EP0000030A1 - Diurethanes containing sulphur, process for their preparation and their use as herbicides - Google Patents

Diurethanes containing sulphur, process for their preparation and their use as herbicides Download PDF

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Publication number
EP0000030A1
EP0000030A1 EP78100050A EP78100050A EP0000030A1 EP 0000030 A1 EP0000030 A1 EP 0000030A1 EP 78100050 A EP78100050 A EP 78100050A EP 78100050 A EP78100050 A EP 78100050A EP 0000030 A1 EP0000030 A1 EP 0000030A1
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Prior art keywords
alkyl
halogen
alkoxy
substituted
phenyl
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EP78100050A
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German (de)
French (fr)
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EP0000030B1 (en
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Ulrich Dr. Schirmer
Bruno Dr. Wuerzer
Wolfgang Dr. Rohr
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BASF SE
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BASF SE
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
    • 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters thereof
    • 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<
    • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/32—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C271/38—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of rings other than six-membered aromatic rings with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C07C2603/62—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing three- or four-membered rings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to new valuable sulfur-containing diurethanes with excellent herbicidal activity, herbicides which contain these compounds, and processes for controlling unwanted plant growth with these compounds.
  • the new diurethanes have the general formula in the Z the rest and Y the rest means, where Z is always different from Y and R 1 and R 2 each independently of one another are hydrogen, alkyl (for example methyl, ethyl, isopropyl), alkoxyalkyl (for example methoxymethyl, 2-methoxyethyl), alkoxycarbonylalkyl (for example methoxycarbonyl-i methyl), haloalkyl (for example chloromethyl) or optionally benzyl substituted by alkyl or halogen, R 3 and R 4 are each independently unsubstituted alkyl or by halogen or alkoxy or alkoxycarbonyl or substituted or unsubstituted aryl , substituted alkyl (e.g.
  • benzyl isopropyl, n-propyl, 4-chlorobenzyl, n-butyl, sec.-butyl, tert.-butyl, iso-butyl, 2 , 4-dichlorobenzyl, 2-ethylhexyl, n-decyl, 2-phenylethyl) or optionally substituted by halogen-substituted alkenyl (e.g.
  • alkynyl optionally substituted by halogen or alkoxy (eg propargyl, butyne (1) yl (3), 1-chlorobutin (2) yl (4)) or optionally substituted by alkyl Cycloalkyl (e.g.
  • cyclopentyl cyclohexyl, 3-methylcyclohexyl, 2,6-dimethylcyclohexyl, cycloheptyl, 4-tert-butylc yclohexyl, cyclooctyl, cyclododecyl, 3,5-dimethylcyclohexyl) or bicycloalkyl (e.g. norbonyl) or tricycloalkyl (e.g. tricyclo (4,3,1,2,501,6) -decyl), a phenyl residue with a fused ring system (e.g.
  • Phenyl or a mono- or polysubstituted phenyl radical with the substituents alkyl, haloalkyl, alkoxyalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, alkoxycarbonylalkoxy, nitro, amino, aryl, aryloxy, thiocyanato, cyano, SR 5 , SO 2 R 5 , OSO 2 R 5 , -CO-R 5 , (e.g.
  • n are the numbers 1-4 and A, B, D, E each independently represent oxygen or sulfur, not all radicals A, B, D, E at the same time mean oxygen and at least one of these residues always means sulfur, have a good herbicidal action against numerous important undesirable plants and, at the same time, are well tolerated by many crop plants. These effects are better than those of the known active substances.
  • the new compounds can be prepared, for example, by the following processes, where the radicals A, B, D, E, R , R 1 , R 2 , R 3 , R4, X and n have the meaning given above.
  • urethanes and chloroformic acid esters in the following, these two collective terms are also to be understood as meaning thiono-, thio- and dithiourethanes as well as chloroformic acid urethionoesters, chloroformic acid thioesters and chloroformic acid dithioesters.
  • meta-nitrophenyliso (thio) cyanates B
  • B meta-nitrophenyliso (thio) cyanates
  • the aminourethanes E can also be obtained by reaction of meta-phenylenediamines (D) with chloroformic acid esters. Another synthesis option The reaction consists of the reaction of aryl-1,3-diiso (thio) cyanates (E) with only one mole of component R 3- BH, which leads to the iso (thio) cyanatourethanes (G) (JA Parker, JJ Thomas and CL Zeise, J. org. Chem. 22, 594 to 596 (1957)), which can also be obtained by (thio) phosgenation of the aminourethanes (F) (DT-OS 19 14 270, page 5, example 8). Subsequent reaction with component R 4 DH leads to the desired end products. Basically, it should be noted that the order of the -CABR 3 or -CEDR 4 groups is arbitrary.
  • connection has the following structural formula:
  • connection has the following structural formula:
  • connection has the following structural formula:
  • aminourethanes (E) can be prepared by appropriate processes:
  • a mixture of 20 parts by weight of N- (3-isothiocyanatophenyl) -0-methylcarbamate (obtainable from N- (3-aminophenyl) -O-methylcarbamate and thiophosgene, mp. 99-100 ° C., 20 parts by weight of methanol, 3 parts by weight of triethylamine and 150 parts by weight of toluene are boiled for 6 hours, after which the mixture is recrystallized from toluene: mp 141-149 ° C. (No. 2).
  • the connection has the following structural formula:
  • Methyl-N- (3- (N '- (3'-methylphenylcarbamoyloxy) -phenyl) -carbamate and ethyl-N- (N'-phenylcarbamoyloxy) -phenyl) -carbamate are characterized by their, albeit different, activity against broad-leaved unwanted plants with a considerable degree of tolerance for sugar beet.
  • Plastic flower pots with a content of 300 cm 3 were filled with loamy sand and equipped with the test plants according to species. This mainly involves sowing seeds or transplanting vegetatively propagated species.
  • the active ingredients were suspended or emulsified in water as a distribution medium and sprayed onto the leaves of the test plants and the still exposed soil surface by means of finely distributing nozzles in post-emergence application.
  • the plants were first grown to a height of 3 to 10 cm in the test vessels, depending on the growth habit, and then treated.
  • the temperature requirements of the test plants were met in that they were set up in cooler or warmer sections of the greenhouse systems.
  • the trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their reaction to the individual treatments evaluated.
  • the application rates of the test substances are considered to be kg / ha of active substance.
  • the agents according to the invention or mixtures containing them can be used in a further large number of crops in addition to the useful plants listed in the tables to eliminate undesired plant growth.
  • the application concentrations can range from 0.1 to 15 kg / ha and more, depending on the control object.
  • the new compounds can be mixed with one another or numerous other herbicidal or growth-regulating compounds can be used as mixing and combination partners.
  • wetting agents and adhesives as well as non-phytotoxic oils can be added.
  • the application is e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprinkling agents, granules, by spraying, atomizing, dusting, scattering or pouring.
  • 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 from medium to high boiling points such as kerosene or diesel oil, furthermore coal tar oils etc., as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example benzene, toluene, Xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, e.g.
  • strongly polar solvents e.g. Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. into consideration.
  • Aqueous application forms can be prepared from emulsion concentrations, pastes or wettable powders (wettable powders), oil dispersions by adding water.
  • emulsions, pastes or oil dispersions the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers.
  • wetting agents, adhesives, dispersants or emulsifiers, and possibly solvents or oil can also be prepared from active substance and are suitable for dilution with water.
  • surfactants are: alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, fatty acid alkali and alkaline earth metal salts, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic
  • Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
  • Solid carriers are, for example, mineral earths, such as silica gel, silicas, silica gels, silicates, talc, kaolin, attack clay, limestone, lime, chalk, boluses, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as For example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.
  • L 1 mineral earths, such as silica gel, silicas, silica gels, silicates, talc, kaolin, attack clay, limestone, lime, chalk, boluses, loess, clay,
  • the formulations contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90 percent by weight.
  • 20 parts by weight of compound 8 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 mol Ethylene oxide consists of 1 mole of castor oil.
  • active ingredient 7 40 parts by weight of active ingredient 7 are intimately mixed with 10 parts of sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion which contains 0.04% by weight of active ingredient.
  • active ingredient 2 20 parts are intimately mixed with 2 parts of calcium salt of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

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Abstract

1. A diurethane of the general formula see diagramm : EP0000030,P50,F6 where Z denotes the radical see diagramm : EP0000030,P50,F7 and Y denotes the radical see diagramm : EP0000030,P50,F8 Z always being different from Y and R**1 and R**2 being identical or different and each denoting hydrogen, alkyl of 1 to 4 carbon atoms, alkoxyalkyl of 2 to 4 carbon atoms, alkoxycarbonylalkyl of 3 to 5 carbon atoms, haloalkyl of 1 to 4 carbon atoms, unsubstituted benzyl, or benzyl substituted by alkyl of 1 to 4 carbon atoms or halogen, R**3 and R**4 being identical or different and each denoting unsubstituted alkyl of 1 to 6 carbon atoms, alkyl of 1 to 4 carbon atoms substituted by halogen, alkoxy of 1 to 2 carbon atoms, halogen-substituted phenyl or unsubstituted phenyl, alkenyl of 2 to 4 carbon atoms, alkynyl of 3 to 4 carbon atoms, unsubstituted or C1 -C4 -alkyl- substituted cycloalkyl of 5 to 8 carbon atoms, bicycloalkyl of 7 to 8 carbon atoms, tricycloalkyl of 10 to 15 carbon atoms, phenyl with a fused ring system, phenyl or mono- or poly-substituted phenyl with the substituents alkyl of 1 to 4 carbon atoms, halogen or alkoxy of 1 to 3 carbon atoms, X denotes hydrogen, alkyl of 1 to 4 carbon atoms, haloalkyl of 1 to 3 carbon atoms, alkoxy of 1 or 2 carbon atoms, halogen, nitro or amino, n denotes one of the integers 1, 2, 3 and 4, and A, B, D and E are identical or different and each denotes oxygen or sulfur (with the proviso that the radicals A, B, D and E are not simultaneously oxygen and one of the radicals always denotes sulfur).

Description

Die vorliegende Erfindung betrifft neue wertvolle schwefelhaltige Diurethane mit ausgezeichneter herbizider Wirkung, Herbizide, die diese Verbindungen enthalten, und Verfahren zur Bekämpfung unerwünschten Pflanzenwuchstums mit diesen Verbindungen.The present invention relates to new valuable sulfur-containing diurethanes with excellent herbicidal activity, herbicides which contain these compounds, and processes for controlling unwanted plant growth with these compounds.

Es ist bekannt, Methyl-N-(3-(N'-(3'-methylphenylcarbamoyl- oxy)-phenyl)-carbamat, Äthyl-N-(N'-phenylcarbamoyloxy)-phenyl)-carbamat, Methyl-N-(3-N'-methyl-N'-phenylcarbamoyl- oxy)-phenyl)-carbamat (DT-AS 15 67 151) oder 3-Isopropyl-2,l,3-benzothiadiazinon-(4)-2,2-dioxid (DT-AS 15 42 836) als Herbizide zu verwenden.It is known that methyl N- (3- (N '- (3'-methylphenylcarbamoyloxy) phenyl) carbamate, ethyl N- (N'-phenylcarbamoyloxy) phenyl) carbamate, methyl N- ( 3-N'-methyl-N'-phenylcarbamoyloxy) phenyl) carbamate (DT-AS 15 67 151) or 3-isopropyl-2, l, 3-benzothiadiazinon- (4) -2,2-dioxide ( DT-AS 15 42 836) to use as herbicides.

Es wurde nun gefunden, daß die neuen Diurethane der allgemeinen Formel

Figure imgb0001
in der Z den Rest
Figure imgb0002
und Y den Rest
Figure imgb0003
bedeutet, wobei Z immer verschieden ist von Y und R1 und R2 jeweils unabhängig voneinander Wasserstoff, Alkyl (z.B. Methyl, Äthyl, iso-Propyl), Alkoxyalkyl (z.B. Methoxymethyl, 2-Methoxyäthyl), Alkoxycarbonylalkyl (z.B. Methoxycarbonyl-i methyl), Halogenalkyl (z.B. Chlormethyl) oder gegebenenfalls durch Alkyl oder Halogen substituiertes Benzyl, R3 und R 4 jeweils unabhängig voneinander unsubstituiertes Alkyl oder durch Halogen oder Alkoxy oder Alkoxycarbonyl oder substituiertes oder unsubstituiertes Aryl, substituiertes Alkyl (z.B. Methyl, Äthyl, 2-Chloräthyl, 2-Methoxyäthyl, Methoxycarbonylmethyl, Benzyl, Isopropyl, n-Propyl, 4-Chlorbenzyl, n-Butyl, sec.-Butyl, tert.-Butyl, iso-Butyl, 2,4-Dichlorbenzyl, 2-Äthylhexyl, n-Decyl, 2-Phenyläthyl) oder gegebenenfalls durch Halogen substituiertes Alkenyl (z.B. Allyl, 2-Chlorpropen(1)yl(3), Buten(1)yl(3), 2,3-Dichlorallyl, 3,3-Dichlor-2-Methylallyl) oder gegebenenfalls durch Halogen oder Alkoxy substituiertes Alkinyl (z.B. Propargyl, Butin(1)yl(3), 1-Chlorbutin(2)yl(4)) oder gegebenenfalls durch Alkyl substituiertes Cycloalkyl (z.B. Cyclopentyl, Cyclohexyl, 3-Methylcyclohexyl, 2,6-Dimethylcyclohexyl, Cycloheptyl, 4-tert.-Butylcyclohexyl, Cyclooctyl, Cyclododecyl, 3,5-Dimethylcyclohexyl) oder Bicycloalkyl (z.B. Norbonyl) oder Tricycloalkyl (z.B. Tricyclo(4,3,1,2,501,6)-decyl), einen Phenylrest mit ankondensiertem Ringsystem (z.B. Naphthyl oder Indyl), Phenyl oder einen ein- oder mehrfach substituierten Phenylrest, mit den Substituenten Alkyl, Halogenalkyl, Alkoxyalkyl, Cycloalkyl, Halogen, Alkoxy, Halogenalkoxy, Alkoxycarbonyl-alkoxy, Nitro, Amino, Aryl, Aryloxy, Thiocyanato, Cyano,
Figure imgb0004
S-R5, SO2R5, OSO2R5, -CO-R5,
Figure imgb0005
(z.B. Phenyl, 4-Fluorphenyl, 2-Methoxyphenyl, 3-Methylphenyl, 2-Fluorphenyl, 3-Methyl-5-isopropylphenyl, 3-Äthylphenyl, 3-Chlorphenyl, 2,4,6-Trimethylphenyl, 3-Fluorphenyl, 3-Chlor-4-fluorphenyl, 3,4-Dimethylphenyl, 3-Trlfluormethylphen;;l, 4-Methylphenyl, 3,4-Difluorphenyl, 3-Chlor-4-methylphenyl, 3-Bromphenyl, 4-Jodphenyl, 4-Chlorphenyl, 2-Chlorphenyl, 3-N,N-Dimethylaminophenyl, 2-Chlor-4-fluorphenyl, 3-Isopropylphenyl, 4-Äthylphenyl, 3-Methoxycarbonylaminophenyl, 4-Äthoxyphenyl, 2-Methylphenyl, 3-Methoxyphenyl, 4-Cyanophenyl, 2,6-Dimethylphenyl, 2,4-Dichlorphenyl, 3-Methyl-4-chlorphenyl, 2-Trifluormethylphenyl, 2,4-Dibromphenyl, 4-Trifluormethylphenyl, 4-Methoxyphenyl, 3-(1'-Äthoxycarbonyl-äthoxy)-phenyl), 2,3,6-Trimethylphenyl, 3-tert.-Butylphenyl, 3-Trifluormethoxyphenyl, 3-α,α,ß,ß-Tetrafluoräthoxyphenyl, 3,5-Dichlorphenyl, 2-Methyl-6-äthylphenyl, 2,3-Dimethylphenyl, 2-Methyl-4-chlorphenyl, 2,4,5-Trichlorphenyl, 2,3,5-Trichlorphenyl, p-Chlorphenoxy-phenyl, wobei R5 und R6 jeweils unabhängig voneinander Wasserstoff oder einen gegebenenfalls ein- oder mehrfach substituierten Arylrest bedeuten oder einen der beiden Substituenten die für R1 genannten Bedeutungen hat, X Wasserstoff, Alkyl (z.B. Methyl), Halogenalkyl (z.B. Trifluormethyl), Alkoxy (z.B. Methoxy), Halogen (z.B. Fluor, Chlor, Brom oder Jod), Nitro oder Amino, n die Zahlen 1 - 4 und A, B, D, E jeweils unabhängig voneinander Sauerstoff oder Schwefel bedeuten, wobei nicht alle Reste A, B, D, E gleichzeitig Sauerstoff und mindestens einer dieser Reste immer Schwefel bedeutet, eine gute herbizide Wirkung gegen zahlreiche wichtige unerwünschte Pflanzen und gleichzeitig eine gute Verträglichkeit bei vielen Kulturpflanzen haben. Diese Wirkungen sind besser als die der - bekannten Wirkstoffe.It has now been found that the new diurethanes have the general formula
Figure imgb0001
 in the Z the rest
Figure imgb0002
 and Y the rest
Figure imgb0003
 means, where Z is always different from Y and R 1 and R 2 each independently of one another are hydrogen, alkyl (for example methyl, ethyl, isopropyl), alkoxyalkyl (for example methoxymethyl, 2-methoxyethyl), alkoxycarbonylalkyl (for example methoxycarbonyl-i methyl), haloalkyl (for example chloromethyl) or optionally benzyl substituted by alkyl or halogen, R 3 and R 4 are each independently unsubstituted alkyl or by halogen or alkoxy or alkoxycarbonyl or substituted or unsubstituted aryl , substituted alkyl (e.g. methyl, ethyl, 2-chloroethyl, 2-methoxyethyl, methoxycarbonylmethyl, benzyl, isopropyl, n-propyl, 4-chlorobenzyl, n-butyl, sec.-butyl, tert.-butyl, iso-butyl, 2 , 4-dichlorobenzyl, 2-ethylhexyl, n-decyl, 2-phenylethyl) or optionally substituted by halogen-substituted alkenyl (e.g. allyl, 2-chloropropene (1) yl (3), butene (1) yl (3), 2,3 -Dichlorallyl, 3,3-dichloro-2-methylallyl) or alkynyl optionally substituted by halogen or alkoxy (eg propargyl, butyne (1) yl (3), 1-chlorobutin (2) yl (4)) or optionally substituted by alkyl Cycloalkyl (e.g. cyclopentyl, cyclohexyl, 3-methylcyclohexyl, 2,6-dimethylcyclohexyl, cycloheptyl, 4-tert-butylc yclohexyl, cyclooctyl, cyclododecyl, 3,5-dimethylcyclohexyl) or bicycloalkyl (e.g. norbonyl) or tricycloalkyl (e.g. tricyclo (4,3,1,2,501,6) -decyl), a phenyl residue with a fused ring system (e.g. naphthyl or indyl), Phenyl or a mono- or polysubstituted phenyl radical, with the substituents alkyl, haloalkyl, alkoxyalkyl, cycloalkyl, halogen, alkoxy, haloalkoxy, alkoxycarbonylalkoxy, nitro, amino, aryl, aryloxy, thiocyanato, cyano,
Figure imgb0004
 SR 5 , SO 2 R 5 , OSO 2 R 5 , -CO-R 5 ,
Figure imgb0005
 (e.g. phenyl, 4-fluorophenyl, 2-methoxyphenyl, 3-methylphenyl, 2-fluorophenyl, 3-methyl-5-isopropylphenyl, 3-ethylphenyl, 3-chlorophenyl, 2,4,6-trimethylphenyl, 3-fluorophenyl, 3- Chloro-4-fluorophenyl, 3,4-dimethylphenyl, 3-trifluoromethylphen ;; 1,4-methylphenyl, 3,4-difluorophenyl, 3-chloro-4-methylphenyl, 3-bromophenyl, 4-iodophenyl, 4-chlorophenyl, 2-chlorophenyl, 3-N, N-dimethylaminophenyl, 2-chloro-4-fluorophenyl, 3-isopropylphenyl, 4-ethylphenyl, 3-methoxycarbonylaminophenyl, 4-ethoxyphenyl, 2-methylphenyl, 3-methoxyphenyl, 4-cyanophenyl, 2,6-dimethylphenyl, 2,4-dichlorophenyl, 3-methyl-4-chlorophenyl, 2-trifluoromethylphenyl, 2, 4-dibromophenyl, 4-trifluoromethylphenyl, 4-methoxyphenyl, 3- (1'-ethoxycarbonyl-ethoxy) -phenyl), 2,3,6-trimethylphenyl, 3-tert-butylphenyl, 3-trifluoromethoxyphenyl, 3-α, α , ß, ß-tetrafluoroethoxyphenyl, 3,5-dichlorophenyl, 2-methyl-6-ethylphenyl, 2,3-dimethylphenyl, 2-methyl-4-chlorophenyl, 2,4,5-trichlorophenyl, 2,3,5-trichlorophenyl , p-chlorophenoxyphenyl, where R 5 and R 6 each independently represent hydrogen or an optionally mono- or polysubstituted aryl radical or one of the two substituents has the meanings given for R 1 , X is hydrogen, alkyl (for example methyl), haloalkyl (e.g. trifluoromethyl), Alkoxy (eg methoxy), halogen (eg fluorine, chlorine, bromine or iodine), nitro or amino, n are the numbers 1-4 and A, B, D, E each independently represent oxygen or sulfur, not all radicals A, B, D, E at the same time mean oxygen and at least one of these residues always means sulfur, have a good herbicidal action against numerous important undesirable plants and, at the same time, are well tolerated by many crop plants. These effects are better than those of the known active substances.

Die neuen Verbindungen können beispielsweise nach folgenden Verfahren hergestellt werden, wobei die Reste A, B, D, E, R, R 1, R2, R3, R4, X und n die oben angegebene Bedeutung haben. Wenn im folgenden von Urethanen und Chlorameisensäureestern die Rede ist, sollen unter diesen beiden Sammelbegriffen auch Thiono- Thio- und Dithiourethane sowie Chlorameisensäurethionoester, Chlorameisensäurethi.oester und Chlorameisensäuredithioester verstanden werden.

Figure imgb0006
The new compounds can be prepared, for example, by the following processes, where the radicals A, B, D, E, R , R 1 , R 2 , R 3 , R4, X and n have the meaning given above. When we talk about urethanes and chloroformic acid esters in the following, these two collective terms are also to be understood as meaning thiono-, thio- and dithiourethanes as well as chloroformic acid urethionoesters, chloroformic acid thioesters and chloroformic acid dithioesters.
Figure imgb0006

Äus dem aufgezigten Reaktionsschema gehen eindeutig die wechselseitigen Beziehungen zwischen den Ausgangsstoffen hervor. Weiterhin wird deutlich, daß je nach Natur der Substituenten A, B, D, E, R1, R2, R3, R4 und X sowie der Verfügbarkeit der jeweiligen Reaktionspartner der eine oder andere Weg vorteilhaft sein kann. Die Umsetzung von F nach H wird bevorzugt.The mutual relationship between the starting materials clearly emerges from the open reaction scheme. It is also clear that, depending on the nature of the substituents A, B, D, E, R 1 , R 2 , R 3 , R 4 and X and the availability of the respective reactants, one way or the other can be advantageous. The conversion from F to H is preferred.

Ausgehend von bekannten meta-Nitranilihen (A) lassen sich meta-Nitrophenyliso(thio)cyanate (B) herstellen (W. Siefken, J. Liebigs Annalen der Chemie, 562, 75 ff. (1949), die ihrerseits mit den Komponenten R -BH glatt zu den Nitro-(thio)urethanen (C) reagieren (S. Petersen in Methoden der Organ. Chemie, Band VIII, Seite 131, Georg-Thieme-Verlag, Stuttgart, 4. Auflage, (1952), die allerdings auch direkt aus den meta-Nitranilinen (A) mit Chlorameisensäureestern (R3B-CA-Cl) (DT-OS 16 43 763) oder mit Schwefelkohlenstoff bzw. Kohlenoxysulfid, Base und Alkylierungsmittel (Methoden der Organischen Chemie, Band IX, Seite 831 ff, Georg Thieme-Verlag, Stuttgart, 4. Auflage, 1955) zugänglich sind. Nachfolgende Reduktion führt zu den Aminoverbindungen (F, R2=H) (S. Schröter in Methoden der Organischen Chemie, Band XI/1, Seite 360 ff., Georg Thieme-Verlag, Stuttgart, 4. Auflage, 1957), die entweder direkt oder nach erfolgter Umwandlung in das am Aminostickstoff monosubstituierte Produkt (F, R2=H) Methoden der Organischen Chemie, Bandk XI/1, Seite 24 ff., Georg Thieme-Verlag, Stuttgart, 4. Auflage 1957) mit Chlorameisensäureestern (R4D-CE-Cl) (DT-OS 16 43 763) oder mit Schwefelkohlenstoff bzw. Kohlenoxysulfid, Base und Alkylierungsmittel; (Methoden der organischen Chemie, Band IX, Seite 831 ff, Georg-Thieme-Verlag, Stuttgart, 4. Auflage, 1955) zu den gewünschten Diurethanen (H) umgesetzt werden. Die Aminourethane E lassen sich aber auch durch Reaktion von meta-Phenylendiaminen (D) mit Chlorameisensäureestern erhalten. Eine weitere Synthesemög- lichkeit besteht in der Reaktion von Aryl-1,3-diiso(thio)-cyanaten (E) mit nur einem Mol Komponente R3-BH, die zu den Iso(thio)cyanatourethanen (G) führt (J.A. Parker, J.J. Thomas und C.L. Zeise, J. org. Chem. 22, 594 bis 596 (1957)), welche auch durch (Thio)phosgenierung der Aminourethane (F) erhältlich sind (DT-OS 19 14 270, Seite 5, Beispiel 8). Anschließende Reaktion mit der Komponente R4DH führt zu den gewünschten Endprodukten. Grundsätzlich ist zu bemerken, daß die Reihenfolge der -CABR3 bzw. -CEDR4-Gruppierungen beliebig ist.Starting from known meta-nitranilines (A), meta-nitrophenyliso (thio) cyanates (B) can be prepared (W. Siefken, J. Liebigs Annalen der Chemie, 562, 75 ff. (1949), which in turn contain the components R - BH smoothly react to the nitro (thio) urethanes (C) (S. Petersen in Methods of Organ. Chemistry, Volume VIII, page 131, Georg-Thieme-Verlag, Stuttgart, 4th edition, (1952), but also directly from the meta-nitranilines (A) with chloroformic acid esters (R 3 B-CA-Cl) (DT-OS 16 43 763) or with carbon disulphide or carbon oxysulfide, base and alkylating agent (Methods of Organic Chemistry, Volume IX, page 831 ff , Georg Thieme-Verlag, Stuttgart, 4th edition, 1955) The subsequent reduction leads to the amino compounds (F, R 2 = H ) (S. Schröter in Methods of Organic Chemistry, Volume XI / 1, page 360 ff. , Georg Thieme-Verlag, Stuttgart, 4th edition, 1957), which either directly or after conversion into the monosubstituted product on amino nitrogen (F, R 2 = H) Methods of Organic Chemistry, Bandk XI / 1, page 24 ff., Georg Thieme-Verlag, Stuttgart, 4th edition 1957) with chloroformic acid esters (R 4 D-CE-Cl) (DT-OS 16 43 763) or with carbon disulfide or carbon oxysulfide, base and alkylating agent; (Methods of Organic Chemistry, Volume IX, page 831 ff, Georg-Thieme-Verlag, Stuttgart, 4th edition, 1955) to the desired diurethanes (H). The aminourethanes E can also be obtained by reaction of meta-phenylenediamines (D) with chloroformic acid esters. Another synthesis option The reaction consists of the reaction of aryl-1,3-diiso (thio) cyanates (E) with only one mole of component R 3- BH, which leads to the iso (thio) cyanatourethanes (G) (JA Parker, JJ Thomas and CL Zeise, J. org. Chem. 22, 594 to 596 (1957)), which can also be obtained by (thio) phosgenation of the aminourethanes (F) (DT-OS 19 14 270, page 5, example 8). Subsequent reaction with component R 4 DH leads to the desired end products. Basically, it should be noted that the order of the -CABR 3 or -CEDR 4 groups is arbitrary.

Nachfolgend werden die bevorzugten Syntheseschritte genauer beschrieben:

  • a) Die Umsetzung von 3-Nitrophenyl(thio)cyanaten (B) erfolgt mit oder ohne einen für Iso(thio)cyanatreak- tionen gebräuchlichen Katalysator, z.B. tert. Amine (Triäthylamin, 1,4-Diazabicyclo-(2.2.2)-octan), stickstoffhaltige Heterocyclen (Pyridin, 1,2-Dimethylimidazol) oder organische Zinnverbindungen (Dibutylzinndiacetat, Dimethylzinndichlorid) gegebenenfalls in einem unter den Reaktionsbedingungen inerten Lösungsmittel, z.B. Kohlenwasserstoffe (Ligroin, Benzin, Toluol, Pentan, Cyclohexan), Halogenkohlenwasserstoffe (Methylenchlorid, Chloroform, Dichloräthan, Chlorbenzol, o-, m- oder p-Dichlorbenzol), Nitrokohlenwasserstoffe (Nitrobenzol, Nitromethan), Nitrile (Acetonitril, Butyronitril, Benzonitril), Äther (Diäthyläther, Tetrahydrofuran, Dioxan), Ester (Essigsäureäthylester, Propionsäuremethylester), Ketone (Aceton, Methyläthylketon) oder Amide (Dimethylformamid, Formamid) (DT-OS 15 68 138) bei Temperaturen im Bereich von 0 bis 150°C, vorzugsweise im Bereich von 40° bis 100°C.
  • b) 3-Nitraniline (A) werden mit Chlorameisensäureester in einem geeigneten Lösungsmittel, z.B. Wasser, Alkohole (Methanol, Äthanol, Isopropanol) oder wie unter a) angegeben, unter Zuhilfenahme eines üblichen Säurebinders, z.B. Alkalihydroxide,-carbonate, -hydrogencarbonate, Erdalkalioxide, -hydroxide, -carbonate, -hydrogencarbonate, tertiäre organische Basen (z.B. Triäthylamin, Pyridin, N,N-Dimethylanilin, N,N-Dimethylcyclohexylamin, Chinolin, Tributylamin) oder Ausgangsprodukt 3-Nitranilin, bei Temperaturen von -20° bis 150°C, vorzugsweise im Bereich von 20 bis 80°C umgesetzt.
  • c) Die Reduktion der Nitrourethane (C) kann nach einem der bekannten Verfahren durchgeführt werden, beispielsweise durch katalytische Hydrierung, durch eine Metall-Säure-Kombination, z.B. eine Kombination Eisen-Säure, durch eine Metall-Alkohol-Kombination, z.B. Zinkstaub-wäßriger Alkohol, Eisen-wäßriger Alkohol.
  • d) Für die Umsetzung von m-Phenylendiaminen (D) gelten vergleichbare Bedingungen wie für b), wobei es aber vorteilhaft sein kann, mit einem Überschuß an m-Phenylendiaminen zu arbeiten.
  • e) Die Reaktion der Aminourethane 2 mit Chlorameisensäureestern erfolgt analog zu b), wobei man auch die z.B. durch katalystische Hydrierung der Nitrourethane C erhaltene Lösung ohne weitere Reinigung direkt einsetzen kann.
The preferred synthesis steps are described in more detail below:
  • a) The reaction of 3-nitrophenyl (thio) cyanates (B) is carried out with or without a catalyst customary for iso (thio) cyanate reactions, for example tert. Amines (triethylamine, 1,4-diazabicyclo- (2.2.2) octane), nitrogen-containing heterocycles (pyridine, 1,2-dimethylimidazole) or organic tin compounds (dibutyltin diacetate, dimethyltin dichloride) optionally in a solvent which is inert under the reaction conditions, e.g. hydrocarbons ( Ligroin, gasoline, toluene, pentane, cyclohexane), halogenated hydrocarbons (methylene chloride, chloroform, dichloroethane, chlorobenzene, o-, m- or p-dichlorobenzene), nitrocarbons (nitrobenzene, nitromethane), nitriles (acetonitrile, butyronitrile, ether (benzonitrile) Diethyl ether, tetrahydrofuran, dioxane), esters (ethyl acetate, methyl propionate), ketones (acetone, methyl ethyl ketone) or amides (dimethylformamide, formamide) (DT-OS 15 68 138) at temperatures in the range from 0 to 150 ° C., preferably in the range from 40 ° to 100 ° C.
  • b) 3-Nitranilines (A) with chloroformate in a suitable solvent, for example water, alcohols (methanol, ethanol, isopropanol) or as indicated under a), with the aid of a conventional acid binder, for example alkali metal hydroxides, carbonates, bicarbonates, alkaline earth metal oxides , hydroxides, carbonates, bicarbonates, tertiary organic bases (e.g. triethylamine, pyridine, N, N-dimethylaniline, N, N-dimethylcyclohexylamine, quinoline, tributylamine) or starting product 3-nitraniline, at temperatures from -20 ° to 150 ° C, preferably in the range from 20 to 80 ° C.
  • c) The reduction of the nitrourethanes (C) can be carried out by one of the known processes, for example by catalytic hydrogenation, by a metal-acid combination, for example a combination of iron and acid, by a metal-alcohol combination, for example aqueous zinc dust Alcohol, iron-water alcohol.
  • d) Similar conditions apply to the reaction of m-phenylenediamines (D) as for b), but it may be advantageous to work with an excess of m-phenylenediamines.
  • e) The reaction of the aminourethanes 2 with chloroformic acid esters is carried out analogously to b), it also being possible to use the solution obtained, for example, by catalytic hydrogenation of the nitrourethanes C without further purification.

Die folgenden Beispiele sollen die Herstellung der neuen Diurethane und ihrer Vorprodukte erläutern:The following examples are intended to explain the production of the new diurethanes and their preliminary products:

I. NitrourethaneI. Nitrourethanes Beispiel AExample A

Einer Lösung von 64,3 Gewichtsteilen 4-Chlorphenol und 3 Gewichtsteilen Triäthylamin in 430 Gewichtsteilen (absolut) wurde unter Rühren bei 20 bis 25°C eine Mischung von 85 Gewichtsteilen 3-Nitrophenylisocyanat und 43 Gewichtsteilen Toluol (absolut) zudosiert.A solution of 64.3 parts by weight of 4-chlorophenol and 3 parts by weight of triethylamine in 430 parts by weight (absolute) was mixed with stirring at 20 to 25 ° C, a mixture of 85 parts by weight of 3-nitrophenyl isocyanate and 43 parts by weight of toluene (absolute).

Zur Vervollständigung der Reaktion wurde 1 Stunde bei Raumtemperatur nachgerührt. Nach Kühlen auf 0°C wurde das Reaktionsprodukt abgesaugt: Fp. 137 bis 138°CTo complete the reaction, the mixture was stirred at room temperature for 1 hour. After cooling to 0 ° C., the reaction product was filtered off with suction: mp 137 to 138 ° C.

Die Verbindung hat folgende Strukturformel:

Figure imgb0007
The connection has the following structural formula:
Figure imgb0007

Beispiel BExample B

Zu 138 Gewichtsteilen m-Nitranilin in 500 Gewichtsteilen Tetrahydrofuran (THF) werden 87 Gewichtsteile Natriumhydrogencarbonat gegeben. Unter Rühren tropft man bei Raumtemperatur 120 Gewichtsteile Chlorameisensäurethiomethylester zu, läßt 16 Stunden bei Raumtemperatur nachrühren, filtriert, destilliert das Lösungsmittel am Rotationsverdampfer ab und rührt das erhaltene Öl in Toluol ein. Die sich abscheidenden Kristalle werden abgesaugt und getrocknet: Fp.: 137 - 138°C.87 parts by weight of sodium hydrogen carbonate are added to 138 parts by weight of m-nitraniline in 500 parts by weight of tetrahydrofuran (THF). 120 parts by weight of methyl chloroformate are added dropwise at room temperature, the mixture is stirred for 16 hours at room temperature, filtered, the solvent is distilled off on a rotary evaporator and the oil obtained is stirred into toluene. The crystals which separate out are filtered off with suction and dried: mp: 137 ° -138 ° C.

Die Verbindung hat folgende Strukturformel:

Figure imgb0008
The connection has the following structural formula:
Figure imgb0008

Beispiel CExample C

Zu 26 Gewichtsteilen 3-Nitro-N-methylanilin in 320 Gewichtsteilen Essigsäureäthylester werden 17,4 Gewichtsteile Natriumhydrogencarbonat gegeben. Unter Rühren fügt man langsam 33 Gewichtsteile Chlorameisensäurem-tolylester zu, läßt 20 Stunden bei Raumtemperatur rühren, filtriert, zieht das Lösungsmittel im Vakuum ab und kristallisiert den verbleibenden Rückstand aus Toluol/Cyclohexan um. Fp.: 114 bis 116 0 C.17.4 parts by weight of sodium hydrogen carbonate are added to 26 parts by weight of 3-nitro-N-methylaniline in 320 parts by weight of ethyl acetate. 33 parts by weight of chloroformic acid methyl ester are slowly added with stirring, the mixture is stirred for 20 hours at room temperature, filtered, the solvent is removed in vacuo and the remaining residue is recrystallized from toluene / cyclohexane. Mp .: 114 to 116 0 C.

Die Verbindung hat folgende Strukturformel:

Figure imgb0009
The connection has the following structural formula:
Figure imgb0009

Nach entsprechenden Verfahren können folgende Nitrourethane (C) hergestellt werden:

Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
 The following nitrourethanes (C) can be prepared by appropriate processes:
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016

II. AminourethaneII. Aminourethane Beispiel DExample D

Eine Lösung von 135 Gewichtsteilen N-(3-Nitrophenyl)-carbaminsäure-4-chlorphenylester in 900 Gewichtsteilen Tetrahydrofuran (absolut) wurden mit 3 Teilen Hydrierkatalysator (Palladium auf Tierkohle, 10 % versetzt und bei Raumtemperatur und 0,02 bar H2-Druck bis zur Konstanz hydriert. Zur Aufarbeitung wurde die vom Katalysator befreite und mit MgSO4 getrocknete Lösung soweit vom Lösungsmittel befreit, daß sich das kristalline Reaktionsprodukt gut absaugen ließ: 186 - 187 C. Struktur:

Figure imgb0017
A solution of 135 parts by weight of N- (3-nitrophenyl) carbamic acid 4-chlorophenyl ester in 900 parts by weight of tetrahydrofuran (absolute) was mixed with 3 parts of hydrogenation catalyst (palladium on animal charcoal, 10% and at room temperature and 0.02 bar H 2 pressure For working up, the solution which had been freed from the catalyst and dried with MgSO 4 was freed from the solvent to such an extent that the crystalline reaction product could be suctioned off well: 186-187 C. Structure:
Figure imgb0017

Beispiel EExample E

Zu einer Lösung von 108 Gewichtsteilen m-Phenylendiamin in 1000 Gewichtsteilen Wasser wurden unter intensivem Rühren sehr langsam 25,2 Gewichtsteile Chlorameisensäurephenylester zugetropft. Nach beendeter Reaktion wurde abgesaugt, der Feststoff mehrmals mit verdünnter Salzsäure ausgewaschen, die vereinigten, sauren Lösungen mit Ammoniak neutralisiert und abgesaugt. Das so erhaltene, getrocknete Produkt schmilzt bei 178 bis 180°C unter Zersetzung.
Struktur:

Figure imgb0018
25.2 parts by weight of phenyl chloroformate were added very slowly to a solution of 108 parts by weight of m-phenylenediamine in 1000 parts by weight of water with vigorous stirring. After the reaction had ended, the mixture was filtered off with suction, the solid was washed out several times with dilute hydrochloric acid, and the combined acidic solutions were neutralized with ammonia and filtered off with suction. The dried product thus obtained melts at 178 to 180 ° C. with decomposition.
Structure:
Figure imgb0018

Beispiel FExample F

Zu 51 Gewichtsteilen 2,4-Diaminonitrobenzol und 43 Gewichtsteilen Natriumhydrogencarbonat in 600 Gewichtsteilen Tetrahydrofuran tropft man langsam unter intensivem Rühren 52,1 Gewichtsteile Chlorameisensäurephenylester. Nach 14-stündigem Rühren wird filtriert, mit Tetrahydrofuran nachgewaschen. Man befreit die Lösung soweit vom Lösungsmittel, daß sich das kristalline Rohprodukt gut absaugen läßt, nach dem Waschen mit Diäthyläther und Trocknen schmilzt die Substanz bei 223 bis 225°C. Laut NMR-Spektrum und Elementaranalyse hat sie folgende Struktur:

Figure imgb0019
52.1 parts by weight of phenyl chloroformate are slowly added dropwise to 51 parts by weight of 2,4-diaminonitrobenzene and 43 parts by weight of sodium hydrogen carbonate in 600 parts by weight of tetrahydrofuran. After stirring for 14 hours, the mixture is filtered and washed with tetrahydrofuran. The solution is freed from the solvent to such an extent that the crystalline crude product can be suctioned off well, after washing with diethyl ether and drying, the substance melts at 223 to 225 ° C. According to the NMR spectrum and elemental analysis, it has the following structure:
Figure imgb0019

Beispiel GExample G

Zu einer auf 80°C erwämten Mischung aus 33 Gewichtsteilen Eisenpulver, 75 Gewichtsteilen Alkohol, 60 Gewichtsteilen Wasser und 3 Gewichtsteilen konz. Salzsäure gibt man unter intensivem Rühren 40 Gewichtsteile 3(S-Methyl- thiocarbamoyl)-nitrobenzol in solchen Portionen, daß die Temperatur ohne zusätzliche Heizung auf 80°C gehalten wird. Danach kocht man noch 1 Stunde am Rückfluß, saugt heiß ab, digeriert den Rückstand und das Filtrat mit etwa 1000 Gewichtsteilen Methylenchlorid, trocknet über Natriumsulfat, engt ein und kristallisiert aus Toluol um: Fp. 101 - 103°C.
Struktur:

Figure imgb0020
To a mixture of 33 parts by weight iron powder, 75 parts by weight alcohol, 60 parts by weight water and 3 parts by weight conc. Hydrochloric acid is added with intensive stirring 40 parts by weight of 3 (S-methyl-thiocarbamoyl) nitrobenzene in portions such that the temperature is kept at 80 ° C. without additional heating. The mixture is then boiled under reflux for 1 hour, suction filtered hot, the residue digested and the filtrate with about 1000 parts by weight of methylene chloride, dried over sodium sulfate, concentrated and recrystallized from toluene: mp 101-103 ° C.
Structure:
Figure imgb0020

Nach entsprechenden Verfahren können folgende Aminourethane (E) hergestellt werden:

Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
 The following aminourethanes (E) can be prepared by appropriate processes:
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026

III. DiurethaneIII. Diurethanes Beispiel 1example 1

Einer Lösung von 22,8 Gewichtsteilen N-(3-Aminophenyl)-carbaminsäurephenylester in 200 Gewichtsteilen Tetrahydrofuran (absolut) wurden 11 Gewichtsteile Natriumcarbonat zugegeben und anschließend bei 20 bis 25°C unter Kühlung 13,3 Gewichtsteile Chlorameisensäurethiomethylester zudosiert. Zur Vervollständigung der Umsetzung wurde 1 Stunde bei Raumtemperatur gerührt. Anschließend wurde die Reaktionsmischung filtriert und das Filtrat im Vakuum eingeeinget. Der ölige Rückstand wurde durch Zugabe von Toluol zur Kristallisation gebracht. Fp. 155 - 157°C (Nr. 1).
Die Verbindung hat folgende Strukturformel:

Figure imgb0027
11 parts by weight of sodium carbonate were added to a solution of 22.8 parts by weight of phenyl N- (3-aminophenyl) carbamate in 200 parts by weight of tetrahydrofuran (absolute), and 13.3 parts by weight of methyl chloroformate were then metered in at 20 to 25 ° C. with cooling. To complete the reaction, the mixture was stirred at room temperature for 1 hour. The reaction mixture was then filtered and the filtrate was concentrated in vacuo. The oily residue was crystallized by adding toluene. Mp 155-157 ° C (No. 1).
The connection has the following structural formula:
Figure imgb0027

Beispiel 2Example 2

Eine Mischung aus 20 Gewichtsteilen N-(3-Isothiocyana- tophenyl)-0-methylcarbamat (erhältich aus N-(3-Aminophenyl)-O-methylcarbamat und Thiophosgen, Fp. 99 - 100°C, 20 Gewichtsteilen Methanol, 3 Gewichtsteilen Triäthylamin und 150 Gewichtsteilen Toluol wird 6 Stunden zum Sieden erhitzt. Nach dem Einengen kristallisiert man aus Toluol um: Fp. 141 - 149°C (Nr. 2). Die Verbindung hat folgende Strukturformel:

Figure imgb0028
A mixture of 20 parts by weight of N- (3-isothiocyanatophenyl) -0-methylcarbamate (obtainable from N- (3-aminophenyl) -O-methylcarbamate and thiophosgene, mp. 99-100 ° C., 20 parts by weight of methanol, 3 parts by weight of triethylamine and 150 parts by weight of toluene are boiled for 6 hours, after which the mixture is recrystallized from toluene: mp 141-149 ° C. (No. 2). The connection has the following structural formula:
Figure imgb0028

Beispiel 3Example 3

Zu einer Lösung von 16,6 Gewichtsteilen N-(3-Aminophenyl)-0-methyluretahn und 10,1 Gewichtsteilen Triäthylamin in 300 Gewichtsteilen Diäthyläther läßt man bei Raumtemperatur 10 Gewichtsteile Schwefelkohlenstoff tropfen. Nach 20-stündigem Rühren wird abgesaugt, der Rückstand in 120 Gewichtsteilen Wasser suspendiert und unter Rühren mit 9,1 Volumenteilen Diäthylsulfat versetzt. Nach 20-stündigem Rühren wird abgesaugt, mit Wasser gewaschen und an der Luft getrocknet: Fp. 122 - 124°C (Nr. 3).
Die Verbindung hat folgende Strukturformel:

Figure imgb0029
Figure imgb0030
Figure imgb0031
Figure imgb0032
Figure imgb0033
Figure imgb0034
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
Figure imgb0044
Figure imgb0045
Figure imgb0046
Figure imgb0047
 A solution of 16.6 parts by weight of N- (3-aminophenyl) -0-methyluretahn and 10.1 parts by weight of triethylamine in 300 parts by weight of diethyl ether is allowed to drip 10 parts by weight of carbon disulfide at room temperature. After stirring for 20 hours, the product is filtered off with suction, the residue is suspended in 120 parts by weight of water and 9.1 parts by volume of diethyl sulfate are added with stirring. After stirring for 20 hours, the product is filtered off with suction, washed with water and air-dried: mp 122-124 ° C. (No. 3).
The connection has the following structural formula:
Figure imgb0029
Figure imgb0030
Figure imgb0031
Figure imgb0032
Figure imgb0033
Figure imgb0034
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
Figure imgb0044
Figure imgb0045
Figure imgb0046
Figure imgb0047

Für die folgenden Versuche wurden bekannte herbizide Wirk- ' stoffe zum Vergleich herangezogen. Methyl-N-(3-(N'-(3'-methylphenylcarbamoyloxy)-phenyl)-carbamat und Äthyl-N-(N'-phenylcarbamoyloxy)-phenyl)-carbamat (DT-AS 15 67 151) zeichen sich.durch ihre, wenngleich unterschiedliche, Wirkung gegen breitblättrige unerwünschte Pflanzen bei einem beachtlichen Maß an Verträglichkeit für Zuckerrüben aus. Hier sind bekanntlich jedoch Unterschiede zu verzeichnen, da Methyl-N-(3-(N'-(3'-methylphenylcarbamoyloxy)-phenyl)-carbamat eine noch günstigere Selektivität in dieser Kultur aufweist als die zweite oben genannte Verbindung dieses Typs. Einen völlig anderen Anwendungsbereich hat 3-Isopropyl-2,1,3-benzothiadiazinon(4)-2,2-dioxid (DT-AS 15 42 836). Mit dieser Verbindung werden verschiedene breitblättrige Unkräuter in Sojabohnen, Erdnüssen, Getreide, Mais und einigen Gemüsearten bekämpft. Hier sind jedoch noch Wirkungslücken vorhanden. Methyl-N-(3-N'-methyl-N'-phenyl-carbamoyl- oxy)-phenyl)-earbamat zeigt bei für seine Klasse guter herbizider Wirkung kaum Kulturpflanzenselektivität, weshalb die Verbindung z.B. für Soja nur zur Unterblattspritzung (postdirected) empfohlen wurde (Arndt, F. and G. Boroschewsky: New Selective Herbicides - VIII International Plant Protection Congress, Reports and Information, Section III Chemical Control, Part I, Moskow 1975, pp. 42-49). Hierbei sollen die jungen Sproßteile und Blätter der Kulturpflanzen von der Spritzbrühe nicht getroffen werden, wohl aber uner-. wünschte Pflanzen, die sich unter diesen befinden.Known herbicidal active ingredients were used for comparison in the following experiments. Methyl-N- (3- (N '- (3'-methylphenylcarbamoyloxy) -phenyl) -carbamate and ethyl-N- (N'-phenylcarbamoyloxy) -phenyl) -carbamate (DT-AS 15 67 151) are characterized by their, albeit different, activity against broad-leaved unwanted plants with a considerable degree of tolerance for sugar beet. As is well known, however, there are differences here, since methyl N- (3- (N '- (3'-methylphenylcarbamoyloxy) phenyl) carbamate has an even more favorable selectivity in this culture than the second compound of this type mentioned above 3-Isopropyl-2,1,3-benzothiadiazinon (4) -2,2-dioxide (DT-AS 15 42 836) has another application area.With this compound various broad-leaved weeds in soybeans, peanuts, cereals, maize and some vegetables are used However, there are still gaps in activity here Methyl-N- (3-N'-methyl-N'-phenyl-carbamoyl-oxy) -phenyl) -earbamate shows hardly any crop plant selectivity for its class of herbicidal activity, which is why the compound, for example for soybeans, only recommended for post-leaf spraying (Arndt, F. and G. Boroschewsky: New Selective Herbicides - VIII International Plant Protection Congress, Reports and Information, Section III Chemical Control, Part I, Moskow 1975, pp. 42-49 ). Here, the young shoots and leaves of the crops should not be hit by the spray mixture, but they should be. wanted plants that are among them.

Beispiele zur herbiziden Wirkung neuer schwefelhaltiger DiurethaneExamples of the herbicidal activity of new sulfur-containing diurethanes

Zahlreiche Testergebnisse beweisen die guten herbiziden Eigenschaften der neuen Verbindungen. Sie werden hinsichtlich ihrer herbiziden Potenz und ihrer Selektivität in Kulturpflanzen anhand der biologischen Wirkung durch die folgenden Versuche charakterisiert:Numerous test results prove the good herbicidal properties of the new compounds. They are characterized in terms of their herbicidal potency and their selectivity in crop plants based on their biological action by the following experiments:

GewächshausversucheGreenhouse trials

Plastikblumentöpfe von 300 cm3 Inhalt wurden mit lehmigem Sand gefüllt und mit den Testpflanzen nach Arten getrennt bestückt. Hierbei handelt es sich vorwiegend um die Einsaat von Samen oder auch um ein Verpflanzen bei vegetativ vermehrten Arten. Die Wirkstoffe wurden in Wasser als Verteilungsmittel suspendiert oder emulgiert und mittels feinverteilender Düsen bei Nachauflaufanwendung auf die Blätter der Testpflanzen und die noch bloß liegende Erdoberfläche gespritzt. Für die Blattbehandlung zog man die Pflanzen je nach Wuchsform in den Versuchsgefäßen erst bis zu einer Höhe von 3 bis 10 cm an und behandelte sie danach. Den Temperaturansprüchen der Testpflanzen kam man insofern entgegen, daß man sie in kühleren oder wärmeren Sektionen der Gewächshaus- anlagen.aufstellte. Die Versuchsperiode dauerte 2 bis 4 Wochen. Während dieser Zeit wurden die Pflanzen gepflegt und ihre Reaktion auf die einzelnen Behandlungen ausgewertet. Die Aufwandmengen der Prüfsubstanzen gelten als kg/ha Aktivsubstanz. Für die Auswertung diente eine Bonitierungsskala von 0 bis 100. Dabei bedeutete 0 = keine Schädigung, 100 = Absterben der Pflanzen.Plastic flower pots with a content of 300 cm 3 were filled with loamy sand and equipped with the test plants according to species. This mainly involves sowing seeds or transplanting vegetatively propagated species. The active ingredients were suspended or emulsified in water as a distribution medium and sprayed onto the leaves of the test plants and the still exposed soil surface by means of finely distributing nozzles in post-emergence application. For the leaf treatment, the plants were first grown to a height of 3 to 10 cm in the test vessels, depending on the growth habit, and then treated. The temperature requirements of the test plants were met in that they were set up in cooler or warmer sections of the greenhouse systems. The trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their reaction to the individual treatments evaluated. The application rates of the test substances are considered to be kg / ha of active substance. A rating scale from 0 to 100 was used for the evaluation. 0 = no damage, 100 = death of the plants.

ErgebnisResult

Das Zahlenmaterial in den beigefügten Tabellen veranschaulicht die Wirkung der Wirkstoffe bei Blattbehandlung nach dem Auflaufen von Kulturpflanzen und unerwünschten Pflanzen (Tab. 2 bis 12). Bemerkenswert ist hierbei, daß die neuen Verbindungen bezüglich der herbiziden Aktivität und des Wirkungsspektrums zu den als Vergleichsmittel herangezogenen Diurethanen hin tendieren. Die Schwerpunkte in der Selektivität für Kulturpflanzen sind jedoch andere. Das läßt sich am Beispiel Sojabohnen und Getreide vortrefflich demonstrieren. Bei diesen Kulturen werden Verträglichkeitsgrade erreicht, welche dem dafür bekannten 3-Isopropyl-2,1,3-ben- zothiadiazinon(4)-2,2-dioxid ebenbürtig sind (Tab. 5, 6.). Daneben existiert eine Reihe von Kulturpflanzen, deren Toleranz gerade gegenüber den erfindungsgemäßen Verbindungen hervorsticht, während die geprüften Vergleichsmittel ungeeignet sind (Tab. 2, 4, 5).The figures in the attached tables illustrate the effect of the active ingredients in leaf treatment after emergence of crop plants and undesirable plants (Tab. 2 to 12). It is noteworthy here that the new compounds, with regard to the herbicidal activity and the spectrum of activity, tend towards the diurethanes used as comparative agents. However, the focus in selectivity for crops is different. This can be demonstrated excellently using the example of soybeans and cereals. With these crops, levels of tolerance are achieved which are on a par with the known 3-isopropyl-2,1,3-benzothiadiazinon (4) -2,2-dioxide (Tab. 5, 6.). In addition, there are a number of crop plants, the tolerance of which particularly stands out for the compounds according to the invention, while the tested comparison agents are unsuitable (Tab. 2, 4, 5).

Als Applikationsmethode können zwar das Einbringen in den Boden oder die Behandlung der Bodenoberfläche in Betracht gezogen werden, aber die Behandlung aufgelaufener Pflanzen verdient den Vorzug. Auch Spezialanwendungen wie die Unterblattspritzung (post directed, lay-ba) kommen in Frage. Hierbei wird der Spritzstrahl so gelenkt, daß die Blätter aufgelaufener, empfindlicher Kulturpflanzen nach Möglichkeit-nicht getroffen werden, während die Mittel auf die darunterliegende Bodenfläche oder dort wachsende unerwünschte Pflanzen gelangen.As an application method, it is possible to consider placing it in the soil or treating the soil surface, but the treatment of emerged plants deserves preference. Special applications such as under-sheet spraying (post-directed, lay-ba) are also possible. Here, the spray jet is directed so that the leaves of accumulated, sensitive crops are not hit, if possible, while the agents get onto the underlying surface or undesired plants growing there.

In Anbetracht der Vielseitigkeit der Applikationsmethoden können die erfindungsgemäßen Mittel oder dieser enthaltende Mischungen außer bei den in den Tabellen aufgeführten Nutzpflanzen noch in einer weiteren großen Zahl von Kulturen zur Beseitigung unerwünschten Pflanzenwuchses eingesetzt werden. 1In view of the versatility of the application methods, the agents according to the invention or mixtures containing them can be used in a further large number of crops in addition to the useful plants listed in the tables to eliminate undesired plant growth. 1

Die Anwendungskonzentrationen können dabei von 0,1 bis 15 kg/ha und mehr betragen je nach dem Bekämpfungsobjekt.The application concentrations can range from 0.1 to 15 kg / ha and more, depending on the control object.

Im einzelnen seien folgende Nutzpflanzen genannt:

Figure imgb0048
Figure imgb0049
Figure imgb0050
Figure imgb0051
 The following useful plants are mentioned:
Figure imgb0048
Figure imgb0049
Figure imgb0050
Figure imgb0051

Zur weiteren Verbreiterung des Wirkungsspektrums der neuen Einzelsubstanzen, zur Erzielung synergistischer Effekte oder zum Verbessern der Residualwirkung über den Boden lassen sich die neuen Verbindungen untereinander mischen oder zahlreiche andere herbizide oder wachstumsregulierende Verbindungen als Mischungs- und Kombinationspartner heranziehen. Je nach Einsatzgebiet und Bekämpfungsvorhaben bieten sich nachstehende Verbindungen oder chemisch ähnliche Derivate als Partner an:

Figure imgb0052
Figure imgb0053
Figure imgb0054
Figure imgb0055
Figure imgb0056
und Salze
Figure imgb0057
Figure imgb0058
Figure imgb0059
Figure imgb0060
Figure imgb0061
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Figure imgb0063
Figure imgb0064
Figure imgb0065
Figure imgb0066
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Figure imgb0084
Figure imgb0085
Figure imgb0086
Figure imgb0087
Figure imgb0088
Figure imgb0089
Figure imgb0090
Figure imgb0091
Figure imgb0092
und Salze X = NO2 CN
Figure imgb0093
Figure imgb0094
Figure imgb0095
Figure imgb0096
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Figure imgb0098
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Figure imgb0100
Figure imgb0101
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Figure imgb0108
Figure imgb0109
Figure imgb0110
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Figure imgb0112
Figure imgb0113
Figure imgb0114
Figure imgb0115
und Salze, Ester
Figure imgb0116
Figure imgb0117
Figure imgb0118
Figure imgb0119
Figure imgb0120
und Na-Salz
Figure imgb0121
Figure imgb0122
Figure imgb0123
Figure imgb0124
Figure imgb0125
Figure imgb0126
und Salze, Ester
Figure imgb0127
Figure imgb0128
Figure imgb0129
Figure imgb0130
Figure imgb0131
Figure imgb0132
Figure imgb0133
Figure imgb0134
und Salze, Ester
Figure imgb0135
und Salze, Ester
Figure imgb0136
Figure imgb0137
und Salze
Figure imgb0138
Figure imgb0139
Figure imgb0140
Figure imgb0141
Salze und Ester
Figure imgb0142
R1 OH CH3
Figure imgb0143
Figure imgb0144
Figure imgb0145
und Salze und Ester
Figure imgb0146
und Salze und Ester
Figure imgb0147
Figure imgb0148
 To further broaden the spectrum of activity of the new individual substances, to achieve synergistic effects or to improve the residual effect via the soil, the new compounds can be mixed with one another or numerous other herbicidal or growth-regulating compounds can be used as mixing and combination partners. Depending on the area of application and control projects, the following compounds or chemically similar derivatives are suitable as partners:
Figure imgb0052
Figure imgb0053
Figure imgb0054
Figure imgb0055
Figure imgb0056
 and salts
Figure imgb0057
Figure imgb0058
Figure imgb0059
Figure imgb0060
Figure imgb0061
Figure imgb0062
Figure imgb0063
Figure imgb0064
Figure imgb0065
Figure imgb0066
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Figure imgb0085
Figure imgb0086
Figure imgb0087
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Figure imgb0089
Figure imgb0090
Figure imgb0091
Figure imgb0092
 and salts X = NO 2 CN
Figure imgb0093
Figure imgb0094
Figure imgb0095
Figure imgb0096
Figure imgb0097
Figure imgb0098
Figure imgb0099
Figure imgb0100
Figure imgb0101
Figure imgb0102
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Figure imgb0109
Figure imgb0110
Figure imgb0111
Figure imgb0112
Figure imgb0113
Figure imgb0114
Figure imgb0115
 and salts, esters
Figure imgb0116
Figure imgb0117
Figure imgb0118
Figure imgb0119
Figure imgb0120
 and Na salt
Figure imgb0121
Figure imgb0122
Figure imgb0123
Figure imgb0124
Figure imgb0125
Figure imgb0126
 and salts, esters
Figure imgb0127
Figure imgb0128
Figure imgb0129
Figure imgb0130
Figure imgb0131
Figure imgb0132
Figure imgb0133
Figure imgb0134
 and salts, esters
Figure imgb0135
 and salts, esters
Figure imgb0136
Figure imgb0137
 and salts
Figure imgb0138
Figure imgb0139
Figure imgb0140
Figure imgb0141
 Salts and esters
Figure imgb0142
 R 1 OH CH 3
Figure imgb0143
Figure imgb0144
Figure imgb0145
 and salts and esters
Figure imgb0146
 and salts and esters
Figure imgb0147
Figure imgb0148

Außerdem ist es möglich, die neuen erfindungsgemäßen Verbindungen allein oder in Kombination mit anderen Herbiziden' auch noch mit weiteren Pflanzenschutzmitteln gemischt gemeinsam auszubringen. Hierbei ist an Mittel zur Bekämpfung von Schädlichen oder phytopathogenen Pilzen bzw. Bakterien zu denken. Von Interesse ist ferner die Mischbarkeit mit Mineralölsalzen, welche zur Behebung von Ernährungs- oder Spurenelementmängeln eingesetzt werden.It is also possible to apply the new compounds according to the invention, alone or in combination with other herbicides, in a mixture with other crop protection agents. Here, means to combat harmful or phytopathogenic fungi or bacteria should be considered. Also of interest is the miscibility with mineral oil salts, which are used to remedy nutritional or trace element deficiencies.

Zur Aktivierung der herbiziden Wirkung können Netz- und Haftmittel sowie nichtphytotoxische öle zugesetzt werden.To activate the herbicidal effect, wetting agents and adhesives as well as non-phytotoxic oils can be added.

Die Anwendung erfolgt z.B. in Form von direkt versprühbaren Lösungen, Pulvern, Suspensionen oder Dispersionen, Emulsionen, öldispersionen, Pasten, Stäubemitteln, Streumitteln, Granulaten, durch Versprühen, Vernebeln, Verstäuben, Verstreuen oder Gießen. Die Anwendungsformen richten sich nach den Verwendungszwecken; sie sollen in jedem Fall möglichst die feinste Verteilung der erfindungsgemäßen Wirkstoffe gewährleisten.The application is e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprinkling agents, granules, by spraying, atomizing, dusting, scattering or pouring. 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.

Zur Herstellung von direkt versprühbaren Lösungen, Emulsionen, Pasten und öldispersionen kommen Mineralölfraktionen von mittlerem bis hohem Siedepunkt, wie Kerosin oder Dieselöl, ferner Kohlenteeröle usw., sowie öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, zum Beispiel Benzol, Toluol, Xylol, Paraffin, Tetrahydronaphthalin, alkylierte Naphthaline oder deren Derivate, z.B. Methanol, Äthanol, Propanol, Butanol, Chloroform, Tetrachlorkohlenstoff, Cyclohexanol, Cyclohexanon, Chlorbenzol, Isophoron usw., stark polare Lösungsmittel, z.B. Dimethylformamid, Dimethylsulfoxid, N-Methylpyrrolidon, Wasser usw. in Betracht.To produce directly sprayable solutions, emulsions, pastes and oil dispersions, mineral oil fractions from medium to high boiling points, such as kerosene or diesel oil, furthermore coal tar oils etc., as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example benzene, toluene, Xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, e.g. Methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., strongly polar solvents, e.g. Dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. into consideration.

Wäßrige Anwendungsformen können aus Emulsionskonzentrationen, Pasten oder netzbaren Pulvern (Spritzpulvern), öldispersionen durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder öldispersionen können die Substanzen als solche oder in einem öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgier- mittel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind.Aqueous application forms can be prepared from emulsion concentrations, pastes or wettable powders (wettable powders), oil dispersions by adding water. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, wetting agents, adhesives, dispersants or emulsifiers, and possibly solvents or oil, can also be prepared from active substance and are suitable for dilution with water.

An oberflächenaktiven Stoffen sind zu nennen: Alkali-, Erdalkali-, Ammoniumsalze von Ligninsulfonsäure, Naphthalinsulfonsäure, Phenolsulfonsäuren, Alkylarylsulfonate, Alkylsulfate, Alkylsulfonate, Alkali- und Erdalkalisalze der Dibutylnaphthalinsulfonsäure, Lauryläthersulfat, Fettalkoholsulfate, fettsaure Alkali- und Erdalkalisalze, Salze sulfatierter Hexadecanole, Heptadecanole, Octadecanole, Salze von sulfatiertem Fettalkoholglykoläther, Kondensationsprodukte von sulfoniertem Naphthalin und Naphthalinderivaten mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsäuren mit Phenol und Formaldehyd, Polyoxyäthylenoctylphenoläther, äthoxyliertes Isooctylphenol, Octylphenol, Nonylphenol, Alkylphenolpolyglykoläther, Tributylphenylpolyglykol- äther, Isotridecylalkohol, Fettalkoholäthylenoxid-Kondensate, äthoxyliertes Rizinusöl, Polyoxyäthylenalkyläther, äthoxyliertes Polyoxypropylen, Laurylalkoholpolyglykolätheracetal, Sorbitester, Lignin, Sulfitablaugen und Methylcellulose.Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, fatty acid alkali and alkaline earth metal salts, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, Polyoxyäthylenoctylphenoläther, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, Tributylphenylpolyglykol- ether, isotridecyl alcohol, Fettalkoholäthylenoxid condensates, ethoxylated Castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester, lignin, sulfite liquor and methy cellulose.

Pulver-, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermahlen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden.Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogengranulate, können durch Bindung der Wirkstoffe an feste Trägerstoffe hergestellt werden. Feste Trägerstoffe sind z.B. Mineralerden, wie Silicagel, Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Attaclay, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Kalcium-und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie z.B. Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte, wie Getreidemehle, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver und andere feste Trägerstoffe. L 1Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are, for example, mineral earths, such as silica gel, silicas, silica gels, silicates, talc, kaolin, attack clay, limestone, lime, chalk, boluses, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as For example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers. L 1

Die Formulierungen enthalten zwischen 0,1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 Gewichtsprozent.The formulations contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90 percent by weight.

Beispiel 4Example 4

Man vermischt 90 Gewichtsteile der Verbindung 2 mit 10 Gewichtsteilen N-Methyl-,t-pyrrolidon,und erhält eine Lösung, die zur Anwendung in Form kleinster Tropfen geeignet ist.90 parts by weight of compound 2 are mixed with 10 parts by weight of N-methyl-, t-pyrrolidone, and a solution is obtained which is suitable for use in the form of tiny drops.

Beispiel 5Example 5

20 Gewichtsteile der Verbindung 8 werden in einer Mischung gelöst, die aus 80 Gewichtsteilen Xylol, 10 Gewichtsteilen des Anlagerungsproduktes von 8 bis 10 Mol Äthylenoxid an 1 Mol ölsäure-N-monoäthanolamid, 5 Gewichtsteilen.Calciumsalz der Dodecylbenzolsulfonsäure und 5 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Äthylenoxid an 1 Mol Ricinusöl besteht. Durch Ausgießen und feines Verteilen der Lösung in 100 000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gewichtsprozent des Wirkstoffs enthält.20 parts by weight of compound 8 are dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 mol Ethylene oxide consists of 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

Beispiel 6Example 6

20 Gewichtsteile der Verbindung 13 werden in einer Mischung gelöst, die aus 40 Gewichtsteilen Cyclohexanon, 30 Gewichtsteilen Isobutanol, 20 Gewichtsteilen des Anlagerungsproduktes von 7 Mol Äthylenoxid an 1 Mol Isooctylphenol und 10 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Äthylenoxid an 1 Mol Ricinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100 000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gewichtsprozent des Wirkstoffs enthält.20 parts by weight of compound 13 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

Beispiel 7Example 7

20 Gewichtsteile der Verbindung 23 werden in einer Mischung gelöst, die aus 25 Gewichtsteilen Cyclohexanol, 65 Gewichtsteilen einer Mineralölfraktion vom Siedepunkt 210 bis 280°C und 10 Gewichtsteilen des Anlagerungsproduktes von 40 Mol Äthylenoxid an 1 Mol Ricinusöl besteht. Durch Eingießen und feines Verteilen der Lösung in 100 000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,02 Gewichtsprozent des Wirkstoffs enthält.20 parts by weight of compound 23 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction with a boiling point of 210 to 280 ° C. and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

Beispiel 8Example 8

20 Gewichtsteile des Wirkstoffs 7 mit 3 Gewichtsteilen des Natriumsalzes der Diisobutylnaphthalin-α-sulfonsäure, 17 Gewichtsteilen des Natriumsalzes einer Ligninsulfonsäure aus einer Sulfit-Ablauge und 60 Gewichtsteilen pulverförmigem Kieselsäuregel gut vermischt und in einer Hammermühle vermahlen. Durch feines Verteilen der Mischung in 20 000 Gewichtsteilen Wasser erhält man eine Spritzbrühe, die 0,1 Gewichtsprozent des Wirkstoffs enthält.20 parts by weight of active ingredient 7 with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel are mixed well and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained which contains 0.1% by weight of the active ingredient.

Beispiel 9Example 9

3 Gewichtsteile der Verbindung 46 werden mit 97 Gewichtsteilen feinteiligem Kaolin innig vermischt. Man erhält auf diese Weise ein Stäubemittel, das 3 Gewichtsprozent des Wirkstoffs enthält.3 parts by weight of compound 46 are intimately mixed with 97 parts by weight of finely divided kaolin. In this way a dust is obtained which contains 3 percent by weight of the active ingredient.

Beispiel 10Example 10

30 Gewichtsteile der Verbindung 4 werden mit einer Mischung aus 92 Gewichtsteilen pulverförmigem Kieselsäuregel und 8 Gewichtsteilen Paraffinöl, das auf die Oberfläche dieses Kieselsäuregels gesprüht wurde, innig vermischt. Man erhält L J auf diese Weise eine Aufbereitung des Wirkstoffs mit guter Haftfähigkeit.30 parts by weight of compound 4 are intimately mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. L J is obtained in this way a preparation of the active ingredient with good adhesiveness.

Beispiel 11Example 11

40 Gewichtsteile des Wirkstoffs 7 werden mit 10 Teilen Natriumsalz eines Phenolsulfonsäure-harnstoff-formaldehyd-Kondensats, 2 Teilen Kieselgel und 48 Teilen Wasser innig vermischt. Man erhält eine stabile wäßrige Dispersion. Durch Verdünnen mit 100 000 Gewichtsteilen Wasser erhält man eine wäßrige Dispersion, die 0,04 Gewichtsprozent Wirkstoff enthält.40 parts by weight of active ingredient 7 are intimately mixed with 10 parts of sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water. A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion which contains 0.04% by weight of active ingredient.

Beispiel 12Example 12

20 Teile des Wirkstoffs 2 werden mit 2 Teilen Calciumsalz der Dodecylbenzolsulfonsäure, 8 Teilen Fettalkohol-polyglykoläther, 2 Teilen Natriumsalz eines Phenolsulfonsäureharnstoff-formaldehyd-Kondensats und 68 Teilen eines paraffinischen Mineralöls innig vermischt. Man erhält eine stabile ölige Dispersion.

Figure imgb0149
Figure imgb0150
Figure imgb0151
Figure imgb0152
Figure imgb0153
Figure imgb0154
Figure imgb0155
Figure imgb0156
Figure imgb0157
Figure imgb0158
Figure imgb0159
Figure imgb0160
Figure imgb0161
Figure imgb0162
Figure imgb0163
Figure imgb0164
Figure imgb0165
Figure imgb0166
Figure imgb0167
 20 parts of active ingredient 2 are intimately mixed with 2 parts of calcium salt of dodecylbenzenesulfonic acid, 8 parts of fatty alcohol polyglycol ether, 2 parts of sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
Figure imgb0149
Figure imgb0150
Figure imgb0151
Figure imgb0152
Figure imgb0153
Figure imgb0154
Figure imgb0155
Figure imgb0156
Figure imgb0157
Figure imgb0158
Figure imgb0159
Figure imgb0160
Figure imgb0161
Figure imgb0162
Figure imgb0163
Figure imgb0164
Figure imgb0165
Figure imgb0166
Figure imgb0167

Claims (4)

1. Diurethan der allgemeinen Formel
Figure imgb0168
in der Z den Rest
Figure imgb0169
und Y den Rest
Figure imgb0170
bedeutet, wobei Z immer verschieden ist von Y und R 1 und R2 jeweils unabhängig voneinander Wasserstoff, Alkyl, Alkoxyalkyl, Alkoxycarbonylalkyl, Halogenalkyl, gegebenenfalls durch Alkyl oder Halogen substituiertes Benzyl, R3 und R4 jeweils unabhängig voneinander unsubstituiertes Alkyl oder durch Halogen oder Alkoxy oder substituiertes oder unsubstituiertes Aryl substituiertes Alkyl, gegebenenfalls durch Halogen substituiertes Alkenyl, gegebenenfalls durch Halogen oder Alkoxy substituiertes Alkinyl, gegebenenfalls durch Alkyl substituiertes Cycloalkyl, Bicycloalkyl, Tricycloalkyl; einen Phenylring mit ankondensiertem Ringsystem, Phenyl, ein- oder mehrfach substituiertes Phenyl, mit den Substituenten Alkyl, Halogenalkyl, Alkoxyalkyl, Alkoxycarbonylalkyl, Alkoxycarbonylalkoxy, Cycloalkyl, Halogen, Alkoxy, Halogenalkoxy, Nitro, Amino, Aryl, Aryloxy, Thiocyanato, Cyano, NH-COR5, NHCOOR5, NHCONR5R6, COOR5,
Figure imgb0171
CONR5R6, SR5, SO2R5, OSO2R5, COR5, S02NR5R6, wobei R5 und R6 jeweils unabhängig voneinander Wasserstoff oder einen gegebenenfalls ein- oder mehrfach substituierten Arylrest bedeuten oder einer der beiden Substituenten die für R1 genannten Bedeu- tungen hat und X Wasserstoff, Alkyl, Halogenalkyl, Alkoxy, Halogen, Nitro oder Amino, n die Zahlen 1 - 4 und A, B, D, E jeweils unabhängig voneinander Sauerstoff oder Schwefel bedeuten, wobei nicht alle Reste A, B, D, E gleichzeitig Sauerstoff und mindestens einer dieser Reste immer Schwefel bedeutet.1. diurethane of the general formula
Figure imgb0168
 in the Z the rest
Figure imgb0169
 and Y the rest
Figure imgb0170
 means, where Z is always different from Y and R 1 and R 2 each independently of one another hydrogen, alkyl, alkoxyalkyl, alkoxycarbonylalkyl, haloalkyl, benzyl optionally substituted by alkyl or halogen, R 3 and R4 in each case independently of one another unsubstituted alkyl or by halogen or alkoxy or substituted or unsubstituted aryl-substituted alkyl, optionally substituted by halogen-substituted alkenyl, optionally substituted by halogen or alkoxy, optionally substituted by alkyl or cycloalkyl, bicycloalkyl, tricycloalkyl; a phenyl ring with a condensed ring system, phenyl, mono- or polysubstituted phenyl, with the substituents alkyl, haloalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkoxy, cycloalkyl, halogen, alkoxy, haloalkoxy, nitro, amino, aryl, aryloxy, thiocyanato, cyano, NH- COR 5 , NHCOOR5, NHCONR 5 R 6 , COOR 5 ,
Figure imgb0171
 CONR 5 R 6 , SR 5 , SO 2 R 5 , OSO 2 R 5 , COR 5 , S02 NR 5 R 6 , where R 5 and R 6 each independently represent hydrogen or an optionally mono- or polysubstituted aryl radical or one the two substituents have the meanings given for R 1 and X is hydrogen, alkyl, haloalkyl, alkoxy, halogen, nitro or amino, n is the numbers 1-4 and A, B, D, E each independently represent oxygen or sulfur, where not all radicals A, B, D, E simultaneously mean oxygen and at least one of these radicals always means sulfur. 2. Herbizid, enthaltend ein Diurethan der Formel
Figure imgb0172
in der Z den Rest
Figure imgb0173
und Y den Rest
Figure imgb0174
bedeutet, wobei Z immer verschieden ist von Y und R1 und R2 jeweils unabhängig voneinander Wasserstoff, Alkyl, Alkoxyalkyl, Alkoxycarbonylalkyl, Halögenalkyl, gegebenenfalls durch Alkyl oder Halogen substituiertes Benzyl, R3 und R4 jeweils unabhängig voneinander unsubstituiertes Alkyl oder durch Halogen oder Alkoxy oder substituiertes oder unsubstituiertes Aryl substituiertes Alkyl, gegebenenfalls durch Halogen substituiertes Alkenyl, gegebenenfalls durch Halogen oder Alkoxy substituiertes Alkinyl, gegebenenfalls durch Alkyl substituiertes Cycloalkyl, Bicycloalkyl, Tricycloalkyl; einen Phenylring mit ankondensiertem Ringsystem, Phenyl, ein- oder mehrfach substituiertes Phenyl, mit den Substituenten Alkyl, Halogenalkyl, Alkoxyalkyl, Alkoxycarbonylalkyl, Alkoxycarbonylalkoxy, Cycloalkyl, Halogen, Alkoxy, Halogenalkoxy, Nitro, Amino, Aryl, Aryloxy, Thlocyanato, Cyano, NH-COR5, NHCOOR5, NHCONR5R6, COOR5,
Figure imgb0175
CONR5R6, SR5, SO2R5, OSO2R5, COR5, SO2NR5R6, wobei R5 und R6 jeweils unabhängig voneinander Wasserstoff oder einen gegebenenfalls ein- oder mehrfach substituierten Arylrest bedeuten oder einer der beiden Substituenten die für R1 genannten Bedeutungen hat und X Wasserstoff, Alkyl, Halogenalkyl, Alkoxy, Halogen, Nitro oder Amino, n die Zahlen 1 - 4 und A, B, D, E jeweils unabhängig voneinander Sauerstoff oder Schwefel'bedeuten, wobei nicht alle Reste A, B., D, E gleichzeitig Sauerstoff und mindestens einer dieser Reste immer Schwefel bedeutet.2. Herbicide containing a diurethane of the formula
Figure imgb0172
 in the Z the rest
Figure imgb0173
 and Y the rest
Figure imgb0174
 means, where Z is always different from Y and R 1 and R 2 each independently of one another hydrogen, alkyl, alkoxyalkyl, alkoxycarbonylalkyl, halogen alkyl, benzyl optionally substituted by alkyl or halogen, R 3 and R 4 each independently of one another unsubstituted alkyl or by halogen or Alkoxy or substituted or unsubstituted aryl substituted alkyl, optionally substituted by halogen alkenyl, optionally substituted by halogen or alkoxy alkynyl, optionally substituted by alkyl cycloalkyl, bicycloalkyl, tricycloalkyl; a phenyl ring with a condensed ring system, phenyl, mono- or polysubstituted phenyl, with the substituents alkyl, haloalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkoxy, cycloalkyl, halogen, alkoxy, haloalkoxy, nitro, amino, aryl, aryloxy, thlocyanato, cyano, NH- COR 5 , NHCOOR 5 , NHCONR 5 R 6 , COOR 5 ,
Figure imgb0175
 CONR 5 R 6 , SR 5 , SO 2 R 5 , OSO 2 R 5 , COR 5 , SO 2 NR 5 R 6 , where R 5 and R 6 each independently represent hydrogen or an optionally mono- or polysubstituted aryl radical or one of the two substituents has the meanings given for R 1 and X is hydrogen, alkyl, haloalkyl, alkoxy, halogen , nitro or amino, n is the numbers 1-4, and a, B, D, e are each independently oxygen or sulfur 'mean wherein not all of the radicals a, B, D, e simultaneously oxygen and at least one of these radicals always denotes sulfur . 3. Verfahren zur Bekämpfung unerwünschten Pflanzenwuchses durch Behandlung mit einem Diurethan der Formel
Figure imgb0176
in der Z den Rest
Figure imgb0177
und Y den Rest
Figure imgb0178
bedeutet, wobei Z immer verschieden ist von Y und R 1 und R2 jeweils unabhängig voneinander Wasserstoff, Alkyl, Alkoxyalkyl, Alkoxycarbonylalkyl, Halogenalkyl, gegebenenfalls durch Alkyl oder Halogen substituiertes Benzyl, R3 und R4 jeweils unabhängig voneinander unsubstituiertes Alkyl oder durch Halogen oder Alkoxy oder substituiertes oder unsubstituiertes Aryl substituiertes Alkyl, gegebenenfalls durch Halogen substituiertes Alkenyl, gegebenenfalls durch Halogen oder Alkoxy substituiertes Alkinyl, gegebenenfalls durch Alkyl substituiertes Cycloalkyl, Bicycloalkyl, Tricycloalkyl; einen Phenylring mit ankondensiertem Ringsystem, Phenyl, ein- oder mehrfach substituiertes Phenyl, mit den Substituenten Alkyl, Halogenalkyl, Alkoxyalkyl, Alkoxycarbonylalkyl, Alkoxycarbonylalkoxy, Cycloalkyl, Halogen, Alkoxy, Halogenalkoxy, Nitro, Amino, Aryl, Aryloxy, Thiocyanato, Cyano, NH-COR5, NHCOOR 5, NHCONR 5 R 6, COOR5,
Figure imgb0179
CONR5R6, SR5, S02R5, OSO2R5, COR5, S02NR5R6, wobei R5 und R6 jeweils unabhängig voneinander Wasserstoff oder einen gegebenenfalls ein- oder mehrfach substituierten Arylrest bedeuten oder einer der beiden Substituenten die für R1 genannten Bedeutungen hat und X Wasserstoff, Alkyl, Halogenalkyl, Alkoxy, Halogen, Nitro oder Amino, n die Zahlen 1 - 4 und A, B, D, E jeweils unabhängig voneinander Sauerstoff oder Schwefel bedeuten, wobei nicht alle Reste A, B, D, E gleichzeitig Sauerstoff und mindestens einer dieser Reste immer Schwefel bedeutet.3. A method for controlling undesirable plant growth by treatment with a diurethane of the formula
Figure imgb0176
 in the Z the rest
Figure imgb0177
 and Y the rest
Figure imgb0178
 means, where Z is always different from Y and R 1 and R 2 each independently of one another hydrogen, alkyl, alkoxyalkyl, alkoxycarbonylalkyl, haloalkyl, optionally substituted by alkyl or halogen, R 3 and R 4 each independently of one another unsubstituted alkyl or by halogen or Alkoxy or substituted or unsubstituted aryl substituted alkyl, optionally substituted by halogen alkenyl, optionally substituted by halogen or alkoxy alkynyl, optionally substituted by alkyl cycloalkyl, bicycloalkyl, tricycloalkyl; a phenyl ring with a fused-on ring system, phenyl, mono- or polysubstituted phenyl, with the substituents alkyl, haloalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkoxy, cycloalkyl, Halogen, alkoxy, haloalkoxy, nitro, amino, aryl, aryloxy, thiocyanato, cyano, NH-COR 5 , NH C OO R 5 , NHCONR 5 R 6 , COOR 5 ,
Figure imgb0179
 CONR 5 R 6 , SR 5 , S0 2 R 5 , OSO 2 R 5 , COR 5 , S02 NR 5 R 6 , where R 5 and R 6 each independently represent hydrogen or an optionally mono- or polysubstituted aryl radical or one of the both substituents have the meanings given for R 1 and X is hydrogen, alkyl, haloalkyl, alkoxy, halogen, nitro or amino, n is the numbers 1-4 and A, B, D, E each independently represent oxygen or sulfur, but not all Residues A, B, D, E simultaneously mean oxygen and at least one of these residues always means sulfur. 4. Verfahren zur Herstellung eines Diurethans der Formel
Figure imgb0180
in der Z den Rest
Figure imgb0181
und Y den Rest
Figure imgb0182
bedeutet, wobei Z immer verschieden ist von Y und R1 und R2 jeweils unabhängig voneinander Wasserstoff, Alkyl, Alkoxyalkyl, Alkoxycarbonylalkyl, Halogenalkyl, gegebenenfalls durch Alkyl oder Halogen substituiertes Benzyl, R3 und R4 jeweils unabhängig voneinander unsubstituiertes Alkyl oder durch Halogen oder Alkoxy oder substituiertes oder unsubstituiertes Aryl substituiertes Alkyl, gegebenenfalls durch Halogen substituiertes Alkenyl, gegebenenfalls durch Halogen oder Alkoxy substituiertes Alkinyl, gegebenenfalls durch Alkyl substituiertes Cycloalkyl, Bicycloalkyl, Tricyc- loalkyl; einen Phenylring mit ankondensiertem Ringsystem, Phenyl, ein- oder mehrfach substituiertes Phenyl, mit den Substituenten Alkyl, Halogenalkyl, Alkoxyalkyl, Alkoxycarbonylalkyl, Alkoxycarbonylalkoxy, Cycloalkyl, Halogen, Alkoxy, Halogenalkoxy, Nitro, Amino, Aryl, Aryloxy, Thiocyanato, Cyano, NH-COR5, NHCOOR5, NHCONR5R6, COOR5,
Figure imgb0183
CONR5R6, SR5, SO2R5, OSO2R5, COR5, SO2NR5R6, wobei R5 und R6 jeweils unabhängig voneinander Wasserstoff oder einen gegebenenfalls ein- oder mehrfach substituierten Arylrest bedeuten oder einer der beiden Substituenten die für R1 genannten Bedeutungen hat und X Wasserstoff, Alkyl, Halogenalkyl, Alkoxy, Halogen, Nitro oder Amino, n die Zahlen 1 - 4 und A, B, D, E jeweils unabhängig voneinander Sauerstoff oder Schwefel bedeuten, wobei nicht alle Reste A, B, D, E gleichzeitig Sauerstoff und mindestens einer dieser Reste immer Schwefel bedeutet, dadurch gekennzeichnet, daß man ein Phenylaminourethan der Formel
Figure imgb0184
in der R 1, R2, R3, A, B, X und n die oben genannte Bedeutung haben, umsetzt mit einem Halogenameisensäureester der Formel
Figure imgb0185
in der R4, D und E die oben genannte Bedeutungen haben und ein Halogenatom bedeutet oder mit Schwefelkohlenstoff Hal und einem Alkylierungsmittel bei einer Temperatur im Bereich von -20° bis +150°C umsetzt.
Figure imgb0186
Figure imgb0187
Figure imgb0188
Figure imgb0189
Figure imgb0190
Figure imgb0191
Figure imgb0192
Figure imgb0193
Figure imgb0194
Figure imgb0195
Figure imgb0196
Figure imgb0197
Figure imgb0198
Figure imgb0199
 4. Process for the preparation of a diurethane of the formula
Figure imgb0180
 in the Z the rest
Figure imgb0181
 and Y the rest
Figure imgb0182
 means, where Z is always different from Y and R 1 and R 2 each independently of one another hydrogen, alkyl, alkoxyalkyl, alkoxycarbonylalkyl, haloalkyl, optionally substituted by alkyl or halogen, R 3 and R 4 each independently of one another unsubstituted alkyl or by halogen or Alkoxy or substituted or unsubstituted aryl-substituted alkyl, optionally substituted by halogen-substituted alkenyl, optionally substituted by halogen or alkoxy, optionally by Alkyl substituted cycloalkyl, bicycloalkyl, tricycloalkyl; a phenyl ring with a condensed ring system, phenyl, mono- or polysubstituted phenyl, with the substituents alkyl, haloalkyl, alkoxyalkyl, alkoxycarbonylalkyl, alkoxycarbonylalkoxy, cycloalkyl, halogen, alkoxy, haloalkoxy, nitro, amino, aryl, aryloxy, thiocyanato, cyano, NH- COR 5 , NHCOOR 5 , NHCONR 5 R 6 , COOR 5 ,
Figure imgb0183
 CONR 5 R 6 , SR 5 , SO 2 R 5 , OSO 2 R 5 , COR 5 , SO 2 NR 5 R 6 , where R 5 and R 6 each independently represent hydrogen or an optionally mono- or polysubstituted aryl radical or one of the two substituents has the meanings given for R 1 and X is hydrogen, alkyl, haloalkyl, alkoxy, halogen, nitro or amino, n is the numbers 1-4 and A, B, D, E each independently represent oxygen or sulfur, but not all radicals A, B, D, E simultaneously mean oxygen and at least one of these radicals always means sulfur, characterized in that a phenylaminourethane of the formula
Figure imgb0184
 in which R 1 , R 2 , R 3 , A, B, X and n have the meaning given above, reacted with a halogen formate of the formula
Figure imgb0185
 in which R 4 , D and E have the meanings given above and represents a halogen atom or react with carbon disulfide Hal and an alkylating agent at a temperature in the range from -20 ° to + 150 ° C.
Figure imgb0186
Figure imgb0187
Figure imgb0188
Figure imgb0189
Figure imgb0190
Figure imgb0191
Figure imgb0192
Figure imgb0193
Figure imgb0194
Figure imgb0195
Figure imgb0196
Figure imgb0197
Figure imgb0198
Figure imgb0199
EP78100050A 1977-06-03 1978-06-01 Diurethanes containing sulphur, process for their preparation and their use as herbicides Expired EP0000030B1 (en)

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JPS5951205A (en) * 1982-06-23 1984-03-24 Toyo Soda Mfg Co Ltd Herbicide containing carbamate derivative
DE19800531A1 (en) * 1998-01-09 1999-07-15 Bayer Ag Process for the preparation of N- (3-amino-4-fluorophenyl) sulfonamides, N- (3-amino-4-fluorophenyl) carboxamides and N- (3-amino-4-fluorophenyl) - carbamates

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