WO1997019076A1 - Isoxazole-4-yl-benzoyl derivatives and the use thereof as herbicides - Google Patents

Isoxazole-4-yl-benzoyl derivatives and the use thereof as herbicides Download PDF

Info

Publication number
WO1997019076A1
WO1997019076A1 PCT/EP1996/005069 EP9605069W WO9719076A1 WO 1997019076 A1 WO1997019076 A1 WO 1997019076A1 EP 9605069 W EP9605069 W EP 9605069W WO 9719076 A1 WO9719076 A1 WO 9719076A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
alkoxy
haloalkyl
haloalkoxy
nitro
Prior art date
Application number
PCT/EP1996/005069
Other languages
German (de)
French (fr)
Inventor
Martina Otten
Wolfgang Von Deyn
Stefan Engel
Regina Luise Hill
Uwe Kardorff
Marcus Vossen
Peter Plath
Helmut Walter
Karl-Otto Westphalen
Ulf Misslitz
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU76271/96A priority Critical patent/AU7627196A/en
Publication of WO1997019076A1 publication Critical patent/WO1997019076A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

  • the present invention relates to new isoxazol-4-yl-benzoyl derivatives with herbicidal activity, processes for the preparation of the isoxazol-4-yl-benzoyl derivatives, compositions which contain them and the use of these derivatives or compositions 10 containing them for weed control / weed control .
  • Herbicidal isoxazolylbenzoyl derivatives are known from the literature, for example from EP 609797 and EP 636622.
  • the task was to find new isoxazolylbenzoyl derivatives with 20 improved properties.
  • L, M is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, these groups optionally having one to five halogen atoms or C 1 -C 4 alkoxy can be substituted; Halogen, cyano, nitro, a group 35 - (A) m -S (0) n R 1 or a group- (A) - "- CO-R 2 ;
  • n zero, one or two;
  • R 2 C ⁇ -C 4 alkyl, C ! -C 4 - haloalkyl, C ⁇ -C 4 alkoxy or NR 14 ;
  • R 3 is hydrogen, -NR 9 R 4 ; C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C ! -C 6 haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl; mono- to polysubstituted phenyl, where the substituents can consist of C ⁇ -C 4 alkyl,
  • R 5 , R 6 independently of one another hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 4 haloalkyl, C 2 -C 6 haloalkenyl, Ci-C ⁇ i-alkoxy, Ci-Ce-haloalkoxy; mono- to polysubstituted phenyl, where the substituents can consist of -CC 4 alkyl, -C ⁇ C 4 -alkoxy, -C-C 4 -haloalkoxy, -C-C 4 -haloalkyl, halogen, cyano, nitro; mono- to polysubstituted benzyl, where the substituents can consist of C 1 -C 4 -alkyl,
  • R 7 are hydrogen, C 6 -alkyl, ⁇ C 4 -alkoxy, C 4 haloalkyl, C ⁇ -C4-haloalkoxy; optionally substituted phenyl, where the substituents can consist of one to three halogens, C ⁇ -C 4 alkyl, C ⁇ ⁇ C 4 alkoxy, Ci-C 4 haloalkoxy, nitro; R 7 and R 21 or R 7 and R 23 or R 7 and R 12 can form a bond;
  • R 8 is hydrogen, C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, substituted phenyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; Substituted benzyl where the substituents can consist of C 1 -C 4 -alkyl,
  • Ri °, RiJ- independently of one another hydrogen, Ci-C ⁇ -alkyl; Phenyl optionally substituted with one to three halogens,
  • R 10 and R 12 or R 10 and R 23 or R 10 and R 21 may form a bond;
  • R 12 , R 13 independently of one another are hydrogen, C 1 -C 6 -alkyl,
  • C 1 -C 6 haloalkyl C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy; given . -. appropriate, substituted phenyl wherein the substituents C ⁇ -C may consist of C ⁇ ⁇ C 4 -alkyl, C ⁇ 4 alkoxy, C ⁇ ⁇ C4 alkoxy -Halo-, 4 -haloalkyl, halogen, cyano, nitro;
  • R 21 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy; optionally substituted phenyl where the substituents can consist of -CC 4 alkyl,
  • R 22 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy; optionally substituted phenyl where the substituents can consist of -CC 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
  • R 23 is hydrogen, -C 6 alkyl, C 2 -C 6 alkenyl, -C 6 alkoxy; optionally substituted with C ⁇ -C 4 -alkyl, C 4 -alkoxy, C 4 -Halo- alkoxy, C ⁇ -C 4 haloalkyl, halo, cyano, nitro substi ⁇ tutechnischs phenyl or benzyl, -
  • R 15 for hydrogen or -C0 2 R 17 , -CC 4 alkyl
  • R 16 for hydrogen, C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl, which may optionally be substituted by one or more halogen atoms or -CC 4 alkyl and
  • R 17 represents Ci-C 4 alkyl
  • J is a carbonyl radical CO or a radical -CHR 18 ;
  • R 1 ⁇ denotes an OH group, a hydroxyl group optionally acylated with C 2 -C 4 ⁇ acyl or a chlorine atom;
  • Benzoic acids of the formula III can be prepared as follows:
  • A1C1 3 or SnCl 4 are preferred as Lewis acids and polyphosphoric acid and sulfuric acid are preferred as protonic acid according to Can. J. Chem. 1981, 59, 199; Chem. Ber. 1925, 58, 1625; Chem. Ber. 1926, 59, 1074; Phosp. and sulf. 1984,
  • Thiochromenonic acids can still be obtained e.g. Elimination of hydrogen halide from 3-halothiochromanonic acids or e.g. by reacting the substituted thiophenolic acids with substituted ⁇ -alkylacetoacetic esters in the presence of phosphorus pentoxide according to Ann. Chem. 1964, 680, 40.
  • the arylthio compounds IV can be obtained, for example, by means of a Sandmeyer reaction from corresponding anilines, which in turn are synthesized by reduction of suitable nitro compounds in accordance with Organikum 19th edition 1992, 552ff.
  • the reactants and the base are expediently used in equimolar amounts.
  • the reaction mixture is preferably stirred at 20-100 ° C., in particular at 20-40 ° C.
  • the work-up is carried out, for example, by pouring the reaction mixture onto 5 water, acidifying the aqueous phase with mineral acids such as hydrochloric acid or sulfuric acid and suctioning off the product of value or by extraction with methylene chloride or Extracted ethyl acetate, dried and freed from the solvent.
  • the ester can be reacted without further purification.
  • the thiochromenone ester can be converted by, for example, reacting an arylthio compound with an acetylenecarboxylic acid derivative React water or solvent at a temperature of 0-140 ° C.
  • Working up is carried out in a manner known per se by adding water and dilute mineral acid such as hydrochloric acid.
  • the product of value is either suctioned off or obtained by extraction with methylene chloride or ethyl acetate, followed by drying and removal of the solvent.
  • the intermediates of formula III can be obtained by reactions known from the literature, such as reduction according to Jerry March "Advanced Organic Chemistry, Fourth Ed., E.g. S.910ff, oximation according to Jerry March” Advanced Organic Chemistry, Fourth Ed., E.g. P.934, 935, 1039, 1226, 405ff, conversion into imines and amines according to Jerry-March "Advanced Organic Chemistry, Fourth Ed., Ketalization, alkylation, halogenation, elimination and oxidation according to Jerry March” Advanced Organic Chemistry, Fourth Ed. be further functionalized.
  • the acids of the 3-alkoxy-l, 2-benzisothiazole-l, 1-dioxide or 3-alkoxy-l, 2-benzisothiazoles can, starting from corresponding saccharin derivatives or 1, 2-benzisothiazoles, for example by reaction with PC1 5 , P0C1 3 or chlorine and alcohol can optionally be obtained in the presence of an auxiliary base such as triethylamine, which is described, for example, in US 4,571,429, Arch. Pharm. 1984, 317, 807, US 4461901, US 450916, J. Med. Chem. 1986, 29, 359 Saccharin carboxylic acids can be synthesized according to Ann. Chem. 427, 231, 1922, Chem. Ber.
  • the benzoic acids of the formula III can also be obtained by the corresponding bromo- or iodo-substituted compound of the formula VII
  • T OH, -CC 4 alkoxy Y, L, M, X and n have the meaning described above
  • the catalysts nickel, cobalt, rhodium and in particular palladium can be metallic or in the form of conventional salts such as in the form of halogen compounds, for example PdCl 2 , RhCl 3 -H 2 O, acetates, for example Pd (OAc) 2 , cyanides etc. in the known valence levels available.
  • halogen compounds for example PdCl 2 , RhCl 3 -H 2 O
  • acetates for example Pd (OAc) 2 , cyanides etc. in the known valence levels available.
  • metal complexes with tertiary phosphines, metal alkylcarbonyls, metal carbonyls, for example C0 2 (CO) 8 , Ni (CO) 4 , metal carbonyl complexes with tertiary phosphines, for example (PPh 3 ) 2 Ni (CO) 2 , or excess complexed with tertiary phosphines ⁇ transition metal salts are present.
  • the latter embodiment is particularly preferred in the case of palladium as a catalyst.
  • phosphine ligand The type of phosphine ligand is widely variable. For example, they can be represented by the following formulas:
  • n is the numbers 1, 2, 3 or 4 and the radicals R 24 to R 26 are low molecular weight alkyl, for example C 1 -C 6 -alkyl, aryl, C 1 -C 4 -alkylaryl, for example benzyl, phenethyl or aryloxy.
  • Aryl is, for example, naphthyl, anthryl and preferably optionally substituted phenyl, but the substituents need only be paid attention to their inertness to the carboxylation reaction, otherwise they can be varied widely and include all inert C-organic radicals such as Cx-Ce-alkyl radicals, for example Methyl, carboxyl radicals such as COOH, COOM (M is, for example, an alkali metal, alkaline earth metal or ammonium salt), or C-organic radicals bound via oxygen, such as -CC 6 alkoxy radicals.
  • Cx-Ce-alkyl radicals for example Methyl
  • carboxyl radicals such as COOH, COOM (M is, for example, an alkali metal, alkaline earth metal or ammonium salt)
  • C-organic radicals bound via oxygen such as -CC 6 alkoxy radicals.
  • the phosphine complexes can be prepared in a manner known per se, for example as described in the documents mentioned at the outset.
  • customary commercially available metal salts such as PdCl 2 or Pd (OCOCH 3 ) 2 are used and the phosphine is added, for example P (C 6 H 5 ) 3 , P (nC 4 H 9 ) 3 , PCH 3 (C 6 H 5 ) 2 , 1, 2-bis (diphenylphosphino) ethane added.
  • the amount of phosphine, based on the transition metal is usually 0 to 20, in particular 0.1 to 10 molar equivalents, particularly preferably 1 to 5 molar equivalents.
  • the amount of transition metal is not critical. Of course, for reasons of cost, you will rather get a small amount, e.g. from 0.1 to 10 mol%, in particular 1 to 5 mol%, based on the starting material II or III.
  • the reaction is carried out with carbon monoxide and at least equimolar amounts of water, based on the starting materials VI.
  • the reaction partner water can also serve as a solvent, i.e. the maximum amount is not critical.
  • Suitable inert solvents for carboxylation reactions are customary solvents such as hydrocarbons, for example toluene, xylene, hexane, pentane, cyelohexane, ethers, for example methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted amides such as dimethylformamide, per-substituted ureas such as tetra-C 1 -C 4 - alkylureas or nitriles such as benzonitrile or acetonitrile.
  • one of the reactants, in particular the base is used in excess, so that no additional solvent is required.
  • Suitable bases for the process are all inert bases which are able to bind the hydrogen iodide or hydrogen bromide released during the reaction.
  • tertiary amines such as tert.
  • Alkylamines for example trialkylamines such as triethylamine, cyclic amines such as N-methylpiperidine or N, N '-dimethyl-10 piperazine, pyridine, alkali metal or hydrogen carbonates, or tetra-alkyl-substituted urea derivatives such as tetra-C C-C 4 -alkyl urea, For example, tetramethyl urea.
  • the amount of base is not critical, usually 1 to 15 10, in particular 1 to 5, mol are used. If the base is simultaneously used as solvent, the amount is generally such that the reactants are dissolved, unnecessarily high excesses being avoided for reasons of practicality, in order to save costs, to be able to use small reaction vessels and to have maximum contact with the reactants to ensure.
  • the carbon monoxide pressure at room temperature is preferably 1 to 25 250 bar, in particular 5 to 150 bar CO.
  • the carbonylation is generally carried out continuously or batchwise at temperatures from 20 to 250 ° C., in particular at 30 to 150 ° C.
  • carbon monoxide is expediently pressed continuously onto the reaction mixture in order to maintain a constant pressure.
  • aryl halogen compounds 35 VII used as starting compounds are known or can easily be prepared by a suitable combination of known syntheses and reaction sequences described above.
  • C ⁇ -C 6 alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1.1 -Dimethylpropyl, 1, 2-dimethylpropyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1 , 3-Dimethylbutyl, 2, 2-Dimethylbutyl, 2, 3-Dimethylbutyl, 3, 3-Dimethylbutyl, 1-Ethylbutyl, 1, 1, 2-Trimethylpropyl, 1, 2, 2-TrimethyIpropyl, 1-Ethyl-l-methylpropyl or l-e
  • C 2 -C 6 ⁇ alkenyl such as 2-propenyl, 2-butenyl, 3-butenyl, l-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl,
  • 3-methyl-2-pentenyl 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl -4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, l-dimethyl-2-butenyl, 1, l-dimethyl-3-butenyl, 1 , 2-dimethyl-2-butenyl,
  • C 2 -C 6 alkynyl such as propargyl, 2-butynyl, 3-butenyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, l-methyl- 2-butynyl, 1, l-dimethyl-2-propynyl, l-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, l-methyl-3 pentynyl, l-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1, l-dimethyl-2-butynyl, 1, l-dimethyl-3-butynyl, 1,2 -Dimethyl-3-butyny
  • -C-C 4 alkoxy such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1, 1-dimethylethoxy,
  • these groups can optionally be substituted by one to five halogen atoms such as fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine or C ⁇ -C 4 alkoxy as mentioned above.
  • halogen atoms such as fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine or C ⁇ -C 4 alkoxy as mentioned above.
  • the group - (A) m -S (O) n R 1 defined above stands for example for
  • C ⁇ -C 4 alkylthio such as methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1-methylpropylthio, 2-methylpropylthio and 1, 1-dimethylethylthio, especially methylthio;
  • C ⁇ -C 4 alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl and 1, 1-dimethylethylsulfinyl, especially methylsulfinyl;
  • C ⁇ -C 4 alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1-methylethylsulfonyl, n-butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and 1, 1-dimethylethylsulfonyl, especially methylsulfonyl;
  • C ⁇ -C 4 alkoxysulfonyl such as methoxysulfonyl, ethoxysulfonyl, n-propoxysulfonyl, 1-methylethoxysulfonyl, n-butoxysulfonyl, 1-methylpropoxysulfonyl, 2-methylpropoxysulfonyl and 1, 1-dimethylethoxysulfonyl, especially methoxysulfonyl;
  • N-C ⁇ -C 4 alkylsulfamoyl such as N-methylsulfamoyl, N-ethylsulfamoyl, Nn-propylsulfamoyl, N-1-methylethylsulfamoyl, Nn-butylsulfamoyl, N-1-methylpropylsulfamoyl, N-2-methylpropylsulfamoyl, N-2-methylpropylsulfamoyl , in particular N-methylsulfamoyl,
  • N-C ⁇ -C 4 alkylsulfinamoyl such as N-methylsulfinamoyl, N-ethyl sulfinamoyl, Nn-propylsulfinamoyl, N-1-methylethylsulfinamoyl, Nn-butylsulfinamoyl, N-1-methylpropylsulfinamoyl, N-2-methyl-1-propylsulfinamoyl -Dimethylethylsulfinamoyl, especially N-methylsulfinamoyl;
  • Di-C ⁇ -C 4 alkylsulfamoyl such as dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl, N-methyl-N-ethylsulfamoyl, N-methyl-N-propylsulfamoyl, N-methyl-N-1-methylethylsulfamoyl, N-methyl , 1-dimethylethylsulfamoyl, di-1-methylethylsulfamoyl, N-ethyl-N-1-methylethylsulfamoyl and N-ethyl-N-1, 1-dimethylethylsulfamoyl; especially dimethylsulfamoyl;
  • Di-C ⁇ -C 4 alkylsulfinamoyl such as dimethylsulfinamoyl, Diethyl ⁇ sulfinamoyl, dipropylsulfinamoyl, dibutylsulfinamoyl, N-methyl-N-ethylsulfinamoyl, N-methyl-N-propylsulfinamoyl, N-methyl-N-1-methyll sulfonamoyl -1, 1-dimethylethylsulfinamoyl, di-1-methylethylsulfinamoyl, N-ethyl-N-1-methylethylsulfinamoyl and N-ethyl-N-1, 1-dimethylethylsulfinamoyl; especially dimethylsulfinamoyl,
  • C ⁇ -C 4 alkylsulfinyloxy such as methylsulfinyloxy, ethylsulfinyloxy, n-propylsulfinyloxy, 1-methylethylsulfinyloxy, n-butylsulfinyloxy, 1-methylpropylsulfinyloxy, 2-methylpropylsulfinyloxy and 1, 1-dimethylethylsulfinyloxy, especially methylsulfinyloxy;
  • C ⁇ -C 4 alkylsulfonyloxy such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, 1-methylethylsulfonyloxy, n-butylsulfonyloxy, 1-methylpropylsulfonyloxy, 2-methylpropylsulfonyloxy and 1, 1-dimethyloxysulfonyloxy;
  • C ⁇ -C 4 alkylsulfinylamino such as methylsulfinylamino, ethylsulfinylamino, n-propylsulfinylamino, 1-methylethylsulfinylamino, n-butylsulfinylamino, 1-methylpropylsulfinylamino, 2-methylpropylsulfinylamino and 1, 1-dimethylethylsulfinylamino,
  • C ⁇ ⁇ C 4 alkylsulfonylamino such as methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, 1-methylethylsulfonylamino, n-butylsulfonylamino, 1-methylpropylsulfonylamino, 2-methylpropylsulfonylaminoethyl and 1, 1-dimonaminoethyl;
  • N-C ⁇ -C 4 alkylsulfinyl-N-methyl-amino such as N-methylsulfinyl-N-methyl-amino, N-ethylsulfinyl-N-methyl-amino, Nn-propylsulfinyl-N-methyl-amino, N-1-methylethylsulfinyl -N-methyl-amino, Nn-butylsulfinyl-N-methyl-amino, N-1-methylpropylsulfinyl-N-methyl-amino, N-2-methylpropylsulfinyl-N-methyl-amino and Nl, 1-dimethylethylsulfinyl-N-methyl -amino, especially N-methylsulfinyl-N-methyl-amino;
  • N-C ⁇ -C 4 -AlkyIsulfinyl-N-ethyl-amino such as N-methylsulfinyl-N-ethyl-amino, N-ethylsulfinyl-N-ethyl-amino, Nn-propylsulfinyl-N-ethyl-amino, N-1-methylethylsulfinyl -N-ethyl-amino, Nn-butylsulfinyl-N-ethyl-amino, Nl-methylpropylsulfinyl-N-ethyl-amino, N-2-methylpropylsulfinyl-N-ethyl-amino and Nl, 1-dimethylethylsulfinyl-N-ethyl amino, in particular N-methylsulfinyl-N-ethylamino;
  • N-C ⁇ -C 4 alkylsulfonyl-N-methyl-amino such as N-methylsulfonyl-N-methyl-amino, N-ethylsulfony1-N-methyl-amino, Nn-propyisulfonyl-N-methyl-amino, N-1-methylethylsulfonyl -N-methyl-amino, Nn-butylsulfony1-N-methyl-amino, N-1-methylpropylsulfonyl-N-methyl-amino, N-2-methylpropylsulfonyl-N-methyl-amino and Nl, 1-dimethylethylsulfonyl-N-methylamino, in particular N-methylsulfonyl-N-methylamino, •
  • N-C1-C4-Alkysulfony1-N-ethyl-amino such as N-methylsulfony1-N-ethy1-amino, N-ethylsulfonyl-N-ethyl-amino, Nn-propylsulfonyl-N-ethyl-amino, N-1-methylethylsulfonyl- N-ethyl-amino, Nn-butylsulfonyl-N-ethyl-amino, N-1-methylpropylsulfonyl-N-ethyl-amino, N-2-methylpropylsulfonyl-N-ethyl-amino and Nl, 1-dimethylethylsulfonyl-N- ethyl-amino, especially N-methylsulfonyl-N-ethyl-amino;
  • C_-C 4 -haloalkylthio such as chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2-difluoroethylthio -2, 2-difluoroethylthio, 2, 2-dichloro-2 fluoroethylthio, 2, 2,2-trichloroethylthio and pentafluoroethylthio, especially trifluoromethylthio.
  • the group - (A) m -CO-R 2 defined above stands for, for example
  • C 1 -C 4 -alkylcarbonyl such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl and 1, 1-dimethylethylcarbonyl, in particular methylcarbonyl;
  • C ⁇ -C 4 alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, n-prop-oxycarbonyl, 1-methylethoxycarbonyl, n-butoxycarbonyl, 1-methyl-propoxycarbonyl, 2-methylpropoxycarbonyl and 1, 1-dimethylethoxycarbonyl, especially methoxycarbonyl;
  • N-C ⁇ -C 4 alkylcarbamoyl such as N-methylcarbamoyl, N-ethylcarbamoyl, Nn-propylcarbamoyl, N-1-methylethylcarbamoyl, Nn-butylcarbamoyl, N-1-methylpropylcarbamoyl, N-2-methylpropylcarbamoyl and Nl, 1-dim , especially N-methylcarbamoyl;
  • Di-C ⁇ -C 4 alkylcarbamoyl such as dimethylcarbamoyl, diethylcarbamoyl, dipropylcarbamoyl, dibutylcarbamoyl, N-methyl-N-ethylcarbamoyl, N-methyl-N-propylcarbamoyl, N-methyl-N-1-methylethylcarbamoyl, N-methyl-N-1 , 1-dimethylethylcarbamoyl, di-1-methylethylcarbamoyl, N-ethyl-N-1-methylethylcarbamoyl and N-ethyl-N-1, 1-dimethylethylcarbamoyl; especially dimethylcarbamoyl; C ⁇ -C 4 alkylcarbonyloxy such as methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, 1-methylethy
  • N-C ⁇ -C 4 -alkylcarbonyl-N-methyl-amino such as N-methylcarbonyl-N-methyl-amino, N-ethylcarbonyl-N-methyl-amino, Nn-propylcarbonyl-
  • Nn-butylcarbony1-N-methylamino N-1-methylpropylcarbonyl-N-methylamino, N-2-methylpropylcarbonyl-N-methylamino and Nl, 1-dimethylethylcarbonyl-N-methylamino, especially N-methylcarbonyl -N-methyl-amino.
  • X stands for:
  • Ci-C ⁇ -alkyl in the L for hydrogen, Ci-C ⁇ -alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Ci-C 4 -alkoxy, Ci-C 4 -alkylthio, Ci-C 4 -haloalkyl, Ci -C 4 haloalkoxy, C 1 -C 4 haloalkylthio, C 1 -C4 alkylsulfonyl, halogen, nitro or cyano and M for hydrogen, -C-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 alkoxy, C 4 alkylthio, C ⁇ -C 4 haloalkyl, C ⁇ -C 4 haloalkoxy, Ci-C4-haloalkoxy, C ⁇ -C 4 haloalkylthio, C 1 -C 4 alkylsulf
  • Isoxazol-4-yl-benzoyl derivatives of the formula I are also preferred, in which the radicals L and M are hydrogen, methyl, methoxy, chlorine, cyano, nitro, trifluoromethyl.
  • Isoxazole -4 -yl-benzoyl derivatives of the formula Ic are preferred,
  • L is hydrogen, Ci-C ⁇ -alkyl, C 2 -C 6 alkenyl, C 2 -C 6 - alkinyl, Ci-C 4 alkoxy, Ci-C4-haloalkyl, Ci-C4 haloalkoxy, Halogen, nitro or cyano and M for hydrogen, C ⁇ -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, Ci-C 4 haloalkyl, C 1 -C 4 haloalkoxy, halogen, nitro or cyano and Q, J, n, Y and R 22 , R 21 , R 12 and R 13 have the meanings given above.
  • Ci-C ⁇ -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkyl, C x -C 4 -haloalkoxy, halogen, nitro or cyano and M are hydrogen, C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C ⁇ -C 4 alkoxy, Ci-C4-haloalkyl, Ci-C 4 -haloalkoxy, halogen, nitro or cyano and Q, J, n, Y and R 12 and R 13 have the meanings given above.
  • Isoxazole-4-yl-benzoyl derivatives of the formula Ig are further preferred
  • Diazonium solution is carefully added dropwise. The mixture is stirred for 1 hour. 106 g (2.65 mol) of sodium hydroxide in 270 ml of water are then added, the mixture is stirred for a further 2 hours, the solution is acidified with hydrochloric acid and the precipitate formed is filtered off with suction. The solid is washed with water and dried.
  • the resulting precipitate is filtered off, washed with water and dried.
  • the compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides.
  • the herbicidal compositions containing I control vegetation very well on non-cultivated areas, especially at high application rates. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. This effect occurs especially at low application rates.
  • the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants.
  • the following crops are considered, for example:
  • Gossypium hirsutum (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon malicuspp , Musa spp. , Nicotiana tabacum (N.
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • the herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active substances are less compatible with certain crop plants, application techniques can be used in which the herbicidal agents are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit, if possible, while the active substances are applied to the leaves underneath growing unwanted plants or the uncovered floor area (post-directed, lay-by).
  • the compounds I or the herbicidal compositions comprising them can be sprayed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprinkling agents or granules , Atomizing, dusting, scattering or pouring can be used.
  • the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example paraffin, tetrahydro- naphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyelohexanone or strongly polar solvents, for example amines such as N-methylpyrrolidone or water.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example paraffin, tetrahydro- naphthalene, alkylated naphthalenes or their derivatives, al
  • Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • the substrates as such or dissolved in a oil or solvent can be homogenized in water using wetting agents, adhesives, dispersants or emulsifiers.
  • wetting agents, adhesives, dispersants or emulsifiers it is also possible to prepare active substances, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or existing concentrates which are suitable for dilution with water.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol arylpolyetheralkohole ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylpheny
  • Powders, materials for spreading and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
  • Solid carriers are mineral soils such as silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, Ammonium phosphate, ammonium nitrate, ureas and vegetable products such as corn flour, tree Bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range.
  • the formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • the compounds I according to the invention can be formulated, for example, as follows:
  • I 20 parts by weight of compound no. 7.1 are dissolved in a mixture consisting of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil.
  • aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
  • a fine spray mixture containing 0.1% by weight of the active ingredient is obtained by finely distributing the mixture in 20,000 parts by weight of water.
  • V 3 parts by weight of active ingredient no. 7.1 are included
  • VIII 1 part by weight of compound no. 7.1 is dissolved in a mixture consisting of 80 parts by weight of cyelohexanone and 20 parts by weight of Emulphor EL. A stable emulsion concentrate is obtained.
  • the isoxazol-4-yl-benzoyl derivatives I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied together.
  • 1,2,4-thiazadiols, 1,3,4-thiadiazoles, amides, aminophosphoric acid and their derivatives, aminotriazoles, anilides, (het) -aryloxyalkanoic acid and their derivatives, benzoic acid and their derivatives, benzothidadiazinones come as mixing partners , Triketones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF 3 phenyl derivatives, carbamates, quinolinic acid and its derivatives, chloroacetanilides, cyclohexanediones, diazines, dichloropropionic acid and their derivatives, dihydrobenzofurans, dihydro-furanit-3
  • the active compound application rates are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (see also)
  • Plastic flower pots with loamy sand with about 3.0% humus served as culture vessels.
  • the seeds of the test plants were sown separately according to species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles.
  • the tubes were lightly watered to encourage germination and growth, and then covered with clear plastic covers until the plants had grown. This cover caused gleichdiesses germination of the test plants, unless this beeintrumble by the active ingredients ⁇ was Untitled.
  • test plants For the purpose of post-emergence treatment, the test plants, depending on the growth habit, are first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. The test plants are ent for ⁇ neither sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted some days before treatment in the reliesgefonne.
  • the application rate for post-emergence treatment was 0.5 and 0.25 kg / ha aS.
  • the plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species.
  • the trial period lasted 2 to 4 weeks. During this time, the plants were cared for, and their reaction to the individual treatments was evaluated.
  • Evaluation was carried out on a scale from 0 to 100. 5 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
  • the plants used in the greenhouse experiments are composed of the following types:

Abstract

The disclosure relates to isoxazole-4-yl-benzoyl derivatives of formula I in which the substituents have the following meanings: L, M - hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy (these groups being optionally substituted by one to five halogen atoms or C1-C4 alkoxy), halogen, cyano, nitro, a -(A)m-S(O)nR1 group or a -(A)¿m-CO-R?2 group; Y - a group consisting of C=O, C=N-R?3, CR7-NR5R6, CR7-OR8, CR10R11, CR7-SR8¿, hydrogen- or C¿1?-C4-alkyl-substituted 1,3-dioxanyl or 1,3-dioxolanyl, a heteroatom selected from the group comprising oxygen, sulphur and nitrogen; X consists of a chain (-CR?12R13¿-), (-CR?12R13-CR21R22¿-), (-CR?12=CR13-), (CR12R13-CR12=CR13¿-), or NR23; the bond between X and Y can be saturated or unsaturated; A - O, NR14; m is 0 or 1; n is 0, 1 or 2; J, Q and R1-R23 have the meanings indicated in claim 1. Also disclosed are processes for producing these isoxazole-4-yl-benzoyl derivatives, agents containing them and the use of the derivatives or agents containing them for weed control.

Description

IS0XAZ0L-4-YL-BENZ0YLDERIVATE UND IHRE VERWENDUNG ALS HERBIZIDE IS0XAZ0L-4-YL-BENZOYL DERIVATIVES AND THEIR USE AS HERBICIDES
Beschreibung 5Description 5
Die vorliegende Erfindung betrifft neue Isoxazol-4 -yl-benzoyl- derivate mit herbizider Wirkung, Verfahren zur Herstellung der Isoxazol-4-yl-benzoylderivate, Mittel welche diese enthalten so¬ wie die Verwendung dieser Derivate oder diese enthaltende Mittel 10 zur Ungräser/Unkrautbekämpfung.The present invention relates to new isoxazol-4-yl-benzoyl derivatives with herbicidal activity, processes for the preparation of the isoxazol-4-yl-benzoyl derivatives, compositions which contain them and the use of these derivatives or compositions 10 containing them for weed control / weed control .
Aus der Literatur sind herbizidwirksame Isoxazolylbenzoylderivate bekannt, beispielsweise aus EP 609797 und EP 636622.Herbicidal isoxazolylbenzoyl derivatives are known from the literature, for example from EP 609797 and EP 636622.
15 Die herbiziden Eigenschaften der bekannten Verbindungen sowie die Verträglichkeit gegenüber Kulturpflanzen können jedoch nur bedingt befriedigen.15 However, the herbicidal properties of the known compounds and the compatibility with crop plants can only satisfy to a limited extent.
Die Aufgabe bestand darin, neue Isoxazolylbenzoylderivate mit 20 verbesserten Eigenschaften zu finden.The task was to find new isoxazolylbenzoyl derivatives with 20 improved properties.
Es wurden Isoxazol-4-yl-benzoylderivate der Formel I gefunden,Isoxazol-4-yl-benzoyl derivatives of the formula I were found
Figure imgf000003_0001
in der die Substituenten folgende Bedeutung haben:
Figure imgf000003_0001
in which the substituents have the following meaning:
3030
L,M Wasserstoff, Ci-Cβ-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Cι-C4-Alkoxy, wobei diese Gruppen gegebenenfalls durch ein bis fünf Halogenatome oder Cι-C4-Alkoxy substituiert sein können; Halogen, Cyano, Nitro, eine Gruppe 35 -(A)m-S(0)nR1 oder eine Gruppe- (A)-„-CO-R2;L, M is hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, these groups optionally having one to five halogen atoms or C 1 -C 4 alkoxy can be substituted; Halogen, cyano, nitro, a group 35 - (A) m -S (0) n R 1 or a group- (A) - "- CO-R 2 ;
Y eine Gruppe bestehend aus C=0, C=N-R3, CR7-NR5R6, CR7-ORB, CRIORII, CR7-SR8; mit Wasserstoff oder Cχ-C4-Alkyl substi¬ tuiertes 1,3-Dioxanyl oder 1, 3-Dioxolanyl; ein Heteroatom 40 ausgewählt aus der Gruppe Sauerstoff, Schwefel und Stick¬ stoff;Y is a group consisting of C = 0, C = NR 3 , CR 7 -NR 5 R 6 , CR 7 -OR B , CRIORII, CR 7 -SR 8 ; 1,3-dioxanyl or 1,3-dioxolanyl substituted with hydrogen or Cχ-C 4 -alkyl; a heteroatom 40 selected from the group consisting of oxygen, sulfur and nitrogen;
X bestehend aus einer Kette <-CR«R13-) , (-CR12R13-CR21R22-) ,X consisting of a chain <-CR «R13-), (-CR 12 R 13 -CR 21 R 22 -),
(_CR12=CRl3-) , (-CR12R13-CR12=CR13-); NR23 (_ CR 12 = C Rl3-), (C -CR12R13- R12 = CR13-); NR23
45 die Bindung zwischen X und Y kann gesättigt oder ungesättigt sein;45 the bond between X and Y can be saturated or unsaturated;
h iXj' - A O , NR14 ;h iXj ' - AO, NR 14 ;
m null oder eins ;m zero or one;
n nul l , eins oder zwei ;n zero, one or two;
R1 Cι-C4 -Alkyl , Cι-C4 -Haloalkyl oder NR14 ,-R 1 -C 4 alkyl, -C 4 C -haloalkyl or NR 14 , -
R2 Cι-C4 Alkyl , C!-C4 - Haloalkyl , Cχ-C4-Alkoxy oder NR14 ;R 2 Cι-C 4 alkyl, C ! -C 4 - haloalkyl, Cχ-C 4 alkoxy or NR 14 ;
R3 Wasserstoff, -NR9R4; Cι-C6-Alkyl, Cι-C6-Haloalkyl, Cι-C6-Alkoxy, C!-C6-Haloalkoxy, C2-C6-Alkenyl, C2-C6-Haloalkenyl, C2-C6 Alkinyl; einfach bis mehrfach substituiertes Phenyl, wobei die Substituenten bestehen können aus Cχ-C4-Alkyl,R 3 is hydrogen, -NR 9 R 4 ; C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C ! -C 6 haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl; mono- to polysubstituted phenyl, where the substituents can consist of Cχ-C 4 alkyl,
Cι~C4-Alkoxy, Cι-C4-Haloalkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro; ein- bis mehrfach substituiertes Benzyl, wobei die Substituenten bestehen können aus Cι-C4-Alkyl, Cχ-C4-Alkoxy, Cι-C4-Haloalkoxy, C;L-C4-Haloalkyl, Halogen, Cyano, Nitro; ein bis mehrfach substituiertes Benzyloxy wobei die Sub¬ stituenten bestehen können aus Cι-C4-Alkyl, Cι-C4-Alkoxy, Cι~C4-Haloalkoxy, Cχ-C4-Haloalkyl, Halogen, Cyano, Nitro;C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano, nitro; mono- to polysubstituted benzyl, wherein the substituents may consist of Cι-C 4 -alkyl, Cχ-C 4 -alkoxy, C 4 haloalkoxy, C; L -C 4 haloalkyl, halogen, cyano, nitro; mono- to polysubstituted benzyloxy where the substituents can consist of -CC 4 alkyl, -C-C 4 alkoxy, -C ~ C 4 -haloalkoxy, Cχ-C 4 -haloalkyl, halogen, cyano, nitro;
R4 Wasserstoff, Cι-C6-Alkyl, Ci-Ce-Haloalkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C=0-NR14; einfach bis mehrfach substituiertes Phenyl, wobei die Substituenten bestehen können aus Cι-C4-Alkyl, Cι~C4-Alkoxy, Cι-C4-Haloalkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro; ein- bis mehrfach substituiertes Benzyl, wobei die Substituenten bestehen können aus Cι-C4-Alkyl, Cι-C4-Alkoxy, Cχ-C4-Haloalkoxy, Cχ-C4-Haloalkyl, Halogen, Cyano, Nitro;R 4 is hydrogen, -CC 6 alkyl, Ci-Ce haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C = 0-NR 14 ; mono- to polysubstituted phenyl, where the substituents can consist of -CC 4 alkyl, -C ~ C 4 -alkoxy, -C-C 4 -haloalkoxy, -C-C 4 -haloalkyl, halogen, cyano, nitro; mono- to polysubstituted benzyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, Cχ-C 4 haloalkoxy, Cχ-C 4 haloalkyl, halogen, cyano, nitro;
R9 Wasserstoff, Cι-C6-Alkyl, C!-C6-Haloalkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C=0-NR14; einfach bis mehrfach substituiertes Phenyl, wobei die Substituenten bestehen können aus C1-C4-Alkyl, Cι-C4-Alkoxy, Cι-C4-Haloalkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro; ein- bis mehrfach substituiertes Benzyl, wobei die Substituenten bestehen können aus Cι~C4-Alkyl, Cι-C4-Alkoxy, Cι-C4-Haloalkoxy, Cι~C4-Haloalkyl, Halogen, Cyano, Nitro;R 9 is hydrogen, -CC 6 alkyl, C ! -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C = 0-NR 14 ; mono- to polysubstituted phenyl wherein the substituents may be made of C 1 -C 4 -alkyl, C 4 -alkoxy, C 4 haloalkoxy, Cι-C 4 haloalkyl, halo, cyano, nitro; mono- to polysubstituted benzyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
R5,R6 unabhängig voneinander Wasserstoff, Cι-C6-Alkyl, C2-C6-Alkenyl, C1-C4 Haloalkyl, C2-C6 Haloalkenyl, Ci-Cβi-Alkoxy, Ci-Ce-Haloalkoxy; einfach bis mehrfach substituiertes Phenyl, wobei die Substituenten bestehen können aus Cι-C4-Alkyl, Cι~C4-Alkoxy, Cι-C4-Haloalkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro; ein- bis mehrfach substituiertes Benzyl, wobei die Substituenten bestehen können aus Cι~C4-Alkyl,R 5 , R 6 independently of one another hydrogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 4 haloalkyl, C 2 -C 6 haloalkenyl, Ci-Cβi-alkoxy, Ci-Ce-haloalkoxy; mono- to polysubstituted phenyl, where the substituents can consist of -CC 4 alkyl, -C ~ C 4 -alkoxy, -C-C 4 -haloalkoxy, -C-C 4 -haloalkyl, halogen, cyano, nitro; mono- to polysubstituted benzyl, where the substituents can consist of C 1 -C 4 -alkyl,
Cι-C4-Alkoxy, Cι-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro;Cι-C 4 -alkoxy, C 4 haloalkoxy, C 1 -C 4 -haloalkyl, halogen, cyano, nitro;
R7 Wasserstoff, Cι-C6-Alkyl, Cι~C4-Alkoxy, Cι-C4-Haloalkyl, Cι-C4-Haloalkoxy; gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus ein bis drei Halogenen, Cχ-C4 Alkyl, Cι~C4-Alkoxy, Ci-C4-Haloalkoxy, Nitro; R7 und R21 oder R7 und R23 oder R7 und R12 können eine Bindung bilden;R 7 are hydrogen, C 6 -alkyl, ~ C 4 -alkoxy, C 4 haloalkyl, Cι-C4-haloalkoxy; optionally substituted phenyl, where the substituents can consist of one to three halogens, Cχ-C 4 alkyl, Cι ~ C 4 alkoxy, Ci-C 4 haloalkoxy, nitro; R 7 and R 21 or R 7 and R 23 or R 7 and R 12 can form a bond;
R8 Wasserstoff, Cι-C6 Alkyl,Cι-C4-Halogenalkyl, substituier¬ tes Phenyl, wobei die Substituenten bestehen können aus Cι-C4-Alkyl, Cι-C4-Alkoxy, Cι-C4-Haloalkoxy, Cι-C4-Halo- alkyl, Halogen, Cyano, Nitro; substituiertes Benzyl wobei die Substituenten bestehen können aus Cι~C4-Alkyl,R 8 is hydrogen, C 1 -C 6 alkyl, C 1 -C 4 haloalkyl, substituted phenyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; Substituted benzyl where the substituents can consist of C 1 -C 4 -alkyl,
Cχ-C4-Alkoxy, Cι-C4-Haloalkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro;Cχ-C 4 alkoxy, -CC 4 -haloalkoxy, -C-C 4 -haloalkyl, halogen, cyano, nitro;
Ri°,RiJ- unabhängig voneinander Wasserstoff, Ci-Cδ-Alkyl; Phenyl gegebenenfalls substituiert mit ein bis drei Halogenen,Ri °, RiJ- independently of one another hydrogen, Ci-C δ -alkyl; Phenyl optionally substituted with one to three halogens,
Cι~C4-Alkyl, Cχ-C4-Alkoxy, Cι-C4-Haloalkoxy, Nitro; R10 und R12 oder R10 und R23 oder R10 und R21 können eine Bindung bilden;Cι ~ C 4 alkyl, Cχ-C 4 alkoxy, Cι-C 4 haloalkoxy, nitro; R 10 and R 12 or R 10 and R 23 or R 10 and R 21 may form a bond;
R12,R13 unabhängig voneinander Wasserstoff, Cι-C6-Alkyl,R 12 , R 13 independently of one another are hydrogen, C 1 -C 6 -alkyl,
Cι-C6-Haloalkyl, Cι-C6-Alkoxy, Cι-C6-Haloalkoxy; gegebe- .- . nenfalls substituiertes Phenyl wobei die Substituenten bestehen können aus Cι~C4-Alkyl, Cι~C4-Alkoxy, Cι~C4-Halo- alkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro;C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy; given . -. appropriate, substituted phenyl wherein the substituents Cι-C may consist of Cι ~ C 4 -alkyl, C ~ 4 alkoxy, Cι ~ C4 alkoxy -Halo-, 4 -haloalkyl, halogen, cyano, nitro;
R14 Cι-C4-Alkyl";R 14 -CC 4 alkyl " ;
R21 Wasserstoff, Cι-C6-Alkyl, Cι-C6-Haloalkyl, Ci-Cö-Alkoxy, Cι-C6-Haloalkoxy; gegebenenfalls substituiertes Phenyl wobei die Substituenten bestehen können aus Cι-C4-Alkyl,R 21 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy; optionally substituted phenyl where the substituents can consist of -CC 4 alkyl,
Cι-C4-Alkoxy, Cχ-C4-Haloalkoxy, Cχ-C4-Haloalkyl, Halogen, Cyano, Nitro;C 1 -C 4 alkoxy, Cχ-C 4 haloalkoxy, Cχ-C 4 haloalkyl, halogen, cyano, nitro;
R22 Wasserstoff, Cι-C6-Alkyl, Cι-C6-Haloalkyl, Cι-C6-Alkoxy, Cι-C6-Haloalkoxy; gegebenenfalls substituiertes Phenyl wobei die Substituenten bestehen können aus Cι-C4-Alkyl, Cι-C4-Alkoxy, Cι-C4-Haloalkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro;R 22 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy; optionally substituted phenyl where the substituents can consist of -CC 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
R23 Wasserstoff, Cι-C6-Alkyl, C2-C6-Alkenyl, Cι-C6 Alkoxy; gegebenenfalls mit Cι-C4-Alkyl, Cι-C4-Alkoxy, Cι-C4-Halo- alkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro substi¬ tuiertes Phenyl oder Benzyl,-R 23 is hydrogen, -C 6 alkyl, C 2 -C 6 alkenyl, -C 6 alkoxy; optionally substituted with Cι-C 4 -alkyl, C 4 -alkoxy, C 4 -Halo- alkoxy, Cι-C 4 haloalkyl, halo, cyano, nitro substi¬ tuiertes phenyl or benzyl, -
ein in Stellung 4 verknüpfter Isoxazolring der Formel lla linked in position 4 isoxazole of formula l l
Figure imgf000006_0001
in welcher
Figure imgf000006_0001
in which
R15 für Wasserstoff oder -C02R17, Cι-C4-Alkyl;R 15 for hydrogen or -C0 2 R 17 , -CC 4 alkyl;
R16 für Wasserstoff, C1-C4-Alkyl oder C3-C6-Cycloalkyl, welches gegebenenfalls durch ein oder mehrere Halogen- atome oder Cι~C4-Alkyl substituiert sein kann undR 16 for hydrogen, C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl, which may optionally be substituted by one or more halogen atoms or -CC 4 alkyl and
R17 für Ci-C4-Alkyl steht;R 17 represents Ci-C 4 alkyl;
J ein Carbonylrest CO oder ein Rest -CHR18;J is a carbonyl radical CO or a radical -CHR 18 ;
Rlβ eine OH-Gruppe, eine ggf. mit C2-C4~Acyl acylierte Hydroxylgruppe oder ein Chloratom bedeutet;R 1β denotes an OH group, a hydroxyl group optionally acylated with C 2 -C 4 ~ acyl or a chlorine atom;
wobei für den Fall, daß Y = C=0 ist, X ungleich NR23 ist,in the event that Y = C = 0, X is not equal to NR 23 ,
sowie^-landwirtschaftliche übliche Salze der Verbindung I.and ^ -agricultural customary salts of the compound I.
Verbindungen der Formel I mit R15 = H erhält man dadurch, daß man die an sich bekannten ß-Ketoester der Formel AI [Y. Oikawa et al., JOC .4JL, 2087 (1978)] mit einem Benzoesäurederivat der Formel III (T = Cl) zu einem Ester der Formel Bl acyliert, dieses durch Umsetzung mit p-Toluolsulfonsäure in Toluol in ein 1,3-Diketon der Formel Cl überführt, danach das 1,3-Diketon Cl entweder mit Orthoameisensäuretriethylester in einen Enolether Dl oder mit Dimethylformamid-dimethylacetal in ein Enamin D2 über¬ führt und Dl oder D2 mit Hydroxylamin zum Isoxazolyl-benzoyl- derivat der Formel Ig umsetzt. Weiterhin läßt sich die Verbindung der Formel I mit J = C=0 dadurch aufbauen, daß man ein Alkinyl- stannat der Formel A2 (z.B. J. Org. Chem 1983, 4JL, 5302; J. Am. Chem. Soc. 1989, Hi, 4120; J. Org. Chem. 1989, üi, 5856), wobei R16 die im Anspruch 1 angegebene Bedeutung hat, mit einem Benzoe- säurederivat der Formel III mit T = Cl und L, M, X, Y und n die in Anspruch 1 genannte Bedeutung haben, zu einem Benzoylalkin der Formel B2 umsetzt. In einer Cycloaddition wird B2 mit Nitriloxi- den der Formel C2, in der R15 für Cι-C4-Alkyl steht, zu Isoxazolen der Formel If weiter umgesetzt (Tetrah. 1985, 41, 5181) . Die Reaktionssequenz ist im nachfolgenden Formelschema zusammen¬ gefaßt :Compounds of the formula I with R 15 = H are obtained by the known β-keto esters of the formula AI [Y. Oikawa et al., JOC . 4JL, 2087 (1978)] with a benzoic acid derivative of the formula III (T = Cl) to an ester of the formula B1, which is converted into a 1,3-diketone of the formula Cl by reaction with p-toluenesulfonic acid in toluene, then the 1st , 3-diketone C1 either with triethyl orthoformate in an enol ether Dl or with dimethylformamide dimethyl acetal in an enamine D2 and Dl or D2 with hydroxylamine to form the isoxazolyl-benzoyl derivative of the formula Ig. Furthermore, the compound of the formula I with J = C = 0 can be built up by reacting an alkynyl stannate of the formula A2 (for example J. Org. Chem 1983, 4JL, 5302; J. Am. Chem. Soc. 1989, Hi , 4120; J. Org. Chem. 1989, üi, 5856), where R 16 has the meaning given in claim 1, with a benzoin acid derivative of the formula III with T = Cl and L, M, X, Y and n have the meaning given in claim 1, to a benzoylalkyne of the formula B2. In a cycloaddition, B2 is further reacted with nitrile oxides of the formula C2, in which R 15 is C 1 -C 4 -alkyl, to give isoxazoles of the formula If (Tetrah. 1985, 41, 5181). The reaction sequence is summarized in the following formula:
Schema IAScheme IA
Figure imgf000007_0001
Figure imgf000007_0001
AI III BlAI III sheet
Figure imgf000007_0002
Figure imgf000007_0002
Cl Dl:Z=OC2H5 D2:Z=N(CH3)2 Cl Dl: Z = OC 2 H 5 D2: Z = N (CH 3 ) 2
Figure imgf000007_0003
Figure imgf000007_0003
ig Schema IBig Scheme IB
Figure imgf000008_0001
Figure imgf000008_0001
Figure imgf000008_0002
Figure imgf000008_0002
C2 IfC2 If
Benzoesäuren der Formel III lassen sich folgendermaßen her¬ stellen:Benzoic acids of the formula III can be prepared as follows:
Benzoylhalogenide wie beispielsweise Benzoylchloride der Formel III (T = Cl) werden in an sich bekannter Weise durch Umsetzung der Benzoesäuren der Formel III (T = OH) mit Thionylchlorid her¬ gestellt.Benzoyl halides such as, for example, benzoyl chlorides of the formula III (T = Cl) are prepared in a manner known per se by reacting the benzoic acids of the formula III (T = OH) with thionyl chloride.
Die Benzoesäuren der Formel III (T = OH) können in bekannterThe benzoic acids of formula III (T = OH) can be known
Weise durch saure oder basische Hydrolyse aus den entsprechenden Estern der Formel III (T = Cι-C4-Alkoxy) hergestellt werden.Be prepared by acidic or basic hydrolysis from the corresponding esters of formula III (T = -C 4 alkoxy).
Die Zwischenprodukte der Formel III sind teilweise bekannt oder lassen sich nach literaturbekannten Verfahren darstellen.Some of the intermediates of the formula III are known or can be prepared by processes known from the literature.
Schema .2Scheme .2
Figure imgf000008_0003
^
Figure imgf000009_0001
h \
Figure imgf000008_0003
^
Figure imgf000009_0001
h \
Danach lassen sich z.B. wie in Schema 2 dargestellt Arylthiover- bindungen IV mit substituierten Haloalkenyl gemäß J. Med. Chem.Then e.g. as shown in Scheme 2, aryl thio compounds IV with substituted haloalkenyl according to J. Med. Chem.
10 1984, 27, 1516, substituierten Alkinylcarbonsäuren gemäß J. Org. Chem. 1980, 45, 4611 oder J. Am. Chem. Soc. 1983, 105, 883, sub¬ stituierten Haloalkylcarbonsäuren gemäß Chem. Ber. 1925, 58, 1612 in Gegenwart einer Base wie Alkalihydroxid, Alkalihydrid oder Alkalicarbonat umsetzen. Die entstehenden Verbindungen V werden10 1984, 27, 1516, substituted alkynylcarboxylic acids according to J. Org. Chem. 1980, 45, 4611 or J. Am. Chem. Soc. 1983, 105, 883, substituted haloalkyl carboxylic acids according to Chem. Ber. 1925, 58, 1612 in the presence of a base such as alkali metal hydroxide, alkali metal hydroxide or alkali metal carbonate. The resulting compounds V will
15 unter Friedel-Crafts Bedingungen unter Zusatz einer Lewissäure oder einer Protonensäure zu VI cyclisiert. Als Lewissäuren werden A1C13 oder SnCl4 und als Protonensäure Polyphoshorsäure und Schwe¬ felsäure bevorzugt gemäß Can. J. Chem. 1981, 59, 199; Chem. Ber. 1925, 58, 1625; Chem. Ber. 1926, 59, 1074; Phosp. and Sulf. 1984,15 cyclized under Friedel-Crafts conditions with the addition of a Lewis acid or a protonic acid to VI. A1C1 3 or SnCl 4 are preferred as Lewis acids and polyphosphoric acid and sulfuric acid are preferred as protonic acid according to Can. J. Chem. 1981, 59, 199; Chem. Ber. 1925, 58, 1625; Chem. Ber. 1926, 59, 1074; Phosp. and sulf. 1984,
20 19, 31.20 19, 31.
Thiochromenonsäuren lassen sich weiterhin durch z.B. Abspaltung von Halogenwasserstoff von 3-Halothiochromanonsäuren oder z.B. durch Umsetzung der substituierten Thiophenolsäuren mit substi- 25 tuierten α-Alkylacetessigestern in Gegenwart von Phosphorpentoxid gemäß Ann. Chem. 1964, 680, 40 darstellen.Thiochromenonic acids can still be obtained e.g. Elimination of hydrogen halide from 3-halothiochromanonic acids or e.g. by reacting the substituted thiophenolic acids with substituted α-alkylacetoacetic esters in the presence of phosphorus pentoxide according to Ann. Chem. 1964, 680, 40.
Die Arylthioverbindungen IV können beispielsweise durch Sand¬ meyer-Reaktion aus entsprechenden Anilinen erhalten werden, die 30 ihrerseits durch Reduktion von geeigneten Nitroverbindungen gemäß Organikum 19.Aufläge 1992, 552ff synthetisiert werden.The arylthio compounds IV can be obtained, for example, by means of a Sandmeyer reaction from corresponding anilines, which in turn are synthesized by reduction of suitable nitro compounds in accordance with Organikum 19th edition 1992, 552ff.
Für den Fall, daß z.B. X gleich (-CR12R13-) bzw. (-CR12R13CR21R22-) , Y gleich C=0 und T gleich Cι~C4-Alkoxy ist, läßt sich der Thio-In the event that, for example, X is (-CR 12 R 13 -) or (-CR 12 R 13 CR 21 R 22 -), Y is C = 0 and T is C 1 -C 4 -alkoxy, the Thio
35 chromanonester bzw. Dihydrobenzothiophenester wie in Schema 2 beschrieben durch Alkylierung der Arylthioverbindung IV in Gegen¬ wart einer der obengenannten Basen in Lösungsmittel oder Wasser mit Halogenpropionsäure bzw. Halogenessigsäure herstellen und cyclisieren zu VI. 0Prepare 35 chromanone esters or dihydrobenzothiophene esters as described in Scheme 2 by alkylating the arylthio compound IV in the presence of one of the bases mentioned above in solvent or water with halopropionic acid or haloacetic acid and cyclize to VI. 0
Die Reaktanden und die Base werden dabei zweckmäßig in äqui- molaren Mengen eingesetzt. Die Reaktionsmischung wird vorzugs¬ weise bei 20-100°C, insbesondere bei 20-40°C, gerührt. Die Auf¬ arbeitung erfolgt beispielsweise so, daß das Reaktionsgemisch auf 5 Wasser gegossen wird, die wäßrige Phase mit Mineralsäuren wie Salzsäure oder Schwefelsäure sauer gestellt und das Wertprodukt abgesaugt wird oder durch Extraktion mit Methylenchlorid oder Essigsäureethylester extrahiert, getrocknet und vom Losungsmittel befreit wird. Der Ester kann ohne weitere Reinigung umgesetzt werden.The reactants and the base are expediently used in equimolar amounts. The reaction mixture is preferably stirred at 20-100 ° C., in particular at 20-40 ° C. The work-up is carried out, for example, by pouring the reaction mixture onto 5 water, acidifying the aqueous phase with mineral acids such as hydrochloric acid or sulfuric acid and suctioning off the product of value or by extraction with methylene chloride or Extracted ethyl acetate, dried and freed from the solvent. The ester can be reacted without further purification.
Durch Ruhren von V in z.B. Polyphosphorsaure bei 40-140°C, ins¬ besondere bei 70-100°C, oder durch Aktivierung der Carbonsäure durch Überführung ins Säurechlorid und Rühren mit 2-6, ins¬ besondere 3.5 bis 4.5, Moläquivalenten einer Lewissäure wie z.B. A1C13 oder SnCl4 in einem Losungsmittel oder durch Ruhren mit oder in Schwefelsäure, erhält man nach an sich bekannter Aufarbeitung, d.h. Zugabe von Eiswasser und Absaugen des Wertproduktes oder Extraktion der wäßrigen Phase mit Essigsäureethylester oder Methylenchlorid, Trocknen und Entfernen des Lösungsmittel eine Zwischenstufe der Formel III.By stirring V in, for example, polyphosphoric acid at 40-140 ° C, in particular at 70-100 ° C, or by activating the carboxylic acid by conversion into acid chloride and stirring with 2-6, in particular 3.5 to 4.5, molar equivalents of a Lewis acid such as A1C1 3 or SnCl 4 in a solvent or by stirring with or in sulfuric acid, one obtains after known work-up, i.e. adding ice water and suctioning off the product of value or extraction of the aqueous phase with ethyl acetate or methylene chloride, drying and removal of the solvent Intermediate stage of formula III.
Für den Fall, daß z.B. X gleich einer Ethylengruppierung (-CR12=CR13~) , Y gleich C=0 und T gleich Cι-C4-Alkoxy läßt sich der Thiochromenonester durch z.B. Umsetzung von einer Arylthio- verbindung mit einem Acetylencarbonsäurederivat in Wasser oder Losungsmittel bei einer Temperatur von 0-140°C umsetzen. Die Aufarbeitung erfolgt nach an sich bekannter Weise durch Zugabe von Wasser und verdünnter Mineralsäure wie z.B. Salzsäure. Das Wertprodukt wird entweder abgesaugt oder durch Extraktion mit Methylenchlorid oder Essigsäureethylester, anschließendem Trocknen und Entfernen des Lösungsmittel erhalten.In the event that, for example, X is an ethylene grouping (-CR 12 = CR 13 ~ ), Y is C = 0 and T is C 1 -C 4 -alkoxy, the thiochromenone ester can be converted by, for example, reacting an arylthio compound with an acetylenecarboxylic acid derivative React water or solvent at a temperature of 0-140 ° C. Working up is carried out in a manner known per se by adding water and dilute mineral acid such as hydrochloric acid. The product of value is either suctioned off or obtained by extraction with methylene chloride or ethyl acetate, followed by drying and removal of the solvent.
Die Zwischenprodukte der Formel III können durch literatur- bekannte Reaktionen wie Reduktion gemäß Jerry March " Advanced Organic Chemistry, Fourth Ed., z.B. S.910ff, Oximierung gemäß Jerry March " Advanced Organic Chemistry, Fourth Ed., z.B. S.934, 935, 1039, 1226, 405ff, Überfuhrung in Imine und Amine gemäß Jerry-March " Advanced Organic Chemistry, Fourth Ed., Ketali- sierung, Alkylierung, Halogenierung, Eliminierung und Oxidation gemäß Jerry March " Advanced Organic Chemistry, Fourth Ed. weiter funktionalisiert werden.The intermediates of formula III can be obtained by reactions known from the literature, such as reduction according to Jerry March "Advanced Organic Chemistry, Fourth Ed., E.g. S.910ff, oximation according to Jerry March" Advanced Organic Chemistry, Fourth Ed., E.g. P.934, 935, 1039, 1226, 405ff, conversion into imines and amines according to Jerry-March "Advanced Organic Chemistry, Fourth Ed., Ketalization, alkylation, halogenation, elimination and oxidation according to Jerry March" Advanced Organic Chemistry, Fourth Ed. be further functionalized.
Die Säuren der 3-Alkoxy-l, 2-benzisothiazol-l, 1-dioxide oder 3-Alkoxy-l,2-benzisothiazole können ausgehend von entsprechenden Saccharinderivaten oder 1, 2-Benzisothiazolen durch z.B. Umsetzung mit PC15, P0C13 oder Chlor und Alkohol gegebenenfalls in Gegenwart einer Hilfsbase wie z.B. Triethylamin erhalten werden, was bei¬ spielsweise beschrieben ist in US 4,571,429, Arch. Pharm. 1984, 317, 807, US 4461901, US 450916, J. Med. Chem. 1986, 29, 359. Saccharincarbonsäuren kόnnen durch Literatur bekannte Verfahren gemäß Ann. Chem. 427, 231, 1922, Chem. Ber. 13, 1554, 1980, Chem. Ber. 25, 1740, 1892, DE-OS 3607343, deutsche Patent¬ anmeldung P 44 27 995.7 erhalten werden. Die Derivate der Benzo-1, 4-oxathiinsäuren sind teilweise bekannt, z.B. aus J. Org. Chem. 1968, 33, 456 oder lassen sich z.B. durch Reaktion aus den entsprechenden Phenolderivaten gemäß Chem. Comm., 1975, 451, J. Org. Chem. 1974, 39, 1811, J. Am. Chem. Soc. 1954, 76, 1068 oder durch Kombination von z.B. Sub¬ stitutionsreaktion an Halogen-substituierten Thiophenolderivaten und weiterführende Reaktionen wie z.B Oxidation, Reduktion oder Addition gemäß J. Het. Chem. 1983, 20, 867 aufbauen.The acids of the 3-alkoxy-l, 2-benzisothiazole-l, 1-dioxide or 3-alkoxy-l, 2-benzisothiazoles can, starting from corresponding saccharin derivatives or 1, 2-benzisothiazoles, for example by reaction with PC1 5 , P0C1 3 or chlorine and alcohol can optionally be obtained in the presence of an auxiliary base such as triethylamine, which is described, for example, in US 4,571,429, Arch. Pharm. 1984, 317, 807, US 4461901, US 450916, J. Med. Chem. 1986, 29, 359 Saccharin carboxylic acids can be synthesized according to Ann. Chem. 427, 231, 1922, Chem. Ber. 13, 1554, 1980, Chem. Ber. 25, 1740, 1892, DE-OS 3607343, German patent application P 44 27 995.7 can be obtained. The derivatives of benzo-1,4-oxathiic acids are known in some cases, for example from J. Org. Chem. 1968, 33, 456 or can be obtained, for example, by reaction from the corresponding phenol derivatives in accordance with Chem. Comm., 1975, 451, J. Org Chem. 1974, 39, 1811, J. Am. Chem. Soc. 1954, 76, 1068 or by combining eg a substitution reaction on halogen-substituted thiophenol derivatives and further reactions such as oxidation, reduction or addition according to J. Het. Chem. 1983, 20, 867.
Die Benzoesäuren der Formel III können auch erhalten werden, indem man die entsprechende brom- oder iodsubstituierte Ver¬ bindung der Formel VIIThe benzoic acids of the formula III can also be obtained by the corresponding bromo- or iodo-substituted compound of the formula VII
Schema 3Scheme 3
Figure imgf000011_0001
Figure imgf000011_0001
in der die Substituenten die folgende Bedeutung haben:in which the substituents have the following meaning:
T OH, Cι-C4-Alkoxy Y,L,M,X und n die oben beschriebene Bedeutung habenT OH, -CC 4 alkoxy Y, L, M, X and n have the meaning described above
in Gegenwart eines Palladium-, Nickel-, Cobalt- oder Rhodium- Übergangsmetallkatalysators und einer Base mit Kohlenmonoxid und Wasser unter erhöhtem Druck umsetzt.in the presence of a palladium, nickel, cobalt or rhodium transition metal catalyst and a base with carbon monoxide and water under elevated pressure.
Die Katalysatoren Nickel, Cobalt, Rhodium und insbesondere Palladium können metallisch oder in Form üblicher Salze wie in Form von Halogenverbindungen, z.B. PdCl2, RhCl3-H20, Acetaten, z.B. Pd(OAc)2, Cyaniden usw. in den bekannten Wertigkeitsstufen vorliegen. Ferner können Metallkomplexe mit tertiären Phosphinen, Metallalkylcarbonyle, Metallcarbonyle, z.B. C02(CO)8, Ni(CO)4, Metallcarbonyl-Komplexe mit tertiären Phosphinen, z.B. (PPh3) 2Ni (CO) 2, oder mit tertiären Phosphinen komplexierte Über¬ gangsmetallsalze vorliegen. Die letztgenannte Ausführungsform ist insbesondere im Fall von Palladium als Katalysator bevorzugt.The catalysts nickel, cobalt, rhodium and in particular palladium can be metallic or in the form of conventional salts such as in the form of halogen compounds, for example PdCl 2 , RhCl 3 -H 2 O, acetates, for example Pd (OAc) 2 , cyanides etc. in the known valence levels available. Furthermore, metal complexes with tertiary phosphines, metal alkylcarbonyls, metal carbonyls, for example C0 2 (CO) 8 , Ni (CO) 4 , metal carbonyl complexes with tertiary phosphines, for example (PPh 3 ) 2 Ni (CO) 2 , or excess complexed with tertiary phosphines ¬ transition metal salts are present. The latter embodiment is particularly preferred in the case of palladium as a catalyst.
Dabei ist die Art der Phosphinliganden breit variabel. Beispiels¬ weise lassen sie sich durch folgende Formeln wiedergeben:The type of phosphine ligand is widely variable. For example, they can be represented by the following formulas:
R24 R24\ ^R26 - R25 o^er P—(CH2)n — P R 24 R 24 \ ^ R 26 - R 25 o ^ er P— (CH 2 ) n - P
^R26 R ^R27 wobei n die Zahlen 1, 2, 3 oder 4 bedeutet und die Reste R24 bis R26 für niedermolekulares Alkyl, z.B. Cι-C6-Alkyl, Aryl, Cι-C4-Alkylaryl, z.B. Benzyl, Phenethyl oder Aryloxy stehen. Aryl ist z.B. Naphthyl, Anthryl und vorzugsweise gegebenenfalls substituiertes Phenyl, wobei man hinsichtlich der Substituenten nur auf deren Inertheit gegenüber der Carboxylierungsreaktion zu achten hat, ansonsten kόnnen sie breit variiert werden und umfassen alle inerten C-organischen Reste wie Cx-Ce-Alkylreste, z.B. Methyl, Carboxylreste wie COOH, COOM (M ist z.B. ein Alkali-, Erdalkalimetall oder Ammoniumsalz) , oder C-organische Reste über Sauerstoff gebunden wie Cι-C6-Alkoxyreste.^ R 26 R ^ R 27 where n is the numbers 1, 2, 3 or 4 and the radicals R 24 to R 26 are low molecular weight alkyl, for example C 1 -C 6 -alkyl, aryl, C 1 -C 4 -alkylaryl, for example benzyl, phenethyl or aryloxy. Aryl is, for example, naphthyl, anthryl and preferably optionally substituted phenyl, but the substituents need only be paid attention to their inertness to the carboxylation reaction, otherwise they can be varied widely and include all inert C-organic radicals such as Cx-Ce-alkyl radicals, for example Methyl, carboxyl radicals such as COOH, COOM (M is, for example, an alkali metal, alkaline earth metal or ammonium salt), or C-organic radicals bound via oxygen, such as -CC 6 alkoxy radicals.
Die Herstellung der Phosphinkomplexe kann in an sich bekannter Weise, z.B. wie in den eingangs genannten Dokumenten beschrieben, erfolgen. Beispielsweise geht man von üblichen kommerziell erwerblichen Metallsalzen wie PdCl2 oder Pd(OCOCH3)2 aus und fügt das Phosphin z.B. P(C6H5)3, P(n-C4H9)3, PCH3(C6H5)2, 1, 2-Bis (diphenylphosphino) ethan hinzu.The phosphine complexes can be prepared in a manner known per se, for example as described in the documents mentioned at the outset. For example, customary commercially available metal salts such as PdCl 2 or Pd (OCOCH 3 ) 2 are used and the phosphine is added, for example P (C 6 H 5 ) 3 , P (nC 4 H 9 ) 3 , PCH 3 (C 6 H 5 ) 2 , 1, 2-bis (diphenylphosphino) ethane added.
Die Menge an Phosphin, bezogen auf das Ubergangsmetall, beträgt üblicherweise 0 bis 20, insbesondere 0,1 bis 10 Moläquivalente, besonders bevorzugt 1 bis 5 Moläquivalente.The amount of phosphine, based on the transition metal, is usually 0 to 20, in particular 0.1 to 10 molar equivalents, particularly preferably 1 to 5 molar equivalents.
Die Menge an Ubergangsmetall ist nicht kritisch. Natürlich wird man aus Kostengrunden eher eine geringe Menge, z.B. von 0,1 bis 10 Mol.-%, insbesondere 1 bis 5 Mol.-%, bezogen auf den Ausgangs¬ stoff II bzw. III verwenden.The amount of transition metal is not critical. Of course, for reasons of cost, you will rather get a small amount, e.g. from 0.1 to 10 mol%, in particular 1 to 5 mol%, based on the starting material II or III.
Zur Herstellung der Benzoesäuren III (T = OH) fuhrt man die Umsetzung mit Kohlenmonoxid und mindestens äquimolaren Mengen an Wasser, bezogen auf die Ausgangsstoffe VI durch. Der Reak¬ tions-partner Wasser kann gleichzeitig auch als Losungsmittel dienen, d.h. die maximale Menge ist nicht kritisch.To prepare the benzoic acids III (T = OH), the reaction is carried out with carbon monoxide and at least equimolar amounts of water, based on the starting materials VI. The reaction partner water can also serve as a solvent, i.e. the maximum amount is not critical.
Es kann aber auch je nach Art der Ausgangsstoffe und der ver¬ wendeten Katalysatoren von Vorteil sein, anstelle des Reaktions- Partners ein anderes inertes Losungsmittel oder die für die Carboxylierung verwendete Base als Lösungsmittel zu verwenden.However, depending on the type of starting materials and the catalysts used, it can also be advantageous to use another inert solvent or the base used for the carboxylation as the solvent instead of the reaction partner.
Als inerte Lösungsmittel kommen für Carboxylierungsreaktionen übliche Lösungsmittel wie Kohlenwasserstoffe, z.B. Toluol, Xylol, Hexan, Pentan, Cyelohexan, Ether z.B. Methyl-tert.butylether, Tetrahydrofuran, Dioxan, Dimethoxyethan, substituierte Amide wie Dimethylformamid, persubstituierte Harnstoffe wie Tetra-Cι-C4- alkylharnstoffe oder Nitrile wie Benzonitril oder Acetonitril in Betracht. In einer bevorzugten Ausführungsform des Verfahrens verwendet man einen der Reaktionspartner, insbesondere die Base, im Überschuß, so daß kein zusätzliches Lösungsmittel erforderlich ist.Suitable inert solvents for carboxylation reactions are customary solvents such as hydrocarbons, for example toluene, xylene, hexane, pentane, cyelohexane, ethers, for example methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane, substituted amides such as dimethylformamide, per-substituted ureas such as tetra-C 1 -C 4 - alkylureas or nitriles such as benzonitrile or acetonitrile. In a preferred embodiment of the process, one of the reactants, in particular the base, is used in excess, so that no additional solvent is required.
5 Für das Verfahren geeignete Basen sind alle inerten Basen, die den bei der Umsetzung freiwerdenden Jodwasserstoff bzw. Brom¬ wasserstoff zu binden vermögen. Beispielsweise sind hier tertiäre Amine wie tert. -Alkylamine, z.B. Trialkylamine wie Triethylamin, cyclische Amine wie N-Methylpiperidin oder N,N' -Dimethyl- 10 piperazin, Pyridin, Alkali- oder -hydrogencarbonate, oder tetra- alkylsubstituierte Harnstoffderivate wie Tetra-Cχ-C4-alkyl- harnstoff, z.B. Tetramethylharnstoff, zu nennen.5 Suitable bases for the process are all inert bases which are able to bind the hydrogen iodide or hydrogen bromide released during the reaction. For example, tertiary amines such as tert. Alkylamines, for example trialkylamines such as triethylamine, cyclic amines such as N-methylpiperidine or N, N '-dimethyl-10 piperazine, pyridine, alkali metal or hydrogen carbonates, or tetra-alkyl-substituted urea derivatives such as tetra-C C-C 4 -alkyl urea, For example, tetramethyl urea.
Die Menge an Base ist nicht kritisch, üblicherweise werden 1 bis 15 10, insbesondere 1 bis 5 Mol verwendet. Bei gleichzeitiger Ver¬ wendung der Base als Losungsmittel, wird die Menge in der Regel so bemessen, daß die Reaktionspartner gelost sind, wobei man aus Praktikabilitätsgründen unnötig hohe Überschüsse vermeidet, um Kosten zu sparen, kleine Reaktionsgefäße einsetzen zu können und 20 den Reaktionspartnern maximalen Kontakt zu gewährleisten.The amount of base is not critical, usually 1 to 15 10, in particular 1 to 5, mol are used. If the base is simultaneously used as solvent, the amount is generally such that the reactants are dissolved, unnecessarily high excesses being avoided for reasons of practicality, in order to save costs, to be able to use small reaction vessels and to have maximum contact with the reactants to ensure.
Während der Umsetzung wird der Kohlenmonoxiddruck so eingestellt, daß immer ein Überschuß an CO, bezogen auf VI vorliegt. Vorzugs¬ weise liegt der Kohlenmonoxiddruck bei Raumtemperatur bei 1 bis 25 250 bar, insbesondere 5 bis 150 bar CO.During the reaction, the carbon monoxide pressure is adjusted so that there is always an excess of CO, based on VI. The carbon monoxide pressure at room temperature is preferably 1 to 25 250 bar, in particular 5 to 150 bar CO.
Die Carbonylierung wird in der Regel bei Temperaturen von 20 bis 250°C, insbesondere bei 30 bis 150°C kontinuierlich oder diskonti¬ nuierlich durchgeführt. Bei diskontinuierlichem Betrieb wird 30 zweckmäßigerweise zur Aufrechterhaltung eines konstanten Druckes kontinuierlich Kohlenmonoxid auf das Umsetzungsgemisch aufge¬ preßt, t-The carbonylation is generally carried out continuously or batchwise at temperatures from 20 to 250 ° C., in particular at 30 to 150 ° C. In the case of discontinuous operation, carbon monoxide is expediently pressed continuously onto the reaction mixture in order to maintain a constant pressure.
Die als Ausgangsverbindungen benutzten Arylhalogenverbindungen 35 VII sind bekannt oder können leicht durch geeignete Kombination bekannter Synthesen und nach oben beschriebenen Reaktionsfolgen hergestellt werden.The aryl halogen compounds 35 VII used as starting compounds are known or can easily be prepared by a suitable combination of known syntheses and reaction sequences described above.
Die Verbindungen I mit J = -CHR17 können aus den Verbindungen der 40 Formel I mit J = CO dadurch erhalten werden, daß man sie mit Natriumborhydrid zu Carbinolen der Formel 1.3 reduziert, und diese entweder mit Methansulfonsäurechlorid zu Chloriden der Formel 1.4 umsetzt oder mit C2-C4-Carbonsäureanhydriden zu Estern der Formel 1.5 acyliert. 5 Schema 4The compounds I with J = -CHR 17 can be obtained from the compounds of the formula I with J = CO by reducing them to carbinols of the formula 1.3 with sodium borohydride and reacting them either with methanesulfonyl chloride to form the chlorides of the formula 1.4 or with C 2 -C 4 carboxylic acid anhydrides acylated to esters of the formula 1.5. 5 Scheme 4
ww
Figure imgf000014_0001
Figure imgf000014_0001
1.51.5
Im Hinblick auf die bestimmungsgemäße Verwendung der Isoxazol-4 yl-benzoylderivate der allgemeinen Formel I kommen als Substi¬ tuenten folgende Reste in Betracht:With regard to the intended use of the isoxazol-4-yl-benzoyl derivatives of the general formula I, the following radicals are suitable as substituents:
L,M Wasserstoff,L, M hydrogen,
Cι-C6-Alkyl wie Methyl, Ethyl, Propyl, 1-Methylethyl, Butyl, 1-Methylpropyl, 2-Methylpropyl, 1, 1-Dimethylethyl, Pentyl, 1-Methylbutyl, 2-Methylbutyl, 3-Methylbutyl, 1,1-Dimethylpropyl, 1, 2-Dimethylpropyl, 2, 2-Dimethylpropyl, 1-Ethylpropyl, Hexyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1, 1-Dimethylbutyl, 1, 2-Dimethylbutyl, 1, 3-Dimethylbutyl, 2, 2-Dimethylbutyl, 2, 3-Dimethylbutyl, 3, 3-Dimethylbutyl, 1-Ethylbutyl, 1, 1, 2-Trimethylpropyl, 1, 2, 2-TrimethyIpropyl, 1-Ethyl-l-methylpropyl oder l-Ethyl-2-methyl-propyl, insbesondere Methyl, Ethyl, 1-Methylethyl, 1-Methylpropyl , 2-Methylpropyl, 1, 1-Dimethylethyl und 1, 1-DimethyIpropyl;Cι-C 6 alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1.1 -Dimethylpropyl, 1, 2-dimethylpropyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1 , 3-Dimethylbutyl, 2, 2-Dimethylbutyl, 2, 3-Dimethylbutyl, 3, 3-Dimethylbutyl, 1-Ethylbutyl, 1, 1, 2-Trimethylpropyl, 1, 2, 2-TrimethyIpropyl, 1-Ethyl-l-methylpropyl or l-ethyl-2-methyl-propyl, in particular methyl, ethyl, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl and 1, 1-dimethylpropyl;
C2-C6~Alkenyl wie 2-Propenyl, 2-Butenyl, 3-Butenyl, l-Methyl-2-propenyl, 2-Methyl-2-propenyl, 2-Pentenyl,C 2 -C 6 ~ alkenyl such as 2-propenyl, 2-butenyl, 3-butenyl, l-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl,
3-Pentenyl, 4-Pentenyl, 3-Methyl-2-butenyl, l-Methyl-2-butenyl, 2-Methyl-2-butenyl, l-Methyl-3-butenyl, 2-Methyl-4-butenyl, 3-Methyl-3 butenyl, 1, l-Dimethyl-2-propenyl, 1, 2-Dimethyl- 2-propenyl, l-Ethyl-2-propenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-Hexenyl, l-Methyl-2-pentenyl, 2-Methyl-2-pentenyl,3-pentenyl, 4-pentenyl, 3-methyl-2-butenyl, l-methyl-2-butenyl, 2-methyl-2-butenyl, l-methyl-3-butenyl, 2-methyl-4-butenyl, 3- Methyl-3-butenyl, 1, l-dimethyl-2-propenyl, 1, 2-dimethyl-2-propenyl, l-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, l -Methyl-2-pentenyl, 2-methyl-2-pentenyl,
3-Methyl-2-pentenyl, 4-Methyl-2-pentenyl, l-Methyl-3 pentenyl, 2-Methyl-3-pentenyl, 3-Methyl-3-pentenyl, 4-Methyl-3-pentenyl, 1-Methyl-4-pentenyl, 2-Methyl-4-pentenyl, 3-Methyl-4-pentenyl, 4-Methyl-4-pentenyl, 1, l-Dimethyl-2-butenyl, 1, l-Dimethyl-3-butenyl, 1, 2-Dimethyl-2-butenyl,3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl -4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, l-dimethyl-2-butenyl, 1, l-dimethyl-3-butenyl, 1 , 2-dimethyl-2-butenyl,
1, 3-Dimethyl-3-butenyl, 2, 2-Dimethyl-3-butenyl,1, 3-dimethyl-3-butenyl, 2, 2-dimethyl-3-butenyl,
2, 3-Dimethyl-2-butenyl, 2 , 3-Dimethyl-3-butenyl, l-Ethyl-2-butenyl, l-Ethyl-3 butenyl, 2-Ethyl-2-butenyl, 2-Ethyl-3-butenyl, 1,1, 2-Trimethyl-2-propenyl, l-Ethyl-l-methyl-2-propenyl und Ethyl-2-methyl-2-propenyl,2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, l-ethyl-2-butenyl, l-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl , 1,1, 2-trimethyl-2-propenyl, l-ethyl-l-methyl-2-propenyl and ethyl 2-methyl-2-propenyl,
insbesondere l-Methyl-2-propenyl, l-Methyl-2-butenyl, 1, l-Dιmethyl-2-propenyl und 1, l-Dimethyl-2-butenyl;in particular l-methyl-2-propenyl, l-methyl-2-butenyl, 1, l-dimethyl-2-propenyl and 1, l-dimethyl-2-butenyl;
C2-C6-Alkinyl wie Propargyl, 2-Butinyl, 3-Butenyl, 2-Pentinyl, 3-Pentinyl, 4-Pentinyl, l-Methyl-3-butinyl, 2-Methyl-3-butinyl, l-Methyl-2-butinyl, 1, l-Dimethyl-2 propinyl, l-Ethyl-2-propinyl, 2-Hexinyl, 3-Hexinyl, 4-Hexinyl, 5-Hexinyl, l-Methyl-2-pentinyl, l-Methyl-3-pentinyl, l-Methyl-4-pentinyl, 3-Methyl-4-pentinyl, 4-Methyl-2-pentinyl, 1, l-Dimethyl-2-butinyl, 1, l-Dimethyl-3-butinyl, 1, 2-Dimethyl-3-butinyl, 2,2-Diraethyl-3-butinyl, l-Ethyl-2-butinyl, l-Ethyl-3-butinyl, 2-Ethyl-3-butinyl und l-Ethyl-l-methyl-2-propinyl;C 2 -C 6 alkynyl such as propargyl, 2-butynyl, 3-butenyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, l-methyl- 2-butynyl, 1, l-dimethyl-2-propynyl, l-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, l-methyl-3 pentynyl, l-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1, l-dimethyl-2-butynyl, 1, l-dimethyl-3-butynyl, 1,2 -Dimethyl-3-butynyl, 2,2-diraethyl-3-butynyl, l-ethyl-2-butynyl, l-ethyl-3-butynyl, 2-ethyl-3-butynyl and l-ethyl-l-methyl-2 -propinyl;
Cι-C4-Alkoxy wie Methoxy, Ethoxy, n-Propoxy, 1-Methylethoxy, n-Butoxy, 1-Methylpropoxy, 2-Methylpropoxy und 1, 1-Dimethyl- ethoxy,-C-C 4 alkoxy such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1, 1-dimethylethoxy,
insbesondere Cχ-C3-Alkoxy wie Methoxy, Ethoxy, i-Propoxy,in particular Cχ-C 3 alkoxy such as methoxy, ethoxy, i-propoxy,
wobei diese Gruppen gegebenenfalls durch ein bis fünf Halogen¬ atome wie Fluor, Chlor, Brom und lod, vorzugsweise Fluor und Chlor oder Cχ-C4-Alkoxy wie vorstehend genannt substituiert sein können. Die vorstehend definierte Gruppe - (A)m-S(O)nR1 steht beispiels¬ weise fürthese groups can optionally be substituted by one to five halogen atoms such as fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine or Cχ-C 4 alkoxy as mentioned above. The group - (A) m -S (O) n R 1 defined above stands for example for
Cι-C4-Alkylthio wie Methylthio, Ethylthio, n-Propylthio, 1-Methyl- ethylthio, n-Butylthio, 1-Methylpropylthio, 2-Methylpropylthio und 1, 1-Dimethylethylthio, insbesondere Methylthio;Cι-C 4 alkylthio such as methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1-methylpropylthio, 2-methylpropylthio and 1, 1-dimethylethylthio, especially methylthio;
Cι-C4-Alkylsulfinyl wie Methylsulfinyl, Ethylsulfinyl, n-Propyl- sulfinyl, 1-Methylethylsulfinyl, n-Butylsulfinyl, 1-Methylpropyl- sulfinyl, 2-Methylpropylsulfinyl und 1, 1-Dimethylethylsulfinyl, insbesondere Methylsulfinyl;Cι-C 4 alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl and 1, 1-dimethylethylsulfinyl, especially methylsulfinyl;
Cι-C4-Alkylsulfonyl wie Methylsulfonyl, Ethylsulfonyl, n-Propyl- sulfonyl, 1-Methylethylsulfonyl, n-Butylsulfonyl, 1-Methylpropyl- sulfonyl, 2-Methylpropylsulfonyl und 1, 1-Dimethylethylsulfonyl, insbesondere Methylsulfonyl;Cι-C 4 alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1-methylethylsulfonyl, n-butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl and 1, 1-dimethylethylsulfonyl, especially methylsulfonyl;
Cχ-C4-Alkoxysulfonyl wie Methoxysulfonyl, Ethoxysulfonyl, n-Prop- oxysulfonyl, 1-Methylethoxysulfonyl, n-Butoxysulfonyl, 1-Methyl- propoxysulfonyl, 2-Methylpropoxysulfonyl und 1, 1-Dimethylethoxy- sulfonyl, insbesondere Methoxysulfonyl;Cχ-C 4 alkoxysulfonyl such as methoxysulfonyl, ethoxysulfonyl, n-propoxysulfonyl, 1-methylethoxysulfonyl, n-butoxysulfonyl, 1-methylpropoxysulfonyl, 2-methylpropoxysulfonyl and 1, 1-dimethylethoxysulfonyl, especially methoxysulfonyl;
N-Cι-C4-Alkylsulfamoyl wie N-Methylsulfamoyl, N-Ethylsulfamoyl, N-n-Propylsulfamoyl, N-1-Methylethylsulfamoyl, N-n-Butyl- sulfamoyl, N-1-Methylpropylsulfamoyl, N-2-Methylpropylsulfamoyl und N-l, 1-Dimethylethylsulfamoyl, insbesondere N-Methylsulfamoyl,-N-Cι-C 4 alkylsulfamoyl such as N-methylsulfamoyl, N-ethylsulfamoyl, Nn-propylsulfamoyl, N-1-methylethylsulfamoyl, Nn-butylsulfamoyl, N-1-methylpropylsulfamoyl, N-2-methylpropylsulfamoyl, N-2-methylpropylsulfamoyl , in particular N-methylsulfamoyl,
N-Cι-C4-Alkylsulfinamoyl wie N-Methylsulfinamoyl, N-Ethyl¬ sulfinamoyl, N-n-Propylsulfinamoyl, N-1-Methylethylsulfinamoyl, N-n-Butylsulfinamoyl, N-1-Methylpropylsulfinamoyl, N-2-Methyl- propylsulfinamoyl und N-l, 1-Dimethylethylsulfinamoyl, ins¬ besondere N-Methylsulfinamoyl;N-Cι-C 4 alkylsulfinamoyl such as N-methylsulfinamoyl, N-ethyl sulfinamoyl, Nn-propylsulfinamoyl, N-1-methylethylsulfinamoyl, Nn-butylsulfinamoyl, N-1-methylpropylsulfinamoyl, N-2-methyl-1-propylsulfinamoyl -Dimethylethylsulfinamoyl, especially N-methylsulfinamoyl;
Di-Cι-C4-Alkylsulfamoyl wie Dimethylsulfamoyl, Diethylsulfamoyl, Dipropylsulfamoyl, Dibutylsulfamoyl, N-Methyl-N-ethylsulfamoyl, N-Methyl-N-propylsulfamoyl, N-Methyl-N-1-methylethylsulfamoyl, N-Methyl-N-1, 1-Dimethylethylsulfamoyl, Di-1-Methylethylsulfamoyl, N-Ethyl-N-1-Methylethylsulfamoyl und N-Ethyl-N-1, 1-dimethyl ethylsulfamoyl; insbesondere Dimethylsulfamoyl;Di-Cι-C 4 alkylsulfamoyl such as dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl, N-methyl-N-ethylsulfamoyl, N-methyl-N-propylsulfamoyl, N-methyl-N-1-methylethylsulfamoyl, N-methyl , 1-dimethylethylsulfamoyl, di-1-methylethylsulfamoyl, N-ethyl-N-1-methylethylsulfamoyl and N-ethyl-N-1, 1-dimethylethylsulfamoyl; especially dimethylsulfamoyl;
Di-Cι-C4-Alkylsulfinamoyl wie Dimethylsulfinamoyl, Diethyl¬ sulfinamoyl, Dipropylsulfinamoyl, Dibutylsulfinamoyl, N-Methyl- N-ethylsulfinamoyl, N-Methyl-N-propylsulfinamoyl, N-Methyl-N-1- methylethylsulfinamoyl, N-Methyl-N-1, 1-Dimethylethylsulfinamoyl, Di-1-Methylethylsulfinamoyl, N-Ethyl-N-1-Methylethylsulfinamoyl und N-Ethyl-N-1, 1-dimethylethylsulfinamoyl; insbesondere Dimethylsulfinamoyl,Di-Cι-C 4 alkylsulfinamoyl such as dimethylsulfinamoyl, Diethyl¬ sulfinamoyl, dipropylsulfinamoyl, dibutylsulfinamoyl, N-methyl-N-ethylsulfinamoyl, N-methyl-N-propylsulfinamoyl, N-methyl-N-1-methyll sulfonamoyl -1, 1-dimethylethylsulfinamoyl, di-1-methylethylsulfinamoyl, N-ethyl-N-1-methylethylsulfinamoyl and N-ethyl-N-1, 1-dimethylethylsulfinamoyl; especially dimethylsulfinamoyl,
Cι-C4-Alkylsulfinyloxy wie Methylsulfinyloxy, Ethylsulfinyloxy, n-Propylsulfinyloxy, 1-Methylethylsulfinyloxy, n-Butylsulfinyl- oxy, 1-Methylpropylsulfinyloxy, 2-Methylpropylsulfinyloxy und 1, 1-Dimethylethylsulfinyloxy, insbesondere Methylsulfinyloxy;Cι-C 4 alkylsulfinyloxy such as methylsulfinyloxy, ethylsulfinyloxy, n-propylsulfinyloxy, 1-methylethylsulfinyloxy, n-butylsulfinyloxy, 1-methylpropylsulfinyloxy, 2-methylpropylsulfinyloxy and 1, 1-dimethylethylsulfinyloxy, especially methylsulfinyloxy;
Cι-C4-Alkylsulfonyloxy wie Methylsulfonyloxy, Ethylsulfonyloxy, n-Propylsulfonyloxy, 1-Methylethylsulfonyloxy, n-Butylsulfonyl- oxy, 1-Methylpropylsulfonyloxy, 2-Methylpropylsulfonyloxy und 1, 1-Dimethylethylsulfonyloxy, insbesondere Methylsulfonyloxy;Cι-C 4 alkylsulfonyloxy such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, 1-methylethylsulfonyloxy, n-butylsulfonyloxy, 1-methylpropylsulfonyloxy, 2-methylpropylsulfonyloxy and 1, 1-dimethyloxysulfonyloxy;
Cι-C4-Alkylsulfinylamino wie Methylsulfinylamino, Ethylsulfinyl- amino, n-Propylsulfinylamino, 1-Methylethylsulfinylamino, n-Butylsulfinylamino, 1-Methylpropylsulfinylamino, 2-Methyl- propylsulfinylamino und 1, 1-Dimethylethylsulfinylamino, ins¬ besondere Methylsulfinylamino;Cι-C 4 alkylsulfinylamino such as methylsulfinylamino, ethylsulfinylamino, n-propylsulfinylamino, 1-methylethylsulfinylamino, n-butylsulfinylamino, 1-methylpropylsulfinylamino, 2-methylpropylsulfinylamino and 1, 1-dimethylethylsulfinylamino,
Cι~C4-Alkylsulfonylamino wie Methylsulfonylamino, Ethylsulfonyl- amino, n-Propylsulfonylamino, 1-Methylethylsulfonylamino, n-Butylsulfonylamino, 1-Methylpropylsulfonylamino, 2-Methyl- propylsulfonylamino und 1, 1-Dimethylethylsulfonylamino, ins¬ besondere Methylsulfonylamino;Cι ~ C 4 alkylsulfonylamino such as methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, 1-methylethylsulfonylamino, n-butylsulfonylamino, 1-methylpropylsulfonylamino, 2-methylpropylsulfonylaminoethyl and 1, 1-dimonaminoethyl;
N-Cι-C4-Alkylsulfinyl-N-methyl-amino wie N-Methylsulfinyl-N- methyl-amino, N-Ethylsulfinyl-N-methyl-amino, N-n-Propylsulfinyl- N-methyl-amino, N-1-Methylethylsulfinyl-N-methyl-amino, N-n-Butylsulfinyl-N-methyl-amino, N-1-Methylpropylsulfinyl-N- methyl-amino, N-2-Methylpropylsulfinyl-N-methyl-amino und N-l, 1-Dimethylethylsulfinyl-N-methyl-amino, insbesondere N-Methylsulfinyl-N-methyl-amino;N-Cι-C 4 alkylsulfinyl-N-methyl-amino such as N-methylsulfinyl-N-methyl-amino, N-ethylsulfinyl-N-methyl-amino, Nn-propylsulfinyl-N-methyl-amino, N-1-methylethylsulfinyl -N-methyl-amino, Nn-butylsulfinyl-N-methyl-amino, N-1-methylpropylsulfinyl-N-methyl-amino, N-2-methylpropylsulfinyl-N-methyl-amino and Nl, 1-dimethylethylsulfinyl-N-methyl -amino, especially N-methylsulfinyl-N-methyl-amino;
N-Cι-C4-AlkyIsulfinyl-N-ethyl-amino wie N-Methylsulfinyl-N-ethyl- amino, N-Ethylsulfinyl-N-ethyl-amino, N-n-Propylsulfinyl-N-ethyl- amino, N-1-Methylethylsulfinyl-N-ethyl-amino, N-n-Butylsulfinyl- N-ethyl-amino, N-l-MethyIpropylsulfinyl-N-ethyl-amino, N-2-Methylpropylsulfinyl-N-ethyl-amino und N-l, 1-Dimethylethyl¬ sulfinyl-N-ethyl-amino, insbesondere N-Methylsulfinyl-N-ethyl- amino;N-Cι-C 4 -AlkyIsulfinyl-N-ethyl-amino such as N-methylsulfinyl-N-ethyl-amino, N-ethylsulfinyl-N-ethyl-amino, Nn-propylsulfinyl-N-ethyl-amino, N-1-methylethylsulfinyl -N-ethyl-amino, Nn-butylsulfinyl-N-ethyl-amino, Nl-methylpropylsulfinyl-N-ethyl-amino, N-2-methylpropylsulfinyl-N-ethyl-amino and Nl, 1-dimethylethylsulfinyl-N-ethyl amino, in particular N-methylsulfinyl-N-ethylamino;
N-Cι-C4-Alkylsulfonyl-N-methyl-amino wie N-Methylsulfonyl-N- methyl-amino, N-Ethylsulfony1-N-methyl-amino, N-n-PropyIsulfonyl- N-methyl-amino, N-1-Methylethylsulfonyl-N-methyl-amino, N-n-Butylsulfony1-N-methyl-amino, N-1-MethyIpropylsulfonyl-N- methyl-amino, N-2-Methylpropylsulfonyl-N-methyl-amino und N-l, 1-Dimethylethylsulfonyl-N-methyl-amino, insbesondere N-Methylsulfonyl-N-methyl-amino,• N-Cι-C 4 alkylsulfonyl-N-methyl-amino such as N-methylsulfonyl-N-methyl-amino, N-ethylsulfony1-N-methyl-amino, Nn-propyisulfonyl-N-methyl-amino, N-1-methylethylsulfonyl -N-methyl-amino, Nn-butylsulfony1-N-methyl-amino, N-1-methylpropylsulfonyl-N-methyl-amino, N-2-methylpropylsulfonyl-N-methyl-amino and Nl, 1-dimethylethylsulfonyl-N-methylamino, in particular N-methylsulfonyl-N-methylamino, •
N-C1-C4-AlkyIsulfony1-N-ethyl-amino wie N-Methylsulfony1-N-ethy1- amino, N-Ethylsulfonyl-N-ethyl-amino, N-n-Propylsulfonyl-N-ethyl- amino, N-1-Methylethylsulfonyl-N-ethyl-amino, N-n-Butylsulfonyl- N-ethyl-amino, N-1-Methylpropylsulfonyl-N-ethyl-amino, N-2-Methylpropylsulfonyl-N-ethyl-amino und N-l, 1-Dimethylethyl- sulfonyl-N-ethyl-amino, insbesondere N-Methylsulfonyl-N-ethyl- amino;N-C1-C4-Alkysulfony1-N-ethyl-amino such as N-methylsulfony1-N-ethy1-amino, N-ethylsulfonyl-N-ethyl-amino, Nn-propylsulfonyl-N-ethyl-amino, N-1-methylethylsulfonyl- N-ethyl-amino, Nn-butylsulfonyl-N-ethyl-amino, N-1-methylpropylsulfonyl-N-ethyl-amino, N-2-methylpropylsulfonyl-N-ethyl-amino and Nl, 1-dimethylethylsulfonyl-N- ethyl-amino, especially N-methylsulfonyl-N-ethyl-amino;
C_-C4-Halogenalkylthio wie Chlormethylthio, Dichlormethylthio, Trichlormethylthio, Fluormethylthio, Difluormethylthio, Trifluor- methylthio, Chlorfluormethylthio, Chlordifluormethylthio, 1-Fluorethylthio, 2-Fluorethylthio, 2,2-Difluorethylthio, 2,2, 2-Trifluorethylthio, 2-Chlor-2, 2-difluorethylthio, 2, 2-Dichlor-2 fluorethylthio, 2, 2,2-Trichlorethylthio und Pentafluorethylthio, insbesondere Trifluormethylthio.C_-C 4 -haloalkylthio such as chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2-difluoroethylthio -2, 2-difluoroethylthio, 2, 2-dichloro-2 fluoroethylthio, 2, 2,2-trichloroethylthio and pentafluoroethylthio, especially trifluoromethylthio.
Die vorstehend definierte Gruppe -(A)m-CO-R2 steht beispielsweise fürThe group - (A) m -CO-R 2 defined above stands for, for example
Cι-C4-Alkylcarbonyl wie Methylcarbonyl, Ethylcarbonyl, n-Propyl- carbonyl, 1-Methylethylcarbonyl, n-Butylcarbonyl, 1-Methylpropyl - carbonyl, 2-Methylpropylcarbonyl und 1, 1-Dimethylethylcarbonyl, insbesondere Methylcarbonyl;C 1 -C 4 -alkylcarbonyl such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl and 1, 1-dimethylethylcarbonyl, in particular methylcarbonyl;
Cι-C4-Alkoxycarbonyl wie Methoxycarbonyl, Ethoxycarbonyl, n-Prop- oxycarbonyl, 1-Methylethoxycarbonyl, n-Butoxycarbonyl, 1-Methyl- propoxycarbonyl, 2-Methylpropoxycarbonyl und 1, 1-Dimethylethoxy- carbonyl, insbesondere Methoxycarbonyl;Cι-C 4 alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, n-prop-oxycarbonyl, 1-methylethoxycarbonyl, n-butoxycarbonyl, 1-methyl-propoxycarbonyl, 2-methylpropoxycarbonyl and 1, 1-dimethylethoxycarbonyl, especially methoxycarbonyl;
N-Cι-C4-Alkylcarbamoyl wie N-Methylcarbamoyl, N-Ethylcarbamoyl, N-n-Propylcarbamoyl, N-1-Methylethylcarbamoyl, N-n-Butylcarba- moyl, N-1-Methylpropylcarbamoyl, N-2-Methylpropylcarbamoyl und N-l, 1-Dimethylethylcarbamoyl, insbesondere N-Methylcarbamoyl;N-Cι-C 4 alkylcarbamoyl such as N-methylcarbamoyl, N-ethylcarbamoyl, Nn-propylcarbamoyl, N-1-methylethylcarbamoyl, Nn-butylcarbamoyl, N-1-methylpropylcarbamoyl, N-2-methylpropylcarbamoyl and Nl, 1-dim , especially N-methylcarbamoyl;
Di-Cι-C4-Alkylcarbamoyl wie Dimethylcarbamoyl, Diethylcarbamoyl, Dipropylcarbamoyl, Dibutylcarbamoyl, N-Methyl-N-ethylcarbamoyl, N-Methyl-N-propylcarbamoyl, N-Methyl-N-1-methylethylcarbamoyl, N-Methyl-N-1, 1-Dimethylethylcarbamoyl, Di-1-Methylethylcarbamoyl, N-Ethyl-N-1-Methylethylcarbamoyl und N-Ethyl-N-1, 1-dimethylethyl- carbamoyl; insbesondere Dimethylcarbamoyl; Cι-C4-Alkylcarbonyloxy wie Methylcarbonyloxy, Ethylcarbonyloxy, n-Propylcarbonyloxy, 1-Methylethylcarbonyloxy , n-Butylcarbonyl - oxy, 1-Methylpropylcarbonyloxy, 2-Methylpropylcarbonyloxy und 1, 1-Dimethylethylcarbonyloxy, insbesondere Methylcarbonyloxy; Cι-C4-Alkylcarbonylamino wie Methylcarbonylamino, Ethylcarbonyl - amino, n-Propylcarbonylamino, 1-Methylethylcarbonylamino, n-Butylcarbonylamino, 1-Methylpropylcarbonylamino, 2-Methyl- propylcarbonylamino und 1, 1-Dimethylethylcarbonylamino, ins¬ besondere Methylcarbonylamino;Di-Cι-C 4 alkylcarbamoyl such as dimethylcarbamoyl, diethylcarbamoyl, dipropylcarbamoyl, dibutylcarbamoyl, N-methyl-N-ethylcarbamoyl, N-methyl-N-propylcarbamoyl, N-methyl-N-1-methylethylcarbamoyl, N-methyl-N-1 , 1-dimethylethylcarbamoyl, di-1-methylethylcarbamoyl, N-ethyl-N-1-methylethylcarbamoyl and N-ethyl-N-1, 1-dimethylethylcarbamoyl; especially dimethylcarbamoyl; Cι-C 4 alkylcarbonyloxy such as methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, 1-methylethylcarbonyloxy, n-butylcarbonyloxy, 1-methylpropylcarbonyloxy, 2-methylpropylcarbonyloxy and 1, 1-dimethylethylcarbonyloxy, especially methylcarbonyloxy; C 1 -C 4 -alkylcarbonylamino such as methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, 1-methylethylcarbonylamino, n-butylcarbonylamino, 1-methylpropylcarbonylamino, 2-methylpropylcarbonylamino and 1, 1-dimethylethylcarbonylamino, in particular methylcarbonylamino;
N-Cι-C4-Alkylcarbonyl-N-methyl-amino wie N-Methylcarbonyl-N- methyl-amino, N-Ethylcarbonyl-N-methyl-amino, N-n-Propylcarbonyl-N-Cι-C 4 -alkylcarbonyl-N-methyl-amino such as N-methylcarbonyl-N-methyl-amino, N-ethylcarbonyl-N-methyl-amino, Nn-propylcarbonyl-
N-methyl-amino, N-1-Methy1ethylcarbony1-N-methyl-amino,N-methyl-amino, N-1-methylethylcarbony1-N-methyl-amino,
N-n-Butylcarbony1-N-methyl-amino, N-1-MethyIpropylcarbonyl-N- methyl-amino, N-2-Methylpropylcarbonyl-N-methyl-amino und N-l, 1-Dimethylethylcarbonyl-N-methyl-amino, insbesondere N-Methylcarbonyl-N-methyl-amino.Nn-butylcarbony1-N-methylamino, N-1-methylpropylcarbonyl-N-methylamino, N-2-methylpropylcarbonyl-N-methylamino and Nl, 1-dimethylethylcarbonyl-N-methylamino, especially N-methylcarbonyl -N-methyl-amino.
X steht beispielsweise für:For example, X stands for:
CH2, CH(CH3) , C((CH3)2), CH(C2H5), C((C2H5)2), CH(C6H5), CH2-CH2,CH 2, CH (CH 3 ), C ((CH 3 ) 2 ), CH (C 2 H 5 ), C ((C 2 H 5 ) 2 ), CH (C 6 H 5 ), CH 2 -CH 2 ,
CH2-CH(CH3), CH2-C( (CH3)2) , CH (CH3) -CH (CH3) , CH (CH3) ~C ( (CH3) 2) ,CH 2 -CH (CH 3 ), CH 2 -C ((CH 3 ) 2 ), CH (CH 3 ) -CH (CH 3 ), CH (CH 3 ) ~ C ((CH 3 ) 2 ),
C( (CH3)2)-C( (CH3)2) ,C ((CH 3 ) 2 ) -C ((CH 3 ) 2 ),
CH2-CH(C2H5) , CH2-C( (C2H5)2) , CH (C2H5) -CH (C2H5) , CH (C2H5) -C ( (C2H5) 2) , C( (C2H5)2)-C( (C2H5)2) , CH2-CH(C3H7) , CH2-CH (iC3H7) , CH2-CH (C4H9) , CH2-CH(iC4H9) ,CH 2 -CH (C 2 H 5 ), CH 2 -C ((C 2 H 5 ) 2 ), CH (C 2 H 5 ) -CH (C 2 H 5 ), CH (C 2 H 5 ) -C ((C 2 H 5 ) 2 ), C ((C 2 H 5 ) 2 ) -C ((C 2 H 5 ) 2 ), CH 2 -CH (C 3 H 7 ), CH 2 -CH (iC 3 H 7 ), CH 2 -CH (C 4 H 9 ), CH 2 -CH (iC 4 H 9 ),
CH2-CH(Br), CH2-C( (Br)2) , CH(Br) -CH(Br) , C( (Br) 2) -C ( (Br) 2) , CH2-CH(C1), CH2-C( (Cl)2) , CH(Cl) -C ( (Cl2) , C ( (Cl) 2) -C ( (Cl) 2) , CH2-CH(C6H5) , CH(C6H5)-CH(C6H5) , CH2-CH(p-N02C6H5) ] CH=CH, C(CH3)=CH, C(CH3)=CCH3, CH=CBr, CH=CC1, CBr=CBr, CC1=CC1, CH=C(OCH3), CH=C(C6H5), C (C6H5)=C(C6H5) , C(C2H5)=CH,CH 2 -CH (Br), CH 2 -C ((Br) 2 ), CH (Br) -CH (Br), C ((Br) 2 ) -C ((Br) 2 ), CH 2 -CH ( C1), CH 2 -C ((Cl) 2 ), CH (Cl) -C ((Cl 2 ), C ((Cl) 2 ) -C ((Cl) 2 ), CH 2 -CH (C 6 H 5 ), CH (C 6 H 5 ) -CH (C 6 H 5 ), CH 2 -CH (p-NO 2 C 6 H 5 )] CH = CH, C (CH 3 ) = CH, C (CH 3 ) = CCH 3 , CH = CBr, CH = CC1, CBr = CBr, CC1 = CC1, CH = C (OCH 3 ), CH = C (C 6 H 5 ), C (C 6 H 5 ) = C (C 6 H 5 ), C (C 2 H 5 ) = CH,
C(C2H5)=C(C2H5) , CH=C(C3H5) , CH=C(C4H7) , CH2-CH=CH, CH (CH3) -CH=CH, C( (CH3)' 2)-CH=CH, CH2-CH=C(CH3) , CH2-C (CH3) =CH, CH2-C (CH3 ) =C (CH3) , CH(CH3)-C(CH3)=C(CH3) , C ( (CH3) 2) -C (CH3) =C (CH3) , N-H, N-CH3 , N-C2H5, N-C3H7, N-C4H9, N-iCH3H7, N-OCH3, N-OC2H5, N-CH2C6H5, N-C6H5--C (C 2 H5) = C (C 2 H 5 ), CH = C (C 3 H 5 ), CH = C (C 4 H 7 ), CH 2 -CH = CH, CH (CH 3 ) -CH = CH, C ((CH 3 ) ' 2 ) -CH = CH, CH 2 -CH = C (CH 3 ), CH 2 -C (CH 3 ) = CH, CH 2 -C (CH 3 ) = C (CH 3 ), CH (CH 3 ) -C (CH 3 ) = C (CH 3 ), C ((CH 3 ) 2 ) -C (CH 3 ) = C (CH 3 ), NH, N-CH 3 , NC 2 H 5 , NC 3 H 7 , NC 4 H 9 , N-iCH 3 H 7 , N-OCH 3 , N-OC 2 H 5 , N-CH 2 C 6 H 5 , NC 6 H 5 -
Y steht beispielsweise für:Y stands for example for:
C=0, CH-OH, CH-OCH3, CH-OC2H5, CH-OC3H7 , CH-OiPr, CH-OC4H9, CH-OiBu, CH-OC5H11, CH-OC6Hι3, CH-OC6H5, C(CH3)-OCH3, C (CH3, _OC2H5, C(CH3)_OC3H7, C(CH3)-OC4H9, C(CH3)-OiPr, C(CH3)-OiBu, C(CH3)-OtBu, C(CH3)-OPh, CH2, CH(CH3) , C( (CH3)2) , C=N-CH3/ C=N-C2H5, C=N-C3H7, C=N-C4H9, C=N-iC4H9, C=N-tC4H9, C=N-iPr, C=N-OCH3 , C=N-OC2H5, C=N-OC3H7, C=N-OC4H9/ C=N-OiC4H9, C=N-OtC4H9 , C=N-OCH2CH=CH2 , C=N-OCH(CH3)CH=CH2, C=N-OCH2CH=CHCH3 , C=N-OCH2CH=C (CH3) 2 ,C = 0, CH-OH, CH-OCH 3 , CH-OC 2 H 5 , CH-OC 3 H 7 , CH-OiPr, CH-OC 4 H 9 , CH-OiBu, CH-OC5H11, CH-OC 6 Hι 3 , CH-OC 6 H 5 , C (CH 3 ) -OCH 3 , C (CH 3 , _OC 2 H 5 , C (CH 3) _OC 3 H 7 , C (CH 3 ) -OC 4 H 9 , C (CH 3 ) -OiPr, C (CH 3 ) -OiBu, C (CH 3 ) -OtBu, C (CH 3 ) -OPh, CH 2 , CH (CH 3 ), C ((CH 3 ) 2 ), C = N-CH 3 / C = NC 2 H 5 , C = NC 3 H 7 , C = NC 4 H 9 , C = N-iC 4 H 9 , C = N-tC 4 H 9 , C = N- iPr, C = N-OCH 3 , C = N-OC 2 H 5 , C = N-OC 3 H 7 , C = N-OC 4 H 9 / C = N-OiC 4 H 9 , C = N-OtC 4 H 9 , C = N-OCH 2 CH = CH 2 , C = N-OCH (CH 3) CH = CH 2 , C = N-OCH 2 CH = CHCH 3 , C = N-OCH 2 CH = C ( CH 3 ) 2 ,
C=N-OCH2CH=CHBr, C=N-0CH2CH=CHC1, C=N-OCH2CH=CHC2H5, C=N-OCH2C≡CH, C=N-OCH2C≡CCH3, C=N-OCH2C6H5, CH-NH(OCH3) , CH-NH (OC2H5) , CH-NH(OiPr), CH-NH(OnPr), CH-NH(OC6H5) , CH-NCH3 (OCH3) , CH-NCH3(OC2H5) , CH-NCH3(OiPr) , CH-NCH3 (OnPr) , CH-NCH3 (OC6H5) , CH-NH(CH3), CH-NH(C2H5), CH-NH(C3H7), CH-NH(C4H9), CH-NH(iPr), CH-NH(iBu), CH-NH (tBu), CH-NH(C6HB), CH-N(CH3)2, CH-NCH3 (C2H5) , CH-NCH3(C3H7) , CH-NCH3 (C4H9) , CH-NCH3 (iPr) , CH-NCH3 (iBu) , C=N-NH2, C=N-NHCH3, C=N-N( (CH3)2) , C=N-NH (C2H5) , C=N-NCH3 (C2H5) , C=N-N{ (C2H5)2) , CH-SCH3, CH-SC2H5, CH-SC3H7, CH-SC4H9, CH-SPr, CH-SiBu, CH-SH, C(CH3)-SCH3, C(CH3) -SC2H5, C(CH3) -SC3H7, 1, 3-Dioxanyl, 1,3-Dioxolanyl, 5, 5-Dimethyl-1, 3-dioxanylC = N-OCH 2 CH = CHBr, C = N-0CH 2 CH = CHC1, C = N-OCH 2 CH = CHC 2 H 5 , C = N-OCH 2 C≡CH, C = N-OCH 2 C ≡CCH3, C = N-OCH 2 C 6 H 5 , CH-NH (OCH 3 ), CH-NH (OC 2 H 5 ), CH-NH (OiPr), CH-NH (OnPr), CH-NH (OC 6 H 5 ), CH-NCH 3 (OCH 3 ), CH-NCH 3 (OC 2 H 5 ), CH-NCH 3 (OiPr ), CH-NCH 3 (OnPr), CH-NCH 3 (OC 6 H 5 ), CH-NH (CH 3 ), CH-NH (C 2 H 5 ), CH-NH (C 3 H 7 ), CH -NH (C 4 H 9 ), CH-NH (iPr), CH-NH (iBu), CH-NH (tBu), CH-NH (C 6 H B ), CH-N (CH 3 ) 2 , CH -NCH 3 (C 2 H 5 ), CH-NCH 3 (C 3 H 7 ), CH-NCH 3 (C 4 H 9 ), CH-NCH 3 (iPr), CH-NCH 3 (iBu), C = N-NH 2 , C = N-NHCH 3 , C = NN ((CH 3 ) 2 ), C = N-NH (C 2 H 5 ), C = N-NCH 3 (C 2 H 5 ), C = NN {(C 2 H 5 ) 2 ), CH-SCH 3 , CH-SC 2 H 5 , CH-SC 3 H 7 , CH-SC 4 H 9 , CH-SPr, CH-SiBu, CH-SH, C (CH 3 ) -SCH 3 , C (CH 3 ) -SC 2 H 5 , C (CH 3 ) -SC 3 H 7 , 1, 3-dioxanyl, 1,3-dioxolanyl, 5, 5-dimethyl-1, 3-dioxanyl
Bevorzugt sind Isoxazol-4-yl-benzoylderivate der Formel la,Isoxazol-4-yl-benzoyl derivatives of the formula Ia are preferred,
Figure imgf000020_0001
Figure imgf000020_0001
in der L für Wasserstoff, Ci-Cβ-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Ci-C4-Alkoxy, Ci-C4-Alkylthio, Ci-C4-Halogenalkyl, Ci-C4-Halogenalkoxy, C1-C4-Halogenalkylthio, C1-C4-Alkylsulfonyl, Halogen, Nitro oder Cyano und M für Wasserstoff, Cι-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C1-C4-Alkoxy, Ci-C4-Alkylthio, Cι-C4-Halogenalkyl, C\-C4-Halogenalkoxy, Ci-C4-Halogenalkoxy, Cι-C4-Halogenalkylthio, C1-C4-Alkylsulfonyl, Halogen, Nitro oder Cyano steht und Q, J, X, n und Y die oben angegebenen Bedeutungen haben, wobei für den Fall, daß Y = C=0 ist, X ungleich NR23 ist.in the L for hydrogen, Ci-Cβ-alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Ci-C 4 -alkoxy, Ci-C 4 -alkylthio, Ci-C 4 -haloalkyl, Ci -C 4 haloalkoxy, C 1 -C 4 haloalkylthio, C 1 -C4 alkylsulfonyl, halogen, nitro or cyano and M for hydrogen, -C-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 -alkynyl, C 1 -C 4 alkoxy, C 4 alkylthio, Cι-C 4 haloalkyl, C \ -C 4 haloalkoxy, Ci-C4-haloalkoxy, Cι-C 4 haloalkylthio, C 1 -C 4 alkylsulfonyl, halogen, nitro or cyano and Q, J, X, n and Y have the meanings given above, where X is not NR 23 if Y = C = 0.
Weiterhin bevorzugt sind Isoxazol-4-yl-benzoylderivate der Formel lb,Isoxazol-4-yl-benzoyl derivatives of the formula Ib are also preferred,
Figure imgf000020_0002
in der L für Cι-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Cι-C4-Alkoxy, Cι-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro oder Cyano und M für Wasserstoff Cι-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Ci-C4-Alkoxy, Cι-C4-Halogenalkyl, Ci-C4-Halogen- alkoxy, Halogen, Nitro steht oder Cyano und Q, J, X, n und Y die oben angegebenen Bedeutungen haben, wobei für den Fall, daß Y = C=0 ist, X ungleich NR23 ist.
Figure imgf000020_0002
in the L for -CC 6 alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, -C-C 4 -alkoxy, -C-C 4 -haloalkyl, C 1 -C 4 -haloalkoxy, halogen , nitro or cyano and M is hydrogen Cι-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Ci-C 4 -alkoxy, C 4 haloalkyl, Ci-C 4 - Haloalkoxy, halogen, nitro or cyano and Q, J, X, n and Y have the meanings given above, where X = NR 23 if Y = C = 0.
Bevorzugt sind auch Isoxazol-4-yl-benzoylderivate der Formel I, in der die Reste L bzw. M für Wasserstoff, Methyl, Methoxy, Chlor, Cyano, Nitro, Trifluormethyl stehen. Bevorzugt sind Isoxazol -4 -yl-benzoylderivate der Formel lc,Isoxazol-4-yl-benzoyl derivatives of the formula I are also preferred, in which the radicals L and M are hydrogen, methyl, methoxy, chlorine, cyano, nitro, trifluoromethyl. Isoxazole -4 -yl-benzoyl derivatives of the formula Ic are preferred,
Figure imgf000021_0001
in der L für Wasserstoff, Ci-Cδ-Alkyl, C2-C6 -Alkenyl , C2-C6- Alkinyl, Ci-C4 -Alkoxy, Ci-C4-Halogenalkyl, Ci -C4 -Halogenalkoxy, Halogen, Nitro oder Cyano und M für Wasserstoff, Cχ-C6-Alkyl, C2-C6-Alkenyl, C2-C6 -Alkinyl, C1-C4 -Alkoxy, Ci-C4 -Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro steht oder Cyano und Q, J, n, Y sowie R22, R21, R12 und R13 die oben angegebenen Bedeutungen haben.
Figure imgf000021_0001
L is hydrogen, Ci-C δ -alkyl, C 2 -C 6 alkenyl, C 2 -C 6 - alkinyl, Ci-C 4 alkoxy, Ci-C4-haloalkyl, Ci-C4 haloalkoxy, Halogen, nitro or cyano and M for hydrogen, Cχ-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 4 alkoxy, Ci-C 4 haloalkyl, C 1 -C 4 haloalkoxy, halogen, nitro or cyano and Q, J, n, Y and R 22 , R 21 , R 12 and R 13 have the meanings given above.
Ebenfalls bevorzugt sind Isoxazol-4-yl-benzoylderivate der Formel Id,Isoxazol-4-yl-benzoyl derivatives of the formula Id are also preferred,
Figure imgf000021_0002
in der L für Wasserstoff, Cι-C6-Alkyl, C2-Ce -Alkenyl, C2-C6- Alkinyl, Cχ-C4-Alkoxy, Ci-C4-Halogenalkyl, Cχ-C4 -Halogenalkoxy, Halogen, Nitro oder Cyano und M für Wasserstoff, Cχ-Cg-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Cι-C4 -Alkoxy, C1-C4-Halogenalkyl, Ci-C4-Halogenalkoxy, Halogen, Nitro steht oder Cyano und Q, J, n, Y sowie R12 und R13 die oben angegebenen Bedeutungen haben.
Figure imgf000021_0002
in the L for hydrogen, -CC 6 alkyl, C 2 -Ce alkenyl, C 2 -C 6 alkynyl, Cχ-C 4 alkoxy, Ci-C 4 haloalkyl, Cχ-C 4 haloalkoxy, halogen , Nitro or Cyano and M for hydrogen, Cχ-Cg-alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Cι-C 4 alkoxy, C 1 -C 4 haloalkyl, Ci-C 4 -Halogenalkoxy, halogen, nitro or cyano and Q, J, n, Y and R 12 and R 13 have the meanings given above.
Auch bevorzugt sind Isoxazol -4 -yl-benzoylderivate der Formel Ie,Isoxazole -4 -yl-benzoyl derivatives of the formula Ie are also preferred,
Figure imgf000021_0003
in der L für Wasserstoff, Ci-Cβ-Alkyl, C2-C6-Alkenyl, C2-C6- Alkinyl, Ci-C4-Alkoxy, Ci-C4-Halogenalkyl, Cx-C4 -Halogenalkoxy, Halogen, Nitro oder Cyano und M für Wasserstoff, Cι-C6 -Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Cι-C4-Alkoxy, Ci-C4-Halogenalkyl, Ci-C4-Halogenalkoxy, Halogen, Nitro steht oder Cyano und Q, J, n, Y sowie R12 und R13 die oben angegebenen Bedeutungen haben. Weiterhin bevorzugt sind Isoxazol-4 -yl-benzoylderivate der For¬ mel Ig
Figure imgf000021_0003
in the L for hydrogen, Ci-Cβ-alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkyl, C x -C 4 -haloalkoxy, halogen, nitro or cyano and M are hydrogen, C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Cι-C 4 alkoxy, Ci-C4-haloalkyl, Ci-C 4 -haloalkoxy, halogen, nitro or cyano and Q, J, n, Y and R 12 and R 13 have the meanings given above. Isoxazole-4-yl-benzoyl derivatives of the formula Ig are further preferred
Figure imgf000022_0001
Figure imgf000022_0001
in der L für Wasserstoff, Cι-C6-Alkyl, C2-C6-Alkenyl, C2-C6- Alkinyl, Ci-C4-Alkoxy, Cι-C4-Halogenalkyl, Ci-C4-Halogenalkoxy, Halogen, Nitro oder Cyano und M für Wasserstoff, Cι-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Cι-C4-Alkoxy, Cι-C4-Halogenalkyl, Cχ-C4-Halogenalkoxy, Halogen, Nitro steht oder Cyano und Q, J, n, Y die oben angegebenen Bedeutungen haben.in the L for hydrogen, -CC 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-C 4 -alkoxy, -C-C 4 -haloalkyl, Ci-C 4 -haloalkoxy, Halogen, nitro or cyano and M for hydrogen, -CC 6 alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, -C-C 4 alkoxy, -C-C 4 -haloalkyl, Cχ-C 4 -haloalkoxy, halogen, nitro or cyano and Q, J, n, Y have the meanings given above.
Bevorzugt sind ebenfalls Isoxazol-4-yl-benzoylderivate der Formel I, in der n für eins oder zwei steht und Y für CR7-OR8, wobei R7 und R8 die oben angegebene Bedeutung haben. Also preferred are isoxazol-4-yl-benzoyl derivatives of the formula I in which n is one or two and Y is CR 7 -OR 8 , where R 7 and R 8 have the meaning given above.
Beispiele für besonders bevorzugte Verbindungen der allgemeinen Formel I sind in den folgenden Tabellen zusammengestellt.Examples of particularly preferred compounds of the general formula I are compiled in the following tables.
5 Tabelle 1: Verbindung der Struktur5 Table 1: Connection of the structure
Figure imgf000023_0001
Figure imgf000023_0001
Figure imgf000023_0002
Figure imgf000023_0002
Figure imgf000024_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000032_0001
Figure imgf000033_0001
Tabelle 2: Verbindungen der FormelTable 2: Compounds of the formula
Figure imgf000034_0001
Figure imgf000034_0001
Figure imgf000034_0002
Figure imgf000034_0002
Tabelle 3: Verbindungen der FormelTable 3: Compounds of the formula
Figure imgf000035_0001
Figure imgf000035_0001
Figure imgf000035_0002
Figure imgf000035_0002
Tabelle 4: Verbindung der StrukturTable 4: Connection of the structure
Figure imgf000036_0001
Figure imgf000036_0001
Figure imgf000036_0002
Figure imgf000036_0002
Figure imgf000037_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000043_0001
HerstellungsbeispieleManufacturing examples
A) Herstellung der Ausgangsmaterialien und ZwischenprodukteA) Preparation of the starting materials and intermediates
1. 3-Thio-2-methylbenzoesäure1. 3-Thio-2-methylbenzoic acid
100 g (0.66 mol) 3-Amino-2-methylbenzoesäure werden zusammen mit 270 g Eis und 127 ml konz. HCl vorgelegt. Bei O-10°C werden dann 45.7 g (0.66 mol) Natriumnitrit in 270 ml Wasser zugetropft.100 g (0.66 mol) of 3-amino-2-methylbenzoic acid together with 270 g of ice and 127 ml of conc. HCl submitted. 45.7 g (0.66 mol) of sodium nitrite in 270 ml of water are then added dropwise at 0 ° C.
In einem zweiten Gefäß werden 84.2 g (0.79 mol) Natrium¬ carbonat und 106 g (0.66 mol) Kaliummethylxanthogenat in 450 ml Wasser gelöst und auf 60-70°C erhitzt. Die84.2 g (0.79 mol) of sodium carbonate and 106 g (0.66 mol) of potassium methylxanthate are dissolved in 450 ml of water in a second vessel and heated to 60-70.degree. The
Diazoniumlösung wird vorsichtig zugetropft. Es wird 1 Stunde nachgerührt. Anschließend gibt man 106 g (2.65 mol) Natrium¬ hydroxid in 270 ml Wasser hinzu, rührt weitere 2 Stunden, stellt die Lösung mit Salzsäure sauer und saugt den ent- stehenden Niederschlag ab. Der Feststoff wird mit Wasser gewaschen und getrocknet.Diazonium solution is carefully added dropwise. The mixture is stirred for 1 hour. 106 g (2.65 mol) of sodium hydroxide in 270 ml of water are then added, the mixture is stirred for a further 2 hours, the solution is acidified with hydrochloric acid and the precipitate formed is filtered off with suction. The solid is washed with water and dried.
Ausbeute: 110 g (100 % d.Th.) an 3-Thio-2-methylbenzoesäure; Schmelzpunkt: 155°C iH-NMR (d6-DMSO) : δ (ppm) : 13.0 (IH, bs) , 7.7 (2H, m) , 7.3 (IH, tr) , 2.4 (3H, s)Yield: 110 g (100% of theory) of 3-thio-2-methylbenzoic acid; Melting point: 155 ° C i H-NMR (d6-DMSO): δ (ppm): 13.0 (IH, bs), 7.7 (2H, m), 7.3 (IH, tr), 2.4 (3H, s)
2. 3-Thio-2-methylbenzoesäuremethylester2. 3-Thio-2-methylbenzoic acid methyl ester
110 g (0.66 mol) 3-Thio-2-methylbenzoesäure werden in 1.6 1 Methanol, der 5 % Schwefelsäure enthält, gelöst und 5 Stunden unter Rückfluß erhitzt. Anschließend wird der Alkohol abdestilliert, der Rückstand wird in Essigsäureethylester aufgenommen, die organische Phase mit Wasser und mit Natrium- carbonatlösung gewaschen, mit Natriumsulfat getrocknet und einrotiert.110 g (0.66 mol) of 3-thio-2-methylbenzoic acid are dissolved in 1.6 l of methanol containing 5% sulfuric acid and heated under reflux for 5 hours. The alcohol is then distilled off, the residue is taken up in ethyl acetate, the organic phase is washed with water and with sodium carbonate solution, dried with sodium sulfate and evaporated.
Ausbeute: 104 g (87 % d.Th.) an 3-Thio-2-methylbenzoesäure- methylester iH-NMR (CDC13): δ (ppm) : 7.6 (IH, d) , 7.4 (IH, d) , 7.1 (IH, d) , 3.9 (3H, s) , 3.4 (IH, s), 2.5 (3H, s) 3. 3-Thio(2'-propionsäure)-2-methylbenzoesäuremethylesterYield: 104 g (87% of theory) of methyl 3-thio-2-methylbenzoate i H-NMR (CDC1 3 ): δ (ppm): 7.6 (IH, d), 7.4 (IH, d), 7.1 (IH, d), 3.9 (3H, s), 3.4 (IH, s), 2.5 (3H, s) 3. 3-Thio (2'-propionic acid) -2-methylbenzoic acid methyl ester
Figure imgf000045_0001
Figure imgf000045_0001
70 g (0.38 mol) 3-Thio-2-methylbenzoesäuremethylester werden in 400 ml Wasser gelöst und mit 30.8 g (0.77 mol) Natronlauge und 58.8 g (0.45 mol) Brompropionsäure 7 Stunden unter Rück¬ fluß erhitzt. Nach dem Abkühlen wird die wäßrige Phase mit MTB-Ether gewaschen. Anschließend säuert man die wäßrige Phase mit 2N HCl an, saugt den entstandenen Niederschlag ab, wäscht ihn mit Wasser und trocknet das Produkt.70 g (0.38 mol) of methyl 3-thio-2-methylbenzoate are dissolved in 400 ml of water and heated under reflux for 7 hours with 30.8 g (0.77 mol) of sodium hydroxide solution and 58.8 g (0.45 mol) of bromopropionic acid. After cooling, the aqueous phase is washed with MTB ether. The aqueous phase is then acidified with 2N HCl, the precipitate formed is filtered off with suction, washed with water and the product is dried.
Ausbeute: 75.5 g (78 % d.Th.) an 3-Thiopropionsäure-2- methylbenzoesäuremethylester; iH-NMR (CDC13) : δ (ppm) : 7.66 (IH, d) , 7.51 (IH, d) , 7.20 (IH, tr) , 3.96 (3H, s), 3.18 (2H, tr) , 2.70 (2H, tr) , 2.63 (3H, s)Yield: 75.5 g (78% of theory) of 3-thiopropionic acid 2-methylbenzoic acid methyl ester; i H-NMR (CDC1 3 ): δ (ppm): 7.66 (IH, d), 7.51 (IH, d), 7.20 (IH, tr), 3.96 (3H, s), 3.18 (2H, tr), 2.70 (2H, tr), 2.63 (3H, s)
8-Methylthiochroman-4-on-7-carbonsäuremethylester8-methylthiochroman-4-one-7-carboxylic acid methyl ester
Figure imgf000045_0002
Figure imgf000045_0002
4 g (15.8 mmol) 3-Thiopropionsäure-2-methylbenzoesäuremethyl- ester werden in 40 g Polyphosphorsäure bei 70°C 15 Minuten gerührt. Danach gibt man die Reaktionslösung auf Eiswasser und saugt den entstandenen Niederschlag ab. Das Produkt wird mit Wasser gewaschen und im Trockenschrank getrocknet. Als Nebenprodukt der Cyclisierung kann 8-Methylthiochromen- 4-on-carbonsäuremethylester entstehen, der durch Chromato¬ graphie abgetrennt werden kann.4 g (15.8 mmol) of methyl 3-thiopropionate 2-methylbenzoate are stirred in 40 g of polyphosphoric acid at 70 ° C. for 15 minutes. Then the reaction solution is poured onto ice water and the precipitate formed is filtered off with suction. The product is washed with water and dried in a drying cabinet. 8-Methylthiochromen-4-one-carboxylic acid methyl ester can form as a by-product of the cyclization and can be separated off by chromatography.
Ausbeute: 3.1 g (83 % d. Th.) an 8-Methylthiochroman- 4-on-7-carbonsäuremethylester iH-NMR (CDC13) : δ (ppm) : 8.00 (IH, d) , 7.30 (IH, d) , 3.94 (3H, s) , 3.15 (2H, m) , 2.98 (2H, m) , 2.50 (3H, s)Yield: 3.1 g (83% of theory) of 8-methylthiochroman-4-one-7-carboxylic acid methyl ester in H-NMR (CDC1 3 ): δ (ppm): 8.00 (IH, d), 7.30 (IH, d ), 3.94 (3H, s), 3.15 (2H, m), 2.98 (2H, m), 2.50 (3H, s)
Nebenkomponente 8-Methylthiochromen-4-on-carbonsäuremethyl- ester: iH-NMR (CDC13): δ (ppm): 8.4 (IH, d) , 7.9 (IH, d) , 7.8 (IH, d) , 7.0 (IH, d) , 4.0 (3H, s) , 2.7 (3H, s) 5. 8-Methylthiochroman-4-on-7-carbonsäureMinor component 8-methylthiochromen-4-one-carboxylic acid methyl ester: iH-NMR (CDC1 3 ): δ (ppm): 8.4 (IH, d), 7.9 (IH, d), 7.8 (IH, d), 7.0 (IH , d), 4.0 (3H, s), 2.7 (3H, s) 5. 8-methylthiochroman-4-one-7-carboxylic acid
41.1 g (0.17 mol) 8-Methylthiochroman-4-on-7-carbonsäure- methylester werden in einer Mischung aus 400 ml Wasser und Methanol mit 10.3 g (0.26 mol) NaOH bei Ruckflußtemperatur hydrolisiert. Anschließend wird das Methanol abdestilliert und der Rückstand mit Wasser verdünnt und mit 2N Salzsaure angesäuert. Das Wertprodukt fällt aus und wird abgesaugt, mit Wasser gewaschen und getrocknet.41.1 g (0.17 mol) of 8-methylthiochroman-4-one-7-carboxylic acid methyl ester are hydrolyzed in a mixture of 400 ml of water and methanol with 10.3 g (0.26 mol) of NaOH at the reflux temperature. The methanol is then distilled off and the residue is diluted with water and acidified with 2N hydrochloric acid. The valuable product precipitates and is filtered off, washed with water and dried.
Ausbeute: 34.4 g (89 % d.Th.) an 8-Methylthiochroman-4- on-7-carbonsäure, Schmelzpunkt: 243-246°CYield: 34.4 g (89% of theory) of 8-methylthiochroman-4- on-7-carboxylic acid, melting point: 243-246 ° C
6. 8-Methyl-l, l-dioxothiochroman-4-on-7-carbonsäure6. 8-methyl-l, l-dioxothiochroman-4-one-7-carboxylic acid
Figure imgf000046_0001
Figure imgf000046_0001
20 g (0.09 mol) 8-Methylthiochroman-4-on-7-carbonsäure werden in 100 ml Essigsäure gelöst. Man gibt eine Spatelspitze Natriumwolframat hinzu. Bei 50°C werden dann 24.9 g20 g (0.09 mol) of 8-methylthiochroman-4-one-7-carboxylic acid are dissolved in 100 ml of acetic acid. A spatula tip of sodium tungstate is added. At 50 ° C then 24.9 g
(0.22 mol) 30 %ige Wasserstoffperoxidlösung zugetropft. Es wird eine Stunde bei RT nachgeruhrt. Die Reaktionslosung wird danach auf Wasser gegeben, wobei ein Niederschlag entsteht der abgesaugt wird. Nach dem Waschen des Produktes mit Wasser wird dieses getrocknet.(0.22 mol) 30% hydrogen peroxide solution was added dropwise. The mixture is stirred at RT for one hour. The reaction solution is then poured onto water, a precipitate being formed which is suctioned off. After washing the product with water, it is dried.
Ausbeute: 18.4 g (80 % d.Th.) 8-Methyl-l, 1-dioxothiochroman- 4-on-7-carbonsäure, Schmelzpunkt: 224-225°CYield: 18.4 g (80% of theory) of 8-methyl-l, 1-dioxothiochroman-4-one-7-carboxylic acid, melting point: 224-225 ° C
7. 4-Hydroxy-8-methylthiochroman-7-carbonsäuremethylester7. 4- Hydroxy-8-methylthiochroman-7-carboxylic acid methyl ester
Figure imgf000046_0002
Figure imgf000046_0002
30 g (0.127 mol) 8-Methylthiochroman-4-on-7-carbonsäure- methylester werden in einer Mischung aus 120 ml Methylen- chlorid und 60 ml Methanol gelöst und auf 0-5°C gekühlt.30 g (0.127 mol) of 8-methylthiochroman-4-one-7-carboxylic acid methyl ester are dissolved in a mixture of 120 ml of methylene chloride and 60 ml of methanol and cooled to 0-5 ° C.
Portionsweise werden dann 2.4 g (0.064 mol) Natriumborhydrid hinzugefügt. Man läßt eine Stunde bei dieser Temperatur nach- rühren. Zu der Reaktionslosung werden 200 ml 2N Salzsäure ge¬ geben. Es bilden sich zwei Phasen. Die organische Phase wird abgetrennt getrocknet und das Lösungsmittel abdestilliert. Das Rohprodukt wird ohne weitere Reinigung direkt weiter umgesetzt.2.4 g (0.064 mol) of sodium borohydride are then added in portions. Allow one hour at this temperature stir. 200 ml of 2N hydrochloric acid are added to the reaction solution. Two phases are formed. The organic phase is separated off and dried, and the solvent is distilled off. The raw product is directly implemented without further purification.
Ausbeute: 27.6 g (91 % d.Th.) an 4-Hydroxy-8-methylthio- chroman-7-carbonsäuremethylesterYield: 27.6 g (91% of theory) of 4-hydroxy-8-methylthio-chroman-7-carboxylic acid methyl ester
8. 4-Ethoxy-8-methylthiochroman-7-carbonsäuremethylester8. 4-Ethoxy-8-methylthiochroman-7-carboxylic acid methyl ester
13.8 g (0.058 mol) 4-Hydroxy-8-methylthiochroman-7-carbon- säuremethylester werden in 60 ml Ethanol unter Zusatz von 1 g Schwefelsäure 4 Stunden unter Siedetemperatur erhitzt. Danach wird das Solvens abdestilliert und der Rückstand mit Wasser aufgenommen. Man extrahiert die wäßrige Phase mit Essigsäure¬ ethylester. Die organische Phase wird mit Natriumhydrogen- carbonatlösung gewaschen, getrocknet und eingeengt. Das Produkt wird durch Chromatographie gereinigt.13.8 g (0.058 mol) of methyl 4-hydroxy-8-methylthiochroman-7-carbonate are heated in 60 ml of ethanol with the addition of 1 g of sulfuric acid for 4 hours at the boiling point. The solvent is then distilled off and the residue is taken up in water. The aqueous phase is extracted with ethyl acetate. The organic phase is washed with sodium bicarbonate solution, dried and concentrated. The product is purified by chromatography.
Ausbeute: 10.1 g (60% d. Th.) an 4-Ethoxy-8-methylthio- chroman-7-carbonsäuremethylester iH-NMR (CDC13) δ (ppm): 7.44 (IH, d) , 7.13 (IH, d) , 4.40 (IH, m) , 3.90 (3H, s) , 3.60 (2H, m) , 3.38 (1 H, dtr) , 2.90 (IH, m) , 2.50 (3H, s) , 2.40 (IH, m ), 1.98 (IH, m) 1.10 (3H, tr)Yield: 10.1 g (60% of theory) of methyl 4-ethoxy-8-methylthio-chroman-7-carboxylic acid in H-NMR (CDC1 3 ) δ (ppm): 7.44 (IH, d), 7.13 (IH, d), 4.40 (IH, m), 3.90 (3H, s), 3.60 (2H, m), 3.38 (1 H, dtr), 2.90 (IH, m), 2.50 (3H, s), 2.40 (IH, m), 1.98 (IH, m) 1.10 (3H, tr)
Die Umsetzung zu 4-Methoxy-8-methylthiochroman-4-on-7-carbon- säuremethylester und 4-Isopropoxy-8-methylthiochroman-4-on-7- carbonsäuremethylester erfolgt analog obiger Vorschrift, wobei im Fall von 4-Methoxy-8-methylthiochroman-4-on-7-carbonsäuremethyl- ester Ethanol durch Methanol und bei 4-Isopropoxy-8-methylthio- chroraan-4-on-7-carbonsäuremethylester Ethanol durch Isopropanol ersetzt wurde.The conversion to 4-methoxy-8-methylthiochroman-4-one-7-carboxylic acid methyl ester and 4-isopropoxy-8-methylthiochroman-4-one-7-carboxylic acid methyl ester takes place analogously to the above procedure, whereby in the case of 4-methoxy-8 -methylthiochroman-4-one-7-carboxylic acid methyl ester ethanol was replaced by methanol and in the case of 4-isopropoxy-8-methylthio-chroraan-4-one-7-carboxylic acid methyl ester ethanol was replaced by isopropanol.
9. 4-Ethoxy-8-methylthiochroman-7-carbonsäure9. 4-ethoxy-8-methylthiochroman-7-carboxylic acid
2.1 g Natronlauge werden in 20 ml Wasser gelöst. Bei RT tropft man 4-Ethoxy-8-methylthiochroman-4-on-7-carbon- säuremethylester in 20 ml Methanol gelöst zu. Man erhitzt 2 Stunden unter Rückfluß. Anschließend destilliert man das Lösungsmittel ab und gibt den Rückstand auf 2N Salzsäure. Die wäßrige Phase wird mit Methylenchlorid extrahiert. Die organische Phase wird getrocknet und eingeengt.2.1 g of sodium hydroxide solution are dissolved in 20 ml of water. At RT, 4-ethoxy-8-methylthiochroman-4-one-7-carboxylic acid methyl ester is added dropwise, dissolved in 20 ml of methanol. The mixture is heated under reflux for 2 hours. The solvent is then distilled off and the residue is poured into 2N hydrochloric acid. The aqueous phase is extracted with methylene chloride. The organic phase is dried and concentrated.
Ausbeute: 9.3 g (100 % d.Th.) an 4-Ethoxy-8-methylthio- chroman-7-carbonsäure, Schmelzpunkt: 89-98°C Die Hydrolyse der entsprechenden Ester zu 4-Methoxy-8-methyl- thiochroman-7-carbonsaure und 4-Isopropoxy-8-methylthiochroman- 7-carbonsäure verläuft analog. Gleiches gilt für die Verseifung der entsprechenden unten aufgeführten Benzo[b] thiophenderivate. 5Yield: 9.3 g (100% of theory) of 4-ethoxy-8-methylthio-chroman-7-carboxylic acid, melting point: 89-98 ° C The hydrolysis of the corresponding esters to 4-methoxy-8-methylthiochroman-7-carboxylic acid and 4-isopropoxy-8-methylthiochroman-7-carboxylic acid proceeds analogously. The same applies to the saponification of the corresponding benzo [b] thiophene derivatives listed below. 5
10. 8-Methyl-4-ethoxy-l, l-dioxothiochroman-7-carbonsaure10. 8-methyl-4-ethoxy-l, l-dioxothiochroman-7-carboxylic acid
8.4 g (0.033 mol) 4-Ethoxy-8-methylthiochroman-7-carbonsaure werden in 60 ml Essigsäure vorgelegt. Man gibt eine Spatel-8.4 g (0.033 mol) of 4-ethoxy-8-methylthiochroman-7-carboxylic acid are placed in 60 ml of acetic acid. You give a spatula
10 spitze Natriumwolframat hinzu. Bei 50°C werden langsam 7.9 g (0.07 mol) 30 %ige Wasserstoffperoxidlosung zugetropft. Man rührt 2 Stunden nach. Der Reaktionsansatz wird dann in Wasser gegossen und die wäßrige Phase mit Essigsäureethylester extrahiert. Die organische Phase wird mit BisulfitlosungAdd 10 pointy sodium tungstates. At 50 ° C, 7.9 g (0.07 mol) of 30% hydrogen peroxide solution are slowly added dropwise. Stir for 2 hours. The reaction mixture is then poured into water and the aqueous phase is extracted with ethyl acetate. The organic phase is with bisulfite solution
15 gewaschen, dann getrocknet und eingeengt.15 washed, then dried and concentrated.
Ausbeute: 9.5 g (100 % d.Th.) an 8-Methyl-4-ethoxy-l, 1- dioxothiochroman-7-carbonsaure, Schmelzpunkt: 150°CYield: 9.5 g (100% of theory) of 8-methyl-4-ethoxy-l, 1-dioxothiochroman-7-carboxylic acid, melting point: 150 ° C
20 11. 8-Methylthiochroman-4-on-7-carbonsaure-0-ethyloxim20 11. 8-Methylthiochroman-4-one-7-carboxylic acid-0-ethyloxime
Figure imgf000048_0001
Figure imgf000048_0001
In 20 ml Methanol werden 0.88 g (9 mmol) Ethylhydroxylamin 30 vorgelegt. Man gibt dann 0.62 g (4.5 mmol) Kaliumcarbonat hinzu. Anschließend werden 2.0 g (9 mmol) 8-Methylthio- chroman-4-on-7-carbonsäure zugegeben. Die Reaktion wird 10 Tage bei RT gerührt. Aufgearbeitet wird durch Zugabe von Wasser und 2N HCl . Der entstehende Niederschlag wird 35 abgesaugt und getrocknet.0.88 g (9 mmol) of ethylhydroxylamine 30 are placed in 20 ml of methanol. Then 0.62 g (4.5 mmol) of potassium carbonate is added. Then 2.0 g (9 mmol) of 8-methylthio-chroman-4-one-7-carboxylic acid are added. The reaction is stirred for 10 days at RT. It is worked up by adding water and 2N HCl. The resulting precipitate is suction filtered and dried.
Ausbeute: 2.2 g (92 % d.Th.) an 8-Methylthiochroman-4- on-7-carbonsäure-O-ethyloxim; Schmelzpunkt: 166°CYield: 2.2 g (92% of theory) of 8-methylthiochroman-4-one-7-carboxylic acid-O-ethyloxime; Melting point: 166 ° C
40 12. 8-Methyl-l, l-dioxothiochroman-4-on-7-carbonsäure-0-ethyloxim40 12. 8-methyl-l, l-dioxothiochroman-4-one-7-carboxylic acid-0-ethyloxime
3.0 g (0.011 mol) 8-Methylthiochroman-4-on-7-carbonsaure-0- ethyloxim werden zusammen mit einer Spatelspitze Natrium¬ wolframat in 30 ml Essigsäure vorgelegt. Bei 50°C tropft man 45 2.8 g (0.024 mol) 30 %ige Wasserstoffperoxidlosung zu. Nach einstundigem Ruhren wird das Reaktionsgemisch in Eiswasser gegossen, der entstehende Niederschlag wird abgesaugt. Das Produkt wird mit Wasser gewaschen und getrocknet.3.0 g (0.011 mol) of 8-methylthiochroman-4-one-7-carboxylic acid 0-ethyloxime are placed together with a spatula tip of sodium tungstate in 30 ml of acetic acid. 45 2.8 g (0.024 mol) of 30% strength hydrogen peroxide solution are added dropwise at 50 ° C. After stirring for one hour, the reaction mixture is poured into ice water poured, the resulting precipitate is suctioned off. The product is washed with water and dried.
Ausbeute: 2.5 g (74 % d.Th.) 8-Methyl-l, 1-dioxothiochroman- 4-on-7-carbonsäure-0-ethyloxim, Schmelzpunkt 198°CYield: 2.5 g (74% of theory) of 8-methyl-l, 1-dioxothiochroman-4-one-7-carboxylic acid-0-ethyloxime, melting point 198 ° C.
13. 8-Methyl-l-oxothiochroman-4-on-7-carbonsäure13. 8-methyl-l-oxothiochroman-4-one-7-carboxylic acid
7.0 g (31.5 mmol) 8-Methylthiochroman-4-on-7-carbonsäure werden zusammen mit einer Spatelspitze Natriumwolframat in7.0 g (31.5 mmol) of 8-methylthiochroman-4-one-7-carboxylic acid are mixed in with a spatula tip of sodium tungstate
70 ml Essigsäure vorgelegt. Bei 50°C werden 3.6 g (31.5 mmol) 30 %ige Wasserstoffperoxidlösung zugetropft. Man rührt 3 Stunden nach. Danach wird die Reaktionslösung in Wasser eingerührt. Man extrahiert mit Essigsäureethylester das Produkt. Die organische Phase wird getrocknet und das70 ml of acetic acid submitted. 3.6 g (31.5 mmol) of 30% strength hydrogen peroxide solution are added dropwise at 50 ° C. Stir for 3 hours. The reaction solution is then stirred into water. The product is extracted with ethyl acetate. The organic phase is dried and that
Lösungsmittel entfernt. Das Produkt wird durch Chromato¬ graphie gereinigt.Solvent removed. The product is purified by chromatography.
Ausbeute: 5.4 g (72 % d. Th.) 8-Methyl-l-oxothiochroman- 4-on-7-carbonsäure iH-NMR (d6-DMS0) , δ (ppm) : 8.0 (2H, m) , 3.5 (3H, m) , 2.8 (IH, m) , 2.7 (3H,s)Yield: 5.4 g (72% of theory) of 8-methyl-l-oxothiochroman-4-one-7-carboxylic acid in H-NMR (d6-DMS0), δ (ppm): 8.0 (2H, m), 3.5 (3H, m), 2.8 (IH, m), 2.7 (3H, s)
14. 3-Thioessigsäure-2-methylbenzoesäuremethylester14. 3-Thioacetic acid, 2-methylbenzoic acid, methyl ester
Figure imgf000049_0001
Zu 1.6 g (0.068 mol) NaH in 40 ml DMF werden 12.4 g
Figure imgf000049_0001
12.4 g become 1.6 g (0.068 mol) NaH in 40 ml DMF
(0.068 mol) 3-Thio-2-methylbenzoesäuremethylester in 80 ml DMF getropft. Es wird 60 min bei RT gerührt. Danach gibt man 8 g (0.068 mol) Chloressigsäure zu. Es wird 4 Stunden bei RT gerührt. Aufgearbeitet wird durch Einrühren des Reaktionsgemisches in salzsaures Eiswasser.(0.068 mol) of 3-thio-2-methylbenzoic acid methyl ester in 80 ml of DMF. The mixture is stirred at RT for 60 min. Then 8 g (0.068 mol) of chloroacetic acid are added. The mixture is stirred at RT for 4 hours. It is worked up by stirring the reaction mixture into hydrochloric ice water.
Der entstehende Niederschlag wird abgesaugt, mit Wasser gewaschen und getrocknet.The resulting precipitate is filtered off, washed with water and dried.
Ausbeute: 14.6 g (89 % d.Th.) 3-Thioessigsäure-2- methylbenzoesäuremethylester iH-NMR (d6-DMSO) δ (ppm) : 7.55 (IH d), 7.45 (IH, d) , 7.21 (IH, tr) , 3.82 (2H,s), 2.50 (3H,s) 15. 7-Methyl-benzo[b] thiophen-3 [2H] -on-6-carbonsäuremethylesterYield: 14.6 g (89% of theory) of methyl 3-thioacetic acid-2-methylbenzoate in the iH-NMR (d6-DMSO) δ (ppm): 7.55 (IH d), 7.45 (IH, d), 7.21 (IH, tr ), 3.82 (2H, s), 2.50 (3H, s) 15. 7-Methyl-benzo [b] thiophene-3 [2H] -one-6-carboxylic acid methyl ester
Figure imgf000050_0001
Figure imgf000050_0001
14.3 g (0.06 mmol) 3-Thioessigsäure-2-methylbenzoesäure werden in 300 ml Methylenchlorid gelöst. 13.1 g (0.11 mmol) Thionylchlorid werden zugetropft. Man erhitzt eine Stunde unter Ruckfluß. Danach wird das Lösungsmittel sowie über¬ schüssiges Thionylchlorid abdestilliert. Der Rückstand wird in 100 ml Methylenchlorid aufgenommen und mit 31.8 g (0.24 mmol) Aluminiumtrichlorid versetzt. Die Reaktion wird 1 Stunde bei RT gerührt. Anschließend gibt man das Gemisch auf Eiswasser und trennt die organische Phase ab. Nach dem Waschen und Trocknen der organischen Phase wird das Losungs- mittel entfernt. Das Produkt wird ohne Reinigung weiter umgesetzt.14.3 g (0.06 mmol) of 3-thioacetic acid-2-methylbenzoic acid are dissolved in 300 ml of methylene chloride. 13.1 g (0.11 mmol) of thionyl chloride are added dropwise. The mixture is heated under reflux for one hour. The solvent and excess thionyl chloride are then distilled off. The residue is taken up in 100 ml of methylene chloride and 31.8 g (0.24 mmol) of aluminum trichloride are added. The reaction is stirred at RT for 1 hour. The mixture is then poured onto ice water and the organic phase is separated off. After washing and drying the organic phase, the solvent is removed. The product is implemented without cleaning.
Ausbeute: 12.9 g (97 % d.Th.) 7-Methyl-benzo[b] thiophen- 3 [2H] -on-6-carbonsäuremethylester iH-NMR (CDC13) , δ (ppm): 7.65 (2H, m) , 3.93 (3H, s) , 3.88 (2H, s) , 2.50 (3H, s)Yield: 12.9 g (97% of theory) of 7-methyl-benzo [b] thiophene-3 [2H] -one-6-carboxylic acid, methyl ester iH-NMR (CDC1 3 ), δ (ppm): 7.65 (2H, m ), 3.93 (3H, s), 3.88 (2H, s), 2.50 (3H, s)
16. 7-Methyl-3-hydroxybenzo[b] thiophen- [2H] -6-carbonsäuremethyl- ester16. 7-Methyl-3-hydroxybenzo [b] thiophene- [2H] -6-carboxylic acid methyl ester
Figure imgf000050_0002
Figure imgf000050_0002
12.8 g (0.058 mol) 7-Methyl-benzo[b] thiophen-3 [2H] -on-6- carbonsäuremethylester werden in 120 ml Methylenchlorid und 60 ml Methanol gelost und auf 0°C gekühlt. 1.1 g (0.029 mol) Natriumborhydrid wird portionsweise zugegeben. Es wird 3 Stunden gerührt. Durch Zugabe von Wasser wird die Reaktion abgebrochen. Die Phasen werden getrennt und die wäßrige Phase wird mit Methylenchlorid extrahiert. Die vereinigten organischen Phasen werden getrocknet. Das Lösungsmittel wird abdestilliert. Das Rohprodukt wird weiter umgesetzt.12.8 g (0.058 mol) of 7-methyl-benzo [b] thiophene-3 [2H] -one-6-carboxylic acid methyl ester are dissolved in 120 ml of methylene chloride and 60 ml of methanol and cooled to 0 ° C. 1.1 g (0.029 mol) of sodium borohydride is added in portions. It is stirred for 3 hours. The reaction is stopped by adding water. The phases are separated and the aqueous phase is extracted with methylene chloride. The combined organic phases are dried. The solvent is distilled off. The raw product will continue to be implemented.
Ausbeute: 13.2 g (100 % d.Th.) 7-Methyl-3-hydroxybenzo- [b] thiophen- [2H] -6-carbonsäuremethylester iH-NMR (CDC13), δ (ppm): 7.6 (2H, m) , 5.3 (IH, m) ,3.9 (3H, s) , 3.7 (IH, m) , 3.3 (IH, rt) , 2.4 (3H, s) 17. 7-Methyl-3-methoxybenzo[b] thiophen- [2H] -6-carbonsauremethyl- esterYield: 13.2 g (100% of theory) of 7-methyl-3-hydroxybenzo- [b] thiophene- [2H] -6-carboxylic acid methyl ester in H-NMR (CDC1 3 ), δ (ppm): 7.6 (2H, m), 5.3 (IH, m), 3.9 (3H, s), 3.7 (IH, m), 3.3 (IH, rt), 2.4 (3H, s) 17. 7-Methyl-3-methoxybenzo [b] thiophene- [2H] -6-carboxylic acid methyl ester
2.4 g (0.059 mol) NaH wird in 50 ml DMF gelost. 13.2 g 7-Methyl-3-hydroxybenzo [b] thiophen- [2H] -6-carbonsäuremethyl- ester gelost in 50 ml werden zugetropft. Anschließend wird 2 Stunden bei RT gerührt. Danach werden 8.4 g (0.059 mol) lodmethan zugefugt und weitere 2 Stunden gerührt. Die Reaktionslosung wird auf Eiswasser gegeben und mit Essigsäureethylester extrahiert. Die organische Phase wird getrocknet und anschließend eingeengt. Das Produkt wird durch Chromatographie gereinigt.2.4 g (0.059 mol) NaH is dissolved in 50 ml DMF. 13.2 g of 7-methyl-3-hydroxybenzo [b] thiophene- [2H] -6-carboxylic acid methyl ester dissolved in 50 ml are added dropwise. The mixture is then stirred at RT for 2 hours. Then 8.4 g (0.059 mol) of iodomethane are added and the mixture is stirred for a further 2 hours. The reaction solution is poured onto ice water and extracted with ethyl acetate. The organic phase is dried and then concentrated. The product is purified by chromatography.
Ausbeute: 3.5g (25% d. Th.) 7-Methyl-3-methoxybenzo [b] thio- phen- [2H] -6-carbonsäuremethylester iH-NMR (CDC13), δ (ppm): 7.60 (IH, d) , 7.20 (IH, d) , 5.04 (IH, m) , 3.90 (3H, s),3.56 (IH, m) , 3.40 (3H, s) , 3.38 (IH, m) , 2.50 (3H, s)Yield: 3.5g (25% of theory) of 7-methyl-3-methoxybenzo [b] thiophene- [2H] -6-carboxylic acid methyl ester in H-NMR (CDC13), δ (ppm): 7.60 (IH, d), 7.20 (IH, d), 5.04 (IH, m), 3.90 (3H, s), 3.56 (IH, m), 3.40 (3H, s), 3.38 (IH, m), 2.50 (3H, s )
Analog der oben beschriebenen Verseifung der Thiochromanonester erhält man auch die entsprechenden Benzothiophensäuren.Analogously to the saponification of the thiochromanone esters described above, the corresponding benzothiophene acids are also obtained.
In analoger Weise werden die in den nachfolgenden Tabellen auf¬ geführten Verbindungen erhalten:The compounds listed in the tables below are obtained in an analogous manner:
Tabelle 5: Zwischenprodukte der FormelTable 5: Intermediates of the formula
Figure imgf000051_0001
Figure imgf000051_0001
Figure imgf000051_0002
Figure imgf000051_0002
Figure imgf000052_0001
Figure imgf000053_0002
Figure imgf000052_0001
Figure imgf000053_0002
Tabelle 6: ZwischenprodukteTable 6: Intermediates
Figure imgf000053_0001
Figure imgf000053_0001
Figure imgf000053_0003
Herstellung der Endprodukte
Figure imgf000053_0003
Manufacture of end products
la. 39 g 8-Methyl-1, 1-dioxo-4, 4-dimethylthiochroman-7 -carbon¬ säure und 3 Tropfen DMF werden in 200 ml Toluol gelöst und mit 13,0 g Thinylchlorid versetzt. Es wird 5 Stunden unter Rückfluß erhitzt. Anschließend wird das Lösungs¬ mittel abdestilliert.la. 39 g of 8-methyl-1, 1-dioxo-4, 4-dimethylthiochroman-7-carboxylic acid and 3 drops of DMF are dissolved in 200 ml of toluene and 13.0 g of thinyl chloride are added. The mixture is heated under reflux for 5 hours. The solvent is then distilled off.
Man erhält 41,3 g 8-Methyl-1, l-dioxo-4, 4-dimethylthio¬ chroman-7-carbonsäurechlorid. iH-NMR (270 MHz, CDC13/ δ in ppm) : 8,10 (d) , 7,48 (d) ,41.3 g of 8-methyl-1, l-dioxo-4,4, 4-dimethylthio-chroman-7-carboxylic acid chloride are obtained. i H-NMR (270 MHz, CDC1 3 / δ in ppm): 8.10 (d), 7.48 (d),
3,43 (m) , 2,91 (s) , 2,36 (m) , 1,47 (s)3.43 (m), 2.91 (s), 2.36 (m), 1.47 (s)
Ib. 0,70 g Magnesium und 4,94 g 3-Oxo-3-cyclopropyl-propion¬ säure-tert.butylester werden in 50 ml Methanol gelöst und mit 3 ml Tetrachlorkohlenstoff versetzt. Man läßtIb. 0.70 g of magnesium and 4.94 g of tert-butyl 3-oxo-3-cyclopropyl-propionate are dissolved in 50 ml of methanol and 3 ml of carbon tetrachloride are added. You leave
2 Stunden rühren und engt dann das Reaktionsgemisch ein. Der Rückstand wird in 30 ml Acetonitril aufgenommen und mit 7,0 g 8-Methyl -1, 1-dioxo-4, 4dimethylthiochroman-7- carbonsäurechlorid, das in 20 ml Acetonitril gelöst ist, versetzt. Es wird über Nacht gerührt und das Reaktions- gemisch dann in 200 ml 2N HCl eingerührt. Man extrahiert mit Essigsäureethylester das Wertprodukt, trocknet die vereinigten organischen Phasen und destilliert das Lösungsmittel ab. Das Produkt wird durch Chromatographie gereinigt.Stir for 2 hours and then concentrate the reaction mixture. The residue is taken up in 30 ml of acetonitrile and mixed with 7.0 g of 8-methyl-1, 1-dioxo-4, 4dimethylthiochroman-7-carboxylic acid chloride, which is dissolved in 20 ml of acetonitrile. The mixture is stirred overnight and the reaction mixture is then stirred into 200 ml of 2N HCl. The product of value is extracted with ethyl acetate, the combined organic phases are dried and the solvent is distilled off. The product is purified by chromatography.
Man erhält 6,8 g 1- (8-Methyl-1, 1 -dioxo-4,4-dimethylthio¬ chroman) -2-tert.butylester-3-cyclopropyl-propan-1, 3-dion. Fp.: 144°C6.8 g of 1- (8-methyl-1,1-dioxo-4,4-dimethylthio-chroman) -2-tert-butyl ester-3-cyclopropyl-propane-1,3-dione are obtained. Mp .: 144 ° C
lc. 6,4 g 1- (8-Methyl-l, l-dioxo-4, 4 -dimethylthiochroman) - 2-tert.butylester-3 -cyclopropyl-propan-1,3-dion werden zusammen mit 150 ml Toluol und 0,85 g p-Toluolsulfonsäurelc. 6.4 g of 1- (8-methyl-l, l-dioxo-4,4, -dimethylthiochroman) -2-tert-butyl ester-3-cyclopropyl-propane-1,3-dione are mixed together with 150 ml of toluene and 0, 85 g p-toluenesulfonic acid
2 Stunden auf Ruckflußtemperatur erhitzt. Anschließend wird die Reaktionslösung mit Wasser gewaschen, getrock- net und vom Lösungsmittel befreit. Man erhält 4,8 gHeated to reflux temperature for 2 hours. The reaction solution is then washed with water, dried and freed from the solvent. 4.8 g are obtained
1- (8-Methyl-1, 1-dioxo-4,4-dimethylthiochroman) -3-cyclo- propyl-propan-1,3-dion. Fp. : 126 °C1- (8-methyl-1, 1-dioxo-4,4-dimethylthiochroman) -3-cyclopropyl-propane-1,3-dione. Mp: 126 ° C
Id. 4,5 g 1- (8-Methyl-l, l-dioxo-4, 4-dimethylthiochroman) -3 - cyclopropyl-propan-1, 3-dion, 2,1 g Essigsaureanhydrid und 30 ml Triethylorthoformiat werden auf 110°C erwärmt undId. 4.5 g of 1- (8-methyl-l, l-dioxo-4, 4-dimethylthiochroman) -3 - cyclopropyl-propan-1, 3-dione, 2.1 g of acetic anhydride and 30 ml of triethyl orthoformate are made up to 110 ° C warmed and
3 Stunden bei dieser Temperatur gerührt. Danach wird die Reaktionslösung eingeengt und durch Einrühren in Diethyl¬ ether das Isomerengemisch aus 1- (8-Methyl-1, 1-dioxo-4,4- dimethylthiochroman) -3-cyclopropyl-2-hydroxymethylen- propan-1, 3-dion und 1- (8-Methyl-1, 1-dioxo-4, 4-dimethyl- thiochroman) -3-cyclopropyl-2-ethoxymethylenpropan-1,3- dion zur Kristallisation gebracht. 1,5 g des so erhaltenen Feststoffes werden zusammen mit 15 ml Dichlor methan und 0,32 g Hydroxylamin Hydrochlorid vorgelegt und bei Raumtemperatur 0,41 g Natriumacetat zugegeben. Nach 2 stundigem Ruhren wird die Reaktionsmischung m 100 ml Wasser eingerührt. Der entstehende Miederschlag wird abgesaugt, mit Wasser gewaschen und getrocknet. Man erhalt 1,3 g 4 - (8-Methyl-1, 1-dioxo-4 , 4 -dimethylthio chroman) -5 -cyclopropylisoxazol . Fp. : 156°CStirred at this temperature for 3 hours. The reaction solution is then concentrated and the isomer mixture of 1- (8-methyl-1, 1-dioxo-4,4-dimethylthiochroman) -3-cyclopropyl-2-hydroxymethylene-propane-1, 3-dione is stirred into diethyl ether and 1- (8-methyl-1, 1-dioxo-4, 4-dimethylthiochroman) -3-cyclopropyl-2-ethoxymethylene propane-1,3- dion brought to crystallization. 1.5 g of the solid obtained in this way are introduced together with 15 ml of dichloromethane and 0.32 g of hydroxylamine hydrochloride, and 0.41 g of sodium acetate are added at room temperature. After stirring for 2 hours, the reaction mixture is stirred into 100 ml of water. The resulting corset is sucked off, washed with water and dried. 1.3 g of 4 - (8-methyl-1, 1-dioxo-4, 4 -dimethylthio chroman) -5 -cyclopropylisoxazole are obtained. Mp: 156 ° C
Tabelle 7: Endprodukte der FormelTable 7: End products of the formula
Figure imgf000055_0001
Figure imgf000055_0001
Figure imgf000055_0002
Figure imgf000055_0002
Dxe Verbindungen I und deren landwirtschaftlich brauchbaren Salze eignen sich - sowohl als Isomerengemische als auch in Form der reinen Isomeren - als Herbizide. Die I enthaltenden herbiziden Mittel bekämpfen Pflanzenwuchs auf Nichtkulturflachen sehr gut, besonders bei hohen Aufwandmengen. In Kulturen wie Weizen, Reis, Mais, Soja und Baumwolle wirken sie gegen Unkräuter und Schad graser, ohne die Kulturpflanzen nennenswert zu schädigen. Dieser Effekt tritt vor allem bei niedrigen Aufwandmengen auf.The compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides. The herbicidal compositions containing I control vegetation very well on non-cultivated areas, especially at high application rates. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crop plants. This effect occurs especially at low application rates.
In Abhängigkeit von der jeweiligen Applikationsmethode können die Verbindungen I bzw. sie enthaltende Mittel noch m einer weiteren Zahl von Kulturpflanzen zur Beseitigung unerwünschter Pflanzen eingesetzt werden. In Betracht kommen beispielsweise folgende Kulturen:Depending on the particular application method, the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants. The following crops are considered, for example:
Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officmalis, Beta vulgaris spp. altissima, Beta vulagris spp. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestπs, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica) , Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max. Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) , Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spp., Manihot esculenta, Medicago sativa, Musa spp. , Nicotiana tabacum (N. rustica) , Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgäre), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.Allium cepa, pineapple comosus, Arachis hypogaea, Asparagus officmalis, Beta vulgaris spp. altissima, Beta vulagris spp. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestπs, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max. Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon malicuspp , Musa spp. , Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spp., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylestre, Ricinus communis, Saccharle officinarum, Seea cereale, Solanum tuberosum, Sorghum bicolor (see vulgar), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.
Darüber hinaus können die Verbindungen I auch in Kulturen, die durch Züchtung einschließlich gentechnischer Methoden gegen die Wirkung von Herbiziden tolerant sind, verwandt werden.In addition, the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
Die Applikation der herbiziden Mittel bzw. der Wirkstoffe kann im Vorauflauf- oder im Nachauflaufverfahren erfolgen. Sind die Wirk¬ stoffe für gewisse Kulturpflanzen weniger verträglich, so können Ausbringungstechniken angewandt werden, bei welchen die herbi¬ ziden Mittel mit Hilfe der Spritzgeräte so gespritzt werden, daß die Blätter der empfindlichen Kulturpflanzen nach Möglichkeit nicht getroffen werden, während die Wirkstoffe auf die Blätter darunter wachsender unerwünschter Pflanzen oder die unbedeckte Bodenfläche gelangen (post-directed, lay-by) .The herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active substances are less compatible with certain crop plants, application techniques can be used in which the herbicidal agents are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit, if possible, while the active substances are applied to the leaves underneath growing unwanted plants or the uncovered floor area (post-directed, lay-by).
Die Verbindungen I bzw, die sie enthaltenden herbiziden Mittel können beispielsweise in Form von direkt versprühbaren wäßrigen Lösungen, Pulvern, Suspensionen, auch hochprozentigen wäßrigen, öligen oder sonstigen Suspensionen oder Dispersionen, Emulsionen, Öldispersionen, Pasten, Stäubemitteln, Streumitteln oder Granu¬ laten durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen angewendet werden. Die Anwendungsformen richten sich nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfindungsgemäßen Wirkstoffe gewähr¬ leisten.The compounds I or the herbicidal compositions comprising them can be sprayed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, including high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprinkling agents or granules , Atomizing, dusting, scattering or pouring can be used. The application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
Als inerte Zusatzstoffe kommen im Wesentlichen in Betracht: Mineralölfraktionen von mittlerem bis hohem Siedepunkt, wie Kerosin oder Dieselöl, ferner Kohlenteeröle sowie Öle pflanz¬ lichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Paraffin, Tetrahydro- naphthalin, alkylierte Naphthaline oder deren Derivate, alkylierte Benzole oder deren Derivate, Alkohole wie Methanol, Ethanol, Propanol, Butanol, Cyclohexanol, Ketone wie Cyelo¬ hexanon oder stark polare Losungsmittel, z.B. Amine wie N-Methyl- pyrrolidon oder Wasser.The following are essentially considered as inert additives: mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example paraffin, tetrahydro- naphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyelohexanone or strongly polar solvents, for example amines such as N-methylpyrrolidone or water.
Wäßrige Anwendungsformen können aus Emulsionskonzentraten, Sus¬ pensionen, Pasten, netzbaren Pulvern oder wasserdispergierbaren Granulaten durch Zusatz von Wasser bereitet werden. Zur Her- Stellung von Emulsionen, Pasten oder Öldispersionen können die Substrate als solche oder in einem 01 oder Losungsmittel gelost, mittels Netz-, Haft-, Dispergier- oder Emulgiermittel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz, Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Losungsmittel oder 01 bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind.Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substrates as such or dissolved in a oil or solvent can be homogenized in water using wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare active substances, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or existing concentrates which are suitable for dilution with water.
Als oberflächenaktive Stoffe kommen die Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsäuren, z.B. Lignin-, Phenol-, Naphthalin- und Dibutylnaphthalinsulfonsäure, sowie von Fettsäuren, Alkyl- und Alkylarylsulfonaten, Alkyl-, Laurylether- und Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Hepta- und Octadecanolen sowie von Fettalkoholglykolether, Kondensati¬ onsprodukte von sulfoniertem Naphthalin und seiner Derivate mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsäuren mit Phenol und Formaldehyd, Polyoxy- ethylenoctylphenolether, ethoxyliertes Isooctyl-, Octyl- oder Nonylphenol, Alkylphenyl-, Tributylphenylpolyglykolether, Alkyl- arylpolyetheralkohole, Isotridecylalkohol, Fettalkoholethylen- oxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkyl¬ ether oder Polyoxypropylenalkylether, Laurylalkoholpolyglykol- etheracetat, Sorbitester, Lignin-Sulfitablaugen oder Methyl¬ cellulose in Betracht.The alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, e.g. Lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol arylpolyetheralkohole ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl, tributylphenyl, alkyl, isotridecyl alcohol, Fettalkoholethylen- oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ¬ ether or polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin sulfite or methyl cellulose.
Pulver, Streu- und Stäubemittel kόnnen durch Mischen oder gemein¬ sames Vermählen der wirksamen Substanzen mit einem festen Träger- stoff hergestellt werden.Powders, materials for spreading and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogengranulate können durch Bindung der Wirkstoffe an feste Trägerstoffe herge¬ stellt werden. Feste Trägerstoffe sind Mineralerden wie Kiesel¬ säuren, Kieselgele, Silikate, Talkum, Kaolin, Kalkstein, Kalk, Kreide, Bolus, Loß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Dunge- mittel, wie Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte wie Getreidemehl, Baum- rinden-, Holz- und Nußschalenmehl, Cellulosepulver oder andere feste Trägerstoffe.Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral soils such as silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, Ammonium phosphate, ammonium nitrate, ureas and vegetable products such as corn flour, tree Bark, wood and nutshell flour, cellulose powder or other solid carriers.
Die Konzentrationen der Wirkstoffe I in den anwendungsfertigen Zubereitungen können in weiten Bereichen variiert werden. Die Formulierungen enthalten im allgemeinen 0,001 bis 98 Gew. -%, vor¬ zugsweise 0,01 bis 95 Gew. -%, Wirkstoff. Die Wirkstoffe werden dabei in einer Reinheit von 90 % bis 100 %, vorzugsweise 95 % bis 100 % (nach NMR-Sektrum) eingesetzt.The concentrations of the active ingredients I in the ready-to-use preparations can be varied over a wide range. The formulations generally contain 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
Die erfindungsgemäßen Verbindungen I können beispielsweise wie folgt formuliert werden:The compounds I according to the invention can be formulated, for example, as follows:
I 20 Gewichtsteile der Verbindung Nr. 7.1 werden in einer Mischung gelöst, die aus 80 Gewichtsteilen alkyliertem Benzol, 10 Gewichtsteilen des Anlagerungsproduktes von 8 bis 10 Mol Ethylenoxid an 1 Mol Ölsäure-N-monoethanolamid, 5 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsäure und 5 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylen- oxid an 1 Mol Ricinusöl besteht. Durch Ausgießen und feines Verteilen der Lösung in 100000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew. -% des Wirkstoffs enthält.I 20 parts by weight of compound no. 7.1 are dissolved in a mixture consisting of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.
II 20 Gewichtsteile der Verbindung Nr. 7.1 werden in einer Mischung gelöst, die aus 40 Gewichtsteilen Cyelohexanon, 30 Gewichtsteilen Isobutanol, 20 Gewichtsteilen des Anlage¬ rungsproduktes von 40 Mol Isooctylphenol und 10 Gewichts¬ teilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew.-% des Wirkstoffs enthält.II 20 parts by weight of compound no. 7.1 are dissolved in a mixture consisting of 40 parts by weight of cyelohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of isooctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil . Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
III 20 Gewichtsteile des Wirkstoffs Nr. 7.1 werden in einer Mischung gelöst, die aus 25 Gewichtsteilen Cyelohexanon,III 20 parts by weight of active ingredient No. 7.1 are dissolved in a mixture consisting of 25 parts by weight of cyelohexanone,
65 Gewichtsteiϊen einer Mineralölfraktion vom Siedepunkt 210 bis 280°C und 10 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Ethylenoxid an 1 Mol Ricinusöl besteht. Durch Ein¬ gießen und feines Verteilen der Lösung in 100000 Gewichts- teilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gew. -% des Wirkstoffs enthält.65 parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.
IV 20 Gewichtsteile des Wirkstoffs Nr. 7.1 werden mitIV 20 parts by weight of active ingredient No. 7.1 are with
3 Gewichtsteilen des Natriumsalzes der Diisobutylnaphthalin- sulfonsaure, 17 Gewichtsteilen des Natriumsalzes einer3 parts by weight of the sodium salt of diisobutylnaphthalenesulfonic acid, 17 parts by weight of the sodium salt one
Ligninsulfonsäure aus einer Sulfit-Ablauge und 60 Gewichts¬ teilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle vermählen. Durch feines Verteilen der Mischung in 20000 Gewichtsteilen Wasser enthält man eine Spritzbrühe, die 0,1 Gew. -% des Wirkstoffs enthält.Lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel mixed well and in milled in a hammer mill. A fine spray mixture containing 0.1% by weight of the active ingredient is obtained by finely distributing the mixture in 20,000 parts by weight of water.
V 3 Gewichtsteile des Wirkstoffs Nr. 7.1 werden mitV 3 parts by weight of active ingredient no. 7.1 are included
97 Gewichtsteilen feinteiligem Kaolin vermischt. Man erhält auf diese Weise ein Stäubemittel, das 3 Gew. % des Wirkstoffs enthält.97 parts by weight of finely divided kaolin mixed. In this way a dust is obtained which contains 3% by weight of the active ingredient.
VI 20 Gewichtsteile des Wirkstoffs Nr. 7.1 werden mitVI 20 parts by weight of active ingredient No. 7.1 are with
2 Gewichtsteilen Calciumsalz der Dodecylbenzolsulfonsäure, 8 Gewichtsteilen Fettalkohol-polyglykolether, 2 Gewichts¬ teilen Natriumsalz eines Phenol-Harnstoff-Formaldehyd- Kondensates und 68 Gewichtsteilen eines paraffinischen Mineralöls innig vermischt. Man erhält eine stabile ölige Dispersion.2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.
VII 1 Gewichtsteil der Verbindung Nr. 7.1 wird in einer Mischung gelöst, die aus 70 Gewichtsteilen Cyelohexanon, 20 Gewichts- teilen ethoxyliertem Isooctylphenol und 10 Gewichtsteilen ethoxyliertem Rizinusöl besteht. Man erhält ein stabiles Emulsionskonzentrat.VII 1 part by weight of compound no. 7.1 is dissolved in a mixture consisting of 70 parts by weight of cyelohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained.
VIII 1 Gewichtsteil der Verbindung Nr. 7.1 wird in einer Mischung gelöst, die aus 80 Gewichtsteilen Cyelohexanon und 20 Gewichtsteilen Emulphor EL besteht. Man erhält ein stabiles Emulsionskonzentrat.VIII 1 part by weight of compound no. 7.1 is dissolved in a mixture consisting of 80 parts by weight of cyelohexanone and 20 parts by weight of Emulphor EL. A stable emulsion concentrate is obtained.
Zur Verbreiterung des Wirkungsspektrums und zur Erzielung syner- gistischer Effekte können die Isoxazol-4-yl-benzoylderivate I mit zahlreichen Vertretern anderer herbizider oder wachstumsregulie¬ render-Wirkstoffgruppen gemischt und gemeinsam ausgebracht werden. Beispielsweise kommen als Mischungspartner 1,2,4-Thia- diazole, 1, 3, 4-Thiadiazole, Amide, Aminophosphorsäure und deren Derivate, Aminotriazole, Anilide, (Het) -Aryloxyalkansäure und deren Derivate, Benzoesäure und deren Derivate, Benzothia- diazinone, Triketone, Hetaryl-Aryl-Ketone, Benzylisoxazolidinone, Meta-CF3-phenylderivate, Carbamate, Chinolinsäure und deren Derivate, Chloracetanilide, Cyclohexandione, Diazine, Dichlor- propionsäure und deren Derivate, Dihydrobenzofurane, Dihydro- furan-3-one, Dinitroaniline, Dinitrophenole, Diphenylether, Dipyridyle, Halogencarbonsäuren und deren Derivate, Harnstoffe, N-Phenyluracile, Imidazole, Imidazolinone, Isoindoldione, Oxadiazole, Oxirane, Phenole, Aryloxy- oder Heteroaryloxyphenoxy- propionsäureester, Phenylessigsäure und deren Derivate, Phenyl- propionsäure und deren Derivate, Pyrazole, Phenylpyrazole, Pyridazine, Pyridincarbonsäure und deren Derivate, Pyrimidyl- ether, Sulfonamide, Sulfonylharnstoffe, Triazine, Tπazmone, Triazolinone, Triazolcarboxamide, Uracile und andere m Betracht.In order to broaden the spectrum of action and to achieve synergistic effects, the isoxazol-4-yl-benzoyl derivatives I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied together. For example, 1,2,4-thiazadiols, 1,3,4-thiadiazoles, amides, aminophosphoric acid and their derivatives, aminotriazoles, anilides, (het) -aryloxyalkanoic acid and their derivatives, benzoic acid and their derivatives, benzothidadiazinones come as mixing partners , Triketones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF 3 phenyl derivatives, carbamates, quinolinic acid and its derivatives, chloroacetanilides, cyclohexanediones, diazines, dichloropropionic acid and their derivatives, dihydrobenzofurans, dihydro-furanit-3-one-furanro-3-one Dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, N-phenyluracils, imidazoles, imidazolinones, isoindoldiones, oxadiazoles, oxiranes, phenols, aryloxy- or heteroaryloxyphenoxypropionic acid esters, phenylacetic acid and their derivatives, phenyl derivatives and their derivatives, phenyl derivatives Phenylpyrazoles, pyridazines, pyridinecarboxylic acid and their derivatives, pyrimidyl ether, sulfonamides, sulfonylureas, triazines, tπazmones, triazolinones, triazolecarboxamides, uraciles and others.
Außerdem kann es von Nutzen sein, die Verbindungen I allein oder in Kombination mit anderen herbiziden auch noch mit weiteren Pflanzenschutzmitteln gemischt, gemeinsam auszubringen, bei¬ spielsweise mit Mitteln zur Bekämpfung von Schädlingen oder phytopathogenen Pilzen bzw. Bakterien. Von Interesse ist ferner die Mischbarkeit mit Mineralsalzlosungen, welche zur Behebung von Ernährungs- und Spurenelementmangeln eingesetzt werden. Es können auch nichtphytotoxische Ole und Olkonzentrate zugesetzt werden.It may also be useful to apply the compounds I alone or in combination with other herbicides, mixed with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.
Die Aufwandmengen an Wirkstoff betragen j e nach Bekämpfungsziel, Jahreszeit, Zielpflanzen und Wachstumsstadium 0.001 bis 3.0, vorzugsweise 0.01 bis 1.0 kg/ha aktive Substanz (a. S.)Depending on the control target, the season, the target plants and the stage of growth, the active compound application rates are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (see also)
AnwendungsbeispieleExamples of use
Die herbizide Wirkung der Isoxazol-4-yl-benzoylderιvate der Formel I ließ sich durch Gewächshausversuche zeigen:The herbicidal action of the isoxazol-4-yl-benzoylderιvate of formula I was demonstrated by greenhouse tests:
Als Kulturgefäße dienten Plastikblumentopfe mit lehmigem Sand mit etwa 3,0% Humus als Substrat. Die Samen der Testpflanzen wurden nach Arten getrennt eingesät.Plastic flower pots with loamy sand with about 3.0% humus served as culture vessels. The seeds of the test plants were sown separately according to species.
Bei Vorauflaufbehandlung wurden die in Wasser suspendierten oder emulgierten Wirkstoffe direkt nach Einsaat mittels fein ver¬ teilender Dusen aufgebracht. Die Gefäße wurden leicht beregnet, um Keimung und Wachstum zu fordern, und anschließend mit durch- sichtigen Plastikhauben abgedeckt, bis die Pflanzen angewachsen waren. Diese Abdeckung bewirkt ein gleichmäßigses Keimen der Testpflanzen, sofern dies nicht durch die Wirkstoffe beeinträch¬ tigt wurde.In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles. The tubes were lightly watered to encourage germination and growth, and then covered with clear plastic covers until the plants had grown. This cover caused gleichmäßigses germination of the test plants, unless this beeinträch by the active ingredients ¬ was Untitled.
Zum Zweck der Nachauflaufbehandlung werden die Testpflanzen je nach Wuchsform erst bis zu einer Wuchshohe von 3 bis 15 cm ange¬ zogen und erst dann mit den in Wasser suspendierten oder emul¬ gierten Wirkstoffen behandelt. Die Testpflanzen werden dafür ent¬ weder direkt gesät und in den gleichen Gefäßen aufgezogen oder sie werden erst als Keimpflanzen getrennt angezogen und einige Tage vor der Behandlung in die Versuchsgefaße verpflanzt. Die Aufwandmenge für die Nachauflaufbehandlung betrug 0,5 bzw. 0,25 kg/ha a.S..For the purpose of post-emergence treatment, the test plants, depending on the growth habit, are first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. The test plants are ent for ¬ neither sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted some days before treatment in the Versuchsgefaße. The application rate for post-emergence treatment was 0.5 and 0.25 kg / ha aS.
Die Pflanzen wurden artenspezifisch bei Temperaturen von 10 - 25°C bzw. 20 - 35°C gehalten. Die Versuchsperiode erstreckte sich über 2 bis 4 Wochen. Während dieser Zeit wurden die Pflanzen gepflegt, und ihre Reaktion auf die einzelnen Behandlungen wurde ausge¬ wertet.The plants were kept at temperatures of 10 - 25 ° C or 20 - 35 ° C depending on the species. The trial period lasted 2 to 4 weeks. During this time, the plants were cared for, and their reaction to the individual treatments was evaluated.
Bewertet wurde nach einer Skala von 0 bis 100. Dabei bedeutet 5 100 kein Aufgang der Pflanzen bzw. vollige Zerstörung zumindest der oberirdischen Teile und 0 keine Schädigung oder normaler Wachstumsverlauf .Evaluation was carried out on a scale from 0 to 100. 5 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.
Die in den Gewächshausversuchen verwendeten Pflanzen setzten sich 0 aus folgenden Arten zusammen:The plants used in the greenhouse experiments are composed of the following types:
55
Figure imgf000061_0002
Figure imgf000061_0002
0 Tabelle 8 Herbizide Aktivität bei Nachauflaufanwendung im Gewächshaus0 Table 8 Herbicidal activity in post-emergence applications in the greenhouse
Figure imgf000061_0001
Figure imgf000061_0001
Bsp. -Nr. 6.1Example no. 6.1
Aufwandmenge 0,5 0,25Application rate 0.5 0.25
(kg/ha a.S. ) Schädigung in %(kg / ha as) damage in%
TestpflanzenTest plants
CHEAL 95 95CHEAL 95 95
POLPE 90 90POLPE 90 90
SETFA 90 80SETFA 90 80
SINAL 95 90 SINAL 95 90

Claims

Patentansprüche claims
1. Isoxazol-4-yl-benzoylderivate der Formel I,1. isoxazol-4-yl-benzoyl derivatives of the formula I,
Figure imgf000062_0001
in der die Substituenten folgende Bedeutung haben:
Figure imgf000062_0001
in which the substituents have the following meaning:
L,M Wasserstoff, Cι-C6-Alkyl, C2-C6-Alkenyl,L, M is hydrogen, -CC 6 alkyl, C 2 -C 6 alkenyl,
C2-C6-Alkinyl, Cχ-C4-Alkoxy, wobei diese Gruppen gegebenenfalls durch ein bis fünf Halogenatome oderC 2 -C 6 alkynyl, Cχ-C 4 alkoxy, these groups optionally having one to five halogen atoms or
Cχ-C4-Alkoxy substituiert sein können; Halogen, Cyano, Nitro, eine Gruppe - (A)m-S (0)nRi oder eine Gruppe- (A)m-CO-R2;Cχ-C 4 alkoxy may be substituted; Halogen, cyano, nitro, a group - (A) m -S (0) n R i or a group - (A) m -CO-R 2 ;
Y eine Gruppe bestehend aus C=0, C=N-R3, CR7-NR5R6, CR7-OR8, CRi°Rii, CR7-SR8; mit Wasserstoff oder Cι~C4-Alkyl substituiertes 1,3-Dioxanyl oder 1, 3-Dioxolanyl; ein Heteroatom ausgewählt aus der Gruppe Sauerstoff, Schwefel und Stickstoff;Y is a group consisting of C = 0, C = NR 3 , CR 7 -NR 5 R 6 , CR 7 -OR 8 , CR i ° Ri i , CR 7 -SR 8 ; 1,3-dioxanyl or 1,3-dioxolanyl substituted with hydrogen or C 1 -C 4 -alkyl; a heteroatom selected from the group consisting of oxygen, sulfur and nitrogen;
X bestehend aus einer Kette (-CR12R13-) , (-CR12R13-CR2lR22-) , (-CR12=CR13-) , (_CR12R13-CR12=CRl3-) ; NR23 X consisting of a chain (-CR 12 R 13 -), (-CR 12 R 13 -CR 2l R 22 -), (-CR 12 = CR 13 -), ( _ CR 12 R 13- CR 12 = CRl3- ); N R 23
die Bindung zwischen X und Y kann gesättigt oder ungesättigt sein;the bond between X and Y can be saturated or unsaturated;
A 0, NR14;A 0, NR 14 ;
m null oder eins ;m zero or one;
n nul l , eins oder zwei ;n zero, one or two;
R1 Cx-C4-Alkyl , C1-C4 Haloalkyl oder NR14 ;R 1 is C x -C 4 alkyl, C 1 -C 4 haloalkyl or NR 14 ;
R2 Cι-C4 Alkyl , Cι.-C4 Haloalkyl , Cι-C4-Alkoxy oder NR14 ; R3 Wasserstoff, -NR9R4; Cι-C6-Alkyl, Cι-C6-Haloalkyl, Cι-C6-Alkoxy, Cι-C6-Haloalkoxy, C2-C6-Alkenyl, C2-C6-Haloalkenyl, C2-C6-Alkinyl; gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus Cι-C4-Alkyl,R 2 C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or NR 14 ; R 3 is hydrogen, -NR 9 R 4 ; Cι-C 6 -alkyl, C 6 haloalkyl, Cι-C 6 -alkoxy, C 6 haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 - Alkynyl; optionally substituted phenyl, where the substituents can consist of -CC 4 alkyl,
Cι-C4-Alkoxy, C1-C4-Haloalkoxy, C1-C4-Haloalkyl, Halogen, Cyano, Nitro; gegebenenfalls substituiertes Benzyl, wobei die Substituenten bestehen können aus Cχ-C4-Alkyl, Cι-C4-Alkoxy, Cι-C4-Haloalkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro; gegebenenfalls substituiertes Benzyloxy wobei die Substituenten bestehen können aus Cι-C4-Alkyl, Cι-C4-Alkoxy, Cι-C4-Haloalkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro;C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro; optionally substituted benzyl, where the substituents can consist of Cχ-C 4 alkyl, -C-C 4 alkoxy, Cι-C 4 -haloalkoxy, Cι-C 4 -haloalkyl, halogen, cyano, nitro; optionally substituted benzyloxy where the substituents can consist of -CC 4 -alkyl, -C-C 4 -alkoxy, -C-C 4 -haloalkoxy, -C-C 4 -haloalkyl, halogen, cyano, nitro;
R4 Wasserstoff, Cι-C6-Alkyl, Cι-C6-Haloalkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C=0-NR14; gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus Cχ-C4-Alkyl, Cι-C4-Alkoxy, Cι-C4-Haloalkoxy, Cι-C4-Haloalkyl,R 4 is hydrogen, -CC 6 -alkyl, -C-C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C = 0-NR 14 ; optionally substituted phenyl, where the substituents can consist of Cχ-C 4 -alkyl, Cι-C 4 -alkoxy, Cι-C 4 -haloalkoxy, Cι-C 4 -haloalkyl,
Halogen, Cyano, Nitro; gegebenenfalls substituiertes Benzyl, wobei die Substituenten bestehen können aus Cι~C4-Alkyl, Cι-C4-Alkoxy, Cχ-C4-Haloalkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro;Halogen, cyano, nitro; optionally substituted benzyl, where the substituents can consist of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, Cχ-C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
R9 Wasserstoff, Cι-C6-Alkyl, Ci-Cβ-Haloalkyl,R 9 is hydrogen, -CC 6 alkyl, Ci-Cβ-haloalkyl,
C2-C6-Alkenyl, C2-C6-Alkinyl, C=0-NR14; gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus Cι-C4-Alkyl,C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C = 0-NR 14 ; optionally substituted phenyl, where the substituents can consist of -CC 4 alkyl,
Cι-C4-Alkoxy, Cι-C4-Haloalkoxy, Cι-C4-Haloalkyl,C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl,
Halogen, Cyano, Nitro; gegebenenfalls substituiertes Benzyl, wobei dieHalogen, cyano, nitro; optionally substituted benzyl, the
Substituenten bestehen können aus Cχ-C4-Alkyl, Cι-C4-Alkoxy, Cι-C4-Haloalkoxy, Cι-C4-Haloalkyl,Substituents can consist of Cχ-C 4 -alkyl, Cι-C 4 -alkoxy, Cι-C 4 -haloalkoxy, Cι-C 4 -haloalkyl,
Halogen, Cyano, Nitro;Halogen, cyano, nitro;
R5,R6 unabhängig voneinander Wasserstoff, Cι-C6-Alkyl, C2-C6 Alkenyl, Cι~C4 Haloalkyl, C2-C6 Haloalkenyl, CI-CÖ Alkoxy, Cι-C6-Haloalkoxy; gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus Cχ-C4-Alkyl, Cι-C4-Alkoxy, Cι-C4-Haloalkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro; gegebenenfalls substituiertes Benzyl, wobei die Substituenten bestehen kόnnen aus Cι~C4-Alkyl, Cχ-C4-Alkoxy, Cχ-C4-Haloalkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro;R 5 , R 6 independently of one another hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 alkenyl, C 1 -C 4 haloalkyl, C 2 -C 6 haloalkenyl, C I -C Ö alkoxy, Cι-C 6 -haloalkoxy; optionally substituted phenyl, where the substituents can consist of Cχ-C 4 -alkyl, -C-C 4 -alkoxy, Cι-C 4 -haloalkoxy, Cι-C 4 -haloalkyl, halogen, cyano, nitro; optionally substituted benzyl, where the substituents can consist of C 1 -C 4 -alkyl, Cχ-C 4 -alkoxy, Cχ-C 4 -haloalkoxy, Cι-C 4 -haloalkyl, halogen, cyano, nitro;
R7 Wasserstoff, Cι-C6 Alkyl, Cι~C4-Alkoxy, Cι~C4-Halo- alkyl, Cι-C4-Haloalkoxy; gegebenenfalls substituier¬ tes Phenyl, wobei die Substituenten bestehen können aus ein bis drei Halogenen, Cι~C4-Alkyl, Cι-C4-Alkoxy, Cι~C4-Haloalkoxy, Nitro; R7 und R21 oderR 7 are hydrogen, C 6 alkyl, Cι ~ C4-alkoxy, Cι ~ C 4 -Halo- alkyl, Cι-C4-haloalkoxy; optionally substituted phenyl, where the substituents can consist of one to three halogens, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, nitro; R 7 and R 21 or
R7 und R23 oder R7 und R12 können eine Bindung bilden;R 7 and R 23 or R 7 and R 12 can form a bond;
R8 Wasserstoff, Cι-C6-Alkyl, Cι-C4-Halogenalkyl, gegebe¬ nenfalls substituiertes Phenyl, wobei die Substituen- ten bestehen können aus Cι-C4-Alkyl, Cχ-C4-Alkoxy,R 8 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 4 -haloalkyl, optionally substituted phenyl, where the substituents can consist of C 1 -C 4 -alkyl, Cχ-C 4 -alkoxy,
Cι-C4-Haloalkoxy, Cχ-C4-Haloalkyl, Halogen, Cyano, Nitro; gegebenenfalls substituiertes Benzyl, wobei die Substituenten bestehen können aus Cι-C4-Alkyl, Cχ-C4-Alkoxy, Cι-C4-Haloalkoxy, Cι~C4-Haloalkyl,C 1 -C 4 haloalkoxy, C 4 -C 4 haloalkyl, halogen, cyano, nitro; optionally substituted benzyl, where the substituents can consist of -C 4 alkyl, C 4 -C 4 alkoxy, C 4 C haloalkoxy, C 1 -C 4 haloalkyl,
Halogen, Cyano, Nitro;Halogen, cyano, nitro;
Riθ,Riι unabhängig voneinander Wasserstoff, C!-C6-Alkyl; gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus ein bis dreiRiθ, Riι independently hydrogen, C ! -C 6 alkyl; optionally substituted phenyl, where the substituents can consist of one to three
Halogenen, Cχ-C4-Alkyl, Cι-C4-Alkoxy, Cχ-C4-Halo- alkoxy, Nitro; R10 und R12 oder R10 und R21 oder Ri° und R23 können eine Bildung bilden;Halogens, Cχ-C 4 alkyl, Cι-C 4 alkoxy, Cχ-C 4 halo alkoxy, nitro; R 10 and R 12 or R 10 and R 21 or Ri ° and R 23 can form a formation;
R12,R13 unabhängig voneinander Wasserstoff, Cχ-C6-Alkyl, Cι-C6-Haloalkyl, Cι-C6-Alkoxy, Cx-Ce-Haloalkoxy; gegebenenfalls substituiertes Phenyl, wobei die Substituenten bestehen können aus Cι-C4-Alkyl, Cι-C4-Alkoxy, Cι-C4-Haloalkoxy, Cι~C4-Haloalkyl, Halogen, Cyano, Nitro;R 12 , R 13 independently of one another hydrogen, Cχ-C 6 -alkyl, Cι-C 6 -haloalkyl, Cι-C 6 -alkoxy, Cx-Ce-haloalkoxy; optionally substituted phenyl, where the substituents can consist of -CC 4 alkyl, -C 4 -alkoxy, -C-C 4 haloalkoxy, -C ~ C 4 -haloalkyl, halogen, cyano, nitro;
R14 Cι-C4-Alkyl;R 14 -CC 4 alkyl;
R21 Wasserstoff, Ci-Cg-Alkyl, Cι-C6-Haloalkyl, C!-C6-Alkoxy, Cι-C6-Haloalkoxy; gegebenenfalls sub¬ stituiertes Phenyl, wobei die Substituenten bestehen können aus Cι-C4-Alkyl, Cι~C4-Alkoxy, Cι-C4-Halo- alkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro; R22 Wasserstoff, Ci-Cβ Alkyl, Cι-C6 Haloalkyl,R 21 is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C ! -C 6 alkoxy, -C-C 6 haloalkoxy; optionally substituted phenyl, where the substituents can consist of -CC 4 alkyl, -C ~ C 4 -alkoxy, -C-C 4 -haloalkoxy, -C-C 4 -haloalkyl, halogen, cyano, nitro; R 22 is hydrogen, Ci-Cβ alkyl, Cι-C 6 haloalkyl,
Ci-Cß-Alkoxy, Cχ-C6-Haloalkoxy; gegebenenfalls sub¬ stituiertes Phenyl, wobei die Substituenten bestehen können aus Cι-C4-Alkyl, Cι-C4-Alkoxy, Cι-C4-Halo- alkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro;Ci-Cß-alkoxy, Cχ-C6-haloalkoxy; optionally substituted phenyl, where the substituents can consist of -CC 4 -alkyl, -C-C 4 -alkoxy, -C-C 4 -haloalkoxy, -C-C 4 -haloalkyl, halogen, cyano, nitro;
R23 Wasserstoff, Cι-C6-Alkyl, C2-C6-Alkenyl, Cχ-C6-Alkoxy; gegebenenfalls mit Cι-C4-Alkyl, Cι-C4-Alkoxy, Cι-C4-Haloalkoxy, Cι-C4-Haloalkyl, Halogen, Cyano, Nitro substituiertes Phenyl oder Benzyl;R 23 is hydrogen, -CC 6 alkyl, C 2 -C 6 alkenyl, Cχ-C 6 alkoxy; phenyl or benzyl optionally substituted with C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, halogen, cyano, nitro;
Q ein in Stellung 4 verknüpfter Isoxazolring der Formel IIQ is an isoxazole ring of the formula II linked in position 4
Figure imgf000065_0001
in welcher
Figure imgf000065_0001
in which
R15 für Wasserstoff oder -C02R17, C1-C4-Alkyl;R 15 is hydrogen or -C0 2 R 17 , C 1 -C 4 alkyl;
R16 für Wasserstoff, Cι-C4-Alkyl oder C3-C6-Cycloalkyl, welches gegebenenfalls durch ein oder mehrere Halogenatome oder Cι-C4-Alkyl substituiert sein kann undR 16 for hydrogen, -CC 4 -alkyl or C 3 -C 6 -cycloalkyl, which may optionally be substituted by one or more halogen atoms or -CC 4 -alkyl and
R17 für Cι-C4-Alkyl steht;R 17 represents C 1 -C 4 alkyl;
J ein Carbonylrest CO oder ein Rest -CHR18;J is a carbonyl radical CO or a radical -CHR 18 ;
Riβ eine OH-Gruppe, eine ggf. mit C2-C4-Acyl acylierte Hydroxylgruppe oder ein Chloratom bedeutet;Ri β represents an OH group, a hydroxyl group optionally acylated with C 2 -C 4 -acyl or a chlorine atom;
wobei für den Fall, daß Y = C=0 ist, X ungleich NR23 ist,in the event that Y = C = 0, X is not equal to NR 23 ,
sowie landwirtschaftlich brauchbare Salze.as well as agriculturally useful salts.
2. isoxazol-4-yl-benzoylderivate der Formel la,2. isoxazol-4-yl-benzoyl derivatives of the formula la,
Figure imgf000065_0002
in der L für Wasserstoff, Cι-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Cι~C4-Alkoxy, C1-C4-Alkylthio, Cι-C4-Halogen- alkyl, Cι-C4-Halogenalkoxy, Cι-C4-Halogenalkylthio, Cι-C4-Alkylsulfonyl, Halogen, Nitro oder Cyano und M für Wasserstoff, C!-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Cι-C4-Alkoxy, Cι-C4-Alkylthio, C!-C4-Halogenalkyl, Cι-C4-Halogenalkoxy, Cι-C4-Halogenalkoxy, Cx-Q-Halogenalkyl- thio, Cι-C4-Alkylsulfonyl, Halogen, Nitro oder Cyano steht und Q, J, X, n und Y die in Anspruch 1 angegebenen Bedeutun- gen haben, wobei für den Fall, daß Y = C=0 ist, X ungleich NR23 ist.
Figure imgf000065_0002
where L are hydrogen, C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Cι ~ C 4 alkoxy, C 1 -C 4 alkylthio, Cι-C 4 -halogen - alkyl, Cι-C4-haloalkoxy, Cι-C4-haloalkylthio, Cι-C 4 alkylsulfonyl, halogen, nitro or cyano and M is hydrogen, C! -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -C-C 4 alkoxy, -C-C 4 alkylthio, C ! -C 4 -Halogenalkyl, -C-C 4 -haloalkoxy, -C-C 4 -haloalkoxy, Cx-Q-haloalkyl-thio, Cι-C 4 -alkylsulfonyl, halogen, nitro or cyano and Q, J, X, n and Y has the meanings given in claim 1, where X is not equal to NR 23 if Y = C = 0.
3. Isoxazol-4 -yl-benzoylderivate der Formel lb,3. Isoxazol-4 -yl-benzoyl derivatives of the formula Ib,
Figure imgf000066_0001
Figure imgf000066_0001
in der L für C!-C6 Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Cι-C4-Alkoxy, Cι-C4-Halogenalkyl, Cι-C4-Halogenalkoxy, Halo¬ gen, Nitro oder Cyano und M für Wasserstoff, Ci-C^ Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Cι-C4-Alkoxy, Cι-C4-Halogenalkyl, C1-C4-Halogenalkoxy, Halogen, Nitro oder Cyano steht und Q, J, X, n und Y die in Anspruch 1 angegebenen Bedeutungen haben, wobei für den Fall, daß Y = C=0 ist, X ungleich NR23 ist.in the L for C ! -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Cι-C 4 -alkoxy, C 4 haloalkyl, Cι-C4-haloalkoxy, Halo¬ gen, nitro or cyano and M is hydrogen, Ci-C ^ alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Cι-C 4 -alkoxy, C 4 haloalkyl, C 1 -C 4 -haloalkoxy, halogen, Is nitro or cyano and Q, J, X, n and Y have the meanings given in claim 1, where, in the case where Y = C = 0, X is not NR 23 .
4. Isoxazol-4-yl-benzoylderivate der Formel I gemäß Anspruch 1 in der die Reste L bzw. M für Wasserstoff, Methyl, Methoxy,4. isoxazol-4-yl-benzoyl derivatives of the formula I according to claim 1 in which the radicals L and M are hydrogen, methyl, methoxy,
Chlor, Cyano, Nitro, Trifluormethyl stehen.Chlorine, cyano, nitro, trifluoromethyl are available.
5. Isoxazol-4-yl-benzoylderivate der Formel lc,5. isoxazol-4-yl-benzoyl derivatives of the formula lc,
M (0)n M (0) n
R21R 2 1
:∞ R22 IC : ∞ R 22 IC
R12 Ri 3 R 12 R i 3
in der L für Wasserstoff, Cχ-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Cι~C4-Alkoxy, Cι-C4-Halogenalkyl, Cι~C4-Halogen- alkoxy, Halogen, Nitro oder Cyano und M für Wasserstoff, Cι-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Cι.-C4-Alkoxy, Cι-C4-Halogenalkyl, Cι~C4-Halogenalkoxy, Halogen, Nitro oder Cyano steht und Q, J, n, Y sowie R22, R21, R12 und R13 die in Anspruch 1 angegebenen Bedeutungen haben. L is hydrogen, Cχ-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Cι ~ C 4 -alkoxy, C 4 haloalkyl, Cι ~ C4 halo- alkoxy, halogen, nitro or cyano and M are hydrogen, C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Cι.-C 4 -alkoxy, C 4 haloalkyl, Cι ~ C 4 haloalkoxy, halogen, nitro or cyano and Q, J, n, Y and R 22 , R 21 , R 12 and R 13 have the meanings given in claim 1.
6. Isoxazol-4 -yl-benzoylderivate der Formel Id,6. isoxazole-4-yl-benzoyl derivatives of the formula Id,
Figure imgf000067_0001
Figure imgf000067_0001
in der L für Wasserstoff, Cι-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Cι-C4-Alkoxy, Cχ-C4-Halogenalkyl, Cχ-C4-Halogen- alkoxy, Halogen, Nitro oder Cyano und M für Wasserstoff, Cχ-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Cι-C4-Alkoxy, Cι-C4-Halogenalkyl# C!-C4-Halogenalkoxy, Halogen, Nitro oder Cyano steht und Q, J, n, Y sowie R12 und R13 die in Anspruch 1 angegebenen Bedeutungen haben.where L are hydrogen, C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Cι-C 4 alkoxy, Cχ-C4-haloalkyl, Cχ-C4-halo alkoxy, halogen, nitro or cyano and M is hydrogen, Cχ-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Cι-C 4 -alkoxy, C 4 haloalkyl # C ! -C 4 haloalkoxy, halogen, nitro or cyano and Q, J, n, Y and R 12 and R 13 have the meanings given in claim 1.
7. Isoxazol-4 -yl-benzoylderivate der Formel Ie7. Isoxazol-4 -yl-benzoyl derivatives of the formula Ie
Figure imgf000067_0002
Figure imgf000067_0002
in der L für Wasserstoff, Cι-C6 Alkyl, C2-C6-Alkenyl,in the L for hydrogen, -CC 6 alkyl, C 2 -C 6 alkenyl,
C2-C6-Alkinyl, C].-C4-Alkoxy, Cι-C4-Halogenalkyl, C!-C4-Halogen- alkoxy, Halogen Nitro oder Cyano und M für Wasserstoff, Cι-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Cι-C4-Alkoxy, Cι-C4-Halogenalkyl, Cι-C4-Halogenalkoxy, Halogen Nitro oder Cyano steht und Q, J, n, Y sowie R12 und R13 die in Anspruch 1 angegebenen Bedeutungen haben.C 2 -C 6 alkynyl, C] . -C 4 alkoxy, -C-C 4 haloalkyl, C ! -C 4 halo-alkoxy, halogen, nitro or cyano and M are hydrogen, C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Cι-C 4 -alkoxy, C 4 -haloalkyl, -CC 4 -haloalkoxy, halogen nitro or cyano and Q, J, n, Y and R 12 and R 13 have the meanings given in claim 1.
8. Isoxazol-4-yl-benzoylderivate der Formel Ig8. Isoxazol-4-yl-benzoyl derivatives of the formula Ig
Figure imgf000067_0003
Figure imgf000067_0003
in der L für Wasserstoff, Cι-C6-Alkyl, C2-C6-Alkenyl, C2-C6- Alkinyl, Cι-C4-Alkoxy, Cι-C4-Halogenalkyl, Ci-C4-Halogen¬ alkoxy, Halogen, Nitro oder Cyano und M für Wasserstoff, Cι-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Cι-C4-Alkoxy,in the L for hydrogen, -CC 6 -alkyl, C 2 -C6 -alkenyl, C 2 -C 6 -alkynyl, -C-C 4 -alkoxy, -C-C 4 -haloalkyl, Ci-C 4 -haloalkoxy , halogen, nitro or cyano and M are hydrogen, C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Cι-C 4 alkoxy,
Cχ-C4-Halogenalkyl, Cι-C4-Halogenalkoxy, Halogen, Nitro oder Cyano steht und Q, J, n, Y die in Anspruch 1 angegebenen Be¬ deutungen haben.Cχ-C 4 haloalkyl, Cι-C 4 haloalkoxy, halogen, nitro or Cyano is and Q, J, n, Y have the meanings given in claim 1.
9. Isoxazol-4-yl-benzoylderivate der Formel I gemäß Anspruch 1 in der n für eins oder zwei steht und Y für CR7-0R8, wobei R 7 und R8 die in Anspruch 1 angegebene Bedeutung haben.9. isoxazol-4-yl-benzoyl derivatives of the formula I according to claim 1 in which n is one or two and Y is CR 7 -0R 8 , where R 7 and R 8 have the meaning given in claim 1.
10. Verfahren zur Herstellung der Isoxazol-4-yl-benzoylderivate der Formel I gemäß Anspruch 1, in der Q einen Rest CO-J dar- stellt, dadurch gekennzeichnet, daß man Alkinylstannate der Formel A210. A process for the preparation of the isoxazol-4-yl-benzoyl derivatives of the formula I according to claim 1, in which Q represents a radical CO-J, characterized in that alkynyl stannates of the formula A2
(C4H9)Sn Cs C R16 A2 mit einem Benzoesäurederivat der Formel III(C 4 H 9 ) Sn Cs CR 16 A2 with a benzoic acid derivative of the formula III
Figure imgf000068_0001
wobei T = Halogen bedeutet und L, M, X, Y und n die in
Figure imgf000068_0001
where T = halogen and L, M, X, Y and n the in
Anspruch 1 genannte Bedeutung haben, zu Benzoylalkinen der Formel B2Claim 1 have meaning to benzoylalkynes of the formula B2
Figure imgf000068_0002
Figure imgf000068_0002
umsetzt und diese mit Nitriloxiden der Formel C2implemented and this with nitrile oxides of the formula C2
Rl5 C ≡≡ N 0 c l Rl 5 C ≡≡ N 0 cl
in der R15 für Cχ-C4-Alkyl steht, einer Cycloaddition zu den Isoxazolen der Formel Ifin which R 15 is Cχ-C 4 alkyl, a cycloaddition to the isoxazoles of the formula If
Figure imgf000068_0003
unterwirft.
Figure imgf000068_0003
submits.
11. Herbizides Mittel, enthaltend mindestens ein Isoxazol-4-yl benzoylderivat der Formel I gemäß Anspruch I und übliche inerte Zusatzstoffe. 11. Herbicidal agent containing at least one isoxazol-4-yl benzoyl derivative of the formula I according to claim I and customary inert additives.
12. Verfahren zur Bekämpfung unerwünschten Pflanzenwuchses, dadurch gekennzeichnet, daß man eine herbizid wirksame Menge eines Isoxazol-4-yl-benzoylderivates der Formel 1 gemäß Anspruch 1 auf die Pflanzen oder deren Lebensraum einwirken I läßt. 12. A method for controlling undesirable plant growth, characterized in that a herbicidally effective amount of an isoxazol-4-yl-benzoyl derivative of the formula 1 according to claim 1 is allowed to act on the plants or their habitat.
PCT/EP1996/005069 1995-11-23 1996-11-18 Isoxazole-4-yl-benzoyl derivatives and the use thereof as herbicides WO1997019076A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU76271/96A AU7627196A (en) 1995-11-23 1996-11-18 Isoxazole-4-yl-benzoyl derivatives and the use thereof as herbicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1995143640 DE19543640A1 (en) 1995-11-23 1995-11-23 Isoxazol-4-yl-benzoyl derivatives
DE19543640.7 1995-11-23

Publications (1)

Publication Number Publication Date
WO1997019076A1 true WO1997019076A1 (en) 1997-05-29

Family

ID=7778193

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/005069 WO1997019076A1 (en) 1995-11-23 1996-11-18 Isoxazole-4-yl-benzoyl derivatives and the use thereof as herbicides

Country Status (4)

Country Link
AR (1) AR004742A1 (en)
AU (1) AU7627196A (en)
DE (1) DE19543640A1 (en)
WO (1) WO1997019076A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0918056A1 (en) * 1997-11-20 1999-05-26 Rhone-Poulenc Agriculture Ltd. Herbicides
US7998983B2 (en) 2004-09-10 2011-08-16 Syngenta Limited Substituted isoxazoles as fungicides

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4410353A (en) * 1981-07-17 1983-10-18 Rhone-Poulenc Agrochimie Herbicidal N-sulfonyl 5-[substituted phenoxy]-2-substituted benzamides
EP0588357A1 (en) * 1992-09-18 1994-03-23 Rhone Poulenc Agriculture Ltd. Isoxazoles derivatives and their use as herbicides
EP0629623A1 (en) * 1992-03-03 1994-12-21 Idemitsu Kosan Company Limited Pyrazole derivative
EP0636622A1 (en) * 1993-07-30 1995-02-01 Rhone Poulenc Agriculture Ltd. Isoxazole derivatives and their use as herbicides
DE4427998A1 (en) * 1994-08-08 1996-02-15 Basf Ag Saccharin derivatives

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4410353A (en) * 1981-07-17 1983-10-18 Rhone-Poulenc Agrochimie Herbicidal N-sulfonyl 5-[substituted phenoxy]-2-substituted benzamides
EP0629623A1 (en) * 1992-03-03 1994-12-21 Idemitsu Kosan Company Limited Pyrazole derivative
EP0588357A1 (en) * 1992-09-18 1994-03-23 Rhone Poulenc Agriculture Ltd. Isoxazoles derivatives and their use as herbicides
EP0636622A1 (en) * 1993-07-30 1995-02-01 Rhone Poulenc Agriculture Ltd. Isoxazole derivatives and their use as herbicides
DE4427998A1 (en) * 1994-08-08 1996-02-15 Basf Ag Saccharin derivatives

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0918056A1 (en) * 1997-11-20 1999-05-26 Rhone-Poulenc Agriculture Ltd. Herbicides
US7998983B2 (en) 2004-09-10 2011-08-16 Syngenta Limited Substituted isoxazoles as fungicides

Also Published As

Publication number Publication date
DE19543640A1 (en) 1997-05-28
AU7627196A (en) 1997-06-11
AR004742A1 (en) 1999-03-10

Similar Documents

Publication Publication Date Title
EP0810998B1 (en) Phenyl diketone derivatives as herbicides
EP0888334B1 (en) 2-hetaroylcyclohexane-1,3-diones
WO1996026200A1 (en) Herbicidal benzoyl derivatives
WO1996026192A1 (en) Isoxazolyl-benzoyl derivatives
EP0847394A1 (en) 2-cyclohexane-1,3-dione benzoyl derivatives
EP0888343B1 (en) Pyrazole-4-yl-hetaroyl derivatives as herbicides
EP0961774B1 (en) Pyrazol-4-yl-benzoyl derivatives and their use as herbicides
DE4423934A1 (en) 3(2H)-Pyridazinone derivatives, their preparation and their use
WO1997019076A1 (en) Isoxazole-4-yl-benzoyl derivatives and the use thereof as herbicides
WO1997019071A1 (en) 2-cyano-1,3-dione derivatives, the production of same and their use as herbicides
EP1135386B1 (en) Method for producing pyrazolylbenzoyl derivatives and novel pyrazolylbenzoyl derivatives
DE19607041A1 (en) New pyrazolyl:carbonyl-oxathiin or -dithiin derivatives
DE19612687A1 (en) New di:oxo:cyclohexyl:carbonyl-oxathiin or -dithiin derivatives
DE19612685A1 (en) New pyrazolyl:carbonyl-oxathiin or -dithiin derivatives
DE19607105A1 (en) New di:oxo:cyclohexyl:carbonyl-oxathiin or -dithiin derivatives
NZ337536A (en) Saccharin-5-carbonyl-cyclohexane-1,3,5-trione derivatives, their preparation and their use as herbicides
MXPA99007920A (en) Saccharine-5-carbonyl-cyclohexane-1,3,5-trione derivatives, their preparation and their use as herbicides

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BG BR BY CA CN CZ GE HU IL JP KR KZ LV MX NO NZ PL RO RU SG SI SK TR UA US UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WA Withdrawal of international application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA