GB2119786A - Novel N-methane sulphonylbenzimidates and their use as herbicides - Google Patents

Description

SPECIFICATION New herbicides derived from phenoxybenzoic acids This invention relates to phenoxybenzoic acid derivatives containing a sulphonimide group which are useful as herbicides.

5-[2'-Chloro-4'-(trifluoromethyl)-phenoxy]-2-nitrobenzoic acid, which is also called acifluorfen, and its salts, are known, as is their herbicidal activity.

It has been proposed, in particular, to apply acifluorfen and its salts to soya crops in a postemergence treatment in order to control weeds, especially dicotyledons. In an application of this type, the properties required for a herbicide, at the dose in question, are: - the ability to control the major weeds or target weeds, - the selectivity in respect of soya.

In attempts to improve the herbicidal properties of acifluorfen and its salts, numerous derivatives of these compounds have been proposed, in particular the alkyl, cycloalkyl, thioalkyl and phenyl esters and also the monoalkylamides or dialkylamides. Such compounds are described in U.S. Patents 3,652,645, 3,784,635, 3,873,302,3,983,168, 3,907,866,3,798,276, 3,928,416 and 4,063,929.

European Patents 3,416 and 23,392 describe sulphonamides derived from phenoxybenzoic acids.

One object of the invention is to provide products having a better combination of herbicidal properties as regards the activity on the weeds and the selectivity on the crops. Another object of the invention is to provide products having a better selectivity for crops other than soya, in particular cereals.

The present invention accordingly provides phenoxybenzoic acid derivatives of the formula:

wherein - W, Y, Y', X, Z' and Z, which may be the same or different, represent the hydrogen atom, a halogen atom, a group NO2 or CN, a polyhalogenoalkyl group, preferably containing 1 to-4 carbon atoms, e.g.

CF3, or an alkyl or alkoxy group, preferably containing 1 to 4 carbon atoms, R' represents an optionally substituted alkyl, alkenyl, alkynyl or phenyl group, R2 represents a halogen atom or a group CN, SCN, OR3, SR4 or NR5R6, wherein R3 R represents an optionally substituted alkyl group or an allyl, propargyi, alkylcarbonyl, alkylideneimino or succinimido group, - R4 represents the hydrogen atom or a cation or has one of the meanings given for R3, -R5 represents the hydrogen atom, an optibnally substituted alkyl group or an alkylcarbonyl or alkylsulphonyl group, and RB has one of the meanings given for R5 or represents a cation, a group ON or a group OR10, wherein R10 represents the hydrogen atom, a cation or an alkyl, carboxylate, carboxamide or alkylcarbonyl group. It is to be understood that in this specification and the accompanying claims: references to cations are to agriculturally acceptable cations; and alkyl groups and moieties may be straight- or branched-chain.

Preferred compounds of formula I are those wherein: - W represents the hydrogen atom, a halogen atom, in particular Cl, Br or F, or a group NO2 or CN, - Y represents the hydrogen atom, a halogen atom, in particular Cl, Br or F, or a group NO2, CN, CF3 or CH3, - Y', Z' and Z represent the hydrogen atom or a halogen atom, in particular Cl, Br or F, - X represents a halogen atom, in particular Cl, Br or F, or a group NO2, CF3, CH3 or C2H5, - R represents: an alkyl group preferably having from 1 to 12 carbon atoms and most preferably from 1 to 6 carbon atoms, which is optionally substituted by:: one or more halogen atoms, in particular CI, Br or F, one or more alkoxy or alkylthio groups preferably having from 1 to 4 carbon atoms, one or more groups CN, or - a phenyl group which is itself optionally substituted, in particular by one or more halogen atoms, preferably CI, Br or F, or R' represents:: an alkenyl or alkynyl group preferably having from 2 to 4 carbon atoms, in particular a vinyl, ethynyl, allyl or propargyl radical, or - a phenyl group which is itself optionally substituted, in particular by one or more halogen atoms, preferably Cl, Br or F, nitro groups or alkyl radicals preferably having from 1 to 4 carbon atoms, - R2 represents a halogen atom, preferably chlorine, a group CN or SCN or a group OR3, SR4 or NR5R6, wherein - R3 represents: - an alkyl group, preferably having from 1 to 4 carbon atoms, which is optionally substituted by:: - one or more halogen atoms, in particular Cl, Br or F, - one or more alkoxy or alkylthio groups, preferably having from 1 to 4 carbon atoms, - one or more groups NO2 or CN, - a carboxyl group or a derivative thereof in the form of a salt, ester or amide, in particular a group COOR7, R7 being the hydrogen atom, an alkyl group preferably having from 1 to 4 carbon atoms, or a metal cation or ammonium cation, - an alkylcarbonyl group, in particular an acetyl group, - a phenyl group which is itself optionally substituted, in particular by one or more halogen atoms, or - group

wherein R8 and R9, which are identical or different, represent the hydrogen atom or an alkyl group preferably having from 1 to 4 carbon atoms, or - R3 represents: - an allyl or propargyl group, - an alkylcarbonyl group, in particular an acetyl group, or - group

wherein R8 and R9 are as hereinbefore defined, -R4 represents the hydrogen atom, or an alkali metal cation or ammonium cation or has one of the meanings given for R3, - R5 represents:: the hydrogen atom, an alkyl group preferably having from 1 to 4 carbon atoms, which is optionally substituted by a carboxyl group or a derivative thereof in the form of a salt, edter or amide, in particular a group COOR7, wherein R7 is as hereinbefore defined, or an alkylcarbonyl or alkylsulphonyl group, in particular an acetyl or methanesulphonyl group, and -R6 has one of the meanings given for R5 or represents an alkali metal cation or ammonium cation, a group CN or a group OR10, wherein OR10 represents:: the hydrogen atom, an alkali metal cation or ammonium cation, an alkyl group preferably having from 1 to 4 carbon atoms, which is optionally substituted by a carboxyl group or a derivative thereof in the form of a salt, ester or amide, in particular a group COOR7, wherein R7 is as hereinbefore defined, - a group COOR7' or a carboxamide group OONHR7, wherein R7 is as hereinbefore defined, and R7 represents an alkyl group preferably having from 1 to 4 carbon atoms, or a metal cation or ammonium cation, or an alkylcarbonyl group, in particular an acetyl group.

Also preferred are those compounds of formula I wherein R' represents an alkyl group containing 1 to 4 carbon atoms optionally substituted by halogen or phenyl, or represents a halogen-substituted phenyl group, R2 represents a chlorine atom, a group OR3 wherein R3 represents alkyl of 1 to 4 carbon atoms optionally substituted by from 1 to 3 halogen atoms, by alkoxy of 1 to 4 carbon atoms, by alkoxycarbonyl of2 to 5 carbon atoms, by a group of the formula::

wherein R8 and R9 represent the hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, by a group of the formula

wherein RB and R9 are as hereinbefore defined, or R3 represents an alkyl or propargyl group, or R2 represents a group -SR4 wherein R4 represents hydrogen, an alkali metal cation or an alkyl group containing from 1 to 4 carbon atoms optionally substituted by an alkoxycarbonyl group containing from 2 to 5 carbon atoms, or R2 represents a group -NR5R6 wherein R5 represents the hydrogen atom, an alkali metal cation or an alkyl group containing 1 to 4 carbon atoms and R6 represents the hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms, an alkylsulphonyl group containing from 1 to 4 carbon atoms or a group OR'O wherein R'O represents the hydrogen atom or an alkyl group containing from 1 to 4 carbon atoms substituted by an alkoxycarbonyl group containing from 2 to 5 carbon atoms.

A preferred sub-family according to the invention consists of the products of the formula (I) in which Xis Cl or CF3, Y' and Z' are H, Y is Cl, Z is Cl or F or, preferably, H, and W is NO2. Also of particular value are the compounds in which R' is an alkyl group, preferably having 1 to 4 carbon atoms, R2 is the chlorine atom or a radical OR3, SR4 or NR5R6, wherein R3 is an alkyl radical preferably having 1 to 4 carbon atoms, R4 is the hydrogen atom or an alkyl group preferably having 1 to 4 carbon atoms, R5 is the hydrogen atom or a methanesulphonyl group and R6 is the hydrogen atom, an alkali metal cation or ammonium cation or an alkyl group preferably having from 1 to 4 carbon atoms. Compounds of formula I wherein Xis CF3, Z is H and R2 is alkoxy are especially preferred.

It will be appreciated that the compounds of formula I can have two diastereoisomeric forms, E and Z, in thermodynamic equilibrium with one another, according to the following scheme:

Furthermore, certain compounds of formula I can have tautomeric forms, and more especially those in the formula of which R4 or R5 is the hydrogen atom, as shown by the following schemes:

These diastereoisomeric and tautomeric forms are included in the invention, as are the physically distinct forms which may result e.g. from differences in conformations, from intramolecular or intermolecular hydrogen bonds or from other similar phenomena. In particular the symbols R', R2, R3, R4, R5 and R6 may represent groups containing an asymmetric carbon atom.It is to be understood that the resulting enantiomeric forms of the compounds of formula I, and mixtures thereof, are within the scope of the present invention.

According to a feature of the invention compounds of formula I wherein R2 represents a halogen atom and the other symbols are as hereinbefore defined are prepared -by reacting a compound of the formula:

(wherein the various symbols are as hereinbefore defined) with a halogenating agent to give an imidoyl halide of the formula:

hal yI =N-so2-R1 x VI wherein hal represents a halogen atom, preferably chlorine, and the other symbols are as hereinbefore defined.

Halogenating agents which may be mentioned are COCI2, SO2CI2, (COCI)2, PCI5, PAL3, POOl3 and SOCK2; COCI2 and PCI5 are preferred. The reaction is advantageously carried out at from -30 to +1 50 C in a solvent, preferably an optionally halogenated aliphatic or aromatic hydrocarbon such as methylene chloride, 1 ,2-dichloroethane, toluene or chlorobenzene; the reaction is carried out in the presence or absence of an acid acceptor such as a tertiary amine (e.g. triethylamine or pyridine).

According to a further feature of the present invention compounds of formula (I) wherein R2 is other than a halogen atom and the other symbols are as hereinbefore defined, may be prepared by reacting an imidoyl halide of formula VI, wherein the various symbols are as hereinbefore defined, with a compound of the formula R2'--H (Vll) (wherein R2 is as hereinbefore defined for R2 with the exclusion of R2 as halogen). The reaction is preferably carried out at from 0 to 1 50C in an inert solvent and in the presence of an acid acceptor such as a tertiary amine (e.g. triethylamine or pyridine). Solvents which may be mentioned are optionally halogenated aliphatic or aromatic hydrocarbons such as methylene chloride, 1 2-dichloroethane, toluene, and ethers ornitriles.

According to a further feature of the invention compounds of the formula (I) wherein R2 is a group OR3, SR4 or NR5R6 wherein R3, R4, R5 and R6 are as hereinbefore defined can also be prepared by reacting an imidoyl halide of formula VI, wherein the various symbols are as hereinbefore defined, with a compound of the formula R30M, R4SM or R5R5NM, wherein M is a hydrogen atom or an alkali metal atom e.g. sodium or potassium and R3, R4, R5 and R6 are as hereinbefore defined. The reaction using a compound R30M is shown in the reaction scheme:

}al ySSoy \C=N-S02R1 x;MNSO2R +3 OM ) Zl Z R3-0 c=N-so2-R1 YI y hal-M + 0- X < 0+W Zg Z wherein the various symbols are as hereinbefore defined.The depicted reaction is advantageously carried out using a compound R30M wherein M is a sodium or potassium atom, at from 10 to 1 50 C; it can also advantageously be carried out in a solvent consisting of a compound of the formula R30H.

The reaction of a compound R4-SM or R5R6NM with an imidoyl halide of formula VI, wherein the various symbols are as hereinbefore defined, is advantageously carried out at from 10 to 1 500C in an inert solvent such as an optionally halogenated aliphatic or aromatic hydrocarbon e.g. toluene, xylene or chlorobenzene.

According to a further feature of the invention, compounds of formula (I) wherein R2 represents a group --NRSOR'O wherein R10 is other than hydrogen, a cation or a carboxamide group, R5 is as hereinbefore defined and the other symbols are as hereinbefore defined, are prepared by reacting a compound of the formula:

(wherein the various symbols are as hereinbefore defined) with a compound of the formula: R10,-hal wherein hal represents a halogen atom and R10, is as hereinbefore defined for R'O with the exclusion of R10 as the hydrogen atom, a cation or a carboxamide group.The reaction is usually carried out at from 0 to 1500C in an inert solvent and in the presence of an acid acceptor such as a tertiary amine or an alkali metal hydroxide, preferably NaOH or KOH. When the acid acceptor is a tertiary amine, solvents which may be mentioned are optionally halogenated aliphatic or aromatic hydrocarbons, ethers or nitriles.

When the acid acceptor is an alkali metal hydroxide, solvents which may be mentioned are aliphatic alcohols such as methanol, ethanol or ethylene glycol, to which water may optionally be added.

The compounds of formula I wherein R4, Re, R7, R7' or R10 is a cation, e.g. an alkali metal cation or ammonium cation, may be prepared by known methods. For example, compounds in which R4, Re, R7 or R10 is an alkali metal cation may be prepared by reaction of the corresponding compound in which R4, R5, R7 or R10 represents hydrogen with an alkali metal hydroxide or alkoxide in a solvent medium, generally at ambient temperature. Compounds of formula I which contain a salified carboxyl group may, in general, be prepared by known methods.

By the expression "known methods" as used in this specification and the accompanying claims is meant methods heretofore used or described in the literature.

The Examples which follow illustrate the invention.

All the structures of the chemical products were checked by NMR (nuclear magnetic resonance) spectrography, IR (infra-red) spectrography and MS (mass spectrography).

The various analytical techniques used showed that: - the compounds of the formula I exist, under the conditions of analysis, in two diastereoisomeric forms, E and Z, where either the proportions of the 2 diastereoisomeric forms are equivalent or the proportion of one or other of them is preponderant, and - the compounds of the formula I in which there is a group SR4 or NR5Rss, wherein R4, R5 or R6 represents the hydrogen atom, exist, under the conditions of analysis, in two tautomeric forms, where either the proportions of the 2 tautomeric forms are equivalent or the proportion of one or other of them is preponderant.

Examples 1 to 31 illustrate the synthesis and the physical properties of the compounds according to the invention.

Example 32 illustrates the application of the products according to the invention in a preemergence herbicidal treatment.

Example 33 illustrates the application of products according to the invention in a post-emergence herbicidal treatment.

In Examples 32 and 33 the crops and weeds used were those indicated in Table (II) and the results obtained are collated in Table (III).

EXAMPLE 1 This example illustrates the preparation of compound No. 1 using PCI5.

5-[2'-Chloro-4'-(trifluoromethyl)-phenoxy]-2-nitro-N-methanesulphonylbenzamide (22 g; 0.05 mol) and PCl5 (10.4 g; 0.05 mol) are suspended in toluene (100 cc).

The suspension is heated to the boil under reflux, with stirring, and the heating is continued until the evolution of HCI gas has ended (about 1/2 hour). The toluene and POCI3 are removed by evaporation, leaving a residual yellow viscous oil (22.8 g), which is purified by chromatography on silica with toluene as the eluent. This gives a white solid, 5-[2'-chloro-4'-(trifluoromethyl)-phenoxyl-2-nitro N-methanesulphonylbenzimidoyl chloride (18.5 g; yield: 81%), melting at 83 C and having the formula:

01N C1 C=N-SO2CH3 CF3oMo2 (Compound No.1) The formula of this product is confirmed by NMR and IR spectrography: IR absorption band at t,650 cm-' (C=N).

In mass spectrography, fragments with masses of 410,437 and 326 are observed.

EXAMPLE 1A This example illustrates the preparation of compound No. 1 using phosgene: 5-[2'-chloro-4'-(trifluoromethyl)-phenoxy]-2-nitro-N-methanesulphonylbenzamide (43.9g; 0.1 mol) is suspended in toluene (400cc).

The suspension is stirred and triethylamine (15.1 g; 0.15 mol) is then added slowly at ambient temperature. The reaction mixture is then cooled to-10 C and kept at this temperature while COCI2 (11.9 g; 0.12 mol) is bubbled in. The stirring is continued art 1000 until the evolution of C02 gas has ended (about 1 hour). The precipitate of triethylamine hydrochloride is filtered off and washed with toluene. The filtrates are combined and the toluene is removed by evaporation. This gives compound No. 1(43.7 g; yield: 96%), i.e. 5-[2'-chloro-4'-(trifluoromethyl)-phenoxy]-2-nitro-Nmethanesulphonylbenzimidoyl chloride.

EXAMPLE 2 In its variants 2a and 2b, this Example illustrates the preparation of compound 2 by means of two reactions using methanol, in one case as the solvent in the presence of sodium methoxide as the reactant, and in the other case both as the solvent and the reactant.

EXAMPLE 2A A solution containing the compound No. (30 g; 0.066 mol) in methanol (70 cc) is prepared. It is stirred and a solution of sodium methoxide (3.6 g; 0.066 mol) in methanol (30 cc) is then added slowly at ambient temperature. The stirring is continued for 1 hour at ambient temperature. The precipitate of NaCI is filtered off and the methanol is removed by evaporation. The residual oil is purified by chromatography on silica with methylene chloride as the eluent. This gives a white solid, methyl 5-[2'chloro-4'-(trifluoromethyl)-phenoxy]-2-nitro-N-methanesulphonylbenzimidate (13g; yield: 44%), melting at 126 C and having the formula:

CH3 Cm 502 -CH3 Cm34 N02 (compound No.2) EXAMPLE 2B A solution containing compound No. 1 (95.4 g; 0.21 mol) and methanol (200 cc) is prepared.The solution is stirred and then heated to the boil under reflux, and the heating is continued until the evolution of HCI gas has ended (about 1/2 hour). The mixture is cooled to 5 C and the precipitate formed is then filtered off and washed with water before being recrystallised from methanol. This gives methyl S[2,chlorn4(trifluornmethyl)phenoxy]2ipy (61.9 g; yield: 65%).

EXAMPLES 3 TO 8 The various compounds 3 to 8 are prepared by processes similar to those of Example 2.

EXAMPLES 9 TO 14 The various compounds 9 to 14 are synthesised by the following general process: A solution containing a compound of the formula R OH(0.01 mol), triethylamine (1.4 cc) and diethyl ether (10 cc) is prepared. The solution is stirred and cooled to 5 C and a solution of 5-[2'-chloro 4'-(trifluoromethyl)-phenoxy1-2-nitro-N-methanesulphonylbenzimidoyl chloride (compound No. 1) (4.6 g) in diethyl ether (20 cc) is added dropwise. The stirring is continued for 4 hours at ambient temperature. The precipitate of triethylamine hydrochloride is filtered off and washed with diethyl ether.

The filtrates are combined, washed with water, dried over sodium sulphate and concentrated; the residual oil is purified by chromatography on silica with methylene chloride as the eluent.

EXAMPLES 15 TO 18 The various compounds 1 5 to 18 are synthesised by the following general process: A solution containing a compound of the formula R30H (0.01 mol), triethylamine (1.4 cc) and toluene (10 cc) is prepared. The solution is stirred and a solution of 5-[2'-chloro-4'-(trifluoromethyl)phenoxy]-2-nitro-N-methanesulphonylbenzimidoyl chloride (compound No. 1) (4.6 g) in toluene (20 cc) is then added slowly at ambient temperature. The reaction mixture is heated to 90 C and the heating is continued for 3 hours at this temperature. The precipitate of triethylamine hydrochloride is filtered off and washed with toluene. The filtrates are combined, washed with water, dried over sodium sulphate and concentrated; the residual oil is purified by chromatography on silica with methylene chloride as the eluent.

EXAMPLES 19TO21 The two compounds 1 9 and 21 are prepared by the general process of Examples 9 to 14, but by replacing the compound of the formula R30H with a compound of the formula R4SH. Compound 20 is synthesised by reacting, in known manner, compound 1 9. (5-[2'-chloro-4'-(trifluoromethyl)-pheno 2-nitro-N-methanesulphonylthiobenzamide), at ambient temperature, with a stoichiometric amount of aqueous sodium hydroxide solution (or of a solution of sodium methoxide in methanol), and then removing the water (or the methanol) by evaporation.

EXAMPLES 22 AND 23 The two compounds 22 and 23 are prepared by the general process of Examples 15 to 18, but by replacing the compound of the formula R30H with a compound of the formula R4SH.

EXAMPLES 24 TO 27 The various compounds 24 to 27 are prepared by the general process of Examples 9 to 14, but by replacing the compound of the formula R30H with a compound of the formula R5R6NH.

EXAMPLE 28 A solution containing compound 27 (3 g; 0.0066 mol), (5-[2'-chloro-4'-(trifluoromethyl)phenoxy]-2-nitro-N-methanesulphonyl-N'-hydroxybenzamidine), ethanol (20 cc) and water (5 cc) is prepared. The solution is stirred and methyl 2-bromopropionate (1.1 g; 0.0066 mol) and sodium hydroxide (0.26 g; 0.0066 mol) are then added successively at ambient temperature. The mixture is heated to the boil under reflux and the heating is continued for 2 hours. The ethanol and the water are removed by evaporation; the residue is taken up in methylene chloride. The organic phase is washed with water, dried over sodium sulphate and concentrated; the residual oil is purified by chromatography on silica with a 97/3 mixture of methylene chloride/methanol as the eluent.This gives a viscous mass, 5-[2 '-ch loro-4t-(trifluoromethyl )-phenoxy]-2-nitro-N-methanesu Iphonyl-Nt- 1 -(methoxycarbonyl)ethoxybenzamidine (1.2 g; yield: 34%), having the formula:

NH - O - cH(OH3)- COOCIi3 Cl C = N-S02 -CH3 CF3 z 0 t N02 (compound No. 28) EXAMPLES 29 AND 30 A suspension of the potassium salt of methanesulphonamide (1.3 g; 0.01 mol) in toluene (30 cc) is prepared. The suspension is stirred and a solution of 5-[2'-chloro-4'-(trifluoromethyl)-phenoxy]-2- nitro-N-methanesulphonylbenzimidoyl chloride (compound No. 1) (4.6 g; 0.01 mol) in toluene (20 cc) is then added at ambient temperature. The mixture is heated to the boil under reflux and the heating is continued for 4 hours. The precipitate of KCI is filtered off. The organic filtrate is washed with water, dried over sodium sulphate and concentrated; the residual oil is purified by chromatography on silica with a 90/10 mixture of methylene chloride/methanol as the eluent. This gives a white solid 5-[2' chloro-4'-(trifluoromethyl)-phenoxy]-2-nitro-N,N'-bis-(methanesulphonyl)-benzamidine (1.5 g; yield: 29%), melting at 211 C and having the formula:

NH - 502 - CH3 Cl C = N-S02 -OH3 CF3 (\+ O NO2 2 (compound No. 29) Compound 30 is synthesised by reacting the above compound, in known manner, at ambient temperature, with a stoichiometric amount of aqueous sodium hydroxide solution (or of a solution of sodium methoxide in methanol), and then removing the water (or the methanol) by evaporation.

The different compounds obtained in the various examples 1 to 30 (a compound has the number of its corresponding example) have the formula:

The meanings of the substituents R1 and R2 for the various compounds and also the yield of the Example and the m.p. of the product, are collected in Table (I).

For compound No. 19, the tautomeric form, of the formula:

is preponderant.

The compounds such as No. 15, No. 16, No. 23 or No. 28, which have an asymmetric carbon, exist in the two enantiomeric forms, R or S. In this case, the formula (I) given above must of course be understood as defining one or other of these two forms or as defining a mixture of the two, where either the proportions are equivalent (racemate) or the proportion of one of them is preponderant.

EXAMPLE 31 5-(2,4-Dichlorophenoxy)-2-nitro-N-methanesulphonylbenzamide (7.4 g; 0.018 mol) and PCls (3.8 g: 0.018 mol) are suspended in toluene (50 cc).

The suspension is heated to the boil under reflux, with stirring, and the heating is continued until the evolution of HCI gas has ended (about 1/2 hour). The toluene and POCI3 are removed by evaporation, leaving a residual brown viscous oil (7.7 g), which is dissolved in methanol (25 cc). This methanol solution is stirred and then heated to the boil under reflux, and the heating is continued until the evolution of HCI gas had ended (about 1/2 hour). The mixture is cooled to 50C and the precipitate formed is then filtered off before being recrystallised from methanol.This gives a white solid, methyl 5 (2',4t-dichlorophenoxy)-2-nitro-N-methanesulphonylbenzimidate (4.6 g; yield: 60%), melting at 1630C and having the formula:

The following compounds can be prepared by a process similar to that of Example 31: methyl 5 [2'-chloro-4'-(trifluoromethyl)-phenoxy]-2-chloro-N-methanesulphonylbenzimidate, methyl 5-[2' chloro-4'-(trifluoromethyl)-phenoxy]-2-bromo-N-methanesulphonylbenzimidate, methyl 5-[2'-chloro 4'-(trifluoromethyl)-phenoxy]-2-cyano-N-methanesulphonylbenzimidate, methyl 5-(2 ',4'- dichlorophenoxy)-2-chloro-N-methanesulphonylbenzimidate, methyl 5-(2',4'-dichlorophenoxy)-2- bromo-N-methanesulphonylbenzimidate, methyl 5-(2',4'-dichlorophenoxy)-2-cyano-N- methanesu Iphonylbenzimidate, methyl 5-[2 ',6'-dichloro-4'-(trifluoromethyl)-phenoxy]-2-chloro-N- metha nesu Iphonylbenzimidate, methyl 5-[2'-bromo-4'-(trifluoromethyl)-phenoxy]-2-nitro-N- methanesul phonylbenzimidate, methyl 5-[2'-iodo-4'-(trifluoromethyl)-phenoxy] -2-nitro-N methanesul phonyl benzi midate, methyl 5-[2'-nitro-4'-(trifluoromethyl)-phenoxy]-2-nitro-N- metha nesulphonylbenzim idate, methyl 5-[2'-cya no-4'-(trif luoromethyl)-phenoxy]-2-nitro-N- methanesulphonylbenzimidate, methyl 5-[2'.4'-bis-(trifl uoromethyl)-phenoxy]-2-nitro-N- methanesulphonylbenzimidate, methyl 5-[2',6'-dichloro-4'-(trifluoromethyl)-phenoxy]-2-nitro-N- methanesulphonylbenzimidate, methyl 5-[2'-chloro-6'-fluoro-4'-(trifluoromethyl)-phenoxy]-2-nitro-Nmethanesulphonylbenzimidate, methyl 5-[2',3',6'-trichloro-4'-(trifluoromethyl)-phenoxy]-2-nitro-Nmethanesulphonylbenzimidate, methyl 5-[2'-nitro-6'-chloro-4'-(trifluoromethyl)-phenoxy]-2-nitro-N- methanesulphonylbenzimidate, methyl 5-[2',3',5',6'-tetrafluoro-4'-(trifluoromethyl)-phenoxy]-2-nitro N-methanesul phonylbenzimidate, methyl 5-(2'-trifl uoromethyl-4'-chlorophenoxy)-2-nitro-Nmethanesulphonylbenzimidate, methyl 5-(2'-methyl-4'-chlorophenoxy)-2-nitro-N methanesulphonylbenzimidate, methyl 5-(2'-nitro-4'-chlorophenoxy)-2-nitro-Nmethanesulphonylbenzimidate, methyl 5-(2',4',6'-trichlorophenoxy)-2-nitro-Nmethanesulphonylbenzimidate, methyl 5-(2',4'-dichloro-6'-fluorophenoxy)-2-nitro-Nmethanesulphonylbenzimidate, methyl 5-(2',3',4'-trichlorophenoxy)-2-nitro-Nmethanesulphonylbenzimidate, methyl 5-(2',4',5'-trichlorophenoxy)-2-nitro-Nmethanesulphonylbenzimidate, methyl 5-(2',3',4',6'-tetrachlorophenoxy)-2-nitro-N- methanesulphonylbenzimidate, methyl 5-(2'-chloro-4'-bromophenoxy)-2-nitro-Nmethanesulphonylbenzimidate, methyl 5-(2',4'-dibromophenoxy)-2-nitro-Nmethanesulphonylbenzimidate, methyl 5-(2',4',6'-tribromophenoxy)-2-nitro-Nmethanesulphonylbenzimidate, methyl 5-(2'-chloro-4'-fluorophenoxy)-2-nitro-Nmethanesulphonylbenzimidate, methyl 5-(2'-chloro-4'-methylphenoxy)-2-nitro-N methanesulphonyl benzim date, methyl 5-(2'-nitro-4'-methylphenoxy)-2-nitro-N- methanesulphonylbenzimidate, methyl 5-(2',3',6'-trichloro-4'-methylphenoxy)-2-nitro-N- methanesulphonylbenzimidate, methyl 5-(2'-chloro-4'-ethylphenoxy)-2-nitro-Nmethanesulphonylbenzimidate, methyl 5-(2',6'-dichloro-4'-ethylphenoxy)-2-nitro-N methanesulphonylbenzim id ate, methyl 5-(2 ',3',5',6'-tetrafluoro-4'-ethylphenoxy)-2-nitro-N- methanesulphonylbenzimidate, methyl 5-(3',5'-dichlorophenoxy)-2-nitro-Nmethanesulphonylbenzimidate, methyl 5-[2 '-chloro-4'-(trifl uoromethyl)-phenoxy]-2-nitro-N-n- propanesulphonylbenzimidate, methyl 5-[2'-chloro-4'-(trifluoromethyl)-phenoxy]-2-nitro-N- trifl uoromethanesu lphonylbenzim idate, methyl 5-[2 '-chloro-4'-(trifluoromethyl)-phenoxy]-2-nitro-N- vinylsulphonylbenzimidate, methyl 5-[2'-chloro-4'-(trifluoromethyl)-phenoxy]-2-nitro-N- ethynylsulphonylbenzimidate, methyl 5-[2'-chloro-4'-trifluoromethyl)-phenoxy]-2-nitro-N- allylsu lphonylbenzimidate and methyl 5-[2'-chloro-4'-(trifluoromethyl)-phenoxy]-2-nitro-N- propargylsul phonyl benzimidate.

EXAMPLE 32 Herbicidal application in the pre-emergence treatment of plant species A number of seeds are sown in 9 x 9 x 9 cm pots filled with light agricultural earth, this number being determined as a function of the plant species and the size of the seed.

The pots are treated by spraying with an amount of spraying mixture which corresponds to a volumetric application dose of 500 litres/ha and contains the active ingredient at the desired concentration.

The treatment with the spraying mixture is therefore carried out on seeds not covered with earth (the term "spraying mixture" is used to denote, in general, the compositions diluted with water, such as they are applied to the plants).

The spraying mixture used for the treatment is an aqueous suspension of the active ingredient containing 0. 1% by weight of Cemulsol Nip 10 (a surface-active agent consisting of an ethylene oxide/alkylphenol condensate, in particular of an ethylene oxide/nonylphenol condensate) and 0.4% by weight of Tween 20 (a surface-active agent consisting of the oleate of an ethylene oxide/sorbitol condensate).

This suspension was obtained by mixing and grinding the ingredients in a microniser so as to give an average particle size of less than 40 microns.

According to the concentration of active ingredient in the spraying mixture, the dose of active ingredient applied was 0.125 to 4 kg/ha.

After treatment, the seeds are covered with an approximately 3 mm thick layer of earth.

The pots are then placed in troughs which are intended to receive the moistening water, by subirrigation, and are kept for 21 days at ambient temperature and under 70% relative humidity.

After 21 days, the number of living plants in the pots treated with the spraying mixture containing the active ingredient to be tested, and the number of living plants in a control pot treated under the same conditions, but by means of a spraying mixture not containing active ingredient, are counted. The percentage destruction of the treated plants, relative to the untreated control, is thus determined. A percentage destruction equal to 100% indicates that there has been complete destruction of the plant species in question, and a percentage of 0% indicates that the number of living plants in the treated pot is identical to that in the control pot.

EXAMPLE 33 Kerbicidal application in the post-emergence treatment of plant species A number of seeds are sown in 9 x 9 x 9 cm pots filled with light agricultural earth, this number being determined as a function of the plant species and the size of the seed.

The seeds are then covered with an approximately 3 mm thick layer of earth and the seed is left to germinate until it has produced a plantlet at the appropriate stage. The treatment stage for the graminaceous plants is the stage of "second leaf forming". The appropriate stage for soya is the stage of "first trifoliate leaf open". The treatment stage for the other dicotyledons is the stage of "cotyledons open, first true leaf developing".

The pots are then treated by spraying with an amount of spraying mixture which corresponds to a volumetric application dose of 500 litres/ha and contains the active ingredient at the desired concentration.

The spraying mixture was prepared in the same manner as in Example 32.

According to the concentration of active ingredient in the spraying mixture, the dose of active ingredient applied was 0.125 to 4 kg/ha.

The treated pots are then placed in troughs which are intended to receive the moistening water, by sub-irrigation, and are kept for 21 days at ambient temperature and under 70% relative humidity.

After 21 days, the number of living plants in the pots treated with the spraying mixture containing the active ingredient to be tested, and the number of living plants in a control pot treated under the same conditions, but by means of a spraying mixture not containing active ingredient, are counted. The percentage destruction of the treated plants, relative to the untreated control, is thus determined. A percentage destruction equal to 100% indicates that there has been complete destruction of the plant species in question, and a percentage of 0% indicates that the number of living plants in the treated pot is identical to that in the control pot.

The results obtained in Examples 32 and 33 are given hereinafter in Tables Ill and IV. These results demonstrate the notably advantageous properties of the compounds according to the invention, both for the pre-emergence treatment of crops and for the post-emergence treatment, in particular of soya, cereals, including maize, sunflower, cotton and beans. In the case of soya, the activity of the compounds is particularly advantageous if this crop is infested with dicotyledon weeds such as abutilon, xanthium and ipomea.

For their use in praciics, the compounds according to the invention are rarely employed by themselves. Most frequently, the form part of compositions. The present invention provides herbicidal compositions which comprise, as active ingredient, a compound of formula I in association with an agriculturally acceptable carrier. The carrier may be solid or liquid. The compositions may also comprise an agriculturally acceptable surface-active agent. In particular, the customary inert carriers and the customary surface-active agents can be used.

These compositions can also contain various other ingredients, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilisers, and sequestering agents, and also other known active ingredients having pesticidal properties (in particular insecticidal, fungicidal or herbicidal properties), properties promoting plant growth (in particular fertilisers) or properties regulating plant growth. More generally, the compounds used in the invention can be combined with any of the solid or liquid additives corresponding to the usual formulation techniques.

The use doses of the compounds of the invention can vary within wide limits, in particular according to the nature of the adventitious plants to be removed and the usual degree of infestation of these crops by these adventitious plants.

In general, the compositions according to the invention usually contain from 0.01 to about 95% (by weight) of active ingredient according to the invention: such compositions generally comprise from 1% to about 95% of one or more solid or liquid carriers and, if appropriate, from 0.1 to about 20% of one or more surface-active agents.

As has already been stated, the compounds used in the invention are generally employed in combination with carriers and, if appropriate, surface-active agents.

In the present account, the term "carrier" denotes an organic or inorganic, natural or synthetic material with which the active ingredient is combined in order to facilitate its application to the plant, to seeds or to the soil. This carrier is therefore generally inert and it must be acceptable in agriculture, in particular on the plant treated.The carrier can be solid (e.g. clays, natural or synthetic silicates, silica, resins, waxes, and solid fertilisers) or liquid (e.g. water, alcohols, in particular butanol, esters, in particular methylglycol acetate, ketones, in particular cyclohexanone and isophorone, petroleum fractions, aromatic hydrocarbons, in particular xylenes, or paraffinic hydrocarbons, aliphatic chlorohydrocarbons, in particular trichloroethane, or aromatic chlorohydrocarbons, in particular chlorobenzenes, water-soluble solvents, such as dimethylformamide, dimethyl sulphoxide and Nmethylpyrrolidone, and liquefied gases).

The surface-active agent can be an emulsifying, dispersing or wetting agent of ionic or non-ionic type or a mixture of such surface-active agents. Examples which may be mentioned are salts of polyacrylic acids, salts of lignosulphonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols, fatty acids or fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (in particular alkyltaurates), phosphoric acid esters of condensates of ethylene oxide with alcohols or phenols, fatty acid esters of polyols, and derivatives of the above compou'nds containing sulphate, sulphonate or phosphate groups.The presence of at least one surface-active agent is generally essential if the active ingredient and/or the inert carrier are not soluble in water and if the vehicle of application is water.

For their application, the compounds of the formula (I) are therefore generally in the form of compositions; these compositions according to the invention are themselves in a fairly wide variety of solid or liquid forms.

As forms of solid compositions, there may be mentioned dusting powders (with a content of compound of the formula (I) which can range up to 100%) and granules, in particular those obtained by extrusion, by compaction, by the impregnation of a granular carrier or by the conversion of a powder to granules (the content of compound of the formula (I) in these granules being between 0.5 and 80% for the latter cases).

As forms of liquid compositions or compositions which are to be made up into liquid compositions on application, there may be mentioned solutions, in particular emulsifiable concentrates, emulsions, suspension concentrates, aerosols, wettable powders (or spraying powders), dry flowables and pastes.

The emulsifiable or soluble concentrates most frequently comprise 10 to 80% of active ingredient, and the emulsions or solutions which are ready for application contain 0.01 to 20% of active ingredient.

In addition to the solvent, the emulsifiable concentrates can contain, where necessary, 2 to 20% of suitable additives, such as stabilisers, surface-active agents, penetrating agents, corrosion inhibitors, dyestuffs and adhesives.

Starting from these concentrates, emulsions of any desired concentration, which are particularly suitable for application to the plants, can be obtained by dilution with water.

Examples of emulsifiable concentrates are now given: EXAMPLE 34 - active ingredient 250 g - ethylene oxide/alkylphenol condensate 30 g - calcium alkylarylsulphonate 50 g - petroleum distillation cut distilling at between 160 and 185"C 670 g Another formulation is: EXAMPLE 35 - active ingredient 350 g - ethylene oxide/castor oil condensate 60 g - sodium alkylarylsulphonate 40 g - cyclohexanone 150g - xylene 400 g Another formulation is: EXAMPLE 36 - active ingredient 400 g - ethylene oxide/alkylphenol condensate 100 g - ethylene glycol methyl ether 250 g - aromatic petroleum cut distilling at between 160and 18500 250 9 Another formulation is: EXAMPLE 37 - active ingredient 400 g - phosphate of ethylene oxide/tristyrylphenol condensate 50 9 - phosphate of ethylene oxide/alkylphenol condensate 65 g - sodium alkylbenzenesulphonate 35 g - cyclohexanone 300 g - aromatic petroleum cut distilling at between 160 and 185 C 150 g Another form ulation is:EXAMPLE 38 - active ingredient 400 g/litre - alkali metal dodecylbenzenesulphonate 24 g/litre - 10:1 ethylene oxide/nonylphenol condensate 16 litre - cyclohexanone 200 g/litre - aromatic solvent q.s.p. 1 litre.

Another formulation of an emulsifiable concentrate uses the following: EXAMPLE 39 - active ingredient 250 g - epoxidised vegetable oil 25 g - mixture of an alkylarylsulphonate and a polyglycol ether of fatty alcohols 100 g - dimethylformamide 50 g - xylene 575 g The suspension concentrates, which can be applied by spraying, are prepared so as to give a stable fluid product which does not form a deposit (by fine grinding), and they usually contain from 10 to 75% of active ingredient, from 0.5 to 1 5% of surface-active ag,ents, from 0.1 to 10% of thixotropic agents, from 0 to 10% of suitable additives, such as anti-foam agents, corrosion inhibitors, stabilisers, penetrating agents and adhesives, and, as the carrier, water or an organic liquid in which the active ingredient is sparingly soluble or insoluble; certain organic solids, or inorganic salts, can be dissolved in the carrier in order to assist in preventing sedimentation or to act as anti-freeze agents for the water.

The composition of a suspension concentrate is now given as an example: EXAMPLE 40 - active ingredient 500 g - phosphate of ethylene oxide/tristyrylphenol condensate 50 g - ethylene oxide/alkylphenol condensate 50 g - sodium polycarboxylate 20 g - ethylene glycol 50 g -- organopolysiloxane oil (anti-foam agent) 1 g - polysaccharide 1.5 g - water 316.59 The wettable powders (or spraying powders) are usually prepared so as to contain 20 to 95% of active ingredient, and they usually contain, in addition to the solid carrier, from 0 to 5% of a wetting agent, from 3 to 10% of a dispersing agent and, where necessary, from 0 to 10% of one or more stabilisers and/or other additives, such as penetrating agents, adhesives, anti-caking agents, and dyestuffs.

Various compositions of wettable powders are now given as examples: percentages are by weight.

EXAMPLE 41 - active ingredient 50% - calcium lignosulphonate (deflocculant) 5% - isopropylnaphthalenesulphonate (anionic wetting agent) 1% - anti-caking silica 5% - kaolin (filler) 39% Another example of a wettable powder, this time of 80% strength, is given below: EXAMPLE 42 - active ingredient 80% - sodium alkylnaphthalenesulphonate 2% - sodium lignosulphonate 2% - anti-caking silica 3% - kaolin 13% Another example of a wettable powder is given below: EXAMPLE 43 - active ingredient 50% - sodium alkylnaphthalenesulphonate 2% - low-viscosity methylcellulose 2% - diatomaceous earth 46% Another example of a wettable powder is given below:: EXAMPLE 44 - active ingredient 90% - sodium dioctyl-sulphosuccinate 0.2% - synthetic silica 9.8% Another composition of a spraying powder, this time of 40% strength, uses the following constituents: EXAMPLE 45 -active ingredient 400 g - sodium lignosulphonate 50g - sodium dibutylnaphthalenesulphonate 10 9 - silica 540 g Another composition of a spraying powder, this time of 25% strength, uses the following constituents:: EXAMPLE 46 - active ingredient 250g - isooctylphenoxy-polyoxyethylene-ethanol 25 g - mixture of equal parts by weight of Champagne chalk and hydroxyethylcellulose 179 - sodium aluminosilicate 543 g - kieselguhr 165g Another composition of a spraying powder, this time of 10% strength, uses the following constituents:: EXAMPLE 47 - active ingredient 100 g - mixture of sodium salts of saturated fatty acid sulphates 30 g - na phthalenesu phonic acid/formaldehyde condensate 50 g - kaolin 820 g To obtain these spraying powders or wettable powders, the active ingredients are intimately mixed with the additional substances in suitable mixers, or the porous filler is impregnated with the molten active ingredient, and the mixture is ground in mills or other suitable grinders. This gives spraying powders of advantageous wettability and suspendability; they can be suspended in water at any desired concentration, and this suspension can be used very advantageously, in particular for application to the leaves of plants.

The dry flowables (more exactly, these are granules which are readily dispersible in water) have a composition substantially similar to that of the wettable powders. They can be prepared by the formation of granules from formulations described for the wettable powders, either by a wet process (bringing of the finely divided active ingredient into contact with ,the inert filler and with a small amount of water, e.g. 1 to 20%, or of an aqueous solution of dispersing agent or binder, followed by drying and sieving) or by a dry process (compaction followed by grinding and sieving).

The formulation of a dry flowable is now given as an example: EXAMPLE 48 - active ingredient 800 g - sodium alkylnaphthalenesulphonate 20 g - sodium methylene-bis-naphthalenesulphonate 80 g - kaolin 100 g In place of the wettable powders, it is possible to produce pastes. The conditions and modes of production and use of these pastes are similar to those of the wettable powders qr spraying powders.

As already stated, the aqueous dispersions and emulsions, e.g. compositions obtained by diluting, with water, a wettable powder or an emulsifiable concentrate according to the invention, are included within the general scope of the compositions which can be used in the present invention. The emulsions can be of the water-in-oil or oil-in-water type and they can have a thick consistency such as that of a "mayonnaise".

All these aqueous dispersions or emulsions, or spraying mixtures, can be applied to the crops in which weeds are to be destroyed, by any suitable method, mainly by spraying, at doses which are generally of the order of 100 to 1,200 litres of spraying mixture per hectare.

The granules, which are intended to be placed on the soil, are usually prepared so as to have dimensions of between 0.1 and 2 mm, and they can be manufactured by agglomeration or impregnation. Preferably, the granules contain 1 to 25% of active ingredient and 0 to 10% of additives, such as stabilisers, slow-release modifiers, binders and solvents.

One example of the composition of granules uses the following constituents: EXAMPLE 49 - active ingredient 50 g - propylene glycol 25 g - boiled linseed oil 50 g - clay (particle size: 0.3 to 0.8 mm) 910 g.

As indicated above, the invention also relates to a method for controlling the growth of weeds at a locus used, or to be used for growing crops, in particular, cereals, such as wheat, barley and maize, and also soya, sunflower, cotton and beans, which comprises applying to the locus an effective amount of a compound. according to the invention. The compound of general formula I, used in an amount which is not phytotoxic to the crop, may be applied to the plants and/or to the soil.

In practice, the compounds are used in the form of herbicidal compositions according to the invention, which have been described above. In general, amounts of active ingredient ranging from 0.01 to 5 kg/ha, preferably from 0.1 to 2 kg/ha, give good results, it being understood that the choice of the amount of active ingredient to be used depends on the severity of the problem to be solved, the climatic conditions and the crop in question. The treatment can be carried out either as a pre-emergence treatment of the crops and adventitious plants, or as a pre-sowing treatment of the crops with incorporation into the soil (such incorporation constitutes a further feature of the method according to the invention), or as a post-emergence treatment.Other embodiments of the treatment method according to the invention can also be used: thus, it is possible to apply the active ingredient to the soil, with or without incorporation, before planting out a crop.

The treatment method of the invention can be used both for annual crops and perennial crops; in the latter case, it is preferred to apply the active ingredients of the invention in a localised manner, e.g.

between the rows of the said crops.

TABLE I

Compound No. R2 R2 Yield in % M.p. in C.

1 CH3 Cl 96 83 CH3 CH30- 65 126 3 CH3 C2HsO 54 102 CH3 (CH3)2CHO- 37 125 5 C3H CH30- 45 112 6 CICH2 OH3O- 54 127 T OCH2 CH3O- 29 100 8 Cl z CH3O- 49 VprSocd uucst CH3 C ClOH3CH2O- 71 101 10 CH3 OH3OOH2OH2O- 34 128 11 CH3 OCl3CH2O- 67 177 12 CH3 OF3OH2O- 92 144 13 CH3 CH,=CHCH,O- 46 88 14 CH3 HC"rrO-CH2O- 67 134 15 CH3 O3H5O2OCHO- 60 Viscous H3 product CH,O CH3\P 73 68 16 CH, CH 18 CH3 1 39 95 19 CH3 HS- 44 182 20 CH3 NaS- 93 220 TABLE I (Continued)

Compound No. R1 R2 Yield in % 1 M.p. in C 21 CH3 OH3S- 75 47 22 CH3 ~ C,HrO-OC-CH,--SS- 70 91 23 CH3 QH5-0-OO-OH-S- 98 Viscous CH3 product 24 CH3 H2N 80 79 25 OH3 (OH3)HN- 76 75 26 1 CH3 (OH3)2N- 61 69 27 CH3 (HO)HN- 100 150 28 CH3 OH3-0-0O-CH-0-NH- 34 Viscous CH3 product 29 CH3 OH3503-NH- 29 211 -30 - CH3 (0H3S02)NaN- 100 110 Compound Nas. 1 and 2 are especially preferred.

TABLE II

American name Latin name Abbreviation Wheat WHE Crops Soybean SOY Barnyard grass Echinochloa ECH crus-gal Ii Velvet leaf Abutilon ABU theophrast Cocklebur Xanthium XAN pennsylvanicum Weeds Wild mustard Sinapis arvensis SIN Morning glory Ipomea purpurea IPO (annual) Rye-grass Lolium multi- LOL florum Cyperus CYP esculentus TABLE III

Doses PRE-EMERGENCE POST-EMERGENCE Compound in No. kg/ha ECH LOL ABU IPO SIN XAN WHE SOY ECH LOL ABU IPO SIN XAN CYP WHE SOY 4 1 1 100 100 100 100 100 100 100 0 100 30 100 80 100 100 50 50 0 0.25 100 50 100 80 100 60 20 0 100 0 50 80 100 100 0 0 0 4 100 100 100 30 100 0 90 80 100 100 100 100 100 100 0 20 30 2 1 100 100 100 0 98 0 60 100 60 80 100 100 100 100 0 0 0 0.25 100 90 100 0 98 0 60 0 50 40 80 100 100 100 0 0 0 4 95 98 100 0 50 0 20 0 80 50 100 100 70 90 0 0 0 3 1 60 80 100 0 0 0 0 0 30 0 20 100 30 90 0 0 0 0.25 50 50 100 0 0 0 0 0 20 0 0 90 30 80 0 0 0 4 40 0 100 0 0 0 0 0 20 20 0 50 60 100 0 0 0 4 1 0 0 100 0 0 0 0 00 20 0 0 50 80 0 0 0 0.25 0 0 100 0 0 0 0 0 0 20 0 0 50 100 0 0 0 TABLE III (Continued)

Doses PRE-EMERGENCE POST-EMERGENCE Compound in No. kg/ha ECH LOL ABU IPO SIN XAN WHE SOY ECH LOL ABU IPO SIN XAN WHE SOY 2 80 90 100 80 80 90 30 0 20 30 80 90 90 10 0 5 0.5 60 80 100 30 90 0 10 20 80 100 90 0 0 0.125 20 40 90 50 20 0 0 10 10 10 10 70 0 0 2 50 50 80 90 80 0 20 20 20 70 100 0 0 6 0.5 40 40 90 60 50 0 10 10 10 40 90 0 0 0.125 0 0 90 50 0 0 0 0 0 0 60 0 0 2 0 0 100 0 20 0 0 40 0 80 100 100 0 0 7 0.5 0 0 20 0 0 0 0 20 0 80 90 50 0 0 0.125 0 0 0 0 0 0 0 0 0 20 80 0 0 0 2 30 10 20 30 100 0 0 50 20 70 90 100 0 0 8 0.5 0 10 20 20 0 0 0 20 0 50 70 90 0 0 0.125 0 0 10 0 0 0 0 10 0 20 0 10 0 0 TABLE III (Continued)

Doses PRE-EMERGENCE POST-EMERGENCE Compound in No. kg/ha ECH LOL ABU IPO SIN XAN WHE SOY ECH LOL ABU IPO SIN XAN WHE SOY 4 100 98 100 90 95 0 0 40 80 50 100 100 0 0 9 1 50 60 98 0 95 0 0 20 50 30 80 95 0 0 0.25 0 0 50 0 0 0 0 0 0 0 100 30 0 0 2 100 100 100 100 100 20 0 100 60 80 100 100 20 0 10 0.5 100 50 100 50 100 0 0 20 30 30 80 100 0 0 0.125 20 0 80 0 100 0 0 0 0 20 30 60 0 0 4 50 0 100 80 100 100 0 50 20 0 0 80 100 100 0 0 11 1 0 0 100 100 100 80 0 50 0 0 0 80 90 50 0 0 0.25 0 0 90 0 90 80 0 0 0 0 0 80 0 0 0 4 30 0 80 60 80 100 0 50 0 0 0 60 80 50 0 0 12 1 30 0 90 90 80 100 0 0 0 0 0 20 0 0 TABLE III (Continued)

Doses PRE-EMERGENCE POST-EMERGENCE Compound in No. kg/ha ECH LOL ABU IPO SIN XAN WHE SOY ECH LOL ABU IPO SIN XAN WHE SOY 4 90 30 95 0 100 50 0 0 60 30 100 30 100 80 0 0 13 1 60 0 80 0 0 0 0 30 30 50 100 100 0 0 0.25 0 0 80 0 0 0 0 0 20 0 20 20 100 50 0 0 4 0 0 50 50 80 100 0 100 0 0 30 60 100 100 0 0 14 1 0 0 0 0 30 0 0 0 0 0 0 0 80 100 0 0 0.25 0 0 0 0 0 0 0 0 0 0 0 0 60 30 0 0 4 100 98 100 100 100 0 20 100 40 100 100 100 0 0 15 1 100 20 95 100 100 0 0 100 30 100 100 100 0 0 0.25 30 0 80 20 100 0 0 100 0 98 98 100 0 0 2 20 0 98 0 95 0 0 30 0 50 100 100 20 0 16 0.5 0 0 80 0 0 0 0 20 0 30 80 0 0 0 0.125 0 0 50 0 0 0 0 0 0 0 80 0 0 0 TABLE III (Continued)

Doses PRE-EMERGENCE POST-EMERGENCE Compound in No. kg/ha ECH LOL ABU IPO SIN XAN WHE SOY ECH LOL ABU IPO SIN XAN WHE SOY 2 100 100 100 100 100 80 0 100 20 100 100 100 20 0 17 0.5 100 30 100 100 100 0 0 98 20 100 100 100 20 0 0.125 0 0 100 0 100 0 0 20 0 30 100 100 0 0 2 100 100 100 100 100 100 0 100 30 90 100 100 20 0 18 0.5 100 100 100 100 100 0 0 98 0 20 100 100 0 0 0.125 80 0 98 50 100 0 0 20 0 0 90 90 0 0 4 100 80 100 100 100 50 0 100 20 100 100 100 100 20 0 19 1 90 30 100 100 100 0 0 0 90 0 100 100 100 100 0 0 0.25 30 0 98 50 100 0 0 0 30 0 100 100 100 100 0 0 4 100 50 100 100 100 100 0 100 90 20 100 100 100 100 0 0 20 1 90 0 100 100 100 100 0 80 80 20 100 100 100 100 0 0 0.25 30 0 95 80 100 100 0 100 20 0 80 100 100 100 0 0 TABLE III (Continued)

Doses PRE-EMERGENCE POST-EMERGENCE Compound in No. kg/ha ECH LOL ABU IPO SIN XAN WHE SOY ECH LOL ABU IPO SIN XAN WHE SOY 4 80 80 100 50 98 0 0 0 30 20 100 100 100 0 0 0 21 1 70 20 100 50 90 0 0 0 30 0 90 100 100 0 0 0 0.25 30 0 100 0 30 0 0 0 30 0 90 80 100 0 0 0 2 90 20 0 0 100 0 0 100 30 80 30 100 0 0 22 0.5 0 0 0 0 100 0 0 100 20 50 30 100 0 0 0.125 0 0 0 0 100 0 0 80 0 0 20 100 0 0 2 90 80 100 0 100 0 0 100 40 90 80 100 20 0 23 0.5 0 0 20 0 100 0 0 100 30 40 40 100 0 0 0.125 0 0 0 0 100 0 0 20 0 20 0 100 0 0 4 100 80 100 100 100 80 30 0 90 0 100 100 100 100 0 0 24 1 30 0 60 0 100 0 0 0 30 0 100 50 30 100 0 0 0.25 0 0 60 0 100 0 0 0 0 0 0 50 20 0 0 0 TABLE III (Continued)

Doses PRE-EMERGENCE POST-EMERGENCE Compound in No. kg/ha ECH LOL ABU IPO SIN XAN WHE SOY ECH LOL ABU IPO SIN XAN WHE SOY 4 90 80 100 50 100 0 30 0 20 0 30 50 0 0 0 0 25 1 0 0 0 0 95 0 0 0 0 0 0 50 0 0 0 0 0.25 0 0 0 0 30 0 0 0 0 0 0 30 0 0 0 0 4 30 70 100 0 100 0 30 0 20 0 40 50 20 0 0 0 26 1 0 0 95 0 100 0 0 0 0 0 0 0 20 0 0 0 0.25 0 0 40 0 30 0 0 0 0 0 0 0 20 0 0 0 2 100 90 100 100 100 50 0 100 0 80 100 100 0 0 27 0.5 30 0 0 20 100 0 0 30 0 30 100 100 0 0 0.125 0 0 0 0 80 0 0 20 0 0 100 30 0 0 2 50 0 100 100 100 0 0 40 20 100 100 0 0 28 0.5 0 0 50 0 20 0 0 30 0 100 100 0 0 0.125 0 0 0 0 0 0 0 20 0 100 100 0 0 TABLE III (Continued)

Doses PRE-EMERGENCE POST-EMERGENCE Compound in No.

kg/ha ECH LOL ABU IPO SIN XAN WHE SOY ECH LOL ABU IPO SIN XAN WHE SOY 2 70 50 100 70 100 10 0 30 0 50 100 100 10 0 29 0.5 30 30 30 0 100 0 0 10 0 30 90 100 0 0 0.125 0 0 70 0 100 0 0 0 0 10 100 80 0 0 2 60 60 100 100 100 10 0 40 20 60 100 100 0 0 30 0.5 30 30 100 70 100 0 0 20 0 20 90 90 10 0 0.125 30 30 100 40 100 0 0 20 0 0 50 50 0 0

Claims (36)

1. A phenoxybenzoic acid derivative of the formula:

wherein: - W, Y, Y', X, Z' and Z, which may be the same or different, represent the hydrogen atom, a halogen atom, a group NO2 or CN, a polyhalogenoalkyl group, or an alkyl or alkoxy group, - R1 represents an optionally substituted alkyl, alkenyl, alkynyl or phenyl group, - R2 represents a halogen atom or a group CN, SCN, OR3, SR4 or NR5R6, wherein - R3 represents an optionally substituted alkyl group or an allyl, propargyl, alkylcarbonyl, alkylideneimino or succinimido group, - R4 represents the hydrogen atom or a cation or has one of the meanings given for R3, - R5 represents the hydrogen atom, an optionally substituted alkyl group or an alkylcarbonyl or alkylsulphonyl group, and - R6 has one of the meanings given for R5 or represents a cation, a group CN or a group OR10, wherein R10 represents the hydrogen atom, a cation or an alkyl, carboxylate, carboxamide or alkylcarbonyl group.

2. A compound according to claim 1 wherein the polyhalogenoalkyl, alkyl and alkoxy groups represented by the symbols W,Y, Y', X, Z' and Z contain from 1 to 4 carbon atoms.

3. A compound according to claim 1 or 2, wherein: - W represents the hydrogen atom, a halogen atom, or a group NO2 or CN, - Y represents the hydrogen atom, a halogen atom, or a group NO2, CN, CF3 or CH3, - Y', Z' and Z represent the hydrogen atom or a halogen atom, - X represents a halogen atom, or a group NO2, CF3, CH3 or C2H5, - R' represents: - an alkyl group having 1 to 12 carbon atoms, which is optionally substituted by: - one or more halogen atoms, - one or more alkoxy or alkylthio groups, - one or more groups CN, or - a phenyl group which is itself optionally substituted, or - R1 represents:: - an alkenyl or alkynyl group, or - a phenyl group which is itself optionally substituted, - R2 represents a halogen atom, a group CN or SON or a group OR3, SR4 or NR5R6, wherein - R3 represents: - an alkyl group which is optionally substituted by:: - one or more halogen atoms, - one or more alkoxy or alkylthio groups, - one or more groups NO2 or CN, - a carboxyl group or a derivative thereof in the form of a salt, ester or amide, - an alkylcarbonyl group, - a phenyl group which is itself optionally substituted, or - a group

wherein R8 and R9, which are identical or different, represent the hydrogen atom or an alkyl group, or - R3 represents:: - an allyl or propargyl group, - an alkylcarbonyl group, or - group

wherein R8 and R9 are as hereinbefore defined, - R4 represents the hydrogen atom, or an alkali metal cation or ammonium cation or has one of the meanings given for R3, - R5 represents: - the hydrogen atom, - an alkyl group, which is optionally substituted by a carboxyl group or a derivative thereof in the form of a salt, ester or amide, or - an alkylcarbonyl or alkylsuiphonyl group, and - R6 has one of the meanings given for R5 or represents an alkali metal cation or ammonium cation, a group CN or a group OR10, wherein R10 represents:: - the hydrogen atom, - an alkali metal cation or ammonium cation, - an alkyl group which is optionally substituted by a carboxyl group or a derivative thereof in the form of a salt, ester or amide, - a group COOT7 or a carboxamide group CONHR7, wherein R7 is as hereinbefore defined, and R7' represents an alkyl group or a metal cation or ammonium cation, or - an alkylcarbonyl group.

4. A compound according to claim 3 wherein the halogen atoms in the definitions of W, Y, Y', Z', Z, X, R1 and R3 are Cl, Br or F; the halogen atom in the definition of R2 is chlorine; alkoxy and alkylthio groups in the definition of R1 and R3 contain from 1 to 4 carbon atoms; phenyl substituents on alkyl groups in the definition of R1 and R3 are substituted by one or more halogen atoms; alkenyl or alkynyl groups in the definition of R1 contain from 2 to 4 carbon atoms; the phenyl group represented by R1 is optionally substituted by one or more halogen atoms, nitro groups or alkyl radicals having from 1 to 4 carbon atoms; alkyl groups in the definitions of R3, R5, R8, R9 and R10 contain from 1 to 4 carbon atoms; the carboxyl group or derivative thereof in the definitions of R3, R5 and R10 is a group --COOR7 wherein R7 represents the hydrogen atom, an alkyl group, or a metal cation or ammonium cation; and the alkylcarbonyl group in the definition of R3 and R5 is an acetyl group.

5. A compound according to any one of the preceding claims wherein R1 represents an alkyl group containing 1 to 4 carbon atoms optionally substituted by halogen or phenyl, or represents a halogensubstituted phenyl group, R2 represents a chlorine atom, a group OR3 wherein R3 represents alkyl of 1 to 4 carbon atoms optionally substituted by from 1 to 3 halogen atoms, by alkoxy of 1 to 4 carbon atoms, byalkoxycarbonyl of 2 to 5 carbon atoms, by a group of the formula:

wherein R8 and R9 represent the hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, by a group of the formula::

wherein R8 and R9 are as hereinbefore defined, or R3 represents an allyl or propargyl group, or R2 represents a group -SR4 wherein R4 represents hydrogen, an alkali metal cation or an alkyl group containing from 1 to 4 carbon atoms optionally substituted by an alkoxycarbonyl group containing from 2 to 5 carbon atoms, or R2 represents a group -NR5R6 wherein R5 represents the hydrogen atom, an alkali metal cation or an alkyl group containing 1 to 4 carbon atoms and R6 represents the hydrogen atom, an alkyl group containing from 1 to 4 carbon atoms, an alkylsulphonyl group containing from 1 to 4 carbon atoms or a group OR'O wherein R10 represents the hydrogen atom or an alkyl group containing from 1 to 4 carbon atoms substituted by an alkoxycarbonyl group containing from 2 to 5 carbon atoms.

6. A compound according to one of the preceding claims, wherein X is Cl or CF3, Grand Z' are H, Y isCl,ZisCl,ForHandWisNO2.

7. A compound according to any one of the preceding claims wherein R1 is an alkyl group, R2 is the chlorine atom or a radical OR3, SR4 or NR5R6 wherein R3 is an alkyl group, R4 is the hydrogen atom or an alkyl group, R5 is the hydrogen atom or a methanesulphonyl group and R6 is the hydrogen atom, an alkali metal atom or ammonium cation or an alkyl group.

8. A compound according to any one of the preceding claims, in which X is CF3, Z is H and R2 is alkoxy.

9. A compound according to any one of the preceding claims wherein X is CF3,Y', Z' and Z are H, Y is Cl and W is NO2.

10. A compound according to any one of claims 1 to 7 and 9, in which RZ is SH, the products being in a tautomeric form.

11. A compound according to claim 1 prepared in any one of Examples 3 to 31.

12. 5-[2'-chloro-4'-(trifluoromethyl)-phenoxy]-2-nitro-N-methanesulphonylbenzimidoyl chloride.

13. Methyl 5-[2 '-chloro-4'-(trifluoromethyl)-phenoxy]-2-nitro-N-methanesulphonylbenzimidate.

14. A process for the preparation of a compound according to claim 1 wherein R2 is a halogen atom and the other symbols are as defined in claim 1, which comprises reacting a halogenating agent with a compound of the formula:

wherein the various symbols are as defined in claim 1.

15. A process according to claim 14 in which the reaction is carried out at from 300 to 1500C in a solvent and in the presence or absence of an acid acceptor.

16. A process according to claim 14 or 15 in which the halogenating agent is chosen from POX3, PCI5, POCI3, SOCI2, COCI2, SO2CI2 and (COCI)2.

17. A process for the preparation of a compound according to claim 1 wherein R2 is other than a halogen atom and the other symbols are as hereinbefore defined, which comprises reacting an imidoyl halide of the formula:

hal y | y =N-S02-R1 (Vl) MM z (wherein the various symbols are as defined in claim 1 and hal represents a halogen atom) with a compound of the formula R2 H, wherein R2 is as defined in claim 1 for R2 with the exclusion of R2 as halogen.

18. A process according to claim 17 in which the reaction is carried out at from 0 to 1 500C and in a solvent medium.

19. A process for the preparation of a compound according to claim 1 wherein R2 is a group OR3, SR4 or NR5R6, wherein R3, R4, R5 and R6 are as defined in claim 1 which comprises reacting an imidoyl halide of formula VI depicted in claim 1 7, wherein hal is as defined in claim 1 and the other symbols are as defined in claim 1, with a compound of the formula R30M, R4SM or R5R6NM, wherein M is a hydrogen atom or an alkali metal atom and R3, R4, R5 and R6 are as defined in claim 1.

20. A process according to claim 19, wherein R2 is a group OR3 as defined in claim 1 and wherein the reaction is carried out at from 10 to 1 500C in a compound of the formula R30H, wherein R3 is as defined in claim 1, as solvent, M being a sodium or potassium atom.

21. A process according to claim 19, wherein R2 is a group SR4 or NR5R6 wherein R4, R5 and R6 are as defined in claim 1 and wherein the reaction is carried out at from 10 to 1 500C in an inert solvent.

22. A process for the preparation of a compound according to claim 1 wherein R2 represents a group -NR50R10 wherein R'O is other than hydrogen, a cation or a carboxamide group, R5 is as defined in claim 1 and the other symbols are as defined in claim 1, which comprises reacting a compound of the formula:

(wherein the various symbols are as defined in claim 1) with a compound of the formula: R'o'-hal wherein hal represents a halogen atom and R is as defined in claim 1 for R'O with the exclusion of R10 as hydrogen, a cation or a carboxamide group.

23. A process according to claim 22 wherein the reaction is carried out at from 0 to 1 50"C in an inert solvent and in the presence of an acid acceptor.

24. A process according to any one of claims 14 to 23 followed by the conversion by known methods of a compound according to any one of claims 1 to 9, into a corresponding compound wherein, R4, R6, R7, R7 or R10 represents an alkali metal cation or ammonium cation.

25. A process according to any one of claims 14 to 24 substantially as hereinbefore described with especial reference to any one of Examples 1 to 31.

26. A compound according to any one of claims 1 to 13 when prepared by a process as claimed in any one of claims 14 to 25.

27. A herbicides composition which comprises, as active ingredient, a compound according to any one of claims 1 to 1 3 and 26, in association with an agriculturally acceptable carrier.

28. A composition according to claim 27, which contains 0.01 to 95% by weight of active ingredient.

29. A composition according to claim 27 or 28, which contains 1 to 95% by weight of carrier and 0.1 to 20% by weight of surface-active agent.

30. A herbicidal composition according to claim 27 substantially as hereinbefore described with especial reference to any one of Examples 34 to 49.

31. A method for controlling the growth of weeds at a locus used, or to be used for growing crops which comprises applying to the locus an effective amount of a compound according to any one of claims 1 to 13 and 26.

32. A method according to claim 31, which comprises applying a composition according to any one of claims 27 to 30 the active ingredient being applied at a rate of 0.01 to 5 kg/ha.

33. A method according to claim 32 in which the active ingredient is applied at a rate of 0.1 to 2 kg/ha.

34. A method according to any one of claims 31 to 33, wherein the crop is soya or a cereal.

35. A method according to any one of claims 31 to 33, in which the crop is maize, sunflower, cotton or beans.

36. A method according to any one of claims 31 to 35 substantially as hereinbefore described.