CA1272890A - Herbicidal mixtures based on a compound of the n- (phosphonomethylglycyl) sulphonylamine type - Google Patents

Abstract

ABSTRACT
HERBICIDAL MIXTURES BASED ON A COMPOUND OF THE
N-(PHOSPHONOMETHYLGLYCYL)SULPHONYLAMINE TYPE
A herbicidal composition comprising A) an active herbicidal substance of formula:
(I) in which:
R1 devotes an optionally substituted hydrocarbon radical:
R denotes a hydrogen atom or is as defined for R1;
R2 and R3, which may be identical or different, denote hydrogen atoms or are such that OR2 and OR3 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, quaternary ammonium compound, uracil, hydroxybenzonitrile or imidazolinone or a salt thereof is disclosed.

Description

. . . _ . _ . .
N-(PHOSPHONOMETHYLGLYCYL)SULPHONYLAMINE TYPE

The present invention relates to new herbicidal compositions containing herbicidal mixtures of one herbicide of the N-(phosphonomethylglycyl)sulphonylamine chemical family, as well as to the application of these herbicidal compositions in agriculture.
Many compounds are known which possess an aminomethylphosphonic group and have herbicidal properties, in particular in French Patents 2,129,327,

2,281,375, 2,251,569, 2,413,398 and ~,463,149, European Patents 53,811, 54,382 and 73,574, US Patents 3,160,632, 3s4S5,675, 3,868,407, 4,388,103 and 4,397,676, British Patent 2,090,596, World Patent WO 83/03608 and Belgian Patents 894~244, 894,245, 894,590, 894,591, 894,592, 894,5~3, 894,594 and 894,595.
It is, however, always desirable to broaden the field of available herbicidal compositions, in order to meet more fully all the needs of farmers. Some amides possessing an aminomethylphosphonic group are known, but these products are either o~ low activity or inactive.
It is also desirable to have herbicidal compositions which are strong and rapid in their activity, and which have good biodegradability.
An object of the present invention is to provide post-emergence herbicidal compositions possessing a :

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broad spectrum of activity, which have at least partially a descending systemic effect and are possibly selective for certain crops.
A further object of the invention is to provide herbicidal compositions which have persis~ence in the soil, in particular sufficient persistence to act against staggered sproutings (i.e. against weeds and o~her plants, the growth and development of which are spread out over a period of time).
It has now been found that the3e objects may be attained, in whole or in part, by means of the compositions according to the inventionO
The present invention provides herbicidal compositions comprising (A) an active substance of formula:
fR
CH2 NH C~2 - CO ~ 7 ~ S2 ~ R (I) OR R

in which:
Rl denotes an optionally substituted hydrocarbon cadical, in particular an alkyl, aryl or cycloalkyl 2- radical, each of which may be substituted; suitable substituents include halogen atoms and phenyl, cyano, alkyl, alkoxy, and alkyl carboxylate groups, in which the alkyl groups and moieties preferably have 1 to 4 carbon atoms; Rl generally has from 1 to 18 carbon .

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- 3 -atoms, preferably from 1 to 7 carbon atoms and rnore especially from 3 to 7 carbon atoms when i~ is a cycloalkyl group; it is most preferably an alkyl radical having from 1 to 4 carbon atoms, which may optionally be halogenated, in particular chlorinated or fluorinated, for example CF3, R denotes a hydrogen atom or has one of the ~eanings given for Rl, and is preferably an alkyl group having 1 to 4 carbon atoms, R2 and R3, which may be identical or different, denote a hydrogen atom or are such that oR2 and oR3 are hydrolysable groups; R2 and R3 can be, in particular, alkyl or aryl radicals, preferably alkyl or phenyl radicals, which are optionally substituted; suitable substituents are those specified in the definition of Rl; R2 and R3 generally have from 1 to 12 carbon atoms, and preferably have from 1 to 8 carbon atoms, or a salt thereof, in particular the salts of the P-OH
groups and those of the nitrogen atom of the NH group, ~ which then becomes an ammonium group, especially the agriculturally acceptable salts of these products, for example the salts with alkali metals, in particular sodium and potassium, alkaline earth metal salts, primary, secondary~ tertiary or quaternary ammonium salts and sulphonium salts, addition salts with acids, such as chlocides, sulphates, phosphates and other salts derived from acids having a p~ value of less than or ', ' ' ' ~ '` .' `' ' ' ~
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equal to 2.5; and B) at least one active substance which is a chloroacetamide (in particular alachlor or metolachlor), triazine (in particular simazine, atrazine or prometryne), phenylurea (in particular diuron, isoproturon or linuron), thiadiazolylurea (in particular tebuthiuron or ethidimuron)~
sulphonylurea (in particular sulfometuron, chlorsulfuron or metsulfuron), benzothiazolylurea (in particular methabenzthiazuron), nitroaniline (in particular oryzalin or trifluralin), phenoxynicotinanilide (in particular diflufenican), amide (in particular napropamide or propanil), oxadiazole (in particular oxadiazon or dimefuron), aminotriazole, picolinic acid (picloram), phenoxybenzoic acid derivative (in particular bifenox, acifluorfen, acifluorfen-sodium, fomesafen, oxyfluorfen or an ester of acifluorfen and an aliphatic alcohol, glycolate or lactate), 2~ phenoxypropionic derivative (in particular quizalofop-ethyl or ~luazifop~butyl), aryloxyacid (in particular 2,4-D, 2,4-DP, MCPA or MCPP), benzoic acid (in particular dicamba), propionic ~cid (in particular dalapon), triazinone (in particular metribu~in), carbamate (in particular carbetamide, EPTC or asulam), pyridazinone~(in particalar norflurazon), pyridone ~in particular '. . . -- : . -~%~72~

fluridone), quaternary ammonium compound (in particular diqua~ or paraquat), uracil (in particular bromacil), hydroxybenzonitrile (in particular bromoxynil or ioxynil) or imidazolinone (in particular imaza~uin or imazapur).
Among the compounds of formula (I), the preferred compounds are those in which R and Rl are each an alkyl group h~ving from 1 to 4 carbon atoms, and R2 and R3 are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or a phenyl group, as well as the salts of these compounds: R2 preferably represents hydrogen.
Among the compounds of the group B), the preferred compounds are, if good persistance is sought:

simazine, atrazine, prometryne, diuron, chlorsulfuron, oryzalin, napropamide, oxadiazon, dimefuron, picloram, fomesafen, bromacil and imazaquin.
The compounds of formula (I) can be prepared, for example, according to the procedure described in European Patent Application No. 135,454.

The compounds of the group B) include known compounds most of them being described in detail in works such as "The Pesticide Manual" published by "The British Crop Protection Council", the 7th edition of which dates from 1983. The chemical names of nost of the products of the group B) used in Tab~e (V) are given in Table (IV).

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The compositions according to the invention are generally of the binary type (a single compound of formula (I) and a single active substance of the group B~) but ternary combinations (eg two active substances of the group B)), quaternary combinations (eg three active substances of the group B)) or others can be used.
The ratio by weight of active substance of formula (I) relative to the active substance of the 1-0 group B) is generally from 0.2:1 to 10:1, and is preferably from G.25:1 to 4:1; this ratio can, however, be higher, e.g. 100:1, when active substances such as picloram and, in particular, sulphonylureas are used.
The Examples in this specification a~e given to illustrate how compositions according to the invention can be produced and employed; except where otherwise stated, the percentages are percentages by weight; the terms pre-sprouting and pre-emergence are synonymous~
The same applies to the terms post-sprouting and post-emergence.
In practice the compositions according to the invention usually contain a solid or liquid carrier which is agriculturally acceptable and/or a sucfactant which is also agriculturally acceptable. In particular, the usual inert supports and usual surfactants can be used.
~hese compositions can also contain other - ' .

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ingredients, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetrants, stabilizers and sequestering agents as well as other known active substances possessing pesticidal (in particular insecticidal, fungicidal or herbicidal) properties or possessing plant growth regulatory properties. More generally, the compounds used in the inven~ion can be combined with solid or liquid additives corresponding to the customary techniques of preparing formulations.
The proportions of active substances used in the compositions of the present invention can vary within wide limits according to the nature of the weeds to be eliminated and the degree of ineestation of the loci which have to be cleared of weeds.
lS In general, the compositions according to the invention usually contain 0.05 to 95~ of active substance [formula (I) and group B)], approximately 1%
to 95% of one or more solid or liquid carriers and optionally approximately 0.1 to 50~ of one or more sur~actants.
In the present disclosure, the term "carrier~
denotes an organic or inorganic natural or synthetic material with which the active substances are combined to facilitate their application on the plant, on seeds or on the soil. This carrier is hence generally inert and it must be agriculturally acceptable, in particular on the treated plant.

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As solid carriecs (or fillers), inorganic or synthetic fillers may be mentioned, e.g. kaolin, attapulgite, montmorillonite, bentonite, talc, ~uller's earth, diatomaceous earth, kieselguhr, calcium and S magnesium carbonates, precipitated synthetic silica, alumina, alkali metal silicates and silicoaluminates, resins, waxes and solid fertilizersO Water-soluble illers, e.g. sodium sulphate or ammonium sulphate and urea, can also be used.
As liquid carriers, there may be mentioned water, alcohols (in particular butanol), esters (in particular methylglycol acetate), ketones (in particular cyclohexanone and isophorone), petroleum fractions, aromatic hydrocarbons (in particular xylenes) or paraffin hydrocarbons, chlorinated aliphatic hydrocarbons (in particular trichloroethane) or chlorinated aromatic hydrocarbons (in particular chlorobenzenes), and water-soluble solvents such as dimethylformamide, dimethyl sulphoxide and 20 ~-methylpyrrolidone~
The surfactant-can be an emulsifying agent, dispersant or wetting agent of the ionic or nonionic type, or a mixture of such surfactants.
As nonionic wetting agents, there may be mentioned ethylene oxide-treated alkylphenols (in particular octyl-, nonyl- and tributylphenols having 6 to 18 oxyethylene units), ethylene oxide-treated fatty .
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alcohols (in particular C10 to C18 alcohols having 6 to 18 oxyethylene units), ethylene oxide-treated ~atty amines (in particular tallow amine or tall oil having from 2 to 40 oxyethylene units), and esters of ~atty acids and polyols (of the glycerine type or sugar type) which have been treated with ethylene oxide tin particular sorbitan laurate and stearate having 5 to 20 oxyethylene units)~
As wetting agents, there may be mentioned alkylnaphthalenesulphonate ester salts (in particular sodium or potassium isopropyl-, butyl- and dibutylnaphthalenesulphonates~, sulphate ester salts of ~atty alcohols (in particular sodium or potassium lauryl sulphate), sulphosuccinate ester salts of fatty alcohols (in particular sodium-or potassium dioctyl sulphosuccinate), and taurine derivatives (in particular alkyltaurates, aryl-N-methyltaurides and sodium oleylmethyltauride).
As nonionic dispersants, there may be mentioned ethylene oxide-treated arylphenols [in particular bis-and tris(phenylethyl) phenols containing 18 to 40 oxyethylene units].
As anionic dispersants, there may be mentioned sali~ied polycarboxylic polymers (such as sodium polycarboxylate and polyacrylate polymers), polycondensates of formaldehyde and diphenolsulphonates or alkylnaphthalenesulph~onates (in particular sodium .

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methylnaphthalenesulphonate) 7 phosphoric acid ester salts or acid esters of ethylene oxide-treatPd alkyl- or arylphenols [in particular phosphoric esters of nonylphenols having 6 to 18 oxyethylene units, in acid form or potassium salt form, as well as phosphoric esters of bis- or tris(phenylethyl)phenol having 18 to 40 oxyethylene uni~s, in acid or salt form], phosphated ethylene oxide-treated fatty alcohols (in particular C
to Clg fatty alcohols having 6 to 18 oxyethylene units), and alkali metal or alkaline earth metal lignosulphonates.
The compositions according to the invention, especially when they are in the form of dry flowables, can also contain a natural or synthetic binder preferably in a proportion of 1 to 50~ by weight relative to the weight of the total compostion.
As a natural binder, there may be mentioned starch and its derivatives (in particular modified .
starch and dextrin), cellulose derivatives (in particular carboxymethylcellulose, hydroxyethylcellulose and hydroxypropylmethylcellulose), sugars (e.g. lactose, mannitol and sorbitol) and gums (e.g. gum arabic and xanthan gums).
As a synthetic binder, there may be mentioned pol~mers (in particular polyvinyl alcohol, polyvinyl acetate, polyvinylpyrrolidone and alkali metal polyacrylates), polycondensates (especially polyethers .
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such as polyglycols; copolycondensates of maleic anhydride; polycondensates of formaldehyde and alkylnaphthalenesulphonates (e.g. the polycondensate of formaldehyde and sodium metnylnaphthalenesulphonate) and alkali metal lignosulphonates.
The presence of at least one surfactant in the compositions according to the invention is generally essential when the active substances and/or inert carrier are not soluble in water and when the vector agent for the application is water.
For their application, the compositions according to the invention may be in solid or liquid form; tbese forms are relatively dilute. The compositions which are suitable for transportation, mark`eting and storage, are, on the whole, concentrated compositions.
As solid forms of compositions, there may be mentioned wettable powders and powders for dusting (with a content of active substances which can range up to 100~) and pellets (preferably dry flowables) in particular those obtained by extrusion, by compaction, by impregnation of a granulated carrier and by granulation starting from a powder, the content of active substances of formula (I) and group B) in these ~5 pellets preferably being between 0.5 and 80~ for these latter cases.
As liquid forms of compositions, or forms .

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intended to make liquid compositions at the time of use, there may be mentioned solutions and flowables, or altecnatively pastes. Concentrated compo~itions in the solid state are preferred.
The flowables, which can be applied by spraying, are prepared so as to obtain a stable fluid product which does not settle (fine grinding) and they usually contain from 10 to 75% of active substances, from 0.5 to 15~ of surfactants, from 0.1 to 10% of thixotropic agents, from 0 to 10% of suitable additives, e.~
antifoams, corrosion inhibitors, stabilizers, penetrants and adhesives, and, as a carrier, water or an organic liquid in which the active substances are of low solubility or insoluble: certain organic solid substances or inorganic salts can be dissolved in the carrier to assist in preventing sedimentation, or as anti~reeze for the water.
~y way of example, a flowable composition is as follows`(Example lj:
~0 - active substances 500 g - polycondensate of ethylene oxide with --tristyrylphenol phosphate 50 g - polycondensate of ethylene oxide with alkylphenol ~ 50 g 25 - sodium polycarboxylate 20 g - ethylene glycol ~antifreeze) 50 g - organopolysiloxane oil (antiEoam) 1 g .

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~ 13 -- polysaccharide (thickener) 1.5 g - water316.5 g According to this Example 1, compositions can be produced with, in particular, the following products:
Products of formula (I):
Compound No. 1: compound of formula (I) in which R and Rl are both methyl groups and R2 and R3 are both hydrogen atoms;
Compound No. 2: compound oE formula (I) in which R and Rl are both methyl groups, R2 is.a hydrogen atom and R3 is a phenyl group;
Compound No. 3: compound of formula (I) in which R and Rl are both methyl groups and R2 and R3 are both phenyl groups.
~roducts of group (B): simazine, atrazine, prometryne, diuron, isoproturon, linuron, metabenzthiazuron~
oryzalin, trifluralin, diflufenican, napropamide, propanil, oxadiazon, aminotriazole, picloram, bifenox, aeifluorfen-sodium, quizalofop-ethyl, 2,4-D~ MCPA, MCPP, ~0 carbetamide, asulam, bromoxynil, ioxynil.
~ Accordiny to Example 1, Examples 2 to 10 are produced as de~ined in the following Table (I):

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TABLE (I) Example Amount iQ grams Nature and amount ln of one of the com- grams of compounds pounds Nos. 1 to 3 of the group B) 2 (No. l) 300 Atrazine 200 3 (No. 2) 250 Oryzalin 250

4 ~No. l) 450 Diflufenican 50 S (No. 2) 350 Oxadiazon 150 6 (No. 2) 250 Aminotriazole 250 7 (No. 3) 300 Bifenox 200 8 (No. l) 350 Acifluorfen Na150 9 (No. 3) 250 Asulam 25 (No. 1) 350 Bromoxynil 150 Wettable powders~(or powders for spraying) and dry flowables are the preferred compositions according lS to the invention. The wettabls powders usually contain 20 to 95% of active substances and they usually contain, in addition to the solid carrier, from 0 to 25% of a wetting agent, from 1 to 15~ o~ a dispersant andj when necessary, from 0 to 10~ of one or more stabilisers and/or other additives e.g. penetrants, adhesives, anti-caking agents and colorants.
By way of example, vacious wettable powder compositions are as follows:
Example 11: -25 - active substances 50%
- calcium lignosulphonate (deflocculant) 5~

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-- 15 -- , - isopropylnaphthalenesulphonate (anionic wetting agent) 1%
- anti-caking silica 5%
- kaolin (filler) 39 Example 12:
- active substances 80 - sodium alkylnaphthalene~ulphona~e 2 - sodium lignosulphonate 2~
- anti-caking silica 3%
10 _ kaolin 13%
Example 13:
- active substances -50%
- sodium alkylnaphthalenesulphonate 2~
- methylcellulose of low viscosity 2%
15 _ diatomaceous earth 46%
Example 14: .
- active substances 90%
- sodium dioctyl sulphosuccinate 0.2 - synthetic Silica 9.8 20 Example 15:
- active substances . 400 g - sodium lignosulphonate 50 g - sodium dibutylnaphthaIenesulphonate 10 g - silica 540 g 25 Example 16:
- active substances 250 g - isooctylphenoxy(polyoxyethylene)ethanol 25 g -' ,.' .' ' ,: ' ' ~' ' . . . :'~ . ' .' ~L27~

_ 16 _ - mixture of equal parts by weighe of ~hiting and hydroxyethylcellulose 17 9 - sodium aluminosilicate 543 9 - kieselguhr 165 9 Example t7:
- active substances 100 9 - mixture of sodium salts of saturated fatty acid sulphates 30 9 - condensation product of naphthalene-sulphonic acid and formaldehyde50 9 - kaolin 820 9 Example t8:
- active s-ubstances - 40%
- sodium ;sopropylnaphthalenesulphonate 2%
15 - sodium lignosulphonate 5~
- precipi~ated silica 10X
- kaolin q.s. 100 Example 19:
- aceive substances 40~
2~ - sodium lauryl sulphate 4Z
- tris(phenylethyl)phenol conta;ning 40 oxy-ethylene units 6X
- precipitated silica t5~
- attapulgite Q.s. t00%
25 Example 20:
- active substances 40 - tallo~ amine containing 25 oxyethylene un;ts tO%

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^ C13 alcohol conta;ning 6 oxyethylene un;ts 5~
- precip;tated silica 15%
- attapulg;te q.s. 100%
Example 21:
.

5 - act;ve substances 50~
- sod;um oleylmethyltauride 2%
- sodium methylnaphehalenesulphonate poLy-condensed ~ith formaldehyde 4 - diatomaceous earth 20~
10 - kieselguhr ~.s. 100%
Example 2 :
. . ~. _ .
- active substances 50%
- nonylphenol containing 18 oxyethylene units 2 - nonylphenol phosphate containing 10 oxy-ethylene units 4X
- precip;tated silica 10Z
- montmorillonite q.s. 100 Example 23:
- active substances 60%
20 - sodium d;oc.tyl sulphosuccinate 2~o - polycondensed sodium methylnaphlenesulphonate 3Z
- sodium s;licoaluminate 15%
- kaol;n q.s. 100%
Example 24:
25 - active substances 60%
- sorbitan stearate ~stearate of dehydrated sorbitol) containing 25 oxyethylene un;ts 5 .
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- phosphated tris(phe-nylethyl)phenoL containing 1B oxyethylene units 3Z
- precipitated siLica 10%
- kieselguhr q.s. 100 Example 25:
- active substances 60Z
- sodium oleylmethyltauride 2X
- phosphated tris(phenylethyl)phenol containing 18 oxyethylene units . 3,~
10 - silica 15%
- kaolin q.s. 100%
Example 26:
- active substances 80%
- sodium ;sopropylnaphthalenesulphonate 2X
- condensed sodium methyln3phthalenesulphonate 3%
- synthetic silica : 15~
- kaolin q.s. 100X
Example 27:
- active substances 80X
~O - sodium lauryl sulphate 3 - sodium polycarboxylate 3~O
- sodium silicoaluminate q.sO 100~
In these Examples 11 to 27, one of the compounds used as an active substance is compound No.
1, 2 or 3 and the other is sima2ine, atrazine, prometryne, diuron, isoproturon, l;nuron, metabenthiazuron, trifluralin, diflufenican, napropamirJe, oxadiazon, dimefuron, bifenox, quizalofop-ethy1, `, ..- : ,' ' , . : .', .. , . - .
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dalapon~ carbet amide or another active substance mentioned in Table (IV).
Examples 30 to 41 are de~ined in Table (II). The mix-S tures given in Table (V) can also be uséd.
TA3LE ~II) Ex- Composition Amount in grams Nature and amount in ample derived from tor percentage) of grams (or percentage) Ex3mples 11 one of the compounds of compound of the to 17 1 to 3 group B) _ _ _ _ __ 11 (No 1) 30X Atraz;ne 20X - .
. _ . .
3t 12 (No. 2) SOX Diuron 30X
32 1~ _ (No. 3) _ 30% Simazine 20%
33 14 tNo. 3~ 60Y Dimefuron 30%
15 34 11 (No. 2) 25X Isoproturon 25%
. . . _ _ _ _ _ 16 (No. 3) 1SO ~ifenox 100 9 , . . , 9_ 36_ 5 _ (No. 1)200 9 _ Napropamide 200 y 3712 (No. 1) 55X Oxadiazon 25%
3817 (No. 2)85 9 Quizalofop-15 9 _ . . ethyl 20 391~ (No. 2) 20X Carbetamide 30%
4015 (No. 3)300 9 DifLufenican 100 9 4114 (No. 1) 30y Dalapon 60%
To obtain po~ders for spraying or wetta~le pow- -ders, the active substa.nces are intimately mixed in suit-able blenders with the additional subs~ances, or the porous filler is impregnated ~ith the molten active ... ~ . ............................ . . .

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substances and ground with suitable mills or q~her grinders.
Po4ders for spraying which have advantageous wettability and suspendibility are thereby obta;ned; they can be sus-pended ;n water at any desired concentration and this sus-S pension can be very advantageously used, especially forapplication on plant leaves.
The "dry flowables" (more precisely~ these are pellets ~hich can be easily dispersed in water) are sub-stantially similar in their composition to the wettable powders. They can be prepared by granulation of formula-tions described for the wettable powders, either by a wet method ~br;nging the finely divided active substances into contact ~ith the inert filler and wi~h a little ~ater, e.g.
1 to 20X, or a little of an aqueous solution of- dispersant or binder (described above), followed by drying and siev-;ng~ or by a dry method tcompaction followed by grinding and sieving~.
8y ~ay of example, a few dry flowable formulat;ons are as follows:
2û ExamPle 50:
~ .
- active substances 800 9 - sodium alkylnaphthalenesulphonate20 9 - sodium methylenebistnaphthalene)sulphonate 80 9 - kaolin 100 9 Example 51:

- active substances 40~

- tallow amine containlng 25 oxyethylene units 10g .

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_ 21 -- precipitated synthetic s;l;ca 10 9 - polyvinylpyrrolidone 5%
- bentonite q.s. 100 E~ample 52:
5 - active substances ~OX
- C13 alcohol containing 6 oxyethylene units 5 - precipitated synthetic silica 5 - ammonium sulphate 20 - hydroxyethylcellulose 2%
10 - starch ~.s. 100%
- Example 53:
- active substances 40%
- nonyLphenol containing 10 oxyethylene units 2Z
- calcium lignosulphonate 10 15 - polyvinylpyrrolidone 5Z
- kaol;n q.s. 100~
The exact examples of active substances and special proport;ons to be produced according to these Examples 50 to 53 are similar to those for the mixtures of active sub-stances in Tables (Il) and (V).
In plare of the ~ettable powders, pastes can be produced. The condi~ions and procedures for the produc-tion and use of these pastes are similar to those for the wettable powders or powders for spraying.
?5 The aqueous ~ispersions and emulsions, e.g. the composit;ons obtained by diluting ~ith - water a wettable powder or a flowable according to the . .

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invention, are included within the general scOQe of the compositions which can be used in the presen~ invention.
The emulsions can be of the water-in-oil or oil-in-water type and they can have a ~hick consistency like that of a "mayonnaise n .
All these dispersions, aqueous emulsions or mixtures can be applied ~o the areas or crops to be cleared of weeds by any suitable means, mainly by sprayins, at doses which are generally of the order of 50 to 1,200 litres of mixture per hectare, and preferably from 80 to ~50 l/ha.
According to one method according to the invention the compounds of formula (I) and the group B) are applied to the areas to be cleared of weeds in a single application; mixing of the two active substances can be carried out beforehand with dilution of the concentrate with water at the time of use, or extemæoraneously by mixing two active substances or concentrates of active substances directly in the water which is to serve for the application.
According to another method of the invention, the compound of formula (I) and the compound of the group B) are applied sequentially: and the latter compounds can then optionally be applied on the soil.
25 Thus, the invention also provides a two component pack comprising a first component which comprises a herbicidally active substance of formula (I) as , ..
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hereinbefore defined and a second component which comprises at least one herbicidally active substance of group B) as hereinbeeore defined which can be applied simultaneously or separately. When sequential treatments are performed, the application intervals between the two treatments is advantageously from 1 to 3 weeks, and the compound of group B) can sometimes be applied first.
Thus to apply compounds of group ~) which possess pre-sprouting activity, it is possible to use, in the invention, pellets which are intended to be placed on the ground.
The present invention also provides a method of combating weeds at a locus which comprises applying thereto an effective amount of a composition according to the invention.
The compositions according to the invention are conveniently applied on vegetation, and in particular on the weeds to be eliminated when the latter possess a green foliage~
The herbicidal compositions and the application thereof can also be employed shortly before harvesting, so as to kill the weeds,~ the roots of which persist in the soil after harvesting. It is thereby possible to sow very guickly after harvesting without the need to perform mechanical weed clearing operations (eg tilling).
In general, the compound of formula ~I) is ' ' ::

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applied at doses o 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 levels of application for the other active substances are given below.

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. .

_ 25 -Thus, ~hen a triazine, e.g~ atraz;ne, is used, it is preferably applied at between 0.125 and 4 kg/ha, the weight ratio of the compound sf formula (I) to the tri-azine advantageously being between 1:32 and 32:1~ prefer-ably bet~een 1:16 and 8:1.
~ hen a herbicide of the phenylurea family. e.g.isoproturon, is used, it is preferably applied at doses of between 0.125 and 2 kg/ha, ehe ~eight ratio of the com-pound of ~ormula (I) to the phenylurea advantageously being bet~een 1:16 and 32:1, especially between 1:12 and 8 : 1' .
~ hen a herbicide of the phenoxybenzoic acid family, e.g. bifenox, is used~ it is generally applied at bet~een 0.125 and 4 kg/ha, preferably between 0.25 and 2 kg/ha, the weight ratio of.the compound of formula (I) to the phenoxybenzoic acid~derivative being bet~een 1:32 and 32:1, more especially between 1:1~ and 8:1.
When, in this same family, aeifluorfen and/or aci-fluorfen-sodium ;s used, it ;s preferably applied at betwee~ 0.06 kg and 1 kg/ha, the ~eight ratio of the com-pound o~ formula tI) to the acifluorfeh (sodium) most frequenely be;ng bet~een 1:8 and 60:1, preferably bet~een 1:4 and 32:1.
When a uracil of the bromac;l type is used, the latter is applied ae doses of between 0.125 and 10 kg/ha, and more espec;ally betaeen 0.125 and 3 kg/ha, the ~eight rat;o of the compound of ~ormula (I) to the uracil .

.
. ~

- - :, : . .
- - ~
- , :
- .

9 ~27;2 ~

advantageously being between 1:80 and 32 1, preferably bet~een 1:24 and 16:1.
If a phenoxy acid derivative, e.g. 2,$-D, is used, it is preferably applied a~ doses of between 0.1 and 5 kg/ha S and more espec;ally between 0.1 and 2 kg/ha. The we;ght `ratio of the compound of ~ormula (1) to the phenoxy acid derivative is then advantageously between 1:40 and 40:1, preferably bet~een 1:16 and 20:1. The phenoxy ac;d is advantageously used in the form of one of its alkal; metal salts, and more espec;ally in the form of an amine salt or in ester form.
If a carbamate, for example asulam, ;s used, it is generally applied at doses of be~een 0.25 and 7 kg/ha, and more especially between 0.25 and 4 kg/ha, the weight rati`o of the compound of formula (I) to the carbamate generally being between 1:56 and 16:1, and more espeeially between 1:32 and 8:1. The asulam is preferably in the form of an alkali metal salt, especially the sodium salt.
~hen an aminotriazo~e is used, it is preferably applied at between 0.5 and 4 kg/ha, the weight ratio of the compound of formula (I) ~o the aminotri-azole generally being between 1:96 and 8:1, preferably between 1:3Z and 4:i.
If propanil is used, it is preferably applied at between û.25 and 6 kg/ha, the weight ratio of the compound of the form~l~l) to propanil 3dvant~geously being betueen 1:48 and 16:1, and preferably bet~een 1:48 and 4:1.

~, ., . ., :

8~

- 27 _ When quizalo~op-ethyl is used, it is preferably applied at between 0.016 and 1 kg/ha, and more especially between 0.03 and 0.5 kg/ha, the weight ratio of the compound of formula (I) to the quizalofop-ethyl S then generally being between 1:8 and 250:1, and more advantageo~sly between 1:4 and 60:1.
If a nicotinamide, e.g. diflufenican, is used, it is generally applied at doses of between 0.1 and 2 kg/ha, the weight ratio of the compound o formula (I) to diflufenican then generally being between 1:16 and 40:1, preferably between 1:6 and 20:1.
If an imidazolinone herbicide i5 used, eg imazapur or imazaquin, the dose is preferably between 0.016 and 0.5 kg/ha, and the weight ratio of the compound of formula (I) to the imidazolinone herbicide `is most frequently between 1:4 and 250:1, more especially between 1:4 and 80:1. Imazapur is advantageously used in the form of it~ amine salts, especially an isopropylamine salt.
When a benzonitrile type herbicide, e.g.
bromoxynil is used, it i~ preferably applied at from 0.06 kg to 1 kg/ha. The weight ratio of the compound of formula (I~ to the benzonitrile derivative is advantageously between 1:8 and 60:1, preferably between 1:5 and 32:1. The bromoxynil can be in the form of alkali metal salts or advantageously in the form of esters (eg the octanoate). Ioxynil can be used in place :

. ". " "' ~ ' : .
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~ 28 of bromoxynil.
Thiadiazolylureas, e.g. ethidimuron, can also be used. They are preferably applied at between 0.125 and 7 kg/ha and more especially between 0.25 and 2 kg/ha.
5 The weight ratio of the compound of formula (I) to the thiadiazolylurea is most frequently between 1-56 and 32:1, especially between 1:16 and 8:10 Among the products of the oxadiazole chemical familyr oxadiazon is preferably used. It is applied at 10 doses of between 0.25 and 4 kg/ha, especially between 0.25 and 2.5 kg/ha. The weight ratio of the compound of formula (I) to the derivative possessing an oxadiazole group is generally between 1:32 and 16:1, preferably between 1:20 and &:1.
In the same chemical family, dimefuron can also - be used, and this is preferably applied at between 0.25 and 2 kg/ha, the weight ratio of the compound of formula (I) to the oxadiazole then being 1:8 and 16:1, in particular between 1:8 and 8:1.
When a benzoic acid, e.g. dicamba, is used, it is preferably applied at doses of between 0.05 and 5 kg/ha, pre~erably between 0.05 and 0.3 kg/ha, the weight ratio of the compound of formula (I) to the benzoic acid derivative lin particular dicamba) then advantageously being between 1:40 and 80:1, preferably between 1:3 and 20:1.
Qua~ternary ammoniom compounds are also used.

:

127~

Thus pacaquat is preferably applied at between 0.125 and 2 kg/ha. The weight ratio of the compound of formula (I) to paraquat is generally between 1:16 and 32:1, more es~ecially between ` ` `

, - . , ' .

7~9~

_ 30 _ 1:8 and 16:1.
~ hen the compound of formula (I) ;s used w;th a tr;a2ine, espec;ally good control of the follow;ng weeds ;s observed: Xan~hium pennsylvanicum, Ipomea purpurea, . ~
Polygonum convolvulus, Ech;nochloa crus-gall;, Chenopodium, Amaranehus, SinaPis, Capsella and Poa.
~ hen ~he compound of ~ormula- (I) is used uith a phenylurea, the activity ;s espec;ally good on ~he fol-lowing weeds: Abutilon theophrasti, Sesbania exaltata, .
Xanthium Pennsylvanicum, Polygonum convolvulus~ Ipomea . . , . ~
purpurea, Echinochloa crus-gall;, Al~pecurus~ Apera, Poa.

Atriplex, Sinapis, Chenopod;um, Chrysanthemum, Matriraria, _anonculus and Stellaria.

~hen the compound of formu~a (I) ;s used with phenoxybenzoic ac;d derivatives, good control of the fol-lowing weeds is observed: Xanthium pennsylvan;cum, Ipomea _ purpurea, Sesbania exaltata, Abut;lon theophrasti, Poly-.... .
gonum convolvulus, Amaranthus, Chenopodium, Sinapis Datura, Solanum, Setaria, Euphorbia, B;dens and Galinsog~

. .
2û ~hen the compound of ; formu1a ~I) is used ~i~h a uraci~, Xanthium pennsylvanicum, Ipomea purpurea, Ech;nochloa crus-galli, Lolium multiflorum, Setaria, .
Digitaria, Promus, Ambros~;a, Amaranthus, Agropyron, Cynodon, taraxacum and ~ are especially well controlled.
~hen the compound of ~ormula (I) is used with the phenoxy acid der;vative, good control of the follo~ing is observed: Portulaca oleracea, Polygonum convolvulus, -.. , - : :
- ': - , ' ~ ' .
- . . ~ , ~7~

Abutilon theophrasti, Xanthium pennsylvanicum, Chenopodium, Sinapis, Solanum, Ramunculus, Amaranthus, Cirsium and Ipomea.
~ hen the compound of ~ormula (I) is used with S a carbamate such as asulam, Xanth;um pennsylvanicum, Abutilon theophrasti and Sesbania exaltata, Sorghum hale-pense, Pteridium, Aquilinicum, Eleusine, Panicum, Digi-taria, Seearia, Rumex and Equisetum are espec;ally well controlled.
When the compound of formula tI) is used with a~inotriazole, good control of Portulaca oleracea, Abutilon theophrasti, Agropyron, Cynodon, Agrost;s, Artemis;a, Aris~ -toloch;a, Rumex, Oxalis, Rubus, Equisetum, Lepidium and . .
Tussilago is noted.
-~hen the compound of ~ormula tI) is used with amides such as propan;l, the efficacy is good on Ipomea purpurea, Polygonum convolvulus and Abutilon theophrasti.
~ hen the compound of formu1a ~I) is used withphenoxypropionic derivatives such as quizalofop-ethyl, good control of Lolium multiflorum and Echinochloa crus-galli as well as,Sesbania exaltata, Alopecurus, Digitaria Hordeum, Panicum miliaceum, Setaria and Sorghum halepense is observed.
When the compound of ~ormu1a ~I) is used with diflufenican, ~he activity beeomes especially good on the following weeds: Portulaca oleracea, Polygonum convol-, ~ vulus, Abutilon theoPhrast;, Sesbania exaltata, Echinochloa - . ' - ,, . ~ .:
, - ~:
, ' ,.
..

~72~

crus-galli, Galium, Veronica, Stellaria, Matricaria, .
Anthemis, Chrysanthemum, Papaver rhoeas, Raphanus and Sinapis.
When the compound of formuLa (I) is used with S an imidazol;none~ good control of the following is observed:
Xanthium pennsylvanicum-, Ipomea purpurea, Portulaca oleracea, Sesbania exaltata, Echinochloa crus-galli, Lolium mult;florum, Amaranthus, Chenopodium, Ambrosia, Hib;scus~

_ _ Sida, Digitar;a, Eleus;ne, Setaria, Cyperus esculentus, _ _ Abut;lon theophrasti and Polygonum.
-bhen the compound of formula (I) is used w;tha benzonitrile derivative, the efficacy is good on Ipomea purpurea, Portulaca oleracea, Polygonum convolvulus, Amaranthus, Chenopodium, Solanum, Ambrosia, Matricaria, 15 Atriplex, Sinapis and Xanthium~

.
~ hen the compound of ~ormula (I) is used w;th a thiadiazolylurea, the efficacy is good on the follo~ing weeds: Xanth;um pennsylvan;cum, Ipomea purpurea, Polygonum convolvulus, Abutilon theoPhrasti, Sesban;a exaltata, 20 chinochloa crus-galli~ Gall;um, Sinapis, SteLlaria, Cheno-podium,~Chrysanthemum, Setaria and Poa.
~ hen the compound of formula (I) is used w;th herbicides of the oxadiazole fam;ly, especially good con-trol of the follow;ng ~eeds is observed: Yanthium pennsyl-25 van;cum, Polygonum convolvulus, Ipomea purpur~ea, Echinochloa crus-galli, Amaranthus, S;nap;s, Capsella, Euphorbia, Portulaca, Agropyron, Agrost;s, Rubus, Festuca, Dactyl;s, ': -' ` .' :
, . :
, :- . :' , ' ~ ' - . :, . .

~2~7Z~

Galium and Polentilla .
When the compound of ~ormula (I) is used with a quaternary ammonium derivative, the efficacy is good on Xanthium penns~lvanicum, Ipomea purpurea, Polygonum 5 convolvulus~ Alopecurus, Setaria, Sinapis, Raphanus, Chrysanthemum and Amaranthus.
` When ~he compound of formula (I) is used with a benzoic acid such as dicamba, good control of Ipomea, Xanthium, Chenopodium, Polygonum, Amaranthus, Abutilon, -Galium, ~atricaria, Stellaria, Mercurialis, Veronica and umex is observed.
The compositions according to the invention can have a very broad spectrum of activity~ the weeds destroyed being annual or perennial, monocotyledonous or lS dicotyledonous. In Table (III), there are mentioned some of the weeds which it is important to destroy to enable crops such as cereals, maize, rice, cotton, soya, beetroot (in particular sugar beet), sunflower, colza, sugarcane and leguminous crops to become well 20 ` established or undergo good subsequent development, as well as to obtain satisfactory clearing of weeds rom perennial crops (vines, orchards). It is sometimes possible to improve the efficacy of weed clearing by carrylng out sequential treatments, optionally involving a soil treatment The example which follows illustrates the invention and shows how it can be employed~

.
- : .

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.
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- 3~-Example 55: Post-sDrouting_herbicidal activity on Dlant species in the qreenhouse.
In pots 9 x 9 x 9 cm fiLled ~;th light agricultu-ral soil, a number of seeds are so~n which i~ determ;ned according to the plant species and the size of the seed.
` The seeds are then covered ~ith a layer of soil approximately 3 mm thick.
AftPr the soil is moistened, the plants are allowed to sprout and gro~ to a he;ght of approximately 5 to 10 cmO
The stage of treatment for grasses is the "second leaf forming'i stage. The seage of treatment for dicotyle-dons ;s the "cotyledons spread, first true leaf develo-ping" stage.
The pots are then treated by SPraying an amount of mixture per pot corresponding to a voLume of 500 l/ha and containing the active substance at the dose in question.
For each active substance, the mixture ~as pre-pared by diluting ~ith a specified amount of ~ater, so as to obtain the desired concentration, on the one hand a formulation of the d;spersible pellet type containing 20 of active substance of the c~mp~und No. 1, and on the other hand one of the formulations of active substances of the group B) .
Depending on the concentration of active substance 25 in the mixture, the dose of active substance appLied -varies according to the products, from 16 to 1000 g/ha.
The treated pots are th~n placed in troughs . .......... . . . . .

.

des;gned to receive irrigation ~ater, subirrigation being employed, and maintained for 35 hours at room temperature and at 70Z relative humidity.
After 35 days, a count is made of the number of S living plants in the pots treated with the mixture con-taining the active substance to be tested and the number of living plants in a control pot treated according to the same condit;ons but with a mixture not containing any active substance. The percentage destruction of treated plants is thereby determined relative to the untreated control. A percentage destruction equal to 100% indicates that there has been comPlete destruction of the plant species in question, and a percentage of OX indicates that the number of ~living plants in the treated pot is identi-cal to that in the control pot.
The plant species on which the tests were per-formed are indicated in Table (III) by the abbreviation adjacent to the latin name.
The results obtained according to this Example 55 are sho~n in Table (V). The doses of active substances employed in this example are generally relatively lo~, so that the result; obtained, even ~hen modest, are fre-~uently evidence of strong potential activity. The use of hiqher doses (in particular double doses) than those sho~n naturally leads to still ~etter results. In many cases, the combinations according to the invention sho~ a syner-gistic effect ~ith respect to the active substances taken , ~ ~ , , ' :' '. . ~

39~

in isolation.
TABLE (II~

I American name I Latin name I pigweed I amaranthus retrofLexùs I
_I
r velvet leaf ~ la~utilûn theopnrasti(A~a~) - T si~ sp~inosa . I ses~ania ` cocklebur ~ I xanthium pennsylvanicum l (XAN) ~ I Di~ions .1 , . I ~, , _ 1 I convolvulus arvensls I ChiCkweea I stellaria me5ia -I corn marigola l cnrysanthemum segetum I crabgrass -T ~igitaria sanguinaIis I Qiant foxtail I setaria faDer ~1 Iblac~ nlgntsha~el solanum nisrum r - I cjperus esculentus lbarnyard grass I ~chinochloa crus-galli I
r wild oat I avena fatua T rya grass~~ I Iolium multiflorum~
¦ b1ack grass raIopecurus myosuro~es I quack grass I agropyron repens ¦ bermuda grass ¦ cyno~on dactylon ;~

I wil~ m.~rS arvensis --- ~ , . . .

' , ' ~272~

_ 37 -¦ bindweed ¦ calys~egia sepium I blackberry I rubus fructicosus I purslane I por~ulaca oleracea (POR)¦
wild buckwheat I polygonum convolvulus ! _ ! (PoL)I
I hemp sesbania I ses~ania exaltata ~5~S) I

: ~ :

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. ~ . , ~. i. ' " . ~
. .
- , , . ~ , . .

.. . . .

~7za~0 T A B L E ( I V ) .
Common names . Chem;cal name (standard IUP~
nomenclature) Atra2;ne 2-chloro-4-ethylam;no-6-;sopropyl-amino-1,3~5-triazine Isoproturon 3-(4'-isopropylphenyl)-1,1-dimethyl-urea Bifenox methyl 5-(2',4'-dichlorophenoxy)-2-n;trobenzoate 10 Bromacil 5-bromo-3-sec-butyl-6-methyluracil 2,4-D ammon;um (2,4-dichlorophenoxy)acetate Asulam methyl 4-aminobenzenesulphonyl-carbamate (sodium salt) Am;notriazole 3-amino-1H-1,2,4-triazole 15 Propanil N-(3-,4-dichlorophenyl)propionamide Qui2alofop-ethyl ethyl 2-~4-(6-chloro-2-qu;noxalinyloxy)-phenyloxy~prop;onate Diflufenican N-(2,~-difluorophenyl)-2-~3-tr;-fluoromethylphenoxy)nicotinamide 2û Ima~ap~r isopropylammonium 2-~4,5-d;hydro-4-methyl-4-(;sopropyl)-5-oxo-1H-;m;dazol-2-yl]-3-pyridinecarboxylate Acifluorfen-sodium sodium 5-~2'-chloro-4'-(trifluoro-methyl)phenoxy]-2-nitrobenzoate 25 3romoxynil 3,5-dibromo-4-hydroxybenzon;trile octanoate ' ~
' ~ 39 ~ ~ 2 ~9 ~

Ethidimuron 1-(5-ethylsulphonyl-1,3,5-thiadiazol-2-yl)-1,3-dimethylurea Oxadiazon 5-ter~-butyl-3-(2',4'-dichloro-5'-isopropyloxyphenyl)~1,3,4-oxadi~
azolin~2-one Para~uat 1,1'-dimethyl-4,4'-bipyridinium chlor;de ` Dimefuron 3-C2-chloro-4-t3,3-dimethylure;do)-phenyl~-5-(1,1-dimethylethyl)-3H-1,3,4-oxadiazol-2-one D;camba dimethylammonium 3,6-dichloro-2-methoxybenzoate .

, ,, : : ; :
-- . ,~ . . , , ~ . , .
,~ . . :
.. , ,, : . ~-" , : ' ;: :' ~L27~
-- ~o TA~LE ( V ) I CompouB) I ~ d rXAN I 1~0 I PO~ I POL ¦
I nab~ ~ dose in ~/ha~
I _~1 latrazine 1 50a 1 L2S Ts~~~l-loo I loo I ~loo ~ 1 _~
1 isopro- I 500~~5 1 90 1 50 I Loo 1 20 I turon 5~1~g~ I ~90r9~ o~60- 1 2G 1~7~--~ I
. I bi~nox I ~ T~ I

1~7T_~ I
I ~romacil ~ I
- ~o I ~_r~rl 1~1 2~4-0 ~5 1 l l l l I , I triazol~
propanil ~ = rl l~ ~oo :1 25~ f loo I~oo T~ so I L~O I
IT-- ~ + I
I ~oo-ethYl I
I caroeta-l `4000 1 250 -I 20 r90 1 30 1 10 --~ .

- - - ~ : . , . ~ , .

~272 I difLufe-l 1000 1 250 1 50 1 40 1 100 1 98 I nican 31 ~ 1 250 I -1~0 1 9C I ~ ~8 1 90 ' l l l 1 imazapurl62 1 125 I 100 1 80 I L00 1 Ib~ I
_~ 1 ~_~0 1 I ~--~1 lacifluor-i 12S rl25 i lOû llO0 I L~ - t-- LOO I
Isodium ~ ~ j 1, , I 1 1, ! ! _I
~romo- IL25 1 125 1 100 I ll~O I O 1 90 xynil r125 i 2-50 i 90 ilOO 1 90 r~l I I I I I I I I
L25 1 250 ~100 I Loo I lOo I Ioo I e t h i d - i muron 125û 1 -250 ¦ 100 ilO0 T l~DS~r~r~
I i250~l 253 ~ 100 IL00 i 100 1 100 1 I oxadia- 1 500 i 125 i 30 1 4û i Ioo i lo~-i I zon l 500 I 25~ I-100-ll00 -I rOO l--iO0 1 ~ I 125 i 250- -¦ lOb l 100 i 98 i 98 -3S I para- 1 250 I 12S` I ~8 1 50 ~ I .lOa . l 90 I quat I ron ~ .

. . . . -. :
. - .~ . . .
.

-- ~
- : , : . ,' ,.
.
.

T A 8 L E ( V ) Compound I Compound I
5 ¦ of the group B) I No. 1 ¦ ABU ¦ SES I EcH
nature I do2sS~i n~250 ~60 1 1 00 1 6 atrazine I ~500 1 12~1100 1 ~8 -250+Z501 ~ 0 ~00 T 60-1 isopro- I S00 ~Ioo ~100 1 50 I turon ¦ 500 1--250 ~1 ~

I -- ~ -500-i 250 igoToo I 20 1 .
~if enox ¦ ~ ~ 125 ~ 0 ~loo 1 20 I --rr--I - I `l~r250 180 1 8~ ~4 ~romacllr----250 Ir -250 1 100 I100- I-5~250 -~a I loo ~--2a 2,4-D r 250 1 lZ5 1 50 1 1 `250 1- 250 1 loo 1100 1 - 50 T
1.= _~ .
amino- Tlooo 1 2sa ~ i loo I lbo- ~sb 40 I tria2ole-l- 500 I-250 1 60 ~
- I propanil l 1000 + ~a r-loO l ~r carDeta- ~OOO~~Z50 -~100 I 20 ~
I mide l . _ l _ I I . !

.

:: .

. .

~2~72~90 I difLufe-l lO00 1 250 1 lO0 llO0 180 1 I nican 1 1 1 31 1 250 1 1~0 1 90 1 90 1 - 5 1 imazapurl 62 1 I251 100 1 95 I 9~ I
_ l l I l~ 62 1 250 -I lO0 l 95 1 100 1 ~ 62 l 250 l 80 ll~ 1 20 laci~luor-Ifen Iso~ium !
lS I 1 62 1 250 1 20 1 ~0 1 30 I bromo- I L25 1~l25 1 50 1 9S I Lo I 1 125 1 250 1 6~ 1 3~ 1 30 -T
! 1 125 1 250 -I 100 1 98 1 lO
ethidi- 1 25~-T 125 --T-100-r--5 --r lO
I muron 1 1 25~-~ 250 1 lOO IlO0 I 60 r 250 1 250 -I lO0 1l~3 1 90 I oxadia- I 500 1 lZ5 -T lO0 llO0 1 98 1 zon 1-1~
_l l ~5 I para-I quat I I I I _ I
_ l l l l l _ l I dimefu- I lO00 r 250 T loO I loo 1- 50 1 40 I ron .

- - , ' ':
,:

.. .. , :
. .
. . ' .
'

Claims (19)

The embodiments of the invention in which an exclusive privilege or property is claimed, are defined as follows:

1) A herbicidal composition comprising A) an active herbicidal substance of formula:

(I) in which:
R1 denotes a C1-18-alkyl, C6-18-aryl or C3-18-cycloalkyl radical and said radicals substituted by halogen, phenyl, cyano, C1-4-alkyl, C1-4-alkoxy or C2-5-alkylcarboxylate; R denotes a hydrogen atom or is as defined for R1; R2 and R3, which may be identical or different, denote hydrogen atoms or each represent a C1-12-alkyl or C6-12 aryl group and said groups substituted by halogen, phenyl, cyano, C1-4-alkyl, C1-4-alkoxy or C2-5-alkylcarboxylate, 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, quaternary ammonium compound, uracil, hydroxybenzonitrile or imidazolinone or a salt thereof; and in which the proportion of compound of formula (I) to the substance B) is from 0.2:1 to 10:1 by weight.

2) A composition according to claim 1 wherein the hydrocarbon radical contains from 1 to 7 carbon atoms or, when the hydrocarbon radical is a cycloalkyl group, from 3 to 7 carbon atoms.

3) A composition according to claim 1 wherein represents an optionally halogenated alkyl radical containing from 1 to 4 carbon atoms.

4) A composition according to claim 1 wherein R
represents an alkyl group containing from 1 to 4 carbon atoms.

5) A composition according to claim 1 wherein R2 and R3 each contain from 1 to 8 carbon atoms.

6) A composition according to claim 1 wherein R and R1, which may be the same or different, each represent an alkyl radical having 1 to 4 carbon atoms and R2 and R3, which may be the same or different, each represent a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms or a phenyl radical.

7) A composition according to claim 1 in which R
and R1, which may be identical or different, are alkyl radicals having 1 to 4 carbon atoms and R2 is a hydrogen atom.

8) A composition according to claim 1 in which R
and R1, which may be identical or different, are alkyl radicals having 1 to 4 carbon atoms and R2 and R3 are hydrogen atoms.

9) A composition according to claim 1 in which the substance B) is alachlor, metolachlor, simazine, atrazine, prometryne, diuron, isoproturon, linuron, tebuthiuron, ethidimuron, sulfometuron, chlorsulfuron, metsulfuron, methabenzthiazuron, oryzalin, trifluralin, diflufenican, napropamide, propanil, oxadiazon, dimefuron, aminotriazole, picloram, bifenox, acifluorfen, acifluorfen-sodium, fomesafen, oxyfluorfen, esters of acifluorfen and aliphatic alcohol, glycolate or lactate, quizalofop-ethyl, fluazifop-butyl, 2,4-D, 2,4-DP, MCPA, MCPP, dicamba, dalapon, metribuzin, carbetamide, EPTC, asulam, norflurazon, fluridone, diquat, paraquat, bromacil, bromoxynil, ioxynil, imazaquin or imazapur.

10) A composition according to claim 1 in which the proportion of compound of formula (I) to the substance B) is from 0.25:1 to 4:1 by weight.

11) A herbicidal composition according to claim 1 additionally comprising at least one inert carrier which is agriculturally acceptable.

12) A composition according to claim 11, which contains 0.05 to 95% of active substances relative to the total weight of the composition.

13) A composition according to claim 11 or 12, which contains 5 to 40% of surfactant relative to the total weight of the composition.

14) A composition according to claim 1 which is in the form of a soluble powder, wettable powder or dry flowable.

15) A two component pack comprising a first component which comprises a herbicidally active substance of formula (I) as defined in claim 1 and a second component which comprises at least one herbicidally active substance defined in group B) in claim 1 which can be applied simultaneously or separately.

16) A method of combating weeds at a locus which comprises applying thereto an affective amount of a composition according to claim 1.

17) A method according to claim 16, wherein the active herbicidal substances are applied in a total amount from 0.1 to 10 kg/ha.

18) A method according to claim 17 wherein the active substances are applied in a total amount of from 0.5 to 8 kg/ha.

19) A method of combating weeds at a locus wherein an active herbicidal substance of formula (I) as defined in claim 1 and an active herbicidal substance defined in group B) of claim 1 are applied sequentially to weeds, the substance of group B) being applied to the soil adjacent to the weed.