WO1997019076A1 - Derives d'isoxazol-4-yl-benzoyle et leur utilisation comme herbicides - Google Patents

Derives d'isoxazol-4-yl-benzoyle et leur utilisation comme herbicides Download PDF

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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
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alkyl
alkoxy
haloalkyl
haloalkoxy
nitro
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PCT/EP1996/005069
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German (de)
English (en)
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Martina Otten
Wolfgang Von Deyn
Stefan Engel
Regina Luise Hill
Uwe Kardorff
Marcus Vossen
Peter Plath
Helmut Walter
Karl-Otto Westphalen
Ulf Misslitz
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Basf Aktiengesellschaft
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Priority to AU76271/96A priority Critical patent/AU7627196A/en
Publication of WO1997019076A1 publication Critical patent/WO1997019076A1/fr

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    • 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:

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  • Chemical & Material Sciences (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne des dérivés d'isoxazol-4-yl-benzoyle de la formule (I) dans laquelle les substituants ont la notation suivante: L, M désignent hydrogène, alkyle C1-C6, alkényle C2-C6, alkinyle C2-C6, alcoxy C1-C4, ces groupes pouvant éventuellement être substitués par un à cinq atomes d'halogène ou par alcoxy C1-C4, halogène, cyano, nitro, un groupe -(A)m-S(O)nR1 ou un groupe -(A)¿m-CO-R?2; Y désigne un groupe comprenant C=O, C=N-R?3, CR7-NR5R6, CR7-OR8, CR10R11, CR7-SR8¿; 1,3-dioxanyle substitué par alkyle C¿1?-C4 ou 1,3-dioxolanyle; un hétéroatome sélectionné dans le groupe oxygène, soufre et azote; X désigne une chaîne (-CR?12R13), (-CR12R13-CR21R22¿-), (-CR12=CR13-), (-CR?12R13-CR12=CR13-); NR23¿, la liaison entre X et Y pouvant être saturée ou insaturée; A désigne O, NR14; m vaut zéro ou un; n vaut zéro, un ou deux; J, Q et R1 à R23 ont la notation mentionnée dans la revendication 1. L'invention concerne des procédés permettant de préparer ces dérivés d'isoxyzol-4-yl-benzoyle, des agents les contenant, ainsi que leur utilisation ou celle d'agents les contenant pour lutter contre les graminées adventices/mauvaises herbes.
PCT/EP1996/005069 1995-11-23 1996-11-18 Derives d'isoxazol-4-yl-benzoyle et leur utilisation comme herbicides WO1997019076A1 (fr)

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
DE19543640.7 1995-11-23
DE1995143640 DE19543640A1 (de) 1995-11-23 1995-11-23 Isoxazol-4-yl-benzoylderivate

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WO1997019076A1 true WO1997019076A1 (fr) 1997-05-29

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AU (1) AU7627196A (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0918056A1 (fr) * 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 (fr) * 1992-09-18 1994-03-23 Rhone Poulenc Agriculture Ltd. Dérivés d'isoxazole et leur utilisation comme herbicides
EP0629623A1 (fr) * 1992-03-03 1994-12-21 Idemitsu Kosan Company Limited Derive de pyrazole
EP0636622A1 (fr) * 1993-07-30 1995-02-01 Rhone Poulenc Agriculture Ltd. Dérivés d'isoxazole et leur utilisation comme herbicides
DE4427998A1 (de) * 1994-08-08 1996-02-15 Basf Ag Saccharinderivate

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 (fr) * 1992-03-03 1994-12-21 Idemitsu Kosan Company Limited Derive de pyrazole
EP0588357A1 (fr) * 1992-09-18 1994-03-23 Rhone Poulenc Agriculture Ltd. Dérivés d'isoxazole et leur utilisation comme herbicides
EP0636622A1 (fr) * 1993-07-30 1995-02-01 Rhone Poulenc Agriculture Ltd. Dérivés d'isoxazole et leur utilisation comme herbicides
DE4427998A1 (de) * 1994-08-08 1996-02-15 Basf Ag Saccharinderivate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0918056A1 (fr) * 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 (de) 1997-05-28
AR004742A1 (es) 1999-03-10
AU7627196A (en) 1997-06-11

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