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WO1998008810A1 - Alkylthio-, alkylsulphinyl- and alkylsulphonylcarbamates as herbicides - Google Patents

Alkylthio-, alkylsulphinyl- and alkylsulphonylcarbamates as herbicides Download PDF

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Publication number
WO1998008810A1
WO1998008810A1 PCT/EP1997/004626 EP9704626W WO9808810A1 WO 1998008810 A1 WO1998008810 A1 WO 1998008810A1 EP 9704626 W EP9704626 W EP 9704626W WO 9808810 A1 WO9808810 A1 WO 9808810A1
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Prior art keywords
formula
compound
meanings given
phenyl
give
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French (fr)
Inventor
Hermann Rempfler
Michel Mühlebach
Fredrik Cederbaum
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Novartis AG
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Ciba Geigy AG
Novartis AG
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Priority to AU44556/97A priority Critical patent/AU4455697A/en
Publication of WO1998008810A1 publication Critical patent/WO1998008810A1/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
    • C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C07C309/66—Methanesulfonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/28—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
    • C07C323/43—Y being a hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention relates to novel herbicidally active alkylthio-, alkylsulfinyl and alkylsulfonylcarbamates, processes for their preparation, to compositions which comprise these compounds, and to their use for controlling weeds, in particular in crops of useful plants, or for inhibiting the growth of plants.
  • the present invention thus relates to compounds of the formula I
  • R is halogen, d-C 3 haloalkyl, cyano, nitro or CrC 3 haloalkoxy;
  • Z is hydrogen, halogen or together with R, -0-CF 2 -0-;
  • R is d-Csalkyl or C 3 -C 6 cycloalkyl
  • R 2 and R 3 independently of one another are hydrogen, C ⁇ -C 4 alkyl or C 3 -C 6 cycloalkyl;
  • R 4 is C ⁇ -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl or C 3 - or C 6 -cycloalkenyl, or is
  • C ⁇ -C 4 alkyl C 2 -C € alkenyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl, each of which is substituted by halogen, cyano, C ⁇ alkyl-CO, phenyl-CO, COOR 5 C ⁇ -C 4 alkoxy, C ⁇ -C4haloalkoxy, oxiranyl, dioxolanyl, tetrahydrofuranyl, tetrahydropyranyl, C 3 -C 6 cycioalkyl, halo-C 3 -C 6 -cycioalkyl, phenyl or phenoxy, it being possible for the phenyl group, in turn, to be substituted by halogen, Chalky!, C 1 -C 4 alkoxy, cyano or CrCjhaloalkyl, or is phenyl or phenyl which is substituted by halogen, C ⁇ Caalkyl
  • R 4 together with one of the R 2 groups forms a C 2 -C 6 alkylene bridge
  • R 5 is d-Csalkyl or C 3 -C 6 cycloalkyl, n is the number 1 , 2 or 3 and m is the number 0, 1 or 2, and the diastereomers and enantiomers of these compounds
  • alkyl groups in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl and the various isome ⁇ c pentyl and hexyl groups
  • Alkoxy, alkenyl and alkynyl groups are derived from the abovementioned alkyl groups
  • the alkenyl and alkynyl groups can be mono- or polyunsaturated
  • Halogen is as a rule, fluorine, chlorine, bromine or iodine This also applies analogously to halogen in connection with other meanings such as haloalkyl or halophenyl
  • Cycloalkyl is for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl
  • optically active compounds of the formula I can be obtained from the racemic mixtures by known separation methods, for example HPLC or chromatography on chiral carrier materials, or by synthesis, for example from the corresponding optically active alcohols of the formula II
  • active ingredients of the formula I are to be understood as meaning both the pure optical antipodes and the racemates Unless specific mention is made of the individual optical antipodes, the formula given is to be understood as meaning those racemic mixtures which result from the preparation process given
  • enantiomers A in Tables 1-23, for example Comp No 1 055 and 2 055 are to be understood as meaning those optically active compounds of the formula I which are prepared from the corresponding optically active alcohols of the formula II ((-)-enant ⁇ omers).
  • Preferred compounds of the formula I are those which have the meaning given for formula I and R 4 is C,-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl, or is C 1 -C 4 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 6 cycloalkyl, each of which is substituted by halogen, cyano, COOR 5 CrCalkoxy, C,-C 4 haloalkoxy or phenyl, it being possible for the phenyl group, in turn, to be substituted by halogen, C,-C 3 alkyl, C ⁇ alkoxy, cyano or C,-C 3 haloalkyl, or is phenyl or phenyl which is substituted by halogen, C,-C 3 alkyl, C,-C 4 alkoxy, cyano or C,-C
  • R is CF 3 or OCF 3 and R, is methyl or ethyl, being, in particular, the number 2
  • the compounds of the formula I can be prepared via processes known per se, for example by a) reacting a compound of the formula II
  • R, Z, R,, R 2 , R 3 R 4 and n have the meanings given for formula I and, to prepare compounds of the formula I in which m is the number 1 or 2, oxidizing this compound to give the compound of the formula lb in which R, Z, R 1 r R 2l R 3 . R 4 and n have the meanings given for formula I or Ic
  • R 6 is C,-C 6 alkyl, phenyl or phenyl which is substituted by halogen, methyl or methoxy in the presence of an inert organic solvent to give a compound of the formula XII
  • Suitable as leaving group X in the compounds of the formula VIII are, in particular, halogens and mesylate or tosylate
  • Process variant a) is advantageously carried out in the presence of an inert aprotic solvent, such as an aliphatic or cyclic ether, for example diethyl ether, 1,2-d ⁇ methoxyethane, tetrahydrofuran or dioxane, or a chlorinated aliphatic hydrocarbon, for example methylene chloride, or an aromatic, for example toluene or xylene, or an aliphatic ester, for example ethyl acetate, in the presence of a catalyst, for example 4-N,N-d ⁇ rnethylam ⁇ nopyr ⁇ d ⁇ ne, triethylamine, dibutyltin dilaurate and/or dibutyltin diacetate, the reaction temperatures preferably being between 20 C C and the reflux temperature of the reaction solution
  • an inert aprotic solvent such as an aliphatic or cyclic ether, for example diethyl ether, 1,2-d ⁇ methoxy
  • reaction of the compounds of the formula IV with the compounds of the formula V in accordance with process variant b) is carried out in the presence of an inert solvent, such as described under variant a), and in the presence of an equivalent of a base, for example triethylamine, pyridine, 4-N,N-d ⁇ methylam ⁇ nopyr ⁇ d ⁇ ne, picoline, N,N-d ⁇ methylan ⁇ i ⁇ e, sodium carbonate or potassium carbonate, at reaction temperatures of from -20°C to 40°C, preferably from 5°C to 20°C
  • the resulting reaction mixture is washed, preferably with water and dilute acid, in order to remove amine by-products in the form of salts
  • phosgene or diphosgene are preferably used as chloroformylating agent
  • the reaction of the compounds of the formula IV with the compounds of the formula VI in accordance with va ⁇ ant c) is carried out under the reaction conditions described for the reaction of the compounds of the formula IV with the compounds of the formula V in variant b)
  • the alkylation of the compound of the formula VII with the compound of the formula VIII is carried out in the presence of an inert organic solvent such as, for example, ketones such as acetone or ethyl methyl ketone, esters such as ethyl acetate, chlorohydrocarbons such as methylene chloride, an aromatic, for example toluene or xylene, or aprotic dipolar solvents such as dimethyl sulfoxide, N-methylpyrro done and N,N-d ⁇ methylformam ⁇ de, at temperatures from 20°C to 50°C
  • the oxidation of the compound of the formula la to give the compounds of the formula lb and Ic is carried out in a solvent which is stable to oxidation, such as water, ethers
  • reaction of the compounds of the formula II to give the compound of the formula IV and the reaction of the compound of the formula IV with the compound of the formula IX is carried out analogously to process va ⁇ ant b)
  • the reaction of the compound of the formula X with the compound of the formula XI is carried out in the presence of an inert solvent, for example esters such as ethyl acetate, ketones such as acetone, ethers such as diethyl ether, chlorohydrocarbons such as chloroform and aromatics such as toluene, and in the presence of at least one equivalent of a base, for example tertiary amines such as triethylamine or inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide
  • an inert solvent for example dimethyl sulfoxide, N-methylpyrrolidone, N.N-dimethylformamide
  • R, R, to R 3 Z and m have the meaning given under formula I, n 0 is 0 or 1 , and n, is
  • Mercaptans of the formula XIII are known and in some cases commercially available These compounds can also be prepared for example analogously to the procedure descnbed in Houben-Weyl, Methoden der Organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, Volume IX, pages 3 et seq or Rec trav chim Pays Bas 89, 593 (1970)
  • novel intermediates of the formula XII are distinguished by a herbicidal activity while being selective in certain crop plants
  • the invention thus also relates to these compounds of the formulae VII, X and XII, to which the same preferences regarding Z, R, R, and n apply as for the compounds of the formula I
  • the end products of the formula I can be isolated in the customary manner by concentration and/or evaporation of the solvent and purified by recrystallization or tnturation of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons, or chlorinated hydrocarbons, or by means of chromatography on silica gel
  • Application methods which are suitable for the use according to the invention of the compounds of the formula I or of compositions comprising them are all application methods which are customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and a variety of methods and techniques, for example the controlled release of active ingredient
  • the active ingredient is applied to mineral granule carriers or polymerized granules (urea/formaldehyde) in the form of a solution and then dried If appropriate, an additional coating can be applied (coated granules), which allows the active ingredient to be released in a controlled manner over a specific period
  • the compounds of the formula I can be employed as such, i e as obtained from synthesis, but they are preferably processed in the customary manner together with the auxiliaries conventionally used in the art of formulation to give, for example, emulsifiable concentrates directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules
  • the application methods such as spraying, atomizing, dusting, wetting, scattering or pouring, and the type of composition are selected to suit the intended aims and prevailing circumstances
  • compositions, i e the compositions, preparations or products comprising the active ingredient of the formula I and at least one active ingredient of the formula I and, as a rule, one or more solid or liquid formulation auxiliaries are prepared in the known manner, for example by intimately mixing and/or grinding the active ingredients with the formulation auxiliaries, for example solvents or solid carriers
  • surface-active compounds surfactants may additionally be used in the preparation of the formulations
  • aromatic hydrocarbons preferably the fractions C ⁇ to C 12 for example xylene mixtures or substituted naphthalenes, phthaltc esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyciohexane or paraffins, alcohols and glycols, and also their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrol ⁇ done, dimethyl sulfoxide or N.N-dimethylformamide, and epoxidized or unepoxidized vegetable oils, such as epoxidized coconut oil or soya oil, or water
  • Substances which are used as solid carriers, for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmo ⁇ llonite or attapulgite
  • ground natural minerals such as calcite, talc, kaolin, montmo ⁇ llonite or attapulgite
  • highly-disperse silica or highly-dtsperse absorptive polymers Suitable as particulate, adsorptive carriers for granules are porous types, for example pumice, brick grit sepiolite or bentonite, and suitable non-sorptive carrier materials are, for example, calcite or sand
  • a large number of pregranulated materials of inorganic or organic nature can be used, such as, in particular, dolomite or comminuted plant residues
  • Suitable surfactants are non-ionic, cationic and/or anionic surfactants and surfactant mixtures which have good emulsifying, dispersing and wetting properties, depending on the type of the active ingredient of the formula I to be formulated
  • Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds
  • Soaps which may be mentioned are the alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts of higher fatty acids (C 10 -C 22 ), for example the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut or tallow oil
  • the fatty acid methyltaurates may also be mentioned
  • the fatty alcohol sulfonates or fatty alcohol sulfates are present in the form of alkali metal alkaline earth metal or substituted or unsubstituted ammonium salts and have an alkyl radical of 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals, for example the sodium or calcium salt of lignosulfonic acid, of the dodecylsulfunc ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids
  • This group also includes salts of the sulfu ⁇ c esters and sulfonic acids of fatty alcohol/ethylene oxide adducts
  • the sulfonated benzimidazole derivatives preferably contain two sulfonyl groups and a fatty acid radical of 8-22 C atoms
  • alkylarylsulfonates are the sodium, calcium or t ⁇ ethanolamine salts of dodecylbenzenesulfonic acid, of dibuty
  • Suitable phosphates for example salts of the phosphoric ester of a p-nonylphenol/(4-14)ethylene oxide adduct, or phospho pids
  • Possible non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids and of alkylphenols which may have 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols
  • non-ionic surfactants are the water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediamtnopolypropylene glycol and alkylpolypropylene glycol which have 1 to 10 carbon atoms in the alkyl chain and contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups Normally, the abovementioned compounds contain 1 to 5 ethylene glycol units per propylene glycol unit
  • non-ionic surfactants examples include nonylphenyl polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, t ⁇ butylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol
  • fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan t ⁇ oleate
  • the cationic surfactants are mainly quaternary ammonium salts which have, as N substituents, at least one alkyl radical of 8 to 22 C atoms and as further substituents lower, halogenated or unhalogenated alkyl, benzyl or lower hydroxyalkyl radicals
  • the salts are preferably present in the form of halides, methylsulfates or ethylsulfates, for example stearylt ⁇ methylammonium chloride or benzyld ⁇ (2-chloroethyl)ethylammon ⁇ um bromide
  • the herbicidal formulations comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of herbicide, 1 to 99.9% by weight, in particular 5 to 99.8% by weight, of a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight, of a surfactant
  • compositions are more preferred as commercially available goods, the end user uses, as a rule, dilute compositions
  • the compositions can also comprise further additives such as stabilizers, for example unepoxidized or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilizers or other active ingredients.
  • stabilizers for example unepoxidized or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil)
  • antifoams for example silicone oil
  • preservatives for example silicone oil
  • viscosity regulators binders
  • tackifiers tackifiers
  • fertilizers or other active ingredients.
  • Emulsifiable concentrates are Emulsifiable concentrates.
  • Active ingredient 1 to 90%, preferably 5 to 50%
  • Active ingredient 0.1 to 50%, preferably 0.1 to 1%
  • Wettable powders Active ingredient 0.5 to 90%, preferably 1 to 80% Surfactant 0.5 to 20%, preferably 1 to 15% Solid carrier 5 to 95%, preferably 15 to 90%
  • Granules Active ingredient 0.1 to 30%, preferably 0.1 to 15% Solid carrier 99.5 to 70%, preferably 97 to 85%
  • the active ingredients of the formula I are successfully applied to the plant or its environment at rates of application of 0.001 to 4 kg/ha, in particular 0.005 to 2 kg/ha.
  • the dosage required for the desired action can be determined by experiments It depends on the type of action, the developmental stage of the crop plant and of the weed, and on application (location, timing, method), and can be varied within wide limits because of these parameters
  • the compounds of the formula I are distinguished by herbicidal and growth-inhibitory properties, which allow them to be used in crops of useful plants, in particular in cereals, cotton, soya, sugarbeet, sugarcane, sunflowers, sorghum, vegetables, fodder crops, plantations, for example fruit, citrus and palm plantations, oilseed rape, maize and rice, and for the non-selective control of weeds.
  • Crops are also to be understood as meaning those which have been made tolerant to herbicides or classes of herbicides by means of conventional plant-breeding or genetic engineering methods
  • the weeds to be controlled can be both mono- and dicotyledoneous weeds, for example Stellana, Nasturtium, Agrostis, Digitana, Avena, Setana, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagitta ⁇ a, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • a solution of 0.9 g (0.003 mol) of 55% 3-chloroperbenzo ⁇ c acid is added to a solution of 0.9 g (0.0024 mol) of 0-[1-(3-trifluoromethylphenoxy)-2-butyl] N-(2-ethylsulf ⁇ nyiethyl)carbamate in 10 ml of methylene chloride.
  • the reactants are allowed to act on each other for 16 hours and the mixture is subsequently extracted with aqueous sodium bicarbonate solution.
  • the organic phase is washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated.
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  • Aromatic hydrocarbon mixture C 9 -C 12 85% 78% 55% 16%
  • Emulsions of any desired concentration can be prepared from such concentrates by dilution with water
  • Aromatic hydrocarbon mixture C 9 -C 12 75% 60%
  • the solutions are suitable for use in the form of microdrops
  • the active ingredient is mixed thoroughly with the additives and ground thoroughly in a suitable mill This gives wettable powders which can be diluted with water to give suspensions of any desired concentration
  • the active ingredient is dissolved in methylene chlo ⁇ de, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo F5 Coated granules a) b) c)
  • the finely ground active ingredient is applied uniformly to the earner material which has been moistened with polyethylene glycol This gives dust-free coated granules
  • the active ingredient is mixed with the additives, and the mixture is ground and moistened with water This mixture is extruded and subsequently dried in a stream of air
  • Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture on a suitable mill F8.
  • the finely ground active ingredient is mixed intimately with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water
  • Monocotyledoneous and dicotyledoneous test plants are sown in standard soil in plastic pots.
  • the test substances are sprayed on in the form of an aqueous suspension (prepared from a 25% wettable powder (Example F3,b)) or in the form of an emulsion (prepared from a 25% emulsion concentrate (Example F1 ,c)), so that the dosage corresponds to 2 kg of a.s./ha (500 I of water/ha).
  • Monocotyledoneous and dicotyledoneous test plants are grown in standard soil in plastic pots in the greenhouse and, in the 4- to 6-leaf stage, sprayed with an aqueous suspension of the test substances of the formula I, prepared from a 25% wettable powder (Example F3,b)) or with an emulsion of the test substances of the formula I, prepared with a 25% emulsion concentrate (Example F1 ,c)), so that the dosage corresponds to 2 kg of a.s./ha (500 I of water/ha).

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Abstract

Compounds of formula (I) in which R is halogen, C1-C3haloalkyl, cyano, nitro or C1-C3haloalkoxy; Z is hydrogen, halogen or together with R, -O-CF2-O-; R1 is C1-C5alkyl or C3-C6cycloalkyl; R2 and R3 independently of one another are hydrogen, C1-C4alkyl or C3-C6cycloalkyl; R4 is C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl or C5- or C6-cycloalkenyl, or is C1-C4alkyl, C2-C6alkenyl, C2-C6alkynyl or C3-C6cycloalkyl, each of which is substituted by halogen, cyano, C1-C4alkyl-CO, phenyl-CO, COOR5, C1-C4alkoxy, C1-C4haloalkoxy, oxiranyl, dioxolanyl, tetrahydrofuranyl, tetrahydropyranyl, C3-C6cycloalkyl, halo-C3-C6-cycloalkyl, phenyl or phenoxy, it being possible for the phenyl group, in turn, to be substituted by halogen, C1-C3alkyl, C1-C4alkoxy, cyano or C1-C3haloalkyl, or is phenyl or phenyl which is substituted by halogen, C1-C3alkyl, C1-C4alkoxy, cyano or C1-C3haloalkyl; or R4 together with one of the R2 groups forms a C2-C6alkylene bridge; R5 is C1-C5alkyl or C3-C6cycloalkyl; n is the number 1, 2, or 3 and m is thenumber 0, 1 or 2; and the diastereomers and enantiomers of these compounds are suitable as herbicides.

Description

ALKYLTHIO-, ALKYLSULPHENΥL- AND ALKYLSULPHONYLCARBAMATES AS HERBICIDES
The present invention relates to novel herbicidally active alkylthio-, alkylsulfinyl and alkylsulfonylcarbamates, processes for their preparation, to compositions which comprise these compounds, and to their use for controlling weeds, in particular in crops of useful plants, or for inhibiting the growth of plants.
Substituted alkyl- and phenylcarbamates which are herbicidally active are described, for example, in US-A-5 078 783, US-A-5 099 059, US-A-5 194 661 , US-A-5 399 545 and WO 96/16941.
There have now been found novel alkylthio-, alkylsulfinyl- and alkylsulfonylcarbamates which have herbicidal and growth-inhibitory properties.
The present invention thus relates to compounds of the formula I
Figure imgf000003_0001
in which
R is halogen, d-C3haloalkyl, cyano, nitro or CrC3haloalkoxy;
Z is hydrogen, halogen or together with R, -0-CF2-0-;
R, is d-Csalkyl or C3-C6cycloalkyl;
R2 and R3 independently of one another are hydrogen, Cι-C4alkyl or C3-C6cycloalkyl;
R4 is Cι-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl or C3- or C6-cycloalkenyl, or is
Cι-C4alkyl, C2-C€alkenyl, C2-C6alkynyl or C3-C6cycloalkyl, each of which is substituted by halogen, cyano, C^alkyl-CO, phenyl-CO, COOR5 Cι-C4alkoxy, Cι-C4haloalkoxy, oxiranyl, dioxolanyl, tetrahydrofuranyl, tetrahydropyranyl, C3-C6cycioalkyl, halo-C3-C6-cycioalkyl, phenyl or phenoxy, it being possible for the phenyl group, in turn, to be substituted by halogen, Chalky!, C1-C4alkoxy, cyano or CrCjhaloalkyl, or is phenyl or phenyl which is substituted by halogen, C^Caalkyl, C-Cialkoxy, cyano or CrCjhaloalkyl, or
R4 together with one of the R2 groups forms a C2-C6alkylene bridge,
R5 is d-Csalkyl or C3-C6cycloalkyl, n is the number 1 , 2 or 3 and m is the number 0, 1 or 2, and the diastereomers and enantiomers of these compounds
The alkyl groups in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl and the various isomeπc pentyl and hexyl groups
Alkoxy, alkenyl and alkynyl groups are derived from the abovementioned alkyl groups The alkenyl and alkynyl groups can be mono- or polyunsaturated
Halogen is as a rule, fluorine, chlorine, bromine or iodine This also applies analogously to halogen in connection with other meanings such as haloalkyl or halophenyl
Cycloalkyl is for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl
The result of the presence of an asymmetric carbon atom in the compounds of the formula I is that the compounds can exist both as optically active isomers and in the form of racemic mixtures The optically active compounds of the formula I can be obtained from the racemic mixtures by known separation methods, for example HPLC or chromatography on chiral carrier materials, or by synthesis, for example from the corresponding optically active alcohols of the formula II In the present invention the active ingredients of the formula I are to be understood as meaning both the pure optical antipodes and the racemates Unless specific mention is made of the individual optical antipodes, the formula given is to be understood as meaning those racemic mixtures which result from the preparation process given
The enantiomers A (enant A) in Tables 1-23, for example Comp No 1 055 and 2 055 are to be understood as meaning those optically active compounds of the formula I which are prepared from the corresponding optically active alcohols of the formula II ((-)-enantιomers).
Preferred compounds of the formula I are those which have the meaning given for formula I and R4 is C,-C6alkyl, C2-C6alkenyl, C2-C6alkynyl or C3-C6cycloalkyl, or is C1-C4alkyl, C2-C6alkenyl, C2-C6alkynyl or C3-C6cycloalkyl, each of which is substituted by halogen, cyano, COOR5 CrCalkoxy, C,-C4haloalkoxy or phenyl, it being possible for the phenyl group, in turn, to be substituted by halogen, C,-C3alkyl, C^alkoxy, cyano or C,-C3haloalkyl, or is phenyl or phenyl which is substituted by halogen, C,-C3alkyl, C,-C4alkoxy, cyano or C,-C3haloalkyl; or R4 together with one of the R2 groups forms a C2-C6alkylene bridge.
Preferred are those compounds of the formula I in which Z and R together form a group -0-CF2-0- in the 2- and 3-posιtιon of the phenyl ring
Preferred are compounds of the formula I in which Z is hydrogen.
Preferred are furthermore those compounds of the formula I in which R is CF3or OCF3 and R, is methyl or ethyl, being, in particular, the number 2
The compounds of the formula I can be prepared via processes known per se, for example by a) reacting a compound of the formula II
Figure imgf000005_0001
in which R, Z and R, have the meanings given for formula with a compound of the formula III
Figure imgf000006_0001
in which R2, R3l R4, m and n have the meanings given for formula I, or b) converting a compound of the formula II
Figure imgf000006_0002
in which R, Z and R, have the meanings given for formula I with a chloroformylating agent to give a compound of the formula IV
Figure imgf000006_0003
in which R, Z and R, have the meanings given for formula I and reacting this compound with a compound of the formula V
Figure imgf000006_0004
in which R2, R3, R4, m and n have the meanings given for formula I, or c) converting a compound of the formula II
Figure imgf000007_0001
in which R, Z and R, have the meanings given for formula I with a chloroformylating agent to give a compound of the formula IV
Figure imgf000007_0002
in which R, Z and R, have the meanings given for formula I, reacting this compound with a compound of the formula VI
Figure imgf000007_0003
in which R2, R3 and n have the meanings given for formula to give a compound of the formula VII
Figure imgf000008_0001
in which R, Z, R,, R2, R3 and n have the meanings given for formula and reacting this compound with a compound of the formula VIM
R4-X (VIII)
in which R4 has the meaning given for formula I and X is a leaving group to give the compound of the formula la
Figure imgf000008_0002
in which R, Z, R,, R2, R3 R4 and n have the meanings given for formula I and, to prepare compounds of the formula I in which m is the number 1 or 2, oxidizing this compound to give the compound of the formula lb
Figure imgf000009_0001
in which R, Z, R1 r R2l R3. R4 and n have the meanings given for formula I or Ic
Figure imgf000009_0002
in which R, Z, R,, R2, R3 R4 and n have the meanings given for formula I, or d) converting a compound of the formula II
Figure imgf000009_0003
in which R, Z and R, have the meanings given for formula I with a chloroformylating agent to give a compound of the formula IV
Figure imgf000010_0001
in which R, Z and R, have the meanings given for formula I, converting this compound with a compound of the formula IX
Figure imgf000010_0002
in which R2, R3 and n have the meanings given for formula I to give a compound of the formula X
Figure imgf000010_0003
in which R, Z, R1 ( R2, R3 and n have the meanings given for formula I, reacting this compound with a sulfonyl chloride of the formula XI
C!-S02-R6 (XI)
in which R6 is C,-C6alkyl, phenyl or phenyl which is substituted by halogen, methyl or methoxy in the presence of an inert organic solvent to give a compound of the formula XII
Figure imgf000011_0001
in which R, Z, R1 t R2, R3 and n have the meanings given for formula I and R6 has the meaning given for formula XI, converting this compound with a compound of the formula XIII
H-S-R4 (XIII)
in which R4 has the meaning given for formula I in the presence of an inert organic solvent to give the compound of the formula la
Figure imgf000011_0002
in which R, Z, R,, R2, R3 R4 and n have the meanings given for formula I and, to prepare compounds of the formula I in which m is the number 1 or 2, oxidizing this compound to give the compound of the formula lb
Figure imgf000012_0001
in which R, Z, R1 t R2, R3 R4 and n have the meanings given for formula I or Ic
Figure imgf000012_0002
in which R, Z, R,, R2, R3 R4 and n have the meanings given for formula I, or e) converting a compound of the formula II
Figure imgf000012_0003
in which R, Z and R, have the meanings given for formula I with a chloroformylating agent to give a compound of the formula IV
Figure imgf000013_0001
in which R, Z and R, have the meanings given for formula I, converting this compound with a compound of the formula XIV
Figure imgf000013_0002
in which R2, R3 and n have the meanings given for formula I and Y is halogen to give a compound of the formula XV
Figure imgf000013_0003
in which R, Z, R^ R2, R3 and n have the meanings given for formula I and Y has the meaning given for formula XIV, reacting this compound with a compound of the formula XIII
H-S-R4 (XIII)
in which R4 has the meaning given for formula I in the presence of a base to give the compound of the formula la
Figure imgf000014_0001
in which R, Z, R,, R2, R3 R and n have the meanings given for formula I and oxidizing this compound to give the compound of the formula lb
Figure imgf000014_0002
in which R, Z, R,, R2, R3 R4 and n have the meanings given for formula I or Ic
Figure imgf000014_0003
in which R, Z, R,, R2, R3 R4 and n have the meanings given for formula
Such processes are described, for example, in US-A-5 399 545 and WO 96/16941 Suitable as leaving group X in the compounds of the formula VIII are, in particular, halogens and mesylate or tosylate
Process variant a) is advantageously carried out in the presence of an inert aprotic solvent, such as an aliphatic or cyclic ether, for example diethyl ether, 1,2-dιmethoxyethane, tetrahydrofuran or dioxane, or a chlorinated aliphatic hydrocarbon, for example methylene chloride, or an aromatic, for example toluene or xylene, or an aliphatic ester, for example ethyl acetate, in the presence of a catalyst, for example 4-N,N-dιrnethylamιnopyrιdιne, triethylamine, dibutyltin dilaurate and/or dibutyltin diacetate, the reaction temperatures preferably being between 20CC and the reflux temperature of the reaction solution
The reaction of the compounds of the formula IV with the compounds of the formula V in accordance with process variant b) is carried out in the presence of an inert solvent, such as described under variant a), and in the presence of an equivalent of a base, for example triethylamine, pyridine, 4-N,N-dιmethylamιnopyrιdιne, picoline, N,N-dιmethylanιiιπe, sodium carbonate or potassium carbonate, at reaction temperatures of from -20°C to 40°C, preferably from 5°C to 20°C On working up, the resulting reaction mixture is washed, preferably with water and dilute acid, in order to remove amine by-products in the form of salts When reacting the compounds of the formula II to give the compounds of the formula IV phosgene or diphosgene are preferably used as chloroformylating agent
The reaction of the compounds of the formula IV with the compounds of the formula VI in accordance with vaπant c) is carried out under the reaction conditions described for the reaction of the compounds of the formula IV with the compounds of the formula V in variant b) The alkylation of the compound of the formula VII with the compound of the formula VIII is carried out in the presence of an inert organic solvent such as, for example, ketones such as acetone or ethyl methyl ketone, esters such as ethyl acetate, chlorohydrocarbons such as methylene chloride, an aromatic, for example toluene or xylene, or aprotic dipolar solvents such as dimethyl sulfoxide, N-methylpyrro done and N,N-dιmethylformamιde, at temperatures from 20°C to 50°C The oxidation of the compound of the formula la to give the compounds of the formula lb and Ic is carried out in a solvent which is stable to oxidation, such as water, ethers such as diethyl ether, esters such as ethyl acetate, chlorohydrocarbons such as methylene chloride, an aromatic such as toluene or xylene or acids such as acetic acid, at temperatures from 0°C to 30°C Examples of oxidants are hydrogen peroxide, peracids such as peracetic acid, perbenzoic acids, monoperphthahc acid, potassium permanganate, sodium periodate, potassium periodate, chromic acid, nitric acid, lodosobenzene, bromine, sodium hypochlorite or potassium hypochlorite The oxidation of the compound of the formula la to give the compound of the formula lb is preferably carried out with one equivalent, the oxidation of the compound of the formula lb to give the compound of the formula Ic with a further equivalent, of oxidaπt If desired, the compound of the formula la can be oxidized directly to give the compound of the formula Ic by using two equivalents of oxidant Furthermore, the compounds of the formula lb and Ic can be obtained alongside each other from the compound of the formula la by using 1 5 equivalents of oxidant
The reaction of the compounds of the formula II to give the compound of the formula IV and the reaction of the compound of the formula IV with the compound of the formula IX is carried out analogously to process vaπant b) The reaction of the compound of the formula X with the compound of the formula XI is carried out in the presence of an inert solvent, for example esters such as ethyl acetate, ketones such as acetone, ethers such as diethyl ether, chlorohydrocarbons such as chloroform and aromatics such as toluene, and in the presence of at least one equivalent of a base, for example tertiary amines such as triethylamine or inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide The reaction of the compound of the formula XII with the compound of the formula XIII is carried out in the presence of an inert solvent, for example dimethyl sulfoxide, N-methylpyrrolidone, N.N-dimethylformamide or alcohols such as methanol, ketones such as acetone or chlorohydrocarbons such as methylene chloride, and in the presence of at least one equivalent of a base, for example tertiary amines such as triethylamine, sodium alkoxides, potassium alkoxides, sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, the reaction temperatures preferably being in the range of from 10°C to 50°C The reaction of the compounds of the formula II to give the compounds of the formula IV and the further reaction to give the compounds of the formula XV in accordance with process variant e) is carried out analogously to the reaction conditions described in process variant b) The substitution reaction with the compound of the formula XIII is carried out analogously to process variant d) The subsequent oxidation reaction is described under process variant c)
Compounds of the formula II and their preparation are described in WO 96/16941 Compounds of the formula III are known or can be prepared analogously to known methods, such as described in standard reference works of organic chemistry (see, for example, Houben-Weyl, ethoden der Organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, Volume VIII, pages 120 et seq )
Compounds of the formula V are known and in some cases commercially available, or they can be prepared analogously to known methods such as described in standard reference works of organic chemistry (see, for example, Houben-Weyl, Methoden der Organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, Volume IX, pages 103 et seq , 211 et seq and 227 et seq )
Compounds of the formula lu
Figure imgf000017_0001
in which R, R, to R3 Z and m have the meaning given under formula I, n0 is 0 or 1 , and n, is
1 , 2, 3, 4 or 5 can be prepared by reacting the dihalides of the formula Vu
Figure imgf000018_0001
in which R, R^ to R3, Z, n0 and n, have the abovementioned meaning and Hal is halogen, in particular chlorine and bromine, with sodium sulfide (m=0) and, if desired, subsequently oxidizing the product (m=1 or 2).
Compounds of the formula VI are known and in some cases commercially available, or they can be prepared analogously to known methods such as described in standard reference works of organic chemistry (see Houben-Weyl, Methoden der Organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, Volume IX, pages 22 et seq and 38 et seq ), and in Z.obsc. khim. 28, 1811 (1958) and J Org. Chem. 28, 981 (1963)
Compounds of the formula VIII are known or can be prepared analogously to known methods.
Compounds of the formula IX are known and in some cases commercially available, or they can be prepared analogously to known methods such as described in standard reference works of organic chemistry (see Houben-Weyl, Methoden der Organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, Volume XI, page 407), and in Z.obsc khim. 28, 1811 (1958). Reactions with sulfonyl chlorides are known to those skilled in the art and described, for example, in Houben-Weyl, Methoden der Organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, Volume IX, pages 663 et seq. Mercaptans of the formula XIII are known and in some cases commercially available These compounds can also be prepared for example analogously to the procedure descnbed in Houben-Weyl, Methoden der Organischen Chemie [Methods in Organic Chemistry], Georg Thieme Verlag Stuttgart, Volume IX, pages 3 et seq or Rec trav chim Pays Bas 89, 593 (1970)
The intermediates of the formulae VII, X and XII are novel and were developed specifically for the synthesis of the compounds of the formula I
The novel intermediates of the formula XII are distinguished by a herbicidal activity while being selective in certain crop plants
The invention thus also relates to these compounds of the formulae VII, X and XII, to which the same preferences regarding Z, R, R, and n apply as for the compounds of the formula I
The end products of the formula I can be isolated in the customary manner by concentration and/or evaporation of the solvent and purified by recrystallization or tnturation of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons, or chlorinated hydrocarbons, or by means of chromatography on silica gel
Application methods which are suitable for the use according to the invention of the compounds of the formula I or of compositions comprising them are all application methods which are customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and a variety of methods and techniques, for example the controlled release of active ingredient To this end, the active ingredient is applied to mineral granule carriers or polymerized granules (urea/formaldehyde) in the form of a solution and then dried If appropriate, an additional coating can be applied (coated granules), which allows the active ingredient to be released in a controlled manner over a specific period
The compounds of the formula I can be employed as such, i e as obtained from synthesis, but they are preferably processed in the customary manner together with the auxiliaries conventionally used in the art of formulation to give, for example, emulsifiable concentrates directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules The application methods, such as spraying, atomizing, dusting, wetting, scattering or pouring, and the type of composition are selected to suit the intended aims and prevailing circumstances
The formulations, i e the compositions, preparations or products comprising the active ingredient of the formula I and at least one active ingredient of the formula I and, as a rule, one or more solid or liquid formulation auxiliaries, are prepared in the known manner, for example by intimately mixing and/or grinding the active ingredients with the formulation auxiliaries, for example solvents or solid carriers Furthermore, surface-active compounds (surfactants) may additionally be used in the preparation of the formulations
The following are suitable as solvents aromatic hydrocarbons, preferably the fractions Cβ to C12 for example xylene mixtures or substituted naphthalenes, phthaltc esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyciohexane or paraffins, alcohols and glycols, and also their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolιdone, dimethyl sulfoxide or N.N-dimethylformamide, and epoxidized or unepoxidized vegetable oils, such as epoxidized coconut oil or soya oil, or water
Substances which are used as solid carriers, for example for dusts and dispersible powders, are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmoπllonite or attapulgite To improve the physical properties of the formulation, it is also possible to add highly-disperse silica or highly-dtsperse absorptive polymers Suitable as particulate, adsorptive carriers for granules are porous types, for example pumice, brick grit sepiolite or bentonite, and suitable non-sorptive carrier materials are, for example, calcite or sand Moreover, a large number of pregranulated materials of inorganic or organic nature can be used, such as, in particular, dolomite or comminuted plant residues
Suitable surfactants are non-ionic, cationic and/or anionic surfactants and surfactant mixtures which have good emulsifying, dispersing and wetting properties, depending on the type of the active ingredient of the formula I to be formulated Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds
Soaps which may be mentioned are the alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts of higher fatty acids (C10-C22), for example the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut or tallow oil The fatty acid methyltaurates may also be mentioned
However, so-called synthetic surfactants are used more frequently, in particular fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates
As a rule the fatty alcohol sulfonates or fatty alcohol sulfates are present in the form of alkali metal alkaline earth metal or substituted or unsubstituted ammonium salts and have an alkyl radical of 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals, for example the sodium or calcium salt of lignosulfonic acid, of the dodecylsulfunc ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids This group also includes salts of the sulfuπc esters and sulfonic acids of fatty alcohol/ethylene oxide adducts The sulfonated benzimidazole derivatives preferably contain two sulfonyl groups and a fatty acid radical of 8-22 C atoms Examples of alkylarylsulfonates are the sodium, calcium or tπethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensate
Other possible substances are suitable phosphates, for example salts of the phosphoric ester of a p-nonylphenol/(4-14)ethylene oxide adduct, or phospho pids
Possible non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, of saturated or unsaturated fatty acids and of alkylphenols which may have 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols
Other suitable non-ionic surfactants are the water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediamtnopolypropylene glycol and alkylpolypropylene glycol which have 1 to 10 carbon atoms in the alkyl chain and contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups Normally, the abovementioned compounds contain 1 to 5 ethylene glycol units per propylene glycol unit
Examples of non-ionic surfactants which may be mentioned are nonylphenyl polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tπbutylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol
Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan tπoleate
The cationic surfactants are mainly quaternary ammonium salts which have, as N substituents, at least one alkyl radical of 8 to 22 C atoms and as further substituents lower, halogenated or unhalogenated alkyl, benzyl or lower hydroxyalkyl radicals The salts are preferably present in the form of halides, methylsulfates or ethylsulfates, for example stearyltπmethylammonium chloride or benzyldι(2-chloroethyl)ethylammonιum bromide
The surfactants conventionally used in the art of formulation, which can also be used in the compositions according to the invention, are described, for example, inter alia, in "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp , Ridgewood New Jersey, 1981 , Stache, H , "Tensid-Taschenbuch" [Surfactants Guide], Carl Hanser Verlag, Munich Vienna, 1981 and M and J Ash, "Encyclopedia of Surfactants", Vol l-lll, Chemical Publishing Co , New York, 1980-81
As a rule, the herbicidal formulations comprise 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of herbicide, 1 to 99.9% by weight, in particular 5 to 99.8% by weight, of a solid or liquid formulation auxiliary and 0 to 25% by weight, in particular 0.1 to 25% by weight, of a surfactant
While concentrated compositions are more preferred as commercially available goods, the end user uses, as a rule, dilute compositions The compositions can also comprise further additives such as stabilizers, for example unepoxidized or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers and fertilizers or other active ingredients.
In particular, preferred formulations are composed as follows: (% = per cent by weight)
Emulsifiable concentrates.
Active ingredient. 1 to 90%, preferably 5 to 50%
Surfactant- 5 to 30%, preferably 10 to 20%
Solvent 15 to 94%, preferably 70 to 85%
Dusts
Active ingredient 0.1 to 50%, preferably 0.1 to 1%
Solid carrier 99.9 to 90%, preferably 99.9 to 99%
Suspension concentrates Active ingredient 5 to 75%, preferably 10 to 50% Water 94 to 24%, preferably 88 to 30% Surfactant 1 to 40%, preferably 2 to 30%
Wettable powders Active ingredient 0.5 to 90%, preferably 1 to 80% Surfactant 0.5 to 20%, preferably 1 to 15% Solid carrier 5 to 95%, preferably 15 to 90%
Granules Active ingredient 0.1 to 30%, preferably 0.1 to 15% Solid carrier 99.5 to 70%, preferably 97 to 85%
As a rule, the active ingredients of the formula I are successfully applied to the plant or its environment at rates of application of 0.001 to 4 kg/ha, in particular 0.005 to 2 kg/ha. The dosage required for the desired action can be determined by experiments It depends on the type of action, the developmental stage of the crop plant and of the weed, and on application (location, timing, method), and can be varied within wide limits because of these parameters
The compounds of the formula I are distinguished by herbicidal and growth-inhibitory properties, which allow them to be used in crops of useful plants, in particular in cereals, cotton, soya, sugarbeet, sugarcane, sunflowers, sorghum, vegetables, fodder crops, plantations, for example fruit, citrus and palm plantations, oilseed rape, maize and rice, and for the non-selective control of weeds.
Crops are also to be understood as meaning those which have been made tolerant to herbicides or classes of herbicides by means of conventional plant-breeding or genetic engineering methods The weeds to be controlled can be both mono- and dicotyledoneous weeds, for example Stellana, Nasturtium, Agrostis, Digitana, Avena, Setana, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaπa, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
The examples which follow illustrate the invention in greater detail without imposing any limitation
Preparation Examples
Example HV Preparation of O-f1-(3-trifluoromethylphenoxy)-2-butyll N-(2-mercaptoethvD- carbamate
Figure imgf000024_0001
89 0 g (0.3 mol) of 0-(3-trifluoromethylphenoxy)-2-butyl chloroformate, dissolved in 100 ml of ethyl acetate, are added dropwise at a temperature of 15°C to a suspension of 25.4 g (0.33 mol) of cysteamine in 900 ml of ethyl acetate. 30.3 g (0.3 mol) of triethylamine are simultaneously added dropwise The reaction mixture is subsequently stirred for another hour at approximately 20°C The salts are filtered off, and the filtrate is washed with dilute hydrochloric acid and then with a saturated sodium chloride solution The organic phase is dried with sodium sulfate and evaporated This gives 1004 g (99 2% of theory) of 0-[1-(3- trιfluoromethylphenoxy)-2-butyl] N-(2-mercaptoethyl)carbamate of refractive index nD 25 1 4880
Example H2 Preparation of 0-f1-(3-trιfluoromethylphenoxy)-2-butyll N-(2-ιsoamylthιoethyl)- carbamate
Figure imgf000025_0001
1 7 g (0 005 mol) of 0-[1-(3-trιfluoromethylphenoxy)-2-butyl] N-(2-mercaptoethyl)carbamate, prepared as described in Example 1 , 0 8 g (0 005 mol) of 1-bromo-3-methylbutane and 1 4 g (0 01 mol of potassium carbonate) are stirred in 50 ml of 2-butanone for 18 hours at room temperature To complete the reaction, the mixture is heated for a further 1 1/2 hours at a temperature of 40°C The salts are filtered off and the filtrate is evaporated The residue is chromatographed on silica gel using a mixture of ethyl acetate and hexane in a ratio of 1 3 This gives 1 7 g (83 4% of theory) of 0-[1-(3-trιfluoromethylphenoxy)-2-butyl] N-(2- ιsoamylthιoethyt)carbamate of refractive index nD 22 1 4825
Example H3 Preparation of 0-f1-(3-tnfluoromethylphenoxy)-2-butvn N-(2-ιsoamylsulfonyl- ethvDcarbamate
Figure imgf000025_0002
A solution of 0 7 g (0 0017 mol) of 0-[1-(3-trιfluoromethylphenoxy)-2-butyl] N-(2-ιsoamylthιo- ethyl)carbamate, prepared as described in Example 2, and 0 6 g (0 0035 mol) of 3-chloroperbenzoic acid in 40 ml of methylene chloride are allowed to act on each other for 20 hours at a temperature of approximately 20°C. The reaction mixture is subsequently extracted with aqueous sodium bicarbonate solution. The organic phase is separated off, dried with sodium sulfate and evaporated. This gives 0-[1-{3-trifluoromethylphenoxy)-2- butyl] N-(2-isoamylsulfonylethyl)carbamate of refractive index nD 25 1.4788 in virtually quantitative yield.
Example H4: Preparation of 0-ri-(3-trifluoromethylphenoxy)-2-butvn N-(2-hydroxypropyl)- carbamate:
Figure imgf000026_0001
1 1.9 g (0.04 mol) of 0-(3-trifluoromethylphenoxy)-2-butyl chloroformate are added dropwise at a temperature of 0°C to a solution of 3.1 g (0.04 mol) of 1-amino-2-propanol and 5 g (0.05 mol) of triethylamine in 150 ml of methylene chloride. After the solution has been stirred for one hour at a temperature of approximately 20°C, it is extracted with dilute hydrochloric acid and washed with saturated sodium chloride solution. The organic phase is dried with sodium sulfate and evaporated. The resulting oil is dried under a high vacuum. This gives 13.2 g (98.4% of theory) of O-[1-(3-trifluoromethylphenoxy)-2-butyl] N-(2-hydroxy- propyl)carbamate of refractive index nD 25 1.4730.
Example H5: Preparation of 0-f1-(3-trifluoromethylphenoxy)-2-butyll N-(2-methylsulfonyloxy- propyDcarbamate:
Figure imgf000026_0002
A solution of 2.4 g (0.021 mol) of methanesulfonyl chloride in 10 ml of methylene chloride is added dropwise at a temperature of 0°C to a solution of 6.7 g (0.02 mol) of 0-[1-(3- tπfluoromethylphenoxy)-2-butyl] N-(2-hydroxypropyl)carbamate and 2.2 g (0.022 mol) of triethylamine in 60 ml of methylene chloride. The reaction mixture is stirred for 1/2 hour at a temperature of approximately 20°C and then extracted with dilute hydrochloric acid. The organic phase is separated off, washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated. This gives 0-[1-(3-trifluoromethylphenoxy)-2-butyl] N-(2- methylsulfonyloxypropyl)carbamate of melting point 47-48°C in virtually quantitative yield
Example H6 0-f1-(3-thfluoromethylphenoxy)-2-butvπ N-(2-ethylthιopropyl)carbamate-
Figure imgf000027_0001
0 25 g (0 011 mol) of metallic sodium are dissolved in 40 ml of ethanol. 0 77 g (0 012 mol) of ethylmercaptan are first added to this solution, followed by 3.7 g (0.009 mol) of 0-[1-(3-trι- fluoromethylphenoxy)-2-butyl] N-(2-methylsu!fony!oxypropyl)carbamate The reaction mixture is stirred for 3 hours at a temperature of approximately 20°C and then for 1 1/2 hours at a temperature of 50°C The salt is filtered off and the filtrate is subsequently evaporated The oily residue is dissolved in diethyl ether, washed with saturated sodium chloride solution, dried with sodium sulfate and reevaporated After drying under a high vacuum, 3 4 g (100% of theory) of O-[1-(3-trifluoromethylphenoxy)-2-butyl] N-(2-ethylthiopropyl)carbamate of refractive index nD 25 1.4850 are obtained. Example H7 0-f1-(3-trιfluoromethylphenoxy)-2-butvn N-(2-ethylsulfonylpropyl)carbamate and O-f 1 -(3-trιfluoromethylphenoxy)-2-butyll N-(2-ethylsulfιnylpropyl)carbamate
Figure imgf000028_0001
3 6 g of 55% 3-chloroperbenzoιc acid (0 0115 mol) are added to 2 9 g (0 0076 mol) of 0-[1- (3-tπfluoromethylphenoxy)-2-butyl] N-(2-ethylthιopropyl)carbamate in 80 ml of methylene chloride The reactants are allowed to act on each other for 16 hours at a temperature of approximately 20°C, and the mixture is then extracted with aqueous sodium bicarbonate solution The organic phase is washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated The residue is chromatographed on silica gel using a mixture of ethyl acetate and hexane in a ratio of 1 1 This gives 1 g (32% of theory) of 0-[1- (3-trιfluoromethy!phenoxy)-2-butyl] N-(2-ethylsulfonylpropyl)carbamate of refractive index nD 25 1 4792 Using a mixture of ethyl acetate and ethanol in a ratio of 10 1 , 1 8 g (59 8% of theory) of 0-[1-(3-trιfluoromethylphenoxy)-2-butyl] N-(2-ethylsulfιnylpropyl)carbamate of refractive index nD 25 1 4870 are eluted
Example H8 0-[1-(3-trιfluoromethylphenoxy)-2-butyll N-(2-cvclopentylthιoethyl)carbarnate
Figure imgf000028_0002
2 4 g (0 008 mol) of the (-)-enantιomer 0-(3-tπfluoromethylphenoxy)-2-butyl chloroformate in 10 ml of methylene chloride are added dropwise at a temperature of 0°C to a solution of 1.2 g (0 008 mol) of 2-cyclopentylthιoethylamιne and 0.95 g (0.009 mol) of triethylamine in 40 ml of methylene chloride. The reaction mixture is stirred for 2 hours at a temperature of approximately 20°C and then extracted with dilute hydrochloric acid The organic phase is washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated The residue is chromatographed on silica gel using a mixture of ethyl acetate and hexane in a ratio of 1.3 This gives 3 1 g (95 6% of theory) of the (-)-enantιomer 0-[1-(3- tπfluoromethylphenoxy)-2-butyl] N-(2-cyclopentylthιoethyl)carbamate with a refractive index of nD 251 4958
Example 9 Preparation of Q-f1-(3-trifluoromethylphenoxy)-2-butvπ N-(2-ethylsulfιnyl- ethvQcarbamate
Figure imgf000029_0001
A solution of 2 2 g of 55% 3-chloroperbenzoιc acid (0.0071 mol) are added dropwise at a temperature of 0°C to a solution of 2 6 g (0 0071 mol) of 0-[1-(3-tπfluoromethylphenoxy)-2- butyl] N-(2-ethylthιoethyl)carbamate in 20 ml of methylene chloride The reaction mixture is stirred for 1 1/2 hours at a temperature of 0°C and then extracted with aqueous sodium bicarbonate solution The organic phase is washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated The residue is chromatographed with ethyl acetate on silica gel This gives 1.9 g (70.4% of theory) of 0-[1-(3-tπfluoromethyiphenoxy)-2- butyl] N-(2-ethylsulfιnylethyl)carbamate of refractive index nD 25 1 4953
Example H10 Preparation of O-f1-(3-trιfluoromethylphenoxy)-2-butyl] N-(2-ethylsulfonyl- ethvDcarbamate
Figure imgf000029_0002
A solution of 0.9 g (0.003 mol) of 55% 3-chloroperbenzoιc acid is added to a solution of 0.9 g (0.0024 mol) of 0-[1-(3-trifluoromethylphenoxy)-2-butyl] N-(2-ethylsulfιnyiethyl)carbamate in 10 ml of methylene chloride. The reactants are allowed to act on each other for 16 hours and the mixture is subsequently extracted with aqueous sodium bicarbonate solution. The organic phase is washed with saturated sodium chloride solution, dried with sodium sulfate and evaporated. This gives 0.9 g (96% of theory) of O-[1-(3-trifluoromethylphenoxy)-2-butyl] N-(2-ethylsulfonylethyl)carbamate of refractive index nD 25 1 4851.
The compounds of the formula I, Vila, Xa and Xlla which are listed in the tables below are prepared analogously.
Table 1 Compounds of the formula la
Figure imgf000031_0001
Figure imgf000031_0002
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0002
Figure imgf000034_0001
1 090 CF, C7 2H' '5 Cl enant A
CH JX Cl
Figure imgf000034_0003
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0003
Figure imgf000037_0001
Figure imgf000037_0002
Figure imgf000037_0004
Figure imgf000038_0001
Figure imgf000039_0002
CH
Figure imgf000039_0003
Figure imgf000039_0001
1.259 CF, C, 2H" 'S CH2CH2O-phenyl rac nD« 1.5172 Table 2 Compounds of the formula lb
Figure imgf000040_0001
R4 Rac/Enant. Phys. Data
CH3 rac
C2H5 rac nD23 1 4878 n-C3H7 rac nD23 1 4835 ι-C3H7 rac n-C4H9 rac sec-C4H9 rac ι-C4H9 rac tert-C4H9 rac cyclopentyl rac cyclohexyl rac
CH3 rac
C2H5 rac nD25 1 4953 n-C3H7 rac ι-C3H7 rac n-C4H9 rac sec-C4H9 rac ι-C4H9 rac tert-C4H9 rac m p 65-72
C5Hn rac i-CsH,, rac sec-CsHn rac neo-C5H,, rac nD22 1 4801 cyclopropyl rac
Figure imgf000040_0002
cyclobutyl rac
Figure imgf000041_0001
Figure imgf000042_0001
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Table 3: Compounds of the formula Ic
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Table 4 Compounds of the formula Id
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X X X X X X X X X X X X x x x x x x x x x x x x x x x x "T P
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cn cn cn cn cn n cn n cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn cn n cn cn Z
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3 3 3 3 o to QJ QJ to
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Tl T| Tl Tl T| Tl zO zO zO zO Oz zO zO ox ox ox ox ox ox ox ox ox ox ox ox ox ox oz oz oz oz oz
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
X X X X X X X X X X X x x x x x x x x x x x x x x x x x x x x P
O O o cn X Φ 3 3 o n o o X o X
X o 'i O-. Φ o o X o o o o X X ro o ?
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Table 6 Compounds of the formula If
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T| T1 T1 T1 T1 T| T1 T1 T| TI T| T| T1 T1 τι o τι o τι
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Tl Tl τι T| Tl o
o o o o o O O O O O O O O O O O O O O O O O O O O O O O
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R4 Rac/Enant. Phys. Data
CH2CH2CH2-phenyl rac
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o o o o O O z z z z ^ ^ o o o o o o o o o o o o o o
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Table 10 Compounds of the formula Ij
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Table 11 Compounds of the formula Ik
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p Q p Q b P b b P b b P Q b yj x J ? X ? x x u* x x x x § u x §
X p p o o o o o o o o o o o o o x x x x x 71
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Table 13: Compounds of the formula In
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3 3 3 3 3 3 p - -i -i -i to to to to to —i -i -i -i — ' to to to to 3 3 3 3 3 to to to to to to to to to to ω α> ω to ω to to o o o j=i f:» r' i Fi o o o o o
Figure imgf000117_0008
o o o o o o o o o 3 o o rπ
3
> > > > > > > > > > > 01
3
TJ
3" «< (A σ to sr
Figure imgf000118_0001
Figure imgf000119_0003
O 0 0 0 0 0 0 0 0 0 0 0 0 ° 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 coτι coτι uτι wτ| Ti O-π Oτι Oτι Oτι Oτι Oτι Oτι Oτι Oτι Oτι Oτι O-π Oτι Oτι Oτι Oτι Oτι Oτι Oτι Oτι Oτι Oτι Oτι Oτι Oτι Oτι θτι 3J
Figure imgf000119_0001
Figure imgf000119_0004
Figure imgf000119_0005
X X -r ° X X X X X X X X X X X X _x oX oX oX oX oX x x x x x x x x x x x * o o
*< ■< o. o.
X X X X o o o o o o o o o o
TJ o o o o o _,.
X X
X X TJ O o o
-n X o
X x x x o X X X X o X X X X x ox ox ox ox ox ox ox ox
TJ TJ
o TJ _ 4k 4k 4k k *■ "2. TJ T TJ TJ TJ TJ TJ TJ TJ o O A A A- A ZT 3" ZT ZT 3" ZT ZT ZT ZT
X X I X o_ p_ o. g_ o_ o_ g_ o_ o_ o. o_ o. o. Φ φ Φ φ φ Φ Φ φ φ φ φ u •< >< •< >< 3 3 3 3 3 3 3 3 3 3 3 s< •< •< •< •< «<
73
Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ φ 01
3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 o to to to to to to to to to to to to to to to
3 3 3 to 3 3 3 3 3 3 to to to to to to to to to ω to o 3 3 3 3 3 to to to to to O O o o o o o o o o o O 3 O o o o
> > > > > > > > > > > > > >
3 3 3 o o σ
Figure imgf000119_0002
Figure imgf000119_0006
Figure imgf000120_0001
Table 21 : Compounds of the formula It
Figure imgf000121_0001
Comp.No. Q Rac/Enant. Phys. Data
S
21.001 rac
Figure imgf000121_0002
21.007 enant.A
Figure imgf000121_0003
Comp.No. Q Rac/Enant. Phys. Data
21.008 enant.A
21.009 enant.A
21.010 enant.A.
Figure imgf000122_0001
ι—S
21.011 enant.A
21.012 enant.A
Figure imgf000122_0002
Table 22: Compounds of the formula lu
Figure imgf000122_0003
Comp.No. Rac/Enant. Phys. Data o
II
22.001 s rac Comp.No. Rac/Enant. Phys. Data
Figure imgf000123_0001
22.003 °- rac *)
Figure imgf000123_0002
0
Figure imgf000123_0003
O
II S
22.007 enant.A
22.008 enant.A
22.009 enant.A
22.010 enant.A.
22.01 1 enant.A
Figure imgf000123_0004
Comp.No. Rac/Enant. Phys. Data
22 012 enant A
Figure imgf000124_0001
*) The mixture of diastereomeπc racemates can be resolved into the diastereomers by means of chromatography on silica gel
Diastereomer a m p 75-77°C, and
Diastereomer b oil
The absolute configuration on the chiral centres (for example on the β carbon atom) is not known
Table 23 Compounds of the formula Iv
Figure imgf000124_0002
Comp.No. Rac/Enant. Phys. Data
C\ .0
23 001 rac
O
II o=s-
23 002 rac Comp.No. Rac/Enant. Phys. Data
Figure imgf000125_0001
°s .0
23.007 V enant.A
O
II o 8 -=s
23.00 3 enant.A
O
23.009 O- enant.A
23.010 °3o enant.A.
23.011 enant.A
Figure imgf000125_0002
Comp.No. Rac/Enant. Phys. Data
O
23.012 o-- enant.A
Table 24: Com ounds of the formula Vila
Figure imgf000126_0001
Formutation examples of active ingredients of the formula I (% = per cent by weight)
F1.Emulsion concentrates a) b) c) )
Active ingredient of
Tables 1-18 and 20-23 5% 10% 25% 50%
Calcium dodecyl- benzenesulfonate 6% 8% 6% 8%
Castor oil polyglycol ether
(36 mol of EO) 4% 4% 4%
Octylphenyl polyglycol ether (7-8 mol of EO) 4% 2%
Cyclohexanone 10% 20%
Aromatic hydrocarbon mixture C9-C12 85% 78% 55% 16%
Emulsions of any desired concentration can be prepared from such concentrates by dilution with water
F2 Solutions a) b) c) d)
Active ingredient of Tables
1-18 and 20-23 5% 10% 50% 90%
1 -Methoxy-3-(3-methoxy- propoxy)propane 20% 20%
Polyethylene glycol MW 400 20% 10%
N-Methyl-2-pyrrolιdone 30% 10%
Aromatic hydrocarbon mixture C9-C12 75% 60% The solutions are suitable for use in the form of microdrops
F3 Wettable powders a) b) c) d)
Active ingredient of Tables 1-18 and 20-23 5% 25% 50% 80% Sodium lignosulfonate 4% 3% Sodium lauryl sulfate 2% 3% 4% Sodium dnsobutyl naphthalenesulfonate 6% 5% 6% Octylphenyl polyglycol ether (7-8 mol of EO) Highly-disperse silica 10% Kaolin
Figure imgf000128_0001
The active ingredient is mixed thoroughly with the additives and ground thoroughly in a suitable mill This gives wettable powders which can be diluted with water to give suspensions of any desired concentration
F4 Coated granules a b c)
15%
2%
83%
83%
Figure imgf000128_0002
The active ingredient is dissolved in methylene chloπde, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo F5 Coated granules a) b) c)
Active ingredient of Tables 1-18 and 20-23 Polyethylene glycol MW 200 Highly-disperse silica Inorganic carrier
Figure imgf000129_0001
(0 0 1 - 1 mm), for example CaCO3 or SiO2
In a mixer, the finely ground active ingredient is applied uniformly to the earner material which has been moistened with polyethylene glycol This gives dust-free coated granules
F6 Extruder granules a) b) c) d)
Active ingredient of Tables 1-18 and 20-23 Sodium lignosulfonate Carboxymethylcellulose Kaolin
Figure imgf000129_0002
The active ingredient is mixed with the additives, and the mixture is ground and moistened with water This mixture is extruded and subsequently dried in a stream of air
b) c)
1% 5%
49% 35%
Figure imgf000129_0003
50% 60% Ό
Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture on a suitable mill F8. Suspension concentrates a) b) c) d)
Active ingredient of Tables
1-18 and 20-23
Ethylene glycol
Nonylphenyl polyglycol ether
(15 mol of EO)
Sodium lignosulfonate
Carboxymethylcellulose
37% aqueous formaldehyde solution
Silicone oil emulsion
Water
Figure imgf000130_0001
The finely ground active ingredient is mixed intimately with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water
Biological examples
Example B1 Herbicidal activity prior to plant emergence (pre-emergence action)
Monocotyledoneous and dicotyledoneous test plants are sown in standard soil in plastic pots. Immediately after sowing, the test substances are sprayed on in the form of an aqueous suspension (prepared from a 25% wettable powder (Example F3,b)) or in the form of an emulsion (prepared from a 25% emulsion concentrate (Example F1 ,c)), so that the dosage corresponds to 2 kg of a.s./ha (500 I of water/ha). The test plants are subsequently grown in the greenhouse under optimal conditions. After a test period of 3 weeks, the experiment is evaluated on the basis of a nine-step scale (1 = complete damage, 9 = no activity). Score figures of 1 to 4 (in particular 1 to 3) mean a good to very good herbicidal activity Table B1 Pre-emer ence action
tellaria
Figure imgf000131_0001
Figure imgf000132_0001
Figure imgf000133_0001
The same results are obtained when the compounds of the formula I are formulated as described in Examples F2 and F4 to F8
Example B2 Post-emergence herbicidal activity
Monocotyledoneous and dicotyledoneous test plants are grown in standard soil in plastic pots in the greenhouse and, in the 4- to 6-leaf stage, sprayed with an aqueous suspension of the test substances of the formula I, prepared from a 25% wettable powder (Example F3,b)) or with an emulsion of the test substances of the formula I, prepared with a 25% emulsion concentrate (Example F1 ,c)), so that the dosage corresponds to 2 kg of a.s./ha (500 I of water/ha). The test plants are subsequently grown in the greenhouse under optimal conditions. After a test period of approximately 18 days, the experiment is evaluated on the basis of a nine-step scale (1 = complete damage, 9 = no activity). Score figures of 1 to 4 (in particular 1 to 3) mean a good to very good herbicidal activity. In this test, a potent herbicidal activity is shown by the compounds of the formula I.
Table B2: Post-emer ence activit
ellaria
Figure imgf000134_0001
Figure imgf000135_0001
The same results are obtained when the compounds of the formula I are formulated as described in Examples F2 and F4 to F8

Claims

WHAT IS CLAIMED IS
1 A compound of the formula I
Figure imgf000136_0001
in which
R is halogen, Cr jhaloalkyl, cyano, nitro or C,-C3haloalkoxy,
Z is hydrogen, halogen or together with R, -0-CF2-O-,
R, is C,-C5alkyl or C3-C6cycloalkyl,
R2 and R3 independently of one another are hydrogen, CrC4alkyl or C3-C6cycloalkyl,
R4 is C,-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl or C5- or C6-cycloalkenyl, or is
CrC4alkyl, C2-C6alkenyl, C2-C6alkynyl or C3-C6cycloalkyl, each of which is substituted by halogen, cyano, C,-C4alkyl-CO, phenyl-CO, COOR5 C,-C4alkoxy, CrC4haloalkoxy, oxiranyl, dioxolanyl, tetrahydrofuranyl, tetrahydropyranyl, C3-C6cycloalkyl, halo-C3-C6-cycloalkyl, phenyl or phenoxy, it being possible for the phenyl group, in turn, to be substituted by halogen, d-C3alkyl, C1-C4alkoxy, cyano or CrC3haloalkyl, or is phenyl or phenyl which is substituted by halogen, CrC^ky!, C,-C4alkoxy, cyano or C,-C3haloalkyl, or
R4 together with one of the R2 groups forms a C2-C6alkylene bridge,
R5 is C,-C5alkyl or C3-C6cycloalkyl, n is the number 1 , 2 or 3 and m is the number 0, 1 or 2, or the diastereomer or enantiomer thereof
2 A compound according to claim 1 in which R4 is C,-C3alkyl, C2-C6alkenyl, C2-C6alkynyl or C3-C6cycloalkyl, or is CrC4alkyl, C2-C6alkenyl, C2-C6alkynyl or C3-C6cycloalkyl, each of which is substituted by halogen, cyano, COOR5 C,-C4alkoxy, C,-C4haloalkoxy or phenyl, it being possible for the phenyl group, in turn, to be substituted by halogen, CrC3alkyl, CrC4alkoxy, cyano or C,-C3haloalkyl, or is phenyl or phenyl which is substituted by halogen, C,-C3alkyl,
CrC4alkoxy, cyano or CrC3haloalkyl; or
R4 together with one of the R2 groups forms a Cz-C6alkylene bridge.
3. A compound according to claim 1 in which Z and R together form a group -0-CF2-0- in the 2- and 3-position of the phenyl ring
4. A compound according to claim 1 wherein Z is hydrogen.
5 A compound according to claim 1 wherein R is CF3or OCF3 and R, is methyl or ethyl
6 A compound according to claim 1 wherein n is the number 2
7 A process for the preparation of a compound of the formula I according to claim 1 , which comprises a) reacting a compound of the formula II
Figure imgf000137_0001
in which R, Z and R, have the meanings given for formula with a compound of the formula III
Figure imgf000137_0002
in which R2, R3, R4, m and n have the meanings given for formula I, or b) converting a compound of the formula II
Figure imgf000138_0001
in which R, Z and R, have the meanings given for formula I with a chloroformylating agent to give a compound of the formula IV
Figure imgf000138_0002
in which R, Z and R, have the meanings given for formula I and reacting this compound with a compound of the formula V
Figure imgf000138_0003
in which R2, R3, R4, m and n have the meanings given for formula I, or c) converting a compound of the formula II
Figure imgf000138_0004
in which R, Z and R, have the meanings given for formula I with a chloroformylating agent to give a compound of the formula IV
Figure imgf000139_0001
in which R, Z and R, have the meanings given for formula I reacting this compound with a compound of the formula VI
Figure imgf000139_0002
in which R2, R3 and n have the meanings given for formula I to give a compound of the formula VII
Figure imgf000139_0003
in which R, Z, R„ R2, R3 and n have the meanings given for formula and reacting this compound with a compound of the formula VIII
R4-X (VIII) in which R4 has the meaning given for formula I and X is a leaving group to give the compound of the formula la
Figure imgf000140_0001
in which R, Z, R,, R2, R3 R4 and n have the meanings given for formula I and, to prepare compounds of the formula I in which m is the number 1 or 2, oxidizing this compound to give the compound of the formula lb
Figure imgf000140_0002
in which R, Z, R,, R2, R3 R4 and n have the meanings given for formula I or Ic
Figure imgf000140_0003
in which R, Z, R,, R2, R3. R4 and n have the meanings given for formula I, or d) converting a compound of the formula II
Figure imgf000141_0001
in which R, Z and R, have the meanings given for formula I with a chloroformylating agent to give a compound of the formula IV
Figure imgf000141_0002
in which R, Z and R1 have the meanings given for formula I, converting this compound with a compound of the formula IX
Figure imgf000141_0003
in which R2, R3 and n have the meanings given for formula to give a compound of the formula X
Figure imgf000142_0001
in which R, Z, R,, R2, R3 and n have the meanings given for formula I, reacting this compound with a sulfonyl chloride of the formula XI
Cl-S02-R6 (XI)
in which R6 is d-Cβal yl, phenyl or phenyl which is substituted by halogen, methyl or methoxy in the presence of an inert organic solvent to give a compound of the formula XII
Figure imgf000142_0002
in which R, Z, R,, R2, R3and n have the meanings given for formula I and R6 has the meaning given for formula XI, converting this compound with a compound of the formula XIII
H-S-R4 (XIII)
in which R4 has the meaning given for formula I in the presence of an inert organic solvent to give the compound of the formula la
Figure imgf000143_0001
in which R, Z, R,, R2, R3 R4 and n have the meanings given for formula I and, to prepare compounds of the formula I in which m is the number 1 or 2, oxidizing this compound to give the compound of the formula lb
Figure imgf000143_0002
in which R, Z, R,, R2, R3 R4 and n have the meanings given for formula I or Ic
Figure imgf000143_0003
in which R, Z, R,, R2, R3 R4 and n have the meanings given for formula I, or e) converting a compound of the formula II
Figure imgf000144_0001
in which R, Z and R, have the meanings given for formula I with a chloroformylating agent to give a compound of the formula IV
Figure imgf000144_0002
in which R, Z and R, have the meanings given for formula I, converting this compound with a compound of the formula XIV
Figure imgf000144_0003
in which R2, R3 and n have the meanings given for formula I and Y is halogen to give a compound of the formula XV
Figure imgf000144_0004
in which R, Z, R1 r R2, R3 and n have the meanings given for formula I and Y has the meaning given for formula XIV, reacting this compound with a compound of the formula XIII
H-S-R4 (XIII)
in which R4 has the meaning given for formula I in the presence of a base to give the compound of the formula la
Figure imgf000145_0001
in which R, Z, R,, R2, R3 R4 and n have the meanings given for formula I and oxidizing this compound to give the compound of the formula lb
Figure imgf000145_0002
in which R, Z, R,, R2, R3 R4 and n have the meanings given for formula I or Ic
Figure imgf000146_0001
in which R, Z, R,, R2, R3 R4 and n have the meanings given for formula I
8 A compound of the formula VII
Figure imgf000146_0002
in which R, Z, R,, R2, R3 and n have the meaning given in claim 1
9 A compound of the formula X
Figure imgf000146_0003
ιn which R, Z, R,, R2, R3 and n have the meaning given in claim 1
10 A compound of the formula XII
Figure imgf000147_0001
in which R, Z, R,, R2, R3 and n have the meaning given in claim 1 and R6 is C,-C6alkyl, phenyl or phenyl which is substituted by halogen, methyl or methoxy
1 1 A herbicidal and plant-growth-inhibitory composition, which comprises a herbicidally active content of compound of the formula I and an inert carrier
12 A composition according to claim 1 1 , which comprises between 0 1% and 95% of active ingredient of the formula I
13 A method of controlling undesirable vegetation, which compπses applying an active ingredient of the formula I, or a composition which comprises this active ingredient, to the crops of useful plants or their environment in such an amount that it acts as a herbicide
14 A method according to claim 13, which compπses applying an amount of between 0 001 and 4 kg of active ingredient per hectare
15 A method of inhibiting vegetation, which comprises applying an active ingredient of the formula I, or a composition which comprises this active ingredient, to the plants or their environment in such an amount that it acts as a herbicide
16. The use of a composition according to claim 11 for controlling undesirable vegetation.
17. A method according to claim 13, wherein the crops of useful plants are cereals, cotton, soya, sugarbeet, sugarcane, sunflowers, sorghum, vegetables, fodder plants, plantations, oilseed rape, maize and rice.
PCT/EP1997/004626 1996-08-26 1997-08-25 Alkylthio-, alkylsulphinyl- and alkylsulphonylcarbamates as herbicides Ceased WO1998008810A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Applications Claiming Priority (4)

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CH2086/96 1996-08-26
CH208696 1996-08-26
CH275596 1996-11-07
CH2755/96 1996-11-07

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5078783A (en) * 1990-08-20 1992-01-07 Imperial Chemical Industries Plc Substituted alkyl carbamates and their use as herbicides
US5194661A (en) * 1990-08-20 1993-03-16 Ici Americas Inc. Substituted benzyl carbamates and their use as herbicides
US5399545A (en) * 1992-11-05 1995-03-21 Ciba-Geigy Corporation Substituted benzyl carbamates with herbicial properties

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5078783A (en) * 1990-08-20 1992-01-07 Imperial Chemical Industries Plc Substituted alkyl carbamates and their use as herbicides
US5194661A (en) * 1990-08-20 1993-03-16 Ici Americas Inc. Substituted benzyl carbamates and their use as herbicides
US5399545A (en) * 1992-11-05 1995-03-21 Ciba-Geigy Corporation Substituted benzyl carbamates with herbicial properties

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