WO2014086738A1 - Herbicidally active 4-amino-6-acyloxymethyl pyrimidine and 4-amino-2-acyloxymethyl pyridine - Google Patents

Herbicidally active 4-amino-6-acyloxymethyl pyrimidine and 4-amino-2-acyloxymethyl pyridine Download PDF

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Publication number
WO2014086738A1
WO2014086738A1 PCT/EP2013/075307 EP2013075307W WO2014086738A1 WO 2014086738 A1 WO2014086738 A1 WO 2014086738A1 EP 2013075307 W EP2013075307 W EP 2013075307W WO 2014086738 A1 WO2014086738 A1 WO 2014086738A1
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Prior art keywords
alkyl
cycloalkyl
halo
halogen
heterocyclyl
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PCT/EP2013/075307
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German (de)
French (fr)
Inventor
Michael Gerhard Hoffmann
Uwe Döller
Marco BRÜNJES
Hansjörg Dietrich
Elmar Gatzweiler
Dirk Schmutzler
Christopher Hugh Rosinger
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Bayer Cropscience Ag
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Publication of WO2014086738A1 publication Critical patent/WO2014086738A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom

Definitions

  • the invention relates to the technical field of herbicides, in particular that of herbicides for the selective control of weeds and weeds in
  • WO 95/19358 A1 and EP 0 222 254 A2 disclose herbicidally active aryl- and heteroarylpyrimidines which carry a nicotinic acid radical.
  • the compounds known from this document often show inadequate herbicidal activity and / or compatibility with crop plants.
  • the object of the present invention is therefore the provision of further herbicidally active compounds. It has now been found that certain 4-amino-6-acyloxymethyl-pyrimidines and 4-amino-2-acyloxymethylpyridine are particularly well suited as herbicides.
  • An object of the present invention are 4-amino-6-acyloxymethyl-pyrimidines and 4-amino-2-acyloxymethylpyridine of the formula (I) or their N-oxides
  • A denotes in each case by s radicals from the group consisting of nitro, halogen, cyano, rhodano, (C 1 -C 6 ) -alkyl, halogeno (C 1 -C 6 ) -alkyl.
  • Heterocyclyl (Ci-C6) alkyl in each case by s radicals selected from the group consisting of halogen, nitro, cyano, (CrC 6) alkyl, halo (Ci-C 6) alkyl, S (0) n - (C -C 6 ) alkyl, (d-Ce) alkoxy and halo (Ci-C6) alkoxy are substituted, and wherein Heterocyclyi n carries oxo groups, or
  • radicals from the group consisting of (Ci-Ce) -alkyl and halogen-substituted
  • R 1 represents LR 1 ', is hydrogen, (Ci-Ce) alkyl, halo (Ci-C 6) alkyl, (C 2 -C 6) - alkenyl, halo (C 2 -C 6) alkenyl, (C 2 -C 6 ) alkynyl, halo (C 3 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl, halo (C 3 -C 6 ) cycloalkyl, (C 3 -C 6 ) -Cycloalkyl- (C 1 -C 6 ) -alkyl, halo (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, COR 6 , COOR 6 , N (R 6 ) 2 , NR 6 COOR 5 , C (O) N (R 6 ) 2 ,
  • R 2 is hydrogen. (CrC 6) alkyl, halo (CrC 6) alkyl, (C 3 -C 6) cycloalkyl, halo (C3-C6) cycloalkyl or halogen,
  • R 3 and R 4 are each independently hydrogen, (Ci-Ce) - alkyl, halo (Ci-C 6) alkyl, (C 2 -C 6) alkenyl, halo (C 2 -C 6) - alkenyl, (C 2 -C 6 ) alkynyl, halo (C 2 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl, halo (C 3 -C 6 ) cycloalkyl, (C 3 - C6) - cycloalkyl- (Ci-C6) alkyl, halo (C 3 -C 6) -cycloalkyl- (Ci-C 6) alkyl, COR 8 or S (0) n R 6,
  • R 5 represents (Ci-COE) alkyl, halo (Ci-C 6) -alkyl, (C2 -Ce) alkenyl, halo (C 2 -C 6) - alkenyl, (C 2 -C 6) Alkynyl, halo (C 3 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl, halo (C 3 -C 6 ) cycloalkyl, (C 4 -C 8 ) cycloalkenyl, halogeno ( C 3 -C 6) cycloalkenyl, (C 3 -C 6) -cycloalkyl- (Ci-C (6) alkyl or halo C 3 -C 6) -cycloalkyl- (Ci-C 6) alkyl,
  • R 6 represents hydrogen, (Ci-C 6) alkyl, halo (Ci-C 6) -alkyl, (C 2 -C 6) alkenyl, halo (C 2 -C 6) alkenyl, (C 2 -C 6) alkynyl, halo (C 3 -C 6) -alkynyl, (C 3 -C 6) cycloalkyl, halo (C 3 -C 6) cycloalkyl, (C4-C8) cycloalkenyl, halogen (C 3 -C 6) -cycloalkenyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl or halogeno (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl,
  • alkyl radicals having more than two carbon atoms may be straight-chain or branched.
  • Alkyl radicals are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1,3-dimethylbutyl.
  • alkenyl is for example allyl, 1-methylprop-2-en-1-yl,
  • Alkynyl means e.g. Propargyl, but-2-yn-1-yl, but-3-yn-yl, 1-methyl-but-3-yn-1-yl.
  • the multiple bond can each be in any position of the unsaturated radical.
  • Cycloalkyl means a carbocyclic saturated ring system having three to six carbon atoms, e.g. Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • cycloalkenyl is a monocyclic alkenyl group having three to six carbon ring members, e.g. Cyclopropenyl, cyclobutenyl,
  • Cyclopentenyl and cyclohexenyl, wherein the double bond may be in any position.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Heterocyclyl means a saturated, partially saturated or fully unsaturated cyclic radical containing from 3 to 6 ring atoms, of which from 1 to 4 are from the group oxygen, nitrogen and sulfur, and additionally by a
  • heterocyclyl is piperidinyl, pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl and oxetanyl.
  • Heteroaryl means an aromatic cyclic radical containing from 3 to 6 ring atoms, of which from 1 to 4 are from the group consisting of oxygen, nitrogen and sulfur, and may additionally be fused by a benzo ring.
  • heteroaryl is benzimidazol-2-yl, furanyl, imidazolyl, isoxazolyl, isothiazolyl, oxazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridinyl, benzisoxazolyl, thiazolyl, pyrrolyl, pyrazolyl, thiophenyl, 1, 2.3-oxadiazolyl, 1, 2,4- Oxadiazolyl, 1, 2,5-oxadiazolyl, 1, 3, 4-oxadiazolyl, 1, 2,4-triazolyl, 1, 2,3-triazolyl, 1, 2,5-triazolyl, 1, 3, 4-triazolyl, 1, 2, 4-triazolyl, 1, 2,4-thiadiazolyl, 1, 3,4-thiadiazolyl, 1, 2,3-thiadiazolyl, 1, 2, 5-thiadiazolyl, 2H-1, 2.3.4-tetrazolyl, 1H-1,
  • the compounds of the general formula (I) can exist as stereoisomers. For example, if one or more asymmetric carbon atoms are present, then enantiomers and
  • stereoisomers occur. Similarly, stereoisomers occur when n is 1 (sulfoxides). Stereoisomers can be obtained from the mixtures obtained in the preparation by customary separation methods, for example by chromatographic separation methods. Likewise, stereoisomers can be prepared by using stereoselective reactions using optically active starting materials and / or
  • the invention also relates to all stereoisomers and mixtures thereof which are of the general formula (I), but not specifically defined.
  • A is in each case substituted by s radicals selected from the group consisting of nitro, halogen, cyano, (Ci-Ce) alkyl, halo (CrC 6) alkyl, (C 2 -C 6) alkenyl, halo (C 2 - C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, halogeno (C 3 -C 6 ) alkynyl, (C 3 -C 6 ) -cycloalkyl, halogeno (C 3 -C 6 ) -cycloalkyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, halogeno (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, COR 6 , COOR 6 , N (R 6 ) 2 , C (O) N (R 6 ) 2
  • R 1 represents LR 1 ', is hydrogen, (CrC 6) alkyl, halo (Ci-C 6) alkyl, (C 2 -C 6) - alkenyl, halo (C 2 -C 6) alkenyl, ( C 2 -C 6 ) alkynyl, halo (C 3 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl, halo (C 3 -C 6 ) cycloalkyl, (C -C 6 ) - Cycloalkyl- (C 1 -C 6 ) -alkyl, halo (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, COR 6 , COOR 6 , N (R 6 ) 2 , NR 6 COOR 5 , C (0) N (R 6 ) 2 ,
  • Heterocyclyl (C 1 -C 6) -alkyl where the six last-mentioned radicals are in each case represented by s radicals from the group consisting of halogen, nitro, cyano, (C 1 -C 6) -alkyl, halogeno (C 1 -C 6) -alkyl, S (0) n - (C 1 -C 6) -alkyl, (C 1 -C 6) -alkoxy and halogeno (C 1 -C 6) -alkoxy, and where heterocyclyl carries n oxo groups,
  • L is in each case substituted by s radicals from the group consisting of (C 1 -C 12 -alkyl, nitro, cyano, halogen and OR 6 and in each case interrupted by s units from the group consisting of O, S (O) n and NR 6 ( Ci-Ce) alkylene, (C2 -Ce) - alkenylene or (C 2 -C 6) alkynylene chain,
  • R 1 ' is (C 3 -C 6 ) -cycloalkyl, halogeno (C 3 -C 6 ) -cycloalkyl, COR 6 , COOR 6 , N (R 6 ) 2 , NR 6 COOR 5 , C (O) N ( R 6 ) 2 , NR 6 C (O) N (R 6 ) 2 . OC (O) N (R 6 ) 2 , C (O) NR 6 OR 6 , OCOR 6 , S (O) n R 5 , SO 2 N (R 6 ) 2 , NR 6 SO 2 R 5 , P (0 ) (OR 6 ) 2 , or
  • radicals from the group consisting of halogen, nitro, cyano,
  • R 3 and R 4 are each independently hydrogen, (C 1 -C 6 ) -alkyl, halogeno (C 1 -C 6 ) -alkyl, (C 2 -C 6 ) -alkenyl, (C 2 -C 6 ) -alkynyl, ( C 3 -C 6 ) -cycloalkyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, COR 8 or S (O) "R 6 , R 5 represents (Ci-C 6) alkyl, halo (Ci-C 6) -alkyl, (C2-C6) alkenyl, (C2-C6) -alkynyl, (C 3 -C 6) -cycloalkyl , (C 4 -C 8) cycloalkenyl, or (C3-C6) cycloalkyl (Ci-C 6) alkyl, R 6 is hydrogen,
  • X is CH or N, n is 0, 1 or 2, s is 0, 1, 2 or 3.
  • A is substituted by s radicals selected from the group consisting of nitro, halogen, cyano, (Ci-C 3) alkyl, halo (Ci-C 3) alkyl, (C 2 -C 3) alkenyl, (C 2 - C 3) -alkynyl, (C 3 -C 6) - cycloalkyl, (C 3 -C 6) -cycloalkyl- (Ci-C 3) alkyl, COR 6, COOR 6, N (R 6) 2, C ( 0) N (R 6 ) 2 , OR 6 , S (O) n R 5 , S0 2 N (R 6 ) 2 and NR 6 S0 2 R 5 substituted phenyl, or
  • R 1 represents LR 1 ', is hydrogen, (Ci-C 6) alkyl, halo (Ci-C 6) alkyl, (C 2 -C 6) - alkenyl, (C2 -Ce) -alkynyl, (C 3 -C 6 ) -cycloalkyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, COR 6 , COOR 6 , N (R 6 ) 2 , NR 6 COOR 5 , C (O) N ( R 6 ) 2 , OR 6 , NR 6 S0 2 R 5 , (C 1 -C 6 ) -alkyl-S (0) n R 5 , (C 1 -C 6 ) -alkyl-OR 6 , (C 1 -C 6 ) alkyl-OS0 2 R 5, (Ci-C 6) alkyl-C0 2 R 6, (Ci-C
  • radicals in each case by s radicals selected from the group consisting of halogen, nitro, cyano, (CrC 6) alkyl, halo (Ci-C 6) alkyl, S (0) n - (Ci-C 6) alkyl, (C 1 -C 6) -alkoxy and halogeno (C 1 -C 6) -alkoxy, and wherein heterocyclyl carries n oxo groups.
  • L is a substituted by s radicals from the group consisting of (d-Ce) - alkyl, nitro, cyano, halogen and OR 6 and each interrupted by s units from the group consisting of O, S (0) n and NR 6 interrupted (C 1 -C 6) -alkylene, (C 2 -C 6) -alkenylene or (C 2 -C 6) -alkynylene chain,
  • R 1 ' is (C 3 -C 6 ) -cycloalkyl, COR 6 , COOR 6 , N (R 6 ) 2 , NR 6 COOR 5 , C (O) N (R 6 ) 2 , NR 6 C (O) N (R 6 ) 2 , OC (O) N (R 6 ) 2 , C (O) NR 6 OR 6 , OCOR 6 , S (O) n R 5 , SO 2 N (R 6 ) 2 ,
  • radicals from the group consisting of halogen, nitro, cyano, (C 1 -C 6 ) -alkyl, halogeno (C 1 -C 6 ) -alkyl, S (O) n - (C 1 -C 6 ) -alkyl, ( -C 6) alkoxy and halo (CrC 6) - alkoxy substituted phenyl, heteroaryl or heterocyclyl, wherein heterocyclyl carries n oxo groups,
  • R 2 is hydrogen or halogen
  • R 3 and R 4 are each independently hydrogen, (C1-C3) - alkyl, halo (Ci-C 3) alkyl, (C 2 -C 3) alkenyl, (C 2 -C 3) alkynyl, (C 3 -C 6) -cycloalkyl, (C 3 -C 6) - cycloalkyl (CrC 3) alkyl, COR 8 or S (0) "R 6, R 5 represents (Ci-C 3) -alkyl, (C 2 -C 3 ) -alkenyl, (C 2 -C 3 ) -alkynyl, (C 3 -C 6 ) -cycloalkyl, (C 4 -C 8 ) -cycloalkenyl or (C 3 -C 6 ) -cycloalkyl- (C 1 -C 3 ) -alkyl.
  • R 6 is hydrogen, (C 1 -C 3 ) -alkyl, (C 2 -C 3 ) -alkenyl, (C 2 -C 3 ) -alkynyl, (C 3 -C 6 ) -cycloalkyl, (C 4 -C 8 ) -Cycloalkenyl or (C 3 -C 6 ) -cycloalkyl- (C 1 -C 3 ) -alkyl,
  • X is CH or N, n is 0, 1 or 2, s is 0, 1. 2 or 3.
  • Hydroxymethyl compound (II) can be prepared with a carboxylic acid chloride (III).
  • the hydroxymethyl compounds (I I) can be prepared by methods known per se to those skilled in the art, for example by reduction of the corresponding carboxylic acid esters.
  • Such carboxylic acid esters are, for example, from WO
  • the listed equipment leads to a modular procedure, in which the individual work steps are automated, but between the work steps, manual operations must be performed.
  • This can be circumvented by the use of partially or fully integrated automation systems in which the respective automation modules are operated, for example, by robots.
  • Such automation systems can be obtained, for example, from Caliper, Hopkinton, MA 01748, USA.
  • Synthesis methods allow a number of protocols known from the literature, which in turn can be carried out manually or automatically.
  • the reactions can be carried out, for example, by means of IRORI technology in microreactors. Nexus Biosystems, 12140 Community Road, Poway, CA92064, USA.
  • the present invention therefore also provides a method for controlling undesirable plants or regulating the growth of plants, preferably in crops, wherein one or more compounds of the invention are applied to the plants (e.g., weeds, such as mono- or dicotyledons
  • the seeds eg grains, seeds or vegetative propagules such as tubers or sprout parts with buds
  • the area on which the plants grow eg the acreage
  • the compounds according to the invention can be applied, for example, in pre-sowing (optionally also by incorporation into the soil), pre-emergence or postemergence process.
  • some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned, which can be controlled by the compounds according to the invention, without the intention of limiting them to certain species.
  • the compounds according to the invention are applied to the surface of the earth prior to germination, either the emergence of the weed seedlings is completely prevented or the weeds grow up to the cotyledon stage, but then stop their growth and finally die after three to four weeks
  • Activity against monocotyledonous and dicotyledonous weeds are crops of economically important cultures such as dicotyledonous cultures of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum , Solanum, Vicia, or monocotyledonous crops of the genera Allium, Pineapple, Asparagus, Avena,
  • Crops such as agricultural crops or ornamental plantings.
  • Influence of phytonutrients and harvest relief e.g. be used by triggering desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of undesirable vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops, since, for example, storage formation can thereby be reduced or completely prevented.
  • the active compounds can also be used to control harmful plants in crops of genetically engineered or conventional mutagenized plants.
  • the transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • Other special special traits for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • transgenic cultures is the use of the invention Compounds in economically important transgenic crops of useful and ornamental plants, eg. As cereals such as wheat, barley, rye, oats, millet, rice and corn or even crops of sugar beet, cotton, soy, rape, potato, tomato, pea and other vegetables.
  • the compounds according to the invention can be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or
  • the application of the compounds of the invention or their salts in economically important transgenic crops of useful and ornamental plants eg.
  • cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn or cultures of sugar beet, cotton, soy, rape, potato, tomato, pea and other vegetables.
  • the compounds according to the invention can be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made genetically resistant.
  • Glufosinate see, for example, EP-A-0242236, EP-A-242246) or glyphosate
  • transgenic crops for example cotton, with the ability
  • Bacillus thuringiensis toxins Bacillus thuringiensis toxins (Bt toxins) to produce, which the
  • transgenic crops characterized by a combination z. B. the o. G.
  • Numerous molecular biological techniques with which new transgenic plants with altered properties can be produced are known in principle, see, for example, BI Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, or Christou, "Trends in Plant Science” 1 (1996) 423-431).
  • nucleic acid molecules can be used in any genetic manipulations.
  • nucleic acid molecules can be used in any genetic manipulations.
  • Plasmids are introduced which allow mutagenesis or a sequence change by recombination of DNA sequences. With the help of standard methods z. For example, base substitutions are made, partial sequences are removed, or natural or synthetic sequences are added. For the connection of the DNA fragments with one another adapters or linkers can be attached to the fragments.
  • the production of plant cells having a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to obtain a
  • Cosuppressions canes or the expression of at least one corresponding engineered ribozyme which specifically cleaves transcripts of the above gene product.
  • DNA molecules may be used which comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules which comprise only parts of the coding sequence, which parts must be long enough to be present in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical.
  • the synthesized protein may be located in any compartment of the plant cell. But to achieve the localization in a particular compartment, z.
  • the coding region can be linked to DNA sequences that ensure localization in a particular compartment.
  • DNA sequences are known in the art (see, for example, Braun et al., EMBO J. 1 1 (1992), 3219-3227, Wolter et al., Proc. Natl. Acad., U.S.A. 85 (1988), 846-850, Sonnewald et al., Plant J. 1 (1991), 95-106).
  • Expression of the nucleic acid molecules can also be found in the
  • transgenic plant cells can be regenerated to whole plants by known techniques.
  • the transgenic plants may, in principle, be plants of any plant species, that is, both monocotyledonous and dicotyledonous plants. Thus, transgenic plants are available, the altered properties by
  • the compounds of the invention can be used in transgenic cultures which are resistant to growth factors, such as. B. Dicamba or against
  • Herbicides containing essential plant enzymes e.g. Acetylactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD) inhibit, respectively against herbicides from the group of sulfonylureas, glyphosate, glufosinate or benzoylisoxazole and analogous agents.
  • ALS Acetylactate synthases
  • EPSP synthases glutamine synthases
  • HPPD hydroxyphenylpyruvate dioxygenases
  • Harmful plants often have effects that are specific for application in the particular transgenic culture, such as altered or specially extended weed spectrum that can be controlled
  • the invention therefore also relates to the use of the compounds according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
  • the compounds of the invention may be in the form of wettable powders
  • the invention therefore also relates to herbicidal and plant growth-regulating agents which contain the compounds according to the invention.
  • the compounds according to the invention can be formulated in various ways, depending on which biological and / or chemical-physical parameters are predetermined. Possible formulation options are, for example: wettable powder (WP), water-soluble powders (SP), water-soluble concentrates,
  • EC emulsifiable concentrates
  • EW emulsions
  • Water-in-oil emulsions sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for litter and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG),
  • the necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and are, for example
  • Injectable powders are preparations which are uniformly dispersible in water and contain surfactants of the ionic and / or nonionic type (wetting agent, dispersing agent) in addition to the active ingredient, apart from a diluent or inert substance.
  • surfactants of the ionic and / or nonionic type (wetting agent, dispersing agent) in addition to the active ingredient, apart from a diluent or inert substance.
  • the herbicidal active compounds for example, in conventional apparatus such as hammer mills, blower mills and Air-jet mills finely ground and at the same time or subsequently with the
  • Formulation aids mixed.
  • Emulsifiable concentrates are made by dissolving the active ingredient in one
  • organic solvents e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers).
  • emulsifiers which may be used are: alkylarylsulfonic acid calcium salts, such as
  • Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as
  • Fatty acid polyglycol esters alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers,
  • Propylene oxide-ethylene oxide condensation products alkyl polyethers, sorbitan esters, e.g. Sorbitan fatty acid esters or polyoxethylenesorbitan esters such as e.g.
  • Dusts are obtained by milling the active ingredient with finely divided solids, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • Suspension concentrates may be water or oil based. They can be prepared, for example, by wet grinding using commercially available bead mills and, if appropriate, addition of surfactants, as described, for example, in US Pat. upstairs with the others
  • Emulsions e.g. Oil-in-water emulsions (EW) can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, as described e.g. listed above for the other formulation types.
  • Granules can be prepared either by spraying the active ingredient on adsorptive, granulated inert material or by applying
  • Water-dispersible granules are generally prepared by the usual methods such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
  • the agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of compounds according to the invention.
  • the drug concentration is e.g. about 10 to 90 wt .-%, the balance to 100 wt .-% consists of conventional formulation ingredients.
  • the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%.
  • Dust-like formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% active ingredient.
  • the active ingredient content depends, in part, on whether the active compound is liquid or solid and which
  • Granulation aids, fillers, etc. are used. In the water
  • the content of active ingredient is for example between 1 and 95 wt .-%, preferably between 10 and 80 wt .-%.
  • the active substance formulations mentioned optionally contain the customary adhesive, wetting, dispersing, emulsifying, penetrating, preserving, Antifreeze and solvents, fillers, carriers and dyes, defoamers,
  • Mixture formulations or in the tank mix are, for example, known active substances which are based on an inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase,
  • Glutamine synthetase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, protoporphyrinogen oxidase can be used, e.g. from Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 15th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2009 and cited therein.
  • the formulations present in commercial form are optionally diluted in a customary manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Dusty preparations, ground or spreading granules and sprayable
  • the type of herbicide used u.a. varies the required application rate of the compounds of formula (I). It can vary within wide limits, e.g. between 0.001 and 1.0 kg / ha or more of active substance, but is preferably between 0.005 and 750 g / ha.
  • a dust is obtained by mixing 10 parts by weight of a compound of formula (I) and / or salts thereof and 90 parts by weight of talc as an inert material and comminuted in a hammer mill.
  • a readily dispersible, water-wettable powder is obtained by: 25 parts by weight of a compound of the formula (I) and / or salts thereof, 64
  • a dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of a compound of the formula (I) and / or salts thereof with 6 parts by weight of alkylphenol polyglycol ether ( ⁇ Triton X 207), 3 parts by weight
  • Isotridecanol polyglycol ether (8 EO) and 71 parts by weight paraffinic Mineral oil (boiling range, for example, about 255 to about 277 C) mixed and ground in a ball mill to a fineness of less than 5 microns.
  • An emulsifiable concentrate is obtained from 15 parts by weight of a
  • a water-dispersible granules are obtained by
  • a water-dispersible granule is also obtained by
  • the compounds according to the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then used as aqueous suspension or
  • test plants Greenhouse under good growth conditions. 2 to 3 weeks after sowing, the test plants are treated in the single leaf stage.
  • the compounds according to the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then used as aqueous suspension or
  • the compounds Nos. 1, 2, 5, 6, 22 and 24 at an application rate of 320 g / ha each have an at least 80% action against Amaranthus retroflexus.
  • Compounds Nos. 27, 49 and 58 each show an at least 80% Veronica persica at an application rate of 320 g / ha.

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Abstract

The invention relates to 4-amino-6-acyloxymethyl pyrimidine and 4-amino-2-acyloxymethyl pyridine of general formula (I) as herbicides. In this formula (I) R11 to R4 represent groups such as hydrogen, organic groups such as alkyl, and other groups such as halogen, nitro, cyano and formyl. A stands for a substituted aryl group.

Description

Herbizid wirksame 4-Amino-6-acyloxymethylpyrimidine und 4-Amino-2- acyloxymethylpyridine  Herbicidally active 4-amino-6-acyloxymethylpyrimidines and 4-amino-2-acyloxymethylpyridines
Beschreibung description
Die Erfindung betrifft das technische Gebiet der Herbizide, insbesondere das der Herbizide zur selektiven Bekämpfung von Unkräutern und Ungräsern in The invention relates to the technical field of herbicides, in particular that of herbicides for the selective control of weeds and weeds in
Nutzpflanzenkulturen. Crops of useful plants.
Aus WO 95/19358 A1 und EP 0 222 254 A2 sind herbizid wirksame Aryl- und Hetero- arylpyrimidine, die einen Nicotinsäurerest tragen, bekannt. Die aus dieser Schrift bekannten Verbindungen zeigen jedoch häufig eine nicht ausreichende herbizide Wirksamkeit und/oder Verträglichkeit gegenüber Kulturpflanzen. Aufgabe der vorliegenden Erfindung ist daher die Bereitstellung von weiteren herbizid wirksamen Verbindungen. Es wurde nun gefunden, dass bestimmte 4-Amino-6-acyloxymethyl- pyrimidine und 4-Amino-2-acyloxymethylpyridine als Herbizide besonders gut geeignet sind. WO 95/19358 A1 and EP 0 222 254 A2 disclose herbicidally active aryl- and heteroarylpyrimidines which carry a nicotinic acid radical. However, the compounds known from this document often show inadequate herbicidal activity and / or compatibility with crop plants. The object of the present invention is therefore the provision of further herbicidally active compounds. It has now been found that certain 4-amino-6-acyloxymethyl-pyrimidines and 4-amino-2-acyloxymethylpyridine are particularly well suited as herbicides.
Ein Gegenstand der vorliegenden Erfindung sind 4-Amino-6-acyloxymethyl-pyrimidine und 4-Amino-2-acyloxymethylpyridine der Formel (I) oder deren N-Oxide An object of the present invention are 4-amino-6-acyloxymethyl-pyrimidines and 4-amino-2-acyloxymethylpyridine of the formula (I) or their N-oxides
Figure imgf000003_0001
Figure imgf000003_0001
worin wherein
A bedeutet jeweils durch s Reste aus der Gruppe bestehend aus Nitro, Halogen, Cyano, Rhodano, (Ci-Ce)-Alkyl, Halogen-(Ci-C6)-alkyl. (C2-C6)-Alkenyl, Halogen-(C2- C6)-alkenyl, (C2-C6)-Alkinyl, Halogen-(C3-C6)-alkinyl, (C3-C6)-Cycloalkyl, Halogen-(C3- C6)-cycloalkyl, (C3-C6)-Cycloalkyl-(Ci-C6)-alkyl, Halogen-(C3-C6)-cycloalkyl-(Ci-C6)- alkyl, COR6, COOR6, N(R6)2, NR6COOR5, C(0)N(R6)2, NR6C(0)N(R6)2, OC(0)N(R6)2, C(0)NR6OR6, OR6, OCOR6, OS02R5, S(0)nR5, S02OR5, S02N(R6)2, NR6S02R5, NR6OR6, (Ci-C6)-Alkyl-S(0)nR5, (CrC6)-Alkyl-OR6, (Ci-C6)-Alkyl-OS02R5, (d-C6)- Alkyl-C02R6, (Ci-C6)-Alky!-S02OR6, (Ci-C6)-Alkyl-CON(R6)2, (CrC6)-Alkyl-S02N(R6)2, (Ci-C6)-Alkyl-NR6COR6, (Ci-C6)-A!kyl-NR6S02R5, P(0)(OR6)2, CH2P(0)(OR6)2, Phenyl, Heteroaryl, Heterocyclyi, Phenyl-(d-C6)-alkyl, Heteroaryl-(d-C6)-alkyl und A denotes in each case by s radicals from the group consisting of nitro, halogen, cyano, rhodano, (C 1 -C 6 ) -alkyl, halogeno (C 1 -C 6 ) -alkyl. (C 2 -C 6) alkenyl, halo (C 2 - C 6) alkenyl, (C 2 -C 6) alkynyl, halo (C 3 -C 6) -alkynyl, (C 3 -C 6 ) cycloalkyl, halo (C 3 - C 6) cycloalkyl, (C3-C6) cycloalkyl (Ci-C 6) alkyl, halo (C 3 -C 6) -cycloalkyl- (Ci-C 6 ) - alkyl, COR 6 , COOR 6 , N (R 6 ) 2 , NR 6 COOR 5 , C (O) N (R 6 ) 2 , NR 6 C (O) N (R 6 ) 2 , OC (O) N ( R 6 ) 2 , C (O) NR 6 OR 6 , OR 6 , OCOR 6 , OSO 2 R 5 , S (O) n R 5 , SO 2 OR 5 , SO 2 N (R 6 ) 2 , NR 6 S0 2 R 5 , NR 6 OR 6 , (C 1 -C 6 ) -alkyl-S (O) n R 5 , (C 1 -C 6 ) -alkyl-OR 6 , (C 1 -C 6 ) -alkyl-OSO 2 R 5 , (dC 6 ) -alkyl-C0 2 R 6 , (C 1 -C 6 ) -alkyl! -SO 2 OR 6 , (C 1 -C 6 ) -alkyl-CON (R 6 ) 2 , (C 1 -C 6 ) -alkyl- S0 2 N (R 6 ) 2 , (C 1 -C 6 ) -alkyl-NR 6 COR 6 , (C 1 -C 6 ) -alkyl-NR 6 S0 2 R 5 , P (O) (OR 6 ) 2 , CH 2 P (O) (OR 6 ) 2 , phenyl, heteroaryl, heterocyclic, phenyl (C 1 -C 6) alkyl, heteroaryl (C 1 -C 6) alkyl and
Heterocyclyl-(Ci-C6)-alkyl substituiertes Phenyl, wobei diese sechs Reste Phenyl, Heteroaryl, Heterocyclyi, Phenyl-(Ci-C6)-alkyl, Heteroaryl-(Ci-Cr,)-alkyl und Heterocyclyl- (Ci-C6) -alkyl-substituted phenyl, wherein these six radicals phenyl, heteroaryl, heterocyclyl, phenyl (Ci-C6) alkyl, heteroaryl (Ci-Cr,) - alkyl and
Heterocyclyl-(Ci-C6)-alkyl jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano, (CrC6)-Alkyl, Halogen-(Ci-C6)-alkyl, S(0)n-(Ci-C6)-Alkyl, (d- Ce)-Alkoxy und Halogen-(Ci-C6)-alkoxy substituiert sind, und wobei Heterocyclyi n Oxogruppen trägt, oder Heterocyclyl (Ci-C6) alkyl in each case by s radicals selected from the group consisting of halogen, nitro, cyano, (CrC 6) alkyl, halo (Ci-C 6) alkyl, S (0) n - (C -C 6 ) alkyl, (d-Ce) alkoxy and halo (Ci-C6) alkoxy are substituted, and wherein Heterocyclyi n carries oxo groups, or
durch s Reste aus der Gruppe bestehend aus (Ci-Ce)-Alkyl und Halogen substituiertesby s radicals from the group consisting of (Ci-Ce) -alkyl and halogen-substituted
(C3-C6)-Cycloalkyl, (C 3 -C 6 ) -cycloalkyl,
R1 bedeutet LR1', Wasserstoff, (Ci-Ce)-Alkyl, Halogen-(Ci-C6)-alkyl, (C2-C6)- Alkenyl, Halogen-(C2-C6)-alkenyl, (C2-C6)-Alkinyl, Halogen-(C3-C6)-alkinyl, (C3-C6)- Cycloalkyl, Halogen-(C3-C6)-cycloalkyl, (C3-C6)-Cycloalkyl-(Ci-C6)-alkyl, Halogen-(C3- C6)-cycloalkyl-(Ci-C6)-alkyl, COR6, COOR6, N(R6)2, NR6COOR5, C(0)N(R6)2, R 1 represents LR 1 ', is hydrogen, (Ci-Ce) alkyl, halo (Ci-C 6) alkyl, (C 2 -C 6) - alkenyl, halo (C 2 -C 6) alkenyl, (C 2 -C 6 ) alkynyl, halo (C 3 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl, halo (C 3 -C 6 ) cycloalkyl, (C 3 -C 6 ) -Cycloalkyl- (C 1 -C 6 ) -alkyl, halo (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, COR 6 , COOR 6 , N (R 6 ) 2 , NR 6 COOR 5 , C (O) N (R 6 ) 2 ,
NR6C(0)N(R6)2, OC(0)N(R6)2, C(0)NR6OR6, OR6, OCOR6, NR6S02R5, NR6OR6, (d- C6)-Alkyl-S(0)nR5, (Ci-C6)-Alkyl-OR6, (Ci-C6)-Alkyl-OS02R5, (Ci-C6)-Alkyl-C02R6, (d- C6)-Alkyl-S02OR5, (Ci-C6)-Alkyl-CON(R6)2, (Ci-C6)-Alkyl-S02N(R6)2, (Ci-C6)-Alkyl- NR6COR6, (Ci-C6)-Alkyl-NR6S02R5, P(0)(OR6)2, CH2P(0)(OR6)2, Phenyl, Heteroaryl, Heterocyclyi, Phenyl-(Ci-C6)-alkyl, Heteroaryl-(Ci-Ce)-alkyl oder Heterocyclyl-(Ci-C6)- alkyl, wobei die sechs letztgenannten Reste jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano, (d-Cö)-Alkyl, Halogen-(Ci-C6)-alkyl, S(0)n-(Ci- Ce)-Alkyl, (Ci-Ce)-Alkoxy und Halogen-(Ci-C6)-alkoxy substituiert sind, und wobei Heterocyclyi n Oxogruppen trägt, L bedeutet eine jeweils durch s Reste aus der Gruppe bestehend aus (C-i-Ce)- Alkyl, Nitro, Cyano, Halogen und OR6 substituierte und jeweils durch s Einheiten aus der Gruppe bestehend aus O, S(0)n und NR6 unterbrochene (Ci-C6)-Alkylen-, (Cz-Ce)- Alkenylen- oder (C2-C6)-Alkinylen-Kette, R1' bedeutet (C3-C6)-Cycloalkyl, Halogen-(C3-C6)-cycloalkyl, COR6, COOR6, N(R6)2, NR6COOR5, C(0)N(R6)2, NR6C(0)N(R6)2, OC(0)N(R6)2, C(0)NR6OR6, OCOR6, OS02R5, S(0)nR5, S02OR5, S02N(R6)2, NR6S02R5, NR6OR6, P(0)(OR6)2, oder jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano, (d-Co)- Alkyl, Halogen-(Ci-C6)-alkyl, S(0)n-(Ci-C6)-Alkyl, (Ci-C6)-Alkoxy und Halogen-(Ci-Ce)- alkoxy substituiertes Phenyl, Heteroaryl oder Heterocyclyl, wobei Heterocyclyl n NR 6 C (O) N (R 6 ) 2 , OC (O) N (R 6 ) 2 , C (O) NR 6 OR 6 , OR 6 , OCOR 6 , NR 6 SO 2 R 5 , NR 6 OR 6 , (C 1 -C 6 ) -alkyl-S (O) n R 5 , (C 1 -C 6 ) -alkyl-OR 6 , (C 1 -C 6 ) -alkyl-OSO 2 R 5 , (C 1 -C 6 ) -Alkyl-C0 2 R 6 , (C 1 -C 6 ) -alkyl-S0 2 OR 5 , (C 1 -C 6 ) -alkyl-CON (R 6 ) 2 , (C 1 -C 6 ) -alkyl-S0 2 N (R 6 ) 2 , (C 1 -C 6 ) -alkyl-NR 6 COR 6 , (C 1 -C 6 ) -alkyl-NR 6 S0 2 R 5 , P (O) (OR 6 ) 2 , CH 2 P ( 0) (OR 6 ) 2 , phenyl, heteroaryl, heterocyclyl, phenyl (Ci-C6) alkyl, heteroaryl (Ci-Ce) alkyl or heterocyclyl (Ci-C6) - alkyl, wherein the six latter radicals each by s radicals from the group consisting of halogen, nitro, cyano, (C 1 -C 6) -alkyl, halogeno (C 1 -C 6) -alkyl, S (O) n - (C 1 -C 6) -alkyl, (C 1 -C 4) ) Alkoxy and halogeno (Ci-C6) -alkoxy are substituted, and wherein Heterocyclyi n carries oxo groups, L means in each case by s remainders from the group consisting of (Ci-Ce) - alkyl, Nitro, Cyano, halogen and OR 6 substituted and substituted by s units from the group consisting of O, S (0) n and NR 6 under Rochene (C 1 -C 6) -alkylene, (C 1 -C 6) -alkenylene or (C 2 -C 6) -alkynylene chain, R 1 'is (C 3 -C 6 ) -cycloalkyl, halogeno (C 3 -C 6 ) -cycloalkyl, COR 6 , COOR 6 , N (R 6 ) 2 , NR 6 COOR 5 , C (O) N ( R 6 ) 2 , NR 6 C (O) N (R 6 ) 2 , OC (O) N (R 6 ) 2 , C (O) NR 6 OR 6 , OCOR 6 , OSO 2 R 5 , S (0) n R 5 , S0 2 OR 5 , S0 2 N (R 6 ) 2 , NR 6 S0 2 R 5 , NR 6 OR 6 , P (0) (OR 6 ) 2 , or in each case by s radicals from the group consisting of Halogen, nitro, cyano, (d-Co) -alkyl, halo (C 1 -C 6 ) -alkyl, S (0) n - (C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -alkoxy and halogen - (Ci-Ce) - alkoxy-substituted phenyl, heteroaryl or heterocyclyl, where heterocyclyl n
Oxogruppen trägt, Wearing oxo groups,
R2 bedeutet Wasserstoff. (CrC6)-Alkyl, Halogen-(CrC6)-alkyl, (C3-C6)-Cycloalkyl, Halogen-(C3-C6)-cycloalkyl oder Halogen, R 2 is hydrogen. (CrC 6) alkyl, halo (CrC 6) alkyl, (C 3 -C 6) cycloalkyl, halo (C3-C6) cycloalkyl or halogen,
R3 und R4 bedeuten unabhängig voneinander jeweils Wasserstoff, (Ci-Ce)- Alkyl, Halogen-(Ci-C6)-alkyl, (C2-C6)-Alkenyl, Halogen-(C2-C6)-alkenyl, (C2-C6)-Alkinyl, Halogen-(C2-C6)-alkinyl, (C3-C6)-Cycloalkyl, Halogen-(C3-C6)-cycloalkyl, (C3-C6)- Cycloalkyl-(Ci-C6)-alkyl, Halogen-(C3-C6)-cycloalkyl-(Ci-C6)-alkyl, COR8 oder S(0)nR6, R 3 and R 4 are each independently hydrogen, (Ci-Ce) - alkyl, halo (Ci-C 6) alkyl, (C 2 -C 6) alkenyl, halo (C 2 -C 6) - alkenyl, (C 2 -C 6 ) alkynyl, halo (C 2 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl, halo (C 3 -C 6 ) cycloalkyl, (C 3 - C6) - cycloalkyl- (Ci-C6) alkyl, halo (C 3 -C 6) -cycloalkyl- (Ci-C 6) alkyl, COR 8 or S (0) n R 6,
R5 bedeutet (Ci-Cö)-Alkyl, Halogen-(Ci-C6)-Alkyl, (C2-Ce)-Alkenyl, Halogen-(C2-C6)- Alkenyl, (C2-C6)-Alkinyl, Halogen-(C3-C6)-Alkinyl, (C3-C6)-Cycloalkyl, Halogen-(C3-C6)- Cycloalkyl, (C4-C8)-Cycloalkenyl, Halogen-(C3-C6)-Cycloalkenyl, (C3-C6)-Cycloalkyl- (Ci-C6)-alkyl oder Halogen-(C3-C6)-Cycloalkyl-(Ci-C6)-alkyl, R 5 represents (Ci-COE) alkyl, halo (Ci-C 6) -alkyl, (C2 -Ce) alkenyl, halo (C 2 -C 6) - alkenyl, (C 2 -C 6) Alkynyl, halo (C 3 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl, halo (C 3 -C 6 ) cycloalkyl, (C 4 -C 8 ) cycloalkenyl, halogeno ( C 3 -C 6) cycloalkenyl, (C 3 -C 6) -cycloalkyl- (Ci-C (6) alkyl or halo C 3 -C 6) -cycloalkyl- (Ci-C 6) alkyl,
R6 bedeutet Wasserstoff, (Ci-C6)-Alkyl, Halogen-(Ci-C6)-Alkyl, (C2-C6)-Alkenyl, Halogen-(C2-C6)-Alkenyl, (C2-C6)-Alkinyl, Halogen-(C3-C6)-Alkinyl, (C3-C6)-Cycloalkyl, Halogen-(C3-C6)-Cycloalkyl, (C4-C8)-Cycloalkenyl, Halogen-(C3-C6)-Cycloalkenyl, (C3- C6)-Cycloalkyl-(Ci-C6)-alkyl oder Halogen-(C3-C6)-Cycloalkyl-(Ci-C6)-alkyl, R 6 represents hydrogen, (Ci-C 6) alkyl, halo (Ci-C 6) -alkyl, (C 2 -C 6) alkenyl, halo (C 2 -C 6) alkenyl, (C 2 -C 6) alkynyl, halo (C 3 -C 6) -alkynyl, (C 3 -C 6) cycloalkyl, halo (C 3 -C 6) cycloalkyl, (C4-C8) cycloalkenyl, halogen (C 3 -C 6) -cycloalkenyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl or halogeno (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl,
X bedeutet CH oder N, n bedeutet 0, 1 oder 2, s bedeutet 0, 1 , 2 oder 3. In der Formel (I) und allen nachfolgenden Formeln können Alkylreste mit mehr als zwei Kohlenstoffatomen geradkettig oder verzweigt sein. Alkylreste bedeuten z.B. Methyl, Ethyl, n- oder i-Propyl, n-, i-, t- oder 2-Butyl, Pentyle, Hexyle, wie n-Hexyl, i-Hexyl und 1 ,3-Dimethylbutyl. Analog bedeutet Alkenyl z.B. Allyl, 1 -Methylprop-2-en-1 -yl, X is CH or N, n is 0, 1 or 2, s is 0, 1, 2 or 3. In formula (I) and all subsequent formulas, alkyl radicals having more than two carbon atoms may be straight-chain or branched. Alkyl radicals are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1,3-dimethylbutyl. Analogously, alkenyl is for example allyl, 1-methylprop-2-en-1-yl,
2-Methyl-prop-2-en-1-yl, But-2-en-1 -yl, But-3-en-1 -yl, 1 -Methyl-but-3-en-1-yl und 1 -Methyl-but-2-en-1 -yl. Alkinyl bedeutet z.B. Propargyl, But-2-in-1 -yl, But-3-in- -yl, 1 -Methyl-but-3-in-1 -yl. Die Mehrfachbindung kann sich jeweils in beliebiger Position des ungesättigten Rests befinden. Cycloaikyl bedeutet ein carbocyclisches, gesättigtes Ringsystem mit drei bis sechs C-Atomen, z.B. Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl. Analog bedeutet Cycloalkenyl eine monocyclische Alkenylgruppe mit drei bis sechs Kohlenstoffringgliedern, z.B. Cyclopropenyl, Cyclobutenyl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methyl-but-3-en-1-yl and 1 - Methyl-but-2-en-1-yl. Alkynyl means e.g. Propargyl, but-2-yn-1-yl, but-3-yn-yl, 1-methyl-but-3-yn-1-yl. The multiple bond can each be in any position of the unsaturated radical. Cycloalkyl means a carbocyclic saturated ring system having three to six carbon atoms, e.g. Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Similarly, cycloalkenyl is a monocyclic alkenyl group having three to six carbon ring members, e.g. Cyclopropenyl, cyclobutenyl,
Cyclopentenyl und Cyclohexenyl, wobei sich die Doppelbindung an beliebiger Position befinden kann. Halogen steht für Fluor, Chlor, Brom oder lod. Cyclopentenyl and cyclohexenyl, wherein the double bond may be in any position. Halogen is fluorine, chlorine, bromine or iodine.
Heterocyclyl bedeutet einen gesättigten, teilgesättigten oder vollständig ungesättigten cyclischen Rest, der 3 bis 6 Ringatome enthält, von denen 1 bis 4 aus der Gruppe Sauerstoff, Stickstoff und Schwefel stammen, und der zusätzlich durch einen Heterocyclyl means a saturated, partially saturated or fully unsaturated cyclic radical containing from 3 to 6 ring atoms, of which from 1 to 4 are from the group oxygen, nitrogen and sulfur, and additionally by a
Benzoring annelliert sein kann. Beispielsweise steht Heterocyclyl für Piperidinyl, Pyrrolidinyl, Tetrahydrofuranyl, Dihydrofuranyl und Oxetanyl. Benzoring can be annealed. For example, heterocyclyl is piperidinyl, pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl and oxetanyl.
Heteroaryl bedeutet einen aromatischen cyclischen Rest, der 3 bis 6 Ringatome enthält, von denen 1 bis 4 aus der Gruppe Sauerstoff, Stickstoff und Schwefel stammen, und der zusätzlich durch einen Benzoring annelliert sein kann. Heteroaryl means an aromatic cyclic radical containing from 3 to 6 ring atoms, of which from 1 to 4 are from the group consisting of oxygen, nitrogen and sulfur, and may additionally be fused by a benzo ring.
Beispielsweise steht Heteroaryl für Benzimidazol-2-yl, Furanyl, Imidazolyl, Isoxazolyl, Isothiazolyl, Oxazolyl, Pyrazinyl, Pyrimidinyl, Pyridazinyl, Pyridinyl, Benzisoxazolyl, Thiazolyl, Pyrrolyl, Pyrazolyl, Thiophenyl, 1 ,2.3-Oxadiazolyl, 1 ,2,4-Oxadiazolyl, 1 ,2,5- Oxadiazolyl, 1 .3,4-Oxadiazolyl, 1 ,2.4-Triazolyl, 1 ,2,3-Triazolyl, 1 ,2,5-Triazolyl, 1 .3.4- Triazolyl, 1 ,2,4-Triazolyl, 1 ,2,4-Thiadiazolyl, 1 ,3.4-Thiadiazolyl, 1 ,2.3-Thiadiazolyl, 1 .2,5-Thiadiazolyl, 2H-1 ,2.3.4-Tetrazolyl, 1 H-1 ,2,3,4-Tetrazolyl, 1 ,2,3.4-Oxatriazolyl, 1 .2,3,5-Oxatriazolyl, 1 ,2.3,4-Thiatriazolyl und 1 ,2,3.5-Thiatriazolyl. Ist eine Gruppe mehrfach durch Reste substituiert, so ist darunter zu verstehen, daß diese Gruppe durch ein oder mehrere gleiche oder verschiedene der genannten Reste substituiert ist. Die Verbindungen der allgemeinen Formel (I) können je nach Art und Verknüpfung der Substituenten als Stereoisomere vorliegen. Sind beispielsweise ein oder mehrere asymmetrische Kohlenstoffatome vorhanden, so können Enantiomere und For example, heteroaryl is benzimidazol-2-yl, furanyl, imidazolyl, isoxazolyl, isothiazolyl, oxazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, pyridinyl, benzisoxazolyl, thiazolyl, pyrrolyl, pyrazolyl, thiophenyl, 1, 2.3-oxadiazolyl, 1, 2,4- Oxadiazolyl, 1, 2,5-oxadiazolyl, 1, 3, 4-oxadiazolyl, 1, 2,4-triazolyl, 1, 2,3-triazolyl, 1, 2,5-triazolyl, 1, 3, 4-triazolyl, 1, 2, 4-triazolyl, 1, 2,4-thiadiazolyl, 1, 3,4-thiadiazolyl, 1, 2,3-thiadiazolyl, 1, 2, 5-thiadiazolyl, 2H-1, 2.3.4-tetrazolyl, 1H-1, 2.3 , 4-tetrazolyl, 1, 2,3,4-oxatriazolyl, 1, 2, 3, 5-oxatriazolyl, 1, 2,3,4-thiatriazolyl and 1,2,3,5-thiatriazolyl. If a group is repeatedly substituted by radicals, it is to be understood that this group is substituted by one or more identical or different radicals. Depending on the nature and linkage of the substituents, the compounds of the general formula (I) can exist as stereoisomers. For example, if one or more asymmetric carbon atoms are present, then enantiomers and
Diastereomere auftreten. Ebenso treten Stereoisomere auf, wenn n für 1 steht (Sulfoxide). Stereoisomere lassen sich aus den bei der Herstellung anfallenden Gemischen nach üblichen Trennmethoden, beispielsweise durch chromatographische Trennverfahren, erhalten. Ebenso können Stereoisomere durch Einsatz stereoselektiver Reaktionen unter Verwendung optisch aktiver Ausgangs- und/oder Diastereomers occur. Similarly, stereoisomers occur when n is 1 (sulfoxides). Stereoisomers can be obtained from the mixtures obtained in the preparation by customary separation methods, for example by chromatographic separation methods. Likewise, stereoisomers can be prepared by using stereoselective reactions using optically active starting materials and / or
Hilfsstoffe selektiv hergestellt werden. Die Erfindung betrifft auch alle Stereoisomeren und deren Gemische, die von der allgemeinen Formel (I) umfasst, jedoch nicht spezifisch definiert sind. Auxiliaries are selectively produced. The invention also relates to all stereoisomers and mixtures thereof which are of the general formula (I), but not specifically defined.
Bevorzugt sind Verbindungen der allgemeinen Formel (I), worin Preference is given to compounds of the general formula (I) in which
A bedeutet jeweils durch s Reste aus der Gruppe bestehend aus Nitro, Halogen, Cyano, (Ci-Ce)-Alkyl, Halogen-(CrC6)-alkyl, (C2-C6)-Alkenyl, Halogen-(C2-C6)-alkenyl, (C2-C6)-Alkinyl, Halogen-(C3-C6)-alkinyl, (C3-C6)-Cycloalkyl, Halogen-(C3-C6)- cycloalkyl, (C3-C6)-Cycloalkyl-(Ci-C6)-alkyl, Halogen-(C3-C6)-cycloalkyl-(Ci-C6)-alkyl, COR6, COOR6, N(R6)2, C(0)N(R6)2, OR6, OCOR6, OS02R5, S(0)nR5, SO2OR5, A is in each case substituted by s radicals selected from the group consisting of nitro, halogen, cyano, (Ci-Ce) alkyl, halo (CrC 6) alkyl, (C 2 -C 6) alkenyl, halo (C 2 - C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, halogeno (C 3 -C 6 ) alkynyl, (C 3 -C 6 ) -cycloalkyl, halogeno (C 3 -C 6 ) -cycloalkyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, halogeno (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, COR 6 , COOR 6 , N (R 6 ) 2 , C (O) N (R 6 ) 2 , OR 6 , OCOR 6 , OSO 2 R 5 , S (O) n R 5 , SO 2 OR 5 ,
S02N(R6)2, NR6S02R5, NR6OR6, (Ci-C6)-Alkyl-S(0)nR5, (Ci-Ce)-Alkyl-OR6, (Ci-Ce)- Alkyl-OS02R5, (Ci-C6)-Alkyl-C0 R6, (Ci-Cc,)-Alkyl-S02ORr>, (Ci-C6)-Alkyl-CON(R6)2, (Ci-C6)-Alkyl-S02N(R6)2, (Ci-C6)-Alkyl-NR6COR6. (Ci-C6)-Alkyl-NR6S02R5, SO 2 N (R 6 ) 2 , NR 6 SO 2 R 5 , NR 6 OR 6 , (C 1 -C 6 ) -alkyl-S (O) n R 5 , (C 1 -C 6 ) -alkyl-OR 6 , ( Ci-Ce) - alkyl-OSO 2 R 5 , (Ci-C 6 ) -alkyl-C0 R 6 , (Ci-Cc,) - alkyl-S0 2 OR r> , (Ci-C 6 ) -alkyl-CON (R 6 ) 2 , (C 1 -C 6 ) -alkyl-S0 2 N (R 6 ) 2 , (C 1 -C 6 ) -alkyl-NR 6 COR 6 . (C 1 -C 6 ) -alkyl-NR 6 S0 2 R 5 ,
P(0)(OR6)2, CH2P(0)(OR6)2. Phenyl, Heteroaryl, Heterocyclyl, Phenyl-(Ci-C6)-alkyl, Heteroaryl-(d-C6)-alkyl und Heterocyclyl-(d-C6)-alkyl substituiertes Phenyl, wobei diese sechs Reste Phenyl, Heteroaryl, Heterocyclyl, Phenyl-(d-C6)-alkyl, Heteroaryl- (Ci-C6)-alkyl und Heterocyclyl-(Ci-C6)-alkyl jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano, (d-CeJ-Alkyl, Halogen-(d-C6)-alkyl, S(0)n-(Cr Ce)-Alkyl, (Ci-Ce)-Alkoxy und Halogen-(Ci-Cr,)-alkoxy substituiert sind, und wobei Heterocyclyl n Oxogruppen trägt, oder durch s Reste aus der Gruppe bestehend aus (Ci-C6)-Alkyl und Halogen substituiertes (C3-C6)-Cycloalkyl, P (0) (OR 6 ) 2 , CH 2 P (0) (OR 6 ) 2 . Phenyl, heteroaryl, heterocyclyl, phenyl- (C 1 -C 6 ) -alkyl, heteroaryl- (C 1 -C 6 ) -alkyl and heterocyclyl- (C 1 -C 6 ) -alkyl-substituted phenyl, where these six radicals are phenyl, heteroaryl, heterocyclyl, phenyl (C 1 -C 6) -alkyl, heteroaryl- (C 1 -C 6) -alkyl and heterocyclyl- (C 1 -C 6) -alkyl in each case by s radicals from the group consisting of halogen, nitro, cyano, (C 1 -C 6 -alkyl, Halo (C 1 -C 6) alkyl, S (O) n - (C 1 -C 4) alkyl, (C 1 -C 6) alkoxy and halo (C 1 -C 6) alkoxy, and wherein heterocyclyl carries n oxo groups , or by radicals from the group consisting of (C 1 -C 6 ) -alkyl and halogen-substituted (C 3 -C 6 ) -cycloalkyl,
R1 bedeutet LR1', Wasserstoff, (CrC6)-Alkyl, Halogen-(Ci-C6)-alkyl, (C2-C6)- Alkenyl, Halogen-(C2-C6)-alkenyl, (C2-C6)-Alkinyl, Halogen-(C3-C6)-alkinyl, (C3-C6)- Cycloalkyl, Halogen-(C3-C6)-cycloalkyl, (C -C6)-Cycloalkyl-(Ci-C6)-alkyl, Halogen-(C3- C6)-cycloalkyl-(Ci-C6)-alkyl, COR6, COOR6, N(R6)2, NR6COOR5, C(0)N(R6)2, R 1 represents LR 1 ', is hydrogen, (CrC 6) alkyl, halo (Ci-C 6) alkyl, (C 2 -C 6) - alkenyl, halo (C 2 -C 6) alkenyl, ( C 2 -C 6 ) alkynyl, halo (C 3 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl, halo (C 3 -C 6 ) cycloalkyl, (C -C 6 ) - Cycloalkyl- (C 1 -C 6 ) -alkyl, halo (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, COR 6 , COOR 6 , N (R 6 ) 2 , NR 6 COOR 5 , C (0) N (R 6 ) 2 ,
OC(0)N(R6)2. OR6, NR6S02R5, (Ci-C6)-Alkyl-S(0)„R5, (Ci-C6)-Alkyl-OR6, (Ci-Ce)-Alkyl- OS02R5, (Ci-C6)-Alkyl-C02R6, (CrC6)-Alkyl-CON(RB)2, (Ci-C6)-Alkyl-S02N(R6)2, (d- C6)-Alkyl-NR6COR6, (Ci-C6)-Alkyl-NR6S02R5, P(0)(OR6) , CH2P(0)(OR6)2, Phenyl, Heteroaryl, Heterocyclyl, Phenyl-(d-C6)-alkyl, Heteroaryl-(Ci-C6)-alkyl oder OC (0) N (R 6 ) 2 . OR 6 , NR 6 S0 2 R 5 , (C 1 -C 6 ) -alkyl-S (0) "R 5 , (C 1 -C 6 ) -alkyl-OR 6 , (C 1 -C 6 ) -alkyl-OSO 2 R 5 , (C 1 -C 6 ) -alkyl-C0 2 R 6 , (C 1 -C 6 ) -alkyl-CON (R B ) 2 , (C 1 -C 6 ) -alkyl-S0 2 N (R 6 ) 2 , (i.e. C 6 ) -alkyl-NR 6 COR 6 , (C 1 -C 6 ) -alkyl-NR 6 S0 2 R 5 , P (0) (OR 6 ), CH 2 P (O) (OR 6 ) 2 , phenyl , Heteroaryl, heterocyclyl, phenyl (C 1 -C 6) alkyl, heteroaryl (C 1 -C 6) alkyl or
Heterocyclyl-(Ci-C6)-alkyl, wobei die sechs letztgenannten Reste jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano, (Ci-C6)-Alkyl, Halogen-(CrCe)- alkyl, S(0)n-(Ci-C6)-Alkyl, (CrCe)-Alkoxy und Halogen-(Ci-Ce)-alkoxy substituiert sind, und wobei Heterocyclyl n Oxogruppen trägt, Heterocyclyl (C 1 -C 6) -alkyl, where the six last-mentioned radicals are in each case represented by s radicals from the group consisting of halogen, nitro, cyano, (C 1 -C 6) -alkyl, halogeno (C 1 -C 6) -alkyl, S (0) n - (C 1 -C 6) -alkyl, (C 1 -C 6) -alkoxy and halogeno (C 1 -C 6) -alkoxy, and where heterocyclyl carries n oxo groups,
L bedeutet eine jeweils durch s Reste aus der Gruppe bestehend aus (Ci-Cej- Alkyl, Nitro, Cyano, Halogen und OR6 substituierte und jeweils durch s Einheiten aus der Gruppe bestehend aus O, S(0)n und NR6 unterbrochene (Ci-Ce)-Alkylen-, (C2-Ce)- Alkenylen- oder (C2-C6)-Alkinylen-Kette, L is in each case substituted by s radicals from the group consisting of (C 1 -C 12 -alkyl, nitro, cyano, halogen and OR 6 and in each case interrupted by s units from the group consisting of O, S (O) n and NR 6 ( Ci-Ce) alkylene, (C2 -Ce) - alkenylene or (C 2 -C 6) alkynylene chain,
R1' bedeutet (C3-C6)-Cycloalkyl, Halogen-(C3-C6)-cycloalkyl, COR6, COOR6, N(R6)2, NR6COOR5, C(0)N(R6)2, NR6C(0)N(R6)2. OC(0)N(R6)2, C(0)NR6OR6, OCOR6, S(0)nR5, S02N(R6)2, NR6S02R5, P(0)(OR6)2, oder R 1 'is (C 3 -C 6 ) -cycloalkyl, halogeno (C 3 -C 6 ) -cycloalkyl, COR 6 , COOR 6 , N (R 6 ) 2 , NR 6 COOR 5 , C (O) N ( R 6 ) 2 , NR 6 C (O) N (R 6 ) 2 . OC (O) N (R 6 ) 2 , C (O) NR 6 OR 6 , OCOR 6 , S (O) n R 5 , SO 2 N (R 6 ) 2 , NR 6 SO 2 R 5 , P (0 ) (OR 6 ) 2 , or
jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano,
Figure imgf000008_0001
in each case by s radicals from the group consisting of halogen, nitro, cyano,
Figure imgf000008_0001
Alkyl, Halogen-(Ci-Ce)-alkyl, S(0)n-(Ci-Ce)-Alkyl, (Ci-Ce)-Alkoxy und Halogen-(Ci-Ce)- alkoxy substituiertes Phenyl, Heteroaryl oder Heterocyclyl, wobei Heterocyclyl n Oxogruppen trägt, R2 bedeutet Wasserstoff oder Halogen, Alkyl, halogeno (C 1 -C 6) -alkyl, S (0) n - (C 1 -C 6) -alkyl, (C 1 -C 6) -alkoxy and halogeno (C 1 -C 6) -alkoxy-substituted phenyl, heteroaryl or heterocyclyl, where heterocyclyl carries n oxo groups, R 2 denotes hydrogen or halogen,
R3 und R4 bedeuten unabhängig voneinander jeweils Wasserstoff, (d-Ce)-Alkyl, Halogen-(Ci-Ce)-alkyl, (C2-C6)-Alkenyl, (C2-C6)-Alkinyl, (C3-C6)-Cycloalkyl, (C3-C6)- Cycloalkyl-(Ci-Ce)-alkyl, COR8 oder S(0)„R6, R5 bedeutet (Ci-C6)-Alkyl, Halogen-(Ci-C6)-Alkyl, (C2-C6)-Alkenyl, (C2-C6)-Alkinyl, (C3-C6)-Cycloalkyl, (C4-C8)-Cycloalkenyl oder (C3-C6)-Cycloalkyl-(Ci-C6)-alkyl, R6 bedeutet Wasserstoff, (Ci-C6)-Alkyl, Halogen-(Ci-C6)-Alkyl, (C2-C6)-Alkenyl,R 3 and R 4 are each independently hydrogen, (C 1 -C 6 ) -alkyl, halogeno (C 1 -C 6 ) -alkyl, (C 2 -C 6 ) -alkenyl, (C 2 -C 6 ) -alkynyl, ( C 3 -C 6 ) -cycloalkyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, COR 8 or S (O) "R 6 , R 5 represents (Ci-C 6) alkyl, halo (Ci-C 6) -alkyl, (C2-C6) alkenyl, (C2-C6) -alkynyl, (C 3 -C 6) -cycloalkyl , (C 4 -C 8) cycloalkenyl, or (C3-C6) cycloalkyl (Ci-C 6) alkyl, R 6 is hydrogen, (Ci-C 6) alkyl, halo (Ci-C 6 ) -Alkyl, (C 2 -C 6 ) -alkenyl,
(C2-C6)-Alkinyl, (C3-C6)-Cycloalkyl, (C4-C8)-Cycloalkenyl oder (C3-C6)-Cycloalkyl-(Ci- Ce)-alkyi, (C 2 -C 6 ) -alkynyl, (C 3 -C 6 ) -cycloalkyl, (C 4 -C 8 ) -cycloalkenyl or (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyi,
X bedeutet CH oder N, n bedeutet 0, 1 oder 2, s bedeutet 0. 1 , 2 oder 3. X is CH or N, n is 0, 1 or 2, s is 0, 1, 2 or 3.
Besonders bevorzugt sind Verbindungen der allgemeinen Formel (I), worin Particular preference is given to compounds of the general formula (I) in which
A bedeutet durch s Reste aus der Gruppe bestehend aus Nitro, Halogen, Cyano, (Ci-C3)-Alkyl, Halogen-(Ci-C3)-alkyl, (C2-C3)-Alkenyl, (C2-C3)-Alkinyl, (C3-C6)- Cycloalkyl, (C3-C6)-Cycloalkyl-(Ci-C3)-alkyl, COR6, COOR6, N(R6)2, C(0)N(R6)2, OR6, S(0)nR5, S02N(R6)2 und NR6S02R5 substituiertes Phenyl, oder A is substituted by s radicals selected from the group consisting of nitro, halogen, cyano, (Ci-C 3) alkyl, halo (Ci-C 3) alkyl, (C 2 -C 3) alkenyl, (C 2 - C 3) -alkynyl, (C 3 -C 6) - cycloalkyl, (C 3 -C 6) -cycloalkyl- (Ci-C 3) alkyl, COR 6, COOR 6, N (R 6) 2, C ( 0) N (R 6 ) 2 , OR 6 , S (O) n R 5 , S0 2 N (R 6 ) 2 and NR 6 S0 2 R 5 substituted phenyl, or
(C3-C6)-Cycloalkyl, (C 3 -C 6 ) -cycloalkyl,
R1 bedeutet LR1', Wasserstoff, (Ci-C6)-Alkyl, Halogen-(Ci-C6)-alkyl, (C2-C6)- Alkenyl, (C2-Ce)-Alkinyl, (C3-C6)-Cycloalkyl, (C3-C6)-Cycloalkyl-(Ci-C6)-alkyl, COR6, COOR6, N(R6)2, NR6COOR5, C(0)N(R6)2, OR6, NR6S02R5, (Ci-C6)-Alkyl-S(0)nR5, (Ci- C6)-Alkyl-OR6, (Ci-C6)-Alkyl-OS02R5, (Ci-C6)-Alkyl-C02R6, (Ci-C6)-Alkyl-CON(R6)2, (C1-C6)-Alkyl-S02N(R6)2, (Ci-C6)-Alkyl-NR6COR6. (CrC6)-Alkyl-NR6S0 R5, R 1 represents LR 1 ', is hydrogen, (Ci-C 6) alkyl, halo (Ci-C 6) alkyl, (C 2 -C 6) - alkenyl, (C2 -Ce) -alkynyl, (C 3 -C 6 ) -cycloalkyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, COR 6 , COOR 6 , N (R 6 ) 2 , NR 6 COOR 5 , C (O) N ( R 6 ) 2 , OR 6 , NR 6 S0 2 R 5 , (C 1 -C 6 ) -alkyl-S (0) n R 5 , (C 1 -C 6 ) -alkyl-OR 6 , (C 1 -C 6 ) alkyl-OS0 2 R 5, (Ci-C 6) alkyl-C0 2 R 6, (Ci-C 6) alkyl-CON (R 6) 2, (C 1 -C 6) alkyl-S0 2 N (R 6 ) 2 , (C 1 -C 6 ) -alkyl-NR 6 COR 6 . (C 1 -C 6 ) -alkyl-NR 6 S 0 R 5 ,
P(0)(OR6)2, CH2P(0)(OR6)2, Phenyl, Heteroaryl, Heterocyclyl, Phenyl-(CrC6)-alkyl, Heteroaryl-(d-C6)-alkyl oder Heterocyclyl-(CrC6)-alkyl, wobei die sechs P (O) (OR 6 ) 2 , CH 2 P (O) (OR 6 ) 2 , phenyl, heteroaryl, heterocyclyl, phenyl- (C 1 -C 6 ) -alkyl, heteroaryl- (C 1 -C 6 ) -alkyl or heterocyclyl- ( CrC6) alkyl, wherein the six
letztgenannten Reste jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano, (CrC6)-Alkyl, Halogen-(Ci-C6)-alkyl, S(0)n-(Ci-C6)-Alkyl, (Ci-Ce)-Alkoxy und Halogen-(d-C6)-alkoxy substituiert sind, und wobei Heterocyclyl n Oxogruppen trägt. L bedeutet eine jeweils durch s Reste aus der Gruppe bestehend aus (d-Ce)- Alkyl, Nitro, Cyano, Halogen und OR6 substituierte und jeweils durch s Einheiten aus der Gruppe bestehend aus O, S(0)n und NR6 unterbrochene (Ci-Ce)-Alkylen-, (C2-Ce)- Alkenylen- oder (C2-Cö)-Alkinylen-Kette, last-mentioned radicals in each case by s radicals selected from the group consisting of halogen, nitro, cyano, (CrC 6) alkyl, halo (Ci-C 6) alkyl, S (0) n - (Ci-C 6) alkyl, (C 1 -C 6) -alkoxy and halogeno (C 1 -C 6) -alkoxy, and wherein heterocyclyl carries n oxo groups. L is a substituted by s radicals from the group consisting of (d-Ce) - alkyl, nitro, cyano, halogen and OR 6 and each interrupted by s units from the group consisting of O, S (0) n and NR 6 interrupted (C 1 -C 6) -alkylene, (C 2 -C 6) -alkenylene or (C 2 -C 6) -alkynylene chain,
R1' bedeutet (C3-C6)-Cycloalkyl, COR6, COOR6, N(R6)2, NR6COOR5, C(0)N(R6)2, NR6C(0)N(R6)2, OC(0)N(R6)2, C(0)NR6OR6, OCOR6, S(0)nR5, S02N(R6)2, R 1 'is (C 3 -C 6 ) -cycloalkyl, COR 6 , COOR 6 , N (R 6 ) 2 , NR 6 COOR 5 , C (O) N (R 6 ) 2 , NR 6 C (O) N (R 6 ) 2 , OC (O) N (R 6 ) 2 , C (O) NR 6 OR 6 , OCOR 6 , S (O) n R 5 , SO 2 N (R 6 ) 2 ,
NR6S02R5, P(0)(OR6)2, oder NR 6 S0 2 R 5 , P (0) (OR 6 ) 2 , or
jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano, (d-Ce)- Alkyl, Halogen-(Ci-C6)-alkyl, S(0)n-(Ci-C6)-Alkyl, (CrC6)-Alkoxy und Halogen-(CrC6)- alkoxy substituiertes Phenyl, Heteroaryl oder Heterocyclyl, wobei Heterocyclyl n Oxogruppen trägt, in each case by s radicals from the group consisting of halogen, nitro, cyano, (C 1 -C 6 ) -alkyl, halogeno (C 1 -C 6 ) -alkyl, S (O) n - (C 1 -C 6 ) -alkyl, ( -C 6) alkoxy and halo (CrC 6) - alkoxy substituted phenyl, heteroaryl or heterocyclyl, wherein heterocyclyl carries n oxo groups,
R2 bedeutet Wasserstoff oder Halogen, R 2 is hydrogen or halogen,
R3 und R4 bedeuten unabhängig voneinander jeweils Wasserstoff, (C1-C3)- Alkyl, Halogen-(Ci-C3)-alkyl, (C2-C3)-Alkenyl, (C2-C3)-Alkinyl, (C3-C6)-Cycloalkyl, (C3-C6)- Cycloalkyl-(CrC3)-alkyl, COR8 oder S(0)„R6, R5 bedeutet (Ci-C3)-Alkyl, (C2-C3)-Alkenyl, (C2-C3)-Alkinyl, (C3-C6)-Cycloalkyl, (C4- C8)-Cycloalkenyl oder (C3-C6)-Cycloalkyl-(Ci-C3)-alkyl. R 3 and R 4 are each independently hydrogen, (C1-C3) - alkyl, halo (Ci-C 3) alkyl, (C 2 -C 3) alkenyl, (C 2 -C 3) alkynyl, (C 3 -C 6) -cycloalkyl, (C 3 -C 6) - cycloalkyl (CrC 3) alkyl, COR 8 or S (0) "R 6, R 5 represents (Ci-C 3) -alkyl, (C 2 -C 3 ) -alkenyl, (C 2 -C 3 ) -alkynyl, (C 3 -C 6 ) -cycloalkyl, (C 4 -C 8 ) -cycloalkenyl or (C 3 -C 6 ) -cycloalkyl- (C 1 -C 3 ) -alkyl.
R6 bedeutet Wasserstoff, (Ci-C3)-Alkyl, (C2-C3)-Alkenyl, (C2-C3)-Alkinyl, (C3-C6)- Cycloalkyl, (C4-C8)-Cycloalkenyl oder (C3-C6)-Cycloalkyl-(Ci-C3)-alkyl, R 6 is hydrogen, (C 1 -C 3 ) -alkyl, (C 2 -C 3 ) -alkenyl, (C 2 -C 3 ) -alkynyl, (C 3 -C 6 ) -cycloalkyl, (C 4 -C 8 ) -Cycloalkenyl or (C 3 -C 6 ) -cycloalkyl- (C 1 -C 3 ) -alkyl,
X bedeutet CH oder N, n bedeutet 0, 1 oder 2, s bedeutet 0, 1 . 2 oder 3. X is CH or N, n is 0, 1 or 2, s is 0, 1. 2 or 3.
Ganz besonders bevorzugt sind Verbindungen der allgemeinen Formel (I), worin R2 für Chlor steht, R3 und R4 jeweils Wasserstoff bedeuten, und die anderen Substituenten und Indices die oben genannten Bedeutungen haben. In allen nachfolgend genannten Formeln haben die Substituenten und Symbole, sofern nicht anders definiert, dieselbe Bedeutung wie unter Formel (I) beschrieben. Very particular preference is given to compounds of the general formula (I) in which R 2 is chlorine, R 3 and R 4 are each hydrogen, and the other substituents and indices have the abovementioned meanings. In all of the formulas below, the substituents and symbols, unless otherwise defined, have the same meaning as described for formula (I).
Erfindungsgemäße Verbindungen der Formel (I) können beispielsweise gemäß nachfolgendem Schema durch basen-katalysierte Umsetzung einer Compounds of the formula (I) according to the invention can be synthesized, for example, by the following scheme by base-catalyzed reaction of a
Hydroxymethylverbindung (II) mit einem Carbonsäurechlorid (III) hergestellt werden. Hydroxymethyl compound (II) can be prepared with a carboxylic acid chloride (III).
Figure imgf000011_0001
Figure imgf000011_0001
Die Hydroxmethylverbindungen (I I) können nach dem Fachmann an sich bekannten Methoden hergestellt werden, beispielsweise durch Reduktion der entsprechenden Carbonsäureester. Solche Carbonsäureester sind beispielsweise aus WO The hydroxymethyl compounds (I I) can be prepared by methods known per se to those skilled in the art, for example by reduction of the corresponding carboxylic acid esters. Such carboxylic acid esters are, for example, from WO
2007/082098 und WO 2010/144380 bekannt. Kollektionen aus Verbindungen der Formel (I) und/oder deren Salzen, die nach den oben genannten Reaktionen synthetisiert werden können, können auch in 2007/082098 and WO 2010/144380 known. Collections of compounds of the formula (I) and / or their salts, which can be synthesized after the abovementioned reactions, can also be found in
parallelisierter Weise hergestellt werden, wobei dies in manueller, teilweise be prepared in a parallelized manner, this manual, in part
automatisierter oder vollständig automatisierter Weise geschehen kann. Dabei ist es beispielsweise möglich, die Reaktionsdurchführung, die Aufarbeitung oder die automated or completely automated way. It is possible, for example, the reaction procedure, the work-up or the
Reinigung der Produkte bzw. Zwischenstufen zu automatisieren. Insgesamt wird hierunter eine Vorgehensweise verstanden, wie sie beispielsweise durch D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screening (Herausgeber Günther Jung), Verlag Wiley 1999, auf den Seiten 1 bis 34 beschrieben ist. Zur parallelisierten Reaktionsdurchführung und Aufarbeitung können eine Reihe von im Handel erhältlichen Geräten verwendet werden, beispielsweise Calpyso- Reaktionsblöcke (Caylpso reaction blocks) der Firma Barnstead International, Automate cleaning of products or intermediates. Overall, this is understood to mean a procedure as described, for example, by D. Tiebes in Combinatorial Chemistry - Synthesis, Analysis, Screening (publisher Günther Jung), Verlag Wiley 1999, on pages 1 to 34. For the parallelized reaction procedure and workup, a number of commercially available devices can be used, for example Calypyso reaction blocks (Caylpso reaction blocks) from Barnstead International,
Dubuque, Iowa 52004-0797, USA oder Reaktionsstationen (reaction stations) der Firma Radleys, Shirehill, Saffron Waiden, Essex, CB 1 1 3AZ, England oder MuliiPROBE Automated Workstations der Firma Perkin Elmar, Waltham, Dubuque, Iowa 52004-0797, USA or reaction stations from Radleys, Shirehill, Saffron Waiden, Essex, CB 1 1 3AZ, England or MuliiPROBE Automated Workstations from Perkin Elmar, Waltham,
Massachusetts 02451 , USA. Für die paralleiisierte Aufreinigung von Verbindungen der allgemeinen Formel (I) und deren Salzen beziehungsweise von bei der Herstellung anfallenden Zwischenprodukten stehen unter anderem Chromatographieapparaturen zur Verfügung, beispielsweise der Firma ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA. Massachusetts 02451, United States. For the paralleiisierte purification of compounds of general formula (I) and their salts or resulting from the production of intermediates are, inter alia, Chromatographieapparaturen available, for example, the company ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.
Die aufgeführten Apparaturen führen zu einer modularen Vorgehensweise, bei der die einzelnen Arbeitsschritte automatisiert sind, zwischen den Arbeitsschritten jedoch manuelle Operationen durchgeführt werden müssen. Dies kann durch den Einsatz von teilweise oder vollständig integrierten Automationssystemen umgangen werden, bei denen die jeweiligen Automationsmodule beispielsweise durch Roboter bedient werden. Derartige Automationssysteme können zum Beispiel von der Firma Caliper, Hopkinton, MA 01748, USA bezogen werden. The listed equipment leads to a modular procedure, in which the individual work steps are automated, but between the work steps, manual operations must be performed. This can be circumvented by the use of partially or fully integrated automation systems in which the respective automation modules are operated, for example, by robots. Such automation systems can be obtained, for example, from Caliper, Hopkinton, MA 01748, USA.
Die Durchführung einzelner oder mehrerer Syntheseschritte kann durch den Einsatz von Polymer-supported reagents/Scavanger-Harze unterstützt werden. In der The implementation of single or multiple synthetic steps can be supported by the use of polymer-supported reagents / Scavanger resins. In the
Fachliteratur sind eine Reihe von Versuchsprotokollen beschrieben, beispielsweise in ChemFiles, Vol. 4, No. 1 , Polymer-Supported Scavengers and Reagents for Solution- Phase Synthesis (Sigma-Aldrich). Technical literature describes a number of experimental protocols, for example in ChemFiles, Vol. 1, Polymer-Supported Scavengers and Reagents for Solution-Phase Synthesis (Sigma-Aldrich).
Neben den hier beschriebenen Methoden kann die Herstellung von Verbindungen der allgemeinen Formel (I) und deren Salzen vollständig oder partiell durch Festphasen unterstützte Methoden erfolgen. Zu diesem Zweck werden einzelne Zwischenstufen oder alle Zwischenstufen der Synthese oder einer für die entsprechende In addition to the methods described herein, the preparation of compounds of general formula (I) and their salts can be carried out fully or partially by solid-phase assisted methods. For this purpose, individual intermediates or all intermediates of the synthesis or one for the corresponding
Vorgehensweise angepassten Synthese an ein Syntheseharz gebunden. Festphasen- unterstützte Synthesemethoden sind in der Fachliteratur hinreichend beschrieben, z.B. Barry A. Bunin in "The Combinatorial Index", Verlag Academic Press, 1998 und Combinatorial Chemistry - Synthesis, Analysis, Screening (Herausgeber Günther Jung), Verlag Wiley, 1999. Die Verwendung von Festphasen- unterstützten  Approach adapted synthesis bound to a synthetic resin. Solid phase assisted synthetic methods are well described in the literature, e.g. Barry A. Bunin in "The Combinatorial Index", Academic Press, 1998 and Combinatorial Chemistry - Synthesis, Analysis, Screening (published by Günther Jung), published by Wiley, 1999. The use of solid phase assisted
Synthesemethoden erlaubt eine Reihe von literaturbekannten Protokollen, die wiederum manuell oder automatisiert ausgeführt werden können. Die Reaktionen können beispielsweise mittels IRORI-Technologie in Mikroreaktoren (microreactors) der Firma Nexus Biosystems, 12140 Community Road, Poway, CA92064, USA durchgeführt werden. Synthesis methods allow a number of protocols known from the literature, which in turn can be carried out manually or automatically. The reactions can be carried out, for example, by means of IRORI technology in microreactors. Nexus Biosystems, 12140 Community Road, Poway, CA92064, USA.
Sowohl an fester als auch in flüssiger Phase kann die Durchführung einzelner oder mehrerer Syntheseschritte durch den Einsatz der Mikrowellen-Technologie unterstützt werden. In der Fachliteratur sind eine Reihe von Versuchsprotokollen beschrieben, beispielsweise in icrowaves in Organic and Medicinal Chemistry (Herausgeber C. O. Kappe und a. Stadler), Verlag Wiley, 2005. Die Herstellung gemäß der hier beschriebenen Verfahren liefert Verbindungen der Formel (I) und deren Salze in Form von Substanzkollektionen, die Bibliotheken genannt werden. Gegenstand der vorliegenden Erfindung sind auch Bibliotheken, die mindestens zwei Verbindungen der Formel (I) und deren Salzen enthalten. Die erfindungsgemäßen Verbindungen der Formel (I) (und/oder deren Salze), im folgenden zusammen als„erfindungsgemäße Verbindungen" bezeichnet, weisen eine ausgezeichnete herbizide Wirksamkeit gegen ein breites Spektrum wirtschaftlich wichtiger mono- und dikotyler annuelier Schadpflanzen auf. Auch schwer bekämpfbare perennierende Schadpflanzen, die aus Rhizomen, Wurzelstöcken oder anderen Dauerorganen austreiben, werden durch die Wirkstoffe gut erfaßt. Both solid and liquid phases can be supported by the implementation of single or multiple synthetic steps through the use of microwave technology. A number of experimental protocols are described in the literature, for example in icrowaves in Organic and Medicinal Chemistry (Editor CO Kappe and A. Stadler), published by Wiley, 2005. The preparation according to the processes described here yields compounds of formula (I) and their salts in the form of substance collections called libraries. The present invention also provides libraries containing at least two compounds of formula (I) and their salts. The compounds of the formula (I) according to the invention (and / or their salts), together referred to as "compounds according to the invention", have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants which expel from rhizomes, rhizomes or other permanent organs are well detected by the active ingredients.
Gegenstand der vorliegenden Erfindung ist daher auch ein Verfahren zur Bekämpfung von unerwünschten Pflanzen oder zur Wachstumsregulierung von Pflanzen, vorzugsweise in Pflanzenkulturen, worin eine oder mehrere erfindungsgemäße Verbindung(en) auf die Pflanzen (z.B. Schadpflanzen wie mono- oder dikotyle The present invention therefore also provides a method for controlling undesirable plants or regulating the growth of plants, preferably in crops, wherein one or more compounds of the invention are applied to the plants (e.g., weeds, such as mono- or dicotyledons
Unkräuter oder unerwünschte Kulturpflanzen), das Saatgut (z.B. Körner, Samen oder vegetative Vermehrungsorgane wie Knollen oder Sprossteile mit Knospen) oder die Fläche, auf der die Pflanzen wachsen (z.B. die Anbaufläche), ausgebracht werden. Dabei können die erfindungsgemäßen Verbindungen z.B. im Vorsaat- (ggf. auch durch Einarbeitung in den Boden), Vorauflauf- oder Nachauflaufverfahren ausgebracht werden. Im einzelnen seien beispielhaft einige Vertreter der mono- und dikotylen Unkrautflora genannt, die durch die erfindungsgemäßen Verbindungen kontrolliert werden können, ohne dass durch die Nennung eine Beschränkung auf bestimmte Arten erfolgen soll. Monokotyle Schadpflanzen der Gattungen: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyl- octenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, ottboellia, Sagittaria, Scirpus, Setaria, Sorghum. Weeds or unwanted crops), the seeds (eg grains, seeds or vegetative propagules such as tubers or sprout parts with buds) or the area on which the plants grow (eg the acreage) are applied. The compounds according to the invention can be applied, for example, in pre-sowing (optionally also by incorporation into the soil), pre-emergence or postemergence process. Specifically, by way of example, some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned, which can be controlled by the compounds according to the invention, without the intention of limiting them to certain species. Monocotyledonous weeds of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyl octenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera , Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, ottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
Dikotyle Unkräuter der Gattungen: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum,
Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, 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. Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, 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.
Werden die erfindungsgemäßen Verbindungen vor dem Keimen auf die Erdoberfläche appliziert, so wird entweder das Auflaufen der Unkrautkeimlinge vollständig verhindert oder die Unkräuter wachsen bis zum Keimblattstadium heran, stellen jedoch dann ihr Wachstum ein und sterben schließlich nach Ablauf von drei bis vier Wochen If the compounds according to the invention are applied to the surface of the earth prior to germination, either the emergence of the weed seedlings is completely prevented or the weeds grow up to the cotyledon stage, but then stop their growth and finally die after three to four weeks
vollkommen ab. completely off.
Bei Applikation der Wirkstoffe auf die grünen Pflanzenteile im Nachauflaufverfahren tritt nach der Behandlung Wachstumsstop ein und die Schadpflanzen bleiben in dem zum Applikationszeitpunkt vorhandenen Wachstumsstadium stehen oder sterben nach einer gewissen Zeit ganz ab, so dass auf diese Weise eine für die Kulturpflanzen schädliche Unkrautkonkurrenz sehr früh und nachhaltig beseitigt wird. Obgleich die erfindungsgemäßen Verbindungen eine ausgezeichnete herbizideWhen the active ingredients are applied to the green parts of the plants postemergence, growth stops after the treatment and the harmful plants remain in the growth stage existing at the time of application or die completely after a certain time, so that in this way a weed competition harmful to the crop plants occurs very early and sustainably eliminated. Although the compounds of the invention are excellent herbicides
Aktivität gegenüber mono- und dikotylen Unkräutern aufweisen, werden Kulturpflanzen wirtschaftlich bedeutender Kulturen z.B. dikotyler Kulturen der Gattungen Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, oder monokotyler Kulturen der Gattungen Allium, Ananas, Asparagus, Avena, Activity against monocotyledonous and dicotyledonous weeds, are crops of economically important cultures such as dicotyledonous cultures of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Nicotiana, Phaseolus, Pisum , Solanum, Vicia, or monocotyledonous crops of the genera Allium, Pineapple, Asparagus, Avena,
Hordeum, Oryza, Panicum, Saccharum, Seeale, Sorghum, Triticale, Triticum, Zea, insbesondere Zea und Triticum, abhängig von der Struktur der jeweiligen Hordeum, Oryza, Panicum, Saccharum, Seeale, Sorghum, Triticale, Triticum, Zea, especially Zea and Triticum, depending on the structure of each
erfindungsgemäßen Verbindung und deren Aufwandmenge nur unwesentlich oder gar nicht geschädigt. Die vorliegenden Verbindungen eignen sich aus diesen Gründen sehr gut zur selektiven Bekämpfung von unerwünschtem Pflanzenwuchs in Compound of the invention and its application rate only insignificantly damaged or not at all. For these reasons, the present compounds are very well suited for the selective control of undesired plant growth in
Pflanzenkulturen wie landwirtschaftlichen Nutzpflanzungen oder Zierpflanzungen. Crops such as agricultural crops or ornamental plantings.
Darüberhinaus weisen die erfindungsgemäßen Verbindungen (abhängig von ihrer jeweiligen Struktur und der ausgebrachten Aufwandmenge) hervorragende In addition, the compounds of the present invention (depending on their respective structure and applied application rate) are excellent
wachstumsregulatorische Eigenschaften bei Kulturpflanzen auf. Sie greifen regulierend in den pflanzeneigenen Stoffwechsel ein und können damit zur gezielten growth regulatory properties in crop plants. They regulate the plant's metabolism and can thus be targeted
Beeinflussung von Pflanzeninhaltsstoffen und zur Ernteerleichterung wie z.B. durch Auslösen von Desikkation und Wuchsstauchung eingesetzt werden. Desweiteren eignen sie sich auch zur generellen Steuerung und Hemmung von unerwünschtem vegetativen Wachstum, ohne dabei die Pflanzen abzutöten. Eine Hemmung des vegetativen Wachstums spielt bei vielen mono- und dikotylen Kulturen eine große Rolle, da beispielsweise die Lagerbildung hierdurch verringert oder völlig verhindert werden kann. Influence of phytonutrients and harvest relief, e.g. be used by triggering desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of undesirable vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops, since, for example, storage formation can thereby be reduced or completely prevented.
Aufgrund ihrer herbiziden und pflanzenwachstumsregulatorischen Eigenschaften können die Wirkstoffe auch zur Bekämpfung von Schadpflanzen in Kulturen von gentechnisch oder durch konventionelle Mutagenese veränderten Pflanzen eingesetzt werden. Die transgenen Pflanzen zeichnen sich in der Regel durch besondere vorteilhafte Eigenschaften aus, beispielsweise durch Resistenzen gegenüber bestimmten Pestiziden, vor allem bestimmten Herbiziden, Resistenzen gegenüber Pflanzenkrankheiten oder Erregern von Pflanzenkrankheiten wie bestimmten Insekten oder Mikroorganismen wie Pilzen, Bakterien oder Viren. Andere besondere Because of their herbicidal and plant growth regulatory properties, the active compounds can also be used to control harmful plants in crops of genetically engineered or conventional mutagenized plants. The transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special
Eigenschaften betreffen z. B. das Erntegut hinsichtlich Menge, Qualität, Lagerfähigkeit, Zusammensetzung und spezieller Inhaltsstoffe. So sind transgene Pflanzen mit erhöhtem Stärkegehalt oder veränderter Qualität der Stärke oder solche mit anderer Fettsäurezusammensetzung des Ernteguts bekannt. Properties concern z. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients. Thus, transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known.
Bevorzugt bezüglich transgener Kulturen ist die Anwendung der erfindungsgemäßen Verbindungen in wirtschaftlich bedeutenden transgenen Kulturen von Nutz- und Zierpflanzen, z. B. von Getreide wie Weizen, Gerste, Roggen, Hafer, Hirse, Reis und Mais oder auch Kulturen von Zuckerrübe, Baumwolle, Soja, Raps, Kartoffel, Tomate, Erbse und anderen Gemüsesorten. Vorzugsweise können die erfindungsgemäßen Verbindungen als Herbizide in Nutzpflanzenkulturen eingesetzt werden, welche gegenüber den phytotoxischen Wirkungen der Herbizide resistent sind bzw. Preferred for transgenic cultures is the use of the invention Compounds in economically important transgenic crops of useful and ornamental plants, eg. As cereals such as wheat, barley, rye, oats, millet, rice and corn or even crops of sugar beet, cotton, soy, rape, potato, tomato, pea and other vegetables. Preferably, the compounds according to the invention can be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or
gentechnisch resistent gemacht worden sind. have been made genetically resistant.
Bevorzugt ist die Anwendung der erfindungsgemäßen Verbindungen oder deren Salze in wirtschaftlich bedeutenden transgenen Kulturen von Nutz-und Zierpflanzen, z. B. von Getreide wie Weizen, Gerste, Roggen, Hafer, Hirse, Reis, Maniok und Mais oder auch Kulturen von Zuckerrübe, Baumwolle, Soja, Raps, Kartoffel, Tomate, Erbse und anderen Gemüsesorten. Vorzugsweise können die erfindungsgemäßen Verbindungen als Herbizide in Nutzpflanzenkulturen eingesetzt werden, welche gegenüber den phytotoxischen Wirkungen der Herbizide resistent sind bzw. gentechnisch resistent gemacht worden sind. Preferably, the application of the compounds of the invention or their salts in economically important transgenic crops of useful and ornamental plants, eg. As cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn or cultures of sugar beet, cotton, soy, rape, potato, tomato, pea and other vegetables. Preferably, the compounds according to the invention can be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made genetically resistant.
Herkömmliche Wege zur Herstellung neuer Pflanzen, die im Vergleich zu bisher vorkommenden Pflanzen modifizierte Eigenschaften aufweisen, bestehen Conventional ways of producing new plants that have modified properties compared to previously occurring plants exist
beispielsweise in klassischen Züchtungsverfahren und der Erzeugung von Mutanten. Alternativ können neue Pflanzen mit veränderten Eigenschaften mit Hilfe for example, in classical breeding methods and the generation of mutants. Alternatively, new plants with altered properties can help
gentechnischer Verfahren erzeugt werden (siehe z. B. EP-A-0221044, EP-A-0131624). Beschrieben wurden beispielsweise in mehreren Fällen genetic engineering methods are produced (see eg EP-A-0221044, EP-A-0131624). For example, several cases have been described
gentechnische Veränderungen von Kulturpflanzen zwecks Modifikation der in den Pflanzen synthetisierten Stärke (z. B. WO 92/1 1376, WO 92/14827, WO 91 /19806),  genetically engineered crop modifications to modify the starch synthesized in the plants (eg, WO 92/1 1376, WO 92/14827, WO 91/19806),
transgene Kulturpflanzen, welche gegen bestimmte Herbizide vom Typ  transgenic crops which are resistant to certain herbicides of the type
Glufosinate (vgl. z. B. EP-A-0242236, EP-A-242246) oder Glyphosate  Glufosinate (see, for example, EP-A-0242236, EP-A-242246) or glyphosate
(WO 92/00377) oder der Sulfonylharnstoffe (EP-A-0257993, US-A-5013659) resistent sind,  (WO 92/00377) or the sulfonylureas (EP-A-0257993, US-A-5013659) are resistant,
transgene Kulturpflanzen, beispielsweise Baumwolle, mit der Fähigkeit  transgenic crops, for example cotton, with the ability
Bacillus thuringiensis-Toxine (Bt-Toxine) zu produzieren, welche die  Bacillus thuringiensis toxins (Bt toxins) to produce, which the
Pflanzen gegen bestimmte Schädlinge resistent machen (EP-A-0142924, EP-A-0193259). transgene Kulturpflanzen mit modifizierter Fettsäurezusammensetzung (WOMake plants resistant to certain pests (EP-A-0142924, EP-A-0193259). Transgenic crops with modified fatty acid composition (WO
91/13972). 91/13972).
gentechnisch veränderte Kulturpflanzen mit neuen Inhalts- oder  genetically modified crops with new content or
Sekundärstoffen z. B. neuen Phytoalexinen, die eine erhöhte  Secondary materials z. B. new phytoalexins, which increased one
Krankheitsresistenz verursachen (EPA 309862, EPA0464461 )  Disease resistance cause (EPA 309862, EPA0464461)
gentechnisch veränderte Pflanzen mit reduzierter Photorespiration, die höhere Erträge und höhere Stresstoleranz aufweisen (EPA 0305398).  genetically modified plants with reduced photorespiration, which have higher yields and higher stress tolerance (EPA 0305398).
Transgene Kulturpflanzen, die pharmazeutisch oder diagnostisch wichtige Proteine produzieren („molecular pharming")  Transgenic crop plants that produce pharmaceutically or diagnostically important proteins ("molecular pharming")
transgene Kulturpflanzen, die sich durch höhere Erträge oder bessere Qualität auszeichnen  Transgenic crops that are characterized by higher yields or better quality
transgene Kulturpflanzen die sich durch eine Kombinationen z. B. der o. g. neuen Eigenschaften auszeichnen („gene stacking") Zahlreiche molekularbiologische Techniken, mit denen neue transgene Pflanzen mit veränderten Eigenschaften hergestellt werden können, sind im Prinzip bekannt, siehe z. B. I. Potrykus und G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, oder Christou, "Trends in Plant Science" 1 (1996) 423-431 ).  transgenic crops characterized by a combination z. B. the o. G. Numerous molecular biological techniques with which new transgenic plants with altered properties can be produced are known in principle, see, for example, BI Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg, or Christou, "Trends in Plant Science" 1 (1996) 423-431).
Für derartige gentechnische Manipulationen können Nucleinsäuremoleküle in For such genetic manipulations, nucleic acid molecules can be used in
Plasmide eingebracht werden, die eine Mutagenese oder eine Sequenzveränderung durch Rekombination von DNA-Sequenzen erlauben. Mit Hilfe von Standardverfahren können z. B. Basenaustausche vorgenommen, Teilsequenzen entfernt oder natürliche oder synthetische Sequenzen hinzugefügt werden. Für die Verbindung der DNA- Fragmente untereinander können an die Fragmente Adaptoren oder Linker angesetzt werden, siehe z. B. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2 Aufl. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY, oder Winnacker "Gene und Klone", VCH Weinheim 2. Auflage 1996 Plasmids are introduced which allow mutagenesis or a sequence change by recombination of DNA sequences. With the help of standard methods z. For example, base substitutions are made, partial sequences are removed, or natural or synthetic sequences are added. For the connection of the DNA fragments with one another adapters or linkers can be attached to the fragments. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2 Ed. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY, or Winnacker "Gene and Clones", VCH Weinheim 2nd edition, 1996
Die Herstellung von Pflanzenzellen mit einer verringerten Aktivität eines Genprodukts kann beispielsweise erzielt werden durch die Expression mindestens einer entsprechenden antisense-RNA, einer sense-RNA zur Erzielung eines The production of plant cells having a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to obtain a
Cosuppressionseffektes oder die Expression mindestens eines entsprechend konstruierten Ribozyms, das spezifisch Transkripte des obengenannten Genprodukts spaltet. Hierzu können zum einen DNA-Moleküle verwendet werden, die die gesamte codierende Sequenz eines Genprodukts einschließlich eventuell vorhandener flankierender Sequenzen umfassen, als auch DNA-Moleküle, die nur Teile der codierenden Sequenz umfassen, wobei diese Teile lang genug sein müssen, um in den Zellen einen antisense- Effekt zu bewirken. Möglich ist auch die Verwendung von DNA-Sequenzen, die einen hohen Grad an Homologie zu den codiereden Sequenzen eines Genprodukts aufweisen, aber nicht vollkommen identisch sind. Bei der Expression von Nucleinsäuremolekülen in Pflanzen kann das synthetisierte Protein in jedem beliebigen Kompartiment der pflanzlichen Zelle lokalisiert sein. Um aber die Lokalisation in einem bestimmten Kompartiment zu erreichen, kann z. B. die codierende Region mit DNA-Sequenzen verknüpft werden, die die Lokalisierung in einem bestimmten Kompartiment gewährleisten. Derartige Sequenzen sind dem Fachmann bekannt (siehe beispielsweise Braun et al., EMBO J. 1 1 (1992), 3219-3227, Wolter et al., Proc. Natl. Acad. Sei. USA 85 (1988), 846-850, Sonnewald et al., Plant J. 1 (1991 ), 95-106). Die Expression der Nukleinsäuremoleküle kann auch in den Cosuppressionseffektes or the expression of at least one corresponding engineered ribozyme which specifically cleaves transcripts of the above gene product. For this purpose, DNA molecules may be used which comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules which comprise only parts of the coding sequence, which parts must be long enough to be present in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical. In the expression of nucleic acid molecules in plants, the synthesized protein may be located in any compartment of the plant cell. But to achieve the localization in a particular compartment, z. For example, the coding region can be linked to DNA sequences that ensure localization in a particular compartment. Such sequences are known in the art (see, for example, Braun et al., EMBO J. 1 1 (1992), 3219-3227, Wolter et al., Proc. Natl. Acad., U.S.A. 85 (1988), 846-850, Sonnewald et al., Plant J. 1 (1991), 95-106). Expression of the nucleic acid molecules can also be found in the
Organellen der Pflanzenzellen stattfinden. Die transgenen Pflanzenzellen können nach bekannten Techniken zu ganzen Pflanzen regeneriert werden. Bei den transgenen Pflanzen kann es sich prinzipiell um Pflanzen jeder beliebigen Pflanzenspezies handeln, d.h., sowohl monokotyle als auch dikotyle Pflanzen. So sind transgene Pflanzen erhältlich, die veränderte Eigenschaften durch Organelles of the plant cells take place. The transgenic plant cells can be regenerated to whole plants by known techniques. The transgenic plants may, in principle, be plants of any plant species, that is, both monocotyledonous and dicotyledonous plants. Thus, transgenic plants are available, the altered properties by
Überexpression, Suppression oder Inhibierung homologer (= natürlicher) Gene oder Gensequenzen oder Expression heterologer (= fremder) Gene oder Gensequenzen aufweisen. Vorzugsweise können die erfindungsgemäßen Verbindungen in transgenen Kulturen eingesetzt werden, welche gegen Wuchsstoffe, wie z. B. Dicamba oder gegen  Overexpression, suppression or inhibition of homologous (= natural) genes or gene sequences or expression of heterologous (= foreign) genes or gene sequences. Preferably, the compounds of the invention can be used in transgenic cultures which are resistant to growth factors, such as. B. Dicamba or against
Herbizide, die essentielle Pflanzenenzyme, z. B. Acetolactatsynthasen (ALS), EPSP Synthasen, Glutaminsynthasen (GS) oder Hydroxyphenylpyruvat Dioxygenasen (HPPD) hemmen, respektive gegen Herbizide aus der Gruppe der Sulfonylharnstoffe, der Glyphosate, Glufosinate oder Benzoylisoxazole und analogen Wirkstoffe, resistent sind. Herbicides containing essential plant enzymes, e.g. Acetylactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD) inhibit, respectively against herbicides from the group of sulfonylureas, glyphosate, glufosinate or benzoylisoxazole and analogous agents.
Bei der Anwendung der erfindungsgemäßen Wirkstoffe in transgenen Kulturen treten neben den in anderen Kulturen zu beobachtenden Wirkungen gegenüber In the application of the active compounds according to the invention in transgenic cultures, in addition to the effects to be observed in other cultures
Schadpflanzen oftmals Wirkungen auf, die für die Applikation in der jeweiligen transgenen Kultur spezifisch sind, beispielsweise ein verändertes oder speziell erweitertes Unkrautspektrum, das bekämpft werden kann, veränderte Harmful plants often have effects that are specific for application in the particular transgenic culture, such as altered or specially extended weed spectrum that can be controlled
Aufwandmengen, die für die Applikation eingesetzt werden können, vorzugsweise gute Kombinierbarkeit mit den Herbiziden, gegenüber denen die transgene Kultur resistent ist, sowie Beeinflussung von Wuchs und Ertrag der transgenen Kulturpflanzen. Application rates that can be used for the application, preferably good combinability with the herbicides to which the transgenic culture is resistant, and influencing growth and yield of the transgenic crops.
Gegenstand der Erfindung ist deshalb auch die Verwendung der erfindungsgemäßen Verbindungen als Herbizide zur Bekämpfung von Schadpflanzen in transgenen Kulturpflanzen. The invention therefore also relates to the use of the compounds according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
Die erfindungsgemäßen Verbindungen können in Form von Spritzpulvern, The compounds of the invention may be in the form of wettable powders,
emulgierbaren Konzentraten, versprühbaren Lösungen, Stäubemitteln oder Granulaten in den üblichen Zubereitungen angewendet werden. Gegenstand der Erfindung sind deshalb auch herbizide und pflanzenwachstumsregulierende Mittel, welche die erfindungsgemäßen Verbindungen enthalten. emulsifiable concentrates, sprayable solutions, dusts or granules are used in the usual preparations. The invention therefore also relates to herbicidal and plant growth-regulating agents which contain the compounds according to the invention.
Die erfindungsgemäßen Verbindungen können auf verschiedene Art formuliert werden, je nachdem welche biologischen und/oder chemisch-physikalischen Parameter vorgegeben sind. Als Formulierungsmöglichkeiten kommen beispielsweise in Frage: Spritzpulver (WP), wasserlösliche Pulver (SP), wasserlösliche Konzentrate, The compounds according to the invention can be formulated in various ways, depending on which biological and / or chemical-physical parameters are predetermined. Possible formulation options are, for example: wettable powder (WP), water-soluble powders (SP), water-soluble concentrates,
emulgierbare Konzentrate (EC), Emulsionen (EW), wie öl-in-Wasser- und emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and
Wasser-in-öl-Emulsionen, versprühbare Lösungen, Suspensionskonzentrate (SC), Dispersionen auf öl- oder Wasserbasis, ölmischbare Lösungen, Kapselsuspensionen (CS), Stäubemittel (DP), Beizmittel, Granulate für die Streu- und Bodenapplikation, Granulate (GR) in Form von Mikro-, Sprüh-, Aufzugs- und Adsorptionsgranulaten, wasserdispergierbare Granulate (WG), wasserlösliche Granulate (SG), Water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for litter and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG),
ULV-Formulierungen, Mikro kapseln und Wachse. ULV formulations, microcapsules and waxes.
Diese einzelnen Formulierungstypen sind im Prinzip bekannt und werden beispielsweise beschrieben in: Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hanser Verlag München, 4. Aufl. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973, K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London. These individual formulation types are known and will be known in principle for example, described in: Winnacker-Kuchler, "Chemische Technologie", Volume 7, C. Hanser Verlag Munich, 4th ed. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY, 1973, K. Martens, "Spray Drying "Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.
Die notwendigen Formulierungshilfsmittel wie Inertmaterialien, Tenside, Lösungsmittel und weitere Zusatzstoffe sind ebenfalls bekannt und werden beispielsweise The necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and are, for example
beschrieben in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid described in Watkins, Handbook of Insecticides Dust Diluents and Carriers, 2nd ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid
Chemistry", 2nd Ed., J. Wiley & Sons, N.Y., C. Marsden, "Solvente Guide", 2nd Ed., Interscience, N.Y. 1963, McCutcheon's "Detergents and Emuisifiers Annual", MC Publ. Corp., Ridgewood N.J., Sisley and Wood, "Encyclopedia of Chemistry, 2nd Ed., J. Wiley & Sons, NY, C. Marsden, "Solvent Guide", 2nd Ed., Interscience, NY 1963, McCutcheon's "Detergents and Emuiversifiers Annual", MC Publ. Corp., Ridgewood NJ, Sisley and Wood, "Encyclopedia of
Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964, Schönfeldt, Surface Active Agents, Chem. Publ. Co. Inc., N.Y. 1964, Schonfeldt,
"Grenzflächenaktive Äthylenoxidaddukte", Wiss. Verlagsgesell., Stuttgart 1976, Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hanser Verlag München, 4. Aufl. 1986. "Surface-active ethylene oxide adducts", Wiss. Verlagsgesell., Stuttgart 1976, Winnacker-Kuchler, "Chemical Technology", Volume 7, C. Hanser Verlag Munich, 4th ed. 1986.
Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit anderen Pestizid wirksamen Stoffen, wie z.B. Insektiziden, Akariziden, Herbiziden, Fungiziden, sowie mit Safenern, Düngemitteln und/oder Wachstumsregulatoren herstellen, z.B. in Form einer Fertigformulierung oder als Tankmix. Geeignete Safener sind On the basis of these formulations, combinations with other pesticidally active substances, such as e.g. Insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a ready-made formulation or as a tank mix. Suitable safeners are
beispielsweise Mefenpyr-diethyl, Cyprosulfamid, Isoxadifen-ethyl, Cloquintocet-mexyl und Dichlormid. Spritzpulver sind in Wasser gleichmäßig dispergierbare Präparate, die neben dem Wirkstoff außer einem Verdünnungs- oder Inertstoff noch Tenside ionischer und/oder nichtionischer Art (Netzmittel, Dispergiermittel), z.B. polyoxyethylierte Alkylphenole, polyoxethylierte Fettalkohole, polyoxethylierte Fettamine, for example, mefenpyr-diethyl, cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and dichloromide. Injectable powders are preparations which are uniformly dispersible in water and contain surfactants of the ionic and / or nonionic type (wetting agent, dispersing agent) in addition to the active ingredient, apart from a diluent or inert substance. polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines,
Fettalkoholpolyglykolethersulfate, Alkansulfonate, Alkylbenzolsulfonate, Fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates,
ligninsulfonsaures Natrium, 2,2'-dinaphthylmethan-6.6'-disulfonsaures Natrium, dibutylnaphthalin-sulfonsaures Natrium oder auch oleoylmethyltaurinsaures Natrium enthalten. Zur Herstellung der Spritzpulver werden die herbiziden Wirkstoffe beispielsweise in üblichen Apparaturen wie Hammermühlen, Gebläsemühlen und Luftstrahlmühlen feingemahlen und gleichzeitig oder anschließend mit den lignosulfonic acid sodium, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalenesulfonate sodium or oleoylmethyltaurine acid. For the preparation of the wettable powders, the herbicidal active compounds, for example, in conventional apparatus such as hammer mills, blower mills and Air-jet mills finely ground and at the same time or subsequently with the
Formulierungshilfsmitteln vermischt. Formulation aids mixed.
Emulgierbare Konzentrate werden durch Auflösen des Wirkstoffes in einem Emulsifiable concentrates are made by dissolving the active ingredient in one
organischen Lösungsmittel z.B. Butanol, Cyclohexanon, Dimethylformamid, Xylol oder auch höhersiedenden Aromaten oder Kohlenwasserstoffen oder Mischungen der organischen Lösungsmittel unter Zusatz von einem oder mehreren Tensiden ionischer und/oder nichtionischer Art (Emulgatoren) hergestellt. Als Emulgatoren können beispielsweise verwendet werden: Alkylarylsulfonsaure Calzium-Salze wie organic solvents e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers). Examples of emulsifiers which may be used are: alkylarylsulfonic acid calcium salts, such as
Ca-Dodecylbenzolsulfonat oder nichtionische Emulgatoren wie Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as
Fettsäurepolyglykolester, Alkylarylpolyglykolether, Fettalkoholpolyglykolether,  Fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers,
Propylenoxid-Ethylenoxid-Kondensationsprodukte, Alkylpolyether, Sorbitanester wie z.B. Sorbitanfettsäureester oder Polyoxethylensorbitanester wie z.B. Propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, e.g. Sorbitan fatty acid esters or polyoxethylenesorbitan esters such as e.g.
Polyoxyethylensorbitanfettsäureester. Polyoxyethylene.
Stäubemittel erhält man durch Vermählen des Wirkstoffes mit fein verteilten festen Stoffen, z.B. Talkum, natürlichen Tonen, wie Kaolin, Bentonit und Pyrophyllit, oder Diatomeenerde. Suspensionskonzentrate können auf Wasser- oder Ölbasis sein. Sie können beispielsweise durch Naß-Vermahlung mittels handelsüblicher Perlmühlen und gegebenenfalls Zusatz von Tensiden, wie sie z.B. oben bei den anderen Dusts are obtained by milling the active ingredient with finely divided solids, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. Suspension concentrates may be water or oil based. They can be prepared, for example, by wet grinding using commercially available bead mills and, if appropriate, addition of surfactants, as described, for example, in US Pat. upstairs with the others
Formulierungstypen bereits aufgeführt sind, hergestellt werden. Emulsionen, z.B. öl-in-Wasser-Emulsionen (EW), lassen sich beispielsweise mittels Rührern, Kolloidmühlen und/oder statischen Mischern unter Verwendung von wäßrigen organischen Lösungsmitteln und gegebenenfalls Tensiden, wie sie z.B. oben bei den anderen Formulierungstypen bereits aufgeführt sind, herstellen. Granulate können entweder durch Verdüsen des Wirkstoffes auf adsorptionsfähiges, granuliertes Inertmaterial hergestellt werden oder durch Aufbringen von Formulation types already listed are produced. Emulsions, e.g. Oil-in-water emulsions (EW) can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, as described e.g. listed above for the other formulation types. Granules can be prepared either by spraying the active ingredient on adsorptive, granulated inert material or by applying
Wirkstoffkonzentraten mittels Klebemitteln, z.B. Polyvinylalkohol, polyacrylsaurem Natrium oder auch Mineralölen, auf die Oberfläche von Trägerstoffen wie Sand, Kaolinite oder von granuliertem Inertmaterial. Auch können geeignete Wirkstoffe in der für die Herstellung von Düngemittelgranulaten üblichen Weise - gewünschtenfalls in Mischung mit Düngemitteln - granuliert werden. Active substance concentrates by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or mineral oils, on the surface of carriers such as sand, kaolinites or granulated inert material. Also, suitable active ingredients in the for the production of fertilizer granules customary way - if desired, mixed with fertilizers - granulated.
Wasserdispergierbare Granulate werden in der Regel nach den üblichen Verfahren wie Sprühtrocknung, Wirbelbett-Granulierung, Teller-Granulierung, Mischung mit Hochgeschwindigkeitsmischern und Extrusion ohne festes Inertmaterial hergestellt. Water-dispersible granules are generally prepared by the usual methods such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
Zur Herstellung von Teller-, Fließbett-, Extruder- und Sprühgranulate siehe z.B. For the preparation of plate, fluid bed, extruder and spray granules, see e.g.
Verfahren in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London, J.E. Browning, "Agglomeration", Chemical and Engineering 1967, Seiten 147 ff, "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, ew York 1973, S. 8-57. Method in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London, J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 et seq., "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.
Für weitere Einzelheiten zur Formulierung von Pflanzenschutzmitteln siehe z.B. G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961 , Seiten 81 -96 und J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, Seiten 101 -103. For further details on the formulation of crop protection agents see, e.g. G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.
Die agrochemischen Zubereitungen enthalten in der Regel 0.1 bis 99 Gew.-%, insbesondere 0.1 bis 95 Gew.-%, erfindungsgemäße Verbindungen. The agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of compounds according to the invention.
In Spritzpulvern beträgt die Wirkstoffkonzentration z.B. etwa 10 bis 90 Gew.-%, der Rest zu 100 Gew.-% besteht aus üblichen Formulierungsbestandteilen. Bei emulgierbaren Konzentraten kann die Wirkstoffkonzentration etwa 1 bis 90, vorzugsweise 5 bis 80 Gew.-% betragen. Staubförmige Formulierungen enthalten 1 bis 30 Gew.-% Wirkstoff, vorzugsweise meistens 5 bis 20 Gew.-% an Wirkstoff, versprühbare Lösungen enthalten etwa 0.05 bis 80, vorzugsweise 2 bis 50 Gew.-% Wirkstoff. Bei wasserdispergierbaren Granulaten hängt der Wirkstoffgehalt zum Teil davon ab, ob die wirksame Verbindung flüssig oder fest vorliegt und welche In wettable powders, the drug concentration is e.g. about 10 to 90 wt .-%, the balance to 100 wt .-% consists of conventional formulation ingredients. For emulsifiable concentrates, the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%. Dust-like formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% active ingredient. In the case of water-dispersible granules, the active ingredient content depends, in part, on whether the active compound is liquid or solid and which
Granulierhilfsmittel, Füllstoffe usw. verwendet werden. Bei den in Wasser Granulation aids, fillers, etc. are used. In the water
dispergierbaren Granulaten liegt der Gehalt an Wirkstoff beispielsweise zwischen 1 und 95 Gew.-%, vorzugsweise zwischen 10 und 80 Gew.-%. dispersible granules, the content of active ingredient is for example between 1 and 95 wt .-%, preferably between 10 and 80 wt .-%.
Daneben enthalten die genannten Wirkstofformulierungen gegebenenfalls die jeweils üblichen Haft-, Netz-, Dispergier-, Emulgier-, Penetrations-, Konservierungs-, Frostschutz- und Lösungsmittel, Füll-, Träger- und Farbstoffe, Entschäumer, In addition, the active substance formulations mentioned optionally contain the customary adhesive, wetting, dispersing, emulsifying, penetrating, preserving, Antifreeze and solvents, fillers, carriers and dyes, defoamers,
Verdunstungshemmer und den pH-Wert und die Viskosität beeinflussende Mittel. Evaporation inhibitors and pH and viscosity affecting agents.
Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit anderen pestizid wirksamen Stoffen, wie z.B. Insektiziden, Akariziden, Herbiziden, Fungiziden, sowie mit Safenern, Düngemitteln und/oder Wachstumsregulatoren herstellen, z.B. in Form einer Fertigformulierung oder als Tankmix. On the basis of these formulations, combinations with other pesticidally active substances, e.g. Insecticides, acaricides, herbicides, fungicides, as well as with safeners, fertilizers and / or growth regulators, e.g. in the form of a ready-made formulation or as a tank mix.
Als Kombinationspartner für die erfindungsgemäßen Verbindungen in As a combination partner for the compounds of the invention in
Mischungsformulierungen oder im Tank-Mix sind beispielsweise bekannte Wirkstoffe, die auf einer Inhibition von beispielsweise Acetolactat-Synthase, Acetyl-CoA- Carboxylase, Cellulose-Synthase, Enolpyruvylshikimat-3-phosphat-Synthase, Mixture formulations or in the tank mix are, for example, known active substances which are based on an inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase,
Glutamin-Synthetase, p-Hydroxyphenylpyruvat-Dioxygenase, Phytoendesaturase, Photosystem I, Photosystem II, Protoporphyrinogen-Oxidase beruhen, einsetzbar, wie sie z.B. aus Weed Research 26 (1986) 441 -445 oder "The Pesticide Manual", 15th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2009 und dort zitierter Literatur beschrieben sind. Glutamine synthetase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, protoporphyrinogen oxidase, can be used, e.g. from Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 15th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2009 and cited therein.
Zur Anwendung werden die in handelsüblicher Form vorliegenden Formulierungen gegebenenfalls in üblicher Weise verdünnt z.B. bei Spritzpulvern, emulgierbaren Konzentraten, Dispersionen und wasserdispergierbaren Granulaten mittels Wasser. Staubförmige Zubereitungen, Boden- bzw. Streugranulate sowie versprühbare For use, the formulations present in commercial form are optionally diluted in a customary manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Dusty preparations, ground or spreading granules and sprayable
Lösungen werden vor der Anwendung üblicherweise nicht mehr mit weiteren inerten Stoffen verdünnt. Solutions are usually no longer diluted with other inert substances before use.
Mit den äußeren Bedingungen wie Temperatur, Feuchtigkeit, der Art des verwendeten Herbizids, u.a. variiert die erforderliche Aufwandmenge der Verbindungen der Formel (I). Sie kann innerhalb weiter Grenzen schwanken, z.B. zwischen 0,001 und 1 ,0 kg/ha oder mehr Aktivsubstanz, vorzugsweise liegt sie jedoch zwischen 0,005 und 750 g/ha. With the external conditions such as temperature, humidity, the type of herbicide used, u.a. varies the required application rate of the compounds of formula (I). It can vary within wide limits, e.g. between 0.001 and 1.0 kg / ha or more of active substance, but is preferably between 0.005 and 750 g / ha.
Die nachstehenden Beispiele erläutern die Erfindung. A Chemische Beispiele The following examples illustrate the invention. A Chemical examples
Synthese von [4-Amino-3-chlor-6-(4-chlor-2-fluor-3-methoxyphenyl)pyridin-2-yl]- propanoat (Tabellenbeispiel-Nr. 2)  Synthesis of [4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxyphenyl) pyridin-2-yl] propanoate (Table Example No. 2)
Zu einer Lösung von 0.49 g (1 .55 mmol) [4-Amino-3-chlor-6-(4-chlor-2-fiuor-3- methoxyphenyl)pyridin-2-yl]methanol und 10 mg 4-Dimethylaminopyridin in 15 ml Pyridin werden 0.16 g (1 .7 mmol) Propanoylchlorid gegeben. Man rührt diese  To a solution of 0.49 g (1 .55 mmol) of [4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxyphenyl) pyridin-2-yl] methanol and 10 mg of 4-dimethylaminopyridine in 15 ml of pyridine are added 0.16 g (1 .7 mmol) of propanoyl chloride. You stir these
Mischung 12 Stunden bei Raumtemperatur und engt sie dann bis zur Trockne ein. Chromatographische Reinigung des Rohprodukts an Kieselgel mit Heptan/Essig- säureethylester (1 :1 ) als Lauf mittel liefert 0.34 g (59%) Produkt als zähes öl. Mixture at room temperature for 12 hours and then concentrate to dryness. Chromatographic purification of the crude product on silica gel with heptane / ethyl acetate (1: 1) as eluant yields 0.34 g (59%) of product as a viscous oil.
Ή-NMR (CDC ): 7.60 (m, 1 H, Phenyl), 7.20 (m, 1 H, Phenyl), 7.10 (s, 1 H, Pyridin), 5.30 (s, 2H, CH2), 4.70 (bs, 2H, NH2), 3.95 (s, 3H, OMe), 2.48 (q, 2H, CH2), 1 .20 (t, 3H, CH3). Ή-NMR (CDC): 7.60 (m, 1H, phenyl), 7.20 (m, 1H, phenyl), 7.10 (s, 1H, pyridine), 5.30 (s, 2H, CH 2 ), 4.70 (bs , 2H, NH 2 ), 3.95 (s, 3H, OMe), 2.48 (q, 2H, CH 2 ), 1 .20 (t, 3H, CH 3 ).
Synthese von [4-Amino-3-chlor-6-(4-chlor-2-fluor-3-methoxyphenyl)pyridin-2-yl]- methyl-3-phenylpropanoat (Tabellenbeispiel-Nr. 5) Synthesis of [4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxyphenyl) pyridin-2-yl] methyl-3-phenylpropanoate (Table Example No. 5)
Zu einer Lösung von 0.2 g (0.63 mmol) [4-Amino-3-chlor-6-(4-chlor-2-fiuor-3- methoxyphenyl)pyridine-2-yl]methanol und 10 mg 4-Dimethylaminopyridin in 15 ml Pyridin werden 0.12 g (0.71 mmol) 3-phenylpropanoylchlorid gegeben. Man rührt diese Mischung 12 Stunden bei Raumtemperatur und engt sie dann bis zur Trockne ein. Chromatographische Reinigung des Rohprodukts an Kieselgel mit Heptan/Essig- säureethylester (1 :1 ) als Laufmittel liefert 0.3 g (79%) Produkt als zähes Öl.  To a solution of 0.2 g (0.63 mmol) of [4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methoxyphenyl) -pyridine-2-yl] -methanol and 10 mg of 4-dimethylaminopyridine in 15 ml Pyridine is added 0.12 g (0.71 mmol) of 3-phenylpropanoyl chloride. This mixture is stirred for 12 hours at room temperature and then concentrated to dryness. Chromatographic purification of the crude product on silica gel with heptane / ethyl acetate (1: 1) as eluant yields 0.3 g (79%) of product as a viscous oil.
Ή-NMR (CDCh) : 7.60 (m, 1 H, Phenyl), 7.20 - 7.40 (m, 6H, 2Phenyl), 7.10 (s, 1 H, Pyridin), 5.35 (s, 2H, CH2), 4.70 (bs, 2H, NH2), 4.00 (s, 3H, OMe), 3.00 (t, 2H, CH2), 2.70 (t, 2H, CH2). Ή-NMR (CDCh): 7.60 (m, 1H, phenyl), 7.20-7.40 (m, 6H, 2-phenyl), 7.10 (s, 1H, pyridine), 5.35 (s, 2H, CH 2 ), 4.70 ( bs, 2H, NH 2 ), 4.00 (s, 3H, OMe), 3.00 (t, 2H, CH 2 ), 2.70 (t, 2H, CH 2 ).
Synthese von [4-Amino-3-chlor-5-fluor-6-(4-chlor-2-fluor-3-methoxyphenyl)pyridin-2- yljmethanol Synthesis of [4-Amino-3-chloro-5-fluoro-6- (4-chloro-2-fluoro-3-methoxyphenyl) pyridin-2-yl] methanol
Zu einer Lösung von 0.26g (0.71 mmol) Methyl-4-amino-3-chlor-5-fiuor-6-(4-chlor-2- fluor-3-methoxyphenyl)pyridin-2-carboxylat in 3 ml Ethanol gibt man 71 mg (1 .79 mmol) Natriumborhydrid. Das Reaktionsgemisch wird zunächst 1 Stunde bei  To a solution of 0.26 g (0.71 mmol) of methyl 4-amino-3-chloro-5-fluoro-6- (4-chloro-2-fluoro-3-methoxyphenyl) pyridine-2-carboxylate in 3 ml of ethanol is added 71 mg (1.79 mmol) sodium borohydride. The reaction mixture is initially at 1 hour
Raumtemperatur und danach 4 Stunden unter Rückfluss gerührt. Zur Aufarbeitung wird das Reaktionsgemisch mit wenig Wasser und ges. NH4CI-Lösung versetzt und mit CH2CI2 extrahiert. Die organische Phase wird über Na2S04 getrocknet und eingeengt. Chromatographische Reinigung an Kieselgel mit Heptan/Essigsäureethylester (1 :1 ) liefert 70 mg (29 %) Produkt als zähes Öl. Room temperature and then stirred for 4 hours under reflux. For workup, the reaction mixture with a little water and sat. NH 4 Cl solution and extracted with CH 2 Cl 2 . The organic phase is dried over Na 2 S0 4 and concentrated. Chromatographic purification on silica gel with heptane / ethyl acetate (1: 1) gives 70 mg (29%) of product as a viscous oil.
Ή-NMR (CDCb): 7.65 m (m, 1 H, Phenyl), 7.25 (m, 1 H, Phenyl), 4.80 (bs, 2H, NH2), 4.70 (d, 2H, CH2), 4.20 (t, 1 H, OH), 4.00 (s, 3H, OMe). Ή-NMR (CDCb): 7.65 m (m, 1H, phenyl), 7.25 (m, 1H, phenyl), 4.80 (bs, 2H, NH 2 ), 4.70 (d, 2H, CH 2 ), 4.20 ( t, 1H, OH), 4.00 (s, 3H, OMe).
Die in der nachfolgenden Tabelle aufgeführten Beispiele wurden analog oben genannten Methoden hergestellt beziehungsweise sind analog oben genannten Methoden erhältlich. Diese Verbindungen sind ganz besonders bevorzugt. Tabelle: Erfindungsgemäße Verbindungen der Formel (I), worin R2 für Chlor, R3 und R4 jeweils für Wasserstoff stehen, und A, X und R1 die jeweils angegebenen Bedeutungen haben. The examples listed in the table below were prepared analogously to the above-mentioned methods or are obtainable analogously to the abovementioned methods. These compounds are most preferred. Table: Compounds of the formula (I) according to the invention in which R 2 is chlorine, R 3 and R 4 are each hydrogen, and A, X and R 1 are each as defined.
Figure imgf000025_0001
Figure imgf000025_0001
Nr. A R1 XNo. AR 1 X
1 4-Chlor-2-fluor-3-met oxyp enyl Cyclopropyl CH1 4-Chloro-2-fluoro-3-metoxyphenyl cyclopropyl CH
2 4-Chlor-2-fluor-3-methoxyp enyl Ethyl CH2 4-Chloro-2-fluoro-3-methoxy-phenyl ethyl CH
3 4-Chlor-2-fluor-3-methoxyphenyl Propyl CH 3 4-Chloro-2-fluoro-3-methoxyphenyl Propyl CH
4 4-C lor-3-met oxyp enyl CH 4 4-chloro-3-metoxyphenyl CH
5 4-C lor-2-fluor-3-met oxyp enyl CH 5 4-chloro-2-fluoro-3-methoxyphenyl CH
6 4-C lor-2-fluor-3-methoxyp enyl 6 4-chloro-2-fluoro-3-methoxyp enyl
CH CH
CI CI
7 4-Chlor-2-fluor-3-methoxyphenyl CH
Figure imgf000025_0002
Figure imgf000026_0001
Nr. A R1 X 7 4-chloro-2-fluoro-3-methoxyphenyl CH
Figure imgf000025_0002
Figure imgf000026_0001
No. AR 1 X
22 Cyclopropyl N 22 cyclopropyl N
CI  CI
23 Cyclopropyl N 23 cyclopropyl N
24 Cyclopropyl N 24 cyclopropyl N
CI CI
N N
25 Cyclopropyl  25 cyclopropyl
N N
26 Cyclopropyl  26 cyclopropyl
27 Cyclopropyl 27 cyclopropyl
N  N
28 Cyclopropyl 28 cyclopropyl
N  N
N N
29 Cyclopropyl  29 cyclopropyl
30 Cyclopropyl 30 cyclopropyl
N  N
31 Cyclopropyl N 31 cyclopropyl N
F  F
32 Cyclopropyl N 32 cyclopropyl N
Ph
Figure imgf000028_0001
Figure imgf000029_0001
Nr. A R1 X Ph
Figure imgf000028_0001
Figure imgf000029_0001
No. AR 1 X
57 4-Chlorphenyl N
Figure imgf000030_0001
57 4-chlorophenyl N
Figure imgf000030_0001
58 4-C lorp enyl N 58 4-C lorp enyl N
F F
59 4-Chlorphenyl N
Figure imgf000030_0002
59 4-chlorophenyl N
Figure imgf000030_0002
N N
60 4-Chlorphenyl  60 4-chlorophenyl
N N
61 4-Chlorphenyl  61 4-chlorophenyl
Gl  gl
62 4-Chlorphenyl YYCH3 N 62 4-chlorophenyl YY CH 3 N
63 4-Chlorphenyl N
Figure imgf000030_0003
63 4-chlorophenyl N
Figure imgf000030_0003
64 4-Chlorphenyl N 64 4-chlorophenyl N
F F
65 4-Chlorphenyl N 65 4-chlorophenyl N
66 4-Chlorphenyl 66 4-chlorophenyl
N  N
67 4-Chlorphenyl N Nr. A R1 X 67 4-chlorophenyl N No. AR 1 X
68 4-Chlorphenyl JO N 68 4-chlorophenyl JO N
69 4-Chlorphenyl N 69 4-chlorophenyl N
N N
70 4-Chlorphenyl  70 4-chlorophenyl
71 4-Chlorphenyl N 71 4-chlorophenyl N
72 4-Fluorphenyl N 72 4-fluorophenyl N
CI  CI
B. Formulierungsbeispiele B. Formulation Examples
a) Ein Stäubemittel wird erhalten, indem man 10 Gew. -Teile einer Verbindung der Formel (I) und/oder deren Salze und 90 Gew. -Teile Talkum als Inertstoff mischt und in einer Schlagmühle zerkleinert.  a) A dust is obtained by mixing 10 parts by weight of a compound of formula (I) and / or salts thereof and 90 parts by weight of talc as an inert material and comminuted in a hammer mill.
Ein in Wasser leicht dispergierbares, benetzbares Pulver wird erhalten, indem
Figure imgf000031_0001
man 25 Gewichtsteile einer Verbindung der Formel (I) und/oder deren Salze, 64 A readily dispersible, water-wettable powder is obtained by:
Figure imgf000031_0001
25 parts by weight of a compound of the formula (I) and / or salts thereof, 64
Gew.-Teile kaolinhaltigen Quarz als Inertstoff, 10 Gewichtsteile  Parts by weight of kaolin-containing quartz as inert material, 10 parts by weight
ligninsulfonsaures Kalium und 1 Gew. -Teil oleoylmethyltaurinsaures Natrium als Netz- und Dispergiermittel mischt und in einer Stiftmühle mahlt. c) Ein in Wasser leicht dispergierbares Dispersionskonzentrat wird erhalten, indem man 20 Gew.-Teile einer Verbindung der Formel (I) und/oder deren Salze mit 6 Gew.-Teilen Alkylphenolpolyglykolether (©Triton X 207), 3 Gew. -Teilen  potassium lignosulfonate and 1 part by weight oleoylmethyltaurine sodium as wetting and dispersing agent and ground in a pin mill. c) A dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of a compound of the formula (I) and / or salts thereof with 6 parts by weight of alkylphenol polyglycol ether (© Triton X 207), 3 parts by weight
Isotridecanolpolyglykolether (8 EO) und 71 Gew.-Teilen paraffinischem Mineralöl (Siedebereich z.B. ca. 255 bis über 277 C) mischt und in einer Reibkugelmühle auf eine Feinheit von unter 5 Mikron vermahlt. Isotridecanol polyglycol ether (8 EO) and 71 parts by weight paraffinic Mineral oil (boiling range, for example, about 255 to about 277 C) mixed and ground in a ball mill to a fineness of less than 5 microns.
Ein emulgierbares Konzentrat wird erhalten aus 15 Gew. -Teilen einer An emulsifiable concentrate is obtained from 15 parts by weight of a
Verbindung der Formel (I) und/oder deren Salze, 75 Gew. -Teilen Cyclohexanon als Lösungsmittel und 10 Gew. -Teilen oxethyliertes Nonylphenol als Emulgator. Compound of formula (I) and / or salts thereof, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.
Ein in Wasser dispergierbares Granulat wird erhalten indem man A water-dispersible granules are obtained by
75 Gew. -Teile einer Verbindung der Formel (I) und/oder deren Salze, 75 parts by weight of a compound of the formula (I) and / or salts thereof,
10 Gew. -Teile ligninsulfonsaures Calcium, 10 parts by weight of lignosulfonic acid calcium,
5 Gew. -Teile Natriumlaurylsulfat, 5 parts by weight of sodium lauryl sulfate,
3 Gew. -Teile Polyvinylalkohol und 3 parts by weight of polyvinyl alcohol and
7 Gew. -Teile Kaolin 7 parts by weight kaolin
mischt, auf einer Stiftmühle mahlt und das Pulver in einem Wirbelbett durch Aufsprühen von Wasser als Granulierflüssigkeit granuliert. milled, ground on a pin mill and granulated the powder in a fluidized bed by spraying water as Granulierflüssigkeit.
Ein in Wasser dispergierbares Granulat wird auch erhalten, indem man A water-dispersible granule is also obtained by
25 Gew. -Teile einer Verbindung der Formel (I) und/oder deren Salze,  25 parts by weight of a compound of the formula (I) and / or salts thereof,
5 Gew. -Teile 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium  5 parts by wt. 2,2'-dinaphthylmethane-6,6'-disulfonate sodium
2 Gew. -Teile oleoylmethyltaurinsaures Natrium,  2 parts by weight oleoylmethyltaurine acid sodium,
1 Gew. -Teil Polyvinylalkohol,  1 part by weight of polyvinyl alcohol,
17 Gew. -Teile Calciumcarbonat und  17 parts by weight calcium carbonate and
50 Gew. -Teile Wasser  50 parts by weight of water
auf einer Kolloidmühle homogenisiert und vorzerkleinert, anschließend auf einer Perlmühle mahlt und die so erhaltene Suspension in einem Sprühturm mittels einer Einstoffdüse zerstäubt und trocknet. Homogenized on a colloid mill and pre-crushed, then grinded on a bead mill and the suspension thus obtained in a spray tower by means of a Einstoffdüse atomized and dried.
C. Biologische Beispiele C. Biological examples
1 . Herbizide Wirkung gegen Schadpflanzen im Vorauflauf  1 . Herbicidal action against weevils in pre-emergence
Samen von mono- bzw. dikotylen Unkraut- bzw. Kulturpflanzen werden in  Seeds of monocotyledonous or dicotyledonous weeds are cultivated in
Holzfasertöpfen in sandiger Lehmerde ausgelegt und mit Erde abgedeckt. Die in Form von benetzbaren Pulvern (WP) oder als Emulsionskonzentrate (EC) formulierten erfindungsgemäßen Verbindungen werden dann als wäßrige Suspension bzw. Wood fiber pots laid in sandy loam soil and covered with soil. The compounds according to the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then used as aqueous suspension or
Emulsion mit einer Wasseraufwandmenge von umgerechnet 600 bis 800 l/ha unter Zusatz von 0,2% Netzmittel auf die Oberfläche der Abdeckerde appliziert. Nach der Behandlung werden die Töpfe im Gewächshaus aufgestellt und unter guten Emulsion with a water application rate of 600 to 800 l / ha with the addition of 0.2% wetting agent applied to the surface of the cover soil. After the treatment the pots are placed in the greenhouse and under good conditions
Wachstumsbedingungen für die Testpflanzen gehalten. Die visuelle Bonitur derMaintained growth conditions for the test plants. The visual rating of the
Schäden an den Versuchspflanzen erfolgt nach einer Versuchszeit von 3 Wochen im Vergleich zu unbehandelten Kontrollen (herbizide Wirkung in Prozent (%): 100% Wirkung = Pflanzen sind abgestorben, 0 % Wirkung = wie Kontrollpflanzen). Dabei zeigen beispielsweise die Verbindung Nr. 1 . 2, 5. 6. 18. 19, 21 , 22, 24, 26, 27, 28, 34, 37 und 43 bei einer Aufwandmenge von 320 g/ha jeweils eine mindestens 80%-ige Wirkung gegen Amaranthus retroflexus auf. Damage to the test plants occurs after a test period of 3 weeks in comparison to untreated controls (herbicidal action in percent (%): 100% effect = plants have died, 0% effect = like control plants). Here, for example, show the compound no. 1. 2, 5. 6. 18. 19, 21, 22, 24, 26, 27, 28, 34, 37 and 43 at an application rate of 320 g / ha each have an at least 80% action against Amaranthus retroflexus.
2. Herbizide Wirkung gegen Schadpflanzen im Nachauflauf 2. Herbicidal action against harmful plants in postemergence
Samen von mono- bzw. dikotylen Unkraut- bzw. Kulturpflanzen werden in Seeds of monocotyledonous or dicotyledonous weeds are cultivated in
Holzfasertöpfen in sandigem Lehmboden ausgelegt, mit Erde abgedeckt und imWood fiber pots laid out in sandy clay soil, covered with soil and in the
Gewächshaus unter guten Wachstumsbedingungen angezogen. 2 bis 3 Wochen nach der Aussaat werden die Versuchspflanzen im Einblattstadium behandelt. Die in Form von benetzbaren Pulvern (WP) oder als Emulsionskonzentrate (EC) formulierten erfindungsgemäßen Verbindungen werden dann als wäßrige Suspension bzw. Greenhouse under good growth conditions. 2 to 3 weeks after sowing, the test plants are treated in the single leaf stage. The compounds according to the invention formulated in the form of wettable powders (WP) or as emulsion concentrates (EC) are then used as aqueous suspension or
Emulsion mit einer Wasseraufwandmenge von umgerechnet 600 bis 800 l/ha unter Zusatz von 0.2% Netzmittel auf die grünen Pflanzenteile gesprüht. Nach ca. 3 Wochen Standzeit der Versuchspflanzen im Gewächshaus unter optimalen Emulsion sprayed with an amount of water equivalent of 600 to 800 l / ha with the addition of 0.2% wetting agent on the green plant parts. After about 3 weeks life of the test plants in the greenhouse under optimal
Wachstumsbedingungen wird die Wirkung der Präparate visuell im Vergleich zu unbehandelten Kontrollen bonitiert (herbizide Wirkung in Prozent (%): 100% Wirkung = Pflanzen sind abgestorben, 0 % Wirkung = wie Kontrollpflanzen). Dabei zeigen beispielsweise die Verbindungen Nr. 1 , 2, 5, 6, 22 und 24 bei einer Aufwandmenge von 320 g/ha jeweils eine mindestens 80%-ige Wirkung gegen Amaranthus retroflexus. Die Verbindungen Nr. 27, 49 und 58 zeigen bei einer Aufwandmenge von 320 g/ha jeweils eine mindestens 80%-ige Veronica persica. Growth conditions, the effect of the preparations is scored visually compared to untreated controls (herbicidal action in percent (%): 100% effect = plants are dead, 0% effect = like control plants). In this case, for example, the compounds Nos. 1, 2, 5, 6, 22 and 24 at an application rate of 320 g / ha each have an at least 80% action against Amaranthus retroflexus. Compounds Nos. 27, 49 and 58 each show an at least 80% Veronica persica at an application rate of 320 g / ha.

Claims

Patentansprüche BCS12-1044 Claims BCS12-1044
1 . 4-Amino-6-acyloxymethyl-pyrimidine und 4-Amino-2-acyloxymethylpyridine der1 . 4-amino-6-acyloxymethyl-pyrimidines and 4-amino-2-acyloxymethylpyridines of
Formel (I) oder deren N-Oxide Formula (I) or their N-oxides
Figure imgf000034_0001
Figure imgf000034_0001
worin wherein
A bedeutet jeweils durch s Reste aus der Gruppe bestehend aus Nitro, Halogen, Cyano, Rhodano, (Ci-C6)-Alkyl, Halogen-(Ci-C6)-alkyl, (C2-C6)-Alkenyl, Halogen-(C2- C6)-alkenyl, (C2-Cr>)-Alkinyl, Halogen-(C3-C6)-alkinyl, (C3-C6)-Cycloalkyl, Halogen-(C3- C6)-cycloalkyl, (C3-C6)-Cycloalkyl-(Ci-C6)-alkyl, Halogen-(C3-C6)-cycloalkyl-(Ci-C6)- alkyl, COR6, COOR6, N(R6)2, NR6COOR5, C(0)N(R6)2, NR6C(0)N(R6)2, OC(0)N(R6)2, C(0)NR6OR6. OR6, OCOR6, OS02R5, S(0)nR5, S02OR5, S02N(R6)2, NR6S02R5, NR6OR6, (Ci-C6)-Alkyl-S(0)nR5, (Ci-C6)-Alkyl-OR6, (Ci-C6)-Alkyl-OS02R5, (CrC6)- Alkyl-C02R6, (CrC6)-Alkyl-S02OR5, (Ci-C6)-Alkyl-CON(R6)2, (Ci-C6)-Alkyl-S02N(R6)2, (CrC6)-Alkyl-NR6COR6, (Ci-C6)-Alkyl-NR6S02R5, P(0)(OR6)2, CH2P(0)(OR6)2, Phenyl, Heteroaryl, Heterocyclyl, Phenyl-(d-C6)-alkyl, Heteroaryl-(d-C6)-alkyl und A is in each case substituted by s radicals selected from the group consisting of nitro, halogen, cyano, thiocyanato, (Ci-C 6) alkyl, halo (Ci-C6) alkyl, (C 2 -C 6) alkenyl, halogen (C 2 - C 6) alkenyl, (C2-Cr>) alkynyl, halo (C 3 -C 6) -alkynyl, (C 3 -C 6) cycloalkyl, halo (C 3 - C 6) cycloalkyl, (C3-C6) cycloalkyl (Ci-C 6) alkyl, halo (C3-C6) cycloalkyl- (Ci-C 6) - alkyl, COR 6, COOR 6, N (R 6 ) 2 , NR 6 COOR 5 , C (O) N (R 6 ) 2 , NR 6 C (O) N (R 6 ) 2 , OC (O) N (R 6 ) 2 , C (O) NR 6 OR 6 . OR 6 , OCOR 6 , OSO 2 R 5 , S (O) n R 5 , SO 2 OR 5 , SO 2 N (R 6 ) 2 , NR 6 SO 2 R 5 , NR 6 OR 6 , (Ci-C 6 ) alkyl-S (0) n R 5, (Ci-C 6) -alkyl-OR 6, (Ci-C 6) alkyl-OS0 2 R 5, (-C 6) - alkyl-C0 2 R 6, (C 1 -C 6 ) -alkyl-S0 2 OR 5 , (C 1 -C 6 ) -alkyl-CON (R 6 ) 2 , (C 1 -C 6 ) -alkyl-S0 2 N (R 6 ) 2 , (C 1 -C 6 ) Alkyl-NR 6 COR 6 , (C 1 -C 6 ) -alkyl-NR 6 S0 2 R 5 , P (O) (OR 6 ) 2 , CH 2 P (O) (OR 6 ) 2 , phenyl, heteroaryl, Heterocyclyl, phenyl (C 1 -C 6) alkyl, heteroaryl (C 1 -C 6) alkyl and
Heterocyclyl-(Ci-Cö)-alkyl substituiertes Phenyl, wobei diese sechs Reste Phenyl, Heteroaryl, Heterocyclyl, Phenyl-(d-C6)-alkyl, Heteroaryl-(d-C6)-alkyl und Heterocyclyl- (C 1 -C 6) -alkyl-substituted phenyl, where these six radicals are phenyl, heteroaryl, heterocyclyl, phenyl- (C 1 -C 6) -alkyl, heteroaryl- (C 1 -C 6) -alkyl and
Heterocyclyl-(Ci-C6)-alkyl jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano, (CrC6)-Alkyl, Halogen-(Ci-C6)-alkyl, S(0)n-(Ci-C6)-Alkyl, (d- Ce)-Alkoxy und Halogen-(Ci-Ce)-alkoxy substituiert sind, und wobei Heterocyclyl n Oxogruppen trägt, oder Heterocyclyl (Ci-C6) alkyl in each case by s radicals selected from the group consisting of halogen, nitro, cyano, (CrC 6) alkyl, halo (Ci-C 6) alkyl, S (0) n - (C -C 6 ) alkyl, (d-Ce) alkoxy and halo (Ci-Ce) -alkoxy are substituted, and wherein Heterocyclyl n carries oxo groups, or
durch s Reste aus der Gruppe bestehend aus (Ci-Ce)-Alkyl und Halogen substituiertes (C3-C6)-Cycloalkyl, by radicals from the group consisting of (C 1 -C 6 ) -alkyl and halogen-substituted (C 3 -C 6 ) -cycloalkyl,
R1 bedeutet LR1', Wasserstoff, (Ci-Cö)-Alkyl, Halogen-(Ci-C6)-alkyl, (C2-C6)- Alkenyl. Halogen-(C2-C6)-alkenyl, (C2-C6)-Alkinyl, Halogen-(C3-C6)-alkinyl, (C3-C6)- Cycloalkyl, Halogen-(C3-C6)-cycloalkyl, (C3-C6)-Cycloalkyl-(Ci-C6)-alkyl. Halogen-(C3- C6)-cycloalkyl-(Ci-C6)-alkyl, COR6, COOR6, N(R6)2, NR6COOR5, C(0)N(R7)2, R 1 represents LR 1 ', is hydrogen, (Ci-COE) alkyl, halo (Ci-C 6) alkyl, (C 2 -C 6) - alkenyl. Halogeno (C 2 -C 6 ) -alkenyl, (C 2 -C 6 ) -alkynyl, halogeno (C 3 -C 6 ) -alkynyl, (C 3 -C 6 ) -cycloalkyl, halogeno (C 3 -) C 6 ) -cycloalkyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl. Halogen- (C 3 - C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, COR 6 , COOR 6 , N (R 6 ) 2 , NR 6 COOR 5 , C (O) N (R 7 ) 2 ,
NR6C(0)N(R6)2, OC(0)N(R6)2, C(0)NR6OR6, OR7, OCOR7, NR6S02R5, NR6OR6, (Ci- C6)-Alkyl-S(0)nRr>, (Ci-C6)-Alkyl-OR6, (CrC6)-Alkyl-OS02Rr>, (Ci-C6)-Alkyl-C02R6, (d- C6)-Alkyl-S02OR5, (Ci-C6)-Alkyl-CON(R6)2, (CrC6)-Alkyl-S0 N(R6)2, (Ci-C6)-Alkyl- NR6COR6, (Ci-C6)-Alkyl-NR6S02R5, P(0)(OR6)2, CH2P(0)(OR6)2, Phenyl, Heteroaryl, Heterocyclyl, Phenyl-(d-C6)-alkyl, Heteroaryl-(Ci-Cö)-alkyl oder HeterocyclyHd-Ce)- alkyl, wobei die sechs letztgenannten Reste jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano, (Ci-C6)-Alkyl, Halogen-(Ci-Ce)-alkyl, S(0)n-(Ci- C6)-Alkyl, (Ci-Ce)-Alkoxy und Halogen-(Ci-Cr,)-alkoxy substituiert sind, und wobei Heterocyclyl n Oxogruppen trägt, NR 6 C (O) N (R 6 ) 2 , OC (O) N (R 6 ) 2 , C (O) NR 6 OR 6 , OR 7 , OCOR 7 , NR 6 SO 2 R 5 , NR 6 OR 6 , (C 1 -C 6 ) -alkyl-S (O) n R r> , (C 1 -C 6 ) -alkyl-OR 6 , (C 1 -C 6 ) -alkyl-OSO 2 R r> , (C 1 -C 6 ) -Alkyl-C0 2 R 6 , (C 1 -C 6 ) -alkyl-S0 2 OR 5 , (C 1 -C 6 ) -alkyl-CON (R 6 ) 2 , (C 1 -C 6 ) -alkyl-S0 N (R 6 ) 2 , (C 1 -C 6 ) -alkyl-NR 6 COR 6 , (C 1 -C 6 ) -alkyl-NR 6 S0 2 R 5 , P (O) (OR 6 ) 2 , CH 2 P (0) ( OR 6 ) 2 , phenyl, heteroaryl, heterocyclyl, phenyl (C 1 -C 6) -alkyl, heteroaryl- (C 1 -C 6) -alkyl or heterocyclyHd-Ce) -alkyl, where the six last-mentioned radicals are each represented by s radicals from the group consisting of halogen, nitro, cyano, (C 1 -C 6) -alkyl, halogeno (C 1 -C 6) -alkyl, S (0) n - (C 1 -C 6) -alkyl, (C 1 -C 6) -alkoxy and halogenated (Ci-Cr,) - alkoxy are substituted, and whereby heterocyclyl carries n oxo groups,
L bedeutet eine jeweils durch s Reste aus der Gruppe bestehend aus (Ci-Ce)- Alkyl, Nitro, Cyano, Halogen und OR6 substituierte und jeweils durch s Einheiten aus der Gruppe bestehend aus O, S(0)n und NR6 unterbrochene (Ci-Ce)-Alkylen-, (C2-Ce)- Alkenylen- oder (C2-C6)-Alkinylen-Kette, L is a substituted by s radicals from the group consisting of (Ci-Ce) - alkyl, nitro, cyano, halogen and OR 6 and each interrupted by s units from the group consisting of O, S (0) n and NR 6 interrupted (C 1 -C 6) -alkylene, (C 2 -C 6) -alkenylene or (C 2 -C 6) -alkynylene chain,
R1' bedeutet (C3-C6)-Cycloalkyl, Halogen-(C3-C6)-cycloalkyl, COR7, COOR7, N(R6)2, NR6COOR5, C(0)N(R6)2, NR6C(0)N(R6)2, OC(0)N(R6)2, C(0)NR6OR6, OCOR6, OS02R5, S(0)nR5, S02OR5, S02N(R6)2, NR6S02R5, NR6OR6, P(0)(OR6)2, oder jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano, (d-Ce)- Alkyl, Halogen-(Ci-C6)-alkyl, S(0)n-(Ci-C6)-Alkyl, (Ci-C6)-Alkoxy und Halogen-(Ci-C6)- alkoxy substituiertes Phenyl, Heteroaryl oder Heterocyclyl, wobei Heterocyclyl n R 1 'is (C 3 -C 6 ) -cycloalkyl, halogeno (C 3 -C 6 ) -cycloalkyl, COR 7 , COOR 7 , N (R 6 ) 2 , NR 6 COOR 5 , C (O) N ( R 6 ) 2 , NR 6 C (O) N (R 6 ) 2 , OC (O) N (R 6 ) 2 , C (O) NR 6 OR 6 , OCOR 6 , OSO 2 R 5 , S (0) n R 5 , S0 2 OR 5 , S0 2 N (R 6 ) 2 , NR 6 S0 2 R 5 , NR 6 OR 6 , P (0) (OR 6 ) 2 , or in each case by s radicals from the group consisting of Halogen, nitro, cyano, (d-Ce) - alkyl, halogeno (Ci-C 6 ) -alkyl, S (0) n- (Ci-C 6 ) -alkyl, (Ci-C 6 ) -alkoxy and halogen - (Ci-C 6 ) - alkoxy-substituted phenyl, heteroaryl or heterocyclyl, wherein heterocyclyl n
Oxogruppen trägt, R2 bedeutet Wasserstoff. (Ci-Cr,)-Alkyl, Halogen-(Ci-C6)-alkyl, (C3-C6)-Cycloalkyl, Halogen-(C3-C6)-cycloalkyl oder Halogen, Carries oxo groups, R 2 is hydrogen. (Ci-Cr,) - alkyl, halo (Ci-C 6) alkyl, (C 3 -C 6) cycloalkyl, halo (C3-C6) cycloalkyl or halogen,
R3 und R4 bedeuten unabhängig voneinander jeweils Wasserstoff, (Ci-Cc>)-Alkyl, Halogen-(CrC6)-alkyl, (C2-C6)-Alkenyl, Halogen-(C2-C6)-alkenyl, (C2-C6)-Alkinyl, Halogen-(C2-C6)-alkinyl, (C3-C6)-Cycloalkyl, Halogen-(C3-C6)-cycloalkyl, (C3-C6)-R 3 and R 4 are each independently hydrogen, (Ci-Cc > ) alkyl, halo (CrC 6 ) alkyl, (C 2 -C 6 ) alkenyl, halo (C 2 -C 6 ) alkenyl , (C 2 -C 6 ) alkynyl, halo (C 2 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl, halo (C 3 -C 6 ) cycloalkyl, (C 3 -C 6 ) -
Cycloalkyl-(Ci-C6)-alkyl, Halogen-(C3-C6)-cycloalkyl-(Ci-C6)-alkyl, COR8 oder S(0)nR6, Cycloalkyl- (Ci-C6) alkyl, halo (C 3 -C 6) -cycloalkyl- (Ci-C 6) alkyl, COR 8 or S (0) n R 6,
R5 bedeutet (CrC6)-Alkyl, Halogen-(Ci-C6)-Alkyl, (C2-C6)-Alkenyl, Halogen-(C2-C6)- Alkenyl, (C2-C6)-Alkinyl, Halogen-(C3-C6)-Alkinyl, (C3-C6)-Cycloalkyl, Halogen-(C3-C6)- Cycloalkyl, (C4-C8)-Cycloalkenyl, Halogen-(C3-C6)-Cycloalkenyl, (C3-C6)-Cycloalkyl- (Ci-C6)-alkyl oder Halogen-(C3-C6)-Cycloalkyl-(Ci-C6)-alkyl, R 5 is (CrC 6) alkyl, halo (Ci-C 6) -alkyl, (C 2 -C 6) alkenyl, halo (C 2 -C 6) - alkenyl, (C 2 -C 6) Alkynyl, halo (C 3 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl, halo (C 3 -C 6 ) - Cycloalkyl, (C 4 -C 8) cycloalkenyl, halo (C 3 -C 6) cycloalkenyl, (C 3 -C 6) -cycloalkyl- (Ci-C 6) alkyl or halo (C3-C6) Cycloalkyl- (C 1 -C 6 ) -alkyl,
R6 bedeutet Wasserstoff, (CrC6)-Alkyl, Halogen-(Ci-C6)-Alkyl, (C2-C6)-Alkenyl, Halogen-(C2-C6)-Alkenyl, (C2-C6)-Alkinyl, Halogen-(C3-C6)-A!kinyl, (C3-C6)-Cycloalkyl, Halogen-(C3-C6)-Cycloalkyl, (C4-C8)-Cyc!oalkenyl, Halogen-(C3-C6)-Cycloalkenyl, (C3- C6)-Cycloalkyl-(Ci-C6)-a!kyl oder Halogen-(C3-C6)-Cycloalkyl-(Ci-Cö)-alkyl, R 6 is hydrogen, (CrC 6) alkyl, halo (Ci-C 6) -alkyl, (C 2 -C 6) alkenyl, halo (C 2 -C 6) alkenyl, (C 2 -C 6 ) -alkynyl, halogen- (C 3 -C 6 ) -alkinyl, (C 3 -C 6 ) -cycloalkyl, halogen- (C 3 -C 6 ) -cycloalkyl, (C 4 -C 8) -cycloalkenyl, Halogeno (C 3 -C 6 ) -cycloalkenyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl or halogeno (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl,
X bedeutet CH oder N, n bedeutet 0, 1 oder 2, s bedeutet 0, 1 . 2 oder 3. X is CH or N, n is 0, 1 or 2, s is 0, 1. 2 or 3.
2. 4-Amino-6-acyloxymethyl-pyrimidine und 4-Amino-2-acyloxymethylpyridine nach Anspruch 1 , worin 2. 4-amino-6-acyloxymethyl-pyrimidines and 4-amino-2-acyloxymethylpyridine according to claim 1, wherein
A bedeutet jeweils durch s Reste aus der Gruppe bestehend aus Nitro, Halogen, Cyano, (CrCö)-Alkyl, Halogen-(CrC6)-alkyl, (C2-C6)-Alkenyl, Halogen-(C2-C6)-alkenyl, (C2-C6)-Alkinyl, Halogen-(C3-C6)-alkinyl, (C3-C6)-Cycloalkyl, Halogen-(C3-C6)- cycloalkyl, (C3-C6)-Cycloalkyl-(Ci-C6)-alkyl, Halogen-(C3-C6)-cycloalkyl-(Ci-C6)-alkyl, COR6, COOR6, N(R6)2, C(0)N(R6)2, OR6, OCOR6, OSO2R5, S(0)nR5, S0 OR5, S02N(R6)2, NR6S02R5, NR6OR6, (Ci-C6)-Alkyl-S(0)nR5, (Ci-Cö)-Alkyl-OR6, (Ci-Ce)- Alkyl-OS02R5, (CrC6)-Alkyl-C02R6, (CrC6)-Alkyl-S02OR5, (Ci-C6)-Alkyl-CON(R6)2, (C1-C6)-Alkyl-S02N(R6)2, (CrC6)-Alkyl-NR6COR6, (CrC6)-Alkyl-NR6S02R5, A represents in each case by s radicals selected from the group consisting of nitro, halogen, cyano, (CrCö) alkyl, halo (CrC 6) alkyl, (C 2 -C 6) alkenyl, halo (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, halo (C 3 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl, halo (C 3 -C 6 ) cycloalkyl, (C 3 -C 6) -cycloalkyl- (Ci-C 6) alkyl, halo (C 3 -C 6) -cycloalkyl- (Ci-C 6) alkyl, COR 6, COOR 6, N (R 6) 2 , C (O) N (R 6 ) 2 , OR 6 , OCOR 6 , OSO 2 R 5 , S (O) n R 5 , SO OR 5 , SO 2 N (R 6 ) 2 , NR 6 SO 2 R 5 , NR 6 OR 6, (Ci-C 6) alkyl-S (0) nR 5, (Ci-COE) -alkyl-OR 6, (Ci-Ce) - alkyl-OS0 2 R 5, (CrC 6) alkyl -C0 2 R 6, (CrC 6) alkyl-S0 2 OR 5, (Ci-C 6) alkyl-CON (R 6) 2, (C 1 -C 6) alkyl-S0 2 N (R 6 ) 2 , (C 1 -C 6 ) -alkyl-NR 6 COR 6 , (C 1 -C 6 ) -alkyl-NR 6 S0 2 R 5 ,
P(0)(OR6)2, CH2P(0)(OR6)2, Phenyl, Heteroaryl, Heterocyclyl, Phenyl-(CrC6)-alkyl, Heteroaryl-(Ci-Ce)-alkyl und Heterocyclyl-(Ci-Cr,)-alkyl substituiertes Phenyl, wobei diese sechs Reste Phenyl, Heteroaryl, Heterocyclyl, Phenyl-(d-C6)-alkyl, Heteroaryl- (Ci-Ce)-alkyl und Heterocyclyl-(Ci-C6)-alkyl jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano, (Ci-Co)-Alkyl, Halogen-(d-C6)-alkyl, S(0)n-(Ci- Cc>)-Alkyl, (Ci-Ce)-Alkoxy und Halogen-(Ci-Cc>)-alkoxy substituiert sind, und wobei Heterocyclyl n Oxogruppen trägt, oder P (O) (OR 6 ) 2 , CH 2 P (O) (OR 6 ) 2 , phenyl, heteroaryl, heterocyclyl, phenyl- (C 1 -C 6 ) -alkyl, heteroaryl- (C 1 -C 6 ) -alkyl and heterocyclyl- ( Ci-Cr,) - alkyl-substituted phenyl, wherein these six radicals phenyl, heteroaryl, heterocyclyl, phenyl (d-C6) alkyl, heteroaryl (Ci-Ce) alkyl and heterocyclyl (Ci-C6) alkyl in each case by radicals from the group consisting of halogen, nitro, cyano, (C 1 -C 6) -alkyl, halogeno (C 1 -C 6) -alkyl, S (O) n - (C 1 -Cc) -alkyl, Ce) alkoxy and halo (Ci-Cc>) - alkoxy substituted, and wherein Heterocyclyl n carries oxo groups, or
durch s Reste aus der Gruppe bestehend aus (Ci-Ce)-Alkyl und Halogen substituiertes (C3-C6)-Cycloalkyl, R1 bedeutet LR1 ' , Wasserstoff, (Ci-C6)-Alkyl, Halogen-(Ci-C6)-alkyl, (C2-C6)- Alkenyl, Halogen-(C2-C6)-alkenyl, (C2-C6)-Alkinyl, Halogen-(C3-C6)-alkinyl, (C3-C6)- Cycloalkyl, Halogen-(C3-C6)-cycloalkyl, (C3-C6)-Cycloalkyl-(Ci-C6)-alkyl, Halogen-(C3- C6)-cycloalkyl-(Ci-C6)-alkyl, COR7, COOR7, N(R7)2, N R7COOR5, C(0)N(R7)2,by radicals from the group consisting of (C 1 -C 6 ) -alkyl and halogen-substituted (C 3 -C 6 ) -cycloalkyl, R 1 represents LR 1 ', is hydrogen, (Ci-C 6) alkyl, halo (Ci-C 6) alkyl, (C 2 -C 6) - alkenyl, halo (C2-C6) alkenyl, (C2-C6) alkynyl, halo (C 3 -C 6) -alkynyl, (C 3 -C 6) - cycloalkyl, halo (C 3 -C 6) cycloalkyl, (C 3 -C 6) Cycloalkyl- (C 1 -C 6 ) -alkyl, halogeno (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, COR 7 , COOR 7 , N (R 7 ) 2 , NR 7 COOR 5 , C (O) N (R 7 ) 2 ,
OC(0)N(R7)2, OR7, N R7S02R5, (Ci-C6)-Alkyl-S(0)nR5, (Ci-C6)-Alkyl-OR7, (Ci-C6)-Alkyl- OS02R5, (Ci-C6)-Alkyl-C02R7, (Ci-C6)-Aikyl-CON(R7)2, (Ci-C6)-Alkyl-S02N(R7)2, (Ci- C6)-Alky!-NR7COR7, (Ci-C6)-Alkyl-NR7S02R5, P(0)(OR7)2, CH2P(0)(OR7)2, Phenyl, Heteroaryl, Heterocyclyl, Phenyl-(Ci-C6)-alkyl, Heteroaryl-(d-C6)-alkyl oder OC (O) N (R 7 ) 2 , OR 7 , NR 7 S0 2 R 5 , (C 1 -C 6 ) -alkyl-S (O) n R 5 , (C 1 -C 6 ) -alkyl-OR 7 , (C 1 -C 6 ) -alkyl-OSO 2 R 5 , (C 1 -C 6 ) -alkyl-C0 2 R 7 , (C 1 -C 6 ) -acyl-CON (R 7 ) 2 , (C 1 -C 6 ) -Alkyl-SO 2 N (R 7 ) 2 , (C 1 -C 6 ) -alkyl! -NR 7 COR 7 , (C 1 -C 6 ) -alkyl-NR 7 SO 2 R 5 , P (O) (OR 7 ) 2 , CH 2 P (O) (OR 7 ) 2 , phenyl, heteroaryl, heterocyclyl, phenyl- (C 1 -C 6) -alkyl, heteroaryl- (C 1 -C 6) -alkyl or
Heterocyclyl-(CrC6)-alkyl, wobei die sechs letztgenannten Reste jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano, (Ci-Ce)-Alkyl, Halogen-(Ci-Ce)- alkyl, S(0)n-(CrC6)-Alkyl, (Ci-Ce)-Alkoxy und Halogen-(Ci-C6)-alkoxy substituiert sind, und wobei Heterocyclyl n Oxogruppen trägt, L bedeutet eine jeweils durch s Reste aus der Gruppe bestehend aus (Ci-Cr,)- Alkyl, Nitro, Cyano, Halogen und OR7 substituierte und jeweils durch s Einheiten aus der Gruppe bestehend aus O, S(0)„ und N R7 unterbrochene (Ci-C6)-Alkylen-, (C2-Ce)- Alkenylen- oder (C2-C6)-Alkinylen-Kette, R1 ' bedeutet (C3-C6)-Cycloalkyl, Halogen-(C3-C6)-cycloalkyl, COR7, COOR7,Heterocyclyl- (C 1 -C 6) -alkyl, where the six last-mentioned radicals are in each case represented by s radicals from the group consisting of halogen, nitro, cyano, (C 1 -C 6) -alkyl, halogeno (C 1 -C 6) -alkyl, S (0) n - (C 1 -C 6) -alkyl, (C 1 -C 6) -alkoxy and halogeno (C 1 -C 6) -alkoxy, and where heterocyclyl carries n oxo groups, L denotes in each case by s radicals from the group consisting of ( Cr,) - alkyl, nitro, cyano, halogen and OR 7 substituted and in each case by s units from the group consisting of O, S (0) "and NR 7 interrupted (Ci-C6) -alkylene, (C 2 -Ce ) - alkenylene or (C 2 -C 6 ) -alkynylene chain, R 1 'is (C 3 -C 6 ) -cycloalkyl, halogen- (C 3 -C 6 ) -cycloalkyl, COR 7 , COOR 7 ,
N(R7)2, N R7COOR5, C(0)N(R7)2, NR7C(0)N(R7)2. OC(0)N(R7)2, C(0)NR7OR7, OCOR7, S(0)nR5, S02N(R7)2, NR7S02R5, P(0)(OR7)2, oder N (R 7 ) 2 , NR 7 COOR 5 , C (O) N (R 7 ) 2 , NR 7 C (O) N (R 7 ) 2 . OC (O) N (R 7 ) 2 , C (O) NR 7 OR 7 , OCOR 7 , S (O) n R 5 , SO 2 N (R 7 ) 2 , NR 7 S0 2 R 5 , P (0 ) (OR 7 ) 2 , or
jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano, (d-Ce)- Alkyl. Halogen-(Ci-C6)-alkyl, S(0)n-(Ci-C6)-Alkyl, (Ci-Ce)-Alkoxy und Halogen-(Ci-Cr,)- alkoxy substituiertes Phenyl, Heteroaryl oder Heterocyclyl, wobei Heterocyclyl n in each case by s radicals from the group consisting of halogen, nitro, cyano, (d-Ce) - alkyl. Halogen- (Ci-C 6 ) -alkyl, S (0) n- (Ci-C 6 ) -alkyl, (Ci-Ce) -alkoxy and halogen- (Ci-Cr,) - alkoxy-substituted phenyl, heteroaryl or heterocyclyl where heterocyclyl n
Oxogruppen trägt, Wearing oxo groups,
R2 bedeutet Wasserstoff oder Halogen, R3 und R4 bedeuten unabhängig voneinander jeweils Wasserstoff, (Ci-Ce)-Alkyl, Halogen-(CrC6)-alkyl, (C2-C6)-Alkenyl, (C2-C6)-Alkinyl, (C3-C6)-Cycloalkyl, (C3-C6)- Cycloalkyl-(Ci-C6)-alkyl, COR8 oder S(0)nR7, R5 bedeutet (CrC6)-Alkyl, Halogen-(Ci-C6)-Alkyl, (C2-C6)-Alkenyl, (C2-C6)-Alkinyl, (C3-C6)-Cyc!oalkyl, (C4-C8)-Cycloalkenyl oder (C3-C6)-Cycloalkyl-(Ci-C6)-alkyl, R 2 is hydrogen or halogen, R 3 and R 4 are each independently hydrogen, (Ci-Ce) alkyl, halogen (CrC 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6) -alkynyl, (C 3 -C 6) -cycloalkyl, (C 3 -C 6) - cycloalkyl, (Ci-C 6) alkyl, COR 8 or S (0) n R 7, R 5 is (CrC 6) alkyl, halo (Ci-C 6) -alkyl, (C 2 -C 6) alkenyl, (C 2 -C 6) -alkynyl, (C 3 -C 6) -Cyc ! oalkyl, (C 4 -C 8 ) -cycloalkenyl or (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl,
R7 bedeutet Wasserstoff, (CrC6)-Alkyl, Halogen-(Ci-C6)-Alkyl, (C2-C6)-Alkenyl, (C2-C6)-Alkinyl, (C3-C6)-Cycloalkyi, (C4-C8)-Cycloalkenyl oder (C3-C6)-Cycloalkyl-(Ci- C6)-alkyl, R 7 is hydrogen, (CrC 6) alkyl, halo (Ci-C 6) -alkyl, (C 2 -C 6) alkenyl, (C 2 -C 6) -alkynyl, (C 3 -C 6) Cycloalkyi, (C 4 -C 8 ) -cycloalkenyl or (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl,
X bedeutet CH oder N, n bedeutet 0, 1 oder 2, s bedeutet 0. 1 . 2 oder 3. X is CH or N, n is 0, 1 or 2, s is 0. 1. 2 or 3.
3. 4-Amino-6-acyloxymethyl-pyrimidine und 4-Amino-2-acyloxymethylpyridine nach3. 4-amino-6-acyloxymethyl-pyrimidines and 4-amino-2-acyloxymethylpyridine according to
Anspruch 1 oder 2, worin Claim 1 or 2, wherein
A bedeutet durch s Reste aus der Gruppe bestehend aus Nitro, Halogen, Cyano, (Ci-C3)-Alkyl, Halogen-(Ci-C3)-alkyl, (C2-C3)-Alkenyl, (C2-C3)-Alkinyl, (C3-C6)- Cycloalkyl, (C3-C6)-Cycloalkyl-(Ci-C3)-alkyl, COR7, COOR7, N(R7)2, C(0)N(R7)2, OR7, S(0)nR5, S02N(R7)2 und NR7S02R5 substituiertes Phenyl, oder A is substituted by s radicals selected from the group consisting of nitro, halogen, cyano, (Ci-C 3) alkyl, halo (Ci-C 3) alkyl, (C 2 -C 3) alkenyl, (C 2 - C 3) -alkynyl, (C 3 -C 6) - cycloalkyl, (C 3 -C 6) -cycloalkyl- (Ci-C 3) alkyl, COR 7, COOR 7, N (R 7) 2, C ( 0) N (R 7 ) 2 , OR 7 , S (O) n R 5 , SO 2 N (R 7 ) 2 and NR 7 S0 2 R 5 substituted phenyl, or
(C3-C6)-Cycloalkyl, (C 3 -C 6 ) -cycloalkyl,
R1 bedeutet LR1', Wasserstoff, (CrC6)-Alkyl, Halogen-(CrC6)-alkyl, (C2-C6)- Alkenyl, (C2-C6)-Alkinyl, (C3-C6)-Cycloalkyl, (C3-C6)-Cycloalkyl-(Ci-C6)-alkyl, COR7, COOR7, N(R7)2, NR7COOR5, C(0)N(R7)2, OR7, NR7S02R5, (Ci-C6)-Alkyl-S(0)nR5, (Ci- C6)-Alkyl-OR7, (Ci-C6)-Alkyl-OS02R5, (Ci-Cc,)-Alkyl-C02R7, (Ci-C6)-Alkyl-CON(R7)2, (Ci-C6)-Alkyl-S02N(R7)2, (CrC6)-Alkyl-NR7COR7, (d-C6)-Alkyl-NR7S02R5, R 1 represents LR 1 ', is hydrogen, (CrC 6) alkyl, halo (CrC 6) alkyl, (C 2 -C 6) - alkenyl, (C 2 -C 6) -alkynyl, (C 3 -C 6 ) -cycloalkyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 6 ) -alkyl, COR 7 , COOR 7 , N (R 7 ) 2 , NR 7 COOR 5 , C (O) N (R 7 ) 2 , OR 7 , NR 7 S0 2 R 5 , (C 1 -C 6 ) -alkyl-S (O) n R 5 , (C 1 -C 6 ) -alkyl-OR 7 , (C 1 -C 6 ) -alkyl OSO 2 R 5 , (Ci-Cc,) - alkyl-C0 2 R 7 , (Ci-C 6 ) -alkyl-CON (R 7 ) 2 , (Ci-C 6 ) -alkyl-S0 2 N (R 7 ) 2 , (C 1 -C 6 ) -alkyl-NR 7 COR 7 , (C 1 -C 6 ) -alkyl-NR 7 SO 2 R 5 ,
P(0)(OR7)2, CH2P(0)(OR7)2, Phenyl, Heteroaryl, Heterocyclyl, Phenyl-(CrC6)-alkyl, Heteroaryl-(d-C6)-alkyl oder Heterocyclyl-(Ci-C6)-alkyl, wobei die sechs P (O) (OR 7 ) 2 , CH 2 P (O) (OR 7 ) 2 , phenyl, heteroaryl, heterocyclyl, phenyl- (C 1 -C 6 ) -alkyl, heteroaryl- (C 1 -C 6 ) -alkyl or heterocyclyl- ( Ci-C6) -alkyl, wherein the six
letztgenannten Reste jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano, (CrC6)-Alkyl, Halogen-(CrC6)-alkyl, S(0)n-(CrC6)-Alkyl, (CrCö)-Alkoxy und Halogen-(Ci-Ce)-alkoxy substituiert sind, und wobei Heterocyclyl n Oxogruppen trägt. L bedeutet eine jeweils durch s Reste aus der Gruppe bestehend aus (d-Ce)- Alkyl, Nitro, Cyano, Halogen und OR7 substituierte und jeweils durch s Einheiten aus der Gruppe bestehend aus O, S(0)n und NR7 unterbrochene (Ci-Ce)-Alkylen-, (C2-Ce)- Alkenylen- oder (C2-Cö)-Alkinylen-Kette, last-mentioned radicals in each case by s radicals selected from the group consisting of halogen, nitro, cyano, (CrC 6) alkyl, halo (CrC 6) alkyl, S (0) n - (CrC 6) alkyl, (CrCö) - Alkoxy and halo (Ci-Ce) -alkoxy are substituted, and wherein Heterocyclyl n carries oxo groups. L is a substituted by s radicals from the group consisting of (d-Ce) - alkyl, nitro, cyano, halogen and OR 7 and each interrupted by s units from the group consisting of O, S (0) n and NR 7 interrupted (C 1 -C 6) -alkylene, (C 2 -C 6) -alkenylene or (C 2 -C 6) -alkynylene chain,
R1' bedeutet (C3-C6)-Cycloalkyl, COR7, COOR7, N(R7)2, NR7COOR5, C(0)N(R7)2, NR7C(0)N(R7)2, OC(0)N(R7)2, C(0)NR7OR7, OCOR7, S(0)nR5, S02N(R7)2, R 1 'is (C 3 -C 6 ) -cycloalkyl, COR 7 , COOR 7 , N (R 7 ) 2 , NR 7 COOR 5 , C (O) N (R 7 ) 2 , NR 7 C (O) N (R 7 ) 2 , OC (O) N (R 7 ) 2 , C (O) NR 7 OR 7 , OCOR 7 , S (O) n R 5 , SO 2 N (R 7 ) 2 ,
NR7S02R5, P(0)(OR7)2, oder NR 7 S0 2 R 5 , P (0) (OR 7 ) 2 , or
jeweils durch s Reste aus der Gruppe bestehend aus Halogen, Nitro, Cyano, (d-Ce)- Alkyl, Halogen-(Ci-C6)-alkyl, S(0)n-(Ci-C6)-Alkyl, (Ci-C6)-Alkoxy und Halogen-(CrC6)- alkoxy substituiertes Phenyl, Heteroaryl oder Heterocyclyl, wobei Heterocyclyl n Oxogruppen trägt, in each case by s radicals from the group consisting of halogen, nitro, cyano, (C 1 -C 6 ) -alkyl, halogeno (C 1 -C 6 ) -alkyl, S (O) n - (C 1 -C 6 ) -alkyl, ( C 1 -C 6 -alkoxy and halogeno (C 1 -C 6 ) -alkoxy-substituted phenyl, heteroaryl or heterocyclyl, where heterocyclyl carries n oxo groups,
R2 bedeutet Wasserstoff oder Halogen, R 2 is hydrogen or halogen,
R3 und R4 bedeuten unabhängig voneinander jeweils Wasserstoff, (Ci-C3)-Alkyl, Halogen-(Ci-C3)-alkyl. (C2-C3)-Alkenyl, (C2-C3)-Alkinyl, (C3-C6)-Cycloalkyl, (C3-Ce)- Cycloalkyl-(Ci-C3)-alkyl, COR8 oder S(0)nR7, R5 bedeutet (d-C3)-Alkyl, (C2-C3)-Alkenyl, (C2-C3)-Alkinyl, (C3-C6)-Cycloalkyl, (C4- C8)-Cycloalkenyl oder (C3-C6)-Cycloalkyl-(Ci-C3)-alkyl, R 3 and R 4 independently of one another each represent hydrogen, (C 1 -C 3 ) -alkyl, halogeno (C 1 -C 3 ) -alkyl. (C 2 -C 3 ) -alkenyl, (C 2 -C 3 ) -alkynyl, (C 3 -C 6) -cycloalkyl, (C 3 -Ce) -cycloalkyl- (C 1 -C 3 ) -alkyl, COR 8 or S (0) n R 7, R 5 is (dC 3) alkyl, (C 2 -C 3) alkenyl, (C 2 -C 3) alkynyl, (C 3 -C 6) -cycloalkyl, (C 4 -C 8 ) -cycloalkenyl or (C 3 -C 6 ) -cycloalkyl- (C 1 -C 3 ) -alkyl,
R7 bedeutet Wasserstoff, (Ci-C3)-Alkyl, (C2-C3)-Alkenyl, (C2-C3)-Alkinyl, (C3-C6)- Cycloalkyl, (C4-C8)-Cycloalkenyl oder (C3-C6)-Cycloalkyl-(Ci-C3)-alkyl, R 7 is hydrogen, (C 1 -C 3 ) -alkyl, (C 2 -C 3 ) -alkenyl, (C 2 -C 3 ) -alkynyl, (C 3 -C 6 ) -cycloalkyl, (C 4 -C 8 ) -Cycloalkenyl or (C 3 -C 6 ) -cycloalkyl- (C 1 -C 3 ) -alkyl,
X bedeutet CH oder N, n bedeutet 0, 1 oder 2, s bedeutet 0, 1 , 2 oder 3. X is CH or N, n is 0, 1 or 2, s is 0, 1, 2 or 3.
4. Herbizide Mittel, gekennzeichnet durch einen herbizid wirksamen Gehalt an mindestens einer Verbindung der Formel (I) gemäß einem der Ansprüche 1 bis 3. 4. A herbicidal composition, characterized by a herbicidally active content of at least one compound of the formula (I) according to one of claims 1 to 3.
5. Herbizide Mittel nach Anspruch 4 in Mischung mit Formulierungshilfsmitteln. 5. A herbicidal composition according to claim 4 in admixture with formulation auxiliaries.
6. Herbizide Mittel nach Anspruch 4 oder 5 enthaltend mindestens einen weiteren pestizid wirksamen Stoff aus der Gruppe Insektizide, Akarizide, Herbizide, Fungizide,6. A herbicidal composition according to claim 4 or 5 containing at least one further pesticidal substance from the group insecticides, acaricides, herbicides, fungicides,
Safener und Wachstumsregulatoren. Safeners and growth regulators.
7. Herbizide Mittel nach Anspruch 6 enthaltend einen Safener. 7. A herbicidal composition according to claim 6 containing a safener.
8. Herbizide Mittel nach Anspruch 7 enthaltend cyprosulfamid, cloquintocet-mexyl, mefenpyr-diethyl oder isoxadifen-ethyl. 8. A herbicidal composition according to claim 7 containing cyprosulfamide, cloquintocet-mexyl, mefenpyr-diethyl or isoxadifen-ethyl.
9. Herbizide Mittel nach einem der Ansprüche 6 bis 8 enthaltend ein weiteres Herbizid. 9. A herbicidal composition according to any one of claims 6 to 8 containing a further herbicide.
10. Verfahren zur Bekämpfung unerwünschter Pflanzen, dadurch gekennzeichnet, daß man eine wirksame Menge mindestens einer Verbindung der Formel (I) gemäß einem der Ansprüche 1 bis 3 oder eines herbiziden Mittels nach einem der Ansprüche 4 bis 9 auf die Pflanzen oder auf den Ort des unerwünschten Pflanzenwachstums appliziert. 10. A method for controlling unwanted plants, characterized in that an effective amount of at least one compound of formula (I) according to any one of claims 1 to 3 or a herbicidal composition according to any one of claims 4 to 9 on the plants or on the place of unwanted plant growth applied.
1 1 . Verfahren zur Bekämpfung unerwünschter Pflanzen, dadurch gekennzeichnet, daß man eine wirksame Menge mindestens einer Verbindung aus der Gruppe bestehend aus 5-Brom-2-(4-chlorphenyl)-6-(diethoxymethyl)pyrimidin-4-amin, 5-Brom- 2-(4-chlorphenyl)-6-(dimethoxymethyl) pyrimidin-4-amin, 5-Chlor-2-(4-chlor-phenyl)-6- (diisopropoxymethyl)pyrimidin-4-amin, 5-Chlor-2-(4-chlorphenyl)-6-(diethoxy- methyl)pyrimidin-4-amin, 5-Chlor-2-(4-chlor-phenyl)-6-(dimethoxymethyl)pyrimidin-4- amin und 5-Chlor-2-(4-chlorphenyl)-6-(dipropoxymethyl)pyrimidin-4-amin auf die Pflanzen oder auf den Ort des unerwünschten Pflanzenwachstums appliziert. 1 1. A method for controlling unwanted plants, characterized in that an effective amount of at least one compound selected from the group consisting of 5-bromo-2- (4-chlorophenyl) -6- (diethoxymethyl) pyrimidin-4-amine, 5-bromo-2 - (4-chlorophenyl) -6- (dimethoxymethyl) pyrimidin-4-amine, 5-chloro-2- (4-chloro-phenyl) -6- (diisopropoxymethyl) -pyrimidin-4-amine, 5-chloro-2 ( 4-chlorophenyl) -6- (diethoxymethyl) pyrimidin-4-amine, 5-chloro-2- (4-chloro-phenyl) -6- (dimethoxymethyl) -pyrimidine-4-amine and 5-chloro-2 ( 4-chlorophenyl) -6- (dipropoxymethyl) pyrimidin-4-amine applied to the plants or to the site of undesired plant growth.
12. Verwendung von Verbindungen der Formel (I) gemäß einem der Ansprüche 1 bis 3 oder von herbiziden Mitteln nach einem der Ansprüche 4 bis 9 zur Bekämpfung unerwünschter Pflanzen. 12. Use of compounds of formula (I) according to any one of claims 1 to 3 or of herbicidal compositions according to any one of claims 4 to 9 for controlling undesirable plants.
13. Verwendung einer Verbindung aus der Gruppe bestehend aus 5-Brom-2-(4- chlorphenyl)-6-(diethoxymethyl)pyrimidin-4-amin, 5-Brom-2-(4-chlorphenyl)-6- (dimethoxymethyl)pyrimidin-4-amin, 5-Chior-2-(4-chlor-phenyl)-6- (diisopropoxymethyl)pyrimidin-4-amin, 5-Chlor-2-(4-chlorphenyi)-6-(diethoxy- methyl)pyrimidin-4-amin, 5-Chlor-2-(4-chlor-phenyl)-6-(dimethoxymethyl)-pyrimidin-4- amin und 5-Chlor-2-(4-chlorphenyl)-6-(dipropoxymethyl)pyrimidin-4-amin zur 13. Use of a compound selected from the group consisting of 5-bromo-2- (4-chlorophenyl) -6- (diethoxymethyl) pyrimidin-4-amine, 5-bromo-2- (4-chlorophenyl) -6- (dimethoxymethyl) pyrimidin-4-amine, 5-chloro-2- (4-chlorophenyl) -6- (diisopropoxymethyl) pyrimidin-4-amine, 5-chloro-2- (4-chlorophenyl) -6- (diethoxymethyl) pyrimidin-4-amine, 5-chloro-2- (4-chlorophenyl) -6- (dimethoxymethyl) -pyrimidin-4-amine and 5-chloro-2- (4-chlorophenyl) -6- (dipropoxymethyl) pyrimidine -4-amin to
Bekämpfung unerwünschter Pflanzen. Control of unwanted plants.
14. Verwendung nach Anspruch 1 1 , dadurch gekennzeichnet, daß die 14. Use according to claim 1 1, characterized in that the
Verbindungen der Formel (I) zur Bekämpfung unerwünschter Pflanzen in Kulturen von Nutzpflanzen eingesetzt werden. Compounds of formula (I) for controlling undesirable plants in crops of crops are used.
15. Verwendung nach Anspruch 14, dadurch gekennzeichnet, daß die Nutzpflanzen transgene Nutzpflanzen sind. 15. Use according to claim 14, characterized in that the crops are transgenic crops.
PCT/EP2013/075307 2012-12-06 2013-12-03 Herbicidally active 4-amino-6-acyloxymethyl pyrimidine and 4-amino-2-acyloxymethyl pyridine WO2014086738A1 (en)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
EP0222254A2 (en) * 1985-11-09 1987-05-20 Bayer Ag Nicotinic-acid derivatives
WO1995019358A1 (en) * 1994-01-12 1995-07-20 Sandoz Ltd. Herbicidal aryl and heteroaryl pyrimidines
WO2005063721A1 (en) * 2003-12-19 2005-07-14 E.I. Dupont De Nemours And Company Herbicidal pyrimidines
WO2009081112A2 (en) * 2007-12-24 2009-07-02 Syngenta Limited Chemical compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0222254A2 (en) * 1985-11-09 1987-05-20 Bayer Ag Nicotinic-acid derivatives
WO1995019358A1 (en) * 1994-01-12 1995-07-20 Sandoz Ltd. Herbicidal aryl and heteroaryl pyrimidines
WO2005063721A1 (en) * 2003-12-19 2005-07-14 E.I. Dupont De Nemours And Company Herbicidal pyrimidines
WO2009081112A2 (en) * 2007-12-24 2009-07-02 Syngenta Limited Chemical compounds

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Title
TERAUCHI H ET AL: "NICOTINAMIDE DERIVATIVES AS A NEW CLASS OF GASTRIC (H+/K+)-ATPASE INHIBITORS. II. SYNTHESIS AND STRUCTURE-ACTIVITY RELATIONSHIPS OF 2-Ä(2,4-DIMETHOXYBENZYL)SULFINYLÜ-N-(4-PYRIDINYL)PYRIDINE-3-CARBOXAMIDES", CHEMICAL AND PHARMACEUTICAL BULLETIN, PHARMACEUTICAL SOCIETY OF JAPAN, JP, vol. 45, no. 6, 1 June 1997 (1997-06-01), pages 1027 - 1038, XP001246819, ISSN: 0009-2363 *

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