WO2000010971A1

WO2000010971A1 - Substituted n-aryl-o-alkyl-carbamates

Info

Publication number: WO2000010971A1
Application number: PCT/EP1999/005909
Authority: WO
Inventors: Hans-Jochem Riebel; Johannes Rudolf Jansen; Ernst Rudolf F. Gesing; Joachim Kluth; Mark Wilhelm Drewes; Markus Dollinger; Ingo Wetcholowsky
Original assignee: Bayer Aktiengesellschaft
Priority date: 1998-08-24
Filing date: 1999-08-11
Publication date: 2000-03-02
Also published as: DE19838297A1; AU5733699A

Abstract

The invention relates to novel substituted N-Aryl-O-alkyl-carbamates of general formula (I), in which: m represents the numbers 0, 1 or 2; n represents the numbers 0 or 1; Ar represents an optionally substituted, monocyclic or bicyclic, if needed, partially saturated, carbocyclic or heterocyclic grouping; Q represents O (oxygen), S (sulfur), SO, SO2 or CH2 (carbene); R1 represents optionally substituted alkyl; R2 represents halogen or optionally substituted alkyl or alkoxy; R3 represents hydrogen or alkyl, and; R4 represents alkyl or cycloalkyl. The invention also relates to methods for producing the novel substituted N-Aryl-O-alkyl-carbamates, and to their use as herbicides.

Description

Substituted N-aryl-O-alkyl-carbamates

The invention relates to new substituted N-aryl-O-alkyl-carbamates, processes for their preparation and their use as herbicides.

It is known that certain substituted N-aryl-O-aryloxyalkyl-carbamates have herbicidal properties (cf. US-A-5099059, US-A-5152827, US-A-5194661). However, the herbicidal activity of these known compounds is not satisfactory in all respects.

The new substituted N-aryl-O-alkyl-carbamates of the general formula (I) have now been found

in which

m represents the numbers 0, 1 or 2,

represents the numbers 0 or 1,

Ar represents an optionally substituted, monocyclic or bicyclic, optionally partially saturated, carbocyclic or heterocyclic grouping,

Q represents O (oxygen), S (sulfur), SO, SO ₂ or CH ₂ (methylene),

R ^{1 represents} optionally substituted alkyl, R ^{2 stands} for halogen or for optionally substituted alkyl or alkoxy,

R ^{3 represents} hydrogen or alkyl, and

R ^{4 represents} alkyl or cycloalkyl.

The compounds of the general formula (I) according to the invention contain at least one asymmetrically substituted carbon atom and can therefore exist in various enantiomeric (R- and S-configured forms) or diasteromeric forms. The invention relates both to the various possible individual enantiomeric or stereoisomeric forms of the compounds of the general formula (I) and to the mixtures of these stereoisomeric compounds.

In the definitions, the hydrocarbon chains, such as alkyl - also in connection with heteroatoms, such as in alkoxy - are each straight-chain or branched.

The invention preferably relates to compounds of the formula (I), but rather

m stands for the numbers 0, 1 or 2.

n represents the numbers 0 or 1,

Ar for an optionally substituted, monoeyclic or bicyclic, optionally partially saturated, carbocyclic or heteroeyclic

Grouping from the series phenyl, naphthyl, tetralinyl, furyl, benzofuryl,

Thienyl, benzothienyl, pyridinyl, quinolinyl, isoquinolinyl or the - also optionally substituted below grouping below

where A is halogen-substituted alkanediyl having 1 to 3 carbon atoms, and where the possible substituents are preferably selected from the following list:

Cyano, nitro, halogen, each optionally substituted by halogen, alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl each having up to 6 carbon atoms,

Q represents O (oxygen), S (sulfur), SO, SO ₂ or CH ₂ (methylene),

R 'represents alkyl which has 1 to 4 carbon atoms and is optionally substituted by halogen,

R ² for halogen or for each optionally substituted by halogen

Is alkyl or alkoxy each having 1 to 4 carbon atoms,

R ^{3 represents} hydrogen or alkyl having 1 to 4 carbon atoms, and

R ^{4 represents} alkyl having 1 to 6 carbon atoms or cycloalkyl having 3 to 6 carbon atoms.

The invention relates in particular to compounds of the formula (I) in which

m represents the numbers 0, 1 or 2,

n represents the numbers 0 or 1, Ar for an optionally substituted, monocyclic or bicyclic, optionally partially saturated, carbocyclic group from the series phenyl, naphthyl, tetralinyl, or one of the - also optionally substituted below groups

where A stands for methylene or dimethylene (ethane-1,2-diyl) which is optionally substituted by fluorine and / or chlorine, and the possible substituents are preferably selected from the following list:

Cyano, nitro, fluorine, chlorine, bromine, each optionally substituted by fluorine and / or chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl,

Q represents O (oxygen), S (sulfur), SO, SO ₂ or CH ₂ (methylene),

R for methyl optionally substituted by fluorine and / or chlorine,

Is ethyl, n- or i-propyl,

R ^{2 represents} fluorine, chlorine, bromine or methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, each of which is optionally substituted by fluorine and / or chlorine,

R ^{3 represents} hydrogen, methyl, ethyl, n- or i-propyl, and R ^{4 represents} methyl, ethyl, n- or i-propyl, or cyclopropyl.

A particularly preferred group are those compounds of the formula (I) in which

m represents the numbers 0, 1 or 2,

n represents the numbers 0 or 1,

Ar represents the grouping below

wherein

A ^{1 represents} cyano, nitro, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy, methylthio, methylsulfinyl, methylsulfonyl or acetyl and

A ^{2 represents} hydrogen, fluorine, chlorine, methyl or trifluoromethyl,

Q represents oxygen or methylene,

R ^{1 represents} methyl, difluoromethyl, ethyl, n- or i-propyl,

R ^{2 represents} fluorine, chlorine, bromine, methyl, ethyl, methoxy or ethoxy,

R ^{3 represents} hydrogen, and R ^{4 represents} methyl, ethyl, n- or i-propyl.

n is most preferably 0.

Ar most preferably represents the grouping below

A

wherein

A ^{1 has} the meaning given above.

Q most preferably represents oxygen.

The general or preferred radical definitions listed above apply both to the end products of the formula (I) and correspondingly to the starting or intermediate products required in each case for the preparation. These radical definitions can be combined with one another, that is to say also between the specified preferred ranges.

The new substituted N-aryl-O-alkyl-carbamates of the general formula (I) are notable for their strong and selective herbicidal activity.

To a certain extent, the compounds of the general formula (I) also have insecticidal activity.

The new substituted N-aryl-O-alkyl-carbamates of the general formula (I) are obtained if (a) arylamines of the general formula (II)

in which

m, n, R, R and R have the meaning given above,

with chloroformic acid esters of the general formula (III)

Ar R O

(Wed)

Cl in which

Ar, Q and R have the meaning given above,

if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,

or if you

in the event that R ³ in the general formula (I) is hydrogen -

(b) aryl isocyanates of the general formula (IV)

in which m, n, R ¹ and R ^{2 have} the meaning given above,

with substituted alkanols of the general formula (V)

Ar, Q and R ^{4 have} the meaning given above,

and optionally on the compounds of the general formula (I) obtained according to process (a) or (b), carry out further chemical conversions in the context of the above definition of substituents by customary methods.

For example, the compounds of the general formula (I) in which m represents the number 0 can be reacted with oxygenating agents, such as hydrogen peroxide (H ₂ O ₂ ) or m-chloroperbenzoic acid, if appropriate in the presence of a diluent such as chloroform or carbon tetrachloride, at temperatures between 0 ° C. and 100 ° C., are converted into corresponding compounds of the general formula (I), in which m then stands for 1 or 2.

If, for example, chloroformic acid [1- (3-methylphenoxymethyl) propyl] ester and 2-difluoromethylthio-aniline are used as starting materials, the course of the reaction in process (a) according to the invention can be outlined using the following formula:

If, for example, 1- (3-trifluoromethyl-phenylthiomethyl) butanol and 2-ethylthiophenyl isocyanate are used as starting materials, the course of the reaction in process (b) according to the invention can be outlined using the following formula:

Formula (II) provides a general definition of the arylamines to be used as starting materials in process (a) according to the invention for the preparation of compounds of the general formula (I). In the general formula (II), m, n, R ¹ , R ² and R ³ preferably or in particular have those meanings which are preferred or particularly preferred in connection with the description of the compounds of the general formula (I) according to the invention for m, n, R ¹ , R ² and R ^{3 have been} specified.

The starting materials of the general formula (II) are known and / or can be prepared by processes known per se (cf. WO-A-97/46540).

Formula (III) provides a general definition of the chloroformate esters to be used further as starting materials in process (a) according to the invention. In the general formula (III), Ar, Q and R ⁴ preferably or in particular have the those meanings which have already been given above in connection with the description of the compounds of the general formula (I) according to the invention preferably or as particularly preferred for Ar, Q and R ⁴ .

The starting materials of the general formula (III) are known and / or can be prepared by processes known per se (cf. US-A-5099059, US-A-5152827, US-A-5399545).

Formula (IV) provides a general definition of the aryl isocyanates to be used as starting materials in process (b) according to the invention for the preparation of compounds of the general formula (I). In the general formula (IV), m, n, R 'and R ² preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the general formula (I) according to the invention preferably or as particularly preferred for m, n, R ¹ and R ^{2 have been} specified.

The starting materials of the general formula (IV) are known and / or can be prepared by processes known per se (cf. J. Med. Chem. 33 (1990), 1932-1935).

Formula (V) provides a general definition of the substituted alkanols to be used further as starting materials in process (b) according to the invention. In the general formula (V), Ar, Q and R ⁴ preferably or in particular have those meanings which are preferred or as particularly preferred for Ar, Q and R already in connection with the description of the compounds of the general formula (I) according to the invention ^{4 have been} specified.

The starting materials of the general formula (V) are known organic synthetic chemicals. Suitable reaction auxiliaries for processes (a) and (b) according to the invention are generally the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates, such as sodium, potassium or calcium acetate, lithium,

Sodium, potassium or calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or Calcium hydroxide, sodium or potassium methoxide, ethanolate, n- or -i-propanolate, -n-, -i-, -s- or -t-butanolate; basic organic nitrogen compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethyl-aniline, N, N-dimethyl benzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 3,4-dimethyl and 3,5-dimethyl-pyridine, 5- Ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,5-diazabicyclo [4,3, 0] -non-5-ene (DBN), or 1,8-diazabicyclo [5,4,0] -undec-7-ene (DBU).

Phase transfer catalysts are also suitable as further reaction aids for processes (a) and (b) according to the invention. As examples of such

Catalysts are mentioned:

Tetrabutylammonium bromide, tetrabutylammonium chloride, tetraoctylammonium chloride, tetrabutylammonium hydrogen sulfate, methyl trioctylammonium chloride, hexadecyl trimethylammonium chloride, hexadecyl trimethylammonium bromide,

Benzyl-trimethylammonium chloride, benzyl-triethylammonium chloride, benzyl-trimethylammonium hydroxide, benzyl-triethylammonium hydroxide, benzyl-tributylammonium chloride, benzyl-tributylammonium bromide, tetrabutylphosphonium bromide, tetrabutylphomide hexadecylphosphonium bromide, butyl triphenylphosphonium chloride, ethyl trioctylphosphonium bromide, tetraphenylphosphonium bromide. The processes according to the invention for the preparation of the compounds of the general formula (I) are preferably carried out using diluents. Suitable diluents for carrying out processes (a) and (b) according to the invention are, in addition to water, above all inert organic solvents. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride; Ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or butyronitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethyl-phosphoric acid triamide; Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide, alcohols such as methanol, ethanol, n- or i-

Propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

The reaction temperatures can be carried out when carrying out the inventive

Processes (a) and (b) can be varied over a wide range. In general, temperatures between 0 ° C and 120 ° C, preferably between 10 ° C and 80 ° C.

The processes according to the invention are generally carried out under normal pressure. However, it is also possible to carry out the processes according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.

To carry out the processes according to the invention, the starting materials are generally used in approximately equimolar amounts. However, it is also possible Lich to use one of the components in a larger excess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction mixture is generally stirred at the required temperature for several hours. The work-up is carried out using customary methods (cf. the manufacturing examples).

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are all plants that grow in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can e.g. can be used in the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Car- duusum, Solus , Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon,

Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis,

Brassica, lactuca, cucumis, cucurbita.

Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria,

Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera, Aegilops, Phalaris.

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.

Depending on the concentration, the active compounds according to the invention are suitable for combating total weeds, e.g. on industrial and track systems and on paths and squares with and without tree cover. The active compounds according to the invention for weed control in permanent crops, e.g. Forest, ornamental trees, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa,

Berry fruit and hop plants, on ornamental and sports turf and pasture land as well as for selective weed control in annual crops.

The compounds of formula (I) according to the invention show strong herbicidal activity and a broad spectrum of activity when used on the soil and on above-ground parts of plants. To a certain extent, they are also suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops, both in the pre-emergence and in the post-emergence process.

The active ingredients can be converted into the usual formulations, such as

Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances as well as very fine encapsulations in polymeric substances. These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, that is liquid solvents and / or solid carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as

Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

The following are suitable as solid carriers: for example ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules Question: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; Possible emulsifiers and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose. Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in their formulations, can also be used for combating weeds, in a mixture with known herbicides, finished formulations or tank mixes being possible.

Known herbicides are suitable for the mixtures, for example

Acetochlor, Acifluorfen (-sodium), Aclonifen, Alachlor, Alloxydim (-sodium), Ametryne, Amidochlor, Amidosulfuron, Anilofos, Asulam, Atrazine, Azafenidin, Azimsulfuron, Benazolin (-ethyl), Benfuresate, Bensulfuron (-methyl) Benzofenap, Benzoylprop (-ethyl), Bialaphos, Bifenox, Bispyribac (-sodium), Bromobutide, Bromofenoxim, Bromoxynil, Butachlor, Butroxydim, Butylate,

Cafenstrole, Caloxydim, Carbetamide, Carfentrazone (-ethyl), Chlomethoxyfen, Chloramben, Chloridazon, Chlorimuron (-ethyl), Chlornitrofen, Chlorsulfuron, Chlortoluron, Cinidon (-ethyl), Cinmethylin, Cinosulfuron, Clethodim (-clodproparofop) , Clomazone, Clomeprop, Clopyralid, Clopyrasulfuron (-methyl), Cloransulam (-methyl), Cumyluron, Cyanazines, Cybutryne, Cycloate, Cyclosulfam-uron, Cycloxydim, Cyhalofop (-butyl), 2,4-D, 2,4-DB , 2,4-DP, Desmedipham, Di- allate, Dicamba, Diclofop (-methyl), Diclosulam, Diethatyl (-ethyl), Difenzoquat, Diflufenican, Diflufenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimethametryn, Dimethenamid, Dimexyflam, Dinitramine, Dihenamidon-, Diquxurflam Dymron, Epoprodan, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), Ethofumesate, Ethoxyfen, Ethoxysulfuron, Etobenzanid, Fenoxaprop (-P-ethyl), Flamprop (-isopropyl), Flamprop (-isopropyl-L), Flamprop (-methyl), flazasulfuron, fluazifop (-P-butyl), fluazolate, flucarbazone, flufenacet, flumet-sulam, flumiclorac (-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen, Flupoxam, flupropacil, flurpyr- sulfuron (-methyl, -sodium), flurenol (-butyl), fluridone, fluroxypyr (-meptyl),

Flurprimidol, Flurtamone, Fluthiacet (-methyl), Fluthiamide, Fomesafen, Glufosinate (-ammonium), Glyphosate (-isopropylammonium), Halosafen, Haloxyfop (- ethoxy ethyl), Haloxyfop (-P-methyl), Hexazinone, Imazamethabenz (- methyl), imazamethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben,

Isoxachlortole, Isoxaflutole, Isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA, MCPP, Mefenacet, Mesotrione, Metamitron, Metazachlor, Methabenzthiazuron, Metobenzuron, Metobromuron, (alpha-) Metolachlor, Metosulamethyl, Metonulonium, Metosulamethyl, Metoxin, Moxin, Sulfur Monolinuron, Naproanilide, Napropamide, Neburon, Nicosulfuron, Norflurazon, Orbencarb, Oryzalin, Oxadiargyl,

Oxadiazon, Oxasulfuron, Oxaziclomefone, Oxyfluorfen, Paraquat, Pelargonic acid, Pendimethalin, Pentoxazone, Phenmedipham, Piperophos, Pretilachlor, Primisulfuron (-methyl), Prometryn, Propachlor, Propanil, Propaquizafop, Propamide, Prosulfon ), Pyrazolates, pyrazo-sulfuron (-ethyl), pyrazoxyfen, pyribenzoxime, pyributicarb, pyridate, pyriminobac (-methyl), pyrithiobac (-sodium), quinchlorac, quinmerac, quinoclamine, quizalofop (-P-ethyl), quizalofop ( -P-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron (-methyl), sulfosate, sulfosulfuron, tebutam, tebuthiuron, tepraloxydim, terbuthylazine, terbutryn, thenylchloride, thiazidiazyriaziazyl Thifensulfuron (-methyl), thioben- carb, tiocarbazil, tralkoxydim, triallates, triasulfuron, tribenuron (-methyl), tri-clopyr, tridiphane, trifluralin and triflusulfuron.

A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.

The active compounds according to the invention can be applied both before and after the plants emerge. They can also be worked into the soil before sowing.

The amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha.

The preparation and use of the active compounds according to the invention can be seen from the examples below. Manufacturing examples:

example 1

(Method (a))

0.9 g (3.6 mmol) chloroformic acid [1- (3-methylphenoxymethyl) propyl] ester are stirred at room temperature (approx. 20 ° C.) to a mixture of 0.7 g (3, 6 mmol) of 2-trifluoromethylthio-aniline, 0.4 g of triethylamine and 20 ml of dichloromethane are added and the reaction mixture is stirred for 15 hours at room temperature. It is then washed with water and the solvent is carefully distilled off from the organic phase under reduced pressure.

1.4 g (97% of theory) of N- (2-trifluoromethylthiophenyl) -O- [l - (3-methylphenoxymethyl) propyl] carbamate with a refractive index n ^ _Q = 1.5089 are obtained .

Analogously to Example 1 and in accordance with the general description of the production process according to the invention, it is also possible, for example, to prepare the compounds of the general formula (I) listed in Table 1 below.

In all cases, these are racemates. Table 1: Examples of the compounds of the formula (I)

The logP values given in Table 1 were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a phase inversion column (C 18). Temperature: 43 ° C.

(a) Eluents for determination in the acidic range: 0.1% aqueous phosphoric acid, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^a ).

(b) Eluents for determination in the neutral range: 0.01 molar aqueous

Phosphate buffer solution, acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile - corresponding measurement results are marked in Table 1 with ^b ).

The calibration was carried out using unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values using the

Retention times by linear interpolation between two consecutive alkanones). The lambda max values were determined using the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals.

Examples of use

In the application examples, the compound (A) listed below is used as a reference substance:

N- (2-trifluoromethylphenyl) -O- [1- (3-trifluoromethylphenoxymethyl) propyl] carbamate (known from US-A-5099059).

Example A

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired level

Concentration.

Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the active ingredient preparation in such a way that the desired amount of active ingredient is applied per unit area. The concentration of the spray liquor is chosen so that the desired amount of active compound is applied in 1000 liters of water per hectare.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.

It means:

0% = no effect (like untreated control)

100% = total annihilation

In this test, for example, the compound according to Production Example 3 shows, at an application rate of 1000 g / ha, a considerably stronger action against weeds than the known compound (A). Example B

Post emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Test plants with a height of 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area. The concentration of the spray liquor is chosen so that in

1000 1 water / ha the desired amounts of active ingredient are applied.

It means:

0% = no effect (like untreated control) 100% = total destruction

In this test, for example, the compound according to Production Example 3 shows, at an application rate of 1000 g / ha, a considerably stronger action against weeds than the known compound (A).

Claims

claims

1. Substituted N-aryl-O-alkyl-carbamates of the general formula (I),

in which

m represents the numbers 0, 1 or 2,

n represents the numbers 0 or 1,

Q represents O (oxygen), S (sulfur), SO, SO ₂ or CH ₂ (methylene),

R ^{1 represents} optionally substituted alkyl,

R ² for halogen or for each optionally substituted alkyl or

Alkoxy stands,

R ^{3 represents} hydrogen or alkyl, and

R ^{4 represents} alkyl or cycloalkyl. Substituted N-aryl-O-alkyl-carbamates according to claim 1, characterized in that

m represents the numbers 0, 1 or 2,

n represents the numbers 0 or 1,

Ar for an optionally substituted, monocyclic or bicyclic, optionally partially saturated, carbocyclic or heterocyclic group from the series phenyl, naphthyl,

Tetralinyl, furyl, benzofuryl, thienyl, benzothienyl, pyridinyl, quinolinyl, isoquinolinyl or the - also optionally substituted below grouping

where A is halogen-substituted alkanediyl having 1 to 3 carbon atoms, and the possible substituents are preferably selected from the following list:

Q represents O (oxygen), S (sulfur), SO, SO ₂ or CH ₂ (methylene),

R 'represents alkyl which has 1 to 4 carbon atoms and is optionally substituted by halogen, R ^{2 represents} halogen or alkyl or alkoxy, each optionally substituted by halogen, each having 1 to 4 carbon atoms,

R ^{3 represents} hydrogen or alkyl having 1 to 4 carbon atoms, and

3. Substituted N-aryl-O-alkyl-carbamates according to claim 1, characterized in that

m represents the numbers 0, 1 or 2,

n represents the numbers 0 or 1,

Ar for an optionally substituted, monocyclic or bicyclic, optionally partially saturated, carbocyclic group from the series phenyl, naphthyl, tetralinyl, or one of the - also optionally substituted below groups

where A stands for methylene or dimethylene (ethane-1,2-diyl) which is optionally substituted by fluorine and / or chlorine, and the possible substituents are preferably selected from the following list: Cyano, nitro, fluorine, chlorine, bromine, each optionally substituted by fluorine and / or chlorine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i- Propylsulfinyl,

Methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, acetyl, propionyl, n- or i-butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl,

Q represents O (oxygen), S (sulfur), SO, SO ₂ or CH ₂ (methylene),

R 'represents methyl, ethyl, n- or i-propyl, each optionally substituted by fluorine and / or chlorine,

R ^{3 represents} hydrogen, methyl, ethyl, n- or i-propyl, and

R ^{4 represents} methyl, ethyl, n- or i-propyl, or cyclopropyl.

4. Substituted N-aryl-O-alkyl-carbamates according to claim 1, characterized in that

m represents the numbers 0, 1 or 2,

n represents the numbers 0 or 1,

Ar represents the grouping below

woπn

A ^{2 represents} hydrogen, fluorine, chlorine, methyl or trifluoromethyl,

Q represents oxygen or methylene,

R ^{1 represents} methyl, difluoromethyl, ethyl, n- or i-propyl,

R ^{3 represents} hydrogen, and

R ^{4 represents} methyl, ethyl, n- or i-propyl.

5. A process for the preparation of substituted N-aryl-O-alkyl-carbamates according to any one of claims 1 to 4, characterized in that

(a) arylamines of the general formula (II)

in which

m, n, R ¹ , R ² and R ^{3 have} the meaning given in one of claims 1 to 4,

with chloroformic acid esters of the general formula (III)

in which

Ar, Q and R ^{4 have} the meaning given in one of claims 1 to 4,

or that one

- in the event that R ³ in the general formula (I) represents hydrogen

(b) aryl isocyanates of the general formula (IV)

in which

m, n, R ¹ and R ^{2 have} the meaning given in one of claims 1 to 4,

with substituted alkanols of the general formula (V)

Ar R ⁴

(V). "H

Ar, Q and R ^{4 have} the meaning given in one of claims 1 to 4,

6. Use of at least one substituted N-aryl-O-alkyl-carbamate according to one of claims 1 to 4 for combating undesirable plants.

7. A method for controlling unwanted plants, characterized in that at least one substituted N-aryl-O-alkyl carbamate according to one of claims 1 to 4 is allowed to act on undesired plants and / or their habitat. Herbicidal agents, characterized by the content of at least one substituted N-aryl-O-alkyl-carbamate according to one of Claims 1 to 4 and conventional extenders.