CS250685B2 - Herbicide - Google Patents

Description

A herbicidal composition comprising, as an active ingredient, O- [3-phenyl-6-chloropyridaziinyl (4)] - S- (6-octyl) thiocarboinate in admixture with 2-chloro-4-ethylamino. 6-isopropyliamino-1,3,5-triazine and chloroacetamide of formula I

O Ri II / Cl — CH2 — C — N

'..... χ. . .. \

R i ^'Ί (I) wherein the substituents are given below and, per 1 part 0 t [3tfe ^ι-6-phenyl PLA' pyridazinyl, (4)] (TST Ot -idktyl) ťhtokarbonátu composition contains 0.25 to 4 parts of 2- chloro-4-methylamino-10'-6-isopropylpylamino-1,3,5-triazine and 0.15-6 parts of chloroacetamide.

The invention relates to a composition having a synergistic effect comprising as active ingredient a mixture of 0- [3-phenyl-6-chiorpyridazinyl (4)] - S- (n-octyl-1) thiokartonátu ^2-Chloro-4-i ^ et ^ R ylh nihoo6-IIsi ^ ^] ^ r ⁱ pollinated Amiina · -1,3,5-triazine and the chloroacetamide.

It is known from Austrian Patent No. 326,137 that 3-phenyl-6-dihalopyridazinylthiocarbonates and diithiociarboinates have herbicidal properties and are particularly useful for suppressing sensitive grasses in the early stages of plant development. In particular, O- [3-phenyl-6-chloropyridazinyl (4)] - S- (n-octyl) thtocarbonate (Pyridate) has practical application as a herbicidal composition. However, it has been shown over time that certain grasses, such as wild millet, cannot be exterminated by Pyridate alone if the plants have more than four developed leaves, or high doses of the composition are required for this purpose.

It is known from "The pesticide Manual" 6th edition, 1979, p. 22, that 2-chloro-4-amino-6-isopropylamincol, 3,5-triazine (Atraziine) can be used as a herbicide before emergence. In other cases, weed control, such as Echinochloa crus galii (hedgehog), cannot be achieved satisfactorily as described in the Mitteilungen aus der Bitologischen Bundesanstalt für Land- und Fostwirtschaft, Berlin. -Dahlen, 1967, workbook 121, p. 237 and a summary on pages 238 and 239.

It is also known that 2-chloroacetainilides are useful as pre-emergence herbicides as described, for example, in Weed Control Handbook; Principles 7th edition, 1982, Blackwell Scientific Publications and "Zeitschrift für Pfla; nzenkrankheiten und Pflanzenschutz, Special Issue X, 1984, published by Eugen Ulmer Stuttgart, pp. 361-367, in particular page 365 and last paragraph and summary on pages 366 and 367. It is also known that 2-chloro-acetanilio, for example, 2-chloro-2 ', 6'-dimethyl-N- (1-pyrazolylmethyl Jacetanilide) (Metazachlorj can be combined with an antidote and Atrazine to The effect on grasses also has a broader action against various other weeds The expression can be achieved before emergence, in one or two leaf stage or directly in the germination stage From the same publication on pages 369 to 376, in particular on page 372 and the summary on pages 375 and 376, it is known that 2-chloroacetamide-α-chloroacet-N- (3,5,5-trimethylcyclohexen-1-yl) -N-isopropylamide (Trimaxachlor) complements the spectrum of activity in combination with Atrazine, e.g. Herbicidal mixtures which have an additive effect are very suitable because one herbicide in the mixture complements the drawbacks of the effect of the other herbicide.

It has now been unexpectedly found that the spectrum of action can be additively expanded in the case of a combination of Pyridate, Atrazine and chloroacetamide, which was not to be expected in principle, with particular emphasis on emergence efficacy, in this case a synergistic effect of herbicides.

The possibility of treating post-emergence stands is very important for practical use, since in this case weed can be used to control grass weeds in all developmental stages from emergence to the beginning of stem formation by a single treatment. to destroy those plants that are currently germinating, so that grasses that germinate later need to be destroyed again, so that reuse of the herbicidal composition is always necessary.

In the case of a synergistic effect, it is possible to reduce the amount of the individual components while maintaining a good effect whilst at the same time completely or almost completely weed control at a concentration at which the individual components would be ineffective. It also means a substantial extension of the effectiveness against various weed species and an increase in the safety of use as regards the health status of crop plants.

Accordingly, the present invention provides a herbicidal composition comprising as active ingredient O- [3-phenyl-6-chloropyridazinyl (4)] - S- (n-octyl) thiocarbonate in admixture with 2-chloro-4-ethylamino- 6-isopropylamino-1,3,5-triazine and chloroacetamide of formula I

O Ri

II /

Cl — CH2 — C — N \

Rž

................... (I) where

R1 represents an alkyl radical, an alkoxyalkyl radical or a pynazol-1-ylmethyl radical a

R 6 represents a phenyl, 2,6-dialkylphenyl or trimethylcyclohexenyl radical, in which R1 and R R each contain alkyl or alkoxy radicals having from 1 to 3 carbon atoms and per part by O- (3-phenynyl-6); -chloropyridaziinyl (4)] - S- (n-octyl) thiocarbonate, the composition comprising 0.25 to 4 parts of 2-chloro-4-ethylamino-6-lisopropylamino-1,3,5-triazine and 0.15 to 6 parts of chloroacetate of amide.

Thus, the synergistic herbicidal composition comprises as active ingredient a mixture of Pyridate, Atrazine and 2-chloroacetamides, in particular 2-chloroacetanilide. For example, compounds such as Trimexachlor, Metazachlor, Alachlor, i.e. 2-chloro-N- (2,6-diethylphenyl) -N- (methoxymethyl Jacetamide, Metolachlor, i.e. 2-chloro-N- (2-ethyl- 6-methylphenyl] -N- (2-methoxy-1-methyl-250585 ethyl) acetamide, Azebochlor, i.e. 2-chloro-N- (2-ethyl-6-methylphenyl) -N- (ethoxymethyl) acetamide or Propachlor, i.e. -chloro-N- (1-methylethyl) -Nphenylacetamide.

Particularly preferred is a synergistic composition comprising as active ingredient a mixture of Pyridate, Atrazine and Alachlor or a mixture of Pyridate, Atrazine and Metolachlor.

The composition of the herbicidal composition of the invention may vary within certain ranges. The composition contains 0.25 to 4 parts of Atrazine and 0.15 to 6 parts of Chloroacetamide per part of Pyridate, preferably 0.5 to 2 parts of Atrazine and 0.3 to 2.5 parts of Chloroacetamide per part of Pyridate.

In addition to the novel active compound combination, the herbicidal composition according to the invention also contains a suitable carrier and / or other additives. They may be solid or liquid substances which are commonly used, for example natural or regenerated minerals, solvents, dispersants, crosslinkers, adhesives, thickeners, antifoaming agents, binders or fertilizers. It is also possible to add agents which lower the melting point of one or more active substances.

Suitable formulations are, for example, sprayable powders, directly applicable or dilutable solutions, suspensions, emulsions, concentrated emulsions, soluble powders, dusts, granules and compositions embedded in, for example, polymer matrices. nebulae, irrigation, etc., depending on the type of composition, the desired result and other circumstances.

Compositions containing the active substances and optionally solid or liquid additives are prepared in a known manner, for example by thoroughly mixing and / or grinding together the active substance and the carrier, the solvent and optionally the surfactant (wetting agent).

Solid carriers for, for example, dispersible granules, powders and dusts include, for example, natural clays, such as bentonite, calcite, chalk, talc, kaolin, monimoriilonite or attapulgite, or synthetic materials such as highly dispersed silicic acid or high dispersed polymeric materials . Suitable carriers in the case of granules are, in particular, porous-type substances, for example pumice stone, crushed stone, septolite or bentonite or else kialcite or sand. In addition, a variety of pre-granulated materials of inorganic or organic nature can be used.

Suitable solvents for concentrated suspensions or emulsions are aromatic hydrocarbons, preferably C8 to C12 fractions, such as mixtures of xylenes or substituted naphthalenes, phthalic esters such as dibutyl phthalate or di-octyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, vegetable oils such as sunflower oil or rapeseed oil, alcohols and glycols as well as it ^; ethers and esters such as ethanol, ethylene glycol, diethylene glycol and alkyl ethers and dialkyl ethers thereof, ketones such as cyclohexanone or iacforone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide and optionally also epoxidized vegetable oils or water.

As the melting point lowering agent, any substance suitable for this purpose in cryostatic measurement, for example camphor, naphthalene, nitrobenzene, dimethylsulfoxide or acetophenone, is suitable.

Wetting agents include nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and crosslinking properties. A surfactant mixture may also be used.

Water-soluble soaps or water-soluble synthetic surfactants can also be used as anionic surfactants.

Soaps include the alkali metal, alkaline earth metal or ammonium salts of the higher aliphatic acids of 10 to 22 carbon atoms, for example the sodium or potassium salts of oleic or stearic acids, or salts with natural mixtures of these acids, e.g. or · tallow. Also mentioned are the salts of aliphatic acids with methyltaurine.

The so-called synthetic surfactants are often used, especially sulfonates or sulfates of aliphatic acids, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The sulphonates of the aliphatic acids or sulphates of these acids are in particular alkali metal, alkaline-earth or ammonium salts, optionally substituted, containing an alkyl radical of 8 to 22 carbon atoms, wherein the term alkyl radical also includes the alkyl part of the acyl radical. that is, for example, the sodium or calcium salt of ligninsulfonic acid, dodecylsulfuric acid ester or natural aliphatic acid in the form of a mixture or aliphatic alcohols, alcohols obtained from the natural mixture. This group also includes the salts of sulfuric and sulfoic acid esters with addition products of aliphatic alcohols and ethylene oxide. The sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and an aliphatic acid residue of 8 to 22 carbon atoms. Alkylarylsulfonates are, for example, sodium or calcium salts or salts of triethanolamine and dodecylbenzenesulfonic acid, dibutylnaphthalenesulfoic acid, or salts with the condensation product of naphthalenesulfonic acid and formaldehyde.

Also contemplated are corresponding phosphates, for example salts of the phosphoric acid ester with the addition product of p-nonylphenol and ethylene oxide (4-14).

Nonionic surfactants include, in particular, derivatives of polyglycol ether and al250685 fatty or cycloaliphatic alcohols, saturated or unsaturated aliphatic acids or alkylphenols containing 3 to 30 glycol ethers and 8 to 20 carbon atoms in the aliphatic hydrocarbon radical and 6 to 18 carbon atoms in the alkyl group. the remainder of the alkylphenols.

Other suitable nonionic surfactants are water-soluble, 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups containing polyethylene oxide / polypropylene glycol addition products, ethylenediaminopolypropylene glycol and C1-C10 alkyl polypropylene glycol in the alkyl chain. Said compounds preferably contain from 1 to 5 ethylene glytool units per unit of propylene glycol.

Examples of nonionic surfactants include: nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene and polyethylene oxide addition products, tributylphenoxypolyethoxyethane, polyethylene glycol and octylphenoxypolyethoxyethanol. Also contemplated are aliphatic acid esters of polyoxyethylene sorbitan, for example polyoxyethylene sorbitan trioleate.

In the case of cationic surfactants, in particular, ammonium salts having at least one alkyl radical of 8 to 22 carbon atoms as substituents on the nitrogen atom are preferred, the other substituents being lower or optionally substituted, in particular halogenated alkyl radicals, benzyl radicals or lower hydroxyalkyl radicals. Suitable salts are, in particular, halides, methylsulphates or ethylsulphates, for example stearyltrimethylammonium chloride or benzyl di- (2-chloroethyl) ethylammonium bromide.

Wetting agents suitable for the above purpose are described, for example, in the following publications:

"McCutcheon Detergens and Emulsifiers Annual" MC Publishing Corp., Ringwod, New Jersey, 1979,

Sisely and Wood, " Encyclopedia & Surface Active Agents ", Chemical Publishing Co., Inc. New York, 1964.

The active compound content of the composition according to the invention is in the range of 0.1 to 95 percent by weight, preferably in the range of 1 to 80 percent by weight.

The active substances Pyridat and Atrazine are usually used in an amount of 0.5 to 2 kg / ha, preferably 0.75 to 1.5 kg / ha, the active compounds of the chloroacetamide type are used in a dose of 0.3 to 3 kg / ha, preferably at a rate of 0.5 to 2 kg / ha. The total amount of active substances in the herbicidal composition according to the invention is therefore 1.3 to 5.0 kg / ha, preferably 2 to 3.5 kg / ha.

The herbicidal composition with a syinergic effect is used after emergence. The main fields of application are maize cultures. However, the composition may also be used in crops of permanent plants, for example in orchards or in vineyards or in plantations of other plants, or also in tiam where all plants need to be exterminated on areas used for non-agricultural purposes, such as industry and k-oil. .

The herbicidal composition according to the invention has a syinergic effect, the calculation of which is based on the purely additive effect according to the following formula:

the formula was derived from L. E. Limpel et al., 1962, Weed control by dimethyl tetrachlorterephthalate alone and in certain cobinatioins. Why. NEWCC 16: 48-53, based on D. P. Gowing, 1960, Coimments on Herbicide Mixtures, Weeds 8: 379-391.

E = expected herbicidal effect (percentage of death) with purely additive effect pb using A + В at p Ц- q kg / ha

X degree of action in ° / o using substance A at p kg / ha

Y = degree of action in ° / o using q in q kg / ha.

The above formula has been extended in Colby, Calculatiom Synergistic and Antagonistic Responses of Herbicide Combiinaticins, Weeds, 15, 20, so that it is also possible to evaluate mixtures of the three components with the considered synergistic effect.

According to the publication, the expected degree of action of a mixture of three components can be calculated from the following formula:

_{E = x + y + z +} ^ _«t yz _L , X. Y. of 10 000

If the experimentally determined degree of action of the mixture of three components proves to be higher than the above calculated value for E, there is a synergistic effect, whereas if the value is lower, it is antagonistic.

The invention will be illustrated by the following examples.

5 O 6 8 N

Example 1 Active ingredient 1

(technical Atrazine) active substance 2 10,20% (technical Alachlor) active substance 22,00% (technical Pyridat) 13,90% technical camphor 3.65 + sodium dibutylnaphthalenesulfonate 5,00% Sodium oleylmethyltauride chalk ‘ 5,00% 6.25% highly dispersed acid siliceous 36,50%

A homogeneous solution is obtained from active substances 2 and 3 and from technical camphor by gentle heating.

From the active ingredient 1 and the remaining excipients, a powder is obtained in the auxiliary mixer and the above solution is sprayed with stirring on. After the spraying is completed, the mixture is stirred vigorously for 15 minutes and then ground in a rod mill. In this way a powder is obtained which can be used directly for spraying.

Example 2

active substance (technical Atrazine) 12.75% active substance. 3 (technical Pyridat) 12.50% active substance (technical Metolachlor) 26,00% technical camphor 3.65% sodium dibutylnatalenesulfonate 2,50% Sodium oleylmethyltauride 5,00% chalk 6.25% a highly dispersed precipitated acid siliceous 31,35%

Tab

The preparation of the composition according to the invention is the same as. in Example 1, only active ingredients 3 and 4 are used instead of active ingredients 2 and 3.

Example 3

The maize-treated experimental areas, which were unilaterally treated with chlortriazine for several years and were heavily populated with Echinochloa crus galii (hedgehog · maize inchaaJ and Setaria viridis (green grass), were divided into fields of 25 m ² each. Once the weeds were largely at the three-leaf stage and at the stem formation stage, different types of investigational formulations with different combinations of active ingredients in the form of an aqueous spray were applied to the individual fields. and water in an amount corresponding to 400 l / ha.

Evaluation was performed such that initially was determined to attack neošotřených plots counting weeds always čtyřikrát'0,25 m ² surface (i.e. 8 x ² = 0.25 m - ^·: 2 m = ²⁾ for each type of test mixture. This degree of attack was considered 100 percent. After treatment, the number of plants remaining in each field after treatment with different combinations of substances was calculated in the same way. The experimental program was carried out in total at 7 different sites.

The value calculated from the Limpel and Colbyh-o equations was used to calculate a possible synergistic effect.

The results of each experiment were shown in Table I below.

ulka I

Herbicidal effect (%) against Echinochloa crus galii

C.

active substance g / hia Atrazine 1 000 AJachlor 1 680 Pyridate 900 ΜεΐβΙ ^ Μω. ’ 1. 980 1 4- 2 1000+ 1 680 1 + 3 _y 1000+ 900 2 3 1 680+ 900 1 + 2 + 3 1000+ 1 680+ 900 1 + 4 1000+ 1 980 3 + 4 ......... 900+ y · Ж 1,980 1 + 3 + 4 “1,000+

900+

1980

found · vypučí-íVm · difference 65 6 - - 60 - 15 Dec - - 70 67 + 3 85 86 - 1 65 62 + 3 100 ALIGN! 87 +13 74 70 + 4 63 66 - 3 99 88 +11

Example 4

The experiments were carried out on plots that had been treated with chlortriazines as the only type of herbicide for several years. As a result of this treatment, Digitaria sain · guinalis grew almost selectively on these plots.

The experiments and their evaluation were:. as described in Example 1.

The results are shown in the following table. '

Table II

Herbicidal effect (%) against Digitaria sanguinalis

C. active substance g / ha detected calculated difference 1 Atrazine 1000 * 0- - 2 Alachlor 1 680 25 - - 3 Pyridate 900 45 - - 14-2 10004- 1 680 37 33 4- 4 1 4- 3 - 10004- 53 51 4- 2 900 2 4-3 16804- 55 59 - 4 900 14-24-3 1000-4 100 ALIGN! 63 4-37

6804900 * Digitaria sanguinalis is resistant to atrazine

Claims (2)

the subject of the invention A herbicidal composition comprising as active ingredient O- [3-phenyl-6-chloropyrididinyl (4)] - S- (in-octyl) thiocarbonate in admixture with 2-chloro-4-ethylamino-6 -isopropylamino-1,3,5-triazine and the chloro-racetamide of formula I O Ri Cl — CH2 — C — N \ R2 (C 1 -C 3 alkyl and alkoxy groups and 1 part O- [3-phenyl-6-chloropyridazinyl (4)] - S- (n-octyl) thiocarbonate, 0.25 to 4 parts 2 ^{chloro-4-ethylamino:} 6-amino-isoprcpylammo-l, 3,5-triazine and 0.15 to 6 parts of chloroacetamide. 2. A herbicidal composition as claimed in claim 1, wherein the active ingredient is O- [3-phenyl-1-6-cycloadiazinyl (4)] -S- (n-octyl) thiocarbonate in admixture with 2-chloro-4-6-ethylamtoo isopD> py] lam ⁱ _I amino-l, 3,5-triazine and a chloroacetamide 2-chloro-N- - (2,6-diethylphenyl) -N-methoxymethyl) acetamide. 3. The herbicidal composition of claim 1, wherein the active ingredient is O- [3-phenyl-6-chloropyridinyl] (4) S- (n-octyl) hiocarbonate in admixture with 2-chloro- 5-ethylamino-6-isopropylamino-1,3,5-triazine and as chloroacetaned 2-chloro-N- - (2-ethyl-6-methylphenyl) -N- (2-methoxy-1-methylethyl) acetamide. where R 1 represents an alkyl radical, an alkoxyalkyl radical or a pyrazolyl-ylmethyl radical; and R2 represents a phenyl radical, a 2,6-dialkylphenyl radical or a trimethylcyclohexenyl radical, wherein in the substituents R1 and R2 have alkyl-