EP1877386A1 - Herbicidally active phenylsulphonyl-urea - Google Patents

Herbicidally active phenylsulphonyl-urea

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Publication number
EP1877386A1
EP1877386A1 EP06724419A EP06724419A EP1877386A1 EP 1877386 A1 EP1877386 A1 EP 1877386A1 EP 06724419 A EP06724419 A EP 06724419A EP 06724419 A EP06724419 A EP 06724419A EP 1877386 A1 EP1877386 A1 EP 1877386A1
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EP
European Patent Office
Prior art keywords
alkyl
sup
sub
formula
substituted
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.)
Ceased
Application number
EP06724419A
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German (de)
French (fr)
Inventor
Dieter Feucht
Klaus-Helmut Müller
Heinz Kehne
Oswald Ort
Hansjörg Dietrich
Christian Waldraff
Thomas Auler
Martin Hills
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Bayer CropScience AG
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Bayer CropScience AG
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Priority to EP06724419A priority Critical patent/EP1877386A1/en
Publication of EP1877386A1 publication Critical patent/EP1877386A1/en
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • 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
    • C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/42—One nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/42—One nitrogen atom
    • C07D251/46—One nitrogen atom with oxygen or sulfur atoms attached to the two other ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • substituted phenylsulfonylureas can have herbicidal properties. These are e.g. phenyl derivatives which are monosubstituted or polysubstituted (for example US 4127405, WO 9209608, BE 853374, WO 9213845, EP 84020, WO 9406778, WO 02072560, US 4169719).
  • phenylsulfonylureas having a general 1,2,3 substitution pattern exhibit herbicidal properties (e.g., WO9732861, WO02062768).
  • the present invention thus relates to compounds of the general formula (I) and / or their salts,
  • R is a hydrocarbon radical or hydrocarbonoxy radical, preferably a radical from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, aryl or aryloxy, which is unsubstituted or substituted and inclusive Substituents 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, or R is a heterocyclyl radical or Heterocyclyloxyrest which is unsubstituted or substituted, or R is a radical OC (O) R 3 , S (O) n R 3 , OS (O) n R 3 , F 1 is Br, I 1 is OH, CN, NO 2 , NH 2 , SF 5 , NR 4 R 5 or Si (R 6 ) 3 , where
  • R 1 is independently halogen, OH, SH, a carbon-free nitrogen-containing radical or a carbon-containing radical having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, I 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, most preferably 0,
  • R 2 is a hydrogen atom or a hydrocarbon radical which is unsubstituted or substituted and contains, including substituents, 1 to 20 C atoms, preferably 1 to 10 C atoms, for example unsubstituted or substituted preferably H or CH 3
  • R 3 is a hydrocarbon radical or hydrocarbonoxy radical, preferably a radical from the group alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, aryl or aryloxy, which is unsubstituted or substituted and is inclusive of substituents 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, or R 3 is a heterocyclyl or heterocyclyl radical which is unsubstituted or substituted, or R 3 is a hydrogen atom, CN or NR 4
  • R 0 represents a hydrogen atom, an acyl radical, a hydrocarbon radical or a heterocyclyl radical, each of the last-mentioned two radicals being unsubstituted or substituted and including substituents 1 to 30 C
  • Q 0 is a direct bond or a divalent group of the formula -O- or -N (R # ) -, wherein R # represents a hydrogen atom, an acyl radical or a hydrocarbon radical and wherein the latter radical is unsubstituted or substituted and includes substituents 1 to 30 C-
  • Atoms preferably 1 to 20 carbon atoms, or R 0 and R # together form a nitrogen-containing heterocyclic ring
  • R 5 is a hydrogen atom, an acyl radical, a hydrocarbon radical or a heterocyclyl radical, each of the latter two radicals being unsubstituted or substituted and having, including substituents, 1 to 30 C atoms, preferably 1 to 20 C atoms, or R 4 and R 5 together form a nitrogen-containing heterocyclic ring,
  • R 6 is a hydrocarbon radical which is unsubstituted or substituted and contains, including substituents, 1 to 30 C atoms, preferably 1 to 20 C atoms, preferably (C 1 -C 4 ) alkyl or (C 6 -C 10 ) alkyl,
  • W is an oxygen atom or a sulfur atom
  • X is unsubstituted 1 Y independently represent a hydrogen atom, halogen, (Ci-C 6) alkyl, (Cr C 6) alkoxy or (C r C 6) alkylthio, where each of the last 3 radicals (4 -C) alkylthio or by one or more radicals from the group halogen, (CrC 4) -alkoxy, and substituted or mono- or di [(d- C6) alkyl] amino, (C 2 -C 6) alkenyl , (C 2 -C 6) alkynyl, (C 3 -C 6) alkenyloxy or (C 3 - C 6) alkynyloxy means, and
  • V, Z are independently CH or N
  • the compounds of formula (I) may form salts, e.g. those in which the hydrogen of the -SCVNH group is replaced by a cation suitable for agriculture.
  • These salts are, for example, metal salts, in particular
  • Alkali metal salts or alkaline earth metal salts especially sodium and potassium salts, or ammonium salts or salts with organic amines.
  • salt formation can take place by addition of an acid to basic groups, such as, for example, amino and alkylamino.
  • Suitable acids for this purpose are strong inorganic and organic acids, for example HCl, HBr, H 2 SO 4 or HNO 3 .
  • Carbon-containing radicals are organic radicals which contain at least one carbon atom, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms and also at least one atom of one or more other elements of the Periodic Table of Elements such as H, Si, N, P, O, S, F, Cl, Br or J included.
  • Examples of carbon-containing radicals are unsubstituted or substituted hydrocarbon radicals which are bonded directly or via a heteroatom such as N, S, P or O may be bonded to the main body, unsubstituted or substituted heterocyclyl radicals which may be bonded to the basic body directly or via a heteroatom such as N, S, P or O, carbon-containing acyl radicals or cyano.
  • the carbon-containing radicals such as alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and / or substituted radicals in the carbon skeleton may each be straight-chain or branched. Unless specifically stated, these radicals are the lower carbon skeletons, e.g. with 1 to 6 C atoms or with unsaturated groups having 2 to 6 C atoms, preferred.
  • Alkyl radicals also in the composite meanings such as alkoxy, haloalkyl, etc., mean e.g.
  • Alkyl radicals corresponding to possible unsaturated radicals Alkenyl means e.g. Allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1 Methyl-but-3-en-1-yl and 1-methylbut-2-en-1-yl;
  • Alkynyl means e.g. Propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methyl-but-3-yn-1-yl.
  • Cycloalkyl means a carbocyclic saturated ring system preferably having 3-8 C atoms, e.g. Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • Carbon-free nitrogen-containing radicals are radicals which preferably contain 1 to 10 N atoms, particularly preferably 1 or 2 N atoms, and also preferably one or more atoms of one or more of carbon-different elements of the periodic table of the elements such as H, O or S.
  • Examples of carbon-free nitrogen-containing radicals are NH 2 , NO 2 , NHOH, NO, NH-NH 2 or N 3 .
  • Halogen is, for example, fluorine, chlorine, bromine or iodine.
  • Haloalkyl, -alkenyl and -alkynyl by halogen preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine, partially or completely substituted alkyl, alkenyl or alkynyl, for example CF 3 , CHF 2 , CH 2 F, CF 3 CF 2 , CH 2 FCHCl, CCI 3 , CHCl 2 , CH 2 CH 2 Cl;
  • Haloalkoxy is, for example, OCF 3 , OCHF 2 , OCH 2 F, CF 3 CF 2 O, OCH 2 CF 3 and OCH 2 CH 2 Cl; the same applies to haloalkenyl and other halogen-substituted radicals.
  • a hydrocarbon radical is a straight-chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic
  • Hydrocarbon radical e.g. Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl;
  • Aryl means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl,
  • Fluorenyl and the like preferably phenyl; a hydrocarbon radical preferably denotes alkyl, alkenyl or alkynyl having up to 12 C atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl.
  • a heterocyclic radical or ring may be saturated, unsaturated or heteroaromatic and unsubstituted or substituted; it preferably contains one or more heteroatoms in the ring, preferably from the group N, O and S; it is preferably an aliphatic heterocyclyl radical having 3 to 7 ring atoms or a heteroaromatic radical having 5 or 6 ring atoms and contains 1, 2 or 3 heteroatoms.
  • the heterocyclic radical may be, for example, a heteroaromatic radical or ring (heteroaryl), for example a mono-, bi- or polycyclic aromatic system in which at least one ring contains one or more heteroatoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, Thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or is a partial or fully hydrogenated radical such as oxiranyl, oxetanyl, pyrrolidyl, piperidyl, piperazinyl, dioxolanyl, Mo ⁇ holinyl, tetrahydrofuryl.
  • heteroaryl for example a mono-, bi- or polycyclic aromatic system in which at least one ring contains one or more heteroatoms, for example pyridyl, pyrimidinyl
  • Suitable substituents for a substituted heterocyclic radical are the substituents mentioned below in question, in addition also oxo.
  • the oxo group may also occur on the hetero ring atoms, which may exist in different oxidation states, eg at N and S.
  • Substituted radicals such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted heterocyclyl or heteroaryl, represent, for example, a substituted radical derived from the unsubstituted radical, where the substituents are, for example, one or more, preferably 1, 2 or 3 3 radicals from the group halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, carboxy, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such as acylamino, mono- and dialkylamino, and Alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and,
  • radicals with C atoms those having 1 to 4 C atoms, in particular 1 or 2 C atoms, are preferred.
  • Substituents from the group halogen for example fluorine and chlorine, (C 1 -C 4 ) alkyl, preferably methyl or ethyl, (C 1 -C 4 ) haloalkyl, preferably trifluoromethyl, (C 1 -C 4 ) alkoxy, preferably methoxy or ethoxy, are generally preferred.
  • C-OHaloalkoxy, Nitro and Cyano.Preferably substituted are the substituents methyl, methoxy and chlorine.
  • Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to three times by identical or different radicals from the group halogen, ( Ci-C 4) alkyl, (CrC 4) alkoxy, (CRC4) haloalkyl, (Ci-C 4) haloalkoxy and nitro, for example o-, m- and p-tolyl, Dimethylphenyle, 2-, 3- and 4 -Chlorophenyl, 2-, 3- and 4-trifluoro and trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.
  • Mono- or disubstituted amino means a chemically stable radical from the Group of substituted amino radicals which are N-substituted, for example, by one or two identical or different radicals from the group consisting of alkyl, alkoxy, acyl and aryl; preferably monoalkylamino, dialkylamino, acylamino, arylamino, N-alkyl-N-arylamino and N-heterocycles; while alkyl radicals having 1 to 4 carbon atoms are preferred;
  • Aryl is preferably phenyl or substituted phenyl; for acyl, the definition mentioned further below applies, preferably formyl, (Ci-C 4) applies alkylcarbonyl or (CrC 4) alkylsulfonyl. The same applies to substituted hydroxylamino or hydrazino.
  • An acyl radical means the radical of an organic acid that is formally through
  • Cleavage of an OH group from the organic acid results, e.g. the radical of a carboxylic acid and radicals derived therefrom, such as the thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the radicals of carbonic acid monoesters, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.
  • the radical of a carboxylic acid and radicals derived therefrom such as the thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the radicals of carbonic acid monoesters, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.
  • An acyl radical is preferably formyl or aliphatic acyl from the group CO-R X, CS-R X, CO-OR X, CS-OR X, CS-SR X, SOR Y or SO 2 R Y, with R x and R ⁇ each represents a Ci-C-io hydrocarbon radical which is unsubstituted or substituted, or aminocarbonyl or aminosulfonyl, wherein the latter two radicals are unsubstituted, N-monosubstituted or N, N-disubstituted.
  • Acyl is, for example, formyl, haloalkylcarbonyl, alkylcarbonyl such as (C 1 -C 4) alkylcarbonyl, phenylcarbonyl, where the phenyl ring may be substituted, for example as indicated above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and others Residues of organic acids.
  • the invention also relates to all stereoisomers which are encompassed by formula (I) and mixtures thereof.
  • Such compounds of formula (I) contain one or more asymmetric C atoms or double bonds, which are not specified separately in the general formula (I).
  • the possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z- and E-isomers are all of the formula (I) and can be obtained by conventional methods from mixtures of stereoisomers or prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials.
  • radicals or ranges of radicals which fall under the general terms such as "alkyl”, “acyl”, “substituted radicals”, etc. are not exhaustive.
  • the general terms also include the definitions given below for residue regions in groups of preferred compounds, in particular residue regions which comprise specific residues from the table examples.
  • Preferred compounds of the formula (I) according to the invention or salts thereof are those in which R (C r C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 6 ) Cycloalkyl, (C 3 -
  • R 1 is independently (C 1 -C 6) AIRyI, (Ci-C 6) haloalkyl, (CrC 6) alkyloxy, (C 1 - is C ⁇ JHaloalkoxy or halogen,
  • I is 0, 1 or 2, preferably 0 or 1, more preferably 0, n is 0, 1 or 2,
  • R 2 is H or CH 3 ,
  • R 3 H (C 1 -C 6 alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl, (C 1 -C 6 ) alkyloxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy, (C 3 -C 6 ) cycloalkyloxy,
  • W is an oxygen atom
  • X, Y independently of one another are (Crd) alkyl, (C 1 -C 4 ) alkyloxy, where each of the latter two radicals is unsubstituted or substituted by one or more halogen atoms, or (C 1 -C 4 ) alkylthio, halogen or NH (C 1 -C 4 ) alkyl or N ((C r C 4 ) alkyl) 2 , and
  • V, Z are independently CH or N
  • Particularly preferred compounds of formula (I) and / or their salts are those wherein R is (CrC 4) alkyl, (C 2 -C 4) alkenyl, (C 2 -C 4) alkynyl, (C 3 -C 6) cycloalkyl , (C 1 -
  • R 1 is halogen (F, Cl, Br, I), (C 1 -C 4) -alkyl, (C r C 4) alkyloxy, (C r C4) haloalkyl, (C 1 - C 4) haloalkyloxy,
  • I is O or 1, preferably O,
  • R 2 is H or (C r C 4 ) alkyl, such as methyl, W is an oxygen atom,
  • X, Y are independently (C 1 -C 4) -alkyl, (CrC 4) haloalkyl, (C- ⁇ -C 4) alkyloxy, (C 1 - C 4) haloalkyloxy, halogen (F, Cl, Br, 1: 1), (C r C 4 ) alkylthio, NH (C r C 4 ) alkyl, N ((C r C 4 ) alkyl) 2 ,
  • V is a nitrogen atom
  • Z is CH or N.
  • OCH 2 OCH 3 OPhenyl, OCH 2 phenyl, OCF 3 , OCHF 2 , OCH 2 F, OCH 2 CF 3 , OCH 2 CHF 2 , OCH (CH 3 ) CF 3 , OCH 2 CF 2 CF 3 , SCH 3 , SCH 2 CH 3 , S (O) CH 3 , S (O) CH 2 CH 3 , SO 2 CH 3 , SO 2 CH 2 CH 3 , SO 2 NHCH 3 , SO 2 N (CH 3 ) 2
  • IO is, R 2 is H,
  • X 1 Y independently of one another CH 3 , CH 2 CH 3 , CF 3 , CHF 2 , CH 2 CF 3 , CH 2 CHF 2 ,
  • Z is CH or N
  • the present invention also provides processes for the preparation of the compounds of the general formula (I) according to the invention and / or salts thereof, wherein
  • R * represents a substituted or unsubstituted C 1 -C 20 -hydrocarbon radical such as aryl or alkyl, preferably optionally substituted phenyl or optionally substituted (C 1 -C 4 ) -alkyl, or
  • R ** is a substituted or unsubstituted CrC 2 o-hydrocarbon radical such as aryl or alkyl, preferably optionally substituted phenyl or optionally substituted (Ci-C 4) alkyl, with an amino heterocycle of the formula (V)
  • Hal is a halogen atom, preferably chlorine, with a (thio) cyanate, for example a metal (thio) cyanate, in particular an alkali metal (thio) cyanate, such as sodium (thio) cyanate, to a lso (thio) cyanate of the formula (VI ) or a solvated (stabilized) derivative thereof, and then reacted with an amino heterocycle of formula (V),
  • a metal (thio) cyanate for example a metal (thio) cyanate, in particular an alkali metal (thio) cyanate, such as sodium (thio) cyanate, to a lso (thio) cyanate of the formula (VI ) or a solvated (stabilized) derivative thereof, and then reacted with an amino heterocycle of formula (V),
  • a (thio) cyanate for example a metal (thio) cyanate, in particular an alkali metal (thio) cyanate, such as
  • DBU 1, 8-diazabicyclo [5.4.0] undec-7-ene
  • alkali tert-butoxides such as NaO-tC 4 H 9
  • alkali hydroxides such as NaOH
  • R * (subst. ) Phenyl
  • the particular base is used, for example, in the range of 1 to 3 molar equivalents, based on the compound of the formula (II).
  • sulfonamides of the formula (X) can be obtained.
  • the sulfonamide is, for example, in inert solvents such as dichloromethane, tetrahydrofuran (THF), dioxane, toluene or dimethylformamide (DMF) at temperatures between - 70 0 C to the boiling point of the solvent used, preferably at 25 0 C.
  • inert solvents such as dichloromethane, tetrahydrofuran (THF), dioxane, toluene or dimethylformamide (DMF)
  • THF tetrahydrofuran
  • DMF dimethylformamide
  • the compounds of the formula (XI) can be diazotised under conventional conditions for diazotization reactions and then converted into compounds of the formula (XII).
  • the diazotization is carried out in the presence of the acid H + X ' , where X "is preferably Cl ' , I " or HSO 4 * , in aqueous solution, optionally with the use of an organic solvent which is inert under the reaction conditions, with a nitrite.
  • Suitable acids are mineral acids or strong organic acids, preferred are hydrochloric acid, or sulfuric acid.
  • the solvent is water or a mixture of water and an inert organic solvent under the reaction conditions.
  • the reaction temperature is generally between -5 0 C and 5O 0 C, preferably 1O 0 C to 2O 0 C (Scheme 3).
  • the reaction of the diazonium salts obtained to give the aryl iodides of the formula (XII) is generally carried out without isolation and is carried out in the same aqueous or aqueous-organic solvent or solvent mixture as the diazotization.
  • alkali metal iodide preferably sodium iodide or potassium iodide.
  • the amount of iodide is, for example, 1.1 to 1.5 moles of iodide per mole of the originally used compound of the formula (XI).
  • the reaction temperature amounts are in general at 1O 0 C to 4O 0 C, preferably 15 0 C to 3O 0 C (see. This example, DE 19625831 and Bioorg. Med. Chem. 2004, 12, 2079) (Scheme 3).
  • the removal of the tert-butyl protective group in the compounds of the formula (XII) to give the sulfonamides of the formula (II) is effected, for example, by treatment with a strong acid (see WO 89/10921).
  • Suitable strong acids are, for example, mineral acids, such as H 2 SO 4 or HCl, or strong organic acids, such as trifluoroacetic acid in question.
  • the reaction takes place for example at temperatures from -20 0 C to the respective reflux temperature of the reaction mixture, preferably at 0 C to 40 0 C.
  • the reaction can be in bulk or in an inert solvent such as dichloromethane or trichloromethane, are carried out (Scheme 4).
  • Substituted f-butylaminosulfonyl compounds of the formula (XII) can also be obtained by obtaining compounds of the formula (XIV) which can be obtained by reacting commercially available sulfochlorides of the formula (XIII) with tert-butylamine (see Scheme 1) (sulfochlorides of the formula (XIII) can also be prepared by diazotization of the corresponding Amino compounds and subsequent sulfochlorination as indicated in Scheme 1), with an organometallic compound, such as alkyl or aryllithium, preferably n- or sec-butyllithium in hexane, if appropriate in the presence of a (further) inert diluent, such as tetrahydrofuran, and under an inert gas atmosphere such as metalated under argon or nitrogen, at temperatures between 0 C and 2O -7O 0 C - that is, the NH-tert in the compound of formula (XIV)
  • the radical R ' is, for example, a hydrocarbon radical such as alkyl, a heterocyclyl radical, CO-R 3 or S (O) n R 3 and Hal is halogen, where alkyl, Halogen, n and R 3 are as defined in formula (I).
  • R ' may in particular be CO-R 3 or S (O) n R 3 .
  • Suitable reaction auxiliaries are generally the customary inorganic or organic bases or acid acceptors. These include preferably alkali metal or alkaline earth metal compounds, such as. B.
  • acetates, amides, carbonates, bicarbonates, hydrides, hydroxides, or alkanoates - in particular potassium carbonate, cesium carbonate, lithium hydroxide, sodium hydroxide and sodium ethanolate are mentioned here - furthermore also basic organic nitrogen compounds, such as. Triethylamine, ethyldiisopropylamine, alkyl-substituted pyridines, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) or 1,8-diazabicyclo [5.4.0] undec-7en (DBU).
  • DABCO 1,4-diazabicyclo [2.2.2] octane
  • DBN 1,5-diazabicyclo [4.3.0] non-5-ene
  • DBU 1,8-diazabicyclo [5.4.0] undec-7en
  • Suitable solvents are, in addition to water, especially inert organic solvents.
  • these include benzene, toluene, XyIoI 1 dichloromethane, chloroform, diethyl ether, dioxane, tetrahydrofuran, acetone, acetonitrile, N 1 N-dimethylformamide, N-methyl-pyrrolidone or ethyl acetate.
  • the reaction temperatures vary between O 0 C and the reflux temperature of the solvent used, preferably between 10 0 C and 12O 0 C (Scheme 6) (see also WO 02/072560).
  • Hydroxybenzenesulfonamides of the formula (XV) can be obtained, for example, from the ortho-alkoxy-substituted benzenesulfonamides of the general formula (II-b) (obtainable, for example, according to the reactions of Schemes 1-6), where R "can in particular denote (C 1 -C -alkyl) in an inert solvent such as dichloromethane, dichloroethane or chloroform, preferably dichloromethane or dichloroethane, the alkoxy compound of the formula (II-b) are treated with a Lewis acid, preferably boron trihalides, such as BBr 3.
  • the reaction temperature is generally between -3O 0 C. and the reflux temperature of the solvent, preferably from 0 ° C to 4O 0 C (scheme 7) (see for example EP044807 and WO 97/03056).
  • Benzenesulfonamides of the general formula (II-d) can be obtained by replacing the fluorine atom in the ortho-fluorobenzenesulfonamide of the general formula (II-c) (obtainable, for example, according to the reactions of Schemes 1-6) by reaction with nucleophiles of the general formula R '"
  • reaction auxiliaries can be used as the usual inorganic or organic bases or acid acceptors.
  • alkali metal or alkaline earth metal compounds such as. B. acetates, amides, carbonates, - hydrogencarbonates, hydrides, hydroxides, or alkanoates - in particular potassium carbonate, cesium carbonate, lithium hydroxide, sodium hydroxide and sodium ethoxide, and especially sodium hydride may be mentioned - also basic organic nitrogen compounds, such as For example, triethylamine, ethyl-diisopropylamine, alkyl-substituted pyridines, 1, 4-diazabicyclo [2.2.2] octane (DABCO), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN) or 1, 8-diazabicyclo [5.4.0] undec-7en (DBU).
  • DABCO 4-diazabicyclo [2.2.2] octane
  • DBU 5-d
  • Suitable solvents are, in addition to water, especially inert organic solvents.
  • these include benzene, toluene, xylene, dichloromethane, chloroform, diethyl ether, dioxane, tetrahydrofuran, acetone, acetonitrile, N 1 N- dimethylformamide, N-methyl-pyrrolidone or ethyl acetate, in particular diethyl ether, dioxane and tetrahydrofuran may be mentioned here highlighted.
  • the reaction temperature is generally between -2O 0 C and Reflux temperature of the solvent used, in particular between O 0 C and reflux temperature of the solvent used.
  • microwave energy can also be used to accelerate the reaction.
  • a commercially available, designed for chemical purposes microwave device can be used.
  • the reactions are generally at temperatures between 2O 0 C and 200 0 C 1 preferably between 4O 0 C and 17O 0 C and with an energy output between 20 and 200 watts, preferably between 50 and 180 watts, during a reaction time between 2 min and 60 min, preferably carried out between 5 min and 45 min.
  • Metachloroperbenzoic acid, hydrogen peroxide, sodium metaperiodate or oxones are converted to the corresponding sulfoxides or sulfones (see, e.g., "Reactions of Organosulfur Compounds", Academic Press, New York, 1978, p.
  • the sulfonyl (thio) carbamates of the general formula (IV) are prepared analogously to reactions known per se (cf EP-A-120 814). It is also possible, for example, to convert the sulfonyl iso (thio) cyanates of the formula (VI) into the (thio) carbamates of the formula (IV) in a smooth reaction in an inert solvent, preferably diethyl ether or dichloromethane, with phenol.
  • the aminoheterocycles of formula (V) are known, in part commercially available synthetic chemicals.
  • the sulfonyl iso (thio) cyanates of the general formula (VI) can be prepared by processes known per se from the sulfonamides of the general formula (II) according to the invention (cf., DE 3208189, EP 23422, EP 64322, EP 44807, EP 216504).
  • the iso (thio) cyanates of general formula (VII) are obtained, for example, from Aminoheterocyclene of type (V) by treatment with oxalyl chloride or (thio) phosphene (in analogy to Angew. Chem. 1971, 83, p. 407, EP 388 873).
  • the reaction of iso (thio) cyanates of type (VII) with the sulfonamides of general formula (II) is carried out, for example, in analogy to variant c) (Scheme 11).
  • the sulfonic acid halides of the formula (VIII) can be prepared by various methods known from the literature, e.g. i) Oxidative Chlorination of Thioethers (Recl. Trav. Chim. Pays-Bas 1982, 101, 91, ii) Diazotization of aromatic amines with sodium nitrite in hydrochloric acid, followed by the reaction of the resulting diazonium salt with sulfur dioxide and copper chloride (J. Org.
  • the reaction mixture obtained by reacting the sulfonic acid halide (VIII) with a (thio) cyanate is used directly for coupling with an amino heterocycle of the formula (V) for the synthesis of the compound of formula (I) used (see, for this purpose, WO 2003 091228 and US 5550238).
  • the salts of the compounds of formula (I) are preferably prepared in inert polar solvents such as water, methanol or acetone at temperatures of 0 0 C to 100 0 C.
  • Suitable bases for the preparation of the inventive Salts are, for example, alkali metal carbonates, such as potassium carbonate, alkali metal and alkaline earth metal hydroxides, for example NaOH or KOH, or alkali metal alkoxides, such as sodium methoxide or sodium tert-butoxide, or ammonia or ethanolamine.
  • inert solvents denoted in the above process variants are meant in each case solvents which are inert under the respective reaction conditions, but need not be inert under any reaction conditions.
  • Collections of compounds of formula (I) and / or their salts, which may be synthesized following the above reactions, may also be prepared in a parallelized manner, which may be done in a manual, partially automated or fully automated manner. It is possible, for example, to automate the reaction procedure, the work-up or the purification of the products or intermediates. Overall, this is understood as a procedure as described, for example, by S.H. DeWitt in "Annual Reports in Combinatorial Chemistry and Molecular Diversity: Automated Synthesis", Volume 1, published by Escom 1997, pages 69 to 77.
  • Microwave oven e.g. Model "Discover” by the company CEM GmbH Microwave Analysis, Carl-Friedrich-Gauss-Str. 9, 47475 Kamp-Lintfort be used.
  • the listed equipment leads to a modular procedure, in which the individual work steps are automated, but between the work steps, manual operations must be performed.
  • This can be circumvented by the use of partially or fully integrated automation systems in which the respective automation modules are operated, for example, by robots.
  • Such automation systems may be obtained, for example, from Zymark Corporation, Zymark Center, Hopkinton, MA 01748, USA.
  • solid-phase assisted synthetic methods allows a number of protocols known from the literature, which in turn can be carried out manually or automatically.
  • the 'teabag method' Houghten, U.S. 4,631,211; Houghten et al., Proc Natl Acad. Sei, 1985, 82, 5131-51305
  • the automation of solid-phase assisted parallel syntheses is accomplished, for example, by the equipment of Argonaut Technologies, Inc., 887 Industrial Road, San Carlos, CA 94070, USA or MultiSynTech GmbH, Wullener Feld 4, 58454 Wirten, Germany ,
  • the preparation according to the methods described herein provides compounds of formula (I) and their salts in the form of substance collections containing libraries to be named.
  • the present invention also provides libraries containing at least two compounds of formula (I) and their salts.
  • the present invention therefore also provides a method for controlling unwanted plants or regulating the growth of plants, preferably in plant crops, wherein one or more compounds according to the invention are applied to the plants (for example harmful plants such as monocotyledonous or dicotyledonous weeds or undesired crop plants), the seed ( For example, grains, seeds or vegetative propagules such as tubers or Sprossmaschine with buds) or the area on which the plants grow (eg the acreage) are applied.
  • the compounds of the invention may be e.g. be applied in pre-sowing, pre-emergence or post-emergence.
  • some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned, which can be controlled by the compounds according to the invention, without the intention of limiting them to certain species.
  • the spectrum of activity extends to species such as Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp. Galium aparine, Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp. and Viola spp., Xanthium spp., on the annual side, as well as Convolvulus, Cirsium, Rumex, and Artemisia in perennial weeds.
  • Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus are also excellently controlled by the active compounds according to the invention.
  • the compounds according to the invention are applied to the surface of the earth before germination, then either the emergence of the weed seedlings is completely prevented or the weeds grow up to the cotyledon stage, but then cease their growth and finally die off completely after a lapse of three to four weeks.
  • Crops of economically important crops such as dicotyledonous crops such as soybean, cotton, rapeseed, sugar beets, or graminaceous crops such as wheat, barley, rye, corn or rice, especially corn and wheat, only marginally or not at all damaged.
  • the present compounds are very well suited for the selective control of undesired plant growth in crops such as agricultural crops or ornamental plants.
  • the compounds of the invention have excellent growth-regulatory properties in crop plants. They regulate the plant's metabolism and can thus be used to specifically influence plant ingredients and facilitate harvesting, eg by triggering desiccation and stunted growth.
  • they are also suitable for the general control and inhibition of undesirable vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops, as this can reduce or completely prevent shelf life.
  • the active compounds can also be used for controlling harmful plants in crops of known or yet to be developed genetically modified plants.
  • the transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • Other special properties relate to z. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients.
  • transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known.
  • the application of the compounds of the invention in economically important transgenic crops of useful and ornamental plants eg.
  • cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn or even
  • the compounds of the invention can be used as herbicides in crops that are resistant to the phytotoxic
  • Bacillus thuringiensis toxins Bacillus thuringiensis toxins (Bt toxins) which render the plants resistant to certain pests (EP-A-0142924 and EP-A-0193259).
  • Bacillus thuringiensis toxins Bacillus thuringiensis toxins (Bt toxins) which render the plants resistant to certain pests (EP-A-0142924 and EP-A-0193259).
  • Transgenic crop plants with modified fatty acid composition (WO 91/13972).
  • nucleic acid molecules can be introduced into plasmids that allow mutagenesis or sequence alteration by recombination of DNA sequences.
  • base exchanges partial sequences removed or natural or synthetic sequences are added.
  • adapters or linkers can be attached to the fragments.
  • Gene product can be obtained, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to obtain a cosuppression effect or the expression of at least one appropriately engineered ribozyme which specifically cleaves transcripts of the above gene product.
  • DNA molecules may be used which comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules which comprise only parts of the coding sequence, which parts must be long enough to be present in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product but are not completely identical.
  • the synthesized protein may be located in any compartment of the plant cell. But to achieve the localization in a particular compartment, z.
  • the coding region can be linked to DNA sequences that ensure localization in a particular compartment. Such sequences are known to the person skilled in the art (see, for example, Braun et al., EMBO J. IJ. (1992),
  • the transgenic plant cells can be regenerated to whole plants by known techniques.
  • the transgenic plants may in principle be plants of any plant species, ie both monocotyledonous and dicotyledonous plants.
  • the compounds of the invention can be used in transgenic cultures which are resistant to herbicides from the group of sulfonylureas, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active ingredients.
  • the invention thus also relates to the use of the compounds according to the invention as herbicides for controlling harmful plants in transgenic and non-transgenic crops.
  • the compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations.
  • the invention therefore also relates to herbicidal and plant growth-regulating agents which contain the compounds according to the invention.
  • the compounds according to the invention can be formulated in various ways depending on which biological and / or chemical-physical parameters are given. Possible formulation options are, for example: wettable powder (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions .
  • WP wettable powder
  • SP water-soluble powders
  • EC emulsifiable concentrates
  • EW emulsions
  • sprayable solutions such as oil-in-water and water-in-oil emulsions, sprayable solutions .
  • SC Suspension concentrates
  • CS capsule suspensions
  • DP dusts
  • mordants granules for litter and soil application
  • granules GR
  • WG water-dispersible granules
  • SG water-soluble granules
  • Fungicides as well as with safeners, fertilizers and / or growth regulators produce, for example in the form of a ready-made formulation or as a tank mix.
  • Injectable powders are preparations which are uniformly dispersible in water and, in addition to the active ingredient, except for a diluent or inert substance, also ionic and / or nonionic surfactants (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines,
  • the herbicidal active compounds are finely ground, for example, in customary apparatus such as hammer mills, blower mills and air-jet mills and mixed simultaneously or subsequently with the formulation auxiliaries.
  • Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents with the addition of one or more ionic and / or nonionic surfactants (emulsifiers).
  • organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents
  • emulsifiers e.g. Butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents.
  • ionic and / or nonionic surfactants emulsifiers
  • suitable emulsifiers are: alkylarylsulfonic acid calcium salts such
  • Fatty acid polyglycol esters alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as e.g. Sorbitan fatty acid esters or polyoxethylenesorbitan esters such as e.g. Polyoxyethylene.
  • Dusts are obtained by milling the active ingredient with finely divided solids, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • finely divided solids e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • Suspension concentrates may be water or oil based. You can, for example, by wet grinding using commercially available bead mills and optionally added surfactants, such as the above with the other Formulation types already listed are produced.
  • Emulsions for example oil-in-water emulsions (EW) 1, can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, as already listed above for the other formulation types.
  • EW oil-in-water emulsions
  • Granules can either be prepared by atomizing the active ingredient on adsorptive, granulated inert material or by applying active substance concentrates by means of adhesives, e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils, on the surface of carriers such as sand, kaolinites or granulated inert material. It is also possible to granulate suitable active ingredients in the manner customary for the production of fertilizer granules, if desired in admixture with fertilizers.
  • adhesives e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils
  • Water-dispersible granules are generally prepared by the usual methods such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
  • the agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of compounds according to the invention.
  • the active ingredient concentration is about 10 to 90 wt .-%
  • the Residual to 100 wt .-% consists of conventional formulation ingredients.
  • the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%.
  • Dusty formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient
  • sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% active ingredient.
  • the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used.
  • the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the active substance formulations mentioned optionally contain the customary adhesion, wetting, dispersing, emulsifying, penetrating, preserving, antifreeze and solvent, fillers, carriers and dyes, antifoams, evaporation inhibitors and the pH and the Viscosity-influencing agent.
  • combination partners for the compounds according to the invention in mixture formulations or in a tank mix are known active compounds which are based on inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthetase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, protoporphyrinogen oxidase, can be used, as described, for example, in Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 13th edition, The British Crop Protection Council and the Royal Soc.
  • herbicides which can be combined with the compounds according to the invention are the following active substances (Note: The compounds are either together with the "common name” according to the International Organization for Standardization (ISO) or with the chemical name, if appropriate together with a common code number) and always include all forms of use such as acids, salts, esters and isomers such as stereoisomers and optical isomers.
  • ISO International Organization for Standardization
  • Fluorochloridones fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl-sodium, fluridone, fluroxypyr, fluroxypyr-butoxypropyl, fluroxypyr-meptyl, flurprimidol, flurtamone, fluthiacet-methyl, fomesafen, foramsulfuron, glufosinate, glufosinate-ammonium, glyphosate, halosulfuron-methyl, Haloxyfop, haloxyfopethoxyethyl, haloxyfopmethyl, haloxyfop-P-methyl, hexazinone, imazamethabenz-methyl,
  • the compounds according to the invention can also be used in combination with one or more compounds which act as safeners.
  • safeners are:
  • n ' is a natural number from 0 to 5, preferably 0 to 3;
  • T is a (C 1 or C 2) alkanediyl chain which is substituted or -CJAlkylresten [(CyC ⁇ Alkoxylcarbonyl unsubstituted or substituted with one or two (C j;
  • W + is an unsubstituted or substituted divalent heterocyclic radical from the group of the unsaturated or unsaturated five-membered ring heterocycles having 1 to 3 hetero-ring atoms of the type N or O, wherein at least one N-atom and at most one O-atom is contained in the ring, preferably one Remainder from the group (W + I) to (W + 4),
  • R 7 , R 9 are identical or different hydrogen, halogen, (C 1 -C 4 ) Al kVl,
  • R 8 , R 10 are the same or different OR 14 , SR 14 or NR 14 R 15 or a saturated or unsaturated 3- to 7-membered heterocycle having at least one
  • N atom and up to 3 heteroatoms preferably from the group O and S, which is connected via the N atom with the carbonyl group in (XVII) or (XVIII) and unsubstituted or by radicals from the group (C 1 -C 4 ) AIkVl,
  • R 14 is hydrogen or an unsubstituted or substituted aliphatic
  • Hydrocarbon radical preferably having a total of 1 to 18 carbon atoms
  • R 15 is hydrogen, (C 1 -C 6 ) Al kVl, (C 1 -C 6 ) alkoxy or substituted or unsubstituted phenyl
  • R 16 is hydrogen, (C 1 -C 8) -alkyl, (C 1 -C 8) HaIOaIRyI 1 (C 1 -C 4) C 1 -C 4 AIkOXyK JaIlCyI 1
  • R 17 , R 18 , R 19 are identical or different hydrogen, (C 1 -C 8 ) AlKyl, (C 1 -C 8 ) haloalkyl, (C 3 -C 12 ) cycloalkyl or substituted or unsubstituted phenyl;
  • R 11 is (C 1 -C 4 ) AlKyl, (C r C 4 ) alkenyl, (C 2 -C 4 ) haloalkenyl,
  • R 12 , R 13 is identical or different hydrogen, (C 1 -C 4 ) alkyl, (C 2 -C 4 ) alkenyl,
  • Methyl-diphenylmethoxyacetate cyanomethoxyimino (phenyl) acetonitrile (cyometrinil), 1,3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile (oxabetrinil), 4'-chloro-2,2,2-trifluoroacetophenone 0-1, 3-dioxolane 2-ylmethyloxime (Fluxofenim),
  • R 20 is hydrogen, a hydrocarbon radical, a hydrocarbonoxy radical, a hydrocarbylthio radical or a heterocyclyl radical, where each of the last-mentioned 4 radicals is unsubstituted or substituted by one or more identical or different radicals from the group halogen, cyano, nitro, amino, hydroxy, carboxy, formyl, carbonamide , Sulfonamide and radicals of the formula -Z a -R a is substituted, wherein each hydrocarbon moiety preferably has 1 to 20 carbon atoms and a C-containing radical R 20 including substituents preferably has 1 to 30 carbon atoms; R 21 is hydrogen or (C 1 -C 4 ) alkyl, preferably hydrogen, or
  • R 20 and R 21 together with the group of the formula -CO-N- denote the radical of a 3- to 8-membered saturated or unsaturated ring;
  • R 22 is identical or different and is halogen, cyano, nitro, amino, hydroxyl, carboxy, formyl, CONH 2 , SO 2 NH 2 or a radical of the formula -Z b -R b ;
  • R 23 is hydrogen or (C 1 -C 4 ) alkyl, preferably H;
  • R 24 is identical or different and is halogen, cyano, nitro, amino, hydroxyl, carboxy, CHO, CONH 2 , SO 2 NH 2 or a radical of the formula -Z c -R c ;
  • R a is a hydrocarbon radical or a heterocyclyl radical, where each of the latter two radicals is unsubstituted or substituted by one or more identical or different radicals from the group of halogen, cyano, nitro, amino, hydroxyl, mono- and di- [( is substituted, or one
  • R b , R c, identically or differently, are a hydrocarbon radical or a
  • Heterocyclyl radical where each of the latter two radicals is unsubstituted or substituted by one or more identical or different radicals from the group consisting of halogen, cyano, nitro, amino, hydroxyl, phosphoryl, halogeno (C 1 -C 4 -alkoxy, mono- and di- [( C ⁇ C ⁇ alkyljamino substituted, or an alkyl radical in which several, preferably 2 or 3, not adjacent
  • CH 2 groups are each replaced by an oxygen atom;
  • Z a is a divalent group of the formula -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -SO- , -SO 2 -, -NR + -, -CO-NR + -,
  • Z b , Z c independently of one another a direct bond or a divalent group of the formula -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -SO-, -SO 2 -, -NR + -, -SO 2 -NR + -, -NR + -SO 2 -, -CO-NR + - or -NR + -CO-, where the binding specified on the right is the respective divalent group is the bond to the radical R b or R c and wherein the R + in the latter 5 radicals independently of one another are each H, (C 1 -C 4 ) alkyl or halo (C 1 -C 4 ) alkyl; n is an integer from 0 to 4, preferably 0, 1 or 2, in particular 0 or 1, and m is an integer from 0 to 5, preferably 0, 1, 2 or 3, in particular 0, 1 or 2;
  • X 3 is CH or N
  • R 25 is hydrogen, heterocyclyl or a hydrocarbon radical, where the latter two radicals are optionally substituted by one or more, identical or different radicals from the group consisting of halogen, cyano, nitro, amino, hydroxyl,
  • R 26 is hydrogen, hydroxy, (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl,
  • R 27 is halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH 2 , SO 2 NH 2 or Z b -R b ;
  • R 28 is hydrogen, (C 1 -C 4 ) AIKyI, (C 2 -C 4 ) alkenyl or (C 2 -C 4 ) alkynyl;
  • R 29 is halogen, cyano, nitro, amino, hydroxy, carboxy, phosphoryl, CHO, CONH 2 ,
  • R a is a (C 2 -C 20 ) alkyl radical whose carbon chain is mono- or polysubstituted
  • Interrupted oxygen atoms, heterocyclyl or a hydrocarbon radical where the latter two radicals optionally substituted by one or more identical or different radicals selected from the group halogen, cyano, nitro, amino, hydroxy, mono- and di - [(C 1 -C 4 ) alkyl] amino;
  • R b , R c identically or differently, denote a (C 2 -C 20 ) alkyl radical whose carbon chain is interrupted one or more times by oxygen atoms, heterocyclyl or a hydrocarbon radical, where the last two radicals are selected from one or more, identical or different radicals the group halogen, cyano, nitro, amino, hydroxy, phosphoryl, (C 1 -C 4 ) -
  • Z a is a divalent unit selected from O, S, CO, CS, C (O) O, C (O) S, SO, SO 2 , NR d , C (O) NR d or SO 2 NR d ;
  • Z b , Z c identically or differently, denote a direct bond or a divalent unit from the group O, S, CO, CS, C (O) O, C (O) S, SO, SO 2 , NR d , SO 2 NR d or C (O) NR d ;
  • R d is hydrogen, (C r C 4 ) alkyl or (C 1 -C 4 ) haloalkyl;
  • n is an integer from 0 to 4, and in the case where X is CH, an integer from 0 to 5, and when X is N, an integer from 0 to 4; e) compounds of the formula (XXII),
  • R 30 is H, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkyl substituted with (C 1 -C 4 ) alkyl or -X 4 or
  • R 31 is H, halogen, (C 1 -C 4 ) AIKyI, CF 3 , (C 1 -C 4 ) AIKoxY or (C r C 4 ) haloalkoxy;
  • R 32 is H, halogen or (C 1 -C 4 ) AIKyI;
  • Q 1 , Q 2 , E, G are identical or different, -O-, -S-, -CR 2 37 -, -CO-, NR 38 - or a group of the formula (XXIII),
  • R a is identical or different H or (C 1 -C 8 ) AIRyI or the two radicals R a together are (C 2 -C 6 ) alkylene;
  • A is R b -Y 3 - or -NR 2 39 ;
  • X 4 is -O- or -S (O) p -;
  • Y 3 is -O- or -S-;
  • R b is H 1 (C 1 -C 8) AIRyI 1 (C 1 -C 8) HaIOaIRyI, (C r C 4) alkoxy (C 1 -C 8 JaIRyI, (C 3 -C 6) -
  • R 33 is H or (C 1 -C 4 ) AIRyI
  • R 34 is identical or different H, (C 1 -C 4) AIRyI 1 (C ⁇ C ⁇ AIRylcarbonyl or the two radicals R 34 together are (C 4 -C 5) AIRylen;
  • R 35 , R 36 are each independently identical or different H, (C 1 -C 4 ) AIRyI, or the two radicals R 35 and / or R 36 are together
  • CH 2 groups replaced by -NR C - can be roughened;
  • R c is H or (C 1 -C 8 ) AIRyI;
  • R 37 is identical or different H, (C 1 -C 8 ) AIRyI or the two radicals R 37 together are (C 2 -C 6 ) AIRylen;
  • R 38 is H, (C 1 -C 8 ) alkyl, substituted or unsubstituted phenyl, or unsubstituted or phenyl ring substituted benzyl;
  • R 39 is identical or different H, (C 1 -C 8 ) -alkyl, phenyl, phenyl- (C 1 -C 8 -alkyl), where a phenyl ring is represented by F, Cl, Br, NO 2 , CN, OCH 3 , (C 1 -C 4 ) AIRyI or CH 3 SO 2 - be substituted Rann; (C 1 -C 4 ) -airoxy- (C 1 -C 8 -alkyl, (C 3 -C 6 ) -airenyl,
  • (C 3 -C 6 ) AIRinyl, (C 3 -C 6 ) cycloalRyl or two radicals R 39 together are (C 4 -C 5 ) -YL.sub.ylene where one CH 2 group is O or S or one or two CK groups by -NR d - replaced his Rönnen; R d is H or (C 1 -C 4 ) AIRyI; m "is 0 or 1 and p is 0, 1 or 2;
  • the formulations present in commercial form are optionally diluted in the usual manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Dust-like preparations, ground or scattered granules and sprayable solutions are usually no longer diluted with other inert substances before use.
  • the type of herbicide used u.a. varies the required application rate of the compounds of the invention. It can vary within wide limits, e.g. between 0.001 and 10.0 kg / ha or more of active substance, preferably between 0.005 and 5 kg / ha.
  • N- (tert-butyl) -2-iodo-6-methoxybenzenesulfonamide (Example No. 2.092b)
  • a solution of 30.00 g (123.29 mmol) of N- (tert-butyl) -2-methoxybenzenesulfonamide in 400 ml of tetrahydrofuran is added.
  • 2-Hydroxy-6-iodobenzenesulfonamide (Example No. 2.300a) 0.50 g (1.60 mmol) of 2-iodo-6-methoxybenzenesulfonamide are initially charged in 10 ml of dichloromethane at room temperature and treated carefully with 0.6 g (2.40 mmol) of boron tribromide. The reaction solution is stirred for a further 45 minutes at room temperature and is then added to 2N hydrochloric acid. After extraction with dichloromethane, the organic phase is dried and evaporated. This gives 0.43 g (90% of theory) of 2-hydroxy-6-iodobenzenesulfonamide.
  • 2-iodo-6- (methylthio) benzenesulfonamide (Example No. 2.208a) 30.00 g (99.64 mmol) of 2-fluoro-6-iodobenzenesulfonamide obtained from the reaction of N- (ferf-butyl) -2-fluoro-6 -iodobenzenesulfonamide with trifluoroacetic acid analogously to Example A3 are presented together with 15.15 g (109.61 mmol) of potassium carbonate in 250 ml of dimethylformamide. At room temperature, 7.68 g (109.61 mmol) of sodium thiomethylate are added in portions, after which it is stirred for 12 h at room temperature.
  • reaction mixture is poured into 150 ml of ice-water, adjusted to pH 4-5 with 2N hydrochloric acid and extracted with ethyl acetate. The organic phase is dried and evaporated.
  • Preparative HPLC Reversed phase, 0.05% trifluoroacetic acid in water / acetonitrile, gradient: in 30 min, 25 to 100%
  • Example No: 1.186 (CDCI 3 ): 12.51 (brs, 1H); 7.80 (m, 1H); 7.39 (brs, 1H); 7.06 (m, 1H); 6.98 (m, 1H); 6.76 (s, 1H); 4.69 (m, 1H); 2.47 (s, 6H); 1.32 (br d, J 6.0, 6H).
  • Example No. 2.300a (CDCI 3 ): 9.91 (s, 1H); 7.60 (m, 1H); 7.05 (m, 2H); 5.49 (brs, 2h).
  • a dust is obtained by mixing 10 parts by weight of a compound of formula (I) and / or salts thereof and 90 parts by weight of talc as inert material and comminuted in a hammer mill.
  • a wettable powder readily dispersible in water is obtained by reacting 25 parts by weight of a compound of formula (I) and / or its salts, 64 parts by weight of kaolin-containing quartz as inert material, 10 parts by weight of potassium lignosulfonate and 1 part by weight Mix oleoylmethyl tauric acid sodium as wetting and dispersing agent and mill in a pin mill.
  • a dispersion concentrate readily dispersible in water is obtained by reacting 20 parts by weight of a compound of the formula (I) and / or salts thereof with 6 parts by weight of alkylphenol polyglycol ether ( ⁇ Triton X 207), 3
  • isotridecanol polyglycol ether 8 EO
  • paraffinic mineral oil oil range, for example, about 255 to more than 277 C
  • An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I) and / or salts thereof, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.
  • Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants were placed in sandy soil in cardboard pots and covered with soil.
  • the compounds of the invention formulated in the form of wettable powders or emulsion concentrates were then applied to the surface of the cover soil as aqueous suspensions or emulsions having a water application rate of 600 to 800 l / ha in different dosages.
  • Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds were placed in sandy loam soil in plastic pots, covered with soil and grown in the greenhouse under good growth conditions. Three weeks after sowing, the test plants were treated at the trefoil stage.
  • the compounds of the invention formulated as wettable powders or as emulsion concentrates were sprayed onto the green plant parts in various dosages with a water application rate of 600 to 800 l / ha. After about 3 to 4 weeks of life of the test plants in the greenhouse under optimal growth conditions, the effect of the preparations was optically scored compared to untreated controls.
  • compositions according to the invention also have a good herbicidal activity against a broad spectrum of economically important weed grasses and weeds in postemergence.
  • dicotyledonous crops such as soybean, cotton, oilseed rape, sugar beets or potatoes in the pre- and postemergence process even with high doses of active ingredient undamaged.
  • some substances also protect graminaceous crops such as barley, wheat, rye, millet, corn or rice.

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Abstract

The invention relates to a compound of formula (I), wherein R is a hydrocarbon or hydrocarboxy unsubstituted or substituted group comprising inclusive substituents of 1 to 30 C atoms, or a heterocyclyle or heterocyclyloxy unsubstituted or substituted group, or R is a OC(O)R<SUP>3</SUP>, S(O)<SUB>n</SUB>R<SUP>3</SUP>, OS(O)<SUB>n</SUB>R<SUP>3</SUP>, F, Br1 I, OH, CN, NO<SUB>2</SUB>, NH<SUB>2</SUB>, SF<SUB>5</SUB>, NR<SUP>4</SUP>R<SUP>5</SUP> or Si(R<SUP>6</SUP>)<SUB>3</SUB>group, n is equal to 1 or 2; R<SUP>1 </SUP>independently represents halogen, OH1 SH, a carbon-free nitrogen group or a carbon group comprising from 1 to 30 C atoms, or R<SUP>0</SUP> and R<SUP>#</SUP> form jointly a nitrogen heterocyclic ring; I is 0, 1, 2, or 3; R<SUP>2</SUP> is a hydrogen atom or a hydrocarbon or hydrocarboxy unsubstituted or substituted group comprising inclusive substituents of 1 to 30 carbon atoms; R<SUP>3</SUP> is a hydrocarbon or hydrocarboxy unsubstituted or substituted group comprising substituents of 1 to 30 C atoms or a heterocyclyle or heterocyclyloxy unsubstituted or substituted group, or R<SUP>3</SUP> is a hydrogen atom, CN or NR<SUP>4</SUP>R<SUP>5</SUP>, R<SUP>4</SUP> is a group of formula R<SUP>0</SUP>-Q<SUP>0</SUP>, wherein R<SUP>0</SUP> is a hydrogen atom, an acyl group, a hydrocarbon group or a heterocyclyle group, wherein each said group is unsubstituted or substituted and comprises substituents of 1 to 30 C atoms and Q<SUP>0</SUP> is a direct link or a divalent group of formula -O- or -N(R<SUP>#</SUP>)-, wherein R<SUP>#</SUP> is a hydrogen atom, an alkyl group or a hydrocarbon group which is unsubstituted or substituted and comprises inclusive substituents of 1 to 30 C atoms, or R<SUP>0</SUP> and R<SUP>#</SUP> R<SUP>0</SUP> and R<SUP>#</SUP> form jointly a nitrogen heterocyclic ring, R<SUP>5</SUP> is a hydrogen atom, an acyl group, a hydrocarbon group or a heterocyclyle group, wherein each said group is unsubstituted or substituted and comprises substituents of 1 to 30 C atoms, or R<SUP>4</SUP> and R<SUP>5</SUP> form jointly a nitrogen heterocyclic ring; R<SUP>6</SUP> is an unsubstituted or substituted hydrocarbon group, W is an oxygen or sulphur atom, X1 and Y are independently a hydrogen, halogen, (C<SUB>1</SUB>-C<SUB>6</SUB>) alkyl, (C<SUB>1</SUB>C<SUB>6</SUB>)alkoxy or (C<SUB>1</SUB>-C<SUB>6</SUB>) alkylthio atom, wherein each of said three groups is unsubstituted or substituted by one or several rests of a halogen, (C<SUB>1</SUB>-C<SUB>6</SUB>)alkyl, (C<SUB>1</SUB>C<SUB>6</SUB>)alkoxy or (C<SUB>1</SUB>-C<SUB>6</SUB>)alkylthio group, or means mono- or Di[(C<SUB>1</SUB>-C<SUB>6</SUB>)alkyl] amino, (C<SUB>2</SUB>-C<SUB>6</SUB>)alkenyl, (C<SUB>2</SUB>-C<SUB>6</SUB>)alkinyl, (C<SUB>3</SUB>-C<SUB>6</SUB>) aIkenyloxy or (C<SUB>3</SUB>-C<SUB>6</SUB>)alkinyloxy and V<SUB>1</SUB>and Z independently mean CH or N. The inventive compound is suitable for plant protection.

Description

Beschreibungdescription
PHENYLSULFONYLHARNSTOFFE MIT HERBIZIDER WIRKUNGPHENYLSULFONYL HARVES WITH HERBICIDAL EFFECT
Es ist bekannt, daß substituierte Phenylsulfonylharnstoffe herbizide Eigenschaften besitzen können. Dabei handelt es sich z.B. um Phenylderivate, die einfach oder mehrfach substituiert sind (z.B. US 4127405, WO 9209608, BE 853374, WO 9213845, EP 84020, WO 9406778, WO 02072560, US 4169719).It is known that substituted phenylsulfonylureas can have herbicidal properties. These are e.g. phenyl derivatives which are monosubstituted or polysubstituted (for example US 4127405, WO 9209608, BE 853374, WO 9213845, EP 84020, WO 9406778, WO 02072560, US 4169719).
Ebenso zeigen Phenylsulfonylharnstoffe mit einem allgemeinen 1 ,2,3- Substitutionsmuster herbizide Eigenschaften (z.B. WO 9732861 , WO 02062768).Also, phenylsulfonylureas having a general 1,2,3 substitution pattern exhibit herbicidal properties (e.g., WO9732861, WO02062768).
Überraschenderweise wurden nun spezielle lod-substituierte Phenylsulfonylharnstoffe gefunden, die sich besonders vorteilhaft als Herbizide oder Pflanzenwachstumsregulatoren eignen.Surprisingly, special iodine-substituted phenylsulfonylureas have now been found which are particularly advantageous as herbicides or plant growth regulators.
Gegenstand der vorliegenden Erfindung sind somit Verbindungen der allgemeinen Formel (I) und/oder deren Salze,The present invention thus relates to compounds of the general formula (I) and / or their salts,
worin wherein
R ein Kohlenwasserstoffrest oder Kohlenwasserstoffoxyrest, vorzugsweise ein Rest aus der Gruppe Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl, Cycloalkinyl, Alkoxy, Alkenyloxy, Alkinyloxy, Cycloalkyloxy, Cycloalkenyloxy, Aryl oder Aryloxy ist, der unsubstituiert oder substituiert ist und inklusive Substituenten 1 bis 30 C-Atome, vorzugsweise 1 bis 20 C-Atome aufweist, oder R ein Heterocyclylrest oder Heterocyclyloxyrest ist, welcher unsubstituiert oder substituiert ist, oder R ein Rest OC(O)R3, S(O)nR3, OS(O)nR3, F1 Br, I1 OH, CN, NO2, NH2, SF5, NR4R5 oder Si(R6)3 ist, wobei n gleich 0, 1 oder 2 ist,R is a hydrocarbon radical or hydrocarbonoxy radical, preferably a radical from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, aryl or aryloxy, which is unsubstituted or substituted and inclusive Substituents 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, or R is a heterocyclyl radical or Heterocyclyloxyrest which is unsubstituted or substituted, or R is a radical OC (O) R 3 , S (O) n R 3 , OS (O) n R 3 , F 1 is Br, I 1 is OH, CN, NO 2 , NH 2 , SF 5 , NR 4 R 5 or Si (R 6 ) 3 , where n is 0, 1 or 2,
R1 unabhängig voneinander Halogen, OH, SH, ein kohlenstofffreier stickstoffhaltiger Rest oder ein kohlenstoffhaltiger Rest ist, der 1 bis 30 C- Atome, vorzugsweise 1 bis 20 C-Atome aufweist, I 0, 1 , 2 oder 3, vorzugsweise 0, 1 oder 2, besonders bevorzugt 0 oder 1 , ganz besonders bevorzugt 0 ist,R 1 is independently halogen, OH, SH, a carbon-free nitrogen-containing radical or a carbon-containing radical having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, I 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1, most preferably 0,
R2 ein Wasserstoffatom oder ein Kohlenwasserstoffrest ist, der unsubstituiert oder substituiert ist und inklusive Substituenten 1 bis 20 C-Atome, vorzugsweise 1 bis 10 C-Atome aufweist, z.B. unsubstituiert.es oder substituiertes vorzugsweise H oder CH3, R3 ein Kohlenwasserstoffrest oder Kohlenwasserstoffoxyrest, vorzugsweise ein Rest aus der Gruppe Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl, Cycloalkinyl, Alkoxy, Alkenyloxy, Alkinyloxy, Cycloalkyloxy, Cycloalkenyloxy, Aryl oder Aryloxy ist, der unsubstituiert oder substituiert ist und inklusive Substituenten 1 bis 30 C-Atome, vorzugsweise 1 bis 20 C-Atome aufweist, oder R3 ein Heterocylylrest oder Heterocylyloxyrest ist, welcher unsubstituiert oder substituiert ist, oder R3 ein Wasserstoffatom, CN oder NR4R5 ist, R4 eine Gruppe der Formel R°-Q°- ist, worinR 2 is a hydrogen atom or a hydrocarbon radical which is unsubstituted or substituted and contains, including substituents, 1 to 20 C atoms, preferably 1 to 10 C atoms, for example unsubstituted or substituted preferably H or CH 3 , R 3 is a hydrocarbon radical or hydrocarbonoxy radical, preferably a radical from the group alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, aryl or aryloxy, which is unsubstituted or substituted and is inclusive of substituents 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, or R 3 is a heterocyclyl or heterocyclyl radical which is unsubstituted or substituted, or R 3 is a hydrogen atom, CN or NR 4 R 5 , R 4 is a group of the formula R ° -Q ° - wherein
R0 ein Wasserstoffatom, ein Acylrest, ein Kohlenwasserstoffrest oder ein Heterocyclylrest bedeutet, wobei jeder der letztgenannten beiden Reste unsubstituiert oder substituiert ist und inklusive Substituenten 1 bis 30 C-R 0 represents a hydrogen atom, an acyl radical, a hydrocarbon radical or a heterocyclyl radical, each of the last-mentioned two radicals being unsubstituted or substituted and including substituents 1 to 30 C
Atome, vorzugsweise 1 bis 20 C-Atome aufweist, und Q0 eine direkte Bindung oder eine divalente Gruppe der Formel -O- oder - N(R#)- bedeutet, wobei R# ein Wasserstoffatom, ein Acylrest oder ein Kohlenwasserstoffrest bedeutet und wobei der letztgenannte Rest unsubstituiert oder substituiert ist und inklusive Substituenten 1 bis 30 C-Atoms, preferably 1 to 20 carbon atoms, and Q 0 is a direct bond or a divalent group of the formula -O- or -N (R # ) -, wherein R # represents a hydrogen atom, an acyl radical or a hydrocarbon radical and wherein the latter radical is unsubstituted or substituted and includes substituents 1 to 30 C-
Atome, vorzugsweise 1 bis 20 C-Atome aufweist, oder R0 und R# miteinander einen stickstoffhaltigen heterocyclischen Ring bilden, R5 ein Wasserstoffatom, ein Acylrest, ein Kohlenwasserstoffrest oder ein Heterocyclylrest ist, wobei jeder der letztgenannten beiden Reste unsubstituiert oder substituiert ist und inklusive Substituenten 1 bis 30 C- Atome, vorzugsweise 1 bis 20 C-Atome aufweist, oder R4 und R5 miteinander einen stickstoffhaltigen heterocyclischen Ring bilden,Atoms, preferably 1 to 20 carbon atoms, or R 0 and R # together form a nitrogen-containing heterocyclic ring, R 5 is a hydrogen atom, an acyl radical, a hydrocarbon radical or a heterocyclyl radical, each of the latter two radicals being unsubstituted or substituted and having, including substituents, 1 to 30 C atoms, preferably 1 to 20 C atoms, or R 4 and R 5 together form a nitrogen-containing heterocyclic ring,
R6 ein Kohlenwasserstoffrest ist, der unsubstituiert oder substituiert ist und inklusive Substituenten 1 bis 30 C-Atome, vorzugsweise 1 bis 20 C-Atome aufweist, vorzugsweise (d-C4)Alkyl oder (C6-C10)AIyI,R 6 is a hydrocarbon radical which is unsubstituted or substituted and contains, including substituents, 1 to 30 C atoms, preferably 1 to 20 C atoms, preferably (C 1 -C 4 ) alkyl or (C 6 -C 10 ) alkyl,
W ein Sauerstoffatom oder ein Schwefelatom ist, X1Y unabhängig voneinander für ein Wasserstoffatom, Halogen, (Ci-C6)Alkyl, (Cr C6)Alkoxy oder (CrC6)Alkylthio ist, wobei jeder der letztgenannten 3 Reste unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, (CrC4)AIkOXy, und (CrC4)Alkylthio substituiert ist, oder Mono- oder Di[(d- C6)alkyl] amino, (C2-C6)Alkenyl, (C2-C6)Alkinyl, (C3-C6)Alkenyloxy oder (C3- C6)Alkinyloxy bedeuten, undW is an oxygen atom or a sulfur atom, X is unsubstituted 1 Y independently represent a hydrogen atom, halogen, (Ci-C 6) alkyl, (Cr C 6) alkoxy or (C r C 6) alkylthio, where each of the last 3 radicals (4 -C) alkylthio or by one or more radicals from the group halogen, (CrC 4) -alkoxy, and substituted or mono- or di [(d- C6) alkyl] amino, (C 2 -C 6) alkenyl , (C 2 -C 6) alkynyl, (C 3 -C 6) alkenyloxy or (C 3 - C 6) alkynyloxy means, and
V,Z unabhängig voneinander CH oder N bedeuten.V, Z are independently CH or N
Die Verbindungen der Formel (I) können Salze bilden, z.B. solche bei denen der Wasserstoff der -SCVNH-Gruppe durch ein für die Landwirtschaft geeignetes Kation ersetzt ist. Diese Salze sind beispielsweise Metallsalze, insbesondereThe compounds of formula (I) may form salts, e.g. those in which the hydrogen of the -SCVNH group is replaced by a cation suitable for agriculture. These salts are, for example, metal salts, in particular
Alkalimetallsalze oder Erdalkalimetallsalze, insbesondere Natrium- und Kaliumsalze, oder auch Ammoniumsalze oder Salze mit organischen Aminen. Ebenso kann Salzbildung durch Anlagerung einer Säure an basischen Gruppen, wie z.B. Amino und Alkylamino, erfolgen. Geeignete Säuren hierfür sind starke anorganische und organische Säuren, beispielsweise HCl, HBr, H2SO4 oder HNO3.Alkali metal salts or alkaline earth metal salts, especially sodium and potassium salts, or ammonium salts or salts with organic amines. Likewise, salt formation can take place by addition of an acid to basic groups, such as, for example, amino and alkylamino. Suitable acids for this purpose are strong inorganic and organic acids, for example HCl, HBr, H 2 SO 4 or HNO 3 .
Kohlenstoffhaltige Reste sind organische Reste, die mindestens ein Kohlenstoffatom, vorzugsweise 1 bis 30 C-Atome, besonders bevorzugt 1 bis 20 C-Atome und außerdem mindestens ein Atom eines oder mehrerer anderer Elemente des Periodensystems der Elemente wie H, Si, N, P, O, S, F, Cl, Br oder J enthalten. Beispiele für kohlenstoffhaltige Reste sind unsubstituierte oder substituierte Kohlenwasserstoffreste, die direkt oder über ein Heteroatom wie N, S, P oder O an den Grundkörper gebunden sein können, unsubstituierte oder substituierte Heterocyclylreste, die direkt oder über ein Heteroatom wie N, S, P oder O an den Grundkörper gebunden sein können, kohlenstoffhaltige Acylreste oder Cyano.Carbon-containing radicals are organic radicals which contain at least one carbon atom, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms and also at least one atom of one or more other elements of the Periodic Table of Elements such as H, Si, N, P, O, S, F, Cl, Br or J included. Examples of carbon-containing radicals are unsubstituted or substituted hydrocarbon radicals which are bonded directly or via a heteroatom such as N, S, P or O may be bonded to the main body, unsubstituted or substituted heterocyclyl radicals which may be bonded to the basic body directly or via a heteroatom such as N, S, P or O, carbon-containing acyl radicals or cyano.
In Formel (I) und allen nachfolgenden Formeln können die kohlenstoffhaltigen Reste wie Alkyl, Alkoxy, Haloalkyl, Haloalkoxy, Alkylamino und Alkylthio sowie die entsprechenden ungesättigten und/oder substituierten Reste im Kohlenstoffgerüst jeweils geradkettig oder verzweigt sein. Wenn nicht speziell angegeben, sind bei diesen Resten die niederen Kohlenstoffgerüste, z.B. mit 1 bis 6 C-Atomen bzw. bei ungesättigten Gruppen mit 2 bis 6 C-Atomen, bevorzugt. Alkylreste, auch in den zusammengesetzten Bedeutungen wie Alkoxy, Haloalkyl usw., bedeuten z.B. Methyl, Ethyl, n- oder i-Propyl, n-, i-, t- oder 2-Butyl, Pentyle, Hexyle, wie n-Hexyl, i-Hexyl und 1 ,3-Dimethylbutyl, Heptyle, wie n-Heptyl, 1 -Methylhexyl und 1 ,4-Dimethylpentyl; Alkenyl- und Alkinylreste haben die Bedeutung der denIn formula (I) and all subsequent formulas, the carbon-containing radicals such as alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio and the corresponding unsaturated and / or substituted radicals in the carbon skeleton may each be straight-chain or branched. Unless specifically stated, these radicals are the lower carbon skeletons, e.g. with 1 to 6 C atoms or with unsaturated groups having 2 to 6 C atoms, preferred. Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyl, etc., mean e.g. Methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1,3-dimethylbutyl, heptyls, such as n-heptyl, 1-methylhexyl and 1, 4-dimethylpentyl; Alkenyl and alkynyl radicals have the meaning of the
Alkylresten entsprechenden möglichen ungesättigten Reste; Alkenyl bedeutet z.B. AIIyI, 1-Methylprop-2-en-1-yl, 2-Methyl-prop-2-en-1-yl, But-2-en-1-yl, But-3-en-1-yl, 1-Methyl-but-3-en-1-yl und 1-Methyl-but-2-en-1-yl; Alkinyl bedeutet z.B. Propargyl, But-2-in-1-yl, But-3-in-1-yl, 1-Methyl-but-3-in-1-yl.Alkyl radicals corresponding to possible unsaturated radicals; Alkenyl means e.g. Allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1 Methyl-but-3-en-1-yl and 1-methylbut-2-en-1-yl; Alkynyl means e.g. Propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methyl-but-3-yn-1-yl.
Alkenyl in der Form (C3-C4)Alkenyl, (C3-C5)AI kenyl, (C3-C6)Alkenyl, (C3-C8)Alkenyl oder (C3-Ci2)Alkenyl bedeutet vorzugsweise einen Alkenylrest mit 3 bis 4, 3 bis 5, 3 bis 6, 3 bis 8 bzw. 3 bis 12 C-Atomen, bei dem die Doppelbindung nicht an dem C-Atom liegt, das mit dem übrigen Molekülteil der Verbindung (I) verbunden ist ("yl"-Position). Entsprechendes gilt für (C3-C4)Alkinyl etc., (C3-C4)AI kenyloxy etc. und (C3-C4)Alkinyloxy etc.Alkenyl in the form (C 3 -C 4 ) alkenyl, (C 3 -C 5 ) AI kenyl, (C 3 -C 6 ) alkenyl, (C 3 -C 8 ) alkenyl or (C 3 -C 2 ) alkenyl preferably an alkenyl radical having 3 to 4, 3 to 5, 3 to 6, 3 to 8 or 3 to 12 C atoms, in which the double bond is not located on the C atom, which is bonded to the remaining moiety of the compound (I) is connected ("yl" position). The same applies to (C 3 -C 4 ) alkynyl etc., (C 3 -C 4 ) Al kenyloxy etc. and (C 3 -C 4 ) alkynyloxy etc.
Cycloalkyl bedeutet ein carbocyclisches, gesättigtes Ringsystem mit vorzugsweise 3-8 C-Atomen, z.B. Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl.Cycloalkyl means a carbocyclic saturated ring system preferably having 3-8 C atoms, e.g. Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Kohlenstofffreie stickstoffhaltige Reste sind Reste die vorzugsweise 1 bis 10 N- Atome, besonders bevorzugt 1 oder 2 N-Atome enthalten und außerdem vorzugsweise eines oder mehrere Atome eines oder mehrerer von Kohlenstoff verschiedener Elemente des Periodensystems der Elemente wie H, O oder S enthalten. Beispiele für kohlenstofffreie stickstoffhaltige Reste sind NH2, NO2, NHOH, NO, NH-NH2 oder N3.Carbon-free nitrogen-containing radicals are radicals which preferably contain 1 to 10 N atoms, particularly preferably 1 or 2 N atoms, and also preferably one or more atoms of one or more of carbon-different elements of the periodic table of the elements such as H, O or S. Examples of carbon-free nitrogen-containing radicals are NH 2 , NO 2 , NHOH, NO, NH-NH 2 or N 3 .
Halogen bedeutet beispielsweise Fluor, Chlor, Brom oder lod. Haloalkyl, -alkenyl und -alkinyl bedeuten durch Halogen, vorzugsweise durch Fluor, Chlor und/oder Brom, insbesondere durch Fluor oder Chlor, teilweise oder vollständig substituiertes Alkyl, Alkenyl bzw. Alkinyl, z.B. CF3, CHF2, CH2F, CF3CF2, CH2FCHCI, CCI3, CHCI2, CH2CH2CI; Haloalkoxy ist z.B. OCF3, OCHF2, OCH2F, CF3CF2O, OCH2CF3 und OCH2CH2CI; entsprechendes gilt für Haloalkenyl und andere durch Halogen substituierte Reste.Halogen is, for example, fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and -alkynyl by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine, partially or completely substituted alkyl, alkenyl or alkynyl, for example CF 3 , CHF 2 , CH 2 F, CF 3 CF 2 , CH 2 FCHCl, CCI 3 , CHCl 2 , CH 2 CH 2 Cl; Haloalkoxy is, for example, OCF 3 , OCHF 2 , OCH 2 F, CF 3 CF 2 O, OCH 2 CF 3 and OCH 2 CH 2 Cl; the same applies to haloalkenyl and other halogen-substituted radicals.
Ein Kohlenwasserstoffrest ist ein geradkettiger, verzweigter oder cyclischer und gesättigter oder ungesättigter aliphatischer oder aromatischerA hydrocarbon radical is a straight-chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic
Kohlenwasserstoffrest, z.B. Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl oder Aryl;Hydrocarbon radical, e.g. Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl;
Aryl bedeutet dabei ein mono-, bi- oder polycyclisches aromatisches System, beispielsweise Phenyl, Naphthyl, Tetrahydronaphthyl, Indenyl, Indanyl, Pentalenyl,Aryl means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl,
Fluorenyl und ähnliches, vorzugsweise Phenyl; vorzugsweise bedeutet ein Kohlenwasserstoffrest Alkyl, Alkenyl oder Alkinyl mit bis zu 12 C-Atomen oder Cycloalkyl mit 3, 4, 5, 6 oder 7 Ringatomen oder Phenyl.Fluorenyl and the like, preferably phenyl; a hydrocarbon radical preferably denotes alkyl, alkenyl or alkynyl having up to 12 C atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl.
Ein heterocyclischer Rest oder Ring (Heterocyclyl) kann gesättigt, ungesättigt oder heteroaromatisch und unsubstituiert oder substituiert sein; er enthält vorzugsweise ein oder mehrere Heteroatome im Ring, vorzugsweise aus der Gruppe N, O und S; vorzugsweise ist er ein aliphatischer Heterocyclylrest mit 3 bis 7 Ringatomen oder ein heteroaromatischer Rest mit 5 oder 6 Ringatomen und enthält 1 , 2 oder 3 Heteroatome. Der heterocyclische Rest kann z.B. ein heteroaromatischer Rest oder Ring (Heteroaryl) sein, wie z.B. ein mono-, bi- oder polycyclisches aromatisches System, in dem mindestens 1 Ring ein oder mehrere Heteroatome enthält, beispielsweise Pyridyl, Pyrimidinyl, Pyridazinyl, Pyrazinyl, Triazinyl, Thienyl, Thiazolyl, Oxazolyl, Furyl, Pyrrolyl, Pyrazolyl und Imidazolyl, oder ist ein partiell oder vollständig hydrierter Rest wie Oxiranyl, Oxetanyl, Pyrrolidyl, Piperidyl, Piperazinyl, Dioxolanyl, Moφholinyl, Tetrahydrofuryl. Als Substituenten für einen substituierten heterocyclischen Rest kommen die weiter unten genannten Substituenten in Frage, zusätzlich auch Oxo. Die Oxogruppe kann auch an den Heteroringatomen, die in verschiedenen Oxidationsstufen existieren können, z.B. bei N und S, auftreten.A heterocyclic radical or ring (heterocyclyl) may be saturated, unsaturated or heteroaromatic and unsubstituted or substituted; it preferably contains one or more heteroatoms in the ring, preferably from the group N, O and S; it is preferably an aliphatic heterocyclyl radical having 3 to 7 ring atoms or a heteroaromatic radical having 5 or 6 ring atoms and contains 1, 2 or 3 heteroatoms. The heterocyclic radical may be, for example, a heteroaromatic radical or ring (heteroaryl), for example a mono-, bi- or polycyclic aromatic system in which at least one ring contains one or more heteroatoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, Thienyl, thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or is a partial or fully hydrogenated radical such as oxiranyl, oxetanyl, pyrrolidyl, piperidyl, piperazinyl, dioxolanyl, Moφholinyl, tetrahydrofuryl. Suitable substituents for a substituted heterocyclic radical are the substituents mentioned below in question, in addition also oxo. The oxo group may also occur on the hetero ring atoms, which may exist in different oxidation states, eg at N and S.
Substituierte Reste, wie substituierte Kohlenwasserstoffreste, z.B. substituiertes Alkyl, Alkenyl, Alkinyl, Aryl, Phenyl und Benzyl, oder substituiertes Heterocyclyl oder Heteroaryl, bedeuten beispielsweise einen vom unsubstituierten Grundkörper abgeleiteten substituierten Rest, wobei die Substituenten beispielsweise einen oder mehrere, vorzugsweise 1 , 2 oder 3 Reste aus der Gruppe Halogen, Alkoxy, Haloalkoxy, Alkylthio, Hydroxy, Amino, Nitro, Carboxy, Cyano, Azido, Alkoxycarbonyl, Alkylcarbonyl, Formyl, Carbamoyl, Mono- und Dialkylaminocarbonyl, substituiertes Amino, wie Acylamino, Mono- und Dialkylamino, und Alkylsulfinyl, Haloalkylsulfinyl, Alkylsulfonyl, Haloalkylsulfonyl und, im Falle cyclischer Reste, auch Alkyl und Haloalkyl sowie den genannten gesättigten kohlenwasserstoffhaltigen Resten entsprechende ungesättigte aliphatische Reste, wie Alkenyl, Alkinyl, Alkenyloxy, Alkinyloxy etc. bedeuten. Bei Resten mit C-Atomen sind solche mit 1 bis 4 C-Atomen, insbesondere 1 oder 2 C-Atomen, bevorzugt. Bevorzugt sind in der Regel Substituenten aus der Gruppe Halogen, z.B. Fluor und Chlor, (CrC4)Alkyl, vorzugsweise Methyl oder Ethyl, (CrC4)Haloalkyl, vorzugsweise Trifluormethyl, (CrC4)AIkOXy, vorzugsweise Methoxy oder Ethoxy, (Ci-C-OHaloalkoxy, Nitro und Cyano. Besonders bevorzugt sind dabei die Substituenten Methyl, Methoxy und Chlor. Gegebenenfalls substituiertes Phenyl ist vorzugsweise Phenyl, das unsubstituiert oder ein- oder mehrfach, vorzugsweise bis zu dreifach durch gleiche oder verschiedene Reste aus der Gruppe Halogen, (Ci-C4)Alkyl, (CrC4)Alkoxy, (CrC4)Halogenalkyl, (Ci-C4)Halogenalkoxy und Nitro substituiert ist, z.B. o-, m- und p-Tolyl, Dimethylphenyle, 2-, 3- und 4-Chlorphenyl, 2-, 3- und 4-Trifluor- und -Trichlorphenyl, 2,4-, 3,5-, 2,5- und 2,3-Dichlorphenyl, o-, m- und p-Methoxyphenyl.Substituted radicals, such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted heterocyclyl or heteroaryl, represent, for example, a substituted radical derived from the unsubstituted radical, where the substituents are, for example, one or more, preferably 1, 2 or 3 3 radicals from the group halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, carboxy, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such as acylamino, mono- and dialkylamino, and Alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals, also alkyl and haloalkyl and said saturated hydrocarbon-containing radicals corresponding unsaturated aliphatic radicals, such as alkenyl, alkynyl, alkenyloxy, alkynyloxy, etc. For radicals with C atoms, those having 1 to 4 C atoms, in particular 1 or 2 C atoms, are preferred. Substituents from the group halogen, for example fluorine and chlorine, (C 1 -C 4 ) alkyl, preferably methyl or ethyl, (C 1 -C 4 ) haloalkyl, preferably trifluoromethyl, (C 1 -C 4 ) alkoxy, preferably methoxy or ethoxy, are generally preferred. C-OHaloalkoxy, Nitro and Cyano.Preferably substituted are the substituents methyl, methoxy and chlorine. Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to three times by identical or different radicals from the group halogen, ( Ci-C 4) alkyl, (CrC 4) alkoxy, (CRC4) haloalkyl, (Ci-C 4) haloalkoxy and nitro, for example o-, m- and p-tolyl, Dimethylphenyle, 2-, 3- and 4 -Chlorophenyl, 2-, 3- and 4-trifluoro and trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.
Mono- oder disubstituiertes Amino bedeutet einen chemisch stabilen Rest aus der Gruppe der substituierten Aminoreste, welche beispielsweise durch einen bzw. zwei gleiche oder verschiedene Reste aus der Gruppe Alkyl, Alkoxy, Acyl und Aryl N-substituiert sind; vorzugsweise Monoalkylamino, Dialkylamino, Acylamino, Arylamino, N-Alkyl-N-arylamino sowie N-Heterocyclen; dabei sind Alkylreste mit 1 bis 4 C-Atomen bevorzugt; Aryl ist dabei vorzugsweise Phenyl oder substituiertes Phenyl; für Acyl gilt dabei die weiter unten genannte Definition, vorzugsweise Formyl, (Ci-C4)Alkylcarbonyl oder (CrC4)Alkylsulfonyl. Entsprechenes gilt für substituiertes Hydroxylamino oder Hydrazino.Mono- or disubstituted amino means a chemically stable radical from the Group of substituted amino radicals which are N-substituted, for example, by one or two identical or different radicals from the group consisting of alkyl, alkoxy, acyl and aryl; preferably monoalkylamino, dialkylamino, acylamino, arylamino, N-alkyl-N-arylamino and N-heterocycles; while alkyl radicals having 1 to 4 carbon atoms are preferred; Aryl is preferably phenyl or substituted phenyl; for acyl, the definition mentioned further below applies, preferably formyl, (Ci-C 4) applies alkylcarbonyl or (CrC 4) alkylsulfonyl. The same applies to substituted hydroxylamino or hydrazino.
Ein Acylrest bedeutet den Rest einer organischen Säure, der formal durchAn acyl radical means the radical of an organic acid that is formally through
Abspaltung einer OH-Gruppe aus der organischen Säure entsteht, z.B. der Rest einer Carbonsäure und Reste davon abgeleiteter Säuren wie der Thiocarbonsäure, gegebenenfalls N-substituierten Iminocarbonsäuren oder die Reste von Kohlensäuremonoestern, gegebenenfalls N-substituierter Carbaminsäuren, Sulfonsäuren, Sulfinsäuren, Phosphonsäuren, Phosphinsäuren.Cleavage of an OH group from the organic acid results, e.g. the radical of a carboxylic acid and radicals derived therefrom, such as the thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the radicals of carbonic acid monoesters, optionally N-substituted carbamic acids, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.
Ein Acylrest ist bevorzugt Formyl oder aliphatisches Acyl aus der Gruppe CO-RX, CS-RX, CO-ORX, CS-ORX, CS-SRX, SORY oder SO2RY, wobei Rxund Rγ jeweils einen Ci-C-io-Kohlenwasserstoffrest bedeutet, der unsubstituiert oder substituiert ist, oder Aminocarbonyl oder Aminosulfonyl, wobei die beiden letztgenannten Reste unsubstituiert, N-monosubstituiert oder N,N-disubstituiert sind. Acyl bedeutet beispielsweise Formyl, Halogenalkylcarbonyl, Alkylcarbonyl wie (CrC4)Alkylcarbonyl, Phenylcarbonyl, wobei der Phenylring substituiert sein kann, z.B. wie oben für Phenyl angegeben, oder Alkyloxycarbonyl, Phenyloxycarbonyl, Benzyloxycarbonyl, Alkylsulfonyl, Alkylsulfinyl, N-Alkyl-1-iminoalkyl und andere Reste von organischen Säuren.An acyl radical is preferably formyl or aliphatic acyl from the group CO-R X, CS-R X, CO-OR X, CS-OR X, CS-SR X, SOR Y or SO 2 R Y, with R x and R γ each represents a Ci-C-io hydrocarbon radical which is unsubstituted or substituted, or aminocarbonyl or aminosulfonyl, wherein the latter two radicals are unsubstituted, N-monosubstituted or N, N-disubstituted. Acyl is, for example, formyl, haloalkylcarbonyl, alkylcarbonyl such as (C 1 -C 4) alkylcarbonyl, phenylcarbonyl, where the phenyl ring may be substituted, for example as indicated above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and others Residues of organic acids.
Gegenstand der Erfindung sind auch alle Stereoisomeren, die von Formel (I) umfaßt sind, und deren Gemische. Solche Verbindungen der Formel (I) enthalten ein oder mehrere asymmetrische C-Atome oder auch Doppelbindungen, die in der allgemeinen Formel (I) nicht gesondert angegeben sind. Die durch ihre spezifische Raumform definierten möglichen Stereoisomeren, wie Enantiomere, Diastereomere, Z- und E-Isomere sind alle von der Formel (I) umfaßt und können nach üblichen Methoden aus Gemischen der Stereoisomeren erhalten oder auch durch stereoselektive Reaktionen in Kombination mit dem Einsatz von stereochemisch reinen Ausgangsstoffen hergestellt werden.The invention also relates to all stereoisomers which are encompassed by formula (I) and mixtures thereof. Such compounds of formula (I) contain one or more asymmetric C atoms or double bonds, which are not specified separately in the general formula (I). The possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z- and E-isomers are all of the formula (I) and can be obtained by conventional methods from mixtures of stereoisomers or prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials.
Die vorstehenden Beispiele für Reste oder Restebereiche, die unter die allgemeinen Begriffe wie "Alkyl", "Acyl", "substituierten Reste" etc., fallen, bedeuten keine vollständige Aufzählung. Die allgemeinen Begriffe umfassen auch die weiter unten angeführten Definitionen für Restebereiche in Gruppen bevorzugter Verbindungen, insbesondere Restebereiche, welche spezifische Reste aus den Tabellenbeispielen umfassen.The above examples of radicals or ranges of radicals which fall under the general terms such as "alkyl", "acyl", "substituted radicals", etc., are not exhaustive. The general terms also include the definitions given below for residue regions in groups of preferred compounds, in particular residue regions which comprise specific residues from the table examples.
Bevorzugte erfindungsgemäße Verbindungen der Formel (I) oder deren Salze sind solche, worin R (CrC6)Alkyl, (C2-C6)AI kenyl, (C2-C6)Alkinyl, (C3-C6)Cycloalkyl, (C3-Preferred compounds of the formula (I) according to the invention or salts thereof are those in which R (C r C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 6 ) Cycloalkyl, (C 3 -
C6)Cycloalkenyl, (C3-C6)Cycloalkinyl, (d-C6)Alkyloxy, (C2-C6)Alkenyloxy, (C2- C6)Alkinyloxy, (C3-C6)Cycloalkyloxy, Phenyl, Phenyloxy, F, Br, I, OH, CN, NO2, NH2, SF5, Si((Ci-Cβ)Alkyl)3, N((C1-C6)Alkyl)2, N H(C1 -C6)AI kyl, ISK(C2- C6)Alkenyl)2, NH(C2-C6)Alkenyl, N((C2-C6)Alkinyl)2, NH(C2-C6)Alkinyl, NH((C3- C6)Cycloalkyl)2, NH(C3-C6)Cycloalkyl, N(CrC6)Alkyl (C3-C6)Cycloalkyl, N(d-C 6) cycloalkenyl, (C 3 -C 6) cycloalkynyl, (dC 6) alkyloxy, (C 2 -C 6) alkenyloxy, (C 2 - C 6) alkynyloxy, (C 3 -C 6) cycloalkyloxy, phenyl, phenyloxy , F, Br, I, OH, CN, NO 2 , NH 2 , SF 5 , Si ((C 1 -C 6 ) alkyl) 3, N ((C 1 -C 6 ) alkyl) 2 , NH (C 1 -C 6 ) Al kyl, ISK (C 2 -C 6 ) alkenyl) 2 , NH (C 2 -C 6 ) alkenyl, N ((C 2 -C 6 ) alkynyl) 2 , NH (C 2 -C 6 ) alkynyl, NH ((C 3 - C 6) cycloalkyl) 2, NH (C 3 -C 6) cycloalkyl, N (C r C6) alkyl (C 3 -C 6) cycloalkyl, N (d-
C6)Alkyl C(O)R3, NHC(O)R3, N(CrC6)Alkyl S(O)nR3, NHS(O)nR3, S(O)n(C1- C4)Alkyl, S(O)n (C3-C6)Cycloalkyl, S(O)n(CrC6)Alkenyl, S(O)n(Ci-Cβ)Alkinyl. S(O)nNHR3, S(O)nN(C1 -C6)Alkyl R3, OSO2(CrC6)Alkyl, OSO2(C3- C6)Cycloalkyl, OSO2(CrC6)Alkenyl, OSO2(CrC6)Alkinyl, OS(O)nPhenyl, OSO2N((CrC6)Alkyl)2, OSO2NH(CrC6)Alkyl, OSO2N((C3-C6)Cycloalkyl)2,C 6 ) alkyl C (O) R 3 , NHC (O) R 3 , N (C r C 6 ) alkyl S (O) n R 3 , NHS (O) n R 3 , S (O) n (C 1 - C 4) alkyl, S (O) n (C 3 -C 6) cycloalkyl, S (O) n (C r C6) alkenyl, S (O) n (Ci-C β) alkynyl. S (O) n NHR 3 , S (O) n N (C 1 -C 6 ) alkyl R 3 , OSO 2 (C r C 6 ) alkyl, OSO 2 (C 3 -C 6 ) cycloalkyl, OSO 2 (C r C 6 ) alkenyl, OSO 2 (CrC 6 ) alkynyl, OS (O) n phenyl, OSO 2 N ((C r C 6 ) alkyl) 2 , OSO 2 NH (C r C 6 ) alkyl, OSO 2 N ( (C 3 -C 6 ) cycloalkyl) 2 ,
OSO2NH(C3-C6)Cycloalkyl, OSO2N((C2-C6)Alkenyl)2, OSO2NH(C2-C6)Alkenyl, OSO2N((C2-C6)Alkinyl)2, OSO2NH(C2-C6)Alkinyl, OC(O)R3 oder Heterocyclyl bedeutet, wobei die genannten Reste Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl, Cycloalkinyl, Alkyloxy, Alkenyloxy, Alkinyloxy, Cycloalkoxy, Phenyl, Phenyloxy, Heterocyclyl unsubstituiert sind oder substituiert sind, z.B. durch einen oder mehrere Reste aus der Gruppe Halogen, CN, (CrC6)Alkyl, (C2-C6)Alkenyl, (C2-C6)Alkinyl, (C-ι-Ce)Alkoxy, (C3-C6)Cycloalkyl, Phenyl, Phenyloxy, Heterocyclyloxy, wobei die beiden letztgenannten Reste einfach oder mehrfach durch Reste aus der Gruppe Halogen, CN, Methyl, Methoxy, Trifluormethyl, Trifluormethoxy substituiert sein können,OSO 2 NH (C 3 -C 6 ) cycloalkyl, OSO 2 N ((C 2 -C 6 ) alkenyl) 2 , OSO 2 NH (C 2 -C 6 ) alkenyl, OSO 2 N ((C 2 -C 6 ) Alkynyl) 2 , OSO 2 NH (C 2 -C 6 ) alkynyl, OC (O) R 3 or heterocyclyl, where the radicals alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, alkyloxy, alkenyloxy, alkynyloxy, cycloalkoxy, Phenyl, phenyloxy, heterocyclyl are unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, (C r C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 1 -C 6 ) alkoxy, (C 3 -C 6 ) cycloalkyl, phenyl, Phenyloxy, heterocyclyloxy, where the latter two radicals may be mono- or polysubstituted by radicals from the group halogen, CN, methyl, methoxy, trifluoromethyl, trifluoromethoxy,
R1 unabhängig voneinander (C1-C6)AIRyI, (Ci-C6)Haloalkyl, (CrC6)Alkyloxy, (C1- CβJHaloalkoxy oder Halogen ist,R 1 is independently (C 1 -C 6) AIRyI, (Ci-C 6) haloalkyl, (CrC 6) alkyloxy, (C 1 - is CβJHaloalkoxy or halogen,
I 0, 1 oder 2, vorzugsweise 0 oder 1 , besonders bevorzugt 0 ist, n 0, 1 oder 2 ist,I is 0, 1 or 2, preferably 0 or 1, more preferably 0, n is 0, 1 or 2,
R2 H oder CH3 ist,R 2 is H or CH 3 ,
R3 H, (d-CβJAlkyl, (C2-C6)Alkenyl, (C2-C6)Alkinyl, (C3-C6)Cycloalkyl, (C1- C6)Alkyloxy, (C2-C6)Alkenyloxy, (C2-C6)Alkinyloxy, (C3-C6)Cycloalkyloxy,R 3 H, (C 1 -C 6 alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl, (C 1 -C 6 ) alkyloxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy, (C 3 -C 6 ) cycloalkyloxy,
Phenyl, Heterocyclyl, CN, NH(CrC6)Alkyl, N((d-C6)Alkyl)2 steht, wobei die genannten Reste Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Alkyloxy, Alkenyloxy, Alkinyloxy, Cycloalkyloxy, Phenyl, Heterocyclyl unsubstituiert oder substituiert sind, z.B. durch einen oder mehrere Reste aus der Gruppe Halogen, CN, (C1- C6)Alkyl, (CrC6)Alkenyl, (CrC6)Alkinyl, (CrC6)Alkyloxy,Phenyl, heterocyclyl, CN, NH (C r C 6 ) alkyl, N ((C 1 -C 6 ) alkyl) 2 , where the radicals alkyl, alkenyl, alkynyl, cycloalkyl, alkyloxy, alkenyloxy, alkynyloxy, cycloalkyloxy, phenyl, heterocyclyl unsubstituted or substituted, for example by one or more radicals from the group halogen, CN, (C 1 - C 6) alkyl, (C r C6) alkenyl, (CrC 6) alkynyl, (C r C 6) alkyloxy,
W ein Sauerstoffatom ist,W is an oxygen atom,
X,Y unabhängig voneinander (Crd)Alkyl, (d-C4)Alkyloxy, wobei jeder der letztgenannten zwei Reste unsubstituiert oder durch einen oder mehrere Halogenatome substituiert ist, oder (d-C4)Alkylthio, Halogen oder NH(C1- C4)Alkyl oder N((CrC4)Alkyl)2 bedeuten, undX, Y independently of one another are (Crd) alkyl, (C 1 -C 4 ) alkyloxy, where each of the latter two radicals is unsubstituted or substituted by one or more halogen atoms, or (C 1 -C 4 ) alkylthio, halogen or NH (C 1 -C 4 ) alkyl or N ((C r C 4 ) alkyl) 2 , and
V,Z unabhängig voneinander CH oder N bedeuten.V, Z are independently CH or N
Besonders bevorzugte Verbindungen der Formel (I) und/oder deren Salze sind solche, worin R (CrC4)Alkyl, (C2-C4)Alkenyl, (C2-C4)Alkinyl, (C3-C6)Cycloalkyl, (C1-Particularly preferred compounds of formula (I) and / or their salts are those wherein R is (CrC 4) alkyl, (C 2 -C 4) alkenyl, (C 2 -C 4) alkynyl, (C 3 -C 6) cycloalkyl , (C 1 -
C4)Alkyloxy, (C2-C4)Alkenyloxy, (C2-C4)Alkinyloxy, (C3-C6)Cycloalkyloxy, Phenyl, Phenyloxy, F, Br, I1 CN1 NO2, NH2, N((CrC4)Alkyl)2, NH(CrC4)Alkyl, NH(C2-C4)Alkenyl, NH(C2-C4)Alkinyl, NH(C3-C6)Cycloalkyl, N(CrC4)Alkyl (C3- C6)Cycloalkyl, S(CrC4)Alkyl, S(C2-C4)Alkenyl, S(C2-C4)Alkinyl, S(C3- C6)Cycloalkyl, S(O)(d-C4)Alkyl, S(O)(CrC4)Alkenyl, S(O)(C2-C4)Alkinyl,C 4 ) alkyloxy, (C 2 -C 4 ) alkenyloxy, (C 2 -C 4 ) alkynyloxy, (C 3 -C 6 ) cycloalkyloxy, phenyl, phenyloxy, F, Br, I 1 CN 1 NO 2 , NH 2 , N ((C r C 4) alkyl) 2, NH (C r C 4) alkyl, NH (C 2 -C 4) alkenyl, NH (C 2 -C 4) alkynyl, NH (C 3 -C 6) cycloalkyl , N (C r C 4) alkyl (C 3 - C 6) cycloalkyl, S (C r C 4) alkyl, S (C 2 -C 4) alkenyl, S (C 2 -C 4) alkynyl, S (C 3 - C 6) cycloalkyl, S (O) (dC 4) alkyl, S (O) (C r C 4) alkenyl, S (O) (C 2 -C 4) alkynyl,
S(O)(C3-C6)Cycloalkyl, SO2(CrC4)Alkyl, SO2(C2-C4)Alkenyl, SO2(C2- C4)Alkinyl, SO2(C3-C6)Cycloalkyl, SO2NH(d-C4)Alkyl, SO2N((CrC4)Alkyl)2, SO2NH(C3-C6)Cycloalkyl, OSO2(CrC4)Alkyl, OSO2NH(C1-C4)AIkYl, OSO2N((C1-C4)Alkyl)2 oder NHC(O)R3, NHSO2R3, OC(O)R3, worin R3 gleich H, (C1-C4)AIkYl, (C2-C4)Alkenyl, (C2-C4)Alkinyl, (C3- C6)Cycloalkyl, (C1-C4)AIkYlOXy, (C2-C4)Alkenyloxy, (C2-C4)Alkinyloxy, (C3- C6)Cycloalkyloxy, (CrC4)Haloalkyl, NH(CrC4)Alkyl oder N((C1-C4)Alkyl)2 ist, wobei die genannten Reste Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Alkyloxy, Alkenyloxy, Alkinyloxy, Cycloalkyloxy, Phenyl, Phenyloxy unsubstituiert sind oder substituiert sind, z.B. durch einen oder mehrere Reste, vorzugsweise ein, zwei oder drei Reste, aus der Gruppe Halogen (F, Cl, Br, I), (C-ι-C4)Alkyl, (CrC4)Alkyloxy, (CrC4)Haloalkyl, (CrC4)Haloalkyloxy, (C3-C6)Cycloalkyl,S (O) (C 3 -C 6) cycloalkyl, SO 2 (C r C 4) alkyl, SO 2 (C 2 -C 4) alkenyl, SO 2 (C 2 - C 4) alkynyl, SO 2 (C 3 -C 6 ) cycloalkyl, SO 2 NH (dC 4 ) alkyl, SO 2 N ((CrC 4 ) alkyl) 2 , SO 2 NH (C 3 -C 6 ) cycloalkyl, OSO 2 (C r C 4 ) alkyl, OSO 2 NH (C 1 -C 4 ) alkyl, OSO 2 N ((C 1 -C 4 ) alkyl) 2 or NHC (O) R 3 , NHSO 2 R 3 , OC (O) R 3 , wherein R 3 is H, (C 1 -C 4 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl , (C 3 -C 6 ) cycloalkyl, (C 1 -C 4 ) alkylalkyl, (C 2 -C 4 ) alkenyloxy, (C 2 -C 4 ) alkynyloxy, (C 3 -C 6 ) cycloalkyloxy, (C r C 4 ) haloalkyl, NH (C r C 4 ) alkyl or N ((C 1 -C 4 ) alkyl) 2 , said alkyl, alkenyl, alkynyl, cycloalkyl, alkyloxy, alkenyloxy, alkynyloxy, cycloalkyloxy, phenyl, phenyloxy are unsubstituted or substituted, for example by one or more radicals, preferably one, two or three radicals from the group halogen (F, Cl, Br, I), (C-ι-C 4) alkyl, (C r C 4 ) Alkyloxy, (C r C 4 ) haloalkyl, (C r C 4 ) haloalkyloxy, (C 3 -C 6 ) cycloalkyl,
R1 Halogen (F, Cl, Br, I), (C1-C4)AIkYl, (CrC4)Alkyloxy, (CrC4)Haloalkyl, (C1- C4)Haloalkyloxy,R 1 is halogen (F, Cl, Br, I), (C 1 -C 4) -alkyl, (C r C 4) alkyloxy, (C r C4) haloalkyl, (C 1 - C 4) haloalkyloxy,
I O oder 1 , vorzugsweise O ist,I is O or 1, preferably O,
R2 H oder (CrC4)Alkyl wie Methyl, W ein Sauerstoffatom,R 2 is H or (C r C 4 ) alkyl, such as methyl, W is an oxygen atom,
X,Y unabhängig voneinander (C1-C4)AIkYl, (CrC4)Haloalkyl, (C-ι-C4)Alkyloxy, (C1- C4)Haloalkyloxy, Halogen (F, Cl, Br1 1), (CrC4)Alkylthio, NH(CrC4)Alkyl, N((CrC4)Alkyl)2,X, Y are independently (C 1 -C 4) -alkyl, (CrC 4) haloalkyl, (C-ι-C 4) alkyloxy, (C 1 - C 4) haloalkyloxy, halogen (F, Cl, Br, 1: 1), (C r C 4 ) alkylthio, NH (C r C 4 ) alkyl, N ((C r C 4 ) alkyl) 2 ,
V ein Stickstoff atom, und Z CH oder N bedeuten.V is a nitrogen atom, and Z is CH or N.
Ganz besonders bevorzugte erfindungsgemäße Verbindungen der Formel ( I ) oder deren Salze sind solche, worinVery particularly preferred compounds of the formula (I) according to the invention or salts thereof are those in which
R CH3, CH2CH3, (CHz)2CH3, CH(CH3)2, C(CH3)3, CH=CH2, C≡CH, CH2CH=CH2, CH2C≡CH, Cyclopropyl, Phenyl, F, Br, I, CN, NO2, NH2, CH2OCH3, CF3,R is CH 3 , CH 2 CH 3 , (CHz) 2 CH 3 , CH (CH 3 ) 2 , C (CH 3 ) 3 , CH = CH 2 , C≡CH, CH 2 CH = CH 2 , CH 2 C≡ CH, cyclopropyl, phenyl, F, Br, I, CN, NO 2 , NH 2 , CH 2 OCH 3 , CF 3 ,
CHF2, NHCH3, N(CH3)2, NH-cyclopropyl, N(CH3)-cyclopropyl, NHC(O)H, NHC(O)CH3, NHC(O)OCH3, NHSO2CH3, NHSO2CF3, NHSO2CHF2, OCH3, OCH2CH3, O(CH2)2CH3, OCH(CH3)2, O(CH2)3CH3, OCH2CH(CH3)2, OCH(CH3)CH2CH3, OC(CH3)3, OCH=CH2, OC≡CH, OCH2CH=CH2, OCH2C≡CH, O-cyclopropyl, OCH^cyclopropyl, O(CH2)2CI, O(CH2)3CI,CHF 2 , NHCH 3 , N (CH 3 ) 2 , NH-cyclopropyl, N (CH 3 ) -cyclopropyl, NHC (O) H, NHC (O) CH 3 , NHC (O) OCH 3 , NHSO 2 CH 3 , NHSO 2 CF 3 , NHSO 2 CHF 2 , OCH 3 , OCH 2 CH 3 , O (CH 2 ) 2 CH 3 , OCH (CH 3 ) 2 , O (CH 2 ) 3 CH 3 , OCH 2 CH (CH 3 ) 2 , OCH (CH 3 ) CH 2 CH 3 , OC (CH 3 ) 3 , OCH = CH 2 , OC≡CH, OCH 2 CH = CH 2 , OCH 2 C≡CH, O-cyclopropyl, OCH 2 -cyclopropyl, O (CH 2 ) 2 Cl, O (CH 2 ) 3 Cl,
OCH2OCH3, OPhenyl, OCH2Phenyl, OCF3, OCHF2, OCH2F, OCH2CF3, OCH2CHF2, OCH(CH3)CF3, OCH2CF2CF3, SCH3, SCH2CH3, S(O)CH3, S(O)CH2CH3, SO2CH3, SO2CH2CH3, SO2NHCH3, SO2N(CH3)2| SO2NHCF3, SO2NHCHF2, OSO2CH3, OSO2CF3, OSO2CHF2, OSO2N(CH3)2, OSO2NHCF3, OSO2NHCHF21 OC(O)H, OC(O)CH3, OC(O)OCH3, OC(O)N(CH3)2,OCH 2 OCH 3 , OPhenyl, OCH 2 phenyl, OCF 3 , OCHF 2 , OCH 2 F, OCH 2 CF 3 , OCH 2 CHF 2 , OCH (CH 3 ) CF 3 , OCH 2 CF 2 CF 3 , SCH 3 , SCH 2 CH 3 , S (O) CH 3 , S (O) CH 2 CH 3 , SO 2 CH 3 , SO 2 CH 2 CH 3 , SO 2 NHCH 3 , SO 2 N (CH 3 ) 2 | SO 2 NHCF 3 , SO 2 NHCHF 2 , OSO 2 CH 3 , OSO 2 CF 3 , OSO 2 CHF 2 , OSO 2 N (CH 3 ) 2 , OSO 2 NHCF 3 , OSO 2 NHCHF 21 OC (O) H, OC (O) CH 3, OC (O) OCH 3, OC (O) N (CH 3) 2,
I O ist, R2 H ist,IO is, R 2 is H,
W Sauerstoff,W oxygen,
X1Y unabhängig voneinander CH3, CH2CH3, CF3, CHF2, CH2CF3, CH2CHF2,X 1 Y independently of one another CH 3 , CH 2 CH 3 , CF 3 , CHF 2 , CH 2 CF 3 , CH 2 CHF 2 ,
OCH3, OCH2CH3, OCF3, OCHF2, OCH2CF3, OCH2CHF2, F1 Cl, Br, I, SCH3, NHCH3, N(CHa)2, vorzugsweise CH3, OCH3, OCH2CH3, Cl, N(CH3)2, V N ist, undOCH 3 , OCH 2 CH 3 , OCF 3 , OCHF 2 , OCH 2 CF 3 , OCH 2 CHF 2 , F 1 Cl, Br, I, SCH 3 , NHCH 3 , N (CHa) 2 , preferably CH 3 , OCH 3 , OCH 2 CH 3 , Cl, N (CH 3 ) 2 , VN, and
Z CH oder N bedeuten.Z is CH or N
Besonders bevorzugt sind auch erfindungsgemäße Verbindungen der Formel (I) und deren Salze, welche eine Kombination von Resten aus den oben genannten bevorzugten Verbindungen enthalten, sowie solche, welche einzelne oder mehrere Reste aus den in der Tabelle 1 dieser Beschreibung aufgeführten Verbindungen enthalten. Ebenfalls bevorzugt sind Verbindungen der Formel (I)1 in denen V = N ist.Particular preference is also given to compounds of the formula (I) according to the invention and salts thereof which contain a combination of radicals from the abovementioned preferred compounds and to those which contain one or more radicals from the compounds listed in Table 1 of this description. Also preferred are compounds of formula (I) 1 in which V = N.
Gegenstand der vorliegenden Erfindung sind auch Verfahren zur Herstellung der erfindungsgemäßen Verbindungen der allgemeinen Formel (I) und/oder deren Salzen, wobei manThe present invention also provides processes for the preparation of the compounds of the general formula (I) according to the invention and / or salts thereof, wherein
a) eine Verbindung der Formel (II)a) a compound of the formula (II)
mit einem heterocyclischen (Thio)Carbamat der Formel (III), with a heterocyclic (thio) carbamate of the formula (III),
worin R* ein substituierter oder unsubstituierter Ci-C2o-Kohlenwasserstoffrest wie Aryl oder Alkyl, vorzugsweise gegebenenfalls substituiertes Phenyl oder gegebenenfalls substituiertes (CrC4)Alkyl bedeutet, umsetzt, oderwherein R * represents a substituted or unsubstituted C 1 -C 20 -hydrocarbon radical such as aryl or alkyl, preferably optionally substituted phenyl or optionally substituted (C 1 -C 4 ) -alkyl, or
b) ein Sulfonyl(thio)carbamat der Formel (IV),b) a sulfonyl (thio) carbamate of the formula (IV),
worin R** ein substituierter oder unsubstituierter CrC2o-Kohlenwasserstoffrest wie Aryl oder Alkyl, vorzugsweise gegebenenfalls substituiertes Phenyl oder gegebenenfalls substituiertes (Ci-C4)Alkyl bedeutet, mit einem Aminoheterocyclus der Formel (V)wherein R ** is a substituted or unsubstituted CrC 2 o-hydrocarbon radical such as aryl or alkyl, preferably optionally substituted phenyl or optionally substituted (Ci-C 4) alkyl, with an amino heterocycle of the formula (V)
umsetzt, oder implements, or
c) ein Sulfonylisocyanat der Formel (VI)c) a sulfonyl isocyanate of the formula (VI)
( vi ) mit einem Aminoheterocyclus der Formel (V) umsetzt, oder(vi) with an amino heterocycle of formula (V), or
d) ein Sulfonamid der Formel (II) mit einem lso(thio)cyanat der Formel (VII)d) a sulfonamide of the formula (II) with an iso (thio) cyanate of the formula (VII)
in Gegenwart einer Base umsetzt, oderin the presence of a base, or
e) einen Aminoheterocyclus der Formel (V) zunächst basenkatalysiert mit einem Kohlensäureester, z.B. Diphenylcarbonat, umsetzt und das gebildete Intermediat in einer Eintopfreaktion mit einem Sulfonamid der Formel (II) (siehe Variante a) umsetzt, odere) an aminoheterocycle of formula (V) initially base catalysed with a carbonic acid ester, e.g. Diphenyl carbonate, reacted and the intermediate formed in a one-pot reaction with a sulfonamide of the formula (II) (see variant a), or
f) ein Sulfonsäurehalogenid der Formel (VIII),f) a sulfonic acid halide of the formula (VIII)
wobei HaI ein Halogenatom, vorzugsweise Chlor ist, mit einem (Thio)Cyanat, beispielsweise einem Metall(thio)cyanat, insbesondere einem Alkalimetall(thio)cyanat, wie Natrium(thio)cyanat, zu einem lso(thio)cyanat der Formel (VI) oder einem solvatisierten (stabilisierten) Derivat davon umsetzt, und anschließend mit einem Aminoheterocyclus der Formel (V) umsetzt,wherein Hal is a halogen atom, preferably chlorine, with a (thio) cyanate, for example a metal (thio) cyanate, in particular an alkali metal (thio) cyanate, such as sodium (thio) cyanate, to a lso (thio) cyanate of the formula (VI ) or a solvated (stabilized) derivative thereof, and then reacted with an amino heterocycle of formula (V),
wobei in den Formeln (II)-(VIII) die Reste, Gruppen bzw. Indizes R, R1, R2, V, W1 X, Y, Z und I wie in Formel (I) definiert sind und auch die gleichen Vorzugsbereiche gelten wie für Formel (I) angegeben. Die Umsetzung der Verbindungen der Formeln (II) und (III) gemäß Variante a) erfolgt vorzugsweise basenkatalysiert in einem inerten organischen Lösungsmittel, wie z.B. Dichlormethan, Acetonitril, Dioxan oder THF bei Temperaturen zwischen 0 0C und dem Siedepunkt des Lösungsmittels, vorzugsweise bei Raumtemperatur. Als Base werden dabei beispielsweise organische Aminbasen, wiewherein in the formulas (II) - (VIII) the radicals, groups or indices R, R 1 , R 2 , V, W 1, X, Y, Z and I are defined as in formula (I) and also the same preferred ranges apply as indicated for formula (I). The reaction of the compounds of the formulas (II) and (III) according to variant a) is preferably carried out under base catalysis in an inert organic solvent such as dichloromethane, acetonitrile, dioxane or THF at temperatures between 0 0 C and the boiling point of the solvent, preferably at room temperature , Examples of bases are organic amine bases, such as
1 ,8-Diazabicyclo[5.4.0]undec-7-en (DBU), Alkali-tert.-butoxide, wie z.B. NaO-t-C4H9, oder Alkalihydroxide, wie z.B. NaOH, insbesondere bei R* = (subst.) Phenyl (vgl. EP-A-44 807), oder Trialkylaluminium wie Trimethylaluminium oder Triethylaluminium, letztere insbesondere bei R* = Alkyl (vgl. EP-A-166 516) verwendet. Die jeweilige Base wird dabei beispielsweise im Bereich von 1 bis 3 Moläquivalenten, bezogen auf die Verbindung der Formel (II) eingesetzt.1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), alkali tert-butoxides, such as NaO-tC 4 H 9 , or alkali hydroxides, such as NaOH, especially when R * = (subst. ) Phenyl (see EP-A-44 807), or trialkylaluminum such as trimethylaluminum or triethylaluminum, the latter in particular for R * = alkyl (see EP-A-166 516). The particular base is used, for example, in the range of 1 to 3 molar equivalents, based on the compound of the formula (II).
Die Sulfonamide der Formel (II), die Verbindungen der Formeln (IV), (VI) und (VIII) sowie die nachfolgend beschriebenen Verbindungen der Formel (XIV) sind neueThe sulfonamides of the formula (II), the compounds of the formulas (IV), (VI) and (VIII) and the compounds of the formula (XIV) described below are novel
Verbindungen, die ebenso wie ihre Herstellung und ihre Verwendung zur Herstellung von Verbindungen der Formel (I) und/oder deren Salzen Gegenstand der vorliegenden Erfindung sind. Für die Verbindungen der Formel (II), (IV), (VI), (VIII) und (XIV) gelten für die Reste R und R1 sowie den Index I die gleichen Vorzugsbereiche wie für die Verbindungen der Formel (I) angegeben.Compounds which, as well as their preparation and their use for the preparation of compounds of the formula (I) and / or their salts are the subject of the present invention. For the compounds of the formula (II), (IV), (VI), (VIII) and (XIV), the radicals R and R 1 and the index I have the same preferred ranges as indicated for the compounds of the formula (I).
Man kann die Verbindungen der Formel (II) z.B. erhalten wie in den nachfolgenden Schemata 1 bis 8 gezeigt.The compounds of formula (II) can be e.g. obtained as shown in the following schemes 1 to 8.
Schema 1Scheme 1
Butylbutyl
Ausgehend von kommerziell erhältlichen Verbindungen der Formel (IX) können, z.B. durch Diazotierung der Aminogruppe mit einem Alkalinitrit, wie z. B. Natriumnitrit, in Gegenwart von Salzsäure bei Temperaturen zwischen -1O0C und 1O0C und nachfolgendem Austausch der resultierenden Diazogruppe z. B. mit Schwefeldioxid in Gegenwart eines Verdünnungsmittels, wie z. B. Dichlormethan, 1 ,2-Dichlorethan oder Essigsäure, und in Gegenwart eines Katalysators, wie z. B. Kupfer(l)chlorid und/oder Kupfer(ll)chlorid, bei Temperaturen zwischen -1O0C und 5O0C die Verbindungen der Formel (IXa) erhalten werden (vgl. Meerwein, Chem. Ber. 1957, 90, 841) (Schema 1 ). Durch Behandlung von Sulfochloriden der Formel (IXa) mit tert.-Butylamin können Sulfonamide der Formel (X) erhalten werden. Die Sulfonamidbildung wird beispielsweise in inerten Lösungsmitteln wie z.B. Dichlormethan, Tetrahydrofuran (THF), Dioxan, Toluol oder Dimethylformamid (DMF) bei Temperaturen zwischen - 700C bis zum Siedepunkt des verwendeten Lösungsmittels, vorzugsweise bei 250C durchgeführt. Dabei kommt bevorzugt eine Aminmenge von 1.5 - 2.5 Äquivalenten bezogen auf das verwendete Sulfochlorid zum Einsatz. Starting from commercially available compounds of formula (IX) can, for example by diazotization of the amino group with an alkali metal nitrite, such as. As sodium nitrite, in the presence of hydrochloric acid at temperatures between -1O 0 C and 1O 0 C and subsequent replacement of the resulting diazo z. B. with sulfur dioxide in the presence of a diluent, such as. For example, dichloromethane, 1, 2-dichloroethane or acetic acid, and in the presence of a catalyst such. As copper (I) chloride and / or copper (II) chloride, at temperatures between -1O 0 C and 5O 0 C, the compounds of formula (IXa) are obtained (see Meerwein, Chem. Ber 1957, 90, 841 ) (Scheme 1). By treating sulfochlorides of the formula (IXa) with tert-butylamine, sulfonamides of the formula (X) can be obtained. The sulfonamide is, for example, in inert solvents such as dichloromethane, tetrahydrofuran (THF), dioxane, toluene or dimethylformamide (DMF) at temperatures between - 70 0 C to the boiling point of the solvent used, preferably at 25 0 C. In this case, preference is given to using an amine of from 1.5 to 2.5 equivalents, based on the sulfonyl chloride used.
Schema 2Scheme 2
Die Reduktion der Nitroverbindungen (X) zu den Aminen der Formel (Xl) erfolgt analog zu bekannten Methoden (vgl. hierzu Houben-Weyl, „Methoden der The reduction of the nitro compounds (X) to give the amines of the formula (XI) takes place analogously to known methods (cf., for this purpose, Houben-Weyl, "Methoden der
Organischen Chemie", 4. Aufl. Bd. XI/1 S. 360 ff., Thieme Verlag Stuttgart, 1957) (Schema 2). Schema 3Organic Chemistry ", 4th edition Bd. XI / 1 p. 360 ff., Thieme Verlag Stuttgart, 1957) (Scheme 2). Scheme 3
( Xl ) ( XII )(XI) (XII)
Der Verbindungen der Formel (Xl) können unter üblichen Bedingungen für Diazotierungsreaktionen diazotiert und anschließend in Verbindungen der Formel (XII) überführt werden. Beispielsweise erfolgt die Diazotierung in Gegenwart der Säure H+X', wobei X" vorzugsweise Cl', I" oder HSO4 * ist, in wässriger Lösung, gegebenenfalls unter Einsatz eines unter den Reaktionsbedingungen inerten organischen Lösungsmittels mit einem Nitrit. Beispielsweise diazotiert man mit einem Alkalimetallnitrit wie NaNO2 (Natriumnitrit) in Mengen von 1.0 - 1.2 Mol Nitrit, vorzugsweise 1 ,01 - 1.05 Mol Nitrit, pro Mol der Verbindung der Formel (Xl). Als Säuren eignen sich Mineralsäuren oder starke organische Säuren, bevorzugt sind Salzsäure, oder Schwefelsäure. Das Lösungsmittel ist Wasser oder eine Mischung aus Wasser und einem unter den Reaktionsbedingungen inerten organischen Lösungsmittel. Die Reaktionstemperatur beträgt in der Regel zwischen -50C und 5O0C, vorzugsweise 1O0C bis 2O0C (Schema 3).The compounds of the formula (XI) can be diazotised under conventional conditions for diazotization reactions and then converted into compounds of the formula (XII). For example, the diazotization is carried out in the presence of the acid H + X ' , where X "is preferably Cl ' , I " or HSO 4 * , in aqueous solution, optionally with the use of an organic solvent which is inert under the reaction conditions, with a nitrite. For example, diazotized with an alkali metal nitrite such as NaNO 2 (sodium nitrite) in amounts of 1.0 to 1.2 moles of nitrite, preferably 1, 01 to 1.05 moles of nitrite, per mole of the compound of formula (Xl). Suitable acids are mineral acids or strong organic acids, preferred are hydrochloric acid, or sulfuric acid. The solvent is water or a mixture of water and an inert organic solvent under the reaction conditions. The reaction temperature is generally between -5 0 C and 5O 0 C, preferably 1O 0 C to 2O 0 C (Scheme 3).
Die Umsetzung der erhaltenen Diazoniumsalze zu den Aryliodiden der Formel (XII) erfolgt in der Regel ohne Isolierung und wird im gleichen wässrigen oder wässrig- organischen Lösungsmittel oder Lösungsmittelgemisch wie die Diazotierung durchgeführt. Bei der Umsetzung wird die Diazoniumgruppe durch das lodatom ausgetauscht, entweder durch das Anion des Diazoniumsalzes (wenn in der Säure X" = I") oder (falls X" nicht I" ist) durch die Reaktion mit zugefügtem lodid, z. B. Alkalimetalliodid, vorzugsweise Natriumiodid oder Kaliumiodid. Die Menge an lodid beträgt dabei beispielsweise 1.1 bis 1.5 Mol lodid pro Mol der ursprünglich eingesetzten Verbindung der Formel (Xl). Die Reaktionstemperatur beläuft sich dabei im allgemeinen auf 1O0C bis 4O0C, vorzugsweise 150C bis 3O0C (vgl. hierzu z.B. DE 19625831 und Bioorg. Med. Chem. 2004, 12, 2079) (Schema 3). Schema 4The reaction of the diazonium salts obtained to give the aryl iodides of the formula (XII) is generally carried out without isolation and is carried out in the same aqueous or aqueous-organic solvent or solvent mixture as the diazotization. In the reaction, the diazonium group is replaced by the iodine atom, either by the anion of the diazonium salt (when X " = I " in the acid) or (if X is " not I " ) by the reaction with added iodide, e.g. For example, alkali metal iodide, preferably sodium iodide or potassium iodide. The amount of iodide is, for example, 1.1 to 1.5 moles of iodide per mole of the originally used compound of the formula (XI). The reaction temperature amounts are in general at 1O 0 C to 4O 0 C, preferably 15 0 C to 3O 0 C (see. This example, DE 19625831 and Bioorg. Med. Chem. 2004, 12, 2079) (Scheme 3). Scheme 4
( XII ) ( H )(XII) (H)
Die Abspaltung dertert.-Butyl-Schutzgruppe in den Verbindungen der Formel (XII) zu den Sulfonamiden der Formel (II) erfolgt z.B. durch Behandlung mit einer starken Säure (siehe WO 89/10921). Als starke Säuren kommen z.B. Mineralsäuren, wie H2SO4 oder HCl, oder starke organische Säuren, wie Trifluoressigsäure in Frage. Die Reaktion erfolgt beispielsweise bei Temperaturen von -200C bis zur jeweiligen Rückflußtemperatur des Reaktionsgemisches, vorzugsweise bei O0C bis 400C. Die Umsetzung kann in Substanz oder auch in einem inerten Solvens, wie z.B. Dichlormethan oder Trichlormethan, durchgeführt werden (Schema 4). Einzelne Sulfonamide der Formel (II) sind bekannt. Eine Verbindung mit R = F- (CH2)2-O- und R = F-(CH2)3-O- ist bekannt aus WO 02/072560, mit R = NH2- aus WO 93/21170, mit R = C2H5-O-CO-CO-NH- aus WO93/21171 , und mit R = I aus HU 44481. Ein Sulfonsäurechlorid der Formel (VIII) mit HaI = Cl, R = CF3 und I = 0 ist bekannt aus Tetrahedron Lett. 1996, 37, 3639.The removal of the tert-butyl protective group in the compounds of the formula (XII) to give the sulfonamides of the formula (II) is effected, for example, by treatment with a strong acid (see WO 89/10921). Suitable strong acids are, for example, mineral acids, such as H 2 SO 4 or HCl, or strong organic acids, such as trifluoroacetic acid in question. The reaction takes place for example at temperatures from -20 0 C to the respective reflux temperature of the reaction mixture, preferably at 0 C to 40 0 C. The reaction can be in bulk or in an inert solvent such as dichloromethane or trichloromethane, are carried out (Scheme 4). Individual sulfonamides of the formula (II) are known. A compound with R = F- (CH 2 ) 2 -O- and R = F- (CH 2 ) 3 -O- is known from WO 02/072560, with R = NH 2 - from WO 93/21170, with R = C 2 H 5 -O-CO-CO-NH- from WO93 / 21171, and with R = I from HU 44481. A sulfonyl chloride of the formula (VIII) with Hal = Cl, R = CF 3 and I = 0 is known from Tetrahedron Lett. 1996, 37, 3639.
Schema 5Scheme 5
Substitituierte f-Butylaminosulfonylverbindungen der Formel (XII) können auch erhalten werden, indem man Verbindungen der Formel (XIV), welche durch Umsetzung von kommerziell erhältlichen Sulfochloriden der Formel (XIII) mit tert.- Butylamin (siehe Schema 1 ) erhalten werden können (Sulfochloride der Formel (XIII) können auch hergestellt werden durch Diazotierung der entsprechenden Aminoverbindungen und nachfolgende Sulfochlorierung wie in Schema 1 ) angegeben, mit einer metallorganischen Verbindung, wie z.B. Alkyl- oder Aryllithium, vorzugsweise n- oder sec-Butyllithium in Hexan, gegebenfalls in Gegenwart eines (weiteren) inerten Verdünnungsmittels, wie z.B. Tetrahydrofuran, und unter Inertgasatmosphäre, wie z.B. unter Argon oder Stickstoff, bei Temperaturen zwischen -7O0C und 2O0C metalliert - d. h. das in der Verbindung der Formel (XIV) in ortho-Position zur Sθ2NH-tert. Butyl-Gruppe befindliche Wasserstoffatom durch ein Metallatom ersetzt - und dann im gleichen Reaktionsmedium mit lod bei Temperaturen zwischen -1000C und 4O0C, vorzugsweise zwischen -7O0C und 2O0C umsetzt - d. h. das Metallatom durch lod ersetzt (Schema 5) (siehe hierzu auch: V. Snieckus et al., J. Org. Chem. 2001 , 66, 3662 und Synlett 2000, (9), 1294).Substituted f-butylaminosulfonyl compounds of the formula (XII) can also be obtained by obtaining compounds of the formula (XIV) which can be obtained by reacting commercially available sulfochlorides of the formula (XIII) with tert-butylamine (see Scheme 1) (sulfochlorides of the formula (XIII) can also be prepared by diazotization of the corresponding Amino compounds and subsequent sulfochlorination as indicated in Scheme 1), with an organometallic compound, such as alkyl or aryllithium, preferably n- or sec-butyllithium in hexane, if appropriate in the presence of a (further) inert diluent, such as tetrahydrofuran, and under an inert gas atmosphere such as metalated under argon or nitrogen, at temperatures between 0 C and 2O -7O 0 C - that is, the NH-tert in the compound of formula (XIV) in ortho-position to the Sθ. 2 Butyl group replaced hydrogen atom replaced by a metal atom - and then in the same reaction medium with iodine at temperatures between -100 0 C and 4O 0 C, preferably between -70 0 C and 2O 0 C - ie the metal atom replaced by iodine (Scheme 5 (see also: V. Snieckus et al., J. Org. Chem. 2001, 66, 3662 and Synlett 2000, (9), 1294).
Schema 6Scheme 6
( XV ) ( XVI-b ) ( ll-a )(XV) (XVI-b) (II-a)
Spezielle Sulfonamide der allgemeinen Formel (ll-a) mit R' = Kohlenwasserstoffrest wie Alkyl, Heterocyclylrest, CO-R3 oder S(O)n-R3 können durch Reaktion von Hydroxybenzolsulfonamiden der Formel (XV) mit Verbindungen der allgemeinen Formel (XVI - a oder XVI - b) hergestellt werden, wobei ein oder mehrere Reaktionshilfsmittel verwendet werden können. Bei den in dieser Reaktion eingesetzten Verbindungen der Formel (XVI - a) steht der Rest R' z.B. für einen Kohlenwasserstoffrest wie Alkyl, einen Heterocyclylrest, CO-R3 oder S(O)nR3 und HaI steht für Halogen, wobei Alkyl, Halogen, n und R3 wie in Formel (I) definiert sind. Bei den Verbindungen der Formel (XVI - b) kann R' insbesondere CO-R3 oder S(O)nR3 sein. Als Reaktionshilfsmittel kommen im allgemeinen die üblichen anorganischen oder organischen Basen oder Säureakzeptoren in Betracht. Hierzu gehören vorzugsweise Alkalimetall- oder Erdalkalimetallverbindungen, wie z. B. - acetate, -amide, -carbonate, -hydrogencarbonate, -hydride, -hydroxide, -oder alkanoate - im besonderen seien hier Kaliumcarbonat, Cäsiumcarbonat, Lithiumhydroxid, Natriumhydroxid und Natriumethanolat genannt - weiterhin auch basische organische Stickstoffverbindungen, wie z. B. Triethylamin, Ethyl- diisopropylamin, alkylsubstituiertes Pyridine, 1 ,4-Diazabicyclo[2.2.2]octan (DABCO), 1 ,5-Diazabicyclo[4.3.0]non-5-en (DBN) oder 1 ,8-Diazabicyclo[5.4.0]undec-7en (DBU).Special sulfonamides of the general formula (II-a) with R '= hydrocarbon radical such as alkyl, heterocyclyl radical, CO-R 3 or S (O) n -R 3 can be prepared by reaction of hydroxybenzenesulfonamides of the formula (XV) with compounds of the general formula (XVI - a or XVI - b) are prepared, wherein one or more reaction auxiliaries can be used. In the compounds of the formula (XVI-a) used in this reaction, the radical R 'is, for example, a hydrocarbon radical such as alkyl, a heterocyclyl radical, CO-R 3 or S (O) n R 3 and Hal is halogen, where alkyl, Halogen, n and R 3 are as defined in formula (I). In the case of the compounds of the formula (XVI-b), R 'may in particular be CO-R 3 or S (O) n R 3 . Suitable reaction auxiliaries are generally the customary inorganic or organic bases or acid acceptors. These include preferably alkali metal or alkaline earth metal compounds, such as. B. acetates, amides, carbonates, bicarbonates, hydrides, hydroxides, or alkanoates - in particular potassium carbonate, cesium carbonate, lithium hydroxide, sodium hydroxide and sodium ethanolate are mentioned here - furthermore also basic organic nitrogen compounds, such as. Triethylamine, ethyldiisopropylamine, alkyl-substituted pyridines, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) or 1,8-diazabicyclo [5.4.0] undec-7en (DBU).
Als Lösungsmittel kommen neben Wasser vor allem inerte organische Lösungsmittel in Betracht. Insbesondere gehören hierzu Benzol, Toluol, XyIoI1 Dichlormethan, Chloroform, Diethylether, Dioxan, Tetrahydrofuran, Aceton, Acetonitril, N1N- Dimethylformamid, N-Methyl-pyrrolidon oder Essigsäureethylester. Die Reaktionstemperaturen variieren zwischen O0C und der Rückflusstemperatur des verwendeten Lösungsmittel, vorzugsweise zwischen 100C und 12O0C (Schema 6) (vgl. hierzu auch WO 02/072560).Suitable solvents are, in addition to water, especially inert organic solvents. In particular, these include benzene, toluene, XyIoI 1 dichloromethane, chloroform, diethyl ether, dioxane, tetrahydrofuran, acetone, acetonitrile, N 1 N-dimethylformamide, N-methyl-pyrrolidone or ethyl acetate. The reaction temperatures vary between O 0 C and the reflux temperature of the solvent used, preferably between 10 0 C and 12O 0 C (Scheme 6) (see also WO 02/072560).
Schema 7Scheme 7
Hydroxybenzolsulfonamide der Formel (XV) können beispielsweise aus den ortho- alkoxysubstituierten Benzolsulfonamiden der allgemeinen Formel (ll-b) (erhältlich z.B. nach den Reaktionen der Schemata 1 - 6) erhalten werden, wobei R" insbesondere (C-i-C-OAlkyl bedeuten kann. Hierzu kann in einem inerten Lösungsmittel wie Dichlormethan, Dichlorethan oder Chloroform, vorzugsweise Dichlormethan oder Dichlorethan, die Alkoxyverbindung der Formel (ll-b) mit einer Lewis-Säure, vorzugsweise Bortrihalogeniden, wie BBr3 behandelt werden. Die Reaktionstemperatur liegt im allgemeinen zwischen -3O0C und der Rückflusstemperatur des Lösungsmittel, vorzugsweise von O0C bis 4O0C (Schema 7) (siehe beispielsweise EP044807 und WO 97/03056). Schema 8Hydroxybenzenesulfonamides of the formula (XV) can be obtained, for example, from the ortho-alkoxy-substituted benzenesulfonamides of the general formula (II-b) (obtainable, for example, according to the reactions of Schemes 1-6), where R "can in particular denote (C 1 -C -alkyl) in an inert solvent such as dichloromethane, dichloroethane or chloroform, preferably dichloromethane or dichloroethane, the alkoxy compound of the formula (II-b) are treated with a Lewis acid, preferably boron trihalides, such as BBr 3. The reaction temperature is generally between -3O 0 C. and the reflux temperature of the solvent, preferably from 0 ° C to 4O 0 C (scheme 7) (see for example EP044807 and WO 97/03056). Scheme 8
Benzolsulfonamide der allgemeinen Formel (ll-d) können durch Austausch des Fluoratoms im ortho-Fluorbenzolsulfonamid der allgemeinen Formel (ll-c) (erhältlich z.B. nach den Reaktionen der Schemata 1 - 6) durch Reaktion mit Nukleophilen der allgemeinen Formel R'" erhalten werden. R'" kann insbesondere Alkyloxy, Cycloalkoxy, Alkenyloxy, Alkinyloxy, Aryloxy, Heterocyclyloxy, Alkylthio, Alkenylthio, Alkinylthio, Arylthio, Heterocyclylthio, N(Alkyl)2, NHAlkyl, N(Alkenyl)2, NHAlkenyl, N(Alkinyl)2, NHAlkinyl, NHAryl, NHHeterocyclyl, NH2 sein, wobei alle genannten Reste (bis auf den letztgenannten) substituiert oder unsubstituiert sein können. Bei dieser Reaktion können auch ein oder mehrere Reaktionshilfsmittel zum Einsatz kommen wie die üblichen anorganischen oder organischen Basen oder Säureakzeptoren. Hierzu gehören vorzugsweise Alkalimetall- oder Erdalkalimetallverbindungen, wie z. B. -acetate, -amide, -carbonate, - hydrogencarbonate, -hydride, -hydroxide, -oder alkanoate - im besonderen seien hier Kaliumcarbonat, Cäsiumcarbonat, Lithiumhydroxid, Natriumhydroxid und Natriumethanolat, und vor allem Natriumhydrid genannt - weiterhin auch basische organische Stickstoffverbindungen, wie z. B. Triethylamin, Ethyl-diisopropylamin, alkylsubstituierte Pyridine, 1 ,4-Diazabicyclo[2.2.2]octan (DABCO), 1 ,5- Diazabicyclo[4.3.0]non-5-en (DBN) oder 1 ,8-Diazabicyclo[5.4.0]undec-7en (DBU). Als Lösungsmittel kommen neben Wasser vor allem inerte organische Lösungsmittel in Betracht. Insbesondere gehören hierzu Benzol, Toluol, XyIoI, Dichlormethan, Chloroform, Diethylether, Dioxan, Tetrahydrofuran, Aceton, Acetonitril, N1N- Dimethylformamid, N-Methyl-pyrrolidon oder Essigsäureethylester, insbesondere seien hier Diethylether, Dioxan und Tetrahydrofuran hervorgehoben. Die Reaktionstemperatur beträgt im allgemeinen zwischen -2O0C und Rückflusstemperatur des verwendeten Lösungsmittels, insbesondere zwischen O0C und Rückflusstemperatur des verwendeten Lösungsmittel.Benzenesulfonamides of the general formula (II-d) can be obtained by replacing the fluorine atom in the ortho-fluorobenzenesulfonamide of the general formula (II-c) (obtainable, for example, according to the reactions of Schemes 1-6) by reaction with nucleophiles of the general formula R '" In particular, alkyloxy, cycloalkoxy, alkenyloxy, alkynyloxy, aryloxy, heterocyclyloxy, alkylthio, alkenylthio, alkynylthio, arylthio, heterocyclylthio, N (alkyl) 2 , NHalkyl, N (alkenyl) 2 , NHAlkenyl, N (alkynyl) 2 , NHAlkinyl, NHAryl, NHHeterocyclyl, NH 2 , where all of said radicals (except for the latter) may be substituted or unsubstituted. In this reaction, one or more reaction auxiliaries can be used as the usual inorganic or organic bases or acid acceptors. These include preferably alkali metal or alkaline earth metal compounds, such as. B. acetates, amides, carbonates, - hydrogencarbonates, hydrides, hydroxides, or alkanoates - in particular potassium carbonate, cesium carbonate, lithium hydroxide, sodium hydroxide and sodium ethoxide, and especially sodium hydride may be mentioned - also basic organic nitrogen compounds, such as For example, triethylamine, ethyl-diisopropylamine, alkyl-substituted pyridines, 1, 4-diazabicyclo [2.2.2] octane (DABCO), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN) or 1, 8-diazabicyclo [5.4.0] undec-7en (DBU). Suitable solvents are, in addition to water, especially inert organic solvents. In particular, these include benzene, toluene, xylene, dichloromethane, chloroform, diethyl ether, dioxane, tetrahydrofuran, acetone, acetonitrile, N 1 N- dimethylformamide, N-methyl-pyrrolidone or ethyl acetate, in particular diethyl ether, dioxane and tetrahydrofuran may be mentioned here highlighted. The reaction temperature is generally between -2O 0 C and Reflux temperature of the solvent used, in particular between O 0 C and reflux temperature of the solvent used.
Neben der rein thermischen Reaktionsführung kann zur Reaktionsbeschleunigung auch Mikrowellenenergie eingesetzt werden. Hierfür kann ein kommerziell erhältliches, für chemische Zwecke ausgelegtes Mikrowellengerät eingesetzt werden. Die Reaktionen werden dabei im allgemeinen bei Temperaturen zwischen 2O0C und 2000C1 vorzugsweise zwischen 4O0C und 17O0C und mit einer Energieleistung zwischen 20 und 200 Watt, vorzugsweise zwischen 50 und 180 Watt, während einer Reaktionszeit zwischen 2 min und 60 min, vorzugsweise zwischen 5 min und 45 min durchgeführt.In addition to the purely thermal reaction, microwave energy can also be used to accelerate the reaction. For this purpose, a commercially available, designed for chemical purposes microwave device can be used. The reactions are generally at temperatures between 2O 0 C and 200 0 C 1 preferably between 4O 0 C and 17O 0 C and with an energy output between 20 and 200 watts, preferably between 50 and 180 watts, during a reaction time between 2 min and 60 min, preferably carried out between 5 min and 45 min.
Benzolsulfonamide der allgemeinen Formel (ll-d) mit R'" = Alkylthio, Alkenylthio, Alkinylthio, Arylthio oder Heterocyclylthio können in Analogie zu literaturbekannten Reaktionen durch Behandlung mit Oxidationsmittel, vorzugsweiseBenzenesulfonamides of general formula (II-d) with R '"= alkylthio, alkenylthio, alkynylthio, arylthio or Heterocyclylthio can in analogy to known literature reactions by treatment with oxidizing agents, preferably
Metachlorperbenzoesäure, Wasserstoffperoxid, Natriummetaperiodat oder Oxone zu den entsprechenden Sulfoxiden oder Sulfonen umgewandelt werden (vgl. z.B. „Reactions of Organosulfur Compounds"; Academic Press, new York, 1978, S. 16).Metachloroperbenzoic acid, hydrogen peroxide, sodium metaperiodate or oxones are converted to the corresponding sulfoxides or sulfones (see, e.g., "Reactions of Organosulfur Compounds", Academic Press, New York, 1978, p.
Die Sulfonyl(thio)carbamate der allgemeinen Formel (IV) werden in Analogie zu an sich bekannten Reaktionen (vgl. EP-A-120 814) hergestellt. Man kann z.B. auch die Sulfonyliso(thio)cyanate der Formel (VI) in glatter Reaktion in einem inerten Lösungsmittel, vorzugsweise Diethylether oder Dichlormethan mit Phenol in die (Thio)Carbamate der Formel (IV) überführen. Die Aminoheterocyclen der Formel (V) sind bekannte, zum Teil im Handel erhältliche Synthesechemikalien. Die Umsetzung der Sulfonyl(thio)carbamate der Formel (IV) mit den Aminoheterocyclen der Formel (V) erfolgt nach bekannten Verfahren (vgl. z.B. WO 2003 091228) (Schema 9). Schema 9The sulfonyl (thio) carbamates of the general formula (IV) are prepared analogously to reactions known per se (cf EP-A-120 814). It is also possible, for example, to convert the sulfonyl iso (thio) cyanates of the formula (VI) into the (thio) carbamates of the formula (IV) in a smooth reaction in an inert solvent, preferably diethyl ether or dichloromethane, with phenol. The aminoheterocycles of formula (V) are known, in part commercially available synthetic chemicals. The reaction of the sulfonyl (thio) carbamates of the formula (IV) with the aminoheterocycles of the formula (V) is carried out by known processes (cf., for example, WO 2003 091228) (Scheme 9). Scheme 9
( IV ) ( V )(IV) (V)
Die Sulfonyliso(thio)cyanate der allgemeinen Formel (VI) können nach an sich bekannten Verfahren aus den erfindungsgemäßen Sulfonamiden der allgemeinen Formel (II) hergestellt werden (vgl. DE 3208189, EP 23422, EP 64322, EP 44807, EP 216504). Man erhält die Arylsulfonyliso(thio)cyanate der Formel (VI), wenn man Arylsulfonamide der allgemeinen Formel (II) mit Phosgen bzw. Thiophosgen, gegebenenfalls in Gegenwart eines Alkylisocyanats, wie z.B. Butylisocyanat, gegebenenfalls in Gegenwart eines Reaktionshilfsmittels, wie Diazabicyclo [2.2.2] octan, und in Gegenwart eines Verdünnungsmiteis, wie Toluol, XyIoI oder Chlorbenzol, bei Temperaturen zwischen 8O0C und 1500C umsetzt und nach Ende der Umsetzung die flüchtigen Komponenten unter vermindertem Druck abdestilliert.The sulfonyl iso (thio) cyanates of the general formula (VI) can be prepared by processes known per se from the sulfonamides of the general formula (II) according to the invention (cf., DE 3208189, EP 23422, EP 64322, EP 44807, EP 216504). The Arylsulfonyliso (thio) cyanates of the formula (VI), if arylsulfonamides of the general formula (II) with phosgene or thiophosgene, optionally in the presence of an alkyl isocyanate, such as butyl isocyanate, optionally in the presence of a reaction auxiliary, such as diazabicyclo [2.2. 2] octane, and in the presence of a Verdünnungsmiteis, such as toluene, xylene or chlorobenzene, at temperatures between 8O 0 C and 150 0 C reacted and distilled off after the completion of the reaction, the volatile components under reduced pressure.
Die Umsetzung der Arylsulfonyliso(thio)cyanate der allgemeinen Formel (VI) mit den Aminoheterocyclen der Formel (V) erfolgt z.B. nach bekannten Verfahren (vgl. WO 2003 091228) (Schema 10).The reaction of the arylsulfonyl iso (thio) cyanates of the general formula (VI) with the amino heterocycles of the formula (V) is carried out, for example. by known processes (see WO 2003 091228) (Scheme 10).
Schema 10Scheme 10
( VI ) ( V )(VI) (V)
Die lso(thio)cyanate der allgemeinen Formel (VII) erhält man z.B. aus den Aminoheterocyclen des Typs (V) durch Behandlung mit Oxalylchlorid oder (Thio)Phosphen (in Analogie nach Angew. Chem. 1971 , 83, S. 407; EP 388 873). Die Umsetzung der lso(thio)cyanate des Typs (VII) mit den Sulfonamiden der allgemeinen Formel (II) erfolgt z.B. in Analogie nach Variante c) (Schema 11).The iso (thio) cyanates of general formula (VII) are obtained, for example, from Aminoheterocyclene of type (V) by treatment with oxalyl chloride or (thio) phosphene (in analogy to Angew. Chem. 1971, 83, p. 407, EP 388 873). The reaction of iso (thio) cyanates of type (VII) with the sulfonamides of general formula (II) is carried out, for example, in analogy to variant c) (Scheme 11).
Schema 11Scheme 11
Die Sulfonsäurehalogenide der Formel (VIII) können nach verschiedenen literaturbekannten Methoden hergestellt werden, z.B. i) Oxidative Chlorierung von Thioether (Recl. Trav. Chim. Pays-Bas 1982, 101 , 91 , ii) Diazotierung von aromatischen Aminen mit Natriumnitrit in Salzsäure, gefolgt von der Reaktion des resultierenden Diazoniumsalzes mit Schwefeldioxid und Kupferchorid (J. Org. Chem. 1960, 1824), iii) Heteroatom- gesteuerte Lithiierung, gefolgt von Sulfonylierung (EP 73562; Org. React. 1979, 26, 1), iv) Newman-Umlagerung und nachfolgende oxidative Chlorierung (US 5157119), v) Umsetzung eines Sulfonsäureamids des Typs (II) mit Thienylchlorid (Bull. Kor. Chem. Soc. 1994, 15, 323). Eine Verbindung der Formel (VIII) mit R = I ist bekannt aus FR 2649698. In einer Ausführungsform der Variante f) wird die durch Umsetzung des Sulfonsäurehalogenids (VIII) mit einem (Thio)Cyanat erhaltene Reaktionsmischung direkt für die Kupplung mit einem Aminoheterocyclus der Formel (V) zur Synthese der Verbindung der Formel (I) eingesetzt (vgl. hierzu WO 2003 091228 und US 5550238).The sulfonic acid halides of the formula (VIII) can be prepared by various methods known from the literature, e.g. i) Oxidative Chlorination of Thioethers (Recl. Trav. Chim. Pays-Bas 1982, 101, 91, ii) Diazotization of aromatic amines with sodium nitrite in hydrochloric acid, followed by the reaction of the resulting diazonium salt with sulfur dioxide and copper chloride (J. Org. Chem , 1960, 1824), iii) heteroatom-controlled lithiation followed by sulfonylation (EP 73562, Org React 1979, 26, 1), iv) Newman rearrangement and subsequent oxidative chlorination (US 5,157,119), v) reaction of a sulfonic acid amide of type (II) with thienyl chloride (Bull. Kor. Chem. Soc. 1994, 15, 323). A compound of formula (VIII) where R = I is known from FR 2649698. In one embodiment of variant f), the reaction mixture obtained by reacting the sulfonic acid halide (VIII) with a (thio) cyanate is used directly for coupling with an amino heterocycle of the formula (V) for the synthesis of the compound of formula (I) used (see, for this purpose, WO 2003 091228 and US 5550238).
Die Salze der Verbindungen der Formel (I) werden vorzugsweise in inerten polaren Lösungsmitteln wie z.B. Wasser, Methanol oder Aceton bei Temperaturen von 00C bis 1000C hergestellt. Geeignete Basen zur Herstellung der erfindungsgemäßen Salze sind beispielsweise Alkalicarbonate, wie Kaliumcarbonat, Alkali- und Erdalkalihydroxide, z.B. NaOH oder KOH, oder Alkalialkoholate, wie Natriummethanolat oder Natrium-tert.-butylat, oder Ammoniak oder Ethanolamin.The salts of the compounds of formula (I) are preferably prepared in inert polar solvents such as water, methanol or acetone at temperatures of 0 0 C to 100 0 C. Suitable bases for the preparation of the inventive Salts are, for example, alkali metal carbonates, such as potassium carbonate, alkali metal and alkaline earth metal hydroxides, for example NaOH or KOH, or alkali metal alkoxides, such as sodium methoxide or sodium tert-butoxide, or ammonia or ethanolamine.
Mit den in den vorstehenden Verfahrensvarianten bezeichneten "inerten Lösungsmitteln" sind jeweils Lösungsmittel gemeint, die unter den jeweiligen Reaktionsbedingungen inert sind, jedoch nicht unter beliebigen Reaktionsbedingungen inert sein müssen.By the term "inert solvents" denoted in the above process variants are meant in each case solvents which are inert under the respective reaction conditions, but need not be inert under any reaction conditions.
Kollektionen aus Verbindungen der Formel (I) und/oder deren Salzen, die nach den oben genannten Reaktionen synthetisiert werden können, können auch in parallelisierter Weise hergestellt werden, wobei dies in manueller, teilweise automatisierter oder vollständig automatisierter Weise geschehen kann. Dabei ist es beispielsweise möglich, die Reaktionsdurchführung, die Aufarbeitung oder die Reinigung der Produkte bzw. Zwischenstufen zu automatisieren. Insgesamt wird hierunter eine Vorgehensweise verstanden, wie sie beispielsweise durch S. H. DeWitt in "Annual Reports in Combinatorial Chemistry and Molecular Diversity: Automated Synthesis", Band 1 , Verlag Escom 1997, Seite 69 bis 77 beschrieben ist.Collections of compounds of formula (I) and / or their salts, which may be synthesized following the above reactions, may also be prepared in a parallelized manner, which may be done in a manual, partially automated or fully automated manner. It is possible, for example, to automate the reaction procedure, the work-up or the purification of the products or intermediates. Overall, this is understood as a procedure as described, for example, by S.H. DeWitt in "Annual Reports in Combinatorial Chemistry and Molecular Diversity: Automated Synthesis", Volume 1, published by Escom 1997, pages 69 to 77.
Für die Durchführung mikrowellenunterstützter Synthesen kann einFor the implementation of microwave assisted syntheses can
Mikrowellengerät, z.B. Modell „Discover" der Firma CEM GmbH Mikrowellen- Analysentechnik, Carl-Friedrich-Gauß-Str. 9, 47475 Kamp-Lintfort verwendet werden.Microwave oven, e.g. Model "Discover" by the company CEM GmbH Microwave Analysis, Carl-Friedrich-Gauss-Str. 9, 47475 Kamp-Lintfort be used.
Zur parallelisierten Reaktionsdurchführung und Aufarbeitung können eine Reihe von im Handel erhältlichen Geräten verwendet werden, wie sie beispielsweise von den Firmen Stern Corporation, Woodrolfe road, Tollesbury, Essex, England, H+P Labortechnik GmbH, Bruckmannring 28, 85764 Oberschleißheim, Deutschland oder der Firma Radleys, Shirehill, Saffron Waiden, Essex, CB 11 3AZ, England angeboten werden. Für die parallelisierte Aufreinigung von Verbindungen der allgemeinen Formel (I) und deren Salzen beziehungsweise von bei der Herstellung anfallenden Zwischenprodukten stehen unter anderem Chromatographieapparaturen zur Verfügung, beispielsweise der Firma ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.For parallelized reaction performance and work-up a number of commercially available devices can be used, as for example by the company Stern Corporation, Woodrolfe road, Tollesbury, Essex, England, H + P Laboratory GmbH, Bruckmannring 28, 85764 Oberschleißheim, Germany or the company Radleys, Shirehill, Saffron Waiden, Essex, CB 11 3AZ, England. For the parallelized purification of compounds of the general formula (I) and their salts or of intermediates obtained during the preparation, inter alia, chromatography apparatuses are available available, for example, the company ISCO, Inc., 4700 Superior Street, Lincoln, NE 68504, USA.
Die aufgeführten Apparaturen führen zu einer modularen Vorgehensweise, bei der die einzelnen Arbeitsschritte automatisiert sind, zwischen den Arbeitsschritten jedoch manuelle Operationen durchgeführt werden müssen. Dies kann durch den Einsatz von teilweise oder vollständig integrierten Automationssystemen umgangen werden, bei denen die jeweiligen Automationsmodule beispielsweise durch Roboter bedient werden. Derartige Automationssysteme können zum Beispiel von der Firma Zymark Corporation, Zymark Center, Hopkinton, MA 01748, USA bezogen werden.The listed equipment leads to a modular procedure, in which the individual work steps are automated, but between the work steps, manual operations must be performed. This can be circumvented by the use of partially or fully integrated automation systems in which the respective automation modules are operated, for example, by robots. Such automation systems may be obtained, for example, from Zymark Corporation, Zymark Center, Hopkinton, MA 01748, USA.
Neben den hier beschriebenen Methoden kann die Herstellung von Verbindungen der allgemeinen Formel (I) und deren Salzen vollständig oder partiell durch Festphasen unterstützte Methoden erfolgen. Zu diesem Zweck werden einzelne Zwischenstufen oder alle Zwischenstufen der Synthese oder einer für die entsprechende Vorgehensweise angepassten Synthese an ein Syntheseharz gebunden. Festphasen- unterstützte Synthesemethoden sind in der Fachliteratur hinreichend beschrieben, z.B. Barry A. Bunin in "The Combinatorial Index", Verlag Academic Press, 1998.In addition to the methods described herein, the preparation of compounds of general formula (I) and their salts can be carried out fully or partially by solid-phase assisted methods. For this purpose, individual intermediates or all intermediates of the synthesis or adapted for the appropriate approach synthesis are bound to a synthetic resin. Solid phase assisted synthetic methods are well described in the literature, e.g. Barry A. Bunin in The Combinatorial Index, Academic Press, 1998.
Die Verwendung von Festphasen- unterstützten Synthesemethoden erlaubt eine Reihe von literaturbekannten Protokollen, die wiederum manuell oder automatisiert ausgeführt werden können. Zum Beispiel kann die 'Teebeutelmethode" (Houghten, US 4,631 ,211; Houghten et al., Proc. Natl. Acad. Sei, 1985, 82, 5131-5135) mit Produkten der Firma IRORI, 11149 North Torrey Pines Road, La JoIIa, CA 92037, USA teilweise automatisiert werden. Die Automatisierung von Festphasen unterstützten Parallelsynthesen gelingt beispielsweise durch Apparaturen der Firmen Argonaut Technologies, Inc., 887 Industrial Road, San Carlos, CA 94070, USA oder MultiSynTech GmbH, Wullener Feld 4, 58454 Wirten, Deutschland.The use of solid-phase assisted synthetic methods allows a number of protocols known from the literature, which in turn can be carried out manually or automatically. For example, the 'teabag method' (Houghten, U.S. 4,631,211; Houghten et al., Proc Natl Acad. Sei, 1985, 82, 5131-5135) may be used with products of IRORI, 11149 North Torrey Pines Road, La JoIIa , CA 92037, USA The automation of solid-phase assisted parallel syntheses is accomplished, for example, by the equipment of Argonaut Technologies, Inc., 887 Industrial Road, San Carlos, CA 94070, USA or MultiSynTech GmbH, Wullener Feld 4, 58454 Wirten, Germany ,
Die Herstellung gemäß der hier beschriebenen Verfahren liefert Verbindungen der Formel (I) und deren Salze in Form von Substanzkollektionen, die Bibliotheken genannt werden. Gegenstand der vorliegenden Erfindung sind auch Bibliotheken, die mindestens zwei Verbindungen der Formel (I) und deren Salzen enthalten.The preparation according to the methods described herein provides compounds of formula (I) and their salts in the form of substance collections containing libraries to be named. The present invention also provides libraries containing at least two compounds of formula (I) and their salts.
Die erfindungsgemäßen Verbindungen der Formel (I) und/oder deren Salze, im folgenden zusammen als „erfindungsgemäße Verbindungen" bezeichnet, weisen eine ausgezeichnete herbizide Wirksamkeit gegen ein breites Spektrum wirtschaftlich wichtiger mono- und dikotyler Schadpflanzen auf. Auch schwer bekämpfbare perennierende Unkräuter, die aus Rhizomen, Wurzelstöcken oder anderen Dauerorganen austreiben, werden durch die Wirkstoffe gut erfaßt.The compounds of the formula (I) according to the invention and / or their salts, together referred to as "compounds according to the invention", have an excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous weeds which are difficult to control perennial weeds Rhizomes, rhizomes or other permanent organs drive out, are well detected by the active ingredients.
Gegenstand der vorliegenden Erfindung ist daher auch ein Verfahren zur Bekämpfung von unerwünschten Pflanzen oder zur Wachstumsregulierung von Pflanzen, vorzugsweise in Pflanzenkulturen, worin eine oder mehrere erfindungsgemäße Verbindungen auf die Pflanzen (z.B. Schadpflanzen wie mono- oder dikotyle Unkräuter oder unerwünschte Kulturpflanzen), das Saatgut (z.B. Körner, Samen oder vegetative Vermehrungsorgane wie Knollen oder Sprossteile mit Knospen) oder die Fläche, auf der die Pflanzen wachsen (z.B. die Anbaufläche), ausgebracht werden. Dabei können die erfindungsgemäßen Verbindungen z.B. im Vorsaat-, Vorauflauf- oder Nachauflaufverfahren ausgebracht werden. Im einzelnen seien beispielhaft einige Vertreter der mono- und dikotylen Unkrautflora genannt, die durch die erfindungsgemäßen Verbindungen kontrolliert werden können, ohne daß durch die Nennung eine Beschränkung auf bestimmte Arten erfolgen soll.The present invention therefore also provides a method for controlling unwanted plants or regulating the growth of plants, preferably in plant crops, wherein one or more compounds according to the invention are applied to the plants (for example harmful plants such as monocotyledonous or dicotyledonous weeds or undesired crop plants), the seed ( For example, grains, seeds or vegetative propagules such as tubers or Sprossteile with buds) or the area on which the plants grow (eg the acreage) are applied. The compounds of the invention may be e.g. be applied in pre-sowing, pre-emergence or post-emergence. Specifically, by way of example, some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned, which can be controlled by the compounds according to the invention, without the intention of limiting them to certain species.
Auf der Seite der monokotylen Unkrautarten werden z.B. Apera spica venti, Avena spp., Alopecurus spp., Brachiaria spp., Digitaria spp., Lolium spp., Echinochloa spp., Panicum spp., Phalaris spp., Poa spp., Setaria spp. sowie Bromus spp. wie Bromus catharticus, Bromus secalinus, Bromus erectus, Bromus tectorum und Bromus japonicus und Cyperusarten aus der annuellen Gruppe und auf Seiten der perennierenden Spezies Agropyron, Cynodon, Imperata sowie Sorghum und auch ausdauernde Cyperusarten gut erfaßt.On the side of the monocotyledonous weeds, e.g. Apera spica venti, Avena spp., Alopecurus spp., Brachiaria spp., Digitaria spp., Lolium spp., Echinochloa spp., Panicum spp., Phalaris spp., Poa spp., Setaria spp. and Bromus spp. such as Bromus catharticus, Bromus secalinus, Bromus erectus, Bromus tectorum and Bromus japonicus and Cyperusarten from the annuelle group and on the part of the perennial species Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperusarten well.
Bei dikotylen Unkrautarten erstreckt sich das Wirkungsspektrum auf Arten wie z.B. Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp. wie Galium aparine, Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharbitis spp., Polygonum spp.,Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp. und Viola spp., Xanthium spp., auf der annuellen Seite sowie Convolvulus, Cirsium, Rumex und Artemisia bei den perennierenden Unkräutern.In dicotyledonous weed species, the spectrum of activity extends to species such as Abutilon spp., Amaranthus spp., Chenopodium spp., Chrysanthemum spp., Galium spp. Galium aparine, Ipomoea spp., Kochia spp., Lamium spp., Matricaria spp., Pharitis spp., Polygonum spp., Sida spp., Sinapis spp., Solanum spp., Stellaria spp., Veronica spp. and Viola spp., Xanthium spp., on the annual side, as well as Convolvulus, Cirsium, Rumex, and Artemisia in perennial weeds.
Unter den spezifischen Kulturbedingungen im Reis vorkommende Schadpflanzen wie z.B. Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus und Cyperus werden von den erfindungsgemäßen Wirkstoffen ebenfalls hervorragend bekämpft.Under the specific culture conditions occurring in rice harmful plants such. Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus are also excellently controlled by the active compounds according to the invention.
Werden die erfindungsgemäßen Verbindungen vor dem Keimen auf die Erdoberfläche appliziert, so wird entweder das Auflaufen der Unkrautkeimlinge vollständig verhindert oder die Unkräuter wachsen bis zum Keimblattstadium heran, stellen jedoch dann ihr Wachstum ein und sterben schließlich nach Ablauf von drei bis vier Wochen vollkommen ab.If the compounds according to the invention are applied to the surface of the earth before germination, then either the emergence of the weed seedlings is completely prevented or the weeds grow up to the cotyledon stage, but then cease their growth and finally die off completely after a lapse of three to four weeks.
Bei Applikation der Wirkstoffe auf die grünen Pflanzenteile im Nachauflaufverfahren tritt ebenfalls sehr rasch nach der Behandlung ein drastischer Wachstumsstop ein und die Unkrautpflanzen bleiben in dem zum Applikationszeitpunkt vorhandenen Wachstumsstadium stehen oder sterben nach einer gewissen Zeit ganz ab, so daß auf diese Weise eine für die Kulturpflanzen schädliche Unkrautkonkurrenz sehr früh und nachhaltig beseitigt wird.Upon application of the active ingredients to the green parts of the plants postemergence also occurs very quickly after treatment, a drastic halt in growth and the weed plants remain in the existing stage of application growth stage or die after a period of time completely, so that in this way one for the crops harmful weed competition is eliminated very early and sustainably.
Obgleich die erfindungsgemäßen Verbindungen eine ausgezeichnete herbizide Aktivität gegenüber mono- und dikotylen Unkräutern aufweisen, werdenAlthough the compounds of the invention have excellent herbicidal activity against mono- and dicotyledonous weeds
Kulturpflanzen wirtschaftlich bedeutender Kulturen z.B. zweikeimblättriger Kulturen wie Soja, Baumwolle, Raps, Zuckerrüben, oder Gramineen-Kulturen wie Weizen, Gerste, Roggen, Mais oder Reis, insbesondere Mais und Weizen, nur unwesentlich oder gar nicht geschädigt. Die vorliegenden Verbindungen eignen sich aus diesen Gründen sehr gut zur selektiven Bekämpfung von unerwünschtem Pflanzenwuchs in Pflanzenkulturen wie landwirtschaftlichen Nutzpflanzungen oder Zierpflanzungen. Darüberhinaus weisen die erfindungsgemäßen Verbindungen hervorragende wachstumsregulatorische Eigenschaften bei Kulturpflanzen auf. Sie greifen regulierend in den pflanzeneigenen Stoffwechsel ein und können damit zur gezielten Beeinflussung von Pflanzeninhaltsstoffen und zur Ernteerleichterung wie z.B. durch Auslösen von Desikkation und Wuchsstauchung eingesetzt werden. Desweiteren eignen sie sich auch zur generellen Steuerung und Hemmung von unerwünschtem vegetativen Wachstum, ohne dabei die Pflanzen abzutöten. Eine Hemmung des vegetativen Wachstums spielt bei vielen mono- und dikotylen Kulturen eine große Rolle, da die Lagerbarkeit hierdurch verringert oder völlig verhindert werden kann.Crops of economically important crops such as dicotyledonous crops such as soybean, cotton, rapeseed, sugar beets, or graminaceous crops such as wheat, barley, rye, corn or rice, especially corn and wheat, only marginally or not at all damaged. For these reasons, the present compounds are very well suited for the selective control of undesired plant growth in crops such as agricultural crops or ornamental plants. Moreover, the compounds of the invention have excellent growth-regulatory properties in crop plants. They regulate the plant's metabolism and can thus be used to specifically influence plant ingredients and facilitate harvesting, eg by triggering desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of undesirable vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops, as this can reduce or completely prevent shelf life.
Aufgrund ihrer herbiziden und pflanzenwachstumsregulatorischen Eigenschaften können die Wirkstoffe auch zur Bekämpfung von Schadpflanzen in Kulturen von bekannten oder noch zu entwickelnden gentechnisch veränderten Pflanzen eingesetzt werden. Die transgenen Pflanzen zeichnen sich in der Regel durch besondere vorteilhafte Eigenschaften aus, beispielsweise durch Resistenzen gegenüber bestimmten Pestiziden, vor allem bestimmten Herbiziden, Resistenzen gegenüber Pflanzenkrankheiten oder Erregern von Pflanzenkrankheiten wie bestimmten Insekten oder Mikroorganismen wie Pilzen, Bakterien oder Viren. Andere besondere Eigenschaften betreffen z. B. das Erntegut hinsichtlich Menge, Qualität, Lagerfähigkeit, Zusammensetzung und spezieller Inhaltsstoffe. So sind transgene Pflanzen mit erhöhtem Stärkegehalt oder veränderter Qualität der Stärke oder solche mit anderer Fettsäurezusammensetzung des Ernteguts bekannt.Due to their herbicidal and plant growth regulatory properties, the active compounds can also be used for controlling harmful plants in crops of known or yet to be developed genetically modified plants. The transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties relate to z. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients. Thus, transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known.
Bevorzugt ist die Anwendung der erfindungsgemäßen Verbindungen in wirtschaftlich bedeutenden transgenen Kulturen von Nutz- und Zierpflanzen, z. B. von Getreide wie Weizen, Gerste, Roggen, Hafer, Hirse, Reis, Maniok und Mais oder auchPreferably, the application of the compounds of the invention in economically important transgenic crops of useful and ornamental plants, eg. As cereals such as wheat, barley, rye, oats, millet, rice, cassava and corn or even
Kulturen von Zuckerrübe, Baumwolle, Soja, Raps, Kartoffel, Tomate, Erbse und anderen Gemüsesorten.Cultures of sugar beet, cotton, soy, rapeseed, potato, tomato, pea and other vegetables.
Vorzugsweise können die erfindungsgemäßen Verbindungen als Herbizide in Nutzpflanzenkulturen eingesetzt werden, welche gegenüber den phytotoxischenPreferably, the compounds of the invention can be used as herbicides in crops that are resistant to the phytotoxic
Wirkungen der Herbizide resistent sind bzw. gentechnisch resistent gemacht worden sind. Herkömmliche Wege zur Herstellung neuer Pflanzen, die im Vergleich zu bisher vorkommenden Pflanzen modifizierte Eigenschaften aufweisen, bestehen beispielsweise in klassischen Züchtungsverfahren und der Erzeugung von Mutanten. Alternativ können neue Pflanzen mit veränderten Eigenschaften mit Hilfe gentechnischer Verfahren erzeugt werden (siehe z. B. EP-A-0221044 und EP-A-0131624). Beschrieben wurden beispielsweise in mehreren Fällen gentechnische Veränderungen von Kulturpflanzen zwecks Modifikation der in den Pflanzen synthetisierten Stärke (z. B. WO 92/11376, WO 92/14827 und WO 91/19806), transgene Kulturpflanzen, welche gegen bestimmte Herbizide vom Typ Glufosinate (vgl. z. B. EP-A-0242236, EP-A-242246) oder Glyphosate (WO 92/00377) oder der Sulfonylharnstoffe (EP-A-0257993, US-A-5013659) resistent sind, - transgene Kulturpflanzen, beispielsweise Baumwolle, mit der FähigkeitEffects of the herbicides are resistant or have been made genetically resistant. Conventional ways of producing new plants which have modified properties in comparison to previously occurring plants consist, for example, in classical breeding methods and the production of mutants. Alternatively, new plants with altered properties can be generated by genetic engineering techniques (see, eg, EP-A-0221044 and EP-A-0131624). For example, in several cases, genetic modifications of cultivated plants have been described for the purpose of modifying the starch synthesized in the plants (for example WO 92/11376, WO 92/14827 and WO 91/19806), transgenic crop plants which have been found to be active against certain glufosinate-type herbicides (US Pat. see, for example, EP-A-0242236, EP-A-242246) or glyphosate (WO 92/00377) or the sulfonylureas (EP-A-0257993, US-A-5013659), - transgenic crop plants, for example Cotton, with the ability
Bacillus thuringiensis-Toxine (Bt-Toxine) zu produzieren, welche die Pflanzen gegen bestimmte Schädlinge resistent machen (EP-A-0142924 und EP-A-0193259). transgene Kulturpflanzen mit modifizierter Fettsäurezusammensetzung (WO 91/13972).Bacillus thuringiensis toxins (Bt toxins) which render the plants resistant to certain pests (EP-A-0142924 and EP-A-0193259). Transgenic crop plants with modified fatty acid composition (WO 91/13972).
Zahlreiche molekularbiologische Techniken, mit denen neue transgene Pflanzen mit veränderten Eigenschaften hergestellt werden können, sind im Prinzip bekannt (siehe z.B. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2. Aufl. CoId Spring Harbor Laboratory Press, CoId Spring Harbor, NY; oder Winnacker "Gene und Klone", VCH Weinheim 2. Auflage 1996 oder Christou, "Trends in Plant Science" 1 (1996) 423-431 ).Numerous molecular biology techniques that can be used to produce novel transgenic plants with altered properties are known in the art (see, eg, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed. CoId Spring Harbor Laboratory Press, CoId Spring Harbor , NY, or Winnacker "Genes and Clones", VCH Weinheim 2nd edition 1996 or Christou, "Trends in Plant Science" 1 (1996) 423-431).
Für derartige gentechnische Manipulationen können Nucleinsäuremoleküle in Plasmide eingebracht werden, die eine Mutagenese oder eine Sequenzveränderung durch Rekombination von DNA-Sequenzen ertauben. Mit Hilfe der obengenannten Standardverfahren können z. B. Basenaustausche vorgenommen, Teilsequenzen entfernt oder natürliche oder synthetische Sequenzen hinzugefügt werden. Für die Verbindung der DNA-Fragmente untereinander können an die Fragmente Adaptoren oder Linker angesetzt werden.For such genetic engineering, nucleic acid molecules can be introduced into plasmids that allow mutagenesis or sequence alteration by recombination of DNA sequences. With the aid of the abovementioned standard methods, z. B. Base exchanges, partial sequences removed or natural or synthetic sequences are added. For the connection of the DNA fragments with one another adapters or linkers can be attached to the fragments.
Die Herstellung von Pflanzenzellen mit einer verringerten Aktivität einesThe production of plant cells with a reduced activity of a
Genprodukts kann beispielsweise erzielt werden durch die Expression mindestens einer entsprechenden antisense-RNA, einer sense-RNA zur Erzielung eines Cosuppressionseffektes oder die Expression mindestens eines entsprechend konstruierten Ribozyms, das spezifisch Transkripte des obengenannten Genprodukts spaltet.Gene product can be obtained, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to obtain a cosuppression effect or the expression of at least one appropriately engineered ribozyme which specifically cleaves transcripts of the above gene product.
Hierzu können zum einen DNA-Moleküle verwendet werden, die die gesamte codierende Sequenz eines Genprodukts einschließlich eventuell vorhandener flankierender Sequenzen umfassen, als auch DNA-Moleküle, die nur Teile der codierenden Sequenz umfassen, wobei diese Teile lang genug sein müssen, um in den Zellen einen antisense-Effekt zu bewirken. Möglich ist auch die Verwendung von DNA-Sequenzen, die einen hohen Grad an Homologie zu den codierenden Sequenzen eines Genprodukts aufweisen, aber nicht vollkommen identisch sind.For this purpose, DNA molecules may be used which comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules which comprise only parts of the coding sequence, which parts must be long enough to be present in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product but are not completely identical.
Bei der Expression von Nucleinsäuremolekülen in Pflanzen kann das synthetisierte Protein in jedem beliebigen Kompartiment der pflanzlichen Zelle lokalisiert sein. Um aber die Lokalisation in einem bestimmten Kompartiment zu erreichen, kann z. B. die codierende Region mit DNA-Sequenzen verknüpft werden, die die Lokalisierung in einem bestimmten Kompartiment gewährleisten. Derartige Sequenzen sind dem Fachmann bekannt (siehe beispielsweise Braun et al., EMBO J. IJ. (1992),In the expression of nucleic acid molecules in plants, the synthesized protein may be located in any compartment of the plant cell. But to achieve the localization in a particular compartment, z. For example, the coding region can be linked to DNA sequences that ensure localization in a particular compartment. Such sequences are known to the person skilled in the art (see, for example, Braun et al., EMBO J. IJ. (1992),
3219-3227; Wolter et al., Proc. Natl. Acad. Sei. USA 85 (1988), 846-850; Sonnewald et al., Plant J.1 (1991 ), 95-106).3219-3227; Wolter et al., Proc. Natl. Acad. Be. USA 85 (1988), 846-850; Sonnewald et al., Plant J.1 (1991), 95-106).
Die transgenen Pflanzenzellen können nach bekannten Techniken zu ganzen Pflanzen regeneriert werden. Bei den transgenen Pflanzen kann es sich prinzipiell um Pflanzen jeder beliebigen Pflanzenspezies handeln, d.h. sowohl monokotyle als auch dikotyle Pflanzen. So sind transgene Pflanzen erhältlich, die veränderte Eigenschaften durch Überexpression, Suppression oder Inhibierung homologer (= natürlicher) Gene oder Gensequenzen oder Expression heterologer (= fremder) Gene oder Gensequenzen aufweisen.The transgenic plant cells can be regenerated to whole plants by known techniques. The transgenic plants may in principle be plants of any plant species, ie both monocotyledonous and dicotyledonous plants. Thus, transgenic plants are available which have altered properties by overexpression, suppression or inhibition of homologous (= natural) genes or gene sequences or expression of heterologous (= foreign) genes or gene sequences.
Vorzugsweise können die erfindungsgemäßen Verbindungen in transgenen Kulturen eingesetzt werden, welche gegen Herbizide aus der Gruppe der Sulfonylharnstoffe, Glufosinate-ammonium oder Glyphosate-isopropylammonium und analoge Wirkstoffe resistent sind.Preferably, the compounds of the invention can be used in transgenic cultures which are resistant to herbicides from the group of sulfonylureas, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active ingredients.
Bei der Anwendung der erfindungsgemäßen Verbindungen in transgenen Kulturen treten neben den in anderen Kulturen zu beobachtenden Wirkungen gegenüber Schadpflanzen oftmals Wirkungen auf, die für die Applikation in der jeweiligen transgenen Kultur spezifisch sind, beispielsweise ein verändertes oder speziell erweitertes Unkrautspektrum, das bekämpft werden kann, veränderte Aufwandmengen, die für die Applikation eingesetzt werden können, vorzugsweise gute Kombinierbarkeit mit den Herbiziden, gegenüber denen die transgene Kultur resistent ist, sowie Beeinflussung von Wuchs und Ertrag der transgenen Kulturpflanzen.In the application of the compounds according to the invention in transgenic crops, in addition to the effects observed in other crops against harmful plants, effects which are specific for the application in the respective transgenic crop often occur, for example a modified or specially extended weed spectrum which can be controlled Application rates that can be used for the application, preferably good combinability with the herbicides to which the transgenic culture is resistant, and influencing growth and yield of the transgenic crops.
Gegenstand der Erfindung ist somit auch die Verwendung der erfindungsgemäßen Verbindungen als Herbizide zur Bekämpfung von Schadpflanzen in transgenen und nicht transgenen Pflanzenkulturen.The invention thus also relates to the use of the compounds according to the invention as herbicides for controlling harmful plants in transgenic and non-transgenic crops.
Die erfindungsgemäßen Verbindungen können in Form von Spritzpulvern, emulgierbaren Konzentraten, versprühbaren Lösungen, Stäubemitteln oder Granulaten in den üblichen Zubereitungen angewendet werden. Gegenstand der Erfindung sind deshalb auch herbizide und pflanzenwachstumsregulierende Mittel, welche die erfindungsgemäßen Verbindungen enthalten.The compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations. The invention therefore also relates to herbicidal and plant growth-regulating agents which contain the compounds according to the invention.
Die erfind ungsgemäßen Verbindungen können auf verschiedene Art formuliert werden, je nachdem welche biologischen und/oder chemisch-physikalischen Parameter vorgegeben sind. Als Formulierungsmöglichkeiten kommen beispielsweise in Frage: Spritzpulver (WP), wasserlösliche Pulver (SP), wasserlösliche Konzentrate, emulgierbare Konzentrate (EC), Emulsionen (EW), wie Öl-in-Wasser- und Wasser-in-ÖI-Emulsionen, versprühbare Lösungen,The compounds according to the invention can be formulated in various ways depending on which biological and / or chemical-physical parameters are given. Possible formulation options are, for example: wettable powder (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions .
Suspensionskonzentrate (SC), Dispersionen auf Öl- oder Wasserbasis, ölmischbare Lösungen, Kapselsuspensionen (CS), Stäubemittel (DP), Beizmittel, Granulate für die Streu- und Bodenapplikation, Granulate (GR) in Form von Mikro-, Sprüh-, Aufzugs- und Adsorptionsgranulaten, wasserdispergierbare Granulate (WG), wasserlösliche Granulate (SG), ULV-Formulierungen, Mikrokapseln und Wachse. Diese einzelnen Formulierungstypen sind im Prinzip bekannt und werden beispielsweise beschrieben in: Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hanser Verlag München, 4. Aufl. 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.Suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for litter and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes. These individual formulation types are known in principle and are described, for example, in: Winnacker-Kuchler, "Chemische Technologie", Volume 7, C. Hanser Verlag, Munich, 4th edition, 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd ed. 1979, G. Goodwin Ltd. London.
Die notwendigen Formulierungshilfsmittel wie Inertmaterialien, Tenside, Lösungsmittel und weitere Zusatzstoffe sind ebenfalls bekannt und werden beispielsweise beschrieben in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Grenzflächenaktive Äthylenoxidaddukte", Wiss. Verlagsgesell., Stuttgart 1976;The necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticides Dust Diluents and Carriers", 2nd ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y .; C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J .; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Grenzflächenaktive Äthylenoxidaddukte", Wiss. Publishing company, Stuttgart 1976;
Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hanser Verlag München, 4. Aufl. 1986.Winnacker-Kuchler, "Chemical Technology", Volume 7, C. Hanser Verlag Munich, 4th ed. 1986.
Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit anderen pestizid wirksamen Stoffen, wie z.B. Insektiziden, Akariziden, Herbiziden,On the basis of these formulations, combinations with other pesticidally active substances, e.g. Insecticides, acaricides, herbicides,
Fungiziden, sowie mit Safenern, Düngemitteln und/oder Wachstumsregulatoren herstellen, z.B. in Form einer Fertigformulierung oder als Tankmix. Spritzpulver sind in Wasser gleichmäßig dispergierbare Präparate, die neben dem Wirkstoff außer einem Verdünnungs- oder Inertstoff noch Tenside ionischer und/oder nichtionischer Art (Netzmittel, Dispergiermittel), z.B. polyoxyethylierte Alkylphenole, polyoxethylierte Fettalkohole, polyoxethylierte Fettamine,Fungicides, as well as with safeners, fertilizers and / or growth regulators produce, for example in the form of a ready-made formulation or as a tank mix. Injectable powders are preparations which are uniformly dispersible in water and, in addition to the active ingredient, except for a diluent or inert substance, also ionic and / or nonionic surfactants (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines,
Fettalkoholpolyglykolethersulfate, Alkansulfonate, Alkylbenzolsulfonate, ligninsulfonsaures Natrium, 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium, dibutylnaphthalin-sulfonsaures Natrium oder auch oleoylmethyltaurinsaures Natrium enthalten. Zur Herstellung der Spritzpulver werden die herbiziden Wirkstoffe beispielsweise in üblichen Apparaturen wie Hammermühlen, Gebläsemühlen und Luftstrahlmühlen feingemahlen und gleichzeitig oder anschließend mit den Formulierungshilfsmitteln vermischt.Fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, lignosulfonic acid sodium, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalenesulfonate sodium or oleoylmethyltaurine acid. To prepare the wettable powders, the herbicidal active compounds are finely ground, for example, in customary apparatus such as hammer mills, blower mills and air-jet mills and mixed simultaneously or subsequently with the formulation auxiliaries.
Emulgierbare Konzentrate werden durch Auflösen des Wirkstoffes in einem organischen Lösungsmittel z.B. Butanol, Cyclohexanon, Dimethylformamid, XyIoI oder auch höhersiedenden Aromaten oder Kohlenwasserstoffen oder Mischungen der organischen Lösungsmittel unter Zusatz von einem oder mehreren Tensiden ionischer und/oder nichtionischer Art (Emulgatoren) hergestellt. Als Emulgatoren können beispielsweise verwendet werden: Alkylarylsulfonsaure Calzium-Salze wie Ca-Dodecylbenzolsulfonat oder nichtionische Emulgatoren wieEmulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents with the addition of one or more ionic and / or nonionic surfactants (emulsifiers). Examples of suitable emulsifiers are: alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers such as
Fettsäurepolyglykolester, Alkylarylpolyglykolether, Fettalkoholpolyglykolether, Propylenoxid-Ethylenoxid-Kondensationsprodukte, Alkylpolyether, Sorbitanester wie z.B. Sorbitanfettsäureester oder Polyoxethylensorbitanester wie z.B. Polyoxyethylensorbitanfettsäureester.Fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as e.g. Sorbitan fatty acid esters or polyoxethylenesorbitan esters such as e.g. Polyoxyethylene.
Stäubemittel erhält man durch Vermählen des Wirkstoffes mit fein verteilten festen Stoffen, z.B. Talkum, natürlichen Tonen, wie Kaolin, Bentonit und Pyrophyllit, oder Diatomeenerde.Dusts are obtained by milling the active ingredient with finely divided solids, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
Suspensionskonzentrate können auf Wasser- oder Ölbasis sein. Sie können beispielsweise durch Naß-Vermahlung mittels handelsüblicher Perlmühlen und gegebenenfalls Zusatz von Tensiden, wie sie z.B. oben bei den anderen Formulierungstypen bereits aufgeführt sind, hergestellt werden.Suspension concentrates may be water or oil based. You can, for example, by wet grinding using commercially available bead mills and optionally added surfactants, such as the above with the other Formulation types already listed are produced.
Emulsionen, z.B. ÖI-in-Wasser-Emulsionen (EW)1 lassen sich beispielsweise mittels Rührern, Kolloidmühlen und/oder statischen Mischern unter Verwendung von wäßrigen organischen Lösungsmitteln und gegebenenfalls Tensiden, wie sie z.B. oben bei den anderen Formulierungstypen bereits aufgeführt sind, herstellen.Emulsions, for example oil-in-water emulsions (EW) 1, can be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, as already listed above for the other formulation types.
Granulate können entweder durch Verdüsen des Wirkstoffes auf adsorptionsfähiges, granuliertes Inertmaterial hergestellt werden oder durch Aufbringen von Wirkstoffkonzentraten mittels Klebemitteln, z.B. Polyvinylalkohol, polyacrylsaurem Natrium oder auch Mineralölen, auf die Oberfläche von Trägerstoffen wie Sand, Kaolinite oder von granuliertem Inertmaterial. Auch können geeignete Wirkstoffe in der für die Herstellung von Düngemittelgranulaten üblichen Weise - gewünschtenfalls in Mischung mit Düngemitteln - granuliert werden.Granules can either be prepared by atomizing the active ingredient on adsorptive, granulated inert material or by applying active substance concentrates by means of adhesives, e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils, on the surface of carriers such as sand, kaolinites or granulated inert material. It is also possible to granulate suitable active ingredients in the manner customary for the production of fertilizer granules, if desired in admixture with fertilizers.
Wasserdispergierbare Granulate werden in der Regel nach den üblichen Verfahren wie Sprühtrocknung, Wirbelbett-Granulierung, Teller-Granulierung, Mischung mit Hochgeschwindigkeitsmischern und Extrusion ohne festes Inertmaterial hergestellt.Water-dispersible granules are generally prepared by the usual methods such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
Zur Herstellung von Teller-, Fließbett-, Extruder- und Sprühgranulate siehe z.B.For the preparation of plate, fluid bed, extruder and spray granules, see e.g.
Verfahren in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, Seiten 147 ff; "Perry's Chemical Engineer"s Handbook", 5th Ed., McGraw-Hill, New York 1973, S. 8-57.Process in "Spray-Drying Handbook" 3rd ed. 1979, G. Goodwin Ltd., London; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 ff; "Perry's Chemical Engineer's Handbook," 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.
Für weitere Einzelheiten zur Formulierung von Pflanzenschutzmitteln siehe z.B. G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961 , Seiten 81-96 und J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, Seiten 101-103.For further details on the formulation of crop protection agents see, e.g. G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pp. 81-96 and J.D. Freyer, S.A. Evans, "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pp. 101-103.
Die agrochemischen Zubereitungen enthalten in der Regel 0.1 bis 99 Gew.-%, insbesondere 0.1 bis 95 Gew.-%, erfindungsgemäße Verbindungen. In Spritzpulvern beträgt die Wirkstoffkonzentration z.B. etwa 10 bis 90 Gew.-%, der Rest zu 100 Gew.-% besteht aus üblichen Formulierungsbestandteilen. Bei emulgierbaren Konzentraten kann die Wirkstoffkonzentration etwa 1 bis 90, vorzugsweise 5 bis 80 Gew.-% betragen. Staubfö rmige Formulierungen enthalten 1 bis 30 Gew.-% Wirkstoff, vorzugsweise meistens 5 bis 20 Gew.-% an Wirkstoff, versprühbare Lösungen enthalten etwa 0.05 bis 80, vorzugsweise 2 bis 50 Gew.-% Wirkstoff. Bei wasserdispergierbaren Granulaten hängt der Wirkstoffgehalt zum Teil davon ab, ob die wirksame Verbindung flüssig oder fest vorliegt und welche Granulierhilfsmittel, Füllstoffe usw. verwendet werden. Bei den in Wasser dispergierbaren Granulaten liegt der Gehalt an Wirkstoff beispielsweise zwischen 1 und 95 Gew.-%, vorzugsweise zwischen 10 und 80 Gew.-%.The agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of compounds according to the invention. In wettable powders, for example, the active ingredient concentration is about 10 to 90 wt .-%, the Residual to 100 wt .-% consists of conventional formulation ingredients. For emulsifiable concentrates, the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%. Dusty formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% active ingredient. In the case of water-dispersible granules, the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used. In the case of the water-dispersible granules, the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
Daneben enthalten die genannten Wirkstofformulierungen gegebenenfalls die jeweils üblichen Haft-, Netz-, Dispergier-, Emulgier-, Penetrations-, Konservierungs-, Frostschutz- und Lösungsmittel, Füll-, Träger- und Farbstoffe, Entschäumer, Verdunstungshemmer und den pH-Wert und die Viskosität beeinflussende Mittel.In addition, the active substance formulations mentioned optionally contain the customary adhesion, wetting, dispersing, emulsifying, penetrating, preserving, antifreeze and solvent, fillers, carriers and dyes, antifoams, evaporation inhibitors and the pH and the Viscosity-influencing agent.
Als Kombinationspartner für die erfindungsgemäßen Verbindungen in Mischungsformulierungen oder im Tank-Mix sind beispielsweise bekannte Wirkstoffe, die auf einer Inhibition von beispielsweise Acetolactat-Synthase, Acetyl- CoA-Carboxylase, Cellulose-Synthase, Enolpyruvylshikimat-3-phosphat-Synthase, Glutamin-Synthetase, p-Hydroxyphenylpyruvat-Dioxygenase, Phytoendesaturase, Photosystem I, Photosystem II, Protoporphyrinogen-Oxidase beruhen, einsetzbar, wie sie z.B. aus Weed Research 26 (1986) 441-445 oder "The Pesticide Manual", 13th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2003 und dort zitierter Literatur beschrieben sind. Als bekannte Herbizide, die mit den erfindungsgemäßen Verbindungen kombiniert werden können, sind z.B. folgende Wirkstoffe zu nennen (Anmerkung: Die Verbindungen sind entweder mit dem "common name" nach der International Organization for Standardization (ISO) oder mit dem chemischen Namen, ggf. zusammen mit einer üblichen Codenummer bezeichnet) und umfassen stets sämtliche Anwendungsformen wie Säuren, Salze, Ester und Isomere wie Stereoisomere und optische Isomere. Dabei sind eine und zum Teil auch mehrere Anwendungsformen genannt: 2,4-D, Acetochlor, Acifluorfen, Acifluorfen-sodium, Aclonifen, Alachlor, Alloxydim, Alloxydim-sodium, Ametryn, Amicarbazone, Amidosulfuron, Aminopyralid, Amitrole, Anilofos, Asulam, Atrazine, Azafenidin, Azimsulfuron, Beflubutamid, Benazolin, Benazolin-ethyl, Benfuresate, Bensulfuron-methyl, Bentazone, Benzfendizone, Benzobicyclon, Benzofenap, Bifenox, Bilanafos, Bispyribac-natrium, Bromacil, Bromobutide, Bromofenoxim, Bromoxynil, Butachlor, Butafenacil, Butenachlor, Butralin, Butroxydim, Butylate, Cafenstrole, Carbetamide, Carfentrazone-ethyl, Chlomethoxyfen, Chloridazon, Chlorimuron-ethyl, Chlornitrofen, Chlorotoluron, Chlorsulfuron, Cinidon-ethyl, Cinmethylin, Cinosulfuron, Clefoxydim, Clethodim, Clodinafop-propargyl, Clomazone, Clomeprop, Clopyralid, Cloransulam-methyl, Cumyluron, Cyanazine, Cyclosulfamuron, Cycloxydim, Cyhalofop-butyl, Desmedipham, Dicamba, Dichlobenil, Dichlorprop, Dichloφrop-P, Diclofop-methyl, Diclosulam, Difenzoquat, Diflufenican, Diflufenzopyr, Dikegulac-sodium, Dimefuron, Dimepiperate, Dimethachlor, Dimethametryn, Dimethenamid, Triaziflam, Diquat- dibromide, Dithiopyr, Diuron, Dymron, EPTC, Esprocarb, Ethalfluralin,Examples of combination partners for the compounds according to the invention in mixture formulations or in a tank mix are known active compounds which are based on inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthetase, p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, protoporphyrinogen oxidase, can be used, as described, for example, in Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 13th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2003 and cited therein. Examples of known herbicides which can be combined with the compounds according to the invention are the following active substances (Note: The compounds are either together with the "common name" according to the International Organization for Standardization (ISO) or with the chemical name, if appropriate together with a common code number) and always include all forms of use such as acids, salts, esters and isomers such as stereoisomers and optical isomers. One and in part also several application forms are mentioned: 2,4-D, acetochlor, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidosulfuron, aminopyralid, amitrole, anilofos, asulam, atrazine, azafenidine, azimsulfuron, beflubutamide, benazoline, benazoline ethyl, benfuresate, bensulfuron-methyl, bentazone, benzofendizone, benzobicyclone, benzofenap, bifenox, bilanafos, bispyribac sodium, bromacil, bromobutide, bromofenoxime, bromoxynil, butachlor, butafenacil, butenachlor, butraline, butroxydim, butylates, cafenstrols, carbetamides, carfentrazone ethyl, chlomethoxyfen, chloridazon, chlorimuron-ethyl, chlornitrofen, chlorotoluron, chlorsulfuron, cinidon-ethyl, cinmethylin, cinosulfuron, clefoxydim, clethodim, clodinafop-propargyl, clomazone, clomeprop, clopyralid, cloransulam-methyl, cumyluron, cyanazine, cyclosulfamuron, cycloxydim, Cyhalofop-butyl, desmedipham, dicamba, dichlobenil, dichlorprop, dichloφrop-P, diclofop-methyl, diclosulam, difenzoquat, diflufenican, diflufenzopyr, dikegulac-sod ium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, triaziflam, dibridibribride, dithiopyr, diuron, dymron, EPTC, esprocarb, ethalfluralin,
Ethametsulfuron-methyl, Ethofumesate, Ethoxyfen, Ethoxysulfuron, Etobenzanid, Fenoxaprop-ethyl, Fenoxaprop-P-ethyl, Fentrazamide, Flamprop-M-isopropyl, Flamprop-M-methyl, Flazasulfuron, Florasulam, Fluazifop, Fluazifop-butyl, Fluazifop- -butyl, Fluazolate, Flucarbazone-sodium, Flucetosulfuron, Fluchloralin, Flufenacet, Flufenpyr, Flumetsulam, Flumiclorac-pentyl, Flumioxazin, Fluometuron,Ethametsulfuron-methyl, ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanide, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fentrazamide, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-butyl, fluazifop-butyl , Fluazolate, Flucarbazone-sodium, Flucetosulfuron, Fluchloralin, Flufenacet, Flufenpyr, Flumetsulam, Flumiclorac-pentyl, Flumioxazin, Fluometuron,
Fluorochloridone, Fluoroglycofen-ethyl, Flupoxam, Flupyrsulfuron-methyl-sodium, Fluridone, Fluroxypyr, Fluroxypyr-butoxypropyl, Fluroxypyr-meptyl, Flurprimidol, Flurtamone, Fluthiacet-methyl, Fomesafen, Foramsulfuron, Glufosinate, Glufosinate- ammonium, Glyphosate, Halosulfuron-methyl, Haloxyfop, Haloxyfop-ethoxyethyl, Haloxyfop-methyl, Haloxyfop-P-methyl, Hexazinone, Imazamethabenz-methyl,Fluorochloridones, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl-sodium, fluridone, fluroxypyr, fluroxypyr-butoxypropyl, fluroxypyr-meptyl, flurprimidol, flurtamone, fluthiacet-methyl, fomesafen, foramsulfuron, glufosinate, glufosinate-ammonium, glyphosate, halosulfuron-methyl, Haloxyfop, haloxyfopethoxyethyl, haloxyfopmethyl, haloxyfop-P-methyl, hexazinone, imazamethabenz-methyl,
Imazamox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, Indanofan, lodosulfuron-methyl-natrium, loxynil, Isoproturon, Isouron, Isoxaben, Isoxachlortole, Isoxaflutole, Ketospiradox, Lactofen, Lenacil, Linuron, MCPA, Mecoprop, Mecoprop- P, Mefenacet, Mesosulfuron-methyl, Mesotrione, Metamifop, Metamitron, Metazachlor, Methabenzthiazuron, Methyldymron, Metobromuron, Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron-methyl, Molinate, Monolinuron, Naproanilide, Napropamide, Neburon, Nicosulfuron, Norflurazon, Orbencarb, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxyfluorfen, Paraquat, Pelargonie acid, Pendimethalin, Pendralin, Penoxsulam, Pentoxazone, Pethoxamid, Phenmedipham, Picloram, Picolinafen, Pinoxaden, Piperophos, Pretilachlor, Primisulfuron-methyl, Profluazol, Profoxydim, Prometryn, Propachlor, Propanil, Propaquizafop, Propisochlor, Propoxycarbazone-sodium, Propyzamide, Prosulfocarb, Prosulfuron, Pyraclonil, Pyraflufen-ethyl, Pyrazolate, Pyrazosulfuron- ethyl, Pyrazoxyfen, Pyribenzoxim, Pyributicarb, Pyridafol, Pyridate, Pyriftalid, Pyriminobac-methyl, Pyrithiobac-sodium, Quinclorac, Quinmerac, Quinoclamine, Quizalofop-ethyl, Quizalofop-P-ethyl, Quizalofop-P-tefuryl, Rimsulfuron, Sethoxydim, Simazine, Simetryn, S-Metolachlor, Sulcotrione, Sulfentrazone, Sulfometuron- methyl, Sulfosate, Sulfosulfuron, Tebuthiuron, Tepraloxydim, Terbuthylazine, Terbutryn, Thenylchlor, Thiazopyr, Thifensulfuron-methyl, Thiobencarb, Tiocarbazil, Tralkoxydim, Triallate, Triasulfuron, Tribenuron-methyl, Triclopyr, Tridiphane, Trifloxysulfuron, Trifluralin, Triflusulfuron-methyl und Tritosulfuron.Imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, indanofan, iodosulfuron-methyl-sodium, loxynil, isoproturon, isourone, isoxaben, isoxachlorotole, isoxaflutole, ketospiradox, lactofen, lenacil, linuron, mcp, mecoprop, mecoprop-p, mefenacet, Mesosulfuron-methyl, mesotrione, metamifop, metamitron, metazachlor, methabenzthiazuron, methyldymron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinates, monolinuron, naproanilides, napropamide, neburon, nicosulfuron, norflurazon, orbencarb, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxyfluorfen, Paraquat, Pelargonium acid, Pendimethalin, Pendralin, Penoxsulam, Pentoxazone, Pethoxamide, Phenmedipham, Picloram, Picolinafen, Pinoxaden, Piperophos, Pretilachlor, Primisulfuron-methyl, Profluazole, Profoxydim, Prometryn, Propachlor , Propanil, Propaquizafop, Propisochlor, Propoxycarbazone-sodium, Propyzamide, Prosulfocarb, Prosulfuron, Pyraclonil, Pyraflufen-ethyl, pyrazolates, Pyrazosulfuron- ethyl, pyrazoxyfen, Pyribenzoxim, Pyributicarb, Pyridafol, Pyridate, Pyriftalid, Pyriminobac-methyl, Pyrithiobac-sodium, Quinclorac , Quinmerac, Quinoclamine, Quizalofop-ethyl, Quizalofop-P-ethyl, Quizalofop-P-tefuryl, Rimsulfuron, Sethoxydim, Simazine, Simetryn, S-Metolachlor, Sulcotrione, Sulfentrazone, Sulfometuron-methyl, Sulfosate, Sulfosulfuron, Tebuthiuron, Tepraloxydim, Terbuthylazine , Terbutryn, thenylchloro, thiazopyr, thifensulfuron-methyl, thiobencarb, tiocarbazil, tralkoxydim, triallates, triasulfuron, tribenuron methyl, triclopyr, tridiphane, trifloxysulfuron, trifluralin, triflusulfuron-methyl and tritosulfuron.
Die erfindungsgemäßen Verbindungen können auch in Kombination mit einem oder mehreren als Safener wirkenden Verbindungen eingesetzt werden. Beispiele für Safener sind:The compounds according to the invention can also be used in combination with one or more compounds which act as safeners. Examples of safeners are:
a) Verbindungen der Formeln ( XVII ) bis ( XIX ),a) compounds of the formulas (XVII) to (XIX),
( XVIl ) ( XVlIl ) ( XIX )(XVIl) (XVIII) (XIX)
wobei die Symbole und Indizes folgende Bedeutungen haben:where the symbols and indices have the following meanings:
n' ist eine natürliche Zahl von 0 bis 5, vorzugsweise 0 bis 3; T ist eine (C1 oder C2)Alkandiylkette, die unsubstituiert oder mit einem oder zwei (Cj-CJAlkylresten oder mit [(CyC^Alkoxylcarbonyl substituiert ist;n 'is a natural number from 0 to 5, preferably 0 to 3; T is a (C 1 or C 2) alkanediyl chain which is substituted or -CJAlkylresten [(CyC ^ Alkoxylcarbonyl unsubstituted or substituted with one or two (C j;
W+ ist ein unsubstituierter oder substituierter divalenter heterocyclischer Rest aus der Gruppe der teilungesättigten oder aromatischen Fünfring-Heterocyclen mit 1 bis 3 Heteroringatomen des Typs N oder O, wobei mindestens ein N-Atom und höchstens ein O-Atom im Ring enthalten ist, vorzugsweise ein Rest aus der Gruppe (W+I) bis (W+4),W + is an unsubstituted or substituted divalent heterocyclic radical from the group of the unsaturated or unsaturated five-membered ring heterocycles having 1 to 3 hetero-ring atoms of the type N or O, wherein at least one N-atom and at most one O-atom is contained in the ring, preferably one Remainder from the group (W + I) to (W + 4),
WM W+2 W+3 W+4WM W + 2W + 3W + 4
m' ist 0 oder 1 ;m 'is 0 or 1;
R7, R9 sind gleich oder verschieden Wasserstoff, Halogen, (C1-C4)AIkVl,R 7 , R 9 are identical or different hydrogen, halogen, (C 1 -C 4 ) Al kVl,
(C1-C4)AIkOXy, Nitro oder (C^C^Haloalkyl;(C 1 -C 4 ) alkoxy, nitro or (C 1 -C 4 ) haloalkyl;
R8, R10 sind gleich oder verschieden OR14, SR14 oder NR14R15 oder ein gesättigter oder ungesättigter 3- bis 7-gliedriger Heterocyclus mit mindestens einemR 8 , R 10 are the same or different OR 14 , SR 14 or NR 14 R 15 or a saturated or unsaturated 3- to 7-membered heterocycle having at least one
N-Atom und bis zu 3 Heteroatomen, vorzugsweise aus der Gruppe O und S, der über das N-Atom mit der Carbonylgruppe in (XVII) bzw. (XVIII) verbunden ist und unsubstituiert oder durch Reste aus der Gruppe (C1-C4)AIkVl,N atom and up to 3 heteroatoms, preferably from the group O and S, which is connected via the N atom with the carbonyl group in (XVII) or (XVIII) and unsubstituted or by radicals from the group (C 1 -C 4 ) AIkVl,
(Ci-C4)AIkOXy oder gegebenenfalls substituiertes Phenyl substituiert ist, vorzugsweise ein Rest der Formel OR14, NHR15 oder N(CH3)2, insbesondere der Formel OR14; R14 ist Wasserstoff oder ein unsubstituierter oder substituierter aliphatischer(C 1 -C 4 ) alkoxy or optionally substituted phenyl, preferably a radical of the formula OR 14 , NHR 15 or N (CH 3 ) 2 , in particular of the formula OR 14 ; R 14 is hydrogen or an unsubstituted or substituted aliphatic
Kohlenwasserstoffrest, vorzugsweise mit insgesamt 1 bis 18 C-Atomen; R15 ist Wasserstoff, (C1-C6)AIkVl, (C1-C6)AIkOXy oder substituiertes oder unsubstituiertes Phenyl; R16 ist Wasserstoff, (C1-C8)AIkYl, (C1-C8)HaIOaIRyI1 (C1-C4)AIkOXyK C1-C4JaIlCyI1 Hydrocarbon radical, preferably having a total of 1 to 18 carbon atoms; R 15 is hydrogen, (C 1 -C 6 ) Al kVl, (C 1 -C 6 ) alkoxy or substituted or unsubstituted phenyl; R 16 is hydrogen, (C 1 -C 8) -alkyl, (C 1 -C 8) HaIOaIRyI 1 (C 1 -C 4) C 1 -C 4 AIkOXyK JaIlCyI 1
(C3-C12)Cycloalkyl oder Tri- (C1-CJaIlCyISiIyI; (C 3 -C 12 ) cycloalkyl or tri- (C 1 -C 1 -alkyl ) silyl;
R17, R18, R19 sind gleich oder verschieden Wasserstoff, (C1-C8)AIkYl, (C1-C8)HaIOaIkYl, (C3-C12)Cycloalkyl oder substituiertes oder unsubstituiertes Phenyl;R 17 , R 18 , R 19 are identical or different hydrogen, (C 1 -C 8 ) AlKyl, (C 1 -C 8 ) haloalkyl, (C 3 -C 12 ) cycloalkyl or substituted or unsubstituted phenyl;
R11 ist (C1-C4)AIkYl, (CrC4)Alkenyl, (C2-C4)Haloalkenyl,R 11 is (C 1 -C 4 ) AlKyl, (C r C 4 ) alkenyl, (C 2 -C 4 ) haloalkenyl,
(C3-C7)Cycloalkyl, vorzugsweise Dichlormethyl; R12, R13 ist gleich oder verschieden Wasserstoff, (C1-C4)AIkYl, (C2-C4)Alkenyl,(C 3 -C 7 ) cycloalkyl, preferably dichloromethyl; R 12 , R 13 is identical or different hydrogen, (C 1 -C 4 ) alkyl, (C 2 -C 4 ) alkenyl,
(C2-C4)Alkinyl, (C1-C4)HaIOaIkYl, (C2-C4)Haloalkenyl, (C1-C4JaIlCyI1 (C2-C4)Alkenylcarbamoyl-( C1-C4JaIlCyI, (C1-C4)AIkOXy-(C 2 -C 4 ) alkynyl, (C 1 -C 4 ) haloalkyl, (C 2 -C 4 ) haloalkenyl, (C 1 -C 4 -alkyl ) (C 2 -C 4 ) alkenylcarbamoyl- (C 1 -C 4 -alkenyl, (C 1 -C 4 ) -alkoxy)
(C1-C4JaIlCyI1 Dioxolanyl-( C1-C4JaIlCyI, Thiazolyl, Furyl, Furylalkyl, Thienyl,(C 1 -C 4 -alkyl ) -dioxolanyl- (C 1 -C 4 -alkenyl, thiazolyl, furyl, furylalkyl, thienyl,
Piperidyl, substituiertes oder unsubstituiertes Phenyl, oder R12 und R13 bilden zusammen einen substituierten oder unsubstituierten heterocyclischen Ring, vorzugsweise einen Oxazolidin-, Thiazolidin-, Piperidin-, Morpholin-, Dihydropyrimidin- oder Benzoxazinring; oderPiperidyl, substituted or unsubstituted phenyl, or R 12 and R 13 together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine, piperidine, morpholine, dihydropyrimidine or benzoxazine ring; or
b) eine oder mehreren Verbindungen aus Gruppe:b) one or more compounds from group:
1 ,8-Naphthalsäureanhydrid,1, 8-naphthalic anhydride,
Methyl-diphenylmethoxyacetat, Cyanomethoxyimino(phenyl)acetonitril (Cyometrinil), 1 ,3-Dioxolan-2-ylmethoxyimino(phenyl)acetonitril (Oxabetrinil), 4'-Chlor-2,2,2-trifluoracetophenon 0-1 ,3-dioxolan-2-ylmethyloxim (Fluxofenim),Methyl-diphenylmethoxyacetate, cyanomethoxyimino (phenyl) acetonitrile (cyometrinil), 1,3-dioxolan-2-ylmethoxyimino (phenyl) acetonitrile (oxabetrinil), 4'-chloro-2,2,2-trifluoroacetophenone 0-1, 3-dioxolane 2-ylmethyloxime (Fluxofenim),
4,6-Dichlor-2-phenylpyrimidin (Fenclorim), Benzyl-2-chlor-4-trifluormethyl-1 ,3-thiazol-5-carboxylat (Flurazole), 2-Dichlormethyl-2-methyl-1 ,3-dioxolan (MG-191 ), N-(4-Methylphenyl)-N'-(1 -methyl-1 -phenylethyl)harnstoff (Dymron), 1 -[4-(N-2-Methoxybenzoylsulfamoyl)phenyl]-3-methylharnstoff,4,6-dichloro-2-phenylpyrimidine (fenclorim), benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate (flurazole), 2-dichloromethyl-2-methyl-1,3-dioxolane ( MG-191), N- (4-methylphenyl) -N '- (1-methyl-1-phenylethyl) urea (Dymron), 1 - [4- (N-2-methoxybenzoylsulfamoyl) phenyl] -3-methylurea,
1-[4-(N-2-Methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylharnstoff, 1-[4-(N-4,5-Dimethylbenzoylsulfamoyl)phenyl]-3-methylharnstoff,1- [4- (N-2-Methoxybenzoylsulfamoyl) phenyl] -3,3-dimethylurea, 1- [4- (N-4,5-Dimethylbenzoylsulfamoyl) phenyl] -3-methyl-urea,
1-[4-(N-Naphthoylsulfamoyl)phenyl]-3,3-dimethylharnstoff,1- [4- (N-Naphthoylsulfamoyl) phenyl] -3,3-dimethylurea,
(2,4-Dichlθφhenoxy)essigsäure (2,4-D),(2,4-dichlorophenoxy) acetic acid (2,4-D),
(4-Chloφhenoxy)essigsäure,(4-Chloφhenoxy) acetic acid,
(R,S)-2-(4-Chlor-o-tolyloxy)propionsäure (Mecoprop),(R, S) -2- (4-chloro-o-tolyloxy) propionic acid (mecoprop),
4-(2,4-Dichloφhenoxy)buttersäure (2,4-DB),4- (2,4-Dichloro-phenoxy) butyric acid (2,4-DB),
(4-Chlor-o-tolyloxy)essigsäure (MCPA),(4-chloro-o-tolyloxy) acetic acid (MCPA),
4-(4-Chlor-o-tolyloxy)buttersäure,4- (4-chloro-o-tolyloxy) butyric acid,
4-(4-Chloφhenoxy)buttersäure,4- (4-Chloφhenoxy) butyric acid,
3,6-Dichlor-2-methoxybenzoesäure (Dicamba),3,6-dichloro-2-methoxybenzoic acid (Dicamba),
1 -(Ethoxycarbonyl)ethyl 3,6-dichlor-2-methoxybenzoat (Lactidichlor) sowie deren Salze und Ester, vorzugsweise (CyCgJ-Ester;1 - (ethoxycarbonyl) ethyl 3,6-dichloro-2-methoxybenzoate (lactidichloro) and salts and esters thereof, preferably (CyC g J-ester;
c) N-Acylsulfonamide der Formel ( XX ) und ihre Salze,c) N-acylsulfonamides of the formula (XX) and their salts,
( XX )(XX)
worinwherein
R20 Wasserstoff, einen Kohlenwasserstoffrest, einen Kohlenwasserstoffoxyrest, einen Kohlenwasserstoffthiorest oder einen Heterocyclylrest, wobei jeder der letztgenannten 4 Reste unsubstituiert oder durch einen oder mehrere gleiche oder verschiedene Reste aus der Gruppe Halogen, Cyano, Nitro, Amino, Hydroxy, Carboxy, Formyl, Carbonamid, Sulfonamid und Reste der Formel -Za-Ra substituiert ist, wobei jeder Kohlenwasserstoffteil vorzugsweise 1 bis 20 C-Atome aufweist und ein C-haltiger Rest R20 inklusive Substituenten vorzugsweise 1 bis 30 C-Atome aufweist; R21 Wasserstoff oder (C1-C4)AIkYl, vorzugsweise Wasserstoff, oderR 20 is hydrogen, a hydrocarbon radical, a hydrocarbonoxy radical, a hydrocarbylthio radical or a heterocyclyl radical, where each of the last-mentioned 4 radicals is unsubstituted or substituted by one or more identical or different radicals from the group halogen, cyano, nitro, amino, hydroxy, carboxy, formyl, carbonamide , Sulfonamide and radicals of the formula -Z a -R a is substituted, wherein each hydrocarbon moiety preferably has 1 to 20 carbon atoms and a C-containing radical R 20 including substituents preferably has 1 to 30 carbon atoms; R 21 is hydrogen or (C 1 -C 4 ) alkyl, preferably hydrogen, or
R20 und R21 zusammen mit der Gruppe der Formel -CO-N- den Rest eines 3- bis 8- gliedrigen gesättigten oder ungesättigten Rings;R 20 and R 21 together with the group of the formula -CO-N- denote the radical of a 3- to 8-membered saturated or unsaturated ring;
R22 gleich oder verschieden Halogen, Cyano, Nitro, Amino, Hydroxy, Carboxy, Formyl, CONH2, SO2NH2 oder einen Rest der Formel -Zb-Rb ;R 22 is identical or different and is halogen, cyano, nitro, amino, hydroxyl, carboxy, formyl, CONH 2 , SO 2 NH 2 or a radical of the formula -Z b -R b ;
R23 Wasserstoff oder (C1-C4)AIKyI, vorzugsweise H;R 23 is hydrogen or (C 1 -C 4 ) alkyl, preferably H;
R24 gleich oder verschieden Halogen, Cyano, Nitro, Amino, Hydroxy, Carboxy, CHO, CONH2, SO2NH2 oder einen Rest der Formel -Zc-Rc ;R 24 is identical or different and is halogen, cyano, nitro, amino, hydroxyl, carboxy, CHO, CONH 2 , SO 2 NH 2 or a radical of the formula -Z c -R c ;
Ra einen Kohlenwasserstoffrest oder einen Heterocyclylrest, wobei jeder der beiden letztgenannten Reste unsubstituiert oder durch einen oder mehrere gleiche oder verschiedene Reste aus der Gruppe Halogen, Cyano, Nitro, Amino, Hydroxy, Mono- und Di-[( substituiert ist, oder einenR a is a hydrocarbon radical or a heterocyclyl radical, where each of the latter two radicals is unsubstituted or substituted by one or more identical or different radicals from the group of halogen, cyano, nitro, amino, hydroxyl, mono- and di- [( is substituted, or one
Alkylrest, in dem mehrere, vorzugsweise 2 oder 3, nicht benachbarte CH2-Gruppen jeweils durch ein Sauerstoffatom ersetzt sind; Rb, Rc gleich oder verschieden einen Kohlenwasserstoffrest oder einenAlkyl radical in which a plurality, preferably 2 or 3, non-adjacent CH 2 groups are each replaced by an oxygen atom; R b , R c, identically or differently, are a hydrocarbon radical or a
Heterocyclylrest, wobei jeder der beiden letztgenannten Reste unsubstituiert oder durch einen oder mehrere gleiche oder verschiedene Reste aus der Gruppe Halogen, Cyano, Nitro, Amino, Hydroxy, Phosphoryl, Halogen- (C1-C4JaIkOXy, Mono- und Di-[( C^C^alkyljamino substituiert ist, oder einen Alkylrest, in dem mehrere, vorzugsweise 2 oder 3, nicht benachbarteHeterocyclyl radical, where each of the latter two radicals is unsubstituted or substituted by one or more identical or different radicals from the group consisting of halogen, cyano, nitro, amino, hydroxyl, phosphoryl, halogeno (C 1 -C 4 -alkoxy, mono- and di- [( C ^ C ^ alkyljamino substituted, or an alkyl radical in which several, preferably 2 or 3, not adjacent
CH2-Gruppen jeweils durch ein Sauerstoffatom ersetzt sind; Za eine divalente Gruppe der Formel -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -SO-, -SO2-, -NR+-, -CO-NR+-,CH 2 groups are each replaced by an oxygen atom; Z a is a divalent group of the formula -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -SO- , -SO 2 -, -NR + -, -CO-NR + -,
-NR+-CO-, -SO2-NR+- oder -NR+-SO2-, wobei die rechts angegebene Bindung der jeweiligen divalenten Gruppe die Bindung zum Rest Ra ist und wobei die R+ in den letztgenannten 5 Resten unabhängig voneinander jeweils H, (C1-C4)AIk^ oder Halo-( CrC4)-alkyl bedeuten;-NR + -CO-, -SO 2 -NR + - or -NR + -SO 2 -, where the bond on the right of the respective divalent group is the bond to the radical R a and wherein the R + in the last-mentioned 5 radicals independently each is H, (C 1 -C 4 ) Alk ^ or halo (C r C 4 ) alkyl;
Zb, Zc unabhängig voneinander eine direkte Bindung oder eine divalente Gruppe der Formel -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -SO-, -SO2-, -NR+-, -SO2-NR+-, -NR+-SO2-, -CO-NR+- oder -NR+-CO-, wobei die rechts angegebene Bindung der jeweiligen divalenten Gruppe die Bindung zum Rest Rb bzw. Rc ist und wobei die R+ in den letztgenannten 5 Resten unabhängig voneinander jeweils H, (C1-C4)AIKyI oder Halo-( C.,-C4)alkyl bedeuten; n eine ganze Zahl von 0 bis 4, vorzugsweise 0, 1 oder 2, insbesondere 0 oder 1 , und m eine ganze Zahl von 0 bis 5, vorzugsweise 0, 1 , 2 oder 3, insbesondere 0, 1 oder 2; bedeuten;Z b , Z c independently of one another a direct bond or a divalent group of the formula -O-, -S-, -CO-, -CS-, -CO-O-, -CO-S-, -O-CO-, -S-CO-, -SO-, -SO 2 -, -NR + -, -SO 2 -NR + -, -NR + -SO 2 -, -CO-NR + - or -NR + -CO-, where the binding specified on the right is the respective divalent group is the bond to the radical R b or R c and wherein the R + in the latter 5 radicals independently of one another are each H, (C 1 -C 4 ) alkyl or halo (C 1 -C 4 ) alkyl; n is an integer from 0 to 4, preferably 0, 1 or 2, in particular 0 or 1, and m is an integer from 0 to 5, preferably 0, 1, 2 or 3, in particular 0, 1 or 2; mean;
d) Acylsulfamoylbenzoesäureamide der allgemeinen Formel ( XXI ), gegebenenfalls auch in Salzform,d) acylsulfamoylbenzoic acid amides of the general formula (XXI), if appropriate also in salt form,
( XXI )(XXI)
worinwherein
X3 CH oder N;X 3 is CH or N;
R25 Wasserstoff, Heterocyclyl oder einen Kohlenwasserstoffrest, wobei die beiden letztgenannten Reste gegebenenfalls durch einen oder mehrere, gleiche oder verschiedene Reste aus der Gruppe Halogen, Cyano, Nitro, Amino, Hydroxy,R 25 is hydrogen, heterocyclyl or a hydrocarbon radical, where the latter two radicals are optionally substituted by one or more, identical or different radicals from the group consisting of halogen, cyano, nitro, amino, hydroxyl,
Carboxy, CHO, CONH2, SO2NH2 und Za-Ra substituiert sind;Carboxy, CHO, CONH 2 , SO 2 NH 2 and Z a -R a are substituted;
R26 Wasserstoff, Hydroxy, (C1-C6)AIKyI, (C2-C6)Alkenyl, (C2-C6)AI kinyl,R 26 is hydrogen, hydroxy, (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl,
(C1-C6)AIkOXy, (C2-C6)Alkenyloxy, wobei die fünf letztgenannten Reste gegebenenfalls durch einen oder mehrere, gleiche oder verschiedene Reste aus der Gruppe Halogen, Hydroxy, (C1-C4)AIkVl, (C1-C4)AIkOXy und(C 1 -C 6 ) alkoxy, (C 2 -C 6 ) alkenyloxy, where the five last-mentioned radicals are optionally substituted by one or more, identical or different radicals from the group consisting of halogen, hydroxy, (C 1 -C 4 ) alkylene, C 1 -C 4 ) alkoxy and
(C1-C4)Alkylthio substituiert sind, oder R25 und R26 zusammen mit dem sie tragenden Stickstoffatom einen 3- bis 8- gliedrigen gesättigten oder ungesättigten Ring; R27 Halogen, Cyano, Nitro, Amino, Hydroxy, Carboxy, CHO, CONH2, SO2NH2 oder Zb-Rb; R28 Wasserstoff, (C1-C4)AIKyI, (C2-C4)Alkenyl oder (C2-C4)Alkinyl;(C 1 -C 4 ) alkylthio, or R 25 and R 26 together with the nitrogen atom carrying them have a 3- to 8-membered saturated or unsaturated ring; R 27 is halogen, cyano, nitro, amino, hydroxy, carboxy, CHO, CONH 2 , SO 2 NH 2 or Z b -R b ; R 28 is hydrogen, (C 1 -C 4 ) AIKyI, (C 2 -C 4 ) alkenyl or (C 2 -C 4 ) alkynyl;
R29 Halogen, Cyano, Nitro, Amino, Hydroxy, Carboxy, Phosphoryl, CHO, CONH2,R 29 is halogen, cyano, nitro, amino, hydroxy, carboxy, phosphoryl, CHO, CONH 2 ,
SO2NH2 oder Zc-Rc; Ra einen (C2-C20)Alkylrest, dessen Kohlenstoffkette ein- oder mehrfach durchSO 2 NH 2 or Z c -R c ; R a is a (C 2 -C 20 ) alkyl radical whose carbon chain is mono- or polysubstituted
Sauerstoffatome unterbrochen ist, Heterocyclyl oder einen Kohlenwasserstoffrest, wobei die zwei letztgenannten Reste gegebenenfalls durch einen oder mehrere, gleiche oder verschiedene Reste aus der Gruppe Halogen, Cyano, Nitro, Amino, Hydroxy, Mono- und Di-[( C1-C4)alkyl]amino substituiert sind; Rb, Rc gleich oder verschieden einen (C2-C20)Alkylrest, dessen Kohlenstoffkette ein- oder mehrfach durch Sauerstoffatome unterbrochen ist, Heterocyclyl oder einen Kohlenwasserstoffrest, wobei die zwei letztgenannten Reste gegebenenfalls durch einen oder mehrere, gleiche oder verschiedene Reste aus der Gruppe Halogen, Cyano, Nitro, Amino, Hydroxy, Phosphoryl, (C1-C4)-Interrupted oxygen atoms, heterocyclyl or a hydrocarbon radical, where the latter two radicals optionally substituted by one or more identical or different radicals selected from the group halogen, cyano, nitro, amino, hydroxy, mono- and di - [(C 1 -C 4 ) alkyl] amino; R b , R c, identically or differently, denote a (C 2 -C 20 ) alkyl radical whose carbon chain is interrupted one or more times by oxygen atoms, heterocyclyl or a hydrocarbon radical, where the last two radicals are selected from one or more, identical or different radicals the group halogen, cyano, nitro, amino, hydroxy, phosphoryl, (C 1 -C 4 ) -
Haloalkoxy, Mono- und Di-[( C1-C4)alkyl]amino substituiert sind; Za eine divalente Einheit aus der Gruppe O, S, CO, CS, C(O)O, C(O)S, SO, SO2, NRd, C(O)NRd oder SO2NRd;Haloalkoxy, mono- and di - [(C 1 -C 4 ) alkyl] amino; Z a is a divalent unit selected from O, S, CO, CS, C (O) O, C (O) S, SO, SO 2 , NR d , C (O) NR d or SO 2 NR d ;
Zb, Zc gleich oder verschieden eine direkte Bindung oder eine divalente Einheit aus der Gruppe O, S, CO, CS, C(O)O, C(O)S, SO, SO2, NRd, SO2NRd oder C(O)NRd; Rd Wasserstoff, (CrC4)Alkyl oder (C1-C4)Haloalkyl; n eine ganze Zahl von O bis 4, und m für den Fall, daß X für CH steht, eine ganze Zahl von O bis 5, und für den Fall, daß X für N steht, eine ganze Zahl von O bis 4 bedeuten; e) Verbindungen der Formel ( XXII ),Z b , Z c, identically or differently, denote a direct bond or a divalent unit from the group O, S, CO, CS, C (O) O, C (O) S, SO, SO 2 , NR d , SO 2 NR d or C (O) NR d ; R d is hydrogen, (C r C 4 ) alkyl or (C 1 -C 4 ) haloalkyl; n is an integer from 0 to 4, and in the case where X is CH, an integer from 0 to 5, and when X is N, an integer from 0 to 4; e) compounds of the formula (XXII),
(XXII)(XXII)
worin die Symbole und Indizes folgende Bedeutungen haben:wherein the symbols and indices have the following meanings:
R30 ist H, (C1-C4)AIkYl, (C1-C4)AIKyI substituiert mit (C1-C4)AIKyI-X4 oderR 30 is H, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkyl substituted with (C 1 -C 4 ) alkyl or -X 4 or
(C1-C4)HaIOaIKyI-X4, (C1-C4)HaIOaIKyI, NO2, CN, -COO-R33, NR2 34, SO2NR2 35 oder CONR2 36; R31 ist H, Halogen, (C1-C4)AIKyI, CF3, (C1-C4)AIKoXy oder (CrC4)HaloalKoxy;(C 1 -C 4 ) haloalkyl-X 4 , (C 1 -C 4 ) haloalkyl, NO 2 , CN, -COO-R 33 , NR 2 34 , SO 2 NR 2 35 or CONR 2 36 ; R 31 is H, halogen, (C 1 -C 4 ) AIKyI, CF 3 , (C 1 -C 4 ) AIKoxY or (C r C 4 ) haloalkoxy;
R32 ist H, Halogen oder (C1-C4)AIKyI;R 32 is H, halogen or (C 1 -C 4 ) AIKyI;
Q1, Q2, E, G sind gleich oder verschieden, -O-, -S-, -CR2 37-, -CO-, NR38- oder eine Gruppe der Formel ( XXIII ),Q 1 , Q 2 , E, G are identical or different, -O-, -S-, -CR 2 37 -, -CO-, NR 38 - or a group of the formula (XXIII),
^C=CH-O-CR2MCO)-A^ C = CH-O-CR 2 MCO) -A
( xx»' ) ( xx »' )
mit der Maßgabe, daßwith the proviso that
a) mindestens eine der Gruppen Q1, Q2, E, G eine Carbonylgruppe ist, daß genau eine dieser Gruppe ein Rest der Formel (XXIII) ist und daß die Gruppe der Formel (XXIII) einer Carbonylgruppe benachbart ist, und b) zwei benachbarte Gruppen Q1, Q2, E und G nicht gleichzeitig Sauerstoff sein Können; Ra ist gleich oder verschieden H oder (C1-C8)AIRyI oder die beiden Reste Ra zusammen sind (C2-C6)Alkylen; A ist Rb -Y3- oder -NR2 39; X4 ist -O- oder -S(O)p-; Y3 ist -O- oder -S-;a) at least one of the groups Q 1 , Q 2 , E, G is a carbonyl group, that exactly one of these group is a radical of formula (XXIII) and that the group of formula (XXIII) is adjacent to a carbonyl group, and b) two adjacent groups Q 1 , Q 2 , E and G are not oxygen at the same time; R a is identical or different H or (C 1 -C 8 ) AIRyI or the two radicals R a together are (C 2 -C 6 ) alkylene; A is R b -Y 3 - or -NR 2 39 ; X 4 is -O- or -S (O) p -; Y 3 is -O- or -S-;
Rb ist H1 (C1-C8)AIRyI1 (C1-C8)HaIOaIRyI, (CrC4)Alkoxy-( C1-C8JaIRyI, (C3-C6)-R b is H 1 (C 1 -C 8) AIRyI 1 (C 1 -C 8) HaIOaIRyI, (C r C 4) alkoxy (C 1 -C 8 JaIRyI, (C 3 -C 6) -
AIRenyloxy-( C1-C8JaIRyI, oder Phenyl-( C1-C8JaIRyI, wobei der Phenylring gegebenenfalls durch Halogen, (C1-C4)AIRyI, CF3, Methoxy oder Methyl-S(O)p substituiert ist; (C3-C6)AIRenyl, (C3-C6)HaloalRenyl, Phenyl-( C3-C6)alRenyl, (C3-C6)AIRinyl, Phenyl-( C3-C6)alRinyl, Oxetanyl, Furfuryl, Tetrahydrofuryl;ALEenyloxy- (C 1 -C 8 -alkyl) or phenyl- (C 1 -C 8 -alkyl) where the phenyl ring is optionally substituted by halogen, (C 1 -C 4 ) -alkyl, CF 3 , methoxy or methyl-S (O) p (C 3 -C 6 ) -airenyl, (C 3 -C 6 ) haloalkenyl, phenyl- (C 3 -C 6 ) alrenyl, (C 3 -C 6 ) -airinyl, phenyl- (C 3 -C 6 ) -alRinyl , Oxetanyl, furfuryl, tetrahydrofuryl;
R33 ist H oder (C1-C4)AIRyI;R 33 is H or (C 1 -C 4 ) AIRyI;
R34 ist gleich oder verschieden H, (C1-C4)AIRyI1 (C^C^AIRylcarbonyl oder die beiden Reste R34 zusammen sind (C4-C5)AIRylen;R 34 is identical or different H, (C 1 -C 4) AIRyI 1 (C ^ C ^ AIRylcarbonyl or the two radicals R 34 together are (C 4 -C 5) AIRylen;
R35, R36 sind unabhängig voneinander jeweils gleich oder verschieden H, (C1-C4)AIRyI, oder die beiden Reste R35 und/oder R36 zusammen sindR 35 , R 36 are each independently identical or different H, (C 1 -C 4 ) AIRyI, or the two radicals R 35 and / or R 36 are together
(C4-C5)AIRylen, wobei eine CH2-Gruppe durch O oder S oder eine oder zwei(C 4 -C 5 ) AIRylene, where one CH 2 group is O or S or one or two
CH2-Gruppen durch -NRC- ersetzt sein Rönnen; Rc ist H oder (C1-C8)AIRyI;CH 2 groups replaced by -NR C - can be roughened; R c is H or (C 1 -C 8 ) AIRyI;
R37 ist gleich oder verschieden H, (C1-C8)AIRyI oder die beiden Reste R37 zusammen sind (C2-C6)AIRylen;R 37 is identical or different H, (C 1 -C 8 ) AIRyI or the two radicals R 37 together are (C 2 -C 6 ) AIRylen;
R38 ist H, (C1-C8)AIRyI, substituiertes oder unsubstituiertes Phenyl, oder unsubstituiertes oder am Phenylring substituiertes Benzyl; R39 ist gleich oder verschieden H, (C1-C8)AIRyI, Phenyl, Phenyl-( C1-C8JaIRyI, wobei ein Phenylring durch F, Cl, Br, NO2, CN, OCH3, (C1-C4)AIRyI oder CH3SO2- substituiert sein Rann; (C1-C4)AIRoxy-( C1-C8JaIRyI, (C3-C6)AIRenyl,R 38 is H, (C 1 -C 8 ) alkyl, substituted or unsubstituted phenyl, or unsubstituted or phenyl ring substituted benzyl; R 39 is identical or different H, (C 1 -C 8 ) -alkyl, phenyl, phenyl- (C 1 -C 8 -alkyl), where a phenyl ring is represented by F, Cl, Br, NO 2 , CN, OCH 3 , (C 1 -C 4 ) AIRyI or CH 3 SO 2 - be substituted Rann; (C 1 -C 4 ) -airoxy- (C 1 -C 8 -alkyl, (C 3 -C 6 ) -airenyl,
(C3-C6)AIRinyl, (C3-C6)CycloalRyl oder zwei Reste R39 zusammen sind (C4-C5)AIRylen, wobei eine CH2-Gruppe durch O oder S oder eine oder zwei CK-Gruppen durch -NRd- ersetzt sein Rönnen; Rd ist H oder (C1-C4)AIRyI; m" ist 0 oder 1 und p ist 0, 1 oder 2;(C 3 -C 6 ) AIRinyl, (C 3 -C 6 ) cycloalRyl or two radicals R 39 together are (C 4 -C 5 ) -YL.sub.ylene where one CH 2 group is O or S or one or two CK groups by -NR d - replaced his Rönnen; R d is H or (C 1 -C 4 ) AIRyI; m "is 0 or 1 and p is 0, 1 or 2;
einschließlich der Stereoisomeren und der in der Landwirtschaft gebräuchlichen Salze.including the stereoisomers and the salts commonly used in agriculture.
Zur Anwendung werden die in handelsüblicher Form vorliegenden Formulierungen gegebenenfalls in üblicher weise verdünnt z.B. bei Spritzpulvern, emulgierbaren Konzentraten, Dispersionen und wasserdispergierbaren Granulaten mittels Wasser. Staubförmige Zubereitungen, Boden- bzw. Streugranulate sowie versprühbare Lösungen werden vor der Anwendung üblicherweise nicht mehr mit weiteren inerten Stoffen verdünnt.For use, the formulations present in commercial form are optionally diluted in the usual manner, e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Dust-like preparations, ground or scattered granules and sprayable solutions are usually no longer diluted with other inert substances before use.
Mit den äußeren Bedingungen wie Temperatur, Feuchtigkeit, der Art des verwendeten Herbizids, u.a. variiert die erforderliche Aufwandmenge der erfindungsgemäßen Verbindungen. Sie kann innerhalb weiter Grenzen schwanken, z.B. zwischen 0.001 und 10.0 kg/ha oder mehr Aktivsubstanz, vorzugsweise liegt sie zwischen 0.005 und 5 kg/ha.With the external conditions such as temperature, humidity, the type of herbicide used, u.a. varies the required application rate of the compounds of the invention. It can vary within wide limits, e.g. between 0.001 and 10.0 kg / ha or more of active substance, preferably between 0.005 and 5 kg / ha.
BeispieleExamples
A. SynthesebeispieleA. Synthesis Examples
Beispiel A1Example A1
N-(tert-Butyl)-2-methoxybenzolsulfonamidN- (tert-butyl) -2-methoxybenzenesulfonamide
Zu einer Lösung von 30.00 g (145.17 mmol) 2-Methoxybenzolsulfonsäurechlorid inTo a solution of 30.00 g (145.17 mmol) of 2-methoxybenzenesulfonyl chloride in
150 ml Dichlormethan werden bei 5-1O0C 22.30 g (304.87 mmol) fe/t-Butylamin zugetropft. Danach lässt man 2 h bei Raumtemperatur rühren. Nach Extraktion mit150 ml of dichloromethane are added dropwise at 5-1O 0 C 22.30 g (304.87 mmol) of Fe / t-butylamine. Then allowed to stir for 2 h at room temperature. After extraction with
Wasser wird die organische Phase über Natriumsulfat getrocknet und zur Trockne eingedampft. Es werden 31.10 g (88 % d. Th.) N-(terf-Butyl)-2-methoxybenzol- Sulfonamid erhalten.Water, the organic phase is dried over sodium sulfate and evaporated to dryness. There are 31.10 g (88% of theory) of N- (terf-butyl) -2-methoxybenzene Obtained sulfonamide.
1H-NMR (CDCI3): 7.91 (dd, J = 1.7, 7.8, 1H); 7.50 (m, 1H); 7.03 (m, 2H); 4.93 (br s, 1 H-NMR (CDCl 3 ): 7.91 (dd, J = 1.7, 7.8, 1H); 7.50 (m, 1H); 7.03 (m, 2H); 4.93 (br
1H); 3.98 (s, 3H); 1.17 (s, 9H).1H); 3.98 (s, 3H); 1.17 (s, 9H).
Beispiel A2Example A2
N-(tert-Butyl)-2-iodo-6-methoxybenzolsulfonamid (Beispiel-Nr. 2.092b) Eine Lösung von 30.00 g (123.29 mmol) N-(terf-Butyl)-2-methoxybenzolsulfonamid in 400 ml Tetrahydrofuran wird auf -7O0C abgekühlt und langsam mit einer Lösung von 110.96 ml (277.41 mmol) einer 2.5 molaren />Butyllithium-Lösung in THF versetzt. Danach erwärmt man die Lösung kurz auf -3O0C und kühlt danach wieder auf -6O0C. Bei dieser Temperatur wird eine Lösung von 31.29 g (123.29 mmol) lod in 200 ml Tetrahydrofuran zugetropft. Anschließend wird die Reaktionslösung über Nacht bei Raumtemperatur gerührt. Nach Extraktion mit Wasser wird die organische Phase über Natriumsulfat getrocknet und zur Trockne eingedampft. Man erhält 42.40 g (93 % d. Th.) N-(teAf-Butyl)-2-iodo-6-methoxybenzolsulfonamid.N- (tert-butyl) -2-iodo-6-methoxybenzenesulfonamide (Example No. 2.092b) A solution of 30.00 g (123.29 mmol) of N- (tert-butyl) -2-methoxybenzenesulfonamide in 400 ml of tetrahydrofuran is added. 7O 0 C and slowly added to a solution of 110.96 ml (277.41 mmol) of a 2.5 molar /> Butyllithium solution in THF. Thereafter, the solution is briefly heated to -3O 0 C and then cooled again to -6O 0 C. At this temperature, a solution of 31.29 g (123.29 mmol) of iodine in 200 ml of tetrahydrofuran is added dropwise. Subsequently, the reaction solution is stirred overnight at room temperature. After extraction with water, the organic phase is dried over sodium sulfate and evaporated to dryness. This gives 42.40 g (93% of theory) of N- (teAf-butyl) -2-iodo-6-methoxybenzenesulfonamide.
Beispiel A3Example A3
2-lodo-6-methoxybenzolsulfonamid (Beispiel-Nr. 2.092a)2-iodo-6-methoxybenzenesulfonamide (Example No. 2,092a)
42.40 g (114.84 mmol) N-(ferf-Butyl)-2-iodo-6-methoxybenzolsulfonamid werden in 265 ml Trifluoressigsäure 3 h bei Raumtemperatur gerührt. Danach gießt man die Reaktionsmischung auf Eiswasser, filtriert den Niederschlag ab und wäscht mit Wasser neutral. Man erhält 32.40 g (90 % d. Th.) 2-lodo-6-methoxybenzol- sulfonamid.42.40 g (114.84 mmol) of N- (ferf-butyl) -2-iodo-6-methoxybenzenesulphonamide are stirred in 265 ml of trifluoroacetic acid at room temperature for 3 hours. Thereafter, the reaction mixture is poured into ice-water, the precipitate is filtered off and washed with water until neutral. This gives 32.40 g (90% of theory) of 2-iodo-6-methoxybenzenesulfonamide.
Beispiel A4Example A4
N-{[(4,6-Dimethoxypyrimidin-2-yl)amino]carbonyl}-2-iodo-6- methoxybenzolsulfonamid (Beispiel-Nr. 1.146)N - {[(4,6-Dimethoxypyrimidin-2-yl) amino] carbonyl} -2-iodo-6-methoxybenzenesulfonamide (Example No. 1,146)
Eine Lösung von 200 mg (0.64 mmol) 2-lodo-6-methoxybenzolsulfonamid in 3 ml Acetonitril wird bei Raumtemperatur zuerst mit 316.49 mg (1.15 mmol) N-(4,6- Dimethoxypyrimidin-2-yl)carbaminsäurephenylester und danach langsam mit 0.19 ml (1.28 mmol) 1 ,8-Diazabicyclo[5.4.0]undec-7-en versetzt. Nach 30 min Rühren bei Raumtemperatur wird die Lösung mittels 2 N Salzlösung langsam auf pH 1 eingestellt. Der ausgefallene Feststoff wird abgesaugt, mit Wasser nachgewaschen und getrocknet. Man erhält so 242 mg (77 % d. Th.) N-{[(4,6-Dimethoxypyrimidin-2- yl)amino]carbonyl}-2-iodo-6-methoxybenzolsulfonamid.A solution of 200 mg (0.64 mmol) of 2-iodo-6-methoxybenzenesulfonamide in 3 ml of acetonitrile is first stirred at room temperature with 316.49 mg (1.15 mmol) N- (4,6-dimethoxypyrimidin-2-yl) -carbamic acid phenyl ester and then slowly with 0.19 ml (1.28 mmol) of 1,8-diazabicyclo [5.4.0] undec-7-ene. After stirring at room temperature for 30 minutes, the solution is slowly brought to pH 1 by means of 2N saline set. The precipitated solid is filtered off, washed with water and dried. This gives 242 mg (77% of theory) of N - {[(4,6-dimethoxypyrimidin-2-yl) amino] carbonyl} -2-iodo-6-methoxybenzenesulfonamide.
Beispiel A5Example A5
2-Hydroxy-6-iodobenzolsulfonamid (Beispiel-Nr. 2.300a) 0.50 g (1.60 mmol) 2-lodo-6-methoxybenzolsulfonamid werden in 10 ml Dichlormethan bei Raumtemperatur vorgelegt und vorsichtig mit 0.6 g (2.40 mmol) Bortribromid versetzt. Die Reaktionslösung rührt weitere 45 min bei Raumtemperatur und wird dann auf 2 N Salzsäure gegeben. Nach Extraktion mit Dichlormethan wird die organische Phase getrocknet und eingedampft. Man erhält 0.43 g (90 % d. Th.) 2-Hydroxy-6-iodobenzolsulfonamid.2-Hydroxy-6-iodobenzenesulfonamide (Example No. 2.300a) 0.50 g (1.60 mmol) of 2-iodo-6-methoxybenzenesulfonamide are initially charged in 10 ml of dichloromethane at room temperature and treated carefully with 0.6 g (2.40 mmol) of boron tribromide. The reaction solution is stirred for a further 45 minutes at room temperature and is then added to 2N hydrochloric acid. After extraction with dichloromethane, the organic phase is dried and evaporated. This gives 0.43 g (90% of theory) of 2-hydroxy-6-iodobenzenesulfonamide.
Beispiel A6 2-lodo-6-propoxybenzolsulfonamid (Beispiel-Nr. 2.095a)Example A6 2-iodo-6-propoxybenzenesulfonamide (Example No. 2,095a)
5.00 g (16.72 mmol) 2-Hydroxy-6-iodobenzolsulfonamid werden in 50 ml5.00 g (16.72 mmol) of 2-hydroxy-6-iodobenzenesulfonamide are dissolved in 50 ml
Dimethylformamid vorgelegt und mit 2,54 g (18.39 mmol) Kaliumcarbonat versetzt.Submitted to dimethylformamide and treated with 2.54 g (18.39 mmol) of potassium carbonate.
Diese Mischung wird 1 h bei Raumtemperatur gerührt. Danach werden 3.13 g (18.39 mmol) Propyliodid zugetropft und die Reaktionsmischung wird 3 h bei Raumtemperatur gerührt. Dann wird auf Wasser gegossen, wobei das Produkt ausfiel. Der Feststoff wird mit Wasser nachgewaschen und getrocknet. Man erhältThis mixture is stirred for 1 h at room temperature. Thereafter, 3.13 g (18.39 mmol) of propyl iodide are added dropwise and the reaction mixture is stirred for 3 h at room temperature. Then it is poured onto water, whereby the product precipitated. The solid is washed with water and dried. You get
4.00 g (70 % d. Th.) 2-lodo-6-propoxybenzolsulfonamid.4.00 g (70% of theory) of 2-iodo-6-propoxybenzenesulfonamide.
Beispiel A7 N-(tert-Butyl)-2-fluoro-6-iodobenzolsulfonamid (Beispiel-Nr. 2.001b)Example A7 N- (tert-butyl) -2-fluoro-6-iodobenzenesulfonamide (Example No. 2.001b)
30 g (0.13 mol) (N-ferf-Butyl)-2-fluorobenzolsulfonamid, erhalten aus der Umsetzung von 2-Fluorobenzolsulfonsäurechlorid mit N-tert-Butylamin analog Beispiel A1 , werden in 300 ml trockenem Tetrahydrofuran vorgelegt. Die Lösung wird auf -7O0C abgekühlt und eine Lösung von 18.28 g (0.285 mol) n-Butyllithium (2.5 molar in Tetrahydrofuran) wird zugetropft. Danach wird die Reaktionslösung während 30 min auf -3O0C erwärmt um dann wieder auf -7O0C abgekühlt zu werden. Dann werden 36.21 g (0.143 mol) lod in 200 ml trockenem Tetrahydrofuran zugetropft. Nach der Zugabe wird die Reaktionslösung langsam auf Raumtemperatur erwärmt und 12 h gerührt. Danach wird mit 50%iger wässriger Natriumthiosulfat-Lösung und Wasser gewaschen. Die organische Phase wird getrocknet und eingedampft. Man erhält 40.8 g (88 % d. Th.) N-(fert-Butyl)-2-fluoro-6-iodobenzolsulfonamid.30 g (0.13 mol) of (N-ferf-butyl) -2-fluorobenzenesulfonamide, obtained from the reaction of 2-fluorobenzenesulfonyl chloride with N-tert-butylamine analogously to Example A1, are initially charged in 300 ml of dry tetrahydrofuran. The solution is cooled to -7O 0 C and a solution of 18.28 g (0.285 mol) of n-butyllithium (2.5 molar in tetrahydrofuran) is added dropwise. Thereafter, the reaction solution is heated to -3O 0 C for 30 min then to be cooled again to -7O 0 C. Then 36.21 g (0.143 mol) of iodine in 200 ml of dry tetrahydrofuran are added dropwise. After Addition, the reaction solution is slowly warmed to room temperature and stirred for 12 h. It is then washed with 50% aqueous sodium thiosulfate solution and water. The organic phase is dried and evaporated. 40.8 g (88% of theory) of N- (tert-butyl) -2-fluoro-6-iodobenzenesulphonamide are obtained.
Beispiel A8Example A8
2-(2,2-Difluoroethoxy)-6-iodobenzolsulfonamid (Beispiel-Nr. 2.187a)2- (2,2-Difluoroethoxy) -6-iodobenzenesulfonamide (Example No. 2.187a)
0.64 g (26.57 mmol) Natriumhydrid werden in 10 ml trockenem Tetrahydrofuran vorgelegt und bei Raumtemperatur langsam mit 2.18 g (26.57 mmol) 2,2- Difluoroethanol versetzt. Die Reaktionsmischung wird bis zum Ende der0.64 g (26.57 mmol) of sodium hydride are initially charged in 10 ml of dry tetrahydrofuran and slowly added at room temperature with 2.18 g (26.57 mmol) of 2,2-difluoroethanol. The reaction mixture will be until the end of
Gasentwicklung bei Raumtemperatur gerührt. Danach werden 4.00 g (13.29 mmol) 2-Fluor-6-iodo-benzolsulfonamid, erhalten aus der Reaktion von N-(ferf-Butyl)-2- fluoro-6-iodobenzolsulfonamid mit Trifluoressigsäure analog Beispiel A3, gelöst in 20 ml trockenem Tetrahydrofuran zugetropft. Diese Reaktionsmischung wird 30 min bei 15O0C 100 Watt Mikrowellenenergie ausgesetzt. Danach wird mit 2 N Salzsäure auf ph 4-5 gestellt und in Wasser/Ethylacetat verteilt, die organische Phase wird getrocknet und eingedampft. Man erhält 3.00 g (62 % d. Th.) 2-(2,2-Difluoroethoxy)- 6-iodobenzolsulfonamid.Gas evolution stirred at room temperature. Thereafter, 4.00 g (13.29 mmol) of 2-fluoro-6-iodo-benzenesulfonamide obtained from the reaction of N- (ferf-butyl) -2-fluoro-6-iodobenzenesulfonamide with trifluoroacetic acid analogously to Example A3, dissolved in 20 ml of dry tetrahydrofuran dropwise. This reaction mixture is exposed for 30 min at 15O 0 C 100 watts of microwave energy. It is then adjusted to pH 4-5 with 2N hydrochloric acid and distributed in water / ethyl acetate, the organic phase is dried and evaporated. 3.00 g (62% of theory) of 2- (2,2-difluoroethoxy) -6-iodobenzenesulphonamide are obtained.
Beispiel A9Example A9
2-lodo-6-(methylthio)benzolsulfonamid (Beispiel-Nr. 2.208a) 30.00 g (99.64 mmol) 2-Fluoro-6-iodobenzolsulfonamid, erhalten aus der Reaktion von N-(ferf-Butyl)-2-fluoro-6-iodobenzolsulfonamid mit Trifluoressigsäure analog Beispiel A3, werden zusammen mit 15.15 g (109.61 mmol) Kaliumcarbonat in 250 ml Dimethylformamid vorgelegt. Bei Raumtemperatur werden 7.68 g (109.61 mmol) Natriumthiomethylat portionsweise zugegeben, wonach 12 h bei Raumtemperatur gerührt wird. Die Reaktionsmischung wird auf 150 ml Eiswasser gegossen, mit 2 N Salzsäure auf pH 4-5 gestellt und mit Ethylacetat extrahiert. Die organische Phase wird getrocknet und eingedampft. Präparative HPLC (Reversed phase, 0.05 % Trifluoressigsäure in Wasser / Acetonitril, Gradient: in 30 min, 25 bis 100 %2-iodo-6- (methylthio) benzenesulfonamide (Example No. 2.208a) 30.00 g (99.64 mmol) of 2-fluoro-6-iodobenzenesulfonamide obtained from the reaction of N- (ferf-butyl) -2-fluoro-6 -iodobenzenesulfonamide with trifluoroacetic acid analogously to Example A3 are presented together with 15.15 g (109.61 mmol) of potassium carbonate in 250 ml of dimethylformamide. At room temperature, 7.68 g (109.61 mmol) of sodium thiomethylate are added in portions, after which it is stirred for 12 h at room temperature. The reaction mixture is poured into 150 ml of ice-water, adjusted to pH 4-5 with 2N hydrochloric acid and extracted with ethyl acetate. The organic phase is dried and evaporated. Preparative HPLC (Reversed phase, 0.05% trifluoroacetic acid in water / acetonitrile, gradient: in 30 min, 25 to 100%
Acetonitril) ergeben 7.40 g (23 % d. Th.) 2-lodo-6-(methylthio)benzolsulfonamid. Die in den nachfolgenden Tabellen 1 und 2 beschriebenen Verbindungen werden analog den obigen Beispielen A1 - A9 erhalten.Acetonitrile) gives 7.40 g (23% of theory) of 2-iodo-6- (methylthio) benzenesulfonamide. The compounds described in Tables 1 and 2 below are obtained analogously to the above Examples A1-A9.
Abkürzungen in den nachfolgenden Tabellen 1 und 2: * = 1H-NMR Daten sind nachfolgend zu den Tabellen 1 bzw. 2 aufgeführt Me = Methyl Ph = Phenyl Het = Heterocyclus, wobei Het für einen der nachfolgenden Reste H1 bis H23 steht Abbreviations in the following Tables 1 and 2: * = 1 H-NMR data are listed below to the Tables 1 and 2 Me = methyl Ph = phenyl Het = heterocycle, wherein Het is one of the following radicals H1 to H23
H2 H3 H4H2 H3 H4
H5 H6 H7 H8H5 H6 H7 H8
H13 H14 H15 H16H13 H14 H15 H16
H17 H18 H19 H20H17 H18 H19 H20
H21 H22 H23 Tabelle 1 : Verbindungen der allgemeinen Formel ( l-a )H21 H22 H23 Table 1: Compounds of the general formula (Ia)
(l-a)(L-a)
1H-NMR Daten: 1 H-NMR data:
Beispiel-Nr.: 1.001 (O6-DMSO): 13.11 (br s, 1H); 10.74 (br s, 1H); 8.04 (brd, J = 7.6, 1 H); 7.49 (ddd, J = 1.1, 8.4, 11.3, 1 H); 7.41 (dt, J = 5.3, 7.9, 1 H); 6.02 (s, 1 H); 3.94 (S, 6H).Example No: 1.001 (O 6 -DMSO): 13.11 (br s, 1H); 10.74 (br s, 1H); 8.04 (brd, J = 7.6, 1 H); 7.49 (ddd, J = 1.1, 8.4, 11.3, 1H); 7.41 (dt, J = 5.3, 7.9, 1H); 6.02 (s, 1H); 3.94 (S, 6H).
Beispiel-Nr.: 1.002 (d6-DMSO): 13.01 (br s, 1 H); 11.15 (s, 1 H); 8.04 (br d, J = 7.6, 1H); 7.49 (ddd, J = 1.1, 8.4, 11.2, 1H); 7.42 (dt, J = 5.3, 7.8, 1H); 3.99 (s, 3H); 2.48 (s, 3H).Example No: 1.002 (d 6 -DMSO): 13.01 (br s, 1 H); 11.15 (s, 1H); 8.04 (br d, J = 7.6, 1H); 7.49 (ddd, J = 1.1, 8.4, 11.2, 1H); 7.42 (dt, J = 5.3, 7.8, 1H); 3.99 (s, 3H); 2.48 (s, 3H).
Beispiel-Nr.: 1.003(CDCI3): 13.51 (brs, 1H); 8.14 (brs, 1H); 7.90 (m, 1H); 7.17 (m, 2H); 6.74 (s, 1H); 2.43 (S, 6H).Example No: 1.003 (CDCI 3 ): 13.51 (brs, 1H); 8.14 (brs, 1H); 7.90 (m, 1H); 7.17 (m, 2H); 6.74 (s, 1H); 2.43 (S, 6H).
Beispiel-Nr.: 1.004(CDCI3): 12.45 (brs, 1H); 7.96 (m, 1H); 7.43 (brs, 1H); 7.22 (m, 2H); 6.51 (s, 1H); 4.05 (s, 6H).Example No: 1.004 (CDCI 3 ): 12.45 (brs, 1H); 7.96 (m, 1H); 7.43 (brs, 1H); 7.22 (m, 2H); 6.51 (s, 1H); 4.05 (s, 6H).
Beispiel-Nr.: 1.012 (CDCI3): 12.81 (s, 1H); 8.02 (d, J = 7.8, 1H); 7.33 (d, J = 7.8, 1H); 7.12 (brs, 1H); 7.05 (t, J = 7.8, 1H); 5.80 (s, 1H); 4.00 (s, 6H); 2.89 (s, 3H). Beispiel-Nr.: 1.016(CDCI3): 12.76 (brs, 1H); 8.02 (brd, J = 7.8, 1H); 7.34 (brs, 1H); 7.33 (brd, J = 7.5, 1H); 7.06 (t, J = 7.8, 1H); 4.06 (s, 3H); 2.88 (s, 3H); 2.59 (s, 3H).Example No: 1.012 (CDCI 3 ): 12.81 (s, 1H); 8.02 (d, J = 7.8, 1H); 7.33 (d, J = 7.8, 1H); 7.12 (brs, 1H); 7.05 (t, J = 7.8, 1H); 5.80 (s, 1H); 4.00 (s, 6H); 2.89 (s, 3H). Example No: 1.016 (CDCI 3 ): 12.76 (brs, 1H); 8.02 (brd, J = 7.8, 1H); 7.34 (brs, 1H); 7.33 (brd, J = 7.5, 1H); 7.06 (t, J = 7.8, 1H); 4.06 (s, 3H); 2.88 (s, 3H); 2.59 (s, 3H).
Beispiel-Nr.: 1.020 (CDCI3): 13.29 (br s, 1 H); 8.01 (dd, J = 0.7, 7.8, 1 H); 7.44 (br s, 1 H); 7.32 (br d, J = 7.5, 1 H); 7.03 (t, J = 7.8, 1 H); 6.78 (s, 1 H); 2.90 (s, 3H); 2.48 (s, 3H).Example No: 1.020 (CDCI 3 ): 13.29 (br s, 1H); 8.01 (dd, J = 0.7, 7.8, 1H); 7.44 (br s, 1 H); 7.32 (br d, J = 7.5, 1H); 7.03 (t, J = 7.8, 1 H); 6.78 (s, 1H); 2.90 (s, 3H); 2.48 (s, 3H).
Beispiel-Nr.: 1.021 (CDCI3): 12.37 (brs, 1H); 8.02 (d, J = 7.8, 1H); 7.35 (brs, 1H); 7.33 (d, J = 7.5, 1 H); 7.05 (t, J = 7.8, 1 H); 6.50 (s, 1 H); 4.06 (s, 3H); 2.89 (s, 3H).Example No: 1.021 (CDCI 3 ): 12.37 (brs, 1H); 8.02 (d, J = 7.8, 1H); 7.35 (brs, 1H); 7.33 (d, J = 7.5, 1H); 7.05 (t, J = 7.8, 1 H); 6.50 (s, 1H); 4.06 (s, 3H); 2.89 (s, 3H).
Beispiel-Nr.: 1.025 (CDCI3): 12.47 (br s, 1 H); 8.02 (dd, J = 0.7, 7.8, 1 H); 7.33 (br d, J = 7.8, 1H); 7.25 (brs, 1H); 7.06 (t, J = 7.8, 1H); 4.08 (s, 6H); 2.88 (s, 3H).Example No: 1.025 (CDCI 3 ): 12.47 (br s, 1H); 8.02 (dd, J = 0.7, 7.8, 1H); 7.33 (br d, J = 7.8, 1H); 7.25 (brs, 1H); 7.06 (t, J = 7.8, 1H); 4.08 (s, 6H); 2.88 (s, 3H).
Beispiel-Nr.: 1.091 (CDCI3): 13.09 (brs, 1H); 8.38 (dd, J = 1.3, 8.0, 1H); 7.96 (br dd, J = 0.7, 8.0, 1 H); 7.28 (td, J = 0.7, 8.0, 1 H); 7.23 (br s, 1 H); 5.81 (s, 1 H); 3.98 (s, 6H).Example No: 1.091 (CDCI 3 ): 13.09 (brs, 1H); 8.38 (dd, J = 1.3, 8.0, 1H); 7.96 (brdd, J = 0.7, 8.0, 1H); 7.28 (td, J = 0.7, 8.0, 1H); 7.23 (br s, 1 H); 5.81 (s, 1H); 3.98 (s, 6H).
Beispiel-Nr.: 1.095 (CDCI3): 13.00 (brs, 1H); 9.96 (s, 1H); 8.26 (dd, J = 1.2, 8.0, 1H); 7.84 (brd, J = 8.0, 1H); 7.19 (t, J = 7.9, 1H); 3.93 (s, 3H); 2.44 (s, 3H).Example No: 1.095 (CDCI 3 ): 13.00 (brs, 1H); 9.96 (s, 1H); 8.26 (dd, J = 1.2, 8.0, 1H); 7.84 (brd, J = 8.0, 1H); 7.19 (t, J = 7.9, 1H); 3.93 (s, 3H); 2.44 (s, 3H).
Beispiel-Nr.: 1.099 (d6-DMSO): 14.08 (brs, 1H); 10.67 (s, 1H); 8.47 (dd, J = 1.1, 7.9, 1H); 8.02 (dd, J = 1.0, 8.0, 1H); 7.46 (t, J = 8.1, 1H); 7.02 (s, 1H); 2.43 (s, 6H).Example No: 1.099 (d 6 -DMSO): 14.08 (brs, 1H); 10.67 (s, 1H); 8.47 (dd, J = 1.1, 7.9, 1H); 8.02 (dd, J = 1.0, 8.0, 1H); 7.46 (t, J = 8.1, 1H); 7.02 (s, 1H); 2.43 (s, 6H).
Beispiel-Nr.: 1.100(CDCI3): 12.62 (brs, 1H); 8.38 (dd, J = 1.3, 8.0, 1H); 7.97 (brdd, J = 0.7, 8.0, 1 H); 7.63 (br s, 1 H); 7.30 ( td, J = 0.7, 8.0, 1 H); 6.51 (s, 1 H); 4.04 (s, 3H).Example No: 1,100 (CDCI 3 ): 12.62 (brs, 1H); 8.38 (dd, J = 1.3, 8.0, 1H); 7.97 (brdd, J = 0.7, 8.0, 1H); 7.63 (br s, 1 H); 7.30 (td, J = 0.7, 8.0, 1H); 6.51 (s, 1H); 4.04 (s, 3H).
Beispiel-Nr.: 1.104 (CDCI3): 12.76 (br s, 1H); 9.40 (br s.1H); 8.32 (dd, J = 1.2, 8.0, 1H); 7.90 (dd, J = 0.7, 8.0, 1H); 7.24 (m, 1H); 4.00 (s, 6H).Example No: 1.104 (CDCI 3 ): 12.76 (br s, 1H); 9.40 (br s.1H); 8.32 (dd, J = 1.2, 8.0, 1H); 7.90 (dd, J = 0.7, 8.0, 1H); 7.24 (m, 1H); 4.00 (s, 6H).
Beispiel-Nr.: 1.146 (de-DMSO): 12.69 (brs, 1H); 10.52 (brs, 1H); 7.81 (m, 1H); 7.28 (m, 2H); 6.03 (s, 1H); 3.93 (s, 6H); 3.73 (s, 3H). Beispiel-Nr.: 1.150 (d6-DMSO): 12.41 (brs, 1H); 10.98 (brs, 1H); 7.81 (m, 1H); 7.29 (m, 2H); 3.99 (s, 3H); 3.79 (s, 3H); 2.50 (s, 3H).Example No: 1.146 (d e -DMSO): 12.69 (brs, 1H); 10.52 (brs, 1H); 7.81 (m, 1H); 7.28 (m, 2H); 6.03 (s, 1H); 3.93 (s, 6H); 3.73 (s, 3H). Example No: 1.150 (d 6 -DMSO): 12.41 (brs, 1H); 10.98 (brs, 1H); 7.81 (m, 1H); 7.29 (m, 2H); 3.99 (s, 3H); 3.79 (s, 3H); 2.50 (s, 3H).
Beispiel-Nr.: 1.154 (d6-DMSO): 13.05 (s, 1H); 10.45 (s, 1H); 7.77 (m, 1H); 7.23 (m, 2H); 7.01 (s, 1 H); 3.70 (s, 3H); 2.42 (s, 6H).Example No: 1.154 (d 6 -DMSO): 13.05 (s, 1H); 10.45 (s, 1H); 7.77 (m, 1H); 7.23 (m, 2H); 7.01 (s, 1H); 3.70 (s, 3H); 2.42 (s, 6H).
Beispiel-Nr.1.155 (d6-DMSO): 11.97(s, 1H); 10.73 (s, 1H); 7.79 (m, 1H); 7.26 (m, 2H); 6.88 (s, 1H); 3.98 (s, 3H); 3.78 (s, 3H).Example No. 1.155 (d 6 -DMSO): 11.97 (s, 1H); 10.73 (s, 1H); 7.79 (m, 1H); 7.26 (m, 2H); 6.88 (s, 1H); 3.98 (s, 3H); 3.78 (s, 3H).
Beispiel-Nr.: 1.159 (CDCI3): 12.13 (s, 1H); 7.81 (dd, J = 1.1, 7.9, 1H); 7.33 (brs, 1H); 7.11 (t, J = 8.3, 1 H); 7.01 (dd, J = 1.0, 8.5, 1 H); 4.07 (s, 6H); 3.91 (s, 3H).Example No: 1.159 (CDCI 3 ): 12.13 (s, 1H); 7.81 (dd, J = 1.1, 7.9, 1H); 7.33 (brs, 1H); 7.11 (t, J = 8.3, 1 H); 7.01 (dd, J = 1.0, 8.5, 1 H); 4.07 (s, 6H); 3.91 (s, 3H).
Beispiel-Nr.: 1.164 (CDCI3): 12.46 (s, 1H); 7.82 (dd, J = 1.2, 7.8, 1H); 7.18 (brs, 1H);Example No: 1.164 (CDCl 3 ): 12.46 (s, 1H); 7.82 (dd, J = 1.2, 7.8, 1H); 7.18 (brs, 1H);
7.08 (t, J = 8.4, 1H); 6.99 (dd, J = 1.2, 8.4, 1H); 5.78 (s, 1H); 4.14 (q, J = 7.0, 2H); 3.97 (s, 6H); 1.32 (t, J = 7.0, 3H).7.08 (t, J = 8.4, 1H); 6.99 (dd, J = 1.2, 8.4, 1H); 5.78 (s, 1H); 4.14 (q, J = 7.0, 2H); 3.97 (s, 6H); 1.32 (t, J = 7.0, 3H).
Beispiel-Nr.: 1.165 (d6-DMSO): 12.25 (s, 1H); 10.99 (s, 1H); 7.79 (m, 1H); 7.26 (m, 2H); 4.14 (q, J = 7.7, 2H); 3.98 (s, 3 H); 2.47 (s, 3H); 1.21 (t, J = 7.0, 3H).Example No: 1.165 (d 6 -DMSO): 12.25 (s, 1H); 10.99 (s, 1H); 7.79 (m, 1H); 7.26 (m, 2H); 4.14 (q, J = 7.7, 2H); 3.98 (s, 3H); 2.47 (s, 3H); 1.21 (t, J = 7.0, 3H).
Beispiel-Nr.: 1.166 (CDCI3): 12.68 (s, 1H); 7.81 (dd, J = 1.2, 7.8, 1H); 7.60 (brs, 1H); 7.07 (t, J = 8.3, 1 H); 6.98 (dd, J = 1.2, 8.4, 1 H); 6.76 (s, 1 H); 4.13 (q, J = 7.0, 2H); 2.46 (s, 6H); 1.37 (t, J = 7.0, 3H).Example No: 1.166 (CDCl 3 ): 12.68 (s, 1H); 7.81 (dd, J = 1.2, 7.8, 1H); 7.60 (brs, 1H); 7.07 (t, J = 8.3, 1H); 6.98 (dd, J = 1.2, 8.4, 1 H); 6.76 (s, 1H); 4.13 (q, J = 7.0, 2H); 2.46 (s, 6H); 1.37 (t, J = 7.0, 3H).
Beispiel-Nr.: 1.167 (CDCI3): 11.83 (s, 1H); 7.82 (dd, J = 1.1, 7.71H); 7.36 (brs, 1H); 7.09 (t, J = 8.3, 1 H); 7.00 (dd, J = 1.1 , 8.4, 1 H); 6.49 (s, 1 H); 4.17 (q, J = 7.0, 2H); 4.01 (s, 3H); 1.41 (t, J = 7.0, 3H).Example No: 1.167 (CDCI 3 ): 11.83 (s, 1H); 7.82 (dd, J = 1.1, 7.71H); 7.36 (brs, 1H); 7.09 (t, J = 8.3, 1H); 7.00 (dd, J = 1.1, 8.4, 1H); 6.49 (s, 1H); 4.17 (q, J = 7.0, 2H); 4.01 (s, 3H); 1.41 (t, J = 7.0, 3H).
Beispiel-Nr.: 1.168 (CDCI3): 11.99 (s, 1H); 7.82 (dd, J = 1.3, 7.8, 1H); 7.29 (brs, 1H);Example No: 1.168 (CDCI 3 ): 11.99 (s, 1H); 7.82 (dd, J = 1.3, 7.8, 1H); 7.29 (brs, 1H);
7.09 (t, J = 8.4, 1 H); 7.00 (dd, J = 1.2, 8.4, 1 H); 4.16 (q, J = 7.0, 2H); 4.06 (s, 6H); 1.43 (t, J = 7.0, 3H). Beispiel-Nr.: 1.171 (CDCI3): 12.41 (s, 1H); 7.82 (dd, J = 1.2, 7.8, 1H); 7.17 (brs, 1H);7.09 (t, J = 8.4, 1H); 7.00 (dd, J = 1.2, 8.4, 1 H); 4.16 (q, J = 7.0, 2H); 4.06 (s, 6H); 1.43 (t, J = 7.0, 3H). Example No: 1.171 (CDCl 3 ): 12.41 (s, 1H); 7.82 (dd, J = 1.2, 7.8, 1H); 7.17 (brs, 1H);
7.07 (t, J = 8.4, 1H); 6.99 (dd, J = 1.1, 8.4, 1H); 5.79 (s, 1H); 4.02 (t, J = 6.7, 2H); 3.97 (s, 6H); 1.74 (m, 2H); 0.96 (t, J = 7.4, 3H).7.07 (t, J = 8.4, 1H); 6.99 (dd, J = 1.1, 8.4, 1H); 5.79 (s, 1H); 4.02 (t, J = 6.7, 2H); 3.97 (s, 6H); 1.74 (m, 2H); 0.96 (t, J = 7.4, 3H).
Beispiel-Nr.: 1.173 (d6-DMSO): 12.81 (brs, 1H); 10.52 (s, 1H); 7.79 (dd, J = 1.7, 7.1, 1H); 7.24 (m, 2H); 7.02 (s, 1H); 4.00 (t, J = 6.4, 2H); 2.41 (s, 6H); 1.56 (m, 2H); 0.87 (t, J = 7.4, 3H).Example No: 1.173 (d 6 -DMSO): 12.81 (brs, 1H); 10.52 (s, 1H); 7.79 (dd, J = 1.7, 7.1, 1H); 7.24 (m, 2H); 7.02 (s, 1H); 4.00 (t, J = 6.4, 2H); 2.41 (s, 6H); 1.56 (m, 2H); 0.87 (t, J = 7.4, 3H).
Beispiel-Nr.: 1.174 (CDCI3): 11.77 (s, 1H); 7.81 (dd, J = 1.2, 7.8, 1H); 7.30 (brs, 1H); 7.08 (t, J = 8.4, 1 H); 7.00 (dd, J = 1.1 , 8.4, 1 H); 6.48 (s, 1 H); 4.04 (t, J = 6.6, 2H); 4.00 (s, 3H); 1.82 (m, 2H); 1.01 (t, J = 7.4, 3H).Example No: 1.174 (CDCI 3 ): 11.77 (s, 1H); 7.81 (dd, J = 1.2, 7.8, 1H); 7.30 (brs, 1H); 7.08 (t, J = 8.4, 1H); 7.00 (dd, J = 1.1, 8.4, 1H); 6.48 (s, 1H); 4.04 (t, J = 6.6, 2H); 4.00 (s, 3H); 1.82 (m, 2H); 1.01 (t, J = 7.4, 3H).
Beispiel-Nr.: 1.175 (CDCI3): 11 ,96 (s, 1 H); 7.80 (dd, J = 1.2, 7.8, 1 H); 7.46 (br s, 1 H);Example No: 1.175 (CDCl 3 ): 11, 96 (s, 1H); 7.80 (dd, J = 1.2, 7.8, 1 H); 7.46 (br s, 1 H);
7.08 (t, J = 8.4, 1H); 6.99 (dd, J = 1.1, 8.4, 1H); 4.05 (s, 6H); 4.03 (t, J = 6.6, 2H); 1.83 (m, 2H); 1.03 (t, J = 7.4, 3H).7.08 (t, J = 8.4, 1H); 6.99 (dd, J = 1.1, 8.4, 1H); 4.05 (s, 6H); 4.03 (t, J = 6.6, 2H); 1.83 (m, 2H); 1.03 (t, J = 7.4, 3H).
Beispiel-Nr.: 1.178 (CDCI3): 12.32 (s, 1H); 7.80 (dd, J = 1.2, 7.7, 1H); 7.17 (brs, 1H);Example No: 1.178 (CDCl 3 ): 12.32 (s, 1H); 7.80 (dd, J = 1.2, 7.7, 1H); 7.17 (brs, 1H);
7.06 (t, J = 8.4, 1 H); 6.99 (br d, J = 8.2, 1 H); 5.78 (s, 1 H); 4.70 (m, 1 H); 3.97 (s, 6H); 1.28 (d, J = 6.1, 6H).7.06 (t, J = 8.4, 1H); 6.99 (br d, J = 8.2, 1 H); 5.78 (s, 1H); 4.70 (m, 1H); 3.97 (s, 6H); 1.28 (d, J = 6.1, 6H).
Beispiel-Nr.: 1.182 (CDCI3): 12.00 (brs, 1H); 7.80 (dd, J = 1.0, 7.8, 1H); 7.43 (brs, 1 H); 7.08 (t, J = 8.2, 1 H); 7.00 (br d, J = 8.1 , 1 H); 4.71 (m, 1 H); 4.05 (s, 3H); 2.58 (s, 3H); 1.35 (d, J = 6.0, 6H).Example No: 1.182 (CDCI 3 ): 12.00 (brs, 1H); 7.80 (dd, J = 1.0, 7.8, 1H); 7.43 (brs, 1h); 7.08 (t, J = 8.2, 1H); 7.00 (br d, J = 8.1, 1 H); 4.71 (m, 1H); 4.05 (s, 3H); 2.58 (s, 3H); 1.35 (d, J = 6.0, 6H).
Beispiel-Nr.: 1.186 (CDCI3): 12.51 (brs, 1H); 7.80 (m, 1H); 7.39 (brs, 1H); 7.06 (m, 1 H); 6.98 (m, 1 H); 6.76 (s, 1 H); 4.69 (m, 1 H); 2.47 (s, 6H); 1.32 (br d, J = 6.0, 6H).Example No: 1.186 (CDCI 3 ): 12.51 (brs, 1H); 7.80 (m, 1H); 7.39 (brs, 1H); 7.06 (m, 1H); 6.98 (m, 1H); 6.76 (s, 1H); 4.69 (m, 1H); 2.47 (s, 6H); 1.32 (br d, J = 6.0, 6H).
Beispiel-Nr.: 1.187 (CDCI3): 11.68 (s, 1H); 7.80 (dd, J = 1.1, 7.8, 1H); 7.33 (brs, 1H);Example No: 1.187 (CDCI 3 ): 11.68 (s, 1H); 7.80 (dd, J = 1.1, 7.8, 1H); 7.33 (brs, 1H);
7.07 (t, J = 8.4, 1 H); 7.00 (br d, J = 7.8, 1 H); 6.48 (s, 1 H); 4.71 (m, 1 H); 4.00 (s, 3H); 1.35 (d, J = 6.1, 6H). Beispiel-Nr.: 1.191 (CDCI3): 11.90 (brs, 1H); 7.79 (dd, J = 1.3, 7.7, 1H); 7.39 (brs, 1H); 7.08 (t, J = 8.4, 1H); 7.00 (dd, J = 1.2, 8.5, 1H); 4.71 (m, 1H); 4.06 (s, 6H); 1.35 (d, J = 6.1,6H).7.07 (t, J = 8.4, 1H); 7.00 (br d, J = 7.8, 1 H); 6.48 (s, 1H); 4.71 (m, 1H); 4.00 (s, 3H); 1.35 (d, J = 6.1, 6H). Example No: 1.191 (CDCI 3 ): 11.90 (brs, 1H); 7.79 (dd, J = 1.3, 7.7, 1H); 7.39 (brs, 1H); 7.08 (t, J = 8.4, 1H); 7.00 (dd, J = 1.2, 8.5, 1H); 4.71 (m, 1H); 4.06 (s, 6H); 1.35 (d, J = 6.1.6H).
Beispiel-Nr.: 1.192 (CDCI3):12.41 (brs, 1H); 7.83 (dd, J = 1.1, 7.8, 1H); 7.11 (brs, 1H); 7.08 (t, J = 7.9, 1H); 7.00 (dd, J = 1.0, 8.5, 1H); 5.79 (s, 1H); 4.06 (t, J = 6.9, 2H); 3.97 (s, 6H); 1.68 (m, 2H); 1.38 (m, 2H); 0.86 (t, J = 7.4, 3H).Example No: 1.192 (CDCI 3 ): 12.41 (brs, 1H); 7.83 (dd, J = 1.1, 7.8, 1H); 7.11 (brs, 1H); 7.08 (t, J = 7.9, 1H); 7.00 (dd, J = 1.0, 8.5, 1H); 5.79 (s, 1H); 4.06 (t, J = 6.9, 2H); 3.97 (s, 6H); 1.68 (m, 2H); 1.38 (m, 2H); 0.86 (t, J = 7.4, 3H).
Beispiel-Nr.: 1.196 (CDCI3): 12.31 (brs, 1H); 7.80 (dd, J = 7.8, 1H); 7.14 (brs, 1H); 7.06 (t, J = 8.5, 1H); 6.98 (br d, J = 8.0, 1H); 5.79 (s, 1H); 4.46 (m, 1H); 3.96 (s, 6H); 1.69 (m, 1H); 1.57 (m, 1H); 1.22 (d, J = 6.1, 3H); 0.89 (t, J = 7.4, 3H).Example No: 1.196 (CDCI 3 ): 12.31 (brs, 1H); 7.80 (dd, J = 7.8, 1H); 7.14 (brs, 1H); 7.06 (t, J = 8.5, 1H); 6.98 (br d, J = 8.0, 1H); 5.79 (s, 1H); 4.46 (m, 1H); 3.96 (s, 6H); 1.69 (m, 1H); 1.57 (m, 1H); 1.22 (d, J = 6.1, 3H); 0.89 (t, J = 7.4, 3H).
Beispiel-Nr.: 1.197 (CDCI3): 12.38 (brs, 1H); 7.82 (dd, J = 1.1, 7.8, 1H); 7.15 (br s, 1H); 7.08 (dd, J = 7.9, 8.4, 1H); 6.99 (dd, J = 1.1, 8.5, 1H); 5.78 (s, 1H); 3.96 (s, 6H); 3.82 (d, J = 6.7, 2H); 2.05 (m, 1H); 0.97 (d, J = 6.7, 6H).Example No: 1.197 (CDCI 3 ): 12.38 (brs, 1H); 7.82 (dd, J = 1.1, 7.8, 1H); 7.15 (br s, 1H); 7.08 (dd, J = 7.9, 8.4, 1H); 6.99 (dd, J = 1.1, 8.5, 1H); 5.78 (s, 1H); 3.96 (s, 6H); 3.82 (d, J = 6.7, 2H); 2.05 (m, 1H); 0.97 (d, J = 6.7, 6H).
Beispiel-Nr.: 1.229 (CDCI3): 12.51 (br s, 1H); 7.82 (dd, J = 1.1, 7.7, 1H); 7.26 (br s, 1H); 7.06 (t, J =8.4, 1H); 6.97 (dd, J = 1.1, 8.5, 1H); 5.78 (s, 1H); 3.97 (s, 6H); 3.89 (d, J = 6.9, 2H); 1.15 (m, 1H); 0.47 (m, 2H); 0.23 (m, 2H).Example No: 1.229 (CDCI 3 ): 12.51 (br s, 1H); 7.82 (dd, J = 1.1, 7.7, 1H); 7.26 (br s, 1H); 7.06 (t, J = 8.4, 1H); 6.97 (dd, J = 1.1, 8.5, 1H); 5.78 (s, 1H); 3.97 (s, 6H); 3.89 (d, J = 6.9, 2H); 1.15 (m, 1H); 0.47 (m, 2H); 0.23 (m, 2H).
Beispiel-Nr.: 1.233 (CDCI3): 12.11 (br s, 1H); 7.83 (dd, J = 1.1, 7.8, 1H); 7.44 (br s, 1H); 7.09 (t, J = 8.2, 1H); 7.00 (dd, J = 1.0, 8.4, 1H); 4.05 (s, 3H); 3.94 (d, J = 6.8, 2H); 2.55 (s, 3H); 1.25 (m, 1H); 0.54 (m, 2H); 0.32 (m, 2H).Example No: 1.233 (CDCI 3 ): 12.11 (br s, 1H); 7.83 (dd, J = 1.1, 7.8, 1H); 7.44 (br s, 1H); 7.09 (t, J = 8.2, 1H); 7.00 (dd, J = 1.0, 8.4, 1H); 4.05 (s, 3H); 3.94 (d, J = 6.8, 2H); 2.55 (s, 3H); 1.25 (m, 1H); 0.54 (m, 2H); 0.32 (m, 2H).
Beispiel-Nr.: 1.237 (CDCI3): 12.70 (brs, 1H); 7.83 (dd, J = 1.1, 7.8, 1H); 7.41 (brs, 1H); 7.07 (t, J = 8.0, 1H); 6.99 (dd, J = 1.0, 8.4, 1H); 6.76 (s, 1H); 3.93 (d, J = 6.7, 2H); 2.45 (s, 6H); 1.22 (m, 1H); 0.47 (m, 2H); 0.29 (m, 2H).Example No: 1.237 (CDCI 3 ): 12.70 (brs, 1H); 7.83 (dd, J = 1.1, 7.8, 1H); 7.41 (brs, 1H); 7.07 (t, J = 8.0, 1H); 6.99 (dd, J = 1.0, 8.4, 1H); 6.76 (s, 1H); 3.93 (d, J = 6.7, 2H); 2.45 (s, 6H); 1.22 (m, 1H); 0.47 (m, 2H); 0.29 (m, 2H).
Beispiel-Nr.: 1.238 (CDCI3): 11.82 (br s, 1H); 7.83 (dd, J = 1.1, 7.8, 1H); 7.33 (br s, 1H); 7.08 (t, J = 8.3, 1H); 6.99 (dd, J = 1.0, 8.4, 1H); 6.48 (s, 1H); 4.02 (s, 3H); 3.93 (d, J = 6.9, 2H); 1.25 (m, 1H); 0.53 (m, 1H); 0.29 (m, 2H). Beispiel-Nr.: 1.242 (CDCI3): 11.97 (br s, 1 H); 7.83 (dd, J = 1.1 , 7.8, 1 H); 7.32 (br s, 1 H); 7.09 (t, J = 8.3, 1 H); 6.99 (dd, J = 1.0, 8.4, 1 H); 4.05 (s, 6H); 3.93 (d, J = 7.0, 2H); 1.28 (m, 1 H); 0.57 (m, 2H); 0.32 (m, 2H).Example No: 1.238 (CDCI 3 ): 11.82 (br s, 1H); 7.83 (dd, J = 1.1, 7.8, 1H); 7.33 (br s, 1H); 7.08 (t, J = 8.3, 1H); 6.99 (dd, J = 1.0, 8.4, 1H); 6.48 (s, 1H); 4.02 (s, 3H); 3.93 (d, J = 6.9, 2H); 1.25 (m, 1H); 0.53 (m, 1H); 0.29 (m, 2H). Example No: 1.242 (CDCI 3 ): 11.97 (br s, 1H); 7.83 (dd, J = 1.1, 7.8, 1H); 7.32 (br s, 1 H); 7.09 (t, J = 8.3, 1H); 6.99 (dd, J = 1.0, 8.4, 1 H); 4.05 (s, 6H); 3.93 (d, J = 7.0, 2H); 1.28 (m, 1H); 0.57 (m, 2H); 0.32 (m, 2H).
Beispiel-Nr.: 1.302 (d6-DMSO): 13.11 (br s, 1H); 10.76 (br s, 1H); 8.26 (dd, J = 0.8, 8.0, 1 H); 7.63 (dt, J = 0.8, 8.0, 1 H); 7.47 (t, J = 8.0, 1 H); 6.03 (s, 1 H); 3.95 (s, 6H).Example No: 1.302 (d 6 -DMSO): 13.11 (br s, 1H); 10.76 (brs, 1H); 8.26 (dd, J = 0.8, 8.0, 1H); 7.63 (dt, J = 0.8, 8.0, 1H); 7.47 (t, J = 8.0, 1H); 6.03 (s, 1 H); 3.95 (s, 6H).
Beispiel-Nr.: 1.306 (CDCI3): 12.77 (br s, 1 H); 8.16 (dd, J = 1.2, 8.0, 1 H); 7.43 (m, 2H); 7.24 (t, J = 8.1 , 1 H); 4.05 (s, 3H); 2.58 (s, 3H).Example No: 1.306 (CDCI 3 ): 12.77 (br s, 1H); 8.16 (dd, J = 1.2, 8.0, 1H); 7.43 (m, 2H); 7.24 (t, J = 8.1, 1H); 4.05 (s, 3H); 2.58 (s, 3H).
Beispiel-Nr.: 1.310 (d6-DMSO): 13.86 (s, 1 H); 10.72 (s, 1 H); 8.24 (dd, J = 1.2, 7.9, 1 H); 7.60 (dt, J = 1.3, 8.3, 1 H); 7.44 (t, J = 8.1 , 1 H); 7.03 (s, 1 H); 2.42 (s, 3H).Example No: 1.310 (d 6 -DMSO): 13.86 (s, 1H); 10.72 (s, 1H); 8.24 (dd, J = 1.2, 7.9, 1 H); 7.60 (dt, J = 1.3, 8.3, 1 H); 7.44 (t, J = 8.1, 1H); 7.03 (s, 1H); 2.42 (s, 3H).
Beispiel-Nr.: 1.311 (CDCI3): 12.38 (br s, 1 H); 8.17 (dd, J = 0.8, 8.0, 1 H); 7.44 (dt, J = 0.8, 8.0, 1 H); 7.37 (br s, 1 H); 7.24 (t, J = 8.0, 1 H); 6.52 (s, 1 H); 4.04 (s, 3H).Example No: 1,311 (CDCI 3 ): 12.38 (br s, 1H); 8.17 (dd, J = 0.8, 8.0, 1H); 7.44 (dt, J = 0.8, 8.0, 1H); 7.37 (br s, 1 H); 7.24 (t, J = 8.0, 1H); 6.52 (s, 1H); 4.04 (s, 3H).
Beispiel-Nr.: 1.315 (CDCI3): 12.51 (s, 1 H); 8.16 (dd, J = 1.2, 8.0, 1 H); 7.43 (dt, J = 1.2, 8.3, 1 H); 7.38 (s, 1H); 7.24 (t, J = 8.0, 1 H); 4.07 (s, 6H).Example No: 1.315 (CDCI 3 ): 12.51 (s, 1H); 8.16 (dd, J = 1.2, 8.0, 1H); 7.43 (dt, J = 1.2, 8.3, 1 H); 7.38 (s, 1H); 7.24 (t, J = 8.0, 1H); 4.07 (s, 6H).
Beispiel-Nr.: 1.321 (CDCI3): 12.87 (br s, 1 H); 8.12 (dd, J = 1.3, 7.9, 1 H); 7.34 (dd, J = 1.2, 8.2, 1 H); 7.21 (br s, 1 H); 7.21 (t, J = 8.0, 1 H); 6.69 (t, J = 74.5, 1 H); 5.81 (s, 1 H); 3.98 (s, 6H).Example No: 1.321 (CDCl 3 ): 12.87 (br s, 1H); 8.12 (dd, J = 1.3, 7.9, 1 H); 7.34 (dd, J = 1.2, 8.2, 1H); 7.21 (br s, 1H); 7.21 (t, J = 8.0, 1H); 6.69 (t, J = 74.5, 1H); 5.81 (s, 1H); 3.98 (s, 6H).
Beispiel-Nr.: 1.325 (CDCI3): 12.84 (br s, 1 H); 9.55 (br s, 1 H); 8.02 (dd, J = 1.2, 7.9, 1 H); 7.25 (dd, J = 1.0, 8.0, 1 H); 7.15 (t, J = 8.0, 1 H); 6.67 (t, J = 74.6, 1 H); 3.97 (s, 3H); 2.49 (s, 3H).Example No: 1.325 (CDCI 3 ): 12.84 (br s, 1H); 9.55 (br s, 1 H); 8.02 (dd, J = 1.2, 7.9, 1H); 7.25 (dd, J = 1.0, 8.0, 1H); 7.15 (t, J = 8.0, 1H); 6.67 (t, J = 74.6, 1H); 3.97 (s, 3H); 2.49 (s, 3H).
Beispiel-Nr.: 1.329 (CDCI3): 13.46 (br s, 1 H); 8.08 (dd, J = 1.2, 7.9, 1 H); 7.97 (br s, 1 H); 7.30 (dd, J = 1.1 , 8.2, 1 H); 7.18 (t, J = 8.0, 1H); 6.76 (s, 1 H); 6.69 (t, J = 74.8, 1 H); 2.45 (s, 6H). Beispiel-Nr.: 1.330 (CDCI3): 12.35 (br s, 1H); 8.11 (cid, J = 1.1 , 7.9, 1H); 7.39 (br s, 1 H); 7.34 (dd, J = 1.1 , 8.2, 1 H); 7.22 (t, J = 8.0, 1 H); 6.68 (t, J = 74.3, 1 H); 6.51 (s, 1H); 4.04 (s, 3H).Example No: 1.329 (CDCI 3 ): 13.46 (br s, 1H); 8.08 (dd, J = 1.2, 7.9, 1H); 7.97 (br s, 1 H); 7.30 (dd, J = 1.1, 8.2, 1H); 7.18 (t, J = 8.0, 1H); 6.76 (s, 1H); 6.69 (t, J = 74.8, 1H); 2.45 (s, 6H). Example No: 1,330 (CDCI 3 ): 12.35 (br s, 1H); 8.11 (cid, J = 1.1, 7.9, 1H); 7.39 (br s, 1 H); 7.34 (dd, J = 1.1, 8.2, 1H); 7.22 (t, J = 8.0, 1H); 6.68 (t, J = 74.3, 1H); 6.51 (s, 1H); 4.04 (s, 3H).
Beispiel-Nr.: 1.342 (CDCI3): 12.45 (br s, 1 H); 7.99 (dd, J = 0.9, 7.8, 1 H); 7.37 (br s, 1 H); 7.18 (t, J = 8.2, 1H); 7.08 (dd, J = 0.9, 8.3, 1 H); 4.49 (q, J = 8.1 , 2H); 4.05 (s, 3H); 2.58 (s, 3H).Example No: 1.342 (CDCl 3 ): 12.45 (br s, 1H); 7.99 (dd, J = 0.9, 7.8, 1H); 7.37 (br s, 1 H); 7.18 (t, J = 8.2, 1H); 7.08 (dd, J = 0.9, 8.3, 1H); 4.49 (q, J = 8.1, 2H); 4.05 (s, 3H); 2.58 (s, 3H).
Beispiel-Nr.: 1.343 (CDCI3): 13.03 (br s, 1 H); 7.98 (br d, J = 7.8, 1 H); 7.46 (br s, 1 H); 7.15 (t, J = 8.2, 1 H); 7.07 (br d, J = 8.1 , 1 H); 6.76 (s, 1 H); 4.48 (q, J = 8.2, 2H); 2.45 (s, 6H).Example No: 1.343 (CDCI 3 ): 13.03 (br s, 1H); 7.98 (br d, J = 7.8, 1 H); 7.46 (br s, 1 H); 7.15 (t, J = 8.2, 1H); 7.07 (br d, J = 8.1, 1 H); 6.76 (s, 1H); 4.48 (q, J = 8.2, 2H); 2.45 (s, 6H).
Beispiel-Nr.: 1.344 (CDCI3): 12.11 (s, 1H); 7.98 (br d, J = 7.6, 1H); 7.32 (br s, 1H); 7.17 (t, J = 8.2, 1H); 7.09 (br d, J = 8.0, 1H); 6.50 (s, 1H); 4.50 (q, J = 8.2, 2H); 4.02 (s, 3H).Example No: 1.344 (CDCI 3 ): 12.11 (s, 1H); 7.98 (br d, J = 7.6, 1H); 7.32 (br s, 1H); 7.17 (t, J = 8.2, 1H); 7.09 (br d, J = 8.0, 1H); 6.50 (s, 1H); 4.50 (q, J = 8.2, 2H); 4.02 (s, 3H).
Beispiel-Nr.: 1.352 (CDCI3): 12.37 (br s, 1 H); 8.31 (br s, 1 H); 7.89 (br d, J = 7.6, 1 H); 7.13 (t, J = 8.1 , 1 H); 7.03 (br d, J = 8.2, 1 H); 6.15 (tt, J = 3.9, 54.9, 1 H); 4.29 (td, J = 3.7, 12.9, 2H); 4.02 (s, 3H); 2.54 (s, 3H).Example No: 1.352 (CDCI 3 ): 12.37 (br s, 1H); 8.31 (br s, 1 H); 7.89 (br d, J = 7.6, 1 H); 7.13 (t, J = 8.1, 1H); 7.03 (br d, J = 8.2, 1 H); 6.15 (tt, J = 3.9, 54.9, 1 H); 4.29 (td, J = 3.7, 12.9, 2H); 4.02 (s, 3H); 2.54 (s, 3H).
Beispiel-Nr.: 1.353 (d6-DMSO): 13.04 (br s, 1 H); 9.33 (br s, 1H); 7.81 (dd, J = 1.1, 7.7, 1 H); 7.08 (t, J = 8.1 , 1 H); 7.02 (dd, J = 1.1 , 8.3, 1 H); 6.69 (s, 1 H); 6.04 (tt, J = 3.9, 55.0, 1H); 4.24 (td, J = 3.9, 13.2, 2H); 2.37 (s, 6H).Example No: 1.353 (d 6 -DMSO): 13.04 (br s, 1H); 9.33 (br s, 1H); 7.81 (dd, J = 1.1, 7.7, 1H); 7.08 (t, J = 8.1, 1H); 7.02 (dd, J = 1.1, 8.3, 1H); 6.69 (s, 1H); 6.04 (tt, J = 3.9, 55.0, 1H); 4.24 (td, J = 3.9, 13.2, 2H); 2.37 (s, 6H).
Beispiel-Nr. 1.354 (CDCI3): 12.10 (br s, 1H); 9.25 (br s, 1H); 7.91 (dd, J = 1.1 , 7.8, 1H); 7.16 (t, J = 8.2, 1H); 7.08 (dd, J = 1.0, 8.4, 1H); 6.47 (s, 1H); 6.17 (tt, J = 3.9, 54.9, 1H); 4.33 (td, J = 4.0, 13.2, 2H); 4.02 (s, 3H).Example no. 1.354 (CDCI 3 ): 12.10 (br s, 1H); 9.25 (br s, 1H); 7.91 (dd, J = 1.1, 7.8, 1H); 7.16 (t, J = 8.2, 1H); 7.08 (dd, J = 1.0, 8.4, 1H); 6.47 (s, 1H); 6.17 (tt, J = 3.9, 54.9, 1H); 4.33 (td, J = 4.0, 13.2, 2H); 4.02 (s, 3H).
Beispiel-Nr.: 1.355 (CDCI3): 12.23 (br s, 1 H); 8.48 (br s, 1 H); 7.88 (br d, J = 7.7, 1 H); 7.12 (t, J = 8.3, 1 H); 7.02 (br d, J = 8.3, 1 H); 6.18 (tt, J = 4.0, 54.8, 1 H); 4.28 (td, J = 4.0, 13.0, 2H); 4.02 (s, 6H). Beispiel-Nr.: 1.362 (CDCI3): 12.52 (br s, 1H); 7.94 (dd, J = 1.1, 7.8, 1H); 7.13 (br s, 1H); 7.13 (t, J = 8.3, 1H); 7.04 (brd, J = 8.2, 1H); 5.79 (s, 1H); 4.85 (m, 1H); 3.96 (s, 6H); 1.52 (d, J = 6.4, 3H).Example No: 1.355 (CDCI 3 ): 12.23 (br s, 1H); 8.48 (br s, 1 H); 7.88 (br d, J = 7.7, 1 H); 7.12 (t, J = 8.3, 1H); 7.02 (br d, J = 8.3, 1 H); 6.18 (tt, J = 4.0, 54.8, 1H); 4.28 (td, J = 4.0, 13.0, 2H); 4.02 (s, 6H). Example No: 1.362 (CDCI 3 ): 12.52 (br s, 1H); 7.94 (dd, J = 1.1, 7.8, 1H); 7.13 (br s, 1H); 7.13 (t, J = 8.3, 1H); 7.04 (brd, J = 8.2, 1H); 5.79 (s, 1H); 4.85 (m, 1H); 3.96 (s, 6H); 1.52 (d, J = 6.4, 3H).
Beispiel-Nr.: 1.363 (CDCI3): 12.30 (br s, 1 H); 7.94 (d, J = 7.7, 1 H); 7.44 (br s, 1 H); 7.14 (t, J = 8.2, 1H); 7.04 (d, J = 8.2, 1H); 4.84 (m, 1H); 4.04 (s, 3H); 2.00 (s, 3H); 1.55 (d, J = 6.1, 3H).Example No: 1.363 (CDCl 3 ): 12.30 (br s, 1H); 7.94 (d, J = 7.7, 1H); 7.44 (br s, 1 H); 7.14 (t, J = 8.2, 1H); 7.04 (d, J = 8.2, 1H); 4.84 (m, 1H); 4.04 (s, 3H); 2.00 (s, 3H); 1.55 (d, J = 6.1, 3H).
Beispiel-Nr.: 1.364 (CDCI3): 7.79 (dd, J = 1.0, 7.7, 1H); 7.01 (t, J = 8.3, 1H); 6.96 (br d, J = 7.8, 1 H); 6.65 (s, 1 H); 4.79 (m, 1 H); 2.33 (s, 6H); 1.37 (d, J = 6.4, 3H).Example No: 1.364 (CDCI 3 ): 7.79 (dd, J = 1.0, 7.7, 1H); 7.01 (t, J = 8.3, 1H); 6.96 (br d, J = 7.8, 1 H); 6.65 (s, 1H); 4.79 (m, 1H); 2.33 (s, 6H); 1.37 (d, J = 6.4, 3H).
Beispiel-Nr.: 1.365 (CDCI3): 11.95 (br s, 1 H); 7.94 (dd, J = 1.1, 7.8, 1 H); 7.29 (br s, 1 H); 7.14 (t, J = 8.4, 1 H); 7.05 (br d, J = 8.2, 1 H); 6.49 (s, 1 H); 4.84 (m, 1 H); 4.00 (s, 3H); 1.57 (Cl1J = 6.5, 3H).Example No: 1.365 (CDCI 3 ): 11.95 (br s, 1H); 7.94 (dd, J = 1.1, 7.8, 1 H); 7.29 (br s, 1 H); 7.14 (t, J = 8.4, 1H); 7.05 (br d, J = 8.2, 1 H); 6.49 (s, 1H); 4.84 (m, 1H); 4.00 (s, 3H); 1.57 (CI 1 J = 6.5, 3H).
Beispiel-Nr.1.366 (CDCI3): 12.17 (br s, 1 H); 7.93 (dd, J = 1.1 , 7.8, 1 H); 7.29 (br s, 1 H); 7.14 (t, J = 8.4, 1 H); 7.06 (br d, J = 8.1 , 1 H); 4.83 (m, 1 H); 4.06 (s, 6H); 1.58 (d, J = 6.5, 3H).Example No. 1,366 (CDCI 3 ): 12.17 (br s, 1 H); 7.93 (dd, J = 1.1, 7.8, 1 H); 7.29 (br s, 1 H); 7.14 (t, J = 8.4, 1H); 7.06 (br d, J = 8.1, 1 H); 4.83 (m, 1H); 4.06 (s, 6H); 1.58 (d, J = 6.5, 3H).
Beispiel-Nr.: 1.370 (CDCI3): 12.40 (brs, 1H); 8.01 (dd, J = 1.0, 7.7, 1H); 7.35 (br s, 1H); 7.19 (t, J = 8.3, 1H); 7.11 (dd, J = 1.0, 8.3, 1H); 4.57 (brt, J = 13.2, 2H); 4.05 (s, 3H); 2.57 (s, 3H).Example No: 1.370 (CDCI 3 ): 12.40 (brs, 1H); 8.01 (dd, J = 1.0, 7.7, 1H); 7.35 (br s, 1H); 7.19 (t, J = 8.3, 1H); 7.11 (dd, J = 1.0, 8.3, 1H); 4.57 (brt, J = 13.2, 2H); 4.05 (s, 3H); 2.57 (s, 3H).
Beispiel-Nr.: 1.371 (CDCI3): 8.00 (dd, J = 1.3, 7.7, 1H); 7.59 (brs, 1H); 7.20 (t, J = 6.9, 1H); 7.10 (dd, J = 1.3, 8.3, 1H); 6.79 (s, 1H); 4.57 (t, J = 13.2, 2H); 2.47 (s, 6H).Example No: 1.371 (CDCI 3 ): 8.00 (dd, J = 1.3, 7.7, 1H); 7.59 (brs, 1H); 7.20 (t, J = 6.9, 1H); 7.10 (dd, J = 1.3, 8.3, 1H); 6.79 (s, 1H); 4.57 (t, J = 13.2, 2H); 2.47 (s, 6H).
Beispiel-Nr.: 1.372 (CDCI3): 12.08 (s, 1H); 8.00 (dd, J = 1.4, 7.6, 1H); 7.28 (brs, 1H); 7.19 (t, J = 8.2, 1H); 7.13 (dd, J = 1.2, 8.2, 1H); 6.50 (s, 1H); 4.59 (brt, J = 12.8, 2H); 4.01 (s, 3H).Example No: 1.372 (CDCI 3 ): 12.08 (s, 1H); 8.00 (dd, J = 1.4, 7.6, 1H); 7.28 (brs, 1H); 7.19 (t, J = 8.2, 1H); 7.13 (dd, J = 1.2, 8.2, 1H); 6.50 (s, 1H); 4.59 (brt, J = 12.8, 2H); 4.01 (s, 3H).
Beispiel-Nr.: 1.373 (CDCI3): 12.27 (br s, 1 H); 7.98 (br d, J = 7.5, 1 H); 7.46 (br s, 1 H); 7.18 (t, J = 8.3, 1H); 7.12 (brd, J = 7.3, 1H); 4.58 (brt, J = 13.2, 2H); 4.05 (s, 6H). Beispiel-Nr.1.389 (CDCI3): 12.99 (br.s, 1H); 8.46 (br s, 1H); 7.96 (cid, J = 1.0, 7.7, 1H); 7.35 (d, J = 7.8, 1H); 7.07 (t, J = 8.0, 1H); 5.79 (s, 1H); 4.00 (s, 6H); 2.45 (s, 3H).Example No: 1.373 (CDCI 3 ): 12.27 (br s, 1H); 7.98 (br d, J = 7.5, 1 H); 7.46 (br s, 1 H); 7.18 (t, J = 8.3, 1H); 7.12 (brd, J = 7.3, 1H); 4.58 (brt, J = 13.2, 2H); 4.05 (s, 6H). Example No. 1389 (CDCI 3 ): 12.99 (br.s, 1H); 8.46 (br s, 1H); 7.96 (cid, J = 1.0, 7.7, 1H); 7.35 (d, J = 7.8, 1H); 7.07 (t, J = 8.0, 1H); 5.79 (s, 1H); 4.00 (s, 6H); 2.45 (s, 3H).
Beispiel-Nr 1.390 (CDCI3): 12.93 (brs, 1H); 10.23(brs, 1H); 7.95 (dd, J = 1.1, 7.8, 1H); 7.36 (d, J = 8.2, 1H); 7.08 (t, J = 7.8, 1H); 4.06 (s, 3H); 2.56 (s, 3H); 2.45 (s, 3H).Example No. 1,390 (CDCI 3 ): 12.93 (brs, 1H); 10.23 (brs, 1H); 7.95 (dd, J = 1.1, 7.8, 1H); 7.36 (d, J = 8.2, 1H); 7.08 (t, J = 7.8, 1H); 4.06 (s, 3H); 2.56 (s, 3H); 2.45 (s, 3H).
Beispiel-Nr.: 1.463(CDCI3): 13.00 (brs, 1H); 8.71 (brs, 1H); 7.98 (dd, J = 1.1, 8.0, 1H); 7.50 (dd, J = 1.1, 8.3, 1H); 7.12 (t, J = 8.1, 1H); 5.66 (s, 1H); 3.85 (s, 6H); 3.26 (s, 3H).Example No: 1.463 (CDCI 3 ): 13.00 (brs, 1H); 8.71 (brs, 1H); 7.98 (dd, J = 1.1, 8.0, 1H); 7.50 (dd, J = 1.1, 8.3, 1H); 7.12 (t, J = 8.1, 1H); 5.66 (s, 1H); 3.85 (s, 6H); 3.26 (s, 3H).
Beispiel-Nr.: 1.471 (CDCI3): 13.54 (brs, 1H); 8.11 (dd, J = 1.2, 8.0, 1H); 7.67 (dd, J = 1.2, 8.3, 1 H); 7.44 (br s, 1 H); 7.23 (t, J = 8.1 , 1 H); 6.78 (s, 1 H); 3.38 (s, 3H); 2.48 (s, 6H).Example No: 1.471 (CDCI 3 ): 13.54 (brs, 1H); 8.11 (dd, J = 1.2, 8.0, 1H); 7.67 (dd, J = 1.2, 8.3, 1H); 7.44 (br s, 1 H); 7.23 (t, J = 8.1, 1H); 6.78 (s, 1H); 3.38 (s, 3H); 2.48 (s, 6H).
Beispiel-Nr.: 1.472 (CDCI3): 12.45 (brs, 1H); 8.12 (brd, J = 8.0, 1H); 7.65 (brd, J = 8.3, 1 H); 7.39 (br s, 1 H); 7.25 (br t, J = 8.0, 1 H); 6.52 (s, 1 H); 4.04 (s, 3H), 3.41 (s, 3H).Example No: 1.472 (CDCI 3 ): 12.45 (brs, 1H); 8.12 (brd, J = 8.0, 1H); 7.65 (brd, J = 8.3, 1H); 7.39 (br s, 1 H); 7.25 (br t, J = 8.0, 1 H); 6.52 (s, 1H); 4.04 (s, 3H), 3.41 (s, 3H).
Beispiel-Nr.: 1.476 (CDCI3): 12.62 (brs, 1H); 9.35 (s, 1H); 8.05 (dd, J = 1.2, 8.0, 1H); 7.55 (dd, J = 1.2, 8.3, 1H); 7.18 (t, J = 8.1, 1H); 4.00 (s, 6H); 3.37 (s, 3H).Example No: 1.476 (CDCI 3 ): 12.62 (brs, 1H); 9.35 (s, 1H); 8.05 (dd, J = 1.2, 8.0, 1H); 7.55 (dd, J = 1.2, 8.3, 1H); 7.18 (t, J = 8.1, 1H); 4.00 (s, 6H); 3.37 (s, 3H).
Beispiel-Nr.: 1.507 (CDCI3): 12.90 (br s, 1 H); 8.02 (dd, J = 1.2, 7.9, 1 H); 7.74 (dd, J = 1.2, 8.4, 1H); 7.20 (dd, J = 8.0, 8.3, 1H); 5.80 (s, 1H); 4.00 (s, 6H); 3.10 (s, 6H).Example No: 1,507 (CDCI 3 ): 12.90 (br s, 1H); 8.02 (dd, J = 1.2, 7.9, 1H); 7.74 (dd, J = 1.2, 8.4, 1H); 7.20 (dd, J = 8.0, 8.3, 1H); 5.80 (s, 1H); 4.00 (s, 6H); 3.10 (s, 6H).
Beispiel-Nr.: 1.509 (CDCI3): 13.38 (br s, 1 H); 8.02 (dd, J = 1.1 , 7.9, 1 H); 7.76 (dd, J = 1.1, 8.4, 1H); 7.40 (brs, 1H); 7.19 (t, J = 8.0, 1H); 6.77 (s, 1H); 3.10 (s, 6H); 2.47 (s, 6H). Beispiel-Nr: 1.510 (CDCI3): 12.31 (brs, 1H); 8.03 (dd, = 1.1, 7.9, 1H); 7.75 (dd, J =Example No: 1.509 (CDCI 3 ): 13.38 (br s, 1H); 8.02 (dd, J = 1.1, 7.9, 1H); 7.76 (dd, J = 1.1, 8.4, 1H); 7.40 (brs, 1H); 7.19 (t, J = 8.0, 1H); 6.77 (s, 1H); 3.10 (s, 6H); 2.47 (s, 6H). Example No: 1.510 (CDCI 3 ): 12.31 (brs, 1H); 8.03 (dd, = 1.1, 7.9, 1H); 7.75 (dd, J =
1.1, 8.4, 1H); 7.39 (brs, 1H); 7.21 (t, J = 8.2, 1H); 6.50 (s, 1H); 4.03 (s, 3H); 3.10 (s, 6H).1.1, 8.4, 1H); 7.39 (brs, 1H); 7.21 (t, J = 8.2, 1H); 6.50 (s, 1H); 4.03 (s, 3H); 3.10 (s, 6H).
Beispiel-Nr.: 1.511 (CDCI3): 12.41 (brs, 1H); 8.04 (dd, J = 1.2, 7.9, 1H); 7.75 (dd, J =Example No: 1.511 (CDCI 3 ): 12.41 (brs, 1H); 8.04 (dd, J = 1.2, 7.9, 1H); 7.75 (dd, J =
1.2, 8.4, 1 H); 7.32 (br s, 1 H); 7.21 (dd, J = 8.0, 8.4, 1 H); 4.07 (s, 6H); 3.10 (s, 6H).1.2, 8.4, 1 H); 7.32 (br s, 1 H); 7.21 (dd, J = 8.0, 8.4, 1H); 4.07 (s, 6H); 3.10 (s, 6H).
Beispiel-Nr.1.550 (CDCI3): 8.88 (br s, 1 H); 7.94 (dd, J = 1.1, 7.8, 1 H); 7.34 (dd, J = 0.5, 8.1 , 1 H); 7.06 (t, J = 7.9, 1 H); 6.81 (br s, 1 H); 2.49 (s, 6H); 2.45 (s, 3H).Example No. 1,550 (CDCI 3 ): 8.88 (br s, 1 H); 7.94 (dd, J = 1.1, 7.8, 1 H); 7.34 (dd, J = 0.5, 8.1, 1H); 7.06 (t, J = 7.9, 1H); 6.81 (br s, 1 H); 2.49 (s, 6H); 2.45 (s, 3H).
Beispiel-Nr.1.551 (CDCI3): 12.41 (brs, 1H); 7.95 (dd, J = 1.1, 7.8, 1H); 7.35 (d, J = 8.2, 1 H); 7.28 (br s, 1 H); 7.06 (t, J = 7.9, 1 H); 6.50 (s, 1 H); 4.06 (s, 3H); 2.47 (s, 3H).Example No. 1.551 (CDCI 3 ): 12.41 (brs, 1H); 7.95 (dd, J = 1.1, 7.8, 1H); 7.35 (d, J = 8.2, 1H); 7.28 (br s, 1H); 7.06 (t, J = 7.9, 1H); 6.50 (s, 1H); 4.06 (s, 3H); 2.47 (s, 3H).
Beispiel-Nr.: 1.553(CDCI3): 12.10 (brs, 1H); 7.83 (dd, J = 1.2, 7.8, 1H); 7.42 (brs, 1H); 7.10 (t, J = 8.4, 1H); 7.01 (dd, J = 1.1, 8.4, 1H); 4.07 (t, J = 6.9, 2H); 4.05 (s, 3H); 2.58 (s, 3H); 1.78 (m, 2H); 1.45 (m, 2H); 0.91 (t, J = 7.4, 3H).Example No: 1.553 (CDCI 3 ): 12.10 (brs, 1H); 7.83 (dd, J = 1.2, 7.8, 1H); 7.42 (brs, 1H); 7.10 (t, J = 8.4, 1H); 7.01 (dd, J = 1.1, 8.4, 1H); 4.07 (t, J = 6.9, 2H); 4.05 (s, 3H); 2.58 (s, 3H); 1.78 (m, 2H); 1.45 (m, 2H); 0.91 (t, J = 7.4, 3H).
Beispiel-Nr.: 1.554 (CDCI3): 12.64 (brs, 1H); 7.82 (dd, J = 1.2, 7.8, 1H); 7.33 (brs, 1H); 7.07 (t, J = 7.9, 1H); 6.99 (dd, J = 1.1, 8.4, 1H); 6.76 (s, 1H); 4.05 (t, J = 6.9, 2H); 2.47 (s, 6H); 1.74 (m, 2H); 1.42 (m, 2H); 0.86 (t, J = 7.4, 3H).Example No: 1.554 (CDCI 3 ): 12.64 (brs, 1H); 7.82 (dd, J = 1.2, 7.8, 1H); 7.33 (brs, 1H); 7.07 (t, J = 7.9, 1H); 6.99 (dd, J = 1.1, 8.4, 1H); 6.76 (s, 1H); 4.05 (t, J = 6.9, 2H); 2.47 (s, 6H); 1.74 (m, 2H); 1.42 (m, 2H); 0.86 (t, J = 7.4, 3H).
Beispiel-Nr.: 1.555 (CDCI3): 11.78 (br s, 1 H); 7.82 (dd, J = 1.0, 7.8, 1 H); 7.27 (br s, 1H); 7.09 (t, J = 8.2, 1H); 7.01 (dd, J = 1.0, 8.5, 1H); 6.49 (s, 1H); 4.08 (t, J = 6.9, 2H); 4.01 (S13H); 1.77 (m, 2H); 1.43 (m, 2H); 0.90 (t, J = 7.4, 3H).Example No: 1.555 (CDCl 3 ): 11.78 (br s, 1H); 7.82 (dd, J = 1.0, 7.8, 1H); 7.27 (br s, 1H); 7.09 (t, J = 8.2, 1H); 7.01 (dd, J = 1.0, 8.5, 1H); 6.49 (s, 1H); 4.08 (t, J = 6.9, 2H); 4.01 (S 1 3H); 1.77 (m, 2H); 1.43 (m, 2H); 0.90 (t, J = 7.4, 3H).
Beispiel-Nr.: 1.556 (CDCI3): 11.95 (br s, 1 H); 7.81 (dd, J = 1.1 , 7.8, 1 H); 7.36 (br s, 1H); 7.09 (t, J = 8.3, 1H); 7.01 (dd, J = 1.1, 8.4, 1H); 4.07 (t, J = 6.8, 2H); 4.06 (s, 6H); 1.79 (m, 2H); 1.46 (m, 2H); 0.92 (t, J = 7.4, 3H).Example No: 1.556 (CDCI 3 ): 11.95 (br s, 1H); 7.81 (dd, J = 1.1, 7.8, 1H); 7.36 (br s, 1H); 7.09 (t, J = 8.3, 1H); 7.01 (dd, J = 1.1, 8.4, 1H); 4.07 (t, J = 6.8, 2H); 4.06 (s, 6H); 1.79 (m, 2H); 1.46 (m, 2H); 0.92 (t, J = 7.4, 3H).
Beispiel-Nr.: 1.557(CDCI3): 12.02 (brs, 1H); 7.80 (dd, J = 1.1, 7.8, 1H); 7.44 (brs, 1H); 7.08 (t, J = 8.4, 1H); 6.99 (brd, J = 8.0, 1H); 4.48 (m, 1H); 4.05 (s, 3H); 2.58 (s, 3H); 1.78 (m, 1 H); 1.64 (m, 1 H); 1.27 (d, J = 6.1 , 3H); 0.93 (t, J = 7.5, 3H). Beispiel-Nr.: 1.558 (CDCI3): 12.50 (br s, 1 H); 7.80 (dd, J = 1.1 , 7.8, 1 H); 7.51 (br s, 1 H); 7.06 (t, J = 8.4, 1 H); 6.97 (br d, J = 8.0, 1 H); 6.77 (s, 1 H); 4.46 (m, 1 H); 2.47 (s, 6H); 1.75 (m, 1 H); 1.60 (m, 1 H); 1.24 (d, J = 6.1 , 3H); 0.90 (t, J = 7.5, 3H).Example No: 1.557 (CDCI 3 ): 12.02 (brs, 1H); 7.80 (dd, J = 1.1, 7.8, 1H); 7.44 (brs, 1H); 7.08 (t, J = 8.4, 1H); 6.99 (brd, J = 8.0, 1H); 4.48 (m, 1H); 4.05 (s, 3H); 2.58 (s, 3H); 1.78 (m, 1H); 1.64 (m, 1H); 1.27 (d, J = 6.1, 3H); 0.93 (t, J = 7.5, 3H). Example No: 1.558 (CDCI 3 ): 12.50 (br s, 1H); 7.80 (dd, J = 1.1, 7.8, 1H); 7.51 (br s, 1 H); 7.06 (t, J = 8.4, 1H); 6.97 (br d, J = 8.0, 1 H); 6.77 (s, 1H); 4.46 (m, 1H); 2.47 (s, 6H); 1.75 (m, 1H); 1.60 (m, 1H); 1.24 (d, J = 6.1, 3H); 0.90 (t, J = 7.5, 3H).
Beispiel-Nr.: 1.560 (CDCI3): 11.88 (br s, 1 H); 7.79 (dd, J = 1.1 , 7.8, 1 H); 7.32 (br s, 1 H); 7.07 (t, J = 8.4, 1 H); 6.99 (br d, J = 8.0, 1 H); 4.48 (m, 1 H); 4.06 (s, 6H); 1.81 (m, 1 H); 1.65 (m, 1 H); 1.27 (d, J = 6.1 , 3H); 0.92 (t, J = 7.5, 3H).Example No: 1.560 (CDCI 3 ): 11.88 (br s, 1H); 7.79 (dd, J = 1.1, 7.8, 1H); 7.32 (br s, 1 H); 7.07 (t, J = 8.4, 1H); 6.99 (br d, J = 8.0, 1 H); 4.48 (m, 1H); 4.06 (s, 6H); 1.81 (m, 1H); 1.65 (m, 1H); 1.27 (d, J = 6.1, 3H); 0.92 (t, J = 7.5, 3H).
Beispiel-Nr.: 1.563 (CDCI3): 11.76 (br s, 1 H); 7.82 (dd, J = 1.2, 7.8, 1 H); 7.28 (br s, 1 H); 7.09 (t, J = 8.4, 1H); 7.00 (dd, J = 1.1 , 8.5, 1 H); 6.49 (s, 1 H); 4.00 (s, 3H); 3.84 (d, J = 6.7, 2H); 2.13 (m, 1H); 1.02 (d, J = 6.7, 6H).Example No: 1.563 (CDCI 3 ): 11.76 (br s, 1H); 7.82 (dd, J = 1.2, 7.8, 1H); 7.28 (br s, 1H); 7.09 (t, J = 8.4, 1H); 7.00 (dd, J = 1.1, 8.5, 1H); 6.49 (s, 1H); 4.00 (s, 3H); 3.84 (d, J = 6.7, 2H); 2.13 (m, 1H); 1.02 (d, J = 6.7, 6H).
Beispiel-Nr.: 1.598 (CDCI3): 12.72 (br s, 1 H); 7.65 (d, J = 9.0, 1 H); 7.02 (d, J = 9.0, 1 H); 7.25 (br s, 1 H); 5.81 (s, 1 H); 3.97 (s, 6H); 3.85 (s, 3H).Example No: 1.598 (CDCI 3 ): 12.72 (br s, 1H); 7.65 (d, J = 9.0, 1H); 7.02 (d, J = 9.0, 1H); 7.25 (br s, 1H); 5.81 (s, 1H); 3.97 (s, 6H); 3.85 (s, 3H).
Beispiel-Nr.: 1.599 (CDCI3): 12.45 (br s, 1 H); 9.35 (br s, 1 H); 7.59 (d, J = 9.0, 1 H); 6.75 (d, J = 9.0, 1H); 3.98 (s, 3H); 3.82 (s, 3H); 2.50 (s, 3H).Example No: 1.599 (CDCI 3 ): 12.45 (br s, 1H); 9.35 (br s, 1 H); 7.59 (d, J = 9.0, 1H); 6.75 (d, J = 9.0, 1H); 3.98 (s, 3H); 3.82 (s, 3H); 2.50 (s, 3H).
Beispiel-Nr.: 1.600 (CDCI3): 13.01 (br s, 1 H); 7.64 (d, J = 9.0, 1 H); 7.56 (br s, 1 H); 7.01 (d, J = 9.0, 1 H); 6.78 (s, 1 H); 3.87 (s, 3H); 2.48 (s, 6H).Example No: 1,600 (CDCI 3 ): 13.01 (br s, 1H); 7.64 (d, J = 9.0, 1H); 7.56 (br s, 1 H); 7.01 (d, J = 9.0, 1H); 6.78 (s, 1H); 3.87 (s, 3H); 2.48 (s, 6H).
Beispiel-Nr.: 1.601 (CDCI3): 12.12 (br s, 1 H); 7.66 (d, J = 9.0, 1 H); 7.34 (br s, 1 H); 7.03 (d, J = 9.0, 1 H); 6.51 (s, 1 H); 4.02 (s, 3H); 3.93 (s, 3H).Example No: 1.601 (CDCI 3 ): 12.12 (br s, 1H); 7.66 (d, J = 9.0, 1H); 7.34 (br s, 1 H); 7.03 (d, J = 9.0, 1 H); 6.51 (s, 1H); 4.02 (s, 3H); 3.93 (s, 3H).
Beispiel-Nr.: 1.602 (d6-DMSO): 12.38 (br s, 1H); 10.99 (br s, 1H); 7.87 (d, J = 9.0, 1 H); 7.35 (d, J = 9.2, 1 H); 3.99 (s, 6H); 3.82 (s, 3H). Tabelle 2: Verbindungen der allgemeinen Formel ( II* )Example No: 1.602 (d 6 -DMSO): 12.38 (br s, 1H); 10.99 (br s, 1H); 7.87 (d, J = 9.0, 1H); 7.35 (d, J = 9.2, 1H); 3.99 (s, 6H); 3.82 (s, 3H). Table 2: Compounds of the general formula (II *)
( II* )(II *)
Verbindungen a: Z* = NH2 Compounds a: Z * = NH 2
Verbindungen b: Z* = NH-tert. ButylCompounds b: Z * = NH-tert. butyl
Verbindungen c: Z* = NH-C(O)O-PhenylCompounds c: Z * = NH-C (O) O-phenyl
Verbindungen d: Z* = NH-C(S)O-PhenylCompounds d: Z * = NH-C (S) O-phenyl
Verbindungen e: Z* = NCOCompounds e: Z * = NCO
Verbindungen f: Z* = NCSConnections f: Z * = NCS
1H-NMR Daten: 1 H-NMR data:
Beispiel-Nr.: 2.001a (d6-DMSO): 7.96 (dt, J = 0.9, 7.8, 1 H); 7.78 (br s, 2H); 7.43Example No: 2.001a (d 6 -DMSO): 7.96 (dt, J = 0.9, 7.8, 1H); 7.78 (br s, 2H); 7:43
(ddd, J = 1.1 , 8.3, 11.2, 1 H); 7.28 (dt, J = 5.4, 8.0, 1 H).(ddd, J = 1.1, 8.3, 11.2, 1H); 7.28 (dt, J = 5.4, 8.0, 1 H).
Beispiel-Nr: 2.004a (d6-DMSO): 7.89 (brd, J = 7.8, 1H); 7.55 (td, J = 0.9, 7.6, 1H); 7.49 (br s, 2H); 7.40 (td, J = 1.2, 7.9, 1H), 3.34 (s, 3H).Example No.: 2.004a (d 6 -DMSO): 7.89 (brd, J = 7.8, 1H); 7.55 (td, J = 0.9, 7.6, 1H); 7.49 (br s, 2H); 7.40 (td, J = 1.2, 7.9, 1H), 3.34 (s, 3H).
Beispiel-Nr.: 2.063a (d6-DMSO): 8.48 (dd, J = 1.0, 7.9, 1H); 7.95 (dd, J = 1.0, 8.0, 1H); 7.74 (br s, 2H); 7.39 (brt, J = 8.3, 1H).Example No: 2.063a (d 6 -DMSO): 8.48 (dd, J = 1.0, 7.9, 1H); 7.95 (dd, J = 1.0, 8.0, 1H); 7.74 (br s, 2H); 7.39 (brt, J = 8.3, 1H).
Beispiel-Nr.: 2.092a (d6-DMSO): 7.70 (dd, J = 1.1, 7.7, 1H); 7.25 (dd, J = 0.9, 8.4, 1H); 7.20 (brs, 2H); 7.17 (t, J = 7.9, 1H); 3.90 (s, 3H).Example No: 2.092a (d 6 -DMSO): 7.70 (dd, J = 1.1, 7.7, 1H); 7.25 (dd, J = 0.9, 8.4, 1H); 7.20 (brs, 2H); 7.17 (t, J = 7.9, 1H); 3.90 (s, 3H).
Beispiel-Nr.: 2.094a (d6-DMSO): 7.70 (dd, J = 1.0, 7.8, 1H); 7.26 (brd, J = 8.4, 1H); 7.15 (t, J = 8.0, 1H); 7.03 (br s, 2H); 4.23 (q, J = 7.0, 2H); 1.37 (t, J = 6.9, 3H).Example No: 2.094a (d 6 -DMSO): 7.70 (dd, J = 1.0, 7.8, 1H); 7.26 (brd, J = 8.4, 1H); 7.15 (t, J = 8.0, 1H); 7.03 (br s, 2H); 4.23 (q, J = 7.0, 2H); 1.37 (t, J = 6.9, 3H).
Beispiel-Nr.: 2.095a (d6-DMSO): 7.70 (dd, J = 1.0, 7.8, 1H); 7.26 (dd, J = 0.9, 8.4, 1H); 7.15 (t, J = 7.9, 1H); 6.98 (brs, 2H); 4.12 (t, J = 6.6, 2H); 1.80 (m, 2H); 0.96 (t, J = 7.4, 3H).Example No: 2.095a (d 6 -DMSO): 7.70 (dd, J = 1.0, 7.8, 1H); 7.26 (dd, J = 0.9, 8.4, 1H); 7.15 (t, J = 7.9, 1H); 6.98 (brs, 2H); 4.12 (t, J = 6.6, 2H); 1.80 (m, 2H); 0.96 (t, J = 7.4, 3H).
Beispiel-Nr.: 2.096a (d6-DMSO): 7.69 (dd, J = 1.0, 1H); 7.29 (brd, J = 8.1, 1H); 7.14 (t, J = 8.0, 1H); 6.91 (brs, 2H); 4.82 (m, 1H); 1.34 (d, J = 6.0, 6H).Example No: 2.096a (d 6 -DMSO): 7.69 (dd, J = 1.0, 1H); 7.29 (brd, J = 8.1, 1H); 7.14 (t, J = 8.0, 1H); 6.91 (brs, 2H); 4.82 (m, 1H); 1.34 (d, J = 6.0, 6H).
Beispiel-Nr.: 2.098a (CDCI3): 7.70 (dd, J = 1.0, 7.8, 1H); 7.27 (dd, J = 0.9, 8.4, 1H); 7.16 (t, J = 8.0, 1H); 6.97 (s, 2H); 4.16 (t, J = 6.7, 2H); 1.77 (m, 2H); 1.42 (m, 2H); 0.92 (t, J = 7.4, 3H).Example No: 2.098a (CDCI 3 ): 7.70 (dd, J = 1.0, 7.8, 1H); 7.27 (dd, J = 0.9, 8.4, 1H); 7.16 (t, J = 8.0, 1H); 6.97 (s, 2H); 4.16 (t, J = 6.7, 2H); 1.77 (m, 2H); 1.42 (m, 2H); 0.92 (t, J = 7.4, 3H).
Beispiel-Nr.: 2.099a (CDCI3): 7.74 (m, 1H); 7.06 (m, 2H); 5.38 (s, 2H); 4.58 (m, 1H); 1.82 (m, 2H); 1.40 (d, J = 6.1, 3H); 1.03 (t, J = 7.5, 3H).Example No: 2.099a (CDCI 3 ): 7.74 (m, 1H); 7.06 (m, 2H); 5.38 (s, 2H); 4.58 (m, 1H); 1.82 (m, 2H); 1.40 (d, J = 6.1, 3H); 1.03 (t, J = 7.5, 3H).
Beispiel-Nr.: 2.100a (CDCI3): 7.77 (dd, J = 1.6, 7.2, 1H); 7.06 (m, 2H); 5.36 (brs, 2H); 3.94 (d, J = 6.5, 2H); 2.20 (spt, J = 6.5, 1H); 1.10 (d, J = 6.8, 6H). Beispiel-Nr.: 2.128a (de-DMSO): 7.71 (dd, J = 1.1, 7.8, 1H); 7.27 (dd, J = 1.1, 8.4, 1H); 7.15 (t, J = 7.8, 1H); 7.01 (brs, 2H); 4.04 (d, J = 7.2, 2H); 1.33 (m, 1H); 0.56 (m, 2H); 0.36 (m, 2H).Example No: 2.100a (CDCI 3 ): 7.77 (dd, J = 1.6, 7.2, 1H); 7.06 (m, 2H); 5.36 (brs, 2H); 3.94 (d, J = 6.5, 2H); 2.20 (spt, J = 6.5, 1H); 1.10 (d, J = 6.8, 6H). Example No: 2.128a (d e -DMSO): 7.71 (dd, J = 1.1, 7.8, 1H); 7.27 (dd, J = 1.1, 8.4, 1H); 7.15 (t, J = 7.8, 1H); 7.01 (brs, 2h); 4.04 (d, J = 7.2, 2H); 1.33 (m, 1H); 0.56 (m, 2H); 0.36 (m, 2H).
Beispiel-Nr.: 2.182a (d6-DMSO): 8.19 (dd, J = 1.1, 7.9, 1H); 7.67 (brs, 2H); 7.55 (dt, J = 1.3, 8.3, 1 H); 7.34 (t, J = 8.1, 1 H).Example No: 2.182a (d 6 -DMSO): 8.19 (dd, J = 1.1, 7.9, 1H); 7.67 (brs, 2H); 7.55 (dt, J = 1.3, 8.3, 1 H); 7.34 (t, J = 8.1, 1 H).
Beispiel-Nr.: 2.184a (CDCI3): 7.96 (dd, J = 1.2, 8.0, 1H); 7.25 (m, 1H); 7.07 (t, J = 8.1, 1H); 6.51 (t, J = 73.8, 1H); 6.37 (brs, 2H).Example No: 2.184a (CDCI 3 ): 7.96 (dd, J = 1.2, 8.0, 1H); 7.25 (m, 1H); 7.07 (t, J = 8.1, 1H); 6.51 (t, J = 73.8, 1H); 6.37 (brs, 2h).
Beispiel-Nr: 2.186a (d6-DMSO): 7.84 (dd, J = 0.9, 7.9, 1H); 7.40 (brd, J = 8.2, 1H);Example No. 2.186a (d 6 -DMSO): 7.84 (dd, J = 0.9, 7.9, 1H); 7.40 (brd, J = 8.2, 1H);
7.23 (t, J = 8.0, 1 H); 7.07 (br s, 2H); 4.99 (q, J = 8.8, 2H).7.23 (t, J = 8.0, 1H); 7.07 (br s, 2H); 4.99 (q, J = 8.8, 2H).
Beispiel-Nr.: 2.187a (d6-DMSO): 7.79 (dd, J = 1.0, 7.8, 1 H); 7.35 (dd, J = 0.8, 8.4, 1H); 7.20 (t, J = 7.9, 1H); 7.10 (brs, 2H); 6.53 (tt, J = 3.7, 54.7, 1H); 4.51 (td, J = 3.7, 14.3, 2H).Example No: 2.187a (d 6 -DMSO): 7.79 (dd, J = 1.0, 7.8, 1H); 7.35 (dd, J = 0.8, 8.4, 1H); 7.20 (t, J = 7.9, 1H); 7.10 (brs, 2H); 6.53 (tt, J = 3.7, 54.7, 1H); 4.51 (td, J = 3.7, 14.3, 2H).
Beispiel-Nr.: 2.189a (d6-DMSO): 7.83 (dd, J = 0.8, 7.9, 1H); 7.46 (brd, J = 8.3, 1H); 7.22 (t, J = 8.1, 1 H); 6.91 (br s, 2H); 5.50 (m, 1 H); 1.48 (d, J = 6.4, 3H).Example No: 2.189a (d 6 -DMSO): 7.83 (dd, J = 0.8, 7.9, 1H); 7.46 (brd, J = 8.3, 1H); 7.22 (t, J = 8.1, 1H); 6.91 (br s, 2H); 5.50 (m, 1H); 1.48 (d, J = 6.4, 3H).
Beispiel-Nr.: 2.192a (d6-DMSO): 7.85 (dd, J = 1.0, 7.9, 1H); 7.42 (brd, J = 8.3, 1H);Example No: 2.192a (d 6 -DMSO): 7.85 (dd, J = 1.0, 7.9, 1H); 7.42 (brd, J = 8.3, 1H);
7.24 (t, J = 8.0, 1 H); 7.00 (br s, 2H); 5.07 (t, J = 13.9, 2H).7.24 (t, J = 8.0, 1H); 7.00 (br s, 2H); 5.07 (t, J = 13.9, 2H).
Beispiel-Nr.: 2.208a (de-DMSO): 7.95 (dd, J = 0.9, 7.7, 1 H); 7.46 (m, 3H); 7.12 (t, J = 7.9, 1H); 2.41 (s, 3H).Example No: 2.208a (d e -DMSO): 7.95 (dd, J = 0.9, 7.7, 1H); 7.46 (m, 3H); 7.12 (t, J = 7.9, 1H); 2.41 (s, 3H).
Beispiel-Nr: 2.259a (d6-DMSO): 8.13 (dd, J = 1.2, 7.9, 1H); 7.60 (brs, 2H); 7.53 (dd, J = 1.2, 8.2, 1 H); 7.31 (t, J = 8.0, 1 H); 3.53 (s, 3H).Example No. 2.259a (d 6 -DMSO): 8.13 (dd, J = 1.2, 7.9, 1H); 7.60 (brs, 2H); 7.53 (dd, J = 1.2, 8.2, 1 H); 7.31 (t, J = 8.0, 1H); 3.53 (s, 3H).
Beispiel-Nr.: 2.279a (d6-DMSO): 8.07 (dd, J = 1.2, 7.9, 1H); 7.52 (dd, J = 1.2, 8.2, 1H); 7.19 (t, J = 8.1, 1H); 5.48 (br s, 2H); 3.10 (s, 6H). Beispiel-Nr: 2.300a (CDCI3): 9.91 (s, 1H); 7.60 (m, 1H); 7.05 (m, 2H); 5.49 (brs, 2H).Example No: 2.279a (d 6 -DMSO): 8.07 (dd, J = 1.2, 7.9, 1H); 7.52 (dd, J = 1.2, 8.2, 1H); 7.19 (t, J = 8.1, 1H); 5.48 (br s, 2H); 3.10 (s, 6H). Example No. 2.300a (CDCI 3 ): 9.91 (s, 1H); 7.60 (m, 1H); 7.05 (m, 2H); 5.49 (brs, 2h).
Beispiel-Nr.: 2.301a (d6-DMSO): 7.76 (d, J = 9.0, 1H); 7.30 (d, J = 9.0, 1H); 7.30 (br s, 2H); 3.91 (s, 3H).Example No: 2.301a (d 6 -DMSO): 7.76 (d, J = 9.0, 1H); 7.30 (d, J = 9.0, 1H); 7.30 (br s, 2H); 3.91 (s, 3H).
Beispiel-Nr.: 2.302a (CDCI3): 7.39 (d, J = 8.5, 1H); 7.00 (d, J = 8.5, 1H); 5.43 (brs, 2H); 4.00 (s, 3H); 2.52 (s, 3H).Example No: 2.302a (CDCI 3 ): 7.39 (d, J = 8.5, 1H); 7.00 (d, J = 8.5, 1H); 5.43 (brs, 2H); 4.00 (s, 3H); 2.52 (s, 3H).
Beispiel-Nr.2.001b (d6-DMSO): 7.99 (dt, J = 0.7, 7.7, 1H); 7.79 (brs, 1H); 7.42 (ddd, J = 1.1, 8.1, 11.0, 1H); 7.28 (td, J = 5.1, 7.7, 1 H); 1.13 (s, 9H).Example No. 2.001b (d 6 -DMSO): 7.99 (dt, J = 0.7, 7.7, 1H); 7.79 (brs, 1H); 7.42 (ddd, J = 1.1, 8.1, 11.0, 1H); 7.28 (td, J = 5.1, 7.7, 1H); 1.13 (s, 9H).
Beispiel-Nr.2.004b (d6-DMSO): 7.92 (dd, J = 1.1, 7.7, 1H); 7.55 (m, 2H); 7.39 (m, 1H); 3.31 (s, 3H); 1.14 (s, 9H).Example No. 2,004b (d 6 -DMSO): 7.92 (dd, J = 1.1, 7.7, 1H); 7.55 (m, 2H); 7.39 (m, 1H); 3.31 (s, 3H); 1.14 (s, 9H).
Beispiel-Nr.2.063b (d6-DMSO): 8.49 (dd, J = 1.1, 7.7, 1H); 7.97 (dd, J = 1.1, 8.1, 1 H); 7.78 (br s, 1 H); 7.40 (td, J = 0.7, 8.1 , 1 H); 1.07 (s, 9H).Example No. 2.063b (d 6 -DMSO): 8.49 (dd, J = 1.1, 7.7, 1H); 7.97 (dd, J = 1.1, 8.1, 1H); 7.78 (br s, 1 H); 7.40 (td, J = 0.7, 8.1, 1H); 1.07 (s, 9H).
Beispiel-Nr.2.092b (CDCI3): 7.80 (m, 1H); 7.06 (m, 2H); 5.28 (brs, 1H); 3.99 (s, 3H); 1.22 (s, 9H).Example No. 0.292b (CDCI 3 ): 7.80 (m, 1H); 7.06 (m, 2H); 5.28 (brs, 1H); 3.99 (s, 3H); 1.22 (s, 9H).
Beispiel-Nr.2.182b (CDCI3): 8.12 (dd, J = 0.8, 8.0, 1H); 7.41 (dt, J = 0.8, 8.0, 1H); 7.18 (t, J = 8.0, 1H); 5.12 (brs, 1H); 1.27 (s, 9H).Example No. 2.182b (CDCI 3 ): 8.12 (dd, J = 0.8, 8.0, 1H); 7.41 (dt, J = 0.8, 8.0, 1H); 7.18 (t, J = 8.0, 1H); 5.12 (brs, 1H); 1.27 (s, 9H).
Beispiel-Nr.2.208b (CDCI3): 7.96 (dd, J = 1.0, 7.5, 1 H); 7.35 (dd, J = 0.7, 8.5, 1 H); 7.00 (t, J = 7.8, 1 H); 5.74 (br s, 1 H); 2.47 (s, 3H); 1.25 (s, 9H).Example No. 2,208b (CDCI 3 ): 7.96 (dd, J = 1.0, 7.5, 1H); 7.35 (dd, J = 0.7, 8.5, 1H); 7.00 (t, J = 7.8, 1H); 5.74 (br s, 1 H); 2.47 (s, 3H); 1.25 (s, 9H).
Beispiel-Nr.: 2.301b (CDCI3): 7.61 (d, J = 8.9, 1H); 7.04 (d, J = 8.9, 1H); 5.43 (brs, 1H); 4.00 (s, 3H); 1.22 (s, 9H).Example No: 2.301b (CDCI 3 ): 7.61 (d, J = 8.9, 1H); 7.04 (d, J = 8.9, 1H); 5.43 (brs, 1H); 4.00 (s, 3H); 1.22 (s, 9H).
Beispiel-Nr.: 2.302b (CDCI3): 7.37 (dd, J = 0.5, 8.5, 1H); 6.97 (d, J = 8.5, 1H); 5.45 (br s, 1 H); 3.97 (s, 3H); 2.53 (s, 3H); 1.21 (s, 9H). B. FormulierungsbeispieleExample No: 2.302b (CDCI 3 ): 7.37 (dd, J = 0.5, 8.5, 1H); 6.97 (d, J = 8.5, 1H); 5.45 (br s, 1 H); 3.97 (s, 3H); 2.53 (s, 3H); 1.21 (s, 9H). B. Formulation Examples
a) Ein Stäubemittel wird erhalten, indem man 10 Gew.-Teile einer Verbindung der Formel (I) und/oder deren Salze und 90 Gew.-Teile Talkum als Inertstoff mischt und in einer Schlagmühle zerkleinert.a) A dust is obtained by mixing 10 parts by weight of a compound of formula (I) and / or salts thereof and 90 parts by weight of talc as inert material and comminuted in a hammer mill.
b) Ein in Wasser leicht dispergierbares, benetzbares Pulver wird erhalten, indem man 25 Gewichtsteile einer Verbindung der Formel (I) und/oder deren Salze, 64 Gew.-Teile kaolinhaltigen Quarz als Inertstoff, 10 Gewichtsteile ligninsulfonsaures Kalium und 1 Gew.-Teil oleoylmethyltaurinsaures Natrium als Netz- und Dispergiermittel mischt und in einer Stiftmühle mahlt.b) A wettable powder readily dispersible in water is obtained by reacting 25 parts by weight of a compound of formula (I) and / or its salts, 64 parts by weight of kaolin-containing quartz as inert material, 10 parts by weight of potassium lignosulfonate and 1 part by weight Mix oleoylmethyl tauric acid sodium as wetting and dispersing agent and mill in a pin mill.
c) Ein in Wasser leicht dispergierbares Dispersionskonzentrat wird erhalten, indem man 20 Gew.-Teile einer Verbindung der Formel (I) und/oder deren Salze mit 6 Gew. -Teilen Alkylphenolpolyglykolether (©Triton X 207), 3c) A dispersion concentrate readily dispersible in water is obtained by reacting 20 parts by weight of a compound of the formula (I) and / or salts thereof with 6 parts by weight of alkylphenol polyglycol ether (© Triton X 207), 3
Gew.-Teilen Isotridecanolpolyglykolether (8 EO) und 71 Gew.-Teilen paraffinischem Mineralöl (Siedebereich z.B. ca. 255 bis über 277 C) mischt und in einer Reibkugelmühle auf eine Feinheit von unter 5 Mikron vermahlt.Parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to more than 277 C) and ground in a ball mill to a fineness of less than 5 microns.
d) Ein emulgierbares Konzentrat wird erhalten aus 15 Gew.-Teilen einer Verbindung der Formel (I) und/oder deren Salze, 75 Gew.-Teilen Cyclohexanon als Lösungsmittel und 10 Gew.-Teilen oxethyliertes Nonylphenol als Emulgator.d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I) and / or salts thereof, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.
e) Ein in Wasser dispergierbares Granulat wird erhalten indem mane) A water-dispersible granules are obtained by
75 Gew.-Teile einer Verbindung der Formel (I) und/oder deren Salze, 10 Gew.-Teile ligninsulfonsaures Calcium, 5 Gew.-Teile Natriumlaurylsulfat, 3 Gew.-Teile Polyvinylalkohol und 7 Gew.-Teile Kaolin mischt, auf einer Stiftmühle mahlt und das Pulver in einem Wirbelbett durch Aufsprühen von Wasser als Granulierflüssigkeit granuliert. f) Ein in Wasser dispergierbares Granulat wird auch erhalten, indem man 25 Gew.-Teile einer Verbindung der Formel (I) und/oder deren Salze, 5 Gew.-Teile 2,21-dinaphthylmethan-6,6'-disulfonsaures Natrium 2 Gew.-Teile oleoylmethyltaurinsaures Natrium,75 parts by weight of a compound of formula (I) and / or salts thereof, 10 parts by weight of calcium lignosulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol and 7 parts by weight of kaolin mixed on one Grinds pin mill and the powder granulated in a fluidized bed by spraying water as Granulierflüssigkeit. f) Water-dispersible granules are also obtained by mixing 25 parts by weight of a compound of formula (I) and / or salts thereof, 5 parts by weight 2.2 1 -dinaphthylmethan-6,6'-disulfonate, sodium 2 parts by weight oleoylmethyltaurine acid sodium,
1 Gew.-Teil Polyvinylalkohol, 17 Gew.-Teile Calciumcarbonat und 50 Gew.-Teile Wasser auf einer Kolloidmühle homogenisiert und vorzerkleinert, anschließend auf einer Perlmühle mahlt und die so erhaltene Suspension in einem Sprühturm mittels einer Einstoffdüse zerstäubt und trocknet.1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water homogenized on a colloid mill and pre-crushed, then grinded on a bead mill and the resulting suspension in a spray tower by means of a Einstoffdüse atomized and dried.
C. Biologische BeispieleC. Biological examples
1. Unkrautwirkung im Vorauflauf1. weed effect in pre-emergence
Samen bzw. Rhizomstücke von mono- und dikotylen Unkrautpflanzen wurden in Papptöpfen in sandiger Lehmerde ausgelegt und mit Erde abgedeckt. Die in Form von benetzbaren Pulvern oder Emulsionskonzentraten formulierten erfindungsgemäßen Verbindungen wurden dann als wäßrige Suspensionen bzw. Emulsionen mit einer Wasseraufwandmenge von umgerechnet 600 bis 800 l/ha in unterschiedlichen Dosierungen auf die Oberfläche der Abdeckerde appliziert.Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants were placed in sandy soil in cardboard pots and covered with soil. The compounds of the invention formulated in the form of wettable powders or emulsion concentrates were then applied to the surface of the cover soil as aqueous suspensions or emulsions having a water application rate of 600 to 800 l / ha in different dosages.
Nach der Behandlung wurden die Töpfe im Gewächshaus aufgestellt und unter guten Wachstumsbedingungen für die Unkräuter gehalten. Die optische Bonitur der Pflanzen- bzw. Auflaufschäden erfolgte nach dem Auflaufen der Versuchspflanzen nach einer Versuchszeit von 3 bis 4 Wochen im Vergleich zu unbehandelten Kontrollen. Wie die Ergebnisse zeigen, weisen erfindungsgemäße Verbindungen eine gute herbizide Vorauflaufwirksamkeit gegen ein breites Spektrum vonAfter the treatment, the pots were placed in the greenhouse and kept under good growth conditions for the weeds. The optical assessment of the plant damage and / or the emergence damage occurred after emergence of the test plants after a test time of 3 to 4 weeks in comparison to untreated controls. As the results show, compounds according to the invention have a good herbicidal pre-emergence activity against a broad spectrum of
Ungräsern und Unkräutern auf. Beispielsweise haben die Verbindungen Nr. 1.001 , 1.002, 1.003, 1.004, 1.012, 1.016, 1.020, 1.021 , 1.025, 1.091 , 1.095, 1.099, 1.100, 1.104, 1.146, 1.150, 1.154, 1.155, 1.159, 1.164, 1.165, 1.166, 1.167, 1.168, 1.171 , 1.173, 1.174, 1.175, 1.178, 1.182, 1.186, 1.187, 1.191 , 1.192, 1.196, 1.197, 1.229, 1.233, 1.237, 1.238, 1.242, 1.302, 1.306, 1.310, 1.311 , 1.315, 1.321, 1.325, 1.329, 1.330, 1.342, 1.343, 1.344, 1.352, 1.353, 1.354, 1.355, 1.362, 1.363, 1.364, 1.365, 1.366, 1.370, 1.371 , 1.372, 1.373, 1.389, 1.390, 1.463, 1.471 , 1.472, 1.476, 1.507, 1.509, 1.510, 1.511 , 1.550, 1.551 , 1.553, 1.554, 1.555, 1.556, 1.557, 1.558, 1.560, 1.563, 1.598, 1.599, 1.600, 1.601 , 1.602 und andere Verbindungen aus Tabelle 1 sehr gute herbizide Wirkung gegen Schadpflanzen wie Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria viridis, Abutilon theophrasti, Amaranthus retroflexus und Panicum miliaceum im Vorauflaufverfahren bei einer Aufwandmenge von 0.3 kg und weniger Aktivsubstanz pro Hektar.Weeds and weeds. For example, compounds Nos. 1.001, 1.002, 1.003, 1.004, 1.012, 1.016, 1.020, 1.021, 1.025, 1.091, 1.095, 1.099, 1.100, 1,104, 1,146, 1,150, 1,154, 1,155, 1,159, 1,164, 1,165,1166,1167,1168,1171,1173,1174,175, 1,178,1182,1186,1187,1191,192,119,197,1229,1233, 1.237, 1.238, 1.242, 1.302, 1.306, 1.310, 1.311, 1.315, 1.321, 1.325, 1.329, 1.330, 1.342, 1.343, 1.344, 1.352, 1.353, 1.354, 1.355, 1.362, 1.363, 1.364, 1.365, 1.366, 1.370, 1.371, 1.372, 1.373, 1.389, 1.390, 1.463, 1.471, 1.472, 1.476, 1.507, 1.509, 1.510, 1.511, 1.550, 1.551, 1.553, 1.554, 1.555, 1.556, 1.557, 1.558, 1.560, 1.563, 1.598, 1.599, 1.600, 1.601, 1.602 and other compounds from Table 1 have very good herbicidal activity against harmful plants such as Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria viridis, Abutilon theophrasti, Amaranthus retroflexus and Panicum miliaceum im Pre-emergence method at an application rate of 0.3 kg and less active substance per hectare.
2. Unkrautwirkung im Nachauflauf2. weed effect postemergence
Samen bzw. Rhizomstücke von mono- und dikotylen Unkräutern wurden in Plastiktöpfen in sandigem Lehmboden ausgelegt, mit Erde abgedeckt und im Gewächshaus unter guten Wachstumsbedingungen angezogen. Drei Wochen nach der Aussaat wurden die Versuchspflanzen im Dreiblattstadium behandelt. Die als Spritzpulver bzw. als Emulsionskonzentrate formulierten erfindungsgemäßen Verbindungen wurden in verschiedenen Dosierungen mit einer Wasseraufwandmenge von umgerechnet 600 bis 800 l/ha auf die grünen Pflanzenteile gesprüht. Nach ca. 3 bis 4 Wochen Standzeit der Versuchspflanzen im Gewächshaus unter optimalen Wachstumsbedingungen wurde die Wirkung der Präparate optisch im Vergleich zu unbehandelten Kontrollen bonitiert. Die erfindungsgemäßen Mittel weisen auch im Nachauflauf eine gute herbizide Wirksamkeit gegen ein breites Spektrum wirtschaftlich wichtiger Ungräser und Unkräuter auf. Beispielsweise haben die Verbindungen Nr. 1.001 , 1.002, 1.003, 1.004, 1.012, 1.016, 1.020, 1.021 , 1.025, 1.091 , 1.095, 1.099, 1.100, 1.104, 1.146, 1.150, 1.154, 1.155, 1.159, 1.164, 1.165, 1.166, 1.167, 1.168, 1.171 , 1.173, 1.174, 1.175, 1.178, 1.182, 1.186, 1.187, 1.191 , 1.192, 1.196, 1.197, 1.229, 1.233, 1.237, 1.238, 1.242, 1.302, 1.306, 1.310, 1.311 , 1.315, 1.321 , 1.325, 1.329, 1.330, 1.342, 1.343, 1.344, 1.352, 1.353, 1.354, 1.355, 1.362, 1.363, 1.364, 1.365, 1.366, 1.370, 1.371 , 1.372, 1.373, 1.389, 1.390, 1.463, 1.471 , 1.472, 1.476, 1.507, 1.509, 1.510, 1.511 , 1.550, 1.551 , 1.553, 1.554, 1.555, 1.556, 1.557, 1.558, 1.560, 1.5631.598, 1.599, 1.600, 1.601 , 1.602 und andere Verbindungen aus Tabelle 1 sehr gute herbizide Wirkung gegen Schadpflanzen wie Sinapis alba, Echinochloa crus-galli, Lolium multiflorum, Chrysanthemum segetum, Setaria viridis, Abutilon theophrasti, Amaranthus retroflexus, Panicum miliaceum und Avena sativa im Nachauflaufverfahren bei einer Aufwandmenge von 0.3 kg und weniger Aktivsubstanz pro Hektar.Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds were placed in sandy loam soil in plastic pots, covered with soil and grown in the greenhouse under good growth conditions. Three weeks after sowing, the test plants were treated at the trefoil stage. The compounds of the invention formulated as wettable powders or as emulsion concentrates were sprayed onto the green plant parts in various dosages with a water application rate of 600 to 800 l / ha. After about 3 to 4 weeks of life of the test plants in the greenhouse under optimal growth conditions, the effect of the preparations was optically scored compared to untreated controls. The compositions according to the invention also have a good herbicidal activity against a broad spectrum of economically important weed grasses and weeds in postemergence. For example, compounds Nos. 1.001, 1.002, 1.003, 1.004, 1.012, 1.016, 1.020, 1.021, 1.025, 1.091, 1.095, 1.099, 1.100, 1.104, 1.146, 1.150, 1.154, 1.155, 1.159, 1.164, 1.165, 1.166, 1,167,1168,1171,173, 1,174,175,1178,1182,1186,1187,1191,1192,1196,197,1229,1233,1237, 1.238, 1.242, 1.302, 1.306, 1.310, 1.311, 1.315, 1.321, 1.325, 1.329, 1.330, 1.342, 1.343, 1.344, 1.352, 1.353, 1.354, 1.355, 1.362, 1.363, 1.364, 1.365, 1.366, 1.370, 1.371, 1.372, 1.373, 1.389, 1.390, 1.463, 1.471, 1.472, 1.476, 1.507, 1.509, 1.510, 1.511, 1.550, 1.551, 1.553, 1.554, 1.555, 1.556, 1.557, 1.558, 1.560, 1.5631.598, 1.599, 1.600, 1.601, 1.602 and other compounds from Table 1 very good herbicidal activity against harmful plants such as Sinapis alba, Echinochloa crus-galli, Lolium multiflorum, Chrysanthemum segetum, Setaria viridis, Abutilon theophrasti, Amaranthus retroflexus, Panicum miliaceum and Avena sativa postemergence at an application rate of 0.3 kg and less active substance per hectare.
3. Kulturpflanzenverträglichkeit3. crop compatibility
In weiteren Versuchen im Gewächshaus wurden Samen einer größeren Anzahl von Kulturpflanzen und Unkräutern in sandigem Lehmboden ausgelegt und mit Erde abgedeckt. Ein Teil der Töpfe wurde sofort wie unter Abschnitt 1 beschrieben behandelt, die übrigen im Gewächshaus aufgestellt, bis die Pflanzen zwei bis drei echte Blätter entwickelt haben und dann wie unter Abschnitt 2 beschrieben mit den erfindungsgemäßen Verbindungen in unterschiedlichen Dosierungen besprüht. Vier bis fünf Wochen nach der Applikation und Standzeit im Gewächshaus wurde mittels optischer Bonitur festgestellt, daß erfindungsgemäßeIn further experiments in the greenhouse, seeds of a larger number of crops and weeds were laid in sandy loam soil and covered with soil. One part of the pots was treated immediately as described in Section 1, the rest in the greenhouse until the plants have developed two to three true leaves and then sprayed as described in Section 2 with the compounds of the invention in different dosages. Four to five weeks after the application and life in the greenhouse was determined by optical Bonitur that invention
Verbindungen zweikeimblättrige Kulturen wie Soja, Baumwolle, Raps, Zuckerrüben oder Kartoffeln im Vor- und Nachauflaufverfahren selbst bei hohen Wirkstoffdosierungen ungeschädigt ließen. Einige Substanzen schonten darüber hinaus auch Gramineen-Kulturen wie Gerste, Weizen, Roggen, Hirsen, Mais oder Reis. Die erfindungsgemäßen Verbindungen zeigen teilweise eine hohe Selektivität und eignen sich deshalb zur Bekämpfung von unerwünschten Pflanzenwuchs in landwirtschaftlichen Kulturen. Connections dicotyledonous crops such as soybean, cotton, oilseed rape, sugar beets or potatoes in the pre- and postemergence process even with high doses of active ingredient undamaged. In addition, some substances also protect graminaceous crops such as barley, wheat, rye, millet, corn or rice. Some of the compounds according to the invention show high selectivity and are therefore suitable for controlling undesired plant growth in agricultural crops.

Claims

Patentansprüche claims
1. Verbindung der Formel (I) und/oder deren Salze1. Compound of the formula (I) and / or salts thereof
worin wherein
R ein Kohlenwasserstoffrest oder Kohlenwasserstoffoxyrest ist, der unsubstituiert oder substituiert ist und inklusive Substituenten 1 bis 30 C- Atome aufweist, oder ein Heterocyclylrest oder Heterocyclyloxyrest ist, welcher unsubstituiert oder substituiert ist, oder R ein Rest OC(O)R3, S(O)nR3, OS(O)nR3, F, Br, I1 OH, CN, NO2, NH2, SF5, NR4R5 oder Si(R6)3 ist, wobei n gleich 0, 1 oder 2 ist,R is a hydrocarbon radical or hydrocarbonoxy radical which is unsubstituted or substituted and has substituents including 1 to 30 carbon atoms, or is a heterocyclyl radical or heterocyclyloxy radical which is unsubstituted or substituted, or R is a radical OC (O) R 3 , S (O ) n R 3 , OS (O) n R 3 , F, Br, I 1 is OH, CN, NO 2 , NH 2 , SF 5 , NR 4 R 5 or Si (R 6 ) 3 , where n is 0, 1 or 2,
R1 unabhängig voneinander Halogen, OH, SH, ein kohlenstofffreier stickstoffhaltiger Rest oder ein kohlenstoffhaltiger Rest sind, der 1 bis 30 C- Atome aufweist,R 1, independently of one another, are halogen, OH, SH, a carbon-free nitrogen-containing radical or a carbon-containing radical which has 1 to 30 C atoms,
I 0, 1 , 2 oder 3 ist,I is 0, 1, 2 or 3,
R2 ein Wasserstoffatom oder ein Kohlenwasserstoffrest ist, der unsubstituiert oder substituiert ist und inklusive Substituenten 1 bis 20 C-Atome aufweist,R 2 is a hydrogen atom or a hydrocarbon radical which is unsubstituted or substituted and, including substituents, has 1 to 20 C atoms,
R3 ein Kohlenwasserstoffrest oder Kohlenwasserstoffoxyrest ist, der unsubstituiert oder substituiert ist und inklusive Substituenten 1 bis 30 C-R 3 is a hydrocarbon radical or Kohlenwasserstoffoxyrest which is unsubstituted or substituted and including substituents 1 to 30 C
Atome aufweist, oder ein Heterocylylrest oder Heterocylyloxyrest ist, welcher unsubstituiert oder substituiert ist, oder R3 ein Wasserstoffatom, CN oder NR4R5 ist,Has atoms, or is a heterocyclyl or heterocylyloxy radical which is unsubstituted or substituted, or R 3 is a hydrogen atom, CN or NR 4 R 5 ,
R4 eine Gruppe der Formel R°-Q°- ist, worin R0 ein Wasserstoffatom, ein Acylrest, ein Kohlenwasserstoffrest oder einR 4 is a group of the formula R ° -Q ° - wherein R 0 is a hydrogen atom, an acyl radical, a hydrocarbon radical or a
Heterocyclylrest bedeutet, wobei jeder der letztgenannten beiden Reste unsubstituiert oder substituiert ist und inklusive Substituenten 1 bis 30 C- Atome aufweist, und Q0 eine direkte Bindung oder eine divalente Gruppe der Formel -O- oder - N(R#)- bedeutet, wobei R# ein Wasserstoffatom, ein Acylrest oder ein Kohlenwasserstoffrest bedeutet und wobei der letztgenannte Rest unsubstituiert oder substituiert ist und inklusive Substituenten 1 bis 30 C- Atome aufweist, oder R0 und R# miteinander einen stickstoffhaltigen heterocyclischen Ring bilden,Heterocyclylrest means, wherein each of the latter two radicals is unsubstituted or substituted and including substituents 1 to 30 carbon atoms, and Q 0 represents a direct bond or a divalent group of the formula -O- or -N (R # ) -, wherein R # represents a hydrogen atom, an acyl radical or a hydrocarbon radical and wherein the latter radical is unsubstituted or substituted and includes substituents 1 to Has 30 C atoms, or R 0 and R # together form a nitrogen-containing heterocyclic ring,
R5 ein Wasserstoffatom, ein Acylrest, ein Kohlenwasserstoffrest oder ein Heterocyclylrest ist, wobei jeder der letztgenannten beiden Reste unsubstituiert oder substituiert ist und inklusive Substituenten 1 bis 30 C- Atome aufweist, oderR 5 is a hydrogen atom, an acyl radical, a hydrocarbon radical or a heterocyclyl radical, each of the last-mentioned two radicals being unsubstituted or substituted and having, including substituents, 1 to 30 C atoms, or
R4 und R5 miteinander einen stickstoffhaltigen heterocyclischen Ring bilden,R 4 and R 5 together form a nitrogen-containing heterocyclic ring,
R6 ein Kohlenwasserstoffrest ist, der unsubstituiert oder substituiert ist und inklusive Substituenten 1 bis 30 C-Atome aufweist,R 6 is a hydrocarbon radical which is unsubstituted or substituted and, including substituents, has 1 to 30 C atoms,
W ein Sauerstoffatom oder ein Schwefelatom ist, X,Y unabhängig voneinander für ein Wasserstoffatom, Halogen, (d-CeJAlkyl, (C1- Cβ)Alkoxy oder (d-CβJAlkylthio ist, wobei jeder der letztgenannten 3 Reste unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, (Ci-C4)Alkoxy, und (CrC4)Alkylthio substituiert ist, oder Mono- oder Di[(Cr C6)alkyl] amino, (C2-C6)Alkenyl, (C2-C6)Alkinyl, (C3-C6)Alkenyloxy oder (C3- Cβ)Alkinyloxy bedeuten, undW is oxygen or sulfur; X, Y are independently hydrogen, halogen, (C 1 -C 6 alkyl, (C 1 -C 6) alkoxy or (C 1 -C 6 alkylthio), each of the last 3 being unsubstituted or substituted by one or more Radicals from the group halogen, (Ci-C 4 ) alkoxy, and (CrC 4 ) alkylthio substituted, or mono- or di [(Cr C 6 ) alkyl] amino, (C 2 -C 6 ) alkenyl, (C 2 -C 6) alkynyl, (C 3 -C 6) alkenyloxy or (C 3 - mean Cβ) alkynyloxy, and
V,Z unabhängig voneinander CH oder N bedeuten.V, Z are independently CH or N
2. Verbindung der Formel (I) und/oder deren Salze gemäß Anspruch 1 , worin R (CrC6)Alkyl, (C2-C6)Alkenyl, (C2-C6)AI kinyl, (C3-C6)Cycloalkyl, (C3- C6)Cycloalkenyl, (C3-C6)Cycloalkinyl, (CrC6)Alkyloxy, (C2-C6)Alkenyloxy, (C2-2. A compound of the formula (I) and / or salts thereof according to Claim 1, in which R (C r C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 - C 6) cycloalkyl, (C 3 - C 6) cycloalkenyl, (C 3 -C 6) cycloalkynyl, (CrC 6) alkyloxy, (C 2 -C 6) alkenyloxy, (C 2 -
C6)Alkinyloxy, (C3-C6)Cycloalkyloxy, Phenyl, Phenyloxy, F, Br, I, OH, CN, NO2, NH2, SF5, Si((CrC6)Alkyl)3, N((CrC6)Alkyl)2l NH(CrC6)Alkyl, N((C2- C6)Alkenyl)2, NH(C2-C6)Alkenyl, N((C2-C6)Alkinyl)2, NH(C2-C6)Alkinyl, NH((C3- C6)Cycloalkyl)2, NH(C3-C6)Cycloalkyl, N(CrC6)Alkyl (C3-C6)Cycloalkyl, N(C1- C6)Alkyl C(O)R3, NHC(O)R3, N(CrC6)Alkyl S(O)nR3, NHS(O)nR3, S(O)n(C1-C 6 ) alkynyloxy, (C 3 -C 6 ) cycloalkyloxy, phenyl, phenyloxy, F, Br, I, OH, CN, NO 2 , NH 2 , SF 5 , Si ((C 1 -C 6 ) alkyl) 3 , N (( CrC 6) alkyl) 2l NH (C r C6) alkyl, N ((C 2 - C 6) alkenyl) 2, NH (C 2 -C 6) alkenyl, N ((C 2 -C 6) alkynyl) 2 , NH (C 2 -C 6) alkynyl, NH ((C 3 - C 6) cycloalkyl) 2, NH (C 3 -C 6) cycloalkyl, N (C r C6) alkyl (C 3 -C 6) cycloalkyl , N (C 1 -C 6 ) alkyl C (O) R 3 , NHC (O) R 3 , N (C r C 6 ) alkyl S (O) n R 3 , NHS (O) n R 3 , S ( O) n (C 1 -
C4)Alkyl, S(O)n (C3-C6)Cycloalkyl, S(O)n(CrC6)Alkenyl, S(O)n(CrC6)Alkinyl, S(O)nNHR3, S(O)nN(CrC6)Alkyl R3, OSO2(CrC6)Alkyl, OSO2(C3- C6)Cycloalkyl, OSO2(Ci-C6)Alkenyl, OSO2(C1-C6)AIkJnYl, OS(O)nPhenyl, OSO2N((Ci-C6)Alkyl)2l OSO2NH(C1-C6)AIkYl1 OSO2N((C3-C6)Cycloalkyl)2, OSO2NH(C3-C6)Cycloalkyl, OSO2N((C2-C6)Alkenyl)2l OSO2NH(C2-C6)AlkenylI OSO2N((C2-C6)Alkinyl)2> OSO2NH(C2-C6)Alkinyl, OC(O)R3 oder Heterocyclyl bedeutet, wobei die genannten Reste Alkyl, Alkenyl, Alkinyl, Cycloalkyl,C 4) alkyl, S (O) n (C 3 -C 6) cycloalkyl, S (O) n (CrC 6) alkenyl, S (O) n (CrC 6) alkynyl, S (O) n NHR 3, S (O) n N (C r C 6 ) alkyl R 3 , OSO 2 (C r C 6 ) alkyl, OSO 2 (C 3 - C 6 ) cycloalkyl, OSO 2 (C 1 -C 6 ) alkenyl, OSO 2 (C 1 -C 6 ) alkynyl, OS (O) n phenyl, OSO 2 N ((C 1 -C 6 ) alkyl) 2 L OSO 2 NH (C 1 -C 6 ) AlKyl 1 OSO 2 N ((C 3 -C 6 ) cycloalkyl) 2, OSO 2 NH (C 3 -C 6 ) cycloalkyl, OSO 2 N ((C 2 -C 6 ) alkenyl) 2l OSO 2 NH (C 2 -C 6 ) alkenyl I OSO 2 N ((C 2 -C 6 ) alkynyl) 2> OSO 2 NH (C 2 -C 6 ) alkynyl, OC (O) R 3 or heterocyclyl, where the radicals mentioned Alkyl, alkenyl, alkynyl, cycloalkyl,
Cycloalkenyl, Cycloalkinyl, Alkyloxy, Alkenyloxy, Alkinyloxy, Cycloalkoxy, Phenyl, Phenyloxy, Heterocyclyl unsubstituiert sind oder substituiert sind,Cycloalkenyl, cycloalkynyl, alkyloxy, alkenyloxy, alkynyloxy, cycloalkoxy, phenyl, phenyloxy, heterocyclyl are unsubstituted or substituted,
R1 (C1-C6)AIkYl, (CrC6)Haloalkyl, (CrC6)Alkyloxy, (C1-C6)HaIOaIkOXy oderR 1 (C 1 -C 6 ) AlKyl, (C r C 6 ) haloalkyl, (CrC 6 ) alkyloxy, (C 1 -C 6 ) haloalkoxy or
Halogen ist, I 0, 1 oder 2 ist, n 0, 1 oder 2 ist,Is halogen, I is 0, 1 or 2, n is 0, 1 or 2,
R2 H oder CH3 ist,R 2 is H or CH 3 ,
R3 H1 (C1-C6)AIkYl, (C2-C6)Alkenyl, (C2-C6)Alkinyl, (C3-C6)Cycloalkyl, (C1-R 3 H 1 (C 1 -C 6 ) AlKyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 6 ) cycloalkyl, (C 1 -
C6)Alkyloxy, (C2-C6)Alkenyloxy, (C2-C6)Alkinyloxy, (C3-C6)Cycloalkyloxy, Phenyl, Heterocyclyl, CN, NH(CrC6)Alkyl, N((CrC6)Alkyl)2 steht, wobei die genannten Reste Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Alkyloxy, Alkenyloxy, Alkinyloxy, Cycloalkyloxy, Phenyl, Heterocyclyl unsubstituiert oder substituiert sind,C 6 ) alkyloxy, (C 2 -C 6 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy, (C 3 -C 6 ) cycloalkyloxy, phenyl, heterocyclyl, CN, NH (C r C 6 ) alkyl, N (( C r C 6 ) alkyl) 2 , where the abovementioned radicals alkyl, alkenyl, alkynyl, cycloalkyl, alkyloxy, alkenyloxy, alkynyloxy, cycloalkyloxy, phenyl, heterocyclyl are unsubstituted or substituted,
W ein Sauerstoffatom ist, X,Y unabhängig voneinander (C1-C4)AIkYl, (CrC4)Alkyloxy, wobei jeder der letztgenannten zwei Reste unsubstituiert oder durch einen oder mehrere Halogenatome substituiert ist, oder (CrC4)Alkylthio, Halogen oder NH(C1- C4)Alkyl oder N((CrC4)Alkyl)2 bedeuten, undW is an oxygen atom, X, Y are independently (C 1 -C 4) -alkyl, (CrC 4) alkyloxy, wherein each of the two last-mentioned radicals is unsubstituted or by one or more halogen atoms, or (CrC 4) alkylthio, halogen or NH (C 1 -C 4 ) alkyl or N ((C r C 4 ) alkyl) 2 , and
V1Z unabhängig voneinander CH oder N bedeuten.V 1 Z are independently CH or N.
3. Verbindung der Formel (I) und/oder deren Salze gemäß Anspruch 1 oder 2, worin3. A compound of formula (I) and / or salts thereof according to claim 1 or 2, wherein
R (CrC4)Alkyl, (C2-C4)Alkenyl, (C2-C4)Alkinyl, (C3-C6)Cycloalkyl, (C1-R (C r C4) alkyl, (C 2 -C 4) alkenyl, (C 2 -C 4) alkynyl, (C 3 -C 6) cycloalkyl, (C 1 -
C4)Alkyloxy, (C2-C4)Alkenyloxy, (C2-C4)Alkinyloxy, (C3-C6)Cycloalkyloxy, Phenyl, Phenyloxy, F, Br, I, CN, NO2, NH2, N((CrC4)Alkyl)2, N H(C1 -C4)AI kyl,C 4 ) alkyloxy, (C 2 -C 4 ) alkenyloxy, (C 2 -C 4 ) alkynyloxy, (C 3 -C 6 ) cycloalkyloxy, phenyl, phenyloxy, F, Br, I, CN, NO 2 , NH 2 , N ((C r C 4) alkyl) 2, NH (C 1 -C 4) alkyl AI,
NH(C2-C4)Alkenyl, NH(C2-C4)Alkinyl, NH(C3-C6)Cycloalkyl, N(CrC4)Alkyl (C3- C6)Cycloalkyl, S(C1 -C4)AI kyl, S(C2-C4)Alkenyl, S(C2-C4)Alkinyl, S(C3- C6)Cycloalkyl, S(O)(CrC4)Alkyl, S(O)(Ci-C4)Alkenyl, S(O)(C2-C4)Alkinyl, S(O)(C3-C6)Cycloalkyl, Sθ2(CrC4)Alkyl, SO2(C2-C4)Alkenyl, SO2(C2- C4)Alkinyl, SO2(C3-C6)Cycloalkyl, SO2NH(CrC4)Alkyl, SO2N((CrC4)Alkyl)2, SO2NH(C3-C6)Cycloalkyl, OSO2(Ci-C4)Alkyl, OSO2NH(Ci-C4)Alkyl, OSO2N((CrC4)Alkyl)2 oder NHC(O)R3, NHSO2R3, OC(O)R3, worin R3 gleich H1 (CrC4)Alkyl, (C2-C4)Alkenyl, (C2-C4)Alkinyl, (C3- C6)Cycloalkyl, (CrC4)Alkyloxy, (C2-C4)Alkenyloxy, (C2-C4)Alkinyloxy, (C3- C6)Cycloalkyloxy, (CrC4)Haloalkyl, NH(d-C4)Alkyl oder N((CrC4)Alkyl)2 ist, wobei die genannten Reste Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Alkyloxy, Alkenyloxy, Alkinyloxy, Cycloalkyloxy, Phenyl, Phenyloxy unsubstituiert sind oder substituiert sind,NH (C 2 -C 4 ) alkenyl, NH (C 2 -C 4 ) alkynyl, NH (C 3 -C 6 ) cycloalkyl, N (C r C 4 ) alkyl (C 3 -C 6 ) cycloalkyl, S (C 1 -C 4 ) alkyl, S (C 2 -C 4 ) alkenyl, S (C 2 -C 4 ) alkynyl, S (C 3 - C 6) cycloalkyl, S (O) (CrC 4) alkyl, S (O) (Ci-C 4) alkenyl, S (O) (C 2 -C 4) alkynyl, S (O) (C 3 -C 6 ) cycloalkyl, Sθ2 (CRC4) alkyl, SO 2 (C 2 -C 4) alkenyl, SO 2 (C 2 - C 4) alkynyl, SO 2 (C 3 -C 6) cycloalkyl, SO 2 NH (C r C 4 ) alkyl, SO 2 N ((C r C 4) alkyl) 2, SO 2 NH (C 3 -C 6) cycloalkyl, OSO 2 (Ci-C 4) alkyl, OSO 2 NH (Ci-C 4) alkyl, OSO 2 N ((C r C 4) alkyl) 2 or NHC (O) R 3, NHSO 2 R 3, OC (O) R 3 wherein R 3 is H 1 (C r C4) alkyl, (C 2 -C 4) alkenyl, (C 2 -C 4) alkynyl, (C 3 - C 6) cycloalkyl, (C r C 4) alkyloxy, (C 2 -C 4) alkenyloxy, (C 2 -C 4) alkynyloxy, (C 3 -C 6 ) cycloalkyloxy, (C r C 4 ) haloalkyl, NH (dC 4 ) alkyl or N ((C 1 -C 4 ) alkyl) 2 , wherein said radicals alkyl, alkenyl, alkynyl, cycloalkyl, alkyloxy, alkenyloxy , Alkynyloxy, cycloalkyloxy, phenyl, phenyloxy are unsubstituted or substituted,
R1 Halogen, (CrC4)Alkyl, (CrC4)Alkyloxy, (CrC4)Haloalkyl, (CrC4)Haloalkyloxy,R 1 is halogen, (C r C 4 ) alkyl, (C r C 4 ) alkyloxy, (C r C 4 ) haloalkyl, (C r C 4 ) haloalkyloxy,
I O oder 1 , vorzugsweise O ist,I is O or 1, preferably O,
R2 H oder (CrC4)Alkyl wie Methyl, W ein Sauerstoffatom,R 2 is H or (C r C 4 ) alkyl, such as methyl, W is an oxygen atom,
X1Y unabhängig voneinander (Ci-C4)Alkyl, (CrC4)Haloalkyl, (Ci-C4)Alkyloxy, (Cr C4)Haloalkyloxy, Halogen, (CrC4)Alkylthio, NH(CrC4)Alkyl, N((CrC4)Alkyl)2,X 1 Y are independently (Ci-C 4) alkyl, (CrC 4) haloalkyl, (Ci-C 4) alkoxy, (Cr C4) haloalkyloxy, halogen, (C r C4) alkylthio, NH (C r C 4 ) Alkyl, N ((C r C 4 ) alkyl) 2 ,
V ein Stickstoffatom, undV is a nitrogen atom, and
Z CH oder N bedeuten.Z is CH or N
4. Verbindung der Formel (I) und/oder deren Salze gemäß einem oder mehreren der Ansprüche 1 bis 3, worin4. A compound of formula (I) and / or salts thereof according to one or more of claims 1 to 3, wherein
R CH3, CH2CH3, (CH2)2CH3, CH(CH3)2, C(CH3)3, CH=CH2, C≡CH, CH2CH=CH2,R is CH 3 , CH 2 CH 3 , (CH 2 ) 2 CH 3 , CH (CH 3 ) 2 , C (CH 3 ) 3 , CH = CH 2 , C≡CH, CH 2 CH = CH 2 ,
CH2C=CH, Cyclopropyl, Phenyl, F, Br, I, CN, NO2, NH2, CH2OCH3, CF3, CHF2, NHCH3, N(CH3)2, NH-cyclopropyl, N(CH3)-cyclopropyl, NHC(O)H,CH 2 C = CH, cyclopropyl, phenyl, F, Br, I, CN, NO 2 , NH 2 , CH 2 OCH 3 , CF 3 , CHF 2 , NHCH 3 , N (CH 3 ) 2 , NH-cyclopropyl, N (CH 3 ) -cyclopropyl, NHC (O) H,
NHC(O)CH3, NHC(O)OCH3, NHSO2CH3, NHSO2CF3, NHSO2CHF2, OCH3, OCH2CH3, O(CH2)2CH3) OCH(CH3)2, O(CH2)3CH3, OCH2CH(CH3)2l OCH(CH3)CH2CH3, OC(CH3)3, OCH=CH2, OC≡CH, OCH2CH=CH2, OCH2C=CH, O-cyclopropyl, OCH^cyclopropyl, O(CH2)2CI, O(CH2)3CI, OCH2OCH3, OPhenyl, OCH2Phenyl, OCF3, OCHF2, OCH2F, OCH2CF3,NHC (O) CH 3 , NHC (O) OCH 3 , NHSO 2 CH 3 , NHSO 2 CF 3 , NHSO 2 CHF 2 , OCH 3 , OCH 2 CH 3 , O (CH 2 ) 2 CH 3) OCH (CH 3 ) 2 , O (CH 2 ) 3 CH 3 , OCH 2 CH (CH 3 ) 2 L OCH (CH 3 ) CH 2 CH 3 , OC (CH 3 ) 3 , OCH = CH 2 , OC≡CH, OCH 2 CH = CH 2, OCH 2 C = CH, O-cyclopropyl, OCH ^ cyclopropyl, O (CH 2) 2 Cl, O (CH 2) 3 CI, OCH 2 OCH 3, OPhenyl, OCH 2 phenyl, OCF 3, OCHF 2, OCH 2 F, OCH 2 CF 3 ,
OCH2CHF2, OCH(CH3)CF3, OCH2CF2CF3, SCH3, SCH2CH3, S(O)CH3, S(O)CH2CH3, SO2CH3, SO2CH2CH3, SO2NHCH3, SO2N(CH3)2, SO2NHCF3, SO2NHCHF2, OSO2CH3, OSO2CF3, OSO2CHF2, OSO2N(CH3)2, OSO2NHCF3, OSO2NHCHF2, OC(O)H1 OC(O)CH3, OC(O)OCH3, OC(O)N(CH3)2,OCH 2 CHF 2 , OCH (CH 3 ) CF 3 , OCH 2 CF 2 CF 3 , SCH 3 , SCH 2 CH 3 , S (O) CH 3 , S (O) CH 2 CH 3 , SO 2 CH 3 , SO 2 CH 2 CH 3 , SO 2 NHCH 3 , SO 2 N (CH 3 ) 2 , SO 2 NHCF 3 , SO 2 NHCHF 2 , OSO 2 CH 3 , OSO 2 CF 3 , OSO 2 CHF 2 , OSO 2 N (CH 3 ) 2 , OSO 2 NHCF 3 , OSO 2 NHCHF 2 , OC (O) H 1 OC (O) CH 3 , OC (O) OCH 3 , OC (O) N (CH 3 ) 2 ,
I O,I O,
R2 H, W Sauerstoff,R 2 H, W oxygen,
X1Y unabhängig voneinander CH3, CH2CH3, CF3, CHF2, CH2CF3, CH2CHF2,X 1 Y independently of one another CH 3 , CH 2 CH 3 , CF 3 , CHF 2 , CH 2 CF 3 , CH 2 CHF 2 ,
OCH3, OCH2CH3, OCF3, OCHF2, OCH2CF3, OCH2CHF2, F, Cl, Br, I1 SCH3, NHCH3, N(CH3)2, vorzugsweise CH3, OCH3, OCH2CH3, Cl, N(CH3)2,OCH 3 , OCH 2 CH 3 , OCF 3 , OCHF 2 , OCH 2 CF 3 , OCH 2 CHF 2 , F, Cl, Br, I 1 SCH 3 , NHCH 3 , N (CH 3 ) 2 , preferably CH 3 , OCH 3 , OCH 2 CH 3 , Cl, N (CH 3 ) 2 ,
V N, und Z CH oder N bedeuten.V N, and Z is CH or N
5. Verfahren zur Herstellung einer Verbindung der Formel (I) und/oder deren Salze, wie in einem oder mehreren der Ansprüche 1 bis 4 definiert, wobei man5. A process for the preparation of a compound of formula (I) and / or salts thereof as defined in one or more of claims 1 to 4, wherein
a) eine Verbindung der Formel (II)a) a compound of the formula (II)
mit einem heterocyclischen (Thio)Carbamat der Formel (III),with a heterocyclic (thio) carbamate of the formula (III),
worin R* ein substituierter oder unsubstituierter CrC2o-Kohlenwasserstoffrest bedeutet, umsetzt, oderwherein R * represents a substituted or unsubstituted CrC 2 o hydrocarbon radical, or
b) ein Sulfonyl(thio)carbamat der Formel (IV), b) a sulfonyl (thio) carbamate of the formula (IV),
worin R** ein substituierter oder unsubstituierter C-i-Cao-Kohlenwasserstoffrest bedeutet, mit einem Aminoheterocyclus der Formel (V)in which R ** denotes a substituted or unsubstituted C 1 -C 20 -hydrocarbon radical, with an aminoheterocycle of the formula (V)
umsetzt, oder implements, or
c) ein Sulfonyliso(thio)cyanat der Formel (VI)c) a sulfonyliso (thio) cyanate of the formula (VI)
mit einem Aminoheterocyclus der Formel (V) umsetzt, oderwith an amino heterocycle of formula (V), or
d) ein Sulfonamid der Formel (II) mit einem lso(thio)cyanat der Formel (VII)d) a sulfonamide of the formula (II) with an iso (thio) cyanate of the formula (VII)
in Gegenwart einer Base umsetzt, oder e) einen Aminoheterocyclus der Formel (V) zunächst basenkatalysiert mit einem Kohlensäureester umsetzt und das gebildete Intermediat in einer Eintopfreaktion mit einem Sulfonamid der Formel (II) (siehe Variante a) umsetzt, oderin the presence of a base, or e) first reacting an aminoheterocycle of the formula (V) base-catalyzed with a carbonic acid ester and reacting the intermediate formed in a one-pot reaction with a sulfonamide of the formula (II) (see variant a), or
f) ein Sulfonsäurehalogenid der Formel (VIII),f) a sulfonic acid halide of the formula (VIII)
wobei HaI ein Halogenatom ist, mit einem (Thio)Cyanat, zu einem lso(thio)cyanat der Formel (VI) oder einem solvatisierten (stabilisierten) Derivat davon umsetzt, und dieses anschließend mit einem Aminoheterocyclus der Formel (V) umsetzt,wherein Hal is a halogen atom, with a (thio) cyanate, to a lso (thio) cyanate of the formula (VI) or a solvated (stabilized) derivative thereof, and then reacted with an amino heterocycle of the formula (V),
wobei in den Formeln (II) bis (VIII) die Reste, Gruppen bzw. Indizes R, R1, R2, V, W, X, Y, Z und I wie in Formel (I) gemäß einem oder mehreren der Ansprüche 1 bis 4 definiert sind.in formulas (II) to (VIII) the radicals, groups or indices R, R 1 , R 2 , V, W, X, Y, Z and I as in formula (I) according to one or more of claims 1 to 4 are defined.
6. Agrochemisches Mittel, enthaltend a) mindestens eine Verbindung der Formel (I) und/oder deren Salze, wie in einem oder mehreren der Ansprüche 1 bis 4 definiert, und b) im Pflanzenschutz übliche Hilfs- und Zusatzstoffe.6. Agrochemical composition containing a) at least one compound of formula (I) and / or salts thereof, as defined in one or more of claims 1 to 4, and b) in crop protection customary auxiliaries and additives.
7. Agrochemisches Mittel, enthaltend a) mindestens eine Verbindung der Formel (I) und/oder deren Salze, wie in einem oder mehreren der Ansprüche 1 bis 4 definiert, und b) einen oder mehrere von Komponente a) verschiedene agrochemische Wirkstoffe, und optional c) im Pflanzenschutz übliche Hilfs- und Zusatzstoffe.7. An agrochemical composition comprising a) at least one compound of the formula (I) and / or salts thereof as defined in one or more of claims 1 to 4, and b) one or more agrochemical active ingredients other than component a), and optionally c) auxiliaries and additives customary in plant protection.
8. Verfahren zur Bekämpfung von unerwünschten Pflanzen oder zur Wachstumsregulierung von Pflanzen, wobei eine wirksame Menge von mindestens einer Verbindung der Formel (I) und/oder deren Salze, wie in einem oder mehreren der Ansprüche 1 bis 4 definiert, auf die Pflanzen, das Saatgut oder die Fläche, auf der die Pflanzen wachsen, appliziert wird.8. A method for controlling undesirable plants or for regulating the growth of plants, wherein an effective amount of at least one compound of formula (I) and / or salts thereof, as in one or more of claims 1 to 4, is applied to the plants, the seed or the area on which the plants grow.
9. Verwendung von Verbindungen der Formel (I) und/oder deren Salze, wie in einem oder mehreren der Ansprüche 1 bis 4 definiert, als Herbizide oder9. Use of compounds of the formula (I) and / or salts thereof as defined in one or more of claims 1 to 4, as herbicides or
Pflanzenwachstumsregulatoren.Plant growth regulators.
10. Verwendung nach Anspruch 9, wobei die Verbindungen der Formel (I) und/oder deren Salze zur Bekämpfung von Schadpflanzen oder zur Wachstumsregulierung in Pflanzenkulturen eingesetzt werden.10. Use according to claim 9, wherein the compounds of the formula (I) and / or salts thereof are used for controlling harmful plants or for regulating growth in plant crops.
11. Verwendung nach Anspruch 10, wobei die Kulturpflanzen transgene oder nicht transgene Kulturpflanzen sind.11. Use according to claim 10, wherein the crop plants are transgenic or non-transgenic crop plants.
12. Verwendung einer Verbindung der Formel (II*)12. Use of a compound of the formula (II *)
worin Z* = NH2, NH-tert. Butyl, NH-C(O)OR**, NH-C(S)OR**, NCO, NCS oder Halogen bedeutet und R, R1 und der Index I wie in Formel (I) gemäß einem oder mehreren der Ansprüche 1 bis 4 definiert sind und R** wie in Formel (IV) in wherein Z * = NH 2 , NH-tert. Butyl, NH-C (O) OR **, NH-C (S) OR * * , NCO, NCS or halogen and R, R 1 and the index I as in formula (I) according to one or more of claims 1 to 4 and R * * are as in formula (IV) in
Anspruch 5 definiert ist, zur Herstellung einer Verbindung der Formel (I) und/oder deren Salze wie in einem oder mehreren der Ansprüche 1 bis 4 definiert.Claim 5, for the preparation of a compound of formula (I) and / or salts thereof as defined in one or more of claims 1 to 4.
13. Verbindung der Formel (II*) wie in Anspruch 12 definiert, wobei ausgenommen sind Verbindungen worin Z*=NH2, I=O und R ein Rest NH2, NH-CO- CO-O-C2H5, O(CH2)2F, O(CH2)3F bedeutet, oder worin Z*=NH2 oder Chlor und R = lod bedeutet, oder worin Z*=CI, I=O und R=CF3 bedeutet. 13. A compound of the formula (II *) as defined in claim 12, wherein excluded are compounds wherein Z * = NH 2 , I = O and R is a radical NH 2 , NH-CO-CO-OC 2 H 5 , O (CH 2 ) 2 F, O (CH 2 ) 3 F, or wherein Z * = NH 2 or chlorine and R = iodine, or wherein Z * = CI, I = O and R = CF 3 .
EP06724419A 2005-04-28 2006-04-19 Herbicidally active phenylsulphonyl-urea Ceased EP1877386A1 (en)

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EP05009272A EP1717232A1 (en) 2005-04-28 2005-04-28 Phenylsulfonylureas with herbicidal activity
EP06724419A EP1877386A1 (en) 2005-04-28 2006-04-19 Herbicidally active phenylsulphonyl-urea
PCT/EP2006/003564 WO2006114220A1 (en) 2005-04-28 2006-04-19 Herbicidally active phenylsulphonyl-urea

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EP1717232A1 (en) 2006-11-02
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