FI82877B - HERBICIDA BLANDNINGAR BASERADE PAO FOERENINGEN AV TYPEN N- (PHOSPHONOMETHYLGLYSYL) -SULPHONYLAMINE. - Google Patents

Abstract

A herbicidal composition comprises (A) an active herbicidal substance of formula: <IMAGE> in which: R<1> denotes an optionally substituted hydrocarbon radical; R denotes a hydrogen atom or is as defined for R<1>; R<2> and R<3>, which may be identical or different, denote hydrogen atoms or are such that OR<2> and OR<3> are hydrolysable groups, or a salt thereof; and (B) at least one active herbicidal substance which is a chloroacetamide, triazine, phenylurea, thiadiazolylurea, sulphonylurea, benzothiazolylurea, nitroaniline, phenoxynicotinanilide, amide, oxadiazole, aminotriazole, picolinic acid, phenoxybenzoic acid derivative, phenoxypropionic acid derivative, aryloxy acid, benzoic acid, propionic acid, triazinone, carbamate, pyridazinone, pyridone, guaternary ammonium compound, uracil, hydroxybenzonitrile or imidazolinone or a salt thereof.

Description

1 82877

Herbicidal mixtures based on a compound of the N- (phosphonomethylglycyl) sulphonylamine type

The present invention relates to novel herbicidal compositions consisting of mixtures of herbicides and in particular containing at least one herbicide belonging to the chemical class of N- (phosphonomethylglycyl) sulfonylamines and to the use of these herbicidal compositions in agriculture.

Several substances belonging to the amonomethylphosphone group with herbicidal properties are known, in particular from FR patents 2129327, 2281375, 2251569, 2413398, 2463149, European patents 53871, 54382, 73574, U.S. patents 3160632, 3455675, 3868407, 2090596, WO 83/03608, BE 894244, 894245, 894590, 894591, 894592, 894593, 894594, 894595.

However, it is always advantageous to expand the field of herbicide mixtures available to better meet all the needs of farmers. Some amides belonging to the aminomethylphosphone group have been known in the past, but these substances were little or not active at all.

It is an object of the present invention to provide herbicidal compositions which have a strong and rapid effect.

Another object of the present invention is to provide herbicidal compositions which degrade well in nature.

It is a further object of the present invention to provide post-emergence herbicidal compositions which have a very broad spectrum of action and which have at least a partially decreasing systemic effect and which are possibly selective for some crops.

It is a further object of the invention to provide herbicide mixtures which are very resistant to soil, in particular 2 82877 resistant enough to act on occasional budding (i.e. weeds and other plants which grow and develop over a longer period of time).

Other objects and advantages of the invention will become apparent from the following description.

It has now been found that these objects can be achieved either in whole or in part by means of the mixtures according to the invention.

The herbicidal compositions according to the invention are characterized in that they contain an active ingredient of the formula: OR2 I, O = P - ch2 - nh - ch2 - CO - n - so2 - R1 (I)

OR3 R

wherein R 1 is a hydrocarbon radical having 1 to 18 carbon atoms, in particular alkyl having 1 to 7 carbon atoms, phenyl or cycloalkyl having 3 to 7 carbon atoms, which radicals may be optionally substituted by the following groups: halogen atoms, phenyl, cyano, alkyl, alkoxy, alkylcarboxyl, the alkyl groups of the substituents of which contain 1 to 4 carbon atoms; R * is preferably an alkyl radical having 1 to 4 carbon atoms, optionally containing halogens, in particular chlorine or fluorine atoms, such as, for example, cf3, R is a hydrogen atom or has one of the meanings given to R1 and is preferably 1 to 4 an alkyl group containing a carbon atom, R2 and R3 are hydrogen atoms or groups such that OR2 and OR3 are hydrolyzable groups; R 2 and R 3 are in particular alkyl or aryl radicals having 1 to 12 carbon atoms (mainly alkyl or phenyl having 1 to 8 carbon atoms) which are optionally substituted by the substituents given in the definition of R 1, 3,82877 and said active ingredient , of formula I, also includes salts of these various substances (especially salts of groups P-OH and salts of the nitrogen atom of group NH, which group then becomes an ammonium group) and especially salts of these substances suitable for agriculture (salts suitable for agriculture are alkali metal salts, especially sodium and potassium salts, alkaline earth metal salts, primary, secondary, tertiary or quaternary ammonium salts, sulfonium salts Other salts of the invention are addition salts with an acid such as chlorides, sulfates, phosphates and other salts derived from acids having less than or equal to 2.5), and said active ingredient of formula I is combined with at least one active ingredient from group II, i.e. with an active ingredient selected from the group consisting of chloroacetamides (especially alachlor and metolachlor), triatriins (especially simazine, atrazine). and promethryn), phenylureas (especially diuron, isoproturon and linuron), thiadiazolylureas (especially tebuthiuron and ethidimuron), sulphonylureas (especially sulfometuron, chlorosulfuron, metsulfuron), benzothiazolylureas (especially methabenthinurea) especially oryzaline and trifluralin), phenoxynicotinic anilides (especially diflufenican), amides (especially napromamide, propanil), oxadiazoles (especially oxadiazon and dimefuron), oxinotriazene-phenoxyfifenoxy, picolinic acid (picloram), phenoxybenzoic acid and azifluorophen and aliphatic esters of alcohols or glycolates or lactates), phenoxypropionic acid derivatives (especially kitsalofop-ethyl, fluazifop, butyl), aryloxy acids (especially 2,4-D, 2,4-DP, MCPA, MCPP), benzoic acids (especially dicamba), propionic acids (especially dalapone), triazinones (especially metribuzin), .. carbamates (especially carbetamide, EPTC, azulam), pyridazinones (especially norflurazone), pyridones (especially fluridone), quaternary ammonium compounds (especially diacat) uracils (especially bromacil), hydroxybenzonitriles (especially bromoxynyl and ioxynyl), imidazolinones (especially imazaquin and imazapur).

4,82877

The compounds of the formula I can be prepared, for example, in accordance with European Patent Application No. 135454.

Group II substances are known and most of them are described in detail in various works such as "The pesticidal manual", published by "The British crop protection council", and its 7th edition is from 1983. The chemical names of the group II substances used in the examples are given in Table IV. .

The mixtures according to the invention are most often of the binary type (single active ingredient from group II, but sometimes ternary combinations (two active ingredients from group II) or quaternary combinations (three active ingredients from group II) are used.

The weight ratio of the active compound of the formula I to the active compound or active compounds of group II is usually between 0.2 and 10, in particular between 0.25 and 4; however, this ratio can rise to higher values, up to 100 such effects. - substances such as picloram and in particular sulphonylureas.

The examples given in this invention are non-limiting and illustrate how the compositions of the invention can be prepared and used; percentages are by weight unless otherwise indicated; the terms "prelevee" and "preemergence" have been used interchangeably as "before sprouting" and "before germination"; and the same is true of the terms "postlevee" and "post-emergence," that is, "after the sprouts have emerged."

Of the compounds of formula I, the preferred compounds are:. · Wherein R and R 1 represent an alkyl group having 1 to 4 carbon-2. 3. atom, R and R represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or a phenyl group as well as salts of these various compounds.

Of the Group II compounds, the following compounds are preferred when looking for good durability: simazine, atrazine, promethryn, diuron, chlorsulfuron, oryzaline, napropamide, oxadiazone, dimefuron, picloram, fomesafen, bromacil, imazacin.

The active ingredients of the mixtures according to the invention are rarely used alone in conventional practice. Most often, these herbicidal mixtures contain the active compounds according to the invention as set out above, together with solid or liquid carriers which are suitable for use in agriculture and likewise with agriculturally acceptable surfactants, in particular inert and customary carriers and surfactants. substances. These mixtures are also part of the invention.

These compositions may also contain all kinds of other ingredients such as colloidal preservatives, adhesives, thickeners, thixotropic agents, penetration enhancers, stabilizers, sequestering agents, etc., as well as other active ingredients known for their pesticidal properties. . substances (especially insecticides, fungicides or herbicides) *; or plant growth regulators. The substances according to the invention can in most cases be combined with all solid or liquid additives which correspond to the conventional recipe-making technique.

The dosages of the compounds used according to the invention can vary within wide limits, in particular depending on the nature of the weeds to be eradicated and the degree of contamination of the areas from which the weeds are to be eradicated.

The compositions of the invention generally contain approximately. 0.05-95% of the active compounds according to the invention (formula I) and group (II)) and approximately 1% to 95% of one or more solid or liquid carriers and optionally approximately 0.1-50% (mainly 5 -40%) of one or more surfactants.

As already stated above, the active ingredients used in the invention are usually combined with carriers and, if appropriate, surfactants.

6,82877

The term "carrier" in this context means an organic or inorganic natural or synthetic substance with which the active substances are combined in order to facilitate their application to the plant, grains or soil. This carrier is therefore usually inert and must be acceptable for use in agriculture, especially suitable for the plant to be treated.

As solid carriers (or fillers) there can be mentioned inorganic or synthetic fillers such as kaolin, atta-pulgite, montmorillonite, bentonite, talc, bleaching earth, diatomaceous earth, silicon, calcium and magnesium carbonates, precipitated synthetic silica, alumina, alumina silicates and silicoaluminates, resins, waxes, solid fertilizers. Water-soluble excipients such as sodium or ammonium sulfates and urea can also be used.

Liquid carriers include water, alcohols (especially butanol), esters (especially methyl glycol acetate), ketones (especially cyclohexanone and isophorone), petroleum distillates, aromatic hydrocarbons (especially xylenes), or paraffinic hydrocarbons, chlorinated hydrocarbons, chlorinated alcohols. ) or chlorinated aromatic hydrocarbons (especially chlorobenzenes), water-soluble solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone.

The surfactant may be an emulsifying, dispersing or wetting agent of the ionic or non-ionic type or a mixture of such surfactants.

• Among the nonionic wetting agents, mention may be made of ethylene oxide-treated alkylphenols (especially octyl, nonyl and tributylphenols having 6-18 oxyethylene units), ethylene oxide-treated fatty alcohols (especially C g-alcohols with 6 to 18 oxyethylene units), fatty amines treated with ethylene oxide (especially fatty amine or tall oil with 2 to 40 oxyethylene units), esters of 7 82877 fatty acids and polyols (glycerol or sugar type) specially treated with ethylene sorbitan laurate and stearate with 5-20 oxyethylene units).

Wetting agents which may be mentioned are alkylnaphthalenesulphonate ester salts (in particular sodium or potassium isopropyl, butyl and dibutylnaphthalenesulphonates, sulphate ester salts of fatty alcohols (especially sodium or potassium lauryl sulphates) or fatty alcohols), dioctyl sulfosuccinates, taurine derivatives (especially alkyl taurates, aryl N-methyl taurides, sodium oleyl methyl tauride).

Among the nonionic dispersants, mention may be made of arylphenols treated with ethylene oxide (in particular di- and tri- (phenylethyl) phenols containing 18 to 40 oxyethylene units).

Among the anionic dispersants, mention may be made of polycarboxylic polymers in the form of a salt (such as sodium polycarboxylate and polyacrylate polymers), polycondensates of formaldehyde and diphenol sulfonates or alkylenephthalene sulfonate aryl esters of ethylene naphthalene sulfonates (especially sodium methylnaphthalene). (especially phosphoric acid esters of nonylphenols with 6 to 18 oxyethylene units, in acid form or in the form of the potassium salt, as well as phosphoric acid esters of di- or tri- (phenylethyl) phenol with 18 to 40 oxyethylene units in the form of acid or salt), phosphatoxidated, ethylated alcohols (especially C1-C4 fatty alcohols having 6 to 18 oxyethylene units), and alkali metal or alkaline earth metal lignosulfonates.

The compositions according to the invention, in particular in the case of self-dispersible granules, may also contain from 1 to 50% by weight of natural or synthetic binder.

8 82877

Among the binders of natural origin, mention may be made of starch and its derivatives (especially modified starch and dextrin), cellulose derivatives (especially carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose), sugars (such as lactose, mannitol, sorbitol, sorbitol, sorbitol, sorbitol).

Synthetic binders include polymers (especially polyvinyl alcohol, vinyylipolyasetaatti, polyvinyl-pyrrolidone, alkalimetallipolyakrylaatit), polycondensates (especially polyethers such as polyglycols; maleiinianhydri-di kopolykondensaatit, formaldehyde and alkyylinaftaleenisul-sulfonates polycondensates (such as formaldehyde and sodium metyylinaftaleenisulfonaatin polycondensate), alkali metal lignosulfonates.

The presence of at least one surfactant in the compositions according to the invention is usually necessary when the active ingredients and / or the inert carrier are insoluble in water and when the application agent is water.

For application, the compositions of the invention are in several different forms; in solid or liquid forms; these are relatively dilute forms, while mixtures suitable for transport, sale and storage are instead concentrated mixtures.

Solid mixtures which may be mentioned are wettable powders and dustable powders (they may contain up to 100% of active ingredients) and granules (mainly autodispersed), in particular by extrusion, compression, impregnation of a granulated carrier, or granulation of a powder obtained from The concentration of active substances according to I and the concentration of active substances according to Group II in these granules is between 0.5 and 80% in the latter cases).

Of the liquid mixtures or those which are intended to be converted into liquid mixtures at the time of application, 9 82877 may be mentioned solutions and concentrated suspensions or further pastes. According to the invention, concentrated mixtures in solid form are preferred.

Concentrated suspensions, which are applied by spraying, are prepared so as to obtain a stable fluid which does not precipitate (fine grinding) and usually contains 10-75% of active ingredients, 0.5-15% of surfactants, 0.1-10% thixotropic agents, 0-10% of suitable additives such as antifoams, anti-corrosion agents, stabilizers, plant builders and adhesives and as a carrier water or organic liquid in which the active ingredients are sparingly soluble or insoluble: some solid organic substances or inorganic salts can be dissolved in the carrier to prevent sedimentation or water freezing.

Example 1:

Concentrated suspension composition - active ingredients 500 g - ethylene oxide and tristyrylphenol - 50 g phosphate polycondensate · ": - ethylene oxide and alkylphenol 50 g polycondensate - sodium polycarboxylate 20 g - ethylene glycol (antifreeze) 1 polysaccharide (thickener) '- water 316.5 g According to this Example 1, combinations of the following substances can be performed:

Substances of formula I.

Compound No. 1: a compound of formula I wherein R and F1 represent a methyl group and R and R are hydrogen atoms ____ Compound No. 2: a compound of formula I wherein R and R * represent a methyl group and R is a hydrogen atom and R is a phenyl group

Compound No. 3: A compound of formula I wherein R and R 1 represent a methyl group and R and R are phenyl groups.

Group II substances: simazine, atrazine, promethrin, diuron, isoproturon, linuron, metabenzthiazuron, oryzaline, trifluralin, diflufenican, naproxen, propanil, oxadiazon, aminotriazole, afenox, picloram, biphenamide, bifloram -D, MCPA, MCPP, carbetamide, asulam, bromoxynyl, ioxynyl.

According to Example 1, Examples 2-10 are performed using the conditions defined in the following Table I:

Table I

Nature of Compounds Nos. 1-3 Group II Compounds Example Amount in Grams and Amount in Grams_ 2 (No. 1) 300 Atrazine 200 3 (No. 2) 250 Oryzaline 250 4 (No. 1) 450 Diflufenican 50 5 (No. 1) : 2) 350 Oxadiazone 150 6 (No. 2) 250 Aminotriazole 250 ____ 7 (No. 3) 300 Biphenoxy 200 8 (No. 1) 350 Asif chlorophenene Na 150 9 (No. 3) 250 Asulam 250 10 (No 1) 350 Bromoxynil 150

Wettable powders (or sprayable powders) are thus the preferred compositions of the invention with auto-dispersible granules. Wettable powders are usually prepared containing 20-95% of active ingredients and usually contain, in addition to a solid carrier, 0-25% of wetting agent, 1-15% of dispersing agent and, if necessary, 0-10 % of one or more stabilizers and / or other additives, plant penetration enhancers, adhesives or anti - caking agents,. - colors, etc.

n 82877

Example 11;

Different compositions of wettable powders: - active ingredients 50% - calcium lignosulphonate (crumb 5% disintegrant) - isopropylnaphthalene sulphonate 1% (anionic wetting agent) - anti-caking silica 5% - kaolin (filler) 39%

Example 12: - active ingredients 80% - sodium alkylnaphthalenesulfonate 2% - sodium lignosulfonate 2% - anti-caking silica 3% - kaolin 13%

Example 13: - active ingredients 50% - sodium alkylnaphthalenesulfonate 2% - methylcellulose, low viscosity 2% 46% - bites Example 14: - active ingredients 90% - sodium dioctyl sulfosuccinate 0.2% - synthetic silica 9.8%

Example 15: - active ingredients 400 g - sodium lignosulfonate 50 g - sodium dibutylnaphthalenesulfonate 10 g - silica 540 g - Example 16: - active ingredients 250 g - isooctylphenoxy (polyoxyethylene) ethanol 25 g - mixture with equal parts Champagne 17 g chalk and hydroxyethylcellulose - sodium aluminosilicate Hi 2 - chicory 165 g i2 82877

Example 17; - active substances 100 g - a mixture of 30 g of sodium salts of sulphates of saturated fatty acids - 50 g of condensation product of naphthalenesulphonic acid and formaldehyde - kaolin 820 g

Example 18: - active ingredients 40% - sodium isopropylnaphthalenesulfonate 2% - sodium lignosulfonate 5% - precipitated silica 10% - kaolin q.s.p. 100%

Example 19: - active ingredients 40% - sodium lauryl sulphate 4% - tri (phenylethyl) phenol with 40 6% oxyethylene units - precipitated silica 15% - attapulgite q.s.p. 100%

Example 20: - active ingredients 40% - fatty amine containing 25 oxyethylene 10% lene units - C 2 -C 6 alcohol f containing 6 oxyethylene 5% units - precipitated silica 15% - attapulgite, q.s.p. 100%

Example 21: - active ingredients 50%: Y - sodium oleylmethyl tauride 2% - sodium methylnaphthalenesulfonate 4% polycondensed with formaldehyde - diatomaceous earth 20% - chicory q.s.p. 100% f i3 82877

Example 22: - active ingredients 50% - nonylphenol with 18 oxyethylene- 2% units - nonylphenyl phosphate with 10 4% oxyethylene units - precipitated silica 10% - montmorillonite q.s.p. 100%

Example 23: active ingredients 60% - sodium dioctyl sulfosuccinate 2% - polycondensed sodium methylnaphthalene - 3% sulfonate - sodium silicoaluminate 15% - kaolin q.s.p. 100%

Example 24; - active ingredients 60% - sorbitan stearate (5% stearate of dehydrated sorbitol) containing 25 oxyethylene units - phosphated tri (phenylethyl) phenol 3% containing 18 oxyethylene units - precipitated silica 10% ... - chicory, q.s.p. 100% •; Example 25: - active ingredients 60% - sodium oleylmethyl tauride 2% - phosphated tri (phenylethyl) phenol containing 3% of 18 oxyethylene units - synthetic silica 15% - kaolin q.s.p. 100%

Example 26: - active ingredients 80% - sodium isopropylnaphthalenesulfonate 2% - condensed sodium methylnaphthalenesulfonate 3% - synthetic silica 15% - kaolin q.s.p. 100% 14,82877

Example 27: active ingredients 80% - sodium lauryl sulphate 3% - sodium polycarboxylate 3% - sodium silicoaluminate q.s.p. 100% In these Examples 11-27, one selected from compounds 1-3 and the other belonging to the following group are used as active ingredients: simazine, atrazine, promethryn, diuron, isoproturon, linuron, metabenzthiazuron, trifluralin, diflufenican, napropamide, oxadiazone, dimefuron, bifenoxy, kitsalofop, dalapone, carbetamide and other active substances from Table IV.

More specifically, Examples 30-41 can be performed under the conditions specified in Table II. The mixtures listed in Table V could also be used.

Table II

Example- Quality of Compound 1-3 Group II Compound. . Of the primary, the amount in grams and the amount in grams (or ·. ·: Sign 11-17 in pess (or in percent) · in rice beings) _ va mixture_ _____ 30 11 (No. 1) 30% Atrazine 20 % 31 12 (No. 2) 50% Diuron 30% 32 13 (No. 3) 30% Simazine 20% '33 14 (No. 3) 60% Dimefuron 30% 34 11 (No. 2) 25 % Isoproturon 25% 35 16 (No. 3) 150 g Biphenoxy 100 g 36 15 (No. 1) 200 g Napropamide 200 g 37 12 (No. 1) 55% Oxadiazon 25% 38 17 (No. 2) ) 85 g Kitsalofop-ethyl 15 g 39 13 (No. 2) 20% Carbetamide 30%: / · 40 15 (No. 3) 300 g Diflufenican 100 g 41 14 (No. 1) 30% Dalapone 60%

In order to prepare powders to be sprayed or wetted, the active ingredients are mixed very efficiently in suitable mixing equipment with additives or the molten active ingredients are impregnated on a porous filler and ground in mills or suitable other grinding equipment. This gives sprayable powders which can be advantageously moistened or suspended; they can be suspended in water to any desired concentration and this suspension can be used advantageously, in particular for application to the leaves of plants.

"Autodispersable" granules ("dry flowable" granules; in particular, these are easily dispersible granules in water) are very close in composition to wettable powders. They can be prepared by granulating the above-described formulation compositions for wettable powders, either by the wet method (finely divided active ingredients are contacted with an inert excipient and a small amount of water, e.g. 1-20%, or an aqueous dispersant or binder solution (described above) or dried). by the dry method (pressing, then grinding and screening).

Here are some recipes for autodispersible granules · '.' ··:

Example 50: active ingredients 800 g - sodium alkylnaphthalenesulfonate 20 g - sodium methylene bis-naphthalenesulfonate 80 g - kaolin 100 g

Example 51: - active ingredients 40% - fatty amine with 25 oxyethylene units 10% - precipitated synthetic silica 10 g - polyvinylpyrrolidone 5% - bentonite q.s.p. 100% ie 82877

Example 52: - active ingredients 40% - C 2 -C 2 alcohol with 6 oxyethylene-5% units - precipitated synthetic silica 5% - ammonium sulphate 20% - hydroxyethylcellulose 2% - starch q.s.p. 100%

Example 53: - active ingredients 40% - nonylphenol with 10 oxyethylene 2% units - calcium lignosulphate 10% - polyvinylpyrrolidone 5% - kaolin q.s.p. 100%

The exact examples of active substances and the proportions of each according to these Examples 50-53 are similar to those of the mixtures of active substances in Tables II and V.

Instead of wettable powders, pastes can be prepared.

; The conditions and methods of preparation and use of these pastes are similar to those of wettable powders or sprayable powders.

As already mentioned, aqueous dispersions and aqueous emulsions, for example those obtained from a powder to be wetted by dilution with water or a concentrated suspension according to the invention, are within the general scope of the mixtures used in the present invention. Emulsions may be of the water-in-oil or oil-in-water type and may have a thick consistency such as "mayonnaise".

All these aqueous dispersions or emulsions or solutions ... can be applied to the areas or cultures from which the weeds are to be eradicated by any suitable means, mainly by spraying, and the doses are usually in the order of 50-1200 liters of solution per hectare, mainly 80-250 l / ha .

i7 82877

By means of the method according to the invention, substances of the formula I and belonging to group II are applied to the areas from which the weeds are to be eradicated in one and the same application; the mixing of the two active ingredients can be carried out in advance and the concentrate diluted with water at the time of use, or the mixing of the two active ingredients or active ingredient concentrates can take place directly at the time of use in the water used for application.

The invention also relates to a method for controlling weeds, in which an effective amount of a mixture according to the invention is applied to the plants to be destroyed.

The mixtures according to the invention are suitably applied to the vegetation and in particular to the weeds which have to be destroyed when they have green leaves.

Herbicide mixtures can also be applied shortly before harvest by destroying weeds whose roots remain after harvest. Thus, it is possible to sow very quickly after harvest without the need to carry out mechanical weeding (plowing or otherwise).

82877 BC

In general, the compound of group I is applied in doses of 0.1 to 10 kg / ha, preferably in the range from 0.1 to 6 kg / ha and in particular from 0.1 to 4 kg / ha. The preferred application rates for the other active substances will then be given.

Thus, for example, triazine, for example atrazine, is applied in particular at 0.125-4 kg / ha and the weight ratio between the group I compound and the triazine is preferably from 1:32 to 32: 1, in particular from 1:16 to 8: 1.

When Herbicides belonging to the class of phenylureas, for example isoproturon, are applied, doses of between 0.125-2 kg / ha are preferably applied and the weight ratio between the group I compound and the phenylurea is preferably between 1:16 and 32: 1, in particular between 1:12 -8: 1.

When a herbicide belonging to the class of phenoxybenzoic acids, for example bifenox, is generally applied, 0.125-4 kg / ha, preferably 0.25-2 kg / ha, and the weight ratio between the group I compound and the phenoxybenzoic acid derivative is 1:32 to 32: 1, more preferably between 1: 16-8: 1.

When acifluorophene and / or acifluorophene sodium belonging to the same class are used, 0.06 kg to 1 kg / ha are mainly applied and the weight ratio between the group I compound and (sodium) acifluorophen is most often between 1: 8-60: 1, primarily between 1: 4-32: 1.

When uracil of the bromacil type type is used, the latter is applied in doses between 0.125 and 10 kg / ha and in particular between 0.125 and 3 kg / ha and the weight ratio between the group I compound and uracil is preferably between 1:80 and 32: 1, between 1: 24-16: 1.

- · If a phenoxy acid derivative, for example 2,4-D, is used, rates of between 0.1-5 kg / ha and more particularly between 0.1-2 kg / ha are mainly applied. The weight ratio between the group I compound and the phenoxy acid derivative is then preferably between 1:40 and 40: 1, more preferably between 1:16 and 20: 1. The phenoxy acid is preferably used in the form of one of its alkali metal salts and in particular in the form of amine salts or esters.

If a carbamate, for example asulam, is used, it is usually applied at doses of between 0.25 and 7 kg / ha and in particular between 0.25 and 4 kg / ha, and the weight ratio between the group I compound and the carbamate is usually between 1: 56 and 16: 1 and even more preferably between 1:32 and 8: 1. The aculam is preferably in the form of an alkali metal salt, especially a sodium salt.

When aminotriazole is used, it is applied primarily at 0.5-4 kg / ha and the weight ratio between the group I compound and aminotriazole is usually 1: 96-8: 1, preferably between 1: 32-4: 1.

If propanil is applied, it is applied at 0.25-6 kg / ha and the weight ratio between the group I compound and propanil is preferably between 1: 48-16: 1, preferably between 1: 48-4: 1.

When kitsalofop-ethyl is applied, it is applied at 0.016-1 kg / ha, in particular 0.03-0.5 kg / ha, and the weight ratio between the group I compound and kitsalofop-ethyl is then usually between 1: 8-250: 1 and further more preferably between 1: 4-60: 1.

If a nicotinamide such as diflufenican is used, doses of between 0.1 and 2 kg / ha are usually applied and the weight ratio between the group I compound and diflufenican is then usually between 1:16 and 40: 1, preferably between 1: 6-20 : 1.

From the chemical class of imidazolinones, imazazur or imazaquin can be applied at doses ranging from 0.016 to 0.5 kg / ha and the weight ratio between the group I compound and the imidazolinone compound is most often between 1: 4 and 250: 1, especially between 1: 4 -80: 1. Imazapur is preferably used in the form of amine salts, especially as the isopropylamine salt.

When a benzonitrile type herbicide is used, for example 208 8277 bromoxynil, it is applied at 0.06-1 kg / ha. The weight ratio between the group I compound and the benzonitrile derivative is preferably between 1: 8 and 60: 1, more preferably between 1: 5 and 32: 1. Bromoxynyl may be in the form of alkali metal salts or, preferably, in the form of esters (octonate). Ioxynil can be used instead of bromoxynil.

Thiadiazolylureas such as ethidimuron may also be used. Ethidimuron is then applied at a rate of 0.125-7 kg / ha and especially 0.25-2 kg / ha. The weight ratio between the group I compound and the thiadiazolyl urea is most often between 1: 56 and 32: 1, in particular between 1:16 and 8: 1.

Oxadiazone can be used for substances belonging to the chemical class of oxadiazoles. It is applied in doses between 0.25-4 kg / ha, especially 0.25-2.5 kg / ha. The weight ratio between the group I compound and the oxadiazole group derivative is usually between 1:32 and 16: 1, preferably between 1:20 and 8: 1.

Dimefuron, preferably applied at 0.25-2 kg / ha, can also be used from the same chemical class, and the weight ratio between the group I compound and oxadiazole is then 1: 8-16: 1, in particular between 1: 8- 8: 1.

When a benzoic acid such as dicamba is used, it is applied at a rate of 0.05-5 kg / ha, mainly 0.05-0.3 kg / ha and the weight ratio between the group I compound and the benzoic acid derivative (specifically dicamba) is then preferably between 1:40 -80: 1, primarily between 1: 3-20: 1.

Quaternary ammonium compounds can also be used. Thus, for example, paraquat is applied at 0.125-2 kg / ha. The weight ratio between the group I compound and the paraquat is usually between 1:16 and 32: 1, in particular between 1: 8 and 16: 1.

: · When a Group I compound is used with triazine, particularly good control can be observed for the following weeds: Xanthium pennsylvanicum, Ipomea purpurea, Polygonum 2i 82877 convolvulus, Echinochloa crus-Galli, Chenopodium, Amaranthus, Sinapis, Capsella, Poa.

When a group I compound is used with phenylurea, the effect is particularly good on the following weeds: Abutilon theoprasti, Sesbania exaltata, Xanthium pennsylvanicum,

Polygonum convolvulus, Ipomea purpurea, Echinochloa crus-Galli, Alopecurus, Apera, Poa, Atriplex, Sinapis, Chenopodium, Chrysanthemum, Matricaria, Ranunculus, Stellaria.

When a Group I compound is used with phenoxybenzoic acid derivatives, good control is observed for the following weeds: Xanthium pennsylvanicum, Ipomea purpurea,

Sesbania exaltata, Abutilon theophrasti. Polygonum convolvulus, Amaranthus, Chenopodium, Sinapis, Datura, Solanum, Setaria, Euphorbia, Bidens, Galinsoga.

When a Group I compound is used with uracil, the following weeds are particularly well controlled: Xanthium pennsyl-. . vanicum, Ipomea purpurea, Echinochloa crus-Galli, Lolium multi-florum, Setaria, Digitaria, Bromus, Ambrosia, Amaranthus,

Agropyron, Cynodon, Taraxacum, Plantago.

When using a group I compound with a phenoxy acid derivative, good control can be observed for the following weeds: Portulaca oleracea, Polygonum convolvulus, Abutilon theophrasti, Xanthium pennsylvanicum, Chenopodium, Sinapis, Solanum, Ranunculus, Amaranthus, Cirsium, Ipomea.

When a Group I compound is used with a carbamate such as asulam, the following weeds are particularly well controlled: Xanthium pennsylvanicum, Abutilon theophrasti and Sesbania exaltata, Sorghum halepense, Pteridium, Aquilinicum, • f. Eleusine, Panicum, Digitaria, Setaria, Rumex, Equisetum.

When a group I compound is used with aminotriazole, a good control result is observed for the following weeds:

Portulaca oleracea, Abutilon theophrasti, Agropyron, Cynodon, Agrostis, Artemisia, Aristolochia, Rumex, Oxalis, Rubus,

Equisetum, Lepidium, Tussilago.

22 82877

When a Group I compound is used with amides such as propanil, it is effective against the following species:

Ipomea purpurea, Polygonum convolvulus, Abutilon theophrasti.

When a Group I compound is used with phenoxypropion derivatives such as kitsalofop-ethyl, good control is observed for: Lolium multiflorum,

Echinochloa crus-Galli, as well as Sesbania exaltata, Alopecurus, Digitaria, Hordeum, Panicum miliaceum, Setaria, Sorghum halepense.

When a group I compound is used with diflufenican, the effect is particularly beneficial for the following weeds: Portulaca oleracea, Polygonum convolvulus, Abutilon theophrasti, Sesbania exaltata, Echinochloa crus-Galli, Galium, Veronica, Stellaria, Matricaria, Anthemis, Chrysanth, Chrysanth Sinapis.

. . When a group I compound is used with imidazolinone, good control is observed for the following weeds:

Xanthium pennsylvanicum, Ipomea purpurea, Portulaca oleracea, Sesbania exaltata, Echinochloa crus-Galli, Lolium multiflorum, Amaranthus, Chenopodium, Ambrosia, Hibiscus, Sida, Digitaria, '· Eleusine, Setaria, Cyperus escus

When a Group I compound is used with a benzonitrile derivative, the efficacy is good for: Ipomea purpurea, - · - Portulaca oleracea, Polygonum convolvulus, Amaranthus, Chenopodium, Solanum, Ambrosia, Matricaria, Atriplex, Sinapis, Xanthium.

When a Group I compound is used with a thiadiazolyl urea, the efficacy is good against weeds: Xanthium pennsylvanicum, Ipomea purpurea, Polygonum convolvulus, Abutilon theophrasti, Sesbania exaltata, Echinochloa crus-Galli, Gallium, Sinapis, Pellaria, Chen, Chen

23 82877

When a Group I compound is used with herbicides belonging to the oxadiazole class, particularly good control is observed for the following weeds: Xanthium pennsylvanicum, Polygonum convolvulus, Ipomea purpurea, Echinochloa crus-Galli, Amaranthus, Sinapis, Capsella, Euphorbia, Portul, , Dactylis, Galium, Polen-tilla.

When a Group I compound is used with a quaternary ammonium derivative, the efficiency is good with respect to:

Xanthium pennsylvanicum, Ipomea purpurea, Polygonum convolvulus, Alopecurus, Setaria, Sinapis, Raphanus, Chrysanthemum, Amaranthus.

When a Group I compound is used with a benzoic acid such as dicamba, good control is observed for Ipomea, Xanthium, Chenopodium, Polygonum, Amaranthus, Abutilon, Galium, Matricaria, Stellaria, Mercurialis, Veronica, Rumex.

The mixtures according to the invention have a very wide spectrum of action and the weeds to be destroyed can be annual or perennial, monocotyledonous or dicotyledonous. Table III summarizes some of these weeds that are important to eradicate in order for the following crops to get off to a good start and then develop well: cereals, maize, rice, cotton, soybeans, beets (especially sugar beets), sunflowers, oilseed rape, sugar cane, vegetable crops, and weeds could be eradicated from perennial crops (vineyards, orchards). Sometimes the efficiency of weed control can be improved by performing successive treatments and possibly combining soil treatment with them.

The following example, given in a non-limiting sense, illustrates the invention and shows how it can be practiced.

24 82877

Example 55:

Herbicidal effect on plant species after germination in greenhouses__ 9 x 9 x 9 cm pots filled with light tillage are sown with a certain amount of seeds, depending on the plant species and seed size.

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

Once the soil is moistened, allow the plants to rise to the seedling and grow to about 5-10 cm in height. The grass processing step is the "second leaf formation step". The processing stage of dicotyledons is "cotyledons opened, the first right leaf evolving".

The pots are then spray-treated with an amount of solution per pot corresponding to a volume of 500 l / ha and containing the desired dose of active ingredient.

For each active ingredient, the solution is prepared by diluting with a certain amount of water to obtain the desired concentration, on the one hand a dispersible granule type composition containing 20% of the active ingredient which is Compound No. 1 and on the other hand a Group II active ingredient composition.

Depending on the concentration of active substance in the solution, the amount of active substance applied varies from 16 to 1000 g / ha, depending on the substance.

The treated pots are then placed in basins designed to allow irrigation water to come underneath, and the pots are kept for 35 days at ambient temperature and 70% relative humidity.

After 35 days, calculate the number of viable plants in the pots treated with the solution containing the test substance 25 82877 and the number of viable plants in the reference pot treated under the same conditions but with the solution not containing the active substance. In this way, the percentage destruction of treated plants relative to the untreated control pot is determined. A percentage of destruction of 100% indicates that complete destruction of the plant species in question has taken place and a percentage of 0% indicates that the number of live plants in the treated pot is the same as in the reference pot.

The plant species tested have been listed in Table III next to the Latin name in abbreviations.

The results obtained according to this Example 55 are shown in Table V. The amounts of active substances used in this example are usually relatively small, so that the results obtained, even when they are modest, often testify to a strong potential effect. By using higher doses (apparently double doses) compared to those reported, even better results are naturally obtained. In many cases, the combinations according to the invention show a synergistic effect with respect to the active ingredients alone.

26 82877

Table III

Finnish name American name Latin name revon tail pigweed Amaranthus retroflexus Japanese rose Velvet leaf abutilon theophrasti (ABU) prickly sida sida spinosa sesbania bile grass cocklebur Xanthium pennsylvanicum (XAN) bidens faberii Koiso black Nightshade Solanum nigrum perennial Cyperus esculentus barnyardgrass Echinochloa crus-Galli (ECH) Oat wild oat Avena fatua ryegrass Rye grass Lolium multiflorum • Alopecurus myosuroldes *:. quackgrass Agropyron repens · '' downy mildew bermudagrass cynodon dactylon mustard wild mustard sinapis arvensis Ipomea morningglory (SES) 27 82877

Table IV

Common names Chemical name (French nomenclature but Anglo-Saxon numbering of substituents)

Atrazine 2-chloro-4-ethylarino-6-isopropylamino-1,3,5-triazine

Isoproturon 3- (4'-Isopropylphenyl) -1,1-dimethylurea

Biphenoxy methyl 5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoate

Bromacil 5-Bromo-3-sec-butyl-6-methyluracil 2,4-D Ammonium (2,4-dichlorophenoxy) acetate

Asulam Methyl 4-Aminobenzenesulfonyl Carbamate (Sodium Salt)

Aminotriazole 3-amino-1H-1,2,4-triazole

Propanil N- (3,4-dichlorophenyl) -propionamide

Kitsalofop-ethyl Ethyl 2- [4- (6-chloro-2-quinoxalinyloxy) -phenyloxy] -propionate

Diflufenican N- (2,4-difluorophenyl) -2- (3-trifluoromethylphenoxy) nicotinamide

Imazapur isopropylammonium 2- [4,5-dihydro-4-methyl-4- (isopropyl) -5-oxo-1H-imidazol-2-yl] -3-pyridinecarboxylate Acifluorophenium sodium sodium 5- (J'-chloro) -4- (Trifluoromethyl) -phenoxy] -2-nitrobenzoate Bromoxynil 3,5-dibromo-4-hydroxybenzonitrile octoate

Ethidimuron 1- (5-ethylsulfonyl-1,3,5-thiadiazol-2-yl) -1,3-dimethylurea

Oxadiazone 5-tert-butyl-3- (21,4'-dichloro-51-isopropyloxyphenyl) -1,3,4-oxadioazolin-2-one

Paraquat 1,1'-dimethyl-4,4'-bipyridinium chloride

Dimefuron / chloro-2- (dimethyl-3,3-ureido) -4-phenyl-3- (dimethyl-1,1-ethyl) -5-3H-oxadiazol-1,3,4-one 2

Dicamba dimethylammonium 3,6-dichloro-2-methoxybenzoate 28 82877

Table V

Total No. 1 XAN IPO POR POL Quality Dose g / ha _ _ _ _ 250 250 90 98 100 90

Atrazine 500 125 80 100 100 100 _500_250_100 100 100 100 250 250 100 98 100 30 ronir ° tU "500 125 90 50 100 20 _500_250_90 · 98 100_60_ 500 250 90 90 100 100

Biphenoxy 1000 125 50 90 100 98 _1000_250_70 90 100 100 125 250 60 50 100 98

Bromacil 250 125 100 98 100 100 _250_250_100 100 100 100 125 250 100 100 100 80 2,4-D 250 125 100 100 100 60 _250_250_100 100 100_98_

Settlement 500 250 100 20 10 20 soli ° triat ”1000 250 20 0 80 20 500 250 90 90 30 60 ... Propanil 1000 125 100 100 100 100 __1000_250_100 100_90 100 ethyl ° f ° P ~ 31 250_20 0 50 20

Carbetamide 4000 250 20 90 30 10 Cap 6111 "1000 250 50 40 100 98 31 250 100 90 98 90

Imatsapuri 62 125 100 80 100 100:: 62_250_100 90 100 100 Ϊ- · Asifluoro- 62 250 80 100 100 100 feni- 125 125 100 100 100 100 sodium_125_250_100 100 100 100 29 82877

Table V (continued)

Compound gY. ^ GlP-.11 Compound n; 0 i Xan ipo por pol

Quality Dose q / ha _ _ _ _ 62 250 100 80 30 80

Bromoch- 125 125 10o 10o 0 90 synyl _125_250_90 100_90 100 125 250 100 100 100 100

Etidimuron 250 125 100 100 100 100 _250_250_100 100_100_100 250 250 100 100 100 100

Oxadiazon 500 125 30 40 100 100 _500_250_100_100_100_100 125 250 100 100 98 98

Parakuat 250 125 98 50 100 90 _250_250_] J30_90_98_90

Dimefuron 1000 250 30 10 100 90

Table V (continued)

Group II Compound Compound No. 1 ABU gES ECH

Quality Dose g / ha_ _ _ _ 250 250 60 100 60

Atrazine 500 125 - 100 98 _500_250_ 100_80_ 250 250 0 100 60

Isoproturon 500 125 100 100 50 _500_250_100 100_100 500 250 90 100 20

Biphenoxy 1000 125 100 100 20 _1000_250_100 98_20_ 125 250 80 80 40

Bromacil 250 125 90 100 98 _250_250_100 100_100 125 250 80 100 20 2,4-D 250 125 50 100 10 __250_250_100 100_50_

Settlement 500 250 90 100 20 3o 82877

Table V (continued)

Group II Compound Compound No. 1 ABU SES ECH

Quality Dose g / ha _ _ _

Aminotriazole 1000 250 100 100 60 500 250 60 100 10

Propanil 1000 125 60 100 20 _1000_250_95_100_70 ethyl ° f ° P ~ _ ^ _ 250_80_100 100

Carbetamide 4000 250 80 100 20

Diflufenican 1000 250 100 100 80 31 250 100 90 90

Imatsapuri 62 125 100 95 90 _ 62_250_100_95 100 62 250 80 100 20 nit “rfeen * 3» _125_250_80_100_30_ 62 250 20 90 30

Bromoxynyl 125 125 50 95 10 _125_250_60_80_30_ 125 250 100 98 10 - Ethidimuron 250 125 100 95 10 __250_250_100_100_60_ 250 250 100 100 90

Oxadiazon 500 125 100 100 98. -; 500_250_100_100 100 125 250 100 100 100

Paraquat 250 125 100 100 95 _250_250_100_100 100

Dimefuron 1000 250 100 100 50

Claims (9)

3i 82877 Herbicidal mixture, characterized in that it contains an active substance of the formula: OR 2 I, O - P - CH 2 - NH - CH 2 - CO - N - SO 2 - R 1 (I) OR 3 R wherein: R 1 is 1-18 a carbon-containing hydrocarbon radical, in particular alkyl having 1 to 7 carbon atoms, phenyl or cycloalkyl having 3 to 7 carbon atoms, which radicals may be optionally substituted by the following groups: halogen atoms, phenyl, cyano, alkyl, alkoxy, alkylcarboxyl, the alkyl groups of which contain 1- 4 carbon atoms, R is a hydrogen atom or has one of the meanings given to R 1 and is preferably an alkyl group having 1 to 4 carbon atoms, R 2 and R 3 are hydrogen atoms or groups such that OR 2 and OR 3 are hydrolyzable groups and are especially Alkyl or aryl radicals having 1 to 12 carbon atoms which are optionally substituted by the substituents defined in R 1, or said active ingredient of formula I is combined with at least one active ingredient from group II, i.e. an active ingredient selected from the group consisting of: chloroacetamides, triazines, phenylureas, thiadiazolylureas, sulfonylureas, benzothiazolylureas, nitroanilines, phenroanilines, phenytoin , amides, oxadiazoles, aminotriazole, picolinic acid, phenoxybenzoic acid derivatives, phenoxypropionic acid derivatives, aryloxy acids, benzoic acids, propionic acids, triazinones, carbamates, pyridazinones, pyridones, pyridones, quaternary 32 82877 Mixture according to Claim 1, characterized in that in the formula I, R and R 1 are alkyl radicals having 1 to 4 carbon atoms and R 1 is a hydrogen atom. Mixture according to Claim 1 or 2, characterized in that the weight ratio between the compound of the formula I and the compound or compounds of Group II is between 0.2 and 10, in particular between 0.25 and 4. Mixture according to one of Claims 1 to 3, characterized in that it contains the active ingredients together with at least one inert, conventional agriculturally acceptable carrier. Mixture according to Claim 4, characterized in that it contains 0.05 to 95% of active ingredient. Mixture according to Claim 4 or 5, characterized in that it contains 5 to 40% of surfactant. Mixture according to one of Claims 1 to 6, characterized in that it is in the form of a soluble powder, a wettable powder or autodispersible granules. A method for controlling weeds, characterized in that an effective dose of a mixture according to any one of claims 1 to 7 is applied in contact with the leaves of the plants to be destroyed. Method according to Claim 8, characterized in that the amount of mixture applied is such that the amount of active ingredients is 0.1 to 10 kg / ha, in particular 0.5 to 8 kg / ha. 33 8 2 8 7 7