent mixture of low volatility and/or a polar organochemical solvent or solvent mixture and/or water and, if appropriate, an emulsifier and/or wetting agent.
  • Organochemical solvents which are preferably employed are oily or oil-type solvents having an evaporation number of above 35 and a flashpoint of above 30° C., preferably above 45° C. Substances which are used as such oily and oil-type solvents which have low volatility and are insoluble in water are suitable mineral oils or their aromatic fractions, or mineral-oil-containing solvent mixtures, preferably white spirit, petroleum and/or alkylbenzene.
  • Substances which are advantageously used are 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 of boiling range 160 to 280° C., essence of terpentine and the like.
  • In a preferred embodiment, liquid aliphatic hydrocarbons with a boiling range of 180 to 210° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180 to 220° C. and/or spindle oil and/or monochloronaphthalene, preferably α-monochloronaphthalene, are used.
  • The organic oily or oil-type solvents of low volatility having an evaporation number of above 35 and a flashpoint of above 30° C., preferably above 45° C., can be partially replaced by organochemical solvents of high or medium volatility, with the proviso that the solvent mixture also has an evaporation number of above 35 and a flashpoint of above 30° C., preferably above 45° C., and that the insecticide/fungicide mixture is soluble or emulsifiable in this solvent mixture.
  • In a preferred embodiment, part of the organochemical solvent or solvent mixture or an aliphatic polar organochemical solvent or solvent mixture is replaced. Substances which are preferably used are aliphatic organochemical solvents having hydroxyl and/or ester and/or ether groups, such as, for example, glycol ethers, esters and the like.
  • The organochemical binders used within the scope of the present invention are the synthetic resins and/or binding drying oils which are known per se and can be diluted with water and/or are soluble or dispersible or emulsifiable in the organochemical solvents employed, in particular binders composed of, or comprising, an acrylate resin, a vinyl resin, for example polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenol resin, hydrocarbon resin, such as indene/cumarone resin, silicone resin, drying vegetable and/or drying oils and/or physically drying binders based on a natural and/or synthetic resin.
  • The synthetic resin used as the binder can be employed in the form of an emulsion, dispersion or solution. Up to 10% by weight of bitumen or bituminous substances can also be used as binders. In addition, colorants, pigments, water repellents, odour-masking substances and inhibitors or anticorrosives known per se and the like can also be employed.
  • The composition or the concentrate preferably comprises, in accordance with the invention, at least one alkyd resin or modified alkyd resin and/or a drying vegetable oil as the organochemical binder. Preferably used according to the invention are alkyd resins with an oil content of over 45% by weight, preferably 50 to 68% by weight.
  • All or some of the abovementioned binder can be replaced by a fixative (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active compounds and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of binder employed).
  • The plasticizers are from the chemical classes of the phthalic esters, such as dibutyl phthalate, dioctyl phthalate or benzyl butyl phthalate, the phosphoric esters, such as tributyl phosphate, the adipic esters, such as di(2-ethylhexyl) adipate, the stearates, such as butyl stearate or amyl stearate, the oleates, such as butyl oleate, the glycerol ethers or relatively high-molecular-weight glycol ethers, glycerol esters and p-toluenesulphonic esters.
  • Fixatives are chemically based on polyvinyl alkyl ethers, such as, for example, polyvinyl methyl ether, or ketones, such as benzophenone or ethylenebenzophenone.
  • Particularly suitable as a solvent or diluent is also water, if appropriate as a mixture with one or more of the abovementioned organochemical solvents or diluents, emulsifiers and dispersants.
  • Particularly effective protection of wood is achieved by large-scale industrial impregnation processes, for example vacuum, double-vacuum or pressure processes.
  • If appropriate, the ready-to-use compositions can additionally comprise other insecticides and, if appropriate, additionally one or more fungicides.
  • Suitable additional components which may be admixed are, preferably, the insecticides and fungicides mentioned in WO 94/29 268. The compounds mentioned in that document are expressly part of the present application.
  • Very particularly preferred components which may be admixed are insecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin, thiacloprid, methoxyphenoxid, triflumuron, chlothianidin, spinosad, tefluthrin,
  • and fungicides, such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid, 3-iodo-2-propynylbutyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.
  • The compounds according to the invention can at the same time be employed for protecting objects which come into contact with saltwater or brackish water, in particular hulls, screens, nets, buildings, moorings and signalling systems, against fouling.
  • Fouling by sessile Oligochaeta, such as Serpulidae, and by shells and species from the Ledamorpha group (goose barnacles), such as various Lepas and Scalpellum species, or by species from the Balanomorpha group (acorn barnacles), such as Balanus or Pollicipes species, increases the frictional drag of ships and, as a consequence, leads to a marked increase in operation costs owing to higher energy consumption and additionally frequent residence in the dry dock.
  • Apart from fouling by algae, for example Ectocarpus sp. and Ceramium sp., fouling by sessile Entomostraka groups, which come under the generic term Cirripedia (cirriped crustaceans), is of particular importance.
  • Surprisingly, it has now been found that the compounds according to the invention, alone or in combination with other active compounds, have an outstanding antifouling action.
  • Using the compounds according to the invention, alone or in combination with other active compounds, allows the use of heavy metals such as, for example, in bis(trialkyltin) sulphides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride, tri-n-butyl-(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenum disulphide, antimony oxide, polymeric butyl titanate, phenyl(bispyridine)bismuth chloride, tri-n-butyltin fluoride, manganese ethylenebisthiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol 1-oxide, bisdimethyldithiocarbamoylzinc ethylenebisthiocarbamate, zinc oxide, copper(I) ethylenebisdithiocarbamate, copper thiocyanate, copper naphthenate and tributyltin halides to be dispensed with, or the concentration of these compounds to be substantially reduced.
  • If appropriate, the ready-to-use antifouling paints can additionally comprise other active compounds, preferably algicides, fungicides, herbicides, molluscicides, or other antifouling active compounds.
  • Preferably suitable components in combination with the antifouling compositions according to the invention are:
  • algicides such as
  • 2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine, dichlorophen, diuron, endothal, fentin acetate, isoproturon, methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;
  • fungicides such as
  • benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide, dichlofluanid, fluorfolpet, 3-iodo-2-propinyl butylcarbamate, tolylfluanid and azoles such as
  • azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazole and tebuconazole;
  • molluscicides such as
  • fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb and trimethacarb; Fe chelates;
  • or conventional antifouling active compounds such as
  • 4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl sulphone, 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridinethiol 1-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine, 2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulphide and 2,4,6-trichlorophenylmaleimide.
  • The antifouling compositions used comprise 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.
  • Moreover, the antifouling compositions according to the invention comprise the customary components such as, for example, those described in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.
  • Besides the algicidal, fungicidal, molluscicidal active compounds and insecticidal active compounds according to the invention, antifouling paints comprise, 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, in particular 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 hardened resins in combination with tar or bitumens, asphalt and epoxy compounds, small amounts of chlorine rubber, chlorinated polypropylene and vinyl resins.
  • If appropriate, paints also comprise inorganic pigments, organic pigments or colorants which are preferably insoluble in saltwater. Paints may furthermore comprise materials such as rosin to allow controlled release of the active compounds. Furthermore, the paints may comprise plasticizers, modifiers which affect the rheological properties and other conventional constituents. The compounds according to the invention or the abovementioned mixtures may also be incorporated into self-polishing antifouling systems.
  • The active compounds are also suitable for controlling animal pests, in particular insects, arachnids and mites, which are found in enclosed spaces such as, for example, dwellings, factory halls, offices, vehicle cabins and the like. They can be employed in domestic insecticide products for controlling these pests alone or in combination with other active compounds and auxiliaries. They are active against sensitive and resistant species and against all development stages. These pests include:
  • From the order of the Scorpionidea, for example, Buthus occitanus.
  • From the order of the Acarina, for example, Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.
  • From the order of the Araneae, for example, Aviculariidae, Araneidae.
  • From the order of the Opiliones, for example, Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.
  • From the order of the Isopoda, for example, Oniscus asellus, Porcellio scaber.
  • From the order of the Diplopoda, for example, Blaniulus guttulatus, Polydesmus spp.
  • From the order of the Chilopoda, for example, Geophilus spp.
  • From the order of the Zygentoma, for example, Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.
  • From the order of the Blattaria, for example, Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.
  • From the order of the Saltatoria, for example, Acheta domesticus.
  • From the order of the Dermaptera, for example, Forficula auricularia.
  • From the order of the Isoptera, for example, Kalotermes spp., Reticulitermes spp.
  • From the order of the Psocoptera, for example, Lepinatus spp., Liposcelis 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.
  • From the order of the Diptera, for example, Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp., Stomoxys calcitrans, Tipula paludosa.
  • From the order of the Lepidoptera, for example, Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
  • From the order of the Siphonaptera, for example, Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
  • From the order of the Hymenoptera, for example, Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
  • From the order of the Anoplura, for example, Pediculus humanus capitis, Pediculus humanus corporis, Phthirus pubis.
  • From the order of the Heteroptera, for example, Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.
  • They are used in the household insecticides sector alone or in combination with other suitable active compounds such as phosphoric esters, carbamates, pyrethroids, neonicotinoids, growth regulators or active compounds from other known classes of insecticides.
  • They are used in aerosols, pressure-free spray products, for example pump and atomizer sprays, automatic fogging systems, foggers, foams, gels, evaporator products with evaporator tablets made of cellulose or polymer, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-free, or passive, evaporation systems, moth papers, moth bags and moth gels, as granules or dusts, in baits for spreading or in bait stations.
  • The active compounds/active compound combinations according to the invention can also be used as defoliants, desiccants, haulm killers and, in particular, as weed killers. Weeds in the broadest sense are understood as meaning all plants which grow at locations where they are undesired. Whether the substances according to the invention act as nonselective or selective herbicides depends essentially on the application rate.
  • The active compounds/active compound combinations according to the invention can be used, for example, in the following plants:
  • Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindemia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.
  • Dicotyledonous crops of the genera: Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia.
  • Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
  • Monocotyledonous crops of the genera: Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea.
  • However, the use of the active compounds/active compound combinations according to the invention is in no way restricted to these genera, but extends in the same manner to other plants.
  • Depending on the concentration, the active compounds/active compound combinations according to the invention are suitable for the nonselective weed control on, for example, industrial terrains and railway tracks and on paths and locations with and without trees. Likewise the active compounds according to the invention can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantations and hop fields, on lawns, turf and pastureland, and for the selective control of weeds in annual crops.
  • The compounds of the formula (I)/active compound combinations according to the invention have strong herbicidal activity and a broad activity spectrum when used on the soil and on aerial plant parts. To a certain extent, they are also suitable for the selective control of monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous crops, both pre- and post-emergence.
  • At certain concentrations or application rates, the active compounds/active compound combinations according to the invention can also be employed for controlling animal pests and fungal or bacterial plant diseases. If appropriate, they can also be used as intermediates or precursors for the synthesis of other active compounds.
  • The active compounds/active compound combinations can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspoemulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
  • These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
  • If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes 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 also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, and also water.
  • Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates, suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.
  • Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other possible additives are mineral and vegetable oils.
  • It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic colorants, such as alizarin colorants, azo colorants and metal phthalocyanine colorants, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • The formulations generally comprise between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • The active compounds/active compound combinations according to the invention, as such or in their formulations, can also be used for weed control purposes as a mixture with known herbicides and/or with substances which improve crop plant tolerance (“safeners”), ready mixes or tank mixes being possible. Mixtures with herbicide products which contain one or more known herbicides and a safener are hence also possible.
  • Herbicides which are suitable for the mixtures are known herbicides, for example
  • acetochlor, acifluorfen (-sodium), aclonifen, alachlor, alloxydim (-sodium), ametryne, amicarbazone, amidochlor, amidosulfuron, aminopyralid, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin (-ethyl), benfuresate, bensulfuron (-methyl), bentazone, bencarbazone, benzfendizone, benzobicyclon, benzolenap, benzoylprop (-ethyl), bialaphos, bifenox, bispyribac (-sodium), bromobutide, bromofenoxim, bromoxynil, butachlor, butafenacil (-allyl), butroxydim, butylate, cafenstrole, caloxydim, carbetamide, carfentrazone (-ethyl), chlomethoxyfen, chloramben, chloridazon, chlorimuron (-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinidon (-ethyl), cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop (-propargyl), clomazone, clomeprop, clopyralid, clopyrasulfuron (-methyl), cloransulam (-methyl), cumyluron, cyanazine, cybutryne, cycloate, cyclosulfamuron, cycloxydim, cyhalofop (-butyl), 2,4-D, 2,4-DB, desmedipham, diallate, dicamba, dichlorprop (—P), diclofop (-methyl), diclosulam, diethatyl (-ethyl), difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, epropodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron (-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop (—P-ethyl), fentrazamide, flamprop (-isopropyl, -iso-propyl-L, -methyl), flazasulfuron, florasulam, fluazifop (—P-butyl), fluazolate, flucarbazone (-sodium), flufenacet, flumetsulam, flumiclorac (-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen (-ethyl), flupoxam, flupropacil, flurpyrsulfuron (-methyl, -sodium), flurenol (-butyl), fluridone, fluoroxypyr (-butoxypropyl, -meptyl), flurprimidol, flurtamone, fluthiacet (-methyl), fluthiamide, fomesafen, foramsulfuron, glufosinate (-ammonium), glyphosate (-isopropylammonium), halosafen, haloxyfop (-ethoxyethyl, —P-methyl), hexazinone, HOK-201, imazamethabenz (-methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron (-methyl, -sodium), ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, KIH 485, lactofen, lenacil, linuron, MCPA, mecoprop, mefenacet, mesosulfuron, mesotrione, metamifop, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-) metolachlor, metosulam, metoxuron, metribuzin, metsulfuron (-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pendralin, penoxsulam, pentoxazone, phenmedipham, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron (-methyl), profluazol, prometryn, propachlor, propanil, propaquizafop, propisochlor, propoxycarbazone (-sodium), propyzamide, prosulfocarb, prosulfuron, pyraflufen (-ethyl), pyrasulfotole, pyrazogyl, pyrazolate, pyrazosulfuron (-ethyl), pyrazoxyfen, pyribenzoxim, pyributicarb, pyridate, pyridatol, pyriftalide, pyriminobac (-methyl), pyrimisulfan, pyrithiobac (-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop (—P-ethyl, —P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron (-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tembotrione, tepraloxydim, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron (-methyl), thiobencarb, tiocarbazil, topramezone, tralkoxydim, triallate, triasulfuron, tribenuron (-methyl), triclopyr, tridiphane, trifluralin, trifloxysulfuron, triflusulfuron (-methyl), tritosulfuron and
  • Figure US20110190493A1-20110804-C00107
  • A mixture with other known active compounds, such as fungicides, insectides, acaricides, nematicides, bird repellents, plant nutrients and soil conditioners, is also possible.
  • The active compounds/active compound combinations can be applied 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. They are applied in the customary manner, for example by pouring, spraying, atomizing, spreading.
  • The active compounds/active compound combinations according to the invention can be applied both before and after plant emergence. They can also be incorporated into the soil prior to planting.
  • The application rate of active compound can vary within a substantial range. Essentially, it depends on the nature of the desired effect. In general, the application rates are between 1 g and 10 kg of active compound per hectare of soil area, preferably between 5 g and 5 kg per ha.
  • The substances/active compound combinations according to the invention have potent microbicidal activity and can be employed for controlling unwanted microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.
  • Fungicides can be employed in crop protection for controlling Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
  • Bactericides can be employed in crop protection for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
  • Some pathogens causing fungal and bacterial diseases which come under the generic names listed above may be mentioned as examples, but not by way of limitation:
  • Xanthomonas species, such as, for example, Xanthomonas campestris pv. oryzae;
  • Pseudomonas species, such as, for example, Pseudomonas syringae pv. lachrymans;
  • Erwinia species, such as, for example, Erwinia amylovora;
  • Pythium species, such as, for example, Pythium ultimum;
  • Phytophthora species, such as, for example, Phytophthora infestans;
  • Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;
  • Plasmopara species, such as, for example, Plasmopara viticola;
  • Bremia species, such as, for example, Bremia lactucae;
  • Peronospora species, such as, for example, Peronospora pisi or P. brassicae;
  • Erysiphe species, such as, for example, Erysiphe graminis;
  • Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
  • Podosphaera species, such as, for example, Podosphaera leucotricha;
  • Venturia species, such as, for example, Venturia inaequalis;
  • Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea
  • (conidia form: Drechslera, syn: Helminthosporium);
  • Cochliobolus species, such as, for example, Cochliobolus sativus
  • (conidia form: Drechslera, syn: Helminthosporium);
  • Uromyces species, such as, for example, Uromyces appendiculatus;
  • Puccinia species, such as, for example, Puccinia recondita;
  • Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;
  • Tilletia species, such as, for example, Tilletia caries;
  • Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
  • Pellicularia species, such as, for example, Pellicularia sasakii;
  • Pyricularia species, such as, for example, Pyricularia oryzae;
  • Fusarium species, such as, for example, Fusarium culmorum;
  • Botrytis species, such as, for example, Botrytis cinerea;
  • Septoria species, such as, for example, Septoria nodorum;
  • Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
  • Cercospora species, such as, for example, Cercospora canescens;
  • Alternaria species, such as, for example, Alternaria brassicae; and
  • Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.
  • The active compounds/active compound combinations according to the invention also have very good fortifying action in plants. Accordingly, they can be used for mobilizing the defences of the plant against attack by unwanted microorganisms.
  • In the present context, plant-fortifying (resistance-inducing) substances are to be understood as meaning those substances which are capable of stimulating the defence system of plants such that, when the treated plants are subsequently inoculated with unwanted microorganisms, they show substantial resistance against these microorganisms.
  • In the present case, unwanted microorganisms are to be understood as meaning phytopathogenic fungi, bacteria and viruses. Accordingly, the substances according to the invention can be used to protect plants for a certain period after the treatment against attack by the pathogens mentioned. The period for which protection is provided generally extends over 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.
  • The fact that the active compounds/active compound combinations are well tolerated by plants at the concentrations required for controlling plant diseases permits the treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.
  • The active compounds/active compound combinations according to the invention are also suitable for increasing the yield of crops. In addition, they show reduced toxicity and are well tolerated by plants.
  • At certain concentrations and application rates, the active compounds/active compound combinations according to the invention can if appropriate also be used as herbicides, for influencing plant growth and for controlling animal pests. If appropriate, they can also be used as intermediates and precursors for the synthesis of further active compounds.
  • In the protection of materials, the compounds according to the invention can be employed for protecting industrial materials against infection with, and destruction by, unwanted microorganisms.
  • Industrial materials in the present context are understood as meaning non-living materials which have been prepared for use in industry. For example, industrial materials which are intended to be protected by active compounds according to the invention from microbial change or destruction can be adhesives, sizes, paper and board, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials which can be infected with, or destroyed by, microorganisms. Parts of production plants, for example cooling-water circuits, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected. Industrial materials which may be mentioned within the scope of the present invention are preferably adhesives, sizes, paper and board, leather, wood, paints, cooling lubricants and heat-transfer liquids, particularly preferably wood.
  • Microorganisms capable of degrading or changing the industrial materials which may be mentioned are, for example, bacteria, fungi, yeasts, algae and slime organisms. The active compounds according to the invention preferably act against fungi, in particular moulds, wood-discolouring and wood-destroying fungi (Basidiomycetes), and against slime organisms and algae.
  • Microorganisms of the following genera may be mentioned as examples:
  • Alternaria, such as Alternaria tenuis,
  • Aspergillus, such as Aspergillus niger,
  • Chaetomium, such as Chaetomium globosum,
  • Coniophora, such as Coniophora puetana,
  • Lentinus, such as Lentinus tigrinus,
  • Penicillium, such as Penicillium glaucum,
  • Polyporus, such as Polyporus versicolor,
  • Aureobasidium, such as Aureobasidium pullulans,
  • Sclerophoma, such as Sclerophoma pityophila,
  • Trichoderma, such as Trichoderma viride,
  • Escherichia, such as Escherichia coli,
  • Pseudomonas, such as Pseudomonas aeruginosa, and
  • Staphylococcus, such as Staphylococcus aureus.
  • Depending on their particular physical and/or chemical properties, the active compounds/active compound combinations can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and microencapsulations in polymeric substances and in coating compositions for seeds, and ULV cool and warm fogging formulations.
  • These formulations are produced in a known manner, for example by mixing the active compounds/active compound combinations with extenders, that is liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers. If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, 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 sulphoxide, or else water. Liquefied gaseous extenders or carriers are to be understood as meaning liquids which are gaseous at standard temperature and under atmospheric pressure, for example aerosol propellants such as halogenated hydrocarbons, or else butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as finely divided silica, alumina and silicates. Suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks. Suitable emulsifiers and/or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates. Suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.
  • Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.
  • It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic colorants such as alizarin colorants, azo colorants and metal phthalocyanine colorants, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • The formulations generally comprise between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
  • The active compounds according to the invention can be used as such or in their formulations, also in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, to broaden, for example, the activity spectrum or to prevent development of resistance. In many cases, synergistic effects are obtained, i.e. the activity of the mixture is greater than the activity of the individual components.
    • Fungicides:
  • 2-phenylphenol; 8-hydroxyquinoline sulphate; acibenzolar-S-methyl; aldimorph; amidoflumet; ampropylfos; ampropylfos-potassium; andoprim; anilazine; azaconazole; azoxystrobin; benalaxyl; benodanil; benomyl; benthiavalicarb-isopropyl; benzamacril; benzamacril-isobutyl; bilanafos; binapacryl; biphenyl; bitertanol; blasticidin-S; bromuconazole; bupirimate; buthiobate; butylamine; calcium polysulphide; capsimycin; captafol; captan; carbendazim; carboxin; carpropamid; carvone; quinomethionate; chlobenthiazone; chlorfenazole; chloroneb; chlorothalonil; chlozolinate; clozylacon; cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram; Dagger G; debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; diclomezine; dicloran; diethofencarb; difenoconazole; diflumetorim; dimethirimol; dimethomorph; dimoxystrobin; diniconazole; diniconazole-M; dinocap; diphenylamine; dipyrithione; ditalimfos; dithianon; dodine; drazoxolon; edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole; famoxadone; fenamidone; fenapanil; fenarimol; fenbuconazole; fenfuram; fenhexamid; fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam; flubenzimine; fludioxonil; flumetover; flumorph; fluoromide; fluoxastrobin; fluquinconazole; flurprimidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; fosetyl-A1; fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil; furmecyclox; guazatine; hexachlorobenzene; hexaconazole; hymexazol; imazalil; imibenconazole; iminoctadine triacetate; iminoctadine tris(albesilate); iodocarb; ipconazole; iprobenfos; iprodione; iprovalicarb; irumamycin; isoprothiolane; isovaledione; kasugamycin; kresoxim-methyl; mancozeb; maneb; meferimzone; mepanipyrim; mepronil; metalaxyl; metalaxyl-M; metconazole; methasulfocarb; methfuroxam; metiram; metominostrobin; metsulfovax; mildiomycin; myclobutanil; myclozolin; natamycin; nicobifen; nitrothal-isopropyl; noviflumuron; nuarimol; ofurace; orysastrobin; oxadixyl; oxolinic acid; oxpoconazole; oxycarboxin; oxyfenthiin; paclobutrazol; pefurazoate; penconazole; pencycuron; phosdiphen; phthalide; picoxystrobin; piperalin; polyoxins; polyoxorim; probenazole; prochloraz; procymidone; propamocarb; propanosine-sodium; propiconazole; propineb; proquinazid; prothioconazole; pyraclostrobin; pyrazophos; pyrifenox; pyrimethanil; pyroquilon; pyroxyfur; pyrroInitrin; quinconazole; quinoxyfen; quintozene; simeconazole; spiroxamine; sulphur; tebuconazole; tecloftalam; tecnazene; tetcyclacis; tetraconazole; thiabendazole; thicyofen; thifluzamide; thiophanate-methyl; thiram; tioxymid; tolclofos-methyl; tolylfluanid; triadimefon; triadimenol; triazbutil; triazoxide; tricyclamide; tricyclazole; tridemorph; trifloxystrobin; triflumizole; triforine; triticonazole; uniconazole; validamycin A; vinclozolin; zineb; ziram; zoxamide; (2S)—N-[2-[4-[[3-(4-chlorophenyl)-2-propynyl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulphonyl)amino]butanamide; 1-(1-naphthalenyl)-1H-pyrrole-2,5-dione; 2,3,5,6-tetrachloro-4-(methylsulphonyl)pyridine; 2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide; 2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide; 3,4,5-trichloro-2,6-pyridinedicarbonitrile; Actinovate; cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol; methyl 1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate; monopotassium carbonate; N-(6-methoxy-3-pyridinyl)cyclopropanecarboxamide; N-butyl-8-(1,1-dimethyl ethyl)-1-oxaspiro[4.5]decan-3-amine; sodium tetrathiocarbonate;
  • and copper salts and preparations such as Bordeaux mixture; copper hydroxide; copper naphthenate; copper oxychloride; copper sulphate; cufraneb; cuprous oxide; mancopper; oxine-copper.
    • Bactericides:
  • bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
  • insecticides/Acaricides/Nematicides:
  • abamectin, ABG-9008, acephate, acequinocyl, acetamiprid, acetoprole, acrinathrin, AKD-1022, AKD-3059, AKD-3088, alanycarb, aldicarb, aldoxycarb, allethrin 1R-isomers, alpha-cypermethrin (alphamethrin), amidoflumet, aminocarb, amitraz, avermectin, AZ-60541, azadirachtin, azamethiphos, azinphos-methyl, azinphos-ethyl, azocyclotin,
  • Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Bacillus thuringiensis strain EG-2348, Bacillus thuringiensis strain GC-91, Bacillus thuringiensis strain NCTC-11821, baculoviruses, Beauveria bassiana, Beauveria tenella, bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, beta-cypermethrin, bifenazate, bifenthrin, binapacryl, bioallethrin, bioallethrin S-cyclopentyl isomer, bioethanomethrin, biopermethrin, bioresmethrin, bistrifluoron, BPMC, brofenprox, bromophos-ethyl, bromopropylate, bromfenvinfos (-methyl), BTG-504, BTG-505, bufencarb, buprofezin, butathiofos, butocarboxim, butoxycarboxim, butylpyridaben,
  • cadusafos, camphechlor, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, CGA-50439, quinomethionate, chlordane, chlordimeform, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorobenzilate, chloropicrin, chlorproxyfen, chlorpyrifos-methyl, chlorpyrifos (-ethyl), chlovaporthrin, chromafenozide, cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrin, cloethocarb, clofentezine, clothianidin, clothiazoben, codlemone, coumaphos, cyanofenphos, cyanophos, cycloprene, cycloprothrin, Cydia pomonella, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyphenothrin (1R-trans isomer), cyromazine,
  • DDT, deltamethrin, demeton-S-methyl, demeton-S-methylsulphone, diafenthiuron, dialifos, diazinon, dichlofenthion, dichlorvos, dicofol, dicrotophos, dicyclanil, diflubenzuron, dimethoate, dimethylvinphos, dinobuton, dinocap, dinotefuran, diofenolan, disulfoton, docusate-sodium, dofenapyn, DOWCO-439,
  • eflusilanate, emamectin, emamectin benzoate, empenthrin (1R isomer), endosulfan, Entomophthora spp., EPN, esfenvalerate, ethiofencarb, ethiprole, ethion, ethoprophos, etofenprox, etoxazole, etrimfos,
  • famphur, fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin, fenitrothion, fenobucarb, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fensulfothion, fenthion, fentrifanil, fenvalerate, fipronil, flonicamid, fluacrypyrim, fluazuron, flubenzimine, flubrocythrinate, flucycloxuron, flucythrinate, flufenerim, flufenoxuron, flufenprox, flumethrin, flupyrazofos, flutenzin (flufenzine), fluvalinate, fonofos, formetanate, formothion, fosmethilan, fosthiazate, fubfenprox (fluproxyfen), furathiocarb,
  • gamma-HCH, gossyplure, grandlure, granulosis viruses,
  • halfenprox, halofenozide, HCH, HCN-801, heptenophos, hexaflumuron, hexythiazox, hydramethylnone, hydroprene,
  • IKA-2002, imidacloprid, imiprothrin, indoxacarb, iodofenphos, iprobenfos, isazofos, isofenphos, isoprocarb, isoxathion, ivermectin, japonilure,
  • kadethrin, nuclear polyhedrosis viruses, kinoprene,
  • lambda-cyhalothrin, lindane, lufenuron,
  • malathion, mecarbam, mesulfenfos, metaldehyde, metam-sodium, methacrifos, methamidophos, Metarhizium anisopliae, Metarhizium flavoviride, methidathion, methiocarb, methomyl, methoprene, methoxychlor, methoxyfenozide, metolcarb, metoxadiazone, mevinphos, milbemectin, milbemycin, MKI-245, MON-45700, monocrotophos, moxidectin, MTI-800,
  • naled, NC-104, NC-170, NC-184, NC-194, NC-196, niclosamide, nicotine, nitenpyram, nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI-9768, novaluron, noviflumuron,
  • OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, omethoate, oxamyl, oxydemeton-methyl,
  • Paecilomyces fumosoroseus, parathion-methyl, parathion (-ethyl), permethrin (cis-, trans-), petroleum, PH-6045, phenothrin (1R-trans isomer), phenthoate, phorate, phosalone, phosmet, phosphamidon, phosphocarb, phoxim, piperonyl butoxide, pirimicarb, pirimiphos-methyl, pirimiphos-ethyl, prallethrin, profenofos, promecarb, propaphos, propargite, propetamphos, propoxur, prothiofos, prothoate, protrifenbute, pymetrozine, pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridalyl, pyridaphenthion, pyridathion, pyrimidifen, pyriproxyfen,
  • quinalphos,
  • resmethrin, RH-5849, ribavirin, RU-12457, RU-15525,
  • S-421, S-1833, salithion, sebufos, SI-0009, silafluofen, spinosad, spirodiclofen, spiromesifen, sulfluramid, sulfotep, sulprofos, SZI-121,
  • tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin, temephos, temivinphos, terbam, terbufos, tetrachlorvinphos, tetradifon, tetramethrin, tetramethrin (1R isomer), tetrasul, theta-cypermethrin, thiacloprid, thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thiometon, thiosultap-sodium, thuringiensin, tolfenpyrad, tralocythrin, tralomethrin, transfluthrin, triarathene, triazamate, triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb,
  • vamidothion, vaniliprole, verbutin, Verticillium lecanii,
  • WL-108477, WL-40027,
  • YI-5201, YI-5301, YI-5302,
  • XMC, xylylcarb,
  • ZA-3274, zeta-cypermethrin, zolaprofos, ZXI-8901,
  • the compound 3-methylphenyl propylcarbamate (Tsumacide Z),
  • the compound 3-(5-chloro-3-pyridinyl)-8-(2,2,2-trifluoroethyl)-8-azabicyclo[3.2.1]octane-3-carbonitrile (CAS Reg. No. 185982-80-3) and the corresponding 3-endo isomer (CAS Reg. No. 185984-60-5) (cf. WO 96/37494, WO 98/25923),
  • and preparations which contain insecticidally active plant extracts, nematodes, fungi or viruses.
  • A mixture with other known active compounds, such as herbicides, or with fertilizers and growth regulators, is also possible.
  • In addition, the compounds of the formula (I)/active compound combinations according to the invention also have very good antimycotic activity. They have a very broad antimycotic activity spectrum in particular against dermatophytes and yeasts, moulds and diphasic fungi (for example against Candida species, such as Candida albicans, Candida glabrata), and Epidermophyton floccosum, Aspergillus species, such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species, such as Trichophyton mentagrophytes,
  • Microsporon species such as Microsporon canis and audouinii. The listing of these fungi by no means limits the mycotic spectrum that can be covered, but is only for illustration.
  • The active compounds/active compound combinations can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. Application is carried out in a customary manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming, spreading, etc. It is further possible to apply the active compounds by the ultra-low-volume method, or to inject the active compound preparation or the active compound itself into the soil. It is also possible to treat the seeds of the plants.
  • When using the active compounds/active compound combinations according to the invention as fungicides, the application rates can be varied within a relatively wide range, depending on the kind of application. For the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10 000 g/ha, preferably between 10 and 1000 g/ha. For seed dressing, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. For the treatment of the soil, the active compound application rates are generally between 0.1 and 10 000 g/ha, preferably between 1 and 5000 g/ha.
  • The preparation and the use of the active compounds/active compound combinations according to the invention are illustrated by the examples below.
    • PREPARATION EXAMPLES Example I-1-a-1
  • Figure US20110190493A1-20110804-C00108
  • 4.88 g (0.042 mol) of potassium tert-butoxide are initially charged in 13 ml of anhydrous dimethylformamide (DMF), 6.82 g of Example II-1 in 14 ml of anhydrous DMF are added dropwise at 60° C. and the mixture is stirred at 80° C. and monitored by thin-layer chromatography.
  • After the reaction has ended, the reaction solution is poured into 150 ml of ice-water and, at 0 to 10° C., acidified to pH=2 using concentrated hydrochloric acid, and the precipitate is filtered off with suction, washed with ice-water and then dried. This is followed by purification by silica gel column chromatography (dichloromethane/acetone=5:1).
  • Yield: 2.5 g (40% of theory), m.p. 233° C.
    • Example I-1-a-8
  • Figure US20110190493A1-20110804-C00109
  • Under argon protective gas, 0.644 g (2 mmol) of the compound of Example XIV-1-1 is initially charged in 30 ml of xylene, 2.083 g (20 mmol) of 1,2-pentanediol and 0.059 g (0.29 mmol) of p-toluenesulphonic acid are added at room temperature, 0.5 g of molecular sieve 4 Å (powder) is added and the mixture is stirred under reflux for three days and monitored by thin-layer chromatography.
  • After reaction has ended, the solvent is distilled off. The product is purified by silica gel column chromatography (dichloromethane/acetone=5:1).
  • Yield: 0.27 g (̂ 35% of theory), m.p. 273° C.
  • The following compounds of the formula (I-1-a) are obtained analogously to Example (I-1-a-1) and in accordance with the general statements on the preparation
  • (I-1-a)
    Figure US20110190493A1-20110804-C00110
    Ex. No. W X Y Z A B m.p. ° C. Isomer
    I-1-a-2 CH3 CH3 CH3 H 4′-O—(CH2)2—O— >220 —
    I-1-a-3 CH3 CH3 CH3 CH3 4′-O—(CH2)2—O— >240 —
    I-1-a-4 CH3 CH3 Cl H 4′-O—(CH2)2—O— >240 —
    I-1-a-5 H CH3 CH3 CH3 4′-O—(CH2)2—O— 240 —
    I-1-a-6 CH3 Cl Cl H 4′-O—(CH2)2—O— >245 —
    I-1-a-7 CH3 CH3 CH3 H 4′-O—CHCH3—CHCH3—O— * mixture
    I-1-a-8 CH3 CH3 CH3 H 4′-O—CHC3H7—CH2—O— 273 A
    logP
    2.73
    I-1-a-9 CH3 CH3 CH3 H 4′-O—CHC3H7—CH2—O— decomp. B
    logP
    2.78
    I-1-a-10 CH3 CH3 CH3 H 4′-O—CHCH3—CHCH3—O— 275 mixture
    I-1-a-11 CH3 Cl Cl H 4′-O—(CH2)3—O— 262 —
    I-1-a-12 H CH3 H CH3 4′-O—(CH2)3—O— 166 —
    I-1-a-13 CH3 CH3 CH3 CH3 4′-O—(CH2)3—O— 263 —
    I-1-a-14 CH3 CH3 Cl H 4′-O—(CH2)3—O— 312 —
    I-1-a-15 H Cl H 4-Cl—Ph 4′-O—(CH2)3—O— 133 —
    I-1-a-16 H CH3 H 4-Cl—Ph 4′-O—(CH2)3—O— 210
    I-1-a-17 H CH3 CH3 CH3 4′-O—(CH2)3—O— 189 —
    I-1-a-18 CH3 CH3 CH3 H 4′-O—(CH2)3—O— 229 —
    I-1-a-19 CH3 CH3 Br H 4′-O—(CH2)3—O— 255 —
    I-1-a-20 CH3 CH3 Cl H 4′-O—CH2—C(CH3)2—CH2—O— 273 —
    I-1-a-21 CH3 CH3 CH3 H 4′-O—CHCH3—CH2—CHCH3— 265 mixture
    I-1-a-22 CH3 CH3 CH3 H 4′-O—CHCH3—C(CH2)2—O— 230 mixture
    I-1-a-23 CH3 CH3 CH3 H 4′-O—CH2—C(CH3)2—CH2—O— 230 —
    I-1-a-24 CH3 OCH3 CH3 H 4′-O—(CH2)3—O— 202 —
    I-1-a-25 CH3 C2H5 CH3 H 4′-O—(CH2)2—O— decomp. —
    I-1-a-26 CH3 CH3 Br H 4′-O—(CH2)2—O— 306 —
    I-1-a-27 H CH3 H 5-(4-Cl—Ph) 4′-O—(CH2)2—O— 154 —
    I-1-a-28 H CH3 H CH3 4′-O—CHCH3—CH2—O— wax mixture
    I-1-a-29 H CH3 H CH3 4′-O—CHCH3—CHCH3—O— 84 mixture
    I- I-a-30 CH3 CH3 Cl H 4′-O—CHCH3—CHCH3—O— 268 mixture
    I-1-a-31 CH3 CH3 Cl H -4′O—CHCH3—CH2—O— 301 mixture
    I-1-a-32 CH3 CH3 Br H 4′-O—CH2—CHCH3—CH2—O— 171 mixture
    I-1-a-33 CH3 CH3 Br H 4′-O—CH2—C(CH3)2—CH2—O— 266 —
    I-1-a-34 CH3 CH3 Cl H 4′-O—CH2—CHCH3—CH2—O— 265 mixture
    I-1-a-35 CH3 CH3 Cl H 4′-O—CHCH3—(CH2)2 —O— 243 mixture
    I-1-a-36 H CH3 H CH3 4′O—CHCH3—CH2—CHCH3—O— 161 mixture
    I-1-a-37 H CH3 H CH3 4′-O—CHCH3—(CH2)2 —O— oil mixture
    I-1-a-38 CH3 CH3 Cl H 4′-O—CHCH3—CH2—CHCH3—O— 276 mixture
    I-1-a-39 CH3 C2H5 Br H 4′-O—(CH2)2—O— 293 —
    I-1-a-40 C2H5 C2H5 CH3 H 4′-O—(CH2)2—O— 269 —
    I-1-a-41 H CH3 Cl CH3 4′-O—(CH2)2—O— 236 —
    I-1-a-42 C2H5 OCH3 Cl H 4′-O—(CH2)2—O— 234 —
    I-1-a-43 CH3 OCH3 CH3 H 4′-O—(CH2)2—O— 237 —
    I-1-a-44 C2H5 Cl Cl H 4′-O—(CH2)2—O— 305 —
    I-1-a-45 C2H5 CH3 Br H 4′-O—CHCH3—CHCH3—O— 148 mixture
    I-1-a-46 CH3 CH3 Br H 4′-O—CHCH3—CHCH3—O— 275 mixture
    I-1-a-47 CH3 CH3 Br H 4′-O—CHCH3—CH2—O— 292 mixture
    I-1-a-48 C2H5 Br CH3 H 4′-O—(CH2)2—O— 296 —
    I-1-a-49 H Cl H 4-Cl—Ph 4′-O—(CH2)2—O— 257 —
    I-1-a-50 CH3 CH3 Br H
    Figure US20110190493A1-20110804-C00111
         		116 mixture
    I-1-a-51 CH3 CH3 H 4-Cl—Ph 4′-O—CHCH3—CH2—O— 288 mixture
    I-1-a-52 H CH3 H 4-Cl—Ph 4′-O—CHCH3—CH2—O— 198 mixture
    I-1-a-53 CH3 C2H5 Br H 4′-O—CHCH3—CH2—O— 255 mixture
    I-1-a-54 H CH3 H 4-Cl—Ph 4′-O—CHCH3—CHCH3—O— 213 mixture
    I-1-a-55 H CH3 Cl CH3 4′-O—CHCH3—CH2—O— 272 mixture
    I-1-a-56 CH3 CH3 Br H 4′-O—CHCH3—CH2—CHCH3—O— 262 mixture
    I-1-a-57 H Cl Cl H 4′-O—(CH2)3—O— 237 —
    I-1-a-58 CH3 CH3 Br H 4′-O—CHCH3—(CH2)2—O— 80 mixture
    I-1-a-59 CH3 Cl Cl H 4′-O—CH2—C(CH3)2—CH2—O— 264 —
    I-1-a-60 CH3 C2H5 Br H 4′-O—CHCH3—(CH2)2 —O— 190 mixture
    I-1-a-61 H CH3 H CH3 4′-O—CH2—C(CH3)2—CH2—O— 240 —
    I-1-a-62 H CH3 H CH3 4′-O—CH2—CHCH3—CH2—O— 276 mixture
    I-1-a-63 CH3 C2H5 Br H 4′O—CHCH3—CH2—CHCH3—O— >300 mixture
    I-1-a-64 H Cl H 4-Cl—Ph 4′-O—CH2—C(CH3)2—CH2—O— 276 —
    I-1-a-65 H Cl H 4-Cl—Ph 4′-O—CH2—CHCH3—CH2—O— 79 mixture
    I-1-a-66 H CH3 H 4-Cl—Ph 4′-O—CHCH3—(CH2)2—O— 67 mixture
    I-1-a-67 H CH3 H 4-Cl—Ph 4′-O—CH2—C(CH3)2—CH2—O— 234 —
    I-1-a-68 H CH3 H CH3 3′-O—(CH2)2—O— 211 —
    I-1-a-69 C2H5 Br CH3 H 3′-O—(CH2)2—O— decomp. —
    I-1-a-70 CH3 CH3 Cl H 3′-O—(CH2)2—O— 260 —
    I-1-a-71 CH3 CH3 CH3 H
    Figure US20110190493A1-20110804-C00112
         		oil mixture
    I-1-a-72 C2H5 Br CH3 H
    Figure US20110190493A1-20110804-C00113
         		oil mixture
    I-1-a-73 H CH3 H CH3
    Figure US20110190493A1-20110804-C00114
         		oil mixture
    I-1-a-74 CH3 CH3 Cl H
    Figure US20110190493A1-20110804-C00115
         		82 mixture
    I-1-a-75 CH3 CH3 Cl H
    Figure US20110190493A1-20110804-C00116
         		67 mixture
    I-1-a-76 H Cl H 4-Cl—Ph 4′-O—CHCH3—CH2—O— 68 mixture
    I-1-a-77 C2H5 Br CH3 H 4′-O—CHCH3—CH2—O— 281 mixture
    I-1-a-78 H Cl H 4-Cl—Ph 4′-O—CHCH3—(CH2)2—O— 232 mixture
    I-1-a-79 H Cl H 4-Cl—Ph 4′-O—CH2—CHCH3—CH2—O— 160 mixture
    I-1-a-80 H Cl H 4-Cl—Ph 4′O—CHCH3—CH2—CHCH3—O— 268 mixture
    I-1-a-81 H Cl H 4-Cl—Ph 4′-O—CH2—C(CH3)2—CH2—O— 151 —
    I-1-a-82 CH3 C2H5 Br H 4′-O—(CH2)3—O— 244 —
    I-1-a-83 CH3 CH3 Cl H 3′-O—CHCH3—CH2—O— 167 mixture
    I-1-a-84 CH3 CH3 Cl H 3′-O—CH2—C(CH3)2—CH2—O— 266 mixture
    I-1-a-85 CH3 CH3 Cl H 3′-O—(CH2)3—O— 261 mixture
    I-1-a-86 CH3 C2H5 4-Cl—Ph H 4′-O—CHCH3—CH2—O— 219-222 mixture
    *1H-NMR (400 MHz, d6-DMSO): δ = 1.05-1.09 (2d, 6H, 2xCHCH3); 4.18-4.23 (m, 2H, 2xCHCH3) ppm
    decomp. = decomposition
    Figure US20110190493A1-20110804-C00117
    • Example I-1-b-1
  • Figure US20110190493A1-20110804-C00118
  • 1.82 g of the compound of Example I-1-a-4 are initially charged in 50 ml of anhydrous ethyl acetate and 0.77 ml (5.5 mmol) of triethylamine under reflux. 0.55 ml (0.0055 mol) of isobutyryl chloride in 5 ml of anhydrous ethyl acetate is added, and the mixture is stirred under reflux.
  • After the reaction has ended (monitored by thin-layer chromatography) the solvent is distilled off and the residue is taken up in dichloromethane. The mixture is washed twice with 30 ml of 0.5 N NaOH and dried, and the solvent is distilled off.
  • The product is purified by silica gel column chromatography (dichloromethane/ethyl acetate=3:1).
  • Yield: 0.3 g (14% of theory), m.p. 215° C.
  • The following compounds of the formula (I-1-b) are obtained analogously to Example (I-1-b-1) and in accordance with the general statements on the preparation
  • (I-1-b)
    Figure US20110190493A1-20110804-C00119
    Ex. No. W X Y Z A B R1 m.p. ° C. Isomer
    I-1-b-2 CH3 C2H5 Br H 4′-O—(CH2)2—O— H3CO—CH2— *3.23 (s, 3H, OCH 3) —
    7.21 (s, 2H, —Ar—H)
    I-1-b-3 CH3 C2H5 Br H 4′-O—(CH2)2—O— i-C3H7 solidified foam —
    I-1-b-4 C2H5 Cl Cl H 4′-O—(CH2)2—O— i-C3H7 106-112 —
    I-1-b-5 C2H5 Br CH3 H 4′-O—CHCH3—CHCH3—O— i-C3H7 198-200 mixture
    I-1-b-6 C2H5 Cl Cl H 4′-O—(CH2)2—O— H3CO—CH2— *2.63(m, 2H, Ar—CH 2) —
    3.29(s, 3H, OCH 3)
    I-1-b-7 C2H5 OCH3 Cl H 4′-O—(CH2)2—O— H3CO—CH2— 170-175 —
    I-1-b-8 C2H5 Br CH3 H 3′-O—(CH2)2—O— i-C3H7 solidified foam —
    **1.07(m, 6H,
    CHCH 2)2)
    2.28(s,3H, ArCH 3)
    I-1-b-9 C2H5 Br CH3 H 3′-O—(CH2)2—O— H3CO—CH2— *2.29(s, 3H, Ar—CH 3) —
    3.26(s, 3H, OCH 3)
    I-1-b-10 C2H5 Br CH3 H
    Figure US20110190493A1-20110804-C00120
         		i-C3H7 oil **1.05(m, 6H, CHCH 3)2) 2.29(s,3H,ArCH 3) mixture
    I-1-b-11 C2H5 Br CH3 H
    Figure US20110190493A1-20110804-C00121
         		H3CO—CH2— oil **2.29(s, 3H, ArCH 3) 3.26(s, 3H, OCH 3) mixture
    I-1-b-12 CH3 C2H5 Br H 4′-O—CHCH3—CH2—CHCH3—O—
    Figure US20110190493A1-20110804-C00122
         		225 mixture
    I-1-b-13 CH3 C2H5 Br H 4′-O—CHCH3—(CH2)2—O— 2-Cl—Ph 225 mixture
    I-1-b-14 CH3 C2H5 Br H 4′-O—CHCH3—CHCH3—O—
    Figure US20110190493A1-20110804-C00123
         		246 mixture
    I-1-b-15 CH3 C2H5 Br H
    Figure US20110190493A1-20110804-C00124
         		t-C4H9 solidified foam mixture
    I-1-b-16 CH3 C2H5 Br H 4′-O—CHCH3—CH2—O— i-C3H7 194 mixture
    I-1-b-17 CH3 C2H5 Br H 4′-O—CHCH3—(CH2)2—O— i-C3H7 *1.06(m, 6H, CH(CH 3)2) 7.21(s, 2H, ArH) mixture
    I-1-b-18 C2H5 CH3 Br H 4′-O—CHCH3—CHCH3—O— H3CO—CH2 *3.24(s,3H, OCH 3) mixture
    7.21(s,2H, Ar—H)
    I-1-b-19 C2H5 CH3 CH3 H 4′-O—(CH2)2—O— i-C3H7 *0.98 (dd, 6H, —
    CH(CH 3)2)
    3.98 (m, 4H, CH 2O)
    6.86 (s, 2H, Ar—H)
    I-1-b-20 C2H5 CH3 Br H 4′-O—CHCH3—CH2—CHCH3—O— i-C3H7 120 mixture
    *1H-NMR (400 MHz, CDCl3); shifts δ in ppm
    **1H-NMR (300 MHz, CDC13): shifts δ in ppm
    • Example I-1-c-1
  • Figure US20110190493A1-20110804-C00125
  • 1.82 g of the compound of Example I-1-a-4 are stirred at 10 to 20° C. in 30 ml of anhydrous dichloromethane and 0.7 ml of triethylamine. 0.5 ml of ethyl chloroformate in 2 ml of anhydrous dichloromethane is added, and the mixture is stirred at room temperature.
  • After the reaction has ended (monitored by thin-layer chromatography), the mixture is washed twice with 10 ml of 0.5 N NaOH and dried over magnesium sulphate. The solvent is then distilled off.
  • The product is purified by silica gel column chromatography (dichloromethane/ethanol=30:1).
  • Yield: 1.15 g (52% of theory), m.p. 198° C.
  • The following compounds of the formula (I-1-c) are obtained analogously to Example (I-1-c-1) and in accordance with the general statements on the preparation:
  • (I-1 -C)
    Figure US20110190493A1-20110804-C00126
    Ex. No. W X Y Z A B M R2 m.p. ° C. Isomer
    I-1-c-2 CH3 CH3 CH3 H 4′-O—(CH2)2—O— O C2H5 181 —
    I-1-c-3 H CH3 CH3 CH3 4′-O—(CH2)2—O— O C2H5 221 —
    I-1-c-4 CH3 Cl Cl H 4′-O—(CH2)2—O— O C2H5 233 —
    I-1-c-5 CH3 CH3 CH3 CH3 4′-O—(CH2)2—O— O C2H5 209 —
    I-1-c-6 CH3 CH3 CH3 H 4′-O—CHCH3—CH2—O— O C2H5 218 mixture
    I-1-c-7 CH3 Cl Cl H 4′—-O—(CH2)3—O— O C2H5 235 —
    I-1-c-8 CH3 CH3 Cl H 4′-O—(CH2)3—O— O C2H5 195 —
    I-1-c-9 H CH3 CH3 CH3 4′-O—(CH2)3—O— O C2H5 235 —
    I-1-c-10 CH3 CH3 Br H 4′-O—(CH2)3—O— O C2H5 234 —
    I-1-c-11 CH3 CH3 CH3 H 4′-O—(CH2)3—O— O C2H5 229 —
    I-1-c-12 CH3 CH3 Cl H 4′-O—CH2—CHCH3—CH2—O— O C2H5 241 mixture
    I-1-c-13 CH3 CH3 Cl H 4′-O—CH2—C(CH3)2—CH2—O— O C2H5 247 —
    I-1-c-14 CH3 C2H5 Br H 4′-O—(CH2)2—O— O C2H5 200-201 —
    I-1-c-15 CH3 C2H5 CH3 H 4′-O—(CH2)2—O— O C2H5 oil —
    I-1-c-16 H CH3 H 4-Cl—Ph 4′-O—(CH2)2—O— O C2H5 197 —
    I-1-c-17 CH3 CH3 Cl H 4′-O—CHCH3—CH2—O— O C2H5 223 mixture
    I-1-c-18 CH3 CH3 Cl H 4′-O—CHCH3—CHCH3—O— O C2H5 232 mixture
    I-1-c-19 H CH3 H CH3 4′-O—CHCH3—CH2—O— O C2H5 141 mixture
    I-1-c-20 CH3 CH3 Br H 4′-O—(CH2)2—O— O C2H5 222 —
    I-1-c-21 H CH3 Cl CH3 4′-O—(CH2)2—O— O C2H5 187 —
    I-1-c-22 H CH3 H CH3 4′-O—CHCH3—CHCH3—O— O C2H5 180 mixture
    I-1-c-23 C2H5 C2H5 CH3 H 4′-O—(CH2)2—O— O C2H5 179 —
    I-1-c-24 CH3 O—CH3 CH3 H 4′-O—(CH2)2—O— O C2H5 176 —
    I-1-c-25 C2H5 O—CH3 Cl H 4′-O—(CH2)2—O— O C2H5 **1.16 —
    (,,q″, 6H, —Ar—CH2—CH3
    and O—CH2—CH3) 3.79
    (s, 3H, Ar—OCH3)
    I-1-c-26 C2H5 Cl Cl H 4′-O—(CH2)2—O— O C2H5 175-183 —
    I-1-c-27 CH3 C2H5 Br H 4′-O—CHCH3—CH2—O— O C2H5 181 mixture
    I-1-c-28 C2H5 Cl Cl H 4′-O—(CH2)2—O— O C6H5—CH2— 173 —
    I-1-c-29 CH3 C2H5 Br H 4′-O—CHCH3—CHCH3—O— O CH2═CH—CH2— 187 mixture
    I-1-c-30 CH3 CH3 Cl H 4′-O—CHCH3—(CH2)2—O— O C2H5 229 mixture
    I-1-c-31 H CH3 H 4-Cl—Ph 4′-O—(CH2)3—O— O C2H5 207 —
    I-1-c-32 CH3 CH3 Br H 4′-O—CH2—CHCH3—CH2—O— O C2H5 242 mixture
    I-1-c-33 CH3 CH3 Br H 4′-O—CH2—C(CH3)2—CH2—O— O C2H5 250 —
    I-1-c-34 CH3 O—CH3 CH3 H 4′-O—(CH2)3—O— O C2H5 222 —
    I-1-c-35 H CH3 H CH3 4′-O—CH2—C(CH3)2—CH2—O— O C2H5 194 —
    I-1-c-36 H CH3 H CH3 4′-O—CH2—CHCH3 —CH2—O— O C2H5 169 mixture
    I-1-c-37 CH3 C2H5 Br H 4′-O—CHCH3—CH2—CHCH3—O— O C2H5 175-178 mixture
    I-1-c-38 CH3 C2H5 Br H 4′-O—CHCH3—(CH2)2—O— O C2H5 97 mixture
    I-1-c-39 H Cl H 4-Cl—Ph 4′-O—(CH2)3—O— O C2H5 237 —
    I-1-c-40 H CH3 H CH3 3′-O—(CH2)2—O— O C2H5 156 —
    I-1-c-41 CH3 CH3 Cl H 3′-O—(CH2)2—O— O C2H5 193 —
    I-1-c-42 C2H5 Br CH3 H 3′-O—(CH2)2—O— O C2H5 **2.58 —
    (m, 2H, Ar—CH2—), 4.08
    (q, 2H,
    OCH 2—CH3)
    I-1-e-43 C2H5 Br CH3 H
    Figure US20110190493A1-20110804-C00127
         		O C2H5 oil**1.18 (,,q″, 6H, Ar—CH2—CH3 and O—CH2—CH3) 2.32 (s, 3H, Ar—CH3) mixture
    I-1-c-44 C2H5 Br CH3 H 3′-O—(CH2)2—O— O (H3C)3 foam —
    C—CH2— **0.8
    (s, 9H,
    C(CH3)3)
    2.28
    (s, 3H, Ar—CH3)
    I-1-c-45 H Cl H 4-Cl—Ph 4′-O—CHCH3—CH2—O— O C2H5 219 mixture
    I-1-c-46 H Cl H 4-Cl—Ph 4′-O—(CH2)2—O— O C2H5 239 —
    *1H-NMR (400 MHz, CDCl3): shifts δ in ppm
    **1H-NMR (300 MHz, CDCl3): shifts δ in ppm
    • Example I-1-d-1
  • Figure US20110190493A1-20110804-C00128
  • 0.159 g of the compound of Example I-1-a-44 is initially charged in 10 ml of trichloromethane, 0.098 ml of diisopropylethylamine and 1.5 mg of DMAP are added at room temperature, 0.037 ml of methanesulphonyl chloride is added and the mixture is stirred for 20 hours, 5 ml of NaCl solution are added, the mixture is stirred at room temperature for about 0.5 hours and the organic phase is separated off, dried with sodium sulphate and concentrated using a rotary evaporator. The resulting crude product is purified by column chromatography on silica gel using an n-heptane/ethyl acetate gradient of from 4:1 to 0:100.
  • Yield: 0.07 g (37% of theory), m.p.: 217° C.
    • Example I-1-g-1
  • Figure US20110190493A1-20110804-C00129
  • 0.233 g of the compound of Example I-1-a-72 is initially charged in 8 ml of chloroform, 0.098 ml of diisopropylethylamine and 1.5 mg of DMAP are added, 0.056 ml of morpholinecarbonyl chloride is then added, the mixture is stirred at room temperature for 20 hours, 5 ml of 5% strength sodium bicarbonate solution are added, the mixture is stirred for another 0.5 hours and the organic phase is separated off, dried with sodium sulphate and concentrated using a rotary evaporator. The crude product is purified by column chromatography on silica gel using an n-heptane/ethyl acetate gradient from 4:1 to 0:100.
  • Yield: 0.148 g (64% of theory), oil
  • 1H-NMR (400 MHz, CDCl3): δ=2.31 (2, 3H, Ar—CH 3), 3.1, 3.2 (each m, 2H, CH2O) ppm.
    • Example II-1
  • Figure US20110190493A1-20110804-C00130
  • 9.56 g of 8-aminomethyl 1,4-dioxaspiro[4.5]decane-8-carboxylate hydrochloride are initially charged in 38 ml of anhydrous acetonitrile, and 17.5 g (0.127 mol) of ground potassium carbonate are added at from 5 to 10° C. 6.94 g of 2,5-dimethylphenylacetyl chloride in 10 ml of anhydrous acetonitrile are then added dropwise over a period of 12 minutes.
  • The mixture is stirred at room temperature for 3 h.
  • The reaction solution is poured into 250 ml of ice-water, and the precipitate is filtered off with suction. The precipitate is washed with water and taken up in dichloromethane, the mixture is dried and the solvent is distilled off. The product is purified by column chromatography on silica gel (dichloromethane/ethyl acetate=3:1).
  • Yield: 6.82 g (49% of theory), m.p. 115° C.
    • Example (II-2)
  • Figure US20110190493A1-20110804-C00131
  • 154.6 g (1.579 mol) of concentrated sulphuric acid are initially charged, and at an internal temperature of from 30 to 40° C., 107.9 g of the compound of Example (XXI-1) in 630 ml of methylene chloride are added dropwise as a suspension. The mixture is stirred at from 30 to 40° C. for 2 h, and 220 ml of anhydrous methanol are then added dropwise such that an internal temperature of 40° C. is obtained.
  • The mixture is stirred at an external temperature of 40 to 70° C. for a further 6 h.
  • The reaction solution is poured onto 1.5 kg of ice, extracted with dichloromethane and washed with NaHCO3 solution. The mixture is dried and the solvent is distilled off.
  • The product is purified by column chromatography on silica gel (toluene/ethyl acetate=1:1).
  • Yield: 11.4 g (10% of theory).
  • The following compounds of the formula (II) are obtained analogously to Examples (II-1) and (II-2) and in accordance with the general statements on the preparation
  • (II)
    Figure US20110190493A1-20110804-C00132
    Ex.
    No. W X Y Z A B R8 m.p. ° C.
    II-2 CH3 CH3 CH3 H 4′-O—(CH2)2—O— CH3 log P 2.68
    II-3 CH3 CH3 CH3 CH3 4′-O—(CH2)2—O— CH3 141
    II-4 CH3 CH3 Cl H 4′-O—(CH2)2—O— CH3 181
    II-5 H CH3 CH3 CH3 4′-O—(CH2)2—O— CH3 129
    II-6 CH3 Cl Cl H 4′-O—(CH2)2—O— CH3 159
    II-7 CH3 CH3 Br H 4′-O—(CH2)2—O— CH3 wax log P 2.81*
    II-8 CH3 C2H5 CH3 H 4′-O—(CH2)2—O— CH3 wax log P 2.95*
    II-9 CH3 C2H5 Br H 4′-O—(CH2)2—O— CH3 wax log P 3.19*
    II-11 CH3 Cl Cl H 4′-O—(CH2)3—O— CH3 175
    II-12 H CH3 H CH3 4′-O—(CH2)3—O— CH3 144
    II-13 CH3 CH3 CH3 CH3 4′-O—(CH2)3—O— CH3 148
    II-14 CH3 CH3 Cl H 4′-O—(CH2)3—O— CH3 184
    II-15 H Cl H 4-Cl—Ph 4′-O—(CH2)3—O— CH3 177
    II-16 H CH3 H 4-Cl—Ph 4′-O—(CH2)3—O— CH3 181
    II-17 H CH3 CH3 CH3 4′-O—(CH2)3—O— CH3 log P 2.59*
    II-18 CH3 CH3 CH3 H 4′-O—(CH2)3—O— CH3 143
    II-19 CH3 CH3 Br H 4′-O—(CH2)3—O— CH3 189
    II-20 CH3 CH3 Cl H 4′-O—CH2—C(CH3)2—CH2—O— CH3 178
    II-21 CH3 CH3 Cl H 4′-O—CH2-CHCH3—CH2—O— CH3 170
    II-22 CH3 CH3 Br H 4′-O—CH2—C(CH3)2—CH2—O— CH3 181
    II-23 CH3 CH3 Br H 4′-O—CH2—CHCH3—CH2—O— CH3 177
    II-24 CH3 OCH3 CH3 H 4′-O—(CH2)3—O— CH3 log P 2.49*
    II-25 CH3 CH3 Br H 4′-O—CHCH3—CHCH3—O— CH3 189
    II-26 CH3 CH3 Br H 4′-O—CHCH3—CH2—O— CH3 161
    II-27 H CH3 H CH3 4′-O—CHCH3—CHCH3—O— CH3 166
    II-28 CH3 CH3 Cl H 4′-O—CHCH3—CHCH3—O— CH3 183
    II-29 CH3 CH3 Cl H 4′-O—CHCH3—CH2—O— CH3 170
    II-30 H CH3 H CH3 4′-O—CHCH3—CH2—O— CH3 141
    II-31 H CH3 H 5-(4-Cl—Ph 4′-O—(CH2)2—O— CH3 log P 3.47*
    II-32 C2H5 C2H5 CH3 H 4′-O—(CH2)2—O— CH3 log P 3.28*
    II-33 CH3 OCH3 CH3 H 4′-O—(CH2)2—O— CH3 139
    II-34 H CH3 Cl CH3 4′-O—(CH2)2—O— CH3 182
    II-35 C2H5 OCH3 Cl H 4′-O—(CH2)2—O— CH3 153
    II-36 C2H5 Br CH3 H 4′-O—(CH2)2—O— CH3 log P 3.04*
    II-37 H CH3 H CH3 4′-O—CHCH3—CH2—CHCH3—O— CH3 122
    II-38 CH3 CH3 Cl H 4 ′-O—CHCH3—CH2—CHCH3—O— CH3 208
    II-39 H CH3 H CH3 4′-O—CHCH3—(CH2)2—O— CH3 144
    II-40 CH3 CH3 Cl H 4′-O—CHCH3—(CH2)2—O— CH3 174
    II-41 CH3 CH3 Br H 4′-O—CHCH3—(CH2)2—O— CH3 175
    II-42 CH3 CH3 Br H 4′-O—CHCH3—CH2—CHCH3—O— CH3 202
    II-43 CH3 C2H5 Br H 4′-O—CHCH3—CH2—CHCH3—O— CH3 200
    II-44 H CH3 H CH3 4′-O—CH2—C(CH3)2—CH2—O— CH3 157
    II-45 H CH3 H CH3 4′-O—CH2—CHCH3—CH2—O— CH3 154
    II-46 CH3 C2H5 Br H 4′-O—CHCH3—(CH2)2—O— CH3 158
    II-47 CH3 Cl Cl H 4′-O—CH2—C(CH3)2—CH2—O— CH3 197
    II-48 CH3 Cl Cl H 4′-O—CH2—CHCH3—CH2—O— CH3 174
    II-49 H Cl H 4-Cl—Ph 4′-O—CH2—C(CH3)2—CH2—O— CH3 205
    II-50 H Cl H 4-Cl—Ph 4′-O—CH2—CHCH3—CH2—O— CH3 166
    II-51 H CH3 H 4-Cl—Ph 4′-O—CH2—C(CH3)2—CH2—O— CH3 184
    II-52 H CH3 H 4-Cl—Ph 4′-O—CH2—CHCH3—CH2—O— CH3 163
    II-53 H CH3 H 4-Cl—Ph 4′-O—CHCH3—CH2—CHCH3—O— CH3 149
    II-54 CH3 C2H5 Br H 4′-O—CH2—C(CH3)2—CH2—O— CH3 241
    II-55 CH3 C2H5 Br H 4′-O—CH2—CHCH3—CH2—O— CH3 147
    II-56 CH3 C2H5 Br H 4′-O—CHCH3—CH2—O— CH3 157
    II-57 CH3 C2H5 Br H 4′-O—CHCH3—CHCH3—O— CH3 167
    II-58 C2H5 Cl Cl H 4′-O—(CH2)2—O— CH3 281
    II-59 H Cl H 4-Cl—Ph 4′-O—(CH2)2—O— CH3
    II-60 CH3 CH3 H 4-Cl—Ph 4′-O—CHCH3—CH2—O— CH3 173
    II-61 H CH3 Cl CH3 4′-O—CHCH3—CH2—O— CH3 165
    II-62 H CH3 H 4-Cl—Ph 4′-O—CHCH3—CH2—O— CH3 174
    II-63 H CH3 H 4-Cl—Ph 4′-O—CHCH3—CHCH3—O— CH3 151
    II-64 H Cl H 4-Cl—Ph 4′-O—CHCH3—CH2—O— CH3 181
    II-65 H Cl H 4-Cl—Ph 4′-O—CHCH3—CHCH3—O— CH3 182
    II-66 H CH3 H CH3 3′-O—(CH2)2—O— CH3 111
    II-67 C2H5 Br CH3 H 3′-O—(CH2)2—O— CH3 174
    II-68 CH3 CH3 Cl H 3′-O—(CH2)2—O— CH3 154
    II-69 CH3 CH3 Cl H
    Figure US20110190493A1-20110804-C00133
         		CH3 oil
    II-70 CH3 CH3 CH3 H
    Figure US20110190493A1-20110804-C00134
         		CH3 oil
    II-71 H CH3 H CH3
    Figure US20110190493A1-20110804-C00135
         		CH3 oil
    II-72 C2H5 Br CH3 H
    Figure US20110190493A1-20110804-C00136
         		CH3 oil
    II-73 C2H5 Br CH3 H 4′-O—CHCH3—CH2—O— CH3 143
    II-74 H Cl H 4-Cl—Ph 4′-O—CH2—CHCH3—CH2—O— CH3 169
    II-75 CH3 C2H5 Br H 4′-O—(CH2)3—O— CH3 165
    II-76 H Cl H 4-Cl—Ph 4′-O—CHCH3—(CH2)2—O— CH3 161
    II-77 H Cl H 4-Cl—Ph 4′-O—CHCH3—CH2—CHCH3—O— CH3 74
    II-78 C2H5 Br CH3 H 4′-O—CHCH3—CH2—CHCH3—O— CH3 84
    *The log P values given in the Preparation Examples and Tables above are determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C 18). Temperature: 43° C.
  • In the acidic range, the determination is carried out at pH 2.3 using 0.1% aqueous phosphoric acid and acetonitrile as mobile phases; linear gradient from 10% acetonitrile to 95% acetonitrile.
  • The determination by LC-MS in the acidic range is carried out at pH 2.7 using 0.1% aqueous formic acid and acetonitrile (comprises 0.1% formic acid) as mobile phases; linear gradient from 10% acetonitrile to 95% acetonitrile.
  • The determination by LC-MS in the neutral range is carried out at pH 7.8 using 0.001 molar aqueous ammonium bicarbonate solution and acetonitrile as mobile phases; linear gradient from 10% acetonitrile to 95% acetonitrile.
  • Calibration is carried out using unbranched alkan-2-ones (having 3 to 16 carbon atoms) with known logP values (determination of the logP values by the retention times using linear interpolation between two successive alkanones).
  • The lambda-max values were determined in the maxima of the chromatographic signals using the UV spectra from 200 nm to 400 nm.
    • Example (XXL-1)
  • Figure US20110190493A1-20110804-C00137
  • 49.4 ml of triethylamine are added to 65 g of 1,4-dioxaspiro[4.5]decane-8-amino-8-carbonitrile in 800 ml of anhydrous tetrahydrofuran (THF). At 0 to 10° C., 70.2 g of mesitylene acetyl chloride in 80 ml of anhydrous THF are added dropwise.
  • The mixture is stirred at room temperature.
  • After the reaction has ended (monitored by thin-layer chromatography), the reaction solution is added with stirring to 1.2 l of ice-water, 200 ml of 1N HCl are added and the precipitate is filtered off with suction. The latter is taken up in dichloromethane, and the aqueous phase is removed. The organic phase is dried, the solvent is distilled off and the residue is recrystallized from 320 ml of toluene/640 ml of n-hexane.
  • Yield: 107.9 g (88% of theory), m.p. >220° C.
    • Example XIV-1-1
  • Figure US20110190493A1-20110804-C00138
  • At room temperature, 20.6 g of the compound of Example I-1-c-2 in 24 g of semiconcentrated aqueous sodium hydroxide solution and about 100 ml of ethanol are stirred under argon protective gas for one hour, and the ethanol is then evaporated off. The solution is then acidified using hydrochloric acid, the entire mixture is dissolved in methylene chloride and the organic phase is separated off and concentrated by evaporation. The residue is stirred at 60° C. in 4 N hydrochloric acid for two hours.
  • The precipitate is separated off and stirred in ethyl acetate.
  • Yield: 6.67 g; m.p.: 293.9° C.
    • Example XVI-1
  • Figure US20110190493A1-20110804-C00139
  • 46 g of 1,4-dioxa[4.5]decane-8-amino-8-carboxylic acid are initially charged in 350 ml of anhydrous methanol, and 32.6 g (0.275 mol) of thionyl chloride are added dropwise at from 0 to 5° C. The mixture is stirred at 0° C. for 30 minutes (suspension) and then at 40° C. overnight.
  • The mixture is cooled, the potassium chloride is filtered off with suction and the solvent is distilled off. The residue is triturated with MTB ether and filtered off with suction.
  • Yield: 48.63 g (83% of theory), m.p.: decomposition
  • The following novel compounds of the formula (XVI) are obtained analogously to Example XVI-1
  • (XVI)
    Figure US20110190493A1-20110804-C00140
    Ex. No. A B R8 m.p. ° C.
    XVI-2 4′-O—CHCH3—CH2—O— CH3 * 1.18-1.19 (2d, 3H, CHCH3)
    3.76 (2s, 3H, OCH3)
    XVI-3 4′-O—CHCH3—CHCH3—O— CH3 * 3.76 (s, 3H, OCH3)
    4.18-4.23 (m, 2H, 2xCH—O)
    XVI 4′-O—(CH2)3—O— CH3 resin
    XVI-5 4′-O—CHCH3—(CH2)2—O— CH3 * 1.07-1.08 (d, 3H, CHCH3)
    3.77 (s, 3H, OCH3)
    XVI-6 —O—CH2—CHCH3—CH2—O— CH3 * 0.77 (d, 3H, CHCH 3)
    8.71 (3H, br, NH 3+)
    XVI-7 4′-O—CHCH3—CH2—CHCH3—O— CH3 * 1.07-1.15 (m, 6H, 2xCHCH 3)
    3.93-4.0 (m, 2H, O—CH)
    XVI-8 4′-O—CH2—C(CH3)2—CH2—O— CH3 * 0.9 (s, 6H, C(CH3)2)
    3.76 (s, 3H, OCH 3)
    XVI-9 3′-O—(CH)2—O— CH3 * 3.74, 3.75 (2s, 3H, CO2 CH 3)
    3.79-3.99 (m, 4H, —O—(CH 2)2—O—)
    XVI-10
    Figure US20110190493A1-20110804-C00141
         		CH3 * 3.28 (2s, 3H, OCH3) 3.73-3.75 (4s, 3H, CO2 CH 3)
    * 1H-NMR (400 MHz, d6-DMSO): shift δ in ppm
  • The substituted 1,4-dioxa[4,5]decane-8-amino-8-carboxylic esters and their salts of the formula (XVI′), the optionally substituted 1,4-dioxa[4,5]decane-7-amino-7-carboxylic esters and their salts of the formula (XVI″) and the optionally substituted 1,5-dioxa[5,5]undecane-9-amino-9-carboxylic esters and their salts of the formula (XVI′″), possible substituents being the substituents mentioned at the outset in the definition of A, B, are novel and form part of the subject-matter of the invention:
  • Figure US20110190493A1-20110804-C00142
  • in which
    • Q3 represents C1-C4-alkyl, C1-C3-haloalkyl, C1-C4-alkoxy or C1-C4-alkoxy-C1-C2-alkyl,
    • q represents 1, 2 or 3 and, in the case of the compounds of the formulae (XVI″) and (XVI′″), may also represent 0,
    • R8 is as defined above.
    Example XIX-1
  • Figure US20110190493A1-20110804-C00143
  • 112 g of the compound of Example are suspended in 710 ml of 30% strength KOH and, under reflux, stirred under an atmosphere of nitrogen.
  • At from 0 to 20° C., the mixture is acidified with concentrated HCl to a pH of from 5.2 to 5.3 and filtered off with suction, the filtrate is subjected to an azeotropic distillation with methanol until a volume of about 0.5 l is obtained, the potassium chloride is filtered off with suction and the filtrate is concentrated using a rotary evaporator and dehydrated azeotropically with methanol.
  • Yield: 46 g (46% of theory).
  • The following novel compounds of the formula (XIX) are obtained analogously to Example XIX-1
  • (XIX)
    Figure US20110190493A1-20110804-C00144
    Ex. No. A B
    XIX-2 4′-O—CHCH3—CH2—O—
    XIX-3 4′-O—CHCH3—CHCH3—O—
    XIX-4 4′-O—(CH2)3—O—
    XIX-5 4′-O—CHCH3—(CH2)2—O—
    XIX-6 4′-O—CH2—CHCH3—CH2—O—
    XIX-7 4′-O—CHCH3—CH2—CHCH3—O—
    XIX-8 4′-O—CH2—C(CH3)2—CH2—O—
    XIX-9 3′—O—(CH2)2—O—
    XIX-10
    Figure US20110190493A1-20110804-C00145
  • Without further purification, the amino acids were directly esterified to give the compounds (XVI). These were characterized. The substituted 1,4-dioxa[4,5]decane-8-amino-8-carboxylic acids (XIX'), the optionally substituted 1,4-dioxa[4,5]decane-7-amino-7-carboxylic acids of the formula (XIX″) and the optionally substituted 1,5-dioxa[5,5]undecane-9-aminocarboxylic acids of the formula (XIX′″), possible substituents of which are the substituents mentioned at the outset in the definition of the radicals A, B, are novel and also form part of the subject-matter of the invention:
  • Figure US20110190493A1-20110804-C00146
  • in which
    • Q3 is as defined above and
    • q represents 1, 2 or 3 and, in the case of the compounds of the formulae (XIX″) and (XIX′″), also 0.
    Example XXIII-1
  • Figure US20110190493A1-20110804-C00147
  • 16.4 g (335 mmol) of sodium cyanide and 128.7 g (1339 mmol) of ammonium carbonate are initially charged in 600 ml of water and, at room temperature, 57 g (335 mmol) of 1,4-dioxa[4,5]decane-2-methyl-8-one (XXIV-1), dissolved in 30 ml of ethanol, are slowly added dropwise.
  • The mixture is stirred at from 55 to 60° C. for about 12 to 15 hours.
  • The mixture is cooled to 0° C., the solid is filtered off with suction and resuspended in water, the suspension is filtered off with suction and the product is washed with hexane and dried.
  • Yield: 73.6 g (92% of theory). 2 Isomers 1:1.
  • The following novel compounds of the formula (XXIII) are obtained analogously to Example (XXIII-1)
  • (XXIII)
    Figure US20110190493A1-20110804-C00148
    Ex. No. A B 1H-NMR (400 MHz) Shifts δ in ppm
    XXIII-1 4 ′-O—CHCH3—CH2—O— d6-DMSO 10.53 (s); 8.35 (s); 4.15 (m, 1H); 4.02
    (m, 1H); 3.37 (m, 1H); 1.93-1.50 (6m,
    8H); 1.18 (dd, J = 6.2 Hz, 6.5 Hz. 3H)
    XXIII-2 4′-O—CHCH3—CHCH3—O— d6-DMSO 10.52 (s); 8.35 (s); 4.18 (m) + 3.59 (m):
    Σ2H; 1.90-1.50 (bm, Σ8H); 1.18 (dd,
    2 diastereomers 2:1 J = 6.3Hz, 5.8 Hz) + 1.06 (dd, J = 6.1 Hz,
    7.7 Hz): Σ6H
    XXIII-3 4′-O—(CH2)3—O— d6-DMSO 10.50 (s); 8.35 (s); 3.81 (m, 4H); 2.12
    (m, 2H); 1.78 (m, 2H); 1.60 (m, 4H);
    1.48 (m, 2H)
    XXIII-4 4′-O—CHCH3—(CH2)2—O— d6-DMSO 10.50 (s); 8.31/8.30 (each s.); 4.09-3.67
    2 diastereomers (6m, 3H); 2.54 (m, 1H); 1.88 (m, 1H);
    1.76-1.39 (6m, 8H); 1.08 (dd, J = 6 Hz)
    XXIII-5 4′-O—CH2—CHCH3—CH2—O— d6-DMSO 10.51 (s); 8.34 (s); 3.73 (m,2H); 3.51
    (dd, J = 9.7 Hz, 11.5 Hz, 1H); 3.43
    (dd, J = 9.7 Hz, 11.5 Hz, 1H); 2.41 (m,
    1H); 1.88-1.41 (bm, 8H); 0,76 (d, J = 6.8
    Hz, 3H)
    XXIII-6 4 ′-O—CHCH3—CH2—CHCH3—O— d6-DMSO 10.53 (s); 8.28 (s); 4.02 + 3.92 (each m,
    2 diastereomers 2:1 Σ2H); 1.95 (6m) + 1.75-1.40 (bm):
    Σ10H; 1.12 (dd, J = 6.3 Hz, 10,8 Hz) +
    1,08 (dd, J = 6.1 Hz, 11.3 Hz): Σ6H
    XXIII-7 4′-O—CH2—C(CH3)2—CH2—O— d6-DMSO 10.50 (s); 8.34 (s); 3.45 (s, 2H); 3.43 (s,
    2H); 2.11 (m, 2H); 1.78 (m, 2H); 1.62
    (m, 2H); 1.50 (m, 2H); 0.89 (s, 6H)
    XXIII-8 3′-O—(CH2)2—O— d6-DMSO 10.6 (bm, 1H), 7.32 (bm, 1H), 3.9 (m,
    4H), 1.71 (m, 4H), 1.61 (m, 1H), 1.52
    (m, 3H)
    XXIII-9
    Figure US20110190493A1-20110804-C00149
         		d6-DMSO isomer mixtures 10.5 (bm ), 7.16 (bm), 6.98 (bm), 6.87 (bm), 6.60 (bm), 4.22 (m), 4.01 (m), 3.64 (m), 3.34 (m), 3.27 (m), 3.17 (s), 2.40 (m), 2.22 (m), 2.01 (m), 1.90-1.60 (bm)
  • The compounds of the formulae (XXIII′), (XXIII″) and (XXIII′″)
  • Figure US20110190493A1-20110804-C00150
  • in which
    • Q3 is as defined above and
    • q represents 1, 2 or 3 and, in the case of the compounds of the formulae (XXIII″) and (XXIII′″), may also represent 0, are novel and form part of the subject-matter of the invention.
    Example XXIV-1
  • Figure US20110190493A1-20110804-C00151
  • 53.7 g (423 mmol) of oxalyl chloride are initially charged in 1000 ml of dichloromethane. At −70° C., a solution of 60 ml of dimethyl sulphoxide in 100 ml of dichloromethane is added dropwise, and the mixture is stirred for 20 min. 66 g (385 mmol) of 1,4-dioxa[4,5]decane-2-methyl-8-ol are dissolved in 300 ml of dichloromethane and, at the same temperature, added dropwise over a period of 1 h to the reaction solution. The mixture is stirred for another hour, the ice bath is then removed and the mixture is allowed to warm to −40° C. over a period of 30 min. The mixture is stirred at this temperature for 30 min, triethylamine (140 ml) is then added and the mixture is allowed to warm to room temperature (1 h) and stirred overnight.
  • The reaction is quenched with 500 ml of water and the mixture is stirred for another 15 minutes.
  • The organic phase is separated off and the aqueous solution is extracted 3× with 200 ml of dichloromethane. The combined organic phases are dried with sodium sulphate and the solvent is distilled off. Purification by chromatography on silica gel, hexane/ethyl acetate 2:1.
  • Yield: 58 g (88% of theory)
  • 1H-NMR (400 MHz, d6-DMSO): δ=4.24 (m, 1H), 3.46 (t, 1H), 4.10 (dd, 1H), 2.36 (m, 4H), 1.94 (m, 4H), 1.23 (d, 3H) ppm.
    • Example XXIV-7
  • Figure US20110190493A1-20110804-C00152
  • 50 g of cyclohexane-1,3-dione, 27.67 g of 1,2-ethanediol, 500 ml of toluene and 0.849 g of 4-toluenesulphonic acid monohydrate are mixed and, on a water separator, boiled under reflux for 3 to 4 h. The mixture is washed with 100 ml of sat. NaHCO3 solution and 2× with sat. NaCl solution, dried and concentrated using a rotary evaporator. The mixture is then subjected to fractional distillation under high vacuum (distillation of the product at 85° C./1 mbar or 62-75° C./0.15 mmHg).
  • Yield: 21.9 g (27% of theory)
  • 1H-NMR (400 MHz, CD3CN): δ=3.9 (m, 4H), 2.52 (s, 2H), 2.27 (m, 2H), 1.87 (m, 2H), 1.79 (m, 2H) ppm.
  • The following novel compounds of the formula (XXIV) are obtained analogously to Examples (XXIV-1) and (XXIV-7)
  • (XXIV)
    Figure US20110190493A1-20110804-C00153
    1H-NMR
    Ex. No. A B (400 MHz) Shifts δ in ppm
    XXIV-1 4′-O—CHCH3—CH2—O— d6-DMSO 4.24 (m, 1H); 3.46 (t, 1H,
    J = 7.7 Hz); 4.10 (dd, 1H,
    J = 5.8 HZ, 7.9 Hz); 2.36 (m,
    4H); 1.94 (m, 4H); 1.23 (d,
    J = 6 Hz/3H)
    XXIV-2 4′-O—CHCH3—CHCH3—O— d6-DMSO 4.28/3.68 (each m, Σ2H);
    2 isomers 2:1 2.35/1.94 (each m, Σ8H);
    1.22 (d.J = 5.7 Hz) + 1.10 (d,
    J = 6.1Hz); Σ6H
    XXIV-3 4′-O—(CH2)3—O— d6-DMSO 3.88 (dd, J = 5.6 Hz, 4H); 2.25
    (m, 4H); 2.08 (m, 4H); 1.64
    (m, 2H)
    XXIV-4 4′-O—CHCH3—(CH2)2—O— in d6-DMSO 4.03 (m, 1H); 3.93 (m, 1H);
    3.80 (m, 1H); 2.30 (m, 2H);
    2.22 (m, 4H); 1.87 (m, 2H);
    1.51 (m, 2H); 1.10 (d, 3H,
    J = 6.1 Hz)
    XXIV-5 4′-O—CH2—CHCH3—CH2—O— d6-DMSO 3.81 (dd, J = 4.7 Hz, 12.0 Hz,
    1 isomer 2H); 3.52 (dd, 2H, J = 9.7
    Hz); 2.28 (m, 2H); 2.21 (m,
    4H); 1.95 (m, 2H); 1.91 (m,
    1H); 0.80 (d, J = 6.8 Hz, 1H)
    XXIV-6 4′-O—CHCH3—CH2—CHCH3—O— d6-DMSO 4.02 (m, 2H); 2.31/2.21/1.97/
    2 isomers = 45:55 1.87/1.61 (in each case m,
    Σ10H); 1.17 (d, 3H, J = 6.3
    Hz); 1.12 (d, 3H, J = 6.1 Hz)
    XXIV-8
    Figure US20110190493A1-20110804-C00154
         		CD3CN isomer mixture 4.23 (m), 4.01 (m), 3.66 (m), 3.38 (m), 3.31 (s), 2.54 (s), 2.26 (m), 1.87 (m), 1.78 (m), 1.56 (m)
  • Some of the ketones of the formula (XXIV) are commercially available, some are known (JACS 108, 2691-2699; 1986; JACS 109, 1363-1370, 1987) and some are novel.
    • Example XXV-1
  • Figure US20110190493A1-20110804-C00155
  • 114 g of 4-hydroxycyclohexanone, 80 g of 1,2 propanediol (77 ml) and 2 g of 4-toluenesulphonic acid dihydrate are added to 500 ml of toluene. The mixture is boiled on a water separtor until no more water separates out. For work-up, 1 ml of triethylamine is added, and the reaction solution is washed with 200 ml of water, dried and concentrated using a rotary evaporator. The residue (104 g) is distilled under reduced pressure.
  • Yield: 76.3 g ̂ 44% of theory
  • The following novel compounds of the formula (XXIV) are obtained analogously to Example (XXIV-1)
  • (XXIV)
    Figure US20110190493A1-20110804-C00156
    Ex. No. A B 1H-NMR (400 MHz, d6-DMSO) Shift δ in ppm
    XXV-1 —O—CHCH3—CH2—O— 4.38 (dd, 1 H J = 4.2 Hz, 5.3 Hz);
    4.12 (m, 1H); 3.97 (m, 1H); 3.54
    (6s, 1H); 3.33 (m, 1H); 1.67 (m,
    4H); 1.44 (m, 4H); 1.16
    (dd, J = 6.1 HZ, 3H);
    XXV-2 —O—CHCH3—CHCH3—O— 4.35 (m); 4.16 (m); 3.54 (m); 1.67
    (m); 1.44 (m); 1.15 (dd, J = 5.7 Hz);
    1.03 (dd, J = 6.1 Hz)
    XXV-3 —O—(CH2)3—O— 4.35 (OH); 3.77 (m, 4H); 3.52 (m, 1H);
    1.96 (m, 2H); 1.57 (m, 4H);
    1.50-128 (m, 4H)
    XXV-4 —O—CHCH3—(CH2)2—O— 4.34 (m, 1H); 3.95 (m, 1H); 3.87
    (m, 1H); 3.67 (m, 1H); 3.53 (m,
    1H); 2.25 (m, 1H); 2.66-2.20 (m,
    10H); 1.06 (dd, J = 6.1 Hz, 3H)
    XXV-5 —O—CH2—CHCH3—CH2—O— 4.41 (bs, OH); 3.69 (m) + 3.53 (m) +
    3.43 (m) + 3.35 (m) + 3.25 (m):
    Σ5 H; 2.12 (m, 1H); 1.74 (m, 2H);
    1.62-1.23 (m, 5H); 0.80 (d, J = 6.8
    Hz) + 0.75 (d, J = 6.8 Hz): Σ3 H
    XXV-6 —O—CHCH3—CH2—CHCH3—O— 4.34 (s,OH); 3.94 (m); 3,53 (m)
    2.20 (m); 1.78 (m); 2.65-2.20 (bm);
    1.10 (dd, J = 6.3 Hz); 1.05 (dd, J = 6 Hz)
  • Some of the compounds of the formula (XXV) are commercially available, some are known (J. Med. Chem. 24, 341-346, 1981) and some are novel.
    • Example I-2-a-1
  • Figure US20110190493A1-20110804-C00157
  • 0.32 g (1.00 mmol) of the compound of Example XIV-2-1, 0.62 g (10 mmol) of ethylene glycol and 50 mg of 4-toluenesulphonic acid in 15 ml of toluene are heated under reflux overnight.
  • For work-up, the mixture is cooled and the solid is filtered off with suction and dried.
  • Yield: 0.35 g (96% of theory), m.p. 267° C.
  • The following compounds of the formula (I-2-a) are obtained analogously to Example (I-2-a-1) and in accordance with the general statements on the preparation:
  • (I-2-a)
    Figure US20110190493A1-20110804-C00158
    Ex. No. W X Y Z A B m.p. ° C.
    I-2-a-2 CH3 CH3 CH3 H 4′-O—(CH2)2—O— >250 
    I-2-a-3 CH3 CH3 Cl H 4′-O—CHCH3—CH2—O— 198
    I-2-a-4 CH3 CH3 Cl H 4′-O—CHCH2Cl—CH2—O— 248
    I-2-a-5 CH3 CH3 Br H 4′-O—(CH2)2—O— 266
    I-2-a-6 CH3 CH3 Cl H 4′-O—(CH2)3—O— 227
    I-2-a-7 CH3 CH3 Cl H 4′-O—CH2—C(CH3)2—CH2—O— 270
    I-2-a-8 H CH3 H 4-Cl—Ph 4′-O—(CH2)2—O— *
    Figure US20110190493A1-20110804-C00159
     *1H-NMR (400 MHz, d6-DMSO): δ = 2.19 (s, 3H, Ar—CH 3), 3.92 (s, 4H, (O—CH 2,-)2), 7.3 (m, 1H, Ar—H), 7.4 (m, 1H, Ar—H), 7.5 (m, 3H, Ar—H), 7.65 (m, 2H-Ar—H) ppm.
    • Example I-2-b-1
  • Figure US20110190493A1-20110804-C00160
  • 0.22 g (0.60 mmol) of the compound of Example (I-2-a-1) is initially charged in 10 ml of dichloromethane, 0.067 g (0.66 mmol) of triethylamine is added, 0.071 g (0.66 mmol) of isobutyryl chloride is added dropwise with ice-cooling and the mixture is stirred at room temperature overnight.
  • For work-up, the mixture is extracted with 10% strength citric acid solution and saturated sodium bicarbonate solution and the organic phase is dried with sodium sulphate and concentrated using a rotary evaporator.
  • Yield: 0.22 g (77% of theory), m.p. 142° C.
  • The following compounds of the formula (I-2-b) are obtained analogously to Example (I-2-b-1) and in accordance with the general statements on the preparation:
  •
    (I-2-b)
    Figure US20110190493A1-20110804-C00161
    Ex. No. W X Y Z A B R1 m.p. ° C.
    I-2-b-2 CH3 CH3 CH3 H 4′-O—(CH2)2—O— t-C4H9 165-169
    I-2-b-3 CH3 CH3 Cl H 4′-O—CHCH2Cl—CH2—O— i-C3H7 240-243
    I-2-b-4 CH3 CH3 Cl H 4′-O—CHCH3—CH2—O— i-C3H7 232
    • Example XIV-2-1
  • Figure US20110190493A1-20110804-C00162
  • 4.59 g (40.89 mmol) of potassium tert-butoxide are initially charged in 35 ml of dimethylformamide, with ice-cooling, a solution of 10.00 g (27.26 mmol) of the compound of Example (III-A-1) in 15 ml of dimethylformamide is added dropwise at from 0 to 10° C. and the mixture is stirred at room temperature overnight.
  • For work-up, most of the DMF is distilled off using a rotary evaporator, and the residue is partitioned between water and ethyl acetate. The aqueous phase is acidified with hydrochloric acid and the precipitated product is filtered off with suction, washed with water and dried.
  • Further purification is carried out by preparative HPLC (silica gel RP-18, mobile phase acetonitrile/water).
  • Yield: 2.20 g (25% of theory), m.p. 210° C.
  • The following compounds of the formula (XIV-2) are obtained analogously to Example (XIV-2-1) and in accordance with the general statements on the preparation of compounds of the formula (XIV-2) in WO 99/16 748:
  •
    (XIV-2)
    Figure US20110190493A1-20110804-C00163
    Ex. No. W X Y Z A B m.p. ° C.
    XIV-2-2 CH3 CH3 CH3 H
    Figure US20110190493A1-20110804-C00164
         		187-190
    XIV-2-3 CH3 CH3 Br H
    Figure US20110190493A1-20110804-C00165
         		222
    • Example III-A-1
  • Figure US20110190493A1-20110804-C00166
  • 5.00 g (26.85 mmol) of ethyl 4-oxo-1-hydroxycyclohexanecarboxylate and 3.26 g (32.22 mmol) of triethylamine are initially charged in 35 ml of dichloromethane, with ice-cooling, a solution of 6.41 g (29.53 mmol) of 2,6-dimethyl-4-chlorophenylacetyl chloride in 15 ml of dichloromethane is added at from 0 to 10° C. and the mixture is stirred at room temperature overnight.
  • For work-up, the mixture is extracted with 10% strength citric acid solution and saturated sodium bicarbonate solution and the organic phase is dried with sodium sulphate and concentrated using a rotary evaporator.
  • Yield: 10.00 g of an oil (67% of theory).
  • The following compounds of the formula (III-A) are obtained analogously to Example (III-A-1) and in accordance with the general statements on the preparation:
  •
    (III-A)
    Figure US20110190493A1-20110804-C00167
    Ex. No. W X Y Z R8 m.p. ° C.
    III-A-2 CH3 CH3 CH3 H C2H5 oil
    III-A-3 CH3 CH3 Br H C2H5 oil
  • The oils were used without further characterization for synthesizing compounds of the formula (XIV-2).
    • Example A Myzus persicae Test (7:1)
  • Solvent: 7 parts by weight of dimethylformamide
  • Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Cabbage leaves (Brassica oleracea) which are heavily infested by the green peach aphid (Myzus persicae) are treated by being dipped into the preparation of active compound of the desired concentration.
  • After the desired period of time, the kill in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
  • In this test, for example, the following compounds of the Preparation Examples show an activity of ≧80% at a concentration of 1000 ppm: Ex. I-1-a-2, Ex. I-1-a-1, Ex. I-1-a-3, Ex. I-1-a-4, Ex. I-1-b-1, Ex. I-1-c-3, Ex. I-1-c-4, Ex. I-1-c-1.
    • Example B Aphis gossypii Test (7:1)
  • Solvent: 7 parts by weight of dimethylformamide
  • Emulsifier: 1 parts by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Cotton leaves (Gossypium hirsutum) which are heavily infested by the cotton aphid (Aphis gossypii) are treated by being dipped into the preparation of active compound of the desired concentration.
  • After the desired period of time, the kill in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
  • In this test, for example, the following compounds of the Preparation Examples show an activity of ≧80% at a concentration of 200 ppm: Ex. I-1-a-2, Ex. I-1-a-3, Ex. I-1-a-4, Ex. I-1-c-1.
    • Example C Phaedon cochleariae-larvae Test (7:1)
  • Solvent: 7 parts by weight of dimethylformamide
  • Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with larvae of the mustard beetle (Phaedon cochleariae) while the leaves are still moist.
  • After the desired period of time, the kill in % is determined. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.
  • In this test, for example, the following compounds of the Preparation Examples show an activity of ≧90% at a concentration of 1000 ppm: Ex. I-2-a-2, Ex. I-2-b-2, Ex. I-1-a-2, Ex. I-1-a-1, Ex. I-1-a-3, Ex. I-1-a-4, Ex. I-1-c-3, Ex. I-1-c-4, Ex. I-1-c-5, Ex. I-1-b-1, Ex. I-1-c-1.
    • Example D Plutella Test (7:1)
  • Solvent: 7 parts by weight of dimethylformamide
  • Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with caterpillars of the diamond back moth (Plutella xylostella) while the leaves are still moist.
  • After the desired period of time, the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.
  • In this test, for example, the following compounds of the Preparation Examples show an activity of 100% at a concentration of 1000 ppm: Ex. I-2-a-2, Ex. I-2-b-2, Ex. I-1-a-2.
    • Example E Spodoptera frugiperda Test (7:1)
  • Solvent: 7 parts by weight of dimethylformamide
  • Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with caterpillars of the army worm (Spodoptera frugiperda) while the leaves are still moist.
  • After the desired period of time, the kill in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.
  • In this test, for example, the following compounds of the Preparation Examples show an activity of ≧85% at a concentration of 1000 ppm: Ex. I-2-a-2, Ex. I-2-b-2, Ex. I-1-a-2, Ex. I-1-a-3, Ex. I-1-c-3.
    • Example F Nephotettix Test (7:1)
  • Solvent: 7 parts by weight of dimethylformamide
  • Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Rice seedlings (Oryza sativa) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with the green rice leaf hopper (Nephotettix cincticeps) while the leaves are still moist.
  • After the desired period of time, the kill in % is determined. 100% means that all leaf hoppers have been killed; 0% means that none of the leaf hoppers have been killed.
  • In this test, for example, the following compounds of the Preparation Examples show an activity of 100% at a concentration of 1000 ppm: Ex. I-2-a-2, Ex. I-2-b-2, Ex. I-1-a-2.
    • Example G Tetranychus Test (7:1) (OP Resistant/Dip Treatment)
  • Solvent: 7 parts by weight of dimethylformamide
  • Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Bean plants (Phaseolus vulgaris) which are heavily infested by all stages of the greenhouse red spider mite (Tetranychus urticae) are treated by being dipped into a preparation of active compound of the desired concentration.
  • After the desired period of time, the activity in % is determined. 100% means that all spider mites have been killed; 0% means that none of the spider mites have been killed.
  • In this test, for example, the following compounds of the Preparation Examples show an activity of ≧98% at a concentration of 100 ppm: Ex. I-1-a-1, Ex. I-1-a-3, Ex. I-1-a-4, Ex. I-1-c-4.
    • Example H Meloidogyne Test (7:1)
  • Solvent: 7 parts by weight of dimethylformamide
  • Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Vessels are filled with sand, solution of active compound, Meloidogyne incognita egg/larvae suspension and lettuce seeds. The lettuce seeds germinate and the plants develop. On the roots, galls are formed.
  • After the desired period of time, the nematicidal activity is determined in % by the formation of galls. 100% means that no galls have been found; 0% means that the number of galls on the treated plants corresponds to that of the untreated control.
  • In this test, for example, the following compound of the Preparation Examples shows an activity of 95% at a concentration of 20 ppm: Ex. I-1-a-4.
    • Example I Myzus persicae Test
  • Solvent: 7 parts by weight of dimethylformamide
  • Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Cabbage leaves (Brassica oleracea) which are heavily infested by the green peach aphid (Myzus persicae) are treated by being dipped into the preparation of active compound of the desired concentration.
  • After the desired period of time, the kill in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
  • In this test, for example, the following compounds of the Preparation Examples show an activity of ≧80% at a concentration of 100 ppm: Ex. Ex. I-1-a-11, Ex. I-1-a-14, Ex. I-1-a-12, Ex. I-1-a-13.
    • Example J Tetranychus Test (OP Resistant/Dip Treatment)
  • Solvent: 7 parts by weight of dimethylformamide
  • Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Bean plants (Phaseolus vulgaris) which are heavily infested by all stages of the greenhouse red spider mite (Tetranychus urticae) are treated by being dipped into a preparation of active compound of the desired concentration.
  • After the desired period of time, the activity in % is determined. 100% means that all spider mites have been killed; 0% means that none of the spider mites have been killed.
  • In this test, for example, the following compounds of the Preparation Examples show an activity ≧90% at a concentration of 100 ppm: Ex. I-1-a-11, Ex. I-1-a-14, Ex. I-1-a-12, Ex. I-1-a-21, Ex. I-1-a-22, Ex. I-1-a-9, Ex. I-1-a-43, Ex. I-1-a-46, Ex. I-1-a-53, Ex. I-1-a-70, Ex. I-1-c-16, Ex. I-1-c-20.
    • Example K Meloidogyne Test
  • Solvent: 7 parts by weight of dimethylformamide
  • Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Vessels are filled with sand, solution of active compound, Meloidogyne incognita egg/larvae suspension and lettuce seeds. The lettuce seeds germinate and the plants develop. On the roots, galls are formed.
  • After the desired period of time, the nematicidal activity is determined in % by the formation of galls. 100% means that no galls have been found; 0% means that the number of galls on the treated plants corresponds to that of the untreated control.
  • In this test, for example, the following compound of the Preparation Examples shows an activity of 80% at a concentration of 20 ppm: Ex. I-1-a-12.
    • Example L Aphis gossypii Test
  • Solvent: 7 parts by weight of dimethylformamide
  • Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Cotton leaves (Gossypium hirsutum) which are heavily infested by the cotton aphid (Aphis gossypii) are treated by being dipped into the preparation of active compound of the desired concentration.
  • After the desired period of time, the kill in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
  • In this test, for example, the following compounds of the Preparation Examples show an activity of ≧80% at a concentration of 100 ppm: Ex. I-1-a-19, Ex. I-1-a-7, Ex. I-1-a-14, Ex. I-1-a-30, Ex. I-1-a-31, Ex. I-1-a-38, Ex. I-1-a-48, Ex. I-1-a-50, Ex. I-1-a-53, Ex. I-1-a-56, Ex. I-1-a-58, Ex. I-1-a-63,
  • Ex. I-1-b-4, Ex. I-1-c-15, Bsp.I-1-c-19, Bsp.I-1-c-20, Bsp.I-1-c-32, Bsp.I-2-a-5.
    • Example M Phaedon cochleariae Larvae Test
  • Solvent: 7 parts by weight of dimethylformamide
  • Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with larvae of the mustard beetle (Phaedon cochleariae) while the leaves are still moist.
  • After the desired period of time, the kill in % is determined. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.
  • In this test, for example, the following compound of the Preparation Examples shows an activity of 100% at a concentration of 100 ppm: Ex. I-1-a-23.
    • Example N Phaedon Test (Spray Treatment)
  • Solvents: 78 parts by weight of acetone
      • 1.5 parts by weight of dimethylformamide
  • Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Discs of Chinese cabbage (Brassica pekinensis) are sprayed with a preparation of active compound of the desired concentration and, after drying, populated with larvae of the mustard beetle (Phaedon cochleariae).
  • After the desired period of time, the activity in % is determined. 100% means that all beetle larvae have been killed; 0% means that none of the beetle larvae have been killed.
  • In this test, for example, the following compounds of the Preparation Examples show an activity of ≧80% at an application rate of 100 g/ha: Ex. I-1-a-15, Ex. I-1-c-9, Ex. I-1-a-21 and an activity of 100% at an application rate 500 g/ha: Ex. I-1-a-18, Ex. I-1-a-20, Ex. I-1-a-22, Ex. I-1-a-8, Ex. I-1-a-10, Ex. I-1-a-7, Ex. I-1-a-9, Ex. I-1-c-6, Ex. I-1-a-16, Ex. I-1-a-24, Ex. I-1-a-27, Ex. I-1-a-30, Ex. I-1-a-31, Ex. I-1-a-32, Ex. I-1-a-33, Ex. I-1-a-34, Ex. I-1-a-38, Ex. I-1-a-39, Ex. I-1-a-43, Ex. I-1-a-45, Ex. I-1-a-46, Ex. I-1-a-47, Ex. I-1-a-49, Ex. I-1-a-51, Ex. I-1-a-52, Ex. I-1-a-53, Ex. I-1-a-54, Ex. I-1-a-56, Ex. I-1-a-61, Ex. I-1-a-63, Ex. I-1-a-64, Ex. I-1-a-65, Ex. I-1-a-66, Ex. I-1-a-67, Ex. I-1-a-68, Ex. I-1-a-71, Ex. I-1-c-19, Ex. I-1-c-31, Ex. I-1-c-34.
    • Example 0 Tetranychus Test (OP Resistant/Spray Treatment)
  • Solvents: 78 parts by weight of acetone
      • 1.5 parts by weight of dimethylformamide
  • Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Bean plants (Phaseolus vulgaris) which are heavily infested by all stages of the greenhouse red spider mite (Tetranychus urticae) are treated by being dipped into a preparation of active compound of the desired concentration.
  • After the desired period of time, the activity in % is determined. 100% means that all spider mites have been killed; 0% means that none of the spider mites have been killed.
  • In this test, for example, the following compounds of the Preparation Examples show an activity of ≧80% at an application rate of 100 g/ha: Ex. I-2-b-1, Ex. I-1-a-16, Ex. I-1-a-15, Ex. I-1-c-9, Ex. I-1-c-11, Ex. I-1-a-23, Ex. I-1-c-6, Ex. I-1-a-24, Ex. I-1-a-27 and Ex. I-1-a-38, Ex. I-1-a-50, Ex. I-1-a-58, Ex. I-1-c-24, Ex. I-1-c-43.
    • Example P Meloidogyne Test (Spray Treatment)
  • Solvent: 80 parts by weight of acetone
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water to the desired concentration.
  • Vessels are filled with sand, solution of active compound, Meloidogyne incognita egg/larvae suspension and lettuce seeds. The lettuce seeds germinate and the plants develop. On the roots, galls are formed.
  • After the desired period of time, the nematicidal activity is determined in % by the formation of galls. 100% means that no galls have been found; 0% means that the number of galls on the treated plants corresponds to that of the untreated control.
  • In this test, for example, the following compound of the Preparation Examples shows an activity of 100% at a concentration of 20 ppm: Ex. I-1-a-15.
    • Example Q Myzus Test (Spray Treatment)
  • Solvents: 78 parts by weight of acetone
      • 1.5 parts by weight of dimethylformamide
  • Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with emulsifying-containing water to the desired concentration.
  • Discs of Chinese cabbage (Brassica pekinensis) which are infested by all stages of the green peach aphid (Myzus persicae) are sprayed with a preparation of active compound of the desired concentration.
  • After the desired period of time, the activity in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
  • In this test, for example, the following compounds of the Preparation Examples show an activity of ≧90% at an application rate of 500 g/ha: Ex. I-1-a-18, Ex. I-1-a-19, Ex. I-1-c-10, Ex. I-1-a-20, Ex. I-1-c-11, Ex. I-1-a-23, Ex. I-1-a-21, Ex. I-1-a-22, Ex. I-1-a-8, Ex. I-1-a-10, Ex. I-1-a-7, Ex. I-1-a-9, Ex. I-1-c-6, Ex. I-2-a-1, Ex. I-2-a-3, Ex. I-2-a-4, Ex. I-2-a-7, Ex. I-2-b-1, Ex. I-2-b-3, Ex. I-2-b-4, Ex. I-2-a-5, Ex. I-1-a-16, Ex. I-1-a-24, Ex. I-1-a-26, Ex. I-1-a-28, Ex. I-1-a-29, Ex. I-1-a-30, Ex. I-1-a-31, Ex. I-1-a-32, Ex. I-1-a-33, Ex. I-1-a-34, Ex. I-1-a-35, Ex. I-1-a-36, Ex. I-1-a-37, Ex. I-1-a-38, Ex. I-1-a-39, Ex. I-1-a-40, Ex. I-1-a-41, Ex. I-1-a-42, Ex. I-1-a-43, Ex. I-1-a-44, Ex. I-1-a-45, Ex. I-1-a-46, Ex. I-1-a-47, Ex. I-1-a-48, Ex. I-1-a-49, Ex. I-1-a-50, Ex. I-1-a-51, Ex. I-1-a-52, Ex. I-1-a-53, Ex. I-1-a-54, Ex. I-1-a-56, Ex. I-1-a-57, Ex. I-1-a-58, Ex. I-1-a-59, Ex. I-1-a-60, Ex. I-1-a-61, Ex. I-1-a-62, Ex. I-1-a-63, Ex. I-1-a-64, Ex. I-1-a-65, Ex. I-1-a-66, Ex. I-1-a-67, Ex. I-1-a-69, Ex. I-1-a-70, Ex. I-1-a-71, Ex. I-1-b-4, Ex. I-1-b-6, Ex. I-1-b-7, Ex. I-1-b-8, Ex. I-1-b-10, Ex. I-1-b-11, Ex. I-1-c-14, Ex. I-1-c-15, Ex. I-1-c-16, Ex. I-1-c-17, Ex. I-1-c-18, Ex. I-1-c-19, Ex. I-1-c-20, Ex. I-1-c-21, Ex. I-1-c-22, Ex. I-1-c-23, Ex. I-1-c-24, Ex. I-1-c-25, Ex. I-1-c-26, Ex. I-1-c-30, Ex. I-1-c-31, Ex. I-1-c-32, Ex. I-1-c-33, Ex. I-1-c-34, Ex. I-1-c-35, Ex. I-1-c-36, Ex. I-1-c-40, Ex. I-1-c-41, Ex. I-1-c-42, Ex. I-1-c-43.
    • Example R Spodoptera frugiperda Test (Spray Treatment)
  • Solvents: 78 parts by weight of acetone
      • 1.5 parts by weight of dimethylformamide
  • Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Discs of maize leaves (Zea mays) are sprayed with a preparation of active compound of the desired concentration and, after drying, populated with caterpillars of the army worm (Spodoptera frugiperda).
  • After the desired period of time, the activity in % is determined. 100% means that all caterpillars have been killed; 0% means that none of the caterpillars have been killed.
  • In this test, for example, the following compounds of the Preparation Examples show an activity of ≧80% at an application rate of 500 g/ha: Ex. I-2-a-7, Ex. I-1-a-16, Ex. I-1-a-21, Ex. I-1-a-22, Ex. I-1-a-8, Ex. I-1-a-10, Ex. I-1-a-27, Ex. I-1-a-31, Ex. I-1-a-49, Ex. I-1-a-51, Ex. I-1-a-52, Ex. I-1-a-54, Ex. I-1-a-64, Ex. I-1-a-65, Ex. I-1-a-66, Ex. I-1-a-67, Ex. I-1-c-16, Ex. I-1-c-19, Ex. I-1-c-31, Ex. I-1-c-36, Ex. I-1-c-40.
    • Example S Myzus persicae Test (Hydroponic Treatment)
  • Solvent: 7 parts by weight of dimethylformamide
  • Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • The preparation of active compound is mixed with water. The stated concentration relates to the amount of active compound per volume unit of water (mg/l=ppm). The treated water is filled into vessels containing a pea plant (Pisum sativum). After the desired period of time, the plant is infected with the green peach aphid (Myzus persicae).
  • After the desired period of time, the kill in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
  • In this test, for example, the following compounds of the Preparation Examples show an activity of ≧95% at a concentration of 20 ppm: Ex. I-1-a-23, Ex. I-1-a-21, Ex. I-1-a-7, Ex. I-1-a-24, Ex. I-1-a-26, Ex. I-1-a-30, Ex. I-1-a-32, Ex. I-1-a-34, Ex. I-1-a-35, Ex. I-1-a-36, Ex. I-1-a-38, Ex. I-1-a-39, Ex. I-1-a-40, Ex. I-1-a-42, Ex. I-1-a-43, Ex. I-1-a-44, Ex. I-1-a-45, Ex. I-1-a-46, Ex. I-1-a-47, Ex. I-1-a-48, Ex. I-1-a-50, Ex. I-1-a-53, Ex. I-1-a-56, Ex. I-1-a-57, Ex. I-1-a-58, Ex. I-1-a-59, Ex. I-1-a-69, Ex. I-1-a-70, Ex. I-1-a-71, Ex. I-1-b-4, Ex. I-1-b-8, Ex. I-1-b-10, Ex. I-1-b-11, Ex. I-1-c-15, Ex. I-1-c-17, Ex. I-1-c-19, Ex. I-1-c-20, Ex. I-1-c-23, Ex. I-1-c-24, Ex. I-1-c-25, Ex. I-1-c-32, Ex. I-1-c-43.
    • Example T Post-Emergence Test
  • Solvent: 5 parts by weight of acetone
  • Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • Test plants of a height of 5-15 cm are sprayed with the preparation of active compounds such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen such that the particular amounts of active compound desired are applied in 1000 l of water/ha.
  • After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
  • The figures denote
      • 0%=no effect (like untreated control)
      • 100%=total destruction
    Example U Pre-Emergence Test (Examination of Active Compounds Herbicides Monheim)
  • Solvent: 5 parts by weight of acetone
  • Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen such that the particular amounts of active compound desired are applied in 1000 l of water/ha.
  • After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
  • The figures denote:
      • 0%=no effect (like untreated control)
      • 100%=total destruction
  •
    Concentration of active
    Greenhouse compound g of a.i./ha Echinochloa Setaria Amaranthus Galium Sinapis
    Ex. I-1-a-4 250 100 100 95 70 70
    Concentration of active
    Greenhouse compound g of a.i./ha Alopecurus Avena fatua Echinochloa Setaria Sinapis
    Ex. I-1-c-4 250 80 — 90 99 80
    Ex. I-1-b-1 250 70 70 80 95 70
    Ex. I-1-a-11 250 90 70 80 90 —
    Concentration of active
    Greenhouse compound g of a.i./ha Sugar beet Alopecurus Avena fatua Echinochloa Setaria
    Ex. I-1-a-14 250 0 95 80 80 90
    Ex. I-1-a-15 250 0 95 80 99 70
    Concentration of active
    Greenhouse compound g of a.i./ha Alopecurus Echinochloa Setaria
    Ex. I-1-a-11 250 80 80 100
    • Example V 1. Herbicidal Pre-Emergence Action
  • Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed in sandy loam in wood fibre pots and covered with soil. The test compounds, formulated in the form of wettable powders (WP), are then, as an aqueous suspension with a water application rate of 600 l/ha (converted), with 0.2% of wetting agent added, applied to the surface of the covering soil in various dosages.
  • After the treatment, the pots are placed in a greenhouse and kept under good growth conditions for the test plants. The visual assessment of the emergence damage on the test plants is carried out after a trial period of 3 weeks by comparison with untreated controls (herbicidal effect in percent (%): 100% effect=the plants have died, 0% effect=like control plants).
  • In addition to the compounds mentioned above, the following compounds, applied by the pre-emergence method at 320 g of a.i./ha, show an activity of ≧80% against Solium multiflorum and Setaria viridis: Ex. I-1-a-24, Ex. I-1-a-39, Ex. I-1-a-40, Ex. I-1-a-42, Ex. I-1-a-43, Ex. I-1-a-44, Ex. I-1-a-45, Ex. I-1-a-48, Ex. I-1-a-69, Ex. I-1-a-71, Ex. I-1-b-4, Ex. I-1-b-5, Ex. I-1-b-8, Ex. I-1-b-9, Ex. I-1-b-10, Ex. I-1-c-14, Ex. I-1-c-15, Ex. I-1-c-23, Ex. I-1-c-25, Ex. I-1-c-42 and Ex. I-1-c-43.
    • 2. Herbicidal Post-Emergence Action
  • Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed into sandy loam in wood fibre pots, covered with soil and cultivated in a greenhouse under good growth conditions. 2-3 weeks after sowing, the test plants are treated at the one-leaf stage. The test compounds, formulated as wettable powders (WP), are then, in various dosages with a water application rate of 600 l/ha (converted), with 0.2% of wetting agent added, sprayed onto the green parts of the plants. After the test plants have been kept in the greenhouse under optimum growth conditions for about 3 weeks, the effect of the preparations is rated visually in comparison to untreated controls (herbicidal effect in percent (%): 100% effect=the plants have died, 0% effect=like control plants).
  •
    Concentration of active
    Greenhouse compound g of a.i./ha Lolium Setaria Sinapis Echinochloa
    Ex. I-1-a-18 320 80 100 — 90
    Ex. I-1-a-19 320 90 90 70 90
    Ex. I-2-a-6 320 80 80 60 60
    Ex. I-2-b-3 320 100 90 — 80
    Ex. I-1-a-2 320 70 90 60 80
    Ex. I-1-a-7 320 80 80 60 60
    Ex. I-1-a-21 320 80 90 70 80
    Ex. I-1-a-22 320 70 80 70 100
    Ex. I-1-c-6 320 90 90 60 80
    Concentration of
    active compound
    Greenhouse g of a.i./ha Lolium Setaria Amaranthus Sinapis Echinochloa
    Ex. I-2-a-2 320 90 100 60 70 80
    Concentration of active
    Greenhouse compound g of a.i./ha Lolium Setaria Amaranthus Stellaria
    Ex. I-2-a-5 320 100 70 70 60
  • In addition to the compounds mentioned above, the following compounds, applied by the post-emergence method at 320 g of a.i./ha, show an activity of ≧80% against Echinocloa crus-galli, Lolium multiflorum and Setaria viridis: Ex. I-1-a-10, Ex. I-1-a-18, Ex. I-1-a-19, Ex. I-1-a-21, Ex. I-1-a-24, Ex. I-1-a-25, Ex. I-1-a-27, Ex. I-1-a-39, Ex. I-1-a-40, Ex. I-1-a-42, Ex. I-1-a-45, Ex. I-1-a-48, Ex. I-1-a-71, Ex. I-1-b-8, Ex. I-1-b-9, Ex. I-1-b-10, Ex. I-1-b-11, Ex. I-1-c-6, Ex. I-1-c-15, Ex. I-1-c-23, Ex. I-1-c-25, Ex. I-1-c-26, Ex. I-1-c-42, Ex. I-1-c-43, Ex. I-2-a-2, and Ex. I-2-b-3.
    • Test Description for Profiling Tests 2. Herbicidal Post-Emergence Action
  • Seeds of monocotyledonous and dicotyledonous weed and crop plants are placed into sandy loam in wood fibre pots or in plastic pots, covered with soil and cultivated in a greenhouse, during the vegetation period also outdoors outside of the greenhouse, under good growth conditions. 2-3 weeks after sowing, the test plants are treated at the one- to three-leaf stage. The test compounds, formulated as wettable powders (WP) or emulsifiable concentrates (EC) are, in various dosages with a water application rate of 300 l/ha (converted), with wetting agent (0.2 to 0.3%) added, sprayed onto the plants and the surface of the soil. 3-4 weeks after the treatment of the test plants, the effect of the preparations is rated visually in comparison to untreated controls (herbicidal effect in percent (%): 100% effect=the plants have died, 0% effect=like control plants).
    • Use of Safeners:
  • If it is additionally to be tested as to whether safeners can improve the plant compatibility of test substances in the case of crop plants, the following options are used for applying the safener:
      • seeds of the crop plants are, before sowing, dressed with the safener substance (the amount of safener stated in percent, based on the weight of the seed)
      • before the application of the test substances, the crop plants are sprayed with the safener at a certain application rate per hectar (usually 1 day before the application of the test substances)
      • the safener is applied together with the test substance as a tank mix (the amount of safener is stated in g/ha or as a ratio, based on the herbicide).
  • By comparing the effect of the test substances on crop plants without or with safener treatment, it is possible to assess the effect of the safener substance.
    • Container Trials with Cereal in a Greenhouse
  • Mefenpyr 1 day prior to herbicide application
  • TABLE 1
    10 days after application
    Application rate Summer barley Summer wheat
    g of a.i./ha observed (%) observed (%)
    I-1-a-25 25 50 40
    12.5 30 20
    I-1-a-25 + 25 + 100 15 10
    mefenpyr 12.5 + 100   10 5
  • TABLE 2
    28 days after application
    Application rate Summer wheat
    g of a.i./ha observed (%)
    I-1-a-25 50 60
    25 20
    12.5 10
    I-1-a-25 + 50 + 100 10
    mefenpyr 25 + 100 5
    12.5 + 100   0
  • TABLE 3
    28 days after application
    Application rate Summer barley Summer wheat
    g of a.i./ha observed (%) observed (%)
    I-1-c-25 23.8 50 70
    11.9 20
    I-1-c-25 + 23.8 20 20
    mefenpyr 11.9 10
    • Example W Critical Concentration Test/Soil Insects—Treatment of Transgenic Plants
  • Test insect: Diabrotica balteata-larvae in the soil
  • Solvent: 7 parts by weight of acetone
  • Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • The preparation of active compound is poured onto the soil. Here, the concentration of active compound in the preparation is virtually immaterial; only the amount by weight of active compound per volume unit of soil, which is stated in ppm (mg/l), matters. The soil is filled into 0.25 l pots, and these are allowed to stand at 20° C.
  • Immediately after the preparation, 5 pregerminated maize corns of the cultivar YIELD GUARD (trademark, of Monsanto Comp., USA) are placed into each pot. After 2 days, the appropriate test insects are placed into the treated soil. After a further 7 days, the efficacy of the active compound is determined by counting the maize plants that have emerged (1 plant=20% activity).
    • Example X Heliothis virescens Test—Treatment of Transgenic Plants
  • Solvent: 7 parts by weight of acetone
  • Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Soybean shoots (Glycine max) of the cultivar Roundup Ready (trademark of Monsanto Comp. USA) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with the tobacco bud worm Heliothis virescens while the leaves are still moist.
  • After the desired period of time, the kill of the insects is determined.

Claims (16)

1-18. (canceled)
19. A compound of the formula (II)
Figure US20110190493A1-20110804-C00168
in which
W represents hydrogen, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkenyloxy, haloalkyl, haloalkoxy or cyano,
X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy, haloalkenyloxy, nitro or cyano,
Y and Z independently of one another represent hydrogen, alkyl, alkenyl, alkynyl, alkoxy, halogen, haloalkyl, haloalkoxy, cyano, nitro, or represents in each case optionally substituted aryl or heteroaryl,
with the proviso that at least one of the radicals W or Z is different from hydrogen if X and Y represent methyl,
A and B and the carbon atom to which they are attached represent a five- to seven-membered ketal, thioketal or dithioketal which is optionally interrupted by a further heteroatom, each of which radicals is optionally substituted by alkyl, haloalkyl, alkoxy, alkoxyalkyl or optionally substituted phenyl,
Q1 and Q2 independently of one another represent hydrogen, alkyl, haloalkyl or alkoxy, and
R8 represents alkyl.
20. A compound of the formula (III)
Figure US20110190493A1-20110804-C00169
in which
W represents hydrogen, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkenyloxy, haloalkyl, haloalkoxy or cyano,
X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy, haloalkenyloxy, nitro or cyano,
Y and Z independently of one another represent hydrogen, alkyl, alkenyl, alkynyl, alkoxy, halogen, haloalkyl, haloalkoxy, cyano, nitro, or represents in each case optionally substituted aryl or heteroaryl,
with the proviso that at least one of the radicals W or Z is different from hydrogen if X and Y represent methyl,
A and B and the carbon atom to which they are attached represent a five- to seven-membered ketal, thioketal or dithioketal which is optionally interrupted by a further heteroatom, each of which radicals is optionally substituted by alkyl, haloalkyl, alkoxy, alkoxyalkyl or optionally substituted phenyl,
Q1 and Q2 independently of one another represent hydrogen, alkyl, haloalkyl or alkoxy, and
R8 represents alkyl.
21. A compound of the formula (XVIII)
Figure US20110190493A1-20110804-C00170
in which
W represents hydrogen, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkenyloxy, haloalkyl, haloalkoxy or cyano,
X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy, haloalkenyloxy, nitro or cyano,
Y and Z independently of one another represent hydrogen, alkyl, alkenyl, alkynyl, alkoxy, halogen, haloalkyl, haloalkoxy, cyano, nitro, or represents in each case optionally substituted aryl or heteroaryl,
with the proviso that at least one of the radicals W or Z is different from hydrogen if X and Y represent methyl,
A and B and the carbon atom to which they are attached represent a five- to seven-membered ketal, thioketal or dithioketal which is optionally interrupted by a further heteroatom, each of which radicals is optionally substituted by alkyl, haloalkyl, alkoxy, alkoxyalkyl or optionally substituted phenyl, and
Q1 and Q2 independently of one another represent hydrogen, alkyl, haloalkyl or alkoxy.
22. A compound of the formula (XXI)
Figure US20110190493A1-20110804-C00171
in which
W represents hydrogen, alkyl, alkenyl, alkynyl, halogen, alkoxy, alkenyloxy, haloalkyl, haloalkoxy or cyano,
X represents halogen, alkyl, alkenyl, alkenyl, alkoxy, alkenyloxy, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy, haloalkenyloxy, nitro or cyano,
Y and Z independently of one another represent hydrogen, alkyl, alkenyl, alkynyl, alkoxy, halogen, haloalkyl, haloalkoxy, cyano, nitro, or represents in each case optionally substituted aryl or heteroaryl,
with the proviso that at least one of the radicals W or Z is different from hydrogen if X and Y represent methyl,
A and B and the carbon atom to which they are attached represent a five- to seven-membered ketal, thioketal or dithioketal which is optionally interrupted by a further heteroatom, each of which radicals is optionally substituted by alkyl, haloalkyl, alkoxy, alkoxyalkyl or optionally substituted phenyl, and
Q1 and Q2 independently of one another represent hydrogen, alkyl, haloalkyl or alkoxy.
23. A compound of the formula (XXII)
Figure US20110190493A1-20110804-C00172
in which
A and B and the carbon atom to which they are attached represent a five- to seven-membered ketal, thioketal or dithioketal which is optionally interrupted by a further heteroatom, each of which radicals is optionally substituted by alkyl, haloalkyl, alkoxy, alkoxyalkyl or optionally substituted phenyl,
Q1 and Q2 independently of one another represent hydrogen, alkyl, haloalkyl or alkoxy, and
R8 represents alkyl.
24. A compound of the formula (XVI′)
Figure US20110190493A1-20110804-C00173
or a salt thereof, in which
Q3 represents C1-C4-alkyl, C1-C3-haloalkyl, C1-C4-alkoxy or C1-C4-alkoxy-C1-C2-alkyl,
q represents 1, 2 or 3, and
R8 is alkyl.
25. A compound of the formula (XVI″)
Figure US20110190493A1-20110804-C00174
or a salt thereof, in which
Q3 represents C1-C4-alkyl, C1-C3-haloalkyl, C1-C4-alkoxy or C1-C4-alkoxy-C1-C2-alkyl,
q represents 0, 1, 2 or 3, and
R8 represents alkyl.
26. A compound of the formula (XVI′″)
Figure US20110190493A1-20110804-C00175
or a salt thereof, in which
Q3 represents C1-C4-alkyl, C1-C3-haloalkyl, C1-C4-alkoxy or C1-C4-alkoxy-C1-C2-alkyl,
q represents 0, 1, 2 or 3, and
R8 represents alkyl.
27. A compound of the formula (XIX′)
Figure US20110190493A1-20110804-C00176
in which
Q3 represents C1-C4-alkyl, C1-C3-haloalkyl, C1-C4-alkoxy or C1-C4-alkoxy-C1-C2-alkyl, and
q represents 1, 2 or 3.
28. A compound of the formula (XIX″)
Figure US20110190493A1-20110804-C00177
in which
Q3 represents C1-C4-alkyl, C1-C3-haloalkyl, C1-C4-alkoxy or C1-C4-alkoxy-C1-C2-alkyl, and
q represents 0, 1, 2 or 3.
29. A compound of the formula (XIX′″)
Figure US20110190493A1-20110804-C00178
in which
Q3 represents C1-C4-alkyl, C1-C3-haloalkyl, C1-C4-alkoxy or C1-C4-alkoxy-C1-C2-alkyl, and
q represents 0, 1, 2 or 3.
30. A compound of the formula (XXIII′)
Figure US20110190493A1-20110804-C00179
in which
Q3 represents C1-C4-alkyl, C1-C3-haloalkyl, C1-C4-alkoxy or C1-C4-alkoxy-C1-C2-alkyl, and
q represents 1, 2 or 3.
31. A compound of the formula (XXIII″)
Figure US20110190493A1-20110804-C00180
in which
Q3 represents C1-C4-alkyl, C1-C3-haloalkyl, C1-C4-alkoxy or C1-C4-alkoxy-C1-C2-alkyl, and
q 0, 1, 2 or 3.
32. A compound of the formula (XXIII′″)
Figure US20110190493A1-20110804-C00181
in which
Q3 represents C1-C4-alkyl, C1-C3-haloalkyl, C1-C4-alkoxy or C1-C4-alkoxy-C1-C2-alkyl, and
q represents 0, 1, 2 or 3.
33. A compound of the formula (XIV)
Figure US20110190493A1-20110804-C00182
in which
W represents hydrogen, alkyl, alkenyl, alkynyl, alkoxy, halogen, alkenyloxy, haloalkyl, haloalkoxy or cyano,
X represents halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkylthio, alkylsulphinyl, alkylsulphonyl, haloalkyl, haloalkoxy, haloalkenyloxy, nitro or cyano,
Y and Z independently of one another represent hydrogen, alkyl, alkenyl, alkynyl, alkoxy, halogen, haloalkyl, haloalkoxy, cyano, nitro, or represents in each case optionally substituted aryl or heteroaryl,
with the proviso that at least one of the radicals W or Z is different from hydrogen if X and Y represent methyl,
D represents NH or oxygen,
Q1 and Q2 independently of one another represent hydrogen, alkyl, haloalkyl or alkoxy,
G represents hydrogen (a), or
Figure US20110190493A1-20110804-C00183
in which
E represents a metal ion or an ammonium ion,
L represents oxygen or sulphur,
M represents oxygen or sulphur,
R1 represents in each case optionally halogen- or cyano-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl or polyalkoxyalkyl, or represents in each case optionally halogen-, alkyl- or alkoxy-substituted cycloalkyl or heterocyclyl, or represents in each case optionally substituted phenyl, phenylalkyl, heteroaryl, phenoxyalkyl or heteroaryloxyalkyl,
R2 represents in each case optionally halogen- or cyano-substituted alkyl, alkenyl, alkoxyalkyl or polyalkoxyalkyl, or represents in each case optionally substituted cycloalkyl, phenyl or benzyl,
R3, R4 and R5 independently of one another represent in each case optionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio or cycloalkylthio, or represent in each case optionally substituted phenyl, benzyl, phenoxy or phenylthio, and
R6 and R7 independently of one another represent hydrogen, in each case optionally halogen- or cyano-substituted alkyl, cycloalkyl, alkenyl, alkoxy, or alkoxyalkyl, or represent in each case optionally substituted phenyl or benzyl, or R6 and R7 together with the N atom to which they are attached form an optionally substituted cycle which optionally contains oxygen or sulphur.
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