PT86064B - PROCESS FOR THE PREPARATION OF HERBICIDAL COMPOSITIONS BASED ON A HERBIBIDAE OF THE TYPE GLYPHOSATE AND A HERBICIDE OF THE PHENOXYBENZOIC TYPE USED IN THE TREATMENT OF UNDESEABLE PLANTS - Google Patents

Description

RHÕNE-POULENC AGROCHIMIE

PROCESS FOR THE PREPARATION OF HERBICIDIC COMPOSITIONS BASED ON A Glyphosate TYPE HERBICIDE AND A PHENOXYBENZOIC TYPE HERBICIDE USED IN THE TREATMENT OF UNDESIRABLE PLANTS

The present invention relates to new herbicidal compositions based on a glyphosate and herbicide type herbicide. phenoxybenzoic type bicide. It also refers to a method of treating undesirable plants, by means of these compositions. Glyphosate (or N-phosphonomethylglycine) and its salts are well-known broad-spectrum herbicides, active against annual and perennial weeds. This class of herbicides is particularly known for its effectiveness in post-emergence and is used in agriculture and gardening. However, it is always desirable to improve the herbicidal activity of these compounds.

However, it is known that glyphosate-type herbicides act relatively slowly. Usually, it takes about three weeks before seeing the effects.

In order to remedy this inconvenience, the PCT patent application WO 84/03607, in the particular case of application in the gardens of amateurs, indicates that the addition of a certain amount of acifluofen or one of its salts, to glyphosate-type herbicides , increases the speed of action of glyphosate-type herbicides. In this framework an effective amount is used

glyphosate herbicide and acifluofen is added, so that the weight ratio is practically between 1 / 8.33 and 4.2. It is noted, however, that the described compositions reveal, in many cases, a marked antagonism which results in a decrease in the effectiveness of the glyphosate-type herbicide. It was also proposed to use extemporaneous mixtures of glyphosate and acifluofen against weeds, not in gardens but in large crops like soy. And as soon as the publication Proceedings, Southernweeds Science Society, 38 th annual meeting of 1985, Samberg et al., On pages 86 to 89, indicate that a dose of 430g / ha of glyphosate, associated with 70g / ha of acifluofen, reveals antagonism accentuated against the tested weeds, decreasing this antagonism as the glyphosate / acyphuophene ratio decreases, that is, as the amount of acifluofen increases.

In a second publication, Ibid. , on pages 64-57, Frost and his collaborators also confirm the fact that it is necessary to increase the dose of acifluofen.

It also appears, according to this latest publication, that the spectrum of activity of glyphosate is reduced, particularly against grasses.

Another drawback linked to the mode of action of glyphosate or its derivatives is that they are very easily leachable. It means that if a very heavy rain falls a few hours after the herbicide is applied, it will be largely eliminated. It is also desirable to improve the action of glyphosate-type herbicides on plants whose growth

cement is decreased by low temperatures and / or low humidity or on plants at the end of their vegetative cycle.

The present invention allows to remedy, in an unforeseen way. these disadvantages and, more particularly, allows one or more of the following objectives to be achieved:

- increase the speed of action of glycophosphate-type herbicides,

- improving the spectrum of activity of glyphosate-type herbicides,

- improve the herbicidal properties of glyphosate-type herbicides,

- avoid leaching of glyphosate-type herbicides,

- improving the activity of glyphosate-type herbicides on plants whose growth is slowed by low temperatures and / or low humidity or on plants at the end of the vegetative cycle.

According to the present invention, the herbicidal composition comprises at least one glyphosate type herbicide of general form I and at least one phenoxybenzoic type herbicide of general formula VIII and is characterized by the fact that the compound ratio of formula general VIII / compound of general formula I is between 1/12 and 1/80, preferably between 1/15 and 1/50.

This is equivalent to a molar ratio VIII / I, taking into account the molar equivalence brought to the acid by the compounds of general formula I and VIII, between 1.2 / 12 and 1.2 / 80 and, preferably, between 1.2 / 15 and 1,2 / 50.

DETAILED DESCRIPTION OF THE INVENTION

Glyphosate-type herbicides

The glyphosate-type herbicides that can be used in the present invention are mainly compounds of general formula I and Ia below, as well as their metabolites and derivatives. These compounds have the general formula

(I) in which

Z represents a cyan group or a group of general formula

COOR;

R represents a hydrogen atom or represents a group chosen from lower alkyl groups, lower alkoxy lower alkoxyalkyl; aryl having 6 to 10 carbon atoms and, possibly, containing 1 to 3 substituents chosen independently from halogen atoms or lower alkyl, lower alkoxy, trifluoromethyl, nitro and cyano groups; or even a compatible cation capable of forming a salt;

R.] and the same or different, each represents a hydrogen atom or a group chosen from lower alkyl groups, aryl, substituted aryl, biphenyl; or even represent compatible cations capable of forming salts.

or the general formula

OR, Z

I ^Jά = P - CH ₂ - NH ₂ - CH ₂ - Z. (Ia)

I + or ₄ in which

Z ₂ is a compatible anion capable of forming a salt;

R3 θ R45 the same or different, each represents a hydrogen atom or a lower alkyl group or optionally substituted aryl or biphenyl;

Z- | represents a cyan group or a group of the general formula COOR ₅ ;

R ₅ has the defined meaning for P, except for the cation.

Preferred compounds of formula I and Ia are those in which the symbols Z and Z4 represent groups of the general formula COOR and COORg, respectively. With respect to the compounds of the general formula I, those in which the symbols R, R.] and R ₂ , the same or different, each represent a hydrogen atom or a compatible cation are preferred. Organic ammonium salts of general form I, namely those in which the symbol R represents a cation derived from isopropylamine, give good results and are available on the market. Similarly, they are also suitable organic sulfonium salts or sulfoxide (for example those in which the symbols R i and / or R _'represent 0 or trimethylsulfonium cation trimethyl sulfoxide 1). An example of a compound of formula I or Ic is the isopropylamine salt of N- (phosphonomethyl) glycine which is the active ingredient in the herbicide marketed by Monsanto under the brand name Roundup.

With respect to the compounds of formula Ia, those in which the same or different R4 and R4 symbols each represent a lower alkyl or aryl group and those in which the symbol represents a group of general formula C00R _5> in which R ^ represents a lower alkyl or aryl group.

Compatible cations and anions, from the herbicidal point of view, are those that are part of the general formula I or Ia salts that do not alter the compound's herbicidal properties. The salt form is generally more soluble in water and more advantageous than the corresponding free acid or free base.

Examples of compatible cations are alkali metal cations such as sodium or potassium, alkaline earth metal cations such as calcium or magnesium; copper, zijn co, iron, nickel, manganese, ammonium or organic ammonium cations, phosphonium, sulfonium or sulfoxide. These cations should preferably have a molecular weight of less than 300. Suitable organic ammonium cations include derivatives of amines, in particular from aliphatic, cyclic or heterocyclic amines containing 1 or 2 amine groups, such as alkylamines, alkenylamines, alkenylamines and alkanolamines. Examples of amine derivatives, while not limiting, are methylamine, ethylamine, n_-propyl 1 amine, i sq propyl 1 amine, n-butyl 1 amine, i sobuti 1 amine, sec.-buti 1 amine , n-amij_

-7 / amine, iso-ami1amine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undeci1amine, dodeci1amine, trideci1amine, tetradeci1amine, pentadeci 1 ami na, hexadeci1amine, heptadeci 1 ami_, octadeci1amina, methietiamine, 1 , methyl 1 pentadeci1amine, methyloctadecylamine, ethylbutylamine, ethyl 1 hepti 1 ami, ethyl 1 octi 1 ami, hexij_heptylamine, hexi1octi1ami na, dimethi 1ami na, di eti1ami na, di-n-propi1ami na, di-i sopropi1 -n-amylamine, di-soamylamine, dihexylamine, diheptamine, dioctylamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butamine, tri -isobutylamine, tri-sec.-butylamine, tri-n-amineamine, n-propanol amine, isopropanol amine, di ethanol amine, N, N '-diethyl, no 1ami, N-ethylpropanolamine, N-butylethanolamine , allylamine, n-butenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexeni1-2-amine and propylenediamine, amines a primary romantic substances, such as aniline, methoxy anion, ethoxy anion, ortho-, and para-toluamine, phenylenodamine, 2,4,6-tribromoanine, benzidine, naphthylamine, ortho- , meta- and para-chlorani1ine, etc .; heterocyclic amines such as pyridine, morpholine, piperidine, pyrrolidine, indoline, azepine, etc.

Among the appropriate organic sulfonium and sulfoxide cations are ^C T ^C 10 alkyl cations (preferably ^C 1 -C 6 lower alkyl) - sulfonium and ^C 1 ^-C 10 alkyl cations (preferably alkyl lower) - sulfoxide, such as trimethyl sulfonium, ethyl dimethyl sulfone, tripropyl sulfonium, trimethyl sulfoxide, triethyl sulfoxide, etc. These salts are described in particular in United States patent ηθ 4 315 765. Suitable phosphonium cations include, but are not limited to, the cations represented by the general formula ^R c ^R d in which R _q , R ^ and R _c , the same or different, each represent a phenyl or C 1-4 alkyl group, preferably lower alkyl. These salts are described in US patent no. 4,341,549. Other cations which are described in U.S. Patent No. 3,799,758 are also suitable. Suitable compatible anions include, but are not limited to, the chloride, bromide, fluoride, sulfate, sulfite, bisulfite, phosphate anions, orthophosphate, carbonate, bicarbonate, acetate, butyrate, benzoate, maleate, etc.

The compounds of general formulas I and Ia are described, for example, in U.S. Patent Nos. 3,799,758, 3,835,000, 3,950,402, 4 067 719, 4 008 296, 4 147 719 and 4 369 142 which are mentioned in this memo, by way of reference.

It is also possible to use a large number of compounds metabolized by green vegetables or functioning in an equivalent way to the active part (from the phytotoxic point of view) of glyphosate. These compounds include, for example, the compounds of general formula I and Ia, as well as those represented by the following general formulas

-9OR.

I ¹

Ο = P - CH ₉

I ²

0R ₂

N - Z

I (II)

OR, Z ²

I ³ + = P - CH ₂ —NH ₂ -Z ₃ or ₄ (Ilb) or, ¹ PI

0R ₂

OR,

I ¹

P = 0

I

0R ₂ (III)

OR,

I ¹ = PI 0R ₂

ch ₂

OR

- P = I 0R ₂ (IV) (V)

Ro-0 OR, d I ₍ j = P- 0- P = 0

I

Z ₃ - NH ₂ - ch ₂ ch ₂ - NH ₂ - Z ₃ ^Z 2 ^Z 2

R, -o ¹ ii o = p - o - P = 0 lI

Z ₄ - NH-CH ₂ ch ₂ - nh - Z ₄ (VI)

in which:

^Z 2 ' ^R 1' ^R 2 ' ^R 3 ^{and R} 4 ΐθ ^{111 0} 9 ⁿⁱ ' ^ca8 ° defined above; is a group of formula CH ^ CN; CONHOH (or its tantomeric form —C (OH) = NOH, or of the general formula CH ^ COOR in which R has the meaning defined above; or the group of general formula CONR? Rg in which the symbols R? And Rg, equal or different, has the meaning defined above for the symbol R; Zg represents a group -CH ^ -CN; -CO-NHOH (or its tantomeric form -C (OH) -NOH; -CH ^; a group of general formula -COOR ^ or CONRgRg in which the different groups Rg, the same or different, have the meaning defined above.

Rgg represents a lower alkyl, lower alkoxy, hydroxy, lower alkanoyl, optionally substituted arylcarbonyl, trifluoracetyl, lower alkylthio, lower alkanoyl; amino; alkylamino, nitro, nitrous, -OCH, or nroups of general formula -COORg, COOR ^ q, - CH? P (0) 0 R -j 5 (OR25), -S (0) mR. |, -SO-X -Rp or -CO-S (O) mR ^ ⁱⁿ which the symbol Rg is a lower alkyl, alkenyl group. upper, optionally substituted aryl, R4 represents a lower alkyl or optionally substituted aryl group; The symbol X represents an oxygen or sulfur atom; R- | 2 represents a group chosen from lower alkyl, lower alkenyl, lower alkynyl, optionally substituted aryl, optionally substituted arylalkyl, m represents zero, 1 or 2;

^R 15 ' ^R 25 ^{and R} 10 ⁰ meaning previously defined for 0 f

The symbol Rp Rg represents a hydrogen atom or a lower alkyl group; an optionally substituted aryl group, optionally substituted lower aryl; optionally substituted lower aralkyl; a group of general formula C00R ₅ or -P (0) (0R) (0) in which R _3> R 4 and R 1. have the meaning defined before.

The products of general formulas II to VII mentioned below are generally known and can be prepared by known processes or by processes similar to those known. These products and processes are described in United States Patent Nos. 4,035,177, 4,175,946, 4,251,258, 4,231,782,

322 238, 4 322 239, 4 323 387, 4,300,942, 4,300,943; the North American research descriptive ηθ 220 001 (Derwent ηθ 73821 E / 35); British patent ηθ 2 090 596; the Belgian patent ηθ 888 001; Japanese patents ηθ 56139408, 57120595 and 57099597; the European publication ηθ 39310; and the German Federal Republic invention patent application ηθ 2 361 382. The patents and patent applications mentioned above are mentioned by way of reference.

Derivatives (substituted phenoxy) -benzoic

Among the (substituted phenoxy) -benzoic derivatives that can be used in the present invention, there are compounds that include benzoic 2-nitro-5-phenoxy-substituted acids and their derivatives, of general formula

VIII

-u- /

^Z 6 represents one atom in chlorine or one group CF ₃ . ^Z 5 represents one atom in cl or or in fluorine; ^Z 7 represents one atom in hydrogen, chlorine or fluorine; ^Z 8 represents one atom in chlorine OR one group nitro; P represents 0 1 number zero or 1 9

R-] 3 θ R-] 4 'the same or different, each represents a hydrogen atom or a methyl group;

Z _g represents a hydroxy or alkoxy group (namely lower alkoxy) or a group of the general formula OM (M represents an alkali or alkaline earth metal atom, more particularly sodium or potassium atoms) or (lower) sulfonamide.

Among these compounds, compounds of formula VIII in which Ζθ represents an FCg group, Zg represents a nitro group, Zg represents a CP and Z? represents a hydrogen atom, because these compounds better meet the objectives of the present invention listed in the preamble.

Among these, we prefer:

- the acifluofen which is the compound in which p represents ze ro and Z _g represents a hydroxy group or the potassium or sodium salts of acifluofen (Z _g represents a group of the general formula OM, in which M represents a sodium atom or potassium),

- fomesafen, which Ó is the compound in which p represents zoro and the symbol Z _g represents the group N-methyl1 sulfonamide (-nh-so ₂ ch ₃ ),

- the benzofluoroene in which the symbol p represents the number 1, R-] 2 and R-j4 each represent a hydrogen atom and the symbol Z _g represents an OEt group.

Among the latter, acifuofen sodium is preferred.

According to the present invention, the new agrochemical compositions may contain mixtures of active substances and classic ingredients known in practice, such as active surfactants, supports and diluents. If the composition contains two substitutes, the systemic herbicide and the phenoxybenzoic derivative or more than two substituents, it is desirable to mix the aforementioned compositions conveniently, homogeneously and / or uniformly, a mixture that can be carried out by means of a particular agitation. The compositions can be mixed in a vat or can be pre-mixed.

The present invention also relates to a method of deburging which consists of applying an effective amount of a herbicidal composition to plants that are to be destroyed. This treatment method has a destructive purpose, which allows

-14 / (* particularly the control of the growth of weeds and, eventually, their total or partial destruction.

Herbicidal compositions or mixtures of active substances as described above and which are usable in accordance with the present invention, are applied in an appropriate manner to the leaves of the vegetables, and in particular; weeds to be eliminated, for example, as soon as they have green foliage.

Herbicidal compositions can also be applied long before harvest to kill weeds whose roots persist in the soil after harvest. It is thus possible to plant a short time after harvest without having to carry out mechanical weeding operations (manual or by other method). However, this method is reserved for cases in which the applied herbicides do not reconstitute and / or are selective in relation to the crop to be planted after harvest.

In general, the systemic compound of the glyphosate type is applied to plants in doses of 0.3 to 0.9 kg / ha, preferably from about 0.4 to about 0.8 kg / ha and, in particular, from about 0.5 to about 0.7 kg / ha.

The compounds of general formula VIII are used as membrane-modifying chemical substances; a dose is advantageously comprised between about 0.005 and about 0.1 kg / ha and preferably between 0.02 and about 0.08 kg / ha.

The weight ratio of phenoxybenzoic herbicide / glyphosate herbicide is between 1/12 and 1/80, preferably between 1/15 and 1/50.

Through the compositions of the present invention an effective fight against the following weeds is observed:

dj coti 1 edõneas: Xanthium, Ipomoea, Sesbania, Abutilon, Polygonum, Amaranthus, Chenopodium, Sinapis, Datura, Solanum, Euphor bia, Bidens, Galinsoga.

Monocoti1edoneas: (gramineas) Setária, Echinochloa.

The method according to the present invention makes it possible to combat a wide spectrum of annual and perennial, monocotyledonous or dicotyledonous weeds. Weeds can be destroyed by the methods and compositions of the present invention, allowing good preparation of the ground for the further development of crops such as cereals, wheat, rice, cotton, soy, beets (namely sugar beet), sunflower , rapeseed, sugar cane, leguminous crops, as well as obtaining an effective weeding of perennial crops (vineyards, orchards).

method and composition, in accordance with the present invention, also make possible a quick fight against plants, namely weeds, making the herbicidal effect apparent and effective shortly after treatment (much earlier than using the glyphosate herbicide, when higher doses are used).

The method according to the present invention also allows to avoid the leaching of glyphosate or its derivatives. The present invention also has as its objective a method that prevents the leaching of glyphosate or one of its derivatives of the general formula I mentioned above, said method being

-16 characterized by the fact that glyphosate or one of its derivatives of general formula I is applied, in combination with a compound of general formula VIII, in the doses and weight ratios defined above.

When practicing the process of the present invention, herbicidal compositions contain, in most cases, one or more ingredients in addition to glyphosate-type compounds and their derivatives (hereinafter called active ingredients). These compositions, which can be used as herbicidal agents, it contains the active ingredients in association with solid or liquid supports and with agriculturally acceptable surfactants. Inert supports and standard surfactants can be used. These compositions are also part of the present invention.

These compositions may also contain other ingredients such as protective colloids, adhesives, thickeners, thixotropic agents, agents that facilitate penetration, activators, stabilizers, sequestering agents, etc., as well as other known active ingredients, with pesticidal properties (in particular insecticides, fungicides or herbicides) or with plant growth regulating properties. More generally, the compositions used in the present invention can contain all solid or liquid additives corresponding to the usual formulation processes.

In the following description of the present invention, the percentages are expressed on a weight basis, unless otherwise specified.

-17- „

Q ί ν

Activators are compounds that, at normal doses, range from 0.5 to 5 kg / ha are normally not herbicides, but have the property of greatly increasing the herbicidal activity of glyphosate-type compounds. Most of these activators are well known. Some activators are surfactants such as those described below, namely polyethylene derivatives of phenol, alcohol or amines. Some activators are ammonium salts, namely chlorides, sulfates, phosphates, inoj; organic or organic ammonium. Other activators can be used. Activators that normally increase the herbicidal activity of glyphosate-type compounds are also useful in the present invention, when phenoxynitro-benzoic acid derivatives are used. The amount of activators used in the compositions of the present invention can be between about 0.1% and about 500% of the amount of the glyphosate type compound, and preferably between about 50% and about 350%. This perception depends on the nature of the activators used.

The doses of compounds used in the present invention can vary within wide limits, in particular according to the nature of the plants to be suppressed and / or the degree of weed infestation of the crops.

In general, the compositions, prepared according to the present invention, usually contain about 0.05 to about 95% of one or more active ingredients, according to the present invention, contain about 1 to about 95 % of one or more solid or liquid supports and, possibly, about 0.1 to about 50% of one or more surfactants.

Preferably, the compositions comprise 10% to 50% by weight of the combination of the two active ingredients of general formula I and VIII, preferably 15% to 30%.

As mentioned above, the active ingredients used in the present invention are generally associated with supports and, eventually, with surfactants.

In the description of the invention the term support refers to an organic or inorganic, natural or synthetic ingredient, to which the active ingredients are associated, in order to facilitate application to plants, grains or soil. This support is, therefore, normally inert and must be acceptable from the point of view of agriculture, in particular in relation to the treated plant. The support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, in particular butanol); esters, in particular methylglycol acetate; ketones, in particular cyclohexanone and isophorone; oil fractions; paraffinic or aromatic hydrocarbons, in particular xylenes; chlorinated aliphatic hydrocarbons, in particular trichloroethane or chlorinated aromatic hydrocarbons, in particular chlorobenzenes; water-soluble solvents, such as dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone; liquefied gases, etc.

surfactant may be an emulsifying agent, a dispersing agent or a wetting agent of the ionic or nonionic type or a mixture of these surfactants. Examples of such compounds include salts of polylacrylic acids, salts of glycosulphonic acids, salts of phenol sulphonic acids or naphtha.

-19- / 1eno-sulfonic acids, polycondensation products of ethylene oxide with fatty alcohols, fatty acids or fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulfosuccinic acid esters, derived from taurine (in particular taurates of alkyl) phosphoric esters of alcohols or polycondensation products of ethylene oxide with phenols, fatty acid esters with polyols and derivatives of the above compounds with a sulfate, sulfonate and phosphate function. It is advantageous to have at least one surfactant. .

To be applied, the active ingredients used in the present invention are generally in the form of compositions. These compositions in accordance with the present invention are, in themselves, in different solid or liquid forms. The forms of the compositions of the present invention include hydrosoluble powders (with a content of active ingredients that can reach 80%) and water-soluble granules, in particular those obtained by extrusion, compaction, impregnation of a granular support or granulation from a powder. (the content of active ingredients in these granules is between about 0.5 and about 80% in the latter cases) and aqueous solutions.

Water-soluble solutions or concentrates (namely powders or granules) generally include, in most cases, about 5 to about 80% of active ingredients, while ready-to-apply emulsions or solutions generally contain about 0.01 to about 20% active ingredients. In addition to the solvent, the solutions or concentrates may contain about 2 to about 50% of suitable additives such as stabilizers, surfactants, agents that facilitate penetration, inhibitors

-20 corrosion painters, dyes or adhesives.

From these concentrates, emulsions, whatever the required concentration, can be obtained by dilution in water, which are particularly suitable for application to plants.

All of these aqueous dispersions, solutions or mixtures for spraying can be applied to the plants of the crops to be molded, by any appropriate means, for example by spraying, at rates that are generally in the range of about 100 to about 1200 liters of water mixture. spraying per hectare.

The compositions prepared in accordance with the present invention apply appropriately to vegetation and in particular to weeds to be eliminated, as soon as they have a green foliage.

The following examples, while not limiting, illustrate the present invention and how it can be applied in practice.

Example 1: Application of the herbicidal composition after the emergence of different plant species (under glass)

7x7x8 cm pots were filled with moving sand for crops and a number of seeds were sown, depending on the function of the plant species and the thickness of the seed.

The seeds are then covered with a layer of earth about 3 mm thick and the seeds are allowed to germinate until the plants sprout to an appropriate crop. 0 are-

The treatment stage for grassy plants is the stage of formation of the second leaf. The stage of treatment of the cotyledons and the stage of unfolding of the cotyledons and the development of the first true leaf.

Then the pots are treated by spraying with an amount corresponding to an application dose, in volume, of 500 1 / ha, containing the active ingredients in the desired concentrations. The spray mix contains a tub mix prepared by mixing:

- Water

- an aqueous solution with 240 g / 1 of acyphuofen sodium (the concentration in g / 1 as well as the doses in g / ha refer to the acid form of acyphuofen),

- an aqueous solution with 360 g / 1 of isopropylammonium salt of N-phosphonomethylglycine (which is the acid form of glyphosate;

the concentration in g / 1 as well as the doses in g / ha refer to the acid form), which also contain 15% surfactant of the polyethoxy derivative type.

Different concentrations of the active ingredients are used in the spray liquid, corresponding to different doses of the applied active substances.

The treated pots are then placed in vats intended to receive irrigation water by sub-irrigation and kept at room temperature for 24 days at a relative humidity of 70%

After 13 and 29 days after treatment, the number of live plants is counted, in the pots treated with the spray liquid containing the active substance to be tested and the number of live plants in a control pot is also counted, treated under the same conditions but by means of a spray liquid which did not contain active ingredients. The percentage equal to 100% indicates that there is a total destruction of the plant species considered and a percentage equal to 0% indicates that the number of live p 1 in the treated pot is identical to that of the control pot.

The plant species used in example 1 are: the purple bell (Ipomoea purpurea) and the edible purslane (Portulaca oleracea).

The tests carried out show the markedly early herbicidal effect of the compositions prepared according to the present invention, for post-emergence treatments (see Tables I, II and III at the end of the description).

Example 2: Field experimentation

The field was divided into plots of 5 square meters. Several species were sown in each plot, in rows separated by 15 cm. These species included the following monocotions:

Balance sheet: Avena fatua (AVEFA)

Roasted millet: Echinochloa crus-galli (ECHCG)

Starry herb: Loli um mui ti f1orum (LDLMU)

Small corn: Pani cum mi 1i aceum (PANMI) and the following dichoti weeds:

Reflected Amaranth: Amaranthus retroflexus (AMARE)

Field mustard: Sinapis arvenis (SINAR)

When all plants reached at least the 2-3 leaf stage, that is to say about three weeks after sowing, treatments were applied by preparing mixtures for vats of active ingredients in appropriate concentrations and spraying them on the rows of chorus plants. a volume of 500 1 per hectare, to obtain the appropriate rates. An untreated plot is placed next to each treated plot for comparison and notation. Notations were made at various intervals after treatment and are expressed as a percentage of destruction of each species, compared to the same species in an untreated plot.

herbicidal effect was observed 5 days after treatment. The same active ingredients and doses were used as in the previous example. An early herbicidal effect was observed, as shown in Table IV at the end of the description.

In this example, a rain (20 mm of water) leached the plates 15 hours after the treatment.

Table 1

Intruder Doses of without acifluorphene: 10 g / ha and dates glyph phosphate aci f1uor Ipomoea Portulaca of work g / ha hay T + 13 T + 29 T + 13 T + 29 treatment 0 0 10 10 Ipomoea 125 T + 13 0 0 /////// /////// /////// T + 29 0 /////// 0 /////// me Portulaca 125 T + 13 0 /////// /////// 80 on one T + 29 10 /////// um h /////// 80 Ipomoea 250 T + 13 0 20 /////// /////// me T + 29 0 /////// 20 /////// nmn Portulaca 250 T + 13 0 /////// Hmm 98 nmn T + 29 20 /////// /////// me 95

Table II

Intruder Doses of without aci f1uorfen 20 g / ha and dates glyph phosphate aci fl uor Ipomoea Portulaca of work g / ha hay T + 13 T + 29 T + 13 T + 29 treatment 0 0 20 10 Ipomoea 125 T + 13 0 0 /////// /////// Π1ΗΗ T + 29 0 /////// 80 /////// /////// Portulaca 125 T + 13 0 /////// /////// 90 /////// T + 29 10 /////// /////// /////// 90 Ipomoea 250 T + 13 0 98 /////// lllllll /////// T + 29 0 /////// 80 /////// /////// Portulaca 250 T + l 3 0 /////// /////// 100 /////// T + 29 20 /////// /////// /////// 100

Table III

Ingredients active Doses g / h AVEFA ECHCG LOIMU PANMI AMARE SINAR aci f1uorfen 50 9 7.5 6.5 7.5 25 22.5 -so i mixtures of 200 + 5 27.5 35 37.5 37.5 60 40 two substa £ active substances: 400 + 5 70 67.5 62.5 67.5 70 65 formulations 400 + 20 70 70 62.5 72.5 85 72.5

of glyphosate salt and sodium fluorine acid solutions

-27R_e_I_v_i_n_d_i_ç „a_ç_d_e_s

Claims (9)

1. - Process for the preparation of herbicidal compositions, characterized by the fact that at least one glyphosate type herbicide of general formula is mixed OR 0 = P - CH _O - NH - CH _O - Z (I) in which Z represents a cyano group or a group of general formula COOR; R represents a hydrogen atom or a lower alkyl, lower alkenyl and lower alkoxyalkyl group; aryl having 6 to 10 carbon atoms possibly containing 1 to 3 substituents independently chosen from halogen atoms or lower alkyl, lower alkoxy, tri-fluoromethyl, nitro or cyano groups or represents a compatible cation capable of form a salt; R. | and the same or different R ^ each represent a hydrogen atom or lower alkyl, aryl, substituted aryl, biphenyl groups or represent compatible cations capable of forming salts; or a glyphosate type herbicide of general formula CH _? - NH _? ^here - CH ₂ - z -28ΒΡ · ' ^? in which : Z ₂ represents a compatible anion, capable of forming a salt; R3 and R3, the same or different, each represent a hydrogen atom or lower alkyl or aryl groups, lower alkyl or substituted aryl or biphenyl; Z 'represents a cyano group or a group of the general formula COOR _g ; Rg represents a hydrogen atom or a lower alkyl, lower alkenyl or lower alkoxyalkyl group; aryl having 6 to 10 carbon atoms, optionally comprising 1 to 3 substituents independently chosen from halogen atoms or lower alkyl, lower alkoxy, tri-fluoromethyl, nitro and cyano groups; with at least one phenoxybenzoic herbicide of general formula 13 ^R 14 ' ^C0 > p ^Z 9 (VIII) in which Ζθ represents a chlorine atom or a group of the general formula CF ₃ ; Zg represents a chlorine or fluorine atom; Zy represents a hydrogen, chlorine or fluorine atom; Zg represents a chlorine atom or a nitro group; p represents zero or one; ^ R ₃ and R _14, identical or different, represent each a hydrogen atom or methyl; Ζθ represents a hydroxy, alkoxy or alkyl 1 (lower) -sulfonamide group or a group of the general formula OM where M represents an atom of an alkali or alkaline earth metal, in which the weight ratio between the phenoxybenzone type herbicide co and the glyphosate type herbicide is between 1/12 and 1/80. 2. Process according to Claim 1, characterized in that the weight ratio between the phenoxybenzoic herbicide and the glyphosate herbicide is between 1/15 and 1/50. 3. Process according to claim 1, characterized in that compounds of formula VIII are used in which the symbol Zg represents a chlorine atom, the symbol Zg represents a trifluoromethyl group, the symbol Z ^ represents a hydrogen atom and the symbol Zg represents a nitro group. 4. Process according to claim 3, characterized in that compounds of the general formula VIII are chosen, chosen from: tomesafen, benzofuofen, lactofen and, preferably -30 / cia, acifluofen or one of its sodium or potassium salts, and more particularly acifluofen-sodium. 5. - Post-emergence weed treatment method, characterized by the fact that an effective amount of a glyphosate-type herbicide and a quantity of a phenoxybenzoic-type herbicide are applied to them, with the dose of herbicide type being glyphosate comprised between 0.3 and 0.9 kg / ha, preferably between 0.4 and 0.8 kg / ha and, to obtain better results, between 0.5 and 0.7 kg / ha, and the dose being of phenoxybenzoic type herbicide between 0.005 and 0.1 kg / ha, preferably between 0.02 and 0.08 kg / ha, and also because the common relationship between phenoxybenzoic type herbicide and glyphosate type herbicide is between 1/12 and 1/80, preferably between 1/15 and 1/50. 6. - Weed treatment method, with destructive purpose, which allows, in particular, the control of the growth of the said weeds and, eventually, their total or partial destruction, with the said weeds at the end of their cycle vegetative growth and / or delayed growth due to low temperatures and / or lack of humidity, characterized by the fact that an effective quarry of a glyphosate-type herbicide and an amount of a herbicide are applied to the weeds. phenoxybenzoic type, the dose of glyphosate herbicide being between 0.3 and 0.9 kg / ha, preferably between 0.4 and 0.8 kg / ha and, even with better results, between 0.5 and 0.7 kg / ha and the dose of phenoxybenzoic herbicide being between 0.005 and 0.1 kg -31 correspondence between 0.02 and 0.08 kg / ha, and because the weight ratio between the benzoyl phenoxy type herbicide and the glyphosate type herbicide is between 1/12 and 1/80, preferably between 1/15 and 1/50. 7. - Process to prevent the leaching of a glyphosate-type herbicide by occasional rains that fall after the herbicide is applied to weeds, characterized by the fact that an effective amount of an herbicide is applied to the weeds. phenoxybenzoic type, the dose of glyphosate herbicide being between 0.3 and 0.9 kg / ha, preferably between 0.4 and 0.8 kg / ha or, to obtain even greater advantages, between 0, 5 and 0.7 kg / ha and the dose of phenoxybenzoic herbicide being between 0.05 and 0.1 kg / ha, preferably between 0.02 and 0.08 kg / ha and because of the weight ratio between the herbicide of type phenoxybenzoic and the glyphosate type herbicide is between 1/12 and 1/80, preferably between 1/15 and 1/50. 8. - Process for the preparation of a composition based on a glyphosate-type herbicide, with good resistance to layering by rain, namely when it is present on the leaves of vegetables, according to any one of claims 1 to 4, expensive. because correspondingly substituted starting compounds are used. Process according to any one of claims 1 to 4, for the preparation of a composition intended to be diluted in water with a view to its application in plants, characterized in that between 10% and 50% by weight of the set of -32 / ( X ί two active ingredients of general formulas I and VIII, preferably between 15 and 30% by weight. Lisbon, November 3, 1987 ί RESUME PROCESS FOR THE PREPARATION OF HERBICIDIC COMPOSITIONS BASIS OF A Glyphosate TYPE HERBICIDE AND A HERBICIDE OF THE PHENOXYBENZOUS TYPE USABLE IN THE TREATMENT OF UNDESIRABLE PLANTS The present invention relates to a process for the preparation of herbicidal compositions, characterized by the fact that at least one glyphosate type herbicide of general formula is mixed: OR-. I 0 = P - CH ₂ - NH - CH ₂ - Z (I) or ₂ or of general formula: ORo I 0 = P - CH _? - JH _? - CH _? - ZA (Ia) l or ₄ with at least one phenoxybenzoic herbicide of general formula: CO- (O-OR ·] 3 ^ i4 -CO) p-Zg (VIII) -34 preferably sodium acyphuofen, where the weight ratio between the phenoxybenzoic herbicide and the glyphosate herbicide is between 1/12 and 1/80, preferably between 1/15 and 1/50. The compositions thus obtained are resistant to leaching caused by rains that occur shortly after their application.