FR2525593A1 - Herbicidal phenoxy benzoic aryl sulphonamide(s) - are prepd. by condensn. of saccharin and phenoxy benzoic acid, and hydrolysis - Google Patents

Abstract

Phenoxybenzoic aryl sulphonamides of formula (I) are new. In (I) W=halogen, NO2, CN, or H; X=halogen or haloalkyl; Y= halogen, CF3, CN, or NO2; Z= halogen or H; R1=H, 1-6C alkyl, alkali metal or ammonium gp; R2=COOR7; R3, R4, R5, R6= halogen, alkyl, esp. 1-6C, H, CN, NO2, CF3, -COOR7, -OR8, or alkyl substd. by Cl, NO2, 1-4C alkoxy or alkyl carboxylate; R7=alkyl, pref. 1-6C, H, metal cation, or ammonium; R8= 1-6C alkyl. Used as selective pre- and post-emergence herbicides, of particular use in cereal crops and soya.

Description

 The invention relates to herbicidal arylsulfonamide group compounds derived from phenoxybenzoic acids.

 5- {2-Chloro-4- (trifluoromethyl) phenyl) -2-nitrobenzoic acid, also known as acifluorfen, and its salts, as well as their herbicidal activity, are known.

 In this paper, chemical products have been designated according to French nomenclature; however, the figures indicating the positions of substituents were placed before the substituents concerned according to the Anglo-Saxon nomenclature.

 In particular, it has been proposed to apply this compound to soybean crops in postemergence treatment to control weeds, especially dicotyledons. In such an application, the qualities required for a herbicide are, at the rate considered - the ability to control the major weeds or target weeds, - selectivity to soybeans.

 In attempting to improve the herbicidal properties of 5-t-chloro-4- (trifluoromethyl) phenoxy] -2-nitrobenzoic acid and its salts, many derivatives of these compounds have been proposed; in particular the alkyl, cycloalkyl, thioalkyl and phenyl esters, as well as the mono or dialkylated amides. Such compounds are described by US Pat. Nos. 3652645, 3784635, 3873302, 3983168, 3907866, 3798276, 3928416, 4063929 and others. European Patents 3416 and 23392 describe sulfonamides derived from phenoxybenzoic acids.

dans laquelle -W représente un atome d'halogène, ou un groupe nitro ou
cyano ou l'atome d'hydrosène, -X représente un atome d'halogène ou un radical alkyle ha
logéné, -Y représente un atome c'halogène ou un groupe CF3, CN ou
NO2' -Z représenté un atome d'halogène ou d'hyorogène, -R représente un atome d'hydrogène ou un radical alkyle de 1 à 6 atomes de carbone ou un atome de métal alcalin (notamment de sodium ou de potassium) ou un groupe ammonium.It is an object of the invention to provide products having a better combination of herbicidal properties with respect to weed activity and crop selectivity. Another object of the invention is to provide products having a better selectivity for other crops including cereals. The invention therefore relates to formula products

wherein -W represents a halogen atom, or a nitro group or
cyano or the hydrosene atom, -X represents a halogen atom or an alkyl radical
logene, -Y represents a halogen atom or a group CF3, CN or
NO 2 '-Z represents a halogen or hyorogen atom, -R represents a hydrogen atom or an alkyl radical of 1 to 6 carbon atoms or an alkali metal atom (especially sodium or potassium) or a ammonium group.

R 2 is a COOR 7 group, R 7 being an alkyl radical, preferably having 1 to 6 carbon atoms, or a hydrogen atom or a metal cation, or ammonium, in particular an alkali metal, -R 3, R 4, R5, R6, which may be identical or different, represent a halogen atom; or an alkyl radical (especially 1 to 6 carbon atoms); or a cyano or nitro group or CF3; or -CO-OR7 or
OR8; or a substituted alkyl group, especially an alkyl group of 1 to 4 carbon atoms substituted with one or more atonia of chlorine or with the group NO2 or with an alkoxyl group having 1 to 4 carbon atoms, or a carboxylate group of alkyl, this alkyl group having 1 to 4 carbon atoms, or, preferably, a hydrogen atom, -8 is an alkyl radical having 1 to 6 carbon atoms.

As preferred compounds, a subfilter is constituted by the compounds of formula (I) in which
X is CF3, Y is C1, Z is H, W is C1 or preferably
NO2, R is COOR7, R6 is H.

 As herbicides, the compounds in which R7 is an alkyl group are also preferred, the compounds in which R7 has another meaning being rather intermediates for the synthesis of other compounds of the invention, in particular those in which R7 is an alkyl group.

 The invention also relates to a process for preparing the products according to the invention.

This process is characterized in that a hydrolysis

 This hydrolysis is carried out by any means known per se and in particular by heating in acidic medium or preferably alkaline; generally heated between 40 and 1400C in the presence of water and / or an inert organic solvent in the operational conoitions. Conveniently it is carried out in water in the presence of sodium hydroxide or potassium hydroxide in a proportion of 1 to 3 moles per mole of compound (II).

The above-described hydrolysis giving rise to a salt, the homologous compounds of the acioe or ester type can be obtained in a manner known per se by acidification or esterification.
Acidification can be done by simple mixing of an acid with the previously prepared salt, in the presence or absence of solvent (water for example). The amount of acioe used is at least equal to 1.5 moles per mole of product of formula (II) subjected to hydrolysis.

 Esterification is by reaction of an alcohol (preferably an alkanol) with the previously prepared acid in the presence of base or preferably an acid. This reaction is quite usual for the esterifications, for example by heating at 40.degree. To 1200.degree. C. and in the presence of an excess of alcohol (for example 1.5 to 10 mol per mol of acid to be esterified). .

The compounds of formula (II) are obtained most often by reaction of a phenoxyben zoic halide of formula

X1 being the halogen atom with a saccharin derivative of formula

 The reaction can be carried out by simple mixing of the reagents, in the presence of a hydracid acceptor such as a tertiary amine, for example triethylamine or pyridine; it is advantageously carried out in an inert solvent medium in the operating conaitions, for example a ketone, or a halogenated aliphatic hydrocarbon or not, or a nitrile; the reaction temperature is often between 0 and 150 C.

 The following examples, given in a non-limiting manner, illustrate the invention and show how it can be practiced.

 Examples 1 to 3 illustrate the preparation and the physicochemical properties of this compound according to the invention.

 Examples 4 to 6 illustrate the application and the herbicidal properties of the compounds according to the invention.

 The terms pre-emergence and pre-emergence are used as synonyms; post-emergence and post-emergence terms are used as synonyms.

Example 1
To a solution of 183 g (1 mole) of saccharin and 110 g of triethylamine (1.1 mole) in 2.5 l of acetone, 380 g (1 mole) of acid chloride are added procressionally and with stirring. 5- [2-chloro-4- (trifluoromethyl) phenyl] -2-nitrobenzoic acid dissolved in 0.5 liters of acetone,
It is refluxed for 6 hours and allowed to cool to room temperature; cooled to -50C and filtered the white precipitate of triethylamine hydrochloride which is washed with acetone; the acetone filtrate is concentrated; the solid residue is recrystallized from methanol. 422% of a white solid is obtained, melting at 179 ° -1800 ° C., having 1765 and 1715 infrared absorption bands and (carbonyl groups) having the formula

Compound A, the name of which is 2- [5- (2-chloro-4- (trifluoromethyl) phenoxy) -2-nitrobenzoyl-2,3-dihydro-3-oxo-1,2-benzisothiazole -1,1 dioxide.

 2.1 liters of an aqueous solution containing 422 g (0.8 mole) of compound A and 64 n (1.6 mole) of sodium hydroxide are then heated at 1000 ° C. for 30 minutes. The solid is then completely dissolved. After cooling, it is acidified to pH less than 1 with concentrated hydrochloric acid.

The solid obtained is filtered, dried, recrystallized from a toluene / acetone mixture. 325 g of a white solid which melts at 193 ° -191 ° C. and which has the following absorption bands at infra-red: 3250 cm -1 (NH); 174B and 1722 cm-1 (CO). This compound B has the formula

Compose R whose name is 5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitro-N [orthocarboxyphenylsulfonyl] benzamide.

Example 2
0.272 g (0.5 mmol) of compound B are dissolved in 10 ml of 0.1N aqueous sodium hydroxide. The pH of the aqueous solution is then 7. The di-salt of compound B of formula

Example 3
A solution comprising 3 liters of methanol, 285 g (0.525 moles) of compound e and 57 g (0.58 moles) of concentrated sulfuric acid are heated to reflux for 7 days. Cool, pour into ice water. The white solid precipitate is filtered off, dried and recrystallized from toluene. 211 g of a solid melting at 155.degree.-1530.degree. C. having infra-red absorption bands at 3230 cm-1 (NH) and 1728 cm-1 are obtained. (CO) and having the formula

Example 4
In terraces of 20 cm x 25 cm containing soil, crop species and bad harrows are available in rows of 10 cm long.

 The species used are shown in Table (I).

 Cotton, corn, soybean and Xanthium are sown at 4 to 5 seeds per row.

 The smaller species (velvetleaf, wild mustard, amaranth, Italian millet and green foxtail) are sown without counting the seeds, but in numbers nevertheless sufficient to subsequently form a tight line of seedlings.

 Initial watering up to the period of emergence is carried out over the soil covering the seeds.

 Preemergence treatment is done less than a day after sowing.

 The application of the compositions according to the invention is made by spraying a mixture of 40 ml of acetone and 40 ml of water with, G, 1% of surfactant (Cemulsol NP 10, ie a polyethoxylated alkyl phenol, especially polyethoxylated nonylphenol).

 After treatment, the irrigation is made by under-irrigation for the seedlings having already emerged and by watering above for the seeds which have not yet given seedlings.

 2 weeks after treatment, activity measurements are made on a scale of 0 to 100 S. For weeds this measure indicates the level of destruction; for crops this measure encodes the degree of attack or degree of phytotoxicity, with the zero score being attributed to plants in the same state as the control and the score being attributed to complete destruction.

In terms of application rates, the correspondence between metric and US units is as follows
Books / acres 10 4 2 1 0.5 0.25 0.125 0.0625
kg / ha 11.2 4.48 2.24 1.12 0.56 0.28 0.14 Q, 07
Table (II) gives the results obtained with the compound of Example 3.

Example 5: Herbicide application, in pre-emergence of plant species.

 In 9 x 9 x 9 cm pots filled with light agricultural soil, a seed number is sown according to the plant species and the size of the seed.

 The seeds are then covered with a layer of soil about 3 mm thick.

 After moistening the soil, the pots are spray-treated in an amount corresponding to a chemical application rate of 500 l / ha and containing the active ingredient at the desired concentration.

 The slurry is prepared as in Example 4.

 Depending on the active ingredient concentration of the slurry, the dose of active ingredient applied was 0.25 to 2 kg / ha.

 The treated pots are then placed in bins for receiving the water. watering, under irrigation, and maintained for 21 days at room temperature under 70 S relative humidity.

 After 21 days, the number of live plants in the pots treated with the slurry containing the active ingredient to be tested and the number of live plants in a control pot treated according to the same conditions, but using a slurry not containing no active ingredient.

This determines the percentage of destruction of the treated plants relative to the untreated control. A percentage of destruction equal to 100% indicates that there has been complete destruction of the plant species considered and a percentage of 0% indicates that the number of live plants in the treated pot is identical to that in the control pot.

Example 6: Application, ierbicide, postemergence of plant species.

 In 9 x 9 x 9 cm pots filled with light agricultural soil, a seed number is sown according to the plant species and the size of the seed.

 The seeds are then covered with a layer of soil about 3 mm thick and the seed is allowed to germinate until it gives rise to a seedling 5 to 10 cm high.

 The pots are then treated by spraying the slurry in an amount corresponding to a volume application dose of 500 l / ha and containing the active ingredient at the desired concentration.

 The slurry was prepared in the same manner as in Example 5.

 Depending on the active ingredient concentration of the slurry, the dose of active ingredient applied was 0.125 to 2 kg / ha.

 The treated pots are then placed in bins intended to receive water spray, underwater, and maintained for 21 days at room temperature at 70% relative humidity.

 After 21 days, the number of live plants in the pots treated with the slurry containing the active ingredient to be tested and the number of live plants in a control pot treated under the same conditions, but using a slurry not containing no active ingredient.

Thus, the percentage of destroyed treated plants is determined relative to the untreated control. A percentage of destruction equal to 100% indicates that there has been complete destruction of the plant species considered and one percent of O S indicates that the number of live plants in the treated pot is icantic to that in the control pot.

 The results of Examples 5 and 6 are shown in Tables (III) and (IV).

 Each of these tables (III) and (IV) comprises on the one hand pre-emergence results obtained according to Example 5 and on the other hand post-emergence results obtained according to Example 6.

 Table (III) gives results in relation to maize, cotton, soybean and corresponding weeds.

 Table (IV) gives results for wheat and barley and the corresponding weeds.

 The products used were the product of Example 3 and a very representative product of the prior art constituted by European patents 3416 and 23392.

This product, called reference product, has the formula:

The tests carried out therefore show the remarkably advantageous properties of the compounds according to the invention, in particular for the treatment of soybeans and maize in pre- and post-emergence, especially when these crops are mixed with weeds, the Abutilon, Amaranth, Ambrosia, Knotweed and Aids, as well as pre-emergent grain treatment, especially when these crops are infested with dicotyledonous weeds such as Lamb's-quarters, Chrysanthemum, Mustard, Knotweed, Stellate and the Gaillet
Compared with the reference product, they show improved activity on cereals.

 For their practical use, the compounds according to the invention are rarely used alone. Most often they are part oe compositions. These cooositions, used as herbicidal agents, contain as active ingredient a compound according to the invention as described above in combination with solid or liquid carriers, acceptable in agriculture and surfactants also acceptable in agriculture. In particular, the usual inert carriers and surfactants are usable. These compositions are also part of the invention.

 These compositions may also contain any other kind of ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilizers, sequestering agents, etc. other known active substances with pesticidal properties (in particular insecticides, fungicides or herbicides) or with properties promoting the growth of plants (in particular fertilizers) or with properties regulating the growth of plants. More generally, the compounds according to the invention can be associated with any solid or liquid aoditive corresponding to the usual techniques of formulation.

 The doses of use of the compounds according to the invention can vary within wide limits, in particular according to the nature of the aoventices to be eliminated and the degree of usual infestation of the crops for these weeds.

 In general, the compositions according to the invention usually contain from about 0.05 to about 95% (by weight) of one or more compounds according to the invention, from about 1% to about 95% to one or more solid carriers. or liquids and optionally from 0.1 to 20% of one or more surfactants.

 According to what has already been said the compounds according to the invention are generally associated with carriers and optionally surfactants.

 By the term "carrier", in the present description, is meant a natural or synthetic organic or inorganic material with which the active ingredient is associated to facilitate its application on the plant, on seeds or on the soil. This support is therefore generally inert and must be acceptable in agriculture, especially on the treated plant. The support may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases , etc ...).

 The surfactant may be an emulsifier, dispersant or wetting agent of ionic or nonionic type. There may be mentioned, for example, salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines. substituted phenols (especially alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (especially alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols. The presence of at least one surfactant is generally indispensable when the active ingredient and / or the inert carrier are not soluble in water and the application carrier is water.

 For their application, the compounds of formula (I) are therefore generally in the form of compositions These compositions according to the invention are themselves in quite diverse forms, solid or liquid.

 As forms of solid compositions, mention may be made of dusting or dispersion powders (with a content of compound of formula (I) up to 100 S) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granulated support, by granulation from a pouch (the content of compound of formula (I) in these granules being between 0.5 and 80% for the latter cases).

 As forms of solid compositions, mention may be made of powders for dusting or dispersion (with an active material content of up to 100%).

 As forms of liquid compositions or intended to constitute liquid compositions during application, mention may be made of solutions, in particular water-soluble concentrates, zmulsifiable concentrates, emulsions, concentrated suspensions, aerosols and powders. wettable (or powder spray), pasta.

 The emulsifiable or soluble concentrates most often comprise 10 to 80% of active material, the emulsions or solutions ready for application containing, for their part, 0.001 to 20% of active ingredient. In addition to the solvent, the emulsifiable concentrates may contain, when necessary, 2 to 20% of suitable additives, such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, colorants, adhesives.

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

 As forms of liquid compositions or intended to constitute liquid compositions during application, mention may be made of concentrated suspensions, wettable powders (or spray powder). and pasta.

 The concentrated suspensions, which are applicable in spraying, are prepared in such a way as to obtain a stable fluid product which does not settle and they usually contain from 10 to 75% of active substance, from 0.5 to 1% of surfactants, from 0.1 to 10% of thixotropic agents, from 0 to 10% of suitable additives, such as defoamers, corrosion inhibitors, stabilizers, penetrants and adhesives and, as carrier, water or an organic liquid in which the active ingredient is poorly soluble or non-soluble: some organic solids or mineral salts may be dissolved in the carrier to help prevent sedimentation or as antifreezes for water.

 Wettable powders (or spray powder) are usually prepared to contain from 20 to 95 percent active material, and usually contain, in addition to the solid support, from 0 to 5 percent of a wetting agent, to 10% of a dispersing agent, and, when necessary, from 0 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, coloring agents, etc ...

By way of example, here are various compositions of wettable powders: - active ingredient 50% - calcium lignosulfonate (deflocculant) 5 X - isopropylnaphthalene sulphonate (agent
anionic wetting agent) 1% - anti-shattering silica 5 S - kaolin (filler) 39 X
Another example of 80 X wettable powder is given below: active ingredient ....................................... 80%. sodium alkylnaphthalene sulfonate .................. 20%. sodium lignosulfonate 2 2% anti-foaming silica 9 3%. kaolin i3%
Another example of wettable powder is given below. active ingredient ..................................... 50%. sodium alkylnaphthalene sulfonate ............ 2%. low viscosity methyl cellulose ............... 2%. diatomaceous earth ................................. 46%
Another example of a wettable powder is thundered below. active ingredient ...................................... 90%. sodium dioctylsulfosuccinate ...................... 0.2%. synthetic silica .................................... 9.8%
Another composition of 70% spraying powder uses the following constituents - active ingredient 700 g - sodium dibutylanphtylsulfonate 50 g - condensation product in proportions
3/2/1 naphthalene sulphonic acid,
of phenolsulfonic acid and
formaldehyde 30 g - kaolin 100 g - chalk of champagne 120 g
Another composition of 40% spraying powder uses the following constituents - active ingredient 400 g - sodium lignosulfonate 50 g - sodium dibutyl naphthalene sulphonate 10 g - silica 540 g
Another composition of 25% spraying powder uses the following constituents - active ingredient 250 g - calcium lignosulfonate 45 9 - equiponderal mixture of Champagne chalk
and hydroxyethylcellulose 19 g - sodium dibutylnaphthalenesulfonate 15 g - silica 195 g - Champagnt craic 195 g - kaolin 281 g
Another composition of 25% spraying powder uses the following constituents - active ingredient 250 g - isooctylphenoxy-polyoxyethylene-ethanol 25 g - equiponderal mixture of chalk
Champagne and hydroxyethylcellulose 17 g - sodium aluminosilicate 543 g - kieselguhr 165 g
Another composition of 10% spraying powder uses the following constituents - active ingredient 100 g - mixture of sodium salts of sulphates
of saturated fatty acids 30 g - product of conoensation of naphthalic acid
sulfonic acid and formaldehyde 50 g - kaolin 820 g
In order to obtain these sprayable powders or wettable powders, the active ingredients are intimately mixed in appropriate mixers with the additional substances and milled with suitable mills or other mills. Spray powders are thus obtained, the wettability and suspension of which are advantageous; they can be suspended in batches at any desired concentration and this suspension is very advantageously used especially for application to the leaves of plants.

 In place of the wettable powders, it is possible to realize the legs. The conditions and methods of production and use of these pastes are similar to those of wettable powders or powders to be sprayed.

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

 All these dispersions or aqueous or boiled emulsions are applicable to the crops to be weeded by any suitable means, mainly by spraying, at doses which are generally of the order of 100 to 1200 liters of slurry per hectare.

 The granules intended to be placed on the ground are usually prepared so that they have dimensions of between 0.1 and 2 m and they can be manufactured by agglomeration or impréynation. Preferably, the granules contain 1 to 25% of this active ingredient and 0 to 10% of additives such as stabilizers, slow release modifiers, binders and solvents.

 According to an example of granule composition, the following constituents are used: active ingredient 50 g - epichlorohydrin 2.5 g - cetyl polyglycol ether 2.5 g - polyethylene glycol 35 g kaolin (particle size: 0.3 to 0, 8 mm) 910 g.

 In this particular case, the active ingredient is mixed with epichlorohydrin and dispersed in 60 g of acetone; polyethylene glycol and cetyl polyglycol ether are then added. The kaolin is sprinkled with the dispersion obtained and the acetone is then evaporated under vacuum.

 As indicated above, the invention also relates to a method for the weeding of crops, in particular cereals such as wheat as well as soybeans, according to which an effective amount of seeds is applied to the plants and / or the soil of the area to be weeded. at least one of the compounds according to the invention. These are used practically in the form of the herbicidal compositions according to the invention which have been described above. Generally, quantities of this active ingredient ranging 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 intensity of the problem to be solved, the climatic conditions and of the crop under consideration.The treatment can be carried out either in the harvest of crops and weeds, or in pre-plant cultures with incorporation into the soil (this incorporaticn is therefore a complementary operation to the process of treatment of the invention), either in post-harvest lifted. Other embodiments of the treatment method according to the invention can still be used: thus the active ingredient can be applied to the soil, with or without incorporation, before transplanting a culture.

 The treatment method of the invention applies both in the case of annual crops and in the case of perennial crops; in the latter case it is preferred to apply the active ingredients of the invention in a localized manner, for example between the rows of said cultures.

TABLE I
Name Name Name Abbreviation
French Latin American
Corn Field Corn CN
Cotton Cotton CT
Crops Wheat Wheat WT
Rice Rice RI
Soybaan Soybaan SB
Panisse Barnyardgrass Echlnochloa BYG
crus-galli
Foxtail Tiant fomtail Setraria faberii GTF
Green foxtail Green foxtail Setaria viriais
Crabgrass Digitizer .Digitaria CG
sanguinalis
Velvet leaf Abutilon VL
theophrasti
Millet of Italy Foxtail millet Setaria italica FM
Bad Cocklebur Xanthium
herbs pennsyylvicicum
Wild mustard Wild mustard Sinapis arvensis WM
Amaranth Pigweed Amarantrus Pw
retroflexus
Morningglory purple bindweed lpomea purpurea MG (annual)
Prickly AIDS AIDS spinosa PS
Wild oat Wild oat Avena fatua WO
Wild buckwheat Polygonum cdnvoîvulus
Ambroisie Rsgweed Ambrosia
artyemisiifolia TABLE II

<SEP> Dose <SEP> in <SEP> Kg / ha <SEP> FM <SEP> GP <SEP> VL <SEP> CB <SEP> WM <SEP> PW <SEQ> CT <SEP> CN <SEP> SB
<tb><SEP> 2.24 <SEP> 70 <SEP> 60 <SEP> 100 <SEP> 20 <SEP> 100 <SEP> 100 <SEP> 20 <SEP> 10 <SEP> 0
<tb><SEP> PRE <SEP> - <SEP> 1.12 <SEP> 30 <SEP> 30 <SEP> 90 <SEP> 10 <SEP> 90 <SEP> 100 <SEP> 20 <SEP> 10 <SEP> 0
<tb> EMERGENCE <SEP> 0.56 <SEP> 20 <SEP> 20 <SEP> 70 <SEP> 0 <SEP> 90 <SEP> 100 <SEP> 0 <SEP> 0 <SEP> 0
<tb><SEP> 0.28 <SEP> 0 <SEP> 0 <SEP> 70 <SEP> 0 <SEP> 90 <SEP> 80 <SEP> 0 <SEP> 0 <SEP> 0
<tb><SEP> 0.14 <SEP> - <SEP> 20 <SEP> 30 <SEP> 60 <SEP> 40 <SEP> 80 <SEP> 0 <SEP> 0 <SEP> 0
<tb><SEP> 0.07 <SEP> - <SEP> 20 <SEP> 20 <SEP> 40 <SEP> 40 <SEP> 70 <SEP> 0 <SEP> 0 <SEP> 30
<tb> TABLE III

STAGE <SEP> PRE <SEP> - <SEP> EMERGENCE <SEP> POST <SEP> - <SEP> EMERGENCE <SEP> PRE <SEP> - <SEP> EMERGENCE <SEP> POST <SEP> - <SEP> EMEFGENCE
<tb> Product <SEP> Product <SEP> of <SEP> Example <SEP> 3 <SEP> Product <SEP> of <SEP> Example <SEP> 3 <SEP> Product <SEP> of <SEP > reference <SEP> Product <SEP> of <SEP> reference
<tb><SEP> kg / ha
<tb> Species <SEP> 2 <SEP> 1 <SEP> 0.5 <SEP> 0.25 <SEP> 0.125 <SEP> 2 <SEP> 1 <SEP> 0.5 <SEP> 0.25 <SEP > 0.125 <SEP> 2 <SEP> 1 <SEP> 0.5 <SEP> 0.25 <SEP> 0.125 <SEP> 2 <SEP> 1 <SEP> 0.5 <SEP> 0.25 <SEP> 0.125
<tb> AGROPYRON <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 100 <SEP> 90 <SEP> 90
<tb> SORHUM <SEP> HALEPENSE <SEP> 100 <SEP> 100 <SEP> 0 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
<tb> ECHINOCHLOA <SEP> 10 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 20 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 100 <SEP> 100 <SEP > 100
<tb> CRUS-GALLI <SEP> 30 <SEP> 10 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 80 <SEP> 20
<tb> PANICUM <SEP> 30 <SEP> 0 <SEP> 0 <SEP> 0
<tb> DIGITARIA <SEP> 100 <SEP> 60 <SEP> 0 <SEP> 0 <SEP> 40 <SEP> 10 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 100 <SEP> 100 <SEP > 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 20
<tb> SETARIA <SEP> 80 <SEP> 20 <SEP> 0 <SEP> 0 <SEP> 20 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 100 <SEP> 100 <SEP > 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 30
<tb> CYPERUS <SEP> ESCULENIUS <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 100 <SEP > 90 <SEP> 70 <SEP> 100 <SEP> 100 <SEP> 90 <SEP> 10
<tb> ABUTILON <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 80 <SEP> 50 <SEP> 20 <SEP> 100 <SEP> 100 <SEP> 100 <SEP > 100
<tb> XANTHIOM <SEP> 90 <SEP> 10 <SEP> 10 <SEP> 0
<tb> PENNSYLVANICUM <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 90 <SEP> 80 <SEP> 80 <SEP> 100 <SEP> 100 <SEP> 100 <SEP > 80 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 80
<tb> AMARANTUS <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP > 100 <SEP> 100 <SEP> 100
<tb> RETPOFLEXUS
<tb> AMBROSIA <SEP> 100 <SEP> 100 <SEP> 80 <SEP> 60 <SEP> 90 <SEP> 90 <SEP> 80 <SEP> 80 <SEP> 100 <SEP> 100 <SEP> 100 <SEP > 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 30
<tb> POLYGONOM <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 80 <SEP> 90 <SEP> 90 <SEP> 90 <SEP> 90 <SEP> 100 <SEP> 100 <SEP> 100 <SEP > 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 98
<tb> IPOMEA <SEP> PURPUREA <SEP> 100 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 95 <SEP> 80 <SEP> 80 <SEP> 100 <SEP> 100 <SEP > 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
<tb> AIDS <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 98 <SEP> 100 <SEP> 100 <SEP> 80 <SEP> 80 <SEP> 100 <SEP> 100 <SEP> 100 <SEP > 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 98
<tb> BUT <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 90 <SEP> 100 <SEP > 98 <SEP> 50 <SEP> 50 <SEP> 0 <SEP> 0
<tb> COTTON <SEP> 0 <SEP> 0 <SEP> 20 <SEP> 20 <SEP> 20 <SEP> 92 <SEP> 98 <SEP> 98 <SEP> 98 <SEP> 80 <SEP> 90 <SEP > 90
<tb> SOJA <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP > 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0
<Tb>

COMPOUND <SEP> AS <SEP> EXAMPLE <SEP> 3 <SEP> PRODUCT <SEP> DE <SEP> REFERENCE
<tb> STAGE <SEP> PRE-EMERGENCE <SEP> POST-EMERGENCE <SEP> PRE-EMERGENCE <SEP> POST-EMERGENCE
<tb><SEP> kg / ha
<tb> Species <SEP> 2 <SEP> 1 <SEP> 1/2 <SEP> 1/4 <SEP> 1/8 <SEP> 2 <SEP> 1 <SEP> 1/2 <SEP> 1/4 <SEP> 1/8 <SEP> 2 <SEP> 1 <SEP> 1/2 <SEP> 1/4 <SEP> 1/8 <SEP> 2 <SEP> 1 <SEP> 1/2 <SEP> 1 / 4 <SEP> 1/8
<tb> AVENA <SEP> FATUA <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 95 <SEP> 40 <SEP > 5 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0
<tb> ALOPECURUS <SEP> 10 <SEP> 10 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 90 <SEP> 30 <SEP > 20 <SEP> 5 <SEP> 0 <SEP> 0 <SEP> 0
<tb> LOLIUM <SEP> 5 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 100 <SEP> 80 <SEP > 50 <SEP> 20 <SEP> 0 <SEP> 0 <SEP> 0
SETARIA <SEP> FABERI <SEP> 80 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 100 <SEP > 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 98
<tb> CHENOPODIUM <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 98 <SEP> 100 <SEP> 100 <SEP> 100 <SEP > 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
<tb> CHRYSANTHEMUM <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 10 <SEP> 10 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 100 <SEP> 100 <SEP > 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
<tb> SINAPIS <SEP> 100 <SEP> 100 <SEP> 90 <SEP> 80 <SEP> 90 <SEP> 90 <SEP> 80 <SEP> 70 <SEP> 100 <SEP> 100 <SEP> 100 <SEP > 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
<tb> POLYGONUM <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 80 <SEP> 60 <SEP> 80 <SEP> 20 <SEP> 50 <SEP> 100 <SEP> 100 <SEP> 100 <SEP > 100 <SEP> 100 <SEP> 100 <SEP> 100 <SEP> 100
<tb> STELLARIA <SEP> 100 <SEP> 100 <SEP> 98 <SEP> 50 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 100 <SEP> 100 <SEP > 98 <SEP> 10 <SEP> 0 <SEP> 0 <SEP> 0
<tb> GALIOM <SEP> 100 <SEP> 98 <SEP> 80 <SEP> 20 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 100 <SEP> 100 <SEP > 95 <SEP> 100 <SEP> 70 <SEP> 100 <SEP> 20
<tb> BLE <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 80 <SEP> 30 <SEP > 10 <SEP> 10 <SEP> 5 <SEP> 0 <SEP> 0
<tb> BARLEY <SEP> 10 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 100 <SEP> 80 <SEP> 10 <SEP > 0 <SEP> 5 <SEP> 0 <SEP> 0 <SEP> 0
<tb> TABLE IV

Claims (2)

1) - Products of formula in which -W represents a halogen atom, or a nitro or cyano group or the hydrogen atom, -X represents a halogen atom or a linear alkyl radical hal, -Y represents a halogen atom or a CF3, CN or NO2 group, -Z represents a halogen or hydrogen atom, -R represents a hydrogen atom or an alkyl radical of 1 to 6 carbon atoms or an atom of alkali metal or an ammonium group, -R2 is a COOR7 group, R7 being an alkyl radical, preferably having from 6 to 6 carbon atoms, or a hydrogen atom or a metal cation, or ammonium, especially alkali metal R3, R4 R5 R6, which may be identical or different, represent a halogen atom; or an alkyl radical (in particular of 1 to 6 carbon atoms). or a hydrogen atom or a cyano or nitro group or CF3; or -CO-OR7 or OR8; or a substituted alkyl group, preferably an alkyl group of 1 to 4 carbon atoms substituted by one or more chlorine atoms or by the group NO 2, or by an alkoxyl group having 1 to 4 carbon atoms, or a carboxylate group o alkyl, this alkyl group having 1 to 4 carbon atoms -R8 is a alkyl radical having 1 to 6 carbon atoms. 2) - Products according to claim 1 characterized in that R7 has from one to 6 carbon atoms and / or at least one of the radicals R to R6 is hydrogen atom 3) - Products according to one of claims 1 or 2 characterized in that X is CF3, Y is Cl, Z is H, W is C1 or NO2 and R1 is H or Na or K4) - Products according to claim 3 characterized in that W is NO2, R6 is H5 - Products according to one of claims 1 to 4 characterized in that R2 is COOR7 and R7 is an alkyl radical having 1 to 6 carbon atoms and R3 to R6 are the hydrogen atom. 6) - Process for the preparation of products according to one of claims 1 to 5 characterized in that one hydrolyzes a product of formula

 in which the various substituents have the meanings indicated in one of claims 1 to 5 and that, optionally, the product resulting from the hydrolysis is acidified, then optionally esterified 7) - Process according to claim 6 characterized in that the hydrolysis is carried out by heating between 40 and 1400C in the presence of water and / or an organic solvent and in an alkaline medium 8) - Process according to claim 7, characterized in that the hydrolysis is carried out in the presence of 1 to 3 moles of potassium hydroxide or sodium hydroxide per mole of compound of formula (II) 9) - Process according to one of claims 6 to 8 characterized in that the esterification is carried out by heating between 40 and 1200C in the presence of an excess of and in the presence of acid i0) - Herbicidal compositions characterized in that they contain as active ingredient a compound according to one of claims 1 to 5, this compound being in association with the inert carriers e conventional, acceptable in agriculture, and optionally the usual surfactants 11) - Compositions according to claim 10 characterized in that they contain 0.05 to 95 SI of active material, from 1 to 95% of support (s) solid (s) or liquid (s) and 0.1 to 20% of surfactant (s) 12.- A process for the selective control of crops, in particular soya beans and cereals, characterized in that applying an effective amount of at least one compound according to one of claims 1 to 5 13) - Process according to claim 12 characterized in that it applies between 0.1 and 2 kg / ha of active material.