CS264338B2 - Herbicide - Google Patents

Description

The present invention relates to novel herbicidal compositions comprising N- (2,4-difluorophenyl) -2- (3-trifluoromethylphenoxy) nicotinamide of the general formula (I) below described in British Patent Application No. 2,087,887A as a pre- and / or post-emergence herbicide. , and their use in agriculture.

Bromoxynil [3,5-dibromo-4-hydroxybenzonitrile] is widely used for the post-emergence control of broadleaf weeds in crops. When used to control weeds at the stage of germinal plants to eliminate competition at an early stage of development of a useful plant, these substances are extremely effective, but lacking residual efficacy in the soil, they do not counteract weeds arising after their application. Because of this, either the application must be repeated / or sprayed postponed until most of the weeds have emerged, but at that time the oldest of the weeds already compete to a large extent with the crop. In addition, certain broadleaf weed species, such as Stellaria media, Galium aparine, Viola tricolor, Viola arvensis and Veronica hederifolia, are very difficult to control with bromoxynil. .

Bromoxynil also shows no useful activity against annual grass weeds

As used herein, the term herbicide HEN refers to bromoxynil [з, -> - dibromo-4-hydroxybenzonitrile] in the form of the basic phenolic derivative (acid equivalent) or its agriculturally acceptable alkali metal or triethylamine salt,. or an ester with heptanoic or octanoic acid.

As a result of extensive research and experimental work, it has now been found that the use of N- (2,4-difluorophenyl) -2- (3-trifluoromethyl / phenoxy) nicotinamide of formula I

(hereafter referred to as the diflufenican by common name) in combination with the herbicide HEN

(a) results in residual soil efficacy that allows early application and prevents weeds from competing without having to repeat application;

(b) extends the spectrum of action of the abovementioned herbicides to such weeds as ftellaria media, Galium aparine and Viola arvensis; and

(c) allows the control of annual grass weeds such as Alopecurus myosuroides (field fox), Apera spica-venti, Poa annua,

Poa trivialis (meadow-grass), Echinochloa crus-galli (hedgehog) and Digitaria sanguinalis, when applied to the crop before emergence of these weeds.

Thus, the use of the above combination is an important enrichment of the prior art.

In addition to the above, it has also surprisingly been found that the herbicidal efficacy of the combination of diflufenican with the herbicide HBN against numerous weed species is much higher than would be expected with postemergence application (e.g. postemergence spray application) of these compounds, i.e. the herbicidal activity of the combination of diflufenican with the herbicide HBN exhibits an unexpected and remarkable degree of synergism in many weed species, such as Setaria viridis (green grass) as defined by PM L, Tammes in the Netherlands Journal of Plant Pathology, 70 (1964), pp. 73-80 in Isoboles, a graphical representation of synergism in pesticides, and in the case of Veronica hederifolia, Anthemis cotula, Vicia sativa, Epilobium paniculatum ), Lamium amplexicaule (Deadnettle hugging), Mo ntia linearis and Sisymbrium altissimum, as defined by L. E. Lirnpel, P. H. Schuldt, and D. Lamont, 1962, Proc. NEWCC 16, 48-53, using the formula.

Ε = X + Y - XY

100 where

E = expected growth inhibition in percent when applied to the herbicide mixture at defined doses

X = growth inhibition in percent at a defined dose of herbicide A

Y = growth inhibition in percent at application of a defined dose of herbicide В

If the observed response is higher than the expected response, then the combination exhibits a synergistic effect.

The remarkable synergistic effect in the post-emergence application of the above mixture results in improved reliability in controlling a large number of different weed species found in cereal crops and allows to reduce the amount of active ingredient needed to control weeds.

Accordingly, the invention provides a method for controlling weed growth in cereal crops comprising the combined use of (a) bromoxynil, i.e., 3,5-dibromo-4-hydroxybenzonitrile, or an agriculturally acceptable alkali metal or triethylamine, or ester salt thereof. with heptanoic or octanoic acid, or mixtures thereof, and (b) diflufenican, i.e. N- (2,4-difluorophenyl) -2- (3-trifluoromethylphenoxy) nicotinamide.

Preferred application rates of components (a) and (b) are between 100 and 500 g of acid equivalent per hectare, respectively. between 25 and 250 g / ha, the ratio of the above components being from 20: 1 to 2: 5, preferably from 8: 1 to 1: 1.

The method can be used to combat a wide variety of weed species in cereals, such as wheat, barley, rice and corn, and may be applied pre-emergence or post-emergence, particularly soon after weeds and crop plants have emerged, without significant permanent damage to the crop. The combined use described above provides both leaf and residual activity.

By pre-emergence application is meant application to the soil in which weed seeds or germinate plants are present prior to the emergence of the weeds above the soil surface. By post-emergence application is meant application to the Weed Parts above the soil surface. The application according to the method described above can be carried out from the pre-emergence or post-emergence state of the weed and the emergence of the crop plant to the post-emergence state of the weeds and the emergence of the crop plant. The term leaf activity refers to the herbicidal activity manifested after application to the weed portions above the soil surface. By residual activity is meant herbicidal activity manifested after application to the soil in which weed seeds or germinal plants are present before weeds are raised above the soil surface, destroying the germinal plants present in the soil at the time of application and the germinated plants after application. from seeds present in the soil when applied.

The subject matter of the invention is a herbicidal composition comprising (a) bromoxynil or an agriculturally acceptable alkali metal or triethylamine salt thereof, or a heptanoic or octanoic acid ester, or a mixture thereof, and (b) difluefenican, in combination with a herbicidally acceptable diluent or carrier and / or a surfactant.

The aforementioned components (a) and (b) are preferably present in the composition according to the invention in a weight ratio between 20: 1 and 2: 5. The aforementioned components (a) and (b) may be applied simultaneously, separately or sequentially.

Weeds which can be controlled by the above-mentioned means and in the manner described above include:

Aethusa cynapium

Abutilon theophrasti (Abutilon)

Amaranthus retroflexus Amsinckia intermedia

Anagallis arvensis (Scarlet Pimpernel)

Anthemis arvensis Anthemis cotula Atriplex putala Bidens pilosa Brassica nigra Capsella bursa-pastoris Chenopodium album (White Goosefoot)

Chrysanthemum segetum (Daisy)

Cirsium arvense (Field Thistle)

Datura stramonium (Durman)

Desmodium tortuosum

Emex australis

Epilobium paniculatum

Euphorbia helioscopia (Spurge Spurge) Fumaria officinalis (Common Fumitory) Galeopí-iis tetrahit (Hemp) Galium aparine (Bedstraw)

Geranium dissectum

Ipomoea purpurea

Lamium amplexicaule

Lamium purpureum (Dead Deadnettle) Lapsana communis (Common Kale) Matricaria inodora (Scentless Chamomile) Monochoria vaginalis

Montia linearis

Papaver rhoeas (Poppy)

Physalis longifolia

Plantago lanceolata (Common Plantain)

Polygonům spp. for example

Polygonum aviculare

Polygons convolvulus (buckwheat - buckwheat) a

Polygonum persicaria

Portulaca oleracea (Common Purslane)

Raphanus raphanistrum

Rotala indica

Rumex obtusifolius

Saponaria vaccaria

Scandix pecten-veneris

Senecio vulgaris (Common Groundsel)

Sesbania florida

Sida spinosa

Silene alba

Sinapis arvensis (Field Mustard)

Sisymbrium altissimum

Solanum nigrum (Black Eggplant)

Sonchus arvensis (Field Sow-thistle)

Spergula arvensis

Stellaria media (Chickweed)

Thlaspi arvense (Field Penny-cress)

Tribulus terrestris

Urtica urens (Stinging Nettle)

Veronica hederifolia (Ivy-leaved Speedwell)

Veronica persica (Persian Speedwell)

Vicia sativa

Viola arvensis (Field Violet) a

Xanthium strumarium (durkoman beet), and grassy weeds like. Alopecurus myosuroides

Apera spica-venti

Agrostis stolonifera

Poa annua (Annual Meadow-grass)

Poa trivialis

Digitaria sanguinalis (European Tree Frog)

Echinochloa crus-galli

Eleusine indica

Setaria viridis (Green Arrays), as well as Scorpionfish such as

Cyperus iria a

Eleocharis acicularis.

The stability of the HBN herbicide and diflufenican makes it possible to practice the above-described method even by applying the individual active ingredients at different times in separate compositions. Usually, however, separate formulations containing individual herbicidal components are mixed (tankmix) prior to use.

The following experiments and examples illustrate the invention but are not intended to limit the scope of the invention in any way.

Experiment 1

The following greenhouse experiment demonstrates the synergistic effectiveness of the combination of bromoxynil and diflufenican in suppressing the growth of Setaria viridis.

Greenhouse experiment demonstrating biological synergism between bromoxynil and diflufenican

To investigate the interaction of bromoxynil and diflufenican over a wide dose range, ie at doses of 0, 125, 250, 500 and 1000 g / ha (calculated on acid equivalent) of bromoxynil in the form of a triethylamine salt (see Example 1 below) and 0,125 , 250, 500 and 1000 g / ha in the case of diflufenican (see example 2 below), an extensive experiment is conducted involving 25 treatments summarized as follows:

bromoxynil salt with triethalamine (grams of acid equivalent / ha) +

diflufenican (g / ha)

(1) (6) Italy (11) (16) Italy (21) 0 125 250 500 1 000 (2) (7) (12) (17) Italy (22) 125 125 250 500 1 000 + + + + 125 125 125 125 (3) (8) (13) (18) Italy (23) 250 125 250 500 1 000 t + + + 250 250 250 250 (4) Italy (9) (14) (19) (24) 500 125 250 500 1 000 + + + 500 500 500 500 (5) (10) (15) Italy (20) Italy (25) 000 125 250 500 1 000 + + + + 1 000 1 oóo 1 000 1 000

Each treatment is carried out in 3 dishes with a diameter of 9 cm. In each dish filled with John Innes No. 1 composting plant, there are always 5 green leaf plants (Setaria viridis) at the 2-leaf stage. The application rate is 260 liters per hectare. After spraying, the trays in randomly arranged clusters are placed in a glass pan for irrigation as needed. After 3 weeks, the phytotoxicity was evaluated in untreated control plants using a scale of 0 to 100 (percentage scale), where 0 means no effect and 100 represents complete destruction.

The results obtained are summarized in the following overview, where the location of the measured values corresponds to the location of the respective doses of the individual compounds or combinations thereof in the previous table:

phytotoxicity in%

0 0 0 0 0 30 40 45 50 70 38 40 50 60 80 45 60 60 80 90 60 70 83 100 ALIGN! 100 ALIGN!

From these results, Εϋ ^ θ (effective dose inducing 50% phytotoxicity) in g / ha was graphically determined for diflufenican alone and for its combinations with increasing proportion of bromoxynil salt with triethylamine. The bromoxynil salt with triethylamine alone does not show any effect. The following Εϋ ^ θ values were found:

ED ₅₀ (g / ha) diflufenican (dif.) 625 dif. + Bromoxynil 125 g / ha 325 dif. + Bromoxynil 250 g / ha 225 dif. + Bromoxynil 500 g / ha 150 dif. + Bromoxynil 1000 g / ha 75

The above values are used to construct isobol for a one-sided effect [see P. M. L. Tammes, Netherlands Journal of Plant Pathology 70, 1964, pp. 73-80. Isoboles, and graphic representation of synergism in pesticides. The resulting isobol clearly corresponds to the type II curve (Tammes, p. 74, Fig. 1), characteristic of synergism.

The resulting isobol is shown in Figure 1, where the D-axis is plotted grams of diflufenican / ha, and the HBN-axis is plotted grams of bromoxynil / ha.

Experiment 2

A 3 to 5 leaf winter wheat culture infested with 10 to 16 leaf Veronica hederifolia is sprayed with bromoxynil octanoate (composition of Example 4) at a dosage of 0.28 kg of acid / ha equivalent, diflufenican (composition of Example 2) in at a rate of 0.14 kg / ha and a mixture (tankmix) of both of these preparations at 225 liters / ha. The treatment is carried out on 4 randomly located plots of 2.4 mx7.6 m. In 47 days after spraying, the percentage of damage to crops and the weed control percentage are evaluated. The average results are shown in the following overview:

v. in damage to the eradication of the Veronica axis of the renal hederifolia plant in% in% bromoxynil octanoate (0.28 kg acid equivalent / ha) 015 diflufenican (0.14 kg / ha) .0 60 * bromoxynil octanoate + diflufenican ( 0.28 + 0.14 kg / ha) 094

Using the Limpel formula

E = X + Y-XY

100 based

E-15 + 60-900 = 66

100 ALIGN!

Since the observed efficacy on Veronica hederifolia is much higher than the expected efficacy, the combination shows clear synergism. Compatibility for the crop is excellent.

Experiment 3

A 2 to 3 leaf winter wheat culture infested with Anthemis cotula (2 to 6 leaves), Vicia sativa (2 to 4 leaves) and Epilobium paniculatum (2 to 6 leaves) were treated in an analogous manner to Experiment 2 and after 47 days evaluate the damage to the crop and the degree of weed control. The results (averages of 4 determinations each) are given in the following overview:

damage to utility extermination (%)

plants (%) Anthemis Vicia Epilobia bromoxynil octanoate (0.28 kg / ha) 0 15 Dec 0 3 Diflufenican (0.14 kg / ha) 0 43 80 75 bromoxynil octanoate + diflufenican (0.28 + 0.14 kg / ha) 0 98 99 100 ALIGN!

When calculating according to the Limpel formula, the expected extinction values for Anthemis, Vicia and Epilobium species are 52, 80 and 80 respectively. 76, which clearly shows that the above combination exhibits synergism. Compatibility for crop is excellent.

Experiment 4

A 4-6 leaf winter wheat culture contaminated with Lamium amplexicaule (4-10 leaf), Montia linearis (6-10 leaf) and Sisymbrium altissimum (4-8 leaf) were treated in an analogous manner to experiment 2 and from 41 days after spraying reveals crop damage and weed control.

The results are shown in the following overview:

treatment of damage to utility extermination%

plants in% Lamium Montia Sisymbrium bromoxynil octanoate (0.28 kg / ha) 0 15 Dec 13 63 Diflufenican (0.14 kg / ha) 0 23 18 18 bromoxynil octanoate + diflufonican ςΰ, 28 + 0.14 kg / ha) 0 94 97 99

Expected extinction values for Lamium, Montia and Sisymbrium are 34, 29 and 29 respectively. 70, from what? it is clear that the above combination exhibits a synergistic effect. Compatibility for crop is excellent.

Experiment 5

The efficacy of the synergistic mixtures of the present invention for controlling a broad spectrum of weeds in spring P ' s and barley was demonstrated by a series of field trials on small plots comparing the effectiveness of a combination of bromoxynil ester and diflufenican alone with bromoxynil ester and diflufenican alone. Diflufenican (see Example 2) at 150 g / ha, bromoxynil octanoate (commercial formulation) at 210 g acid / ha equivalent, and a mixture (tankmix) were applied to 2 wheat cultures and 1 barley culture each at 2 to 5-leaf stages. ) of these two preparations at a volume of 102.9 liters / ha. Each treatment is applied to three parcels with an area of 17.5 to 25 cm, using a motor sprayer. Weed efficacy and crop safety assessments are performed visually over 2 weeks, using the following scales:

weed control tolerance for crop

9 complete destruction 9 Complete tolerance 8 excellent effect commercially acceptable 8 possible effect 7 good effect 7 meek effect 6 considerable effect 6 sure effect 5 bad effect 5 hard damage 4 slight damage 4 hard damage 3 certain effect 3 hard damage 2 weak effect 2 hard damage 1 possible effect 1 hard damage 0 without effect 0 completely destruction

The above-described experiment was conducted in 1983 in western Canada.

The results obtained are shown in Table I below:

Table I

Average weed control and crop safety values

Treatment Setaria viridis Thlaspi arvense Chenopodium album Fagopyrum tertaricum Amaranthus retroflexus wheat barley diflufenican (150 g / ha) 4.8 5 1 0 6 9 9 diflufenican (150 kg / ha) + 8.8 9 9 9 9 9 9 bromoxynil octanoate (210 g acid equivalent / ha) bromoxyni 1-octanoate (210 g acid equivalent / ha) 2.1 7.8 9 8 7.3 9 9 Number of occurrences 2 1 2 1 1 2 1

Experiment 6

The efficacy of the compositions according to the invention for controlling Galium aparine, Veronica hederifolia and Viola tricolor was demonstrated by the following field trials in which the effectiveness of a mixture (tankmix) of bromoxynil ester and diflufenican was compared with bromoxynil ester alone.

For small fields (15 to 30 m ^{* 2} ) of two winter wheat varieties and two winter barley varieties, bromoxynil octanoate (commercial product) is applied at a rate of 250 g of acid / ha equivalent and a tankmix mixture of bromoxynil- octanoate and 150 g / ha of diflufenican (see Example 2) in a volume corresponding to 330 to 500 liters / ha. Each treatment is carried out on two plots. 20 to 30 days after spraying, weed extinction rates and crop safety were evaluated as phytotoxicity in% compared to untreated control plots.

The results obtained are shown in Table II below.

Table II

Average phytotoxicity in%

Treatment

Galium

Veronica

Winter Viola aparine hederifolia tricolor wheat barley bromoxynil octanoate (250 g acid / ha) 70 bromoxynil octanoate (250 g acid / ha) +95 diflufenican (150 g / ha) occurrences1

7 47 1 1 82 98 1 3 2 2 2 2

Attempt 7

The efficacy of the mixtures according to the invention is demonstrated by the following field trials, in which the efficacy of a mixture (tankmix) of bromoxynil potassium salt (see Example 3 below) and diflufenican (see Example 2 below) is compared with that of diflufenican alone.

One area with winter wheat culture and three areas with winter barley culture are post-emergence treated with 125 g / ha of diflufenican and a mixture (tankmix) of diflufenican (125 g / ha) and bromoxynil potassium salt (300 g of acid equivalent / ha). The application is carried out with the aid of a small motor sprayer with a spray volume of 220 to 235 liters per hectare.

Three plots of 30 m each are sprayed for each determination on each surface.

After early spring and winter application, weed status is determined late in the spring by counting the number of weed plants on two 0.5 square meters squares per plot and the degree of weed control expressed as a percentage of weed reduction on untreated control plots. Crop safety is assessed visually and evaluated as phytotoxicity as a percentage, with 0% indicating no effect and 100% representing complete destruction.

The results obtained are shown in Table III below:

i O

P • H> N □

Ф

0 No. ÍX чв d е -Р WITH • ч • н с N υ • Н 0 Ф • н 43 □ X 0 О • Η С Р Οι ф 0 > (Л Р О > 1 0 Гч >

P Ф> cu 0 cu Ф cu ω

<0 Φ o Д

P

Ή P +>

d • н (Л д О О 'ф Р1> 1 Λ d (л r-Ч-н <4 iр

Ф dо го

O diflufenican 69 90 95 90 100 100 (125 g / ha) to <0 υ • н с ф чч

Г-Н ЧЧ • н Ό d л ио

C4J oo

WHAT

CO ιΛ со из из со

AND

(0 гЧ > • н 1 (Л »4 > ф • н (Л 40 с ф > 1 с > 1 d гЧ X 01 Л ф 0 <л е о -Р > 1 d о о с С р Р го ф • «Ч 43 л н гЧ

ГО гм

CN

ГО

ГО <м «о р

+1 ф> □ о

The results of the above experiments clearly show a broad spectrum of action of the synergistic compositions according to the invention, including weeds such as Setaria viridis, Galium aparine, Veronica and Viola species.

As mentioned above, the present invention provides herbicidal compositions comprising (a) 3,5-dibromo-4-hydroxybenzonitrile or an alkali metal salt thereof, or a triethylamine salt or heptanoic or octanoic acid ester or a mixture thereof, and (b) diflufenican, wherein the weight ratio of components (a) and (b) is preferably from 20: 1 to 2: 5, in particular from 8: 1 to 1: 1, in combination with, preferably homogeneously dispersed in one or more compatible herbicidally usable diluents or carriers and / or surfactants (i.e., diluents or carriers or surfactants of those types generally considered suitable for use in herbicidal compositions that are compatible with the HBN herbicide and diflufenican).

Homogeneously dispersed refers to those compositions in which the herbicidally HBN and diflufenican are dissolved in the other components. Herbicidal compositions are broadly understood to mean not only compositions suitable for immediate use as herbicides, but also concentrates which have to be diluted before use. Preferably, the compositions of the invention comprise from 0.05 to 90% by weight of HBN herbicide and diflufenican.

The herbicidal compositions may contain both a diluent or carrier and a surfactant (for example, a wetting, dispersing or emulsifying agent). The surfactants which may be included in the herbicidal compositions of the invention may be of the inogenic or non-inogenic type. Examples include sulforicinoleate, quaternary ammonium derivatives, condensate products of ethylene oxide nonyl or octylphenols or carboxylic acid esters with anhydrosorbitols, which have been converted to a robust form by etherification of free hydroxyl groups by condensation with ethylene oxide, and salts of esters of sulfuric acid and sulfonic acids with alkali and alkaline earth metals and alkaline earth metals such as dinonyl and dioctyl sodium sulfoxide succinates and salts of higher molecular weight sulfonic acid derivatives with alkali metals and alkaline earth metals such as sodium and calcium lignosulfonates.

Examples of suitable solid diluents or carriers include aluminum silicate, talc, magnesium oxide, diatomaceous earth, calcium phosphate, cork powder, activated carbon and clays such as kaolin or bontonite. Solid compositions (which may be in the form of dusts, granules or wettable powders) are preferably prepared by grinding HBN herbicide and diflufenican with solid diluents or impregnating solid carriers or diluents with solutions of HBN herbicide and diflufenican in volatile solvents, evaporating solvents and optionally grinding the resulting products. powder. Granular formulations may be prepared by adsorbing HBN herbicide and diflufenican (dissolved in volatile solvents) to solid diluents or carriers in granular form followed by solvent evaporation, or granulating powder formulations prepared as described above. Solid herbicidal compositions, in particular wettable powders, may contain wetting or dispersing agents (for example wetting or dispersing agents of the aforementioned types) which, when solid, may also serve as diluents or carriers.

The liquid compositions of the invention may take the form of suitable, organic or aqueous-organic solutions, suspensions and emulsions which may contain a surfactant. Suitable liquid diluents for the preparation of liquid compositions include water, acetophenone, cyclohexanone, N-methylpyrrolidone, isophorone, toluene, xylene and mineral, animal and vegetable oils (and mixtures of these diluents). Surfactants suitable for the preparation of the liquid compositions of the present invention may be ionic and non-ionic (such as those of the types described above) and, when liquid, may also serve as diluents or carriers.

Wettable powders and liquid compositions in the form of concentrates may be diluted with water or other suitable diluents, for example mineral or vegetable oils, at least in the case of liquid concentrates in which the diluent or carrier is an oil, to form compositions suitable for use. If desired, liquid HBN herbicide formulations and diflufenican can be used in the form of self-emulsifiable concentrates containing the active ingredients dissolved in emulsifiers or solvents containing emulsifying agents compatible with the active ingredients. By simply adding water to these concentrates, formulations suitable for immediate use are obtained. use.

Liquid concentrates in which the diluent or carrier is oil can be used without further dilution when applied by electrostatic spray technique.

The herbicidal compositions of the invention may optionally also contain conventional adjuvants such as adhesives, protective colloids, thickeners, penetration agents, stabilizers, complexing agents, anti-caking agents, colorants and corrosion inhibitors. Said excipients may also serve as carriers or diluents.

Preferred herbicidal compositions of the present invention are aqueous suspension concentrates containing from 10 to 70% (w / v) of HBN herbicide and diflufenican, 2 to 10% (w / v) of a surfactant, 0.1 to 5% (w / v) thickeners and 15 to 87.9% by volume water, wettable powders containing 10 to 90% (w / w) HBN herbicide and diflufenican, 2 to 10% (w / w) surfactant and 10 to 88% (w / w) solid diluents or carriers, further water-soluble liquid concentrates containing 10 to 30% (w / v) of HBN herbicide and diflufenican, 5 to 25% (w / v) of surfactant and 45 to 85% by volume of miscible solvent water, for example dimethylformamide or N-methylpyrrolidone; further, liquid emulsifiable suspension concentrates containing 10 to 70% (w / v) HBN herbicide and diflufenican, 5 to 15% (w / v) surface an active agent, 0.1 to 5% (w / v) of a thickener and 10 to 84.9% by volume of an organic solvent, and granules containing 2 to 10% (w / w) of HBN herbicide and diflufenican, 0.5 to 2%. % (w / w) surfactant and 88 to 97.5% (w / w) granular carrier, and finally emulsifiable concentrates containing 0.05 to 90% (w / v), preferably 1 to 60% (w / v) by volume) of HBN and diflufenican herbicide, 0.01 to 10% (w / v), preferably 1 to 10% (w / v) of surfactant, and 0.99 to 99.94% by volume, preferably 39 to 98 99% by volume of organic solvent.

The herbicidal compositions of the invention may also contain the herbicide HBN and diflufenican in combination with, preferably homogeneously dispersed in one or more other pesticide active compounds and optionally one or more other compatible diluents or carriers, surfactants and conventional excipients as described above, useful for preparing pesticidal compositions.

By way of example, other pesticidally active compounds that may be included in the compositions of the present invention. or which may be used in conjunction with the compositions of the invention may be used. crbicides used, for example, to extend the spectrum of activity to other weed species, such as alachlor [and chloro-2,6-diethyl-N- (methoxymethyl) acetanilide], thyl- (4-aminobenzenesulfonyl) carbamate], asulam [mc alloxydim Na [2- (1-allyloxyaminobutylidine) -5,5-dimethyl-4-methoxycarbonylcyclohexane-1,3-dione sodium], atrazine [2-chloro-4-ethylamino ”6-isopropylamino-1,3,5-triazine] , barban [4-chlorobut-2-ynyl-N- (3-chlorophenyl) carbamate], benzoylprop-ethyl [ethyl-N-benzoyl-N- (3,4-dichlorophenyl-2-aminopropionate), butachloro-n (butoxymethyl) - .alpha.-chloro-2,6-diethylacetanilide], butylate [S-ethyl-N, N-diisobutyl (thiocarbamate)], carbetamide [DN-ethyl-2- (phenylcarbamoyloxy) propionamide], chlorophenpropylmethyl [methyl-2-chloro- 2- (4-chlorophenyl) propionate], chlorpropham [isopropyl-N- (3-chlorophenyl) carbamate], chlortoluron C. N '- (3-chloro-4-methylphenyl) -N, N-dimethylurea], cyanazine [2 -chloro-4- (1-cyano-1-methylethylamino) -6-ethylamino-1,3,5-triazine], Cn'-cyclohexyl-N-ethyl-Se cycloate thyl (thiocarbamate)],

2,4-D C2,4-dichlorophenoxyacetic acid], dalapone [2,2-dichloropropionic acid],

2,4-DB [4- (2,4-dichlorophenoxy) butyric acid], desmedipham [3- (ethoxycarbonylamino) phenyl-N-phenylcarbamate], diallate [S-2,3-dichlorallyl-N, N-diisopropyl (thiocarbamate)] , dicamba [3,6-dichloro-2-methoxybenzoic acid], dichlorprop [(+) -2- (2,4-dichlorophenoxy) propionic acid], diclofop [(RS) -2- 4- (2,4-dichlorophenoxy) (phenoxy) propionic acid], difenzoquate [1,2-dimethyl-3,5-diphenylpyrazolium salt], dimefuron [4- [2-chloro-4- (3,3-dimethylureido) phenyl] -2-tert-butyl- 1,3,4-oxazolidin-5-one], dinitramine [N ¹ , N 4 -diethyl-2,6-dinitro-4-trifluoromethyl-m-phenylenediamine], diuron [ν '- (3,4- dichlorophenyl) -N, N-dimethylurea],

EPTC CS-ethyl-N, N-dipropyl (thiocarbamate)], ethofumesate [2-ethoxy-2,3-dihydro-3,3-dimethylbenzofuran-5-ylmethylsulfonate], flamprop-isopropyl [isopropyl - (+) - 2- (N-benzoyl-3-chloro-4-fluoroanilino) propionate], flamprop-methyl {methyl- (+) - 2- (N-benzoyl-3-chloro-4-fluoroanilino) propionate], fluometuron [ν '- (3-trifluoromethylphenyl) -N, N-dimethylurea], isoproturon [ν' - (4-isopropylphenyl) -N, N-dimethylurea], linuron [Ν '- (3,4-dichlorophenyl) -N-methoxy- N-methylurea],

MCPA [4-chloro-2-methylphenoxyacetic acid],

MCPB E 4- (4-chloro-2-methylphenoxy) butyric acid], mecoprop [(+) -2- (4-chloro-2-methylphenoxy) propionic acid], metamitron Q4-amino-3-methyl-6-phenyl -1,2,4-triazin-5 (4H) -one], methabenzthiazuron [N- (benzothiazol-2-yl) -N, N'-dimethylurea], metribuzin [4-amino-6-tert-butyl-3 - (methylthio) -1,2,4-triazin-5 (4H) -one], [S-ethyl-N, N-hexamethylene (thiocarbamate)] molinate, oxadiazone [3- (2,4-dichloro-5-) isopropoxyphenyl) -5-tert-butyl-1,3,4-oxadiazolin-2-one], paraquat (1,1'-dimethyl-4,4'-bipyridylium salt), pebulat L S-propyl-N-butyl- N-ethyl (thiocarbamate)], phenmedipham [3- (methoxycarbonylamino) phenyl-N- (3-methylphenyl) carbamate], prometryn [4,6-bis-isoporpylamino-2-methylthio-1,3,5-triazine], propachlor Qa -chloro-N-isopropylacetanilide], propanil [N- (3,4-dichlorophenyl) propionamide], propham [isopropyl-N-phenylcarbamate], pyrazone 1,5-amino-4-chloro-2-phenylpyridazine-3 ( 2H) -one], simazine 2-chloro-4,6-bis-ethylamino-1,3,5-triazine],

TCA [trichloroacetic acid],.

thiobencarb [S- (4-chlorobenzyl) -Ν, Ν-diethylthiocarbamate], triallate [S-2,3,3-trichlorallyl-N, N-diisopropyl (thiocarbamate)] and triflurrin 2,4-cinitro-N, N-dipropyl-4-trifluoromethylaniline], insecticides; for example carbaryl [< - &gt; - riaphthyl-N-methylcarbamate], synthetic pyrethroids, e.g. permethrin and cypermethrin, and fungicides, e.g.

2,6-dimethyl-4-tridecylmorpholine, methyl N- (1-butylcarbamoylbenzimidazol-2-yl) carbamate,

1,2-bis (3-methoxycarbonyl-2-thioureido) benzene, isopropyl-1-carbamoyl-3- (3,5-dichlorophenyl) hydratoin; and

1- (4-chlorophenoxy-3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-one).

Other biologically active materials that can be added to or used in conjunction with the herbicidal compositions of the present invention are plant growth regulators such as succinic monoamide, (2-chloroethyl) trimethylammonium chloride and 2-chloroethanephosphonic acid, or mineral fertilizers such as nitrogen, potassium and phosphorus containing fertilizers as well as trace elements required for the successful development of plants, such as iron, magnesium, zinc, manganese, cobalt and copper

The pesticidally active compounds and other biologically active materials which can be added to or used in conjunction with the herbicidal compositions of the invention, such as those listed above having the acid character, can be used in the form of conventional derivatives, for example alkali metal salts , salts with amines or esters.

Preferred herbicidal compositions of the invention, comprising HBN and diflucanate together with another herbicide, are those wherein the further herbicide is diclofop, MCPA or mecoprop, or an agriculturally acceptable salt or ester thereof.

The present invention also relates to a process as described above for controlling weeds in cereals, in particular small grain cereals such as wheat and barley, in which diclofop, MCPA or mecoprop, or an agriculturally acceptable salt or ester, is applied at a dose of between 500 and 1,500 g. / ha, 100 and 1 500 g / ha respectively. 1,000 and 2,500 g / ha, preferably between 570 and 1,140 g / ha, 150 and 1,000 g / ha, respectively. 1 000 and 2 000 g / ha.

The compositions according to the invention may be prepared as products comprising HBN herbicide and diflufenican and optionally other pesticidal active compounds as described above, preferably as the herbicidal compositions described above, and in particular as herbicidal concentrates to be diluted before use containing HBN herbicide and diflufenican , in a container or container provided with instructions describing how the above-mentioned HBN herbicide and diflufenican are to be used, or a herbicidal composition containing them for use in weed control. The aforementioned containers may be those commonly used for the storage of ambient temperature chemicals and herbicidal compositions, in particular in the form of concentrates, for example cans and metal drums, which may optionally be internally coated, and plastic containers, glass and glass bottles. and, if the content is solid, such as granular herbicidal compositions, boxes, for example cardboard boxes, plastic boxes and metal boxes, or bags. These packages should normally be large enough to contain the necessary amount of active ingredients or herbicidal composition to treat at least about 40 ares of land to control weeds, but their size should not exceed the dimensions suitable for normal handling.

The instructions provided with these packages may be printed directly on the packages, or the packages may be labeled or labeled with the instructions. These instructions usually state that the contents of the package, optionally after dilution, are applied to control weed growth at rates of application of between 100 g and 500 g of acid equivalent per hectare for the herbicide HBN and between 25 g and 250 g for diflufenican. hectare in the manner and for the purposes described above.

Accordingly, the invention also includes products comprising (a) 3,5-dibromo-4-hydroxybenzonitrile or an agriculturally useful alkali salt thereof.

264238 metal or triethylamine or an ester with a heptanoic or octanoic acid or a mixture thereof, and (b) diflufenican, as a combination means for simultaneous, separate or sequential use in controlling weed growth in crop crops.

The following non-limiting examples illustrate the herbicidal compositions of the present invention for controlling weeds.

Example 1

A water-miscible formulation containing a bromoxynil salt with triethylamine is prepared from the following components:

bromoxynil triethylamine Soprophor BSU (condensation product of tristyrylphenol with ethylene oxide containing 18 moles of ethylene oxide) diethylene glycol water up to% (w / v)% (w / v)

1 ^ 5% (w / v)% (w / v)

100% vol

The above composition is prepared by mixing part of the water, diethylene glycol, bromoxynil and triethylamine (15% w / v of triethylamine represents a 2.6% excess of triethylamine over the stoichiometric amount required to prepare the bromoxynil salt with triethylamine). This mixing is performed with heating and stirring. The condensation product of tristyrylphenol with ethylene oxide is then added to the resulting mixture and the volume of the preparation is brought to 100% by the addition of water.

Example2

An aqueous suspension concentrate is prepared from the following ingredients:

Diflufenican Ethylan BCP (condensation product of nonylphenol with ethylene oxide containing 9 moles of ethylene per mole); FD (silicone antifoam) Rhodigel 23 (xanthan) 40% (w / w) solution of dichlorophenate and water to% (w / v)

0.5 и (weight / volume)

1.0% (w / v)

0.5% (w / v)

0.1% (w / v)

0.2% (w / v)

0.25% (weight volume)

100% vol

Example 3

A water-miscible formulation containing bromoxynil potassium salt is prepared from the following ingredients:

bromoxynil potassium hydroxide tetrahydrofurfuryl alcohol water to% (w / v)

5.1% (w / v)% (w / v)

100% vol

The above composition is prepared by mixing part of the water, tetrahydrofurfuryl alcohol, bromoxynil and potassium hydroxide with stirring and heating, then adjusting the volume to 100% by adding additional water.

Example 4

An emulsifiable composition containing bromoxynil octanoate is prepared from the following ingredients:

bromoxynil octanoate with an acid equivalent of 63.9% (w / w) of 35.2% (w / v)

Atlox 4,855 (mixture of anionic and non-ionic surfactants 3.75% (w / v)

Agrilan A (mixture of anionic and nonionic surfactants) 3,75% (w / v)

Solvesso 150 (aromatic oil fraction - C _1Q ) up to 100% by volume

The above composition is prepared by mixing a portion of the aromatic oil fraction (C ^ _Q ), Atlox 4,855, Agrilan A and bromoxynil octanoate while mixing and heating, then adjusting to 100 volumes by adding the aromatic oil fraction (C ^). %.

Example 5

An aqueous suspension concentrate containing bromoxynil in free phenol form is prepared from the following components:

bromoxinyl

Soprophor FL (arylphenol ethoxylate ester with phosphoric acid)

Sopropon T36 (natriumpolycarboxylate)

Ethylan BCP (the condensation product of nonylphenol with ethylene oxide containing 9 moles of ethylene oxide)

56.25% (w / v)

3.5% (w / v)

0.3% (w / v)

0.5% (w / v) is prepared by thoroughly mixing the ingredients and comminuting the mixture with pressure.

Antifoam FD (silicone antifoam)

Attagel 50 (swellable attapulgite clay) propylene glycol water

0.1% (w / v) to

2,0

5.0

100% (w / v)% (w / v)

The above-mentioned means pass through the ball mill under ad 6

An aqueous suspension concentrate containing bromoxynil octanoate and diflufenican is prepared in proportions from the following components

5.87: 1:

bromoxynil octanoate containing 63.9% equivalent of 35.2 acid Arylan CA (70% butanolic calcium dodecylbenzenesulfonate solution) Synperonic NPE 1800 (nonylphenol - ethylene oxide - propylene oxide block copolymer) Solvesso 200 (aromatic petroleum fraction - C. _n / C ₁₇ ) ^υ diflufenican ¹⁰ Soprophor 3D33 (ethoxylated polyaryl phenol phosphate neutralized triethanolami.nem), Olin 10G (the condensation product of nonylphenol and glycidol containing 10 moles of glycidol) Antifoam FD (silicone antifoam), Attagel 50 (attapulgite swellable ^г Inca) ammonium chloride water (weight / volume ) do

2,0

3.0

6.0

6.0 (w / v) (w / v) (w / v) (w / v)

0.16% (w / v)

0.08% (w / v)

0.2

2,0

5.0

100% (w / v) (w / v) (w / v) vol

The above composition is prepared by first mixing, under heating and stirring, a solution of calcium dodecylsulphosulfonate, a nonylphenol-ethylene oxide-propylene oxide block copolymer, an aromatic petroleum fraction ^and bromoxynil octanoate. Thereafter, thorough mixing of the water by volume with diflufenican, ethoxylated polyarylphenol phosphate neutralized with triethanolamine, a condensation product of nonylphenol with glycidol, a silicone anti-foaming agent, attapulgite clay and ammonium chloride, followed by pulverizing through a ball mill under pressure, prepared. The above-prepared bromoxynil octanoate solution was then added to this suspension concentrate and the volume was adjusted to 100% by the addition of water.

Dilute 1.5 liters of the resulting formulation with 200 liters of water and apply the preparation postemer264338 gently by spraying on 1 hectare of winter wheat to eradicate Stellaria medium, Viola arvensis and Veronica persica.

Example 7

By mixing (tankmix) 888 ml of the composition of Example 5 with 100 ml of the composition of Example 5 in 100 liters of water, a 10: 1 mixture is prepared. The resulting spray is applied per hectare of emerging barley to exterminate the polygons convolvulus, Sinapis arvensis and Amaranthus retroflexus.

Example 8

By mixing (tankmix) 888 ml of the composition of Example 5 and 50 ml of the composition of Example 2 in 100 liters of water, a 20: 1 mixture is prepared. The resulting spray is applied per hectare of emerging barley to exterminate the polygons convolvulus, Sinapis arvensis and Amaranthus retroflexus.

Example 9

By mixing (tankmix) 444 ml of the composition of Example 4 with 500 ml of the composition of Example 4 in 300 liters of water, a 2: 5 mixture is prepared. The resulting spray is applied soon after emergence to 1 hectare of spring wheat to eradicate emerging and germinating plants of Setaria viridis and Amaranthus retroflexus.

Example 10

A mixture (tankmix) consisting of 600 ml of the composition of Example 6 and 1800 ml of a stable aqueous solution containing MCPA potassium, sodium and dimethylammonium salt in an amount corresponding to 500 g / liter of 2-methyl-4-chlorophenoxyacetic acid in 200 liters of water is prepared. The resulting preparation was postemergently applied per hectare of winter wheat to eradicate Stellaria media, GaleopsiB tetrahit, Sinapis arvensis and Viola arvensis.

In the compositions of the preceding examples, said HBN herbicide may be replaced by any other HBN herbicide or mixture of HBN herbicides.

Claims (3)

. SUBJECT OF THE INVENTION A herbicidal composition comprising (a) 3,5-dibromo-4-hydroxybenzonitrile or an ester thereof with octanoic or heptanoic acid, or an alkali metal or triethylamine salt thereof, or a mixture thereof, and (b) N- (2,4-difluorophenyl) -2- (3-trifluoromethylphenoxy) nicotinamide, in a weight ratio of (a) :( b) from 20: 1 to 2: 5, in combination with a herbicidally usable diluent or carrier and / or surface active agent. 2. A composition according to claim 1, wherein component (a) comprises 3,5-dibromo-4-hydroxybenzonitrile octanoate or 3,5-dibromo-4-hydroxybenzonitrile heptonate. 3. A composition according to claim 1, comprising components (a) and (b) in a weight ratio between 10: 1 and 2: 5, calculated on the weight of acid equivalents, wherein component (a) forms 3,5-dibromo-4-hydroxybenzonitrile in the form of a free phenolic derivative, an alkali metal or triethylamine salt, or an ester with heptanoic or octanoic acid.