NO860188L - HERBICIDE PREPARATIONS. - 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

Herbicidal preparations

The present invention relates to new herbicidal preparations containing herbicidal mixtures and in particular at least one herbicide from the chemical family N-(phosphonomethyl-glycyl)sulfonylamine, as well as the use of these herbicidal preparations in agriculture.

Mange forbindelser med aminometylfosfon-gruppe og herbicide egenskaper er kjent, særlig franske patenter 2,129,327, 2,281,375, 2,251,569, 2,413,398 og 2,463,149, europeiske patenter 53,871, 54,382 og 73,574, US patenter 3.160,632, 3.455,675, 3,868,407, 4,388,103 og 4,397,676, britisk patent 2,090,596, PCT WO 83/03608 and Belgian patents 894,244, 894,245, 894,590, 894,591, 894,592, 894,593, 894,594 and 894,595.

However, it is always desirable to expand the range of available herbicidal preparations, in order to meet the farmers' needs. Some amides with an aminomethylphosphonic group were well known, but these products either had low activity or were inactive.

An aim of the present invention is to provide herbicidal preparations with a powerful and rapid activity.

Another purpose of the invention is to provide herbicidal preparations with good biodegradability.

Another object of the invention is to provide post-emergence herbicidal preparations with a wide range of activity, which have, at least partially, a decreasing systemic effect and which are possibly selective for certain types of crops.

Another object of the invention is to provide herbicidal preparations which are very resistant in the soil, which in particular are sufficiently resistant so that they work

important information

For archival reasons, the Norwegian Patent Office only has access to documents for this generally available patent application that contain handwritten notes, comments or crossing outs, or that may be stamped "Expired" or the like. We have therefore had to use these documents for scanning to create an electronic edition.

Handwritten remarks or comments have been part of the proceedings, and must not be used to interpret the content of the document.

Cross-outs and stampings with "Expired" etc. indicates that newer documents have been received during the proceedings to replace the earlier document. Such crossing out or stamping must not be understood as meaning that the relevant part of the document does not apply.

Please ignore handwritten remarks, comments or crossing outs, as well as any stamps with "Expired" etc. which have the same meaning.

in the case of prolonged germination (i.e. effect on weeds and other plants where growth and development are delayed over a period of time).

Other purposes and advantages of the invention will appear in the following description.

It has now been found that these purposes can be achieved, in whole or in part, by means of the preparations in accordance with the present invention.

The herbicidal preparations in accordance with the invention are therefore preparations containing an active compound with the general formula:

where:

R"<*>" is a hydrocarbon radical 1, in particular an alkyl, aryl or cycloalkyl radical 1, as these various radicals may optionally be substituted; whereby, as substituents, particular mention will be made of halogen atoms and phenyl, cyano, alkyl, carboxyl and alkyl carboxylated groups, where the alkyl groups preferably have 1 to 4 carbon atoms; usually from 1 to 18 carbon atoms, preferably from 1 to 7 carbon atoms and more particularly from 3 to 7 carbon atoms

when it is a cycloalkyl group; r}~ is preferably an alkyl radical with 1 to 4 carbon atoms, which is optionally

halogenated, especially with chlorine or fluorine, e.g. CF^,

R is a hydrogen atom or has one of the definitions given for , and is preferably an alkyl group with 1 to 4 carbon atoms,

2 3

R and R are a hydrogen atom or such that OR and OR

2 3

are hydrolyzable groups; R and R can be, in particular, an alkyl or aryl radical (preferably an alkyl or phenyl radical1), which can optionally be substituted, in particular with substituents given for R"<*>";

they generally have from 1 to 12 carbon atoms, and preferably

ket from 1 to 8 carbon atoms,

4

in that the above-mentioned active compounds of general formula I also include the salts of these various compounds (especially the salts from the P-OH groups and those from the nitrogen atom in the NH group, which then becomes an ammonium group), and in particular agriculturally tolerable salts of these compounds (agriculturally tolerable salts include the salts of alkali metals, especially sodium and potassium, alkaline earth metal salts, primary, secondary, tertiary and quaternary ammonium salts and sulphonium salts. Other salts in accordance with the invention are salts obtained with an acid, such as chloride -ers, sulphides, phosphates and other salts derived from acids with a pK value less than or equal to 2.5),

the above-mentioned active compound of general formula I is combined with at least one active compound from group II, i.e. an active compound selected from the group consisting of chloroacetamides (in particular alachlor and metolachlor), triazines (in particular simazine, atrazine and promethrin), phenylurea (in in particular diuron, isoproturon and linuron), thiadiazolylurea (in particular tebuthiuron and ethidimuron), sulphonylureas (in particular sulfometuron, chlorosulfuron and metsulfuron), benzothiazolylurea (in particular metabenzthiazuron), nitroanilines (in particular oryzalin and triflura lin), phenoxynictoinanides ( in particular diflufenican), amides (in particular napropamide and propanil), oxadiazoles (in particular oxadiazone and dimefuron), aminotriazole, picolinic acid (picloram), phenoxy-benzoic acid derivatives (in particular bifenox, acifluorfen, acifluorfen sodium, fomesafen, oxyfluorfen and esters of acifluorfen and aliphatic alcohols or glycolates or lactates), phenoxypropone derivatives (in particular stupidity

quizalofob-ethyl and fluazifop-butyl), aryloxyacids (in particular 2,4-D, 2,4-DP, MCPA and MCPP), benzoic acids (in particular dicamba), propionic acids (in particular dalapon), triaziones (in particular metribuzin) , carbamates (in particular carbetamide, EPTC and asulam), pyridazinones

(in particular norflurazon), pyridones (in particular fluridone), quaternary ammonium compounds (in particular diquat and paraquat), uracils (in particular bromacil), hydroxybenzonitriles (in particular bromoxynil and ioxynil) and imidazolinones (in particular imazaquin and imazapur).

The compounds of general formula (I) can be prepared, for example, in accordance with the method described in European Patent Application No. 135,454.

The compounds of the group (II) are known compounds and most of them are described in detail in works such as "The pesticide manual" published by "The British Crop Protection Council", 7th edition, 1983. The chemical designations of the compounds of the group (II) used in the examples are given in table (IV).

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

The weight ratio of the active compound of general formula (I) in relation to the active compound or compounds from group (II) is generally between 0.2 and 10, preferably between 0.25 and 4; however, this ratio can have higher values, up to 100, with active compounds such as picloram and, in particular, sulphonylureas.

In the present description, the given examples show how the preparations in accordance with the invention can be prepared and used; and when not stated otherwise, percentage is equal to percentage by weight.

Among the compounds of general formula (I), the preferred compounds are those in which R and R<1> are an alkyl group of 1 to 2 3 4 carbon atoms, and R and R are a hydrogen atom or an alkyl group of 1 to 4 carbon atoms or a phenyl group , as well as the agriculturally tolerable salts.

Among the compounds from group (II), the following compounds are preferred when preparations that are resistant are desired: simazine, atrazine, promethrin, diuron, chlorosulfuron, oryzalin, nafropramide, oxadiazon, dimefuron, picloram, fomesafen, bromacil and imazaquin.

When used in practice, the active compounds in the preparations in accordance with the invention are rarely used alone. Generally, these herbicidal preparations contain the active compounds in accordance with the invention, as described above, in combination with solid or liquid carriers which are agriculturally tolerable, and surfactants which are also agriculturally tolerable. In particular, the commonly used internal carriers and surfactants can be used. These preparations are also part of the invention.

These preparations may also contain other types of additives, such as e.g. protective colloids, adhesives, thickeners, thioxotropic agents, penetrating agents, stabilizers, sequestering agents, etc., as well as other known active compounds with pecticidal properties (especially insecticide, fungicide or herbicide), or with plant growth-regulating properties. More generally, the compounds used in the present invention can be combined with all solid or liquid additives that correspond to commonly used techniques for preparation.

The amounts to be used of the compounds in accordance with the invention may vary within a certain area, particularly with regard to the type of weed to be removed and the degree of attack on the areas where the weed is to be removed.

In general, the preparations in accordance with the invention usually contain about 0.05 to 95% active compounds (formula (1) and group (II)) in accordance with the invention, about 1 to 95% of one or more solid or liquid carriers and optionally about 0 .1 to 50% of one or more surfactants.

It has already been established that the active compounds used in accordance with the invention are generally combined with carriers and possibly surface-active agents.

In the present specification, the term "carrier" denotes an organic or inorganic natural or synthetic material with which the active compounds are combined to facilitate their application to the plant, the seeds or to the soil. This carrier is therefore generally inert and it must be agriculturally tolerable, in particular for the treated plant.

As solid carriers (or fillers), one can mention inorganic or synthetic fillers, e.g. kaolin, attapulgite, montmorillonite, talc, talc, diatomaceous earth,

kieselguhr, calcium and magnesium carbonates, precipitated synthetic silica, aluminium, alkali metal silicates and silicoaluminuates, resins, waxes and fertilizers in solid form. Water-soluble fillers, i.e. sodium sulphate or ammonium sulphate and urea, can also be used.

As liquid carriers, mention may be made of aqueous alcohols (especially butanol), esters (especially methyl glucolacetate), ketones (especially cyclohexanone and isophorone), petroleum fractions, aromatic hydrocarbons (especially xylenes) or paraffin hydrocarbons, chlorine-substituted aliphatic hydrocarbons (especially trichloroethane) or chlorine-substituted aromatic hydrocarbons (especially chlorobenzenes), and water-soluble solvents such as dimethylformamide, dimethylsulfoxide and N-methylpyrrolidone.

The surface-active agent can be an emulsifying agent, dispersant or wetting agent of ionic or non-ionic type, or a mixture of such surface-active agents.

As non-ionic wetting agents, one can thus mention ethylene oxide-treated alkylphenols (especially octyl, nonyl and tributylphenols with 6 to 18 oxyethylene units), ethyloxide-treated fatty alcohols (especially C n to Clg alcohols with 6 to 18 oxyethylene units ), ethylene oxide-treated fatty amines (in particular tallow or tallow oil with from 2 to 40 oxyethylene units), and esters of fatty acids and polyols (of the glycerin or sugar type) which have been treated with ethylene oxide (in particular sorbitan laurate and stearate with 5 to 20 oxyethylene units).

As a wetting agent, one can mention a 1 cold phthalenesulfona tester salts (especially sodium or potassium isopropyl, butyl and dibutyl naphthalene sulfonates), sulfate ester salts of fatty alcohols (especially sodium or potassium lauryl sulfate), sulfosuccinate ester salts of fatty alcohols (especially sodium or potassium dioctyl sulfosuccinate), and taurine derivatives (especially alkyl taurates, aryl-N-methyl taurides and sodium oleylmethyl tauride.

As non-ionic dispersants, one can mention ethylene oxide-treated arylphenols (especially bis- and tris(phenylethyl)phenols containing from 18 to 40 oxyethylene units).

As anionic dispersants, one can mention polycarboxylic acid polymers in salt form (such as sodium polycarboxylate and polyacrylate polymers), polycondensates of formaldehyde and diphenol sulfonates or alkyl naphthalene sulfonates (especially sodium methyl naphthalene sulfonate), phosphoric acid ester salts or esters of ethylene oxide-treated alkyl or arylphenols (especially phosphoric acid esters of nonylphenols with 6 to 18 oxyethylene units, in the form of acid or potassium salt, as well as phosphoric acid esters of bis- or tris(phenylethyl)phenol with 18 to 40 oxyethylene units, in the form of acid or salt), phosphated ethylene oxide-treated fatty alcohols (especially C. to C. g. fatty alcohols with 6 to 18 oxyethylene units), and alkali metal or alkaline earth metal lignosulfonates.

The preparations in accordance with the invention, especially when they are in the form of a dry powder, can also contain from 1 to 50% by weight of natural or synthetic binder.

As natural binders, mention can be made of starch and its derivatives (especially modified starch and destrin), cellulose derivatives (especially carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose), sugars (i.e. lactose, mannitol and sorbitol) and gums (i.e. gum arabic and xanthan -rubbers).

As a synthetic binder, mention may be made of polymers (in particular polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone and alkali metal polyacrylates), polycondensates (in particular polyethers such as polyglycols; copolycondensates of maleic anhydride; polycondensates of formaldehyde and alkyl naphthalene sulphonates (i.e. polycondensates of formaldehyde and sodium methyl naphthalene sulphonate) and alkali metal lignosulfonates.

The presence of at least one surface-active agent in the preparations in accordance with the invention is generally necessary when the active compounds and/or inert carrier are not soluble in water and when the carrier in use is water.

When used, the preparations in accordance with the invention are in various solid or liquid forms which are relatively diluted, while the preparations suitable for transport, sale and storage are mostly concentrated preparations. Preparations in solid form can be moist powders or powders that can be spread in dry form (with a content of active compounds that can reach up to 100%) and pellets (preferably dry powder form), especially those obtained by extrusion, with compression, by impregnation of a carrier in the form of grains and^ by granulation starting from a powder (the content of: active compounds of formula (1) and group (II) in these pellets is between 0.5 and 80% for the latter cases.

The preparations in liquid form, or a form in which the preparations must be liquefied before use, can be solutions and dispersants, or possibly pastes. In the present invention, however, concentrated preparations in the solid state are preferred.

The spraying agents, which can be used by spraying, are prepared so that a stable liquid product is obtained that does not precipitate (finely ground), and they usually contain from 10 to 75% active compounds, from 0.5 to 15% surfactants, from 0.1 to 10% texotropic agents, from 0 to 10% suitable additives, i.e. antifoam agents, corrosion inhibitors, stabilizers, penetrating agents over adhesives, and, as carrier, water or an organic solution in which the active compounds are little or no -soluble: certain organic compounds in solid form or inorganic salts can be dissolved in the carrier as an aid to prevent precipitation, or as an anti-freeze agent for the water.

An injectable preparation is given in the following example.

Example 1

In accordance with example 1, in particular the following preparations can be prepared.

Preparations from the compounds of formula (I):

Compound 1: compound of formula (I) where R and R"*" are

2 3

a methyl group and R and R is a hydrogen atom.

Compound 2: compound of formula (I) wherein R and R 2 are

a methyl group, R<2> is a hydrogen atom and R<3> is a phenyl group.

Compound 3: compound of formula (I) wherein R and R are

2 3

a methyl group and R and R is a phenyl group.

Group (II) compounds: simazine, atrazine, promethrin, diuron, isoproturon, linuron, metabenzthiazuron, orysaline, trifluralin, diflufencikan, napropamide, propanil, oxadiazone, aminotriazole, picloram, fibenox, acifluorfen sodium, quizalofob, 2,4-D , MCPA, MCPP, carbetamide, asulam, bromoxynil, ioxynil.

In accordance with example 1, examples 2 to 10 have been obtained using conditions described in the following table (I):

The moist powders (or sprayable powders) are therefore, together with dry powder, the preferred preparations in accordance with the invention. The wet powders are usually prepared to contain 20 to 95% active compounds and they usually contain, in addition to solid carrier, from 0 to 25% of a wetting agent, from 1 to 15% of a dispersing agent and, when required from 0 to 10% of one or more stabilizers and/or other additives, i.e. penetrating agents, adhesives, or anti-caking agents, coloring agents etc.

The following example shows the composition of various moist powder preparations.

Example 11

Example 12 Example 13 Example 14 Example 15

Example 16

Example 17 Example 18 Example 19

Example 20

- precipitated silica 15% - attapulgite, up to 100% - t active compounds 50% sodium oleylmethyl tauride 2% sodium methyl naphthalene sulfonate polycondensed with formaldehyde 4% diatomaceous earth 20% diatomaceous earth, up to 100%

active compounds 50% nonylphenol containing 18 oxyethylene- units 2% nonylphenol phosphate containing 10 oxyethylene units 4% precipitated silica 10% montmorillonite, up to 100%

active compounds 60% sodium dioctylsulfosuccinate 2% polycondensed sodium methylnaphthalene sulfonate 3% sodium silicoaluminate 15% kaolin, up to 100%

active compounds 60% sorbitan stearate (stearate of dehydrated

sorbitol) containing 25 oxyethylene-

units 5%

Example 25 Example 26 Example 27

In these examples 11 to 27, one of the active compounds is selected from compounds No. 1 to 3 and the others belong to the following groups: simazine, atrazine, promethrin, diuron, isoproturon, linuron, methabentiazuron, trifluralin, diflufenican, napropamide, oxadiazon, dimefuron, bifenox, quizalofob, dalapon, carbetamide and other active compounds in table

(IV. )

More particularly, examples 30 to 41 are obtained under conditions shown in table (II). The mixtures given in table (V) can also be used.

To obtain the powder that can be used by spraying or wet powders, the active compounds are mixed well in suitable mixers together with additional additives, or the porous filler mass is impregnated with active compounds in molten form and ground in suitable mills or other grinding devices. One thereby obtains the powder for use by spraying, which has advantageous wetting ability and dissolving ability; they are dissolved in water in any desired concentration, and this suspension can be used very advantageously, especially when applied to plant leaves.

The "dry powders" (ie pellets that can be easily dissolved in water) are very similar to the moist powders in terms of composition. They can be prepared by the granulation of grids described for moist powders, either by a method using moisture (the finely divided active compounds are brought into contact with the inert filler and with some water, i.e. 1 to 20%, or of an aqueous solution of a dispersant or binder (described above, followed by drying and sieving) or by a "dry" process (compression followed by grinding and sieving).

The following examples show the composition of a few preparations in dry form.

Example 50

Example 51

Example 52

Example 53

Exact examples of active compounds and particular conditions prepared in accordance with these Examples 50 to 53 are similar to those obtained for the mixtures of active compounds in accordance with Tables (II) and (V).

Instead of moist powders, pastes can be prepared. The conditions and methods for the production and use of these pastes are similar to those used for moist powders or powders used by spraying.

As already established, the aqueous dispersions and emulsions, i.e. preparations obtained by diluting wettable powder with water or a spraying agent in accordance with the invention, are included in the general area with respect to preparations that can be used in accordance with the present invention . The emulsions can be of the water-in-oil or oil-in-water type, and they can have a thick consistency similar to mayonnaise.

All these dispersions, aqueous emulsions or mixtures can be used on areas or crops where the weeds are to be removed by means of suitable means, mainly by means of spraying, in doses which are generally of the order of 50 to 1200 liters of mixture per hectare, and preferably from 80 to 250 l/ha.

In accordance with the method described so far, the compounds of formula (I) and group (II) are used on areas where weeds are to be removed in a single application; mixing of the two active compounds can be carried out in advance by diluting the concentrate with water before it is used, or simply by mixing two active compounds or concentrates of active compounds directly in the water used for application.

In accordance with another method for removing weeds, the compounds of formula (I) and the compound or compounds from group (II) are used consecutively at different periods, the latter compounds possibly being used on soil. However, the invention also relates to herbicidal preparations containing active compounds of general formula (I) and the group (II) in combination, having a simultaneous herbicidal application, individually or spread over a period of time. When such continuous treatment is carried out, the intervals for application between the two treatments are advantageously between 1 and 3 weeks, and the compound or compounds from group (II) can sometimes be used first.

In order to use advance compounds from group (II), it is possible, in accordance with the invention, to use pellets that can be deployed on the ground.

The present invention also relates to a method for removing weeds, which comprises applying an effective amount of preparation to the plants to be destroyed.

The preparations in accordance with the invention are advantageously used for plant growth, and in particular for weeds which are to be removed when the latter has green foliage.

The herbicidal preparations can also be used just before harvesting, to kill the weeds, whose roots are present in the soil after harvesting. In this way, it is possible to sow very quickly after harvesting, without having to carry out mechanical removal of the weeds (ploughing etc.).

In general, the compound from group (I) is used in amounts between 0.1 and 10 kg/ha, preferably between 0.1 and 6 kg/ha, and especially between 0.1 and 4 kg/ha. The preferred application amounts for other active compounds are as given below.

When a triazine is thus used, i.e. atrazine, an amount between 0.125 and 4 kg/ha is preferably used, the weight ratio between the compound from group (I) in relation to the triazine being advantageously between 1:32 and 32:1, preferably between 1 :16 and 8:1.

When a herbicide from the phenylurea family is used, i.e. isoproturon, it is advantageously used in amounts between 0.125 and 2 kg/ha, the weight ratio of the compound from group (I) in relation to phenylurea being advantageously between 1:16 and 32 :1, especially between 1:12 and 8:1.

When a herbicide from the phenoxybenzoic acid family is used, i.e. bifenox, it is generally used in an amount between 0.125 and 4 kg/ha, preferably between 0.25 and 2 kg/ha, the weight ratio between the compound from group (I) in relation to to the phenoxybenzoic acid derivative is between 1:32 and 32:1, especially between 1:16 and 8:1.

When, from the same family, acifluorfen and/or sodium acifluorfen are used, it is preferably used in an amount between 0.06 kg and 1 kg/ha, the weight ratio between the compound from group (I) and acifluorfen (sodium) is most often between 1:8 and 6:1, preferably between 1:4 and 32:1.

When using a uracil of the bromacil type, the latter is used in amounts between 0.125 and 10 kg/ha, and more particularly between 0.125 and 3 kg/ha, the weight ratio between the compound from group (I) and uracil being advantageously between 1 :80 and 32:1, preferably between 1:24 and 16:1.

If a phenoxy acid derivative is used, i.e. 2,4-D, it is preferably used in amounts between 0.1 and 5 kg/ha, and more particularly between 0.1 and 2 kg/ha. The weight ratio between the compounds from group (I) and the phenoxy acid derivative is advantageously between 1:40 and 40:1, preferably between 1:16 and 20:1. The phenoxy acid is advantageously used in the form of an alkali metal salt, and particularly in the form of an amine salt or in the form of an ester.

If you use a carbamate, e.g. asulam, it is usually used in amounts between 0.25 and 7 kg/ha, and more particularly between 0.25 and 4 kg/ha, the weight ratio between the compound from group (I) and the carbamate being generally between 1:56 and 16: 1, and more especially between 1:32 and 8:1. Asulam is preferably in the form of an alkali metal salt, especially the sodium salt.

When an aminotriazole is used, it is preferably used in an amount between 0.5 and 4 kg/ha, the weight ratio between the compound from group (I) and aminotriazole being generally between 1:96 and 8:1, preferably between 1:32 and 4:1.

If a propanil is used, it is advantageously used in an amount between 0.25 and 6 kg/ha, the weight ratios between the compound from group (I) and propanil being advantageously between 1:48 and 16:1, preferably between 1:48 and 4:1.

When using guizalofob-ethyl, an amount of between 0.016 and 1 kg/ha is used, and in particular between 0.03 and 0.5 kg/ha, the weight ratio between the compound from group (I) and guizalofob-ethyl being generally between 1 :8 and 250:1, and advantageously between 1:4 and 60:1.

If a nicotinamide is used, i.e. diflufenican, it is generally used in amounts between 0.1 and 2 kg/ha, the weight ratio between the compound from group (I) and diflufenican being generally between 1:16 and 40:1, preferably between 1 :6 and 20:1.

Within the imidazolinone chemical family, imazapur and imazaquin can be used in amounts between 0.016 and 0.5 kg/ha, and the weight ratio between the compound from group (I) and the compound from the imidazolinone family is usually between 1:4 and 250:1, and especially between 1:4 and 80:1. Imizapur is advantageously used in the form of amine salts, especially isopropylamine salt.

When using a benzonitrile-type herbicide, i.e. bromoxynil, it is used in amounts from 0.06 kg to 1 kg/ha. The weight ratio between the compound from group (I) and the benzonitrile derivative is advantageously between 1:8 and 60:1, preferably between 1:5 and 32:1. Bromoxynil can be in the form of an alkali metal salt or advantageously in the form of esters (octa-noate). Ioxynil can be used instead of bromoxynil.

Thiadiazolylureas, i.e. ethidimuron, can also be used. Etidimuron is then used in an amount between 0.125 and 7 kg/ha, and advantageously between 0.25 and 2 kg/ha. The weight ratio between the compound from group (I) and the thiadiazolylurea is usually between 1:56 and 32:1, in particular between 1:16 and 8:1.

Among the compounds from the oxadiazole chemical family, oxadiazone can advantageously be used. It is used in amounts between 0.25 and 4 kg/ha, especially between 0.25 and 2.5 kg/ha. The weight ratio between the compound from group (I) and the derivative with an oxadiazole group is generally between 1:32 and 16:1, preferably between 1:20 and 8:1.

In the same chemical family, dimefuron can also be used, preferably in an amount between 0.25 and 2 kg/ha, the weight ratio between the compound from group (I) and oxadiazole being between 1:8 and 16:1, in particular between 1: 8 and 8:1.

When mar. uses a benzoic acid, i.e. dicamba, it is used in an amount between 0.05 and 5 kg/ha, preferably between 0.05 and 0.3 kg/ha, the weight ratio between the compound from group (I) and the benzoic acid derivative ( especially dicamba) advantageously is between 1:40 and 80:1, preferably between 1:3 and 20:1.

Quaternary ammonium compounds can also be used. Thus, paraquat is used in a quantity between 0.125 and 2 kg/ha. The weight ratio between the compound from group (I) and paraquat is generally between 1:16 and 32:1, and in particular between 1:8 and 16:1.

When the compound from group (I) is used with a triazine, particularly good control of the following weed types is observed: Xanthium pennsy1 va nicum, Ipomea purpurea, Polygonum convolvulus, Echinochloa crus-galli, Chenopodium, Amaranthus, Sinapis, Ca psella and Poa.

When the compound from group (I) is used with a phenylurea, the activity is particularly good against the following weed species: Abutilon theophrasti, Sesbania exaltata, Xanthium pennsylvanicum, Polygonum convolvulus, Ipomea purpurea, Echinochloa crusga11i, Alopecurus, Apea r, Poa, Atriplex, Sinapis, Chenopodium, Chrysa nthemum, Matricaria, Ranonculus and Stellaria.

When the compound from group (I) with phenoxybenzoic acid derivatives, good control of the following weed species is observed: Xanthium pennsylvanicum, Ipomea purpurea, Sesbania exaltata, Abutilon theophrasti, Polygonum convolvulus, Amaranthus, Chenopodium, Sinapis, Da tura, Sola num, Setaria, Euphorbia , Bidens and Galinsoga.

When the compound from group (I) is used with a uracil, Xanthium pennsylvanicum, Ipomea purpurea, Echinochloa crusgalii, Lolium multiflorum, Seta ria, Digitaria, Bromus, Ambrosia, Amaranthus, Agropyron, Cynodon, Taraxacum and Plantago are particularly well controlled.

When the compound from group (I) is used with a phenoxy acid derivative, a good control of the following is observed: Portulaca oleracea, Polygonum convolvulus, Abutilon theophrasti, Xanthium pennsylvanicum, Chenopodium, Sinapis, Solanum, Ramunculus, Amaranthus, Cirsium and Ipomea.

When the compound from group (I) is used with a carbamate such as asulam, Xanthium pennsylvanicum, Abutilon theophrasti, Sesbania exaltata, Sorghum halepense, Pteridium, Aquilinicum, Eleusine, Pa nicum, Digita ria, Setaria, Rumex and Equisetum are particularly well controlled.

When the compound from group (I) is used with aminotriazole, a particularly good control of: Portulaca oleracea, Abutilon theophrasti, Agropyron, Cynodon, Agrostis, Artemisia, Aristolochia, Rumex, Oxalis, Rubus, Equisetum, Lepidium and Tussilago is observed.

When the compound from group (I) is used with amides such as propanil, a good effect is achieved on: Ipomea purpurea, Polygonum convolvulus and Abutilon theophrasti.

When the compound from group (I) is used with phenoxypropionic acid derivatives such as quizalofob-ethyl, a qod control of: Lolium multiflorum, Echinochloa crusqalli, Sesbania exaltata, Alopecurus, Digitaria, Hordeum, Panicum miliaceum, Seta ria and Sorghum halepense.

When the compound from group (I) is used with diflufenican, the activity is particularly good for the following weed species: Portulaca oleracea, Polygonum convolvulus, Abut i lon theophrasti, Sesbania exaltata, Echinochloa crus-galli, Galium, Veronica, Stellaria, Ma trica ria, Anthemis, Chrysanthemum, Papaver rhoeas, Raphanus and Sinapis.

When the compound from group (I) is used with an imidazolinone, good control of the following is observed: Xanthium pennsylvanicum, Ipomea purpurea, Portulaca oleracea, Sesbania exaltata, Echinochloa crus-galli, Lolium multiflorum, Amaranthus, Chenopodium, Ambrosia, Hibiscus, Sida, Digitaria, Elusine, Setaria, Cyperus esculentus, Abutilon theophrasti and Polygonum.

When the compound from group (I) is used with a benzonitrile derivative, a good effect is achieved on: Ipomea purpurea, Portulaco oleracea, Polygonum convolvulus, Amaranthus, Chenopodium, Sola num, Ambrosia, Ma trica ria, Atriplex, Sinapis and Xanthium.

When the compound from group (I) is used with a thiadiazolyl urea, a good effect is achieved on the following weed species: Xanthium pennsylvanicum, Ipomea purpurea, Polygonum convolvulus, Abutilon theophrasti, Sesbania exaltata, Echinochloa crus-galli, Gallium, Sinapis, Stellaria, Chenopodium, Chrysanthemum, Setaria and Poa.

When the compound from group (I) is used with herbicides of the oxadiazole family, a particularly good control of the following weed species is observed: Xanthium pennsylvanicum, Polygonum convolvulus, Ipomea purpurea, Echinochloa crus-galli, Amaranthus, Sinapis, Capsella, Euphorbia, Portula ca, Agropyron , Agrostis, Rubus, Festuca, Dactylis, Galium and Polen-tilla.

When the compound from group (I) is used with a quaternary ammonium derivative, the effect is good for: Xanthium pennsylvanicum, Ipomea purpurea, Polygonum convolvulus, Alopecurus, Seta ria, Sinapis, Rapha nus, Chrysanthemum and Amaranthus.

When the compound from group (I) is used with a benzoic acid, such as dicamba, a good control of: Ipomea, Xanthium, Chenopodium, Plygonum, Amara nthus, Abutilon, Galium, Ma tricaria, Stellaria, Mercurialis, Veronica and Rumex is observed.

The compounds in accordance with the present invention have a broad activity spectrum, as the destroyed weeds can be annual or perennial plants, or with one or more cotyledons. In Table No. (III), some of the weeds that are important to destroy have been collected to enable plants such as corn, maize, rice, cotton, soy, beet (especially sugar beet), sunflower, colxa, sugarcane and legumes to be well established or undergoing good subsequent development, as well as achieving satisfactory removal of weeds from perennial plants (vines, fruit trees). It is sometimes possible to improve the effect of weed removal by carrying out subsequent treatments, possibly with treatment of the soil.

The following example illustrates the invention and shows how it can be used.

Example 55: Post-shoot herbicidal activity on plant species in greenhouses.

In pots of 9 x 9 x 9 cm filled with fine potting soil, sow a number of seeds determined in accordance with the plant species and the size of the seed.

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

After the soil is watered, the plants are allowed to germinate and grow to a height of approximately 5 to 10 cm. The time of treatment of grass species is the "second leaf formed" stage. The timing of dicot treatment is the "dicot's first true leaf development" stage.

The pots are then treated by spraying a quantity of the mixture per pot which corresponds to a volume of 500 l/ha, and which contains the active compound in the appropriate amount.

For each active compound, the mixture was prepared by diluting with a certain amount of water, to achieve the desired concentration, on the one hand a preparation of the soluble pellet containing 20% of active compound of compound no. 1, on the other hand one of the preparations of active compounds from group (II).

Depending on the concentration of active compound in the mixture, the amount of active compound used varies according to the different compounds, from 16 to 1000 g/ha.

The treated pots are then placed in vessels that can receive sprinkler water, using root irrigation that is maintained for 35 hours at room temperature and 70% relative humidity.

After 35 days, count the number of living plants in the pots treated with the mixture containing the active compound to be examined and the number of living plants in a control pot treated under the same conditions, but with a mixture containing no active compound. Percentage destruction of treated plants is thus determined in relation to the untreated control. A percentage destruction equal to 100% indicates that a complete destruction of the relevant plant species has been achieved, and 0% indicates that the number of living plants in the treated pot is equal to the number in the control pot.

The plant species that were examined are shown in table (III).

The results obtained in connection with example 55 are shown in table (V). The amounts of active compounds used in this example are generally relatively small, so that the results obtained, even in moderate form, are evidence of strong activity. Using larger amounts (especially double amounts) than those shown naturally leads to even better results. In many cases, combinations according to the invention will show a synergistic effect with respect to the active compounds if used alone.

Claims (11)

1. Herbicidal preparation containing a -a-kti-v compound of general formula J characterized by ^_t__c|fiJ-^ i ~~ i —■ — fi vtfrr R is a hydrocarbon radical, especially alkyl, aryl or cycloalkyl radicals1, as these radicals are optionally substituted, in particular with halogen atoms or phenyl, cyano, alkyl, carboxyl or alkylcarboxylated groups, - R is a hydrogen atom or R^, preferably an alkyl group with 1 to 4 carbon atoms, - R 2 and R <3> are a hydrogen atom or hydrolyzable groups 2 3 per OR and OR , especially alkyl or aryl groups, optionally substituted and in particular with substituents similar to those given for R"^ , or a tolerable salt thereof^ ' kombnlCAjJV ) —Ldefe—©-v-e-n-n-&v-rrt-e—fo r bTmtre-l-s-e-r— m-ed-g-errere-ii—f-e-r-me-1—K-)—teøms=_ b-ine-&e-s| -with|-m±n-s t\- a |a-k-t-i-v| compound selected from the group (II) comprising chloroacetamides, triazines, phenylurea, thiadiazolylurea, sulfonylurea, benzothiazolylurea, nitroanilines, phenoxynicotinanilides, amides, oxadiazoles, aminotriazole, picolinic acid, phenoxybenzoic acid derivatives, phenoxypropionic acid derivatives, aryloxy acids, benzoic acids, propionic acids , triazinones, carbamates, pyridaziones, pyridones, quaternary ammonium compounds, uracils, hydroxybenzonitriles and imidazolinones. 2. Herbicidal preparation as stated in claim 1, characterized in that R and R"*" are alkyl radicals with 1 to 4 carbon atoms and R 2 is a hydrogen atom. 3. Herbicidal preparation as specified in claim 1 or 2, characterized in that the compound from group (II) is selected from the group consisting of alachlor, metolachlor, simazine, atrazine, promethrin, diuron, isoproturon, linuron, tebuthiuron, ethidimuron, sulfometuron, chlorsulfuron, metsulfuron, metabenztiazuron, oryzalin, trifluralin, diflufenican, napropamide, propanil, oxadiazon, dimefuron, aminotriazole, picloram, bifenox, acifluorfen, Na- acifluorfen, fomesafen, oxyfluorfen, esters of acifluorfen and aliphatic alcohols or glycolates or lactates, quizalofob-ethyl, fluaziphob-butyl, 2,4-D, 2,4-DP, MCPA, MCPP, dicamba, dalapon, metribuzin, carbetamide, EPTC , asulam, norflurazon, fluridone, diquat, paraquat, bromacil, bromoxynil, ioxynil, imazaquin oq imazapur. 4. Herbicidal preparation as stated in claims 1 3, characterized in that the ratio between the compounds of general formula (I) and the compound(s) from group (II) is between 0.2 and 10, preferably between 0.25 and 4. 5. Herbicidal preparation as stated in claims 1-4, characterized in that the preparation contains active compounds in combination with at least one common inert carrier which is agriculturally tolerable. 6. Herbicidal preparation as stated in claim 5, characterized in that the preparation contains 0.05 to 95% of the active compound and 5 to 40% surfactant. 7. Herbicidal preparation as specified in claims 1-6, characterized in that the preparation is in the form of a soluble powder, powder that can be softened or dry powder. 8. Herbicidal preparation containing compounds in the form and conditions specified in claims 1-7, characterized in that the preparation is in compound form for herbicide application simultaneously, separately or over a period of time. 9. ' Procedure for weeding, characterized in that an effective amount of a preparation in accordance with claims 1-8 is brought into contact with the plant leaves to be removed. 10. Method as stated in claim 9, where a preparation as stated in claims 1-8 is used, characterized in that the active compounds are used in a ratio of 0.1 to 10 kg/ha, preferably 0.5 to 8 kg/ha. 11. Procedure for weed removal, characterized by which compounds, with formula (I) and compounds from group (II), in the form of quantities as stated in claims 1 to 10, which are used continuously and in different periods, as the compound or compounds from group (II) can be used directly on the soil. SUMMARY Herbicide preparations on the basis of the compound with general formula where R, R 1( r 2 and R 3 have different meanings, as these compounds are combined with compounds such as chloroacetamides, triazines, phenylurea, thiadiazolylurea, sulfonylurea, benzothiazolylurea, nitroanilines, phenoxynicotinanilides, amides, oxadiazoles, aminotriazoles, picolinic acid, phenoxybenzoic acid derivatives , phenoxypropionic acid derivatives, aryloxy acids, benzoic acids, propionic acids, triazinones, carbamates, pyridazinones, pyridones, quaternary ammonium compounds, uracils, hydroxybenzonitriles and imidazolinones. The preparation of the preparations is illustrated.