LU84298A1 - HERBICIDE COMPOUNDS DERIVED FROM PHENOXYBENZOIC ACIDS - Google Patents

Description

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The present invention relates to certain derivatives of phenoxybenzoic acids with a sulfonamide function which are useful as herbicides and in particular as herbicides against the weeds present in soybean crops.

Herbicides derived from phenoxybenzoic acids and their esters are widely known in particular from US patents 3652645, 3784635, 37S8276, 3873302, 3907866, 3928416, 3983168, 4063929 and European patent applications Nos 3416 and 23392.

The present invention relates to these derivatives of benzoic acids with a sulfonamide function, characterized in that they have the formula: VX „Xc 15 I4 I5 X2 co-y3-ch-co-n-so2-x6 ^ fS ~ ° hV) - X3 (I> * 1-2 2G in which: - Xp X2 and Xj represent a halogen atom, such as fluorine, chlorine or bromine; a polyhalogenated alkyl radical having from 1 to 4 carbon atoms, especially CF ^; Nü2; CN; an alkyl radical having from 1 to 4 25 carbon atoms; an SO2 ~ alkyl radical having this 1 to 4 carbon atoms; SO2NH2; NO; COO-alkyl, the alkyl part having from 1 to 4 atoms carbon.

- is -h = or -CH =,

- Y2 is -N = or -CX7 = provided that Y ^ is not N

30 when Y2 is -CX. ,, - Υ ^ is the oxygen or sulfur atom, - X is the hydrogen atom or an alkyl radical, having

H

ce 1 to 4 atoms this caroone, substituted or not, in particular by these halogen atoms, 35 - Xj. is the atom of hydrogen had an atom this alkali metal / in particular of sociuro had potassium; had a cationic group ^ / '* there j · 2 ammonium, quaternary or not; or an alkyl radical, having from 1 to 4 atoms of this carbon, whether or not substituted, in particular by halogen atoms; or a halogen atom, in particular of chlorine, 5 - X6 is an alkyl radical, substituted or unsubstituted, preferably having 1 to 4 carbon atoms; or an aryl radical, in particular phenyl, substituted or not; as substituents there may be mentioned the halogen atoms, or the alkyl, amino, cyano, nitro, alkoxyl, hydroxyl, formyl, mercapto, etc. groups, - Xy is the hydrogen atom or a halogen atom .

A preferred subfamily according to the invention is characterized in that: - is CF ^, X2 is the chlorine atom,, - X ^ is Cl or, preferably, N02, - X5 is H, ha or Cl , - and Y2 are -CH =.

The processes for preparing the products of this formula (I) also form part of the invention.

According to a first process, an acid chloride is reacted with the formula: X4 _ * 2 _ „CO-Y3-CH-COC1 25. (ii) Y1 Y2 with a sulfonamide this formula: X6-SO2-NH-X5 (III) in which the various symbols have the meanings given for the formula (I).

The reaction is advantageously carried out between 50 and 150 ° C, preferably between 80 and 110 ° C, in a solvent such as aliphatic or aromatic, halogenated or non-halogenated hydrocarbons; the concentration of products of formula (II) / and (I) is generally between 1 and 60%. this pref / d / if * 3 m rence between 10 and 30%. The presence of an acid acceptor such as tertiary amines, in particular triethylamine and pyridine, is also preferred.

In the process which has just been described with reaction between the products of formula (II) and (III), it is preferred that X ,. is not a halogen atom. The compounds of formula (I) in which is a halogen atom are generally prepared by the action of a hypo-halogenite on the corresponding product in which X ,.

10 is the hydrogen atom. This reaction is generally carried out in an aqueous medium at a pH greater than 10, preferably greater than 11.5 and at a temperature between 0 and 50 ° C.

The acid chloride of formula (II) is obtained in the usual way by the action of SGC ^ on the corresponding acid of formula X „I4

X2 COY -CH-COOH

xrtö- ° -0 · ** 11 v) 20 12

The preparation of the acid or formula (IV) and of the sulphonamide of the closure (III) can be carried out by methods known in the literature.

According to a second process for the preparation of products according to the invention in which X is not a halogen atom, an acid of formula (IV) is reacted with an isocyanate of formula: X - S0 „-N = C = 0 oe formula (V) Ο Δ in which the various symbols have the meanings already given for formula (I); this reaction is advantageously carried out in a solvent medium, preferably in the presence of a catalytic amount of organic base; the temperature is most often between 20 and 100 ° C, preferably between 40 and 80 ° C; the concentration of products 35 oe formula (IV) and (I) is generally between 5 and / 70% by weight. ^ i; 4 * ß

As solvents which can be used, there may be mentioned aliphatic or aromatic solvents, optionally halogenated, such as benzene, toluene, xylene.

As organic base, there may be mentioned para (5-dimé-thylamino) pyridine.

The isocyanates of this formula (V) can be prepared according to known methods.

The first preparation process according to the invention using the reagent of formula (III) is preferred when X is of an aliphatic nature and the second process

O

using an isocyanate, this formula (V) is preferred when X is of aromatic nature.

O

The transition to the products of this formula (I) in which X ^ is the hydrogen atom to the corresponding products in which X ^ is an alkali metal atom can be carried out in a manner known per se, in particular according to the methods applicable to derivatives known phenoxybenzoic acid sulfonamiae function.

The following examples, given without limitation, illustrate the invention and show how it can be put into practice.

In these examples the products are designated using the modified French nomenclature in that the figures designating the position of the radicals are placed, not after, but before the radical concerned in accordance with the Anglo-Saxon nomenclature. Furthermore, the words pre-emergence and preemergence are used as synonyms, as well as the words postemergence and postemergence.

30 Example 1:

In 15 ml of toluene containing 2 g of tnionyl chloride is dissolved 3 g (6.9 millimoles) of 5- | j2-chloro-4-trifluoromethylohénoxyj-2-nitro benzcate from 1- (1-carboxy-ethyl).

The mixture is heated to boiling under reflux for 4 hours / then cooled. By distillation under reduced pressure, οόπ / 5 s> “eliminates the solvent and the excess of thionyl chloride. The residue is taken up in 25 cm "this tetrahyarofuran. 0.9 g of methane sulfcnamiae (CH ^ S02MH2) is added as well as a catalytic amount (about 5ng) of para (5 dimé-tnylamine) pyrioine. Another drop is added. dropwise 10 ml o'a solution of 0.77 g of triethylamine in anhyaric tetrahy-drofuran. After aoaition, stirring is continued for 2 h, 50 ml of tetrahydrofuran are added again, the solution is washed with both , each time, 25 ml of 5% aqueous solution in hydrochloric acid poios, then with brine, dried over MoS0., filtered and the solvent is removed by distillation under reduced pressure.

The residue is purified by liquid chromatography, on a silica column (solvent: 10% acetic acid in 15 or CHC1,).

j

0.5 g of this product of formula: CH I 3 is obtained

Cl COO-CH-CO-NH-SC> 2-CH3 20 CF ^ / ^ - N02

EXAMPLE 2 150 ml of a solution of 50 g (261 millimoles) of 25 paratoluenesulfonylisocyanate in toluene are added dropwise and with stirring to 350 ml of a solution v in toluene containing 100 g (239 millimoles) of 5 -Jj2- chloro-4- (trifluorométny1) phenoxyj2-nitro benzoate of car-boxymethyl as well as a catalytic amount (about 5 30 mg) ae para (dimethylamino) pyridine.

After addition, the mixture is heated to boiling under reflux for 6 h. It is cooled, the solvent is removed by distillation under reduced pressure; a crude product is obtained which is recrystallized from a toluene / hexane mixture.

35 Gn thus obtains 115 mc (209 millimoles) of 5- £ 2- / chloro-4- (tri 1luoromethyl) pnénoxyj-2-nitro benzoate de / 1 /

H

40 6 * (4-methylphenyl) sulfonylaminocarbonyl methyl of formula:

Cl C0-0-CH2-C0-NH-S02- ^ Vj ^ -CH3 5 CP3 ^ H / °

This product melts at around 130 ° C, it has infrared absorption bands (in KBr) at 3205, 1705 and 10 1580 cm. In NMR spectrography (nuclear magnetic resonance; measurement carried out in hexadeuterated acetone; chemical delta displacement expressed in ppm relative to the control this tetramethylsilane), peaks are observed at 2.35 ppm (singlet for 3 protons), 5 ppm (singlet for 2 protons), 15 7.3 to 8.5 ppm (multiplet for 10 protons).

Example 3:

The salt ae soaium proce oe Example 2 (group N-Na) is obtained by reacting the latter with socior hyoride oans gu tetrahydrofuran anhyore; the solvent is then removed by vacuum distillation. In infrared we observe absorption dances at 1600 and 1735 cm “1.

Example 3a:

The procedure is the same as in Example 3 but with the product of Example 1, from which the socium salt (N-Na group) is thus obtained.

Example 4:

The procedure is as in Example 2, but reacting or reacting 5- [2-chloro-4- (carboxyethyl trifluoromethyphenphenJ-2-nitrobenzoate) with paratoluene sulfonylisocyanate.

We obtain 0.3 g of product of formula: ÇH3 / ^ Λ, / Cl ^ COO-CH-CO-NH-SO ^ 4 VCH3 / 35 CF3-0- ° ~ <7> N ° 2 d * 7

We observe an infrared absorption band at 1690 cm 1 and in NMR we observe chemical shifts (expressed in Dpm) of: 1.42 (corresponding doublet s 3 protons; constant this 5 coupling = 14 Hz), 2.4 (singlet corresponding to 3 protons), 3.24 (quadruplet corresponding to one proton; coupling constant = 14 Hz), 7.2 to 8.2 (multiplet corresponding to 10 protons).

10 Example 5:

Example 1 is reproduced, but this reagent is used 5- [j2-chloro-4-trif luoromethylphenox ^ J -2-nitro benzoate ae carboxymethyl.

1 g of an oil is obtained, consisting of the product of formula:

Cl C00-CH2-C0-NH-S02-CH3 ° ^ 2> -no2 20

This formula is confirmed by the IR and NMR spectra. Example 6:

Example 5 is repeated, but the methanesulfonamiae is replaced by CH ^ -SO ^ -NH-CH ^. Heating is continued for 89 hours. 3 g of an oil are obtained; consisting of the product of formula:

Cl CO— 0-CH2-C0-N -SO2-CH3 30 CF3 ^^ - 0 - ^ - N02 CH3

This formula is confirmed by the IR and NMR SDecters.

35 Example 7 fl

In these terrines 20 cm x 25 cm containing lyj / 8 "soil, we have species of crops and weeds in these rows long o 10 cm.

The species used are shown in table (I).

5 Cotton, corn, soybeans and Xanthium are sown at a rate of 4 to 5 seeds per row.

The smaller species (Abutilon, wild mustard, amaranth, Italian millet and green foxtail) are sown without counting the seeds but in sufficient numbers 10 to later form a tight line of seedlings.

The initial watering until the emergence period is carried out over the soil covering the seeds.

Pre-emergence treatment is carried out less than 15 days after sowing.

The desired stage of this development for post-emergence treatments with cotton, soybeans, xanthium, velvetleaf, wild mustard and lamb's quarters is the stage of a true leaf or of a first trifo-20 linked leaf. For corn, the desired stage is a height of 7.5 to 10 cm, while for grasses the desired stage is a height of 2.5 cm.

Application to the compositions of the invention is carried out by spraying at a pressure of 2.5 bar (= 36 25 psi) at a rate of 375 l / ha (= 40 gallons / acre). The sprayed compositions consisted of a mixture in respective volume proportions of this 20 cm g of water and 0.1¾ g of surface-active agent (mixture of polyoxyethylene ether and of alkyl (C 1 -C) benzene. alkali sulfonates).

6 16 30 After treatment, irrigation is done by surigation for the seedlings which have already emerged and by sprinkling with cease for the seeds which have not yet given these seedlings.

2 weeks after treatment, the measurements are made at activity 35 on a scale that is 100%. For the bad heroes this measurement inoioué the level this estruction 'Jf / 53 9 * - for the cultures this measurement inaiaue the degree of attack or degree this phytotoxicity, the zero score being attributed to plants in the same state as the witness and the note cent being attributed to a complete Destruction.

5 With regard to the application doses, the correlation between metric and American units is as follows:

Pounds / acres 10 4 2 1 0.5 0.25 0.125 0.0625 10 kg / ha 11.2 4.48 2.24 1.12 0.56 0.28 0.14 0.07

Table (II) gives the results obtained with the compounds of Examples 1 to 6.

Example 8: Neroicide application, pre-empting plant species.

In 9 x 9 x 9 cm pots filled with this light agricultural soil, a number of seeds is sown, determined 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 humicification of the soil, the pots are treated by spraying with a boiled spray in an amount corresponding to a volume application rate of 500 l / ha and containing the active material at the desired concentration.

The slurry was prepared by diluting an emulsifiable concentrate itself consisting of: 5 g of active material - 83 g of xylene 30 - 8 g of nonylphenoldecaoxyethylenated 4 g of calcium aooecylbenzene sulfonate.

Depending on the concentration of active ingredient in the spray, the dose of active ingredient applied was 0.25 to 2 kg / na. , 35 The treated puts are then placed in these tanks r \ f ““ “" · ™ - y 10 kept there for 21 days at a temperature of 22-24 ° C under 70¾ relative humidity.

At the end of 21 days, the number of living plants is counted in the pots treated with the spray containing the active ingredient to be tested and names this living plants in a control pot treated according to the same conditions, but by means of a spray. not containing active material, thus determining the percentage of destruction of the treated plants compared 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 living plants in the treated pot is ioentic to that in the pot witness.

Example 9: Herbicide application, post-emergence of plant species.

In these 9 x 5 x 9 cm pots filled with light agricultural soil, a number of seeds is determined 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 birth to a seedling 5-10 cm high.

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

The slurry was prepared in the same manner as in Example 8.

Depending on the concentration of active ingredient in the spray, the dose of this active ingredient applied was 0.125 to 1 kg / ha.

The treated pots are then placed in a greenhouse cans / 35 aes trays intended to receive the irrigation water, to be subjected to it, and kept for 14 days at a temperature of / 1 / if.

11 22-24 ° C under 70 â> relative humidity.

At the end of this 14 days, the number of living plants in the pots treated with the spray containing the active ingredient to be tested is counted and the number of living plants 5 in a control pot treated according to the same conditions, but by means of a spray. not containing active ingredient.

The percentage of destruction of the treated plants is thus determined relative to the untreated control. A percentage of construction 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 living plants in the treated pot is identical to that in the control pot.

. The results of Examples 8 and 9 are shown in Tables (III) and (IV).

Each of these tables (III) and (IV) comprises on the one hand preemergence results obtained according to Example 8 and on the other hand postemergence results obtained according to Example 9.

Table (III) gives results obtained with the active material of Example 2.

The stopper (IV) gives results obtained with the active material of Example 5.

The tests carried out therefore show the remarkably advantageous properties of the compounds according to the invention, for the treatment of crops and more particularly of soybeans and cereals (including corn), both pre-emergence and post-emergence.

In the case of soybeans, the activity of the compounds is particularly advantageous when this crop is infested with dicotyledonous weeds such as velvetleaf, xanthiurn, ipomea and knotweed. In the case of cereals, the activity of the compounds is particularly advantageous when these crops are infested with aicotyleaous weeds such as lamb's quarters, amaranth, ragweed, knotweed, chrysanthemum, mustard. and particularly the stellar and the cleavers.

For their practical use, the compounds according to the invention are rarely used alone. Most often these compounds are part of compositions. These compositions, which can be used as herbicidal agents, contain as active material 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, 10 are used the inert and usual supports and the usual surfactants. These compositions also form part of the invention.

These compositions can also contain all kinds of other ingredients such as, for example, these protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilizers, sequestering agents, etc. other known active ingredients with pesticidal properties (in particular insecticides, fungicides or herbicides) or with properties which promote plant growth (in particular fertilizers) or with properties which regulate plant growth. More generally, the compounds used in the invention can be combined with any solid or liquid additive corresponding to the usual techniques for formulation.

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

In general, the compositions according to the invention usually contain from 0.05 to S5% approximately (by weight), one or more active materials according to the invention, this 1% to 95% approximately from one or more liquid or liquid supports and possibly ae 0.1 to 20% / ”i 13“ s-

According to this yes, the compounds used in the invention have already been said, are generally associated with these supports and optionally surfactants.

By the term "support", in the present description, is meant an organic or mineral material, natural or synthetic, with which the active material is associated to facilitate its application on the plant, on seeds or on the soil. This support is generally inert and must be acceptable in agriculture, in particular on the treated plant. The support can be solice (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water; alcohols, in particular butanol; esters, in particular methyl acetate. Glycol; ketones, in particular cyclohexanone and isophorone; petroleum fractions; aromatic hydrocarbons, in particular xylenes, or paraffinics; aliphatic chlorinated hydrocarbons, in particular trichloroethane, or aromatic, especially chlorobenzenes; water-soluble solvents such as dimethylformamide, dimethyl -20 sulîoxyce, N-methyl-pyrrolioone; liquefied gases, etc.).

The surfactant can be an emulsifier, aispersant or wetting agent of ionic or nonionic type or a mixture of such surfactants. Mention may be made, for example, of salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenol-sulfonic or naphthalenesulfonic acids, polyconoensates of ethylene oxide on fatty alcohols or on fatty acids or on these fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulfosuccinic esters, taurine derivatives (especially alkyltaurates), phosphoric esters of alcohols or this polyoxyethylated phenols , esters o fatty acids and polvols, derivatives containing sulfates, sulfonates and phosphates of the above compounds. The presence of at least one surfactant is generally essential when the inert active material and / or support is not soluble in water and the carrier agent is the application. water.

For their application, the compounds of formula (I) are generally found in this form; 5 these compositions according to the invention are themselves in fairly diverse forms, solid or liquid.

As forms of solid compositions, mention may be made of powders for pouoraye (with a content of compound or formula (I) which can range up to 100 ×>) and granules, in particular those obtained by extrusion, by compaction, by impregnation a granulated support, by granulation from a powder (the content of compound this formula (I) in these granules being between 0.5 and 80 £ for the latter cases).

The solice compositions most often contain 20 to 80% of active material.

As forms of this liquid compositions or intended to constitute liquid compositions during application, mention may be made of solutions, in particular emulsifiable concentrates, emulsions, con-centered suspensions, aerosols, wettable powders (or spray), self-dispersing granules, pasta.

The liquid compositions generally contain 80% of the active ingredient.

The emulsifiable or soluble concentrates also generally comprise 10 to 80% of active material, the emulsions or solutions ready for application containing, for their part, 0.01 to 20% of this active material. In addition or solvent, the emulsifiable concentrates can contain, when necessary, 2 to 20% with suitable additives, such as stabilizers, surfactants, penetrating agents, these corrosion inhibitors, dyes, adhesives .

From these concentrates, emulsions or solutions of any desired concentration can be obtained by dilution with water, or are particularly suitable for application to plants. / j / * 3 15 As an example, here is the composition of some emulsionnal concentrates: - active material 250 g - polyphenoxylated alkylphenol 30 g 5 - calcium alkylarylsulfonate 50 g - cuts this petroleum distillation, distilling between 160 and 185 ° C 670 g

Other formula: - active ingredient 35U g 10 - polyethoxylated castor oil 60 g - alkylarylsulfonate oe sooium 40 g - cyclohexanone 150 g - xyiene 400 g, Other formula: 15 - active ingredient 400 g - polyethoxylated alkyl phenol 100 g - methyl ether ce ethylene glycol 250 g - aromatic petroleum cut distilling between 16Ü-185 ° C 250 g 20 Other formula: - active ingredient 400 g - polyethoxylated tristyrylphenol phosphate 50 g - polyethoxylated alkylphenol phosphate 65 g - sodium alkyl benzene sulfonate 35 g 25 - cyclohexanone 300 g - aromatic petroleum cut distilling between lôG-185 ° C 150 g

Other formula: - active ingredient 400 g / 1 30 - alkali dodecylbenzene sulfonate 24 g / 1 - oxyethylated nonylphenol with 10 molecules of ethylene oxide 16 g / 1 - cyclohexanone 200 g / 1 - aromatic solvent q.s.p. 1 litre. / 35 According to another formula, this emulsifiable concentrate is used: / dd f 16 - active material 250 g - epoxidized vegetable oil 25 g - mixture of on'alkylaryl sulfonate and ether this polyglycol and fatty alcohols 100 g 5 - aimethylfQrmamide 50 g - xylene 575 g

The concentrated suspensions, which are applicable in spraying, are prepared so as to obtain a stable fluid product which does not deposit (fine grinding) and they usually contain 10 to 75% of active material, from 0.5 to 15% of surfactants, from 0.1 to 10% of thixotropic agents, from 0 to 10% of suitable additives, such as anti-foaming agents, corrosion inhibitors,. stabilizers, penetrants and adhesives and, as a carrier, water or an organic liquid in which the active ingredient is sparingly soluble or insoluble: certain organic solids or mineral salts may be dissolved in the carrier for help prevent sedimentation or as antifreeze for water.

20 By way of example, here is a concentrated suspension composition: - active ingredient 50 g - polyethoxylated tristyrylphenol phosphate 50 g - polyphenoxylated alkylphenol 50 g 25 - sodium polycarboxylate 20 g - ethylene glycol 50 g - organopolysiloxane oil (defoamer) 1 g - polysaccharice 12.5 g - water 316.5 g 30 The wet mushrooms (or spraying powder) are usually prepared in this way that they contain 20 to 95% of the active ingredient, and they usually contain, in addition of the soliae support, oe 0 to 5% of a wetting agent, from 3 to 10% c'a dispersing agent, and, / 35 when necessary, oe 0 to 10% c'une or several sta- / bilissnts and / or other agents, such as penetration agents, adhesives, or anti-caking agents, dyes, etc.

For example, here are Giverses compositions of wettable powders: 5 active ingredient 50% - calcium lignosulfonate (deflocculant) 5% - isopropylnaphthalene sulfonate (anionic wetting agent) 1 ¾ - anti-clumping silica 5% 10 - kaolin (filler) 39%

Another example of an 80% wettable powder is given below: - active material 80% - alkylnaphthalene sulfonate this sodium 2% 15 - soolignal sulfonate 2 λ - anti-clumping silica - Kaolin 13%

Another example of a wettable powder is given below: 20 - active material 50% - sodium alkylnaphthalene sulfonate 2 ¾ - methyl cellulose oe low viscosity 2% - diatomaceous earth 46%

Another example of a wettable powder is given below: - active material 90% - sodium dioctylsulfosuccinate 0.2% - synthetic silica 9.8%

Another 40% powder composition 30 uses the following constituents: - active ingredient 400 g - lignosulfonate oe socium 50 g - sodium dibutylnaphthalene sulfonate 10 g - silica 540 g / 35 Another composition ae powder powder at 25% / uses the following constituents: / jf 18 - active ingredient 250 c - isooctylphenoxy-polyoxyethylene-ethanol 25 g - equipment mixture this chalk ae

Champagne and hyuroxyethylcellulose 17 g 5 - sodium aluminosilicate 543 g - kieselçunr 165 g

Another composition oe powder to be sprayed at 10% uses the following constituents: - active ingredient 100 g 10 - mixture of sodium salts o sulfates of saturated fatty acids 30 g - proouis ae conuensation of aciae naphthalene sulfonic and formaldehyde 50 g - kaolin 820 g 15 To obtain these spraying powders or wettable powders, the active ingredients are intimately mixed in the appropriate mixers with the additional substances or the darkened active ingredient is impregnated on the porous load and the mixture is milled with mills or other mills appropriate, thereby obtaining spraying powders whose wettability and suspension are advantageous; they can be suspended with water at any desired concentration and this suspension is very advantageously usable, in particular for application to the leaves of plants.

The “self-dispersible” granules (in English “ory flowable”; more precisely, this granules which are easily dispersible in water) have a composition substantially similar to that of wettable powders. They can be prepared by granulation of the formulations described for wettable powders, either by the wet method (bringing the finely divided active ingredient into contact with the inert filler and with a little water, for example 1 to 20%, or ae auus solution this dispersant or binder, then / 35 drying and sieving), either dry (compacting then ^ / grinding and sieving). / v * 19 As an example, here is a self-dispersible granule formulation: - active ingredient 8ÛU ç - alkylnaphthalene sulfonate ce sodium 20 g 5 - methylene bis naphthalene sulfonate oe socium 80 g - Kaolin 100 g Instead of wettable pores, you can make this pasta. The conoitions and modalities oe realization 10 and use oe these pastes are similar to those of soft pores or spray powders.

As has already been said, aqueous dispersions and emulsions, for example compositions obtained in. diluting a wettable powder or an emulsifiable concentrate according to the invention with the aid of water is included in the general list of 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 like that of a "mayonnaise".

2. All of these aqueous or boiled dispersions or emulsions are applicable to crops to be oeshered by any suitable means, mainly by spraying, to these ooses which are generally o orare oe 100 to 1,200 liters of porridge per hectare.

The granules estestées to be placed on the ground are usually prepared so that they have dimensions between 0.1 and 2 mm and they can be manufactured by agglomeration or impregnation. Preferably, the granules contain 1 to 25% of active material and 0 to 50% IG of additives such as stabilizers, slow release modifiers, these binders and solvents.

According to an example, this granule composition, on. uses the following constituents: / - active ingredient 50 c /} / 35 - propylene glycol 25 g J // - clay (particle size: 0.3 to 0.8 mm) 925 g y.

f 20. As indicated above, the invention also relates to a process for the caesherbage of crops, in particular cereals such as wheat as well as soybeans, according to which one applies to the plants and / or to the soil of the “· - 5 zone to aerating an effective and non-phytotoxic amount with respect to the culture considered, of 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 active material ranging from 0.5 to 5 kg / ha, preferably from 0.1 to 2 kg / ha, give good results, it being understood that the choice of the quantity of active material to be used is dependent the intensity of the problem to be solved, the climatic conditions and the culture considered. The treatment can be carried out either in pre-emergence from crops and weeds, or in pre-sowing of crops with incorporation into the soil (this incorporation is therefore a complementary operation to the treatment process of the invention), or post-emergence. Other embodiments of the treatment method according to the invention can also be used: thus the active material can be applied to the soil, with or without incorporation, before transplanting a culture.

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

TfibLEAU I

9 21

Name Name Name Abbreviation

French American Latin

Corn Field corn CN

- Cotton Cotton CT

Wheat Wheat V * T

Rice Rice RI

Soybean soya bean

Panisse Barnyarograss Echinochloa BYG

raw-galli

Foxtail Giant foxtail Setaria faberii GTF

Foxtail Green Green foxtail Setaria viriois GF

Crabgrass Digitaria CG

sanguinalis

Velvet leaf Abutilon VL

theophrasti

Millet from Italy Foxtail millet Setaria italica FM

Bad Cocklebur Xanthium CB

pennsylvanicum herbs

Wild mustard Wilc mustard Sinapis arvensis WM

Amaranth Pigweed Amaranthus py; retroflexus

Bindweed Morningglory Ipomea purpurea MG

(annual)

Prickly AIDS Sica spinosa PS

"

Wild oats wila oat Avens fatus VtO

Wild Buckwheat Knotweed Polygonum convolvulus

Ambrosia Ragweed Ambrosia - == ^.

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3 'tf'ÎCNCN'tf'ÎCMCMCMCM

CD 3 CNJrHrHrHCMCMrHrHrHrH

C0 ** v *, v ** v ". ***" v

Q 3 "s 04 <—I i — I 04 04 1 — I‘ —I 1 — I 1 — I

Tl M

CD

o ‘3 3 3 3 3 + J 3 3

CD 3 COCO \ Q} COCOCO \ (DCO \ CDCO

co 0 0030003030 3 3 (D \ (D co g 3 o \ <D Qa 0a _

CQ CO

0 0 -H

3 2 E rH 04 n oo ^ ld o o L — y 23

Table (III): _I_PRELEVEc_ | _PUSTLbVEti_:: üüse in kg / na: 2 · 1 · 0.5; 0.25 (1 ί 0.5 Î 0.25 ίθ, 125!: Mgropyrûn i: iii:: i Γ : _: 90: 50: 20: 0: _; _; _: _ ç_ iborghum; ioo; ioo; ioo; ioo;;;;;: LchinochiDä · 100; ioo (100; 90; 50 20; 0 0!: Pamcun.; Ioo; ioo; ioo; ioo; 80; 80; 0; 0;: üigj.tarià; ioo; 100; i00 (IOO; 100; 90; 10; 0;: Rbutiiûn · ioo jioo; ioo; 60; ioo; so; 50; 20;: Xantniuiïi · 100 · 0; 0; 0; IOO; i00 \ IOO;: uhenoponiutii · 100: l00: l00 * ioo; 100; 80; 80; 30;: ΜΠιαΓαηι.ϋ5 jioo jioo ; ioo; ioo; 100; ioo; ioo; 90;: hinbiosia: 100: 100: 100; 90: 100; 90; 90; 20;: Poiygoriun,: 100: 100: 100 * 100; 100 * 100 * 100; 90;: îpoiiiea::::: \:;:: 100: 50::; 100; -L00:: b 1 ü aiiiiiiii Γ:; 100; 100: 100 ·; 100; 100: 100: 100; 90: ; Gaiium; ioo; 100; 90; 80; 90! 50; 20 i 0!: Riopecurus: iiiiiii:: _; 90; 80; 20; 10; 0; 0; 0; Q; • Sefeana viridis *; 100; 100. '; 100'. 100 *: 100 -.9 0 | 10 0! : Set & ria raberii: i: i i i! : Γ; .100 .100 .100 .100; 90; 60: 20: 0; : Lhry Scntheniuni ::::::::::. .100 .100 .100 .90 .100: 100: 100; 100: - ibinapis i i i i i i: i Γ. .100 .100 .80 .80 .100 .100 .100. 100.

: Stej.iDiiü :::::::::. .100 .100 .100 .100 .80 .20 .0 .0.

: bïb i i i: i i i i Γ:; °. 0 .0.0.10.0 .0; 0; : urat ::::::::::. “.10. 10. 0. 0. 10. 0 .0. 0.

: Corn: i i i t i i; : .10. 0. 0. 0. 0. 0. 0. 0.

: Loion i i i i i i i: Γ:. 0; 0; 0; 0. . . . .

r Sûia: *! ! ; i - *>. .30 .0. 0. 0. 60. 0 .0. 0 /.

s% 24

Table (IV):: PhbLEVEti: PUSTLtVrb ~ ':: uose in kg / ha:; ::. λ 2. 1. 0.5. 0.25. 1. 0.5 .0.25 .0.125.

; Gaiium j îoo; îoo; 100 \ 60; îoo; 90; 90; 90; : Setaria Viridis * * · ·: 90: 20: 20 0:: tchinochioa i:: *:: * i Γ:::::. 60. 10. 10. 0.

:: -: - -:: j r; ::::. 90. 20. 20. 10.

: üiqitaria i i i:: i ~: ~ i ~ Γ. . . . . .40.40.40.20.

•: Abutiion i: iii ~ j 7 "* i Γ. 90. 50. 10. 0: Xantniun. I S iii ·: TT i ~ Γ. 100. 100. 100;: LhenopüLium: 1Q0: 100: 100; χοο :. 100:. 100 100 | 80;

I HÎTiôrbnt.US · !! ··! «! I

: _: _: _: _: _: _: 100: 100: 100:: Hiiibiosia::::: 10010o ‘100; 90: PoiyGonuni :::::::::; _; 100; 100; 100; 100; 100; 1QQ; 1QQ; 1QQ; : ipomea: ::::::::: _: _: _: _: _: _: 100: 100: 100: 100; : biaa ::::::::::: _: _; _: ’: _: _: _: 100: 90:: Avena tatua; 80; 20: 0: 0::::: Aiopecurus; 90; 30: 50: 0::::: Loiiun. ; 100: 30: 0: 0:::::: Setaria fabeni: 100: 100: ioo: i00:: 80: 10: 0:: Chrysantheriiuni: i: i i i i i Γ:; 100. 100. 100; 100. 100. 100; 100: 100:: b i n a p i s: i î * i i: i Γ:: 100. 100. 100. 100; 100: 100. 100: 100; : Stexiana. 100; 10; 0; 0; ; . ; ; : bit::::::::: / /? / : : 30 . 10. 0. 0. 20. 0. 0. 0 / U / | j; not a word ; j

in in η n on τη η n / sW

Claims (18)

1. Derived compounds of phenoxybenzoic aciaes characterized in that they have the formula: X. X, 5 I5 I5 x CO-Y -CH-CON-SO -X, xl ~ 2 - IC in which: - X ^, X2 and X ^ represent an o'halogen atom, such as fluorine, colors or bromine; a polyhalocenated alkyl radical; Nü2; CN; an alkyl radical; SO2NH2; Nü; CDÜ-alkyl, 15. Y ^ is -N = or -Ch =, - Y2 is -N = or -CX ^ = provided that Y ^ is not N quana Y2 is -CX. ,, - Y ^ is the oxygen atom or sulfur, - is the hydrogen atom or an alkyl radical, substituted or not, - X ^ is the hydrogen atom or an alkali metal atom; or a cationic ammonium group, quaternary or not; or a substituted or unsubstituted alkyl racical; or a halogen atom, 25. X is an alkyl radical, substituted or unsubstituted; or an aryl, in particular pnenyl, substituted or not substituted racyl, - Xy is the hydrocene atom or a halogen atom. 2. Compounds according to claim 1) characterized in that: 30. X, is Cf. ,, X ^ is the atom Ch chlorine, x y 4— - is Cl eu Nü2, - X ^ is h, Na or Cl, - Y, and Y0 feels -Oi-i =. 3. Compounds according to either of Claims 1 and 2) characterized in that the alkyl group or groups which they contain / have this 1 to 4 carbon atoms. / y. i 26 4. Compounds according to one of claims 1 to 3) characterized in that is substituted by halogen atoms and / or that is substituted by halogen atoms or alKyle, amino, cyano, nitro groups, alkoxyl, hydroxyl, formyl, mercaoto. 3. A process for preparing qe compounds according to one oes claims 1 to 4) characterized in that one reacts a chloride ü'acice ae formula: 1 η, 4 _ * 2 _ „co-y3-ch-coci 0Η ^ -Ζ3. (II) ΥΓΥ 2 "15 with a sulfonamide oe formula: X _so -NHXC (III) 6 2 3 20 in which the various symbols have the meanings indicated in these claims 1 to 4). 6. Method according to Revenaication 5) characterized in that the temperature is between 50 and 150 ° C, preferably between 80 and 110 ° C, in a solvent, and at a concentration of products of formula (II) and (I) between 1 and - »80. by weight. 7. Process for the preparation of the compounds according to one of claims 1 to 4) characterized in that an acid of the formula: '4 / X2 CO-Y CH-COOK / ÎlV) // ÜB 27 is reacted with an isocyanate of formula: X.-SÜ0-NCG 6 2 5 in which the various symbols have the meanings indicated in these claims 1 to 4). 8. Method according to claim 7) characterized in that the reaction is carried out between 20 and 100 ° C, preferably between 40 and 80 ° C, in a solvent and the concentration of product of formula (IV) and (I) being between 5 and 7ü & in pcios. 5) 'Herbicide compositions characterized in that a contain as active material a compound according to one of claims 1 to 4), this active material being in association with at least one inert support acceptable in agriculture. HERE) Compositions according to claim 9) characterized in that they contain 0.05 to 55% by weight of active material. 11. Compositions according to one of these claims 9 or 10) characterized in that they are liquid and that they contain 10 to 80% of this active material. 12. Compositions according to either of claims 9 or 10) characterized in that they are solid and contain 20 to 80% of active material. * 13. Compositions according to one of revenoications 9 to 12) characterized in that they contain 0.1 to 20% of surfactant. 14) Method oe weeding oes crops, characterized in that an effective and non-phytotoxic amount is applied vis-à-vis the culture of a composition according to one of claims o to 13). 15. Proceaé according to revencicaticn 1a) characterized in that the culture is a “culture this soybean infested or susceptible / likely to be infested by the kidneys one of the bad / D / 28 k -t nerDes: abutilon, xanthiurn, iporr.éa, knotweed. 16. Method according to claim 14) characterized in that the culture is a cereal culture infested or liable to be infested with at least one of these 5 weeds: lamb's quarters, amaranth, ragweed, knotweed, chrysanthemum, mustard, stellar , hack. 17. Method according to one of these claims 14 to 16) characterized in that the compound oe formula (I) is applied in an amount of 0.1 to 2 kc / ha. Drawings: —..... plates pages of which -.Λ .......... cover page ........... description pages „-....... ..k - pages of claims --- descriptive abstract Luxembourg, JUL 26 M82 Le mml ^ ire: nf ^ ________. Charles München • r