EP1289970A1 - 3-arylisothiazoles et leur utilisation en tant qu'herbicides - Google Patents

3-arylisothiazoles et leur utilisation en tant qu'herbicides

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Publication number
EP1289970A1
EP1289970A1 EP01940469A EP01940469A EP1289970A1 EP 1289970 A1 EP1289970 A1 EP 1289970A1 EP 01940469 A EP01940469 A EP 01940469A EP 01940469 A EP01940469 A EP 01940469A EP 1289970 A1 EP1289970 A1 EP 1289970A1
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EP
European Patent Office
Prior art keywords
alkyl
alkoxy
phenyl
compounds
haloalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP01940469A
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German (de)
English (en)
Inventor
Ingo Sagasser
Olaf Menke
Michael Rack
Gerhard Hamprecht
Michael Puhl
Robert Reinhard
Matthias Witschel
Cyrill Zagar
Helmut Walter
Karl-Otto Westphalen
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BASF SE
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BASF SE
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Publication of EP1289970A1 publication Critical patent/EP1289970A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
    • C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
    • C07D275/03—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to 3-arylisothiazoles and their agriculturally useful salts and their use as herbicides, desiccants or defoliants.
  • Herbicidal compounds with 5-ring heteroaromatic substructures are described in large numbers in the prior art, for example in EP-A 18 080, EP-A 18 497, 25 EP-A 29 171, EP-A 49 760, EP-A 81 730, 38, EP-A 709 380,
  • JP-A 63233 982 describes herbicidally active isothiazol-4-sul-30 fonamides which are substituted by a 6-ring hetaryl group or a 6-ring hetaralkyl group.
  • WO 97/38987, WO 97/38988 and WO 97/38996 describe highly effective herbicides with a benzoylisothiazole structure.
  • 5-ring heterocycles sometimes leave something to be desired in terms of their activity and / or selectivity towards harmful plants.
  • the present invention is therefore based on the object of providing new herbicides with which harmful plants can be controlled better than hitherto.
  • the new herbicides should advantageously have a high activity against harmful plants.
  • crop tolerance is desirable.
  • This object is achieved by 3-arylisothiazoles which have a substituent in the 5-position of the isothiazole ring which is selected from C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C haloalkoxy, C 1 -C 4 -Alkylthio, -C-C 4 -Halogenalkylthio, -C-C 4 -Alkylsul- finyl, C ⁇ -C 4 -Halogenalkylsulfinyl, C ⁇ -C 4 -Alkylsulfonyl, C ⁇ -C 4 -Halogenated alkylsulfonyl C ⁇ -C 4 -Alkylsulfonyl
  • the invention relates to 3-arylisothiazoles of the general formula I.
  • X is a chemical bond or a methylene, 1,2-ethylene,
  • R 1 C ⁇ -C4-haloalkyl, C ⁇ -C 4 -alkoxy, C 4 haloalkoxy, C 1 -C 4 - alkylthio, C ⁇ -C4-haloalkylthio, C ⁇ -C4-alkylsulfinyl,
  • C ⁇ -C haloalkylsulfinyl C 1 -C 4 alkylsulfonyl, C ⁇ -C 4 -Haloge- nalkylsulfonyl C ⁇ -C 4 alkylsulfonyloxy or C ⁇ -C sulfonyloxy 4 haloalkyl;
  • R 2 is hydrogen, halogen, amino, cyano, nitro, -CC alkyl or -CC 4 haloalkyl;
  • R 3 is hydrogen or halogen
  • R 4 is hydrogen, cyano, nitro, halogen, C ⁇ -C4 alkyl, dC 4 -Haloge- nalkyl, C ⁇ -C 4 alkoxy or C ⁇ -C 4 haloalkoxy;
  • R 5 is hydrogen, nitro, cyano, halogen, halosulfonyl, -OYR 7 , -O-CO-YR 7 , -N (YR 7 ) (ZR 8 ), -N (YR 7 ) -S0 2 -ZR 8 , -N (S0 2 -YR 7 ) (S0 2 -ZR 8 ), -N (YR 7 ) -CO-ZR 8 , -N (YR 7 ) (OZR 8 ), -SYR 7 , -SO-ZR 7 , -S0 2 -YR 7 , -S0 2 -0-YR 7 , -S0 2 -N (
  • Q is nitrogen or a group CR 6 , wherein R 6 is hydrogen;
  • R 4 and XR 5 or XR 5 and R 6 are a 3- or 4-membered chain, the chain links of which, in addition to carbon, can have 1, 2 or 3 heteroatoms, selected from nitrogen, oxygen and sulfur atoms, which are unsubstituted or in turn have one , can carry two or three substituents, and the members of which can also comprise one or two non-adjacent carbonyl, thiocarbonyl or sulfonyl groups,
  • XR 5 is different from hydrogen and in which the variables Y, Z, R 7 , R 8 and R 9 have the meanings given below:
  • Y, Z independently of one another: a chemical bond, a methylene or ethylene group, which may be unsubstituted or bear one or two substituents, each selected from the group consisting of carboxy, C 1 -C 4 -alkyl, C 4 -C 4 - Haloalkyl, (-CC 4 alkoxy) carbonyl and phenyl;
  • R 7 , R 8 independently of one another:
  • C 3 -C 8 cycloalkyl which may contain a carbonyl or thiocarbonyl ring member, phenyl or 3-, 4-, 5-, 6- or 7-membered heterocyclyl, which may contain a carbonyl or thiocarbonyl ring member, wherein any cycloalkyl, phenyl and any Heterocyclyl ring may be unsubstituted or may carry one, two, three or four substituents, each selected from the group consisting of cyano, nitro, amino, hydroxy, carboxy, halogen, C ⁇ -C 4 -alkyl, C 4 haloalkyl, C ⁇ -C 4 -alkoxy, C 4 haloalkoxy, C ⁇ -C-alkylthio, C ⁇ -C4-haloalkylthio, C ⁇ -C 4 alkylsulfonyl, C ⁇ -C4-haloalkylsulfonyl, (C ⁇ -C4 alkyl)
  • R 9 is hydrogen, Ci-C ⁇ - alkyl, Ci-C ö -haloalkyl,
  • R 12 , R 13 independently of one another hydrogen, Ci-C ⁇ - alkyl, Ci-C ö -haloalkyl, C ⁇ -C 4 -alkoxy-C ⁇ -C 4 -alkyl, C 2 -C 6 alkenyl, C 2 - C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 2 -C 6 -haloalkynyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl-C 1 -C 8 -alkyl, phenyl, phenyl -C-C-alkyl, 3- to 7-membered heterocyclyl or heterocyclyl -CC 4 -alkyl, where each cycloalkyl and heterocyclyl ring can contain a carbonyl or thiocarbonyl ring member, and wherein each cycloalkyl , The phenyl and each heterocyclyl
  • the invention also relates to the use of compounds I as herbicides and / or for the desiccation and / or defoliation of plants, herbicidal compositions and agents for desiccation and / or
  • the compounds of the formula I can have one or more centers of chirality in the substituents and are then present as enantiomer or diastereomer mixtures.
  • the invention relates both to the pure enantiomers or diastereomers and to their mixtures.
  • Agriculturally useful salts include, in particular, 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, as well as the ammonium ion, if desired one to four C ⁇ -C 4 -Alkyl- and / or a phenyl or benzyl substituent can carry, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, further phosphonium ions, sulfonium ions, preferably tri (-C 4 -alkyl) sulfonium and sulfoxonium ions, preferably tri (C ⁇
  • 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, benzoate, and the anions of C 1 -C 4 -alkanoic acids, preferably Formate, acetate, Propionate and butyrate. They can be formed by reacting I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • All carbon chains ie all alkyl, haloalkyl, phenylalkyl, cycloalkylalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkenyl -, Haloalkenyl, alkynyl and haloalkynyl groups and corresponding parts of groups in larger groups such as alkoxycarbonyl, phenylalkyl, cycloalkylalkyl,
  • Alkoxycarbonylalkyl etc. can be straight-chain or branched, the prefix C n -C m each indicating the possible number of carbon atoms in the group. halogenated
  • Substituents preferably carry one, two, three, four or five identical or different halogen atoms.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • -C-C 4 alkyl for: CH 3 , C 2 H 5 , n-propyl, CH (CH 3 ) 2 , n-butyl, CH (CH 3 ) -C 2 H 5 , CH 2 -CH (CH 3 ) 2 and C (CH 3 ) 3 ;
  • haloalkyl for: a C 1 -C 4 -alkyl radical as mentioned above which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example CHF, CHF, CF 3 , CH 2 C1, Dichloromethyl, trichloromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl1, 2- Chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, C 2 F 5 , 2-fluoropropyl, 3-fluoropropyl, 2,
  • Ci-C ⁇ -haloalkyl for: a -CC 6 alkyl radical as mentioned above, which is partially or completely by fluorine, chlorine,
  • Bromine and / or iodine is substituted, e.g. one of the radicals mentioned under C 1 -C -haloalkyl and for 5-fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodo-1-pentyl, 5,5,5- Trichloro-l-penyl, undecafluoropentyl, 6-fluoro-l-hexyl, 6-chloro-l-hexyl, 6-bromo-l-hexyl, 6-iodo-l-hexyl, 6,6, 6-trichloro-l- hexyl or dodecafluorohexyl;
  • Phenyl-C 1 -C 4 -alkyl for: benzyl, 1-phenylethyl, 2-phenylethyl,
  • Heterocyclyl -CC 4 -alkyl for: heterocyclylmethyl, 1-heterocyclyl-ethyl, 2-heterocyclyl-ethyl, 1-heterocyclyl-prop-l-yl, 2-heterocyclyl-prop-l-yl, 3-heterocycly1-prop- l-yl, 1-heterocyclyl-but-l-yl, 2-heterocyclyl-but-l-yl, 3-heterocyclyl-but-l-yl, 4-heterocyclyl-but-l-yl, l-heterocyclyl-but- 2-yl, 2-heterocyclyl-but-2-yl, 3-heterocyclyl-but-2-yl, 3-heterocyclyl-but-2-yl, 4-heterocyclyl-but-2-yl, 1- (heterocyclyl-methyl ) -eth-l-yl, 1- (hetero
  • C ⁇ -C 6 alkylthio for: SCH 3 , SC 2 H 5 , n-propylthio, SCH (CH 3 ) 2 , n-butylthio, SCH (CH 3 ) -C 2 H 5 , SCH 2 -CH (CH 3 ) 2 or SC (CH 3 ) 3 , preferably for SCH 3 or SC 2 H 5 ;
  • C ⁇ -C4-haloalkylthio for: a C ⁇ -C4-alkylthio as mentioned above which is partially or fully substituted by, iodine of fluorine, chlorine, bromine and / or substituted, eg SCH 2 F, SCHF 2, SCH 2 C1, SCH (Cl) 2 , SC (C1) 3 , SCF 3 , chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2, 2, 2-trifluoroethylthio, 2-chloro-2-fluoroethylthio,
  • C 1 -C 4 -alkoxy-C 4 -C 4 -alkyl for: C 1 -C 4 -alkoxy - as mentioned above - substituted C C-C 4 -alkyl, for example for CH 2 -0CH 3 , CH 2 -0C 2 H 5 , n-propoxymethyl, CH 2 -0CH (CH 3 ) 2 , n-butoxymethyl, (1-methylpropoxy) methyl, (2-methylpropoxy) methyl, CH 2 -0C (CH 3 ) 3 , 2- (methoxy) ethyl, 2- (ethoxy) ethyl, 2- (n-propoxy) ethyl, 2- (1-methylethoxy) ethyl, 2- (n-butoxy) ethyl, 2- (1-methylpropoxy) ethyl,
  • C ⁇ -C 4 -alkylthio-C ⁇ -C -alkyl for: C ⁇ -C -alkylthio - as mentioned above - substituted -CC 4 -alkyl, for example for CH 2 -SCH 3 , CH 2 -SC 2 H 5 , n-propylthiomethyl, CH 2 -SCH (CH 3 ) 2 , n-butylthiomethyl, (1-methylpropylthio) methyl, (2-methylpropylthio) methyl, CH 2 -SC (CH 3 ) 2 , 2- (methylthio) ethyl,
  • (C 1 -C 4 alkyl) carbonyl for: CO-CH 3 , CO-C 2 H 5 , CO-CH 2 -C 2 H 5 , CO-CH (CH 3 ) 2 , n-butylcarbonyl, CO-CH (CH 3 ) -C 2 H 5 , C0-CH 2 -CH (CH 3 ) 2 or C0-C (CH 3 ) 3 , preferably for C0-CH 3 or CO-C 2 H 5 ;
  • (C 1 -C 4 -Halogenalkyl) carbonyloxy for: a (C 1 -C 4 -alkyl) carbonyl radical - as mentioned above - which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 0-C0-CH 2 F, 0-CO-CHF 2 , 0-C0-CF 3 , 0-C0-CH 2 Cl, 0-C0-CH (Cl) 2 , 0-C0-C (Cl) 3 ,
  • Chlorofluoromethylcarbonyloxy dichlorofluoromethylcarbonyloxy, chlorodifluoromethylcarbonyloxy, 2-fluoroethylcarbonyloxy, 2-chloroethylcarbonyloxy, 2-bromoethylcarbonyloxy, 2-iodoethylcarbonyloxy, 2, 2-difluoroethylcarbonyloxy, 2,2, 2-trifluoroethylcarbonyloxy, 2-chloro-2-fluoro-carbonyloxy, 2 2-difluoroethylcarbonyloxy, 2, 2-dichloro-2-fluoroethylcarbonyloxy, 2,2, 2-trichloroethylcarbonyloxy, 0-C0-C 2 F 5 , 2-fluoropropylcarbonyloxy, 3-fluoropropylcarbonyloxy,
  • (C ⁇ -C 4 -alkoxy) carbonyl - as mentioned above - substituted -CC 4 alkyl for example for methoxycarbonyl-methyl, ethoxycarbonyl-methyl, n-propoxycarbonyl-methyl, (1-methylethoxycarbonyl) methyl, n-butoxycarbonylmethyl, (1-methylpropoxycarbonyl) methyl, (2-methylpropoxycarbonyl) methyl, (1, 1-dimethylethoxycarbonyl) methyl, 1- (methoxycarbonyl) ethyl, 1- (ethoxycarbonyl) ethyl, 1- (n-propoxycarbonyl) ethyl,
  • (-C-C 4 -alkoxy) carbonyl-C ⁇ -C 4 -alkylthio for: by (-C-C 4 -alkoxy) carbonyl - as mentioned above - substituted C ⁇ -C 4 -alkylthio, for example for methoxycarbonylmethylthio, ethoxycarbonylmethylthio, n-propoxycarbon 1-methylthio,
  • -C-C 4 alkylsulfinyl for: S0-CH 3 , S0-C 2 H 5 , S0-CH 2 -C 2 H 5 , SO-CH (CH 3 ) 2 , n-butylsulfinyl, S0-CH (CH 3 ) -C 2 H 5 , S0-CH 2 -CH (CH 3 ) 2 or SO-C (CH 3 ) 3 , preferably for SO-CH 3 or SO-C 2 H 5 ;
  • Nonafluorobutylsulfinyl preferably for SO-CF 3 , S0-CH 2 C1 or
  • C ⁇ -C4-haloalkylsulfonyl for: a C ⁇ -C4-alkylsulfonyl - as mentioned above - which is partially or fully substituted by fluorine, iodine, chlorine, bromine and / or substituted, eg S0 2 -CH 2 F, -CHF 2 S0 2 , S0 2 -CF 3 , S0 2 -CH 2 C1, S0 2 -CH (C1) 2 , S0 2 -C (Cl) 3 , chlorofluoromethylsulfonyl,
  • N, N-dipropylamino N [CH (CH 3 ) 2 ] 2 , N, N-dibutylamino, N, N-di- (l-methylpropyl) amino, N, N-di- (2-methylpropyl) amino,
  • Di- (-C 4 -alkyl) -aminocarbonyl for example N, N-dimethylaminocarbonyl, N, N-diethylaminocarbonyl,
  • Di- (C ⁇ -C alkyl) aminocarbonyl monosubstituted C ⁇ -C 4 alkyl for example, di- (C ⁇ -C4 alkyl) aminocarbonylmethyl, 1- or 2-di (C 1 -C 4 alkyl) —Aminocarbonylethyl, 1-, 2- or 3-di- (-C-C 4 alkyl) —aminocarbonylpropyl; Di- (C 1 -C 4 alkyl) aminocarbonyl-C ⁇ -C 4 alkoxy: By di- (C ⁇ -C4 alkyl) aminocarbonyl monosubstituted C ⁇ -C 4 alkoxy, such as di- (C ⁇ -C -alkyl) —aminocarbonylmethoxy, 1- or 2-di- (-C-alkyl) —aminocarbonylethoxy, 1-, 2- or 3-di- (-C-C 4 -alkyl) —aminocarbonylpropoxy;
  • Di- (C ⁇ -C4 alkyl) -minocarbonyl-C ⁇ -C 4 alkyl by di- (C ⁇ -C4 alkyl) aminocarbonyl monosubstituted C ⁇ -C 4 alkylthio, for example, di- (C 1 -C -alkyl) -aminocarbonylmethylthio, 1- or
  • C 2 -C 6 alkenyl for: vinyl, prop-1-en-l-yl, allyl, 1-methylethenyl, 1-buten-l-yl, l-buten-2-yl, l-buten-3-yl , 2-butene-1-yl, 1-methyl-prop-1-en-1-yl, 2-methyl-prop-1-en-1-yl, 1-methyl-prop-2-en-1-yl , 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-l-en-l-yl, l-methyl-but-2-en-l -yl, 2-methyl-but-2-en-l-yl, 3-methyl-but-2-en-l-yl, l-methyl
  • C 2 -C 6 haloalkenyl for: C 2 -C 6 alkenyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for example 2-chlorovinyl, 2-chloroallyl, 3-chloroallyl, 2 , 3-dichloroallyl,
  • C 2 -C 6 alkynyl for: ethynyl and C 3 -C 6 alkynyl such as prop-1-in-1-yl, prop-2-in-1-yl, n-but-1-in-1-yl , n-but-l-in-3-yl, n-but-l-in-4-yl, n-but-2-in-l-yl, n-pent-1-in-l-yl, n Pent-1-in-3-yl, n-pent-1-in-4-yl, n-pent-1-in-5-yl, n-pent-2-in-1-yl, n-pent -2-in-4-yl, n-pent-2-yn-5-yl, 3-methyl-but-l-yn-3-yl, 3-methyl-but-l-yn-4-yl, n Hex-1-in-yl, n-hex-1-in-3-yl, n-hex
  • C 2 -C 6 haloalkynyl for: C 2 -C 6 alkynyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for example
  • C 3 -C 8 cycloalkyl for: cyclopropyl, cyclobutyl, cyclopentyl,
  • C 3 -C 8 cycloalkyl-C 4 -C 4 alkyl for: cyclopropylmethyl, 1-cyclopropyl-ethyl, 2-cyclopropyl-ethyl,
  • C 3 -C 8 cycloalkyl -CC 4 -alkyl which contains a carbonyl or thiocarbonyl ring member, for example for cyclobutanon-2-ylmethyl, cyclobutanon-3-ylmethyl, cyclopentanon-2-ylmethyl, cyclopentanon-3-ylmethyl , Cyclohexanon-2-ylmethyl, Cyclohexanon-4-ylmethyl, Cycloheptanon-2-ylmethyl, Cyclooctanon-2-ylmethyl, Cyclobutanthion-2-ylmethyl, Cyclobutanthion-3-ylmethyl, Cyclopentanthion-2-ylmethyl, Cyclopentanthion-3-ylmethyl -2-ylmethy1, cyclohexanthion-4-ylmethy1, cycloheptanthion-2-ylmethy1, cyclooctanthion-2-ylmethy1,
  • 3- to 7-membered heterocyclyl is to be understood as meaning both saturated, partially or completely unsaturated and aromatic heterocycles having one, two or three heteroatoms, the heteroatoms being selected from nitrogen atoms, oxygen and sulfur atoms.
  • Saturated 3- to 7-membered heterocyclyl can also contain a carbonyl or thiocarbonyl ring member.
  • saturated heterocycles which may contain a carbonyl or thiocarbonyl ring member are: oxiranyl, thiiranyl, aziridin-1-yl, aziridin-2-yl, diaziridin-1-yl, diaziridin-3-yl, oxetan-2- yl, 0xetan-3-yl, thietan-2-yl, thietan-3-yl, azetidin-1-yl, azetidin-2-yl, azetidin-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, Tetrahydrothiophene-2-y1, tetrahydrothiophene-3-y1, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, l, 3-dioxolan-2-yl, l, 3-diox
  • unsaturated heterocycles which can contain a carbonyl or thiocarbonyl ring member are: dihydrofuran-2-yl, l, 2-oxazolin-3-yl, l, 2-oxazolin-5-yl, 1, 3-oxazolin 2-yl.
  • aromatic heterocyclyl examples include the 5- and 6-membered aromatic, heterocyclic radicals, for example furyl such as 2-furyl and 3-furyl, thienyl such as 2-thienyl and 3-thienyl, pyrrolyl such as 2-pyrrolyl and 3-pyrrolyl, isoxazolyl such as 3-isoxazolyl, 4-isoxazolyl and 5-isoxazolyl, isothiazolyl such as 3-isothiazolyl, 4-isothiazolyl and 5-isothiazolyl, pyrazolyl such as 3-pyrazolyl, 4-pyrazolyl and 5-pyrazolyl, oxazolyl such as 2-0xazolyl and 4-0xazolyl 5-0xazolyl, thiazolyl such as 2-thiazolyl, 4-thiazolyl and 5-thiazolyl, imidazolyl such as 2-imidazolyl and 4-imidazolyl, oxadiazolyl such as l, 2,4-
  • fused rings in addition to phenyl are the aforementioned heteroaromatic groups, in particular pyridine, pyrazine, pyridazine, pyrimidine, furan, dihydrofuran, thiophene, dihydrothiophene, pyrrole, dihydropyrrole, 1,3-dioxolane, 1,3-dioxolan-2-one, isoxazole , Oxazole, oxazolinone, isothiazole, thiazole, pyrazole, pyrazoline, imidazole, imidazolinone, dihydroimidazole, 1,2,3-triazole, 1, 1-dioxodihydroisothiazole, dihydro-l, 4-dioxin, pyridone, dihydro-l, 4-oxazine , Dihydro-1, 4-oxazin-2-one, Dihydro-l, 4-oxazin-3-one, Dihydro
  • 3-arylisothiazoles I as herbicides or desiccants / defoliants, those compounds I are preferred in which R 2 ⁇ hydrogen or R 4 ⁇ hydrogen and preferably in which R 2 and R 4 ⁇ hydrogen. Furthermore, compounds I are preferred in which the variables have the following meaning, in each case individually or in combination:
  • R 2 halogen, preferably chlorine, cyano, -CC 4 alkyl, preferably methyl, and especially chlorine;
  • R 3 is hydrogen, fluorine or chlorine
  • R 4 halogen, especially chlorine, or cyano
  • X is a chemical bond, methylene, ethane-1, 2-diyl,
  • Ethen-l, 2-diyl which may be unsubstituted or a substituent selected from C 1 -C 4 -alkyl, especially methyl, or halogen, especially chlorine, for example 1- or
  • R 5 hydrogen, fluorine, nitro, chlorosulfonyl, -OYR 7 , -O-CO-YR 7 , -N (YR 7 ) (ZR 8 ), -N (YR 7 ) -S0 2 -ZR 8 , -N (S0 2 -YR 7 ) (S0 2 -ZR 8 ),
  • variables R 7 , R 8 , R 9 , Y, Z mentioned in the definition of the variables R 5 preferably have the following meanings:
  • Y, Z independently of one another are a chemical bond or methylene
  • C 6 haloalkyl in particular, are hydrogen, C 6 haloalkyl, C ⁇ -C 4 -alcohol xy-C ⁇ -C alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -CH (R 10) (R 11 ), -C (R 10 ) (R 1: L ) -C0-0R 12 , -C (R 10 ) (R 11 ) -CO-N (R 12 ) R 13 , phenyl or C 3 -C 8 cycloalkyl , particularly preferably hydrogen,
  • R 10 , R 11 , R 12 and R 13 independently of one another preferably have the meanings given below:
  • R 10 is hydrogen or -CC 4 alkyl, especially methyl;
  • R 11 is hydrogen or methyl;
  • R 12, R 13 are independently hydrogen, Ci-C ö alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-C ⁇ - C-alkyl, or -CC 4 alkoxy -CC-alkyl, especially hydrogen or -CC 6 alkyl;
  • R 9 C ⁇ -C 6 -alkyl, C 4 alkoxycarbonyl-C ⁇ -C 4 alkyl, C 2 -C 6 alkenyl, in particular methyl or ethyl.
  • R 4 and XR 5 or XR 5 and R 6 in formula I can also form a 3- or 4-membered chain which, in addition to carbon, can have 1, 2 or 3 heteroatoms, selected from nitrogen, oxygen and sulfur atoms, which may be unsubstituted or in turn bear one, two or three substituents, and the members of which may also comprise one or two non-adjacent carbonyl, thiocarbonyl or sulfonyl groups.
  • Such connections are referred to below as connections IC or ID.
  • R 17 is hydrogen, hydroxy, C ⁇ -C6 alkyl, Ci-C ⁇ -haloalkyl, C 2 -C 6 alkenyl, CC 6 haloalkenyl, C 2 -C 6 alkynyl, C ⁇ -C 4 -alkoxy, C 4 -haloalkoxy, C 3 -C 6 -alkenoxy, C 3 -C 6 -alkynyloxy, -C-C 4 -alkylsulfonyl, -C-C 4 -haloalkylsulfonyl, -C-C 4 -alkylcarbonyl, C ⁇ -C 4 -haloalkylcarbonyl, C ⁇ - C 4 -alkoxycarbonyl, -C-C 4 -alkoxy-C 1 -C 4 -alkyl, C ⁇ -C 4 -alkoxycarbonyl-C 1 -C-alkyl, C ⁇ -C 4 -alkoxycarbonyl
  • R 18 is hydrogen, halogen, cyano, amino, -CC 6 alkyl,
  • C ⁇ -C 6 haloalkyl C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C ⁇ -C 4 -alkoxy, C 4 haloalkoxy, C 3 -C 6 -Alkenyloxy, C 3 -C 6 -alkynyloxy, -C-C 4 -alkylamino, di- (-C-C 4 -alkyl) amino, C ⁇ -C 4 -haloalkoxy, C ⁇ -C 4 -alkylthio, C ⁇ -C 4 -haloalkylthio , C ⁇ -C alkylsulfinyl, C ⁇ -C4-haloalkylsulfinyl, C ⁇ -C4-alkylsulfonyl, C ⁇ -C4-haloalkylsulfonyl, C ⁇ -C -Alcarbony1, C ⁇ -C 4
  • Ring heteroatom selected from oxygen, nitrogen or sulfur.
  • R 15 to R 18 preferably have the following meanings:
  • R 15 , R 16 independently of one another are hydrogen or methyl
  • R 17 is hydrogen, hydroxy, -CC 4 -alkyl, -C-C 4 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C ⁇ -C 4 -alkoxy, C ⁇ -C 4 -haloalkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -alkynyloxy, -CC -alkoxycarbonyl -CC-C 4 -alkyl, Cj-C 4 -alkoxycarbonyl- C ⁇ -C 4 -alkoxy, C 3 -C 8 -cycloalkyl , C 3 -C 8 cycloalkyl -CC 4 -alkyl or phenyl -CC 4 -alkyl or 3-, 4-, 5- or 6-membered, preferably 5- or 6-membered, preferably saturated heterocyclyl, which has a ring heteroatom selected from oxygen, nitrogen or sulfur
  • R 18 is hydrogen, halogen, amino, C ⁇ -C 6 -alkyl, C ⁇ -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -halogenalkenyl, C 2 -C 6 -alkynyl, C ⁇ -C - Alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C ⁇ -C 4 alkylamino, di- (C ⁇ -C alkyl) amino, C ⁇ -C 4 alkylthio, C ⁇ -C 4 alkoxycarbonyl-C ⁇ -C 4 alkyl c ⁇ , -C 4 alkoxycarbonyl-C ⁇ -C 4 alkoxy,
  • Q and R 3 have the meanings mentioned above, Q being in particular CH and R 3 in particular having the meanings indicated as preferred.
  • the compounds IC those compounds are particularly preferred in which R 4 together with XR 5 for a chain of the formula -0-CH (R 15 ) -CO-N (R 17 ) -, -S-CH (Ri 5 ) - CO-N (Ri 7 ) - stands.
  • R 15 and R “have in particular the meanings given as preferred.
  • the compounds IC are particularly preferred in which the nitrogen atom of the chain -0-CH (R 15 ) -CO-N (R 17 ) -,
  • R 3 and R 4 in these compounds have the meanings mentioned above, in particular the meanings given as preferred.
  • 3-arylisothiazoles of the formula I according to the invention can be prepared based on known processes for the preparation of 3-arylisothiazoles and in particular by the synthetic routes described below.
  • aryl means a radical of the formula:
  • the compounds of the formula I can be prepared, for example, by building up the isothiazole ring from suitably substituted aryl compounds.
  • I An example of this is the construction of 4-amino-3-arylisothiazoles of the formula A4 from benzyl nitriles of the formula AI in accordance with the following reaction sequence:
  • the Z radical in 4-amino-3-arylisothiazole A4 is then converted into the substituents R 1 using standard methods.
  • the conversion of the NH 2 group into other substituents R 2 is also possible using standard methods. In principle, it is irrelevant whether the amino group in A4 is first converted into another substituent R 2 , giving a compound A5, or the group Z into a substituent R 1 , giving a compound A5 '.
  • a benzyl nitrile of the formula AI is nitrosated in the presence of a base with a nitrosating agent, for example an alkyl nitrite such as i-amyl nitrite, and then converted into tosyloxime A2 with tosyl chloride ,
  • Aryl has the aforementioned meaning in the formulas AI, A2 and A4.
  • the tosyloxime A2 is then reacted in the presence of a base with a mercaptan of the formula A3, in which Z represents an electron-withdrawing radical, for example a carboxy-C 1 -C 4 -alkyl or cyano radical, to give the 3-arylisothiazole of the formula A4 ,
  • a base with a mercaptan of the formula A3, in which Z represents an electron-withdrawing radical, for example a carboxy-C 1 -C 4 -alkyl or cyano radical, to give the 3-arylisothiazole of the formula A4 .
  • Z represents an electron-withdrawing radical, for example a carboxy-C 1 -C 4 -alkyl or cyano radical
  • Suitable bases for the nitrosation of Al are, for example: alkali metal hydroxides, e.g. B. sodium hydroxide, alkali metal carbonates such as potassium and sodium carbonate, alkali metal alcoholates such as sodium ethanolate, alkali metal hydrides such as sodium hydride and tertiary amines such as triethylamine.
  • alkali metal hydroxides e.g. B. sodium hydroxide
  • alkali metal carbonates such as potassium and sodium carbonate
  • alkali metal alcoholates such as sodium ethanolate
  • alkali metal hydrides such as sodium hydride and tertiary amines such as triethylamine.
  • bases for the conversion of A2 with A3 to A4 for example, the following are suitable: nitrogen ases such as pyridine, morpholine, or alkali metal alcoholates or sodium ethanolate.
  • benzyl nitriles used as starting compounds can be prepared from a corresponding benzoic acid compound A6 by processes known per se from the literature, for example by the following reaction sequence: i) ii) iii)
  • A6 (A7) (A8) (AI) i Reduction of A6 to benzyl alcohol A7, for example by reacting A6 with a borane complex such as BH 3 -S (CH 3 ) 2 in an inert organic solvent, for example an ether such as Diethyl ether or tetrahydrofuran or in a halogenated hydrocarbon such as dichloromethane or in a mixture of the abovementioned solvents; ii halogenation of A7 to benzyl bromide A8, for example by reacting A7 with CBr 4 / PPh 3 in one of the abovementioned solvents, and subsequently iii reacting the bromide A8 in the sense of a Kolbe nitrile synthesis with NaCN in an org.
  • Solvents for example in acetone, ethanol or triethylene glycol.
  • Suitable nitrosating reagents are: nitrosonium tetrafluoroborate, nitrosyl chloride, nitrosylsulfuric acid, alkyl nitrites, such as e.g. t-butyl nitrite or salts of nitrous acid, e.g. Sodium nitrite.
  • a 5-amino-3-arylisothiazole B2 is first prepared by cyclization of a ⁇ -iminothioamide of the formula B1.
  • a compound of the formula B3 according to the invention is then prepared from B2 by converting the amino group in the 5-position of the isothiazole ring.
  • R 2 ' is hydrogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl, preferably hydrogen.
  • R2 'in B2 stands for hydrogen, one can convert the group R2' into a halogen atom before converting the 5-amino group into a group R 1 (cf. T. Naito et al., Chem. Phar. Bull. 1968, 16 (1), 148-159, and the halogenation of the 4-position of the isothiazole part of I) described below under B).
  • the conversion is initiated by nitrosation of the amino group in the 5-position of the isothiazole ring.
  • the diazonium compound obtained is then further converted as follows:
  • R 1 alkoxy or haloalkoxy: conversion of the diazonium group into hydroxy ⁇ eg by phenol boiling: cf. for example Org. Synth. Coll. Vol. 3 (1955), p. 130 ⁇ .
  • the hydroxy compounds are then converted in the sense of ether synthesis by reaction with alkyl halides, alkoxy or halogenoalkoxy groups.
  • the hydroxy group can also be converted to the corresponding (halogen) alkylsulfonyloxy group by reaction with (halogen) alkylsulfonyl chloride.
  • R 1 mercapto, -CC 6 alkylthio or haloalkylthio
  • the mercapto compounds are then converted in the sense of a thioether synthesis by reaction with alkyl halides into alkthio or halogenalkthio groups, for example by reaction with methyl halide in the methylthio group or by reaction with chloro- or bromo-difluoromethane in the diefluoromethylthio group.
  • the Alkthio- or Halogenalkthio phenomenon can then be converted by selective oxidation in (halogen) alkylsulfinyl or (halogen) alkylsulfonyl groups.
  • the 5- (halogen) alkylsulfonyl-4-ha- can be obtained from the 5- (halogen) alkylthio-4-halogenoisothiazoles.
  • Produce logenisothiazoles see T. Naito, Chem. Pharm. Bull. 1968, 16 (1), 148-159).
  • the reaction is preferably carried out in the presence of a strong base.
  • R 1 difluoromethoxy
  • This reaction is preferably carried out in the presence of a base.
  • suitable bases are alkali metal hydroxides such as sodium or potassium hydroxide, alkali metal carbonate and hydrogen carbonate such as potassium or
  • Sodium carbonate or bicarbonate or an organic base e.g. Alcoholates such as sodium or potassium methylate or ethylate, especially tertiary amines such as triethylamine or pyridine.
  • the gaseous chlorodifluoromethane is preferably slowly introduced into the reaction mixture which contains the 5-hydroxyisothiazole B3d, which is preferably dissolved or suspended in a solvent, optionally a base and / or further catalysts.
  • excess chlorodifluoromethane gas is preferably retained by a low-temperature cooler.
  • the reaction can also be carried out under elevated chlorodifluoromethane pressure in a closed apparatus (autoclave) at pressures between approximately 0.1 and 100 bar.
  • the reaction temperature is usually between the melting point and the boiling point of the reaction mixture, preferably at temperatures in the range from 50 to 150 ° C.
  • chlorodifluoromethane based on the 5-hydroxyisothiazole B3d.
  • the excess can, for example, be up to five times the molar amount of the 5-hydroxyisothiazole B3d used.
  • Suitable solvents are inert organic solvents, for example hydrocarbons such as toluene or hexane,
  • Ethers such as diethyl ether, dimethoxyethane, methyl t-butyl ether, dioxane or tetrahydrofuran (THF), amides such as dimethylformamide (DMF), N, N-dimethylacetamide (DMA) or N-methylpyrrolidone (NMP), -C-C 6 alkanols such as methanol or ethanol, or also mixtures of such solvents with one another or with water.
  • a phase transfer catalyst e.g.
  • a tetraalkylammonium salt such as tetrabutylammonium chloride or a crown ether such as 18-crown-6 or 15-crown-5 in catalytic amounts (0, 01-20 mol%, based on 5-hydroxyisothiazole).
  • the reaction is preferably carried out in the presence of a base such as triethylamine pyridine or dimethylaminopyridine.
  • the halogenation of the alkyl group of the 5-alkylisothiazoles is achieved, for example, by radical halogenation with, for example, chlorine, sulfuryl chloride or N-halosuccinimides such as N-chloro- or N-bromosuccinimide. As a rule, the monohalogen compound will be obtained here.
  • the 5-trichloromethyl-3-arylisothiazoles can be obtained from the corresponding 5-methyl compounds by photochlorination using standard methods (for example analogous to Houben Weyl 5/3, Methods of Organic Chemistry, Georg Thieme Verlag, p. 735 ff. Or analogous to organic agents, 17th edition, p. 161 ff.).
  • 3-aryl-5-trifluoromethylisothiazoles of the formula I can also be prepared from the 5-trichloromethylisothiazoles by chlorine-fluorine exchange.
  • the conversion is accomplished, for example, by reacting the trichloromethyl compound with HF, HF / SbCl 5 or SbF 5 (see, for example, Houben-Weyl E 10a, p. 133ff; Houben-Weyl 5/3, p. 119).
  • A4 5-alkylthio-4-cyanoisothiazoles can also be prepared analogously to a method described in the literature (see Houben-Weyl E8a, p. 686) according to the following scheme.
  • A5 3-arylisothiazoles can also be prepared according to the scheme below by reacting 5-aryl-l, 3,4-oxthiazoles with acetylene carboxylic acid esters and then converting the carboxylic ester group located in the 5-position of the isothiazole ring into a radical R 1 .
  • the conversion of 5-aryl-l, 3,4-oxthiazoles with acetylenecarboxylic acid esters into 3-arylisothiazole-5-carboxylic acid esters was carried out by RK Howe 'et al. (J. Org. Chem. 43 1978 3742-3745 and cited therein).
  • 5-Aryl-l, 3,4-oxthiazoles are in turn accessible starting from aryl carboxylic acids.
  • the arylcarboxylic acids are reacted in a known manner to give the carboxamide, which is then reacted with chlorocarbonylsulfenyl chloride (Cl-C (O) -S-Cl) in an inert organic solvent to give 5-aryl-1,3,4-oxthiazole.
  • 3-arylisothiazoles I can be prepared by functionalizing the 4-position of the isothiazole ring, for example by halogenating 3-arylisothiazoles in which R 2 is hydrogen:
  • Suitable halogenating agents are, for example, fluorine, DAST (diethylaminosulfur trifluoride), chlorine, N-chlorosuccinimide, sulfuryl chloride, thionyl chloride, phosgene, phosphorus trichloride, phosphorus oxychloride, bromine, N-bromosuccinimide, phosphorus tribromide and phosphorus oxybromide.
  • DAST diethylaminosulfur trifluoride
  • an inert solvent / diluent e.g. in a hydrocarbon such as n-hexane and toluene, a halogenated hydrocarbon such as dichloromethane, carbon tetrachloride and chloroform, an ether such as methyl 1-tert. -butyl ether, an alcohol such as methanol and
  • Ethanol a carboxylic acid such as acetic acid or in a polar aprotic solvent such as acetonitrile.
  • the reaction temperature is usually between the melting point and the boiling point of the reaction mixture, preferably from 0 to 100 ° C.
  • the halogenating agent is used in an approximately equimolar amount or in excess, up to about five times the molar amount, based on the amount of starting compound.
  • Suitable nitration reagents are, for example, nitric acid in different concentrations, also concentrated and fuming nitric acid, mixtures of sulfuric acid and nitric acid, and also acetyl nitrates and alkyl nitrates.
  • the reaction can be carried out either solvent-free in an excess of the nitrating reagent or in an inert solvent or diluent, e.g. Water, mineral acids, organic acids, halogenated hydrocarbons such as methylene chloride, anhydrides such as acetic anhydride and mixtures of these solvents are suitable.
  • an inert solvent or diluent e.g. Water, mineral acids, organic acids, halogenated hydrocarbons such as methylene chloride, anhydrides such as acetic anhydride and mixtures of these solvents are suitable.
  • the reaction temperature is normally from -100 ° C to 200 ° C, preferably from -30 to 50 ° C
  • the reduction is usually achieved by reacting the nitro compound with a metal such as iron, zinc or tin or with
  • SnCl 2 take place under acidic reaction conditions or with a complex hydride such as lithium aluminum hydride or sodium borohydride, it being possible for the reduction to be carried out in bulk or in a solvent or diluent.
  • the solvents used are, for example, water, alcohols such as methanol, ethanol and isopropanol or ethers such as diethyl ether, methyl tert-butyl ther, dioxane, tetrahydrofuran and ethylene glycol dimethyl ether.
  • the procedure is preferably solvent-free in an inorganic acid, especially in concentrated or dilute hydrochloric acid, or in a liquid organic acid such as acetic acid or propionic acid.
  • the acid can also be treated with an inert solvent, e.g. dilute one of the above.
  • the reduction with complex hydrides is preferably carried out in a solvent, for example an ether or an alcohol.
  • the amount of acid is not critical. In order to reduce the starting compound as completely as possible, it is expedient to use at least an equivalent amount of acid.
  • the reaction temperature is generally in the range from -30 ° C. to 200 ° C., preferably in the range from 0 ° C. to 80 ° C.
  • the reaction mixture is usually diluted with water and the product by filtration, crystallization or extraction with a solvent which is largely immiscible with water, e.g. isolated with ethyl acetate, diethyl ether or methylene chloride. If desired, the product can then be cleaned as usual.
  • Suitable catalysts for this purpose are, for example, Raney nickel, palladium on carbon, palladium oxide, platinum and platinum oxide, a quantity of catalyst of 0.05 to 10.0 mol%, based on the compound to be reduced, generally being sufficient.
  • the procedure is either solvent-free or in an inert solvent or diluent, for example in acetic acid, a mixture of acetic acid and water, ethyl acetate, ethanol or in toluene.
  • reaction solution can be worked up to the product in the customary manner.
  • the hydrogenation can be carried out under normal hydrogen pressure or under elevated hydrogen pressure.
  • a nitrosating agent for example a nitrite such as sodium nitrite and potassium nitrite in an aqueous acid solution, for example in hydrochloric acid, hydrobromic acid or sulfuric acid.
  • an nitrous acid ester such as tert-butyl nitrite and isopentyl nitrite under anhydrous reaction conditions, for example in chlorine water Glacial acetic acid, in absolute alcohol, in dioxane or tetrahydrofuran, in acetonitrile or in acetone.
  • a copper (I) salt such as copper (I) cyanide, chloride, -bromide and iodide, or with an alkali metal salt solution (see. AI).
  • an aqueous acid preferably sulfuric acid.
  • a copper (II) salt such as copper (II) sulfate can have an advantageous effect on the course of the reaction, which is generally carried out at 0 to 100 ° C., preferably at the boiling point of the reaction mixture.
  • Meerwein arylation is usually the reaction of the diazoniu salts with alkenes or alkynes.
  • the alkene or alkyne is preferably used in excess, up to about 3000 mol%, based on the amount of the diazonium salt.
  • reaction temperatures are normally from -30 ° C. to 50 ° C.
  • All reactants are preferably used in approximately stoichiometric amounts, but an excess of one or the other component, up to approximately 3000 mol%, can also be advantageous.
  • Usable reducing agents are, for example, transition metals such as iron, zinc and tin (see, for example, "The Chemistry of the Thiol Group", John Wiley, 1974, p. 216).
  • Halosulfonation can be carried out without solvent in excess sulfonating reagent or in an inert solvent / diluent, e.g. in a halogenated hydrocarbon, an ether, an alkyl nitrile or a mineral acid.
  • Chlorosulfonic acid is both the preferred reagent and solvent.
  • the reaction temperature is usually between 0 ° C and the boiling point of the reaction mixture.
  • reaction mixture is e.g. mixed with water, after which the product can be isolated as usual.
  • IA ⁇ XR 5 CH (halogen) 2 ⁇
  • Suitable solvents are organic acids, inorganic acids, aliphatic or aromatic hydrocarbons, which can be halogenated, and ethers, sulfides, sulfoxides and sulfones.
  • halogenating agents are chlorine, bromine, N-bromosuccinimide, N-chlorosuccinimide or sulfuryl chloride.
  • a radical initiator for example an organic peroxide such as dibenzoyl peroxide or an azo compound such as azobisisobutyronitrile, or irradiation with light can have an advantageous effect on the course of the reaction.
  • the amount of halogenating agent is not critical. Both substoichiometric amounts and large surpluses
  • a catalytic amount is usually sufficient.
  • the reaction temperature is normally from -100 ° C to 200 ° C, especially at 10 to 100 ° C or the boiling point of the reaction mixture.
  • IA ⁇ X CH 2 ;
  • R 5 -OYR 7 , -O-CO-YR 7 , -N (YR 7 ) (ZR 8 ),
  • ⁇ XR 5 CH 2 -halogen ⁇ -N (YR 7 ) (- 0-ZR 8 ), - SYR 7 ⁇
  • the nucleophile used is either the corresponding alcohols, thiols, carboxylic acids or amines, in which case the reaction is preferably carried out in the presence of a base (for example an alkali metal or alkaline earth metal hydroxide or an alkali metal or alkaline earth metal carbonate), or the reaction of the alcohols, Thiols, carboxylic acids or amines with a base (for example an alkali metal hydride) of alkali metal salts of these compounds.
  • a base for example an alkali metal or alkaline earth metal hydroxide or an alkali metal or alkaline earth metal carbonate
  • a base for example an alkali metal hydride
  • Aprotic organic solvents e.g. Tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, or hydrocarbons such as toluene and n-hexane.
  • the reaction is carried out at a temperature between the melting point and the boiling point of the reaction mixture, preferably at 0 to 100 ° C.
  • the reaction temperature is usually 0 to 120 ° C
  • Dimethyl sulfoxide for example, is suitable as a solvent.
  • the olefination is preferably carried out by the Wittig method or one of its modifications, phosphorylides, phosphonium salts and phosphonates being suitable as reaction partners, or by aldol condensation.
  • alkali metal alkyls such as n-butyllithium
  • alkali metal hydrides and alcoholates such as sodium hydride, sodium ethanolate and potassium tert-butanolate
  • alkali metal and alkaline earth metal metal hydroxides such as calcium hydroxide are particularly suitable.
  • reaction temperature is -40 to 150 ° C.
  • the phosphonium salts, phosphonates or phosphorylides required as reactants are known or can be prepared in a manner known per se ⁇ cf. see, for example, Houben-Weyl, Methods of Organic Chemistry, Vol. El, pp. 636ff. and Vol. E2, pp. 345ff., Georg Thieme Verlag Stuttgart 1982; Chem. Ber. 95, 3993 (1962) ⁇ .
  • I ⁇ XR 5 -CO-YR 7 ⁇
  • the reaction is carried out in the manner described for the alkylation of phenols (see for example for the ethersynthesis J. March "Advanced Organic Chemistry" 3rd ed. p. 342 f. and literature cited therein), preferably in the presence of a base such as NaOH or an alkali metal carbonate or sodium hydride.
  • Aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone or dimethylacetonitrile are preferred as reaction media.
  • hydrogen peroxide or organic peracids e.g.
  • Suitable solvents are organic solvents which are inert to oxidation, such as hydrocarbons such as toluene or hexane, ethers such as diethyl ether, dimethoxyethane, methyl t-butyl ether, dioxane or tetrahydrofuran, alcohols such as methanol or ethanol, or else mixtures of such solvents with one another or with water ,
  • the solvent used is preferably the underlying organic acid, for example formic, acetic or trifluoroacetic acid, if appropriate in a mixture with one or more of the abovementioned solvents.
  • the reaction temperature is normally between the melting point and the boiling point of the reaction mixture, preferably at 0-150 ° C.
  • Halogenating agents are phosphoryl halides such as P0C1 3 or POBr 3 , phosphorus halides such as PC1 5 , PBr 5 , PC1 3 or PBr 3 , phosgene or organic or inorganic acid halides such as, for example, trifluoromethanesulfonic acid chloride, acetyl chloride, bromoacetyl bromide, acetyl bromide, benzoyl bromide, benzyl , Phthaloyl dichloride, toluenesulfonyl chloride, thionyl chloride or sulfuryl chloride. If appropriate, it can be advantageous to carry out the reaction in the presence of a base, such as trimethylamine or triethylamine or hexamethyldisilazane.
  • a base such as trimethylamine or triethylamine or hexamethyldisilazane.
  • Suitable solvents are inert organic solvents, such as hydrocarbons such as toluene or hexane, ethers such as diethyl ether, dimethoxyethane, methyl t-butyl ether, dioxane or tetrahydrofuran, amides such as DMF, DMA or NMP, or mixtures thereof. If a reaction is carried out with a liquid halogenating agent, this can preferably also be used as a solvent, possibly in a mixture with one of the aforementioned.
  • the reaction temperature is usually between the melting and boiling point of the reaction mixture, preferably at 50-150 ° C.
  • halogenating agent or base in up to about a five-fold molar excess, based on the IX used.
  • the following diagram gives examples of the connection classes that can be obtained in this way.
  • IB ⁇ XR 5 -N (YR 7 ) (ZR 8 ) ⁇
  • IB ⁇ XR 5 -N (YR 7 ) (OZR 8 ) ⁇
  • Nitroalkanes such as nitromethane, malonic acid derivatives such as diethyl malonate or cyanoacetic acid derivatives such as methyl cyanoacetate are considered. What was said under C.3 applies to carrying out this reaction.
  • the compounds IC-1, IC-2, ID-1 and ID-2 can be prepared in analogy to known processes by ring closure reaction from the corresponding ortho-aminophenols or ortho-mercaptoanilines of the formulas IA-1, IA-2, IA-3 or IA-4 are built; numerous methods for this are known from the literature (see, for example, Houben-Weyl, Methods of Organic Chemistry, vol. E8a, pp. 1028ff., Georg-Thieme-Verlag, Stuttgart 1993 and vol. E8b, pp. 881ff., Georg- Thieme-Verlag, Stuttgart 1994).
  • the variables R 1 , R 2 , R 3 and R 4 have the abovementioned meanings.
  • the variables X 1 , X 2 , X 3 and X 4 stand independently for OH or SH.
  • This process comprises the reaction of an aminophenylisothiazole of the formula IA-5, IA-6, IA-7 or IA-8 with halogen and ammonium thiocyanate or with an alkali metal or alkaline earth metal thiocyanate.
  • This gives compounds of the general formulas iC-la, iC-lb or ID-la or ID-Ib (compounds IC-1 or ID-1 in which R 18 is NH 2 ).
  • Preferred halogen is chlorine or bromine; among the alkali / alkaline earth metal thiocyanates, sodium thiocyanate is preferred.
  • the reaction is carried out in an inert solvent / diluent, e.g. in a hydrocarbon such as toluene and hexane, in a halogenated hydrocarbon such as dichloromethane, in an ether such as tetrahydrofuran, in an alcohol such as ethanol, in a carboxylic acid such as acetic acid, or in a polar aprotic solvent / diluent such as dimethylformamide, acetonitrile and dimethyl sulfoxide.
  • an inert solvent / diluent e.g. in a hydrocarbon such as toluene and hexane, in a halogenated hydrocarbon such as dichloromethane, in an ether such as tetrahydrofuran, in an alcohol such as ethanol, in a carboxylic acid such as acetic acid, or in a polar aprotic solvent / diluent such as dimethylformamide,
  • the reaction temperature is usually between the melting point and the boiling point of the reaction mixture, preferably from 0 to 150 ° C.
  • halogen and ammonium thiocyanate or alkali metal / earth alkali metal thiocyanate are preferably used in an approximately equimolar amount or in excess, up to about 5 times the molar amount, based on the amount of IA-5, IA- 6, IA-7 or IA-8.
  • a variant of the process consists in first of all adding the NH 2 group of the aminophenylisothiazoles IA-5, IA-6, IA-7 or IA-8 to a thiourea group (NH - with ammonium thiocyanate or an alkali metal or alkaline earth metal thiocyanate).
  • the conversion of the amino group in the aminophenylisothiazoles of the formula IA-5, IA-6, IA-7 or IA-8 into an azide group usually takes place in two stages, i.e. by diazotization of the amino group and subsequent treatment of the diazonium salt thus obtained with an azide.
  • the information given in process C1) applies to carrying out the diazotization.
  • the conversion into the arylazides is preferably carried out by reacting diazonium salts with an alkali metal or alkaline earth metal azide such as sodium azide or by reaction with trimethylsilyl azide.
  • a mineral acid such as phosphoric acid or a silylating reagent such as a mixture of phosphorus pentoxide and hexamethyldisiloxane
  • the reaction is preferably carried out at elevated temperature, for example at the boiling point of the mixture.
  • those compounds of the formula I in which XR 5 forms a chain -0-C (R i5 , R i6 ) -CO-N (R i7 ) - with R 4 or with R 6 can also form from the nitrophenoxyacetic acid derivatives of Formulas IA-9, IA-10, IA-11 and IA-12 can be prepared.
  • the conversion is achieved by reducing the nitro groups in IA-9, IA-10, IA-11 or IA-12, with a ring-closing reaction to the compounds of the formula IC-3a, IC-3b, ID-3a generally occurring simultaneously with the reduction or ID-3b occurs.
  • R i7 stands for H or OH.
  • R a is a nucleophilically displaceable leaving group, for example a C 1 -C 4 -alkyl radical such as methyl or ethyl.
  • reaction products can be converted into further compounds of the formula IC-3 or ID-3 by alkylation.
  • the statements made in Section C.4 apply analogously to the implementation of these reactions.
  • transition metal compounds examples include compounds of manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver or gold, in particular of copper, manganese, palladium, cobalt or nickel.
  • Examples of compounds of the aforementioned transition metals are their halides such as MnCl 2 , MnBr 2 , Mnl 2 , ReCl 3 , ReBr 3 , Rel 3 , ReCl 4 , ReBr 4 , Rel 4 , ReCl 5 , ReBr 5 , ReCl 6 , FeCl 2 , FeBr 2 , Fel 2 , FeCl 3 , FeBr 3 , RuCl 2 , RuBr 2 , Rul 2 , RuCl 3 , RuBr 3 , Rul 3 , Osl, OsI 2 , OsCl 3 , OsBr 3 , 0sl 3 , OsCl 4 , OsBr, OsCl 5 , C ⁇ Cl 2 , C ⁇ Br 2 , C0I 2 , RhCl 3 , RhBr 3 , Rhl 3 , IrCl 3 , IrBr 3 ,
  • a copper (II) and / or a copper (I) compound, in particular a copper (I) halide is used as the transition metal, for example copper (I) chloride, copper (I) bromide or copper (I) iodide.
  • a cocatalyst in addition to the transition metal compound which catalyzes the cyclization of X to I-D, a cocatalyst can also be used, which is a compound which is a complex ligand for the respective transition metal.
  • cocatalysts examples include phosphines such as triphenylphosphine, tri-o-tolylphosphine, tri-n-butylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, phosphites such as trimethyl-, triethyl- or Triisopropylphosphite, sulfides such as dimethyl sulfide, and cyanide or carbon monoxide. If desired, the cocatalyst is generally used in at least an equimolar amount, based on the transition metal.
  • phosphines such as triphenylphosphine, tri-o-tolylphosphine, tri-n-butylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane, phosphites such as
  • the transition metal compounds can also be used as complex compounds which preferably have one or more of the aforementioned cocatalysts as ligands.
  • Examples of such compounds are [NiCl 2 (PPh 3 ) 2 ], [Pd (PPh 3 )], [PdCl 2 (PPh 3 ) 2 ], [PdCl 2 (dppe)], [PdCl 2 (dppp)], [ PdCl 2 (dppb)],
  • the transition metal compounds can also be immobilized on an inert carrier material, for example on activated carbon, silica gel, aluminum oxide, or on an insoluble polymer e.g. a styrene-divinylbenzene copolymer.
  • an inert carrier material for example on activated carbon, silica gel, aluminum oxide, or on an insoluble polymer e.g. a styrene-divinylbenzene copolymer.
  • the transition metal compounds can be used both in an equimolar amount, based on the compound X, and in a substoichiometric or superstoichiometric amount.
  • the molar ratio of transition metal to compound X used is usually in the range from 0.01: 1 to 5: 1, preferably in the range from 0.02: 1 to 2: 1, and in particular in the range from 0.05: 1 to about 1: 1.5.
  • an equimolar amount of transition metal compound is used, ie the molar ratio of transition metal to compound X used is about 1: 1.
  • the transition metal compound is particularly preferably used in a catalytic, ie sub-stoichiometric amount.
  • the molar ratio of transition metal to compound X used is then ⁇ 1: 1.
  • the molar ratio of transition metal compound to compound X used is particularly preferably in the range from 0.05: 1 to 0.8: 1, for example 0.1: 1 to 0.3: 1.
  • the process is carried out in the presence of a base.
  • Bases such as alcoholates, amides, hydrides, hydroxides, hydrogen carbonates and carbonates of alkali metals or alkaline earth metals, in particular lithium, potassium, sodium, cesium or calcium, are preferred.
  • Suitable bases are the sodium or potassium alcoholates of methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, furthermore sodium hydride and potassium hydride, calcium hydride, sodium amide, potassium amide, Sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • sodium hydride is used as the base.
  • the base used is potassium carbonate and / or potassium hydrogen carbonate.
  • the base can be used in substoichiometric, superstoichiometric or equimolar amounts.
  • At least one equimolar amount of base is preferably used.
  • the molar ratio of base (calculated as base equivalents) to compound X is in the range from 1: 1 to 1: 5 and particularly preferably in the range from 1: 1 to 1: 1.5.
  • organic solvent which are inert under the reaction conditions are suitable as solvents.
  • organic solvents which are inert under the reaction conditions are suitable as solvents.
  • these are, for example, hydrocarbons such as hexane or toluene, halogenated hydrocarbons such as 1,2-dichloroethane or chlorobenzene, ethers such as dioxane, tetrahydrofuran (THF), methyl tert-butyl ether, dimethoxyethane, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether, aprotic polar solvents, e.g.
  • hydrocarbons such as hexane or toluene
  • halogenated hydrocarbons such as 1,2-dichloroethane or chlorobenzene
  • ethers such as dioxane, tetrahydrofuran (THF), methyl tert-butyl ether, dimethoxyethane, diethylene glyco
  • organic amides such as dimethylformamide (DMF), N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), organic nitriles such as acetonitrile or propionitrile as well as tertiary nitrogen bases, e.g. Pyridine.
  • DMF dimethylformamide
  • NMP N-methylpyrrolidone
  • DMA dimethylacetamide
  • DMSO dimethyl sulfoxide
  • organic nitriles such as acetonitrile or propionitrile as well as tertiary nitrogen bases, e.g. Pyridine.
  • Aprotic polar solvents such as DMSO, DMF, NMP, DMA, acetonitrile, propionitrile, pyridine, dimethoxyethane, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether or mixtures thereof are preferably used.
  • the reaction temperature naturally depends on the reactivity of the compound X in question. As a rule, the reaction temperature will not fall below room temperature.
  • the conversion from X to ID is preferably carried out at temperatures below 200.degree by. Often one will work at elevated temperature, for example above 50 ° C, in particular above 70 ° C and particularly preferably above 100 ° C.
  • the reaction is preferably carried out at temperatures below 180 ° C. and in particular below 160 ° C.
  • the reaction product can be worked up to obtain the target compound I-D by the methods customary for this. As a rule, one will first work up extractively or remove the solvent used by customary methods, for example by distillation.
  • the target compound I-D can also be extracted from the reaction mixture after dilution of the reaction mixture with water with a volatile organic solvent, which in turn is removed by distillation.
  • the target compound can also be precipitated from the reaction mixture by adding water. This gives a crude product which contains the valuable product I-D.
  • the usual methods such as crystallization or chromatography, for example on aluminum oxides or silica gels, can be used. It is also possible to chromatograph the substances obtainable by the process on optically active adsorbates to obtain the pure isomers.
  • Compounds X are preferably used for the cyclization from X to ID, wherein R 2 in formula X preferably represents a radical other than hydrogen.
  • Compounds of the formula X are preferably used in which the variables R 1 to R 4 and R i8 independently of one another, but preferably in combination with one another, have the meanings given below:
  • R 2 halogen, cyano, -CC 4 alkyl; especially chlorine;
  • R 3 is hydrogen or halogen; especially fluorine or chlorine;
  • R 4 fluorine, chlorine or cyano
  • R i8 are hydrogen, C 4 -alkyl, C haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C ⁇ -C 4 alkoxy-C ⁇ - C -alkyl, -C-C 4 -alkoxycarbonyl-C ⁇ -C 4 -alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 -cycloalkyl-C ⁇ -C -alkyl, phenyl, phenyl-C ⁇ -C- alkyl, 4- to
  • R 18 in particular represents hydrogen, -CC 4 -alkyl, -CC-alkoxy -CC-C 4 -alkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkyl -CC-C 4 -alkyl, Phenyl or phenyl -CC 4 alkyl.
  • the compounds of the formula X are new and represent valuable intermediates in the preparation of benzoxazoles of the formula I-D.
  • the compounds of the formula X are therefore also an object of the present invention.
  • the process for the preparation of the compounds X from the compounds IA comprises the following process steps:
  • the 2-halo-3- (isothiazol-3-yl) anilines of the general formula XI and the N, N-diacyl-2-halo-3- (isothiazol-3-yl) anilines of the general formula XII are also new and represent are valuable intermediates in the production of ID from X.
  • the brominating agents and the iodizing agents are preferred among the aforementioned halogenating agents, elemental bromine being used in a preferred embodiment of the process.
  • a Lewis or Bronsted acid catalyst for example aluminum chloride or bromide, iron (III) chloride or bromide, or sulfuric acid, or a catalyst precursor from which the actual catalyst is formed during the reaction, for example iron.
  • a Lewis or Bronsted acid catalyst for example aluminum chloride or bromide, iron (III) chloride or bromide, or sulfuric acid, or a catalyst precursor from which the actual catalyst is formed during the reaction, for example iron.
  • nitric acid, iodic acid, sulfur trioxide, hydrogen peroxide or an aluminum chloride / copper (II) chloride complex can also be used as catalyst.
  • the desired halogen is used in the form of a salt-like halide, from which the halogen is released by adding an oxidizing agent.
  • halogenating agents are mixtures of sodium chloride or sodium bromide with hydrogen peroxide.
  • the halogenation is usually carried out in an inert solvent, for example a hydrocarbon such as hexane, a halogenated hydrocarbon such as dichloromethane, trichloromethane, 1,2-dichloroethane or chlorobenzene, in a cyclic ether such as dioxane, in a carboxylic acid such as acetic acid, propions - Acid or butanoic acid, a mineral acid such as hydrochloric acid or sulfuric acid or in water.
  • a hydrocarbon such as hexane
  • a halogenated hydrocarbon such as dichloromethane, trichloromethane, 1,2-dichloroethane or chlorobenzene
  • a cyclic ether such as dioxane
  • carboxylic acid such as acetic acid, propions - Acid or butanoic acid
  • mineral acid such as hydrochloric acid or sulfuric acid or in water.
  • reaction is carried out in the presence of a base, for example an alkali metal hydroxide such as KOH or the alkali metal salt of a carboxylic acid such as sodium acetate or sodium propionate.
  • a base for example an alkali metal hydroxide such as KOH or the alkali metal salt of a carboxylic acid such as sodium acetate or sodium propionate.
  • the reaction temperature is usually determined by the melting point and the boiling point of the respective solvent.
  • the process is preferably carried out at temperatures in the range from 0 to 100 ° C. and in particular in the range from 0 to 80 ° C.
  • the 2-halo-3- (isothiazol-3-yl) aniline of the formula XI obtained in the reaction i) is reacted in step ii) with an acylating agent R i8 -C (0) -L.
  • R i8 has the meanings mentioned above.
  • L stands for a usual leaving group.
  • the acylating agent is preferably used in an amount of 1.0 to 5 mol and in particular in an amount of 1.0 to 2.0 mol, based on 1 mol of compound XI.
  • an acidic or basic catalyst is used in catalytic or stoichiometric amounts in the acylation of XI.
  • the catalyst is preferably used in an amount of 0.001 to 5 mol and in particular in an amount of 0.01 to 1.2 mol, based on 1 mol of compound XI.
  • Examples of basic catalysts are nitrogen bases, e.g. Trialkylamines such as triethylamine, pyridine compounds such as pyridine itself or dimethylaminopyridine, furthermore oxobases such as sodium or potassium carbonate or the hydroxides of sodium, potassium or calcium.
  • nitrogen bases e.g. Trialkylamines such as triethylamine, pyridine compounds such as pyridine itself or dimethylaminopyridine, furthermore oxobases such as sodium or potassium carbonate or the hydroxides of sodium, potassium or calcium.
  • acidic catalysts are, in particular, mineral acids such as sulfuric acid.
  • Suitable solvents are the optionally liquid acylating agent itself or the optionally liquid catalyst.
  • Suitable solvents are also inert organic solvents, for example hydrocarbons such as hexane or toluene, halogenated hydrocarbons such as dichloromethane, trichloromethane, 1,2-dichloroethane or chlorobenzene, furthermore ethers such as dioxane, tetrahydrofuran, methyl tert-butyl ether or dimethoxyethane.
  • the reaction of XI is carried out in a liquid anhydride in the presence of concentrated sulfuric acid.
  • the reaction is carried out in a two-phase system consisting of water and a water-immiscible organic solvent. This configuration is particularly suitable when solid acylating agents, for example solid acid chlorides, are used.
  • Basic catalysts, in particular inorganic bases, are then frequently used as catalysts.
  • the reaction of XI with an anhydride (R i8 _co) 2 0 or R i8 -CO-0-CHO or a carboxylic acid R 8 -COOH is carried out in the presence of concentrated sulfuric acid in an inert solvent , Usually you need smaller amounts of acylating agents, z. B. 1 to 1.5 moles, per mole of compound XI.
  • the mono-N-acyl compounds X are surprisingly obtained directly with good yields and high selectivity, without appreciable amounts of the N, N-diacyl compounds XII being formed.
  • the diacyl compound of the general formula XII is often formed in addition to the anilide X. Depending on the type of reaction, this can also be obtained as the sole reaction product.
  • the diacyl compound XII optionally in a mixture with the compound X, is subjected to partial solvolysis.
  • Suitable solvolysis agents are water or alcohols, for example C ⁇ -C 4 -alkanols, such as methanol, ethanol or isopropanol, or mixtures of these alcohols with water.
  • the partial solvolysis of XII is preferably carried out in the presence of an acidic or basic catalyst.
  • basic catalysts are the alkali metal hydroxides such as sodium hydroxide or potassium hydroxide or the alcoholates of C 1 -C 4 -alkanols, in particular sodium or potassium methoxide, or sodium or potassium ethylate.
  • acidic catalysts are mineral acids such as hydrochloric acid or sulfuric acid.
  • the solvolysis catalyst is usually used in an amount of 0.1 to 5 moles per mole of compound XII. In a preferred variant of this process step, the catalyst is used in an amount of at least 0.5 mol / mol of compound XII and in particular approximately equimolar or in a molar excess, preferably up to 2 mol, based on compound XII.
  • Preferred solvolysis agents are -C 4 alkanols.
  • Preferred catalysts are the alkali metal hydroxides or the alkali metal C 4 -C 4 -alcoholates such as sodium hydroxide, sodium methylate and sodium ethylate.
  • Partial solvolysis is usually carried out in a solvent.
  • Solvolysis agents themselves, in particular the C 1 -C 4 -alkanols or mixtures, come in particular as solvents of these solvolysis agents with inert solvents. Examples of inert solvents are the aforementioned solvents.
  • the solvolysis from XII to X is carried out in a C 1 -C 4 -alkanol in the presence of the corresponding alcoholate, preferably in methanol or ethanol with sodium methylate or sodium ethylate.
  • the solvolysis temperature is often above 0 ° C and is usually only limited by the boiling point of the solvent.
  • the reaction temperature is preferably in the range from 0 to 100 ° C. and in particular in the range from 20 to 80 ° C.
  • the products XI, XII and X obtained in steps i), ii) and iii) can be isolated using the usual working-up methods. If necessary, the reaction products of reaction ii) can be used in subsequent step iii) without further working up. Frequently, the crude product of compound X obtained in the reaction ii) or iii) is subjected to a crystallisative and / or chromatographic purification before the cyclization to the benzoxazole I-D.
  • reaction mixtures are generally worked up in a manner known per se. Unless stated otherwise in the processes described above, the valuable products are obtained e.g. after dilution of the reaction solution with water by filtration, crystallization or solvent extraction, or by removing the solvent, distributing the residue in a mixture of water and a suitable organic solvent and working up the organic phase onto the product.
  • the 3-arylisothiazoles of the formula I can be obtained as mixtures of isomers in the preparation, but can, if desired, be separated into the largely pure isomers by the customary methods such as crystallization or chromatography, including on an optically active adsorbate. Pure optically active isomers can advantageously be prepared from corresponding optically active starting products.
  • Agricultural salts of the compounds I can be reacted 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 the Hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid are formed.
  • a base of the corresponding cation preferably an alkali metal hydroxide or hydride
  • an acid of the corresponding anion preferably the Hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid are formed.
  • Salts of I can also 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 compounds I or their herbicidal compositions comprising salts control vegetation very well on nonculture areas, particularly when high amounts are applied. In crops such as wheat, rice, maize, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. This effect occurs especially at low application rates.
  • the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants.
  • the following crops are considered, for example:
  • 3-arylisothiazoles according to the invention of the general formula I and their agriculturally useful salts are also suitable for the desiccation and / or defoliation of plants.
  • desiccants are particularly suitable for drying out the aerial parts of crops such as potatoes, rapeseed, sunflower and soybeans. In this way a completely mechanical harvesting of these important crop plants is made possible.
  • the compounds of the formula I according to the invention or the herbicidal compositions comprising them can be, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents or Granules can be applied by spraying, atomizing, dusting, scattering, pouring or treating the seed or mixing with the seed.
  • 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 agents according to the invention contain a herbicidally effective amount of at least one compound of the general formula I or one used in agriculture usable salt of I and the auxiliaries customary for the formulation of crop protection agents.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. B. paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, eg. B. amides such as N-methylpyrrolidone or water.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e.g. B. paraffin, tetrahydronaphthalene, alkylated naphthal
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • emulsions, pastes or oil dispersions the compounds I as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates consisting of an active substance, wetting agent, tackifier, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. B. lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its Derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tribu
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. B. coating, impregnation and homogeneous granules can be prepared by binding the active ingredients to solid carriers.
  • Solid carriers are mineral earths like pine Seic acids, 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 substances
  • Products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range.
  • Formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredient.
  • the active ingredients are used 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:
  • I 20 parts by weight of compound No. IAa.10 (cf. Table 1) are dissolved in a mixture consisting of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 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.
  • aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
  • IAa.10 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene sulfonic acid, 17 parts by weight of the sodium salt of lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill.
  • a spray liquor is obtained which contains 0.1% by weight of the active ingredient.
  • V 3 parts by weight of active ingredient No. IAa.727 (R enantiomer) are mixed with 97 parts by weight of finely divided kaolin. In this way, a dust is obtained which contains 3% by weight of the active ingredient.
  • VIII 1 part by weight of compound no. IAa.14 is dissolved in a mixture consisting of 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol® EM 31 (non-ionic emulsifier based on ethoxylated castor oil). A stable emulsion concentrate is obtained.
  • the herbicidal compositions or the active compounds which contain the 3-arylisothiazoles of the general formula I and / or their salts can be applied pre-emergence, post-emergence or together with the seeds of a crop.
  • the active compound application rates are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (see also).
  • the compounds of the general formula I according to the invention can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
  • 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphorous acid and their derivatives, aminotriazoles, anilides, (het) -aryloxyalkanoic acid and their derivatives, benzoic acid and their derivatives come as mixing partners , Benzothiadiazinone, 2-aroyl-l, 3-cyclohexanedione, hetaryl-aryl-ketone, benzylisoxazolidinone, meta-CF 3 -phenylderivate, carbamate, quinoline carboxylic acid and its derivatives, chloroacetanilide, cyclohexane-l, 3-dione derivative, diazine , Dichloropropionic acid and its derivatives, dihydrobenzofur
  • Example compounds I were prepared starting from 4-chloroisothiazole-5-carboxylic acid methyl star, which in turn was prepared in accordance with the processes described in the literature. See also the synthesis sequence described in Example 1 (steps 1.1 to 1.7), as well as that in US 4544752, US 4346094 (steps 1.4 to 1.7) J. Org. Chem. 1963, 28, 2436 (step 1.4) Houben-Weyl 10/4, p. 31 (step 1.4) Liebigs Ann. Chem. 1979, 1534-1546 (step 1.5) J. Heterocyclic Chem. 1987, 24 243-245 (step 1.6) and the literature cited therein, methods to which reference is hereby made in full.
  • the contents of the reactor were poured onto 500 g of ice, made alkaline with 50% sodium hydroxide solution and mixed with 350 ml of methylene chloride. After filtration through diatomaceous earth, the methylene chloride phase was separated off and dried with magnesium sulfate. The methylene chloride phase was concentrated in vacuo and cyclohexane was added, the title compound precipitating as a solid. The solid was filtered off and the cyclohexane phase was further concentrated, as a result of which further product precipitated. A total of 8 g (65%) of the title compound was obtained with a purity of 98.8% (GC).
  • Plastic pots with loamy sand with about 3.0% humus as substrate served as culture vessels.
  • the seeds of the test plants were sown separately according to species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles.
  • the tubes were lightly sprinkled to promote germination and growth, and then covered with clear plastic covers until the plants had grown. This cover causes the test plants to germinate evenly, unless this was affected by the active ingredients.
  • test plants were first grown to a height of 3 to 15 cm, depending on the growth habit, and then treated with the active ingredients suspended or emulsified in water.
  • the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and a few days before Treatment transplanted into the test vessels.
  • the application rate for post-emergence treatment was 31.3 and 15.6 g aS / ha.
  • the plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species.
  • the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated.
  • Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
  • the plants used in the greenhouse experiments are composed of the following types:
  • the young cotton plants were treated to runoff with an aqueous preparation of the active compound which additionally contained 0.15% by weight, based on the total weight of the preparation, of a fatty alcohol ethoxylate (Plurafac® LF 700).
  • the amount of water applied was about 1000 l / ha. After 13 days, the number of leaves dropped and the degree of defoliation were determined. The untreated control plants showed no defoliation.

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Abstract

La présente invention concerne des 3-arylisothiazoles, de formule générale (I), dans laquelle les variables X, Q, R?1, R2, R3, R4, R5¿ ont les significations énoncées à la revendication 1, leurs sels, ainsi que leur utilisation pour lutter contre les végétaux nuisibles.
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US4144047A (en) * 1977-11-16 1979-03-13 Monsanto Company 3-Aryl-4-isoxazolecarboxylic acids as plant growth regulants
GB2201672A (en) * 1986-12-18 1988-09-07 Shell Int Research Diphenyl ether compounds
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WO2001087863A1 (fr) 2001-11-22
US20040023807A1 (en) 2004-02-05
JP2003533517A (ja) 2003-11-11
CA2408686A1 (fr) 2002-11-12
AU2001274034A1 (en) 2001-11-26

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