HU180832B - Process for selective extirpation of weeds of cereals and for producing synergetic herbicide composition for sellective extirpation of weeds of cereals - Google Patents

Abstract

The mixing rate of compd. I (Bigenox) and compd. II[M.C. P.A., when X=CH2-.; M.C.P.B., when X=-(CH2)3-.; Mecoprop, When x=-CH(CH3)-, as herbicides is described. Thus, wt% of bifenox and mecoprop was faborable at the rate of 1:3˜1.5:1. The mixt. of bifenox 20, nicoprop (K-salt) 40, Na-lauryl-sulfate 3, Na-lignin-sulfate 3, precipritated silica 8 wt%, and caolin 26 inhibited the growth of Anethum Graveolens, caspella Bursa-pastorsm Centaruea Cyanusm Fumaria officinalis, Lamium amplexicaulem Papaver rhoeasm Silene, and Syerallia Media by 80%

Description

The present invention relates to a novel method for the selective control of weeds grown in cereals. The present invention also provides herbicidal compositions containing a synergistic active compound combination for this purpose.

The broadleaf weeds of the family Matricaria spp are known to be particularly resistant to a variety of conventional herbicide formulations, causing severe damage to spring and autumn cereals such as wheat, barley, oats and rye. It has been found that by using a suitable combination of known herbicides these herbicides are particularly well controlled, surprisingly superior to those of known herbicidal formulations, and using the well-known Colby equation (Weeds, 15, 20-22 (1967)). synergistic effect. The formulations also showed good activity against other harmful weeds and synergism was observed in many of these cases.

According to the method of the invention, the selective weed control is carried out by applying a herbicidal composition comprising a combination of the active compounds of formula (I) and (II) to the area to be treated. In formula (II), X is -CH (CH ₃ ) -, -CH ₂ - or - (CH ₂ ) ₃ .

When X is -CH (CH ₃ ) -, 0.25-3.0 kg / ha of the compound of formula I and 0.5-3.0 kg / ha of the compound of the formula II amount of the composition.

When X is -CH ₂ -, 0.7-2.0 kg / ha of the compound of formula I and 0.7-3.0 kg / ha of the compound 180832 of the general formula II an appropriate amount of formulation is used.

When X is - (CH ₂ ) ₃ -, 0.25-3.0 kg / ha of the compound of the formula I and 0.1-3.5 kg / ha of the compound of the general formula II in an amount corresponding to the amount of the composition. According to the invention, it is also possible to use a combination of several compounds of formula II in addition to the compound of formula I. When the composition used is a combination of a compound of formula (I) and a single compound of formula (II) wherein X is -CH (CH ₃ ) -, the composition is used to treat cereals other than spring wheat.

Generally, the amount of compound (I) is 0.7 to 2.0 kg per hectare, and that of compound (II) is 0.7 to 3.0 kg / ha.

The compound of formula (I), commonly known as bifenox, is disclosed in British Patent No. 1,232,368. The use of herbicides as an active ingredient in Proc. N. E. Weed Sci. Conf. 27, 31 (1973).

The compound of formula (II) having the substituent X as a substituent is -CH (CH ₃ ) - is known as mecoprop.

The compound of formula (II) having the substituent X as -CH _{2 is} called MCPA

The compound of formula (II) containing the substituent X as - (CH ₂ ) ₃ - is named MCPB

Mecoprop, M.C.P.A., M.C.P.B., and their salts and esters, their preparation and herbicidal properties have been described in numerous publications.

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The compounds of formula (II) may be used in the form of the free base, salts or esters, provided that they are not phytotoxic to the cereals. Salts include, for example, alkali metal salts such as sodium and potassium; ammonium, alkyl ammonium and 5 alkanolammonium salts such as ethanolammonium salts. Among the esters, for example, C 1 -C 8 alkyl esters such as methyl and octyl esters can be used. The invention also relates to the use of salts and esters.

In the process according to the invention, the compound of formula (I) is preferably applied in an amount of 0.7-1.5 kg / ha, more preferably 0.75-1.0 kg / ha. The preferred application rates for compounds of formula II where X is -CH (CH ₃ ) - or - (CH ₂ ) ₃ - mecoprop and MCPB are from 1.0 to 2.0 kg / ha. Preferably, the compound of formula (II) having the substituent X, which is -CH ₂ -, i.e. MCPA, is used in an amount of 0.7-1.5 kg / ha, more preferably 0.75-1.0 kg / ha.

The weight ratio of the compounds of formula (I) to the formula (II) is generally from 1: 4 to 3: 1. If bifenox and mecoprop or M.C.P.B. the weight ratio of the former to the latter is preferably from 1: 3 to 1.5: 1, more preferably 1: 2. When bifenox is combined with M.C.P.A., the weight ratio of the former to the latter is preferably in the range 1: 2 to 2: 1, more preferably 1: 1.

When salts or esters of the compounds of formula (II) are used, the weights and ratios given refer to the acid equivalent. 30

Preferably, the process of the invention is carried out between the development of the first leaf and the appearance of the first knot.

The treatment according to the invention has been found to be most advantageous for winter wheat, spring barley and winter barley. 35

The compounds of formula (I) and (II) may be formulated separately and may be used together or separately. When formulations containing the active ingredient of Formula I and Formula II are administered separately, the time between administration is preferably short, so as to ensure that the time elapsed is preferably within one day. However, it is by far the most advantageous to use the active compounds simultaneously in a single formulation. For ease of processing, storage and transport, herbicidal compositions are generally formulated in the form of 45 concentrates which, when diluted with water, yield the desired amounts of active ingredient per hectare. The formulations contain from 0.1 to 90% by weight, preferably from 1 to 90% by weight, most preferably from 15 to 85% by weight of the active ingredient, in combination with one or more inhaled non-phytotoxic carriers. These formulations are generally formulated as wettable powders, emulsifiable concentrates, or aqueous suspensions or solutions.

The invention also relates to the herbicidal compositions themselves. The herbicidal compositions of the present invention which are useful after carrying out the process of the invention comprise a weight ratio of a compound of formula (I) to a compound of formula (II) or a salt or ester thereof [in the formula (II). ), with non-phytotoxic diluents or carriers. The preferred range is given above.

The invention also relates to herbicidal compositions comprising a compound of formula (I) and a compound of formula (II) in which X - (CH ₂ ) ₃ - or a salt or ester thereof is 1: 4. -3: 1 by weight (in terms of acid equivalent of the compound of formula (II)) in combination with a non-phytotoxic diluent or carrier. The preferred weight ratio is as given above.

The formulations of the invention include not only the so-called concentrates, but also the ready-to-use diluted formulations. These include tank mixes and ready-to-use sprays. These formulations are generally prepared by appropriate dilution of the concentrates, but may, if desired, be prepared by directly weighing the appropriate amounts of each component in a suitable diluent or carrier.

Returning to the concentrates, wettable powders are a well-formulated mixture of the active ingredient and one or more tendon carriers and one or more surfactants. The inert carrier may be, for example, attapulgite clay, montmorillonite clay, diatomaceous earth, kaolin, mica, clay or purified silicate. Examples of active surfactants include sulfonated lignins, naphthalene sulfonates and condensed naphthalene sulfonates, alkyl succinates, alkyl benzene sulfonates, alkyl sulfates, and adducts of nonionic surfactants such as ethylene oxide and phenol. Wettable powders according to the invention may, for example, have the following composition:

Wettable Powders Compound of Formula I Compound of Formula II Surfactant (s) Dispersant Composition Inhibitor

1-73% by weight

1-79% by weight

1-10% by weight 0-10% by weight 0-10% by weight of injected vehicle (s) in quantities of 100% by weight

The amount of compound of formula (II) is expressed in terms of acid equivalents.

Emulsifiable concentrates contain solutions of the active compounds in one or more solvents and a surfactant. Examples of the solvent include alkyl substituted benzene derivatives, o-chlorotoluene, heavy aromatic naphthalene compounds, glycol ethers and cyclic ketones. Emulsion concentrates typically have the following composition:

Emulsifiable Concentrates Compound of Formula I Compound of Formula II Surfactant (s) Co-Solvent

1-55% by weight

1-60% by weight

2-10% by weight

0-40% by weight of solvent

100% by weight

The amount of compound of formula (II) is expressed in terms of acid equivalents.

Aqueous suspensions and solutions contain the active compounds suspended or dissolved in water, optionally with surfactants, thickeners, anti-freeze and / or preservatives. The range of surfactants that can be used is the same as that for wettable powders. Thickening agents are generally selected from cellulose-based materials and natural gums, while glycols are generally used as antifreeze-2180832

used. Preservatives are made from a wide range of materials. Designation of ingredients Quantity (% by weight) be postponed. These include the various antibacterial 5. bifenox 30 g., phenol, o-chlorocresol, phenylmercury nitrate and formaldehyde. M.C.P.A. (Sodium salt) 30 bridge. Aqueous suspensions have the following typical composition: sodium laureth sulfate 2 5 Sodium lignin sulfonate 3 Aqueous suspensions precipitated silica 5 montmorillonite 100% required A compound of formula (I) 4-59% (w / v) quantity. Compound of Formula II 5 to 65% (w / v) humectant 0-10% (w / v) 10 The components given in each example are appropriate dispersant 0-6% (w / v) proportions in a conventional mixing equipment thickener / suspending agent 0-5% (w / v) mixed. Then the mixture is further ground in a liquid mill- antifreeze 0-15% (w / v) until the particle size reaches it 1-10 microns. preservative 0-2% (w / v) water for 100% 15 6-10. examples The amount of the compound of formula (II) in an acid equivalent Emulsifiable concentrates given in terms of lens. The following compositions are emulsifiable concentrates Aqueous suspensions or wettable powders are preferably used in the process of this invention because they are 20 we produce: they are significantly less phytotoxic to crops, Designation of ingredients Quantity (%) as emulsifiable concentrate w / v. products. 6. bifenox 15 Further details of our invention are provided in the with the following examples mecoprop 30 illustrated where mecoprop, M.C.P.A and M.C.P.B. 25 calcium dodecylbenzene sulfonate 3 is expressed in acid equivalents. A- alkylphenoxy polyethylene ethanols 3 the chemical name of the compounds designated by the trade name isophorone 20 previously given, for simplicity in the examples, xylene 100% required we use trade names. quantity 30 7. bifenox 15 1-5. examples mecoprop ester 20 alkylaryl sulfonate 4 Wettable powder preparations polyoxyethylene triglyceride 4 Wettable powder formulations having the following composition cyclohexanone 20 we produce: 35 o-chlorotoluene 100% required quantity Designation of ingredients Quantity (% by weight) 8. bifenox 10 1. bifenox 20 becoprop 25 mecoprop (potassium salt) 40 the amine salt of dodecylbenzenesulfonic acid 3 sodium laureth sulfate 3 40 polyoxyethylene sorbitan fatty their esters 4 Sodium lignin sulfonate 3 rek 15 precipitated silica 8 isophorone 100% required kaolin 100% required heavy aromatic naphthalene derivatives quantity quantity 2. bifenox 20 45 9. bifenox 20 mecoprop (sodium salt) 27 M.C.P.B. (mixed butyl esters) 30 ethoxylated alkyl phenol 4 calcium dodecylbenzene sulfonate 3 lignin sulfonate 3 alkyl phenoxy polyoxyethylene ethanols 4 pyrolytic silica 6 isophorone 30 attapulgite 100% required 50 100% required quantity o-chlorotoluene quantity 3. bifenox 10 mecoprop (diethanolamine salt) 25 10. bifenox 20 condensed naphthalenesulfonic acids M.C.P.A. 20 Sodium salt 6 55 calcium dodecylbenzene sulfonate 3 precipitated silica 10 alkyl phenoxy polyoxyethylene ethanols 4 sodium aluminosilicate 100% required isophorone 30 quantity 100% required 4. bifenox 30 o-chlorotoluene quantity M.C.P.B. (Sodium salt) 45 60 sodium laureth sulfate 2 The active ingredients are mixed and given in the case of dissolution Sodium lignin sulfonate 3 during auxiliary heating, add suitable solvent (s) - precipitated silica 5 offer. The resulting concentrate is then added to the montmorillonite 100% required active substances. Insoluble impurities by filtration quantity 65 remove from the solutions.

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11-13. examples

Aqueous suspensions

Aqueous suspensions were prepared as follows:

Designation of ingredients Quantity (% by weight) 11. bifenox 30 M.C.P.A. (Amine salt) 30 (Ethyl) hydroxyethyl cellulose 0.2 lignin sulfonate 3 propylene glycol 2 water 100% required 12. bifenox 20 M.C.P.B. (Amine salt) 35 hydroxyethyl cellulose 0.2 amine ethoxylate 3 water 100% required 13. bifenox 25 mecoprop (amine salt) 50 hydroxyethyl cellulose 0.5 phosphate ester 3 ethylene glycol 2 water 100% required Designation of ingredients Quantity (% by weight) 14. bifenox 30 mecoprop (amine salt) 55 hydroxyethyl cellulose 0.5 phosphate ester 3 ethylene glycol 2 water 100% required

Example 15

We conducted some field trials on winter wheat and one on spring barley on sandy and clay soils. The test formulations were sprayed on the soil in a tank mix of 300-800 liters / ha. At the time of treatment, the development of the plants varied between the appearance of the first stem shoots and the development of the second bunch. A visual evaluation of the herbicidal effect was made 2 to 15 weeks after application, using the evaluation system of Barratt and Horsfall (1945).

The following table shows the% herbicidal activity against the weeds of the Matricaria family: bifenox, mecoprop and M.C.P.A. single application of both bifenox and mecoprop and bifenox and M.C.P.A. when used together as a tank mix. The additive control value calculated from the Colby equation is also given. The aqueous sprays are 80% wettable powder with bifenox, 55% aqueous solution with mecoprop and M.C.P.A. of the active compound in the form of a 40% aqueous solution.

Spreadsheet

Dose ° 'herbicide (Kglia) observed Colby equation 5 bifenox 1.0 16.1 SO bifenox 1.5 25.5 SO bifenox 2.0 40.3 SO M.C.P.A. (Amine salt) 0.8 38.5 SO 10 M.C.P.A. (Amine salt) 1.6. 64.8 SO mecoprop (amine salt) 2.0 54.8 SO bifenox + M.C.P.A. (Amine salt) 1.0 + 0.8 85.1 48.4 1.5 + 0.8 93.4 54.2 15 2.0 ± 1.6 95.3 79.0 bifenox + mecoprop (Amine salt) 1.0 + 2.0 86.0 62.1 1.5 + 2.0 89.0 66.3

It is clear from the table that the process of the present invention achieves a tremendous amount of synergistic effect.

A slight scorching of the grain was observed, but the plants grew out of development.

Matricaria spp. of weeds belonging to the family for kö25 we sin weeds were observed weed control in excess _{o with} 80 ° in case of the use described above, tank mixes: Anethum graveolens, Capsella bursapastoris, Centaurea cyanus, Fumaria officinalis, Lamium amplexicaule, Papaver rhoeas, Silene spp and Stellaria media. The formulations containing the combination of bifenox and MCPA also showed herbicidal activity of more than 80 ° ₀ against the following weeds: Anagallis arvensis, Chenopodium album, Polygonum aviculare, Ranunculus arvensis, Ranucules repens, Raphanus raphanistrum, Ru35 mex crispus, Sinap crispus arvensis and Veronica hederifolia.

In addition, preparations containing a combination of bifenox and mecoprop have controlled the Galium aparine species by more than 80%.

Example 16

Bifenox and M.C.P.B. The following greenhouse experiment was performed to investigate the herbicidal activity of preparations containing a combination of the two.

Method

Magok Galium aparine

Matricaria recutita

Veronica persica

Planting: 0.5 cm deep (light cover for Matricaria sp) Temperature / Illumination: if required

Irrigation: if necessary

Fertilization: None

Experimental layout: random block, 4 replicates Treated area: 10 x 10 cm pots

Soil structure: clay

Equipment: one sprayer microsprayer, 50 cm bandwidth, 50ml / m ²

Condition of weeds at treatment: 3-5 true leaves

The following table shows the average of the 65% herbicide values measured during the experiment and the Colby equation

-4180832. The effect against Veronica persica was evaluated visually. For the other two species, fresh weights of shoots were measured.

The bifenox from which the spray liquor was prepared was available in the form of wettable powder formulations containing 80% active ingredient. M.C.P.B was used as a 48% aqueous solution. A tank mix was prepared from the two formulations given.

Weed species,% weed control

Application rate (kg / ha) Matricaria Sp Gallium aparine Veronica persica Observed Colby Observed Colby Observed Colby bifenox 0.75 56.5 SO 62.5 SO 77.0 SO M.C.P.B. 1.0 7.5 SO 0.0 SO 73.0 SO M.C.P.B. 1.5 2.4 SO 0.0 SO 78.0 SO bifenox + MCPB 0.75 + 1.0 73.0 60.0 72.1 62.5 100.0 94.0 bifenox + MCPB 0.75 + 1.5 82.0 57.5 78.3 62.5 100.0 96.0

From the data in the table, it can be seen that the compositions of the present invention can be used in accordance with the process of the invention to achieve an astonishing synergistic effect.

Example 17

This example further illustrates the synergistic effect of the combination of bifenox and mecoprop in Matricaria spp. family broadleaf weeds.

In France, winter wheat was sown to a depth of 3 cm in October. The amount of seed sown per hectare was 150 kg. The grain was allowed to grow untreated until the following March, when the plants reached a growth stage of 4-5 (Plant Pathol., 1954, 3, 128-129).

The plants were then treated with formulations containing bifenox and mecoprop, followed by formulations containing a combination of the two. The treatment was carried out using conventional equipment, spraying with 300 liters of spray liquid per hectare. The% herbicidal activity was evaluated 2 and 5 weeks after treatment.

Spreadsheet Application rate (g / ha) Matricaria spp% * herbicide bifenox 1000 6 bifenox 1500 15 bifenox + mecoprop 1000 + 2000 87 bifenox + mecoprop 1500 + 2000 88 mecoprop 2000 50 Patent claims

1. A herbicidal composition which breed in corn fields for controlling weeds, characterized in that the formula (I) and a compound (II) is a compound of formula wherein X is -CH ₂ group, 60

Claims (21)

CLAIMS 1. A herbicidal composition for controlling weeds grown on cereal crops, characterized in that the compound of formula I and a compound of formula II in which X is -CH ₂ - or a non-phytotoxic salt or ester thereof for cereals 1 : 4 to 3: 1 by weight, in a total amount of 0.1 to 90% by weight, one or more inert solid and / or liquid carriers, preferably natural stone flours and / or benzene derivatives, and optionally 65 surfactants, preferably sulfonated lignins, naphthalene sulfonates or alkylaryl sulfonates. (Priority: July 13, 1979) An embodiment of the herbicidal composition according to claim 1, characterized in that it is in the form of an aqueous suspension or wettable powder. 25 (Priority: July 13, 1979) A process for controlling weeds grown on cereals, preferably winter wheat, spring barley or winter barley, characterized in that the crop is a compound of formula (I) and a compound of formula (II): 30 equation X is -CH ₂ or a non-phytotoxic salt or ester thereof of the latter in a single or combined combination prepared from a combination prepared from an aqueous solution of 0.7-2.0 kg, preferably in the form of an aqueous dilution of an aqueous suspension or powder. / ha of the compound of the formula I and 0.7-3.0 kg / ha of the compound of the formula II, preferably by spraying, preferably when the cereal plants are in the stage of development between the first leaf and the appearance of the second lump. (Priority: July 13, 1979) 4. A process according to claim 3, wherein the treatment is carried out with an amount of 0.7-1.0 kg / ha of active compound of formula (I). 45 zuk. (Priority: July 13, 1979) 5. The process according to claim 3 or 4, characterized in that the treatment with 0.7-1.5 kg / ha of active compound of the formula II - X in claim 3 50 with the meanings given - a sufficient amount of the composition. (Priority: July 13, 1979) 6. A process according to claim 3 wherein the compound of formula (I) and (II) The compound of formula 55 is as defined in claim 3 in a weight ratio of 2: 1 to 2: 1. (Priority: July 13, 1979) 7. A herbicidal composition for controlling weeds grown on cereals, characterized in that the compound of formula I and a compound of formula II in which X is - (CH ₂ ) ₃ - or a non-phytotoxic salt of the latter in cereals or containing from one to four percent by weight of one or more solids of its ester in a weight ratio of 1: 4 to 3: 1 -5180832 and / or liquid inert excipients, preferably with natural stone flour and / or benzene derivatives, and optionally with surfactants, preferably sulfonated lignins, naphthalenesulfonates or alkylarylsulfonates. (Priority: December 21, 1978) 8. An embodiment of the herbicidal composition according to claim 7, characterized in that it is in the form of an aqueous suspension or wettable powder. (Priority: December 21, 1978) 9. A method of controlling weeds grown on cereals, preferably winter wheat, spring barley or winter barley, wherein the crop is a compound of formula (I) and a compound of formula (II): X is - _{(CH2) 3} -csopon, cereals or the latter is ready for use of the combination of individually formulated or co-formulation, preferably an aqueous suspension, or liquid formulation composition thus obtained is treated with aqueous dilution of a non-phytotoxic salt or ester thereof, 0.25 3.0 kg / ha of the compound of the formula I and 0.1 to 3.5 kg / ha of the compound of the formula II, preferably by spraying, preferably when the cereal plants are in the stage of development between the appearance of the first leaf and the second lump. (Priority: December 21, 1978) 10. The process according to claim 9, wherein the treatment is between 0.7 and 2.0 kg / ha of the active ingredient of formula (I) and 0.7 to 3.0 kg / ha of the active ingredient of the formula (II). X is formulated as defined in claim 9 in an appropriate amount. (Priority: December 21, 1978) 11. The method according to claim 9 or 10, wherein the treatment is carried out in an amount of 0.7-1.5 kg / ha of the active compound of formula (I). (Priority: December 21, 1978) 12. A process according to any one of claims 1 to 4, characterized in that the treatment is carried out with a suitable amount of the compound of the formula II, X as defined in claim 9, in an amount of 0.75-1.0 kg / ha. (Priority: December 21, 1978) 13. The process of claim 9, wherein the compound of formula (I) and the compound of formula (II) are used in a weight ratio of from 1: 3 to 1.5: 1 X. (Priority: December 21, 1978) 14. A herbicidal composition for controlling weeds grown on cereal crops, characterized in that the compound of formula (I) and a compound of formula (II) X is a combination of -CH (CH ₃ ) or a non-phytotoxic salt or ester thereof of the latter in a weight ratio of 1: 4 to 3: 1 in a total amount of 0.1 to 90% by weight with one or more solid and / or liquid inches a carrier, preferably natural stone flour and / or benzene derivatives, and optionally surfactants, preferably sulfonated lignins, naphthalene sulfonates or alkylarylsulfonates. (Priority: July 15, 1978) 15. An embodiment of the herbicidal composition according to claim 14, characterized in that it is in the form of an aqueous suspension or wettable powder. (Priority: July 15, 1978) 16. A method of controlling weeds grown on cereals, preferably winter wheat, spring barley or winter barley, wherein the crop is a compound of formula (I) and a compound of formula (II): X is -CH (CH ₃ ), or a salt thereof, or a non-phytotoxic salt or ester thereof, in the form of a solution prepared from a mixture of the latter or a phytotoxic salt thereof, preferably in the form of an aqueous suspension or dilution powder, 0.25-3.0 kg / ha of the compound of the formula I and 0.5 to 3.0 kg / ha of the compound of the formula II, preferably by spraying, preferably when the cereal plants are in the stage of development between the appearance of the first leaf and the second lump. with the proviso that we treat crops other than spring wheat. (Priority: July 15, 1978) 17. The method of claim 16, wherein the treatment comprises 0.7-2.0 kg / ha of active ingredient of formula (I) and 0.7-3.0 kg / ha of active ingredient of formula (II). X is as defined in claim 16 in an appropriate amount. (Priority: July 15, 1978) 18. The method according to claim 16 or 17, wherein the treatment is carried out in an amount of 0.7-1.5 kg / ha of the active compound of formula (I). (Priority: July 15, 1978) 19, pp. 16-18. A process according to any one of claims 1 to 4, characterized in that the treatment is carried out with a suitable amount of a compound of the formula (II) - X - as defined in claim 16 - in an amount of 0.7-1.5 kg / ha. (Priority: July 15, 1978) 20. The method of claim 19, wherein the treatment is carried out in an amount of from 0.75 to 1.0 kg / ha of the compound of formula (II). (Priority: July 15, 1978) 21. A process according to claim 16, wherein the compounds of formula I and X are as defined in claim 16 in a weight ratio of 1: 3 to 1.5: 1. .