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WO1996014304A1 - Urees n-acyle-n-alkyleaminophenylesulfonyle a substituants soufre, leurs procedes de preparation et leur utilisation comme herbicides et regulateurs de croissance pour vegetaux - Google Patents

Urees n-acyle-n-alkyleaminophenylesulfonyle a substituants soufre, leurs procedes de preparation et leur utilisation comme herbicides et regulateurs de croissance pour vegetaux Download PDF

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Publication number
WO1996014304A1
WO1996014304A1 PCT/EP1995/004183 EP9504183W WO9614304A1 WO 1996014304 A1 WO1996014304 A1 WO 1996014304A1 EP 9504183 W EP9504183 W EP 9504183W WO 9614304 A1 WO9614304 A1 WO 9614304A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
alkoxy
haloalkyl
formula
alkenyl
Prior art date
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PCT/EP1995/004183
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German (de)
English (en)
Inventor
Gerhard Schnabel
Lothar Willms
Klaus Bauer
Hermann Bieringer
Christopher Rosinger
Original Assignee
Hoechst Schering Agrevo Gmbh
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 Hoechst Schering Agrevo Gmbh filed Critical Hoechst Schering Agrevo Gmbh
Priority to JP8515006A priority Critical patent/JPH10509443A/ja
Priority to EP95937843A priority patent/EP0790985A1/fr
Priority to BR9509609A priority patent/BR9509609A/pt
Priority to AU38695/95A priority patent/AU3869595A/en
Publication of WO1996014304A1 publication Critical patent/WO1996014304A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D521/00—Heterocyclic compounds containing unspecified hetero rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof

Definitions

  • N-acyl-N-alkylaminophenylsulfonylureas with sulfur substituents process for their preparation and use as herbicides and
  • Plant growth regulators in particular herbicides for the selective control of weeds and weeds in crops of useful plants.
  • heterocyclically substituted phenylsulfonylureas which carry an amino or a functionalized amino group or a sulfur substituent on the phenyl ring have herbicidal and plant growth-regulating properties (EP-A-1515; EP-A-7687; EP-A-30138; US -A-4,892,946; US-A-4,981,509; US-A-4,664,695; US-A-4,632,695; EP-A-116518;
  • Plant growth regulators are particularly well suited.
  • the present invention relates to compounds of the formula (I) and their salts,
  • W is an oxygen or sulfur atom, preferably O,
  • n 0, 1 or 2
  • R 1 is hydroxy, amino, mono- or disubstituted amino, hydroxylamino, substituted hydroxylamino, hydrazino, substituted hydrazino, an aliphatic hydrocarbon or hydrocarbonoxy radical, aryl, heteroaryl, aryloxy or heteroaryloxy, each of the 6 latter radicals being unsubstituted or substituted,
  • R 2 is halogen, CN, NO 2 , amino, mono- or disubstituted amino, alkyl or alkoxy, each of the latter two radicals being unsubstituted or substituted,
  • R 3 is an aliphatic hydrocarbon radical which is unsubstituted or
  • R 4 is an acyl radical
  • R 5 is hydrogen, hydroxy, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, (C 2 -C 4 ) alkenyl or (C 2 -C 4 ) alkynyl, each of the latter 4 radicals being unsubstituted or is substituted by halogen, preferably F, Cl or Br,
  • X, Y independently of one another hydrogen, hydroxy, amino, mono- or
  • Z is CH, N or, where R 0 is halogen, cyano, alkyl, alkoxy,
  • the alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio radicals and the corresponding unsaturated and / or substituted radicals in the carbon skeleton can each be straight-chain or branched.
  • the lower carbon skeletons for example having 1 to 6 carbon atoms or, in the case of unsaturated groups, having 2 to 6 carbon atoms, are preferred for these radicals.
  • Alkyl radicals also in the composite meanings such as alkoxy, haloalkyl, etc., mean, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i -Hexyl and 1,3-dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl;
  • Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals;
  • Alkenyl means, for example, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl , 1-methyl-but-3-en-1-yl and 1-methyl-but-2
  • Halogen means, for example, fluorine, chlorine, bromine or iodine.
  • Haloalkyl, alkenyl and alkynyl mean partly or completely by halogen, preferably by fluorine, chlorine and / or bromine, in particular by fluorine or chlorine
  • Haloalkoxy is, for example, OCF 3 , OCHF 2 .
  • a hydrocarbon residue is a straight-chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic
  • Hydrocarbon residue e.g. Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl
  • Aryl here means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, pentalenyl, fluorenyl and the like, preferably phenyl;
  • a hydrocarbon radical is preferably alkyl, alkenyl or alkynyl having up to 12 carbon atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or phenyl; the same applies to a hydrocarbon residue in one
  • heterocyclic radical or ring can be saturated, unsaturated or heteroaromatic; it preferably contains one or more
  • Hetero units in the ring preferably from the group N, O, S, SO 2 , SO 2 ;
  • heterocyclic residue can e.g. be a heteroaromatic residue or ring (heteroaryl), e.g.
  • Hetero ring atoms which can exist in different oxidation states, e.g. at N and S, occur.
  • Substituted residues such as substituted hydrocarbon residues e.g. Substituted alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted heterocyclyl or heteroaryl, mean, for example, one of the unsubstituted
  • radicals with carbon atoms those with 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred.
  • Substituents from the group halogen, for example fluorine and chlorine, (C 1 -C 4 ) alkyl, preferably methyl or ethyl, (C 1 -C 4 ) haloalkyl, preferably trifluoromethyl, (C 1 -C 4 ) alkoxy are generally preferred , preferably methoxy or ethoxy, (C 1 -C 4 ) haloalkoxy, nitro and cyano.
  • the substituents methyl, methoxy and chlorine are particularly preferred.
  • Mono- or disubstituted amino means a chemically stable radical from the group of substituted amino radicals, which is N-substituted, for example, by one or two identical or different radicals from the group consisting of alkyl, alkoxy, acyl and aryl; preferably monoalkylamino, dialkylamino,
  • Aryl is preferably phenyl or substituted phenyl; for acyl the following applies
  • Optionally substituted phenyl is preferably phenyl which is unsubstituted or one or more times, preferably up to three times, by identical or different radicals from the group halogen, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, (C 1 -C 4 ) haloalkyl, (C 1 -C 4 ) haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyl, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4- Trifluoro- and -Trichlorphenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and
  • An acyl residue means the residue of an organic acid, e.g. the rest of a carboxylic acid and residues derived therefrom such as thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the rest of
  • Carbonic acid monoesters optionally N-substituted carbamic acid,
  • Acyl means, for example, formyl, alkylcarbonyl such as (C 1 -C 4 alkyl) carbonyl, Phenylcarbonyl, where the phenyl ring can be substituted, for example as shown above for phenyl, or alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and other residues of
  • the invention also relates to all stereoisomers which are encompassed by formula (I) and mixtures thereof.
  • Such compounds of the formula (I) contain one or more asymmetric carbon atoms or else double bonds which are not indicated separately in the general formula (I).
  • the possible stereoisomers defined by their specific spatial shape, such as enantiomers, diastereomers, Z and E isomers, are all encompassed by the formula (I) and can be obtained from mixtures of the stereoisomers by customary methods or else by stereoselective reactions in combination with the use of
  • the compounds of formula (I) can form salts in which the hydrogen of the -SO 2 -NH group is replaced by a cation suitable for agriculture.
  • These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or also ammonium salts or salts with organic amines.
  • R 2 halogen, (C 1 -C 3 ) alkyl. (C 1 -C 3 ) haloalkyl, (C 1 -C 5 ) alkoxyalkyl, NO 2 ,
  • R 3 (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 3 -C 7 ) cycloalkyl or
  • R 4 CO-H, CO-R 20 , CO-OR 21 , CO-NR 22 R 23 , CO-SR 24 , CS-R 25 , CS-OR 26 .
  • R 5 is H, OH, (C 1 -C 3 ) alkyl, (C 2 -C 3 ) alkenyl, (C 2 -C 3 ) alkynyl or (C 1 -C 3 ) alkoxy, preferably H or (C 1 -C 4 ) alkyl,
  • R 6 H OH, NH 2 , mono- or di - [(C 1 -C 3 ) alkyl] amino, (C 1 -C 4 ) alkyl,
  • each of the eight last-mentioned radicals unsubstituted or by one or more radicals from the group halogen, (C 1 -C 3 ) alkoxy, (C 1 -C 3 ) haloalkoxy, (C 1 -C 3 ) alkylthio and
  • R 7 H (C 1 -C 4 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, [(C 1 -C 4 ) alkyl] carbonyl, [(C 2 -C 4 ) alkenyl] carbonyl, [(C 2 -C 4 ) alkynyl] carbonyl,
  • (C 1 -C 3 ) haloalkoxy, (C 1 -C 3 ) alkylthio and (C 1 -C 3 ) haloalkylthio, or NR 6 R 7 together is a heterocyclic radical which, in addition to the N atom, contains further hetero units from the group O, N, S, SO or SO 2 im
  • R 8 H (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) haloalkenyl, (C 2 -C 4 ) alkynyl, ( C 2 -C 4 ) haloalkynyl, OH, (C 1 -C 3 ) alkoxy or
  • R 9 H (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) haloalkenyl, (C 2 -C 4 ) alkynyl, ( C 2 -C 4 ) haloalkynyl, CO-H, CO 2 CH 3 , CO-CH 3 , CO-NH 2 , CO-NHCH 3 or CON (CH 3 ) 2 , or NR 8 R 9 together form a heterocyclic radical which in addition to the N atom, further hetero units from the group O, N, S, SO or SO 2 im May contain ring structure and which is unsubstituted or by one or more radicals from the group halogen, OH, NH 2 , NO 2 , CONH 2 ,
  • CONHCH 3 CON (CH 3 ) 2 , NHCH 3 , N (CH 3 ) 2 , CN, CO 2 CH 3 , COCH 3 , CO-H, (C 1 -C 3 ) alkyl, (C 1 -C 3 ) Haloalkyl, (C 1 -C 3 ) alkoxy, (C 1 -C 3 ) haloalkoxy and oxo function is substituted,
  • R 10 H (C 1 -C 3 ) alkyl, (C 1 -C 3 ) haloalkyl, (C 1 -C 3 ) alkoxy, (C 1 -C 3 ) haloalkoxy, (C 1 -C 3 ) alkylthio, ( C 1 -C 3 ) haloalkylthio, NH 2 , NHCH 3 , N (CH 3 ) 2 or OH, R 11 (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl, (C 2 -C 5 ) Alkoxyalkyl, (C 2 -C 4 ) alkenyl,
  • R 13 H (C 1 -C 3 ) alkyl, (C 1 -C 3 ) haloalkyl, (C 1 -C 3 ) alkoxy, (C 1 -C 3 ) haloalkoxy or OH and
  • R 14 H (C 1 -C 3 ) alkyl, (C 1 -C 3 ) haloalkyl, CHO, COCH 3 , CO 2 CH 3 , CO 2 C 2 H 5 , SO 2 CH 3 , SO 2 C 2 H 5 or CN, or NR 13 R 14 together form a heterocyclic radical which, in addition to the N atom, contains further hetero units from the group O, N, S, SO or SO 2 im
  • R 17 (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl, (C 1 -C 6 ) alkoxyalkyl, (C 3 -C 6 ) cycloalkyl, (C 3 -C 6 ) halocycloalkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) haloalkenyl,
  • R 20 is (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl or (C 3 -C 7 ) cycloalkyl, each of the last four radicals being unsubstituted or by one or more Radicals from the group halogen, (C 1 -C 3 ) - alkoxy,
  • R 21 is a radical analogous to R 20 .
  • R 22 is a radical analogous to R 6 and
  • R 23 is a radical analogous to R 7 or
  • R 24 is a radical analogous to R 21 ,
  • R 25 is a radical analogous to R 20 .
  • R 26 is a radical analogous to R 21 ,
  • R 27 is a radical analogous to R 6 and
  • R 28 is a radical analogous to R 7 or
  • R 29 is a radical analogous to R 21 , R 30 H, OH, (C 1 -C 4 ) alkoxy, (C 1 -C 4 ) haloalkoxy, (C 2 -C 4 ) alkenyloxy,
  • (C 2 -C 4 ) haloalkinoxy NH 2 , mono- or di [(C 1 -C 4 ) alkyl] amino or mono- or di [(C 1 -C 4 ) haloalkyl] amino, R 32 (C 1 - C 4 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, (C 1 -C 4 ) alkoxy,
  • R 33 is a radical analogous to R 6 and
  • R 34 is a radical R 7 or
  • radicals X and Y halogen one of the radicals X and Y halogen, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, (C 1 -C 4 ) haloalkyl, (C 1 -C 4 ) haloalkoxy, mono- or di- [ (C 1 -C 4 ) alkyl] amino and the other of the radicals X and Y (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy or (C 1 -C 4 ) haloalkoxy and
  • Z is CH or N.
  • R 1 (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl or mono- or di - [(C 1 -C 4 ) alkyl] amino,
  • R 2 halogen, (C 1 -C 2 ) alkyl, (C 1 -C 2 ) alkoxy, NO 2 , CN or N (CH 3 ) 2 ,
  • R 3 (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl or cyclopropyl,
  • R 4 CHO, COR 20 , COOR 21 , CONR 22 R 23 , SO 2 R 32 or SO 2 NR 33 R 34 ,
  • R 20 (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl, cyclopropyl, (C 2 -C 4 ) alkenyl,
  • R 21 (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl or (C 1 -C 3 ) alkoxy- (C 1 -C 4 ) alkyl,
  • R 22 is H or (C 1 -C 4 ) alkyl
  • R 23 is H or (C 1 -C 4 ) alkyl
  • R 32 is (C 1 -C 4 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, (C 1 -C 4 ) haloalkyl or
  • R 33 is H or (C 1 -C 4 ) alkyl
  • R 34 H, (C 1 -C 4 ) alkyl or (C 1 -C 4 ) alkoxy
  • Preferred compounds of the formula (I) and their salts are those in which R 1 dimethylamino, methyl, ethyl, n-propyl, isopropyl or cyclopropyl, m zero,
  • R 3 (C 1 -C 4 ) alkyl
  • R 4 CHO, COCH 3 , COC 2 H 5 , CO 2 CH 3 , CO 2 C 2 H 5 , CO- c Pr, CO i Pr, CO n Pr,
  • CO-CH 2 CH CH 2 , CO-CH 2 C ⁇ CH, [(C 1 -C 2 ) haloalkyl] carbonyl, SO 2 NH 2 ,
  • (C 1 -C 2 ) haloalkoxy and the other of X and Y are methyl, ethyl, methoxy, ethoxy or 2,2,2-trifluoroethoxy and
  • Z is CH or N.
  • the present invention also relates to processes for the preparation of the compounds of the formula (I) or their salts, characterized in that a) a compound of the formula (II)
  • R * is unsubstituted or substituted phenyl or C 1 -C 4 alkyl, or b) a sulfochloride of the formula (IV)
  • a cyanate for example an alkali metal cyanate such as sodium or potassium cyanate, or c) a sulfonamide of the formula (II) (see variant a) in succession with an aryl chloroformate of the formula (VI)
  • the reaction of the compounds of the formula (II) and (III) is preferably carried out in a base-catalyzed manner in inert solvents, such as, for example, dichloromethane, acetonitrile, dioxane, dimethylformamide (DMF) or dimethyl acetic acid amide or THF, at temperatures from -10 ° C. to the boiling point of the particular solvent .
  • inert solvents such as, for example, dichloromethane, acetonitrile, dioxane, dimethylformamide (DMF) or dimethyl acetic acid amide or THF, at temperatures from -10 ° C. to the boiling point of the particular solvent .
  • the bases used are, for example, organic amine bases such as 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), triethylamine or also hydroxides, such as, for example
  • the sulfonamides of the formula (II) can be obtained, for example, in the following way (cf. Scheme 1): The reaction of the sulfonic acids (X) or their
  • a chlorinating agent - such as PCI 3 , POCI 3 or SOCI 2 - leads to the sulfochloride of the formula (XI).
  • This reaction takes place in bulk or in inert solvents such as dichloromethane, sulfolane, acetonitrile or in a solvent mixture of inert components.
  • the subsequent reaction with ammonia or tert-butylamine leads to the sulfonamides of the formula (XII) with R H or t-butyl.
  • the aniline of the formula (XIV) is obtained with iron in acetic acid medium or other common methods (for example hydrogenation with Pd-C / hydrogen) (cf. H. Berri, GT Neuhold, FS Spring, J. Chem. Soc. 1952 , 2042; M.
  • the alkyl group (R 3 ) can be introduced by methods known from the literature by monoalkylation of anilines.
  • the aniline of the formula (XIV) is acylated, for example with an acid chloride or acid anhydride, and the amide function formed is subsequently transformed with suitable reducing agents, such as, for example, boranedimethyl sulfide complex, to give the N-alkylaniline (see p.
  • the sulfonamides (II) are obtained from the compounds of the formula (XVI) by reaction with strong acids.
  • the strong acids are e.g.
  • Trifluoroacetic acid in question Trifluoroacetic acid in question.
  • the t-butyl protective group is split off for example at temperatures of -20 ° C and the respective
  • Reflux temperature of the reaction mixture preferably at 0 ° C to 40 ° C.
  • the reaction can be carried out in bulk or in an inert solvent, e.g. Dichloromethane or trichloromethane.
  • R 1 NR "R '"
  • the sulfonylureas of the formula (I) can alternatively be obtained by reacting sulfonylureas of the formula (VII) with an acylating reagent of the formula R 4 -Nuc.
  • the compounds of formula (VII) at temperatures between -10 ° C and 150 ° C - preferably at 0 ° C to 80 ° C in an inert
  • Solvents such as e.g. Dichloromethane, trichloromethane, dimethylformamide or N, N-dimethylacetic acid amide - submitted and reacted with a suitable electrophile, (cf. the description of the implementation of
  • Aryl chloroformates (VI) and heterocyclic amines of the formula (V) also lead to the compounds of the formula (I).
  • the corresponding sulfonyl carbamates of the formula (XVIII) are converted from the sulfonamides of the formula (II) and aryl chloroformate (Ar, e.g. phenyl)
  • a suitable base e.g. Triethylamine or
  • the phenylsulfonyl isocyanates of formula (IX) can e.g. analogous to the processes from EP-A-184 385 from compounds (II), e.g. with phosgene,
  • reaction of the compounds (IX) with the amino heterocycles of the formula (V) is preferably carried out in inert, aprotic solvents, such as e.g. Dioxane, acetonitrile or tetrahydrofuran at temperatures between 0 ° C and the boiling point of the solvent.
  • aprotic solvents such as e.g. Dioxane, acetonitrile or tetrahydrofuran at temperatures between 0 ° C and the boiling point of the solvent.
  • cyanates such as sodium cyanate and potassium cyanate takes place e.g. in aprotic solvents, e.g. Acetonitrile, sulfolane, N-methylpyrrolidone, dimethylformamide, pyridine, picoline or lutidine or a mixture of these
  • aprotic solvents e.g. Acetonitrile, sulfolane, N-methylpyrrolidone, dimethylformamide, pyridine, picoline or lutidine or a mixture of these
  • Components at temperatures between -10 ° C and 100 ° C, preferably at 0 ° C to 50 ° C (see. US-A-5,517,119).
  • the (thio) isocyanates of the formula (VIII) can be obtained by processes known from the literature (EP-A-232067, EP-A-166516).
  • the (thio) isocyanates (VIII) are reacted with compounds (II) at -10 ° C. to 100 ° C., preferably at 20 to 100 ° C., in an inert aprotic solvent, such as acetone or acetonitrile, in the presence of a suitable base, for example N (C 2 H 5 ) 3 or K 2 CO 3 .
  • the compounds of formula (II), (IV), (XVI) and (XVIII) are new and also a subject of the invention; they correspond to compounds of the formula (XIX), wherein U * denotes NH 2 , Cl, mono- or disubstituted amino, such as alkylamino or aryloxyamino, preferably NH 2 , Cl, t-butylamino or aryloxacarbonylamino, and R 1 , R 2 , R 3 , R 4 , n and m as in Formula (I) are defined.
  • the salts of the compounds of formula (I) are preferably in inert solvents such as e.g. Water, methanol, acetone, dichloromethane,
  • Suitable bases for the preparation of the salts according to the invention are, for example, alkali carbonates, such as potassium carbonate, alkali and
  • Alkaline earth metal hydroxides such as NaOH, KOH and Ca (OH) 2 , ammonia or a suitable amine base, such as triethylamine or ethanolamine.
  • a suitable amine base such as triethylamine or ethanolamine.
  • Salt formation is suitable for example HCl, HBr, H 2 SO 4 or HNO 3 .
  • Solvents "mean solvents which are inert under the respective reaction conditions, but not under any
  • the compounds of formula (I) according to the invention have excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants. Even difficult to fight
  • Post-emergence also occurs very rapidly after the treatment and the weed plants remain in the growth stage at the time of application or die completely after a certain time, so that one for the Crops harmful weed competition is eliminated very early and sustainably.
  • Cultivated plants of economically important crops such as Wheat, barley, rye, rice, corn, sugar beet, cotton and soy are only slightly or not at all damaged.
  • the present compounds are suitable from these
  • the substances according to the invention have excellent growth-regulating properties in crop plants. They intervene in the plant's metabolism in a regulating manner and can thus be used to influence plant constituents in a targeted manner and to facilitate harvesting, e.g. by triggering desiccation and stunted growth. Furthermore, they are also suitable for general control and
  • Inhibiting unwanted vegetative growth without killing the plants. Inhibiting vegetative growth plays a major role in many mono- and dicotyledon crops, as this can reduce or completely prevent storage.
  • the compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations.
  • the invention therefore also relates to herbicidal and plant growth-regulating compositions which comprise compounds of the formula (I).
  • the compounds of formula (I) can be formulated in different ways, depending on which biological and / or chemical-physical parameters are specified. Possible formulation options are, for example: wettable powder (WP), water-soluble powder (SP), water-soluble powder Concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions,
  • SC Suspension concentrates
  • CS capsule suspensions
  • DP dusts
  • pickling agents granules for spreading and soil application
  • granules GR
  • WG water-dispersible granules
  • SG water-soluble granules
  • Microcapsules and waxes are Microcapsules and waxes.
  • the necessary formulation aids such as inert materials, surfactants,
  • Solvents and other additives are also known and are described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry”; 2nd Ed., J. Wiley & Sons, N.Y .; C. Marsden, “Solvent Guide”; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's “Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J .; Sisley and Wood, “Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Interface-active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1976; Winnacker-kuchler, "Chemical Technology", Volume 7, C.
  • Manufacture growth regulators for example in the form of a ready-to-use formulation or as a tank mix.
  • Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain not only a diluent or an inert substance, but also ionic and / or nonionic surfactants (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines,
  • the herbicidal active ingredients are used, for example, in customary equipment such as hammer mills,
  • Blower mills and air jet mills are finely ground and mixed simultaneously or subsequently with the formulation auxiliaries.
  • Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers).
  • organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents.
  • surfactants of ionic and / or nonionic type emulsifiers
  • Alkylarylsulfonic acid calcium salts such as
  • Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as
  • Fatty acid polyglycol esters alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as, for. B. sorbitan fatty acid esters or polyoxethylene sorbitan esters such. B.
  • Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • finely divided solid substances e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • Suspension concentrates can be water or oil based. You can, for example, by wet grinding using commercially available pearl mills and optionally addition of surfactants, such as. B. above with the others
  • Emulsions e.g. B. oil-in-water emulsions (EW) can be, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants such as z. B. are already listed above for the other types of formulation.
  • Granules can either by spraying the active ingredient
  • adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g.
  • Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.
  • Water-dispersible granules are usually made according to the usual
  • the agrochemical preparations usually contain 0.1 to 99
  • the active substance concentration in wettable powders is e.g. about 10 to 90 wt .-%, the rest of 100 wt .-% consists of conventional formulation components.
  • the active substance concentration can be about 1 to 90, preferably 5 to 80,% by weight.
  • Dust-like formulations contain 1 to 30% by weight of active ingredient, preferably mostly 5 to 20% by weight of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50% by weight of active ingredient.
  • the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulating aids, fillers, etc. are used.
  • the active ingredient content of the water-dispersible granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • active ingredient formulations mentioned may contain the usual adhesive, wetting, dispersing, emulsifying, penetrating,
  • Preservatives Preservatives, antifreeze and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and agents that influence pH and viscosity.
  • Active substances can be used, as are described, for example, in Weed Research 26, 441-445 (1986) or "The Pesticide Manual", 9th edition, The British Crop Protection Council, 1990/91, Brackneli, England, and the literature cited therein.
  • Herbicides known from the literature, which can be combined with the compounds of the formula (I) are, for.
  • the following active substances are to be mentioned (note: the compounds are identified either with the "common name” according to the International Organization for Standardization (ISO) or with the chemical name, possibly together with a usual code number):
  • bromofenoxim bromoxynil; bromuron; buminafos; busoxinone; butachlor;
  • chlorimuron ethyl chloronitrofen; chlorotoluron; chloroxuron; chlorpropham;
  • clethodim clethodim
  • clodinafop and its ester derivatives e.g. clodinafop-propargyl
  • clomazone clomeprop; cloproxydim; clopyralid; cumyluron (JC 940); cyanazine; cycloate; cyclosulfamuron (AC 104); cycloxydim; cycluron; cyhalofop and its ester derivatives (e.g. butyl ester, DEH-112); cyperquat; cyprazine;
  • diclofop-methyl diethatyl; difenoxuron; difenzoquat; diflufenican; dimefuron; dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimethazone, clomazone; dimethipin; dimetrasulfuron, dinitramine; dinoseb; dinoterb;
  • fluchloralin flumetsulam; flumeturon; flumiclorac and its esters (e.g.
  • Pentyl ester S-23031); flumioxazin (S-482); flumipropyn; flupoxam (KNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil (UBIC-4243); fluridone;
  • flurochloridone fluroxypyr; flurtamone; fomesafen; fosamine; furyloxyfen;
  • glufosinate glyphosate
  • halosates halosulfuron and its esters
  • Methyl ester, NC-319); haloxyfop and its esters; haloxyfop-P ( R-haloxyfop) and its esters; hexazinone; imazamethabenz-methyl; imazapyr; imazaquin and salts such as the ammonium salt; imazethamethapyr; imazethapyr; imazosulfuron; ioxynil; isocarbamide; isopropaline; isoproturon; isouron; isoxaben; isoxapyrifop; carbutilates; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidide; metamitron; metazachlor; methabenzthiazuron; metham; methazole; methoxyphenone; methyldymron; metabenzuron, methobenzuron; metobromuron; metolachlor; me
  • dihydrogen sulfates monolinuron; monuron; MT 128, i.e. H. 6-chloro-N- (3-chloro-2-propenyl) -5-methyl-N-phenyl-3-pyridazinamine; MT 5950, i.e. H. N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide; naproanilide; napropamide; naptalam; NC 310, i.e. H.
  • orbencarb oryzalin; oxadiargyl (RP-020630); oxadiazon; oxyfluorfen; paraquat; pebulate; pendimethalin; perfluidone; phenisopham; phenmedipham; picloram; piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl;
  • procyazine prodiamine; profluralin; proglinazine-ethyl; prometon; prometryn; propachlor; propanil; propaquizafop and its esters; propazine; propham;
  • Formulations optionally diluted in the usual way e.g. for wettable powders, emulsifiable concentrates, dispersions and water-dispersible
  • Granules using water Granules using water. Dust-like preparations, soil or
  • Scatter granules and sprayable solutions are usually no longer diluted with other inert substances before use.
  • Compounds of formula (I) can fluctuate within wide limits, e.g. between 0.001 and 10.0 kg / ha or more of active substance, but it is preferably between 0.005 and 5 kg / ha.
  • the reaction mixture was concentrated in a high vacuum.
  • the backlog is in
  • a dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of a compound of the formula (I) with 6 parts by weight of alkylphenol polyglycol ether (®Triton X 207) and 3 parts by weight
  • Isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range e.g. approx. 255 to above 277 ° C) are mixed and ground in a friction ball mill to a fineness of less than 5 microns.
  • An emulsifiable concentrate is obtained from 15 parts by weight of a compound of formula (I), 75 parts by weight of cyclohexanone
  • Emulsifier e) A water-dispersible granulate is obtained by:
  • the spray tower is atomized and dried using a single-component nozzle.
  • Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants are placed in sandy loam in plastic pots and covered with soil.
  • the compounds according to the invention formulated in the form of wettable powders or emulsion concentrates are then applied as an aqueous suspension or emulsion with a water application rate of the equivalent of 600 to 800 l / ha in different dosages to the surface of the covering earth.
  • the pots are placed in the greenhouse and kept under good growth conditions for the weeds.
  • the visual assessment of the damage to the plants or the soiling occurs after the soiling
  • Compounds according to the invention have a good herbicidal pre-emergence activity against a broad spectrum of grass weeds and weeds.
  • Compounds according to the invention have a good herbicidal pre-emergence activity against a broad spectrum of grass weeds and weeds.
  • Harmful plants such as Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus and Panicum miliaceum im
  • Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds are placed in sandy loam soil in plastic pots, covered with soil and grown in the greenhouse under good growth conditions. Three weeks after sowing, the test plants are treated at the three-leaf stage.
  • Compounds according to the invention are sprayed onto the green parts of the plant in various dosages with a water application rate of the equivalent of 600 to 800 l / ha. After about 3 to 4 weeks of standing
  • the agents according to the invention also have good herbicidal activity against a broad spectrum of economically important grasses and weeds, even after emergence.
  • the compounds of Examples 1-204, 3-1, 3-13, 3-35, 3-40, 3-43, 3-47, 3-48, 3-103, 3-108, 3-168, 3-186, 3-191, 3-204, 3-209, 3-240, 3-258 and 3-294 from Tables 1 and 3 very good herbicidal activity against harmful plants such as Sinapis alba, Stellaria media, Echinochloa crus-galli , Lolium multiflorum, Chrysanthemum segetum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus Panicum miliaceum and Avena sativa in a post-emergence process with an application rate of 0.3 kg and less active ingredient per hectare. 3. Crop tolerance

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • 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)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Electrostatic Separation (AREA)

Abstract

Urées N-acyle-N-alkyleaminophénylesulfonyle à substituants soufre, leurs procédés de préparation et leur utilisation comme herbicides et régulateurs de croissance pour végétaux. Des composés de la formule (I) et leurs sels s'utilisent comme herbicides et comme régulateurs de croissance pour végétaux. Dans ladite formule, R?1, R2, R3, R4, R5¿, X, Y, Z, W, n et m ont la notation mentionnée dans la revendication 1. Leur préparation s'effectue de manière similaire aux procédés connus, en partie à l'aide d'intermédiaires de la formule (XIX) où U* = NH¿2?, Cl, amino (subst.) et R?1 à R4¿, n et m ont la notation mentionnée dans la formule (I).
PCT/EP1995/004183 1994-11-07 1995-10-25 Urees n-acyle-n-alkyleaminophenylesulfonyle a substituants soufre, leurs procedes de preparation et leur utilisation comme herbicides et regulateurs de croissance pour vegetaux WO1996014304A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP8515006A JPH10509443A (ja) 1994-11-07 1995-10-25 硫黄置換分を有するｎ−アシル−ｎ−アルキルアミノフェニルスルホニル尿素、その製造方法ならびに除草剤および植物生長調整剤としての使用
EP95937843A EP0790985A1 (fr) 1994-11-07 1995-10-25 Urees n-acyle-n-alkyleaminophenylesulfonyle a substituants soufre, leurs procedes de preparation et leur utilisation comme herbicides et regulateurs de croissance pour vegetaux
BR9509609A BR9509609A (pt) 1994-11-07 1995-10-25 N-Acil-N-Alquilaminofelilsulfoniluréias com substituintes de enxofre processos para preparação e emprego como herbicidas e reguladores do crescimento das plantas
AU38695/95A AU3869595A (en) 1994-11-07 1995-10-25 N-acyl-n-alkylamino phenyl sulphonyl ureas with sulphur substituents, process for their production and use as herbicides and plant growth regulators

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4439675.9 1994-11-07
DE19944439675 DE4439675A1 (de) 1994-11-07 1994-11-07 N-Acyl-N-alkylaminophenylsulfonylharnstoffe mit Schwefelsubstituenten, Verfahren zur Herstellung und Verwendung als Herbizide und Pflanzenwachstumsregulatoren

Publications (1)

Publication Number Publication Date
WO1996014304A1 true WO1996014304A1 (fr) 1996-05-17

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EP (1) EP0790985A1 (fr)
JP (1) JPH10509443A (fr)
AU (1) AU3869595A (fr)
BR (1) BR9509609A (fr)
CA (1) CA2204610A1 (fr)
DE (1) DE4439675A1 (fr)
WO (1) WO1996014304A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19619628A1 (de) * 1996-05-15 1997-11-20 Hoechst Schering Agrevo Gmbh (Hetero)Arylsulfonylharnstoffe mit einer Iminofunktion, ihre Darstellung und Verwendung als Herbizide und Pflanzenwachstumsregulatoren
DE19702200A1 (de) * 1997-01-23 1998-07-30 Hoechst Schering Agrevo Gmbh Phenylsulfonylharnstoffe, Verfahren zu ihrer Herstellung und ihre Verwendung als Herbizide und Pflanzenwachstumsregulatoren

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0023141A2 (fr) * 1979-07-20 1981-01-28 E.I. Du Pont De Nemours And Company Sulfonamides à activité herbicide, leur préparation et utilisation, compositions les contenant, composés intermédiaires et leur préparation
EP0116518A1 (fr) * 1983-02-04 1984-08-22 Ciba-Geigy Ag Urées N-phénylsulfonyl-N'-pyrimidinyl- et -triazinyl
DE4236902A1 (de) * 1992-10-31 1994-05-05 Hoechst Ag Neue Phenylsulfonylharnstoffe, Darstellung und Verwendung als Herbizide und Pflanzenwachstumsregulatoren

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0023141A2 (fr) * 1979-07-20 1981-01-28 E.I. Du Pont De Nemours And Company Sulfonamides à activité herbicide, leur préparation et utilisation, compositions les contenant, composés intermédiaires et leur préparation
EP0116518A1 (fr) * 1983-02-04 1984-08-22 Ciba-Geigy Ag Urées N-phénylsulfonyl-N'-pyrimidinyl- et -triazinyl
DE4236902A1 (de) * 1992-10-31 1994-05-05 Hoechst Ag Neue Phenylsulfonylharnstoffe, Darstellung und Verwendung als Herbizide und Pflanzenwachstumsregulatoren

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 55, no. 19, 18 September 1961, Columbus, Ohio, US; abstract no. 18666h *
CHEMICAL ABSTRACTS, vol. 84, no. 8, 23 February 1976, Columbus, Ohio, US; abstract no. 52076, W.F. SMITH ET AL. *
DATABASE REGISTRY CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; *

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JPH10509443A (ja) 1998-09-14
CA2204610A1 (fr) 1996-05-17
AU3869595A (en) 1996-05-31
DE4439675A1 (de) 1996-05-09
BR9509609A (pt) 1997-10-28
EP0790985A1 (fr) 1997-08-27

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