CA2307344A1 - Substituted n-aryl-o-aryloxyalkyl carbamates and their use as herbicides - Google Patents

Abstract

The invention relates to novel substituted n-aryl-o-aryloxyalkyl carbamates of general formula (I), wherein m represents the numbers 0, 1 or 2, n represents the numbers 0, 1, 2, 3 or 4, R1 represents cyano, halogen or alkyl or alkoxy, said alkyl or alkoxy being optionally substituted by cyano, halogen or C1-C4 alkoxy and each having 1 to 4 carbon atoms; R2 represents alkyl optionally substituted by cyano, halogen or C1-C4 alkoxy and each having 1 to 4 carbon atoms, R3 represents cyano, fluorine, bromine, iodine or alkyl, alkoxy or alkoxy carbonyl optionally substituted by cyano, halogen or C1-C4 alkoxy, each having up to 4 carbon atoms; and R4 represents cyano, bromine, iodine or alkyl, alkoxy or alkoxy carbonyl optionally substituted by cyano, halogen or C1-C4 alkoxy, each having up to 4 carbon atoms, excluding the compound N-(2-methoxy-5-methyl-phenyl)-O-[1-(3-trifluoromethyl-phenoxymethyl)-propyl]-carbamate. The invention also relates to methods for producing the inventive substituted n-aryl-o-aryloxyalkyl carbamates and to their use as herbicides.

Description

Le A 32 695-Foreign Countries Kri/Kr/W6/VO1/12/99 Substituted O-arvloxyalkvl N-aryl-carbamates The invention relates to novel substituted O-aryloxyalkyl N-aryl-carbamates, to processes for their preparation and to their use as herbicides.
It is known that certain substituted O-aryloxyalkyl N-aryl-carbamates, such as, for example, the compounds O-[1-(3-trifluoromethyl-phenoxymethyl)-propylJ N-(2-chloro-phenyl)-carbamate, O-[1-(3-trifluoromethyl-phenoxymethyl)-propylJ N-(2-trifluoromethyl-phenyl)-carbamate and O-[1-(3-trifluoromethyl-phenoxymethyl)-propylJ N-(3-trifluoromethyl-phenyl)-carbamate, have herbicidal properties (cf.
US-A-S 099 059 and US-A-S 152 827). However, the herbicidal activity of these known compounds is not always satisfactory.
This invention, accordingly, provides the novel substituted O-aryloxyalkyl N-aryl-carbamates of the general formula (I), ~Re)~ O R2 O ~ CF3 (1)~

~R~~m in which m represents the numbers 0, 1 or 2, n represents the numbers 0, 1, 2, 3 or 4, with the proviso that in each individual case the sum of m and n is at least 1, Rl represents cyano, halogen or in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl or alkoxy having in each case 1 to 4 carbon atoms, Le A 32 695-Foreign Countries R2 represents optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having 1 to 4 carbon atoms, R3 represents cyano, fluorine, bromine, iodine or in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy or alkoxycarbonyl having in each case up to 4 carbon atoms, and - in the event that m represents 1 or 2 -also represents chlorine, and R4 represents cyano, bromine, iodine or in each case optionally cyano-, halogen-or C1-C4-alkoxy-substituted alkyl, alkoxy or alkoxycarbonyl having in each case up to 4 carbon atoms, and - in the event that m represents 1 or 2 - also represents fluorine or chlorine, except for the prior-art compound O-[1-(3-trifluoromethyl-phenoxymethyl)-propyl]
N-(2-methoxy-5-methyl-phenyl)-carbamate - cf. US-A-5099059 and US-A-5152827, in each case Table I, Compound No. 40 - which is excluded by disclaimer.
The compounds of the general formula (I) according to the invention contain an asymmetrically substituted carbon atom and can therefore be present in various enantiomeric (R- and S-configured forms) or diastereomeric 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 combination with heteroatoms, such as in alkoxy- are in each case straight-chain or branched.
The invention preferably provides compounds of the formula (I) in which m represents the numbers 0, 1 or 2, Le A 32 695-Foreign Countries n represents the numbers 0, 1, 2 or 3, with the proviso that in each individual case the sum of m and n is at least 1, R1 represents cyano, fluorine, chlorine, bromine or in each case optionally cyano-fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, R2 represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, R3 represents cyano, fluorine, bromine, iodine or in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, and - in the event that m represents 1 or 2 - also represents chlorine, and R4 represents cyano, bromine, iodine or in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, and - in the event that m represents 1 or 2 - also represents fluorine or chlorine, except for the prior-art compound O-[1-(3-trifluoromethyl-phenoxymethyl)-propyl]
N-(2-methoxy-5-methyl-phenyl)-carbamate - cf. US-A-5099059 and US-A-S 152827, in each case Table I, Compound No.40 - which is excluded by disclaimer.
The invention relates in particular to compounds of the formula (I) in which m represents the numbers 0 or 1, Le A 32 695-Foreign Countries n represents the numbers 0, 1 or 2, with the proviso that in each individual case the sum of m and n is at least 1, R1 represents cyano, fluorine, chlorine, bromine or in each case optionally fluorine- or chlorine-substituted methyl, ethyl, methoxy or ethoxy, R2 represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, R3 represents cyano, fluorine, bromine or in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, and - in the event that m represents 1 - also represents chlorine, and R4 represents cyano, bromine, iodine or in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i propoxycarbonyl, and - in the event that m represents 1 - also represents fluorine or chlorine, except for the prior-art compound O-[1-(3-trifluoromethyl-phenoxymethyl)-propyl]
N-(2-methoxy-5-methyl-phenyl)-carbamate - cf. US-A-5099059 and US-A-5152827, in each case Table I, Compound No.40 - which is excluded by disclaimer.
The abovementioned general or preferred radical definitions apply both to the end products of the formula (I) and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with one another at will, i.e. including combinations between the given preferred ranges.

Le A 32 695-Foreign Countries ' -S-The novel substituted O-aryloxyalkyl N-aryl-carbamates of the general formula (I) exhibit strong and selective herbicidal activity.
Surprisingly, the novel substituted O-aryloxyalkyl N-aryl-carbamates of the general formula (>] have considerably higher herbicidal activity than the prior-art compounds O-[1-(3-trifluoromethyl-phenoxymethyl)-propyl] N-(2-chloro-phenyl)-carbamate, O-[1-(3-trifluoromethyl-phenoxymethyl)-propyl] N-(2-trifluoromethyl-phenyl)-carbamate and O-[1-(3-trifluoromethyl-phenoxymethyl)-propyl] N-(3-trifluoromethyl-phenyl)-carbamate.
To a certain extent the compounds of the formula (I) also exhibit fungicidal and insecticidal activity.
Examples of the compounds of the general formula (I) according to the invention are listed in the groups below.

Le A 32 695-Forei~ Countries Group 1 ~R4~n \ ~ N~O~O ,~ CFs 3 H ~ /
here, n, R3 and R4 have, for example, the meanings given in the list below:
(position) (position) (position) R3 (R4)n R3 (R4)n R3 (R4)n CH3 (3) CH3 CH3 (4) CH3 CH3 (5) CH3 CH3 (6) CH3 CH3 (6) C2H5 CH3 (4,5) ~ (CH3)2 CH3 (3,5) CH3 (4,6) CH3 (4) CH3 (CH3)2 (CH3)2 (6) C2H5 CH3 (3) CF3 CH3 (4) CF3 CH3 (5) CF3 CH3 (3) Br CH3 (4) Br CH3 (5) Br CH3 (3) CN CH3 (4) CN CH3 (5) CN

CH3 (3) OCH3 CH3 (4) OCH3 CH3 (5) OCH3 F (3) CH3 F (4) CH3 F (5) CH3 F (6) CH3 F (6) C2H5 F (4,5) (CH3)2 F (3,5) F (4,6) F (4) CH3 (CH3)2 (CH3)2 (6) C2H5 F (3) CF3 F (4) CF3 F (5) CF

F (3) Br F (4) Br F (5) Br F (3) CN F (4) CN F (5) CN

F (3) OCH3 F (4) OCH3 F (5) OCH

Br (3) CH3 Br (4) CH3 Br (5) CH3 Le A 32 695-Foreign Countries 7_ (position) (position) (position) R3 (R4)n R3 (R4)n R3 (R4)n Br (6) CH3 Br (6) C2H5 Br (4,5) (CH3)2 Br (3,5) Br (4,6) Br (4) CH3 (CH3)2 (CH3)2 (6) C2Hs Br (3) CF3 Br (4) CF3 Br (5) CF3 Br (3) Br Br (4) Br Br (5) Br Br (3) CN Br (4) CN Br (5) CN

Br (3) OCH3 Br (4) OCH3 Br (5) OCH

CF3 (3) CH3 CF3 (4) CH3 CF3 (5) CH3 CF3 (4) Br CF3 (4) OCH3 CF3 (4) CN

CF3 (3) CF3 CF3 (4) CF3 CF3 (5) CF3 OCH3 (3) CH3 OCH3 (4) CH3 OCH3 (5) OC2H5 OCH3 (6) CH3 OCH3 (6) C2H5 OCH3 (4,5) ~ (CH3)2 OCH3 (3,5) OCH3 (4,6) OCH3 (4) CH3 (CH3)2 (CH3)2 (6) C2Hs OCH3 (3) CF3 OCH3 (4) CF3 OCH3 (5) CF3 OCH3 (3) Br OCH3 (4) Br OCH3 (5) Br OCH3 (3) CN OCH3 (4) CN OCH3 (5) CN

OCH3 (3) OCH3 OCH3 (4) OCH3 OCH3 (5) OCH3 OCH3 (3) COOEt OCH3 (4) COOEt OCH3 (5) COOEt Group 2 ~R4~n / O CzHs \ ~ N~O~O \ CF3 3 H ~ /
here, n, R3 and R4 have, for example, the meanings given above in Group 1.

Le A 32 695-Foreign Countries -g-Group 3 (R4)n / O CH(CH3)2 \ ~ N/\ ~O \ CFs O

S here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 4 (R4)n \ ~ N~O~O \ CF3 R3 H ~ /
here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group S
(R4)n / O CzHs CI
\ ~ N~O~O \ CF3 R3 H ~ /
here, n, R3 and R4 have, for example, the meanings given above in Group 1.

Le A 32 695-Foreign Countries Groin 6 (R4)n / O CH(CH3)z CI
\ ~ N/\ ~O \ CFs O

here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 7 (R4)n \ ~ N~O/~O \ CFs R3 H ( /
CI
here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 8 (R4)n / O CzHs \ ~ N~O~O \ CF3 R3 H ~ /

here, n, R3 and R4 have, for example, the meanings given above in Group 1.

Le A 32 695-Foreign Countries Group 9 (R4)n O CH(CH3)z \ ~ N~O~O \ CF3 3 H ~ /
CI
here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Gro ~ 10 (R4 )n \ ~ N~O~O \ CF3 3 H ~ /
CI
here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 11 (R4)n / O CzHs \ ( N~O~O \ CF3 3 H ~ /

here, n, R3 and R4 have, for example, the meanings given above in Group 1.

Le A 32 695-Foreign Countries Group 12 (R4 )n / O CH(CH3)z \ ~ N~ ~O \ CFs O

CI
S here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 13 (R4)n \ ~ N~O~O \ CF3 R3 H ~ /
CI
here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 14 (R4 )n / O CzHs \ ~ N~O~O \ CF3 R3 H ~ /
CI
here, n, R3 and R4 have, for example, the meanings given above in Group 1.

Le A 32 695-Foreign Countries Group 15 (R4)n / O CH(CH3)z \ ~ N~O~O \ CF3 H ~ /
CI
S here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 16 (R4)n \ ~ N~O~O \ CF3 H ~ /
here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 17 (R4 )n \ ~ N~O~O \ CF3 H ~ /
here, n, R3 and R4 have, for example, the meanings given above in Group 1.

Le A 32 695-Foreign Countries Group 18 (R4)n / O CH(CH3)Z F
\ ~ N~O~O \ CF3 3 H ~ /
here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 19 (R4)n \ ~ N~O~O \ CF3 3 H ~ /
F
here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 20 (R4)n / O C2Hs \ ~ N~O~O \ CF3 3 H ~ /
F
here, n, R3 and R4 have, for example, the meanings given above in Group 1.

Le A 32 695-Foreign Countries Group 21 (R4)n / O CH(CH3)2 \ ~ N~O~O \ CF3 3 H ~ /
F
here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 22 (R4)n \ ~ N~O~O \ CF3 3 H ~ /
F
here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 23 (R4 )n / O C2Hs \ ~ N~O~O \ CF3 3 H ~ /
F
here, n, R3 and R4 have, for example, the meanings given above in Group 1.

Le A 32 695-Foreign Countries Group 24 (R4)n / O CH(CH3)2 \ ~ N~O~O \ CF3 3 H ~ /
F
here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 25 (R4)n \ ~ N~O~O \ CF3 3 H ~ /
C
1~
here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 26 (R4)n / O CzHs \ ~ N~O~O \ CF3 3 H ~ /
F
here, n, R3 and R4 have, for example, the meanings given above in Group 1.

Le A 32 695-Foreign Countries Group 27 (R4 )n / O CH(CH3)z N~O~O ~ CF3 R3 H ( /
F
here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 28 (R4)n N~O~O ~ CF3 3 H ~ /

here, n, R3 and R4 have, for example, the meanings given above in Group 1.
Group 29 (R4)n / O CzHs N~o~O ~ CF3 3 H ~ /

here, n, R3 and R4 have, for example, the meanings given above in Group 1.

Le A 32 695-Foreign Countries Group 30 (R4)n / O CH(CH3)z \ ~ N~O~O \ CF3 R3 H ~ /

here, n, R3 and R4 have, for example, the meanings given above in Group 1.
The novel substituted O-aryloxyalkyl N-aryl-carbamates of the general formula (I) are obtained when (a) aryloxyalkyl chloroformates of the general formula (II) O Rz CI~O~O \ CF3 (R, )m in which m, R1 and R2 are as defined above, are reacted with arylamines of the general formula (III) (R4)n i\
(nl) /
NHz Rs in which Le A 32 695-Foreign Countries n, R3 and R4 are as defined above, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or (b) aryloxyalkanols of the general formula (N) RZ
H~ ~O CF3 O ~ ~ (IV) yR~ )m in which 1 S m, R 1 and R2 are as defined above, are reacted with aryl isocyanates of the general formula (V) (R4)n (~) NCO

in which n, R3 and R4 are as defined above, Le A 32 695-Foreign Countries if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent.
Using, for example, (1-(2-fluoro-5-trifluoromethyl-phenoxymethyl)-propyl]
S chloroformate and methyl 2-amino-4-ethyl-benzoate as starting materials, the course of the reaction in the process (a) according to the invention can be illustrated by the following scheme:
CzHS O CZHS CzHS
'f' C~~O~O ~ ~ CF3 ~ ~ O CZHS
NH / N~O~O ~ CF3 z F H

Using, for example, 2-(3,5-bis-trifluoromethyl-phenoxy)-1-methyl-ethanol and 2-bromo-6-methyl-phenyl isocyanate as starting materials, the course of the reaction of the process (b) according to the invention can be illustrated by the following scheme:
Br CH3 Br H ~O ~ CF ~ O CH3 NCO \O I --~ ~ / N O~O ~ CF3 CH3 ~ H

The formula (II) provides a general definition of the aryloxyaryl chloroformates to be used as starting materials in the process (a) according to the invention for preparing compounds of the formula (I). In the formula (II), m, R1 and R2 each preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly preferred for m, R1 and R2 .

Le A 32 695-Foreign Countries The starting materials of the general formula (II) are known and/or can be prepared by processes known per se (cf. US-A-5099059, US-A-5152827, US-A-5399545).
The formula (III) provides a general definition of the arylamines further to be used as starting materials in the process (a) according to the invention. In the formula (III), n, R3 and R4 each preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly preferred for n, R3 and R4.
The starting materials of the general formula (III) are known chemicals for synthesis.
The formula (IV) provides a general definition of the aryloxyalkanols to be used as starting materials in the process (b) according to the invention for preparing 1 S compounds of the formula (I). In the formula (N) m, R1 and R2 each preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly preferred for m, R1 and R2 .
The starting materials of the general formula (N) are known and/or can be prepared by processes known per se (cf. US-A-5099059, US-A-5152827, US-A-5399545).
The formula (V) provides a general definition of the aryl isocyanates further to be used as starting materials in the process (b) according to the invention. In the formula (V), n, R3 and R4 each preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly preferred for n, R3 and R4.
The starting materials of the general formula (V) are known chemicals for synthesis.

Le A 32 695-Foreign Countries Suitable reaction auxiliaries for the processes (a) and (b) are, in general, 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 alkoxides, such as, for example, sodium acetate, potassium S acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bicarbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, sodium methoxide, ethoxide, n- or -i-propoxide, n-, i-, s- or -t-butoxide or potassium methoxide, ethoxide, n- or i-propoxide, n-, i-, s- or t-butoxide; furthenmore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclo-hexylamine, ethyl-dicyclohexylamine, N,N-dimethyl-aniline, N,N-dimethyl-benzyl-1 S amine, 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-S-ene (DBN), or 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU).
Suitable diluents for carrying out the processes (a) and (b) according to the invention are especially inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, 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 ether or ethylene glycol diethyl ether; ketones, such as acetone, butanone or methyl isobutyl ketone; nitrites, such as acetonitrile, propionitrile or butyronitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene Le A 32 695-Foreign Countries glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, mixtures thereof with water or pure water.
When carrying out the processes (a) and (b) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the processes are carried out at temperatures between 0°C and 150°C, preferably between 10°C and 120°C.
The processes (a) and (b) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to carry out the processes according to the invention under elevated or reduced pressure - in general between 0.1 bar and 10 bar.
For carrying out the processes (a) and (b) according to the invention, the starting 1 S materials are generally employed in approximately equimolar amounts.
However, it is also possible to use a relatively large excess of in each case one of the components.
The reaction is generally carned out in a suitable diluent, if appropriate in the presence of a reaction auxiliary, and the reaction mixture is generally stirred for several hours at the required temperature. Work-up is carried out by customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weedkillers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are undesired. 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 be used, for example, in connection with the following plants:
Dicotyledonous weeds of the enera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Le A 32 695-Forei~ Countries Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
S
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the enera: 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 and Apera.
Monocotyledonous crops of the enera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
Depending on the concentration, the compounds are suitable for total weed control, for example on industrial terrain and rail tracks, and on paths and areas with or without tree stands. Equally, the compounds can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pastures, and for selective weed control in annual crops.
The compounds of the formula (I) according to the invention are suitable in particular for the selective control of monocotyledonous and dicotyledonous weeds in Le A 32 695-Foreign Countries monocotyledonous and dicotyledonous crops, both by the pre- and the post-emergence method.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspoemulsion concentrates, natural and synthetic materials impregnated with active compound, and microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the ' active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers.
If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Liquid solvents which are mainly suitable are:
aromatics such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulphoxide, and water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly disperse silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks;
suitable emulsifiers and/or foam formers are: for example non-ionic and anionic emulsifiers, Le A 32 695-Foreign Countries such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.
S
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of 1 S iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, readymixes or tank mixes being possible.
Possible components for the mixtures are known herbicides, such as, for example, acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin(-ethyl), benfuresate, bensulfuron(-methyl), bentazone, 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, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clomeprop, clopyralid, Le A 32 695-Foreign Countries clopyrasulfuron(-methyl), cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, 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, S dimethametryn, dimethenamid, dimexyflam, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymrone, epoprodan, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop(-P-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-L), flamprop(-methyl), flazasulfuron, fluazifop(-P-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, flumetsulam, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurpyrsulfuron(-methyl, -sodium), flurenol(-butyl), fluridone, fluroxypyr(-meptyl), flurprimidol, flurtamone, fluthiacet(-methyl), fluthiamide, fomesafen, glufosinate{-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), haloxyfop(-P-methyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isouron, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, (alpha-)metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, 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, propisochlor, propyzamide, prosulfocarb, prosulfuron, pyraflufen(-ethyl), pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyribenzoxim, 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, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.

Le A 32 695-Foreign Countries _2~_ A mixture with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and soil conditioners, 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 customary manner, for example by watering, spraying, atomizing or spreading.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the application rates are between 1 g and 10 kg of active compound per hectare of soil surface, 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 which follow.

Le A 32 695-Foreign Countries _2g_ Preparation Examples:
Example 1 / O C2Hs HsC \ N~O/~O \ CF3 CH3 H ~ /
(Process (a)) At room temperature (approximately 20°C), 3.0 g (25 mMol) of 1-(3-trifluoromethyl-phenoxymethyl)-propyl chloroformate (racemic) are added with stirring to a solution of 2.5 g (10 mMol) of 2,3-dimethyl-aniline in 80 ml of toluene, and the reaction mixture is stirred at room temperature for 1 S hours. The mixture is subsequently washed with water and 1N hydrochloric acid, dried with sodium sulphate and filtered. The solvent is carefully distilled off from the filtrate under water pump vacuum.
This gives 3.5 g (92% of theory) of O-[1-(3-trifluoromethyl-phenoxymethyl)-propyl]
N-(2,3-dimethyl-phenyl)-carbamate (racemate) as a crystalline residue of melting point 76°C.
Analogously to Preparation Example 1 and in accordance with the general description of the preparation process according to the invention, it is also possible to prepare, for example, the compounds of the formula (I) listed in Table 1 below.
~R4y 2 O R
N- -O v 0 ~ CF3 (I), ~R~~m Le A 32 695-Foreign Countries In all cases, they are racemates. The position of Rl is - if required - stated such that the CF3 group is in each case in the 3-position. The structures were confirmed by 'H NMR spectra.

Le A 32 695-Foreign Countries Table 1: Examples of compounds of the formula (I) Ex.- (position) (position) Melting point No. m R1 R2 R3 (R4) (~C) 2 0 C2H5 CH3 (4) CH3 58 3 0 C2H5 CH3 (5) CH3 102 4 0 C2H5 CH3 (6) CH3 61 0 C2H5 CH3 (4,5) (CH3)2 6 0 C2H5 CH3 (3,5) (CH3)2 7 0 C2H5 CH3 (3) Br 8 0 C2H5 CH3 (4) Br 9 0 C2H5 CH3 (5) Br 0 C2H5 CH3 (3) CN

11 0 C2H5 CH3 (4) CN

12 0 C2H5 CH3 (5) CN

13 0 C2H5 CH3 (5) CF3 14 0 C2H5 CH3 (3) OCH3 0 C2H5 CH3 (4) OCH3 (amorphous) 16 0 C2H5 CH3 (5) OCH3 (amorphous) 17 0 CZHS CH3 (3) COOC2H5 18 0 C2H5 CH3 (4) COOC2H5 19 0 C2H5 CH3 (5) COOC2H5 0 C2H5 F (3) CH3 21 0 C2H5 F (4) CH3 (amorphous) 22 0 C2H5 F (5) CH3 (amorphous) 23 0 C2H5 F (6) CH3 24 0 C2H5 F (4) Br 0 C2H5 F (3) CF3 26 0 C2H5 F (4) CF3 27 0 CZHS F (5) CF3 28 0 C2H5 F (6) CF3 Le A 32 695-Foreign Countries Ex.- (position)~ (position) Melting point No. m R1 R2 R3 (R4 (C) 29 0 C2H5 F (5) OCH3 (6) CH3 30 0 C2H5 F (3) OCH3 31 0 C2H5 F (4) OCH3 32 0 C2H5 F (6) OCH3 33 0 C2H5 CF3 (6) Br 34 0 C2H5 CF3 (4) OCH3 35 0 C2H5 CF3 (4) Br 36 0 C2H5 CF3 (4) CN

37 0 C2H5 CF3 (3) CF3 38 0 CZHS CF3 (4) CF3 39 0 C2H5 CF3 (5) CF3 40 0 C2H5 OCH3 (3) CH3 41 0 C2H5 OCH3 (4) CH3 42 0 CZHS OCH3 (S) CH3 43 0 C2H5 OCH3 (S) COOC2H5 44 0 C2H5 CN (3) CH3 45 0 C2H5 CN (4) CH3 46 0 C2H5 CN (5) CH3 47 0 C2H5 COOC2H5 (3) CH3 48 0 C2H5 COOC2H5 (4) CH3 49 0 C2H5 COOC2H5 (5) CH3 50 0 C2H5 Br (3) CH3 S 1 0 C2H5 Br (4) CH3 52 0 C2H5 Br (S) CH3 53 0 C2H5 Br (6) CH3 54 0 CZHS Br (4) CF3 55 0 C2H5 OCH3 (4-)OCH3 (amorphous) 56 0 C2H5 CH3 (6-)C2H5 (amorphous) Le A 32 695-Foreign Countries Ex.- (position) (position) Melting point No. m R1 R2 R3 (R4 (C

57 0 C2H5 OCH3 (5-)OCH3 (amorphous) 58 0 C2H5 OCH3 (3-)OCH3 (amorphous) 59 0 CH3 CH3 (4-)CH3 (amorphous) 60 0 CH3 CH3 (5-)CH3 (amorphous) 61 0 CH3 CH3 (4-)OCH3 (amorphous) 62 0 CH3 OCH3 (5-)OCH3 (amorphous) 63 0 CH3 OCH3 {3-)OCH3 (amorphous) 64 1 (6-)F C2H5 CH3 (3-)CH3 (amorphous) 65 1 (6-)F C2H5 CF3 (amorphous) 66 1 (2-)F C2H5 CH3 (3-)CH3 (amorphous) 67 1 (2-)F C2H5 Cl (3-)Cl (amorphous) 68 1 (2-)F C2H5 CF3 (amorphous) 69 1 (2-)F C2H5 Cl (3-)Cl (np = 1.5263) 70 1 (2-)F C2H5 CH3 (3-)CH3 (amorphous) 71 1 (4-)F C2H5 CF3 (np = 1.4842) 72 1 (4-)F C2H5 CH3 (4-)F (amorphous) 73 1 (4-)Cl C2H5 CH3 (3-)CH3 (amorphous) 74 1 (4-)Cl C2H5 CH3 (4-)F 76C

75 1 (5-)CF3 C2H5 CH3 (4-)F 113C

76 1 (5-)CF3 C2H5 CH3 (3-)CH3 140C

77 0 C4H9-n CH3 (3-)CH3 92C

78 1 (4-)F C2H5 F (4-)F 40C

79 1 (4-)F C3H~-n F (4-)F 71C

80 1 (4-)F C3H~-n Cl (3-)Cl 81C

81 1 (4-)F C3H~-n CH3 (3-)CH3 73C

82 1 (6-)F C2H5 F (4-)F (np = 1.4876) (4-)F
83 1 (2-)F C H F (np = 1.4874) 84 1 (5-)CF3 C2H5 CF3 (amorphous) Le A 32 695-Foreign Countries Ex.- (position) (position) Melting point No. m Rl R2 R3 R4) (C

85 0 CH3 F (S-)CH3 (amorphous) 86 0 CH3 CH3 (5-)OCH3 (amorphous) 87 0 CH3 F (4-)CH3 (amorphous) Le A 32 695-Foreign Countries Example A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare 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 the emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After approximately 24 hours, the soil is watered with the preparation of active compound such that the particular 1 S amounts of active compound desired are applied per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 1000 1 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % - no effect (like untreated control) 100 % - total destruction In this test, for example, the compounds of Preparation Examples 1, 2, 3 and 4 exhibit strong activity against weeds, and some of them are tolerated well by crop plants, such as, for example, maize, barley and Soya beans.

Le A 32 695-Foreign Countries Example B
Post-emergence test S Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare 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 of a height of 5-15 cm are sprayed with the preparation of active compound such that the particular amounts of active compound desired are applied 1 S per unit area. The concentration of the spray liquor is chosen so that the particular amounts of active compound desired are applied in 1000 1 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % = no effect (like untreated control) 100 % = total destruction In this test, for example, the compounds of Preparation Examples 1, 2 and 4 exhibit strong activity against weeds, and some of them are tolerated well by crop plants, such as, for example, maize.

Claims (6)

claims

1. Substituted O-aryloxyalkyl N-aryl-carbamates of the general formula (I) in which m represents the numbers 0, 1 or 2, n represents the numbers 0, 1, 2, 3 or 4, with the proviso that in each individual case the sum of m and n is at least 1, R1 represents cyano, halogen or in each case optionally cyano-, halogen-or C1-C4-alkoxy-substituted alkyl or alkoxy having in each case 1 to 4 carbon atoms, R2 represents optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having 1 to 4 carbon atoms, R3 represents cyano, fluorine, bromine, iodine or in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy or alkoxy-carbonyl having in each case up to 4 carbon atoms, and - in the event that m represents 1 or 2 - also represents chlorine, and R4 represents cyano, bromine, iodine or in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl, alkoxy or alkoxycarbonyl having in each case up to 4 carbon atoms, and - in the event that m represents 1 or 2 - also represents fluorine or chlorine, except for the compound O-[1-(3-trifluoromethyl-phenoxymethyl)-propyl]
N-(2-methoxy-5-methyl-phenyl)-carbamate.

2. Substituted O-aryloxyalkyl N-aryl-carbamates of the general formula (I) according to Claim 1, characterized in that m represents the numbers 0, 1 or 2, n represents the numbers 0, 1, 2 or 3, with the proviso that in each individual case the sum of m and n is at least 1, R1 represents cyano, fluorine, chlorine, bromine or in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, R2 represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s-or t-butyl, R3 represents cyano, fluorine, bromine, iodine or in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, and - in the event that m represents 1 or 2 - also represents chlorine, and R4 represents cyano, bromine, iodine or in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxy-carbonyl, and - in the event that m represents 1 or 2 - also represents fluorine or chlorine, except for the compound O-[1-(3-trifluoromethyl-phenoxymethyl)-propyl]
N-(2-methoxy-5-methyl-phenyl)-carbamate.

3. Substituted O-aryloxyalkyl N-aryl-carbamates of the general formula (I) according to Claim 1, characterized in that m represents the numbers 0 or 1, n represents the numbers 0, 1 or 2, with the proviso that in each individual case the sum of m and n is at least 1, R1 represents cyano, fluorine, chlorine, bromine or in each case optionally fluorine- or chlorine-substituted methyl, ethyl, methoxy or ethoxy, R2 represents in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, R3 represents cyano, fluorine, bromine or in each case optionally fluorine-chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, and - in the event that m represents 1 - also represents chlorine, and R4 represents cyano, bromine, iodine or in each case optionally fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, and - in the event that m represents 1 - also represents fluorine or chlorine, except for the compound O-[1-(3-trifluoromethyl-phenoxymethyl)-propyl]
N-(2-methoxy-5-methyl-phenyl)-carbamate.

4. Process for preparing substituted O-aryloxyalkyl N-aryl-carbamates of the general formula (I) according to any of Claims 1 to 3, characterized by reacting (a) arylalkoxyalkyl chloroformates of the general formula (II) in which m, R1 and R2 are each as defined in any of Claims 1 to 3, with arylamines of the general formula (III) in which n, R3 and R4 are each as defined in any of Claims 1 to 3, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, or (b) aryloxyalkanols of the general formula (IV) in which m, R1 and R2 are each as defined in any of Claims 1 to 3, with aryl isocyanates of the general formula (V) in which n, R3 and R4 are each as defined in any of Claims 1 to 3, if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent.

5. Use of at least one substituted O-aryloxyalkyl N-aryl-carbamate according to any of Claims 1 to 3 for controlling undesirable plants.

6. Herbicidal composition, characterized in that it comprises at least one substituted O-aryloxyalkyl N-aryl-carbamate according to any of Claims 1 to 3.