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WO2004007467A1 - Nouveaux 3-(3-[aminosulfonylamino]-4-cyano-phenyl)-6-trifluoromethyluraciles - Google Patents

Nouveaux 3-(3-[aminosulfonylamino]-4-cyano-phenyl)-6-trifluoromethyluraciles Download PDF

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WO2004007467A1
WO2004007467A1 PCT/EP2003/007357 EP0307357W WO2004007467A1 WO 2004007467 A1 WO2004007467 A1 WO 2004007467A1 EP 0307357 W EP0307357 W EP 0307357W WO 2004007467 A1 WO2004007467 A1 WO 2004007467A1
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Prior art keywords
cyano
alkyl
alkoxy
phenyl
hydrogen
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English (en)
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Robert Reinhard
Gerhard Hamprecht
Michael Puhl
Ingo Sagasser
Werner Seitz
Cyrill Zagar
Matthias Witschel
Andreas Landes
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BASF SE
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BASF SE
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    • 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
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy 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
    • A01N43/48—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

Definitions

  • the present invention relates to new 3- (3- [aminosulfonylamino] -4-cyano-phenyl) -6-trifluoromethyl-uracils of the general formula I
  • R 1 is hydrogen, methyl or amino
  • R 2 is hydrogen or halogen
  • R 3 is hydrogen or -CC 6 alkyl
  • R 4 is hydrogen, -CC 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl,
  • Ci-C ⁇ -alkoxy or C 3 -C 8 cycloalkyl where each of the latter 5 radicals can optionally carry one to three substituents, each selected from the group consisting of halogen, nitro, cyano, hydroxy, C 3 -C 8 cycloalkyl , Ci-Cg-alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, Ci-Cg-alkylthio, Ci-C ⁇ -alkylsulfenyl, Ci-C ⁇ - alkylsulfonyl and (Ci-C ⁇ -alkoxy ) - carbonyl, and
  • R 5 is hydrogen, -CC 6 alkyl, C 3 -C 6 alkenyl,> C 3 -C 6 alkynyl,
  • Ci-C ß- alkoxy or C 3 -C 8 cycloalkyl where each of the latter 5 radicals can optionally carry one to three substituents, each selected from the group consisting of halogen, nitro, cyano, hydroxy, C 3 -C 8 - cycloalkyl, C ⁇ -C 5 oxy -Alk-, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, Ci-C ⁇ alkylthio, C ⁇ -C6 alkylsulfenyl, C ⁇ -C 6 alkylsulfonyl and (C ⁇ -C 6 alkoxy) carbonyl,
  • phenyl which can be unsubstituted or carry one to three substituents, each selected from the group consisting of halogen, hydroxy, nitro, cyano, amino, Ci-C ß- alkyl, -C-C 6 alkoxy and Ci-C ⁇ -haloalkyl,
  • R 4 and R 5 together form a 3- to 7-membered bridge of 0 to 7 methylene members, 0, 2 or 4 methine members and 0, 1 or 2 oxo, thio, carbonyl or imino members, each imino member having one Ci-Ce-alkyl or (Ci-Cg-alkyl) carbonyl radical can carry;
  • the invention also relates to the use of the compounds I as herbicides and / or for the desiccation and / or defoliation of plants, herbicidal compositions and agents for the desiccation / defoliation of plants which contain the compounds I as active substances,
  • R for hydrogen or halogen
  • R b for halogen or cyano
  • R d for hydrogen, halogen or optionally substituted alkyl
  • R e for hydrogen, halogen or optionally substituted alkyl
  • R f represents hydrogen, hydroxyl, amino or optionally substituted alkyl, alkoxy, alkenyl or alkynyl, and X and Y represent oxygen or sulfur, described as herbicides.
  • WO 95/17391 also relates to compounds of the type of the formula II, where
  • R a for hydrogen or halogen
  • R c inter alia for an aminosulfonylamino grouping
  • R d for hydrogen, cyano, halogen or for optionally substituted alkyl
  • R e for optionally substituted alkyl or together with R d for alkanediyl
  • R f represents hydrogen or optionally substituted alkyl
  • WO 98/28280 describes l-amino-3-phenyluracils as herbicides which differ from the present compounds I by p-chlorine instead of p-cyano on the phenyl ring.
  • the task also extends to the provision of new desiccant / defoliant connections.
  • herbicidal compositions which contain the compounds I and have a very good herbicidal action. Processes for the preparation of these agents and processes for Control of undesired plant growth with the compounds I found.
  • the compounds I are also suitable for defoliation and desiccation of parts of plants, for which crop plants such as cotton, potatoes, rapeseed, sunflower, soybeans or field beans, in particular cotton, are suitable.
  • crops plants such as cotton, potatoes, rapeseed, sunflower, soybeans or field beans, in particular cotton
  • agents for the desiccation and / or defoliation of plants, methods for producing these agents and methods for the desiccation and / or defoliation of plants with the compounds I have been found.
  • the compounds of the formula I can contain one or more centers of chirality and are then present as mixtures of enantiomers or diastereomers.
  • E / Z isomers may also be possible.
  • the invention relates both to the pure enantiomers or diastereomers and to their mixtures.
  • Agriculturally useful salts include, above all, the salts of those cations or the acid addition salts of those acids whose cations or anions do not adversely affect the herbicidal activity of the compounds I. So come as cations in particular the ions of the alkali metals, preferably sodium and potassium, the alkaline earth metals, preferably calcium, magnesium and barium, and the transition metals, preferably manganese, copper, zinc and iron, and the ammonium ion, if desired one to four C ⁇ -C 4 alkyl, hydroxy -CC 4 alkyl and / or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium and trimethyl- (2-hydroxyethyl) ammonium, further phosphonium ions, sulfonium ions, preferably tri (C ⁇ -C4-alkyl) sul
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, bemnzoate, and the anions of C 1 -C 4 -alkanoic acids Formate, acetate, propionate and butyrate.
  • Halogen for: fluorine, chlorine, bromine or iodine
  • Ci-Ce-alkyl for: CH 3 , C 2 H 5 , CH 2 -C 2 H 5 , CH (CH 3 ) 2 , CH 2 -CH 2 -C 2 H 5 CH (CH 3 ) -C 2 H 5 , CH 2 -CH (CH 3 ) 2 C (CH 3 ) 3 / CH 2 -CH 2 -CH 2 -C 2 H 5 , 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2- Wench hylpropyl, 1-ethylpropyl, 1, 1-dirnethylpropyl, 1, 2-dirnethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dirnethylbutyl, 1,2-dirnethylbutyl , 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3
  • Ci-C ⁇ -haloalkyl for: a Ci-C ⁇ -alkyl radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl , Trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro -2,2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, petafluoroethyl, 2-fluoroprop
  • Cx-Ce alkoxy for: 0CH 3 , OC 2 H 5 / OCH 2 -C 2 H 5 , OCH (CH 3 ) 2 , 0 (CH 2 ) 3 -CH 3 , OCH (CH 3 ) -C 2 H 5 , OCH 2 -CH (CH 3 ) 2 , OC (CH 3 ) 3 , 0 (CH 2 ) 4 -CH 3 , 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, 1-dimethylpropoxy, 1, 2-dirnethylpropoxy, 2, 2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2-dimethylbutoxy, 1, 3- Dirnethylbutoxy, 2,2-Dirnethylbutoxy, 2,3-Dirnethylbutoxy, 3, 3-dimethylbutoxy, 1-ethy
  • C ⁇ -C 6 -Alkylthio for: SCH 3 , SC 2 H 5 , SCH 2 -C 2 H 5 , SCH (CH 3 ) 2 , SCH 2 -CH 2 -C 2 H 5 , SCH (CH 3 ) -C 2 H 5 , SCH 2 -CH (CH 3 ) 2 , SC (CH 3 ) 3 , SCH 2 - (CH 2 ) 3 -CH 3 , 1-methylbutylthio, 2-methylbuylthio, 3-methylbutylthio, 2, 2- Dimethylpropylthio, 1-ethylpropylthio, n-hexylthio, 1, 1-dimethylpropylthio, 1, 2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1, 1-dimethylbutylthio 1,2-dimethylbutylthio, 1, 3-di
  • C ⁇ -C 6 alkylsulfonyl for: S0 2 -CH 3 , S0 2 -C 2 H 5 , S0 2 -CH 2 -C 2 H 5 , S0 2 -CH (CH 3 ) 2 , S0 2 - (CH 2 ) 3 -CH 3 , S0 2 -CH (CH 3 ) -C 2 H 5 , S0 2 -CH 2 -CH (CH 3 ) 2 , S0 2 -C (CH 3 ) 3 , S0 2 - (CH 2 ) 4 -CH 3 , 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 2, 2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, 1, 1-dimethylpropylsulfonyl, 1, 2-dimethylpropylsulfonyl, n-hexyls
  • C 3 -C 6 alkenyl for: prop-1-en-l-yl, prop-2-en-l-yl, 1-methylethenyl, n-buten-1-yl, n-buten-2-yl , n-buten-3-yl, 1-methyl-prop-1-en-1-yl, 2-methyl-prop-1-en-1-yl, 1-methyl-prop-2-en-1-yl or 2-methyl-prop-2-en-l-yl, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methyl -but-l-en-l-yl, 2-methyl-but-l-en-l-yl, 3-methyl-but-1-en-l-yl, 1-methyl-but-2-en-l -yl, 2-methyl-but-2-en-l-yl, 3-methyl-but-2-en-l-yl, l-methyl-but-3-en-l-
  • C 3 -C 6 alkenyloxy for: prop-1-en-l-yloxy, prop-2-en-l-yloxy, 1-methylethenyloxy, n-buten-1-yloxy, n-buten-2-yloxy, n-butene-3-yloxy, 1-methyl-prop-l-en-l-yloxy, 2-methyl-prop-l-en-l-yl-oxy, l-methyl-prop-2-en-l- yloxy, 2-methyl-prop-2-en-l-yloxy, n-penten-1-yloxy, n-penten-2-yloxy, n-penten-3-yloxy, n-penten-4-yloxy, 1- Methyl-but-l-en-l-yloxy, 2-methyl-but-1-en-l-yloxy, 3-methyl-but-l-en-l-yloxy, 1-methyl-but-2-en- 1-yloxy, 2-methyl-but-2-en-l-
  • C 3 -C 6 alkynyloxy for: prop-1-in-1-yloxy, prop-2-in-1-yloxy, but-1-in-1-yloxy, but-1-in-3-yloxy, But-l-in-4-yloxy, but-2-in-l-yloxy, pent-1-in-l-yloxy, n-pent-l-in-3-yloxy, n-pent-l-in- 4-yloxy, n-pent-l-in-5-yloxy, n-pent-2-in-l-yloxy, n-pent-2-in-4-yloxy, n-pent-2-in-5- yloxy, 3-methyl-but-l-in 3-yloxy, 3-methyl-but-l-in-4-yloxy, n-hex-1-in-l-yloxy, n-hex-l-in 3-yloxy, n-hex-l-in-4-yloxy, n-hex-
  • cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • 3- to 7-membered heterocycles are oxiranyl, aziridinyl, oxetanyl, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl, isothiazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, dioxolanyl and 1, 3-dioxanol such as 1,3-dioxanol Dioxolan-4-yl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dithian-2-yl, 1,2,4-oxadiazolidinyl, 1,3,4- 0xadiazolidinyl, 1, 2, 4-thiadiazolidinyl, 1,3, 4-thiadiazolididinyl, 1, 2, 4-triazolidinyl, 1, 3, 4-triazolidin
  • All phenyl and heterocyclic rings are preferably unsubstituted or bear a substituent.
  • the variables preferably have the following meanings, individually or in combination:
  • R 1 is methyl or amino, particularly preferably methyl
  • R 2 is hydrogen, fluorine or chlorine, in particular hydrogen or fluorine;
  • R 4 is hydrogen, -CC 6 alkyl, C 3 -C 6 ⁇ alkenyl, C 3 -C 6 alkynyl,
  • Ci-C ⁇ -alkoxy or C 3 -C 8 cycloalkyl where each of the latter 5 radicals can optionally carry one or two substituents, each selected from the group consisting of halogen, nitro, cyano, hydroxy, C 3 -C 8 cycloalkyl , C ⁇ -C 6 oxy -Alk-, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, Ci-C ⁇ -alkylthio, C ⁇ -C6 alkylsulfenyl, Cx-C ö alkylsulfonyl and (C ⁇ -C 6- alkoxy) carbonyl, in particular Ci-C ⁇ - alkyl, such as methyl, ethyl, propyl or isopropyl; very preferably methyl;
  • R 5 is hydrogen, C ⁇ . -C 5 alkyl, C 3 -C 6 alkenyl, C 3 -C 5 alkynyl, Ci-C ⁇ alkoxy or C 3 -C 8 cycloalkyl, where each of the latter 5 radicals can optionally carry one or two substituents , each selected from the group consisting of Halogen, nitro, cyano, hydroxy, C 3 -C 8 cycloalkyl, Ci-C ⁇ -alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, Ci-C ß- alkylthio, Ci-C ⁇ - alkylsulfenyl, Ci-C ⁇ -alkylsulfonyl and (Ci-C ⁇ -alkoxy) carbonyl; or
  • Phenyl which may be unsubstituted or bear one or two substituents, each selected from the group consisting of halogen, hydroxy, nitro, cyano, amino, Ci-C ß- alkyl, C ⁇ -C 6 -alkoxy and Ci-C ⁇ -haloalkyl ;
  • R 4 and R 5 together form a 3- to 7-membered bridge of 0 to 7 methylene members, 0, 2 or 4 methine members and
  • oxo, thio, carbonyl or imino member where the imino member can carry a Ci-Cg-alkyl or (C ⁇ -C 6 -alkyl) carbonyl radical, particularly preferably R 4 and R 5 together a 4- to 5-membered bridge made of methylene members.
  • connections Ip. l - Ip. 107 which differ from the corresponding compounds Ia. l - Ia. 107 differ only in that R 1 is amino, R 2 is chlorine and R 3 is methyl:
  • L 1 means low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
  • cyclization is carried out in an inert organic solvent or diluent which is aprotic, for example in an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aromatic compound such as benzene and toluene or in a polar solvent such as dimethylformamide and dimethyl sulfoxide.
  • a polar solvent such as dimethylformamide and dimethyl sulfoxide.
  • polar solvent such as dimethylformamide and dimethyl sulfoxide
  • water can also be suitable as a diluent.
  • Suitable bases are preferably alkali metal alcoholates, in particular the sodium alcoholates, alkali metal hydroxides, in particular sodium hydroxide and potassium hydroxide, alkali metal carbonates, in particular sodium carbonate and potassium carbonate, and metal hydrides, in particular sodium hydride.
  • sodium hydride it has proven advantageous to work in an aliphatic or cyclic ether, in dimethylformamide or in dimethyl sulfoxide.
  • reaction temperature is from (-78) ° C to the boiling point of the respective reaction mixture, in particular from (-60) to 60 ° C.
  • Process product obtained as a metal salt the metal corresponding to the cation of the base used.
  • Suitable methylating agents are methyl halides, preferably methyl chloride, iodide or bromide, and also dimethyl sulfate, methanesulfonate (methyl mesylate), methyl benzenesulfonate, methoxy (p-toluenesulfone) (methyl tosylate), p-bromobenzenesulfonyl methane (methyl brosylate), trifluoromethane (Methyl triflate) and diazo ethane.
  • methyl halides preferably methyl chloride, iodide or bromide
  • dimethyl sulfate methanesulfonate
  • methanesulfonate methyl mesylate
  • methyl benzenesulfonate methoxy (p-toluenesulfone) (methyl tosylate)
  • p-bromobenzenesulfonyl methane methyl bros
  • an inert organic solvent or in an aprotic solvent e.g. in an aliphatic or cyclic ether, preferably in 1,2-dimethoxyethane, tetrahydrofuran or dioxane, in an aliphatic ketone, preferably in acetone, in an amide, preferably in dimethylformamide, in a sulfoxide, preferably in dimethyl sulfoxide, in a urea such as Tetramethylurea and 1, 3-dimethyltetrahydro-2 (1H) -pyrimidinone, in a carboxylic acid ester such as ethyl acetate, or in a halogenated aliphatic or aromatic hydrocarbon such as dichloromethane and chlorobenzene.
  • an inert organic solvent or in an aprotic solvent e.g. in an aliphatic or cyclic ether, preferably in 1,2-dimethoxyethane, tetrahydrofuran or diox
  • Suitable bases are inorganic bases, for example carbonates such as sodium carbonate and potassium carbonate, hydrogen carbonates such as sodium and potassium hydrogen carbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, and organic bases, for example amines such as triethylamine, pyridine and N, N-diethylaniline, or Alkali metal alcoholates such as sodium methoxide, sodium ethoxide and potassium tert-butoxide.
  • carbonates such as sodium carbonate and potassium carbonate
  • hydrogen carbonates such as sodium and potassium hydrogen carbonate
  • alkali metal hydrides such as sodium hydride and potassium hydride
  • organic bases for example amines such as triethylamine, pyridine and N, N-diethylaniline, or Alkali metal alcoholates such as sodium methoxide, sodium ethoxide and potassium tert-butoxide.
  • the amount of base and methylating agent is in each case preferably 0.5 to 2 times the molar amount, based on the amount of starting compound.
  • reaction temperature is from 0 ° C to the boiling point of the reaction mixture, in particular from 0 to 60 ° C.
  • the excess base for example sodium hydride, sodium alcoholate or Sodium carbonate, may contain to methylate.
  • the salts of those compounds I in which R 1 is hydrogen can also be obtained in a manner known per se from the process products of method A).
  • the aqueous solution of an inorganic or organic base is mixed with the substituted 3- (3- [aminosulfonylamino] - 4-cyano-phenyl) -6-trifluoromethyl-uracil I, in which R 1 stands for hydrogen. Salt formation normally takes place at a sufficient rate at 20-25 ° C.
  • the salt of 3- (3- [aminosulfonylamino] -4-cyano-phenyl) -6-trifluoromethyl-uracil can then be isolated, for example, by precipitation with a suitable inert solvent or by evaporation of the solvent.
  • Salts of 3- (3- [aminosulfonylamino] -4-cyano-phenyl) -6-trifluoromethyl-uracile I can usually be prepared by salting the corresponding alkali metal salt in aqueous solution.
  • 3- (3- [aminosulfonylamino] -4-cyano-phenyl) -6-trifluoromethyl-uracil metal salts which are insoluble in water can be prepared.
  • the precursors of the compounds of the formulas V, VI, VIII, IX, X, XI, XII, XIII, mentioned below, can also, if desired XIV, XV and XVI, insofar as R 1 is hydrogen, in the corresponding other precursors of formulas V, VI, VIII, IX, X, XI, XII, XIII, XIV, XV and XVI, in which R 1 is methyl, be transferred.
  • R 1 is methyl
  • 2,4-dinitrophenoxyamine has proven particularly useful as an amination reagent, however, e.g. hydroxylamine-O-sulfonic acid (HOSA) can also be used, which is already known from the literature as an amination reagent (see, for example, E. Hofer et al., Synthesis 1983, 466; W. Friedrichsen et al., Heterocycles 20 (1983) 1271 ; H. Hart et al., Tetrahedron Lett. 25 (1984) 2073; B. Vercek et al., Monthly H. Chem. 114 (1983) 789; G. Sosnousky et al., Z.
  • HOSA hydroxylamine-O-sulfonic acid
  • the amination can be carried out in a manner known per se (see, for example, T. Sheradsky, Tetrahedron Lett. 1968, 1909; MP Wentland et al., J. Med. Chem. 27 (1984) 1103 and in particular EP-A 240 194 , EP-A 476 697 and EP-A 517 181, where the amination of uracil is taught).
  • the reaction is usually carried out in a polar solvent, for example in dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or in ethyl acetate, which has hitherto proven to be particularly suitable.
  • Suitable bases are, for example, alkali metal carbonates such as potassium carbonate, alkali metal alcoholates such as sodium methylate and potassium tert-butanolate or alkali metal hydrides such as sodium hydride.
  • the amount of base and aminating agent is preferably 0.5 to 2 times the molar amount, based on the amount of starting compound.
  • Process D Alkylation of a 3- (3- [aminosulfonylamino] -4-cyano-phenyl) 6-trifluoromethyl-uracil of the formula I, where R 3 is hydrogen, in the presence of a base:
  • the alkylation can be carried out, for example, with the halide, preferably the chloride or bromide, the sulfate, sulfonate, preferably the methanesulfonate (mesylate), benzenesulfonate, p-toluenesulfonate (tosylate), p-bromobenzenesulfonate (brosylate), the trifluoromethanesulfonate (triflate) or the diazo compound of an unsubstituted or substituted alkane, cycloalkane, haloalkane, alkene or alkyne.
  • the halide preferably the chloride or bromide
  • the sulfate, sulfonate preferably the methanesulfonate (mesylate), benzenesulfonate, p-toluenesulfonate (tosylate), p-bromobenzenesulf
  • aprotic solvents for example aliphatic and cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, aliphatic ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, ureas such as tetramethyl urea and 1, 3-dimethyltetrahydro-2 (1H) -pyrimidinone, carboxylic acid esters such as ethyl acetate, or halogenated aliphatic or aromatic hydrocarbons such as dichloromethane and chlorobenzene.
  • aprotic solvents for example aliphatic and cyclic ethers such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, aliphatic ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, ureas such
  • Both inorganic bases e.g. B. Alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrogen carbonates such as sodium and potassium hydrogen carbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, as well as organic bases, e.g. A ine such as triethylamine, pyridine and N, N-diethylaniline, or alkali metal alcoholates such as sodium methanolate, ethanolate and potassium tert. -butanolate.
  • Alkali metal carbonates such as sodium carbonate and potassium carbonate
  • alkali metal hydrogen carbonates such as sodium and potassium hydrogen carbonate
  • alkali metal hydrides such as sodium hydride and potassium hydride
  • organic bases e.g. A ine such as triethylamine, pyridine and N, N-diethylaniline, or alkali metal alcoholates such as sodium methanolate, ethanolate and potassium tert. -butanolate.
  • reaction temperature 0 ° C. to the boiling point of the reaction mixture is recommended, in particular from 0 to 60 ° C.
  • Shark represents a halide, preferably fluoride, bromide or iodide.
  • Suitable cyanides are in particular metal cyanides, e.g. the alkali metal cyanides such as lithium, sodium and potassium cyanide, the alkaline earth metal cyanides such as magnesium cyanide, or also transition metal cyanides such as copper and zinc cyanide.
  • metal cyanides e.g. the alkali metal cyanides such as lithium, sodium and potassium cyanide, the alkaline earth metal cyanides such as magnesium cyanide, or also transition metal cyanides such as copper and zinc cyanide.
  • an ether such as tetrahydrofuran, dioxane and 1, 2-dimethoxyethane
  • an aprotic, polar solvent for example an alkyl nitrile such as aceto-, propio- and butyronitrile, an alkyl urea such as N, N, N ', N' - Tetramethyl urea, such as an open chain or cyclic dialkyl amide Dimethylformamide, N-methyl-2-pyrrolidone, 1,2-dimethyl-imidazolin-din-2-one and 1, 2-dimethyl-3, 4,5, 6-tetrahydro-2 (1H) -pyrimidinone, a dialkyl sulfoxide such as Dimethyl sulfoxide, or in hexamethyl phosphoric acid triamide.
  • an alkyl nitrile such as aceto-, propio- and butyronitrile
  • an alkyl urea such as N, N, N ', N' -
  • Useful catalysts are e.g. Transition metals and their complexes or salts, e.g. Iron or compounds of copper such as copper (I) chloride, iodide, cyanide, or nickel such as nickel bis-triphenylphosphine dibromide.
  • Transition metals and their complexes or salts e.g. Iron or compounds of copper such as copper (I) chloride, iodide, cyanide, or nickel such as nickel bis-triphenylphosphine dibromide.
  • a base in particular weakly nucleophilic bases
  • inorganic bases for example alkali metal carbonates such as sodium and potassium carbonate, alkali metal hydrogen carbonates such as sodium and potassium hydrogen carbonate , or alkali metal hydrides such as sodium hydride and potassium hydride, as well as organic bases, for example amines such as triethylamine, pyridine and N, N-diethylaniline.
  • the proportions are usually not critical. In general, about one to ten times the amount of cyanide and base, based on the amount of V, is sufficient.
  • the reaction temperature is usually 50 to 250 ° C; To increase the selectivity of the reaction, it may also be advisable to work at lower temperatures, in particular at about 20 ° C.
  • Shark represents a halide, preferably chloride.
  • the free acids of the sulfamoyl halides VII are also suitable as reactants for the compounds VI, especially when working in the presence of a condensing agent such as carbonyldiimidazole or dicyclohexylcarbodiimide.
  • Both inorganic bases e.g. Alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrides such as sodium hydride and potassium hydride or alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, as well as organic bases, e.g. Amines such as triethyla in, pyridine, diisopropylethyne in and N, N-diethylaniline.
  • an inert organic solvent or diluent which is preferably aprotic, e.g. in an aliphatic or cyclic ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, an aliphatic nitrile such as acetonitrile, a halogenated aliphatic or aromatics such as dichloromethane, dichloroethane, chloroform and chlorobenzene, an amide such as dimethylformamide, one Carboxylic acid esters such as ethyl acetate or an aromatic such as benzene, toluene and xylene.
  • aprotic e.g. in an aliphatic or cyclic ether such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, an
  • the amounts of bases and sulfamoylating agents are preferably 0.5 to 2 times the molar amount, based on the amount of VI.
  • reaction temperature 0 ° C. to the boiling point of the reaction mixture is recommended, in particular from 0 to 60 ° C.
  • a reducing agent for example metallic zinc or iron
  • an acid such as hydrochloric acid
  • Common precious metal catalysts for treatment with elemental hydrogen contain elemental nickel, palladium or platinum.
  • Suitable complex hydrides are e.g. Sodium boranate, sodium cyanoborohydride and sodium borohydride triacetate.
  • the alkylation is carried out in an inert organic solvent, primarily aromatic hydrocarbons such as benzene and toluene, halogenated aliphatic hydrocarbons such as dichloromethane, alcohols such as methanol, ethanol and butanol, amides such as dimethylformamide and dimethylacetamide and carboxylic acids such as acetic acid and trifluoroacetic acid.
  • aromatic hydrocarbons such as benzene and toluene
  • halogenated aliphatic hydrocarbons such as dichloromethane
  • alcohols such as methanol, ethanol and butanol
  • amides such as dimethylformamide and dimethylacetamide
  • carboxylic acids such as acetic acid and trifluoroacetic acid.
  • the starting compounds VI are preferably present by reduction of the corresponding 3- (4-cyano-3-nitrophenyl) -6-trifluoromethyl-uracile VIII in a manner known per se either with hydrogen in the presence of a metal catalyst or with a reducing agent or with a complex hydride of a transition metal salt available:
  • Suitable metal catalysts are usually Raney nickel, palladium and platinum, which can be supported on a support.
  • Suitable reducing agents are, for example, tin (II) salts, iron and zinc.
  • Suitable complex hydrides are, for example, sodium boranate.
  • Shark represents a halide, preferably fluoride, bromide or iodide.
  • 3- (4-halo-3-nitrophenyl) -6-trifluoromethyl-uracile IX are preferred by nitration of the correspondingly substituted 3- (4-halophenyl) -6-trifluoromethyl-uracile X using nitric acid, nitrating acid, an inorganic Nitrate such as sodium, potassium and ammonium nitrate, or available with an organic nitrate such as amyl nitrate:
  • Suitable solvents for the nitration are preferably inorganic acids such as nitric acid and sulfuric acid, organic acids such as acetic acid, or anhydrides such as acetic anhydride.
  • the reaction temperature is usually (-20) to 50 ° C, preferably (-10) to 30 ° C.
  • the amount of nitrating agent is not critical; it is usually from one to ten times the molar amount, based on the amount of VI.
  • This type of reaction is usually carried out by converting the amino group into the diazonium salt in a manner known per se, and then in the presence of a transition metal catalyst, in particular a copper (I) salt, advantageously copper (I) cyanide, with a metal cyanide, preferably with lithium, sodium or potassium cyanide.
  • a transition metal catalyst in particular a copper (I) salt, advantageously copper (I) cyanide, with a metal cyanide, preferably with lithium, sodium or potassium cyanide.
  • the starting compounds XI are preferably by reduction of the corresponding 3- (3- [aminosulfonylamino] -4-nitro-phenyl) -6-trifluoromethyl-uracile XII with hydrogen in the presence of a metal catalyst, which is usually made from Raney nickel, palladium or platinum exists and can be mounted on a carrier, or with a reducing agent, for example a tin (II) salt, iron or zinc, or with a complex hydride such as sodium boranate in the presence of a transition metal salt.
  • a metal catalyst which is usually made from Raney nickel, palladium or platinum exists and can be mounted on a carrier, or with a reducing agent, for example a tin (II) salt, iron or zinc, or with a complex hydride such as sodium boranate in the presence of a transition metal salt.
  • the reactions are usually carried out in a polar, aprotic solvent or diluent, e.g. in an amide such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, an aliphatic or cyclic ether such as dioxane, dimethoxyethane and diethylene glycol dimethyl ether, or in dimethyl sulfoxide.
  • a polar, aprotic solvent or diluent e.g. in an amide such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, an aliphatic or cyclic ether such as dioxane, dimethoxyethane and diethylene glycol dimethyl ether, or in dimethyl sulfoxide.
  • Alkali metal hydrides such as sodium and potassium hydride, alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate are suitable.
  • the reaction temperature is preferably from 20 ° C. to the reflux temperature of the reaction mixture, in particular from 20 to 150 ° C.
  • the 3- (3- [chlorosulfonylamino] -4-cyano-phenyl) -6-trifluoromethyl-uracils XVIII are obtainable in a manner known per se from the 3- (3-amino-4-cyanophenyl) -6-trifluoromethyl-uracils VI , for example by reaction of VI with chlorosulfonic acid and a chlorinating agent such as phosphorus pentachloride: XVIII
  • the enamine esters of formula III are new and also the subject of the present invention. They can also be used as herbicides.
  • L 1 means low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
  • Suitable solvents or diluents are, in particular, water solvents which are azeotropically miscible with water, for example aromatics such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, aliphatic and cyclic ethers such as 1 , 2-dimethoxyethane, tetrahydrofuran and dioxane, or cyclohexane, but also alcohols such as methanol and ethanol, into consideration.
  • aromatics such as benzene, toluene and o-, m-, p-xylene
  • halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene
  • aliphatic and cyclic ethers such as 1 , 2-dimethoxye
  • Suitable acidic catalysts are preferably strong mineral acids such as sulfuric acid and hydrochloric acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid, organic acids such as p-toluenesulfonic acid and acidic cation exchangers such as "Amberlyst 15" (Fluka).
  • Suitable basic catalysts are e.g. Metal hydrides such as sodium hydride and particularly preferably metal alcoholates such as sodium methoxide and ethanolate.
  • XIX and the ß-ketoester XX in an approximately stoichiometric ratio or to work with a slight excess of one or the other component, up to about 10 mol%.
  • an amount of catalyst of 0.5 to 2 mol%, based on the amount of a starting material, is sufficient.
  • reaction is carried out at a temperature of 60 to 120 ° C., for the rapid removal of water formed, preferably at the boiling point of the reaction mixture.
  • L 1 means low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
  • L 2 means -CC alkyl or phenyl.
  • This reaction can be carried out, for example, in an inert, water-miscible, organic solvent, for example an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, or a lower alcohol, in particular ethanol, the reaction temperature being normally from 50 to 100 ° C, preferably at the boiling point of the reaction mixture.
  • an inert, water-miscible, organic solvent for example an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane
  • a lower alcohol in particular ethanol
  • reaction can also be carried out in an aromatic diluent such as benzene, toluene and o-, m-, p-xylene, in which case the addition of either an acidic catalyst such as hydrochloric acid and p-toluenesulfonic acid or a base, e.g. an alkali metal alcoholate such as sodium methoxide and sodium ethanolate is recommended.
  • an acidic catalyst such as hydrochloric acid and p-toluenesulfonic acid or a base
  • an alkali metal alcoholate such as sodium methoxide and sodium ethanolate
  • reaction temperature is usually 50 to 100 ° C, but preferably 60 to 80 ° C.
  • the enamine ester III obtained is converted directly (ie “in situ”) with excess base into the corresponding product of value I according to process A.
  • Procedure N :
  • L 1 means low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
  • an essentially anhydrous aprotic organic solvent or diluent for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, Benzene, toluene and o-, m-, p-xylene, a halogenated, aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of the solvents mentioned.
  • an essentially anhydrous aprotic organic solvent or diluent for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethan
  • a metal hydride base such as sodium and potassium hydride or an organic tertiary base such as triethylamine and pyridine, where the organic base can simultaneously serve as a solvent.
  • the starting materials are expediently used in a stoichiometric ratio or one works with a slight excess of one or the other component up to about 10 mol%. If one works without solvent in the presence of an organic base, this is present in a large excess.
  • the reaction temperature is preferably (-80) to 50 ° C, in particular (-60) to 30 ° C.
  • the enamine ester III obtained is converted directly (ie “in situ”) with excess base into the corresponding product of value I according to process A.
  • L 1 means low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
  • L 3 means -C 4 alkyl or phenyl.
  • This reaction is advantageously carried out in an aprotic, polar solvent or diluent such as dimethylformamide, 2-butanone, dimethyl sulfoxide and acetonitrile, advantageously in the presence of a base, for example an alkali metal or alkaline earth metal alcoholate, in particular a sodium alkanolate such as sodium methoxide, an akali metal or alkaline earth metal carbonates, in particular sodium carbonate, or an alkali metal hydride such as lithium and sodium hydride.
  • a base for example an alkali metal or alkaline earth metal alcoholate, in particular a sodium alkanolate such as sodium methoxide, an akali metal or alkaline earth metal carbonates, in particular sodium carbonate, or an alkali metal hydride such as lithium and sodium hydride.
  • the reaction temperature is generally 80 to 180 ° C, preferably at the boiling point of the reaction mixture.
  • a sodium alcoholate is used as the base and the alcohol formed in the course of the reaction is distilled off continuously.
  • the enamine esters III prepared in this way can be cyclized to a salt of 3- (3- [aminosulfonylamino] -4-cyano-phenyl) -6-trifluoromethyl-uracile I without isolation from the reaction mixture according to process A).
  • XXV R J XXVI L 1 means low molecular weight alkyl, preferably C ⁇ -C 4 alkyl, or phenyl.
  • This reaction is advantageously carried out in an essentially anhydrous, aprotic, organic solvent or diluent, for example in the presence of an aliphatic or cyclic ether such as diethyl ether, 1, 2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n -Hexane, benzene, toluene and o-, m-, p-xylene, a halogenated, aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide , or a mixture of the named solvents.
  • an aliphatic or cyclic ether such as diethyl ether, 1, 2-dimethoxyethane,
  • a metal hydride base such as sodium and potassium hydride, an alkali metal or alkaline earth metal alcoholate such as sodium methoxide, ethanolate and potassium tert-butoxide, or an organic nitrogen base such as triethylamine and pyridine, the organic base being used simultaneously can serve as a solvent.
  • a metal hydride base such as sodium and potassium hydride
  • an alkali metal or alkaline earth metal alcoholate such as sodium methoxide, ethanolate and potassium tert-butoxide
  • an organic nitrogen base such as triethylamine and pyridine
  • the starting materials are expediently used in stoichiometric amounts or one of the components is used in excess, up to about 20 mol%. If one works without solvent in the presence of an organic base, this is advantageously present in an even larger excess.
  • the reaction temperature is generally from (-80) to 150 ° C, preferably from (-30) ° C to the boiling point of the reaction mixture.
  • the enamine carboxylates of the formula IV are also new and Ge ⁇ subject matter of the present invention; They can also be prepared in a manner known per se, for example from an aniline derivative of the formula XXVII according to the following reaction scheme:
  • L 1 means low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
  • reaction according to reaction equation 1 is preferably carried out in an anhydrous inert aprotic solvent, for example in a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, an aromatic hydrocarbon such as benzene, toluene and o-, m-, p-xylene, or an aliphatic or cyclic ether such as Diethyl ether, dibutyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane.
  • a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene
  • an aromatic hydrocarbon such as benzene, toluene and o-, m-, p-xylene
  • an aliphatic or cyclic ether such as Diethyl ether, dibutyl ether, 1,2-dimethoxyethan
  • the reaction temperature is generally about 70 to 140 ° C, in particular 100 to 120 ° C.
  • reaction according to reaction equation 2 is an aminolysis, which is usually either without a solvent [cf. e.g. J. Soc. Dyes Col. 42, 81 (1926), Ber. 64, 970 (1931); Org. Synth., Coll. Vol. IV, 80 (1963) and J.A.C. S. 70., 2402 (1948)] or in an inert anhydrous solvent / diluent, in particular in an aprotic solvent, for example in an aromatic such as toluene and o-, m-, p-xylene or a halogenated aromatic such as chlorobenzene becomes.
  • a solvent cf. e.g. J. Soc. Dyes Col. 42, 81 (1926), Ber. 64, 970 (1931); Org. Synth., Coll. Vol. IV, 80 (1963) and J.A.C. S. 70., 2402 (1948)
  • an inert anhydrous solvent / diluent in particular in an
  • a basic catalyst for example a higher boiling amine [see e.g. B. Helv. Chi. Acta 11, 779 (1928) and US 2,416,738] or pyridine.
  • the reaction temperature is preferably about 130 to 160 ° C.
  • the starting compounds are expediently used in approximately stoichiometric amounts or one works with a slight excess of one or the other component up to approximately 10 mol%. If one works in the presence of a basic catalyst, a catalyst amount of 0.5 to 2 mol%, based on the amount of one of the starting materials, is normally sufficient.
  • Suitable solvents / diluents are, in particular, water which is azeotropically miscible with water, for example aromatics such as benzene, toluene and o-, m-, p-xylene or halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene.
  • Suitable catalysts are, in particular, strong mineral acids such as sulfuric acid, organic acids such as p-toluenesulfonic acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid or acidic cation exchangers such as "Amberlyst 15" (Fluka).
  • reaction temperature is about 70 to 150 ° C; however, to rapidly remove the water of reaction formed, the reaction mixture is advantageously carried out at the boiling point of the reaction mixture in question.
  • aniline derivatives of the formula XXVII can also be converted directly into the compounds I by reaction with an isocyanate and subsequent elimination of water, in accordance with
  • M stands for an alkali metal ion such as sodium and potassium or for the equivalent of an alkaline earth metal ion such as calcium and magnesium.
  • the reactions can be carried out both in an inert aprotic solvent, for example in a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, an aromatic hydrocarbon such as benzene, toluene and o-, m-, p-xylene, an aliphatic or cyclic ether such as Diethyl ether, dibutyl ether, 1, 2-dimethoxyethane, tetrahydrofuran and dioxane, as well as in protic solvents such as acetic acid and propionic acid.
  • the reaction temperature is generally from 20 ° C. to the boiling temperature of the reaction mixture.
  • aniline derivative XXVII and the isocyanate are advantageously used in approximately stoichiometric amounts, or an excess of isocyanate is used. This excess can be up to 10 times the stoichiometric amount of XXVII. The 1.5 to 6 times the amount of isocyanate, based on the amount of aniline derivative XXVII, is preferred.
  • reaction mixtures are generally worked up by methods known per se, for example by diluting the reaction solution with water and then isolating the product by means of filtration, crystallization or solvent extraction, or by removing the solvent, distributing the residue in a mixture of water and a suitable one organic solvents and working up the organic phase towards the product.
  • the 3- (3- [aminosulfonylamino] -4-cyano-phenyl) -6-trifluoromethyl-uracile I can be prepared by one of the synthesis methods mentioned above. For economic or procedural reasons, however, it may be more appropriate to select some compounds I from similar 3- (3- [aminosulfonylamino] - 4-cyano-phenyl) -6-trifluoromethyl-uracils (which, however, differ in particular in the meaning of the R 4 and / or to differentiate R 5 ) in a manner known per se, for example by re-amidation.
  • the 3- (3- [aminosulfonylamino] -4-cyano-phenyl) -6-trifluoromethyl uracils of the formula I can contain one or more centers of chirality and are then usually obtained as mixtures of enantiomers or diastereomers. If desired, the mixtures can be separated into the largely pure isomers by the methods customary for this, for example by means of crystallization or chromatography on an optically active adsorbate. Pure optically active isomers can also be produced, for example, from corresponding optically active starting materials.
  • Further salts can be formed by reaction of I with a base of the corresponding cation, preferably an alkali metal hydroxide or hydride, or by reaction with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • a base of the corresponding cation preferably an alkali metal hydroxide or hydride
  • an acid of the corresponding anion preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • Salts of I can be prepared in a conventional manner by salting the corresponding alkali metal salt, as can ammonium, phosphonium, sulfonium and sulfoxonium salts using ammonia, phosphonium, sulfonium or sulfoxonium hydroxides.
  • the compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides.
  • the herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly at high application rates. In crops such as wheat, rice, maize, soybeans and cotton, they act against weeds and grass weeds without causing any significant damage to crops. This effect occurs especially at low application rates.
  • the compounds I or herbicidal compositions comprising them can also be used in a further number of crop plants for eliminating undesirable plants.
  • the following crops can be considered: Allium cepa, pineapple comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spp. altissima, Beta vulgaris spp. rapa, Brassica napus var. napus, Brassica napus var. napo- brassica, Brassica rapa var.
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • 3- (3- [aminosulfonylamino] -4-cyano-phenyl) -6-trifluoromethyl-uracile I are also suitable for the desiccation and / or defoliation of plants.
  • desiccants are particularly suitable for drying out the above-ground parts of crops such as potatoes, rapeseed, sunflower and soybeans. This enables these important crops to be harvested completely mechanically.
  • the waste promoted by the use of active compounds of the formula I according to the invention is based on the formation of separating tissue between the fruit or leaf and shoot part of the plants.
  • Cotton defoliation is of particular economic interest because it makes harvesting easier.
  • the shortening of the time interval in which the individual plants ripen leads to an increased quality of the harvested fiber material.
  • the compounds I or the compositions comprising them can be sprayed, for example in the form of directly sprayable aqueous solutions, powders, suspensions, also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprays or granules, Nebulization, dusting, scattering or pouring can be used.
  • the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • the herbicidal compositions comprise a herbicidally effective amount of at least one active compound of the formula I and auxiliaries customary for the formulation of crop protection agents.
  • Mineral oil fractions from medium to high boiling point such as kerosene and diesel oil, also coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, e.g. Amines such as N-methylpyrrolidone and water.
  • Paraffins etrahydronaphthalene
  • alkylated naphthalenes and their derivatives alkylated benzenes and their derivatives
  • alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol
  • ketones such as cyclohex
  • Aqueous use forms can be made from emulsion concentrates,
  • Suspensions, pastes, wettable powders or water-dispersible granules can be prepared by adding water.
  • emulsions, pastes or oil dispersions the 3- (3- [aminosulfonylamino] -4-cyano-phenyl) -6-trifluoromethyl-uracile I as such or dissolved in an oil or solvent, by means of wetting, adhesive or dispersing agents - or emulsifier can be homogenized in water.
  • concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • the surface-active substances are the alkali, alkaline earth and ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts sulfated hexa-, hepta- and octadecanols as well as fatty alcohol glycol ether, Condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers.
  • Solid carriers are mineral soils such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Urea and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range.
  • the formulations generally contain about 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient I.
  • the active ingredients are in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • the compounds I according to the invention can be formulated, for example, as follows:
  • Dissolved mixture which consists of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.
  • Wise a dust containing 3 wt .-% of the active ingredient.
  • the active ingredients I or the herbicidal compositions can be applied pre- or post-emergence. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not struck wherever possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (post-directed, lay-by).
  • the application rates of active ingredient I are 0.001 to 3.0, preferably 0.01 to 1 kg / ha of active substance (a.S.) depending on the control target, the season, the target plants and the growth stage.
  • the 3- (3- [aminosulfonylamino] - 4-cyano-phenyl) -6-trifluoromethyl-uracile I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied together.
  • Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels.
  • the seeds of the test plants were sown 15 according to species.
  • test plants For the purpose of post-emergence treatment, the test plants, depending on the growth habit, were first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. The test plants were
  • the plants were kept in a species-specific manner at temperatures of 10 to 35 25 ° C and 20 to 35 ° C.
  • the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment evaluated.
  • Compound 1 had a very good herbicidal activity against the unwanted plants Abuthilon theophrasti, Chenopodium album and Echinochloa crus-galli at a rate of 15.6 g / ha post-emergence.
  • the young cotton plants were dripping wet with aqueous preparations of the leaf treated active compounds I (with the addition of 0.15 wt .-% of the fatty alcohol alkoxylate Plurafac LF 700 ® *), based on the spray mixture).
  • the amount of water applied was the equivalent of 1000 l / ha. After 13 days, the number of leaves dropped and the degree of defoliation in% were determined.

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Abstract

L'invention concerne des 3-(3-[aminosulfonylamino]-4-cyano-phényl)-6-trifluorométhyluraciles correspondant à la formule (I), et leurs sels. Dans ladite formule (I) : R<1> représente H, CH3, NH2; R2 représente H, halogène; R<3> représente H, alkyle C1-C6; R<4> représente H, alkyle C1-C6 éventuellement substitué, alcényle C3-C6, alkinyle C3-C6, alcoxy C1-C6 ou cycloalkyle C3-C8; R<5> représente alkyle C1-C6 éventuellement substitué, alcényle C3-C6, alkinyle C3-C6, alcoxy C1-C6 ou cycloalkyle C3-C8, ou phényle éventuellement substitué ; ou bien R<4> et R<5> représentent ensemble un pont à 3-7 éléments constitués de 0-7 éléments méthylène, 0, 2 ou 4 éléments méthine et 0, 1 ou 2 éléments oxo, thio, carbonyle ou imino éventuellement substitué. Ces composés peuvent être utilisés comme herbicides et pour la dessiccation/défoliation de plantes.
PCT/EP2003/007357 2002-07-12 2003-07-09 Nouveaux 3-(3-[aminosulfonylamino]-4-cyano-phenyl)-6-trifluoromethyluraciles Ceased WO2004007467A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0714602A1 (fr) * 1994-12-02 1996-06-05 Nihon Bayer Agrochem K.K. Sulphonylaminophényluracile-herbicides pour rizières
EP0831091A2 (fr) * 1996-09-23 1998-03-25 Novartis AG Procédé de préparation de 3-aryl-uraciles
WO1998028280A1 (fr) * 1996-12-23 1998-07-02 Fmc Corporation Certains derives de 3-[2,4 disubstituee-5-(substituee amino)phenyle]-1-substituee-6-trifluorure-2,4-(1h,3h)-pyrimidinedione utilises en tant qu'herbicides
WO2001039597A2 (fr) * 1999-12-03 2001-06-07 Bayer Aktiengesellschaft Herbicide a base de n-aryl-uraciles
WO2001058883A1 (fr) * 2000-02-07 2001-08-16 Bayer Aktiengesellschaft Procede pour la production de 1-amino-3-aryl-uraciles

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0714602A1 (fr) * 1994-12-02 1996-06-05 Nihon Bayer Agrochem K.K. Sulphonylaminophényluracile-herbicides pour rizières
EP0831091A2 (fr) * 1996-09-23 1998-03-25 Novartis AG Procédé de préparation de 3-aryl-uraciles
WO1998028280A1 (fr) * 1996-12-23 1998-07-02 Fmc Corporation Certains derives de 3-[2,4 disubstituee-5-(substituee amino)phenyle]-1-substituee-6-trifluorure-2,4-(1h,3h)-pyrimidinedione utilises en tant qu'herbicides
WO2001039597A2 (fr) * 1999-12-03 2001-06-07 Bayer Aktiengesellschaft Herbicide a base de n-aryl-uraciles
WO2001058883A1 (fr) * 2000-02-07 2001-08-16 Bayer Aktiengesellschaft Procede pour la production de 1-amino-3-aryl-uraciles

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