CS208674B2 - Herbicide means - Google Patents

Abstract

1. A herbicidal agent for the selective control of unwanted plant growth in Indian corn, characterized in that it contains a substituted acetanilide of the formula I see diagramm : EP0009091,P5,F1 where R denotes methyl or ethyl, R**1 denotes methyl or ethyl, and A denotes a pyrazole radical which may be substituted by methyl groups in the 3- and 5-positions and which is attached via a ring nitrogen atom, as herbicidal active ingredient and N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine as antagonistic agent.

Description

The present invention relates to herbicidal compositions comprising substituted acetane and humans, as herbicidal active ingredients and N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine as an antagonist, and to a method for selectively combating undesirable plant growth by such herbicidal agents. resources.

Substituted acetanilides of the general formula I / Н = \ CH ₂ -N Ί (I) _{1 7} 7 ^_N \

R ¹ CO-CH ₂ -Cl in which _a

R and r 'represent a straight-chain or branched alkyl group having 1 to 5 carbon atoms, are herbicidally excellent, but lead to damage to useful plants when used in crops such as maize or in 2 crops of grasses ·

The object of the present invention was therefore to find antagonists which would compensate for this intolerance of herbicidally active acetanilides by certain crop plants.

Antagonistic agents (antidotes, antidotes) are chemical compounds whose presence results in increased compatibility of herbicidally active substances which are not selective or insufficiently selective by certain crop plants ·

The activity of herbicidal active substances against undesirable plants remains unaffected.

Herbicidal agents that beside. chloroacetanilides as herbicides 'comprises the antagonist' effective dichloroacetamides are known from U.S. Pat. No. 4 ⁰⁵³ 2 ^{9-DOS 2 218 0} 97 ⁴⁰² and DOS ⁹⁸ the third ^two addition! yin ^é it in those with ^p isech Mention ^d dichloroacetamides antidotes as possible where both eubetituenty on the nitrogen atom together with this nitrogen atom form a heterocyclic ring that contains additional heteroatorn eat and can be substituted by alkyl groups. As representative of this class of compounds, inter alia, N-dlchloroacetyl-2,2-diaethyl-1,3-oxazolidine is mentioned.

DOS 2 218 097 recommends this antagonist compound, but only in combination with herbicidally active thiolcarbamates, whereas from DOS 2 402 983 and U.S. Pat. No. 4,053,297 it is known that - K-dichloroacetyl-2,2-dbael-1-yl-1,333oaazolidine is useful as an antidote for reducing the damage caused to maize by the use of herbicidally active chloroacetanilides. '·

The chloroacetanilides used in this case contain chloroacetyl groups substituted with alkyl, alkoxyalkyl, alkenyloxyalkyl or cycloalkyloxyalkyl radicals or oxygen and / or sulfur-containing saturated rings bonded via a methylene group on the nitrogen atom of the solvent.

It has now found that N-dichloroacetyl-2,2-dimethyl-1,3 ^<oOxazolidin is suitable to increase snáěitelnosti herbicidal substituted acetanilides of the formula I to crop plants.

^H er ^{bi ID} N c ^ thanks to ^both plain ^to otaahuj are exercised and ^l es ^p on one subsUtuovaný tes ^{t ili} d n of formula ¹ and N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine can be used without difficulty In this case, the good herbicidal effect of acetanilides is maintained, while damage to the useful plants is avoided.

Acethanilides whose compatibility with crop plants can be improved by N-dichloroacatyl-2,2-dimathyl-1,3-oazazolidinam are represented by those acetanilides in which

Rafl 'are nominal ^or ALK ^y sk-yne with 1 ^and 5 atom as Math ^{ylз y} ^ amino ethyl ^p ro ^pylз isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or normal and branched pentyl groups.

In addition, the pyrazolyl moiety can also be salt-bound to any of the usual strong inorganic or organic such as strong inorganic or organic acids, such as hydrochloric acid, hydrobromic acid, mental acid, sulfuric acid, tetrafluoroboric acid, fluorosulfonic acid, formic acid, halogenated carboxylic acid , for example, trichloroacetic acid, alkanesulfonic acid, for example, mmnsulfonate, halogenated alkanesulfonic acid, for example, trifluoromethanesulfonic acid, perfluorohexanesulfonic acid, arylsulfonate (for example dodecylbenzenesulfonic acid).

Acetanilides which contain a methyl or ethyl group at the 2-position and the 6-position on the phenyl ring are preferred.

In particular, the herbicidal compositions according to the invention comprise the following acetanilides:

2-chloro-2 ^(pl xeLZO ^L - ¹ a ^{l y} l ^ thyl cetaniHd,

2-chloro-2 '-me 6 &apos; -ethyl-N- ^(p yrazol- ^1-yl methyl) ECET ^{and ethyloxanilide,}

2-chloro-2 ^* a * б ^{diethyelene l} lo ^Η- (plrazo ^l-1-l LMA ^t h ^ l ^ C ^ uxilid.

Particularly preferred compositions according to the invention comprises beside dichlorecatylo2,2 ^{Η-O-dimethyl-1,} 3o ^oχ ezolidinu as erb ^h ci ^{i o} n ^e l ^s TKU employed ^for chlorinating 2 -2 ^R *, ^{3 б-d im, and Thy-l Η -} (pl ^rezolo1- yl ^about methyDacetanilid.

Acethanilides of formula I are disclosed in DOS 2,648,008 and DOS 2,744,396. They can be prepared by reacting 2-halo-N-halomethyl acetanilides of formula II 8 with pyrazole according to the following reaction scheme:

R

(II) / СН2-С1

X co-ch ₂ -ci

(AND)

R @ 1 and R @ ^{1 are} as defined above.

The preparation of N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine is described in DOS 2 218 097 and in DOS 2 402 983.

N-Dichloro-ethyl-2,2-dimethyl-1,3-oxazolidine alone has no effect on germination and growth of both crop plants and undesirable plants, or, if it does, 89 it is a minor effect, even when an amount administered that is significantly higher than that required to achieve an antagonistic effect.

However, they have the ability to significantly reduce or eliminate the phytotoxicity of the herbicidally active acetanilides of the formula I towards crop plants such as maize.

For herbicidally effective assimilation of people which are not very aggressive to crop plants, the slight addition of N-dichlo-racyl-2,2-dimethyl-1,3-oxazolidine is sufficient. The ratio of acetanilide: N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine can vary within wide limits. It depends on the acetanilides used. Suitable ratios of herbicidally active substance: N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine are between 1: 2 and 1: 0.01 parts by weight.

Acethanilides and antagonists may be incorporated into the soil together or separately, before or after sowing.

For acetanilides of the formula I, the most preferred method of application to the soil surface is immediately after sowing of seeds or in the time between sowing and emergence of young plants. Treatment during and shortly after emergence is also possible. In any case, the antagonist active compound may be administered concurrently with the herbicidally active agent.

Separate use is also possible, wherein the antagonist is applied first and then the herbicide is applied or the herbicide is applied first to the plot and then the antagonist, unless in the latter case the time interval is so long that the herbicide already causes damage to the crop plants.

The herbicide and the antagonist can be used in the form of spraying agents in suspendable, emulsifiable or soluble form or in the form of granules and can be prepared separately or together.

It is also possible to treat the seeds of the crop plants with an antagonist active substance before sowing. The herbicide is then applied alone in the usual manner.

The novel herbicidal compositions may contain, in addition to acetanilides and an antagonist, other herbicidal or plant growth regulating agents of another chemical structure, such as 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, without N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine antagonist effect.

The compositions according to the invention, if appropriate for the separate application of the herbicidal active ingredient and the antidote, are used, for example, in the form of directly sprayable solutions, powders, suspensions, also high percentage aqueous, oily or other suspensions, or dispersions, emulsions, oil dispersions, pastes, dusts, dusts or granules. it by spraying, for

208674 4 Fogging, dusting, tossing or watering. The dosage forms are entirely guided by purposes; use. These forms are intended in each case to ensure the finest possible distribution of the compositions according to the invention or of the individual components.

For the production of directly sprayable solutions, emulsions, pastes and oil dispersions, suitable fractions are those of a medium to high boiling point mineral oil such as kerosine or oil for diesel engines, as well as tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or derivatives thereof such as methanol, ethanol, propanol, butanol, chloroform, tetrahydrofuran, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents such as dlastbylformamide, dimethylsulfoxide, N-methylpyrrolidone or water.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders, oil dispersions by adding water. For the preparation of emulsions, pastes or oil dispersions, the herbicidally active substances and / or the antidotes as such or dissolved in an oil or solvent can be homogenized using wetting agents, adhesives, dispersants or emulsifiers in water.

However, concentrates consisting of the active ingredient and / or an antidote, an adhesive, a wetting agent, a dispersing agent or an emulsifying agent and optionally a solvent or an oil which are suitable for dilution with water can also be prepared.

The following surfactants are suitable:

alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, ammonium salts, naphthalenesulfonic acids, phenolaulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, alkali metal dibutylnaphthalenesulfonic acid salts and alkaline earth metal salts, lauryl ether sulfate, sulfated fatty acid salts, and with alkaline earth metals, salts of sulfated hexadecanols, heptadecanols, octadecanols, salts of sulfated glycol ethers of fatty alcohols, condensation products of sulfonated naphthalene and derivatives of naphthalene and formaldshyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol ethoxyl-ethylenehydroxyol, phenoxyethylene oxide, , alkylphenol glycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, condensation products of fatty alcohols and ethylene oxide, ethoxylated castor o oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powder, spreading agents and dusts can be prepared by mixing or co-grinding the herbicidally active substance and / or the antidote with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral clays such as silica gel, silicic acid, silica gels, silicates, talc, kaolin, attaclay, limestone, chalk, bolus, dust, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground plastic masses, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and plant products such as ground grain, tree bark meal, wood meal and nut shell meal, powdered cellulose and other solids.

The compositions contain between 0.1 and 95% by weight of the herbicidal active ingredient and / or an antidote, preferably between 0.5 and 90% by weight. The application rate of the herbicidally active compound is applied together or separately with 8 amounts of the antidote such that the ratio of the herbicidally active compound to the antagonist is 1: 2 to 1: 0.05 parts by weight.

Examples illustrating the composition and preparation of formulations:

6708674 parts by weight of a mixture of 4 parts by weight of 2-chloro-2% 6'-aminomethyl-N- (pyrrol-1-ylmethyl) acetamide and 1 part by weight of N-dichloroacetyl-2,2'-dimethyl-1,3 ' The oxazolidine was thoroughly mixed with 10 parts of the sodium salt of the phenol sulfonic acid, urea and formaldehyde condensation product, 2 parts of silica gel and 48 parts of water.

A stable aqueous dispersion is obtained. Dilution with 100,000 parts by weight of water gives an aqueous dispersion containing 0.04% by weight of the active ingredient.

2, 3 parts by weight of a mixture consisting of 1 part by weight of 2-chloro-2 ^', 6, ⁴ &apos; -dimethyl-N- • (pyrazol-1-ylmathyl) acetanilide and 1 part by weight of N-dichloroacetyl-2,2-dimethyl- 1,3-oxazolidine is mixed thoroughly with 97 parts by weight of finely dispersed kaolin. In this way, a dust containing 3% by weight of the active ingredient is obtained.

30 parts by weight of a mixture consisting of 1 part by weight of 2-chloro-2'-methyl-6-ethyl-N- (pyrazol-1-ylmethyl) acetanilide and 2 parts by weight of N-dichloroacetyl-2,2-dimethyl-1-oxazolidine ee is intimately mixed mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin _oil which has been sprayed onto the surface of this silica gel aa. In this way, an effective agent with good adhesion is obtained.

Fourth 20 parts of a mixture consisting of 8 parts 2₽chlcr-2 ^{<l -methyl-6} &apos; -ethyl-N- (pyrazol-1-ylmethyl) -acetanilide and 1 part by weight of N-dichl.Grac®tyl- 2 _? The 2-dimethyl-1,3-oxazolidine is thoroughly mixed with 2 parts of calcium dodecylbenzenesulfonic acid, 8 parts of polyglycol ether of the bridge alcohol, 2 parts of sodium salt, phenolsulfonic acid, urea and formaldehyde condensation product and 68 parts of paraffinic mineral oil. In this way, a stable oil dispersion is obtained.

5. 20 parts by weight of mixtures comprising 10 parts by weight of 2-chloro-2 ', 6'-dimethyl-N- (pyrazol-1-ylmethyl) acetanilides and 1 part by weight of N, N-dichloroacetyl-2,2-dimethyl hyl-1,3-oxazolidine is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the editorial product of 7 moles of ethylene oxide with 1 mole of ooctylphenol and 10 parts by weight of the editorial product of 40 moles of ethylene oxide with 1 mol of castor oil ·

By pouring and finely distributing this solution in 100,000 parts by weight of water, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

Greenhouse experiments show that the use of the herbicidal compositions of the present invention will increase the tolerability of the herbicidally active acetanilides by the crop plants without reducing the herbicidal activity.

Plastic boxes with a length of 51 cm, a clear 32 cm and a height of 6 cm are filled with clay sandy soil or clay with a pH of 6-7 containing about 1.5% humus.

In this row, maize (Zea mays) is sown in this substrate as a crop plant. In addition, the corn-eared echinch (Echinochloa crus galii) is widely sown as an undesirable plant. The non-sterilized soil also contains viable weed seeds that contribute! to reproduce unwanted plants. This simulates a plot sown with a cultural plant and a flood of weeds

The active compounds and the antagonist compound are administered both individually and in the mixtures described. These substances, emulsified or suspended in water as the vehicle, are applied by spraying onto the soil surface using fine nozzles immediately after sowing or before emergence of the test plants. After sowing and treatment, the boxes are irrigated and covered with transparent plastic foils until the plants have emerged. This will ensure even germination and growth of the plants.

208673 <6

Placing те greenhouse is carried out in parts where the average temperature is from 18 to 30 ° C. The experiments carried out in the greenhouse are monitored until the maize has developed 3 to 5 leaves.

The activity of the compositions is evaluated on a scale of 0 to 100. In this case, 0 means normal emergence and normal plant development relative to untreated control plants. A value of 100 means that the seeds have not germinated or the plants have died. It should be taken into account that, for example, in maize, even in normal conditions and without any chemical treatment, individual dwarf or otherwise inhibited plants are present.

The following table shows the extent to which N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine increases the tolerability of the acetanilides of formula I, e.g. ) acetanilide, corn.

Table

Improvement of the compatibility of 2-chloro-2 *, 6'-dimethyl-N- (pyrezol-1-ylmethyl) acetanilide by maize due to the action of X-dichloroacetyl-2,2-dimetbyl-1,3-oxazolidine in pre-emergence treatment in a greenhouse herbicidally effective substance antagonist used active substance amount (kg / ha) of the test plant and% damage Zea mays Echinochloa crua galii

AND

В

1.0 64 99 £ 0 В r ~ \ 2,0 79 99 AND CI ₂ CH-C- 4.0 2 0 ^H ₃ C CH ₃ ♦ AND 1,0 + 0.25 15 Dec 98 1.0 4 · 2.0 10 98 2,0 ♦ 0.5 14 99 2,0 + 2,0 10 100 ALIGN! 1.0 4 · 0.125 13 99 1,0 4- 0.4 17 99 1, 0 4 it 6 96 2,0 ► 0.2 8 100 ALIGN! , ^ch 2 ~ ⁿ _in J> ',O 61 99 COCH ₂ CJ 2,0 78 99 1 1,0 + 0.25 12 100 ALIGN! 1,0 + 0.125 17 100 ALIGN! 2,0 + 0.5 10 f 00

= no damage

100 = plants not dead or dead

Claims (1)

SUBJECT OF THE INVENTION A herbicidal composition comprising a solid or liquid carrier and 0.1 to 95% by weight of a mixture consisting of a compound of formula (X) CO-CH ₂ -Cl (I) wherein R @ ¹ and R @ ¹ denote an unbranched or branched alkyl group having from 1 to 5 carbon atoms, which groups may be the same or different from each other as the herbicidally active compounds and N-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine as antagonists 1: 2 to 1: 0.01.