CS197329B2 - Herbicide means - Google Patents

Abstract

1. N-phenyl-N'-methyl-N'-methoxyurea derivatives of the formula see diagramm : EP0001225,P12,F2 where R denotes a branched alkyl of from 3 to 5 carbon atoms.

Description

The present invention relates to a herbicidal composition comprising as active ingredient novel valuable N-phenyl-N'-methyl-N'-methoxyurea derivatives. Said novel derivatives have a good herbicidal effect.

It is already known that N- (4-isopropylphenyl) -N ´, N´-dimethylurea (cf. U.S. Pat. No. 2,655,447, DOS 2,107,774, DOS

039 041) is well tolerated by winter wheat. At the same time, this compound has the ability to control unwanted grasses such as field fox (Alopecurus myosuroides) and some broadleaf weed species. However, this compound has quite insufficient activity against Galium aparine and other dicotyledonous weed species.

Considered in parallel to this compound, the known N- (4-isopropylphenyl) -N'-methoxy-N'-methyl-urea (cf. German Patent · 1,062,059), then the compound exhibits similar herbicidal activity. .

The known · N- (3-tert-butylphenyl) -N ´, N´-dimethylurea (cf. DOS 2,436,108) is a compound with a more intense herbicidal action. However, sometimes this compound is not well tolerated by cereals. Compared to this substance, it shows on average a weaker herbicidal effect, while at the same time somewhat more favorable - albeit very minor - selectivity in cereals known N- (3-methylphenyl) -N'-methoxy-N'-methylurea · (cf. DOS 1 905 598).

Surprisingly, it has now been found that derivatives of methoxymethyl urea in general

in which

R is a C 3 -C 5 branched alkyl group (e.g., isopropyl, isobutyl, sec-butyl, tert-butyl, 1,1-dimethylpropyl, 1-ethylpropyl, 1-methylbutyl, 2-dimethylpropyl group, 2-methylbutyl group (or 3-piethylbutyl group), have a very good herbicidal effect on undesirable monocotyledonous (dicotyledonous) and dicotyledonous (grassy and broadleaf) plants, including the bedstraw (Galium aparine) and are highly tolerated by cereals especially winters (rye, wheat, barley) in pre-emergence and post-emergence application.

The compounds of the invention are novel and can be prepared as follows:

After step 1

According to known methods, the aniline of formula II, wherein R is as defined above, is converted to the corresponding arylisocyanate of formula III by phosgene, which, in the absence of a solvent or diluent, is reacted with hydroxylamine or a salt thereof, the use of a salt also uses an organic or inorganic auxiliary base. The N-aryl-N ' -hydroxyurea of formula (IV) thus obtained is. according to known methods, in the presence of organic or inorganic auxiliary bases in a solvent or diluent, it is converted to the compound by treatment with a strong methylating agent, for example dimethyl sulfate. of formula I according to the invention:

Instead of hydroxylamine or a salt thereof, N-methylhydroxylamine or nebo, Ν-dimethylhydroxylamine or its salts can also be used, and in the case of the use of dimethylhydroxylamine, the subsequent methylation is naturally not carried out.

Procedure 2

Another method for obtaining ureas of the formula I according to the invention is to treat the aniline of the formula II in the presence of a diluent with N-methoxy-N-methylcarbamic acid chloride of the formula V in the presence of an inorganic auxiliary base:

CC-C-N 11 o

хсн, ^ ocw,

sCH 'OCH

Suitable anilines are, for example: m-tert-butylaniline, boiling point 73 ° C / 1.3 Pa, m-isopiropylanil, boiling point 65 ° C / 1.3 Pa.

Example 1

To a solution of 14.9 parts (parts by weight) of the mAniline of the formula II used for the production of ureas according to the invention can be prepared, for example, according to the procedure of H. G. Gilman et al., J. Org. Chem. 19, 1071 (1954).

Preference is given to the process referred to as process ₁₄

t-butylaniline and 10.1 parts of triethylamine in 100 parts of toluene were added dropwise at 20 to 40 ° C with 12.4 parts of N-methoxy-N-methylcarbamic acid chloride. After stirring for half an hour, the reaction mixture was washed with water, the organic phase was separated and evaporated.

Recrystallization from methylcyclohexane gave 17.2 parts of N-m-tert-butylphenyl-N '-methoxy-N'-methylurea, boiling 82-83 ° C.

Example 2

To a stirred mixture of 287 parts of hydroxylamine hydrochloride, 367 parts of water and 770 parts of dichloromethane are added dropwise at 0-5 ° C 330 parts of 33% sodium hydroxide. 443 parts of meta-isopropylphenyl isocyanate, which is dissolved in 400 parts of dichloromethane, are then added dropwise and the reaction mixture is allowed to stir overnight at room temperature. The precipitate formed is filtered off, washed with water and dried. 505 parts of N-m-isopropylphenyl-N'-hydroxyurea having a melting point of 120-123 ° C are obtained. This product was suspended in 1350 parts of water and dissolved by dropwise addition of 1000 parts of 39% sodium hydroxide solution. 920 parts of dimethyl sulphate are then added dropwise with stirring at 20 to 40 ° C, the mixture is stirred for 1 hour at room temperature, cooled to 5 ° C, the precipitate is filtered off, washed with water and dried. 480 parts of N-m-isopropylphenyl-N'-methoxy-N'-methylurea are obtained, which melts at 78-79 ° C after recrystallization from methylcyclohexane.

As application methods for the new active substances, the following may be applied: application to the soil, treatment of the soil surface or treatment of emerging plants. Special applications, such as post-directed, lay-by spraying, can also be considered. In this method of application, the spray of the spray liquid is directed so that the leaves of the emerging, sensitive crop plants are not sprayed as far as possible, while the composition is sprayed onto the soil surface underneath the plants or undesirable plants therein.

In view of the versatility of the application methods, the compositions according to the invention or mixtures containing them can be used in addition to the crop plants listed in the table for a wide range of crop plants in order to eliminate the growth of undesirable plants. The application rate can vary from 0.1 to 15 kg / ha, depending on the object to be coated.

The following examples demonstrate the control of grassy and broadleaf undesirable plants in winter with good crop tolerance. The experiments were carried out in a greenhouse and on a field plot.

1. Experiments in greenhouse

300 ml plastic pots filled with clayey soil with about 1.5 why humus as a substrate served as culture pots. The seeds of the test plants correspond to Table 1 and were sown separately by species. Immediately thereafter, the active substances were applied to the soil surface during the pre-emergence treatment. The active compounds were suspended in water or emulsified in water as dispersing medium and applied by means of fine nozzles. After application of the compositions, the containers were slightly sprinkled to allow germination and growth while simultaneously activating the chemical compositions. The containers are then covered with a transparent plastic sheet until the plants start growing. This cover causes simultaneous germination of the test plants, unless it is affected by chemicals, and prevents evaporation of easily volatile substances.

For the purpose of post-emergence treatment, the plants are first grown up to a height of 3 to 10 cm, depending on the form of growth, in the test vessels before the treatment is carried out. Covering is not performed. The test vessels are placed in a greenhouse. The duration of the experiment is 4 to 6 weeks. During this time the plants are cared for and their reaction to the individual treatments evaluated. The following tables contain data on the test substances, the amount in which they are applied in kg / ha and the species of plants tested. The evaluation is carried out on a scale of 0 to 100. In this case, 0 means no damage or normal growth, and 100 means that the plants do not appear or are completely destroyed, at least above the shoot.

2. Field experiments

These are trials on small plots at standard sites with clayey soil with a pH of 5 to 6 and containing 1 to 1.5% humus. Pre-emergence applications are described which are carried out immediately after sowing up to three days after sowing at the latest. In post-emergence treatment, the plants had germinal leaves up to several true leaves. However, cereals or undesirable grasses have not yet reached the rooting stage. The natural flora of weeds with various species was present. The substances are emulsified or suspended in water as a carrier and dispersing medium and applied to the plot using a tractor-mounted sprayer and powered by a motor. Natural rainfall was sufficient to ensure germination and growth of crops and weeds. All experiments are carried out for several months. During this time period, a rating of 0 to 100 is performed at certain intervals.

Result

Tables 2 to 8 contain numerical values of the results. The compounds according to the invention are distinguished by good properties. efficacy against a broad spectrum of undesirable plants. Winter tolerance is also good. Compared to known comparatives, the compounds according to the invention have a markedly better ability to control broad-leaved plants. In particular, these are species which have so far been difficult to control with cereal selective urea derivatives. A further advantage of the novel compounds is their low phytotoxicity compared to known active substances.

Table 1

List of tested plants Botanical name Alopecurus myosuroides Anthemis / Maaricaria Apera spica venti Chenopodium album Echinochloa crus galii Galinsoga parviflora Galium aparine Hordeum vulgare Lamium spp. Papaver spp. Polygonum persicaria Stellaria media Triticum aestivum Veronica spp.

Viola arvensis abbreviation in tables

Alopec. myos. Anthem./Matric. Apera spica v. Chenop. album Echin. c.

Galins. parv. Galium apar.

Hordeum vulg.

Polyg. pers.

Tritic. aest.

Viola arv.

English name foxtail / chamomile chundelka whisker goosefoot white hedgehog corn feet five-footed bedstraw barley deadnet poppy poppy chickweed frog wheat. Field Speedwell

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The novel herbicidally active substituted urea derivatives of the invention can be mixed with numerous representatives of other herbicidally active classes or growth-regulating active ingredients and then applied together. Such combinations serve to broaden the efficiency spectrum, and moreover, synergistic effects are often achieved. Among the many active substances which, together with the novel compounds, provide valuable mixtures, for example:

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H

H

H

CH2-OCH3

H and salts

Cl and salts

F and salts

CH3 and salts

H

i-C3H7

X

N - c - S - CH 2 - CCl = CHCl

Z II i — C3 H7 O

X

R1-C-C-O-R2

YR ²

Η СНз

СНз C2H5

СНз СНз

СНз. C 1 -C 3 H 7

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H CH3OSO3

Br CH3OSO3

CH3 CH3OSO3

CH3 * CF3SO3

COOH ^RR & salts, & smears &

R1 R2 R3. R ⁴ Cl H Cl ' OCH3 Cl Cl H Cl Cl Cl Cl OCH3

R @ 21 .dbd.CH - C - O - R @ ³

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H & SOtl.ftSURy> 0

SOlijtsUby

HIM . COOH α-Z / o-CH 2 CH 2 CH 3 COOH and others, (¾

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In addition, it is useful to mix the novel compounds of the invention alone or in combination with other herbicides also ^; with other plant protection products to be applied together Pest control agents, phytopathogenic fungi or growth regulators must be mentioned. Also of interest is the mixing with mineral fertilizer solutions which are used to eliminate deficiencies in plant nutrition or to eliminate deficiencies of trace elements.

Application is carried out, for example, in the form of directly sprayable solutions, powders, suspensions, as well as high percentage aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scatters, granules by spraying, misting, dusting, sprinkling or potting. The use forms depend entirely on the intended use. In any case, they are intended to ensure the finest possible distribution of the active compounds according to the invention.

For the preparation of directly sprayable solutions, emulsions, pastes and oil dispersions, suitable fractions of medium to high boiling mineral oil, such as kerosene or diesel oil, tar oils, etc., 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, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone etc., strongly polar solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, water, etc.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders, oil dispersions by the addition of water. For the preparation of emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized with wetting agents, adhesives, dispersing agents or emulsifiers in water. Concentrates consisting of the active ingredient, wetting agent, adhesive, dispersant or emulsifier and even solvent or oil can also be prepared, which concentrates are suitable for dilution with water.

Among the surfactants there may be mentioned:, alkali metal ligninsulfonic acid salts, alkaline earth metal salts, ammonium salts, naphthalenesulfonic acids, phenolsulfonic acids, alkylarylsulfonates, alkylsulfonates, alkali metal dibutylnaphthalenesulfonic acid salts and alkali earth metals, sulfated fatty alcohols, fatty salts alkali metal and alkaline earth metal acids, salts of sulfated hexadecanols, heptadecanols, octadecanols, salts of sulfated glycol ethers with fatty alcohols, condensation products of sulfonated naphthalene and derivatives of naphthalene with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and phenol and phenol and phenol , octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, condensation products of fatty alcohols with ethylene oxide, ethoxylates castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methylcellulose.

Powder formulations, dusts and dusts can be prepared by mixing or grinding the active ingredients 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, for example, mineral clays such as silica gel, silica, silica gel, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomite, calcium sulfate. and network. magnesium wounds, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and plant products such as cereal flour, tree bark flour, wood flour and shell nut flour197329 gait, powdered cellulose and other solid carriers.

The compositions contain between 0.1 and 95% by weight of active ingredients, preferably between 0.5 and 90% by weight.

Oils of various types, wetting agents or adhesives, nematicides, bactericides, antifoams (e.g. silicones) may be added to the mixtures or to the individual active ingredients. The admixture to these herbicide compositions according to the invention may be in a weight ratio of 1: 10 to 1: 1. The same applies to oils, wetting agents or adhesives, fungicides, nematicides, insecticides, bactericides and plant growth regulators.

EXAMPLE 1 3 parts by weight of the compound of Example 1 are mixed with 10 parts by weight of N-methyl-.alpha.-pyrrolidone to give a solution which is suitable for application as minimal drops.

Example 4 parts by weight of the compound of Example 2 are dissolved in the mixture. consisting of 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide with 1 mol of N-monoethanolamide oleic acid, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the addition product of 40 moles of ethylene oxide with 1 mol. castor oil. Pour this solution into 100,000 parts by weight of water and finely disperse it. to give an aqueous dispersion which contains 0.02% by weight of the active ingredient.

EXAMPLE 5 parts by weight of the compound of Example 2 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 7 moles of ethylene oxide with 1 mole of isooctylphenol, and parts by weight of the addition product of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring this solution into 100,000 parts by weight of water and finely distributing it gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example 6 parts by weight of the compound of Example 2 are dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point of 210 to 280 ° C and 10 parts by weight of an adduct of 40 moles of ethylene oxide. 1 mol of castor oil. Pouring this solution into 100,000 parts by weight of water and finely distributing it gives an aqueous dispersion containing 0.02% by weight of the active ingredient.

Example 7 parts by weight of the active compound of Example 2 are well mixed with 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts by weight of ligninsulfonic acid sodium salt from sulphite waste liquors and 60 parts by weight of powdered silica gel and milled in a hammer mill. . Gently disperse this mixture in 20,000 parts by weight of water. a spray suspension is obtained which contains 0.1% by weight of active ingredient.

Example parts by weight of the compound of. Example 1 was thoroughly mixed with 97 parts by weight of finely dispersed kaolin. A dust containing 3% by weight of the active ingredient is obtained.

Example 9 parts by weight of the compound of Example 2 is intimately mixed with a mixture of 92 parts by weight of silica gel powder and 8 parts by weight. of paraffin oil which has been sprayed onto the surface of this silica gel. In this way, an active substance preparation with good adhesion is obtained.

Example 10 parts by weight of active ingredient. according to Example 1, 10 parts by weight of sodium salt of the condensation product phenolsulfonic acid, urea and formaldehyde, 2 parts of silica gel and 48 parts of water are thoroughly mixed. A stable aqueous dispersion is obtained. . Dilute 100,000 parts by weight of water to make up. to give an aqueous dispersion which contains 0.04% by weight of the active ingredient.

Example 11 parts of the active compound of Example 2 are intimately mixed with 2 parts of calcium dodecylbenzenesulfonic acid, 8 parts of polyglycol ether of fatty alcohol, 2 parts of sodium salt of phenol, urea and formaldehyde condensation product and 68 parts of paraffinic mineral oil. Gets. with a stable oil dispersion.

Claims (1)

A herbicidal composition comprising, in addition to a solid or liquid carrier, at least one N-phenyl-N'-methyl-N'-methoxyurea derivative of the formula I as an active ingredient, in which: R is C 3 -C 5 branched alkyl. NH-CN ° ^С Ъ