EP0862569A1 - Benzthiazoles substitues a action herbicide - Google Patents

Benzthiazoles substitues a action herbicide

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Publication number
EP0862569A1
EP0862569A1 EP96930105A EP96930105A EP0862569A1 EP 0862569 A1 EP0862569 A1 EP 0862569A1 EP 96930105 A EP96930105 A EP 96930105A EP 96930105 A EP96930105 A EP 96930105A EP 0862569 A1 EP0862569 A1 EP 0862569A1
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EP
European Patent Office
Prior art keywords
alkyl
formula
substituted
compounds
halogen
Prior art date
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EP96930105A
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German (de)
English (en)
Inventor
Elisabeth Heistracher
Gerhard Hamprecht
Olaf Menke
Peter Schäfer
Cyrill Zagar
Karl-Otto Westphalen
Ulf Misslitz
Helmut Walter
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • 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
    • A01N43/74—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 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/70—Sulfur atoms
    • C07D277/76—Sulfur atoms attached to a second hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to new substituted benzothiazoles of the general formula I
  • X 1 , X 2 independently of one another oxygen or sulfur;
  • R 1 is hydrogen, amino, -CC 6 -alkyl or C -.- C 6 haloalkyl
  • R 2 is hydrogen, halogen, C ⁇ -C 6 -alkyl, C 6 haloalkyl, C ⁇ -C 6 alkylthio, Ci-C 6 alkylsulfinyl or C ⁇ -C6 alkyl sulfonyi;
  • R 3 is hydrogen, halogen or Ci-C 6 alkyl
  • R 4 is hydrogen or halogen
  • R 5 cyano, halogen, Ci-C 6 haloalkyl, Ci-C ⁇ -alkoxy or Ci-C ⁇ -haloalkoxy;
  • Y is a chemical bond, oxygen, sulfur, -SO- or -S0 2 -;
  • R 6 is hydrogen, cyano, halogen, C 3 -C 6 cycloalkyl
  • -C-C 6 haloalkyl C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl or C ! -C 6 alkyl, the cycloalkyl, alkyl, alkenyl and alkynyl radicals mentioned by cyano, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio, (C 1 -C 6 alkoxy) carbonyl, C - L -Ce-alkylaminocarbonyl, di (C ! -C 6 -alkyl) amino-carbonyl, (Ci-C ⁇ -alkyl) carbonyloxy, C!
  • R 6 can only mean cyano when Y represents a chemical bond, oxygen or sulfur and R 6 can only be halogen if Y represents a chemical bond,
  • the invention also relates to the use of the compounds I as herbicides or for the desiccation and / or defoliation of plants, herbicidal compositions and agents for the desiccation / defoliation of plants which contain the compounds I as active substances,
  • WO 92/20675 Herbicidally active benzothiazoles with certain heterocycles in the 7-position are already known from WO 92/20675 and DE-A 42 41 658.
  • WO 92/20675 also refers to a possible desiccant / defoliant effect of the compounds described there.
  • the object of the present invention was therefore to provide new benzothiazoles with better herbicidal properties.
  • the task also extends to the provision of new desiccant / defoliant connections.
  • substituted benzothiazoles of the formula I defined at the outset were found. Furthermore, herbicidal compositions have been found which contain the compounds I and have a very good herbicidal action. In addition, processes for the preparation of these compositions and processes for controlling unwanted vegetation using the compounds I have been found.
  • the compounds I are also suitable for the desiccation and defoliation of parts of plants, for which crop plants such as cotton, potato, rapeseed, sunflower, soybean or field beans, in particular cotton, are suitable.
  • crop plants such as cotton, potato, rapeseed, sunflower, soybean or field beans, in particular cotton, are suitable.
  • the compounds of the formula I can contain one or more centers of chirality and can then be present as mixtures of enantiomers or diastereomers.
  • the object of the invention is both the pure enantiomers or diastereomers and mixtures thereof.
  • the substituted benzothiazoles I can be in the form of their agriculturally useful salts, the type of salt generally not being important. In general, the salts of such bases and those acid addition salts in which the herbicidal action is not adversely affected in comparison with the free compound I are suitable.
  • Particularly suitable basic salts are those of the alkali metals, preferably the sodium and potassium salts, those of the alkaline earth metals, preferably calcium and magnesium salts, those of the transition metals, preferably zinc and iron salts, and also ammonium salts in which the ammonium ion, if desired, is one to four C 1 -C 4 -alkyl, hydroxy-C 4 -C 4 alkyl substituents and / or a phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium and trimethyl (2-hydroxyethyl ) -ammonium salts, furthermore phosphonium salts, sulfonium salts such as preferably tri- (C 1 -C 4 alkyl) sulfonium salts, and sulfoxonium salts such as preferably tri- (C 1 -C 4 al
  • acid addition salts are primarily the hydrochlorides and bromides, sulfates, nitrates, phosphates, oxalates or the dodecylbenzenesulfonates.
  • the organic molecule parts mentioned in the definition of the substituents R 1 to R 6 are collective terms for individual lists of the individual group members.
  • All carbon chains that is to say all alkyl, haloalkyl, alkoxy, alkylthio, alkylsulfinyl, , Alkylsulfonyl, haloalkoxy, haloalkylthio, alkoxycarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkyl ⁇ carbonyloxy, alkenyl, haloalkenyl and alkynyl parts can be straight-chain or branched.
  • Multi-halogenated haloalkyl, haloalkoxy, haloalkylthio and haloalkenyl radicals can carry the same or different halogen atoms. In detail, for example:
  • Halogen for: fluorine, chlorine, bromine or iodine
  • Cyano-Ci-C ⁇ - alkyl for: for example cyanomethyl, 1-cyanoethyl,
  • 2-cyanoethyl 1-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyano-prop-1-yl, 1-cyanobut-1-yl, 2-cyanobut-l-yl, 3-cyanobutyl 1-yl, 4-cyanobut-l-yl, l-cyanobut-2-yl, 2-cyanobut-2-yl, 3-cyano-but-2-yl, 3-cyanobut-2-yl, 4-cyanobut- 2-yl, 1- (cyanomethyl) eth-1-yl, 1- (cyanomethyl) -1- (methyl) -eth-l-yl, 1- (cyanomethyl) prop-1-yl and 2-cyanohex- 6-yl;
  • Ci-C ⁇ -haloalkyl for: a -CC 6 alkyl radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, Chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2, 2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro 2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, petafluoroethyl, 2-fluoropropyl, 3-fluor
  • 2-broropropylthio 3-bromopropylthio, 2,2-difluoropropylthio, 2, 3-difluoropropylthio, 2,3-dichloropropylthio, 3, 3, 3-trifluoropropylthio, 3,3,3-trichloropropylthio, 2,2,3, 3, 3-pentafluoropropylthio, heptafluoropropylthio, 1- (fluoromethyl) -2-fluoroethylthio, 1- (chloromethyl) -2-chloroethylthio, 1- (bromomethyl) - 2-bronethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio, 5-fluoropentylthio, 5-chloropentylthio, 5-bromopentylthio, 5-iodopentylthio, undecafluoropentylthio,
  • C ⁇ -C 6 alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1, 1-dimethylethylsulfinyl, n-pentylsulfinyl, 1-methylbutylmetrinyl .ylbutylsulfinyl, 3-methylbutylsulfinyl, 1, 1-dimethylpropylsulfinyl, 1, 2-dimethylpropylsulfinyl, 2, 2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, n-hexylsulfinyl, 1-Methylpentylsulfinyl
  • Ci-C ⁇ -alkylsulfonyl for: methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1-methylethylsulfonyl, n-butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, n-pentylsulfonylsulfonylsulfonylsulfonyl, 1-methylsulfonyl, 1-methylsulfonyl, 1-methylsulfonyl , 3-Methylbutylsulfonyl, 1, 1-Dirnethyl-propylsulfonyl, 1,2-Dimethylpropylsulfonyl, 2,2-Dimethyl-propylsulfonyl, 1-Ethylpropylsulf
  • C 3 -C 6 cycloalkyl-Ci-C ⁇ -alkyl for: e.g. cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, 2- (cyclopropyl) ethyl, 2- (cyclobutyl) ethyl, 2- (cyclopentyl) ethyl, 2- (cyclohexyl ) ethyl, 3- (cyclopropyl) propyl, 3- (cyclobutyl) propyl, 3- (cyclopentyl) propyl, 3- (cyclohexyl) propyl, 4- (cyclopropyl) butyl, 4- (cyclobutyl) butyl, 4- ( Cyclopentyl) butyl, 4- (cyclohexyl) butyl, 5- (cyclopropyl) pentyl, 5- (cyclobutylpentyl, 5- (cyclopentyl) pent
  • Cyano-C 3 -C 6 alkenyl for: eg 2-cyanoallyl, 3-cyanoallyl, 4-cyanobut-2-enyl, 4-cyanobut-3-enyl and 5-cyanopent-4-enyl;
  • C 3 -C 6 ⁇ haloalkenyl C 3 -C 6 ⁇ alkenyl as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example 2-chloroallyl, 3-chloroallyl, 2, 3 -Dichlorallyl, 3, 3-dichlorallyl, 2, 3, 3-trichloro-allyl, 2, 3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl, 2, 3-dibromallyl, 3, 3-dibromallyl, 2 , 3, 3-tribromoallyl and 2,3-dibromobut-2-enyl;
  • Cyano-C 3 -C 6 -alkynyl for: e.g. 3-cyanopropargyl, 4-cyanobut-2-in-l-yl, 5-cyanopent-3-in-l-yl and 6-cyanohex-4 -in-l- yl.
  • the variables preferably have the following meanings, in each case individually or in combination:
  • R 1 is amino, C ⁇ -C6 alkyl or C ⁇ -C 6 -haloalkyl, in particular amino or C ⁇ -C6 alkyl, more preferably methyl;
  • R 2 is halogen, C ⁇ -C6 alkyl, Ci-C 6 haloalkyl or C ⁇ -C 6 -Alkyl ⁇ sulfonyl, in particular C ⁇ -C 6 -haloalkyl, particularly preferably trifluoromethyl, chlorodifluoromethyl or pentafluoroethyl, - is very particularly preferably trifluoromethyl;
  • R 3 is hydrogen or halogen, especially hydrogen
  • R 4 is hydrogen, fluorine or chlorine
  • R 5 cyano or halogen, in particular cyano, chlorine or bromine, particularly preferably chlorine;
  • Y is a chemical bond, sulfur, -SO- or -S0 2 -, in particular a chemical bond or sulfur;
  • R 6 is hydrogen, halogen, C 3 -C 6 -cycloalkyl, -C-C 6 -haiogenalkyl, C 3 -C6-alkenyl or -C-C 6 -alkyl, the cyclo-alkyl, alkyl and alkenyl radicals mentioned by Cyano, -CC 6 alkoxy, (Ci-C ⁇ -alkoxy) carbonyl, (CI-C ⁇ -alkyl) carbonyloxy or Ci-C ⁇ -haloalkoxy may be substituted, with the proviso that R 6 can only be halogen if Y stands for a chemical bond.
  • R 6 The compounds II.1 to 11.186, which differ from the compounds ia.l to la.186 only in that R 5 is cyano:
  • R 6 The compounds lo.l3 to I0.I86, which differ from the compounds Ia.13 to la.186 only in that R 1 is amino, R 5 is cyano and Y is oxygen:
  • the substituted benzothiazoles of the formula I can be obtained in various ways, for example by one of the following processes:
  • Li stands for a common leaving group such as halogen, preferably chlorine, bromine or iodine, (halogen) alkylsulfonyloxy, preferably methylsulfonyloxy or trifluoromethylsulfonyloxy, arylsulfonyloxy, preferably toluenesulfonyloxy, and alkoxysulfonyloxy, preferably methoxysulfonyloxy or ethoxysulfonyloxy.
  • halogen preferably chlorine, bromine or iodine
  • alkylsulfonyloxy preferably methylsulfonyloxy or trifluoromethylsulfonyloxy
  • arylsulfonyloxy preferably toluenesulfonyloxy
  • alkoxysulfonyloxy preferably methoxysulfonyloxy or ethoxysulfonyloxy.
  • an inert organic solvent for example in a protic solvent such as the lower alcohols, preferably in methanol or ethanol, if desired in a mixture with water, or in an aprotic solvent, for example in an aliphatic or cyclic ether such as methyl -tert.-butyl ether, 1, 2-dirnethoxyethane, tetrahydrofuran and dioxane, in one aliphatic ketone such as acetone, diethyl ketone and ethyl methyl ketone, in an amide such as dimethylformamide and N-methyl pyrrolidone, in a sulfoxide such as dimethyl sulfoxide, in a urea such as tetramethyl urea and 1,3-dimethyltetrahydro-2 (IH) pyrimidinone, in a carboxylic acid ester such as ethyl acetate, or in a halogenated aliphatic solvent, for example in
  • a base both inorganic bases, e.g. Carbonates such as sodium carbonate and potassium carbonate, hydrogen carbonates such as sodium and potassium hydrogen carbonate, or alkali metal hydrides such as sodium hydride and potassium hydride, as well as organic bases, e.g. Amines such as triethylamine, pyridine and N, N-diethylaniline, or alkali metal alcoholates such as sodium methoxide, sodium ethoxide and potassium tert. -butanolate are suitable.
  • inorganic bases e.g. Carbonates such as sodium carbonate and potassium carbonate, hydrogen carbonates such as sodium and potassium hydrogen carbonate, or alkali metal hydrides such as sodium hydride and potassium hydride
  • organic bases e.g. Amines such as triethylamine, pyridine and N, N-diethylaniline, or alkali metal alcoholates such as sodium methoxide, sodium ethoxide and potassium tert. -butanolate
  • reaction temperature is from 0 ° C. to the boiling point of the reaction mixture, in particular from 0 to 60 ° C.
  • the salts of those compounds I in which R x is hydrogen can also be obtained in a manner known per se from the process products of methods D) to I) .
  • the aqueous solution of an inorganic or organic base is substituted with the substituted benzothiazole I, in which R ⁇ is hydrogen. Salt formation then usually takes place at a sufficient rate at 20 to 25 ° C.
  • the corresponding salt of benzothiazole I can then be isolated, for example by precipitation with a suitable inert solvent or by evaporation of the solvent.
  • Salts of the substituted benzothiazoles I can usually be prepared by salting the corresponding alkali metal salt in aqueous solution, as can ammonium, phosphonium, sulfonium and sulfoxonium salts using ammonia, phosphonium, sulfonium or sulfoxonium hydroxides. In this way, e.g. Produce benzthiazole metal salts that are insoluble in water.
  • HOSA hydroxylamine-0-sulfonic acid
  • the amination can be carried out in a manner known per se (see, for example, T. Sheradsky, Tetrahedron Lett. 1968, 1909; MP We ⁇ tland et al., J. Med. Chem. 21 (1984) 1103 and in particular EP-A 240 194, EP-A 476 697 and EP-A 517 181, where the amination of uracil is taught).
  • reaction is carried out in a polar solvent, e.g. in dimethylformamide, N-methyl pyrrolidone, dimethyl sulfoxide or in ethyl acetate, which has so far been found to be particularly suitable.
  • a polar solvent e.g. in dimethylformamide, N-methyl pyrrolidone, dimethyl sulfoxide or in ethyl acetate, which has so far been found to be particularly suitable.
  • Suitable bases are, for example, alkali metal carbonates such as potassium carbonate, alkali metal alcoholates such as sodium methylate and potassium tert. -butanolate or alkali metal hydrides such as sodium hydride.
  • the amount of base and aminating agent is preferably in each case 0.5 to 2 times the molar amount, based on the amount of starting compound.
  • the sulfurization is usually carried out in an inert solvent or diluent, for example in an aromatic hydrocarbon such as toluene and the xylenes, in an ether such as diethyl ether, 1, 2-dimethoxyethane and
  • Tetrahydrofuran or in an organic amine such as pyridine.
  • Phosphorus (V) sulfide and 2,4-bis (4-methoxyphenyl) -1,3,2,4-dithiaciphosphetane-2,4-dithione are particularly suitable as the sulfurization reagent.
  • reaction temperature is normally 20 to 200 ° C, preferably 40 ° C to the boiling point of the reaction mixture.
  • the reaction is expediently carried out in an inert solvent, for example in an ether such as diethyl ether, methyl tert-butyl ether, dimethoxyethane, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane, a ketone such as acetone, diethyl ketone, ethyl methyl ketone and cyclohexanone, a dipolar aprotic solvent such as acetonitrile, dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide, a protic solvent such as methanol and ethanol, an aromatic, optionally halogenated hydrocarbon such as benzene, chlorobenzene and 1,2-dichlorobenzene, a heteroaromatic solvent such as pyridine and quinoline or in one Mixture of such solvents. Tetrahydrofuran, acetone, diethyl ketone and dimethylformamide are preferred.
  • the bases here can be, for example, the hydroxides, hydrides, alkoxides, carbonates or hydrogen carbonates of alkali metal and alkaline earth metal cations, tertiary aliphatic amines such as triethylamine, N-methylmorpholine and N-ethyl-N, N-diisopropylamine, bi- and tricyclic amines such as diazabicycloundecane (DBU) and diazabicyclooctane (DABCO), or aromatic nitrogen bases such as pyridine, 4-dimethylaminopyridine and quinoline. Combinations of different bases are also possible.
  • Preferred bases are sodium hydride, sodium hydroxide, sodium carbonate, potassium carbonate, sodium methylate, sodium ethylate and potassium tert. -butylate.
  • the molar ratio of alcohol or mercaptan III to base is generally 1: 1 to 1: 3.
  • the concentration of the starting materials in the solvent is normally 0.1 to 5.0 mol / 1.
  • the reaction can be carried out at from 0 ° C. to the reflux temperature of the particular solvent (mixture).
  • Suitable oxidizing agents are e.g. Hydrogen peroxide, organic peroxides such as acetic acid peroxide, trifluoroacetic acid peroxide, m-chloroperbenzoic acid, tert-butyl hydroperoxide and tert. -Butyl hypochlorite, as well as inorganic compounds such as sodium metaiodate, chromic acid and nitric acid.
  • an organic acid such as acetic acid and trichloroacetic acid
  • a chlorinated hydrocarbon such as methylene chloride, chloroform and 1,2-dichloroethane
  • an aromatic see hydrocarbon like benzene, chlorobenzene and toluene or in a protic solvent like methanol and ethanol.
  • a protic solvent like methanol and ethanol.
  • the reaction temperature is generally from (-30) ° C. to the boiling point of the respective reaction mixture, with the lower temperature range normally being preferred.
  • the starting compound and the oxidizing agent are expediently used in an approximately stoichiometric ratio, but one or the other component can also be used in excess.
  • Suitable oxidizing agents are hydrogen peroxide, organic peroxides such as acetic acid peroxide, trifluoroacetic acid peroxide and m-chloroperbenzoic acid, and also inorganic oxidizing agents such as potassium permanganate.
  • a catalyst e.g. Tungsten
  • Tungsten can have a beneficial effect on the course of the reaction.
  • the reaction is carried out in an inert solvent, depending on the oxidizing agent, for example organic acids such as acetic acid and propionic acid, chlorinated hydrocarbons such as methylene chloride, chloroform and 1,2-dichloroethane, aromatic hydrocarbons or halogenated hydrocarbons such as benzene, chlorobenzene and toluene, or Water are usable. Mixtures of the solvents mentioned are also suitable. Usually one works at (-30) ° C to the boiling point of the respective reaction mixture, preferably at 10 ° C to the boiling point.
  • organic acids such as acetic acid and propionic acid
  • chlorinated hydrocarbons such as methylene chloride, chloroform and 1,2-dichloroethane
  • aromatic hydrocarbons or halogenated hydrocarbons such as benzene, chlorobenzene and toluene
  • Water Water are usable. Mixtures of the solvents mentioned are also suitable. Usually one works at (-30) ° C to the boiling
  • L 2 means low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
  • cyclization is carried out in an inert organic solvent or diluent which is aprotic, for example in an aliphatic or cyclic ether such as 1,2-dimethoxyethane, tetrahydrofuran and dioxane, in an aromatic compound such as benzene and toluene or in a polar solvent such as Dirr .ethylformamide and dimethyl sulfoxide.
  • polar solvent such as Dirr .ethylformamide and dimethyl sulfoxide.
  • Water can also be suitable as a diluent.
  • Suitable bases are preferably alkali metal alcoholates, in particular the sodium alcoholates, alkali metal hydroxides, in particular sodium hydroxide and potassium hydroxide, alkali metal carbonates, in particular sodium carbonate and potassium carbonate, and metal hydrides, in particular sodium hydride.
  • sodium hydride it has proven advantageous to work in an aliphatic or cyclic ether, in dimethylformamide or in dimethyl sulfoxide.
  • reaction temperature is from (-78) ° C to the boiling point of the respective reaction mixture, in particular from (-60) to 60 ° C.
  • R 1 in formula IV or V is hydrogen
  • the product of the process is obtained as a metal salt, the metal corresponding to the cation of the base used.
  • VI -YR 6 halogen, CN, -SCN, -OCN)
  • the 2-aminobenzothiazole VI is first converted into a diazonium salt, advantageously in a manner known per se by reacting the 2-aminobenzothiazole VI in an aqueous acid solution, for example in aqueous hydrochloric acid, hydrobromic acid or sulfuric acid with a nitrite such as sodium nitrite and potassium nitrite.
  • a nitrite such as sodium nitrite and potassium nitrite.
  • the diazonium salt thus obtained can then without further purification in the presence of a transition metal catalyst, in particular a copper (I) salt such as copper (I) chloride, copper (I) bromide, copper (I) cyanide, copper (I) rhodanide and copper (I) cyanate, with a corresponding acid HYR 6 such as hydrochloric acid and hydrobromic acid, or with a corresponding metal salt of HYR 6 such as lithium, sodium and potassium chloride, lithium, sodium and potassium bromide, lithium, sodium and potassium cyanide and lithium, sodium and potassium rhodanide.
  • a transition metal catalyst in particular a copper (I) salt such as copper (I) chloride, copper (I) bromide, copper (I) cyanide, copper (I) rhodanide and copper (I) cyanate, with a corresponding acid HYR 6 such as hydrochloric acid and hydrobromic acid, or with a corresponding metal salt of HYR 6 such as lithium, sodium
  • a further possibility for the preparation of the benzothiazole diazonium salt of VI consists of VI in a water-free system - for example in glacial acetic acid containing hydrogen chloride, in dioxane, absolute ethanol, tetrahydrofuran, acetonitrile or in acetone - with a nitric acid ester such as tert . Butyl nitrite and isopropyl nitrite to implement. In this case, the diazotization can take place in the presence of the transition metal catalyst and the corresponding metal salt of -YR 6 as described above.
  • the reaction temperature is usually (-30) to 80 ° C.
  • the components of the diazotization reaction are usually used in approximately stoichiometric amounts, but an excess of one of the components, e.g. with a view to implementing one of the other components as completely as possible.
  • the transition metal catalyst can be used in a deficit, approximately equimolar or in excess, the acids and the metal salts either in approximately equimolar amounts or preferably in a large excess.
  • the 2-aminobenzothiazole VI is in an anhydrous system - for example in an ether such as dioxane and tetrahydrofuran, a nitrile such as acetonitrile or a halogenated hydrocarbon such as methylene chloride and 1,2-dichloroethane - with a nitrous acid ester such as tert-butyl nitrite and Isopropyl nitrite converted into the corresponding benzothiazole diazonium salt.
  • the latter is then reacted with the corresponding disulfide R 6 -SS-R 6 .
  • the diazotization itself can also be carried out in the presence of the disulfide.
  • the reaction is usually carried out at temperatures from (-30) to 80 ° C.
  • reaction components are expediently used in approximately stoichiometric amounts unless an excess of one or more of the components, e.g. with regard to the most complete possible implementation of VI.
  • Substituted benzothiazoles of the formula I with one or more chiral centers are usually obtained as mixtures of enantiomers or diastereomers which, if desired, can be obtained using the methods customary for this, e.g. by means of crystallization or chromatography on an optically active adsorbate into which largely pure isomers can be separated. Pure optically active isomers can also be produced, for example, from corresponding optically active starting materials.
  • L 2 stands for low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
  • the process is preferably carried out essentially free of water in an inert solvent or diluent, particularly preferably in the presence of an acidic or basic catalyst.
  • Suitable solvents or diluents are, in particular, organic solvents which are azeotropically miscible with water, for example aromatics such as benzene, toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, aliphatic and cyclic ethers such as 1 , 2-Dirnethoxyethan, tetrahydrofuran and dioxane, or cyclohexane, but also alcohols such as methanol and ethanol, into consideration.
  • aromatics such as benzene, toluene and o-, m-, p-xylene
  • halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene
  • aliphatic and cyclic ethers such as 1 , 2-Dirnet
  • Strong mineral acids such as sulfuric acid and hydrochloric acid, acids containing phosphorus such as orthophosphoric acid and polyphosphoric acid, organic acids such as p-toluenesulfonic acid and acidic cation exchangers such as "Amberlyst 15" (Fluka company) are preferably suitable as acidic catalysts.
  • Suitable basic catalysts are, for example, alkali metal hydrides such as sodium hydride and particularly preferably alkali metal alcoholates such as sodium methoxide and ethanolate.
  • VIII and the ⁇ -ketocarboxylic acid ester VII are used in approximately stoichiometric amounts or one works with a slight excess of one or the other component, up to about 10 mol%.
  • an amount of catalyst of 0.5 to 2 mol%, based on the amount of one of the starting compounds, is sufficient.
  • reaction is carried out at a temperature of 60 to 120 ° C., for the rapid removal of water formed, preferably at the boiling point of the reaction mixture.
  • L 2 and L 3 each represent low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
  • the reaction is preferably carried out in an inert, water-miscible organic solvent, for example an aliphatic see the or cyclic ether such as 1,2-dimethoxyethane, tetra ⁇ hydrofuran and dioxane, or a lower alcohol, into ⁇ particular ethanol, performed with Reaction temperature
  • the temperature is usually from 50 to 100 ° C., preferably at the boiling point of the reaction mixture.
  • reaction can also be carried out in an aromatic diluent such as benzene, toluene and o-, m-, p-xylene, in which case the addition of either an acidic catalyst such as hydrochloric acid and p-toluenesulfonic acid or one Ba ⁇ e, e.g. an alkali metal alcoholate such as sodium methoxide and sodium ethanolate is recommended.
  • an acidic catalyst such as hydrochloric acid and p-toluenesulfonic acid or one Ba ⁇ e
  • an alkali metal alcoholate such as sodium methoxide and sodium ethanolate is recommended.
  • the reaction temperature is normally 50 to 100 ° C., but preferably 60 to 80 ° C.
  • L 2 represents low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
  • an essentially anhydrous aprotic organic solvent or diluent for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, Toluene and o-, m-, p-xylene, a halogenated, aliphatic hydrocarbon substance such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of the solvents mentioned.
  • an essentially anhydrous aprotic organic solvent or diluent for example an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxye
  • work can also be carried out in the presence of a metal hydride base such as sodium and potassium hydride or an organic tertiary base such as triethylamine and pyridine. the, wherein the organic base can simultaneously serve as a solvent.
  • a metal hydride base such as sodium and potassium hydride
  • an organic tertiary base such as triethylamine and pyridine.
  • the starting materials are expediently used in stoichiometric amounts or one works with a slight excess of one or the other component, up to about 10 mol%. If one works without solvent in the presence of an organic base, this is present in a larger excess.
  • the reaction temperature is preferably (-80) to 50 ° C, in particular (-60) to 30 ° C.
  • the enamine ester IV obtained is converted directly (i.e. "in situ") into the corresponding product of value I using process G>.
  • L 2 and L 4 independently of one another represent low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
  • This reaction is advantageously carried out in an aprotic, polar solvent or diluent such as dimethylformamide, 2-butanone, dimethyl sulfoxide and acetonitrile, advantageously in the presence of a base, for example an alkali metal or alkaline earth metal alcoholate, in particular a sodium alcoholate such as sodium methoxide, an alkali metal or alkaline earth metal carbonates, in particular sodium carbonate, or an alkali metal hydride such as lithium and sodium hydride.
  • a base for example an alkali metal or alkaline earth metal alcoholate, in particular a sodium alcoholate such as sodium methoxide, an alkali metal or alkaline earth metal carbonates, in particular sodium carbonate, or an alkali metal hydride such as lithium and sodium hydride.
  • the reaction temperature is generally 80 to 180 ° C, preferably at the boiling point of the reaction mixture.
  • a sodium alcoholate is used as the base and the alcohol formed in the course of the reaction is distilled off continuously.
  • L 2 stands for low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
  • This reaction is conveniently carried out in an essentially anhydrous, aprotic, organic solvent or diluent, for example in the presence of an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, an aliphatic or aromatic hydrocarbon such as n-hexane, benzene, toluene and o-, m-, p-xylene, a halogenated, aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane and chlorobenzene, an aprotic, polar solvent such as dimethylformamide, hexamethylphosphoric triamide and dimethyl sulfoxide, or a mixture of the solvents mentioned.
  • an aliphatic or cyclic ether such as diethyl ether, 1,2-dimethoxyethane, tetra
  • a metal hydride base such as sodium and potassium hydride
  • an alkali metal or alkaline earth metal alcoholate such as sodium methoxide, ethanolate and Potassium tert. butanolate
  • an organic nitrogen base such as triethylamine and pyridine, where the organic base can simultaneously serve as a solvent.
  • the starting materials are expediently set at approximately stoichiometric
  • Amounts of one or one of the components are used in excess, up to about 20 mol%. If one works without solvent in the presence of an organic base, this is advantageously present in an even larger excess.
  • the reaction temperature is generally from (-80) to 150 ° C., preferably from (-30) ° C. to the boiling point of the respective reaction mixture.
  • the enamine carboxylates of the formula V are also new; They too can be prepared in a manner known per se, for example by reacting an amide XV with a urethane XVI in accordance with process P>:
  • L 2 stands for low molecular weight alkyl, preferably C 1 -C 4 alkyl, or phenyl.
  • the reaction is advantageously carried out in a largely water-free solvent / diluent at atmospheric pressure, particularly preferably in the presence of an acid catalyst.
  • Suitable solvents / diluents are, in particular, organic liquids which are azeotropically miscible with water, for example aromatics such as benzene, toluene and o-, m-, p-xylene or halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene.
  • Suitable catalysts are in particular strong mineral acids such as sulfuric acid, organic acids such as p-toluenesulfonic acid, phosphorus-containing acids such as orthophosphoric acid and polyphosphoric acid or acidic cation exchangers such as "Amberlyst 15" (Fluka).
  • reaction temperature of about 70 to 150 ° C is sufficient; however, to rapidly remove the reaction water formed, the procedure is expediently carried out at the boiling temperature of the respective reaction mixture.
  • XV and XVI are usually used in approximately stoichiometric amounts; vorzug ⁇ wei ⁇ e XVI is used in a slight excess up to about 20 mol%.
  • the amide XV can be prepared as follows:
  • the reaction is preferably carried out in an anhydrous, inert aprotic solvent, for example in a halogenated hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene, an aromatic hydrocarbon such as benzene, toluene and o-, m-, p-xylene, or an aliphatic or cyclic ethers such as
  • the reaction temperature is generally about 70 to 140 ° C, in particular 100 to 120 ° C.
  • XVII and XIV are usually used in approximately ⁇ toichiometric amounts, or one of the components is used in excess, up to about 10 mol%. 41
  • the "aminolysis" of VII with XIV can be carried out without a solvent (see, for example, J. Chem. Soc. Dyes Col. AI, 81 (1926); Ber. £ !, 970 (1931); Org. Synth. Coli. Vol. IV , 80 (1963), J. Am. Chem. Soc. 7_0, 2402, (1948)) or in an inert water-free solvent / diluent, in particular in an aprotic solvent, for example an aromatic such as toluene and the xylols or a halogenated aromatics such as chlorobenzene.
  • aprotic solvent for example an aromatic such as toluene and the xylols or a halogenated aromatics such as chlorobenzene.
  • the reaction temperature is preferably about 130 to 160 ° C.
  • the starting compounds are expediently reacted in approximately stoichiometric amounts, or one works with a slight excess of one or the other component up to approximately 10 mol%. If one works in the presence of a basic catalyst, a catalyst amount of 0.5 to 2 mol%, based on the amount of one of the starting materials, is normally sufficient.
  • the starting compounds specified for the individual processes are either known or can be obtained in a manner known per se or in analogy to one of the processes described.
  • the isocyanates XI and the aniline derivatives XIV are new when Y is -SO- or -SO; -.
  • Preferred are those compounds XI and XIV in which R 4 , R 5 and / or R 6 have the following meaning: R 4 is hydrogen, fluorine, chlorine or bromine;
  • R 5 cyano or halogen, especially cyano, fluorine, chlorine or bromine;
  • R 6 C ⁇ -C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or C ⁇ -C 6 - alkyl which is unsubstituted or by cyano, C ⁇ -C 6 alkoxy, ( Ci-C ⁇ - alkoxy) carbonyl, (C ⁇ -C6 alkyl) carbonyloxy or C ⁇ -C 6 haloalkoxy may be substituted.
  • isocyanates XIa to Xlh and the aniline derivatives XlVb to XlVh are very particularly preferred, in particular
  • the isocyanates XI can be obtained, for example, from the aniline derivatives XIV according to process S-:
  • the process can be carried out in an inert, essentially water-free solvent or diluent or without solvent, the amines XIV preferably being reacted with phosgene, a "phosgene equivalent” such as diphosgene, triphosgene and carbonyldiimidazole or with chloroformic acid trichloromethyl ester.
  • phosgene a "phosgene equivalent” such as diphosgene, triphosgene and carbonyldiimidazole or with chloroformic acid trichloromethyl ester.
  • Particularly suitable solvents or diluents are aprotic, organic solvents, for example aromatics such as toluene and o-, m-, p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene, aliphatic or cyclic ethers such as 1 , 2-Dirnethoxyethan, tetrahydrofuran and dioxane, or esters such as ethyl acetate, as well as mixtures of these solvents.
  • aromatics such as toluene and o-, m-, p-xylene
  • halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and chlorobenzene
  • aliphatic or cyclic ethers such as 1 , 2-Dirnethoxyethan, tetrahydrofuran and dioxane
  • the starting materials are expediently used in approximately stoichiometric amounts, or one of the components in excess, up to about 200 mol%.
  • the addition of a base such as triethylamine can be advantageous, for example in 0.5 to 2 times the molar amount, based on the amount of XIV.
  • the reaction temperature is generally from (-20) ° C to the reflux temperature of the solvent or reaction mixture.
  • the aniline derivatives XIV on their part are known per se (cf. for example Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag, vol. Xl / 1, 4th edition 1957, p. 431 ff.) By reducing the corresponding nitroderivate XVIII available:
  • Particularly suitable reducing agents are elemental metals such as iron, tin and zinc, hydrogen in the presence of suitable catalysts such as palladium or platinum on carbon or Raney nickel, or complex hydrides such as LiAlH 4 and NaBH 4 , if appropriate in the presence of catalysts.
  • suitable catalysts such as palladium or platinum on carbon or Raney nickel
  • complex hydrides such as LiAlH 4 and NaBH 4 , if appropriate in the presence of catalysts.
  • suitable solvents are usually carboxylic acids such as acetic acid and propionic acid, alcohols such as methanol and ethanol, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane, aromatics such as benzene and toluene, and mixtures of such solvents.
  • carboxylic acids such as acetic acid and propionic acid
  • alcohols such as methanol and ethanol
  • ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane
  • aromatics such as benzene and toluene, and mixtures of such solvents.
  • the reactions can be carried out at temperatures from (-100) ° C. to the boiling point of the respective reaction mixture.
  • the starting compounds are usually used in approximately stoichiometric amounts; in individual cases, however, an excess of one or the other component, up to about 10 mol%, can also be advantageous.
  • Compounds XI and XIV can also have one or more
  • Chirality centers contain and are then usually obtained as mixtures of enantiomers or diastereomers.
  • the mixtures can, if desired, be separated into the largely pure isomers by the methods customary for this, for example by means of crystallization or chromatography on an optically active adsorbate.
  • Pure optically active isomers can be, for example also produce from appropriate optically active starting materials.
  • reaction mixtures are generally worked up by methods known per se, for example by diluting the reaction mixture with water and then isolating the product of value by means of filtration, crystallization or solvent extraction, or by removing the solvent, and distributing the residue in a mixture Water and a suitable organic solvent and working up the organic phase on the product.
  • substituted benzothiazoles I can be prepared by one of the synthesis methods mentioned above. For economic or procedural reasons, however, it may be more expedient to produce some compounds I from similar substituted benzothiazoles I, which differ, however, particularly in the meaning of the radical R 6 .
  • 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 them 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 harmful grasses without significantly damaging the crop plants. This effect occurs especially at low application rates.
  • the compounds I or the herbicidal compositions comprising them can also be used in a further number of crop plants for eliminating unwanted plants.
  • the following crops are considered, for example:
  • the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.
  • substituted benzothiazoles I are also suitable for the desiccation and / or defoliation of plants.
  • desiccants are particularly suitable for drying out the above-ground parts of crops such as potatoes, rapeseed, sunflower and soybeans. This enables a completely mechanical harvesting of these important crop plants.
  • the compounds I or the herbicidal compositions comprising them can be sprayed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, also 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 and diesel oil, also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives , alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, for example amines such as N-methylpyrrolidone and water.
  • mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives , alkylated benzene
  • 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 an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • concentrates consisting of active substance, wetting agent, adhesive agent, dispersant or emulsifier and possibly solvent or oil can also be prepared which are suitable for dilution with water.
  • the surfactants are 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 as well as of fatty alcohol glycol ethers, condensation products with sulfonated derivatives and their derivatives Formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethyleneoetylphenolether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl
  • Powders, materials for spreading and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules e.g. 3. Coated, impregnated and homogeneous granules can be produced 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 cereal 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 at least one active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • 1.7 are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene- ⁇ -sulfonic acid, 17 parts by weight of sodium ⁇ alze ⁇ of a lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel and ground in a hammer mill.
  • a spray liquor is obtained which contains 0.1% by weight of the active ingredient.
  • the active ingredients I or the herbicidal compositions can be applied pre- or post-emergence. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit as far as possible, while the active ingredients are applied to the leaves of unwanted plants growing underneath or the uncovered floor area (post-directed, lay-by).
  • the application rates of active ingredient I are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance ( as ) , depending on the control target, the season, the target plants and the growth stage.
  • the substituted benzothiazoles I can be mixed with numerous representatives of other herbicidal or growth-regulating active compound groups and applied together.
  • 4-chloro-6-fluoro-7-isocyanato-2- (methylthio) benzothiazole was prepared by adding a solution of 7 g (28 mmol) of 7-amino-4-chloro-6-fluoro-2- ( methylthio) benzothiazole and 55 g (0.28 mol) of diphosgene in 200 ml of toluene were heated to reflux for 7 hours, then treated with 20 g of diphosgene (0.1 mol), heated to reflux for a further 8 hours and finally concentrated.
  • Plastic flower pots with loamy sand with about 3.0% humus served as a culture vessel.
  • the seeds of the test plants were sown according to species.
  • the 20 or emulsified active ingredients suspended in water were applied directly after sowing by means of finely distributing nozzles.
  • the vessels were sprinkled lightly to promote germination and growth, and then covered with transparent plastic hoods until the plants had grown. This cover causes the test plants to germinate evenly, provided that this has not been impaired by the active ingredients.
  • the application rate for the pre-emergence treatment was 0.0156 or 0.0078 kg / ha a.S. (active substance).
  • test plants 30, depending on the growth habit were 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 were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers some 35 days before the treatment.
  • the application rate for post-emergence treatment was 0.0156, 0.0078 or 0.0039 kg / ha a.S. (active substance).
  • the plants were kept in a species-specific manner at temperatures of 10 to 40 25 ° C and 20 to 35 ° C.
  • the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to each treatment was evaluated.
  • the plants used in the greenhouse experiments are composed of the following types:
  • Compound No. 1.7 was also in the post-emergence process at a rate of 0.0156 or 0.0078 kg / ha a.S. very effective against Amaranthus retroflexus, Galium aparine, Ipomoea subspecies and Soianum nigrum.
  • Compound No. 1.5 showed a better herbicidal activity against Amaranthus retroflexus, Galium aparine, at a rate of 0.0078 or 0.0039 kg / ha aS in the post-emergence process.
  • the young cotton plants were treated to runoff with aqueous preparations of the active ingredients (with the addition of 0.15% by weight of the fatty alcohol alkoxylate Plurafac® LF 700 1 -, based on the spray mixture).
  • the amount of water applied was the equivalent of 1000 l / ha. After 13 days, the number of leaves dropped and the degree of defoliation in% were determined.

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Abstract

L'invention concerne des benzthiazoles substitués de la formule (I) et leurs sels, dans laquelle X1, X2 = O ou S; R1 = H, NH¿2?, alkyle C1-C6 ou halogénure d'alkyle C1-C6; R?2¿ = H, halogène, alkyle C¿1?-C6, halogénure d'alkyle C1-C6, alkylthio C1-C6, alkylsulfinyle C1-C6 ou alkylsulfonyle C1-C6; R?3¿ = H, halogène ou alkyle C¿1?-C6; R?4¿ = H ou halogène; R5 = CN, halogène, alkyle C¿1?-C6, halogénure d'alkyle C1-C6, alcoxy C1-C6 ou halogénure d'alcoxy C1-C6; Y = liaison chimique, -O-, -S-, -SO- ou -SO2-; R?6¿ = hydrogène, CN, halogène, cycloalkyle C¿3?-C6, halogénure d'alkyle C1-C6, alkényle C3-C6, halogénure d'alkényle C3-C6, alkinyle C3-C6 ou alkyle C1-C6, les restes cycloalkyle, alkyle, alkényle et alkinyle mentionnés pouvant être substitués par CN, alcoxy C1-C6, alkylthio C1-C6, alcoxycarbonyle C1-C6, alkylaminocarbonyle C1-C6, di(alkyle C1-C6)aminocarbonyle, alkylcarbonyloxy C1-C6, halogénure d'alcoxy C1-C6, halogénure d'alkylthio C1-C6 ou cycloalkyle C3-C6, sous réserve que R?6¿ ne désigne que cyano, lorsque Y désigne une liaison chimique, oxygène ou soufre et R6 ne puisse désigner qu'halogène, lorsque Y désigne une liaison chimique. Ces agents s'utilisent comme herbicides, dans la dessiccation/l'abscission de végétaux.
EP96930105A 1995-08-31 1996-08-26 Benzthiazoles substitues a action herbicide Withdrawn EP0862569A1 (fr)

Applications Claiming Priority (3)

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DE19532048A DE19532048A1 (de) 1995-08-31 1995-08-31 Substituierte Benzthiazole als Pflanzenschutzmittel
DE19532048 1995-08-31
PCT/EP1996/003760 WO1997008171A1 (fr) 1995-08-31 1996-08-26 Benzthiazoles substitues a action herbicide

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UA53679C2 (uk) 1996-12-16 2003-02-17 Басф Акцієнгезелльшафт Заміщені піразол-3-ілбензазоли, спосіб їх одержання (варіанти), гербіцидний засіб та спосіб його одержання, засіб для десикації і/або дефоліації рослин та спосіб його одержання, спосіб боротьби з небажаним ростом рослин та спосіб десикації і/або дефоліації рослин
US6391414B1 (en) 1997-03-07 2002-05-21 Pharmacia Ab Structure and method for joining parts
HUP0004151A3 (en) 1997-10-27 2001-12-28 Isk Americas Inc Concord Herbicidal substituted benzene derivatives, intermediates, preparation and use thereof
DE19755926A1 (de) * 1997-12-17 1999-06-24 Basf Ag Herbizide 3-(Benzazol-4-yl)pyrimidindion-Derivate
EP1111993A4 (fr) 1998-09-09 2002-12-04 Ishihara Sangyo Kaisha Derives benzeniques condenses utilises comme herbicides
EP1131319B1 (fr) * 1998-11-16 2003-09-03 Basf Aktiengesellschaft 3- benz(ox/thi)azol-7-yl]-1h-pyrimidin-2,4-diones
JP4619543B2 (ja) * 1999-02-16 2011-01-26 ワイス・ホールディングズ・コーポレイション カルバメート化合物からの６−（ペルフルオロアルキル）ウラシル化合物の製造方法
JP2003507377A (ja) * 1999-08-12 2003-02-25 ビーエーエスエフ アクチェンゲゼルシャフト 置換ベンゾオキサゾール
EP1209154A1 (fr) * 2000-11-17 2002-05-29 Aventis CropScience GmbH Procédé de préparation d'alcènes monofluorés
CN100396681C (zh) * 2006-06-13 2008-06-25 华中师范大学 一类2-取代苯并噻唑-1,2,4-三唑啉酮衍生物的合成及除草活性

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US5888940A (en) 1999-03-30
AU6928796A (en) 1997-03-19
KR19990044269A (ko) 1999-06-25
GEP20002031B (en) 2000-04-10
IL123081A0 (en) 1998-09-24
CZ60398A3 (cs) 1998-08-12
EA199800232A1 (ru) 1998-08-27
SK22598A3 (en) 1998-12-02
MX9801334A (es) 1998-07-31
CA2228563A1 (fr) 1997-03-06
ZA967359B (en) 1998-03-02
PL325247A1 (en) 1998-07-06
DE19532048A1 (de) 1997-03-06
NZ316934A (en) 1999-07-29
BG102268A (en) 1998-12-30
BR9609988A (pt) 1999-07-06
TW339334B (en) 1998-09-01
JPH11514343A (ja) 1999-12-07
EA000623B1 (ru) 1999-12-29
AU716701B2 (en) 2000-03-02
HUP9802373A2 (hu) 1999-01-28
WO1997008171A1 (fr) 1997-03-06

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